Polymers and Polymeric Composites:

A Reference Series

Mohammad Abu Jafar Mazumder

Heather Sheardown
Amir Al-Ahmed Editors

Functional
Polymers
Polymers and Polymeric Composites:
A Reference Series
This series provides a comprehensive collection of reference handbooks on all
aspects around polymers and polymeric composites. Polymeric materials of all
sorts have been emerging as key materials for many applications and for meeting
the challenges of the twenty-first century. From commodity applications to engi-
neering and high-tech applications, even including aerospace subsystems, these
materials have an important role to play. The study of polymeric and polymeric
composite materials is one of the most important and vibrant focus areas in chemical
and material scientific research. “Polymers and Polymeric Composites: A Reference
Series” compiles the most comprehensive reference handbooks on these materials
under one roof. Readers will find all they need to know in well-organized and
thoroughly structured reference works covering various topics, such as the structures
and properties of polymers, polymeric materials and composites (e.g. structures of
amorphous and crystalline polymers, viscoelastic properties, mechanical and ther-
mal properties, and many more); methods and methodology (including polymer
characterization, polymerization reaction engineering, polymer processing, and
many more); and different compound classes (from polymer additives, polymer
blends, and fiber reinforced composites to liquid crystalline polymers, nano-
polymers and nano-polymeric composites, and even bio-polymeric materials).
While each volume is dedicated to a selected topic, concisely structured and thor-
oughly edited by experts, with contributions written by leading scientists, the
complete collection provides the most comprehensive and most complete overview
over the entire field of polymers and polymeric composites. Volumes in this series
serve as reference compilation for every scientist working with or on polymers and
polymeric materials and composites, whether at universities or in industry, from
graduate student level to practitioners and lead scientists alike.

More information about this series at http://www.springer.com/series/15068

Mohammad Abu Jafar Mazumder
Heather Sheardown • Amir Al-Ahmed
Editors

Functional Polymers

With 473 Figures and 65 Tables

Editors
Mohammad Abu Jafar Mazumder Heather Sheardown
Chemistry Department McMaster University
King Fahd University of Petroleum Hamilton, ON, Canada
and Minerals
Dhahran, Saudi Arabia

Amir Al-Ahmed
Center of Research Excellence in
Renewable Energy
King Fahd University of Petroleum
and Minerals
Dhahran, Saudi Arabia

ISSN 2510-3458 ISSN 2510-3466 (electronic)

ISBN 978-3-319-95986-3 ISBN 978-3-319-95987-0 (eBook)
ISBN 978-3-319-95988-7 (print and electronic bundle)
https://doi.org/10.1007/978-3-319-95987-0
© Springer Nature Switzerland AG 2019
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the
material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,
broadcasting, reproduction on microfilms or in any other physical way, and transmission or information
storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology
now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors, and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
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Preface

Functional polymers contain chemically bound functional groups on their backbone,

which make these polymers chemically active for various applications, for example, as
reagents, catalysts, protecting groups, and many others. Normally, functional polymers
are prepared from monomers containing the desired functional group. The preformed
polymer backbone can also be chemically modified with a preferred functional group.
The second approach is more suitable for linear polymers, but in most applications,
cross-linked polymers are preferred. Suspension polymerization is the most commonly
used technique for cross-linked polymers, but several other techniques, such as photo
polymerization, electrochemical polymerization, and different controlled radical poly-
merizations are also attaining their place. The physicochemical properties of these
polymers can be modified as required by chemical or physical means. Specific induced
properties by functionalization of polymers have great importance in their applications.
Advance technologies require improved material performance. Polymers, especially
functional polymers can easily be tuned by new or improved design and processing
techniques, which can provide better or specific material characteristics. This facilitates
their innovative and technically demanding applications.
To edit or compile a book on functional polymers, one should be very careful to
keep a fine balance between the built up knowledge developed over the years, based
on experience and intuition, and the new scientific endeavors that continue to
advance their development. Our approach is to give a rich collection of data on
functional polymers. In this regard, this reference book covers some key aspects of
functional polymers, such as synthesis, surface modification, composites and nano-
composites, and important applications. All chapters are contributed by experts in

v
vi Preface

their respective field and contain up-to-date theoretical and experimental informa-
tion, which will be helpful for students and researchers to create new avenues for
functional polymers – in terms of material development and advance applications.

Chemistry Department Mohammad Abu Jafar Mazumder, Ph.D.

King Fahd University of Petroleum
and Minerals, Dhahran, Saudi Arabia
McMaster University, Hamilton, ON, Canada Heather Sheardown, Ph.D.
Center of Research Excellence in Renewable Energy Amir Al-Ahmed, Ph.D.
King Fahd University of Petroleum and Minerals, The Editors
Dhahran, Saudi Arabia
Acknowledgments

We are thankful to all contributing authors and co-authors for their valued contribu-
tion to this book. The project would never have been possible without their sincere
supports and contributions. We would also like to express our gratitude to the
publisher, authors, and others for granting us the copyright permission to use their
illustrations. Although sincere efforts were made to obtain the copyright permissions
from the respective owners to include the citation with the reproduced materials, we
would like to offer our sincere apologies to any copyright holder if unknowingly
their right is being infringed. Among the editors, Dr. Mohammad A. Jafar Mazumder
would like to take this opportunity to express his sincere thanks to Drs. Abdulaziz
A. Al-Saadi (Dean, College of Sciences, KFUPM) and Khalid R. Alhooshani
(Chairman, Chemistry Department, KFUPM) and also to his colleagues at the
King Fahd University of Petroleum and Minerals (KFUPM), Saudi Arabia.
Dr. Amir Al-Ahmed, would like to take this opportunity to express his sincere
thanks to Dr. Fahad Al-Suliman (Director CORE-RE, KFUPM) and also to his
colleagues at the King Fahd University of Petroleum and Minerals, Saudi Arabia.
Without their continuous encouragement, this book would have not been brought
into its final form. We would also like to acknowledge the sincere efforts of Springer
team, especially Dr. Sylvia Blago, Dr. Sofia Costa, and Dr. Judith Hinterberg and
others who were always so helpful and provided us their assistance in evolving this
book into its final shape. We are most grateful to all of them.

vii
Contents

1 Photo-polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Prem Prabhakaran and Kwang-Sup Lee
2 Polymer Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Lindsey A. Bultema, Xia Huang, Daniel D. Brauer, and Patrick Theato
3 Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Gertrude Fomo, Tesfaye Waryo, Usisipho Feleni, Priscilla Baker, and
Emmanuel Iwuoha
4 Polymer Processing and Rheology . . . . . . . . . . . . . . . . . . . . . . . . . 133
Nickolas D. Polychronopoulos and John Vlachopoulos
5 Porous Coordination Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Abdul Malik P. Peedikakkal and N. N. Adarsh
6 Polyurethane and Its Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 225
Mohammad Mizanur Rahman, Mohammad Mahbub Rabbani, and
Joyanta Kumar Saha
7 Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Shah Mohammed Reduwan Billah
8 Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
Balappa B. Munavalli, Satishkumar R. Naik, Anand I. Torvi, and
Mahadevappa Y. Kariduraganavar
9 Surfaces and Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Manfred Stamm
10 Membrane Surface Modification and Functionalization . . . . . . . . 391
Syed Mohammed Javaid Zaidi, Kenneth A. Mauritz, and Mohammad
K. Hassan
11 Fiber-Reinforced Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
Ajithkumar Manayan Parambil, Jiji Abraham, Praveen
Kosappallyillom Muraleedharan, Deepu Gopakumar, and Sabu
Thomas
ix
x Contents

12 Composites and Nanocomposites .......................... 447

Shah Mohammed Reduwan Billah
13 Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
Ibrahim Khan, Muhammad Mansha, and Mohammad Abu Jafar
Mazumder
14 Conducting Polymers and Composites . . . . . . . . . . . . . . . . . . . . . . 551
Abd Almonam Baleg, Milua Masikini, Suru Vivian John, Avril Rae
Williams, Nazeem Jahed, Priscilla Baker, and Emmanuel Iwuoha
15 Shape-Memory Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
Magdalena Mazurek-Budzyńska, Muhammad Yasar Razzaq, Marc
Behl, and Andreas Lendlein
16 Self-Healing Polymers: From Biological Systems to Highly
Functional Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
Stefan Zechel, Martin D. Hager, and Ulrich S. Schubert
17 Drug Delivery: Polymers in the Development of Controlled
Release Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 719
Scott Campbell and Niels Smeets
18 Conjugated Organic Polymers for Optoelectronic Devices ...... 749
Shahid Pervez Ansari and Farman Ali
19 Electrochromic Polymers for Solar Cells . . . . . . . . . . . . . . . . . . . . 789
Suru Vivian John and Emmanuel Iwuoha
20 Textile Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
Shah Mohammed Reduwan Billah
21 Anticorrosive Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883
Mazen K. Nazal and Mohammad Abu Jafar Mazumder
22 Conducting Polymer Nanocomposites as Gas Sensors . . . . . . . . . . 911
Mohammad Omaish Ansari, Sajid Ali Ansari, Moo Hwan Cho,
Shahid Pervez Ansari, Mohamed Shaaban Abdel-wahab, and Ahmed
Alshahrie
23 Polymeric Membranes for Natural Gas Processing: Polymer
Synthesis and Membrane Gas Transport Properties . . . . . . . . . . . 941
Jimoh K. Adewole and Abdullah S. Sultan
24 Proton Conductions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977
N. Awang, Juhana Jaafar, A. F. Ismail, T. Matsuura, M. H. D. Othman,
and M. A. Rahman
25 Desalination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1011
Rasel Das, Syed Mohammed Javaid Zaidi, and Sayonthoni Das Tuhi
Contents xi

26 Enhanced Oil Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045

Muhammad Shahzad Kamal and Abdullah S. Sultan

27 Drug Delivery: Localized and Systemic Therapeutic Strategies

with Polymer Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1079
Scott Campbell and Niels Smeets

28 Organic-Inorganic Hybrid Materials and Their Applications . . . . 1135

Rizwana Mobin, Tauseef Ahmad Rangreez, Hamida Tun Nisa Chisti,
Inamuddin, and Mashallah Rezakazemi
About the Editors

Dr. Mohammad Abu Jafar Mazumder is an Associate

Professor of Chemistry at King Fahd University of Petro-
leum and Minerals (KFUPM), Saudi Arabia, who has a
wide experience in design, synthesis, modification and
characterization of various organic compounds, ionic
and thermo-responsive polymers using various spectro-
scopic and chromatographic techniques. Dr. Jafar
Mazumder earned his Ph.D. in Chemistry) (2009) from
McMaster University, Canada followed by 2 years
MITACS-postdoctoral fellowship in Chemical and Bio-
medical engineering at McMaster University, Canada.
In 17 years of academic research, Dr. Jafar
Mazumder has had the opportunity to work with several
international collaborative research groups and has
exposed himself to a broad range of research areas,
including chemistry, engineering and material sciences
where he developed and engineered synthetic and natu-
ral organic and polymeric materials for various applica-
tions. Moreover, he has over three years of working
experience in pharmaceutical and polymer industry,
worked on the development, optimization and charac-
terization of various polymers/chemicals and exposed
with a variety of analytical techniques/instruments.
Dr. Jafar Mazumder secured 5 US patents, 2 books
edited, 6 invited book chapters, published more than
50 journal articles in synthesis, characterization and appli-
cations based peer reviewed journal of Chemistry and
material sciences, and had the opportunity to present his
research more than 25 international conferences. Dr. Jafar
Mazumder has conducted and completed several internally
and externally funded research projects from KFUPM,
Saudi Aramco, KACST and NSTIP. Currently, he is
actively involved in a number of ongoing university, and

xiii
xiv About the Editors

client funded research projects in a capacity of principal

and co- investigators where he is responsible for synthesis
and characterization of various materials including modi-
fication of monomers and polymers for their potential use
as corrosion inhibitors and for the removal of heavy metal
ions and organic contaminants from aqueous samples.

Heather Sheardown is a Professor in the Department of

Chemical Engineering with a cross appointment to the
Department of Pathology and Molecular Medicine and
an adjunct appointment with the School of Optometry at
the University of Waterloo. She holds a Tier 1 Canada
Research Chair in Ophthalmic Biomaterials and Drug
Delivery and has published more than 140 peer reviewed
papers on this subject. She is currently the Scientific Direc-
tor of C20/20, an ORF funded incubator aimed at the
commercialization of ophthalmic biotechnologies.
Sheardown was previously the Scientific Director of the
20/20 NSERC Ophthalmic Materials Research Network
which brought together 12 researchers and more than
10 companies aimed at the early stage development of
novel materials based treatments for ophthalmic condi-
tions. Sheardown is the Associate Director of Biomedical
Engineering and Advanced Manufacturing (BEAM), a
McMaster partnership with the Fraunhofer IZI which part-
ners with companies for incubation and commercialization
of cell based therapies, diagnostics and biomaterials. She
holds 18 patents or provisional patents and is currently the
Chief Scientific Officer of 20/20 OptimEyes, a McMaster
based spin out focused on developing and commercializ-
ing a micelle based technology developed in her labora-
tory. She runs a large and vibrant research group with more
than 10 post doctoral fellows, and graduate students.

Dr. Amir Al-Ahmed is working as a Research Scientist-

II (Associate Professor) in the Center of Research Excel-
lence in Renewable Energy (CoRE-RE), at King Fahd
University of Petroleum and Minerals (KFUPM), Saudi
Arabia. He graduated in chemistry from the Department
of Chemistry, Aligarh Muslim University (AMU), India.
Then completed his M.Phil. (2001) and Ph.D. (2003)
degree in Applied Chemistry from the Department of
Applied Chemistry, AMU, India, followed by three
consecutive postdoctoral fellowships in South Africa
About the Editors xv

and Saudi Arabia. During this period he worked on various

multidisciplinary projects in particular, electrochemical
sensors, nano-materials, proton exchange membranes,
DMFC, electro-catalysis and solar cells. At present, his
research activity is fundamentally focused on 3rd genera-
tion solar cell devices such as low band gap semiconductor
quantum dot structures, perovskite cells and silicon nano-
wire base tandem cells. At the same time, he is also having
projects on PCM based latent heat energy storage, evalu-
ation of electricity storage devices and dust repellent coat-
ing for Harsh Saudi Arabian weather condition. He has
worked on different KACST, NSTIP and Saudi Aramco
funded projects in the capacity of a co-investigator and
principle investigator. Dr. Amir has two US patents, over
60 journal articles, invited book chapters and conferences
publications. He has edited nine books with Trans Tech
Publication, and Elsevier and several other books are in
progress. He is also the Editor-in-Chief of an international
journal “Nano Hybrids and Composites” along with Pro-
fessor Y. H. Kim.
Contributors

Mohamed Shaaban Abdel-wahab Center of Nanotechnology, King Abdulaziz

University, Jeddah, Saudi Arabia
Materials Science and Nanotechnology Department, Faculty of Postgraduate Studies
for Advanced Sciences, Beni-Suef University, Beni-Suef, Egypt
Jiji Abraham International and Inter University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India
N. N. Adarsh Solid State and Materials Chemistry, School of Chemical Sciences,
Mahatma Gandhi University, Kottayam, Kerala, India
Jimoh K. Adewole Center for Integrative Petroleum Research, College of
Petroleum Engineering and Geosciences, King Fahd University of Petroleum and
Minerals, Dhahran, Saudi Arabia
Farman Ali Department of Applied Chemistry, Faculty of Engineering and
Technology, Aligarh Muslim University, Aligarh, India
Ahmed Alshahrie Center of Nanotechnology, King Abdulaziz University, Jeddah,
Saudi Arabia
Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah,
Saudi Arabia
Mohammad Omaish Ansari Center of Nanotechnology, King Abdulaziz Univer-
sity, Jeddah, Saudi Arabia
School of Chemical Engineering, Yeungnam University, Gyeongbuk, South Korea
Sajid Ali Ansari Department of Energy and Materials Engineering, Dongguk
University, Seoul, Republic of Korea
Shahid Pervez Ansari Department of Applied Chemistry, Faculty of Engineering
and Technology, Aligarh Muslim University, Aligarh, India
N. Awang Advanced Membrane Technology Research Centre (AMTEC),
Universiti Teknologi Malaysia, Johor Bahru, Malaysia
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, Johor
Bahru, Malaysia
xvii
xviii Contributors

Priscilla Baker SensorLab, Department of Chemistry, University of the Western

Cape, Bellville, South Africa
Abd Almonam Baleg Department of Chemistry, University of the Western Cape,
Bellville, South Africa
Marc Behl Institute of Biomaterial Science, Helmholtz-Zentrum Geesthacht,
Teltow, Germany
Shah Mohammed Reduwan Billah University of East London, Stratford Campus,
London, UK
CCIRA UK limited, Galashiels, UK
Department of Chemistry, Durham University, Durham, UK
School of Textiles and Design, Heriot-Watt University, Galashiels, UK
Daniel D. Brauer Institute of Technical and Macromolecular Chemistry, Univer-
sity of Hamburg, Hamburg, Germany
Lindsey A. Bultema Institute of Technical and Macromolecular Chemistry,
University of Hamburg, Hamburg, Germany
Scott Campbell Department of Chemical Engineering, McMaster University,
Hamilton, ON, Canada
Hamida Tun Nisa Chisti National Institute of Technology, Srinagar, India
Moo Hwan Cho School of Chemical Engineering, Yeungnam University,
Gyeongbuk, South Korea
Rasel Das Chemical Department, Leibniz Institute of Surface Engineering,
Leipzig, Germany
Usisipho Feleni SensorLab, University of Western Cape, Cape Town, South Africa
Nanotechnology and Water Sustainability Research Unit, University of South
Africa, Johannesburg, South Africa
Gertrude Fomo SensorLab, University of Western Cape, Cape Town, South Africa
Deepu Gopakumar International and Inter University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India
Martin D. Hager Laboratory of Organic and Macromolecular Chemistry (IOMC),
Friedrich Schiller University Jena, Jena, Germany
Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Jena,
Germany
Mohammad K. Hassan Center for Advanced Materials, Qatar University, Doha,
Qatar
Contributors xix

Xia Huang Institut für Technische Chemie und Polymerchemie, Karlsruher Institut
für Technologie, Karlsruhe, Germany
Inamuddin Advanced Functional Materials Laboratory, Department of Applied
Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University,
Aligarh, India
A. F. Ismail Advanced Membrane Technology Research Centre (AMTEC),
Universiti Teknologi Malaysia, Johor Bahru, Malaysia
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, Johor
Bahru, Malaysia
Emmanuel Iwuoha SensorLab, Department of Chemistry, University of the
Western Cape, Bellville, South Africa

Juhana Jaafar Advanced Membrane Technology Research Centre (AMTEC),

Universiti Teknologi Malaysia, Johor Bahru, Malaysia
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, Johor
Bahru, Malaysia
Mohammad Abu Jafar Mazumder Chemistry Department, King Fahd University
of Petroleum and Minerals, Dhahran, Saudi Arabia

Nazeem Jahed Department of Chemistry, University of the Western Cape,

Bellville, South Africa
Suru Vivian John Department of Chemistry, University of the Western Cape,
Bellville, South Africa
Mahadevappa Y. Kariduraganavar Department of Chemistry, Karnatak Univer-
sity, Dharwad, India

Ibrahim Khan Chemistry Department, King Fahd University of Petroleum and

Minerals, Dhahran, Saudi Arabia
Praveen Kosappallyillom Muraleedharan International and Inter University
Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University,
Kottayam, Kerala, India
Department of Mechanical Engineering, Saintgits College of Engineering,
Kottayam, Kerala, India

Kwang-Sup Lee Department of Advanced Materials and Chemical Engineering,

Hannam University, Daejeon, South Korea
Andreas Lendlein Institute of Biomaterial Science, Helmholtz-Zentrum
Geesthacht, Teltow, Germany
Institute of Chemistry, University of Potsdam, Potsdam, Germany
xx Contributors

Ajithkumar Manayan Parambil International and Inter University Centre for

Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala,
India
Muhammad Mansha Chemistry Department, King Fahd University of Petroleum
and Minerals, Dhahran, Saudi Arabia
Milua Masikini Department of Chemistry, University of the Western Cape,
Bellville, South Africa
T. Matsuura Advanced Membrane Technology Research Centre (AMTEC),
Universiti Teknologi Malaysia, Johor Bahru, Malaysia
Department of Chemical Engineering, University of Ottawa, Ottawa, ON, Canada
Kenneth A. Mauritz School of Polymers and High Performance Materials, The
University of Southern Mississippi, Hattiesburg, MI, USA
Magdalena Mazurek-Budzyńska Institute of Biomaterial Science, Helmholtz-
Zentrum Geesthacht, Teltow, Germany
Rizwana Mobin Government College for Women, Srinagar, India
Balappa B. Munavalli Department of Chemistry, Karnatak University, Dharwad,
India
Satishkumar R. Naik Department of Chemistry, Karnatak University, Dharwad,
India
Mazen K. Nazal Centre for Environment and Water (CEW), King Fahd University
of Petroleum and Minerals, Dhahran, Saudi Arabia
M. H. D. Othman Advanced Membrane Technology Research Centre (AMTEC),
Universiti Teknologi Malaysia, Johor Bahru, Malaysia
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, Johor
Bahru, Malaysia
Abdul Malik P. Peedikakkal Department of Chemistry, King Fahd University of
Petroleum and Minerals, Dhahran, Kingdom of Saudi Arabia
Nickolas D. Polychronopoulos Polydynamics Inc., Dundas, ON, Canada
Prem Prabhakaran Department of Advanced Materials and Chemical Engineer-
ing, Hannam University, Daejeon, South Korea
Mohammad Mahbub Rabbani Department of Chemistry, American International
University-Bangladesh (AIUB), Dhaka, Bangladesh
M. A. Rahman Advanced Membrane Technology Research Centre (AMTEC),
Universiti Teknologi Malaysia, Johor Bahru, Malaysia
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, Johor
Bahru, Malaysia
Contributors xxi

Mohammad Mizanur Rahman Center of Research Excellence in Corrosion, King

Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Tauseef Ahmad Rangreez National Institute of Technology, Srinagar, India
Muhammad Yasar Razzaq Institute of Biomaterial Science, Helmholtz-Zentrum
Geesthacht, Teltow, Germany
Mashallah Rezakazemi Faculty of Chemical and Materials Engineering, Shahrood
University of Technology, Shahrood, Iran
Joyanta Kumar Saha Department of Chemistry, Jagannath University, Dhaka,
Bangladesh
Ulrich S. Schubert Laboratory of Organic and Macromolecular Chemistry
(IOMC), Friedrich Schiller University Jena, Jena, Germany
Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Jena,
Germany
Muhammad Shahzad Kamal Center for Integrative Petroleum Research, King
Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Department of Petroleum Engineering, King Fahd University of Petroleum and
Minerals, Dhahran, Saudi Arabia
Niels Smeets EcoSynthetix, Burlington, ON, Canada
Manfred Stamm Institute of Physical Chemistry and Physics of Polymers, Leib-
niz-Institut für Polymerforschung Dresden e. V., Dresden, Germany
Abdullah S. Sultan Department of Petroleum Engineering, College of Petroleum
Engineering and Geosciences, King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
Center for Integrative Petroleum Research, King Fahd University of Petroleum and
Minerals, Dhahran, Saudi Arabia
Patrick Theato Institut für Technische Chemie und Polymerchemie, Karlsruher
Institut für Technologie, Karlsruhe, Germany
Sabu Thomas International and Inter University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India
Anand I. Torvi Department of Chemistry, Karnatak University, Dharwad, India
Sayonthoni Das Tuhi Department of Microbiology, University of Chittagong,
Chittagong, Bangladesh
John Vlachopoulos Department of Chemical Engineering, McMaster University,
Hamilton, ON, Canada
Tesfaye Waryo SensorLab, University of Western Cape, Cape Town, South Africa
xxii Contributors

Avril Rae Williams Department of Biological and Chemical Sciences, The Uni-
versity of the West Indies, Cave Hill, Barbados
Syed Mohammed Javaid Zaidi Center for Advanced materials, Qatar University,
Doha, Qatar
Stefan Zechel Laboratory of Organic and Macromolecular Chemistry (IOMC),
Friedrich Schiller University Jena, Jena, Germany
Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Jena,
Germany
Photo-polymerization
1
Prem Prabhakaran and Kwang-Sup Lee

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1 A Physical View of Photoexcitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Radical Photopolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1 Photoinitators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2 Monomers/Oligomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.3 Visible Light–Sensitized Radical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.4 Thiol-Ene Photopolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3 Cationic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.1 Ionic Photoacid Generators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2 Spectral Broadening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.3 NonIonic Photoacid Generators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.4 Monomers for Cationic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4 Anionic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
5 Two-Photon Induced Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
6 Scope and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

Abstract
The synthesis of functional polymers by photopolymerization thrives on the rich
tradition of industrial photochemistry. Photo-induced polymerization can be
broadly divided based on the initiation mechanism as radical, cationic, and
anionic photopolymerization. A wide variety of initiators, photosensitizers, and
polymerizable materials have been studied for various applications. This chapter
is intended to be a primer to major concepts of photopolymerization. In the
beginning of the chapter, physical aspects of light matter interactions are

P. Prabhakaran · K.-S. Lee (*)

Department of Advanced Materials and Chemical Engineering, Hannam University,
Daejeon, South Korea
e-mail: [email protected]; [email protected]; [email protected]

© Springer Nature Switzerland AG 2019 1

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_1
2 P. Prabhakaran and K.-S. Lee

presented followed by photochemical pathways leading to reactions. In the

subsequent sections radical polymerization is discussed by introducing different
types of initiating systems and polymerizable materials. Within the section on
radical polymerization, visible light polymerization and thio-ene photochemistry
are also discussed. The section on thiol-ene looks at the fundamentals of thiol-ene
reactions, their initiation, reactivity, and advantages over other radical driven
polymerizations. Cationic polymerization is covered based on the material sci-
ence of ionic and nonionic photoacid generators (PAGs). This section also
discusses spectral broadening of reactivity in PAGs to visible wavelengths
through electron transfer sensitization and free radical promoted cationic poly-
merization (FRPCP). Unlike radical and cationic polymerization there are little or
no reports of commercial application of anionic polymerization. However, due to
typical monomers employed in anionic polymerization and the control over the
extent of polymerization afforded by this techniques makes it very attractive for
functional applications. The section on anionic polymerization summarizes recent
developments in this field. Finally in the section about two-photon initiated
polymerization, we discuss the scope of nonlinear optical phenomena in
photopolymerization.

1 Introduction

Photopolymerization became popular due to the wide-spread application of ultravi-

olet radiation for cross-linking of photoactive materials in various industries. Any
polymeric species capable of undergoing a chemical change when exposed to light
can be termed a photopolymer. Photopolymers started out as materials used in
packaging and encapsulation of goods and printing technologies. Their early appli-
cation in the industry was largely driven by the possibility of formulating photo-
active materials that reduced the use of solvent while allowing for a remote
triggering of chemical phenomena through irradiation. The subsequent growth of
microelectronic industry with its demand for progressive miniaturization of compo-
nents has led to the increased importance of photopolymers. In fact, the progression
of microelectronics predicted by Moore’s law would be hardly possible without
negative photoresists. This was achieved due to the progress in the development,
synthesis, and understanding of the chemistry of photopolymers and the resultant
rational design. This has been the case with photopolymers applied to many different
fields of activity. Need for efficiency and cost effectiveness has driven the develop-
ment of the field in various directions.
Depending on how they chemically respond to light, photoresponsive polymers
or their precursors can be divided into five classes [1]. The first class constitutes
multifunctional monomers or oligomers containing functional groups that undergo
radical, cationic, or anionic chain growth polymerization in the presence of a suitable
photoinitiator (PI) leading to photo-crosslinked polymer networks (see Fig. 1a).
When irradiated with a suitable wavelength, the PI initiates the polymerization
reaction, leading to the addition of monomer or oligomers to form polymeric
1 Photo-polymerization 3

Fig. 1 Five different classes of photopolymers. (Reproduced from Ref. [1])

molecules. The second class of photopolymers consists of oligomers/monomers with

integrated photoactive groups capable of initiating polymerization when irradiated
with light (see Fig. 1b). In the second class of photopolymeric materials, there is no
requirement of a PI. They typically undergo step growth polymerization where
polymeric groups are added step by step (e.g., dimer then trimer then tetramer so on).
The third class of photopolymer precursors involves component materials with
complementary functional groups on them that interact with each under irradiation
in the presence of a suitable PI (see Fig. 1c). The fourth category involves photo-
polymers with functional groups which, in the presence of a suitable mediator
(PI) and light, transform to another functional group with a difference in solubility
(see Fig. 1d). The fifth class of photopolymer also undergoes a solubility change due
to the photo-induced degradation of polymeric materials (see Fig. 1e).
This chapter deals with photopolymerization and materials for photo-
polymerization which can be included in categories (a–c) in Fig. 1.
4 P. Prabhakaran and K.-S. Lee

Photopolymerization reactions are normally achieved by combining a number of

different materials playing specific roles during polymerization. The combinations
are often referred to as photopolymerizable formulations or just formulations.
Formulations used for imaging applications are often referred to as photoresists.
The most abundant component of a photoresist is a monomer or an oligomer with
chemical functionalities capable of undergoing photoinduced chemical change.
Different photopolymerization reactions are restricted to certain types of mono-
mers/oligomers. For example, olefins and acrylic monomers/oligomers figure prom-
inently in the materials for radical polymerization, while epoxides and vinyl ethers
figure in cationic polymerization. The absorption of light and the initiation of the
chemical reaction are mediated by a photoinitiator (PI).
Often another component called photosensitizer (PS) is present in the formula-
tion. The photosensitizer is a molecule that is highly sensitive to light and plays a
part in assisting the initiation of the photopolymerization. The PS has a higher
sensitivity to a relevant wavelength and would serve to efficiently initiate the
reaction in combination with the PI. The photoexcited PS molecule interacts with
PI through energy or the electron transfer interaction. Apart from these components,
photosensitive systems might contain inhibitor molecules aimed at nullifying the
effects of spontaneous degradation of the high-energy bonds in initiators over time
during their shelf life. For commercial applications, additional components meant to
shape the physical properties of the photopolymerizable medium, such as viscosity,
color, wetting, gloss, and matting, are also added to photosensitive systems.
A crucial factor governing the photopolymerization reaction is the choice of the
light source. A wide range of optical sources like lamps, lasers, and sun light have
been put to use depending on the requirement of the application. Recently, there have
been numerous attempts to use sunlight to trigger polymerization, minimizing thus
the cost of fabrication. Source like the Xe lamp and sunlight are broad spectrum
sources that contain multiple wavelengths. Required wavelength can be filtered out
of these sources by using filters. UV producing mercury lamps also converts a high
amount of energy it takes up to heat. Mercury lamp emits at specific wavelengths.
Doped mercury lamps emit in a range of wavelengths. Microwave lamp, excimer
lamp, both continuous and pulsed laser sources are some other examples of the light
sources used [2].
In the following chapter, we will discuss photopolymerization based on its modes
of initiation. An exhaustive coverage of this broad topic is beyond the scope of the
present chapter. Instead, we will focus on initiating the reader to the nuances of the
field by providing insights into major developments. In the beginning, we provide a
brief physical description of the light-matter interaction; the subsequent sections
discuss various types of polymerization from the material perspective.

1.1 A Physical View of Photoexcitation

Photoinitiators and photosensitizers feature polar high-energy bonds between

carbon and heteroatoms or metals. Polar bonds have a greater interaction with
1 Photo-polymerization 5

electromagnetic radiation due to their strong interactions with the electrical field of
light. When the intensity of radiation increases, the materials give rise to new
phenomena which can be termed nonlinear optical (NLO) phenomena [3]. In essence,
all optical processes are nonlinear, but they become relevant observables only when
subjected to an intense radiation. The electric component of the electromagnetic wave
is capable of attracting or deflecting the electronic cloud in a molecule, the resultant
polarization in the molecule shows a linear behavior at lower intensities. However, in
the presence of intense radiations, the polarization of the molecule shows a nonlinear
response to light. The polarization (P) or the induced dipole moment (μi) of a
molecule interacting with radiation can be written as follows (see Eq. 1):

Pi ¼ μi ¼ αij Ej (1)

where αij is the linear polarizability tensor and Ej is the electric field associated with
the electromagnetic radiation. The induced dipole moment of a molecule interacting
with high intensity radiation can be written as follows (see Eq. 2):

βijk γ ijkl
μi ðEÞ ¼ μ0 þ αij E j þ Ej Ek þ Ej Ek El . . . . . . (2)
2 8
where μ0 is the inherent polarizability of the molecule, αij is the linear polarizability
of the molecule βijk, and γ ijkl refers to the first and second hyperpolarizabilities. The
terms Ei, Ej and Ek describe the electric field components of light. The first two terms
explain the single-photon absorption of the molecule, while βijk and γ ijkl describe
the NLO interactions of the molecule with light in the microscopic scale.
For a bulk of molecules, the polarization can be written using Eqs. 3 and 4.

P ¼ P 0 þ P i ðE Þ (3)

Pi ðEÞ ¼ χ ij ð1Þ E j þ χ ijk ð2Þ E j Ek þ χ ijkl ð3Þ E j Ek E l . . . : (4)

In Eq. 3, P0 is the inherent polarization of a molecule and Pi(E) the induced

polarization where χ (n)E is the nonlinear susceptibility tensor of (n + 1)th order. The
first term in Eq. 4 describes the linear polarizability of the molecule. The terms χ ijk(2)
and χ ijkl(3) are the bulk analogues of βijk and γ ijkl, respectively, and are called first and
second hyperpolarizability. A number of optical effects arise out of both the first and
second hyperpolarizabilities, such as sum and difference-frequency generation,
second-harmonic generation, direct four-wave mixing, optical rectification,
parametric amplification, self-phase modulation, Kerr lensing, four-wave mixing,
two-photon absorption, etc. [4]. In this chapter, we mainly discuss photochemical
and photopolymerization triggered by the one-photon absorption (OPA) and
two-photon absorption (TPA) excitation of molecules.
The range of wavelengths between 10 nm and 400 nm are defined as ultraviolet
(UV) region of the spectrum. Almost all materials including air absorbs UV wave-
lengths between 10 and 180 nm making it difficult to work with it in the absence of a
6 P. Prabhakaran and K.-S. Lee

vacuum, this range of wavelengths is called far UV region. Wavelengths

between 180 and 280 nm constitute the middle-UV region, and those in the
range 300–400 nm constitute the near UV region. The range of wavelengths
between 200 and 400 nm has been most commonly used in photopolymerization
reactions. The energy corresponding to this range of wavelengths can initiate
electronic transition in a wide range of materials and cause bond rupture in
organic molecules. For a given molecule, the scope of photophysical processes
occurring on irradiation is defined by its frontier molecular orbitals, the
absorbed wavelength, and the intensity of the light source. All potential photo-
physical processes during the evolution of a photoexcited molecule are summa-
rized in Fig. 2. Common organic molecules feature σ-bonding molecular
orbitals, σ* antibonding molecular orbitals, π-bonding molecular orbitals, π*
antibonding molecular orbitals, and nonbonding orbitals (n). The transitions
between these molecular orbitals (MOs) are subject to conditions of energy
difference, symmetry, and occupancy of MOs. The most commonly encountered
transitions in organic photoinitiators are π ! π* and n ! π* transitions. The
π ! π* and n ! π* transitions are localized transitions associated with active
bonds in the molecule.
Another set of transitions called charge transfer (CT) transitions are found in the
molecules containing extensive conjugation and strong donor and acceptor sub-
stitutions. In the CT transitions, the excitation energy is delocalized throughout the
molecule. The NLO phenomena are particularly strong in the molecules with strong
CT states. The simplest photochemical process in a molecule happens when it
absorbs ultraviolet radiation, resulting in the excitation of an electron in its singlet
ground state (S0) to the first singlet excited state (S1). Photoexcitation is a fast process
that occurs at the timescale centering around 1015 s. Alternatively, the absorption of
two near IR photons can lead to a singlet excited state. The OPA- and TPA-excited
singlet states may or may not be the same, depending on the symmetry of the
molecule. They coincide in non-centrosymmetric molecules and differ in symmetric
ones. The excited singlet state can follow any of the different paths outlined in Fig. 2,
depending on the molecular orbitals and the source of radiation. In the presence of a
high intensity laser or non-laser light sources, the excited electron can be further
excited to a higher singlet state due to the phenomenon termed excited-state absorp-
tion (ESA). The probability of the ESA phenomenon depends on the intensity the
light source.
Photoexcitation of a molecule results in the formation of chemically reactive
species due to the redistribution of electronic cloud within the molecule. The heavy
atoms in the molecule hold their positions (Franck-Condon principle), while the
electronic cloud undergoes redistribution. The Franck-Condon principle restricts the
inversion of the electronic spin during excitation due to the rules of quantum
mechanics. Due to these restrictions, the initial geometry of the excited molecule
is not the one that corresponds to an energy minimum (read stable). If an excited state
is not immediately quenched after excitation, it undergoes vibrational relaxation to
achieve energetically stable geometries, leading to the formation of triplet states
[5]. The triplet excited states are more reactive than singlet excited states and lead to
1 Photo-polymerization 7

Fig. 2 The fate of the photophysical properties associated with an excited molecule is summarized
in the Jablonski’s diagram. Sn stands for the nth singlet energy level of the molecules, Tn stands for
the nth triplet energy level of the molecule. OPA one-photon absorption, TPA two-photon absorp-
tion, ESA excited-state absorption, ISC inter system crossing, IC internal conversion, RT radiation-
less transfer of electrons

the products that are otherwise inaccessible [6]. Photoexcitation of PI can lead to the
following eventualities.
(i) The excited molecules undergo vibronic relaxation to reach a stable geometry,
followed by a release of energy into solvent.
(ii) The excited electron can undergo intersystem crossing to give a triplet state
which further undergoes vibrational relaxation to reach an energy minimum.
(iii) The emission of energy from the singlet or the triplet excited state, leading to
luminescence, fluorescence, or phosphorescence.
(iv) The excited molecule can undergo excitation quenching through interaction
with other molecules; further, the molecule can return to ground state through
radiationless thermal or vibrational processes.
(v) Singlet and triplet excited molecular states can herald photochemical reactions.

Thermally driven reactions go through the singlet excited state. The probability of
intersystem crossing and triplet formation in photochemical reactions lead to the
formation of the products that are otherwise inaccessible. The use of photoexcitation
for driving the reaction also leads to energy-rich excited states. Frequently, such excited
states also feature electrons occupying nonbonding molecular orbitals. A photoexcited
molecule is susceptible to three different primary photochemical pathways (see
Fig. 3a). The first pathway involves the formation of a chemically reactive intermediate
(RI) which then leads to the product. The second photochemical pathway leads to the
formation of a funnel intermediate by the excited molecule, the funnel intermediate then
leads to a product. IUPAC defines a photochemical funnel intermediate as a molecular
8 P. Prabhakaran and K.-S. Lee

Fig. 3 (a) The photochemical pathways taken by the photoexcited molecule. (b) Potential energy
surfaces of a photoreaction from photoexcitation to the formation of the product [8]

structure by means of which the excited-state reactant or intermediate is delivered to the

ground state to initiate product formation [7].
The term funnel intermediate itself comes from the local shape of the potential
energy surfaces of the ground and excited states (see Fig. 3b) [8]. For many organic
reactions, the structure of the funnel can take the form of a conical intersection or a
singlet-triplet crossing. The third pathway involves the formation of an excited inter-
mediate state RI* or an excited state product P* that eventually gives rise to the product.
Most photoinitiators work through the primary photochemical pathway which pro-
gresses through the formation of a reactive intermediate, RI. The RIs formed can
include radicals, biradicals, or zwitter ions that then directly or indirectly play a part
in the initiation of the polymerization reactions. The role of photosensitizer is primarily
that of a mediator in the photoinitiation process. The energy or electron transfer
between the photosensitizer and the photoinitiator depends on their frontier molecular
orbitals. The LUMO level of the sensitizer should be above the HOMO level of the
initiator; when the energy difference is larger, the probability of energy transfer
increases. Apart from this, the phase of the polymerizing medium governs the interac-
tion between the photosensitizer and the photoinitiator. In samples permitting flow of
materials, diffusion plays a key role in the dynamics and fate of the excited photosen-
sitizer. The transfer of energy between the sensitizer and the initiator could take place
through a coulombic interaction or by swapping of a high-energy electron [8].
1 Photo-polymerization 9

2 Radical Photopolymerization

Radical photopolymerization reactions are initiated by the generation of a free

radical (R•) by a photoexcited photoiniator (see Fig. 4). The generation of R• may
proceed through the unimolecular process (Type 1) or the bimolecular process (Type 2).
The first photochemical pathway outlined in Fig. 3b is responsible for the generation
of the free radical. During its course, radical polymerization proceeds through
different distinctive steps (see Fig. 4). During the propagation step, the free radical
reacts with the monomer/oligomer to give rise to a radical bearing monomer or
oligomer (RM•) called a macroradical. The macroradical then proceeds to grow by
addition to more monomers. The reaction proceeds through the propagation step and
eventually terminates through coupling or disproportionation reactions.
The presence of inhibitors, such as dissolved oxygen or other added components
capable of consuming the radicals in the polymerizing medium, has a detrimental
effect on the initiation process. Reactive species formed during initiation react with
inhibitors, leading to a period of almost no polymerization reaction at the beginning
(see Fig. 5). This phase of the reaction is termed the induction phase. Upon the total
consumption of the inhibitors through reactions, the initiating species react with

Fig. 4 Different stages of

free radical polymerization
10 P. Prabhakaran and K.-S. Lee

Fig. 5 Conversion of
monomer versus time during
photopolymerization

monomer forming a macroradical. The diffusion of the macroradicals throughout the

medium leads to a rapid increase in the rate of polymerization until it reaches a
maximum.
The development of polymerization is associated with a change in viscosity and
refractive index of the polymerizable medium. Viscosity of the polymerizing
medium progressively increases to the point where monomers are trapped between
growing polymer chains. At this point, the polymerization reaction is terminated by
the limited diffusion of the monomer. Due to this, photopolymerization reactions
never run to 100% conversion of monomer. A graphical representation of the
progression of photopolymerization can be seen in Fig. 5. The induction period is
the relatively flat part at the initiation region.

2.1 Photoinitators

Photoinitiation occurs when the absorption of photon leads to the generation of a free
radical. This process is governed by the stability of the photoexcited state, as well as
by the energy of the bonds within the excited molecule. As mentioned above, free
radical photoinitiators can be classified into two types, based on the number of
molecular species involved in the process. Type I photoinitiators constitute a
unimolecular process accompanied by a rapid bond cleavage upon the absorption
of light. Type II photoinitiators involve more than one molecule. A simple Type II
photoinitiator consists of a bimolecular system involving an initiator and a
co-initiator. The initiator is first excited into a long-lived triplet state, followed by
an electron-transfer or a hydrogen-abstraction reaction with a co-initiator.
Type I photoinitiators are prominently benzoyl compounds; they undergo C–C
cleavage at α, β, or γ positions on photo,excitation. The dissociation energy of the
C–C bond next to the benzoyl is less than the energy of excitation of the molecule.
1 Photo-polymerization 11

Fig. 6 (a) A model Type I photoinitiator followed by different typical examples; (b) benzoin
derivatives; (c) benzoin ether derivatives; (d) halogenatedketones; (e) dialkyacetophenone; (f)
morpholinoketone; (g) aminoketone; (h) hydroxyalkylacetophenones; (i) ketone sulfonic ester; (j)
thiobenzoate derivatives; (k) sulfonylketone; (l) oxosulfonylketone (m) oximeester; (n) furan
hydroxyl alkyly ketone derivative; (o) organometallic ketone; (p) 2,4,6-trimethylbenzoyl
diphenylphosphine oxide; (q) organosilanes

The carbonyl chromophore constitute three important molecular orbitals, namely

n (nonbonding orbital on oxygen), π (bonding), and π*(anti-bonding) molecular
orbitals on carbonyl double bond. The π ! π* is a high-energy allowed transition
and n ! π* transition is a low-energy forbidden transition. Both these transitions can
give rise to singlet and triplet states on excitation. A model Type I radical photo-
initiator is shown in Fig. 6a. The substituted groups X and Y influence the optical
properties of the benzoyl compounds through electronic interactions, such as elec-
tronegativity, +I or I effects, and delocalization. Some examples of Type I photo-
initiators are shown in Fig. 6.
12 P. Prabhakaran and K.-S. Lee

Fig. 7 Photocleavage of type

I radical photoinitiator (a)
model compound undergoing
cleavage at α-carbon; (b–c)
benzoin derivatives
undergoing photoexcited
α-cleavage; (d) sulfonyl
ketone derivative undergoing
β-cleavage on photoexcitation

The photoinduced cleavage of a model type 1 PI molecule can be seen in Fig. 7a.
The rest of Fig. 7 shows the generation of radicals in two benzoin derivatives. The cases
in Fig. 7a–c demonstrate cleavage at α-carbon. However, certain type 1 initiators, like
sulfonyl ketones, sulfonyloxy ketones, thiosulfonyl ketones, and oxime esters, undergo
cleavage at β-carbon upon photoexcitation (see Fig. 7d) [9–11]. The benzoyl radicals in
type I photoinitiators are generated by the cleavage of σ bond oriented orthogonally to
the π-orbitals of the aromatic group [2]. The substitution on the aromatic ring has little
or no effect on the reactivity of the benzoyl radical. Radicals centered on carbon add at a
high rate to monomers like acrylate. The nucleophilicity of the radical influences its
addition to monomers. In the case of an alkyl radical, the tertiary carbon exhibits the
highest nucleophilicity, followed by secondary carbon and primary carbon. Alkyl
radicals with -OH substitution are more nucleophilic and would show a greater addition
to electron deficient monomers like methacrylates. Carbonyl or nitrile substituted alkyl
radical show a greater addition to electron rich monomers. The addition of benzoyl
radical to the double bond on a monomer is around two-orders or magnitude (~100-
fold) higher as compared a radical centered on an alkyl carbon. Both these species are
equally vulnerable to dissolved oxygen in the photopolymerizable medium. Most of the
PIs in Fig. 6 feature benzoyl moiety, indicating the prominence of this group in
developing useful photoinitiators. There have been several attempts to engineer com-
pounds that do not contain this group in order to address the control over the excitation
dynamics or choice of monomers. In compound Fig. 6n, the phenyl ring is substituted
with the electron rich five-membered ring furan. Compound in Fig. 6p is organome-
tallic germanium derivative where the germanium atom is attached to a ketone, during
photo exposure the Ge–C bond undergoes cleavage to give initiating species. The
substituted dislane derivative in Fig. 6q when irradiated undergoes cleavage at the Si–Si
to give highly reactive silyl radicals. The advantage of using silyl radical as an initiating
species is its ability to overcome oxygen inhibition of polymerization. The ambient
oxygen has been shown to play an active part in accelerating the addition of the silyl
1 Photo-polymerization 13

Fig. 8 Reactions governing the excitation and evolution of the photoinitiator

radical to monomers [2, 12, 13]. Another factor governing the effective action of the
initiator is the effect of solvent on the stability of the photoexcited transition state. The
stabilization of a charged transition state by a polar solvent can lead to an increase in
cleavage of the photoinitiator and hence increase the reaction with the monomer.
The mechanism of photopolymerization can be studied through different tech-
niques, such as chemical trapping [14], nuclear magnetic resonance (NMR) [15],
time resolved Fourier Transform-Infrared (FT-IR) measurements [16, 17], laser flash
photolysis [18], electron spin resonance (ESR) spectroscopy [19–21], chemically
induced dynamic nuclear polarization (CIDNP), chemically-induced dynamic elec-
tronic polarization [CDEP] [22], femtosecond pump-probe experiments [23, 24],
ultrafast fluorescence quenching [25], time-resolved stimulated emission [26],
femtosecond-stimulated raman experiments [27], photothermal and photoacoustic
methods [28], etc. For further details on the characterization and study of the kinetics
of photopolymerization, the readers are referred to previous works [29–33].
Reactions leading to the formation of the macroradical RM ̇ can be seen in Fig. 8.
The rate of polymerization for the early stages of radical polymerization in a
deaerated medium can be written as follows (see Eq. 5):


Rp ¼ kp =kt 0:5 Ri 0:5 ½M (5)

where the rate constants kp and kt correspond to propagation and termination steps of
polymerization (see Fig. 8), respectively.

Ri ¼ Ia φi (6)

Here Ri is the rate of initiation that depends on the amount of absorbed light, Ia,
and photoinitiation quantum yield φi which defines the efficiency of photoinitiation
taking into account all the side processes that could occur during photoexcitation.
The initiation quantum yield φi describes the number of initiation events associated
with the absorption of a photon (or photons, e.g., two-photon-initiated polymeriza-
tion). It is given by the product of the quantum yield of intersystem crossing φisc,
quantum yield of initiating radical φc which is the number of free radical species
formed as a result of the absorption of a photon and the quantum yield of the
macroinitiator formed by the initial reaction between the initiator radicals and the
14 P. Prabhakaran and K.-S. Lee

monomer φmonomer. For a Type I initiator that undergoes cleavage in its triplet state,
the initiation quantum yield is given by Eq. 7 [2].

φi ¼ φisc φc φmonomer (7)

The bond cleavage of the photoinitiator is described by the product of φc and φisc
(see Eq. 8) and is called dissociation quantum yield φdissociation.

φdissociation ¼ φisc φc (8)

The quantum yield of formation of radical R ̇ depends on the rate at which triplets
are generated by the photoinitiator kc and the bimolecular quenching of the triplet by
the monomer kq. It is inversely proportional to the triplet life time τT0 (see Eq. 9).


φc¼ kc = 1=τT 0 þ kq ½M (9)

The quantum yield of the formation of the macroradical (RM) is denoted by

φmonomer (see Eq. 10). It depends on ki, the initiation rate constant that governs the
interaction between R ̇ and monomer M, as well as kr0 the pseudo first-order rate
constant which is sum of all rate constants leading to the disappearance of Ṙ (see the
processes represented by blue arrows in Fig. 8).


φmonomer¼ ki ½M= kr 0 þ ki ½M (10)

Type II PIs form a long-lived triplet state on photoexcitation. Instead of under-

going cleavage, they interact with a co-initiator via a direct hydrogen transfer or an
electron transfer reaction (see Fig. 9a). During the direct hydrogen transfer, the
excited triplet state of the PI reacts with a co-initiator capable of donating a
hydrogen radical to form a new radical species (PI–H˙). This radical hydrogen
adduct of the PI then initiates polymerization. Alternatively, the donor molecule
(RH) forms an electron transfer complex with the photoexcited PI. The degradation
of this charge transfer complex leads to PI–H˙. Benzophenone initiates polymeri-
zation reactions through the formation of the charge transfer complex with amines.
A wide range of amines are commonly employed as co-initiators. Other types of
molecules, such as mercaptobenzothiazole, substituted silanes, germanes,
silylamine derivatives, metal containing amines, boron derivatives, etc., have also
been used. Examples of type II PIs and co-initiators can be seen in Figs. 10 and 11,
respectively.
The initiation quantum yield for the type II initiators can be written as follows
(see Eq. 11):

φi ¼ φisc φH φR φmonomer (11)

where φisc is the intersystem crossing quantum yield, φH is quantum yield describing
the direct transfer of hydrogen, φR is the quantum yield of initiating radicals, and
φmonomer is the yield of the macroradical.
1 Photo-polymerization 15

Fig. 9 Mechanism of initiation by type II initiators in the combination with an amine co-initiator

2.2 Monomers/Oligomers

Photopolymerization reactions involving a large variety of monomers/oligomers can

be initiated by free radicals. This is because the radical is a neutral species stabilized
through interactions with many common groups in monomers, such as halogen,
phenyl, and many electron withdrawing groups. Radicals are nonspecific in their
reactivity and interact with any available π-bond. Due to different rates of addition of
the photogenerated radicals to the monomers, the reactivity of the monomers
towards different initiators is variable [34]. Other factors, such as viscosity of the
reactive medium, the thickness of the photopolymerizable film, the duration of
irradiation, and the dark reaction after the light has been switched off, all govern
the end results. Some prominent examples of molecules with chemical groups
found in photoresists undergoing radical polymerization are provided in Fig. 12.
Multifunctional monomers like epoxyacrylates, polyetseracrylate, polytheracrylates,
urethane acrylates, etc. are used in commercial formulations for photo-
polymerization (see Fig. 13).
Depending on the requirement of the application, photopolymerization can be
carried out in solutions of monomers in suitable solvents, bulk monomers, or thin
films. Due to the relative ease of following reaction and reactive species spectro-
scopically in solutions, reaction kinetics is often studied in solution. The propagating
radical at a low concentration describes a second-order rate constant, while at a high
concentrations, it is subject to a pseudo first-order rate constant. The termination
reactions in solution phase photopolymerization are diffusion controlled [2, 35].
For many practical applications, polymerization takes place in bulk or thin films.
Due to the effects of diffusion, the dynamics of polymerization can be entirely
different in solution and in bulk. Owing to its ease of applicability for packaging
of materials, photopolymerization has been intensely studied for decades. Despite
this, determining the rate constants for addition of the radical produced by the
initiator and a monomer is quite difficult. The viscosity of monomer in a bulk sample
can be one or two orders of magnitude higher than the monomer solution.
16 P. Prabhakaran and K.-S. Lee

Fig. 10 Examples of type II photoinintiators: (a–e) benzophenone derivatives; (f–h) thioxanthone

derivatives; (i–k) diketone (benzil) derivatives; (l–m) coumarin; (n) ketocoumarin; (o) anthraqui-
none derivatives; (p) terephthalophenone derivatives

The diffusion of the triplet radicals in the medium and its bimolecular quenching in
the reactive medium are controlled by the viscosity of the reactive formulation. The
rate constant for bimolecular quenching of the triplet radical by monomer (kq)
decreases with viscosity due to the decrease in diffusion, while it increases due to
the increased presence of monomers in the bulk material. For a given monomer, the
rate of polymerization increases with viscosity and then decreases. Viscosity also
governs the cage effects involving the confinement of photogenerated reactive
species by solvent molecules. For polymerization to take place, the radical has to
escape the cage and react with monomers. In the solution phase, the cage effects are
negligible; however, for increased viscosity, it is more difficult for a radical to escape
the cage, resulting in a slower reaction [2, 35].
1 Photo-polymerization 17

Fig. 11 Co-initiators for type II photoinitiators: (a) methyl diethanolamine; (b) triethanolamine;
(c) ethyl 4-(dimethylamino)benzoate; (d) 2-(dimethylamino)ethyl 4-(dimethylamino)benzoate; (e)
2-butoxyethyl 4-(dimethylamino)benzoate; (f) amine containing polyether acrylate; (g) mercapto-
benzothiazole; (h) tris(trimethylsilyl)silane; (i) tris(trimethylsilyl)germane; (j–k) silylamine deriv-
atives; (l) acetal derivatives; (m) metal containing amines; (n) phosphorus containing co-initiator;
(o) boron containing co-initiator

2.3 Visible Light–Sensitized Radical Polymerization

A molecule which can absorb visible wavelength and is capable of initiating a

polymerization either by itself or in combination with other molecules can be termed
a visible light initiator (or initiating systems, in cases when more than one molecule is
involved) [36]. They are chosen for their high molar absorptivity at a visible wave-
length or wavelengths, their specific interaction with monomers, and their long-lived
excited states. Visible light initiating organic molecules can be constructed around UV
photoinitiators by incorporating structural changes, such as those shown in Fig. 14a–d
which are derivatives of Fig. 10f. The high-energy bonds in UV photoinitiators, when
incorporated into molecules with extended conjugation, lead to visible light photo-
initiators. The molecules in Fig. 14d are synthesized by incorporating benzophenone,
thioxanthone, and pyrene on to a truxene moiety [37, 38]. The planar conjugated
truxene moiety forms an efficient bridge for electrons, leading to a red-shifted absorp-
tion of the chromophore. The resulting molecules also show very high molar absorp-
tivities, which makes them efficient initiators.
18 P. Prabhakaran and K.-S. Lee

Fig. 12 Some common

monomers/oligomers used in
radical photopolymerization:
(a) ethylene; (b) halogenated
alkenes; (c) 1,3-dienes; (d)
styrene; (e) a-methyl styrene;
(f) vinyl ester; (g) acrylate; (h)
methacrylate; (i) acrylonitrile;
(j) methacrylonitrile; (k)
acrylamide; (l)
methacrylamide; (m) N-vinyl
carbazole; (n) N-vinyl
pyrrolidone

Due to their high interaction with light and stability of the photogenerated
species, many organometallic compounds are highly suited for visible light photo-
initiation. It should be noted that some organometallic molecules are cytotoxic and
care should be taken on their selection in a photoinitiating system. The germane
derivatives in Fig. 14i–k initiate radical polymerization in the presence of visible
light due to free radicals generated by α-clevage at the C–Ge bond [39–41]. An
increase in the number of germanium atoms in the structure leads to a bathochromic
shift in the absorption of the initiator. The photocleavage of germane initiators yield
long-lived triplet species that are very efficient radical initiators [42]. Iridium com-
plexes like those in Fig. 14l–m can be combined with suitable co-initiators to be used
in free radical polymerization [43, 44]. The introduction of formyl moiety in the
latter results in its higher extinction coefficient. Both compounds combine with tris
(trimethylsilyl)silane and an iodonium salt to form a photoinitiator system for free
radical polymerization. The mechanism of initiation is shown in Fig. 15.

2.4 Thiol-Ene Photopolymerization

Some of the earliest commercially available formulations for photopolymerization

were based on photo-induced thiol-ene crosslinking. However, concerns over their
shelf life, the odor of the thiols in the formulation, as well as the gradual degradation
of the bezophenone photoinitiators used in these formulations causing discoloration
led to their failure and disappearance. Many decades of ensuing research rectified the
1 Photo-polymerization 19

Fig. 13 (a) General structure of multifunctional monomers for free radical polymerization; (b)
polyether acylate; (c) epoxy acrylates; (d) polyester acrylate; (e) polyurethane acrylate; (f)
crosslinker monomer trimethylolpropane triacrylate; (g) crosslinker monomer pentaerythritol
triacrylate

above problems, leading to the reemergence of this very useful chemistry. The
polymer network resulting from thiol-ene polymerization has been suggested as
the most ideal from any free-radical polymerization [45, 46]. Since it has been
tagged as a “Click reaction,” it has been extensively employed for the synthesis of
functional polymers, hybrid materials, and microdevices [47–52]. Thiol-ene reac-
tions are specific and proceed at mostly mild conditions making them attractive
for a wide variety of chemical syntheses. Thiol-ene chemistry has been used
in the synthesis of various monomers [53–56], polymers, or copolymers
[57–65]. Thiol-ene additions are used as a method of direct synthesis or are used
for post polymerization modification of polymers [66]. The versatility and mild
conditions of thiol-ene reactions are very attractive for chemical modification of
monomers, polymers and nanoparticles for biotechnological applications [66–70].
Thiol-ene photopolymerization shows a high curing speed with little or no
oxygen and moisture sensitivity to give polymeric films with a very low shrinkage
stress and a narrow glass transition temperature [45–47]. The mechanism of thio-ene
polymerization shares the characteristics of both addition and condensation poly-
merization (see Fig. 16a) [46]. Some common enes and thiols that have been
employed in thiol-ene polymerization reactions are shown in Fig. 16b.
20 P. Prabhakaran and K.-S. Lee

Fig. 14 Some examples of visible light photoinitiators; they are used either by themselves or in
combination with other molecules to effect initiation. The absorption maxima or band width of
activity are provided underneath each structure

The reaction is easily initiated by a radical photoinitiator and leads to a near

quantitative addition of thiol to carbon-carbon double bond. Type I photoinitiators
are favored for thiol-ene polymerization due to the improved hydrogen abstraction
from thiols [71, 72]. Sterically, unhindered terminal enes show the highest reaction
1 Photo-polymerization 21

Fig. 15 Initiation of visible light photoinitiating combination; inorganic complexes play the role of
the initiator

rates during thiol-ene photopolymerization compared to hindered enes [73, 74].

Electron rich or strained enes show higher reaction rates during photopolymerization
with a particular thiol. Norbornene seen in Fig. 16b is an example of a strained ene as
that undergoes rapid reaction with the thiyl radical leading to an addition product
with reduced ring strain at the double bond. Hence, as compared to other enes, the
reaction between thiyl and norbornene proceeds quite fast.
Vinyl ethers are examples of electron-rich enes that are highly reactive during
thiol-ene polymerization. Conjugated dienes, methacrylates, styrene, and
maleimides are examples of low reacting enes (see Fig. 16b) [46, 73]. Alkyl thiols,
thiolglycolate esters, and thiol propionate esters have been used in thiol-ene reac-
tions. Esters show a higher reactivity to alkenes, as compared to alkyl thiols.
Common multifunctional thiols and enes used in thio-ene photopolymerization are
shown in Fig. 17.
As shown in Fig. 16, the propagation of thiol-ene reaction proceeds in two distinct
steps. The first step is called propagation involving the attack of the thiyl radical on the
ene. The subsequent step is called the chain transfer step where the thiol-ene adduct
radical abstracts hydrogen from a new thiol molecule to regenerate the thiyl radical. The
chemical nature of the thiol and ene determines whether the propagation or the chain
transfer step forms the rate-determining step during the reaction. Enes that are less
reactive cause propagation to be the rate-limiting step. Thiols that structurally limit the
abstractability of the hydrogen lead the chain transfer step to be the rate-limiting step.
Unlike the conventional free-radical polymerization, a typical thiol-ene polymerization
maintains a low cross-linking density characterized by the formation of low molecular
weight oligomers for an extended period during the reaction. This, in turn, delays the
gel point during polymerization, leading to ease of diffusion of species resulting in the
buildup of a uniform network of polymers [75, 76]. In thiol-ene generated polymers,
glass transition occurs over a small range of temperature, indicating the uniformity of
the formed network. The narrow window of glass transition results in well-defined
mechanical properties for the resultant polymers [77].
Thiol-acrylate and thiol-ene-acrylate formulations have been studied to diversify the
properties of the thiol-ene crosslinked polymer. In the binary thiol-acrylate systems,
multifunctional thiols are combined with traditional acylate-based monomers. This
22 P. Prabhakaran and K.-S. Lee

Fig. 16 (a) Thiol-ene polymerization, initiation, propagation, and termination steps and the
examples of thios and enes that could be employed in such reactions. The propagation step can
be divided in two steps, namely, propagation (i) where the thiyl radical adds to the double bond, and
(ii) which involves hydrogen abstraction by the formed monomer radical from thiol is termed chain
transfer step (ii). (b) Some enes and thiols that have been used in thiol-ene reaction
1 Photo-polymerization 23

Fig. 17 Common multifunctional ene and thiol monomers employed in thiol-ene

photopolymerization

combination leads to polymerization with low oxygen sensitivity, higher conversion, as

well as delayed gel point without sizable compromise on the thermo-mechanical
properties of the formed polymers, as compared to pure methacrylate polymers. The
ternary combination of thiol, ene, and methacrylate is more robust than the binary
combinations. Ternary mixtures result in polymers with the high glass transition
temperatures similar to those in methacrylate polymers, while imparting the positive
traits of thiol-ene polymerization in the system, such as oxygen inhibition and uniform
polymerization [78]. With the careful choice of the monomers, there is the possibility of
creating polymerization-induced phase separations. Phase separated double polymer
networks could be interesting substrates for many applications. Thiol-ene polymeriza-
tion of some thiol-ene-acrylate formulations results in the formation of two-phases and
leads to a reduction in shrinkage stress. The ternary thiol-ene-acrylate formulations are
less sensitive to stoichiometry of individual components and hence provide dexterity in
designing polymers with desirable properties [78–81].

3 Cationic Polymerization

The oxygen sensitivity of radical polymerization is one of its major drawbacks

requiring photocuring to be carried out under inert atmosphere. The high processing
costs associated with maintaining inert atmosphere during applications lead to the
24 P. Prabhakaran and K.-S. Lee

exploration of new chemistries capable of delivering effective photopolymerization

under ambient conditions [82]. The discovery of photoacid generators enabled the
use of chemical amplification reactions to carry out efficient polymerization without
inter atmosphere. Chemical amplification refers to a single photochemical event
leading to an increasing number of chemical events. Since each photochemical event
leads to hundreds of chemical events during chemical amplification reactions, they
can be used even with low doses of radiation. Ambient oxygen shows little of no
effect on cationic polymerization. In cationic formulations, the photochemical reac-
tion is initiated by a photoacid generator (PAG). A photoacid generator can be an
ionic, nonionic, or organometallic compound [1].

3.1 Ionic Photoacid Generators

Photoacid generators (PAGs) are compounds that can generate acidic species on
irradiation. Diaryl iodonium and triaryl sulfonium are among the earliest types of
PAGs that were investigated for cationic polymerization [83–85]. The light-sensitive
organic part of these PAGs features a heteroatom hosting a positive charge; PAGs are
also associated with a metal complex anion that acts a counter ion. The counter ion
combines with the photogenerated H+ ion to form Brønsted acids (super acids) capable
of catalyzing ring-opening polymerizations. Photoacid generators can be applied to
ring-opening reactions of a wide variety of materials, such as multifunctional epoxides,
oxetanes, vinyl ethers, cyclic ethers, cyclic acetals, cyclic siloxanes, etc.
Most common onium salt PAGs include iodonium derivatives, sulfonium
dervatives, phosphonium derivatives, N-alkoxy pyridinium salts, etc. (see
Fig. 18a–l). Some organometallic compounds are also used as cationic photo-
initiators. Most PAGs absorb radiation in the UV region; however, their activity
can be extended to longer wavelength by the use of photosensitizers by the appli-
cation of free-radical promoted cationic polymerization [86]. Cationic photo-
polymerization is initiated by either the photogenerated acid or by a stable cation
formed due to the photo-scission of the PAG.
Compounds (a–c) in Fig. 18 are examples of iodonium PAGs. The cationic and
anionic species in the iodonium salt PAG play specific roles defining its properties.
The onium cationic part defines the photochemistry of the PAG. It influences the
absorption maximum (λmax), the molar absorption coefficient, quantum yield, pho-
tosensitization, and thermal stability of the PAG. The anion determines the acid
strength, initiation efficiency (during polymerization), and propagation rate con-
stants (during polymerization). Once the photoacid is generated, the anion deter-
mines its role during polymerization. The importance of having non-nucleophilic
counteranions was realized during the early investigation of diaryliodonium PAGs.
The interaction of the photogenerated cationic species with a nucleophilic anion
leads to the suppression of the initiating cationic species and hence the polymeriza-
tion. In the presence of a suitable anion, the aryl and aryliodine cationic species
formed by photolysis of iodonium PAG can react with monomers, solvents, or
impurities to give superacids of the form HMXn (MXn: BF4, PF6, AsF6,
1 Photo-polymerization 25

Fig. 18 Onium (ionic) photoacid generators and ring-opening polymerization: (a–c) Idonium-
based PAGs; (d–h) sulfonium-based; (i–j) phosphonium salts; (k–l) N-alkoxy pyridinium salts; and
(m) ring-opening polymerization of epoxide monomer in the presence of photogenerated acid

SbF6, (C6H5)4B etc.). For a series of onium salt with the same cation, the
polymerization is dependent on the counterion. The extent of polymerization
depends on the nucleophilicity and size of the couterion in the following order,
SbF6 > AsF6 > PF6 > BF4 [87]. These PAGs undergo photolysis with
quantum yields in the range of 0.7–0.9. The λmax and the intensity of absorption of
iodonium PAGs can be engineered by substitutions on the aromatic ring. The super
acids go on to initiate ring-opening polymerization reactions (see Fig. 18m) [82].
A simplified version of the mechanism of photolysis and photoacid generation in
iodonium PAGs is shown in Fig. 19. A diaryliodonium salt undergoes photo-induced
scission either through homolytic or through heterolytic cleavage (see Fig. 19). The
photoexcited intermediate interacts with water or other protic solvents present during
the reaction to give a strong Brønsted acid which can initiate cationic polymerization.
In the viscous reaction media, the photogenerated species are subject to cage effects.
26 P. Prabhakaran and K.-S. Lee

Fig. 19 Mechanism of photoacid generation in an iodonium salt PAG. Here RH is a protic solvent

Sulfonium-based PAGs form another important class of onium salt PAG.

Compounds (d–g) in Fig. 18 are examples of sulfonium PAGs. They have a higher
reduction potential, than idonium PAGs, and hence show better thermal stability,
allowing them to be used in formulation that is more shelf stable. The higher
reduction potential also leads to a lower photosensitivity of the sulfonium-based
PAG. The mechanism of photolysis of sulfonium PAGs closely resembles that of
iodonium PAGs (see Fig. 20). Homolytic photo-scission pathway is more prominent
in sulfonium PAGs, as compared to heterolytic cleavage pathway. Sulfonium PAGs
show a longer wavelength absorption band at 305 nm. The substitution of
thiophenoxyphenyl groups in compounds (g) and (h) in Fig. 18 increases the
molar absorption coefficient of these compounds, as compared to compound (d).
This makes them more sensitive photoinitiators. Ferrocenium-based PAGs form a
newer class of organometallic initiators that are used mainly with monomers that
could complex with iron atom in ferrocenium. They are mainly used for epoxide
monomers. Some examples of ferrocenium PAGs and the mechanism of photo-
initiation of ferrocenium PAGs are shown in Fig. 21.

3.2 Spectral Broadening

Spectral broadening refers to the technique of increasing the sensitivity of onium salt
initiators to visible wavelengths to enable the use of new light sources in the near UV
and visible regions of the spectrum. With the use of electron transfer sensitization,
1 Photo-polymerization 27

Fig. 20 Mechanism of photoacid generation in sulfonium salt PAG, here RH is a protic solvent

Fig. 21 Examples of ferrocenium photoinitiators and the mechanism of their action as cationic
initiators

the absorption of both iodonium and sulfonium PAGs can be shifted to longer
wavelengths [88]. Electron-transfer sensitization involves the combination of a
photosensitizer (PS) with the PAG to achieve photoinitiation as shown in Fig. 22a.
The photoexitation of PS leads to an electron transfer reaction from PS to the PAG,
28 P. Prabhakaran and K.-S. Lee

Fig. 22 (a) Mechanism of

electron transfer sensitization
in aryliodonium PAGs; (b)
mechanism of free-radical
promoted cationic
polymerization

leading to the formation of an excited state complex (exciplex) followed by a

reduction of the onium cation. This is followed by the irreversible decomposition
of the resulting Ar2I֗ free radical; this process is very efficient and restricts back
electron transfer to the photosensitizer from happening [84, 90]. The positively
charged photosensitizer either directly initiates polymerization or generates photo-
acids through further reactions. Polyaromatic compounds, such as pyrene deriva-
tives, athracene derivatives, carbazole derivatives, etc., are used as electron transfer
sensitizers.
Free-radical promoted photosensitization of cationic polymerization (FRPCP) is
another method for achieving spectral broadening. In FRPCP a radical initiator is
added alongside the PAG. Free radicals formed by the radical intiator interact with
onium salt PAG to generate a corresponding cation and Ar2I֗. The cation formed from
the free radical initiator then goes on to initiate polymerization reactions. The Ar2I֗
undergoes a fast and irreversible decay. The mechanism for electron-transfer sensi-
tization is shown in Fig. 22b. Typically, free radicals formed during FRPCP are
oxidized to form species containing a positive charge capable of initiating cationic
polymerization. A combination of aromatic ketone, disilane, and diaryliodonium salt
is a typical example of a FRPCP initiator [89, 90]. Irradiation of the mixture leads to
the formation of silyl radical which is then oxidized to give a positively charged
initiating species. Acylgermanes like Fig. 14i can be used as a free radical initiator in
1 Photo-polymerization 29

FRPCP [91–93]. They give germyl radicals on irradiation; these radicals are then
oxidized to germanium ions which can initiate polymerization. Supramolecular
complexes of iodonium PAGs-crown ethers and combination of onium salt and
zinc halide have also been used for FRPCP [94–97]. Apart from this a combination
of an organometallic compound of ruthenium, iridium, selenium or germanium with
an organo silane and photoacid generator like those discussed in Sect. 6 can be used
for initiating cationic polymerization in the near UV to visible wavelengths [39, 43,
93, 98–103]. These ambivalent initiating systems capable of initiating both radical
and cationic polymerization have the potential to be used in complex photo-
polymerizable materials.

3.3 NonIonic Photoacid Generators

Nonionic or nonsalt PAGs are another subclass of PAGs extensively studied in recent
years. Unlike common onium PAGs, nonionic or nonsalt PAGs exhibit a broad
wavelength activity and a good solubility in organic media and polymeric films.
On irradiation, nonionic PAGs give rise to various organic acids, such as sulfinic
acid, sulfonic acid, carboxylic acid, phosphoric acid, etc. [104, 105]. Some examples
of nonionic PAGs are shown in Fig. 23. Under photoirradiation, nonionic PAGs
generate organic acids capable of initiating polymerization. Compounds (a–i),
except for (h) (see Fig. 23), generate sulfonic acids on irradiation [9]. Compound
(f) in Fig. 23 generates a carboxylic acid on irradiation. Sulfone compounds (j) and
(k) give rise to sulfinic acid on irradiation. Diphenyl selenide compound (m) in
Fig. 23 yields a cationic radical capable of initiating polymerization in the presence
of a photosensitizer [106]. The mechanism of photoacid generation in ortho-
nitrobenzyl sulfonates, iminosulfonates, and N-hydroxyimide sulfonates is shown
in Fig. 24a–c, respectively. Apart from the photoproducts shown in Fig. 24, there are
other radical and ionic species that might be formed during the photoacid generation.
These side products may or may not intervene in the progress of polymerization
depending on the conditions during polymerization. Cage effects in the reaction
medium, as well as the interaction of atmospheric oxygen with radical species
generated during photoacid generation, can control the dynamics of polymerization.
Compound (e) gives an 88% yield of p-toluene sulfonic acid in solution and 52–61%
of the same compound in polymer films in air [107]. Interestingly, under vacuum
conditions, due to the formation of ammonia by hydrolysis of imine, the yield of
p-toluene sulfonic acid was found to be lower than both cases specified above.

3.4 Monomers for Cationic Polymerization

A wide range of functional groups are compatible to cationic polymerization (see

Fig. 25) [82, 86, 109]. They include vinyl derivatives, vinyl ethers, various cyclic
ethers, thiiranes, cyclic esters, and cyclic siloxane derivatives. Apart from these,
30 P. Prabhakaran and K.-S. Lee

Fig. 23 Some examples of nonionic PAGs: (a–d) based on sulfonates; (e–f) iminosulfonates; (g)
acetylferrocene oxime; (h) sulfonylferrocene oxime; (i–j) N-hydroxyimide sulfonates; (k–l) sul-
fones, and (m) selenide-based photoacid generators [106]

many unconventional monomers, such as benzoxazine, epoxy, end functionalized

poly caprolactone, thiophene, etc. also undergo cationic polymerization [86, 110].
Practical application demands high reactivity, leading to a high cure speed, lack of
oxygen inhibition, low-volume shrinkage, good mechanical properties, little or no
toxicity, and good adhesion to various substrates from the monomer. The electron-
rich carbon-carbon double bonds in vinyl ethers exhibit a higher curing rate than
epoxy functionalized monomers. The high rate of conversion in vinyl ethers is also
due to the low glass-transition temperature of the formed polymers [87]. Some
examples of multifunctional epoxide monomers that can be polymerized by cationic
photoinitiators are shown in Fig. 26a–d. Due to their extensive application in many
different fields [1, 87], multifunctional epoxide monomers are the most important
class of monomers in cationic polymerization. These monomers polymerize to form
three-dimensional networks. The rate of photocuring increases rapidly for multi-
functional epoxy groups, reaches a maximum, and then decreases. The presence of
the soft counter ion associated with the photoacid minimizes the interaction between
polymer chains containing cationic end groups. Cationic polymerization proceeds
1 Photo-polymerization 31

Fig. 24 The mechanism of photoacid generation in nonionic PAGs: (a) Orthonitrobenzyl sulfo-
nates give rise to sulfonic acid and other photoproducts [103]; (b) iminosulfonates give rise to
sulfonic acid and other photoproducts [107]; (c) N-hydroxyimide sulfonates give rise to sulfonic
acid [108]

uninhibited in the dark state; after the light source has been switched off, this process
can be accelerated by heating and is called a post-cure step.
The material requirement for applications dictates the design of monomers. The
rate of curing of difunctional epoxides monomers was found to be inferior to that of
difunctional acrylate monomers. Hence, there have been many attempts to increase
the curing speed of the epoxy- based monomers through design. Of the different
classes of monomers explored, cycloaliphatic epoxides were found to have the
highest curing rates. Rapid polymerization in multifunctional epoxy monomers
can lead to gel point, trapping large quantities of residual monomer inside the
crosslinked network. This can be circumvented by prolonging the gel point during
polymerization by the use of chain transfer agents that attack the cationic end of the
polymer while initiating new polymeric chains [111]. Alcohols are among the most
efficient chain transfer agents, the oxygen in the alcohol interacts with the cationic
end of the growing polymer chain. This results in end-capping of the cationic chain.
Further release of an H+ ion from the alcohol terminated polymer chain initiates free
32 P. Prabhakaran and K.-S. Lee

Fig. 25 Various monomers that can be polymerized by cationic polymerization; top to bottom:
vinyl, vinyl ether, epoxy, thiirane, oxetane, tetrahydrofuran, 1,3,5-trioxane,,4,6-trioxaspiro[4.4]
nonane, 6-caprolactone, hexamethylcyclotrisiloxane [82, 86]
1 Photo-polymerization 33

Fig. 26 Ring-opening polymerization in epoxide monomer; examples of multifunctional mono-

mers that can be polymerized by cationic photoinitiators

monomers to progress the reaction. This method of activation of the growing

polymer chain is called the activated chain-end mechanism [87, 112]. Apart from
this, it has also been proposed that the monomer can be directly activated by alcohol,
leading to the activated monomer mechanism [113, 114]. Both these mechanisms
check the rapid growth of molecular mass or cross linking and delay the gel point,
leading to higher conversions and better mechanical properties.
The high polymerization rates of multifunctional cycloaliphatic monomers make
them popular for many commercial applications. Apart from the high curing rates,
commercial applications demand high thermo-mechanical properties, chemical sta-
bility, abrasion resistance, adhesion, and solvent resistance. The presence of low
molecular weight components in the cured polymer after photocuring can adversely
affect its thermo-mechanical properties and increase its toxicity. The obvious low
molecular weight materials in the cured polymers would be the photosensitizer, the
PAG, or its photo-degradation products. Photosensitizers can be functionalized to be
incorporated into the polymer; the epoxy functionalized pyrene molecule in Fig. 26e
is one such example [115]. Another approach is the development of photosensitizers
34 P. Prabhakaran and K.-S. Lee

attached to a polymer [116]. The photoacid generator can be substituted with long
alkyl chains or bound to polymers to increase its molecular weight. The increasing
substitution on the photoacid also dictates the diffusion of the photodegration
products from the PAG [117].
Volume shrinkage is one of the major problems faced by radical polymerizable
acrylate photopolymers. Simple methyl methacrylate monomer shrinks by about
20–25% of its volume [118]. Multifunctional acrylate monomers show shrinkage
lower than the above value (c.a. 10%), but shrinkage is still substantial to hamper
application [119–121]. Shrinkage in multifunctional epoxide photopolymers is less
than that of acrylate-based photoresists [122]. Some applications, such as dental
fixtures, demand minimal shrinkage of the photocured structure. Volume shrinkage
can be reduced by designing suitable monomers or a combination of monomers. For
example, monomers (f) and (g) in Fig. 26 are used together to make rigid, solvent-
resistant films with a low volume shrinkage [123]. Controlled addition of diol
derivatives of compound (g) was found to decrease volume shrinkage. Epoxy
functionalized hybrid silicone monomers, as the one in Fig. 26h, also undergo
rapid polymerization, but yield soft elastomeric and transparent films [124]. Careful
selection of monomers and initiators allows the engineering of properties in the final
cured film or structure.

4 Anionic Polymerization

The idea of anionic photopolymerization has been around for a long time, but it has
been only sporadically advanced over many years [125, 126]. In recent years, the
interest in anionic photopolymerization has been renewed, mainly due to the control
it provides over the composition and structure of the polymer. Monomers undergo-
ing anionic polymerization should be able to stabilize a negative charge through
inductive or resonance effects. Anionic photopolymerization reactions can be initi-
ated by inorganic complexes of chromium, organometallic complexes of chromium,
as well as tungsten, metallocenes, triarylmethyl derivatives, Zwitter ions, etc.
[127–133]. Ethyl and methyl cyanoacrylates are the most widely studied monomers
for anionic photopolymerization. Anionic photopolymerization is initiated by the
formation of an anionic species by the photoexcited initiator as shown in see Fig. 27a
[127, 129, 134–136]. The photogenerated anion adds to the carbon–carbon double
bond in the monomer to generate an anionic adduct setting off the propagation
reaction shown in Fig. 27b. Anionic polymerization of ethyl or methyl cyanoacry-
lates can be carried out in neat samples. Recently, ketoprofen has been used to
initiate the polymerization of methoxy acrylate in neat as well as solutions in the
presence of a mixture of sodium hydride and sodium hydroxide [137]. Ketoprofen
initiated polymerization of methoxy acrylate is shown in Fig. 28.
Sila(I)ferrocenophanes can undergo photoinduced anionic ring-opening polymer-
ization in the presence of a lithium or sodium salt of cyclopentadienyl
[138–141]. Though such polymers have been previously prepared by conventional
means, the photocontrolled reaction permits the use of ferrocenophanes with
1 Photo-polymerization 35

Fig. 27 Anionic photopolymerization of alkyl cyanoacrylate; (a) various photoinitiators; (b) the
general scheme for anionic polymerization of alkyl cyanoacrylate [133]

sensitive functional groups as pendants [139, 142, 143]. The scheme in Fig. 29
elaborates the ring-opening polymerization of ferrocenophanes. The mechanism of
the photoinduced anionic polymerization is not completely understood, but it is
postulated that the strained sila bridge plays a role in weakening the bond between
the cyclopentadiene and iron. This bond-weakening effect, alongside with photo-
induced ligand to metal charge transfer, increases the electrophilicity of iron.
36 P. Prabhakaran and K.-S. Lee

Fig. 28 Ketoprofen in the

presence of NaH and NaOH
can polymerize
methoxyacrylate with high
yields in both liquid and solid
state polymerization. The
initiation and propagation step
of the anionic polymerization
of methoxyacrylate can be
seen here [137]

Fig. 29 Ring-opening photopolymerization of ferrocenophanes in the presence of lithium or

sodium salt of cyclopentadienyl cation

The nucleophilic metal center then drives the formation of a reactive ring opened
species containing cyclopentadienyl anion. This anion is stabilized by a positively
charged metal counter ion and leads to the propagation of the ring-opening poly-
merization by addition of ferrocenophane monomers. The photoreactions are
induced using wavelengths greater than 310 nm. This reaction proceeds only in
the presence of light, which makes it convenient to add new monomers to make
complex polymers [140]. Due to this remarkable control over the addition of mono-
mers, polyferrocenophanes with low polydispersities and a high degree of control
1 Photo-polymerization 37

Fig. 30 Photoinitiation of photobase generator that could simultaneously initiate anionic and
sol-gel polymerization

over the molecular weights can be obtained. The reaction can be terminated by the
addition of a protic solvent which adds hydrogen to the growing negative end of the
polymer. Photoinitiated ferrocenophanes have been applied to the synthesis of block
copolymers, opening up the possibility of tailoring block copolymers properties
suited for different applications [142, 144, 145]. Metal containing polymers and
block copolymers synthesized from ferrocenophanes are highly promising func-
tional materials for applications like high refractive index materials, charge tansport
materials, redox active gels, photoresists for electron beam, plasma etching as well as
nanolithography, catalytic materials, etc. [146–156].
Photobases are photolatent compounds capable of releasing a powerful base
on irradiation. They have a high reactivity with oxirane type monomers monomer
[2, 104, 157]. A recent report featured the simultaneous photoinitiation of anionic
and sol-gel polymerization of 3-(glycidyloxypropyl)trimethoxysilane (GPTMS) by
an aminoketone based photobase generator [158]. The α-amino acetophenone-based
photoinitiators are shown in Fig. 30a–b. They are both well-known type I radical
photoinitiators. Upon photoexcitation, the cleavage of the excited photoinitiator
yields highly reactive α-amino alkyl and benzoyl radicals.
38 P. Prabhakaran and K.-S. Lee

In the absence of monomers capable of yielding radicals, they undergo

H-abstraction and disproportionation, leading to the formation of tertiary amines.
The tertiary amino group could initiate both anionic polymerization and sol-gel
reaction. The hybrid monomer GPTMS in Fig. 30c undergoes cationic polymeriza-
tion at the epoxy functional group and sol-gel reaction at the alkoxy silane groups.
The aromatic groups around the tertiary amine in the initiator make it stable towards
base-sensitive compounds in the patterning media and hence ensure longer shelf
stability. After photocleavage, there is a stearic release at the amine leaving it highly
reactive [11]. The polymerization was carried out in neat monomer with 4 wt% of the
photoinitiator. The photoirradiation of the sample was followed by a thermal curing
step which was used for the complete drying of the polymerized film. The control
over structure and functionality provided by anionic polymerization makes it very
desirable for the synthesis of functional materials. A wider application of known
techniques and an exploration of new initiating systems and monomers are required
to meet this potential.

5 Two-Photon Induced Polymerization

The discussions up to this point have dealt with photopolymerization reactions

initiated by the absorption of single photons. Under the condition of a very high-
intensity radiation, it is possible for molecules absorbing in UVor visible radiation to
simultaneously absorb two lower energy near-IR photons to get excited. This
phenomenon is called two-photon absorption. Two near-IR photons of the same or
different wavelengths can be absorbed during two-photon absorption. As defined
previously, two-photon absorption is a third-order nonlinear optical effect. The
energy level to which the electron is excited during a two-photon absorption
would be determined by the symmetry of the molecule. In non-centrosymmetric
molecules, the lowest two-photon allowed energy level coincides with the lowest
one-photon allowed energy level. In a centrosymmetric molecule, the first allowed
two-photon energy level is lower than the first one-photon allowed energy level.
Two-photon process is an intensity-dependent phenomenon that is confined to the
focus of a tightly focused laser beam. Because of this strong confinement,
two-photon absorption can be used to initiate spatially confined chemical reactions.
Photopolymerization reactions initiated by two-photon absorption are called
two-photon polymerization (TPP). Two-photon lithography (TPL) is a lithographic
technique based on TPP.
Two-photon absorption has been used to initiate free-radical, cationic, and
anionic polymerizations [159]. The efficiency of two-photon absorption by a mol-
ecule is described in terms of two-photon absorption cross-section (TPACS)
expressed in the GM units (1 GM = 1050 cm4 s/photonmolecule). Due to the
low TPACS of common free radical and cationic photoinitiators, early efforts were
focused on designing two-photon absorbing molecules with high TPACS. Efficient
organic two-photon absorbing (TPA) molecules contain electron-accepting and
electron-donating groups bridged by conjugated aromatic constructs of diverse
1 Photo-polymerization 39

arrangements. Two-photon absorbers can be dipolar [160–163], quadrupolar

[160–172], triagonal [173–177], multibranched [178, 179], dendritic [180–182],
oligomeric [170, 183, 184], or polymeric molecules [185–188]. Some typical exam-
ples of two-photon sensitizers are shown in Fig. 31.
Two-photon sensitized radical polymerization can be initiated by either a single
molecule or a combination of two or more molecules. Single molecules that initiate
two-photon polymerization do so from a charge separated excited state. In a
two-component initiating system, the excited two-photon absorbing (TPA) molecule
interacts with another initiator through electron or energy transfer. Compounds like
those shown in Fig. 31 can be combined with previously discussed radical initiators
to give efficient initiating systems.
Two-photon absorbing unimolecular initiators for cationic polymerization
are rarer than one- component radical initiators [189–191]. Examples of
one-component photoinitiating systems used in cationic TPP are shown in Fig. 32.
One-component cationic initiators have faced some design challenges due to
conflicting electronic criteria for efficient two-photon absorption and photoacid
generation [191]. More research is required to reach a molecular understanding of
efficient two-photon sensitized photoacid generation from a single molecule. The
evidence available so far indicates that PAGs constructed around quadrupolar
molecular motifs show a high efficiency as compared to the dipolar ones. Most
reports on two-photon initiated cationic polymerization involve two-component
initiating system constituting a two-photon absorber and a cationic photoinitiator
that interacts with the TPA molecules [192]. Given the availability of the TPA
molecule, two-component PI systems can be easily formulated and used. For
many applications where high-resolution microstructures are not required, common
commercial UV initiators can be used in combination with commercially available
PAGs. Two-photon sensitized polymerization is growing in popularity due to the
availability of commercial lithographic systems operating with femoto-second
and picosecond lasers as light sources [193]. TPL has seen a wide adaption in
the structuring of biologically relevant microstructures’ changes to hardware and
light sources are currently driving the maturity of this technique towards commer-
cialization. The recent demonstration of ultra-fast fabrication techniques is a game
changer and is poised to revolutionize the applications of TPL in the near future.

6 Scope and Outlook

The application of photopolymers and photopolymerization continues to develop

and expand based on the demand of new materials. The demand for sub ten
nanometer to few ten nanometer components in electronic circuits has driven the
demand for extreme UV (EUV) lithographic systems and materials. The high energy
of EUV radiation can cause ionization of materials and excited electrons from inner
energy levels. This scenario presents new challenges to the material chemist
[194–197]. A new class of photoresists based on nanoparticles is being studied for
EUV patterning [198–203]. The emergence and the growth of 3D printing is also a
40 P. Prabhakaran and K.-S. Lee

Fig. 31 Examples of two-photon sensitizers; (a) and (b) are examples of dipolar molecules, (c) and
(d) are examples of quadrupolar molecules; and (e) is an example of a triagonal molecule
1 Photo-polymerization 41

Fig. 32 Examples of
unimolecular TPA initiators
for cationic TPP

major driver behind the growth of novel photopolymerization systems. Recently, De

Semione et al. reported unltrafast 3D printing of monolithic 3D structures by
engineering the oxygen inhibition of polymerization at the interface between the
photopolymer and the cured structure [204]. The development of fast two-photon
polymerization and holographic systems demand polymer precursors showing fast
response to light and undergoing controlled polymerization [205, 206]. Material
demand from medical and industrial applications has led to the development of new
photopolymerizable materials [207–210]. The research into medical implants has
spurred the growth of many new soft materials which are biocompatible or can be
combined with biomaterials to give photo processable materials [211–215]. Human
industrial activity and its effect on the environment has been a concern since the turn
of the twenty-first century. This concern has contributed to need and awareness of
sustainability in the sciences. Many research groups are starting to address the
environment in their research for new photopolymers [216–224]. Photopolymers
42 P. Prabhakaran and K.-S. Lee

will continue to play a major role in the future; research into nanomaterial based
resists mentioned above may lead to new functional films and microstructures.
Large-scale industrial application will continue to be driven by conditions of cost
effectiveness. High value applications like microelectronics, biotechnology, health,
and space provides a lot of space for growth and development.

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Polymer Functionalization
2
Lindsey A. Bultema, Xia Huang, Daniel D. Brauer, and Patrick Theato

Contents
1 General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
1.1 Methods for Functional Polymer Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
1.2 Classifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2 Short History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3 Functional Groups Employed in Chemical Modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.1 Activated Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2 Anhydrides, Isocyanates, and Ketenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.3 Oxazolones and Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.4 Aldehydes and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.5 Azides and Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.6 Dienes and Dienophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.7 Tetrazines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.8 Triazolinediones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.9 Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.10 Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.11 Future Prospects in Polymer Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.12 Dibromomaleimide Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.13 Use of Thiolactone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4 Conclusion and Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

L. A. Bultema · D. D. Brauer
Institute of Technical and Macromolecular Chemistry, University of Hamburg, Hamburg, Germany
e-mail: [email protected]; [email protected]
X. Huang · P. Theato (*)
Institut für Technische Chemie und Polymerchemie, Karlsruher Institut für Technologie, Karlsruhe,
Germany
e-mail: [email protected]; [email protected]

© Springer Nature Switzerland AG 2019 53

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_2
54 L. A. Bultema et al.

Abstract
This chapter provides an overview of the many facets of polymer functiona-
lization. To build upon the basic foundation of polymer functionalization, some
general considerations are outlined first. This includes various methods to syn-
thesize functional polymers and an overview of reactions frequently employed in
postpolymerization modification. Additionally a brief history of polymer
functionalization dating back to the vulcanization of rubber in 1840 is discussed.
Following the general considerations, the chapter is divided into specific func-
tional groups and modern reactions. The functional groups discussed here
include activated esters, anhydrides, isocyanates, and ketenes, oxazolones and
epoxides, aldehydes and ketones, azides and alkynes, dienes, and dienophiles,
tetrazines, halides, and thiols. To showcase the versatility of the functional
groups, side chain modification and end group modification are included within
each section. Finally, future prospects in polymer functionalization are briefly
mentioned.

1 General Considerations

1.1 Methods for Functional Polymer Synthesis

Functional polymers can be prepared by the direct polymerization of a functional

monomer. However, when more than one functional group is required in a polymer,
typically a copolymerization of two or more monomers, each featuring one particular
functional group, is conducted. These approaches of direct polymerization or copo-
lymerization are only feasible when the functional groups of interest do not interfere
with the respective polymerization mechanism.

1.1.1 Copolymerization
Generally in a copolymerization two or more comonomers are reacted to form the
respective copolymer. Depending on the nature of the comonomers, a random
copolymer, statistical copolymer, or alternating copolymer is formed. If at least
one comonomer features reactive characteristics, a postfunctionalization is possible.
One of the most classical examples is the alternating copolymerization of maleic
anhydride (MA) with styrene (St) resulting in the alternating copolymer poly(St-alt-MA).
Here MA acts as a reactive anhydride and can react with numerous nucleophiles,
such as alcohols or amines [1, 2]. Noteworthy, when copolymerizing other func-
tional monomers, the reactivity ratios of the monomer influence the composition and
structure of the obtained copolymer. This may limit the application if the respective
distribution of functional groups is not desired. Therefore, the postpolymerization
functionalization of a reactive homopolymer with more reactants can be advanta-
geous, as it can lead to a different, often more preferred distribution of functional
units in a copolymer.
2 Polymer Functionalization 55

1.1.2 End-Functionalization
End functionalization is possible by the various routes of modifying preexisting
polymer chain ends, or halting of the chain growth, followed by end functiona-
lization. These instances are traditionally performed with agents or chemical groups
that already contain the desirable functional group [3, 4].

1.1.3 Functionalization-Grafting
Functionalization-grafting briefly consists of the following techniques: (i) use of
preexisting polymer chains possessing functional species or chain ends with a
chemical affinity to chemical groups on the backbone of another polymer chain.
This is considered a “grafting-onto” technique (Fig. 1a) and is frequently used for
synthesis of comb polymers. Saldivar-Guerra and coworkers use a grafting from
method to functionalize polybutadiene and polyisoprene with different kinds of
nitroxide moieties which could further address the controlled growth of poly(maleic
anhydride-co-styrene) and thus can be used as compatibilizers [5]. (ii) Interchange or
reaction of labile atoms on a polymeric backbone by reactive species or functional
monomers; use of macromonomers containing highly polymerizable groups, partic-
ularly vinyl groups. The addition of a second monomer (comonomer) can lead to
various structures, such as brushes, regular grafts, centipede, barbwire, etc.,
depending on the reactivity ratios and distance between grafts. This is considered
“grafting-through” (Fig. 1b). The group of Herrea used the grafting-to method to
achieve functionalization of single-walled carbon nanotubes with polystyrene by
cycloaddition of polystyrene with N3-end-groups [6]. (iv) Utilizing a polymer that
consists of functional species, reactive groups, or initiator moieties located along the

Fig. 1 (a) grafting-onto, (b)

grafting-through, (c) grafting-
from methods [7]. (Reprinted
with permission of Wiley)

(a)

CH2=CH
Monomer

(b)

* * Monomer

* *
(c)
56 L. A. Bultema et al.

polymer backbone, which in the presence of monomers results in a growth of grafts

from the polymer backbone. This is considered a “grafting-from” technique (Fig. 1c)
[7]. The group of Wooley reported the usage of grafting through methodology as
well as RAFT and ROMP polymerization method for the synthesis of cylindrical
molecular brushes with well controlled grafting density and low dispersity [8].

1.2 Classifications

A variety of different organic reactions can be used for the chemical modification
(also called functionalization) of polymers. Thus, a brief overview of various
reactions will be described in this section to provide a general classification of
postpolymerization modifications based on the mechanistic aspects. Subsequently
classifications based on functional groups will be provided with modern reactions in
greater detail.

1.2.1 Additions
Simplistically speaking an addition reaction involves the reaction of small molecules
with functional groups, resulting in a single reaction product containing all atoms of
all components. One of the most important addition reactions is the addition of
halogens, hydrogen, or oxygen to macromolecules containing carbon-carbon C=C
double bonds. Noteworthy, through addition reactions, the solubility and chemical
stability of polymers can be altered.
Hydrogenation of polymers is technologically one of the most important modi-
fication methods. Hydrogenation of polystyrene has gained interest over the years
along with the hydrogenation of polydienes due to the ability to vary the micro-
structure [9]. Halogenation and hydrohalogenation of unsaturated polymers have
also been explored. One example is the bromination of polybutadiene, which results
in flame-retardant materials. An alternative method to introduce halogens to poly-
mers is by radiation-induced addition[10]. Finally the epoxidation of double bonds is
another useful approach for the functionalization of unsaturated polymers, for
example, the epoxidation of polybutadiene [11]. In recent years, the modification
of unsaturated polymers with thiols via a thiol-ene reaction has become extremely
popular. Details of this are described later in this chapter (Sect. 3.11).

1.2.2 Substitutions
Substitution reactions also belong to a useful class of reactions to produce functional
polymers. A practical example would be the chlorination of polyethylene (PE) by
free radical substitution. Here chlorination begins in the amorphous areas of the
crystalline surface [12]. Esterification and hydrolysis reactions are also numerously
utilized. A particularly common reaction is the esterification of poly(methylacrylic
acid) utilizing carbodiimides as condensing agents. Often during this reaction, the
cyclic anhydride forms first as an intermediate structure, which in turn reacts with the
presence of alcohol, to yield an ester. Another common example is the esterification
of cellulose, which is still commercially produced [13, 14].
2 Polymer Functionalization 57

An important example of a hydrolysis reaction is the hydrolysis of poly(vinyl

acetate) yielding poly(vinyl alcohol), which is a particularly important reaction
because of the inability to directly synthesize the polymer from the respective
monomer [10]. Furthermore, varying the degree of hydrolysis can result in polymers
with different properties. In particular, increasing the degree of hydrolysis of
poly(vinyl alcohol) results in polymers with decreased solubility in water at room
temperature due to the high crystallinity of the polymer.

1.2.3 Eliminations
Elimination of water, alcohols, hydrogen halides, or other small molecules are some
of the most important polymer modification methods. Following the elimination,
unsaturated double or triple bonds or even heterocycles are formed in the macro-
molecule of the initial polymer. Various polymer elimination reactions are shown in
Fig. 2 [15].

1.2.4 Isomerizations
Unlike the previously mentioned reaction classes, isomerizations result in a change
in the chemical structure without changing the molecular weight of the
macromolecule.
Configurational isomerization is, for example, the cis-trans isomerization of
polydienes, which can be triggered through UV irradiation in the presence of a
radical transfer agent. Additionally, polymers with chromophoric groups have been
of interest, in particular azobenzene containing polymers due to cis-trans isomeri-
zation of azobenzene [10, 16].
Another example that has been developed for protein chemistry is the native
chemical ligation. In this reaction, a reversible transthioesterification of a N-terminal
cysteine residue leads to a thioester intermediate that undergoes a S,N-acyl shift
isomerization step, resulting in a native amide bond [17].

2 Short History

The transformation of natural rubber into a tough elastic material after treatment with
sulfur marks the industrial beginning of the long history of polymer functionalization
by postpolymerization modification [18]. This process is called vulcanization and
was invented independently by Hancock in England, Ludersdorf in Germany and
Charles Goodyear in USA in 1840. Subsequently in 1847, Schönbein introduced
cellulose to nitric acid, which resulted in the formation of nitro-cellulose [19]. In
1865, Schützenberger heated cellulose with acetic anhydride which resulted in
cellulose acetate. Cellulose acetate subsequently found use in photographic film,
membrane material, and artificial silk [20]. Although the use and modification of
natural polymers widely occurred during the late nineteenth and early twentieth
centuries, there was limited understanding of the mechanism behind the modification
reaction of the various materials.
58 L. A. Bultema et al.

Dehydrochlorination of poly(vinyldene chloride)

n n
-HCl
Cl Cl

Dehydrochlorination of poly(vinyldene chloride)

n -HCl n
Cl
Dehydrogenation of polycyclohexadiene Dehydration of poly(vinyl alcohol)

n -H O n
-H2 2
OH
Cyclodehydration of polyoxyamides
R
H
R N
N
-H2O
O
OH n O n
Cyclodehydration of poly(amido acids)
H
N O O
O O
n
N N N
H -H2O
n
HC2O CO2H O O

Cyclodehydration of polyhydrazides
H H N N
R N N R'
-H2O R R'
O O n O n

Cyclodehydration of poly(methacrylic acid)

H2
-H2O C
n
CO2H CO2H O O O n

Fig. 2 Various elimination reactions. (Redrawn after [15])

The acceptance and improved understanding of macromolecules came around the

time when Staudinger coined the term polymer analogous reactions. He defined it as
reactions that involve a transformation of a polymer into a derivative of equivalent
molecular weight [21]. However, nowadays we refer to reactions that result in
derivatives of equivalent degree of polymerization. Following, Sernuik et al. utilized
2 Polymer Functionalization 59

a thiolene addition to functionalize butadiene polymers with aliphatic thiols

[22]. During the early 1950s the use of chlorinated polystyrene-divinylbenzene
beads as ion exchange resins rose in popularity [23]. In the late 1950s, Merrifield
introduced solid state peptide synthesis [24]. The 1960s brought on the modification
of halogenated poly(meth)acrylates and postpolymerization modification of poly-
mers with pendant epoxide groups [25, 26].
The development of living/controlled radical polymerization techniques in the
early 1990s allowed for the increase in postpolymerization modification reactions.
Note living or controlled radical polymerizations are recommended by IUPAC to be
called “reversible deactivation radical polymerizations” and encompass numerous
polymerizations of which atom-transfer radical polymerization (ATRP), reversible
addition-fragmentation chain transfer (RAFT), and nitroxide mediated polymeriza-
tion (NMP) are the most popular ones [27–29]. By employing these polymerization
techniques under mild conditions, well-defined polymers with a variety of functional
groups can be obtained that allow a quantitative and selective modification.
Parallel to the growth of reversible deactivation radical polymerizations, the
development of several chemoselective coupling reactions was also taking place.
These include, for example, copper-catalyzed azide-alkyne cycloaddition (CuAAC)
and thiol-ene addition, often coined as “click chemistry.” All of these developments
helped pave the way for the expansion of postpolymerization reactions since the
1990s. A detailed review of click chemistry will not be included in this chapter.
Instead click chemistry will be introduced within the respective functional group
sections. For a thorough and insightful review on the many facets of click chemistry,
the review of Tasdelen et al. is recommended [30]. Thus, the focus of this chapter is
solely the development of various classes of postpolymerization modification
reactions.

3 Functional Groups Employed in Chemical Modifications

3.1 Activated Esters

First examined by Ferruti and Ringsdorf in the 1970s, postpolymerization modifi-

cation reactions involving activated ester containing polymers have become one of
the most common types of post polymerization modifications [31, 32]. Activated
esters are most frequently used for the covalent attachment of functional amines to
form amides. This substitution occurs selectively in the presence of weaker nucle-
ophiles like alcohols and without the need for protecting groups or metal catalyst.
The production of an amide linkage offers applications in a number of fields, such as
peptide chemistry and materials science.

3.1.1 Side-Chain Modification

Polymeric activated esters may be prepared from various monomers using both radical
polymerization and metal-catalyzed polymerization. Controlled radical polymeriza-
tion techniques such as nitroxide-mediated polymerization (NMP), atom-transfer
60 L. A. Bultema et al.

radical polymerization (ATRP), and reversible addition fragmentation chain-transfer

(RAFT) polymerization have offered unprecedented precision in the synthesis of
polymers containing reactive functional groups like activated esters. Traditionally
derivatives of N-hydroxysuccinimide (NHS) ester polymers prepared from
N-acryloxysuccinimide (NAS) or N-methacryloxysuccinimide (NMAS) monomers
have been used for postmodification because they react with amines under mild
conditions and are acceptably resistant to hydrolysis [33, 34]. This polymerization
and subsequent postmodification provides access to polyacrylamide and poly-
methacrylamide derivatives that typically cannot be prepared via direct polymeriza-
tion of their corresponding acrylamide monomers. Polymerization of the respective
activated ester monomers directly offers a number of advantages over the transfor-
mation of poly(acrylic acid) with dicyclo-hexylcarbodiimide (DCC) or 1-ethyl-3-
[3-dimethyl-aminopropyl]carbodiimide hydrochloride (EDC). The reaction of
poly(acrylic acid) with carbodiimides proceeds through cyclic anhydrides and thus
limits subsequent conversion. Additionally, urea is formed in the reaction and may
be difficult to remove. Further, the change in solubility in the conversion from the
starting monomer to polymer causes problems during the synthesis. These NHS ester
homopolymers however suffer from poor solubility in solvents other than DMF and
DMSO and are susceptible to some side reactions, such as the formation of
N-substituted glutarimide groups or succinimide ring-opening [35]. These side
reactions can be suppressed by the addition of proton scavengers such as DMAP
or TEA, or through the use of excess amine [36].
The solubility of activated ester polymers may be improved either by copolymer-
ization or replacement of the NHS ester group with other activating groups [37]. For
example, NAS is often copolymerized with N-isopropylacrylamide (NIPAM) to
produce reactive polyNIPAM. It is possible to adjust the activated ester content of
poly(NIPAM-co-NAS) by merely altering the comonomer feed ratio. Additionally,
the final molecular weight of the copolymer produced from the polymerization in
THF/toluene using AIBN as an initiator may be controlled by altering the solvent
composition. Higher toluene to THF ratios lead to an increase in molecular weight of
poly(NIPAM-co-NAS) [38]. PolyNIPAM is normally employed as a thermo-
sensitive polymer with a lower critical solution temperature (LCST) in water of
32
C, which is near body temperature. By varying the amine groups used to
postmodify reactive polyNIPAM, one may shift the LCST to higher temperatures
via the installation of more hydrophilic units or to lower temperatures with more
hydrophobic groups [39].
Thiazolidine-2-thione (TT) bearing activated ester polymers represent a substitute
to polyNAS and polyNMAS activated esters which undergo rapid aminolysis in
aqueous media and possess good hydrolytic stability [40]. The modification effi-
ciency is influenced by pH, temperature, polymer concentration, and water content.
It was found that a pH between 7.4 and 8.0 offers the greatest difference between
aminolysis and hydrolysis rates. Unfortunately under identical reaction conditions,
TT esters show low selectivity between amines and thiols.
A particularly appealing alternative to NHS-ester monomers is pentafluorophenyl
(PFP) ester-based polymers. PFP ester derivatives show higher reactivity than NHS
2 Polymer Functionalization 61

Fig. 3 Pendant amide

formation using polyPFPA n
n
activated ester
O O NH2
HN O
F F

F F

esters and PFP ester polymers are soluble in a wider range of organic solvents
[41]. Both PFP acrylate and methacrylate polymers display good reactivity towards
primary and secondary amines, but low conversion rates with aromatic amines and
alcohols have been determined. Theato and Nilles examined the reactivity of 4-vinyl
benzoic acid-based PFP polymers and found poly(pentafluorophenyl 4-vinyl benzo-
ate) (PolyPFP4VB) to have the highest reactivity among tested polymers [42]. Poly-
PFP4VB quantitatively reacts with less nucleophilic aromatic or secondary amines.
In a subsequent study, they utilized the difference in reactivity between PFP4VB and
pentafluorophenyl methacrylate (PFMA) to fabricate bifunctional polymers
[43]. Statistic and block copolymers from PFP4VB and PFMA were prepared and
sequentially modified with an aromatic and aliphatic amine, respectively.
An exciting new potential for activated ester postpolymerization modification is
the trans-esterification of activated esters with alcohols. Theato and coworkers
demonstrated for the first time a general methodology for the quantitative conversion
of polyPFPA to corresponding polyacrylates [44]. They reported that a DMAP
catalyzed transesterification occurs quantitatively and selectively in DMF between
PFP groups and primary and secondary alcohols as well as phenols. The reaction
strongly prefers primary alcohols and provides an advantage over activated ester
postmodification with amines because alcohols tolerate the presence of various
functional groups that are reactive towards amines, such as acids, aldehydes, and
α, β-unsaturated carbonyl derivatives. Employing this trans-esterification method,
fabrication of a number of functional materials was possible, including a pH
responsive hydrogel (Fig. 3).

3.1.2 End-Group Modification

Though less commonly employed than side-chain activated ester postmodification,
modification via activated ester end groups is a valuable tool for the production of
star polymers [45], protein-conjugates [46], and block copolymers [47]. Activated
ester groups are installed at the chain end of polymers through the incorporation of
activated ester reactive groups in chain-transfer agents or initiators for controlled
radical polymerizations. Different derivatives of nitroxide SG1 were studied for use
in NMP. The NHS ester of MAMA-SG1 was examined for the polymerization of
styrene, n-butyl acrylate, and methyl methacrylate. The resultant polymers bearing
62 L. A. Bultema et al.

NHS ester terminated chains were grafted to amino-coated silica particles. Through
this method, grafting densities of 0.1–0.2 chains per nm-2 were possible. An
improved grafting density of 0.9 chains per nm-2 was achieved using a one-pot
grafting approach. In this method, amino-coated silica, NHS ester, and the respective
monomer were added to the same reaction flask. Additionally, the NHS ester of
MAMA-SG1 could be employed in the synthesis of polystyrene-block-poly(D,
L-lactide) or polystyrene-block-poly(propylene oxide) block copolymers [47].
Reactive initiators for ATRP have also been installed with activated ester units
successfully, namely, with NHS 2-bromopropionate and NHS 2-bromoisobutyrate.
These initiators have mostly been used to prepare protein-polymer conjugates, for
example, using glycopolymers functionalized with end group activated esters, bio-
compatible poly(2-methacryloxethyl phosphorylcholine) [48, 49], or poly(oligo(eth-
ylene glycol) methyl ether methacrylate) [50–53]. The conjugation may employ
either grafting-to or grafting-from approaches. RAFT polymerizations using acti-
vated ester bearing chain-transfer agents have also been explored to prepare end
group functionalized polymers. NHS and PFP esters have both been incorporated
into chain-transfer agents and used for subsequent preparation of functional poly-
mers and block copolymers. Some notable examples include the preparation of
fluorescently labeled thermoresponsive block copolymers from NHS-based
dithioesters and the synthesis of poly(N-acryloylmorpholine) featuring a biotin or
galactose derivative end group [54, 55]. PFP ester-based trithiocarbonates or
dithioester also could be used to prepare corresponding PFP ester α-chain terminated
polymers [56, 57]. These polymers have been studied for use in conjugation of
responsive triblock copolymers to collagen-like peptides [58, 59]. Additionally such
polymers could be conjugated to photochromic dyes, leading to thermo- and light-
responsive polymers [60].

3.2 Anhydrides, Isocyanates, and Ketenes

Reactive polymer precursors containing anhydrides can easily be synthesized by

copolymerization with maleic anhydride. In principle, anhydride and isocyanate
containing monomers do not homopolymerize readily but may be copolymerized
by radical polymerization techniques with various monomers [61]. Davies has
demonstrated the copolymerization of maleic anhydride with various styrene como-
nomers through RAFT. The obtained series of alternating copolymers of maleic
anhydrides have defined structure with a definite and narrow molar mass distribution
[62]. Anhydride groups can easily react with alcohols and amines [63]. Functiona-
lization of anhydrides with amines was reported almost quantitatively at ambient
temperatures under buffer conditions of dimethyl sulfoxide (DMSO) – 0.5 M
NaHCO3) [63, 64].
Isocyanates, characterized by a N=C=O group, provide reactive carbonyl groups
that can react with alcohols, or amines [61]. But reactive isocyanates have also been
used in the conjunction of thiol-end-group polymers [65]. The most widely used
fabrication method for synthesis of isocyanates is the phosgenation of amines;
however, highly toxic phosgenes are used as reagents and involve environmental
2 Polymer Functionalization 63

Fig. 4 Quantitatively
modified of isocyanate
NH
functionalized polymers. R-NH2
(Redrawn after [68–70]) O
TEA
N
R
N NH
R-OH O
C DBTDL
O
O
R
NH
R-SH
TEA O
S
R

and safety problems. Knolker reported that alkyl-and arylamines can be converted
into isocyanates in high yields by reacting activated carbonates (di-tert-butyl
dicarbonate) in the presence of catalytic amounts of a nucleophilic nitrogen base at
room temperature [66]. Modification of isocyanates with amines or thiols proceeds
quantitatively, under ambient conditions, and within minutes. Furthermore, this
could be facilitated with the addition of TEA or 1,8-diazabicyclo[5.4.0]undec-7-
ene (DBU). However, quantitative conversion with alcohols is only possible either in
the presence of a catalyst such as dibutyltin dilaurate (DBTDL) or an excess of
alcohol (Fig. 4) [67, 68].
Ketenes as an alternative reactive groups in polymer chemistry have the inherent
ability to lead to crosslinking by dimerization and can be used as a reactive chemical
handle. Both of these features may be used together to provide a simple methodol-
ogy for preparing a variety of functionalized polymeric materials [71]. Ketenes
provide highly reactive carbonyl and alkenyl groups and may undergo various
transformations of one or both, which make ketenes versatile organic reactive
intermediates [72, 73]. By thermal treatment of 5,5-dialkyl-2,2-dimethyl-1,3-
dioxa-4,6-dione (or 5,5-dialkyl Meldrums acid), ketene derivatives can be prepared.
The innovation of Meldrum’s acid [74] allowed Hamish’s group to prepare ketene
intermediates through the pyrolysis of Meldrum’s acid (2,2-dimethyl-1,3-dioxane-
4,6-dione) derivatives. Further, Leibfarth et al. investigated the preparation of dialkyl
ketene precursors based on the modular chemistry of Meldrum’s acid by radical and
ring-opening metathesis polymerization leading to applications in thin films [75].

3.3 Oxazolones and Epoxides

Oxazolones (or azlactones) and epoxides have long been used in polymer chemistry
with monomers bearing these functional moieties. Noteworthy, the functional groups
64 L. A. Bultema et al.

Fig. 5 General
postmodification scheme of
oxazolones and epoxides

themselves can be polymerized. Oxazolones and epoxides can both be polymerized

via cationic polymerization, while epoxides can also be polymerized by anionic
polymerization. Additionally, it has been shown that vinyl monomers featuring these
groups can be polymerized by radical polymerization (both conventional and con-
trolled) without affecting the epoxide or oxazolone group. Furthermore, the post-
polymerization modification of oxazolone or epoxide containing polymers has
primarily allowed access to modification with amine, alcohol, and thiol groups
(Fig. 5).

3.3.1 Oxazolones
Taylor and coworkers were the first to produce polymers equipped with oxazolone
side chains via the polymerization of 2-vinyl-4,4-dimethyl-5-oxazolone (VDM)
[76]. PolyVDM was shown to react quantitatively with amines such as benzylamine
at room temperature and produce amide-functional polyacrylamides [77, 78]. This
modification can take place rapidly even in aqueous solutions with minimal com-
petitive hydrolysis [79]. The tendency for polyVDM to selectively react with amines
in aqueous media was used for the rapid and high-density immobilization of proteins
onto polyVDM functionalized beads at pH 7.5 [80]. While less common, oxazolones
may also react with alcohols in the presence of either an acid or a base catalyst. The
best catalysts for the reaction are trialkylphosphines and cyclic amidines [81].
Postpolymerization modification, where the reactive polymer precursor is directly
functionalized, frequently employs some form of click chemistry; however, protec-
tion/deprotection chemistries are usually required for “clickable” scaffolds
containing the traditional latent functionalities (alkenes and alkynes) when con-
trolled radical polymerizations are used. Thus, to circumvent this alkenyl azlactones
such as 2-vinyl-4,4-dimethylazlactone (VDMA) has been used. In particular, Jones
et al. used polyVDMA scaffolds as reactive precursors for direct and tandem
postpolymerization modifications and subsequent modifications to glycopolymers
for antiadhesion therapies against pathogenic toxins [82].
Microphase-separated block copolymers (BCPs) that are separated into periodic
domains allow for defined nanoscale structures, interfacial behavior of soft materials,
and bulk properties. In particular lamellar or cylindrical morphologies have gained
interest with the advancement in lithography to create well defined periodic chemical
2 Polymer Functionalization 65

Fig. 6 Reaction of azlactone

group with primary amine.
(Redrawn after [86])
O N H
N R
O N
H
O O
R-NH2

patterns and biological groups on the surface for design of substrates that allow
direct growth, deposition, or capture of various molecules. The group of Lynn
reported an approach to fabricate reactive microphase-separated azlactone
containing BCP thin films that allow for systematic, postfabrication [83].
The azlactone containing block was selected due to the ability of azlactones to
react with a wide range of nucleophiles via ring-opening reactions (Fig. 6)
[81]. Reactions with primary amines result in amide bonds under mild conditions
[81] that maintain phase stability under typical BCP thermal processing conditions
[84]. Copolymerization of vinyl azlactones with other vinyl monomers with living/
controlled methods results in BCPs with various side chain functionalities [85]. Tak-
ing these things into consideration, azlactone-containing BCPs were fabricated that
separate into lamellae structures and were subsequently functionalized, through
treatment with aqueous solutions containing primary amines [83].
Formation of reactive polyanions was possible via the semi-batch copolymeri-
zation of 4,4-dimethyl-2-vinyl-oxazoline-5-one (VDMA) and methacrylic acid
(MAA) through free radical and photoinduced radical polymerization. The subse-
quent 50:50 VDMA:MAA copolymer (PMV50) had up to 40% of the azlactone
groups hydrolyzed by water. Further transhydration was possible following the
storage in organic solvents. Additionally, solid PMV50 showed a stability for at
least 6 months at room temperature. Reduction of transhydration was possible via
increasing the VDMA comonomer content, likely due to decreasing the methacrylic
acid diads in the backbone. Subsequently the reactive polyanions could bind to
poly-L-lysine-coated alginate hydrogel beads and crosslink with polyamines. The
resulting covalent networks allow the beads to be used for long term therapeutic cell
encapsulation [87].
Post-polymerization modification of azlactone functionalized polymers can read-
ily occur through treatment with a variety of nucleophilic species. It has been
reported on postpolymerization modification of small molecule diamines for rapid
synthesis of amine functionalized polymers. Here tertiary amines did not react with
the azlactone ring, but resulted in polymers containing tertiary amine functionalized
side chains. Additionally under physiological pH, they exhibited a positive charge
and formed electrostatic complexes with DNA in aqueous media.
Furthermore, they reacted PVDMA with hydroxyl-functionalized molecules to
result in cationic “charge-shifting” polyelectrolytes (Fig. 7). Here PVDMA was
reacted with a molecule containing a hydroxyl and tertiary amine, with DBU
66 L. A. Bultema et al.

HO
n N n

O N O NH
DBU, 50°C, 48h
O
O
O
n
n NH
HO

O NH n Ester Hydrolysis
NH
O

Fig. 7 Synthesis and hydrolysis of “charge-shifting” cationic polymers. ([88]- Reproduced by

permission of the Royal Society of Chemistry)

catalyzing the reaction between hydroxyl and azlactone functionality. The resulting
polymer consisted of a protonatable tertiary amine side-chain that was attached via
an amide/ester functionalized linker. Following hydrolysis of the ester bond, the
negatively charged carboxylate group was unmasked, thus resulting in a change or
shift in the net charge of the polymer. This concept of charge-shifting materials was
utilized to develop multilayered polyelectrolyte thin films for controlled DNA
release from surfaces [88].

3.3.2 Epoxides
Epoxide-bearing polymers may be prepared from the radical polymerization of
corresponding epoxide functionalized vinyl monomers, such as commercially avail-
able glycidyl methacrylate (GMA) and glycidyl acrylate (GA). Epoxide rings are
reactive towards a number of functional groups, including amines, alcohols, carbox-
ylic acids, thiols, and anhydrides [89].
The post-polymerization modification of these functional polymers was first
explored by Iwakura and coworkers [90–92]. They showed that the post-
polymerization modification of polyGA and polyGMA with simple secondary
amines (1.0–4.0 equivalents) proceeded with low to moderate yields. Kalal showed
in 1974 that postpolymerization modification through epoxide ring opening may be
catalyzed with a tertiary amine (TEA) and reported 80 percent conversion of epoxide
groups on polyGMA with carboxylic acids [93]. The catalytic ability of TEA for
epoxide ring opening modification was furthered by Barbey and Klok, who prepared
polyGMA-co-polyDMAEMA brushes [94]. The brushes contained pendent TEA
groups that could be utilized to accelerate the postpolymerization modification rate
of the epoxide groups with amines in aqueous media at room temperature.
2 Polymer Functionalization 67

The fabrication of fluorescently labeled coreshell nanoparticles was also possible

through the use of polyGMA postmodification [95]. Deposition of polyGMA on a
silica nanoparticle enabled epoxide-bearing nanoparticles, which subsequently con-
jugated with Rhodamine B to produce fluorescently modified particles.
Monodisperse poly(glycidyl methacrylate)/polystyrene (PGMA/PS) particles
have been fabricated in Janus, raspberry, acorn, and hollow with open mouth shapes.
Moreover, the surfaces of these microparticles are high in epoxy groups, which make
them applicable for applications in biomolecule immobilization and super-
hydrophilic/superhydrophobic coatings [96].
Functionally soft interfaces are a great interest for various technologies. Soto-
Cantu et al. demonstrated the ability to covalently attach a thin layer of polyGMA to
a silica wafer and the versatility of the epoxide groups via a subsequent modification
with either propargylamine or 5-hexynoic acid. These modifications resulted in
interfacial polymers decorated with alkyne groups that could later undergo various
click reactions [97].
It should be noted that one disadvantage to epoxide-bearing polymers is that their
reaction with primary amines can lead to crosslinking [98]. Crosslinking occurs
because the reaction between a primary amine and an epoxide produces a secondary
amine after the epoxide ring opening, which will subsequently react with an
unopened epoxide ring. However, taking into consideration that crosslinking can
occur, self-assembled morphologies can be produced. Qin et al. demonstrated this
with their bulk self-assembly of diblock copolymer poly(tert-butyl acrylate)-block-
poly(glycidyl methacrylate) (PtBA-b-PGMA). Here PGMA bears epoxy groups that
act as crosslinkable segments and PtBA as a hydrolyzable segment [99].

3.4 Aldehydes and Ketones

Oxidation of alcohols is a commonly used method for the synthesis of aldehydes and
ketones [100]. The group of Einhorn has reported a high yielding and convenient
method for the fabrication of aldehydes via oxidation of primary alcohols in biphasic
dichloromethane-aqueous buffer systems (Fig. 8a) [101, 102]. The reaction works
efficiently under ambient temperature with a high selectivity for the oxidation of
primary alcohols into aldehydes. In addition, the inorganic-based supports for
chromium and metal-based oxidants such as iron(III)nitrate/montmorillonite K10
are also able to convert less active compounds such as acetals and alkanes into
aldehydes and ketones [103]. Hydrocarbons are found oxidized into corresponding
ketones in the presence of N-hydroxyphthalimide (NHPI), molecular oxygen, and
acetaldehyde (Fig. 8b) [104]. Additionally, the α, β-unsaturated aldehydes can be
generated from allylic methyl groups by means of microwave activation using
selenium dioxide [105].
Also mild reductive methods have been developed for preparing aldehydes and
ketones. For instance, under mild conditions β-keto sulfones can result in their
corresponding ketones from a reduction by TiCl4-Zn (Fig. 8c) [106]. Also,
68 L. A. Bultema et al.

Fig. 8 Fabrication of O
aldehydes and ketones OH
functionalized polymer. TEMPO (10mol%, NCS) (a)
(Redrawn after [101, 102, R H
R Bu4N+Cl-, CH2Cl2-H2O
104, 108, 109])

O2, NHPI (10mol%)

CH3CHO (1 equiv.) (b)

OMe OMe

O O

SO2Ph TiCl 4-Zn

Ph (c)
Ph
2h, room temp.
R R

O
O
R' disiamylborane
R N THF, 25°C (d)
R H
R''

N,N-dialkylamides can react with disiamylborane in THF resulting in aldehydes at

room temperature (Fig. 8d) [107].
As previously reported, the acylation reaction is an important method for the
synthesis of aromatic ketones. For example, Jia et al. reported the preparation of
aromatic ketones by means of palladium-catalyzed regioselective acylations of
aromatic C-H bonds. This reaction provided a convenient and atom-economic
method for the direct synthesis of aromatic ketones [108].
Aldehydes and ketones are electrophilic groups which can react with
alkoxyamines, amines, and hydrazides thus forming oximes, imines and hydrazones,
respectively [61]. Besides, aldehydes are also versatile groups which can react with
proteins and peptides in aqueous solutions under mild conditions enforcing the
biomolecules attaching to surfaces [110]. It was reported that aldehyde
functionalized polymers can be polymerized by free radical polymerization as well
as ATRP and RAFT conditions from 3,30 -diethoxypropyl polymerization [111–113].

3.4.1 Side Chain Modifications

The polymerization of aldehyde containing monomers dates back to the 1950s.
Wiley and Hobson reported the conventional radical polymerization between iso-
phthalaldehyde and malonic acid [114]. Theato’s group has synthesized a hybrid
2 Polymer Functionalization 69

polymer which composed of poly(methylsilsesquioxane) and poly(4-vinyl benzalde-

hyde) and further modified the silica surface in order to achieve zwitterionic thin films
containing α-amino phosphonic acid moieties [115]. Another alternative method for
the fabrication of aldehyde-functionalized polymers is anionic polymerization. Hirao
and Nakahama reported the synthesize of linear poly(4-vinylbenzaldehydes) via
anionic living polymerization of 1,3-dimethyl-2-(4-vinylphenyl)imidazolidine;
the aldehyde functionality was protected by N,N0 -dimethylethylenediamine
[116]. However, the strict conditions and complex procedures impeded the applica-
bility of this synthetic route [117, 118].
In the past 20 years, RAFT polymerization has found a facile route for homoge-
neous controlled polymerization of monomers under mild reactive conditions
[119]. In order to further simplify the procedures and reaction condition, Wooley
and co-workers investigated controlled radical polymerization of aldehyde
functionalized monomers. They reported the RAFT polymerization of
4-vinylbenzaldahyde (VBA) for the construction of well-defined aldehyde
containing polymers [118]. Afterwards, synthesis of poly(ethylene oxide)-block-
poly(2-formal-4-vinylphenyl ferrocenecarboxylate) (PEO-b-PFVFC) (containing
reactive aldehyde groups) was achieved by means of RAFT polymerization; fur-
thermore, the aldehyde group can be covalently modified under simple and mild
conditions [120].
Another common synthesis is via the protection of aldehydes as acetals, which is
conducted to allow a polymerization of the respective monomers. Maynard’s group
prepared poly(3,30 -diethoxypropyl methacrylate) (PDEPMA) with acetal
functionalized side chains by ATRP, afterwards the acetal protecting group could
be hydrolyzed into active aldehyde groups in dilute acids [111]. Polymers with
aldehyde side chains are especially useful in the synthesis of polymer drug conju-
gates. Peptides and antibodies are ubiquitously targeted with amine moieties, which
can subsequently react with aldehydes through reductive amination, thus forming a
stable bond [109].
Furthermore, ketone containing monomers such as vinylmethylketone (VMK),
isopropenyl methyl ketone (IMK), and phenyl vinyl ketone (PVK), can be poly-
merized via RAFT polymerization as well as free-radical polymerization (FRP). As
early as 1938 free-radical polymerization of VMK and its conversion with hydrox-
ylamine was investigated [121]. Cheng and coworkers have studied RAFT poly-
merization of vinyl ketones and showed that it is a facile way for the synthesis
of well-defined ketone containing polymers [122]. These ketone-functionalized
polymers can quantitatively be modified with different nucleophiles [123]. Addi-
tionally, Yang and Weck reported that via ring-opening metathesis polymerization
(ROMP) poly(norbornene)-based copolymers featuring ketone and aldehyde
side chain functionalities can be further functionalized and result in hydrazone
formation [124, 125].

3.4.2 End-Group Modifications

Aside from functional polymer side groups, aldehyde and ketone functional groups
also exist at end groups and could be used for end-group modification. In 1995,
70 L. A. Bultema et al.

Kataoka and coworkers synthesized a poly(ethylene oxide)-block-poly(lactide)

(PEO-b-PLA) block copolymer which contained an acetal terminal group on the
PEO block. As reported, the acetal group could be transformed into an aldehyde
group, hence forming an aldehyde end group copolymer which could be further used
for conjugation with proteins [126]. With the same method, Kataoka’s group also
synthesized aldehyde end capped poly(ethylene glycol) (PEG) polymers and PEG-b-
PLA copolymers, which were utilized for biomedical applications and for the
fabrication of supramolecular architectures [127, 128]. Haddleton and Tao synthe-
sized α-aldehyde terminated poly(methoxyPEG) methacrylates by means of ATRP
and further conjugated it with lysozymes [129]. In regard to ω-aldehyde-
functionalized polymers, Register and Notestein prepared polystyrene and polyiso-
prene containing an aldehyde at the end of the molecular chain via a prompt and
complete termination reaction of a ROMP [130].
In addition to the modification methods which have been mentioned above,
utilization of functional initiators or functional chain transfer agents (CTA) has led
to polymer end chain functionalization. Fulton and Jackson prepared aldehyde
containing trithiocarbonate CTAs in order to fabricate aldehyde end-functionalized
polymers via RAFT polymerization methods [131]. It was with ROMP of
norbornene (NB) or dicyclopentadiene (DCDP) that Matyjaszewski and Coca
reported the preparation of macroinitiators and subsequent chain capping with
p-(bromomethyl) benzaldehyde for homogeneous ATRP to synthesize styrene
block copolymers [132].

3.5 Azides and Alkynes

In 1963, Huisgen was the first to introduce the 1,3-cycloaddition between azides and
alkynes, resulting in 1,4- and 1,5-substituted 1,2,3-triazoles (Fig. 9) [133, 134]. Tra-
ditionally cycloaddition reactions are an equilibrium process; however, one can push
the reaction towards a certain direction with the aid of catalysis, heat, light, and
ultrasound [30]. Thus, it was not until 2001 when Meldal and Sharpless promoted
the use of copper-catalyzed azide-alkyne cycloaddition (CuAAC) that the

R
R
N
N R'
1,4-adduct
N N
N (preferred)
N
R' H R
1,5-adduct
N
N
R' N

Fig. 9 1,3-Dipolar cycloaddition between azides and alkynes

2 Polymer Functionalization 71

1,3-cycloaddition gained notoriety. The use of copper as a catalyst not only accel-
erates the result of a 1,4-adduct but also improves the yield while working under
mild conditions in a variety of organic solvents. However, a drawback of the CuAAC
is the removal of the copper catalyst, which can be work intensive due to the
formation of a complex with a triazole ring, which in turn diminishes the solubility
of functionalized polymers [135]. Copper (I) (Cu) species are required for CuAAC
reactions; however, the disproportion of Cu(I) to Cu(II) and Cu(0) or the oxidation of
Cu(I) to Cu(II) species often is considered catalytic poisoning for the reactions.
Luckily reduction of Cu(II) salts is conveniently possible to produce Cu(I). Addi-
tionally, Cu(I) can be generated via other reducing agents [136], photochemically
[137], electrochemical redox processes [138], and copper containing nanoparticles
[139]. Today, Cu(I)-tris((1benzyl-1H-1,2,3-triazolyl)methyl) amine complex and Cu
(I)-bathophenanthrolinedisulfonic acid complex are the two most frequently used
catalysts for CuAAC reactions [30].
Additionally in 2001, Kolb et al. [140] introduced the concept of click chemistry
with “spring loaded” reactions inspired by nature. The following criteria must be met
for a reaction to fall under the term “click chemistry”: a modular reaction that is wide
in scope, results in high yields, and results in mild byproducts. If purification is
required, nonchromatographic methods should be employed. Thus, only reactions
that do not employ a copper catalyst will fall under the term click chemistry.
A detailed investigation of the mechanism and kinetics will not be discussed here
in length. Instead, the use of CuAAC and metal free 1,3-dipolar cycloadditions for
modification of polymer side chains and end groups will be the focus. For an in depth
overview of the kinetics and mechanistic studies, the review by Binder and
Sachsenhofer [141] is recommended.
To ensure the required azide and alkyne functional groups are present, they can
either be incorporated during polymerization or directly after polymerization. For
example with ATRP, introduction of the azide end group after polymerization
frequently occurs due to the simplicity of a nucleophilic substitution of a bromide
or chloride substituent. Whereas for the reactive group to be directly incorporated
into the polymer side chain, a monomer with the desired functionality is utilized.
When the later approach is used, polymerization requirements need to be taken into
account. For example when ATRP is used, there is a possibility of alkyne groups
(e.g., propargyl methacrylate) interacting with the copper catalyst needed for ATRP
[142]. Additionally, the acidic terminal proton of an alkyne group can terminate the
propagation of the polymer chain when using anionic polymerization, hence requir-
ing the use of protecting groups for alkynes [143]. Furthermore, terminal alkyne
groups can also interfere with radical polymerization, resulting in crosslinking and
insolubility in organic solvents in some instances. Although the degree of
crosslinking depends partly on the chosen polymerization conditions, i.e., tempera-
ture and time. When crosslinking is not warranted, again the use of a protective
group is recommended. In contrast azide groups can provide difficulties with
cationic ring-opening polymerization (CROP) and decompose at elevated tempera-
tures [144, 145]. Although postpolymerization modifications involving the azide-
alkyne cycloaddition are highly efficient, the triazole moiety is often formed which
72 L. A. Bultema et al.

results in catalytic effects on subsequent cycloaddition reactions and turns the

modification into an autocatalytic process [146].

3.5.1 Polymer Side-Chain Modifications

Ring opening polymerization (ROP) has also been employed to synthesize
polymers with alkyne side groups. A particular example is the synthesis of poly
(α-propargyl-δ-valerolacone) and the copolymerization with ε-caprolactone.
Subsequent functionalization occurred with azide-terminated PEG mono-
methylether. Additionally an azide functionalized pentapeptide (GRGDS) was con-
jugated with the use of copper(II) sulfate and sodium ascorbate in an acetone/water
mixture at 80
C. However, it was found that when less stable polylactides (PLA) are
employed nonaqueous conditions should be used, such as copper(I) iodine with
triethylamine in THF at 35
C [147]. Additionally a biocompatible functionalization
was possible with an azide functionalized pentapeptide (GRGDS) [148].
Binder and Kluger investigated the preparation of various poly(oxynorbornene)s
via ROMP. In particular they found that due to the interaction of the alkyne moiety
with the catalyst the polymerization of exo-N-prop-2-ynyl-7-oxabicyclo[2.2.1]-hept-
5-ene-2,3-dicarboximide resulted in dispersities (Ð) over 1.5. To synthesize poly
(oxynorbornene)s with alkyne or azide side groups, postpolymerization modification
of the reactive polymers has occurred where CuAAC with bromotris(tri-
phenylphosphine) copper(I) was the catalyst and N,N-diisopropylethylamine in
dimethylformamide (DMF) at 50
C for 48 h.
RAFT polymerization has also been used to polymerize methacrylate- or styrene-
based monomers containing alkyne side groups. One example is the polymerization
of propargyl methacrylate with S-1-dodecyl-S0 -(α, α0 -dimethyl-α-acetic acid) trithio-
carbonate and 2,20 -azobisisobutyronitrile (AIBN) in toluene at 80
C for 3 h.
Subsequently, the resulting poly(propargyl methacrylate) could be grafted with
azide-terminated poly(vinyl acetate) in a CuAAC [149].
Postpolymerization modification on azide containing macromolecules has also
proven beneficial in the labeling of methionine analogs, found on bacterial cell
surface proteins, as azidoalanine with acetylene-functionalized PEG via CuAAC
with CuBr [149]. Additionally for biological applications, e.g., drug delivery, sen-
sors, therapeutics, orthogonal multifunctionalization of polymers plays an important
role. The orthogonal functionalization of a random copolymer of poly(norbornene)
containing azide- and ketone-containing side groups. Here the one-pot strategy
proceeded with the copolymer reacting simultaneously with phenylacetylene and
benzhydrazide, with copper(II) sulfate and sodium ascorbate for 2 h at 25
C,
wherein the azide and ketone side groups were converted into triazoles and
hydrazones, respectively [125].

3.5.2 Polymer End-Group Modifications

Not only can the azide or alkyne end groups be incorporated via post polymerization
modification, but also they can be incorporated directly to the initiators used in
ATRP, unimers for NMP, or CTAs for RAFT polymerization.
2 Polymer Functionalization 73

With ATRP, the introduction of an azide at the ω-end group of a polymer is

frequently executed through the simple nucleophilic substitution of the resulting
halide with sodium azide [149–152]. Subsequently the polymers with azide func-
tionalities could form block copolymers via the conversion with acetylene-
terminated polymers [145, 153–155].
Additionally an azide carrying initiator for ATRP has been used for controlled
polymerization of methyl methacrylate in combination with N-alkyl-2-
pyridylmethanimine and copper(I) bromide. The resulting polymer was
functionalized via CuAAC at the terminal azide with the same copper catalyst [156].
Chain transfer agents (CTAs) with azide or alkyne groups have been designed for
RAFT polymerization. Boyer et al. synthesized heterotelechelic polymers with an
azide α-end group and a dithiopyridine ω-end group. Subsequently a hetero-
telechelic poly(N-isopropyl acrylamide) (PNIPAAm) was shown to react with an
alkyne-modified biotin using copper(II) sulfate with sodium ascorbate. Under these
conditions, the ω-end group was left unmodified, allowing it to be used for further
conjugation to thiol containing biomolecules. In this instance, the unmodified end
group was conjugated to the protein bovine serum albumin (BSA) [157].
Overall when combining controlled polymerization techniques and this form of
click chemistry at polymer end groups, various polymer architectures are possible
such as linear architectures of: block copolymers, biohybrids, macromonomers, or
heterotelechelic polymers, and other architectures of: cyclic polymers, graft and star
copolymers, polymeric networks, dendritic architectures, and nanoparticles [10].

3.5.3 Metal-Free 1,3-Dipolar Cycloaddition

The previously mentioned examples relied mostly on the use of a copper catalyst;
however, instances arise in which the toxicology of the catalyst needs to be taken
into consideration, in particular for the synthesis of biomedical and pharmaceutical
applications. Thus, great efforts have been made to develop copper free click
methods. In particular is the use of alkyne species with increased reactivity via a
strain-promoted azidealkyne coupling (SPAAC), i.e., cyclooctynes as alkyne com-
ponents (Fig. 10). First generation cyclooctynes were truly based on ring strain;
however, second- and third-generations exhibit one or two fluoro substituents in the
α-position, respectively. This leads to accelerated reaction with azides. Additionally
4-dibenzocyclooctynol and benzenes are used as alkynes and result in benzotriazoles
following the conversion with azides.

3.6 Dienes and Dienophiles

First described by Diels and Alder in 1928, the cycloaddition reaction between a
diene and a dienophile has been widely used for organic synthesis over the years and
earned the pioneering scientists a Nobel Prize in Chemistry in 1950 [158]. The
reaction specifically involves a molecule containing 1,3 conjugated double bonds
(diene) and a molecule that should contain an alkene, alkyne, or double bonds
between heteroatoms (dienophile). The resultant product forms via a [4 + 2]
74 L. A. Bultema et al.

Fig. 10 Chemical structures O F

of various cyclooctynes used
in metal-free 1,3-dipolare
cycloaddition. (Redrawn after R
[10]) R

F
F

O O

R R

Fig. 11 Diels-Alder reaction O O

between furan and maleimide

O O O O

O O

cycloaddition in what may be considered “click” chemistry, as the reaction proceeds

quantitatively without side reactions, is tolerant to various functional groups and is
orthogonal with other chemistries, for example, CuAAC [159]. Notably, these
“Diels-Alder” reactions are highly thermally dependent and their cycloadducts
may be thermally fragmented via a retro Diels-Alder reaction to obtain new products
or recover starting materials from the forward reaction [160]. The stability of the
product and thus the ability to reverse the reaction depends upon the compatibility of
the chosen diene and dienophile. The energy gap between the highest occupied
molecular orbital (HOMO) of the diene and the lowest unoccupied molecular orbital
(LUMO) of the dienophile determines their reactivity. As such, electron-rich dienes
and dienophiles with electron-deficient double bonds form cycloadducts most readily.
Due to this quality, one may tune the reaction temperatures for a number of polymers
via adjustment of the diene-dienophile pairs.
The versatile qualities of the Diels-Alder reaction have proved invaluable in
multiple areas of chemistry including the preparation of protein-polymer conjugates
[161], hydrogels [162–164], dendrimers [165], block copolymers [166], graft, star,
telechelic polymers, H-shaped polymers, and dendrimers [167].
One of the most frequently employed pairings for the Diels-Alder reaction in
polymer chemistry is the furan-maleimide pair (Fig. 11). The reaction can be
adjusted to take place at temperatures up to 80
C and as low as room temperature
with differing reaction kinetics. The temperatures of the reaction are adjusted via the
addition of electron-donating or electron-withdrawing substituents to the diene
2 Polymer Functionalization 75

moiety. One may additionally greatly enhance low temperature reaction rates with
the utilization of a Lewis acid catalyst or with high pressure reaction conditions
[168]. The coordination of the Lewis acid to the carbonyl oxygen of the dienophile
increases the electron withdrawing capacity of the carbonyl group, and in turn its
reactivity. Frequently utilized Lewis acids include: trifluoroacetic acid, BF3, SnCl4,
ZnCl2, AlCl3, and their derivatives [30].
The ability of furan-maleimide cycloadducts to undergo a cycloreversion reaction
can be taken advantage of as a protection-deprotection method for diene or
dienophile containing polymers [168]. For effective use in this manner,
cycloreversion should take place at temperatures below the degradation temperature
of the polymer. The cycloreversion of the furan-maleimide cycloadduct occurs
around 100
C and thus presents a viable option for the protection and subsequent
unmasking of thiol-reactive maleimide groups.
Another popular diene-dienophile pairing in polymer chemistry is the anthracene-
maleimide combination. This reaction takes place at slightly higher temperatures,
usually near 110
C. The corresponding cycloreversion reaction takes place at
temperatures above 200
C and as such is less desirable for alkene functional
group masking. Still, the robust and regioselective nature of anthracene as a diene
has led to its widespread use in polymer post-modification.

3.6.1 Polymer End-Group Modifications

A useful strategy for harnessing the value of the Diels-Alder reaction in polymer
systems is through the synthesis of polymers with either a diene or dienophile at the
chain termini. The advances made in living polymerization techniques have pro-
duced numerous options for the incorporation of dienes and dienophiles as end
groups, such as ATRP, RAFT polymerization, NMP, and ROP. With these living
polymerizations, one may design initiators containing the desired functional moiety.
Following polymerization, the resultant product will contain the chosen terminal
functional group, allowing for subsequent modification through postpolymerization
reactions. A benchmark example of producing Diels-Alder accessible end groups to
a polymer was reported by Haddleton and coworkers [169]. They presented the first
example of the Diels-Alder/retro Diels-Alder reaction for the masking of
a dienophile during ATRP. A radical initiator for ATRP in the presence of a
Cu(I) catalyst was synthesized bearing a maleimide group. The maleimide was
protected by furan, then ATRP took place to produce a poly(ethylene glycol)
methacrylate polymer containing furan-maleimide cycloadducts at the chain ends.
Finally the maleimide was unmasked quantitatively through reflux in toluene with
no polymer degradation. The postmodification of such maleimide end group poly-
mers may even take place in the same step as the deprotection cycloreversion.
Reported by Durmaz et al., multiarm polymers and graft copolymers have been
prepared via the one-pot cycloreversion of furanmaleimide adducts and subsequent
Diels-Alder reaction with anthracene-bearing polymers [170]. PMMA terminated with a
furan-protected maleimide was refluxed in toluene with an anthracene terminated poly
(styrene) to produce the maleimide-anthracene conjugate without separate removal of
the furan. The orthogonality of the [4 + 2] cycloaddition and the copper-catalyzed
76 L. A. Bultema et al.

Huisgen [3 + 2] cycloaddition between azides and alkynes was demonstrated in the

formation of ABC triblock polymer structures [171]. A bifunctional poly(styrene)
capable of click reaction via both [4 + 2] and [3 + 2] cycloaddition was prepared by
ATRP of an anthracene bearing initiator followed by the substitution of the terminal
bromide with azide. The heterotelechelic polymer underwent a one-pot Diels-Alder
click reaction and azide-alkyne click reaction with a maleimide terminated PMMA
polymer and alkyne terminated poly(ethylene glycol) polymer, respectively.

3.6.2 Polymer Side-Chain Modifications

The application of the Diels-Alder cycloaddition to pendent polymer groups is an
additional useful strategy. Shi et al. exploited maleimide side-chains to affix polyenic
chromophores to maleimide containing vinyl copolymers. They first synthesized
maleimide-functional polymers by the sequential additions of 4-maleimido benzoyl
chloride and acetyl chloride under basic conditions to poly[(4-vinylphenol)-co-
(methyl methacrylate)]. These chemically sensitive anthracene-functional polyenic
chromophores could then be attached efficiently via a mild Diels-Alder reaction to
produce polymers with pendant novel nonlinear optic functionalities [172].
A diene such as furan may also be installed as a reactive side group for post-
polymerization modification. ( p-vinylphenyl)furfuryl ether was copolymerized with
styrene to produce a polymer possessing furan side groups. Subsequently the
polymer could be linked to a bismaleimide dienophile [173]. Using a similar
concept, a copolymerization of N-dimethylacrylamide and furfuryl methacrylate
was used to produce hydrogels through bismaleimide crosslinking. Due to the
potential for cycloreversion of the Diels-Alder reaction, produced gels were ther-
mally sensitive [174]. The capability of Diels-Alder to readily undergo both the
forward and reverse reaction has found application in producing self-healing poly-
mers via side-chain Diels-Alder chemistry [167]. Magana and coworkers were able
to produce a furan-maleimide crosslinked poly(ethylene) copolymer film that may be
repaired multiple times by adjusting temperature [175].

3.7 Tetrazines

The reaction between tetrazines and strained alkenes or alkynes has been used for
bioconjugation reactions. In particular the use of tetrazine-norbornene for post-
functionalization of synthetic polymers (Fig. 12) [176].
Additionally the progress of the reaction can be tracked with UV/Vis spectros-
copy by the decrease of the absorbance of the tetrazine at roughly 546 nm [177].

3.8 Triazolinediones

Although the Diels-Alder reaction first appeared in the 1920s, due to the problematic
synthesis and purification of triazolinedione (TAD) compounds it was not before the
1960s when Cookson et al. obtained the pure crystalline 4-phenyl-TAD (Cookson’s
reagent) that it was used as a dienophile in the Diels-Alder reaction. Due to the
2 Polymer Functionalization 77

R R
R' R'
N N HN
N N N

R R

Fig. 12 The tetrazine-norbornene reaction. (Redrawn after [177])

150W halogen lamp O N O

O N O
CCl4
N N
N N
N N n

O N O

Fig. 13 Homopolymerization of BuTAD

unique reactivity of TADs, the polymer community took an interest during the 1970s
with the modification of polydienes. Detailed investigation regarding this early
investigation can be found in the review by Butler from the early 1980s [178].
Direct polymerization of TAD-based monomers was first investigated by Pirkle
and Stickler in 1970. Here the obtained polymers exhibited an exotic all nitrogen
backbone (Fig. 13). However, the obtained polymer had a limited lifetime in the
CCl4 solution (30 min to a few days) and was fully degraded within minutes in the
presence of trace amounts of pyridine [178].
It was not until 1985, when Butler et al. investigated the decomposition behavior
of TAD molecules that homopolymerization of BuTADs was possible. Here catalytic
amounts of pyridine, a solution of a bifunctional TAD molecule in
1,2-dichloroethane was polymerized within 45 minutes and exhibited thermal sta-
bility [179] (Fig. 14).
Block copolymers are possible with TAD molecules due to their electron-
accepting activity which can react with a variety of electron donating alkenes.
Additionally the abundance of research focused on TAD compounds is on their
ability to be used as reactive dienophiles or enophiles. However, a major application
78 L. A. Bultema et al.

O O

N
N N
N n

O O

Fig. 14 Resulting structure from the polymerization of 3,30 -dimethyl-4,40 -bis(1,2,4-triazoline-3,5-

dione)diphenyl with pyridine. (Redrawn after [179])

of triazolinediones is the low temperature modification of polydienes [180]. Here the

alkene-TAD ene reaction results in atom-efficient and site-selective functionalization
of substrates [180]. Additionally monofunctional TAD molecules were used in the
modification of a variety of polydienes (polybutadiene, polyisoprene, random
styrene-butadiene copolymer, and a 1:1 alternating copolymer of furan and maleic
anhydride).
Cuttes et al. investigated the use of TAD (mono- and bifunctional) components
for surface modification of elastomers. Here the adhesion was improved along with a
reduction in peeling of flexible paints. Prior chlorination and halogen donor tech-
niques were used for elastomer modification; thus, this relatively mild and non-
corrosive technique became the preferred method [181].
Although hetero-Diels-Alder reactions have been referred to as representations of
click chemistry, TAD based chemistry has not widely been discussed in terms of
click chemistry, even though TAD compounds have been referred to being the most
reactive dienophiles. In particular triazolinediones have been explored as a strategy
for tyrosine bioconjugation. Additionally the enetype reaction with tryptophan side
chains is not accelerated, thus allowing a way for site selective labeling of tyrosine
residues in a natural peptide and protein substrate. The tyrosine-selective click
modification was furthered by site-selective and orthogonal protein multi-
functionalizations in Barbas’ group. Here, orthogonal trifunctionalization of tyro-
sine, cysteine, and lysine residues on bovine serum albumin (BSA) and human
serum albumin (HSA) was conducted. In particular the tyrosine units were reacted
with TAD derivatives and cysteine and lysine modified with a maleimide and
11-(dansylamino)-undecanoic acid [182].
An alternative to TAD-based functionalization of peptides was achieved by
Madder and coworkers (Fig. 15). Here they incorporated a furan residue into a
synthetic peptide with the commercially available furylalinine amino acid. The
classical maleimide-furan Diels-Alder conjugation was not very efficient; thus, the
more reactive triazolinediones were investigated. However, following investigation
it became clear that the expected Diels-Alder adduct was not observed, but a clean
furan-TAD electrophilic aromatic substitution. Subsequently this reaction proved
useful for quantitative and site selective peptide labeling [178].
The group of Du Prez has recently investigated the control of the TAD-indole
reversible click reactions. Here they modified indole reaction parameters to result in
easily accessible indole derivatives that result in dynamic TAD-adduct formation at
2 Polymer Functionalization 79

OH R O R O
N N

N NH
O O O
N N
H
N PBS buffer (pH=7)
N OH
H up to 99%
O
O
H
N
N
H
O

Fig. 15 Model reaction of tyrosine bioconjugation. (Reprinted with permission from [182]. Copy-
right 2013 American Chemical Society)

lower temperatures [183]. Additionally they demonstrated an simple method to

produce TAD endcapped peptides, via different molecular weight, diene
end-functionalized poly(ϵ-caprolactone). Here a buildup of N-terminal amines of
peptides is built up on a resin and functionalized with urazole moieties; following the
cleavage from the resin, the TAD is formed from oxidation. Subsequently this reacts
with dienes end-capped poly(ϵ-caprolactone) [184].
However, truly expansive development of TAD reagents has been hindered due to
the limited availability of reagents required for tailored TAD synthesis. Thus, TAD
reagents have found applications that do not require large amounts or cost of
synthesis is not an issue [178].

3.9 Halides

3.9.1 Substitution
Aryl halides usually can be activated via reduction and participate in substitution
reactions [185]. Among all the transition metal catalysis, palladium is one of the
most versatile catalysts that can couple aryl halides to arenes, alkenes, and aryl
Grignard reagents as summarized in Fig. 16 [186]. Furthermore, the substitution of
aryl halides (X = Cl, Br, F) with aryl methyl ethers via organomagnesium reagents
catalyzed by manganese chloride (MnCl2) has been reported [187].

3.9.2 Palladium-Catalyzed Coupling and Cross-coupling Reactions

It is reported that in the presence of copper salts alkyl halides could form C-C bonds,
whereas from aryl and alkenyl halides, palladium and nickel complexes are the most
used catalysis [188]. C-C cross coupling is one of the most straightforward methods
in organic synthesis. It is tolerant to a versatile range of functional groups; thus, alkyl
halides containing amide, alcohol, conjugated enone, ester, ether, furan, indole,
80 L. A. Bultema et al.

H Ar
Pd Catalysis (2e- Redox)
or
SRN1 Pathway (1e- Redox
= This topic)
Ar' Ar'
Ar-X H Ar
(Base)

BrMg Ar

Fig. 16 Palladium catalyzed coupling

nitrile, pyrrole, thioether, and aryl halide moieties were coupled to give high isolated
yields of products with functional group stability [189]. Knochel et al. reported that
aryl Grignard reagents containing ester or nitrile groups and pyridyl Gringnard
reagents can be coupled to alkenyl halides, halopyridones, and aryl bromides
[190–192]. Additionally, alkyl halides containing heterocyclic groups could be
coupled to give furan, indole, and pyrrole derivates. Vechorkin’s group reported
that in presence of nickel pincer complex catalysis, Kumada-Corriu-Tamao cross-
coupling of nonactivated alkyl halides with aryl and heteroaryl Grignard reagents is
possible [192].

3.9.3 Atom Transfer Radical Polymerization

ATRP is one facile polymerization method for the fabrication of a versatile array of
materials which could be conveniently modified in post-polymerization modifica-
tion. End-functionalized polymers can be prepared from initiators containing the
desired functional group by means of ATRP [193]. Halide containing initiators such
as benzyl halide, p-tosyl chloride, 2-bromopropionitrile, and methyl
2-halopropionate could trigger an ATRP reaction [194, 195]. Unprotected functional
halides and pseudohalides groups also can serve as an initiation site for radical
polymerization techniques [196].
Additionally, alkyl halides can quantitatively form into azides by the reaction
with trimethylsilyl azide in the presence of tetrabutylammonium fluoride under mild
conditions [197]. The allyl halides can produce radicals by homolytic cleavage of
C-X bond in ATRP reaction.

3.10 Thiols

Reactions involving thiols proceed rapidly with high selectivity, result in high yields,
and require minimal purification, thus, making thiols a highly versatile functional
group that can be employed in a variety of reactions. Additionally due to many
biomolecules containing thiols or reducible disulfides, thiol click chemistry is a
2 Polymer Functionalization 81

useful tool for the preparation of hybrid polymerbiomolecules. Furthermore, thiols

can coordinate with metals and enable surface modification via self-assembly
[10]. Thiol-ene reactions have also gained notoriety in polymer chemistry due to
their similarity to click chemistry. In particular, thiol-ene reactions proceed under
two routes: (i) anti-Markovnikov radical addition and (ii) base- or nucleophilic-
catalyzed thiol-ene addition reaction. The anti-Markovnikov reaction falls under
photochemical conditions and the later with various catalysis (acid/base, nucleo-
philic) and a solvent promoted process [30].
This section will comprise two main areas of focus: the various click reactions
thiols can undergo and a general overview of postpolymerization modifications
involving thiols.

3.10.1 Thiol Reactions

Nucleophilic Substitution
Weak bases can be used to deprotonate thiols in aqueous solutions, these resulting
thiolates are strong nucleophiles. Nucleophilicity increases on the order of alkyl,
propionate, glycolate, and aromatic substituents [198]. Formation of thioethers is
possible via ring opening of epoxides with Lewis acid [199].

Nucleophilic Addition
Thiols act as strong nucleophiles, in the presence of a weak base, and can add readily
to activated electron poor enes (Fig. 17). Some of the first thiol-ene reactions were
reported in 1948 when Serniuk et al. documented the functionalization of butadiene
polymers with aliphatic thiols [22]. Reaction of thiols with acrylates, vinylsulfones,
or maleimides results in thioethers (Fig. 18). The reaction rate of thiol-Michael
addition of esters increases with increasing nucleophilicity of the catalyst. Addition-
ally, increasing electron deficiency of the double bond increases the thiol addition
rate [198]. These reactions can occur under physiological conditions and are highly
efficient and orthogonal to a variety of functional groups, thus, making them suitable
candidates for bioconjugation [10, 198, 200].
However, a drawback to the thiol-ene coupling reaction is the oxidation of the
free thiol functionality into disulfide. This can be mitigated by excluding oxygen
from the reaction, addition of a reducing agent, or using protected thiol derivatives
[198]. If protecting groups are used, they should be quantitatively removed under
mild conditions and result in nontoxic byproducts.

Radical Addition
Thiyl radicals can be electrophilic and electrophilicity increases in the order of
aromatic, glycolate, propionate, and alkyl substituents and can react with electron-
rich enes, and alkynes[10], whereas for cyclic enes increased ring strain increases
reaction rates [207]. Generation of radicals is possible via the thermal decomposition
of initiators or photo-cleavable initiators. When high temperatures should be
avoided, UV light can be used[10]. Photoinitiation has enormous advantages for
small molecule synthesis and the modification of surfaces and polymers by allowing
82 L. A. Bultema et al.

F F
O O F R1 F R1
R-SH R-SH
Br R1 S R1
O cat. R O cat. R
F F S F
F F
OH
O R-SH N S R1 R1
S S R-SH
cat. R R1 S S
R1 cat. R
O O
R1 S
O S R-SH R
S R S S N R1 R-SH N R1
O cat. R cat.
O O

O S O R1 R1
R-SH R S R-SH S
R S
O cat. O O cat. O
R1 R1 O O

R-SH O R-SH
OCN-R R R1 R S
cat. S N cat. R R1
H

R
R-SH ox.
R1 R S S R1 2 HS-R S S
cat.
red. R
R1

Fig. 17 Overview of reactions of thiols with various substrates. Cat., catalyst; rad., radical; ox.,
oxidation; red., reduction

the control and manipulation of the reaction rate and extent by simply altering the
light intensity, or the duration of the exposure [208].
Generally thiol-ene reactions involve three steps: (i) hydrogen atom abstraction
from a thiol by an initiating radical, (ii) the thiyl radical subsequently adding to an
alkene or alkyne functionality resulting in a carbon radical, and (iii) the chain
transfer of the carbon radical to another thiol, where the resulting thiyl radical
propagates a new alkene [30]. The rate of the thiol-ene reaction can be adapted
based on the chemical structure of the alkene. A more rapidly occurring reaction
would involve electron-rich or strained alkenes as compared to electron-poor
alkenes.
Thiyl radicals can be generated from thermal, photo, and redox initiators. Photo-
initiation allows control over the whole process through absorption wavelength, light
2 Polymer Functionalization 83

O
(a) R2
R1 SH R1 S R2

O
O O
(b) S S
R1 SH R2 R1 S R2
O O

O O

(c)
N R2 N R2
R1 SH

O O
S
R1
(d) R3 R3
R1 SH R2 R2

S R1

Fig. 18 Thiol-ene reaction variations (a) Michael addition between thiols and acrylates [201],
(b) thiols and vinyl sulfones [202, 203], (c) thiols and maleimides [204], (d) thiols and alkenes [205,
206] (R2 and R3 are electron withdrawing groups)

intensity, and length of exposure. Additionally, it can take place under ambient
conditions, without metal catalyst, and used with a variety of functional groups.
High temperature (over 100
C, irradiation with UV light with UV lamps λmax at
254 or 365 nm), sunlight, or cobalt-60 gamma ray source all can be used for
generation of thiyl radicals [30].

Oxidation and Reduction

The half-reaction of RS-SR + 2e ! 2RS has a reduction potential of 0.25 V.
Formation of symmetrical disulfides from thiols is possible with easy-to-handle
oxidizing agents, such as oxygen, iodine, hydrogen peroxide, or Fe(III) salts,
whereas disulfides can be reduced to thiols with various reducing agents, i.e.,
dithiothreitol (DTT), tris-(carboxyethyl)phosphine (TCEP), or sodium dithionite
(Na2S2O4) [10].
Jonkheijm et al. demonstrated the bioorthogonality of radical thiol-ene reac-
tions with the immobilization of biomolecules resulting in patterned surfaces. In
particular they first treated a silicon oxide surface with aminocaproic acid (acts as a
spacer), followed by covalently attaching polyamidoamine dendrimers, and sub-
sequent coupling with previously reduced cystamine to result in a thiol
84 L. A. Bultema et al.

functionalized surface. Furthermore, the patterned surface was produced via the
coating of the surface with ene functional biomolecules, in particular ene-bearing
biotin, and directly covering with a photomask and irradiation of the surface.
Visualization of the patterned surface was made possible via a Cy5-labeled
streptavidin (SAv) [209].
Thiocarbonylthio end groups remaining on polymers synthesized via RAFT
polymerization can result in instability of the final polymers [210]. Different
methods can been used to remove the RAFT end-group, such as thermolysis, radical
transfer, oxidation to give sulfine, and aminolysis [211, 212]. Of these methods,
aminolysis (reduction) is frequently used to yield polymers with thiol end-groups
that can be further modified. However, a major drawback of aminolysis is the
oxidation of the resultant thiol to disulfides, resulting in bimodal populations of
polymers containing thiol and disulfide functional polymers [213]. To overcome
this problem, Boyer et al. have performed aminolysis of the RAFT containing
endgroups with pyridyldisulfide-bearing, ene-bearing, or other thiol reactive com-
pounds. This resulted in a simultaneous protection/functionalization of the thiols,
while still controlling the functionality and polymer architecture via thiol-ene
reactions [213].

3.10.2 Polymer End-Group Modifications

Various thiol end groups that remain after modification of dithioester, tri-
thiocarbonate, or xanthogenate end group moieties from RAFT polymerization
subsequently can be modified to obtain terminal thiols via ester/carbon cleavages.
In particular, terminal thiols can react with modified maleimides or acrylates as
thiol-Michael acceptors in RAFT end group modification. Additionally, star
shaped polymers are possible by reacting thiol-terminated polymers with a tri-
acrylate core [214].
Terminal-functionalized disulfides are possible via aminolysis of terminal
dithoesters on poly(meth)acrylates, poly[(meth)acyrlamides] in the presence of
functional methane thiosulfonate reagents. Subsequently this approach was
employed to various polymers to result in butynyl end groups in CuAAC [214].
Nucleophilic substitution of activated bromides, or thiol-bromo click chemistry,
can be employed during aminolysis of RAFT polymers to result in thioether-bound
functional groups [214].
Xu et al. demonstrated the efficiency of thiolisocyanate click chemistry on thiol-
terminated poly (N,N-diethylacrylamide) with isocyanates [215].
Thiol-modified biomolecules can be coupled to RAFT generated polymers by
addition of thiolreactive compounds during aminolysis followed by converting
trithiocarbonate end group to (i) a stable thiol reactive group that can be used for
bio-conjugation or directly (ii) to a bioconjugate (Fig. 19) [216].
ATRP is a good method of choice to produce polymers terminated with halides.
Subsequently terminal bromides of poly(methyl acrylate) have been modified with
thioglycerol in a thiol-bromo click substitution reaction. In turn, this was used as an
effective synthetic pathway for bromoterminated macromolecular dendrimers via
2 Polymer Functionalization 85

Fig. 19 Atom-efficient (bio)functionalization of a RAFT polymer via simultaneous aminolysis and

thiol-specific reactions [216]. Reprinted from permission of JOHN WILEY and SONS

acylation of two terminal hydroxyl groups with 2-bromopropionyl bromide which

equipped the end groups with two initiators for ATRP.

3.10.3 Polymer Side-Chain Modifications

Pentafluorostyrene is a readily available monomer that contains a thiol-reactive site
that can undergo substitution of the para-fluoride with base catalysis after
polymerization [217].
Another candidate for side group thiol-ene modification is poly(butadiene), with
its pendant vinyl groups. Here the polymer can react with thiolated biomolecules
such as amino acids, sugars, or cholesterol. However, the side reaction of cyclization
of neighboring side groups can occur due to the closeness of the vinyl groups [218].
Pyridyl disulfide ethyl methacrylate has also been used in thiol conjugation
following the polymerization by RAFT and ATRP, resulting in a styrenic derivative
carrying two pyridyl disulfide groups that can easily attach to thiolated PEG without
endangering the integrity of the acetal bridges within the polymer. Subsequently
these bioinspired polymeric carriers became membrane-disruptive and were studied
for cellular uptake at different pH [219].
86 L. A. Bultema et al.

3.11 Future Prospects in Polymer Functionalization

3.11.1 Sulfur Fluoride Exchange

Recently revived by the Sharpless group, the sulfur(VI) fluoride exchange
(SuFEx) represents a useful and previously unexplored platform of click chemis-
try [220]. SuFEx click chemistry is based on the tendency of sulfonyl fluorides to
exchange S-F bonds for S-O bonds in the presence of proton or silicon centers.
Sulfonyl fluorides exhibit unique properties that make them more suitable for
highly efficient reactions than other sulfonyl halides. First, the SO2-F is incredibly
resistant to unwanted hydrolysis in harsh reaction conditions. Additionally, the
fluoride radical is energetically inaccessible, which allows SuFEx chemistry to
avoid radical pathways that hinder other sulfur (VI) halides. Lastly, the SO2-O
bonds form rapidly and stably nonprotic conditions with the use of silicon centers,
as Si-F forms the strongest single bond found in nature. The Locklin group has
successfully employed SuFEx chemistry in the postmodification of polymer
brushes [221]. 3-(fluorosulfonyl)propyl methacrylate (FSPMA) monomer was
polymerized via UV initiated radical polymerization on an azo-based silane
initiator monolayer to form poly(FSPMA) brushes. Subsequently the brushes
were exposed to silyl ethers in the presence of a catalyst to encourage the
exchange reaction. Sulfonate esters were rapidly formed bearing a number of
functional moieties for continued postmodification, notably alkynes, azides,
thiols, alkenes, dienes, and dienophiles. The reaction remained dormant until
the addition of a catalyst such as triazabicyclodecene and produced an inert silyl
fluoride byproduct. Due to its click chemistry features and ability to install other
click moieties to for postpolymerization modification, SuFEx functionalization
stands as a promising new option for widely expanding the toolbox for polymer
tunability.

3.11.2 Nitrile Oxides

The group of Takata has recently reported an attractive new method for 1,3-dipolar
cycloaddition to polymers containing unsaturated bonds [222]. Their work incorpo-
rates nitrile N-oxides as agents for efficient cycloaddition to both alkynes and
alkenes. This reaction is advantageous to CuAAC click chemistry because it avoids
the use of metal catalysts and solvents, and is safer at higher temperatures than azides
[223]. Due to their instability with respect to self-reactions, nitrile N-oxides have
received relatively little attention in polymer science thus far [224, 225]. However,
the Takata group has developed kinetically stabilized nitrile N-oxide polymers for
subsequent postmodification. Nitrile N-oxide terminated polymers were produced
via Michael addition of trans-β-nitrostyrene to vinyl polymers such as PMMA or
PtBMA. The resultant polymers displayed high reactivity towards both pendant and
internal olefin-containing polymers at moderate temperatures. With further explora-
tion, nitrile N-oxides show promise in accessing 1,3-dipolar cycloadditions in a
wider range of systems.
2 Polymer Functionalization 87

3.11.3 Multicomponent Reactions

Multicomponent reactions (MCR) were first discovered by Strecker in 1850. They
refer to reactions that are conducted as one-pot reactions employing at least two
starting materials and atoms from starting materials are incorporated in the end
product [226]. MCRs have gained attraction over the years and have been utilized
in a variety of fields of life sciences, pharmaceutics, and organic chemistry due to the
decrease in chemicals, solvents and their time saving [227]. MCRs also capacitate
postpolymerization modifications with a variety of functional groups [228]. Hence,
the MCR derived product can be used as a synthetic hub to plenty of novel cyclic or
acyclic scaffolds such as branched and star-shaped polymers [229].
As an example of a side chain modification utilizing MCRs, Li’s group used poly
( p-nitrophenyl-methacrylate)-block-poly(diethoxypropyl methacrylate) block
copolymer as starting materials, afterwards, poly( p-nitrophenylmethacrylate) was
modified by allylamine and poly(diethoxypropyl methacrylate) was then modified
by O-benzylhydroxylamine hydrochloride [230].
In order to obtain end-chain modification, Sumerlin’s group performed
aminolysis of poly(N-isopropylacrylamide) into sulfhydryl terminated polymers
and further connected with bismaleimide. Thus, they obtained maleimido-terminated
macromolecules which allowed near-quantitative coupling with model low molec-
ular weight thiols or dienes [231].
Polymers with tunable properties were synthesized via a Kabachnik-Fields poly-
condensation reaction in Theato’s group. Here the Kabachnik-Fields reaction was
chosen to result in α-amino phosphonates in a metal-free reaction that can lead to
zwitterionic structures with potential antifouling applications. In particular they
investigated the synthesis of various polycondensation polymers with 1,10-bis
(4-formylphenyl)-1,4,7,10-etraoxadecane as a dialdehyde with different diamines
and phosphites. It was found that the α-amino phosphonates within the main chain
can be deprotected to form zwitterionic species and the glass transition temperature
could be varied with different diamines and phosphites [232], thus, allowing for an
efficient and diverse synthesis of functional polymers.
Recently Tao’s group has developed a strategy for performing MCRs during
controlled radical polymerization (CRP) to build one-pot tri-component (enzymatic
reaction/click reaction/CRP) and tetracomponent (Biginelli/CRP, Kabachnik-Fields
(KF)/CRP) MCR-CRP systems [227]. To build the proper MCR, they utilized
components that are efficient and robust under radical conditions and result in
excellent yields. Therefore, they investigated the preparation of poly
(1,4-dihydropyridine)s through the combination of a Hantzsch reaction and RAFT
polymerization (Fig. 20). Hantzsch reactions traditionally consist of four starting
materials: an aldehyde, 2 equivalents of β-ketoester, and ammonia to generate
1,4-dihydropyridines (1,4-DHPs). Additionally this reaction can occur under benign
conditions, overall efficient, and is atom-economic with the only generated
byproduct being water.
Thus, a typical Hantzsch-RAFT system was used to prepare poly
(1,4-dihydropyridine), this included: 2-(acetoacetoxy)ethyl methacrylate (AEMA),
88 L. A. Bultema et al.

O R
Hantzsch reaction n
CHO
O O
One Pot
NH4OAc O O
O
RAFT

O O
O O

O R NH

R-CHO:
OH F
S
CHO
CHO

CHO CHO CHO CHO

Fig. 20 Hantzsch-RAFT polymerization to one-pot well-defined poly(1,4-DHP)s. (Adapted with

permission from [227]. Copyright 2015 American Chemical Society)

benzaldehyde, dimedone, and excess ammonium acetate (1.5 equiv. to AEMA),

glycine (10% equiv. to ammonium acetate), azodiisobutyronitrile (AIBN) (initiator
for RAFT), and 4-cyano-4-(ethylthio-carbonothioylthio) pentanoic acid (chain trans-
fer agent for RAFT). The reaction proceeded under Schlenk conditions at 70
C.
Under optimal conditions, 1,4-DHP was generated in about 3 h with roughly 90%
conversion and RAFT polymerization proceeded with 90% conversion (in relation to
vinyl groups) in 12 h. The obtained polymers had controlled molecular weight and
narrow dispersities (1.20) [227].

3.11.4 Catalytic Transesterifications

Sawamoto and coworkers demonstrated the use of versatile tandem catalysis in
ruthenium-catalyzed living radical polymerization in a one-pot synthesis of
multisequence-regulated copolymers (random-gradient and gradient-block
2 Polymer Functionalization 89

copolymers) and random and block copolymers [233]. The synthesis of gradient
polymers takes place by combining the ruthenium-catalyzed living radical polymer-
ization with the in situ transformation of a fed methacrylate (R1MA) into another
(R2MA) via transesterification with an alcohol (R 2OH) and a metal oxide [Al(Oi-
Pr)3, Ti(Ii-Br)4, etc.] [234].
Here, the metal alkoxide takes on two rolls: first acting as a cocatalyst for
promoting propagation and second concurrently catalyzing in situ monomer trans-
formation, which in turn provides a second monomer for copolymerization
[233]. Furthermore, efficient transesterification relies on the following factors: (i) it
has a higher activity for monomers than the polymers, independent of the monomer
concentration (polymerization stage), living radical polymerization is never
deactivated or retarded by the cocatalyst, and (iii) the transesterification into the
second monomer is kinetically synchronized with the copolymerization [233].
In particular, gradient copolymers based on methyl methacrylate (MMA) and
dodecyl methacrylate (DMA) were synthesized with MMA, 1-dodecanol, and tita-
nium isopropoxide. To ensure complete synchronization of the two reactions,
molecular sieves were employed to remove methanol from MMA transesterification
into DMA. Furthermore, the resulting gradient copolymers exhibited a broad glass
transition temperature, making it a potential material for vibration or acoustic
dampening [234].
The group of Sawamoto also showed terminal-selective transesterification of
chlorine-capped poly (methyl methacrylate)s with alcohols, resulting in telechelic
and pinpoint-functionalized polymers that can subsequently be used as a micro-
initiator in living radical polymerization due to the chlorine atom at the
ω-terminal [235].
The transesterification reactions described by Sawamoto require several purifica-
tion steps, which limits the development of this creative methodology. To overcome
these limitations, enzymatic reactions can be used that exhibit specific catalytic
abilities. In particular the use of Lipase B from Candida antarctia for the trans-
acylation reaction between esters and nucleophilic compounds (alcohols). Further-
more, to obtain controlled polymerization under mild conditions with external
stimuli, light-mediated polymerization has been employed. Tao et al. introduced a
photoinduced electron transfer-reversible addition-fragmentation chain transfer
(PET-RAFT) polymerization. This technique was used to synthesize (meth)acrylate,
(meth)acylamide, vinyl acetate, monomers with great control over the molecular
weight and molecular weight distribution. In particular, they prepared functional
monomers via transacylation of 1,1,1-trifluoroethylacrylate (TFEA) with different
alcohols in the presence of Candida antarctia. Following these monomers were
polymerized via PET-RAFT to result in high-ordered multiblock copolymers [236].

3.12 Dibromomaleimide Chemistry

Baker et al. reported that bromomaleimides undergo efficient, clean, and selective
substitution reactions with the thiol group of cysteines for protein modification and
bioconjugation [237]. This rapid and quantitative substitution under mild conditions
90 L. A. Bultema et al.

Fig. 21 dBMIB as a O
coupling agent to couple two Br
thiol-terminated polymers into
a polymer dimer N
[238]. (Reprinted with 2 Polymer-SH
permission from John Wiley Br
and Sons) O Br

dBMIB
pH 6.2/TCEP/6h

O
S
Polymer
N
Polymer
S
O Br

P2MIB

showed characteristics of an ideal click reaction and potential use as a polymer-

polymer coupling agent for topological polymer engineering [238].
Wang et al. showed that N-(4-bromobutyl) dibromomaleimide (dBMIB) can
efficiently couple two thiol-terminated polymers that results in double the molecular
weight (Fig. 21). Additionally the bromobutylene unit at the chain center may be
transferred into an azido unit. This subsequently can be used in a CuAAC reaction
for a coupling reaction to a third polymer chain resulting in an A2B star
polymer [238].

3.13 Use of Thiolactone

Although thiols can readily react with alkyl halides, epoxides, isocyanates, and
double and triple bonds; the issues of smell, shelf life, and synthetic availability
have led to the recent development of thiolactones (cyclic thioesters of mercapto-
acids) in synthetic polymer science. Traditionally four-, five-, and six-membered
rings are used, β-, γ-,δ-thiolactones, respectively. Here the ring is opened by the
functional amine (aminolysis) and the resulting thiol subsequently reacts in an
orthogonal manner with a thiol “scavenger” (Fig. 22). This allows for the introduc-
tion of two distinct functionalities at the same reactive site. This synthetic approach
has two distinct advantages over other chemistries applied in post-polymer modifi-
cation and polymer synthesis. Thiolactone chemistry results in 100% atom-efficient
conjugation reactions and the ability to doubly modify the polymer scaffold [239].
2 Polymer Functionalization 91

O O O
Aminolysis Thiol-X R1
R1
S N N
NH2 H H
R1 HS S
R2

Fig. 22 Thiolactone entity: release of the thiol by nucleophilic ring-opening of the cyclic thioester
and a subsequent reaction with a thiol “scavenger.” [239]. (Reprinted with permission from
Elsevier)

Additionally, the double modification can occur in a one-pot fashion leading to

simplified experimental set-ups [240].
Preparation of saturated γ- and δ-thiolactones occurs by the direct lactonization of
the corresponding mercapto-acid. Although several nucleophiles can be used for the
ring opening (water, alcohol, etc.) aminolysis requires no additives and can be
performed in an aqueous medium, thus, making it an ideal choice for the ring
opening [239].

4 Conclusion and Summary

This chapter outlined ways to functionalize polymers by taking a look at specific

functional groups and modern reactions. Additionally to showcase the versatility of
the functional groups, side chain and end chain modification were included within
each section. Polymer functionalization is a versatile tool to tailor a polymer for a
specific purpose and in turn develop novel polymer architecture. Additionally
through the understanding of various synthetic concepts of organic reactions, the
synthesis of well-defined multifunctional polymers is possible. Finally, future pros-
pects in polymer functionalization were briefly mentioned.

Acknowledgments X. Huang kindly acknowledges the financial support of The China Scholar-
ship Council (CSC, Grant 201506240019). D. D. Brauer kindly acknowledges the support of the
German American Fulbright Commission through a Fulbright grant.

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Electrochemical Polymerization
3
Gertrude Fomo, Tesfaye Waryo, Usisipho Feleni, Priscilla Baker, and
Emmanuel Iwuoha

Contents
1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
2 Background on Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
3 General Principle of Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4 Materials and Equipment Used for Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . 110
4.1 Electrodes Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
4.2 Supporting Electrolyte Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.3 Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
5 Reactivity of the Monomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
6 Techniques for Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
6.1 Galvanostatic Polymerization Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
6.2 Potentiostatic Polymerization Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
6.3 Potentiodynamic Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
7 Factors that Affect Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
7.1 Monomer Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
7.2 pH of Medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
7.3 Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
7.4 Mode of Initial Scan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
8 Advantages and Application of Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 125
8.1 Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

G. Fomo (*) · T. Waryo

SensorLab, University of Western Cape, Cape Town, South Africa
e-mail: [email protected]; [email protected]
U. Feleni
SensorLab, University of Western Cape, Cape Town, South Africa
Nanotechnology and Water Sustainability Research Unit, University of South Africa,
Johannesburg, South Africa
e-mail: [email protected]
P. Baker · E. Iwuoha (*)
SensorLab, Department of Chemistry, University of the Western Cape, Bellville, South Africa
e-mail: [email protected]; [email protected]

© Springer Nature Switzerland AG 2019 105

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_3
106 G. Fomo et al.

8.2 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

9 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

Abstract
Advances in molecular electronic devices such as sensors, organic solar cells, and
organic light emitting diodes have increased the interest and research on electro-
synthetic conducting polymers. This chapter focuses on electrochemical poly-
merization (or electropolymerization) as a cost-effective and easy-to-use method
for the preparation of electrosynthetic conducting polymer films. Electro-
polymerized materials, characteristically, possess unique morphological, physi-
cal, electronic, and electrochemical proprieties which make them amenable to
various applications. Electropolymerization is initiated by the oxidation of a
monomer in an electrochemical cell, followed by the growth of the polymer
film on the surface of the working electrode, which may be a carbonaceous, a
metallic, or a conducting glass material. As the oxidation of the monomer is
voltage- or current-induced, electrochemical polymerization is, therefore, a green
chemistry methodology. Being devoid of the use of toxic oxidants, the technique
ensures real-time controlled production of very high purity conducting polymer
films. The films exhibit excellent electrical, electronic, magnetic, optical, and
rheological properties. Polyaniline films in their pristine and doped forms and the
films of other conducting polymers are discussed in this chapter.

1 History

Electrochemistry was born as a science especially in chemistry at the end of the

eighteenth century by Galvani. Indeed, based on the experiments on the relationship
between electricity and muscle contractions by Galvani, Volta (Alessandro Volta,
Professor at University of Pavia) announced to the scientific community in 1800, the
invention of the electric pile – a “device” which would later revolutionize the
concept of energy production [1]. Later, it was found that Galvani’s conclusions
were wrong, but his experiments elicited Volta’s interest in this area of study, and
today Volta is regarded as the “Father of the Electrochemistry.” For many years,
electrochemistry has been an important area of chemistry where technological
advances result from the interaction of materials and the electrode in electrochemical
cells. The very first effort related to this topic involved the oxidation of aniline in
1835 [2], and the term “aniline black” was given to the resulting polyaniline (PANI).
The electrochemical synthesis method came from the notion of conjugated
conducting polymers or synthetic metals, where Lethe (a Professor of Chemistry at
the College of London Hospital) in 1862 reported the synthesis of a thick layer of
dirty bluish-green pigment via the electrochemical polymerization of aniline in
aqueous sulfuric acid on a platinum electrode [3]. Within the years 1968–1988,
many researchers became interested in the synthesis of polyaniline, using both
3 Electrochemical Polymerization 107

chemical and electrochemical techniques with different oxidizing agents and elec-
trolyte solutions [4–9].

2 Background on Electrochemical Polymerization

Current advancement in electronics and electrochemical technology demands the

development of highly sensitive sensors for electrocatalysis and detection, stable
photovoltaic cells with high power conversion efficiency, and rechargeable batteries
with high specific energy and power. A possible approach for attending to these
needs involves the use of electroactive conducting polymer films to fabricate the
associated devices [1, 10, 11]. As mentioned earlier, electrochemical polymerization
is a typical method that is generally used for the synthesis of electroactive conducting
polymers films because of its simplicity and reproducibility [12]. Potentiostatic,
galvanostatic, potential step and potential sweep methods are usually used for the
electropolymerization of monomers and their derivatives [13–16]. Therefore, factors
such as applied potential, doping effect, electrolyte solution, direction of potential
sweep, nature of the monomer, pH, solvent effect, temperature, and the voltammetric
potential window determine the properties and applications of the polymer films
formed [17–19]. Basically, in this method a potential is applied to a working electrode
that is immersed in an electrochemical cell containing a monomer, a doping agent
(where necessary), and the electrolyte solution. The monomer can, thus, be electro-
chemically oxidized to form free radicals that initiate the polymerization process and
the deposition of the conducting polymer film on the working electrode surface.

3 General Principle of Electrochemical Polymerization

Electrochemical polymerization or electropolymerization is based on the deposition

of the polymer onto the surface of a solid electrode material. This occurs through a
generally accepted mechanism that involves the formation of cationic radical by the
oxidation of the monomer on the solid electrode material. The electrochemical
polymerization method can be divided into two important groups, which are anodic
and cathodic electrochemical polymerization.
The anodic electrochemical polymerization is the most suitable method of oxi-
dizing monomer species for the preparation of conducting compounds. This process
begins with the formation of an oxidative monomer radical cation [20, 21]. The
electrochemical stoichiometry of the electro-oxidation process involves
2.07–2.6 F mol
1 monomer [15]. In most cases, the polymer film formation process
requires two electrons per molecule of the monomer, that is, 2 F mol
1. The excess
charge is used for the oxidation of the oligomeric compounds that could be observed
on the cyclic voltammogram. The mechanism of polymer formation and growth is
believed to involve either the coupling between radical cations or the reaction of a
radical cation with a neutral monomer. The radical cations can react either with
neighboring radical cations or with neutral monomers to produce the polymer.
108 G. Fomo et al.

Scheme 1 Mechanism for the anodic electrochemical polymerization of polyaniline

3 Electrochemical Polymerization 109

An example of the mechanism of an electrochemical polymerization involving

radical cation-radical cation coupling is illustrated in Scheme 1. It informs that the
first step of the electrosynthesis process is the formation of a cation radical via the
transfer of an electron from a sp3 orbital of the atom to the electrode surface when
oxidation occurred. During the electropolymerization of aniline, a nonconducting
PANI (leucoemeraldine state) is formed, while the most conducting PANI
(emeraldine) is formed in the reduced state [22–24].
The cathodic electrochemical polymerization is rarely used for the synthesis
of conducting polymers. Indeed, this type of polymerization involves reductive
electrosynthetic processes which lead to very low yield of conducting polymers.
Only the poly(p-phenylenevinylenes) (PPVs) conducting polymers, used as
materials for organic light emitting devices [21, 25], have been produced by
the cathodic polymerization method. In Sect. 7.4 of this chapter, the synthesis
of conducting blue p-doped PANI-PSSA thin films by the cathodic polymeriza-
tion is presented, together with its successful application as biocompatible
conducting film for smart DNA aptamer-based biosensor for fish toxin
[26]. The mechanism for the cathodic electropolymerization of aniline is as
described in Scheme 2 [27].

Scheme 2 Mechanism for the cathodic electrochemical polymerization of aniline

110 G. Fomo et al.

4 Materials and Equipment Used for Electrochemical

Polymerization

Electrochemical polymerization experiments are carried out with potentiostatic or

galvanostatic electrochemical workstations (see Fig. 1), such as Amel Model 7050
Potentiostat-Galvanostat, Princeton Applied Research (PAR) Potentiostat Model
273, Eco Chemie Metrohm Autolab Potentiostats, Bioanalytical Systems, Incorpo-
rated (BASi) 50 and 100 Electrochemical Analyzers, BASi EC Epsilon Potentiostat,
Radiometer Analytical VoltaLab 80 Electrochemical Laboratory, and Zhaner IM6e
Potentiostat [23, 28–31]. There are also potable, miniaturized, and hand-held elec-
trochemical instruments such as Metrohm Dropsens Potentiostat-Galvanostat,
PalmSens Compact Electrochemical Interfaces, and Uniscan/PAR PG580
Potentiostat-Galvanostat that are also used by several laboratories for electrochem-
ical polymerization.

4.1 Electrodes Materials

For electrochemical polymerization, a three-electrode convention in electrochemical

cell is used. The working electrode, i.e., the electrode on which the desired reaction
takes place, can be an inert metal (e.g., Au, Pt, and Ti) [32–38], a carbon material
(e.g., glassy carbon, GC, pyrolytic graphite, PG, and boron-doped diamond (BDD))
[17, 23, 39–45], a conducting glass (e.g., indium tin oxide (ITO)) [46–48], or an
alloy. The nature of the working electrode surface [49] influences the ease of the
monomer oxidation, the rate of polymerization, and the growth of the polymer films.
The use of alloys as working electrodes is limited by the very high potentials

Fig. 1 Examples of instruments used for electrochemical polymerization

3 Electrochemical Polymerization 111

Fig. 2 Examples of working electrodes used for the electropolymerization of conducting polymers

required for the oxidation of monomers. Hence, many researchers use metal, carbon,
and ITO glass materials for the electrochemical synthesis of conducting polymer films.
The reference electrode in an electropolymerization cell measures the potential at the
working electrode surface. It is made of a piece of silver wire immersed in 3 M
Ag/AgCl solution, when working with aqueous electrolytes [50]. Silver wire or
Ag/AgCl wire is used as pseudoreference electrodes when the medium of the electro-
polymerization reaction is organic. The auxiliary electrode or counter electrode used for
electropolymerization is usually made of an inert material, such as Pt wire [51]. The
counter electrode is used to close the current circuit in the electrochemical cell (Fig. 2).

4.2 Supporting Electrolyte Solution

Electrochemical polymerization is known to be a very effective technique for the

synthesis of electroactive conductive polymers. The rate of polymer growth, the
morphology, and properties of the polymer films deposited on the electrode are strongly
influenced by the nature of the supporting electrolyte [19]. Thus, the supporting
electrolyte is an important parameter to be taken into account and optimized when
designing the electrochemical polymerization protocol. Aqueous and organic solutions
have been used as supporting electrolyte, and some examples are listed in Table 1.
In addition to organic and aqueous media used as electrolytes for electrochemical
polymerization, new approaches have emerged for the electrochemical polymeriza-
tion in microemulsion media [15]. Many studies have identified aqueous media as
ideal for the electrosynthesis of conducting polymers because of their low pollution
and suitability for large-scale applications. However, there are some limitations in
the use of aqueous media, including low solubility of many of the organic monomers
in water. Microemulsions were introduced as supporting electrolytes for electro-
polymerization, in order to solve the problem of insolubility of some monomers in
aqueous media. This is because a microemulsion is a complex mixture of water,
hydrophobic organic material, and surfactant that forms a micellar solution, which is
112 G. Fomo et al.

Table 1 Some supporting electrolytes used for electrochemical polymerization

Medium Electrolyte Polymer References
Aqueous H2SO4, HCl, HNO3, copper (II) nitrate, sodium PANI [20, 30,
solution sulfate, sodium sulfate/sodium perchlorate, 52, 53]
lithium perchlorate, sodium benzoate, propylene
carbonate/lithium perchlorate, phosphoric acid,
and trifluoroacetic acid
Aqueous sulfuric acid and boron trifluoride Polyindole [54–57]
diethyl etherate
Organic HClO4/acetonitrile, tetramethylammonium PANI [23, 55,
solution trifluoromethane-sulfonate/acetonitrile, periodic 58, 59]
acid/tetraethylammonium tetrafluoroborate/
acetonitrile, tetrabutylammonium
tetrafluoroborate /trifluoroacetic acid,
tetrabutylammonium perchlorate/acetonitrile,
and perchloric acid/benzenesulfonic acids
Acetonitrile and dichloromethane Polyindole [21, 56,
60]
Acetonitrile, dichloromethane, nitrobenzene, Polypyrrole [61]
and propylene carbonate
Ionic liquids Polypyrrole, [62–64]
PANI, and
polypyrrole

stabilized thermodynamically by the amphiphilic surfactant [65]. Microemulsions have

been successfully applied in the electrochemical polymerization of aniline derivatives,
benzene, pyrrole, and thiophenes, which are usually insoluble in water [18, 66–70].

4.3 Solvent

In addition to the supporting electrolyte, the electrochemical cell also contains the
solvent in which the monomer is dissolved. Studies have shown that the rate of
electrochemical reaction had affected the nature of the solvent in which the monomer
was dissolved [71]. The choice of the solvent normally depends on the nucleophilicity
and polarity of the solvent [72]. These two properties determine the interaction between
the solvent and the aromatic radical cation intermediates formed during the polymer-
ization process. The choice of solvent depends on the solubility of the monomer in the
solvent, which should be very pure and oxygen free to avoid the reaction of oxygen
with the radical intermediates to form hydroxides on the electrode surface [21].

5 Reactivity of the Monomer

As most of the materials used as monomers for electrochemical polymerization are

aromatic compounds (see Table 2), the coupling reaction step is likely to involve
electrophilic aromatic substitution. If the nucleophilic character of the solvent
3 Electrochemical Polymerization 113

Table 2 The electrophilic reactivity sites of some monomers and their idealized polymer structures
obtained on the material surface
Monomer Electrophilic reactive site(s) Ideal polymer structure References
[34]

4-Aminoindole
[71]

Carbazole

[73]

Thiophene
[73]

Pyrrole
[73]

Benzene
[73]

Aniline
[15]

Azulene
[15]

Isothionaphthalene
[15]

Ithienothiophene
[15]

Dithienylbenzene
(continued)
114 G. Fomo et al.

Table 2 (continued)
Monomer Electrophilic reactive site(s) Ideal polymer structure References
[74]

Ethylenedioxythiophene
[15]

Phenylenevinylene
[75]

Bithiophene
[76]

Thieno[3,2-b]pyrrole
[75]

Fluorene

Scheme 3 Reactivity of the monomer depending on the solvent

(in which the monomer is dissolved) is lower than that of the monomer, the solvent
can react with the radical cation in the electrolytic solution as shown in Scheme 3.
Thus, the monomer’s nucleophilicity or reactivity with the radical cation has a
limiting effect on polymer film formation. The introduction of an electron donating
3 Electrochemical Polymerization 115

substituent into the monomer improves the reactivity of the monomer and favors
polymerization in more nucleophilic solvents. If the monomer is very reactive, it
could react with other compounds in the electrolyte solution or with the monomers at
an undesired position on the aromatic ring that may not lead to polymerization.
Another case where there will be no formation of polymer is where the monomer
exhibits high stability, which makes it to diffuse away from the anode and thus
unavailable for further reaction [20].

6 Techniques for Electrochemical Polymerization

Electrochemical polymerization being the most important method for the synthesis
of electroconducting polymer films, the properties of the film formed depend on the
choice of technique [22]. Generally, electrochemical polymerization can be achieved
by the use of galvanostatic, potentiostatic, or potentiodynamic techniques [39].

6.1 Galvanostatic Polymerization Technique

Galvanostatic polymerization is performed at a constant current, and it often results

in the formation of a doped polymer [77]. This technique is advantageous as it is
simple, suitable for practical application, and the thickness of the polymer film can
be controlled during the polymerization process by specifying the polymerization
time. The current density should be properly chosen to avoid an increase in the
resistance at the electrode surface during the growth of the polymer, which might
affect the intermediate reactions [78].

6.2 Potentiostatic Polymerization Technique

Potentiostatic technique, on the other hand, involves polymerization reaction carried

out at a constant potential. The magnitude of the potential should be such that it will
oxidize the monomer, since the polymerization process is initiated by the oxidation
of the monomer. Also, the choice of potential should be such that it will avoid
overoxidation or secondary reactions [15, 78]. Linear sweep voltammetry (LSV) is
first used to oxidize the monomer. This is in order to obtain the potential window
within which electro-polymerization can occur without the overoxidation of the
monomer – which may impede the polymerization process or cause undesired
reactions to take place [15, 78]. Some monomers can easily be oxidized in the
presence of oxygen or other oxidizing agents in acid media. Overoxidation of
monomers may lead to the formation of polymers with reduced electroactivity and
conductivity. In addition, overoxidation may lead to the formation of hydroxyl and
oxo derivatives as well as dimer and trimer products rather than the polymer
[47]. For example, aniline was oxidized on pyrrolytic graphite electrode (PGE) in
perchloric acid/acetonitrile (HClO4/CH3CN) by LSV (Fig. 3). Two oxidation peaks,
116 G. Fomo et al.

Fig. 3 Linear sweep P2

voltammograms of aniline in μΑ
0.1 M HClO4/CH3CN on PG
electrode Aniline

P1
Bare PG

0.0 0.4 0.8 1.2 1.6 2.0

Potential vs. Ag wire (V)

P1 and P2, were observed at 1.03 and 1.75 V, respectively. The first peak, P1, refers to
the oxidation of aniline, while the second peak, P2, is characteristic of the oxidation
of p-aminodiphenylamine to form the benzidine species diffusing close to the
electrode [35]. Moreover, the second peak can be related to the overoxidation of
aniline, which results in the deposition of excess of cation on the electrode surface to
form dimers. Therefore, the oxidation potential at P1, which is the potential
corresponding to the oxidation of aniline, helps to determine the onset potential
(Eonset). Indeed, the onset potential is the potential where there is a quick rise of
current from a value close to zero and where the oxidation reaction starts taking
place. From Eonset, the final potential (E2) used for the electrochemical polymeriza-
tion can be calculated using the following equation:

E2 ¼ E onset þ x (1)

where x can be 0.1  x  0.5 V.

6.3 Potentiodynamic Technique

Potentiodynamic technique in electrochemical polymerization involves the use of

cyclic voltammetry (CV) technique. During this process, the monomer on the
electrode surface is exposed to cyclic (switching between oxidative and reductive
scans) regular changes of the applied potential within a potential window. This
results in the formation of a conducting polymer film which alternates between the
nonconducting (undoped) and the conducting (doped) forms [15], depending on the
direction of the cyclic scan. Also, the thickness of the film depends on the number of
CV scans performed. Potentiodynamic polymerization results in the formation of
cyclic voltammograms (CVs) with several characteristic peaks, depending on the
reaction mechanism of the polymerization process. For example, Fig. 4 shows
the CVs of PANI film grown on a PG electrode in 0.1 M HClO4/CH3CN
solution (Fig. 4a) [23] and polypyrrole film grown on Pt electrode in propylene
3 Electrochemical Polymerization 117

Fig. 4 Cyclic
voltammograms of the (a)
1st cycle
formation of (a) 15 cycles of μA
PANI film on PG electrodes in
0.1 M HClO4/CH3CN
containing 0.05 M aniline at
50 mV s
1; and (b) 10 cycles
of polypyrrole film on Pt
electrode in PC/TBAPF6
containing 0.1 M pyrrole at
100 mV s
1

0.0 0.3 0.6 0.9 1.2

Potential vs. Ag wire (V)
(b)
mA

-1.0 -0.5 0.0 0.5 1.0

Potential vs.Ag wire (V)

carbonate/tetrabutylammonium hexafluorophosphate (PC/TBAPF6) solution

(Fig. 4b) [79]. The oxidation peak observed for the first cycle in Fig. 4a from 0.9
to 1.4 V is typically the characteristic of the oxidation of aniline, which initiates the
polymerization process. This peak is absent in subsequent cycles, indicating that
once the cation radicals are activated, the self-catalytic polymerization of aniline
controls the film growth in subsequent voltammetry cycles [80]. In the case of
polypyrrole and polythiophene [15], as well as polypyrene [81], for example, the
first oxidation peak and the entire CV peak currents increase gradually with the
number of CV cycles performed, which indicates the growth of conducting film.
For the PANI CV (Fig. 4a), the first redox couple between 0.2 and 0.3 V
corresponds to the transformation of the reduced leucoemeraldine state to the
partly oxidized emeraldine state. Further increase in potential leads to the appear-
ance of another redox couple between 0.65 and 0.9 V, which is attributed to the
transition from the reduced leucoemeraldine state to the fully oxidized
pernigraniline state. Intermediate products formed during the polymerization pro-
cess are trapped in the polymer [82], and the associated redox couple appears
between 0.5 and 0.6 V. For polypyrrole, only one redox couple is formed and the
properties of the redox peaks depend on the solvent system used in the electro-
polymerization reaction [79].
118 G. Fomo et al.

7 Factors that Affect Electrochemical Polymerization

7.1 Monomer Concentration

The concentration of the monomer added into electrolyte solution is one of the
important parameters affecting the polymerization reaction and the electrical conduc-
tivity properties of the polymer films formed [83]. It has been reported that the current
density increases with the increase of concentration of the monomer which is due to
the faster dimerization [12], this can also be express by the following equations:

ð1
αÞnF ðE
EOCV Þ
ia ¼ i0 e (2)
RT
bulk ð1
αÞ bulk ðαÞ
i0 ¼ nFAC R C0 ka (3)

where ia is the oxidation current, i0 is the exchange current, ka is the rate of oxidation, R is
the ideal gas constant, T is the temperature, CR and C0 are concentration of the reduced
and oxidized monomer, respectively, F is the Faraday constant, n is the number of
electrons exchanged, E is the oxidation potential, and EOCV is the open circuit voltage.
However, for some conducting polymers, increase in monomer concentration results in a
decrease in the oxidation potential. For example, Fig. 5 contains the oxidation LSVs of
different concentration of aniline recorded on PG electrode in 0.1 M HClO4/CH3CN at
25 mV s
1. The LSVs show that the aniline oxidation potential decreases as the aniline
concentration increases, due to the formation of electro-conductive oligomers on the
electrode surface [84] that makes the aniline oxidation process less energetic.

7.2 pH of Medium

In their base form polymers are insulating, regardless of the extent of their oxidation.
It means that at pH values greater than 6, no significant protonation of a polymer can

Fig. 5 Linear scan 0 mM

voltammograms of aniline on
10 mM
PG electrode performed in μA
25 mM
0.1 M HClO4/CH3CN
50 mM

0.0 0.6 1.2 1.8

potential vs. Ag wire (V)
3 Electrochemical Polymerization 119

occur and it will be electrochemically inactive. However, under acidic pH condi-

tions, protonation of the partly oxidized form of the polymer occurs, which makes it
conducting. For electrosynthetic polymers, the part that is in contact with the
electrode surface can undergo electrochemical redox reactions and serve as a
conducting medium for electron transportation to the rest of the polymer chain
[85, 86]. Also, some studies have shown that the oxidation and reduction processes
of polymers do not occur at pH > 4 [86]. In addition, during polymerization, pH is
used to control the critical potential beyond which the degradation of the polymer can
occur [17]. Indeed, when polymerization is carried out at low pH, the potential
exceeds the critical value for a brief period soon after the start of the polymerization
process. The potential subsequently decreases with time to a constant potential value,
which is low enough to prevent the degradation of the polymer chain. On the other
hand, for polymerization at high pH, the opposite behavior is observed, whereby the
increased deposition of insulating polymer species reduces the conductivity of
the working electrode. This increases the polymerization potential, resulting in the
degradation of the already deposited polymer film, due to the formation of hetero-
junctions or other unusual chemical bonds [87]. Other parameters, such as the rate of
the polymerization reaction and the cathodic charge that determines the mechanisms
of polymer growth, strongly depend on the pH of the polymerization medium.

7.3 Doping

With regard to electrochemical polymerization, doping involves the introduction

species called dopants or counter ions into a polymer structure. This usually occurs
stoichiometrically in order to compensate the positive charge of the polymeric species
for it to attain electroneutrality. The insertion of dopants into a polymer is one way of
improving its properties, such as morphology, conductivity, electrochemical activity,
and the rate of polymerization [17, 88]. The dopant should be both chemically and
electrochemically stable within the potential range for the polymerization process [22].
Beside the enhancement of the conductivity and the electroactivity of a polymer,
counter ion dopants have significant effect on the polymer growth rate and its redox
characteristics. The doping of a conductive polymer is classified as either chemical or
electrochemical doping. Chemical doping is more frequently achieved by exposing the
polymer to an oxidant (such as iodine or bromine), and less frequently by using a
reductant (typically an alkali metal). In electrochemical doping, on the other hand, a
polymer film deposited on a working electrode is suspended in an electrolyte solution
(in which the polymer is insoluble) along with separate counter and reference elec-
trodes. An electric potential difference is created which charges the polymer and causes
appropriate counter ions from the electrolyte to enter the polymer. This charge transfer
process creates a localized negative (n-doping) or positive (p-doping) charge on the
polymer. This often leads to the distortion of the bonding structure of the polymer
backbone and the formation of polarons and bipolarons (i.e., intergap electronic states)
which can delocalize along the polymer chain or in an electric field. Electrochemical
n-doping is far more common because of the ease of excluding oxygen from a solvent
120 G. Fomo et al.

in a sealed flask. The interaction between the polymer and the p-type dopant usually
leads to the partial oxidation of the organic polymer π-backbone – a phenomenon
known as oxidative doping. The transfer of electrons from the valence band of the
polymer to the acceptor dopant leads to the delocalization of holes within the polymer
backbone and the enhancement of the conductivity of the polymer system [89]. The
illustration of the concept of n- and p-doping is as shown in Fig. 6.
Many dopants (such as anthracene sulfonic acid, benzene sulfonic acid, chloride
ion, dibenzenesulfonic acid, hydrochloric acid, methane sulfonic acid, naphthalene
sulfonic acid, perchloric acid, poly(acrylic acid), poly(anilinesulfonic acid), poly
(4-styrenesulfonic acid) (PSSA), poly(vinylsulfonic acid), p-toluene sulfonic acid
and sulfuric acid) have been used in the electrochemical doping of polymers
[90–93]. Figure 7 depicts the electrochemical polymerization of aniline on PG
electrodes in the presence and absence of the following dopants: 8-anilino-1-
naphthalenesulfonoic acid (ANSA), ethylenediaminetetraacetic acid (EDTA),
2-naphthalenesulfonoic acid (NSA), and poly(4-styrenesulphonic acid) (PSSA).
The CVs obtained during the potentiodynamic polymerization of aniline vary from
one dopant to another. It can be observed that the CVs of the undoped PANI have
three redox couples, while those of doped PANI have two redox peaks, with the
exception of the EDTA-doped PANI that has three redox peaks. On the other hand,
Fig. 8 (which contains the CVs of PANI and PANI doped with PSSA in phosphate
buffer pH 7) demonstrates the effect of doping on the electroactivity of the PANI
films in aqueous medium, at neutral pH. It can be seen that the undoped PANI films
formed on the electrode surface loses its electroactivity after the first scan (Fig. 8a).
The first cycle shows weak oxidation (Epa) and reduction (Epc) peak potentials at 0.7
and 0.3 V, respectively. The redox peaks disappear on the third scan, indicating that

Fig. 6 Schematic representation of the n- and p-doping processes

3 Electrochemical Polymerization 121

Fig. 7 Cyclic voltammograms (15 cycles) of the polymerization of doped 0.05 M aniline on PG
electrode in 0.1 M HClO4/CH3CN, at 50 mV s
1

the undoped PANI film has decreased electroactivity, which limit its application.
Figure 8b shows a voltammogram of PANI-PSSA films which exhibits pronounced
Epa and Epc at 0.274 and
0.199 V, respectively, and has a corresponding peak
separation (ΔEp = Epa
Epc) value of 0.473 V, which is the characteristic of
electroactive polymer films.
Polymers can also be doped with other polymers. For example, Fig. 9 contains the
CVs for the doping of poly(3,4-ethylenedioxythiophene) (PEDOT) with poly
122 G. Fomo et al.

Fig. 8 Cyclic voltammograms of (a) PANI/PG and (b) PANI-PSSA/PG (3 cycles) in phosphate
buffer pH 7

Fig. 9 Cyclic voltammograms of PEDOT–PANS film formation on GCE in 0.2 M HNO3 solution
containing 1.0 mM of ANS and 0.01 M EDOT at 100 mV s
1
3 Electrochemical Polymerization 123

(5-amino-2-naphthalenesulfonic acid) (PANS) from a solution containing PEDOT

polymer and 5-amino-2-naphthalenesulfonic acid (ANS) monomer. PANS deposits
in situ on the PEDOT as it is being electropolymerized from ANS. The PEDOT–PANS
polymer films on GCE have been applied in the electrooxidation of dopamine [94].

7.4 Mode of Initial Scan

When the monomer is electrochemically polymerized onto an electrode surface,

polymer films of different colors are obtained. The color of the polymeric product
obtained depends on the initial scan direction. Indeed, if the scan is carried cathod-
ically, p-doped polymer film is formed, while when the scan is carried out anodically,
the polymer formed is neutral. Both form p-doped and neutral polymer vary in
solubility, electrochemical properties, and conductivity. For example, PANI–PSSA
was electrochemically synthesized in phosphoric acid on Au, GC, PG, and Pt
electrodes in order to evaluate the solubility, electrode kinetics, and the influence
of the initial scan direction.
Figure 10 shows the CVs of electroactive green neutral and blue p-doped
PANI
PSSA thin films recorded during the potentiodynamic polymerization of
aniline on four different electrodes in 1 M H3PO4, containing PSSA. The CVs of
the neutral PANI
PSSA films exhibit three redox couples between 0.02 to 0.09 V,
the actual value of the peak potential depending on the electrode used (Fig. 10a).
Compared with the CVs obtained for the electropolymerization of aniline alone
(Fig. 4), it is found that the dopant (PSSA) reduced the magnitude of both the Epc and
Epa values of the PANI–PSSA films, due to the doping and undoping of PANI film
by protons and anions. The redox peaks between 0.1 and 0.4 V (for Au, GC, PG, and
Pt electrodes of Fig. 10a) is attributed to leucoemeraldine/emeraldine transformation
of PANI
PSSA, while the redox couple that occurs between 0.35 and 0.9 V is due to
emeraldine/pernigraniline transformation [95]. Pt does not exhibit the redox couple
that occurs between 0.3 and 0.6 V, which is attributed to the formation of interme-
diates products [82].
A major drawback for the application of PANI films is its insolubility in many
solvents. To overcome this problem, sulfonated heteronuclear aromatic hydrocar-
bons (or any dopant) can be incorporated into the PANI backbone and the polymer-
ization mode (anodic or cathodic scan) chosen according to the desired polymer
properties and application. Solubility studies showed that the neutral and p-doped
PANI
PSSA films exhibited improved solubility in polar organic solvents such as
DMSO and DMF compared to PANI. However, it was found that the neutral
PANI
PSSA was very dispersed in DMSO, while the p-doped PANI
PSSA was
more dispersed in DMF. Similar results have been reported for doped PANI [90, 96,
97] in which the degree of dispersion depended on whether the polymer was neutral
or p-doped. The neutral PANI
PSSA films formed on the electrode surface gave a
green color in DMSO but not in DMF.
Other factors that influence electrochemical polymerization reactions include
temperature and the nature of substituents of the monomer starting materials,
124 G. Fomo et al.

600 (a)
100
Au 300 GC
Current (μA)

0 0

-100 -300

0.0 0.4 0.8 1.2 0.0 0.4 0.8 1.2

160
700
PG Pt
0 0

-700 -160

0.0 0.4 0.8 1.2 0.0 0.4 0.8 1.2

Potential vs Ag wire (V)

600 (b)
120
Au 300 GC
60
0 0
Current (μA)

-60 -300
-120
0.0 0.6 1.2 0.0 0.6 1.2
150
PG 60 Pt
0 0

-150 -60
-120
0.0 0.3 0.6 0.9 0.0 0.6 1.2
potential vs Ag wire (V)

Fig. 10 Cyclic voltammograms (15 cycles) of PANI
PSSA films synthesized (a) anodically and
(b) cathodically, at 0.050 V s
1 on Au, GC, PG, and Pt electrodes, in 1 M H3PO4 containing 0.05 M
aniline and 0.025 M PSSA

particularly in the case of aromatic monomers [39]. Temperature affects the kinetics
of the polymerization reaction process and may also determine the extent of the
undesired side reactions. For example, since the oxygen species in the reaction
medium are sensitive to high temperature, they can easily react with free radicals
3 Electrochemical Polymerization 125

formed from anodic processes, thus decreasing the polymerization efficiency [98]. On
the other hand, the rate of polymerization increases with temperature due to improved
conductivity and electroactivity of the monomer at high temperatures [99].

8 Advantages and Application of Electrochemical

Polymerization

8.1 Advantages

The electrochemical synthesis of polymer has the advantage of combining the

synthesis and modification steps in one procedure. In this method, the electrochemical
oxidation of a monomer gives rise to free radicals that are adsorbed on the electrode
surface, which can subsequently undergo a wide variety of reactions, including the
primary reaction that produces the desired polymer films. The polymer film formed on
the surface of the electrode can be conducting or nonconducting polymer. The differ-
ence is that due to the intrinsic conductivity of the conducting polymers, the film
thickness can be controlled, and a multilayer film can be also obtained. Electroactive
conducting polymer films obtained through electrochemical polymerization can be
easily and directly characterized. On the other hand, chemically synthesized polymer
may require further purification and characterization in order to confirm the product.
Another advantage of electrochemical polymerization is that the polymer formed
exhibits physical properties that are inherent to metals or semiconductors, while
retaining the mechanical properties of conventional polymers [100].

8.2 Applications

Due to their excellent conductivity and stability, as well as their good magnetic,
optical, and electronic properties, conducting polymers are viewed as organic
molecular electronic materials. They have thus, found applications as materials for
the development of solar cells, light weight batteries, electrochromic devices, sen-
sors, and electronic devices [101–110]. Conducting polymers have been demon-
strated to be suitable materials for developing electrochemical capacitors, because of
the combination of high charge density and thermal stability with predicted low
material cost [111]. Due to their biocompatibility or ease of derivatization,
conducting polymers have emerged as promising materials for the development of
compact and portable probes and sensors for the detection of biologically significant
molecules [112]. Also, heterojunction solar cells have been fabricated by electro-
chemical polymerization of pyrrole on n-silicon [113]. Moreover, many other
conducting polymers, including polyacetylene, polythiophene, polyindole, poly-
pyrrole, and polyaniline, have been used as electrode materials for rechargeable
batteries [114–116].
In analytical chemistry, the problem of selectivity, particularly at the low con-
centrations of analyte and in the presence of interfering substances is extremely
126 G. Fomo et al.

important. Conducting polymers have numerous applications in sensors either as

highly selective sensing layers or as suitable materials for sensor development. They
have also found applications in biosensors, biotechnology, production of pharma-
ceuticals, food manufacturing, wastewater treatment, health care products, and
organic solar energy production [105].

9 Conclusion

Most conducting polymer films used as transducers in sensors and electrocatalysis are
synthesized by chemical and electrochemical polymerization of the monomers, on solid
electronic conductor materials with high work function as described in this chapter.
However, chemical polymerization has the limitation of requiring more purification and
further characterization for their confirmation. Electrochemical polymerization has the
disadvantage of low yield and poor solubility of the product, the former making the
method unsuitable for large scale production of polymers. However, in electrochemical
polymerization, the nature of the product formed can be controlled by doping, redox
scan mode, polymerization cycle, and type of electrode material used. Dopant
ion-recognition sites can be incorporated into a conducting polymer film as counter
ions during electropolymerization, not only to improve the solubility but also to
increase the conductivity, electroactivity, and stability of the polymer.

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114. R. Saraswathi, M. Gerard, B.D. Malhotra, Characteristics of aqueous polycarbazole batteries.
J. Appl. Polym. Sci. 74, 145–150 (1999)
115. T. Kawai, T. Kuwabara, S. Wang, K. Yoshino, Secondary battery characteristics of poly
(3-alkylthiophene). Jap. J. Appl. Phys. 29, 602–605 (1990)
116. K.S.V. Santhanam, N. Gupta, Conducting-polymer electrodes in batteries. TRIP 1, 284–289
(1993)
Polymer Processing and Rheology
4
Nickolas D. Polychronopoulos and John Vlachopoulos

Contents
1 Types of Polymers and Their Flow Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2 Rheology of Polymer Melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
2.1 Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
2.2 Elongational Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
2.3 Normal Stresses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
2.4 Stress Relaxation and Dynamic Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
2.5 The Role of Shear and Elongation in Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.6 Extrudate Swell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
2.7 Wall Slip, Sharkskin, Melt Fracture, and Die Lip Buildup . . . . . . . . . . . . . . . . . . . . . . . . . . 153
2.8 Rheology of Filled Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
2.9 Rheology of Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
3 Polymer Melt Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
3.1 Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
3.2 Calendering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
3.3 Injection Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
3.4 Compression Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
3.5 Blow Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.6 Thermoforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.7 Rotational Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
3.8 Melt Spinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
3.9 Additive Manufacturing of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
4 Considerations in the Polymer Processing Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177

N. D. Polychronopoulos
Polydynamics Inc., Dundas, ON, Canada
e-mail: [email protected]
J. Vlachopoulos (*)
Department of Chemical Engineering, McMaster University, Hamilton, ON, Canada
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 133

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_4
134 N. D. Polychronopoulos and J. Vlachopoulos

Abstract
This chapter is devoted to the presentation of the fundamental rheological prop-
erties of polymers and their processing technologies. Measurements of the rheo-
logical properties offer a fast and reliable way to determine molecular weight
distribution and long-chain branching, which, in combination with the processing
conditions, have a decisive influence on the end-use product properties. Shear
viscosity, elongational viscosity, normal stress differences, stress relaxation, and
some other measures and rheological phenomena, of relevance to polymer pro-
cessing, are discussed. The most widely used polymer processing technologies of
extrusion and injection molding are discussed with some details. The discussion
includes key features of equipment used and design and operation challenges.
Brief descriptions are presented on calendering, compression molding, blow
molding, thermoforming, rotational molding, fiber spinning, and additive
manufacturing. It is argued that computer-aided flow analysis and rheological
measurements are necessary for equipment design, troubleshooting, and optimi-
zation in the processing of thermoplastics.

Abbreviations
ABS Acrylonitrile butadiene styrene
AM Additive manufacturing
CaBER Capillary breakup extensional rheometer
EVA Ethylene-vinyl acetate
FDM Fused deposition modeling
HDPE High-density polyethylene
HLMI High load melt index
LAOS Large amplitude oscillatory shear
LDPE Low-density polyethylene
LLDPE Linear low-density polyethylene
LVE Linear viscoelasticity
MFI Melt flow index
MFR Melt flow rate
MI Melt index
MWD Molecular weight distribution
OEMs Original equipment manufacturers
PA Polyamide
PC Polycarbonate
PE Polyethylene
PET Polyethylene terephthalate
PP Polypropylene
PLA Polylactic acid
PMMA Polymethyl methacrylate
PS Polystyrene
PVC Polyvinyl chloride
RIM Reaction injection molding
4 Polymer Processing and Rheology 135

RPM Revolutions per minute

SAOS Small amplitude oscillatory shear
SER Sentmanat extensional rheometer
SLS Selective laser sintering
SMEs Small and medium enterprises
SSE Single screw extruder
TSE Twin screw extruder
WFC Wood fiber composite

List of Symbols
α Fitting parameter in Carreau-Yasuda model
γ Strain
γ_ Shear rate
γ_app Shear rate (apparent)
γ_true Shear rate (true)
γ_w Wall shear rate
ΔP Pressure drop
ΔPe Excess pressure drop
e_ Elongation rate
η Viscosity
ηc Viscosity of the filled system
ηd Viscosity of the dispersed phase
ηe Elongational viscosity
ηm Viscosity of the matrix
ηo Zero shear viscosity
η* Complex viscosity
ηref Viscosity at a reference temperature
θ Screw helix angle
λ Fitting parameter in Carreau-Yasuda, cross models
ρ Melt density
σ 11 Tensile stress
τ Shear stress
τw Wall shear stress
φ Volume fraction
φmax Maximum volume fraction
ω Frequency
A Area
Ac Cross section of a cylindrical fluid element
a Pressure coefficient
b Temperature sensitivity coefficient
Ca Capillary number
d Extrudate diameter
D Capillary diameter
Db Barrel diameter
136 N. D. Polychronopoulos and J. Vlachopoulos

E Activation energy
F Force
G0 Storage modulus
G00 Loss modulus
h Gap between plates
H Channel depth in an extruder
Ho Minimum distance between two rollers
k Einstein coefficient frequently denoted as [η]
K Consistency index
L Capillary length
Mw Weight average molecular weight
N Rotational speed
N1 First normal stress difference
N1w First normal stress difference at the wall
N2 Second normal stress difference
n Power law index
nB Bagley correction
p Pressure
Pmax Maximum pressure in calendering
Q Volume rate of flow
R Gas constant
Rc Capillary radius
Rd Drop radius
Rrol Roller radius
S Interfacial tension
SR Stress ratio
t Time
T Temperature
Tref Reference temperature
U Velocity/speed

1 Types of Polymers and Their Flow Behavior

Synthetic polymers may be classified into two main categories: thermoplastics and
thermosets. Thermoplastics (by far the largest volume with over 300 million tons
produced annually) can be melted by heating, shaped by flowing through dies
or filling molds, and subsequently solidified into final useful products. In their
molten state, they are highly viscous materials, and their viscosity can be more
than a million times higher than that of water, under usual processing conditions.
This type of polymers can be either amorphous (without regular structure)
or semicrystalline (amorphous with embedded regular substructures). Major types
are polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene
terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), poly-
styrene (PS), and polyamide (PA, nylon). Thermosets can be hardened by applying
4 Polymer Processing and Rheology 137

heat or pressure, due to cross-linking, i.e., the creation of permanent three-

dimensional networks. They cannot be softened, by heating for reprocessing. Most
common types of thermosets are Bakelite, epoxies, melamine, and many polyure-
thanes. Processing of thermosets is beyond the scope of the present chapter.
Thermoplastics are seldom processed on their own. They are often blended or
compounded with other materials to produce pellets, powders, or flakes to be used in
subsequent processing operations [1]. The compounds may involve fillers, colorants,
other polymers, flame retardants, reinforcements, stabilizers, and various processing
aids. The compounded polymers are usually referred to simply as plastics. Polymer
processing deals with the conversion of raw polymeric materials into “value-added”
finished products, and in addition to compounding and shaping, it may occasionally
involve chemical reactions [2]. Several processes are practiced for the processing of
thermoplastics, and the most common are extrusion (largest in volume), injection
molding (largest in number of people involved), extrusion and injection blow
molding, film blowing, film and sheet casting, calendering, fiber spinning, compres-
sion molding, and rotational molding. A common characteristic in these processes is
that the polymer is processed in its molten state and it flows. Thus, before describing
the various processing methods involving thermoplastics, we present the fundamen-
tals of rheology, which is defined as the science of flow and deformation of materials
[3, 4].
Fluids are characterized by a viscosity, which is a quantitative measure of
resistance to flow. In Newtonian fluids the viscosity is independent of the shear
rate and depends only on temperature and pressure. In polymer melts the viscosity
depends also on shear rate. As the shear rate increases, the viscosity decreases due to
molecular alignments and disentanglements of the polymer chains. The higher the
shear rate, the easier is for the molten polymer to flow through channels of the
process equipment. Aside from their viscous behavior, molten polymers and poly-
mer solutions behave as elastic materials, which means that they can exhibit a
response resembling that of a rubber-like solid. Due to this dual nature, polymeric
liquids are frequently referred to as viscoelastic, and they exhibit some unusual and,
perhaps, counterintuitive flow behavior, which can have significant impact on
processing and product properties. Such effects are discussed in the rheology section
of this chapter and include the rod-climbing effect on a rotating shaft inside a liquid
container, the extrudate or die swell phenomenon where the cross-sectional area of
the emerging melt from a shaping die is larger than that of the die, and large vortex
phenomena in entrance flow from a large reservoir into a smaller diameter tube and
various flow instabilities.
For equipment design, optimization, and troubleshooting, both the viscous and
elastic nature of polymers must be taken into consideration. Rheology is involved in
all aspects of polymer processing from resin characterization to the determination of
structure and end-use properties. Such measurements are used for differentiating
between different polymer grades. They are more sensitive and easier than many
physical or chemical methods for detecting high molecular weight fractions and
long-chain branching in polymers. Rheological measurements are necessary as input
into computer simulation software, for design of process equipment like extruders,
dies, and molds.
138 N. D. Polychronopoulos and J. Vlachopoulos

2 Rheology of Polymer Melts

2.1 Viscosity

Viscosity represents the resistance to shearing, i.e., forced movement of imaginary

fluid slices like a deck of cards. It is the most important polymer processing property.
Referring to Fig. 1, we can define viscosity as the ratio of the imposed shear stress
(force F applied tangentially, divided by the area A) and the shear rate (velocity U
divided by the gap h)

shear stress F=A τ

η¼ ¼ ¼ (1)
shear rate U =h γ_

This relation is known as Newton’s law of viscosity. The viscosity is measured in

Pas in SI units (1 Pas = 10 poise). When the viscosity is independent of the shear
rate, a fluid is called Newtonian. Molten polymers have viscosities dependent on
shear rate, exhibit several other unusual flow properties, and are referred to as
non-Newtonian. One remarkable property of polymeric liquids (melts and solutions)
is their shear-thinning behavior (also known as pseudoplastic behavior). As the shear
rate increases, the viscosity decreases, as shown in Fig. 2.

Fig. 1 Shear flow between two plates

Fig. 2 Newtonian and shear-

thinning viscosity behavior
4 Polymer Processing and Rheology 139

This reduction of viscosity is due to molecular alignments and disentanglements

of the long polymer chains. The higher the shear rate, the easier it is for polymers to
flow through dies and process equipment. The most frequently used model to
express the shear-thinning behavior of polymers is the power law:

η ¼ K γ_n1 (2)

This expression is a straight line when plotted on double logarithmic coordinates.

This relation does a poor job in fitting low shear rate data (as shear rate approaches
zero, the viscosity goes to infinity). The value of the consistency index K is the
viscosity at γ_ ¼ 1s1. The exponent (n1) is the slope, because

logη ¼ logK þ ðn  1Þlogγ_ (3)

For n = 1, the power law model reduces to Newton’s law (constant viscosity).
As n decreases, the polymer becomes more shear thinning. The power law exponent
of commercial polymers varies between 0.8 (for some polycarbonate, PC, grades)
and 0.2 (for some rubber compounds). For various polyethylene (PE) grades, the
range is 0.3<n<0.6 and depends on molecular weight distribution and chain
branching and does not change much with temperature. The consistency K varies a
lot with temperature, and under usual processing conditions, the consistency index
for the most common molten polymers varies between 1,000 Pasn (for some
polyethylene terephthalate (PET) resins) and 100,000 Pasn for highly viscous
rigid polyvinyl chloride (PVC). The value depends on chain mobility, molecular
weight, and temperature.
During single screw extrusion, shear rates may reach 200 s1 in the screw channel
near the barrel wall and much higher between the flight tips and the barrel. At the die
lip or exit, the shear rate can be as high as 1000 s1. During cavity filling in injection
molding, shear rates can reach 10,000 s1, and in some wire coating applications,
shear rates may exceed 1,000,000 s1. However, in the process of rotational mold-
ing, shear rates are much less than 1 s1.
Melt index (MI), melt flow index (MFI), or melt flow rate (MFR) (for polypro-
pylene) refers to the grams per 10 min pushed out of a die of prescribed dimensions
according to an ASTM standard [5] under the action of a specified load, as
shown in Fig. 3. For PE (ASTM D-1238), the load is 2.16 kg and the die dimensions
are D = 2.095 mm and L = 8 mm. The corresponding shear rate at the die
wall is approximately γ_w = 2.4  MFI, and the wall shear stress is
τw = 8982  2.16 = 19,401 Pa. The experiment is carried out at 190  C. For PP,
the same load and die dimensions are used, but the experiment is carried out at
230  C. A low melt index means a high molecular weight, highly viscous polymer.
A high melt index means a low molecular weight, low-viscosity polymer. When the
melt index is less than 1, the material is said to have a fractional melt index. Such
materials are used for film extrusion. For some film grades, MI can be less than 0.1.
Most extrusion PE grades seldom exceed MI = 12; however, for injection molding,
MI is usually in the range of 5–50. The MI (inversely) corresponds to just one point
140 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 3 Schematic of a melt

indexer

Fig. 4 Velocity, shear rate, and shear stress profiles for pressure-driven flow through a tube of
radius Rc

on a viscosity curve (usually at low shear rates). Frequently, the so-called high load
melt index (HLMI) is measured, usually with either a 21.6-kg or a 10-kg load on the
melt indexer. From two points it is possible to obtain a power law viscosity fit, but
such approximations should always be used with extreme caution due to inherent
inaccuracies in the melt index measurement method.
For fully developed pressure-driven axial flow (z direction) of a polymeric fluid in
a tube (capillary) of radius Rc, the velocity profile is quasi-parabolic, and the shear
stress varies linearly with the radius and the shear rate nonlinearly as shown in Fig. 4.
For Newtonian fluids the velocity profile is parabolic, the shear rate varies
linearly, and its value at the wall is given by
4 Polymer Processing and Rheology 141

4Q
γ_app: ¼ (4)
πRc 3
where Q is the volume rate of flow. This relation is referred to as apparent shear rate
when used in non-Newtonian flows. A correction is necessary (Rabinowitsch) for
shear-thinning fluids. For the power law model, the true (Rabinowitsch corrected)
shear rate becomes


3n þ 1 4Q
γ_true ¼ (5)
4n πRc 3

The above equations are used in capillary viscometry for measurement of

viscosity from pressure drop ΔP versus volume flow rate Q data. The pressure
drop ΔP is measured in the reservoir of the viscometer, and at the entrance to the
capillary, there is an excess pressure drop ΔPe. The easiest way to determine the
excess pressure drop ΔPe is to carry out the experiment using a twin-bore viscom-
eter having two capillaries. One of them has very short length (L  0), and the
pressure drop recorded is essentially the excess pressure due to the entrance
(orifice). This correction is necessary when capillaries are relatively short (L/Rc
less than 50) and is known as the Bagley correction. The Bagley correction is
usually expressed as

ΔPe
nB ¼ (6)
2τw

The Bagley correction (nB) may reach perhaps 20 when polymeric materials are
extruded at high shear stresses. For a Newtonian fluid, the value for nB is 0.587. For
information on the Bagley correction and entrance and exit pressure drops, the reader
is referred to the monographs by Han [6]. Without the Rabinowitsch and Bagley
corrections, there can be significant errors in viscosity data obtained from capillary
instruments.
In addition to the power law model, two other expressions are frequently used for
better fitting of data over the entire range and to include the Newtonian plateau at low
shear rates.
The Carreau-Yasuda Model

η ¼ ηo ½1 þ ðλγ_Þα 
n1
a
(7)

where ηo is the viscosity at zero shear and λ, α, and n are fitted parameters. The
meaning of the fitting parameters is shown in Fig. 5.
The Cross Model

ηo
η¼ (8)
1 þ ðλγ_Þ1n
142 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 5 Meaning of Carreau-

Yasuda model parameters

where ηo is the viscosity at zero shear and λ and n are fitted parameters. Note that in
this model when λ ¼ 1=γ, _ then η = ηo/2.
Regarding viscosity measurements, capillary viscometers are normally used for
the shear rate range from 1 s1 to 3,000 s1. Rotational viscometers (parallel plate or
cone and plate) are normally used for the range 102–5 s1 in steady flow. At higher
rotational speeds, secondary flows and instabilities may occur which invalidate the
simple shear assumption, of imaginary fluid slices motion. For more information
about viscosity measurements, the reader is referred to [7].
The viscosity of polymer melts varies with temperature, and it obeys the Arrhe-
nius relation in the form


E 1 1
η ¼ ηref exp  (9)
R T T ref

where E is the activation energy, R is the gas constant, and Tref is the reference
temperature. In polymer processing (especially extrusion), this relation is frequently
reduced to a simple exponential which applies over a shorter temperature range

η ¼ ηref exp½bðT  T ref Þ (10)

The temperature sensitivity coefficient b is usually between 0.01 and 0.1  C1.
For HDPE (linear polymer), the value of b is roughly 0.01, while for LDPE
(branched), it may reach 0.03.
The viscosity increases with pressure in the form

ηðpÞ ¼ ηð0Þexpða  pÞ (11)

The a coefficient is probably of the order 2  108 Pa1. Cogswell [8] expresses
pressure dependence in terms of an equivalent temperature change. His results
suggest that applying 10 MPa is equivalent to decreasing the temperature by about
5  C. Usually, pressure dependence of viscosity is not taken into consideration in
extrusion, but it is necessary in injection molding calculations and simulations.
Pressure drops in die extrusion may reach at most 50 MPa, while in injection
molding cavity filling, the pressure may reach 200 MPa.
4 Polymer Processing and Rheology 143

Fig. 6 The influence of various parameters on polymer viscosity

The effects of factors such as shear rate, molecular weight distribution, pressure,
filler, temperature, and additives on viscosity are summarized in Fig. 6, as adapted
from Cogswell [8]. Linear narrow molecular weight distribution polymers (meta-
llocene catalyzed) are more viscous than their broad distribution counterparts of
same average molecular weight. Fillers may increase viscosity (greatly). Various
additives are available and are designed to decrease viscosity. The zero shear
viscosity increases dramatically with the weight average molecular weight

ηo ¼ const M w 3:4 (12)

For some metallocene-catalyzed PEs with long-chain branching, the exponent

might be much higher (perhaps 6.0).

2.2 Elongational Viscosity

Elongational (or extensional) viscosity is the resistance of a fluid to extension

[4, 7]. While stretching a low-viscosity fluid like water is difficult to imagine,
polymer melts exhibit measurable resistance. The elongational viscosity is defined as

σ 11 F=Ac
ηe ¼ ¼ (13)
e_ e_
144 N. D. Polychronopoulos and J. Vlachopoulos

where σ 11 is the tensile stress in the stretching direction, Ac the cross section of a
cylindrical fluid element, and e_ the elongation rate.
Over 100 years ago, Trouton [7] measured the stretching and shearing resistance
of some “stiff” (i.e., thick) liquids, including pitch, and found that the extensional-to-
shear viscosity ratio is equal to 3

ηe
¼3 (14)
η
This relation, known as the Trouton ratio, is valid for all Newtonian fluids and has
a rigorous theoretical basis that confirms Trouton’s experiments [9]. Note that ηe
varies from ~3η to 100η or more for polymers in molten or semi-molten state,
depending upon molecular structure and processing conditions. For the case of
polymer solutions, it can reach much higher values. Haward et al. [10] measured
ηe ~ 4000η.
Measuring elongational viscosity is considerably more difficult than measuring
shear viscosity. One device used involves capillary extrusion and subsequent
stretching with a pair of rollers. The maximum force required to break an extruded
strand is referred to as melt strength, which is an engineering measure of
elongational viscosity for quality control purposes. In industrial practice, the terms
elongational (extensional) viscosity and melt strength are sometimes confused.
Several processes involve extension, such as film blowing, melt spinning, blow
molding, thermoforming, compression molding, and sheet or film drawing.
The excess pressure drop encountered in flow from a large reservoir to a smaller
diameter capillary is due to elongational viscosity. In fact, Cogswell [8] has devel-
oped a method for measurement of elongational viscosity ηe from excess pressure
drop ΔPe (i.e., the Bagley correction):

9ðn þ 1Þ2 ðΔPe Þ2

ηe ¼ (15)
32ηγ_2

4ηγ_2
e_ ¼ (16)
3ðn þ 1ÞΔPe

Shear and extensional viscosity measurements reveal that LLDPE (which is

linear) is “stiffer” than LDPE (branched) in shear, but “softer” in extension. In
extension, the linear LLDPE chains slide by without getting too much entangled.
However, the long branches of the LDPE chains result in significantly larger
resistance in extension. In the film blowing process, LDPE bubbles exhibit more
stability because of their high extensional viscosity. Typical LDPE and LLDPE
behavior in shear and extension is shown in Fig. 7. LDPE is often blended with
LLDPE to improve the melt strength and consequently bubble stability in film
blowing. Most PP grades are known to exhibit very low melt strength. However,
recent advances in polymerization catalysts have led to the production of some high
melt strength PP grades (with long-chain branching).
4 Polymer Processing and Rheology 145

Fig. 7 Schematic representation of LDPE and LLDPE behavior in shear and extension

Measurements of elongational viscosity of polymer melts have been plagued by

experimental complexities, lack of repeatability, and considerable inaccuracies over
the years. The recently developed SER rheometer [11, 12] seems to have put these
problems to rest, and it is expected to play a significant role in the analysis and
optimization of polymer processes involving extension in the future. Measuring the
elongational viscosity of polymer solutions or, in general, low-viscosity substances
(say of the order of 0.1 Pas) is even more challenging. Apparently, the capillary
breakup extensional rheometer (CaBER) [13] gives satisfactory measurements.

2.3 Normal Stresses

Stress is defined as force divided by the area on which it acts. It has units of N/m2
(Pascal, Pa) in SI. When a force is acting tangentially on a surface, the corresponding
stress is referred to as shear stress. When a force is perpendicular (normal) to a
surface, it is termed normal stress. Pressure is a normal stress. When a fluid flows
through a conduit, it is acted by the normal (pressure) forces, and it exerts both
normal and shear (stress) forces on the conduit walls. For flow through a planar die,
the shear stress is zero at the midplane and maximum at the wall, while the
corresponding velocity profile is quasi-parabolic. Weissenberg discovered in the
1940s [4, 7] that polymer solutions and melts, when subjected to shearing, tend to
develop normal stresses that are unequal in the x (direction of flow), y, and z (normal
directions), which are added to or subtracted from the local pressure. They are
generated because a polymer’s long molecular chains exhibit anisotropic or non-
uniform properties when they flow. Any further explanation of the physical origin of
normal stresses is likely to be controversial. When an (elastic) polymer solution or
melt flows along a pressure gradient, it is less compressed in the direction of flow
than in the other two normal directions.
146 N. D. Polychronopoulos and J. Vlachopoulos

The first normal stress difference N1 is defined as the total normal stress in the
direction of the flow (σ xx) minus the perpendicular (σ yy) stress
 
N 1 ¼ σ xx  σ yy ¼ ðP þ τxx Þ  P þ τyy ¼ τxx  τyy (17)

The second normal stress difference is

 
N 2 ¼ σ yy  σ zz ¼ P þ τyy  ðP þ τzz Þ ¼ τyy  τzz (18)

We use normal stress differences rather than just normal stresses to remove the
value of the pressure present, so that N1 and N2 are fluid properties. Experiments show
that N1 is positive for usual polymers (i.e., extensive, while the compressive pressure
forces are negative). For liquid-crystal polymers, N1 can be negative under certain
conditions. N2 is negative and of the order of 20% of N1 for most common polymers.
N1 is very sensitive to the high molecular weight tail of a polymer. Broad molecular
weight distribution polymers exhibit high N1 values. The normal stress differences
can be very large in high shear rate extrusion through the lips of a die. Some authors
suggest a variation for the normal stress difference at the wall in the form

N 1w ¼ Aτw b (19)

The stress ratio

N 1w
SR ¼ (20)
2τw
can reach a value of 10 or more at a flow instability known as melt fracture in
extrusion through dies.
The rod-climbing effect observed by Weissenberg when a cylinder rotates in a
polymeric liquid is due to some sort of “strangulation” force exerted by the extended
polymer chains as shown in Fig. 8a, which results in an upward movement normal to
the direction of rotation (normal stress difference). The extrudate swell phenomenon
[4, 14] shown in Fig. 8b is due mainly to the contraction of the exiting polymer that
is under extension in the die due to N1. The uneven extension/compression in the
various directions results in a number of unusual flow patterns and instabilities. The
secondary flow patterns in square channels observed by Dooley and co-workers [15,
16] are due to the second normal stress difference. Bird et al. [4] state: “A fluid that’s
macromolecular is really quite weird, in particular the big normal stresses the fluid
possesses give rise to effects quite spectacular.”

2.4 Stress Relaxation and Dynamic Measurements

When flow stops, the stresses become immediately zero for small-molecule Newto-
nian fluids like water or glycerin. For polymer melts and solutions, the stresses decay
4 Polymer Processing and Rheology 147

Fig. 8 Phenomena due to normal stresses. (a) Weissenberg (or rod-climbing) effect and (b)
extrudate (or die) swell of a Newtonian (left) versus a polymeric (right) liquid. (Adapted from [4])

exponentially after flow stops. Stress relaxation can be measured in a parallel plate or
a cone-and-plate rheometer by applying a given shear rate level (rotation speed/gap)
and measuring the stress decay after the rotation is brought to an abrupt stop. Such
tests, however, are not performed routinely, because of experimental limitations
associated with abrupt stopping of rotation and the subsequent measurement of
strains and stresses. At start-up of flow, Newtonian fluids reach immediately a stress
plateau. The calculated response time for water is of the order of 1012 s. Polymer
melts and solutions exhibit a shear and normal stress overshoot and subsequent drop
to a plateau. The response times are of the order of 102 s to a few seconds. Polymer
melts that exhibit long relaxation times and large overshoots are likely to produce
plastic products having significant amount of frozen-in stresses in case of rapid
cooling, which may be released upon reheating. Release of frozen-in stresses results
in warpage and other problems.
Dynamic measurements involve the response of a material to an imposed sinu-
soidal stress or strain on a parallel plate or cone-and-plate instrument. In general,
controlled stress rheometers are preferred for polymer solutions and controlled strain
rheometers for polymer melts. A perfectly elastic material that behaves like a steel
spring, by imposition of extension (strain), would develop stresses that would be
in-phase with the strain, because

StressðτÞ ¼ ModulusðGÞ  Strainðγ Þ (21)

However, for a Newtonian fluid subjected to a sinusoidal strain, the stress and
strain will not be in phase because of the time derivative (strain rate) involved

τ ¼ ηγ_ (22)
dγ d  
τ¼η ¼ η ðγ o sin ωt Þ ¼ ηωγ o cos ωt ¼ ηωγ o sin ωt þ 90 (23)
dτ dτ
148 N. D. Polychronopoulos and J. Vlachopoulos

where ω is frequency of oscillation. That is, a Newtonian fluid would exhibit 90
phase difference between stress and strain. Polymeric liquids, which are partly
viscous and partly elastic (viscoelastic), will be 0  φ  90 out of phase.
We can define

storage
in  phase stress
G 0 ð ωÞ ¼ modulus (24)
maximum strain
ðelastic partÞ

loss
out  of  phase stress
G00 ðωÞ ¼ modulus (25)
maximum strain
ðviscous partÞ

where ω ranges usually from 0.01 to 500 rad/s in most commercially available instru-
ments. Larger G0 implies more elasticity. Further, we can define the dynamic viscosity

G00 ðωÞ
η0 ¼ (26)
ω
G0 ðωÞ
η00 ¼ (27)
ω
and the magnitude of the complex viscosity
 1=2
jη j ¼ η0 þ η00
2 2
(28)

An empirical relationship called the Cox-Merz rule states that the shear rate
dependence of the steady state viscosity η is identical to the frequency dependence
of the complex viscosity η*, that is:

ηðγ_Þ ¼ jη ðωÞj (29)

The usefulness of this rule, which holds for most conventional polymers, is that
while steady measurements of shear viscosity are virtually impossible for shear rates
larger than 5/s with rotational instruments, the dynamic measurements can easily be
carried out up to 500 rad/s (corresponds to shear rate of 500 s1) or even higher.
Thus, the full range of viscosity needed in extrusion can be covered. Some typical
results involving narrow and broad molecular weight distribution samples are shown
in Fig. 9. The relative behavior of G0 versus ω can be used to identify whether a
sample is of narrow or broad molecular weight distribution [17]. In fact, from the
crossover point where G0 = G00 (see also Sect. 2.9), it is possible to get a surprisingly
good estimate of the polydispersity Mw/Mn for PP [18]. For such experiments to
be meaningful, the imposed strain amplitude must be low, so that the measured G0
and G00 values do not vary with the strain, but they are intrinsic properties of the
polymer structure. This is the region of the so-called linear viscoelasticity (LVE), and
the experiments are frequently referred to as small amplitude oscillatory shear
(SAOS) tests. Linearity of the measurements is usually checked by performing strain
4 Polymer Processing and Rheology 149

Fig. 9 Storage modulus G0

and dynamic viscosity η*
behavior of broad and narrow
molecular weight distribution
polymers

sweeps, i.e., measurements of G0 and G00 as a function of strain amplitude at a fixed

frequency. After the material’s LVE is defined, its structure may be further charac-
terized performing frequency sweeps at a strain amplitude within the LVE region. If
the strain amplitude is increased systematically, we enter to the nonlinear viscoelastic
regime. In this case the imposed strain amplitude disrupts the polymer network
structure, and the test is referred to as large amplitude oscillatory shear (LAOS)
test [19]. A review regarding LAOS tests can be found in [20].
Another interesting result is the relation between storage modulus and first
normal stress difference at very small deformations (ω!0, γ_ !0)

2G0 ¼ N 1 (30)

For higher frequencies an expression developed by Laun [17, 21] is used

"
0 2 #0:7
G0 G
N1 ¼ 2 2 1 þ (31)
ω G00

It is possible to measure N1 using a cone-and-plate rotational rheometer. The

Weissenberg effect results in a separating force between the cone and the plate which
can be measured to give N1, for very low shear rates (usually less than about 2 s1),
because of secondary flows at higher rates. Instruments capable of measuring N1
require high-precision construction and very sensitive force gauges. However,
measurement of G0 and G00 can be carried out more easily and at frequencies
corresponding to much higher shear rates.

2.5 The Role of Shear and Elongation in Mixing

Polymers are often compounded (mixed) with pigments, reinforcing agents, fillers,
and other polymers for value-added purposes. This is a crucial process operation in
the following sense: the minor component must be dispersed (i.e., broken-up,
150 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 10 Effects of dispersive and distributive mixing as adapted from Gale [22]

reduced in size) and distributed (i.e., spread randomly) throughout the polymer
matrix as shown schematically in Fig. 10.
Dispersion, in general, is determined by the balance of cohesive forces holding
solid agglomerates or liquid drops together and the hydrodynamic disruptive forces.
Dispersive mixing is dominated by the stress level within the deforming liquid
matrix: a critical stress level must be exceeded to break up whatever cohesive forces
hold a solid or liquid particle together. In Newtonian liquids the stresses must exceed
the interfacial tension forces.
Taylor [23, 24] studied the breakup of a single Newtonian drop in a simple shear
field. The drop size was modeled using the capillary number

τRd viscous stress  drop radius

Ca ¼ ¼ (32)
S interfacial tension
and the viscosity ratio

ηd viscosity of dispersed phase

¼ (33)
ηm viscosity of matrix phase
4 Polymer Processing and Rheology 151

Fig. 11 Grace curves for breakup of droplets in a matrix in shear and elongational flow. (Adapted
from [25])

Fig. 12 Schematic representation of baker’s transformation. (Adapted from [26])

Grace [25] has performed leading work on breakup of Newtonian drops in both
simple shear and elongational flows. The results are summarized in Fig. 11 which are
frequently referred to as Grace curves. In shear flow when roughly ηd/ηm > 4, the matrix
does not exert sufficient stress to cause rupture, whereas the elongational flow is very
effective in causing rupture for virtually all ηd/ηm values. Although Grace curves are for
Newtonian fibrils or threads, they correlate qualitatively very well with concentrated
blends of polymers. However, it is also possible to have coalescence of small drops.
The coalescence process strongly depends on the interface between the drops.
Distributive (or laminar) mixing is quantified by the growth of the interfacial area
between two components. This can best be understood by the so-called baker’s
transformation, since it resembles to the way dough is mixed by repeatedly rolling
and folding [26] as shown in Fig. 12. For the distributive mixing to be effective, the
152 N. D. Polychronopoulos and J. Vlachopoulos

layers of the material need to undergo a combination of stretching, folding, and

reorientating steps. Devices that do just that can be part of an extruder screw (mixing
elements) or attached after the end of an extruder (static mixers).

2.6 Extrudate Swell

In extrusion through dies, the extrudate diameter (d) is larger than the die diameter
(D). Extrudate swell ratios (d/D) reach values of 400% or more, under certain
conditions. This phenomenon (also known as die swell) has been studied by several
researchers and is of considerable theoretical and practical importance. While the
primary mechanism is the release of normal stresses at the exit, other effects are also
important. Extrudate swell is largest for zero-length dies (i.e., orifices). It decreases,
for the same throughput, with increasing die length due to fading memory as the
residence time in the die increases. Even Newtonian fluids exhibit some swell exiting
dies (13% for round extrudates, 19% for planar extrudates). This Newtonian swell is
due to streamline rearrangement at the exit. The swell ratio can be influenced by
thermal effects due to viscosity differences between the walls and die center.
Maximum thermal swell can be obtained when a hot polymer flows through a die
with colder walls. Swell ratio of about 5% on top of other mechanisms can be
obtained from temperature differences. For linear polymers the swell ratio dramat-
ically increases as the molecular weight distribution broadens as shown in Fig. 13.
Several attempts have been made to predict extrudate swell through equations
relating the swell ratio d/D (extrudate diameter/die diameter) to the first normal
stress difference at the wall N1w. Based on the theory of rubber elasticity, the
following equation is obtained [27]
"

2 #!1=2
d 4 d
N 1w ¼ 2τw 3 þ2 3 (34)
D D

Based on stress release for a Maxwell fluid [3] exiting from a die, Tanner’s
equation can be derived [27, 28]

Fig. 13 Schematic of the

effect of the molecular weight
distribution (MWD) on
extrudate swell (d/D) of linear
polymers. The horizontal axis
corresponds to the wall shear
stress
4 Polymer Processing and Rheology 153

"
6 #1=2
pffiffiffi d
N 1w ¼ 2 2τ w  0:13 1 (35)
D

Although this equation has a more rigorous derivation and theoretical basis, the
rubber elasticity theory is believed to give better predictions. Unambiguous evalu-
ations are virtually impossible to carry out, because there are no reliable methods for
measuring N1w at high shear rates and stresses. At low shear rates (up to perhaps
2 s1), the first normal stress difference can be determined by measuring the
separation force that develops in a cone-and-plate instrument due to the Weissenberg
effect. However, in industrial extrusions through dies, wall shear rates at the exit
reach or exceed 1000 s1.

2.7 Wall Slip, Sharkskin, Melt Fracture, and Die Lip Buildup

The no-slip condition at the wall along which a fluid is flowing is a cornerstone of
fluid mechanics. The fluid layer adjacent to a wall has the same velocity as the wall
itself (zero if not moving). Polymer melts exhibit wall slip when the shear stress level
exceeds a certain critical level (about 0.1 MPa for molten HDPE). The existence of
wall slip is frequently associated with the onset of polymer flow instabilities or the
elimination thereof. The phenomenon of loss of surface gloss on an extrudate is
commonly known as sharkskin (also mattness) and occurs at high output rates
though dies. The gross flow instability of an extrudate is known as melt fracture
occurs at even higher output rates. These phenomena have been studied extensively
in the open literature [29, 30]. Die lip buildup, known also as die drool, is not
related to sharkskin or melt fracture, and very few studies are available in the open
literature.
The sharkskin phenomenon is shown in Fig. 14. It may be described as the
appearance of ridges perpendicular to the flow direction, visible to the naked eye.

Fig. 14 Typical sharkskin on

an extrudate of about 2 mm,
exaggerated due to the
enlargement. Note the
formation of ridges
perpendicular to flow
direction
154 N. D. Polychronopoulos and J. Vlachopoulos

The onset of sharkskin occurs at a critical wall shear stress about τw  0.14 MPa, and
it is associated with stick-slip phenomena at the die exit.
Ramamurthy [31] suggested that loss of adhesion is responsible for sharkskin,
i.e., good adhesion prevents sharkskin. He used dies made of different materials and
noticed that the die material has some influence on the loss of extrudate surface
gloss. Recent evidence shows that adhesion may diminish sharkskin, but continuous
slip is more beneficial. Stick-slip phenomena have always a detrimental effect. With
additives, we can postpone sharkskin to higher apparent shear rates (than that
corresponding to a critical shear stress of value of 0.14 MPa). For instance, minute
amounts of fluorocarbon polymers are used as processing aids in LLDPE [32]. The
most recent evidence suggests that sharkskin is the result of tensile failure (rupture)
of the emerging extrudate surface [29, 30].
While sharkskin (critical τw  0.14 MPa) originates at the die exit, melt fracture
as shown in Fig. 15 (with apparent wall shear stress being in the range of
τw = 0.25~0.5 MPa) is a gross flow instability and probably the result of more
than one mechanism such as (1) entry vortex instability (at high shear rates, the
vortex becomes unstable), (2) elastic instability during flow in the extrusion die land
when

Normal stress N 1
¼ constant 10 (36)
Shear stress 2τw
and (3) stick-slip phenomena at the die wall.
It should be noted that the surface tearing phenomenon frequently observed in
wood fiber composites (WFC) is not sharkskin nor melt fracture. It appears like some
sort of exaggerated sharkskin at very low shear rates as discussed in Sect. 2.8.
For very high loadings (over 50%), the tearing disappears due to wall slip. Also at
very high shear rates, the surface tearing is reduced [33, 34].
Die lip buildup is the gradual formation of deposit at the extrusion die exit as
shown in Fig. 16. Generally, sharp die lips produce more buildup that may be
partially relieved using small angle at exit (flaring), e.g., 6 –12 . Many additives
can cause the severest buildup, and resins with a broad MWD cause more problems.

Fig. 15 Distorted extrudates.

Top sample exhibits sharkskin
and bottom samples exhibit
melt fracture. The defect on
the second from the top
specimen (HDPE) is due to
stick-slip
4 Polymer Processing and Rheology 155

Fig. 16 Schematic
representation of the die lip
buildup (drool)

Addition of fluorocarbon polymers may sometimes be helpful. According to Gander

and Giacomin [35], the main causes of die lip buildup are (1) low molecular weight
species, (2) volatiles, (3) fillers, (4) poor dispersion of pigments, (5) drawdown,
(6) die swell, (7) low die exit angle, (8) short land length, (9) pressure fluctuations
in screw, (10) dissimilar viscosities in blends, (11) dirty die at start-up, (12) high melt
temperature, and (13) processing near degradation temperature. An attempt to
provide an explanation of die lip buildup has been made by Musil and
Zaltoukal [36].

2.8 Rheology of Filled Polymers

Rigid particles are added to polymers either to improve the mechanical properties
(reinforcements) or to reduce the cost (fillers) in weight fractions of up to about 70%.
Sometimes there might be both improvement of properties and cost reduction.
Calcium carbonate is a frequently used filler. Talc is added to increase stiffness
and high-temperature creep resistance. Rubber is added to some thermoplastics to
increase the impact strength. Carbon black, glass fibers, wood flour, and other
natural fibers are also used for a variety of applications.
Einstein solved the problem of resistance to shearing caused by spheres of neutral
density, and he showed that the viscosity of the suspensions is related to the viscosity
of the matrix ηm as

ηc ¼ ηm ð1 þ 2:5φÞ (37)

where φ is the volume fraction. This relation is valid for concentrations up to

φ = 0.01. For higher concentrations, the particle-particle interactions are important,
and Batchelor’s equation is valid up to φ = 0.1. For strong Brownian motion of
spheres,
 
ηc ¼ ηm 1 þ 2:5φ þ 6:2φ2 (38)

and for weak Brownian motion,

 
ηc ¼ ηm 1 þ 2:5φ þ 7:6φ2 (39)
156 N. D. Polychronopoulos and J. Vlachopoulos

In very dilute solutions, particles will rotate due to the action of the shear field. As
the concentration is increased, hydrodynamic interactions between the particles
become important. Particles come close to particles on nearby streamlines, and the
fluid is disturbed in their vicinity. As the concentration is further increased, colloidal
interactions (of attraction or repulsion) involve three, four, or more particles, and the
rigorous analyses used in the derivation of the above equations no longer apply [37, 38].
To this end, several semiempirical equations have been proposed by plotting the
relative viscosity ηc/ηm as a function of φ/φmax where φ is the volume fraction and
φmax the limiting concentration called the “maximum packing fraction” of the filler.
It is generally difficult to determine the maximum packing fraction φmax in real
situations. For monodisperse spheres packed on a simple cubic lattice, the maximum
packing fraction will be φmax = (4π/3)/8 = 0.524, while for random close packing,
φmax = 0.637. This value decreases with increasing asymmetry or flocculation due to
poorer space filling [38, 39]. The Maron-Pierce equation is used frequently


ηc φ 2
¼ 1 (40)
ηm φmax

or the Krieger-Dougherty equation


ηc φ kφmax
¼ 1 (41)
ηm φmax

with k being frequently denoted as [η] (the intrinsic viscosity) and usually referred to
as the Einstein coefficient equal to 2.5 for spheres. High values of k (roughly more
than 20), means existence of high aspect ratios. An example of fitting the
abovementioned equations to measurements for a relatively wide range of fillers
and filler loadings is shown in the semilogarithmic plot of Fig. 17, where the zero

Fig. 17 Relative consistency

index as a function of filler
volume fraction. K is the
consistency index of the
power law equation, index c
for composite, and m for the
matrix. (Adapted from [40])
4 Polymer Processing and Rheology 157

shear viscosity was replaced by the consistency index K (which is the viscosity at
shear rate of 1 s1).
Measurement of viscosity in filled systems is necessary for extruder and die
design purposes and for process optimization. It still remains a challenge, because
of significant wall slip as the loading is increased and some problems associated with
interference of the relatively large fibers with the walls, in the narrow gaps of
rheometrical devices. Another problem is that the Cox-Merz rule (equivalence of
steady and dynamic viscosity measurements) is not applicable.
Wood fiber composites have attracted considerable interest in recent years. They
are extruded mostly for decking and fencing applications in North America, housing
applications in Japan, and injection molded in Europe, for the automotive industry.
Fiber loadings usually reach up to 60%. The low cost of the wood fibers and very
good end-use properties are strong incentives. Rheologically, they exhibit significant
increase in viscosity (Fig. 18a) and storage modulus (Fig. 18b), wall slip phenomena,
and a characteristic surface tearing which appears as some sort of exaggerated
sharkskin as shown in Fig. 19.

2.9 Rheology of Nanocomposites

Polymeric nanocomposites were first developed and commercialized in the late

1980s by the Toyota research group. They dispersed layered silicate nanofillers in
a polymer matrix. Nanosized particles have significant influence on end-use prop-
erties of the composites, such as impact strength, flame retardance, liquid and gas
permeability reduction, abrasion resistance, and reduced shrinkage, and on electrical
and optical properties.
Rheological trends are similar to other filled polymers, with the following
differences: (a) loadings are low (less than 10%), (b) the nanosized fillers have
very large aspect (length/thickness) ratios, (c) the nanosized fillers have extremely
large area-to-volume ratios, and (d) there are interactions at the atomic level [41].
Layered silicate nanocomposites are particle-filled polymers for which at least
one dimension of the dispersed phase is in the nanometer range. Three morphologies
are possible as shown in Fig. 20: (a) phase-separated, polymer chains do not
penetrate into clay; (b) intercalated, polymer chains penetrate deep within the layers
of the silicate; and (c) exfoliated, individual layers (~1 nm) are well dispersed and
randomly distributed throughout the polymer matrix (maximum reinforcement due
to large surface area of contact).
In steady shear measurements, the viscosity increases with silicate content, and
the Newtonian plateau is shifted to lower-and-lower shear rates as shown in Fig. 21a
[43]. Similar trends are observed using oscillatory measurements as shown in
Fig. 21b for a composite system of montmorillonite and polyethylene using melt
compounding. It is evident that “η* increased substantially at low frequencies and the
Newtonian plateau disappeared as clay content increased above 5 wt%. Increases of
such magnitude arise in conventional composites at much higher filler loadings
158 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 18 Effect of wood loading in HDPE on (a) complex viscosity at 180  C and (b) storage and
loss modulus. (Adapted from [33])

(above 20–30 wt%) and may be attributed to weak structure that may remain intact at
very low frequencies” [44].
In any dispersion macro-, micro-, or nano-, there will be significant particle-
particle interactions at increased concentrations. At some point (threshold), a three-
dimensional network is formed. Studies with carbon black show significant changes
in electrical properties at the percolation threshold. At the percolation threshold,
there are also rheological changes as evidenced by dynamic measurements of storage
4 Polymer Processing and Rheology 159

Fig. 19 Extrudate surface

morphologies under various
conditions of wood-filled
mPE. In (a) increasing the
filler loading for L/D = 6,
D = 15 mm, γ_a ¼ 2:5 s1 and
in (b) increasing the apparent
shear rate for 60% filler
loading, L/D = 8 and
D = 1 mm. (Adapted from
[34])

Fig. 20 Morphologies of polymer-layered silicate nanocomposites. (Adapted from [42])

160 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 21 (a) Steady shear viscosity as a function of shear rate at 130  C for different bentonite clay
loadings in EVA28 adapted from [43] and (b) complex viscosity as a function of frequency at
170  C for different montmorillonite clay loadings (0-10%) in polyethylene, adapted from [44]

G0 and loss modulus G00 . This critical point is dependent upon polymer matrix, filler
loading, and temperature. According to a summary of recent publications by
Bhattacharya et al. [45], percolation threshold nanocomposite filler loadings range
between 0.5% and 6% by weight.
4 Polymer Processing and Rheology 161

Fig. 22 Typical G0 and G00

behavior of a melt or a
concentrated solution

When dynamic measurements in the linear viscoelastic regime are performed, the
typical G0 and G00 behavior of a melt or a concentrated solution is exhibited in Fig. 22
with G0 ~ ω2 and G00 ~ ω at low frequencies (of less than 0.1 rad/s and preferably less
than 0.01 rad/s). If at low frequencies G00 > G0 , the material exhibits a liquid-like
behavior, and if G00 < G0 , the behavior is more solid-like. An example of such a
behavior is shown in Fig. 23a for an EVA28 nanocomposite [46]. At low frequencies
the nanocomposite exhibits a liquid-like behavior, and as the filler loading is
increased, the behavior tends to be solid-like. It must be noted that the bigger
changes in G0 and G00 are exhibited in the low frequency range, and therefore G0 ,
in this range, is more sensitive in detecting structural changes. By plotting the slope
of logG0 versus logω at low frequencies (<0.01 rad/s) as a function of the filler
loading, the percolation threshold can be determined as shown in Fig. 23b [43].

3 Polymer Melt Processing

3.1 Extrusion

Extrusion is one of the most important polymer processing operations. It involves

a sequence of the following steps: (a) heating and melting the polymer, (b) pumping
the melted polymer to the shaping unit, (c) forming the melt into the required shape
and dimensions via an extrusion die, and (d) cooling and solidification. Steps (a) and
(b) above are taking place in an extruder, which consists of a heated hollow cylinder
(barrel) into which a screw (single screw extruders – SSE) or a pair of screws rotate
(twin screw extruders – TSE). The screw is the heart of the extruder, and it is usually
referred to as an Archimedean screw, even though Egyptians were using similar
devices before Archimedes. Modern developments, based on understanding of the
thermomechanical phenomena, are less than 70 years old [2, 47–49].
Polymer resins in the form of pellets, powders, or flakes flow from a hopper to the
gap between the rotating screw and the heated barrel as shown in Fig. 24. The depth
162 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 23 (a) Storage and loss moduli for EVA28 and EVA28 nanocomposites at 130  C
adapted from [46] and (b) percolation threshold of EVA28 nanocomposites where α = logG0 /logω,
adapted from [43]

of the conveying channel in the screw is contoured from large to small in the flow
direction, to account for the density change from the particulate solid feed to the
molten polymer extrudate, and for pressure development. The SSEs normally have
diameters between 25 and 250 mm and length/diameter ratios between 20 and 40.
Usual rotation speeds range from 20 to 150 RPM. A 60-mm-diameter machine may
deliver up to 200 kg/h, while a 150-mm-diameter machine can exceed 1000 kg/h.
4 Polymer Processing and Rheology 163

Fig. 24 Schematic diagram

of a single screw extruder

Fig. 25 Typical screw

terminology

Recently developed high-speed single screw extruders can produce much higher
output rates at rotation speeds exceeding 1000 RPM, usually with small-diameter
machines.
In the first region or solids conveying zone of a SSE, the solid polymer particles
are compacted together in the screw channel by the rotating action of the screw to
form a solid bed of material. At the start of the next extruder section, the plasticating
(melting) zone, barrel heaters cause a thin film of molten polymer to form in the gap
between the solid bed and the barrel wall. The melt film is subjected to intense
shearing in the thin gap, and because of the extremely high viscosities of molten
polymers, high rates of viscous dissipation result. The generated heat melts
completely the solid packed bed of pellets or powders, usually at 2/3 of the screw
length from the feed, in well-designed extruders. In the last zone of the extruder, the
metering section, the polymer melt flow is stabilized in the shallow screw channels,
and finally the material passes through the die at the end of the machine.
Screw design is very important for achieving high output rates of homogeneous
high-quality melt without any solid particles (unmelts). The standard screw has a
single flight with 17.66 helix angle (square pitched with the pitch being equal to the
diameter as shown in Fig. 25 that represents a typical screw section). Used increas-
ingly in the extrusion industry are barrier screws. Barrier screws have a secondary
screw flight in the melting section of the screw, which serves to segregate the solid
bed from the molten polymer as shown in Fig. 26. By independently controlling the
164 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 26 Schematic diagram of a typical barrier screw

dimensions of the solids and melt channels, the melting process can be accelerated
and made more stable, thereby increasing the extruder output and melt quality.
To improve melting and mixing, cutting of the flow field, reorientation, and
smearing into thinner sections are necessary. This is achieved by pins or pegs,
broken flight sections, reverse flight sections, multiple flighted sections, unflighted
torpedo sections, or similar configurations. These devices are normally located at the
downstream end of a screw and improve melt quality by reducing temperature
non-homogeneities in the polymer stream and improving the dispersion and distri-
bution of additives.
Industrial experience shows that for good functioning extruders, the throughput
should not be less than 25% of the drag flow equation

1
m_ D ¼ ρπ 2 Db 2 HN sin θ cos θ (42)
2
where ρ is the melt density, Db barrel diameter, H channel depth in the metering
section, N the rotational speed of the screw, and θ the helix angle, as shown in Fig. 25.
Grooved barrel extruders feature axial grooves or slots in the part of the barrel
immediately following the feed throat (usually up to 4Db). The grooved barrel can
significantly enhance the solid transport rate due to high friction on the barrel and
increase the pressure buildup significantly, very close to the feed throat. In these
extruder types, the compression ratio (i.e., the channel depth in the feed over the
depth in metering section) is roughly 1–1.2, while in smooth barrels higher com-
pression ratios are met ranging from 2 to 4. Grooved barrel extruders can deliver
double the output rate given by the drag flow equation above. High-speed extruders
usually have the entire barrel grooved [50, 51] and even higher outputs.
The power provided by the rotating action of the screw goes to heating the
polymer from room temperature to the extrusion temperature, melting the polymer
and pumping it through the die [52]. The barrel heaters usually provide less than
25% of the power required to raise the temperature and melt the polymer. Extruders
have poor pumping efficiency. The energy required for pumping is about 10% of the
total motor power supplied by the rotating screw.
4 Polymer Processing and Rheology 165

Twin screw extruders (TSEs) are extruders with two screws of the same diameter
which turn side by side within the extruder barrel at the same speed [2, 52, 53]. They
are used increasingly, in recent years, mainly for mixing, blending, and
compounding of thermoplastics with additives, devolatilization, and reactive extru-
sion. The disadvantage of TSEs compared with SSEs is their significantly higher
capital cost. There are twin screw extruders with intermeshing or non-intermeshing
screws, depending on whether they engage or not each other’s flights. The screws
can be corotating or counterrotating. Screws are made up of conveying, kneading
blocks and mixing sections. The screw design is frequently modular, which
allows for a nearly unlimited number of possible screw configurations. Kneading
blocks comprise several disks staggered at an angle to one another. Dispersive
mixing takes place in the elongational flow regions formed by thick kneading blocks
(shaped like oval disks) wiping the barrel wall. Corotating intermeshing twin screw
extruders with thick kneading blocks have excellent mixing capabilities (both
distributive and dispersive). Counterrotating intermeshing twin screw extruders
operate almost like positive displacement pumps, have limited mixing capabilities,
and are used for extruding temperature-sensitive materials (mostly PVC).
Once a polymer has been melted, mixed, and pressurized in an extruder, it is
pumped through an extrusion die for continuous forming (after cooling and solidi-
fication) into a final product. The most common die types are flat, annular, round,
and profile. Products made by extrusion include pipe, tubing, coating of wire, plastic
bottles, plastic films and sheets, plastic bags, coating for paper and foil, fibers,
filaments, yarns, tapes, and a wide array of profiles (e.g., window frames and sealing
systems) [52].
Blown film extrusion is the most important continuous process for the production
of thin plastic films from polyethylene. A typical blown film extrusion line is shown
in Fig. 27. The molten polymer is extruded through an annular die (normally of spiral
mandrel construction as shown in Fig. 28), to form a thin-walled tube which is
simultaneously axially drawn and radially expanded. Polymer has the tendency to
flow right above the ports of the spiral die, therefore producing tubes of circumfer-
entially thick-thin regions. A good die, in general, should not have thickness
variation of more than 5% [54]. This may lead to defects far downstream in the
production line. Either way, computer-aided design and knowledge of the polymer’s
rheology may be used to eliminate or at least suppress in a cost-/time-effective way
the above-described thickness variations. In most cases the blown film bubble is
formed vertically upward. The maximum bubble diameter is usually 1.2–4 times
larger than the die diameter. The hot melt is cooled by annular streams of high-speed
air jets from external air rings and occasionally also from internal air distributors.
The solidified film passes through a frame which pinches the top of the bubble and is
taken up by rollers. Coextruded films with 3–8 layers (sometimes up to 11) are
produced by this process, for use in food packaging, having at least 1 polymeric
layer with very low permeability to oxygen and moisture. Outputs frequently exceed
1000 kg/h.
Cast film and sheet extrusion is a continuous process and involves extruding
a polymer through a flat die, having die lip gap of a couple of mm and width from a
166 N. D. Polychronopoulos and J. Vlachopoulos

Fig. 27 Schematic
representation of a typical film
blowing process

Fig. 28 Schematic of a
typical spiral die
4 Polymer Processing and Rheology 167

Fig. 29 Schematic representation of cast film extrusion process (a) front and (b) side view.
Figure not to scale

Fig. 30 Schematic
representation of a typical coat
hanger die for film or sheet
extrusion

few cm (for tapes) to a few meters. It is subsequently stretched by a chilled steel

roller or rollers which quench and solidify the molten material shown in Fig. 29. The
final product has reduced width (due to necking) and thickness compared to the
corresponding dimensions of the die. The final dimensions are mainly affected by the
ratio of the roller speed to the extrusion speed, which is often referred to as draw
ratio. Upon emergence from the die, the final product will locally swell. It has been
recently shown via numerical methods that this local amount of swell is affected
dramatically by the draw ratio [55]. Film is generally defined as a product thinner
than 0.25 mm, while sheet is thicker than this. The cast film process is used for very
tight tolerances of thin film or for low-viscosity resins. Most flat dies are of T-slot or
coat hanger designs, which contain a manifold to spread the flowing polymer across
the width of the die, followed downstream by contoured slits to create the desired
flow distribution and pressure drop. A typical coat hanger flat die is shown in Fig. 30.
Most cast film lines manufactured today are coextrusion lines, combining layers
from as many as seven extruders into the product through multi-manifold dies, or
single manifold dies with the aid of feedblocks [56].
Pipe extrusion involves dies having lips of annular geometry. Two types of dies
are used: either spiral dies (like those used in film blowing but having much wider
gaps) or spider leg dies, in which a central mandrel (also called torpedo) is supported
by steel supports (rods) around the circumference. Behind the spider legs, weldlines
form [57]. Weldlines are lines of weakness in mechanical properties, and their
impact must be reduced for avoiding premature pipe failure. PE, PVC, and PP are
used extensively in pipe and tube extrusion for a variety of products for water and
gas distribution and numerous other applications in housing, automotive, and health
industries. Diameters can range from millimeters for medical applications to meters
168 N. D. Polychronopoulos and J. Vlachopoulos

for sewage and storm water installations. Usually very-high-viscosity materials are
used in pipe extrusion (e.g., HDPE having melt index (at 190  C, 2.16 kg) as low as
0.1 for pressure pipes).
Profile extrusion is a manufacturing process used for products of constant cross
section. These can range from simple shapes to very complex profiles with multiple
chambers and fingers. Examples range from picture frame moldings and automotive
trims to edging for tabletops and window lineals. The extruded materials are
classified (roughly) as rigid or flexible. The typical profile extrusion line consists
of an extruder pumping a polymer through a profile die, followed by a sizing tank or
calibrator, additional cooling troughs, a puller, and a cutoff device. The design of
profile dies requires considerable experience and patience. Output limitations in
profile extrusion are encountered owing to either sharkskin (for thin products
produced from high-viscosity polymers) or the ability to cool thick-walled products.
It should be noted that extrusion die design is a challenging task. Design is much
more complex than optimization. In fact, the optimization problem is a standard
mathematical one, i.e., to maximize a function subject to constraints. In engineering
design, we use inequality specifications of satisfactory performance, rather than
maxima and minima, along the lines of Herbert Simon [58] who tried to introduce
the term “satisfice” as opposed to “optimize.” In extrusion die design, there are
certain considerations that should be taken into account: (a) flow balancing, to
produce uniform outflow (i.e., film, profiles of equal thickness), (b) reasonable
pressure drop (not too high not too low), (c) no hot spots, (d) no stagnation flow
regions, (e) avoidance of die lip buildup, (f) delay onset of sharkskin/melt fracture,
(g) avoidance of weldlines or reduction of their influence, and (h) residence time
(long enough for homogenized extrudate, but not too long to cause degradation or
cross-linking). The nowadays powerful computer systems along with a suitable user-
friendly flow analysis software offer a fast way to assess whether a die design can be
characterized as satisfactory or not. This is usually carried out by performing a
repetitive set of computer simulations before arriving at a satisfactory design. Of
course, good viscosity measurements are absolutely necessary for computer simu-
lation of molten polymer flows through dies.

3.2 Calendering

Calendering is a widely used manufacturing continuous process that involves a pair

or more of counterrotating heated calenders (rolls) for the production of thin plastic
sheets and films. The thermoplastic melt is fed behind the minimum gap of the two
calenders, as shown in Fig. 31. The rotational movement forces the material to flow
in the machine direction (downstream) and in the lateral direction, with subsequent
detachment from the rollers’ surface at a specific thickness [59]. Two-roll calender-
ing lines are usually used for rubber processing, whereas four-roll calenders are
generally used for the production of double-coated products meeting strict surface
quality requirements. The major plastic materials calendered are PVC and ABS.
4 Polymer Processing and Rheology 169

Fig. 31 Schematic representation of a typical calendering line. Figure not to scale

Products range from wall covering and upholstery fabrics to reservoir linings and
agricultural mulching materials. Calendering is also widely used in the food, paper,
and rubber industries.
Calendering may be characterized as a generally mild process for plastic sheet or
film production in terms of the shear rates involved. Typical shear rates are of the
order 100 s1, much lower than in other processes. Assuming the polymer melt
viscosity may be expressed by the power law model, the maximum pressure
developed Pmax, between rotating rolls, which can be roughly approximated by

n1

0:5
2 U U Rrol
Pmax ¼ 0:535K (43)
3 Ho Ho Ho

where K is the consistency index, n the power law index, U roller speed, Ho the
minimum distance between the rollers, and Rrol their radius. Two-roll mills are
frequently used in the rubber industry, for laboratory mixing trials. It has also been
shown that use of a three-roll calendering-type machine may be an effective process
to disperse a nanocomponent in a polymeric matrix such as carbon nanotubes [60] or
perhaps graphene [61]. This is mainly due to the strong extensional flow developed
in the converging region between the rollers that leads to disaggregation of the
agglomerated nanocomposite, resulting in a relatively good dispersion (exfoliation).
At the same time, the low shear rates are less likely to cause attrition of the individual
nanocomposite particles so that the properties of the added nanocomponent may be
exploited to a large degree. For example, it has been recently concluded in the work
of Prolongo et al. [62] that the calendering process is an effective technique for the
dispersion of graphene nanofiller, as compared to a high shear mixing process that
could induce a reduction of the graphene nanofiller’s lateral size by breakage.
Determination of the extensional and shear rates in the calendering gap region,
using fully 3D numerical analysis, such as in Polychronopoulos et al. [59], combined
with rheological measurements, is of critical importance and may offer new insights
in a fast and relatively inexpensive manner.
170 N. D. Polychronopoulos and J. Vlachopoulos

3.3 Injection Molding

Injection molding is a two-step cyclical process: (a) melt generation by a rotating

screw and (b) filling of the mold with molten polymer by the forward ramming of the
screw (called a reciprocating screw), followed by a very short packing stage neces-
sary to pack more polymer in the mold to offset the shrinkage after cooling and
solidification. The material is held in the mold under high pressure until it has
solidified sufficiently to allow ejection.
In polymer injection molding, the melt path into the mold starts with a sprue and
splits off into individual melt tubes (called runners) each feeding one of the multi-
plicities of mold cavities through flow entrances (called gates). Figure 32 shows
schematically how these mold components are connected. Molds can contain over
100 cavities, each producing a part per injection cycle. One problem facing mold
design is the balancing or runners. Figure 33a shows naturally balanced runners (i.e.,
it takes the same time for the polymer melt to reach the 16 cavities). Figure 33b

Fig. 32 Schematic
representation of injection IM
molding Product

sprue

gate

nozzle runner

Reciprocating screw cavity

Fig. 33 (a) Naturally balanced and (b) naturally unbalanced runners in injection molding
4 Polymer Processing and Rheology 171

shows naturally unbalanced runners. To balance a naturally unbalanced system of

runners, we must size the runner diameters and lengths so that all cavities fill at the
same time. For just a few runners, it is possible to use simple pressure drop versus
flow rate equations. For numerous runners, as it is frequently the case, flow simu-
lation software is required.
Hydraulic and electric (or hybrid) systems are used, for the purpose of holding the
mold closed with sufficient force to resist the injection pressure. The clamping force
is determined by multiplying the injection pressure by the projected area, and it is
usually reported in tons (1000 kg force). Line pressures can reach up to perhaps
200 MPa. Obviously the larger the projected area, the larger the clamping force
required. Commercially available machines range from a few tons to a few thousand
tons of clamping capacity.
Cycle times usually range from a few seconds to over a minute. Numerous
products ranging from boat hulls, lawn chairs, and appliance housings to radio
knobs and bottle caps are injection molded. Very high shear rates arise in injection
molding operations (usually up to 104 s1), and to limit temperature increases from
viscous heating and to facilitate easy filling, low-viscosity thermoplastic polymer
grades are used.
Mold cavity filling is characterized by the fountain effect, in which elements of the
molten polymeric fluid undergo complex shear and stretching motions as they catch
up to the free flow front and then move outward to the cold walls. This phenomenon
can impart considerable orientation to the resulting injection-molded part. While
molecular orientation is used in extrusion to improve the mechanical properties, in
injection molding, orientation is generally a nuisance [1]. The orientation is further
exacerbated during the packing stage. The consequent frozen-in stresses can cause
finished parts to become distorted, especially at elevated temperatures. Figure 34
shows streamlines and fluid element deformation in fountain flow [63].
When two flow fronts meet (e.g., when a cavity is filled from two gates from
opposite directions), a weldline is formed. Weldlines are also formed behind flow
obstructions, just like in the case of spider leg extrusion dies. These are lines of poor
bonding and low mechanical strength, due to the relatively large time required for
large polymer chains to interdiffuse. Determination of the location of weldlines can
be done with the help of suitable flow analysis software. It is advisable to avoid
weldlines in load-bearing areas of a molded product.

Fig. 34 Illustration of
fountain flow streamlines as
seen by an observer moving
with the flow front (bottom
half) and fluid element
orientation (top half)
172 N. D. Polychronopoulos and J. Vlachopoulos

Simulation of cavity filling is generally carried out on the basis of the Hele-Shaw
flow approximation [64, 65] which applies to viscous flow between two closely
spaced plates. Recently fully 3D and non-isothermal simulation software packages
have also been developed. Computer simulation is used extensively in injection
mold design and process/product optimization. Rheological data are absolutely
necessary for carrying out reliable simulations of flow of molten polymers through
runners and mold cavities.
Among the challenging problems faced in computer simulation is the predic-
tion of shrinkage and warpage. Shrinkage is the difference in dimensions between
the mold and the cooled molded part. The main cause is the density increase,
which occurs as the melt freezes. Crystalline polymers such as polyamide (PA,
nylon), high-density PE, PET, and PP give the worst problems [1] with shrink-
ages of 1–4%. Amorphous polymers such as PS, PMMA, and PC have fewer
problems, shrinking only 0.3–0.7%. Warpage is caused by the density changes
mentioned above and orientation imparted to the part during cavity filling and
packing, decidedly in a nonuniform manner. In addition to the rheological data,
pressure-volume-temperature measurements and knowledge of crystallization
behavior are necessary for computer analysis of packing, shrinkage, and warpage
phenomena.
Gas-assist injection molding involves the injection of nitrogen with the plastic,
which creates a hollow void in the molded part [66]. This allows large parts to be
molded with lower clamp tonnage and significant material savings. This innovative
process started in the 1980s and its use is growing.
The process of reaction injection molding (RIM) involves the injection of
low-viscosity liquids, which become reactive when mixed and polymerize within
the mold [67]. The advantage of this process is that the pressures are low owing to
the low viscosities. A disadvantage is the requirement to handle highly toxic sub-
stances. Although initial projections called for significant growth in RIM, this did
not materialize. In fact, some manufacturers of automotive parts by RIM have
switched to conventional injection molding of thermoplastics.

3.4 Compression Molding

Compression molding is the oldest technique for the production of polymer prod-
ucts [64] and is mainly used for thermosets. In this process the compound is pressed
in the mold by the heated platens of a hydraulic press. This process is to some extent
analogous to sheet metal stamping. Injection molding of polymers has replaced
compression molding for some polymers, because of the advantages in material
handling and automation. However, compression molding has an advantage in the
processing of reinforced polymers [68]. Owing to modest levels of deformation and
stress involved in compression molding, the reinforcing fibers are not damaged. Very
high fiber concentrations and longer fibers can be included in compression-molded
products.
4 Polymer Processing and Rheology 173

3.5 Blow Molding

Blow molding is the process by which articles are formed by inflation of a molten
polymer to fill a mold cavity having the desired shape and dimensions. Bottles for
soft drinks and other liquids are blow molded. The two most important process
variants are extrusion blow molding and injection blow molding [69]. In extrusion
blow molding, an extruder pumps the melt through an annular die to form a molten
tube or parison with well-defined and controlled dimensions. The parison is clamped
between the two mold halves and is inflated by internal air pressure to take the shape
of the mold cavity, which is usually cooled. Finally, the formed article solidifies as a
result of cooling, and the mold is opened to eject the article without damage. The fuel
tanks of cars and trucks are extrusion blow-molded multilayer parisons (usually
more than 6 layers with at least 1 layer of a barrier to gasoline vapors).
Injection blow molding is a two-stage process. In the first stage, the plastic is
injected into a cavity where the preform is molded. The preform is then transferred to
the blow mold for inflation. Injection blow molding offers the advantages of accurate
dimensional control, the elimination of scrap, and the molding in of threads before
blowing. Extrusion blow molding is preferred for containers with high length/
diameter ratios and for products with handles [70].
Polyethylene terephthalate or PET is the polymer most widely used in injection
blow molding, for carbonated drinks and water bottles. Stretch blow molding is used
to produce PET bottles of enhanced physical properties. In this process, stretching
induces the formation of small lamellar crystals. These crystals result in more
transparent and tougher products than those produced without stretch blowing,
which have spherulitic crystals.

3.6 Thermoforming

Thermoforming techniques involve the softening of thermoplastic sheets by heat,

followed by forming by the application of vacuum, pressure, or a moving
plug [71]. The sheet may be stretched over a male mold (positive forming) or into
a female mold (negative forming). On contact with the mold, heat is lost and the
material regains stiffness as it cools. Geometries of thermoformed products are
usually simple (boxes, food trays, various containers, refrigerator liners, computer
cases). Thermoforming competes with blow molding and injection molding. The
main advantages of this process are the relatively low cost of thermoforming
machines and the very low cost of the molds and the ease of forming large area,
thin section parts. Disadvantages are the limited product shapes possible, difficulties
in obtaining the required thickness distribution, difficulty in controlling molecular
orientation, and limitations in service temperature which may induce strain recovery
or shrinkage. Thermoforming of thermoplastics has certain similarities to sheet metal
forming [72]. However, the strain rates involved in polymer sheet forming are much
larger than for metals. Figure 35 shows a vacuum thermoforming process. When the
174 N. D. Polychronopoulos and J. Vlachopoulos

Plastic sheet

Clamp

Seal

Mould

Vacuum holes Vacuum

Fig. 35 Thermoforming by application of vacuum

ratio of area of the thermoformed product over the initial area of the sheet (draw
ratio) is large, polymers of good melt strength are required.

3.7 Rotational Molding

In rotational molding, a charge of plastic powder is placed in one half of a metal

mold. The mold halves are then clamped together and heated, while the mold rotates
biaxially. The powder particles melt and coalesce to form a homogeneous layer on
the surface of the mold. The mold is then cooled, and the polymer layer densifies and
solidifies [73, 74]. Rotational molding competes with blow molding, thermo-
forming, and injection molding for the production of hollow parts. The main
advantages of this process are the simplicity of the molds and the low capital
investment requirement. Cycle times are large, ~15–30 min. Rotational molding is
mainly used for large tanks (up to 85 m3 reported), toys, and hollow parts that require
frequent design modifications. The process of coalescence and subsequent densifi-
cation [75, 76] is usually referred to as sintering by rotational molding practitioners.
In powder metallurgy, however, the term sintering usually refers to compaction of
powders below their melting point. Molten particle coalescence is driven by the
surface tension and resisted by their viscosity and elasticity [76]. Polymers with melt
index of less than 1.5 are not “rotomoldable” due to their high viscosity.

3.8 Melt Spinning

In melt spinning the polymer is melted in an extruder and is delivered under pressure
to a die (called spinneret) having numerous small holes, and subsequently the molten
filaments (sometimes more than 1000) are heat treated, cooled, and stretched to
the desired diameter [14, 77, 78]. Frequently the molten polymer goes through a melt
metering pump (for more stable flow) and a filter (to remove impurities and unmelts)
upstream of the spinneret holes. The spinneret holes can have circular, square,
4 Polymer Processing and Rheology 175

pentagonal, octagonal, trilobal, and other cross sections. Structure development

occurs as a function of melt spinning conditions involving molecular orientation
and morphology of the crystalline structure. Significant enhancement of fiber prop-
erties can be achieved, such as in tensile modulus and strength, through proper
cooling and drawing conditions. The fibers are, usually, characterized by their
linear density expressed in denier or tex. Denier is the weight in grams of 9000 m
of synthetic fiber. Tex the weight in grams of 1000 m, and dtex is the weight in grams
of 10,000 m. Polyethylene, polypropylene, poly(ethylene terephthalate), and nylon
are the most frequently melt-spun polymers.

3.9 Additive Manufacturing of Polymers

Additive manufacturing (AM) is the technology of building 3D objects layer

by layer, as opposed to some traditional machining methods like drilling, milling,
and grinding which can be classified as subtractive. Frequently, AM is referred to as
3D printing in the mass media, and it is not limited to polymers. AM includes several
technologies [79] which offer unique product customization opportunities. From
them, selective laser sintering (SLS) and fused deposition modeling (FDM) appear
as the most promising methods for the production of plastic parts. In SLS a high-
powered laser is used to fuse together small particles. It is similar to the process of
particle coalescence (sintering) encountered in rotational molding with the difference
that in SLS the heating is localized selectively. At present, polyamide (nylon) 12 is
the most frequently used polymer for commercial production, with limited other
material options [79]. In FDM a molten polymer is injected from an extrusion nozzle
and deposited layer by layer [80, 81]. Modeling the flow in the FDM extrusion
nozzle is a relatively straightforward task due to the simplicity of the nozzle
geometry (usually of circular cross section). However, modeling the material behav-
ior just after it emerges from the nozzle is a challenging task. Extrudate swell,
especially if the material possesses large normal stresses, must be taken into con-
sideration. A lot of research efforts are devoted to SLS and FDM, and it is widely
believed that additive manufacturing will spearhead the next industrial
revolution [82].

4 Considerations in the Polymer Processing Industry

Commodity polymers (like PE, PP, PVC, PS) and engineering polymers (like PA,
PC) are produced by large chemical corporations perhaps numbering less than
100 around the world. However, polymer processing companies number more
than 100,000 with their size varying from a handful of employees to several
thousand. The vast majority of them can be classified as small or medium enterprises
(SMEs). Also, the vast majority of original equipment manufacturers (OEMs) are
also SMEs. While polymer (frequently referred to as resin) producers have well-
equipped laboratories for physicochemical and rheological characterization, this is
176 N. D. Polychronopoulos and J. Vlachopoulos

not the case with the SME processing polymers or designing and manufacturing
equipment. Traditionally, processors rely heavily on the resin producers and machin-
ery manufacturers for their technology. There is frequent dialogue between pro-
cessors, OEMs, and polymer suppliers for prevention, reduction, or elimination of
problems during processing and defects in the final plastic products.
Extrusion (including extrusion blow molding), calendering, and melt spinning are
continuous production methods. Injection molding, compression molding, thermo-
forming, rotational molding, and additive manufacturing are for production of parts.
The decision on which process to use for a particular product is based on several
considerations relating product shape and size, quality, quantity, and economics. For
example, hollow parts can be produced by injection molding, thermoforming, blow
molding, rotational molding, or additive manufacturing. Injection molding requires
expensive machines and molds, while for thermoforming and rotational molding the
tooling is inexpensive. Injection-molded parts have well-defined surfaces and crisp
appearance, and cycle times are very short. Thermoforming is a slow process and
rotational molding even slower, but they both have advantages for large parts.
Additive manufacturing offers unique advantages for complex designs and custom-
ized products. However, it is slow, the raw material selection is limited, and the
mechanical properties are likely to be inferior to those of injection molding, due to
the poor bonding during the layer-by-layer process in the absence of external
pressure.
A typical polymer property data sheet will include solid density and melt index
(MI) for the standard load of 2.16 kg. As explained, above, the melt index is inversely
proportional to viscosity at one point of a viscosity curve and an indirect measure of
the average molecular weight. Frequently the high load melt index (HLMI) for either
10 kg or 21.6 kg is also provided. The ratio HLMI/MI gives an indication of shear
thinning; the larger, the more. Melt index is considered as a quality control measure.
Detailed rheological characterization can be time-consuming and expensive and
might not be always necessary. For problem-solving, it is necessary to have a
good understanding of the thermomechanical phenomena and physicochemical
interactions that may be involved. Problems may originate from the macromolecular
architecture, the processing equipment, or the operating conditions. The rheological
measurements must be carefully targeted. The sensitivity of rheological behavior to
high molecular weight fractions and long-chain branching is frequently used for
differentiating various polymer grades. Rheological measurements and understand-
ing [7, 8, 11, 17, 28, 83] are indispensable in differentiating polymer resin grades and
in problem-solving.
Computer flow simulation [2, 52, 54, 56, 65, 84] using suitable non-Newtonian
models of viscosity is widely practiced in injection molding for mold design and
various other problem-solving purposes. Similarly, computer software is indispens-
able for extrusion die design and identification of problems originating in dies. In
extruder screw design, computer flow analysis is less effective due to the complex
aspects of solid transport and melting, before the molten polymer is pumped.
Some problems may be due to other factors, not obviously related to rheology,
and not easily amenable to computer flow simulations. For example, inadequate
4 Polymer Processing and Rheology 177

drying of the raw material may result in surging (fluctuations in output and pressure)
in extrusion due to slippage on the barrel wall in the solids conveying zone. Moisture
also may result in hydrolysis in processing of PET, nylon, and PLA. Inclusion of
even a very small number of tiny air bubbles in the feed of an extruder may result in
serious defects in the production of films or fibers. Inclusion of cross-linked gels and
other contamination frequently results in deterioration of optical qualities of trans-
parent films. Identification of the root causes of such problems is frequently very
difficult. Rheology and computer simulation are sometimes used to exclude other
potential causes in the challenging task of fault diagnosis and troubleshooting.

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Porous Coordination Polymers
5
Abdul Malik P. Peedikakkal and N. N. Adarsh

Contents
1 Coordination Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3 Topology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
4 Interpenetration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
5 Surface Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
6 Gas Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6.1 Hydrogen Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
6.2 Methane Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
6.3 Carbon Dioxide Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
7 Conclusion and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218

Abstract
This chapter discusses about porous coordination polymers (PCPs) and/or metal-
organic frameworks and mainly emphasizes the historical background, their
synthesis, structural properties, and potential applications (mainly gas storage).
We organize the gas storage application of PCPs into three sections – H2, CH4,
and CO2 storage – in order to highlight the important concerns we must know
before designing new functional MOFs. In the case of H2 storage application of
MOFs, we have discussed four important parameters which effect their successful
design for H2 storage application with examples from the literature, such as (1) H2

A. M. P. Peedikakkal (*)
Department of Chemistry, King Fahd University of Petroleum and Minerals,
Dhahran, Kingdom of Saudi Arabia
e-mail: [email protected]
N. N. Adarsh
Solid State and Materials Chemistry, School of Chemical Sciences, Mahatma Gandhi University,
Kottayam, Kerala, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 181

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_5
182 A. M. P. Peedikakkal and N. N. Adarsh

adsorption condition (pressure and temperature), (2) inclusion of reducing agents

in the MOF, (3) effect of structural defect in MOF, and (4) effect of adsorption
sites in the MOF structure (examples: MOF-177, Pt/AC/IRMOF-8, UiO-66(Zr),
Yb-BTC). Further, we highlight the investigation results of methane storage
application of MOFs, with appropriate examples such as PCN-14, M2(dhtp)
[M: open metal = Mg, Mn, Co, Ni, Zn; dhtp = 2,5-dihydroxyterephthalate],
and UTSA-20. And then we discuss more details of various factors which we
must take care before the successful design and synthesis of new MOFs for more
CO2 storage such as: (1) the effect of open metal sites in the MOF, (2) the effect of
the pore size and surface area of the framework, (3) effect of doping metals,
(4) effect of amine functionalization in MOFs, (5) effect of nitrogen-rich MOFs,
(6) effect of water molecules, with some important examples such as M-MOF-74
(M = Mg, Co, Fe, Zn, Ni), HKUST-1, etc.

1 Coordination Polymers

Coordination polymers (CPs) are rapidly emerging inorganic–organic solid state

materials which provide boundless opportunity for designing their chemical and
physical properties [1]. These highly crystalline materials are constructed from
assembling of metal ion or metal cluster with organic ligands through coordination
bonds to form one-, two-, and three-dimensional structures. CPs are also known as
metal-organic frameworks (MOFs) [1], and some of these solid networks exhibit
permanent porosity which is termed as porous MOFs or porous coordination polymers
(PCPs). These extended solid networks collectively are also termed as metal-organic
materials (MOMs) [2]. These materials have drawn ever-increasing scientific and
technological interest due to their widespread application such as gas storage/
separation, catalysis, ion exchange, drug delivery, and optoelectronics, etc. A col-
lective approach such as design and synthesis, molecular modeling, functional
properties towards application from several research groups have significantly
helped the growth and development of these materials in the last two decades.
The spectacular growth of these materials attracted researchers from material
science, biology, and medicine. In the beginning of 1990, Robson uncovered the
remarkable discovery using Wells net-based approach [3] in his laboratory which
was the greatest success that helped the rapid expansion and development of the
coordination polymers [4]. Robson and co-workers proposed a novel design
approach to synthesize these new classes of materials with interesting properties [5].
Supramolecular chemistry and crystal engineering have enhanced the development
of the coordination polymers. Lehn defined supramolecular chemistry as the chem-
istry beyond the molecules [6]. A single crystal is the best example of a super-
molecule with repetitive arrangement of molecules in three-dimension, according to
Dunitz as, “Supermolecule(s) par excellence” [7].
In 1970, G.M.J Schmidt coined the term “crystal engineering” to understand the
crystal structure of cinnamic acid derivatives and their photochemical reactivity in
the solid-state [8]. Schmidt’s investigations provide the information that the physical
5 Porous Coordination Polymers 183

and chemical properties of crystalline solids profoundly depend on the distribution

of the components inside the lattice. Later, this field has been developed rapidly due
to its importance in material science. Desiraju’s significant contribution for the past
two decades evolves systematic and logical ways to design and understand the
properties which led to the development of crystal engineering [9]. Desiraju pro-
vided a wider definition for crystal engineering as “the understanding of
intermolecular interaction in the context of crystal packing and in the utilization
of such understanding in the design of new solids with desired physical and chemical
properties.” Although crystal engineering was first designed for solid-state reaction
in crystals, it has been rediscovered in various fields in designing the solids which
have the properties such as porosity, luminescence, nonlinear optical activity, ferro-
electricity, and piezoelectricity. The mutual coincidence of supramolecular chemis-
try and crystal engineering assisted in understanding the self-assembly process and
understanding the intermolecular interactions and structure-function relationships in
solids. The terminologies such as synthons and tectons have been used for directing
the packing arrangement of molecules in the organic solids in crystal engineering.
A similar terminology has been used for designing the infinite network solid of
coordination polymers. The organic ligands are linked by metal cation or metal
clusters in constructing coordination polymers. Rapid developments in the last
28 years indicate the predictability of the coordination polymers relatively easier
since they are more controllable than organic solids (directed via hydrogen bonding).
Even though reasonable achievement has been occurred in engineering crystals, the
structural predication or Maddox’s statement “One of the continuing scandals in the
physical sciences is that it remains in general impossible to predict the structure of
even the simplest crystalline solids from a knowledge of their chemical composition”
is still valid today [10]. Even, absolute prediction of the dimensionality and connec-
tivity in coordination polymers is still a challenge when assembling a chosen ligand
with a metal center. Depending on the properties of metal cations (various geometry
can be used such as linear, tetrahedral, square-planar, square-pyramidal, trigonal-
bipyramidal, octahedral, trigonal-prismatic, pentagonal-bipyramidal, and the
corresponding distorted forms), binding strength, and directionality of ligands and
the reaction conditions, coordination polymers exhibit a wide variety of infinite (1D,
2D, and 3D) networks [1a, 2]. This has been realized through self-organization of
various metal cations, and bifunctional ligands (e.g., 4,40 -bipy) can form linear,
zig-zag, ladder, honeycomb, square-grid, diamondoid, and octahedral frameworks
(Scheme 1) [11].
The diversity of above network structures is very well-known. Zaworotko pro-
posed this diversity of structures as supramolecular isomerism is the existence of
more than one type of network superstructures for the same molecular building
blocks in coordination polymers [12]. It has been categorized to structural, confor-
mational, catenane, and optical supramolecular isomerism. Supramolecular isomer-
ism has its own importance in coordination polymers due to various reasons: (1) it is
an opportunity to get better understanding of the factors that influence the crystal
nucleation and growth, (2) it represents a significant limitation on the number of the
possible superstructures, (3) it provides an opportunity to control the supramolecular
184 A. M. P. Peedikakkal and N. N. Adarsh

Scheme 1 Schematic representation of some of the simple 1D, 2D, and 3D coordination polymers
formed from the metal “nodes”(red) and organic “spacers” (blue): (a) cubic, (b) cubic diamondoid,
(c) hexagonal diamondoid, (d) square grid, (e) molecular ladder, (f) zigzag chain, and (g) helix
[12]. (This figure is reprinted from Ref. [12] with permission. Copyright 2001, American Chemical
Society)

isomers and help to design the desired one, (4) implication of gaining better
understanding of polymorphism in crystals, (5) the diversity of these structures
profoundly effect on their bulk properties, and (6) it provides the information that
the structures can occur from the same building blocks under similar crystallization
conditions.
The diversity of networks does not absolutely depend on the geometrical features
of metal cations. For example, a zig-zag network can be formed from a linear,
square-planar, trigonal-bipyramidal, and octahedral metal cation. In some instances,
the assemblies of networks are metal-to-ligand ratio dependent. For example, 4,40 -
bipy by coordinating to metals 1:1 metal:ligand ratios can afford molecular polygons
or chains (zig-zag, linear, or helical) and 1:1.5 stoichiometry can form 1-D molecular
ladder; 1:2 stoichiometry can afford 2-D square grid or 3-D diamondoid topologies;
and 1:3 stoichiometry has been shown to produce a 3-D cubic framework
(Scheme 1). Different products can be isolated from a reaction that proceeds through
kinetically favorable conditions.
Transition metal ions or metal clusters are the most well-known joints (or
connectors) in coordination polymers [1]. The main reason is the easiness of
designing the coordination polymers from the labile M-L coordination bond and
5 Porous Coordination Polymers 185

Scheme 2 A few examples of neutral pyridyl donor ligands used in coordination polymers. The
ligands exhibit variation in ligand length, rigidity, flexibility, and functionality

the strength of the ordered crystalline network solid formed from the coordination
bond with high regularity. The more directional strong coordination bond of metal
ions with ligands provides more robust materials.
Ligand design is one of the important factors in getting the desired topological
network. Pyridyl donor ligands are one of the most versatile building blocks (or linkers)
in the construction of coordination polymers [13]. In these ligands, two-connecting
linear bifunctional spacer and three-connecting trifunctional ligands are the most
common; four-connecting ligands are far less than two- and three-connecting ligands.
Several coordination polymers have been reported using linear and angular spacer
ligands (Scheme 2). An anionic source (e.g., ClO4ˉ, BF4ˉ, NO3ˉ, NCSˉ, PF6ˉ, SiF62ˉ,
CNˉ, and CF3SO3ˉ, etc.) neutralizes the overall charge of the compound.
Later, several modified two-connecting ligands (Scheme 2) are used such as
modification in ligand length or flexibility by introducing aliphatic or aromatic
group and modification of binding angle via changing position of nitrogen atom in
the pyridyl rings. This provides wide variety of structures through ligand design.
However, cationic frameworks formed from nitrogen donor ligands can collapse
while guest exchange or evacuation. In these two-connecting ligands, 4,40 -bpe
(4,40 -bpe: 1,2-bis(4-pyridyl)ethylene) have given particular interest which is the
modified form of bpy in terms of ligand length and functionality by introducing
C=C bonds [14].
Because of their diverse coordination modes and bridging ability, poly-
carboxylates have been widely used in the construction of coordination polymers.
Carboxylic acid ligands provides wide range of rigid network due to their ability to
aggregate metal ions into M-O-C clusters termed as secondary building (SBU) units.
Yaghi and co-workers introduced SBU units with large rigid vertices that can be
joined by rigid organic links to produce extended frameworks of high structural
stability (Scheme 3).
186 A. M. P. Peedikakkal and N. N. Adarsh

Scheme 3 The formation of MOF is shown from rigid metal carboxylate clusters linked by
benzene to form rigid extended frameworks with large void space [1d]

The need for counterions in their cavities is obviating since the frameworks is
neutral. In this way, large class of metal-organic frameworks (MOFs) materials has
been synthesized and termed as “Reticular Chemistry” which concerns the linking of
molecular building blocks into predetermined structures using strong bonds [15]. It
was one of the major breakthroughs of coordination polymeric materials due to their
superior capacity of gas storage properties which can be used for clean energy
purpose such as hydrogen and methane storage and CO2 capture [16].
The stability of coordination polymers is also improved by introducing mixed
ligands or mixed functionality in single ligand. For example, ligands containing both
pyridyl and carboxylic functional groups have been successfully used for the
construction of various coordination polymers [17]. Further, several coordination
polymers have been designed and synthesized from more than one bridging ligand
[18]. In this case, controlling the reaction may be more challenging since the
building blocks can interfere with the reaction which affords various topologies
and obviating the desired network. For example, both dicarboxylate ligands and
pyridyl ligands can be used to construct pillar-like networks. Similarly, mono-
carboxylate ligands with pyridyl donors affords ladder like networks [19]. Owing
to their bridging ability, acetate and trifluoroacetate are efficiently utilized to orient
the C=C double bonds of bpe ligands in ladder coordination polymers for photo-
dimerization reaction [20].

2 Synthesis

Normally, coordination polymer is prepared in single step through self-assembly

process such as slow evaporation of the solution of the reactants, layering of two
solutions, or slow diffusion of the one component to another and other methods have
been implemented to get the crystalline products of coordination polymers. The
formation of coordination polymers not only depends on the properties of metal
5 Porous Coordination Polymers 187

cation, ligand, and metal-to-ligand ratio but also the crystallization conditions such
as solvent, temperature, concentration, pH, time, and inorganic counterion. This
exemplifies the complexity of predicting the desired connectivity, dimensionality,
and topology of the networks. The normal synthetic methods may take weeks and
months to get the product which is hampered in some extent in studying of these
materials. Hydrothermal/solvothermal techniques have been found to be quite suc-
cessful by greatly reducing the time for crystallization of coordination polymers to
few days [21]. The important parameters such as pH, concentrations, and tempera-
tures can be varied to produce variety of network topologies. There are several other
methods being developed for the synthesis of coordination polymers such as elec-
trochemical route [22], microwave synthesis [22, 23], high-throughput synthesis
[24], etc. Microwave synthesis has been found very promising since the method
provides an efficient way to synthesize in a short period of time. A good under-
standing of the properties and interactions of the building blocks (noncovalent
interactions), the effect of solvent system, and counterion will provide advantage
of the stepwise control in constructing the predictable topology.

3 Topology

In 1977, Wells in his famous book described the crystal structures in term of their
topology through reducing them to networks (or nets) [3]. Net is formed from series
of points (nodes) that are connected to a fixed number of other points. These
structures coined with mathematical notations which can be discrete (0D), polyhe-
dra, or infinite (1D, 2D, and 3D) periodic nets. Robson, Hoskins, and co-workers
who pioneered the development of coordination polymers applied the net approach
to design the coordination polymers by using the metal ion (nodes) and ligands
(connection between the nodes) with certain geometries towards targeting a partic-
ular topology [4, 5]. For example, diamondoid (dia) topology has been known to
form from tetrahedral metal ions (Cu(I), Zn(II), and Cd(II)) and linear bridging
ligands (cyanide) [5b]. Similarly, dia topology also can be formed from tetrahedral
bridging ligands and tetrahedral ligands. In this way, 2D and 3D coordination
polymers have topologies comparable to minerals. For example, coordination poly-
mers adopt similar structure of PtS (pts), SrAl2 (sra), α-Po (pcu), NbO (nbo), rutile,
sodalite, and several analogues of zeolites [1d, g]. Figure 1 represents some of the
common inorganic topologies.
Topological description has been found very useful in describing the connectivity
of coordination polymers [1d, g]. There are several excellent reviews which are
devoted to the topology of coordination polymers [1d, g, 25]. Based on the Wells’s
description, large number of topological networks has been identified in coordina-
tion polymers. Robson and co-workers described the net as the collection of
interlinked nodes; each link connects two nodes and each node is linked to three
or more other nodes [5]. In each net, a shortest circuit can be formed around the
nodes. If net form uniform net (same sized circuits), and similar connectivity, the net
can be described by the mathematical notation (n, p), where n is the size of shortest
188 A. M. P. Peedikakkal and N. N. Adarsh

Fig. 1 Common inorganic topologies found in MOFs or coordination polymers. (This figure is
reprinted from Ref. [1g] with permission. Copyright 2012, American Chemical Society)

circuit and p is the connectivity of the nodes. Examples of such nets are given in
Fig. 2. Specifically, not all the net follow this criterion. For example, the net contains
dissimilar shortest circuits or connectivity. In such cases, a modified description is
used, called the Schläfli symbol (or point symbol).
Schläfli symbol is also useful in the description of the nets that contain more than
one node (e.g., binodal and trinodal net) and interpenetrated nets. A node or link can
be formed from a metal cation or metal cluster or ligand. For example, three- and
four-connecting ligands can act as three- and four-connecting nodes, respectively.
Connectivity and geometry of the node can be different from the geometry of metal
cation or metal cluster. For example, octahedral metal can act as three-connecting
nodes through bonding in bidentate fashion. A tetrahedral metal can act as square-
planar nodes if they are linked by bent ligands. Finally, a topological description
should always simplify the structural description of coordination polymers and not
complicate it [1d].

4 Interpenetration

One of the most exciting features of the coordination polymer is exceptional porous
nature of the frameworks due to large voids formed from the net. These voids can
accommodate either solvent or guest molecules or multiple interpenetrating networks
since “nature abhors a vacuum” in crystals. A crystal can increase its packing efficiency
through intercalation, interdigitation, or interpenetration [1d, 26]. A rectangular channel
5 Porous Coordination Polymers 189

Fig. 2 (a) Topology ptt (pts twisted) net with Schläfli symbol for the net is (4.63.82)2-(42.62.82)
(62.84). (b) Showing the underlying shortest circuits and connectivity in ptt with two tetrahedral and
two square planar nodes

of 2D (4,4) sheet can accommodate guest molecules or solvent molecules (interca-

lation), 2D sheets can align themselves like fingers of folded hands (interdigitation)
as shown in Fig. 3. Batten et al. defined interpenetration occurs when two or more
polymeric networks are not strictly connected but cannot be separated topologically
without breaking of bond. If the network can be separated without breaking the
bonds, then it is interwoven.
Interpenetration has been thought as a negative factor for long time since it reduces
the pore size in coordination polymers. However, recent reports show that interpen-
etration enhances the stability and selectivity of binding guest molecules [27, 28]. The
interpenetrated networks have been shown higher hydrogen uptake compared to the
noninterpenetrated counterpart [29]. This may be due to the reduction of pore size,
which eventually increases the interaction of dihydrogen molecules and wall of the
network. The topology of the interpenetrated networks will be completely different
190 A. M. P. Peedikakkal and N. N. Adarsh

from the parent structure; hence, the properties also changed. To describe a complete
structure of coordination polymeric structure, the topology of the network must be
illustrated with network topology. Batten et al. defined a notation, mD!nD for the
description of entangled networks, where mD represents the dimensionality of the
constituent net, and nD represent the overall entanglement [1d].
Due to their predictable pore size and selective inclusion of guest molecules,
square-grid networks with (4,4) topology have gained special attention
[30]. Zaworotko et al. have described topologically different modes of interpenetra-
tion for (4,4) networks such as parallel/parallel, diagonal/diagonal, and parallel/
diagonal inclined interpenetrations (Fig. 4) [30].
The diagonal/diagonal interpenetration contains windows of sheets with the
nodes of their interpenetrating partners [25a]. The first diagonal/diagonal networks
has been reported by Robson and co-workers in 1990 [4b]. Although diagonal/
diagonal interpenetration is commonly encountered in inclined interpenetration,
exact diagonal/diagonal inclined sheets with connecting at the midpoint of square-
grid sheets are very rare.

Fig. 3 (a) Interpenetration of 3D nets, (b) interpenetration 2D nets, and (c) interwoven of 1D chains

Fig. 4 A schematic representation that demonstrates three modes of inclined interpenetration that
have been found in 2D square grid networks: (a) diagonal/diagonal (b) parallel/parallel, (c) parallel/
diagonal interpenetration [30]. (This figure is reprinted from Ref. [12] with permission. Copyright
2001, American Chemical Society)
5 Porous Coordination Polymers 191

The structural motifs observed with T-shaped connecting nodes are of particular
interest in constructing ladders, brick wall, bilayer, and 3D frameworks [31]. Inter-
penetration of molecular ladders is not very common due to the guest solvent
molecules in the cavities [1e]. Long linear spacer ligands favor the formation of
square-grid networks or tend to favor higher-folded interpenetrated 3D nets
[32]. Despite a few three-fold interpenetrated ladder structures have been reported,
molecular ladders formed by bpe spacer ligand with rigid backbone is not fully
understood [18].

5 Surface Area

The research activities on porous coordination polymers (PCPs) have been intensi-
fied in the past three decades because of the obvious flexibility to control their
structure and property by tuning the organic ligand and proper choice of metal center
[1]. PCPs are usually synthesized under mild conditions by bottom-up approach
[33]. The possibilities of generating new materials with intriguing properties based
on PCPs were initially demonstrated by Robson, Moore, Yaghi and Fujita. In 1990,
Robson et al. reported a PCP that was capable of exchanging anions [4], and later in
1994, Fujita and co-workers demonstrated the catalytic properties of a 2D PCP
[34]. In 1995, the adsorption of guest molecules in porous materials was studied by
Yaghi et al. [35], and in 1997, gas adsorption at ambient temperature was reported by
Kitagawa [36]. Later, contribution by the group of Yaghi on the structure of MOF-5
in late 1999 [37] motivated the interest in the field of PCPs. Surface area is one of the
crucial properties which determine the sorption property of PCPs, which depend on
their pore size, shape and volume. Depending upon the dynamic nature of the
coordination polymer, the deformation of the pore occurs by involving two funda-
mental operations, namely, shrinking and expansion. Based on these observations,
Kitagawa [38] proposed the pore behaviors of PCPs which can be classified into four
types based on the correlation between the pores (shape/size) and guest molecules
(Fig. 5).

1. Induced-fit type pores: The shrinkage occurs on guest molecule inclusion and
gives rise to a pore that is well-suited to the size and shape of the guest molecule,
and therefore, short range attractive interactions work effectively.
2. Breathing type pores: The expansion makes a guest molecule fit tightly into the
host when the size of the pore is smaller than the guest molecule.
3. Guest-exchange deformation type pores: The pore shape is induced to change
responding to guest shape in simultaneous guest exchange.
4. Healing type pores: The collapsed pore in the absence of guest molecules are
regenerated with the guest accommodation.

The specific surface area of the porous structure can be determined by

Brunauer–Emmett–Teller (BET) method. Due to the high surface area of PCPs,
192 A. M. P. Peedikakkal and N. N. Adarsh

Fig. 5 Schematic a
representation of microporous
behaviors observed in + Guest
adsorption/desorption of guest
molecules: (a) induced-fit − Guest
typed pores, (b) breathing
pores, (c) guest-exchanging
open open
pores with deformation, and
(d) healing pores. (This figure
is reprinted from Ref. [38] b + Guest
with permission. Copyright
2005, Elsevier) − Guest

close open
c
Guest
Exchange

open open

d
+ Guest

− Guest

close open

≡ Guests

it tends to have low-density compounds. Some of the early reported PCPs

showed excellent surface area in their porous structure having a surface area in
the range of 4000–6260 m2 g1 (Fig. 6). One of the first innovations in obtaining
MOFs with permanent microporosity was reported by Yaghi et al., who demon-
strated the material, namely, Zn(BDC) (BDC = 1,4-Benzenedicarboxylate),
having a Langmuir surface area of 310 m2/g [39]. Later, the same group synthe-
sized MOF-5, which shows a BET surface area of 3800 m2 g1 [37]. Inspired by
the intriguing results of MOF-5, later a series of MOFs, namely, MOF-177 [40]
and MOF-200, were also synthesized by the self-assembly of Zn4O cluster with
1,3,5-benzenetribenzoate (btb) and 4,40 ,400 -[benzene-1,3,5-triyltris(benzene-4,1-
diyl)]tribenzoate (bbc), respectively; both MOF-177 [40] and MOF-200 [41]
also showed high porosity having a BET surface area of 4746 and
6260 m2 g1, respectively.
Interpenetration is one of the intrinsic challenges of PCPs [42], as their pores were
blocked by the coordination networks. In order to get rid of from this problem,
5 Porous Coordination Polymers 193

bdc btb bbc

MOF-5

MOF-177
MOF-200

Fig. 6 Crystal structures of MOF-5, MOF-177, and MOF-200. Note the lengthening of the linkers
and the increased size of the yellow sphere representing free pore space. (This figure is reprinted
from Ref. 37, 39, 40] with permission. Copyright 1999 and 2004, Nature Publishing Group, and
2010, American Association for the Advancement of Science)

judicious choice of ligand and metal ion are important. Bai and co-workers reported
a mesoporous MOF, namely, {[Zn (BCP)H2O]3.5H2ODMF}n (where BCP = 3,5-
bis[4-carboxyanilino-carbonyl]pyridine and DMF = N,N-dimethylformamide), also
called as NJU-Bai9 [43]. In fact NJU-Bai9 exhibits a three-dimensional
(3D) structure having Archimedean-solid-type cages and the structure is highly
mesoporous in nature. The mesoporous structure undergoes interpenetration with
pbz topology. Interestingly, NJU-Bai9 exhibits unprecedented breaking edges off
truncated cuboctahedral cage structure in which the coordination network assembled
into a 3D network (Fig. 7).
BET surface area analysis of NJU-Bai9 revealed its uptake of H2, CH4, and
CO2 with a surface area of 4258 m2 g1 which is the highest surface area among
the interpenetrated porous MOFs reported to date. Many efforts for even better
surface area were carried out by various research groups, despite the daunting
task to achieve it due to the tendency of these materials to collapse upon removal
194 A. M. P. Peedikakkal and N. N. Adarsh

Fig. 7 (a) Edge breaking off

in NJU-Bai9; (b) overall
packing of NJU-Bai9
displaying the four various
types of cages, even after
interpenetration. (This figure
is reprinted from Ref. [43]
with permission. Copyright
2013, Wiley-VCH Verlag)

of lattice occluded solvent molecules [44]. Two MOFs, namely, MOF-210 [45]
and NU-100 [46] (NU = Northwestern University; NU-100 is also known as
PCN-610 [47]), were reported by Farha et al., which show large cavity structure
(surface area > 6000 m2 g1) and robustness even after evacuating the guest
molecules. Recently, Farha and co-workers reported two MOFs, namely, NU-109
and NU-110, derived from two hexacarboxylic acid ligands (Fig. 8), which
showed the highest experimental BET surface areas of any porous materials
reported to date (7000 m2 g1). In the same work, they showed computationally
that by simply changing phenyl groups with “space efficient” acetylene func-
tionalities as linker expansion units, the hypothetical maximum surface area for a
MOF material is substantially greater than previously envisioned (14,600 m2 g1
(or greater) versus 10,500 m2 g1).
5 Porous Coordination Polymers 195

Fig. 8 Top – the hexacarboxylic acid ligands; down – crystal structure of NU-109 and NU-110,
displaying the various cages (shown in purple color). (This figure is reprinted from Ref. [52c] with
permission. Copyright 2012, American Chemical Society)

6 Gas Storage

Porous materials were explored by various groups for gas storage application. For
example, activated carbon and zeolites have been widely investigated due to easy
availability, cheap, and nontoxic nature. Despite of its positive aspects, these porous
materials do not exhibit enough gravimetric and volumetric storage capacity due to
their relatively weak interactions with adsorbate gas molecules [48a]. In fact the
adsorption enthalpies within these materials are significantly less than 15
to 20 kJ/mol, an ideal storage capacity at ambient temperature and 100 bar [48b].
Interestingly, MOFs or PCPs have been emerged as smart materials to overcome the
aforementioned problems to some extent. Due to the comparable size of gas molecules
with the host microporous compounds having a pore size of nanometer scale,
196 A. M. P. Peedikakkal and N. N. Adarsh

PCPs or MOFs has been developed as an efficient material to entrap or adsorb gas
molecules, which plays a crucial roles in modern gas technology [48c].
The gas adsorption application of PCPs was first reported by Kitagawa
and co-workers, exploring a three-dimensional framework built from 4,40 -bpy =
4,40 -bipyridine and M(II) = Co, Ni, Zn [36]. Later, owing to their intrinsic property
of porosity and tunability (by changing the metal node and organic liker), PCPs/
MOFs were already proved as an ideal candidate for gas storage application [20].
A wide variety of isoreticular MOFs were reported by Yaghi, by modifying their
structure, pore size, and functional groups of organic linkers [21]. The thermody-
namic and kinetic aspects of sorption behavior are very important factors to be
considered while designing new PCPs for selective gas adsorption or separation.
One of the most crucial factors affecting the gas storage property of PCP is the size of
their pore. In fact, once the pore size become equivalent to the molecular size of the
gaseous molecules, the adsorption energy potential increases due to the overlapping
of energy potentials from the surrounding walls. As a result, the guest gas molecules
tend to strongly bind to the framework of PCPs [49]. In the following section, we
discuss the H2, CH4, and CO2 storage application of PCPs or MOFs.

6.1 Hydrogen Storage

Hydrogen is one of the intriguing fuel gases which is used as an excellent energy
source [50]. Among various hydrogen storage materials such as metal hydrides
[51a], carbohydrates [51b], clathrates [51c], and nanotubes [51d], PCPs or MOFs
have attracted considerable interest because of their diverse structure, extraordinarily
high surface areas (experimental value of up to 7140 m2 g1, against theoretical limit
of 14,600 m2 g1), ultrahigh porosity (up to 90% free volume), tunable pore size,
and adaptable internal surface [52]. One of the first MOFs investigated for hydrogen
storage was the cubic carboxylate-based framework MOF-5, which showed a
hydrogen gas uptake of 4.5 weight % at 78 K and 1.0 weight % at room temperature
and pressure of 20 bar [53a]. Secondly, Férey and co-workers reported two MOFs
derived from 1,4-benzenedicarboxylic acid and Al3+, Cr3+; these MOFs showed a
hydrogen adsorption capacity of 3.8 and 3.1 wt.%, respectively when the sample
loaded at 77 K under 1.6 MPa [53b]. Motivated from these seminal results of MOF-5
by Yaghi et al., and MOFs developed by Férey et al., many research groups gave
dedicated efforts for the investigation of H2 storage in MOFs at low temperature and
room temperature [54]. Later, MOF-5 has been explored by many research groups.
One of the first studies exhibited an excess gravimetric uptake of 1.3 wt% at 1 bar
66 and 5.1 wt% at 50 bar at 77 K [55]. Interestingly, it was later proved that the
method of synthesis and activation of MOF-5 sample is one of the crucial factors for
the successful H2 sorption capability; Langmuir surface areas range between 1010
and 4400 m2 g1 and H2 uptake capacity vary accordingly.
In fact, the research of MOFs for hydrogen sorption application emphasizes on
various approaches for the design and synthesis of MOFs to increase the hydrogen
storage capacity as much as possible, in order to achieve greater gravimetric and
5 Porous Coordination Polymers 197

volumetric storage capacity. These approaches depends on various parameters such

as (1) H2 adsorption condition (pressure and temperature), (2) inclusion of reducing
agents in the MOF, (3) effect of structural defect in MOF, and (4) effect of adsorption
sites in the MOF structure. Hereafter we will discuss the hydrogen storage applica-
tion of MOFs according to these parameters.

6.1.1 H2 Adsorption Condition (Pressure and Temperature)

Various research groups have investigated the effect of adsorption condition of a
particular MOF on their H2 storage capacity. For example, MOF-177 exhibits a
maximum storage of H2 at temperature 77 K and pressure 100 atm [40]. Interestingly,
Deng et al. synthesized MOF-177 by following a modified method and the resultant
material showed a hydrogen saturation uptake of 11.0 wt% at about 100 atm and
77 K. Freundlich isotherm model correlation plot revealed that the absolute amount
of hydrogen adsorbed in MOF-177 at these conditions is about 19.67 wt% (Fig. 9).
The reason behind the more hydrogen uptake is the high surface area (5994 m2 g1)
of MOF-177 synthesized by Deng et al. [56].

6.1.2 Inclusion of Reducing Agents in the MOF

Yang and Li reported the synthesis of a modified form of MOF, which showed
greater hydrogen binding within their porous framework [57], constructed by intro-
ducing the phenomena “hydrogen spillover” [58] by following two methods: (1) by
mixing the individual components such as IRMOF-8 and Pt/AC mixture and syn-
thesize a modified MOF, namely, Pt/AC/IRMOF-8, and (2) by bridging the Pt/AC
with IRMOF-8, namely, Pt/AC-bridges-IRMOF-8, where AC = activated carbon.
Thus by the inclusion of reducing agents Pt/AC, Pt performs as a catalyst and
participates in the reduction of H2 or spillover of H2 into hydrogen atoms and finally
increases the hydrogen storage in MOFs. This study revealed the importance of

Fig. 9 Hydrogen adsorption 20

plot of MOF-177 at high
18
pressure and 77 K, displaying
H2 Adsorption Amount (wt.%)

the excess, absolute, 16

Langmuir and Freundlich
14
adsorption. (This figure is
reprinted from Ref. [56a] and 12
[56b] with permission.
10
Copyright 2008, Elsevier Ltd.,
and Copyright 2005, Wiley- 8
VCH Verlag) Excess Adsorption
6
Absolute Adsorption
4
Langmuir model
2 Freundlich model
0
0 20 40 60 80 100
H2 Pressure (bar)
198 A. M. P. Peedikakkal and N. N. Adarsh

spillover for the hydrogen storage using MOFs. The Pt/AC/IRMOF-8 and
Pt/AC-bridges-IRMOF-8 showed a reversible H2 uptake of 1.8 wt % and 4.0 wt %,
respectively at room temperature and 10 atm pressure. Interestingly, the modified
forms of IRMOF-8 showed a spillover enhancement factors for hydrogen storage of
3.1 and 6.8 times more than the original form of IRMOF-8 (Fig. 10). These results
gave motivation to the materials chemist researchers for the development of other
MOFs by spillover and concomitant capacity enhancement of the modified MOFs.

6.1.3 Effect of Structural Defect in MOF

It is well-known that the kinetic diameter of the porous material must be within the
rage of the kinetic diameter 2.89 Å, for a successful H2 adsorption material. This is due
to the fact that as the diameter having a pore size of more or equal to 2.89 Å is essential
for the passage of hydrogen molecules through the MOF material [59]. Various
research groups investigated to tune the pore size of the MOFs within this range and
some groups focused on the effect of defects for the same case, which makes the

Fig. 10 (a) Primary spillover

of hydrogen atom supported
by Pt and activated carbon
(top), primary and secondary
spillover resulted from carbon
(shown in dark color)
(bottom); (b) hydrogen
adsorption and desorption
isotherms at 298 K, of pure
IRMOF-8, Pt/AC, and
IRMOF-8 physical mixture.
(This figure is reprinted from
Ref. [57b] with permission.
Copyright 2006, American
Chemical Society)
5 Porous Coordination Polymers 199

hydrogen molecule to adsorb on the MOF matrix via physisorption at low pressure and
ambient temperature [60]. Bai et al. [61] and Feng et al. [62] demonstrated the synthesis
of defected MOFs with the incorporation of micro- and mesopores and its capability of
improved H2 adsorption than the nondefected counterpart. Ren et al. studied the structural
defects in core-shell MIL-101(Cr)@UiO-66(Zr) by comparing with the parent Zr-based
MOF, UiO-66(Zr) [63]. The organic compounds [1,4-benzenedicarboxylic acid (BDC)
linker and modulator (HCOOH)], especially the modulator and time of the reaction,
played a crucial role for the formation of defects in the parent MOF UiO-66(Zr), which
lead to the formation of core-shell MIL-101(Cr)@UiO-66(Zr). Longer synthesis time
facilitated to the formation of larger crystals and the presence of the modulator promotes
defects in the MOF. Interestingly, the defects created on the MOF structure of UiO-66(Zr)
enhanced the diffusion of H2 and thus store more H2.
More recently, Erkartal and Sen explored boronic acid functionalities into UiO-66
and thus examine the effect of structural defects on the H2 adsorption behavior [64]. In
order to compare the H2 sorption behavior of pure parent MOF UiO-66 and defect-
induced (with boronic acid) MOF, namely, UiO-66B, both MOFs were synthesized
separately via hydrothermal synthesis method. The UiO-66B having various stoichio-
metric ratios (BDC/CPB ratios from 0.87:0.13 to 0.50:0.50) of the ligands
1,4-benzenedicarboxylic acid (BDC) and 4-carboxyphenylboronic acid (CPB) were
synthesized (Fig. 11a) in the presence and absence of HCl and characterized by powder
X-ray diffraction (PXRD). The stoichiometric ratios of BDC/CPB present in various
samples of UiO-66B were further characterized by proton nuclear magnetic resonance
spectroscopy (1H NMR) and X-ray photoelectron spectroscopy (XPS). The
as-synthesized UiO-66Bs having boronic acid functionality showed higher BET sur-
face area (BDC:CPB = 0.25:0.75, BET surface area of 1512 m2/g) and facilitate
considerably the hydrogen uptake, 3.44 wt% at 21 bar, 77 K (Fig. 11b) than the pure
phase of UiO-66 (BET surface area 1361 m2/g and 2.38 wt% H2 uptake). Interestingly,
UiO-66 exhibits fully reversible isotherm whereas UiO-66B samples showed hysteric
adsorption. This unprecedented result is due to the replacement of coordination envi-
ronment form fully occupied (UiO-66) to partially occupied coordination sites in UiO-
66B, which gave more flexibility to the defected MOF (UiO-66B).

6.1.4 Effect of Adsorption Sites in the MOF Structure

In order to understand the mechanism of adsorption in the MOF structure, Yaghi and
co-workers studied the inelastic neutron scattering experiment on the H2 adsorbed
MOFs. This study confirmed that both the metal-oxide clusters and the ligand units
are responsible for the adsorption sites for hydrogen molecules [53a]. Later, a series
of reports were published by various research groups, illustrating the hydrogen
storage enhancement by simply replacing the metal ions (for example, Zn2+ with
other similar metal ions, such as, Mg2+, Ni2+,or Cu2+) or organic linkers [57a]. Zhou
et al. demonstrated that the presence of open metal sites in the MOFs have more
tendency to attract the hydrogen molecule and facilitate to store H2, with the support
of experimental and computational evidence [65]. Postsynthetic functionalization of
MOF, based on conversion of pendant alcohols to metal alkoxides, was explored by
Karen and co-workers for better adsorption of H2 [66].
200 A. M. P. Peedikakkal and N. N. Adarsh

Fig. 11 (a) Schematic a HO

O
representation for the HO
O O

OH
synthesis of UiO-66 and ZrCl4 + ZrCl4 + +

OH
O

HO
defect-induced MOF,

OH

B
UiO-66B; (b) hydrogen
O

HO
uptake isotherms of UiO-66-
HCI and UiO-66B-HCI at
high pressure and 77 K. (This
figure is reprinted from Ref.
[64] with permission.
Copyright 2018, American
Chemical Society)

UIO-66 UIO-66B
b Zr SBU
4.0
DMF/HCl
Gravimetric H2 Uptake (wt %)

3.5

3.0

2.5

2.0
77 K
1.5
BDC:CPB
1:0
1.0 0.75:0.25
0.50:0.50
0.25:0.75
0.5
0 10 20 30 40 50 60
Pressure (bar)

A thermally stable porous MOF derived from Ytterbium and 1,3,5-

benzenetricarboxylate (BTC) and its unprecedented H2 adsorption property was
reported [67]. In order to understand the mechanism of interaction of H2 on the
Yb-BTC framework, powder neutron diffraction experiment was carried out. The
diffraction data revealed that optimal pore size (6 Å) of the framework reinforces
between the H2 molecule and pore walls, which resulted in the H2 adsorption. Thus it
is confirmed that in this case of MOF, the interaction is between H2 and the pore
walls, not with the open metal sites within the framework. There are four D2
adsorbing sites found within the framework of Yb-MOF (Fig. 12).

6.2 Methane Storage

Methane is one of the important components of natural gas, and primary concerned
fuel due to its potentiality of environment friendliness, compare to other
5 Porous Coordination Polymers 201

Fig. 12 Structure of Yb-BTC

MOF, displaying the two
distinct adsorption sites of H2
(shown in green and orange
ball). (This figure is reprinted
from Ref. [67] with
permission. Copyright 2008,
American Chemical Society)

components. Methane is the first member of saturated hydrocarbon having least

number of carbon atoms and more number of hydrogen atoms, and as a result, it
exhibits greater octane number. Moreover, combustion of methane yields least
amount of CO2 as the byproduct for each unit of energy released from vehicles.
Therefore, it is important to use methane as the fuel gas because of the climate
change issue and economy concern. One of the primary and important challenges of
the environmental scientists and engineers is to find a best solution to replace petrol
with the methane as the fuel for vehicles. In the current scenario, methane is stored as
compressed natural gas (>200 atm), in cylinder, which is quite expensive. There-
fore, serious efforts were explored by researchers to discover an alternative storage
method by using adsorption phenomena on a porous solid compound at low pressure
and ambient temperature. In order to attain the practical application of methane
storage in vehicles, the U.S. Department of Energy (DOE) has fixed a targeted goal
for methane storage at 180 v/v at STP for the adsorbent material [68]. PCPs or MOFs
already showed a reasonable uptake of methane at 298 K and lower pressure [69].
Kitagawa et al. reported the first functional coordination polymer CuSiF6(4,40 -
bipyridine)2, which showed remarkable methane adsorption [70]. In the crystal
structure, Cu(II) metal center exhibits distorted octahedral geometry, in which the
equatorial and axial positions are occupied with 4,40 -bipyridine and counter anion
SiF62. Interestingly, the extended coordination of both equatorial and axial ligands
resulted in a three-dimensional (3D) porous structure with square shape channels
(8  8 Å2) and exhibited very good methane adsorption property than zeolite 5 Å,
under low pressure (0–36 atm) and room temperature (Fig. 13).
Yaghi and co-workers self-assembled a series of nanoporous isoreticular MOFs
(IRMOFs) having an open space of up to 91.1% of the crystal volume and homo-
geneous square shape channels within the range of 3.8 to 28.8 Å [71]. Interestingly,
IRMOF-6 derived from BDC with cyclobutyl functionality showed exceptionally
202 A. M. P. Peedikakkal and N. N. Adarsh

a b

c 7

6
[[CuSiF6(4,4’-bpy)2]n]
5

3 Zeolite 5A

A,l
mmol g-1 2

0
0 5 10 15 20 25 30 35 40
P l atm

Fig. 13 (a) Coordination geometry of Cu(II) in CuSiF6(4,40 -bipyridine)2, displaying the equatorial
and axial coordination of 4,40 -bipyridine and SiF62, respectively. (b) 3D porous structure of
CuSiF6(4,40 -bipyridine)2, along the crystallographic axis “c.” (c) Methane adsorption of
CuSiF6(4,40 -bipyridine)2 and zeolite 5 Å at various pressure. (This figure is reprinted from Ref.
[70] with permission. Copyright 2000, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)

high methane storage capacity having 240 cm3 at standard temperature and pressure
per gram at 36 atm and ambient temperature. This result is a breakthrough in the
research of methane storage application of MOF, because the methane uptake of
IRMOF-6 is much more than other well-known crystalline materials like zeolite 5 Å
(87 cm3 (STP)g1) [72] and other coordination compounds (until 213 cm3 (STP)
g1) [73].
Zhou and co-workers synthesized a MOF, namely, PCN-14, derived from car-
boxylate ligand having anthracene backbone [74]. The single crystal X-ray structure
analysis of PCN-14 confirmed the presence of cuboctahedral nanoscopic cages, in
the structure. The crystal structure exhibits a void volume of 1150 Å3 having capable
5 Porous Coordination Polymers 203

for uptake of gas molecules. The BET surface area measurement of PCN-14 further
revealed its porous structure having a surface area of 2176 m2/g and pore volume of
0.87 cm3/g. Interestingly, PCN-14 displays an absolute methane adsorption capabil-
ity of 230 v/v [74], which is much greater than (28% more) than the DoE fixed goal
(180 v/v) (Fig. 14) [68]. And PCN-14 is the first member of MOFs which come
across the target of DoE. This unprecedented methane adsorption behavior of
PCN-14 is due to two structural features such as (1) the anthracene backbone present
in the ligand presumably participates in the intermolecular interaction with the
methane molecules and thus binds strongly with the framework and (2) the size
and shape of the nanopores present in the PCN-14 are almost ideal for various
interactions between the CH4 molecules and the host framework.
The observation of coordinatively unsaturated Cu ions present in PCN-14
inspired Wu and co-workers to study the effect of unsaturated metal sites in the
MOFs on their methane uptake capacity [75]. The effect of open metal sites on the
binding strength of H2 is already discussed (vide supra) by various research groups
[65–67]. Thus Wu et al. selected a series of isostructural M2(dhtp) [M: open
metal = Mg, Mn, Co, Ni, Zn), dhtp = 2,5-dihydroxyterephthalate] MOFs because
of the presence of open metal sites in the crystal structure of these series. Moreover,
these isostructural series have significantly higher densities of open metal sites in
their crystal structures (4.5 sites/nm3) than PCN-14 (1.6 sites/nm3). The single

Fig. 14 3D porous structure of PCN-14, displaying (a) cuboctahedral net, (b) space-filling model
on the [1 0 3] plane. (This figure is reprinted from Ref. [74] with permission. Copyright 2008,
American Chemical Society)
204 A. M. P. Peedikakkal and N. N. Adarsh

crystal X-ray structure of M2(dhtp) revealed their porous structure with large
one-dimensional (1D) channels having pore diameter of 13.6 Å, and such structure
can be utilized for methane gas uptake. From the methane adsorption isotherms of
the isostructural series, it is revealed that Ni2(dhtp) exhibits the highest absolute
methane uptake (200 cm3(STP)/cm3) and known as the second member of MOFs
to potentially exceed the DOE’s targeted goal. Neutron diffraction experiment
analysis revealed that there are two CH4 adsorption sites in the crystal structure
and the CH4 molecules interact with the open metal sites via intermolecular inter-
actions. Moreover, initial first-principles calculations of this molecular system
displayed that the binding energies associated with the CH4 on the open metal
sites are higher than the MOFs having characteristic adsorption sites reported so
far (Fig. 15).
A 3D porous MOF, namely, UTSA-20, was reported by Chen et al. and are
synthesized via coordination-driven supramolecular assembly of paddle-wheel Cu2-
(COO)4 SBU and a hexacarboxylate organic linker H6BHB (H6BHB = 3,30 ,300 ,5,50 ,500 -
benzene-1,3,5-triylhexabenzoic acid) [76]. The 3D structure of UTSA-20 was
determined by using high resolution PXRD data, which helped to refine the crystal

Fig. 15 (a) Crystal structure

of Mg2(dhtp), displaying the
adsorption of methane at two
distinct sites (shown in
orange-white and blue-white
ball and stick model). (b) The
CH4 adsorption isotherm plots
on M2(dhtp), displaying the
highest uptake of CH4 by Ni
derivative of the series. (This
figure is reprinted from Ref.
[75] with permission.
Copyright 2009, American
Chemical Society)
5 Porous Coordination Polymers 205

structure. The structure analysis revealed that the extended coordination of paddle-
wheel Cu2-(COO)4 SBUs with the BHB linkers, resulted in a 3D porous architecture
having a novel “zyg” topology involving two kinds of three-coordinated nodes and a
four-coordinated paddlewheel Cu2(CO2)4 cluster (as shown in Fig. 16a). Interestingly,
the crystal structure consists of two type of channels having a rectangular (3.4  4.8 Å)
and a cylindrical (8.5 Å) shape, along the c’ axis with a total accessible free volume of
3471.0 Å3, or 63.0% of the unit volume 5512.9Å3. Such kind of porous MOF involving
open metal (Copper in UTSA-20) sites and enough pore size are crucial factors for the
binding of CH4 molecules in the framework. Nitrogen sorption isotherm at 77 K on the
activated sample of UTSA-20 revealed the type I reversible sorption isotherm and
moderate porosity, corresponding to a BET surface area of 1156 m2 g1 (Fig. 16).
Despite of the moderate porosity and surface area exhibited by UTSA-20, compared to
other well-known MOFs, the presence of open copper sites and optimal pore spaces
helped UTSA-20 to achieve a high density methane storage (0.222 g cm3) and listed
to third position in absolute volumetric methane storage, among other MOF materials
such as PCN-14, Ni2(dhtp), IRMOF-6, etc.
Snurr et al. demonstrated a computational approach to find out the best MOFs
(known or unknown) for a particular application, for example, methane storage

Fig. 16 (a) Crystal structure illustration of UTSA-20, displaying the SBU and 3D porous structure
with augmented zyg net topology. (b) N2 adsorption isotherm of UTSA-20 at 77 K. (c) CH4
adsorption isotherm of UTSA-20 at variable temperature and high pressure. (This figure is reprinted
from Ref. [76] with permission. Copyright 2011, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim)
206 A. M. P. Peedikakkal and N. N. Adarsh

capacity of a MOF [77]. They selected a library of 102 building blocks of MOFs,
generated 137,953 hypothetical MOFs from these selected building blocks, and
finally calculated the pore size, surface area, and methane storage capacity of each
MOFs by computational method. Among these MOFs, 300 showed very good
methane uptake capacity than the MOFs reported so far. Interestingly, methyl
functionalized ligands (building block) showed very good methane adsorption
capability.
Zhang et al. engineered a series of mesoporous MOFs UMCM-1, MOF-205,
MUF-7a, and the newly synthesized MOFs, termed ST-1, ST-2, ST-3, and ST-4
(ST = ShanghaiTech University), and demonstrated the importance of tuning of
mesoporosity for the successful design and synthesis of new MOFs for methane
storage application at ultrahigh pressure [78]. All mesoporous MOFs were synthe-
sized from Zn4O(COO)6 by mixing with tritopic linkers and ditopic linkers
(Fig. 17). Interestingly, one of the mesoporous MOFs, namely, ST-2, exhibit excel-
lent capacity of methane uptake (289 cm3 STP/cm3 (567 mg/g) at 298 K and
5–200 bar), which is the highest record to date.

6.3 Carbon Dioxide Storage

The emission of CO2 from industrial waste, mainly from coal-fired power plant, oil,
and natural gas, is one of the issues facing by the environmental concern due to
climatic change [79]. The coal-fired power plant produces post-combustion flue
gases having a concentration of ~15% CO2. Moreover, a recent investigation
revealed that average concentration of CO2 emission to earth reached 406.75 parts
per million (ppm) in January, 2018 [80]. This is mainly due to the contribution from
human activities in the past decades. Thus, various research groups have contributed
different approaches to find a good solution to solve the problem of CO2 such as
(1) by cooling and forcing power plant emission and convert CO2 to CaCO3 by using
lime water and (2) by passing the fumes through aqueous amine solution. These two
methods are very expensive and incompetent [81]. Several porous materials were
explored to capture and store CO2 by chemisorption and physisorption [82]. Among
these porous materials, MOFs or PCPs show very high CO2 storage ability even at
ambient temperature and pressure, due to their capability for adsorption of gases via
physisorption, and tunability of their structure [83].
One of the first results of CO2 adsorption property of MOFs was reported by
Yaghi et al. They explored a series of nanoporous MOFs, such as MOF-2, MOF-505,
MOF-74, Cu3(BTC)2, IRMOF-11, IRMOF-3, IRMOF-6, IRMOF-1, MOF-177, and
systematically study their gravimetric uptake of CO2 [84]. From the room-
temperature CO2 adsorption isotherms of these MOFs, it is clear that the MOFs
having open metal sites in their framework showed type I isotherm with high uptake
of CO2 at low pressure. In contrast to this result, MOFs with Zn4O(O2C)6-type
frameworks, such as IRMOFs-1, -3, -6, and, -11, exhibit sigmoidal shape isotherms
with high uptake of CO2 at ambient pressure. The amine functionalized IRMOF-3 is
more attracted towards CO2 uptake, compared to others, due to the nonbonded
5 Porous Coordination Polymers 207

Fig. 17 Schematic representation of the synthesis of MOFs derived from Zn4O(COO)6 and
tritopic linkers/ditopic linkers. (This figure is reprinted from Ref. [78] with permission. Copyright
2017, American Chemical Society)

interaction of adsorbed CO2 with the –NH2 group of the framework. Interestingly,
the comparison of volumetric CO2 uptake data of MOF-177 with other well-known
CO2-capturing materials like zeolite 13X and Maxsorb revealed that MOF-177 can
uptake nine times more CO2 relative to an adsorbent-free container and about two
times more than that of zeolite 13X and Maxsorb at 35 atm. These remarkable results
of CO2 storage capacity of MOFs indicate the importance of MOFs to represent a
strong candidate for the capturing of CO2 from coal-fired power plants and exhaust
208 A. M. P. Peedikakkal and N. N. Adarsh

gases. Later, the same research group explored the possibility of Zeolitic imidazolate
frameworks (ZIFs) to mimic Zeolite behavior for adoption and retention of CO2 and
discovered that the ZIFs showed unprecedented selectivity for CO2 from a mixture
of other gaseous molecules. One liter of ZIF-69 showed a capacity to store and
sustain 83 liters of CO2 at 273 K and ambient pressure [85].
In fact, there are several factors which effect on the successful adsorption capacity
of CO2 on MOFs, which are discussed below.

6.3.1 The Effect of Open Metal Sites in the MOF

The coordination environments in some of the MOFs become unsaturated, once the
loosely bound solvent molecules escape from the metal ions, when we activate the
MOF crystals by heat or vacuum. For example, M-MOF-74 series derived from the
ligand 2,5-dihydroxyterephthalic acid and metal ion (M = Mg, Co, Fe, Zn, Ni) have
very high density of open metal sites [86]. Among these series, Mg-MOF-74 showed
the best record of CO2 capture of 228 cm3/g at 273 K, 180 cm3/g at 298 K and 1 atm.
The reason behind such unprecedented CO2 uptake of Mg-MOF-74 than other metal
series of MOF-74 is due to the fact that the more ionic behavior of Mg–O bond in
Mg-MOF-74 helps the CO2 molecule to bind to the framework more strongly
(Fig. 18).
Thus, the result of Mg-MOF-74 showed the importance of main group elements
in designing new high-performance gas sorption materials, than that of the transition
metals. Inspired by this thought, Zhai and co-workers developed a series of mixed-
metal isostructural MOFs, namely, CPM-200, having a combination of trivalent
(In3+, Ga3+, Fe3+, V3+, Sc3+) and divalent (Mg2+, Mn2+, Co2+, Ni2+) metal ions, by
using heterometallic cooperative crystallization (Fig. 19a) [87]. The idea behind
such an attempt may be due to the fact that the presence of different metal contents
(as nodes) lead to defects in the resultant MOFs, and such defects may influence the
CO2 sorption capacity. The crystal structures of these MOF series were determined
by single-crystal X-ray diffraction and the phase purity was confirmed by PXRD
technique. The stoichiometric ratio between M2+ and M3+ was determined by site
occupancy refinement and further supported by energy dispersive X-ray analysis
(EDS) analysis. Interestingly, CPM-200-Fe/Mg showed significant CO2 uptake
(9.27 mmol/g at 273 K and 1 bar) which is the best among the other trimer based
and other heterometallic MOFs under the same conditions. Moreover, the CPM-200-
V/Mg exhibits the highest isosteric heat of adsorption (79.6 kJ/mol) for CO2
binding, compared to other MOFs with Lewis acid sites.
HKUST-1 is another example of MOF having high density of open metal sites,
which was synthesized from Cu paddle-wheel SBU and terephthalic acid. The
solvent DMF coordinated to the Cu metal center in HKUST-1 can be easily removed
by ethanol/NH4Cl solvent exchange, and the resultant activated (with open metal
site) showed excellent CO2 uptake 7.5 mmol g1 at 1 bar and 298 K [88]. Various
research groups further established the importance of open CuII sites to the enhance-
ment of CO2 adsorption capacity [89]. Outstanding CO2 volumetric uptake observed
in rare earth (RE) MOFs is due to the localized charge density induced by the
presence of high nuclear clusters [90].
5 Porous Coordination Polymers 209

Fig. 18 (a) Crystal structure of M-MOF-74 (where M = Mg, Co, Fe, Zn, Ni), displaying 1D
channels (left). Porous structure of Mg-MOF-74 (space-filling model), displaying the adsorption of
CO2 molecules (blue color) (right). (b) CO2 adsorption isotherm of M-MOF-74 series at 296 K and
various temperatures (0 to 1 atm). Inset – low pressure range (0 to 0.1 atm). Adsorption and
desorption plots are shown in filled and open marks, respectively. (This figure is reprinted from Ref.
[86] with permission. Copyright 2008, American Chemical Society)

6.3.2 The Effect of the Pore Size and Surface Area of the Framework
The pore size and surface area of the MOFs also play a crucial factor for the CO2
adsorption capacity, along with the presence of open metal sites. It is worthwhile to
mention here that there are examples of MOFs (PCN-61, PCN-66 and PCN-68) [91]
with open metal sites which showed very less CO2 adsorption at low pressures.
These MOFs [92] are built from huge dendritic hexacarboxylic acids ligands and
showed rht-type topology or (3,24)-connected nets with mesoporous cages in their
structure and exhibit very high surface areas. In fact, despite of their mesoporous
structure, they did not show any reasonable CO2 adsorption capacity at low pressure.
210 A. M. P. Peedikakkal and N. N. Adarsh

Fig. 19 (a) Heterometallic

a M3+
cooperative crystallization of
CPM-200 MOF series e C
Cr oop
tiv M2+
involving trivalent divalent ra ion M2+ ys er
o pe lizat ta at
l lliz ive
metal ions and bis-pyridyl Co sta at
y ion
Cr charge neutral
ligand. (b) CO2 adsorption [M2+2M3+ (OH)(COO)6]
isotherms of In/M MOF M3+ M2+
(CPM-200) series Sc3+
(M = Mg+2, Co+2, Mn+2, Mg2+
V3+
Ni+2). (c) CO2 adsorption Mn2+
Mg2+ Fe3+ In3+
isotherms of M/Mg MOF Co2+
Ga3+
(CPM-200) series (M = Fe3+, Ni2+
In3+
In3+, V3+, Ga3+, Sc3+). (This
figure is reprinted from Ref.
[87] with permission.
Copyright 2016, American
Chemical Society) b 200
In/Mg
180 In/Co
In/Mn 273 K
160
CO2 uptake (STP,cm3/g)

In
In/Ni
140
120
100
80
60
40
20
0
0 100 200 300 400 500 600 700 800
Pressure (Torr)
c 220
Fe/Mg
200 In/Mg
273 K
V/Mg
CO2 uptake (STP,cm3/g)

180 Ga/Mg
160 Sc/Mg

140
120
100
80
60
40
20
0
0 100 200 300 400 500 600 700 800
Pressure (Torr)

Thus, with the intention to improve the CO2 adsorption capacity of these kind of
mesoporous MOFs, Zaworotko and co-workers designed a flexible C3-symmetric
hexacarboxylate ligand with acylamide functionality and built the MOF, namely,
Cu3(TPBTM), with open metal sites, which is isostructural with PCN-61 derived
5 Porous Coordination Polymers 211

from hexacarboxylate ligand with alkyne groups: TPBTM = N,N0 ,N00 -tris(iso-
phthalyl)-1,3,5-benzenetricarboxamide [93]. The single crystal X-ray structure anal-
ysis of Cu3(TPBTM) revealed the structure consists of three polyhedra
[cuboctahedron (cub-Oh), truncated tetrahedron (T-Td), and truncated octahedron
(T-Oh)] packed in a 1:2:1 ratio. The thermal and crystal phase stability of
Cu3(TPBTM) was confirmed by using PXRD and thermogravimetric analysis
(TGA); the material showed stability until 300  C. The high surface area
(3570 m2 g1) and large pore volume (1.268 cm3 g1) of Cu3(TPBTM) MOF
prompted the authors to perform CO2 adsorption experiment. The gas adsorption
(CO2 and N2) isotherm data at 298 K and various pressure (0 to 20 bar) revealed the
unsaturation excess CO2 uptake of Cu3(TPBTM) MOF (23.53 mmolg1), which is
lower than that of MOF-177 (28 mmolg-1) [84] under the same experimental
conditions. Moreover, Cu3(TPBTM) MOF showed excellent volume of CO2
adsorbed per volume of sample (330 v/v), which is almost near to MIL-101 (330 v/
v at 50 bar and 304 K) [94]. From the ligand structures (TPBTM and BTEI), it is
known that the difference between Cu3(TPBTM) and PCN-61 is the replacement of
the acetylene moiety in PCN-61 with an amide moiety in Cu3(TPBTM). In order to
get a better understanding of this functionality difference, coverage-dependent iso-
steric heats of CO2 adsorption (Qst) for Cu3(TPBTM) and PCN-61 was calculated
separately. It is observed from this data that the adsorption enthalpy for Cu3(TPBTM)
is high (26.3 kJ/mol) at zero load of CO2, indicates strong CO2 interaction with the
framework, and decrease to 23.4 kJ/mol at 15 mmolg1. On the other hand, the Qst
for PCN-61 is much lower than Cu3(TPBTM). This difference in the values of Qst of
Cu3(TPBTM) and PCN-61 may be due to the fact that the amide groups (-CONH)
having more dipole moments lead to the dipole-quadrupole interactions between
acylamide groups in Cu3(TPBTM) and CO2, and N-H. . .O hydrogen bonding
involving amide and CO2 (Fig. 20).

6.3.3 Effect of Doping Metals

The metallic doping on MOFs and its consequential effect on CO2 adsorption
capacity was first demonstrated by Botas et al. by taking MOF-5 as the precursor
MOF. The doping of Co on MOF-5 resulted in the doped MOF-5, namely,
Co-MOF-5, which showed higher adsorption of CO2 than that of the parent
MOF-5 [95]. Postsynthetic exchange of a metal ion with another is a well-known
method in MOF chemistry (for example, exchange of Zr with Ti ions) to build up or
enhance any application-related property of MOFs [96]. In fact, the small size of Ti
ions assist to decrease the pore size of the framework and bring to ideal size for CO2
uptake, and further boost the CO2 uptake of Ti exchanged with Zr in UiO-66. Lau
et al. explored this approach in the famous Zr-based MOF, namely, UiO-66, in order
to increase their CO2 adsorption capacity [97]. The Zr(IV) in the parent MOF
UiO-66(Zr100) was postsynthetically exchanged with Ti(IV) by soaking it into a
DMF solution containing TiCl4(THF)2. Thus, a series of Ti-incorporated MOFs
derived from the parent Zr-MOF, such as UiO-66(Ti32), UiO-66(Ti44), and UiO-66
(Ti56), were synthesized and characterized by various techniques. The BET surface
areas of all Ti-doped MOFs are greater than [UiO-66(Ti32) = 1418 m2 g1, UiO-66
212 A. M. P. Peedikakkal and N. N. Adarsh

a b –
CO2
–
O2C

NH
O

O
H –
CO2
– N
HN
O2C
O

–
– CO2
CO2 TPBTM6–in 1

c – –
d 24 I I
O2C CO2 (CO2)
PCN-61 PCN-61
CO2 or N2 Uptake (mmol/g)

20 PCN-66
PCN-68
16

12
– –
O2 C CO2 8

4 (N2)
– –
CO2 CO2
0
btei6– in PCN-61
0 5 10 15 20
Pressure (bar)
e 28
26
24 1
Qst (kJ/mol)

22
20
PCN-61
18
16
14
12
10
0 5 10 15 20
CO2 Uptake (mmol/g)

Fig. 20 (a) Crystal structure of Cu3(TPBTM) MOF derived from C3-symmetric hexacarboxylate
ligand with acylamide functionality having (3, 24)-connected rht-type topology. Chemical structure
of TPBTM (b) and BTEI (c). Gravimetric excess CO2 and N2 adsorption isotherms at 298 K and
high pressure. (d) and (e) Isosteric heats of CO2 adsorption comparison plot of Cu3(TPBTM) and
PCN-61. (This figure is reprinted from Ref. [93] with permission. Copyright 2011, American
Chemical Society)
5 Porous Coordination Polymers 213

(Ti44) = 1749 m2 g1, and UiO-66(Ti56) = 1844 m2 g1] the precursor MOF,
UiO-66(Zr100) [1390 m2 g1]. This is due to a well-known fact that the surface
area of MOFs increase with the replacement of heavy metals with light metals
[98]. Interestingly, the theoretical and experimental CO2 uptake data of the parent
UiO-66 and the Ti-doped MOFs revealed that, with increase in the % of Ti, the
amount of CO2 adsorption increases (Fig. 21).

6.3.4 Effect of Amine Functionalization in MOFs

MOFs derived from amine functionalized ligands [99] attracted many chemists and
materials scientists owing to their basic character and its affinity to acidic gas
molecules, for example, CO2, which helps the MOF to capture CO2. Furthermore,
such MOFs act as an excellent precursor for postsynthetic modification. In fact,
alkylamine have more basicity than aromatic amine, and therefore, MOFs derived
from alkylamine functionalized ligands exhibit more active Lewis acid behavior and
CO2 capture capacity. Ferey et al. reported the alkyl-derived MOFs for the first time
via postsynthetic functionalization on the open Cr(III) sites of MIL-101(Cr) by using
ethylenediamine or diethylenetriamine, and the resultant functionalized MOF
showed excellent catalytic activity in Knoevenagel condensation reaction
[100]. Later, Long and co-workers reported a MOF, namely, [Mg2(dobpdc)-
(mmen)1.6(H2O)0.4(mmen-Mg2(dobpdc))] [where dobpdc4 = 4,40 -dioxido-3,
30 -biphenyldicarboxylate, mmen = N,N0 -dimethylethylenediamine], and the single
crystal X-ray structure analysis revealed that the extended coordination of dobpdc4
and Mg2+ resulted in a 3D porous structure having honeycomb architecture, with
one-dimensional channels of ~ 18.4 Å in width [101]. Interestingly, this Mg-MOF
showed unprecedented CO2 adsorption capacity of 2.0 mmol/g at 0.39 mbar, 25  C
and 3.14 mmol/g at 0.15 bar, 40  C, ideal condition for CO2 capture from air and flue
gas, respectively (Fig. 22). It is worthwhile to mention here that the structure of this
MOF is basically an expanded variant of MOF-74 [102].

6.3.5 Effect of Nitrogen-Rich MOFs

Another important factor for the successful adsorption capacity of CO2 is the
presence of uncoordinated N atoms in the pore walls of the MOFs, which can
boost the CO2 uptake via base-acid and dipole-quadrupole interactions involving
CO2 and N atoms of the uncoordinated ligands. For example, Qin et al. developed a
porous MOF, namely, IFMC-1, derived from a bis-tetrazole ligand having 1,2,3-
triazole backbone and Zn(II) [103]. Single crystal X-ray structure analysis revealed
that the metal ion [Zn(II)] exhibits tetrahedral geometry, and the four coordination
sites are occupied by the N atoms of the bridging ligands and its extended coordi-
nation lead to the formation of an infinite 3D framework. The structure of IFMC-1 is
similar to classical zeolitic SOD topology, which consist of truncated octahedral
supercages with eight hexagonal faces and six square faces shared with neighboring
cages. The nitrogen adsorption isotherm analysis revealed that the BET and Lang-
muir surface areas of IFMC-1 were 780 m2 g1 and 932m2 g1, respectively with a
214 A. M. P. Peedikakkal and N. N. Adarsh

Fig. 21 (a) Crystal structure of MOF UiO-66(Zr100) and its Ti(IV) derivatives, displaying the
decrease in the cage size with increase in the % of Ti(IV) than that of Zr(IV). (b) Theoretical and
experimental CO2 adsorption-desorption isotherms of MOF UiO-66(Zr100) and its Ti
(IV) derivatives. The empty and solid circles represent desorption and adsorption data, respectively.
(This figure is reprinted from Ref. [96] with permission. Copyright 2013, Royal Society of Chemistry)

micropore volume of 0.37 cm3 g1. The crystals of IFMC-1 were used to explore
CO2 adsorption isotherm experiment at various temperature, which revealed that CO2
uptake capacity at saturation of 166.9 cm3 g1 (7.5 mmolg1, 184.9 L/L),
91.4 cm3 g1 (4.1 mmolg1, 101.3 L/L), and 60.3 cm3 g1 (2.7 mmolg1, 66.8 L/L),
 5
Porous Coordination Polymers

Fig. 22 The schematic representation of the route of synthesis of mmen-Mg2 (dobpdc). (Reproduced with permission. This figure is reprinted from Ref. [100]
with permission. Copyright 2012, American Chemical Society)
215
216 A. M. P. Peedikakkal and N. N. Adarsh

respectively at 195 K, 273 K, and 298 K. The CO2 uptake greater than 60 L/L at 298 K
is a remarkable result, owing to the fact that MOFs coming in this category of list of
CO2 uptake at 298 K are very rare [104]. Such unprecedented CO2 adsorption
capability of IFMC-1 is due to the promising nonbonded interactions involving
uncoordinated N atoms from N-rich bis-tetrazole ligand and CO2 molecules (Fig. 23).

6.3.6 Effect of Water Molecules

The presence of water molecules within the pore and the open metal sites of MOFs
usually decrease their CO2 adsorption capacity [105]. In contrast to this general concept,
there are a few reports in which the MOFs showed good CO2 uptake in the presence of
metal bound or lattice included water molecules. The effect of water molecules in the
MOF on their CO2 adsorption capacity was, experimentally and theoretically (molecular
simulations), studied by Yazaydin et al. [106] by taking Cu-BTC MOF as an example.
The Cu-BTC MOF having water molecules (coordinated to open-metal sites in the
framework) showed enhanced CO2 uptake and selectivity over N2 and CH4. The reason
behind such unprecedented CO2 adsorption was investigated by using simulation and
experimental data. The combination of these two data revealed that the nonbonded
interaction between the CO2 and water molecules via quadrupole moment and electric
field, respectively is responsible for such great CO2 uptake.

7 Conclusion and Future Perspectives

A brief introduction of porous coordination polymers (PCPs) and/or metal organic

frameworks (MOFs), their synthesis, structure, and gas storage application have
been highlighted in this chapter. Several research groups have been contributed well
to the development of functional PCPs by following various approaches such as
design and synthesis, molecular modeling, structure-property correlation study, etc.
We started this chapter with answering several questions: What are CPs? How CPs
are formed? What are the factors effecting the final structure of CPs? What are the
potential applications of CPs? etc. From the results of various research groups, it is
evident that the metal to ligand stoichiometric ratio, reaction condition for the
synthesis, the type of counter-anion, nature of the ligand (flexible or rigid), etc. are
the important factors, for the design and synthesis of CPs. So we must be seriously
concerned of all these factors before we go to synthesize a CP for a particular
application. The crystal structures of PCPs are sometime difficult to understand
due to their complicated network topology (for example, interpenetrated networks).
Thus, a detailed description is very important to understand the topology of CPs, and
nowadays, it is easy to analyze the topology of CPs by using TOPOS [107]. Another
important issue we need to consider is the phenomena of “interpenetration,” owing
to the fact that it may lead to blockage of the free space (voids) in the crystal lattice
of CPs.
Further, we emphasize the gas storage application of PCPs or MOFs, especially
the storage of H2, CH4, and CO2. The intrinsic properties of PCPs or MOFs such as
surface area, pore size, pore volume, etc. influence their gas storage application.
5 Porous Coordination Polymers 217

Fig. 23 Crystal structure

illustration of IFMC-1: (a)
coordination environment of
Zn(II) in IFMC-1, (b)
hexagonal and (c) square
windows present in IFMC-1,
(d) tiling, and (e) stick
diagram, displaying the SOD
cage topology. SOD cage
topology present in IFMC-1
(f), and ZIF-8 displaying pore
size of 6.4 Å and 3.4 Å,
respectively. (h) CO2 and N2
adsorption isotherm at various
temperatures (olive: 195 K,
pink: 273 K, blue: 298 K).
Filled symbols: adsorption;
open symbols: desorption.
(This figure is reprinted from
Ref. [103] with permission.
Copyright 2012, The Royal
Society of Chemistry)

The research development of MOFs for gas storage is basically focused on different
approaches, which indeed influence to achieve more gravimetric and volumetric gas
storage capacity. In fact, the interaction of a gas molecule with the framework of the
MOF is basically via van der Waals forces and hydrogen bonding, which is
218 A. M. P. Peedikakkal and N. N. Adarsh

supported by the pore size/volume of MOFs. Moreover, some specific open metal
sites, various functional groups present in the framework, N-rich ligands associated
with the framework, etc. further support the MOF–gas molecules interactions.

Acknowledgments A. M. P. Peedikakkal would like to acknowledge the support provided by

KACST for funding through NSTIP. Project No. 14-ENE2278-04 for his research.

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Polyurethane and Its Derivatives
6
Mohammad Mizanur Rahman, Mohammad Mahbub Rabbani, and
Joyanta Kumar Saha

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2 Chemistry of Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
3 Synthesis of Polyurethane and Their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
3.1 Polyol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.2 Isocyanate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
3.3 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
3.4 Chain Extenders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
3.5 Cross-Linker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4 Types of Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.1 Polyurethane Ionomers (PUI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.2 Polyurethane Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.3 Coatings, Adhesives, Sealants, and Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.4 Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
4.5 Waterborne Polyurethane (WBPU) Dispersions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
5 Recent Advances in Polyurethane and Their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
5.1 Polyurethane Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
5.2 Polyurethane Click Coupling Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
5.3 Heterocyclic Compound-Based Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
5.4 Polyurethane from Renewable Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
6 Polyurethane Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
6.1 Building Material Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
6.2 Automotive Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236

M. M. Rahman (*)
Center of Research Excellence in Corrosion, King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
e-mail: [email protected]
M. M. Rabbani
Department of Chemistry, American International University-Bangladesh (AIUB),
Dhaka, Bangladesh
J. K. Saha
Department of Chemistry, Jagannath University, Dhaka, Bangladesh

© Springer Nature Switzerland AG 2019 225

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_7
226 M. M. Rahman et al.

6.3 Marine Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236

6.4 Coating and Adhesive Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
6.5 Medical Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
6.6 Appliances Flooring, and Packaging Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

Abstract
Polyurethane (PU) is one of the widely used materials with great potential for
multipurpose applications due to their excellent physical, chemical, and mechan-
ical properties. PU materials are widely being used in many applications all over
the world. The targeted PU properties for different applications can be achieved
by changing the base monomers and their ratios as well as different synthesis
process. This chapter highlights the PU application, its chemistry, and its base
monomers. The latest modification and new application of PU and its derivatives
are also considered.

1 Introduction

Any polymer which contains urethane group is called polyurethane (PU). German
Scientist Otto Bayer and his co-workers first introduced PU. Nowadays PU are used
in multipurpose applications such as coatings, paints, elastomers, textiles, insulators,
elastic fibers, foams, foot wear, etc. At early stage most of the PU was prepared by
using toxic solvents and monomers. Later less toxic solvent and water were consid-
ered to make PU to make it environmentally friendly. Recently, introducing
monomers from natural sources makes PU more attractive in industry due to green
nature of PU materials [1–5].
The basic PU structure is shown in Fig. 1. The urethane and urea are the major
repeating units in PU. The urethane group is produced from the reaction between
isocyanate (NCO) and hydroxyl (–OH) groups, whereas the urea group formed by
the reaction between isocyanate (NCO) and amine (–NH2) groups [2, 6–10]. PU also
contains other groups, such as esters, ethers, and some aromatic groups. As there are
varieties of monomers in PU preparation and thus given a wide range of specific
applications, PU derivatives can be classified into several groups such as flexible,
rigid, thermoplastic, waterborne, coating, binders, sealants, adhesives, and elasto-
mers. Every year the use of PU derivatives is being increased in significant level.
Counting all different uses, PU foam is one of the leading derivatives, which is being

Fig. 1 Urethane/urea group in PU

6 Polyurethane and Its Derivatives 227

used globally in significant amounts. Both rigid and flexible foams are being used in
different sectors. PU foams can be simply modified to get specific properties by
changing blowing agents, isocyanates, fillers, surfactants, and polyols used in their
preparation. PU finds a strong level in coatings and adhesives as these materials have
excellent mechanical and adhesive strength. Elastomer is another attractive using
area of PU, such kind of PU can easily incorporated into different engineered
products and extend their properties [1, 11, 12].
PU can be prepared from different monomers of polyols, diisocyanates, and chain
extenders; their properties also varied with changing the contents of polyols,
diisocyanates, and chain extenders [13, 14]. At early stage of mid-1980s, the
major monomers were come from fossil fuel; however, due to environmental
concerns, the necessity for more environmentally friendly polyol was shown by
many researchers. This has recently drawn enormous commercial and academic
attention to renewable resources, such as vegetable oils which mainly consist of
triglyceride molecules with different reactive sites, such as carbon–carbon double
bonds, hydroxyl, and ester groups. Unfortunately, most of the diisocyanates and
chain extenders are toxic and nonnatural sources. To make more environmentally
friendly PU, few researchers also made PU without isocyanates [15–19].
To improve the properties of PU and their derivatives, recently nanotechnology
has been introduced for these polymers. Different PU nanomaterials have been
prepared by using different nanoparticles. The nanomaterial-based PU broadened
its applications. PU is being used for 60 years. Plenty of studies have been carried
out in academic and industry. In this chapter, a summary of the advances made in the
preparation of PU, as well as their application into several products in multisectors,
has been highlighted. The basic monomers to prepared PU are also considered [1, 2,
20–23].

2 Chemistry of Polyurethanes

The chemistry of polyurethane is very straightforward. Usually, PU can be prepared

by the reaction of polyol and isocyanate. This is commonly used catalyst to fast the
reaction between polyol and isocyanate. Isocyanate (termed as hard segment) and
polyol (termed as soft segment) may contain single or multiple reactive groups
which ultimately determine the properties of final materials. The different ratios
between isocyanate and polyol also contribute to achieve the properties. Soft seg-
ment maintains elastomeric properties, whereas hard segment controls rigid and
tough properties. This is also common to make cross-linkable PU. The cross-linking
can be obtained by adding either excess isocyanate or external cross-linker. The
cross-linkable PU has better mechanical properties. However, excess cross-linkable
PU structure decreased the mechanical properties. A combination of hard segment
and soft segment with average cross-linking can produce foam PU. The soft seg-
ment, hard segment, and additional cross-linker contribute the molecular weight
which finally make small or giant molecule. Besides, the addition of nanofillers and
228 M. M. Rahman et al.

Fig. 2 Structure of different polyols

additives and the processing conditions (temperature, time, addition method, etc.)
make PU suitable for different applications [1, 2, 24–28].
One of the important monomers of PU is polyol which can be obtained commer-
cially, as well as it can be synthesized in laboratories by different techniques.
Different structures of various polyols are presented in Fig. 2. The widely used
polyols are poyether polyol and polyester polyol. It is also common to use mixed
polyols with different molecular weights and ratios to obtain specific properties [1].
Phase incompatibility is the vital factor of speed as polyol (polar and less dense)
and isocyanates (nonpolar and denser) are opposite in nature. Therefore, a suitable
surfactant/catalyst is usually used to make a faster reaction rate between polyol and
isocyanate. Isocyanate is very reactive to polyol especially with the presence of
catalyst. Aromatic isocyanates are more preferable to aliphatic isocyanates due to
high reactivity and low cost. Besides, the final PU products possess high mechanical
strength using aromatic isocyanates. Using mixed isocyanates of aliphatic and
aromatic is also common in PU materials [2, 29–31].

3 Synthesis of Polyurethane and Their Derivatives

PU and its derivatives are prepared by different processes [1]. Figure 3 illustrates the
typical synthesis of a conventional PU. Different cross-linkers, additives, and nano-
particles may also be incorporated during synthesis of PU.
Based on the applications, surfactants, blowing agents, and pigments are also
mixed into the PU. Widely used monomers in PU synthesis is summarized in
Table 1.
6 Polyurethane and Its Derivatives 229

Fig. 3 General way of PU synthesis

Table 1 Polyurethane monomers/additives and their specific reason for using

Monomer/additives Specific reason for using
Polyol Maintain elastomeric properties
Isocyanate Reactivity and curing properties
Chain extender Control molecular weight
Catalyst Speed up the reaction between polyol and isocyanate
Cross-linker Structural modification to improve the mechanical and barrier
properties
Filler Improve thermal, mechanical, and barrier properties
Plasticizer Reduce material hardness
Hardener Post crosslinking reaction to improve adhesive strength
Smoke retardant Reduce smoke
Flame retardant Reduce flammability
Bowing agent/surfactant Control the formation of bubble during synthesis
Hydrophilic agent Make dispersion stable
Pigment Produce colored materials

3.1 Polyol

One of the major monomers in PU synthesis is polyol, which usually termed as a soft
segment. Widely used polyols are either polyester polyols or polyether polyols. The
polyether polyol is prepared from epoxy monomers through the ring-opening poly-
merization, whereas polyester polyol is prepared from polycondensation reaction
using carboxylic acid with hydroxyl group. Recently, hydroxy-terminated siloxane
is also being used in PU synthesis. It is important to choose the proper polyol as the
properties highly depend on polyol and its contents. Different molecular weight of
similar generic type of polyols is also available. Low molecular weight polyol
controls rigidity, whereas high molecular weight polyol contributes to elastomeric
properties. Besides polycaprolactone (PCL), polycarbonate (PC), polysulfide (PS),
230 M. M. Rahman et al.

and polybutadiene (PB), polyol is also being used in PU materials. Polyether polyol
of different molecular weight is also used in PU [2, 32–35].
Poly(tetramethylene ether) glycol (PTMG) is prepared through polymerization
of tetrahydrofuran with different molecular weights. PTMG is being widely used
in many different PU preparations to broaden their application. Besides, poly(pro-
pyleneoxide) glycol (PPG) and poly(ethyleneoxide) glycol (PEG) can be prepared
using different weight of ethylene oxide/propylene oxide. By changing the total
hydroxyl group and polymer chain, the polyol properties such as reactivity, com-
patibility, and solubility also can be changed. Usually polyol of propylene oxide
is less reactive than those for ethylene oxide. There are available different high
molecular weight graft polyols which are prepared by using polyurea, acrylonitrile,
or styrene-acrylonitrile, with polyether ketone. Fluoro-based polyol such as
fluoroethylene vinyl ether (FEVE) polyols which can be obtained by the copoly-
merization reaction of tetrafluoroethylene or chlorotrifluoroethylene with vinyl
ethers containing hydroxyalkyl vinyl ethers. PU with fluro-based polyol is useful
for antibacterial and antifouling materials [1, 2, 36–45].
Very recently polyols can also be obtained from natural resources. The polyol can
be obtained from fatty acid-rich soybean, castor, neem, and cotton seed. Different
PU elastomers and foams have been made by using triacylglyceride-based vegetable
oils. The presence of such kind of oils used to produce flexible molded foams,
elastomers, etc. The advantage of using natural polyols is unmodified synthetic
process. Even changing the solvent systems, the PU can be prepared. Nowadays
PU is being prepared using renewable resources such as polyol in both solvent- and
water-based coating, adhesive, and foam materials without sacrificing their proper-
ties [2, 36, 39, 46–53].

3.2 Isocyanate

Isocyanate is one of the important monomers in PU. Mainly diisocyanates (aliphatic/

aromatic) are used in PU and their derivatives. Widely used diisocyanates
are summarized in Table 2. Aromatic isocyanates are comparatively cheaper. The
properties of PU and their derivatives are also influenced by aliphatic or aromatic
isocyanates. Aromatic isocyanate-based PU has higher mechanical properties; how-
ever, yellowing with time of PU material is one important drawback of using aromatic
isocyanates. Recently PU without isocyanates is getting priority due to toxicity of
isocyanates. Few researchers have already prepared PU without diisocyanate [1–5, 45].

3.3 Catalysts

Using proper catalyst is also important in PU synthesis because a small amount of

catalyst makes a faster reaction between polyol and isocyanates. Popular catalysts
for PU synthesis and their derivatives are summarized in Table 3. Both metal
complexes and amine compounds are being used as a catalyst for PU synthesis [1, 2].
6 Polyurethane and Its Derivatives 231

Table 2 Structure of widely used isocyanates

Isocyanate Structure
4,40 -Methylenebis(phenyl isocyanate), MDI

Toluene 2,4-diisocyanate, TDI

Isophorone diisocyanate, IPDI

4,40 -Methylenebis(cyclohexyl isocyanate), HMDI

Hexamethylene diisocyanate, HDI

Table 3 Widely used Name Nature

catalyst in PU synthesis
Dibutyltin dilaurate Organometallic catalyst
Dibutyltin dilauryl mercaptide Organometallic catalyst
Stannous octoate Organometallic catalyst
Dibutyltin diacetate Organometallic catalyst
Pentamethyldipropylenetriamine Amine catalyst
Dimethylethanolamine Amine catalyst
Dimethylaminoethoxyethanol Amine catalyst
1,8-Diazabicyclo[5,4,0]undec-7-ene Amine catalyst

Unfortunately, the metal-based catalysts especially tin, lead, and mercury are
reported as very toxic, thus leading to the recent use of very less toxic such as
zinc and bismuth as replacements. Scientists are also trying to avoid catalyst by
using mixer of aliphatic and aromatic diisocyanates. The selection of catalyst also
depends on the solvent systems of PU materials. Tin-based catalysts (such as
dibutyltindilaurate) are widely being used in PU synthesis.

3.4 Chain Extenders

Chain extender is usually termed as terminator of the PU reaction. The molecular

weight of PU highly depends on the nature of chain extenders and their contents.
The chain extenders are usually hydroxyl and amine terminated, with low molec-
ular weights. They are also highly useful for improving the morphology of PU
adhesives, coatings, and foams. The mechanical properties also highly depend on
chain extender content. Very less amount of chain extender makes PU to have less
mechanical strength; with increasing chain extender, the mechanical strength
also increased. However, a very higher amount of chain extender makes PU brittle
[1, 2, 45].
232 M. M. Rahman et al.

3.5 Cross-Linker

Polyisocyanate hardener, melamine, and multifunctional polyol are usually used as

a cross-linker. The content and addition step of cross-linker also influence the
properties. Excess cross-linker has detrimental effect on properties [1, 2].

4 Types of Polyurethanes

4.1 Polyurethane Ionomers (PUI)

Different ionic groups in PU backbone make PU ionomer which have identical

properties such as mechanical strength, thermal stability, and dispersion stability
in polar solvents. Especially, PUI is very useful in biomedical devices (such as
artificial hearts, connector tubing for heart pacemakers) due to shape memory effect.
PUI can be prepared by incorporation of ionic groups as a pendant group or using
ionic diols during PU synthesis. PUI can be classified as a cationomer or anionomer.
Quaternization (for nitrogen) or ternization (for sulfur) makes a cationomer PU [1, 2].

4.2 Polyurethane Foams

Different types (rigid and flexible) of PU foams are being used in different sectors.
The major applications of rigid PU foam are insulation and flame retardant. The
main applications of flexible PU are packaging, cushion materials, bedding
furniture, carpet underlays, biomedicine automotive interior parts, and nano-
composites. The main two steps of PU preparation are blowing and gelling. By
controlling the monomers and their ratios, the properties of PU foam are usually
modified [1, 2].

4.3 Coatings, Adhesives, Sealants, and Elastomers

The most promising fields of PU and its derivatives are adhesives, coatings, liners,
and elastomers. This is due to excellent mechanical, thermal, chemical, and physical
properties. Different PU adhesives offer excellent bonding properties. PU coating
possess sufficient adhesive strength, low temperature flexibility, excellent barrier and
UV resistance, adequate corrosion and scratch resistance, and high chemical resis-
tivity. It is easy to apply PU-coating and PU-adhesive materials on different metals,
leather, textile, and wood substrates. Another important application of PU and their
derivatives is elastomer for shoe soles, ski boots, goggles, and household and car
items. These elastomers are attractive as it is easy to make different shapes and
colors. The elastomers are light and possess stress-recovering properties. Most
6 Polyurethane and Its Derivatives 233

importantly PU and their derivative elastomers withstand several critical environ-

mental factors. Recently the mentioned properties dramatically improved by using
different nanomaterials in PU and their derivative elastomers [1, 2].

4.4 Binders

PU binders which act as a glue are usually used to bond materials. This is useful
in fiberboards, particle boards, ink-jet printing, flooring surfaces, wood panel,
sand casting, and foundry industries. Like other PU materials, the properties such
as thermal stability, hydrophobicity, and rubbery state all depend on monomer
and their contents. To improve the mentioned properties, other functional groups
such as acrylate, siloxane, etc. are also incorporated in PU and their derivatives
[1, 2].

4.5 Waterborne Polyurethane (WBPU) Dispersions

PU and their derivatives are prepared by using either organic solvent or water. When
water is used as main solvent, the PU and their derivatives are termed as waterborne
PU (WBPU). WBPU is an environmentally friendly material as this material is free
from toxic solvent. WBPU has advantages such as low viscosity, cheaper, and easy
application. WBPU is a two-phase colloidal system, in which the PU particle
dispersed in water. A pendant salt in PU parent chain makes the PU dispersible in
water. The types and amount of polyol, isocyanate, ionomers, and chain extender
used are responsible for different properties of this dispersion [1, 2]. The typical
synthesis process of WBPU is summarized in Fig. 4.

5 Recent Advances in Polyurethane and Their Derivatives

5.1 Polyurethane Nanocomposites

Since the last decade, the PU and their derivatives’ properties have been improved
by using different nanomaterials. There are many different types of nanoparticles,
which are being considered as pristine or functionalized nanoparticles. The widely
used nanoparticles are different clay, carbon nanotube, graphene, hydroxyapatite,
cellulose, and fly ash. The mechanical, thermal, and barrier properties are
improved by using nanoparticle in PU and their derivatives. However, it is
important to use proper content, because excess nanoparticle can cause detrimen-
tal effect on properties. The proper or optimum content depends on nanoparticle
nature, PU monomers and their contents, and nanoparticle addition during syn-
thesis [1, 2, 51–53].
 234

Fig. 4 Typical synthesis of waterborne polyurethane

M. M. Rahman et al.
6 Polyurethane and Its Derivatives 235

5.2 Polyurethane Click Coupling Reaction

Very recently, click coupling reaction attracted in PU and their derivative synthesis.
Click chemistry is a copper(I)-catalyzed alkyne-azide cycloaddition reaction which
produces a single compound with high yield. The main advantages of click chem-
istry are highly selective, able to work on both homogeneous and heterogeneous, and
fast. Properties such as flame retardant, thermal, mechanical, anti-microbial, and
anti-corrosion have improved significantly of PU materials synthesized by click
coupling reaction. Different monomers are functionalized by click coupling reaction
followed by in situ or atom transfer radical polymerization process to synthesize PU
and their derivatives [54–57].

5.3 Heterocyclic Compound-Based Polyurethanes

Heterocyclic compounds have advantages in corrosion protection, anti-flammability,

and heat release. Different heterocyclic compounds in PU and their derivatives are
used as a monomer. Toxic halogen-based compound is widely used as nonflammable
material, but nitrogen-phosphorus-based heterocyclic compound in PU is proved to
be a proper replacement for halogen as a flame-retardant material. Imidazole-based
compound is used in PU material to improve the corrosion protection [1, 2].

5.4 Polyurethane from Renewable Resources

Most of the monomers of PU are usually based on fossil feedstocks. However, global
warming and increasing oil prices push a change from fossil feedstocks to renewable
resources. Recently, researchers use vegetable oils and animal fats as a renewable
resource for polyol monomer. Different polysaccharides and lignin have been used
as filler, chain extender, and cross-linker. The properties of using natural resources
are almost the same as the fossil feedstock monomers [1, 2, 45–47].

6 Polyurethane Applications

At early stage, PU application was not very wide. With increasing the choice of
monomers, the application of PU material also increased. Besides, with the use of
less toxic solvent and green solvent, the application of PU increased rapidly [1, 2].

6.1 Building Material Application

The use of PU in building material is not new. Due to excellent strength, heat
insulation capacity, and durability, PU materials are being used in building materials.
Every year the use of PU in building material is increasing. Another advantage of PU
236 M. M. Rahman et al.

in building material is their light weight. The cheap price of PU building materials also
makes it attractive to replace the current concrete material. PU material can be used in
flooring, roofing, and wall. Besides, PU also can be used in concrete structure [1, 2, 58].

6.2 Automotive Application

PU has a huge application in automotive industry. Different parts such as doors,

bumpers, windows, and wheels are made by PU and their derivatives. Due to less
weight and proper insulation, the PU materials are attractive in automotive sector.
PU adhesive and coating materials are also used in automotive industry. Due to
excellent adhesive strength and UV and corrosion resistance, the PU materials are
being widely used in this sector. Proper monomer and nanofiller make PU as
a suitable material in automotive application [2, 59].

6.3 Marine Applications

Marine area is a new application field for PU and its derivatives. Different PU foams are
being used as an insulator for extreme noise and temperature. PU coating for corrosion
and fouling protection is another area in marine field. The most successful antifouling
coating was tin-based compound which has been banned since 2008. The reason was
toxicity of tin-based compound for aquatic environment. PU consists of hard segment
and soft segment. The soft segment usually moves to the surface due to its less free
surface energies. Using siloxane- and fluorine-based monomer makes PU surface as
foul-release coating to protect the surface from fouler attachment. Besides, different
biocides can be used in PU coating to protect the surface from fouling [60–62].

6.4 Coating and Adhesive Application

A continuous research is going on PU materials for adhesive and coating application

for different purposes. PU possesses different structures such as linear, cross-
linkable, and hyperbranched which can be useful in coating and adhesive application
by increasing thermal stability, mechanical strength, adhesive strength, and hydro-
phobicity. Available polyols and diisocyanates give an opportunity to choose
a proper combination of PU coating and adhesive material to combat harsh condi-
tion. Different biodegradable monomers make PU coating and adhesive material less
toxic and replace other toxic coating and adhesive materials [1, 2].

6.5 Medical Application

PU materials are used in different medical applications due to their proper mechan-
ical strength and biocompatibility. It is mainly used in wound dressing, surgical
drapes, tubing, hospital bedding, and injection equipment implants. Recently PU
6 Polyurethane and Its Derivatives 237

implants attracted due to cost-effectiveness with similar or better protective proper-

ties of metals and their alloys and ceramics. Very recently biocompatible and
biodegradable PUs were synthesized to apply on biomedical devices [63–65].

6.6 Appliances Flooring, and Packaging Application

Different PU foams are leading in appliance application especially in freezers and

refrigerators. The main advantage of using PU foam is its prevention capacity of heat
transfer due to close structure. Flooring by PU material is also common as this type
of floor is durable, easy to maintain, and good looking. The carpets’ life span can be
increased by using PU foam as underlays of those carpets. Packaging industry also
considered PU as an important material due to excellent barrier properties, super
mechanical strength, and antibacterial properties. Using different filler and biode-
gradable monomers in PU material makes it more attractive as many countries have
regulation to avoid the toxic and non-biodegradable packaging products [66, 67].

7 Conclusion

Available monomer, easy synthesis, and variety of applications make PU an impor-

tant material to the industry. Excellent mechanical strength, long time durability, and
low price make PU an alternative to rubber, plastic, and metal in many different
products. PU is useful as paint, elastomer, adhesive material, foam, and elastic fiber.
At early stage, PU material was made mainly from petroleum sources. The new
techniques to use monomers of renewable resources make PU more promising in
respect of environmental legislation. Most of the commercially available PU and
their derivatives are made using organic solvents. Only few products are made using
water as a solvent in PU. Besides, isocyanate which is a very toxic material makes a
huge barrier to make PU as a nontoxic material. Very recently few researchers
synthesize PU without isocyanate. To broaden PU application, it is necessary to
use all nontoxic monomer without sacrificing their properties.

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Dielectric Polymers
7
Shah Mohammed Reduwan Billah

Contents
1 Dielectric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2 Basic Concept of Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.1 Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
3 Dielectric Mechanism of Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4 Useful Terms Usually Used to Analyze Dielectric Materials or Dielectric Polymers . . . . 247
4.1 Dielectric Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
4.2 Dielectric Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
4.3 Dielectric Loss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
4.4 Dissipation Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
5 Basic Characteristic of Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
5.1 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
5.2 Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
5.3 Water Absorption, Planarization, and Chemical Resistance . . . . . . . . . . . . . . . . . . . . . . . . 250
6 Different Types of Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
6.1 Low-k Dielectric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
6.2 Property Requirements of Low-k Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
6.3 High-k Dielectric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
7 Different Selected Aspects of Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
7.1 Dielectric Fluoropolymers and their Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
7.2 Dielectric Polymer Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
7.3 Dielectric Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
8 Performance Enhancement of High-k Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
8.1 Filler Size Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
8.2 Micron-Sized Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265

S. M. R. Billah (*)
University of East London, Stratford Campus, London, UK
CCIRA UK limited, Galashiels, UK
Department of Chemistry, Durham University, Durham, UK
School of Textiles and Design, Heriot-Watt University, Galashiels, UK
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 241

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_8
242 S. M. R. Billah

8.3 Controlled Dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265

8.4 Control of Dielectric Loss for Conductive Filler/Polymer Nanocomposites . . . . . . . 265
9 Dielectric Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
9.1 Bioinspired Dielectric Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
9.2 Different Aspects of Dielectric Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
9.3 Large Deformation Capability and Typical Failure Modes of
Dielectric Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
10 Dielectric Breakdown of Other Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
10.1 Dielectric Breakdown Behavior of Polymer Composites and
Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
11 Recent Trends in Dielectric Polymer Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
11.1 Microelectronic and Dielectric Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
12 Challenges for Embedded Capacitor Materials and Dielectric Polymers and
Composites and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
13 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

Abstract
Polymer-based dielectric materials have attractive features making them poten-
tially promising alternatives to usually used inorganic and ceramic-based
dielectric materials due to a number of reasons including (a) higher flexibility;
(b) easy, cost-effective processing feasibility; and (c) attractive chemical stabil-
ity along with readily changeable characters. However, one of the main disad-
vantages of this type of polymer dielectric is their lower thermal stability which
limits their wider application potentials. In addition, usually polymer dielectric
materials show low dielectric constants compared to inorganic dielectric mate-
rials. In addition, dielectric characters can be designed by introducing polariz-
able groups into polymer chains by increasing free volume by inducing porosity
as well as copolymerization. Besides this, the value of dielectric constant can be
effectively increased by synthesizing nanocomposites by introducing inorganic
fillers into composite structure to acquire high dielectric constants. Dielectric
polymers have many applications in electronics. For example, the performance
of advanced polymer dielectrics is useful to realize high-power electronic
circuits in a miniature form. However, these polymeric materials are required
to fulfill different criteria (such as thermal, environmental, and electrical stabil-
ity, low moisture uptake, high breakdown voltage or low leakage current, low
dielectric constant, low loss tangent, high glass transition temperature, and low
surface roughness) for their effective applications in different devices including
in microelectronics. Many investigations have been reported on the use of
polymer dielectrics and evaluated the feasibility of utilizing these materials
for various applications. Briefly three types of polymer dielectrics (such as
dielectric polymers, organic-inorganic material-based hybrid composites, and
coated polymer dielectrics) along with other necessary elements are selectively
discussed in this chapter. In addition, behaviors of dielectric elastomers are also
briefly covered.
7 Dielectric Polymers 243

Keywords
Dielectric polymers · Composites · Nanocomposites · Ferroelectric · Dielectric
breakdown

1 Dielectric Materials

Dielectricity, a physical model, is commonly used to state how an electric field interacts
with atoms or molecules inside a material. For example, when a metal body is exposed to
an electric field, the free electrons flow due to the impact of the electric forces against the
field until the field in the body vanishes. It gives rise to a charge transport or conduction.
The word dielectric is derived from the prefix “dia,” originally from Greek, which
usually refers to “through” or “across.” So, the dielectric material can be termed as a
material that permits the passage of the electric field or electric flux; however, they are
not any type of charge carriers. In addition, in strict consideration, there is no a truly
insulating substance which will resist the transport of electric charge through it under all
circumstances. Dielectric materials are nonconducting substances, such as insulators.
However, the term “dielectric” is usually used to consider the effect of alternating electric
fields on the substance, whereas the term “insulator” is often used to express the electrical
nature of the material when it is exposed to withstand high electric field. Dielectric
materials have different applications where one of the main applications is their use in
controlling and storing electrical charges and electrical energies which play key role in
modern electronics and electric power systems. For example, a dielectric capacitor is
usually made by sandwiching a dielectric material between two metal plates as elec-
trodes where an external electric potential is applied between the metal plates. When the
electron distributions around constituent atoms or molecules in dielectric materials are
polarized due to charge separation, they can be used as capacitors to store electrical
energy in the form of electric field [1–18]. Dielectric materials are frequently applied to
electrical energy for charge separation when the electron distributions around constituent
atoms or molecules are polarized due to the impact of an external electric field; for this
type of system, the complex permittivity (e*) of a dielectric material can be given as

e
¼ e0  je00 (1)

For this equation, e0 represents real permittivity, while e00 indicates imaginary parts
of the complex permittivity, and j is equal to √1. In addition, Kramers-Kronig
relation is popularly used to relate the magnitudes of e0 and e00 that depend on the
frequency ω of the applied electric field; the Kramers-Kronig relation is expressed as:

ð
1
0 2 ue00 ðuÞ
e ð ωÞ ¼ e 0 þ du (2)
π u 2  ω2
0
244 S. M. R. Billah

Additionally, the real part of the permittivity is expressed as:

e0 ¼ e0 er (3)

For the Eq. 3, e0 indicates the permittivity of vacuum (8.85  1012 F/m) and er
represents the relative permittivity or dielectric constant of the material and the
magnitude of e0 (or the dielectric constant er) imparts the ability of the material to
store energy from the applied electric field [7–17].

2 Basic Concept of Dielectric Polymers

Generally, the term dielectric is used to indicate the energy storing capacity of the
material by means of polarization. When exposed to an external electric field, materials
show polarization due to a dielectric displacement. Typically, most common polariza-
tion mechanisms are (a) electronic polarization, (b) orientational polarization,
(c) vibrational polarization, and (d) interfacial polarization, which are shown in
Fig. 1. Electronic polarization is effective in every atom or molecule as the center of
charge of electrons surrounding the positive atomic cores that are displaced by the
action of the electric field in order to create a dipole moment. Orientational polariza-
tion or dipolar polarization occurs in materials that contain molecules with permanent
dipole moments (such as water) where the dipoles show some type of alignment on
exposure to an electric field in order to induce a polar character to the material [1–7].
Orientation of molecular dipoles is a relatively slow process in comparison with
electronic transitions or molecular vibrations. In addition, when an orientational
polarization is measured immediately after an electric field is applied, the observed

Fig. 1 Schematic representation of (a) electronic, (b) vibrational, (c) orientational, and
(d) interfacial polarization mechanisms
7 Dielectric Polymers 245

instantaneous relative permittivity is usually low due to the fact that no time is
allowed for the orientation of the dipoles. In contrast, when a sufficient time is
allowed after the application of an electric field, maximum orientational polarization
is usually achieved that corresponds to the highest observable relative permittivity
(also called the static relative permittivity). Besides this, atomic polarization occurs
when an applied electric field distorts the arrangement of atomic nuclei in a molecule
or lattice, and it happens at a lower frequency than electronic polarization due to the
larger mass of the atom when compared to the electron [1–7].
A dielectric material, a poor conductor of electricity, efficiently supports electro-
static fields. When the flow of current between opposite electric charge poles is kept
to a minimum while the electrostatic lines of flux are not impeded or interrupted, an
electrostatic field can store energy which is essential for capacitors (particularly at
radio frequencies). Dielectric materials are also useful for the construction of radio-
frequency transmission lines. Practically, most dielectric materials are solid, for
example, porcelain (ceramic), mica, glass, plastics, and the oxides of various metals.
In addition, some liquids and gases also show good dielectric properties. For
example, dry air shows dielectric character which is usually used in variable
capacitors and some specific types of transmission lines. Distilled water also
shows a fair dielectric character, and a vacuum also indicates an exceptionally
efficient dielectric behavior. An important property of a dielectric polymer or a
dielectric material is its ability to support an electrostatic field while dissipating
minimal energy in the form of heat. When a material shows a low dielectric loss (the
amount of energy lost as heat), it is considered to be a good dielectric material. The
dielectric constant is the extent to which a substance concentrates the electrostatic
lines of flux. Substances with a low dielectric constant include a perfect vacuum, dry
air, and most pure, dry gases (e.g., helium and nitrogen). As for instances, some
materials with moderate dielectric constants are – (a) ceramics, (b) distilled water,
(c) paper, (d) mica, (e) polyethylene, (f) glass; whereas, typically, metal oxides have
high dielectric constants [18–55]. Dielectric materials have a wide range of appli-
cations, for example, they are widely used in transistors. In organic thin-film
transistors, polymer-based dielectric materials are frequently used. A brief general
introduction of the use of dielectric materials in transistors is shown in Fig. 2.
Organic thin-film transistors can have different configurations depending on the
position of the gate electrode (G) and the sequence of the source (S) and drain
(D) electrodes deposited relative to the semiconductor layer. These configurations
are stated as (1) top-gate top-contact, (2) top-gate bottom-contact, (3) bottom-gate
top-contact, and (4) bottom-gate bottom-contact [8, 56–61].
In principle, the characteristic that best defines organic thin-film transistors is the
presence of an electric field which controls and modulates the conductivity of the
channel between the source and drain, and this electric field is created by the voltage
applied between the source and the gate electrodes (such as gate voltage, VG).
Application of a negative (or positive) gate voltage will induce holes (or electrons)
at the dielectric-semiconductor interface where charge transport takes place, and the
density of accumulated charge carriers in the channel is modulated by VG and is
dependent on the capacitance C of the dielectric layer [62–69].
246 S. M. R. Billah

Fig. 2 Schematic representation of (1) top-gate top-contact-, (2) top-gate bottom-contact-,

(3) bottom-gate top-contact-, and (4) bottom-gate bottom-contact-based thin-film transistors

2.1 Dielectric Polymers

Polymers (e.g., epoxies, benzocyclobutenes, polyimides) have been applied as dielec-

trics in microelectronic industry by various coating techniques followed by moderate
temperature cure. At first, in 1990, Peng et al. reported the use of polymers as gate
dielectrics in OTFTs [70]. They fabricated devices with different types of organic
polymer insulators using evaporated R-sexithienyl films to serve as the semiconduc-
tor. Polymer-based dielectric materials have some advantage and disadvantages. Most
polymers are para-electric capable to provide stable capacitance with regard to tem-
perature and frequency. In addition, they possess good mechanical property, easy
processing, low dissipation factor, and high dielectric breakdown strength. Dielectric
polymers include (a) polypropylene, (b) cyclic transparent optical fluoropolymer
(CYTOP), (c) polypropylene-co-1-butene, (d) poly-p-xylylene, (e) polyisobutylene,
(f) polyvinylphenol, (g) polyvinyl alcohol, (h) PMMA, (i) polyethylene terephthalate,
and (j) poly-α-methylstyrene. In contrast, a group of polymers with a polar backbone,
so-called ferroelectric polymers, possess higher values of dielectric constant [70–78].

3 Dielectric Mechanism of Dielectric Polymers

The dielectric mechanism of a dielectric polymer is directly related to resonance and

relaxation processes (Fig. 3). Resonances process depends on two polarizations, and
they are (a) electronic polarization (occurs in a neutral atom when the electric displaces
the electronic density relative to the nucleus in its surrounding environment) and
7 Dielectric Polymers 247

Dielectric
Mechanism

Relaxation Resonance
process process

Dielectric Ionic Dipole Atomic Electronic

relaxation relaxation relaxation polarization polarization

Fig. 3 Dependence of dielectric mechanism

(b) atomic polarization (occurs when the electronic cloud is deformed under the force
of the applied field). However, relaxation process relies on three types of relaxation
processes, which are (i) dipole relaxation (permanent and induced dipoles aligning to
an electric field), (ii) ionic relaxation (compromises ionic conductivity and interfacial
and space charge relaxation), and (iii) dielectric relaxation (it is a result of a movement
of dipoles due to dipole relaxation and electric charges due to ionic relaxation) [1–7].

4 Useful Terms Usually Used to Analyze Dielectric Materials

or Dielectric Polymers

4.1 Dielectric Constant

Dielectric constant (e0 ) is considered to be a critical electrical parameter for a

dielectric polymer where the magnitude of e0 is a function of the amount of mobile
(polarizable) electrical charges and the degree of mobility of these charges in the
polymer or material. Charge mobility and e0 exhibit temperature dependency. Addi-
tionally, since polarization of the material requires a finite amount of time, the
frequency of the electric field also influences the measurement of dielectric constant.
Besides this, a lower dielectric constant allows for wider signal traces and decrease in
the dielectric thickness. It also allows to maintain the same characteristic impedance
while lowering the line resistance and crosstalk. A good dielectric polymer usually
has different attractive properties including the invariance of the dielectric constant
with respect to frequency and temperature. For example, polyimides typically have
dielectric constants greater than 3.0, unless they are modified through the inclusion of
fluorinated groups. In additions, it has also been shown that low-stress polyimides
show highly anisotropic dielectric constants, for example, BCBs and fluoropolymers
show dielectric constants which are less than 3.0 [61–78]. The dielectric constant is
termed as the permittivity of a material which represents the ability of a material to
concentrate electrostatic lines of flux. In other way, it shows the ability of a material to
store electrical energy in the presence of an electric field. When placed in an electric
field, all materials (including vacuum) store energy and the permittivity of vacuum is
defined as the physical constant (e0, which is approximately e0 = 8.854  1012
farads per meter). This constant appears in many electromagnetism formulas.
248 S. M. R. Billah

4.2 Dielectric Strength

Dielectric strength or breakdown voltage is used to illustrate the voltage at which

current begins to flow through the insulating dielectric film and for thin films, for
example, avalanche breakdown ultimately defines the breakdown strength of the
polymer. In addition, it is possible that a breakdown can also occur due to thermal
effects as power dissipated by the insulation, in which an exponential increase in
conductivity creates thermal runaway and most polymeric materials show spe-
cific values for breakdown voltage. For instance, BCBs have slightly higher
values which are suitable for high-voltage power applications. Besides this, an
insulator has a limited capability to withstand the voltage before conducting
electricity, and all materials have an upper voltage limit which is termed as
breakdown voltage. Air is considered as an insulator, however, it can flow current
under certain circumstances, for example, during a lightning strike air works as a
conductor. During this case, air is ionized (electrons are torn away from the
atom’s nucleus) when the breakdown field strength is exceeded, and electrons
begin moving under the influence of the electric field to produce electrical current
[61–78].

4.3 Dielectric Loss

Dielectric loss is a loss of energy during heating of an object made of a dielectric

material when a variable voltage is applied to it. However, a dielectric loss is
strongly influenced by the changes of material polarization where a tiny electron
shifts can be deemed as a tiny alternating current flow. Additionally, at different
frequencies, different materials have different losses which must be taken into
account for an effective design of dielectric materials with suitable high frequency
applications.

4.4 Dissipation Factor

At high frequencies, different electrical parameters such as dissipation factor (e00 ) and
loss tangent (e00 /e0 or tan δ) are significantly important. With an increase in the
frequency, the inertia of the charged particles has an impact to prohibit the disloca-
tions of the particles from keeping in phase with the field changes that causes a
frictional damping mechanism and eventually results in a power loss (due to the
work performed in order to overcome these damping forces). Ohmic losses (due to
free charge carriers) are also included in the complex permittivity, and the effects of
both the damping and the ohmic losses in the imaginary part of the complex
permittivity, e*, are also considered (to deduce Eq. 4) [61–78].

σ ¼ ωe00 (4)
7 Dielectric Polymers 249

5 Basic Characteristic of Dielectric Polymers

Dielectric polymers have many characteristic properties. For example, a dielectric

electrical insulator is different from a conductor or a semiconductor and contains a
large band gap so that no electric charges can freely flow through this material. The
inherent physical characters of polymers are highly important criteria in order to
select their suitability as dielectric materials; some of these characters are (a) signal
speed, (b) power consumption, (c) thermal stability, (d) interaction with other
materials, and (e) wiring density. These polymers should also show particular
properties, such as electrical, mechanical, and thermal properties in order to provide
easy processing capability [18–43, 79–80].

5.1 Electrical Properties

Dielectric polymers are similar to insulators since they resist electrical conduction to
some extent. However, these polymers should have some important electrical char-
acters to be suitable for particular applications. For example, when this type of
material is exposed to an electric field, the electric charges of this dielectric material
including permanent and induced electric dipoles can be moved to show change in
the polarization of the material. Additionally, the equilibrium polarization of this
material is constant for a given electrical field (also called the dielectric constant e or
also symbolized by k) which is used to characterize the dielectric properties of this
dielectric polymer [79–80]. However, for an alternating electrical field, the dielectric
constant is a complex quantity (e*) expressed as the combination of a real compo-
nent termed as the relative permittivity or dielectric constant (e0 ) and an imaginary
component called as the dielectric loss or dissipation factor (e00 ). In addition, this
form is also termed as the complex dielectric permittivity usually defined by the
following:

e
¼ e0  je00 (5)

A key issue is the variation of both e0 and e00 with respect to frequency.

5.2 Physical Properties

Different suitable polymers, such as high thermal stability polymers, are very
attractive as dielectric polymers for their particular uses in thin-film multilayer
interconnections (however, silicon oxide-based products can also provide similar
performances). Usually, dielectric polymers are popular for their attractive electrical
characters and their easy processing (e.g., deposition and patterning) and their
relative stability in the presence of chemical attack and extreme tolerance in tem-
perature and humidity. For example, polyimides (which show stability over 400  C)
250 S. M. R. Billah

exhibit higher mechanical stability and flexibility and resistance to solvents and
chemicals. In addition, a dielectric polymer is expected to planarize the interconnect
topology, and it should have a coefficient of thermal expansion closely matched with
the substrate and also capable to be applied in thick layers (up to 25 μm) with low
stress and no cracks or pinholes [79–80].

5.3 Water Absorption, Planarization, and Chemical Resistance

The electrical properties and the processing capability of dielectric polymers show
direct impacts due to water absorption which is usually measured by the maximum
amount of water uptake (that depends upon the degree of cure, on temperature, and
on relative humidity of the dielectric polymers). The surface roughness of a substrate
surface (either due to existing interconnect structures or the polymer deposition
process) can directly affect the resolution, and quality of subsequent thin-film layers
and the planarity of the multilayer structure are useful for the uniformity of electrical
properties across the entire substrate. In addition, one of the main functions of the
dielectric layer is to planarize the underlying topography in order to provide a flat
focal plane for the next layer. Besides this, dielectric polymers are expected to show
chemical resistance when exposed to different chemicals during processing and
cleaning. Swelling, cracking, and crazing of the polymer layer are some of the
signs of poor chemical resistance. However, thermosetting polymers are usually
more chemically resistant compared to thermoplastic materials [18–43, 79–80].

6 Different Types of Dielectric Polymers

Dielectric materials can be grouped into two groups using a simple method of
classification, which are (a) low-k dielectric materials and (b) high-k dielectric
materials. Both low-k and high-k materials can be used with different suitable
polymeric materials to produce composite- or nanocomposite-based dielectric poly-
mers. As a result in this section, both dielectric polymers and other dielectric
materials are briefly described.

6.1 Low-k Dielectric Materials

Two primary approaches are usually used to achieve low-k dielectric materials, and
they are (a) lowering the electronic contribution by adding fluorine (F) and/or carbon
(C), to provide the material with an inherently lower electronic polarizability, and
(b) lowering the contribution due to the orientation and or the ionic contribution
(by introducing free volume in a material in order to decrease the number of
polarizable groups per unit volume and also to lower the atomic or dipolar contri-
butions) [18–43]. Low-k materials can usually be divided into three groups –
(a) inorganic, (b) organic, and (c) hybrid (e.g., organo-silicates). Organic dielectric
7 Dielectric Polymers 251

materials show lower k values than from inorganic materials because of their low
polarizability and hydrophobic character. However, inorganic materials retain a
SiO2-like matrix that assists their easy integration to the existing SiO2-like processes,
whereas hybrid materials, on the other hand, are usually doped with carbon (C) for
taking advantages of both organic and inorganic characters. As a result, in most
cases, it is observed that when the base material is selected (organic/inorganic/
hybrid), usually the next step is the integration of the material in the sub-100 nm
device. Selection of ideal low-k dielectric materials usually depends on their appli-
cations and the chip architecture in electronic devices.
Fundamental requirements for a processed dielectric material are quite a few in
number, however, for simplicity, some of the desired criteria are selectively men-
tioned here, they are (in particular for sub-100 nm level electronic devices) (Table 1):

(a) dielectric constant <3.0;

(b) sufficient thermal stability at least at the processing temperatures of the device,
and low coefficient of thermal expansion;
(c) strongly adherence to the substrate along with conformity after deposition;
(d) low thermal shrinkage, ability to resist cracking and compatible with chemical
mechanical polishing;
(e) having isotropic dielectric constant (k);
(f) high dielectric breakdown, low charge trapping and leakage current;
(g) low solubility in H2O and low moisture absorption from the ambient;
(h) friendly to surrounding environments and safe during handling;
(i) simple to process and relatively cheap;
(j) chemically inert;
(k) having high etch selectivity;
(l) Strong mechanical characters (such as, the film should have sufficient mechanical
strength in order to prevent cohesive failure, and interfaces delamination). [79–124].

6.2 Property Requirements of Low-k Dielectric Polymers

Dielectric polymers have many stringent property requirements in order for their
successful integration into the interconnect structures as low-k dielectric materials,

Table 1 Low-k dielectric materials

Materials Dielectric constant
Silicon dioxide 3.8–3.9
Carbon-doped silicon dioxide 2.2–2.7
Benzocyclobutane 2.49–2.65
Diamond-like carbon 2.7–2.8
Fluorinated diamond-like carbon 2.4–2.8
Aromatic thermosets 2.6–2.8
Polyarelene 2.8
252 S. M. R. Billah

which have required characteristics that show (a) electrical characters, (b) thermal
stability, (c) thermomechanical and thermal stress characters, and (d) chemical
stability. In that case, desired electrical properties include (i) low dielectric con-
stant, (ii) low dielectric loss and leakage current, and (iii) high breakdown voltage.
Many polymeric materials satisfy these electrical criteria; the dimensional stability,
thermal and chemical stability, mechanical strength, and thermal conductivity of
polymers are inferior to those of silicon dioxide. Low-k dielectric polymers are
required to show certain electrical, chemical, mechanical, and thermal properties.
These electrical characters are specific range of dielectric constant, anisotropy, low
dissipation, low leakage current, low charge trapping, high electric field strength,
and high reliability. They should also show particular chemical properties which
include certain level of chemical resistance, etch selectivity, low moisture uptake,
low solubility in water, low gas permeability, high purity, no corrosion to metal,
long storage life, and environmentally safe. They should exhibit particular
mechanical properties, some of which are uniform thickness, good adhesion, low
stress, high hardness, low shrinkage, crack resistance, and high tensile modulus.
They should also show particular thermal properties, some of which include
(a) high thermal stability, (b) low coefficient of thermal expansion, (c) low thermal
weight loss, and (d) high thermal conductivity [44–60, 80–131]. Table 2 shows
dielectric constants of important low-k dielectric materials or polymers with
respect to 1 MHz frequency.

6.3 High-k Dielectric Materials

High-k dielectric materials are highly important for a wide range of electronic
applications. However, there are many issues with high-k dielectric materials. For
example, an important issue that prevents the implementation of high-k gate material
is charge trapping in preexisting traps inside the dielectric material, which affects the

Table 2 Important low-k dielectric materials @ 1 MHz

Dielectric materials Dielectric constant
SiOxFy 3.20–3.50
Hydrogen silsesquioxane 3.00
Polysiloxane 2.89
Benzocyclobutane 2.70
Black diamond 2.70
Polyethylene 2.40
Polypropylene 2.30
Fluoropolymer 2.24
Perylene 2.20
Air 1.00
Carbon dioxide 1.00
7 Dielectric Polymers 253

threshold voltage. In this context, scaling the thickness of the gate dielectric has long
been recognized as one of the keys to scaling devices. However, when the oxide is
made thinner and the substrate doping is increased, the electric field applied to the
oxide/silicon interface results in a significant quantization of the carrier’s perpen-
dicular to the interface. In addition, during device fabrication with high-k, etching of
Si wafer is usually carried out with hydrofluoric acid followed by an ammonium
hydroxide surface treatment. The operation reduces but degrades mobility because
of surface nitridation, whereas the chemical oxidation by ozone contributes to
increase mobility at the expense of equivalent oxide thickness. But compared to
chemical oxide, in situ steam generated interfaces usually observed to show higher
overall electrical performances [79–124].
Different metal oxides (and some nitrides) and similar type of compounds are
popular high-k dielectric materials, some of which include (a) nitrides and
oxynitrides, (b) tantalum oxide (Ta2O5), (c) titanium oxide (TiO2), (d) hafnium
oxide (HfO2), (e) zirconium oxide (ZrO2), (f) lanthanum aluminate (LaAlO3),
(g) titanate compounds of barium (BaTiO3), barium strontium (BaSrTiO3), and
lead (PbTiO3). High-k dielectric materials have recently become important mainly
in three areas: (a) memory cell dielectrics, (b) gate dielectrics, and (c) passive
components [125–158]. For example, Table 3 exhibits the dielectric constants of
some important high-k dielectric materials and their usual applications. These types
of dielectric materials can be used with suitable polymers to produce high-k dielec-
tric composites and nanocomposites using different techniques.
High-k gate dielectrics have been investigated as alternative gate dielectrics for
certain technology (such as the 65 nm CMOS technology), and it also studied the
feasibility to replace conventional SiO2 or silicon oxynitrides (SiOxNy). Most
important requirements for high-k dielectric applications include – (a) high dielectric
constant and large band gap, (b) high band offset with electrodes, (c) thermally and
chemically stable in contact with semiconductor substrate, (d) scalable equivalent
oxide thickness (EOT) <10Å, (e) compatibility with gate electrode material, (f)
density of interface states comparable to SiO2, (g) low lattice mismatch and similar

Table 3 Important high-k dielectric materials

Dielectric materials Dielectric constant Applications
PbMgNbO3 + PbTiO3 22,600 Capacitor dielectrics
PbLaZrTiO3 1000 Capacitor dielectrics
BaSrTiO3 300 Capacitor dielectrics
TiO2 50 Gate dielectrics,
Capacitor dielectrics
Ta2O5 25 Gate dielectrics,
Capacitor dielectrics
CeO2 20 Gate dielectrics
BaZrTiO3 17.3 Gate dielectrics for organic transistors on plastic
Al2O3 9 Capacitor dielectrics
CaF2, SrF2 7.3 Epitaxial dielectrics
254 S. M. R. Billah

thermal expansion coefficient with Si mobility comparable to SiO2, (h) negligible

capacitance-voltage hysteresis (<20 mV), and (i) good reliability (no charge trap-
ping, high breakdown voltage) [44–60, 125–158]. Table 4 demonstrates the values
of dielectric permittivity of generally used ceramics for capacitors.
On the contrary, polymers are easily processed into large-area films, and
several polymers have relatively high breakdown field strengths; however, they
also have low dielectric constants (Table 5) and thus have low-energy densities.
Table 5 indicates a list of dielectric permittivities of commonly used polymers in
capacitors.

Table 4 Dielectric permittivity values of generally used ceramics for capacitors

Composition Dielectric permittivity
La1.8Sr0.2NiO4 ~100,000
CaCu3Ti4O12 ~60,000
SrTiO3 2000
BaTiO3 1700
TiO2 80
La2O3 30
a-LaAlO3 30
ZrO2 25
HfO2 25
Ta2O5 22
Y2O3 15
HfSiO4 11
Al2O3 9
SiO2 3.9

Table 5 List of dielectric permittivities of commonly used polymers in capacitors

Polymer Dielectric permittivity
Poly(vinylidene fluoride-co-hexafluoropropylene) ~12
Poly(ether ketone ketone) ~3.5
Nonfluorinated aromatic polyimides ~3.2–3.6
Silsesquioxane 2.8–30
Poly(arylene) 2.9
Fluorinated polyimide 2.6–2.8
Poly(phenyl quinoxaline) 2.8
Fluorinated poly(arylene ether) 2.7
Polystyrene 2.6
Poly(norbornene) 2.4
Perfluorocyclobutane polyether 2.4
Polynaphthalene 2.2
Poly(tetrafluoroethylene) 1.9
7 Dielectric Polymers 255

7 Different Selected Aspects of Dielectric Polymers

Many polymers are dielectrics or insulators which have poor bulk conductivity and can
survive high electric fields as they have no free charge carrier and large band gaps in
their electronic structures. Because of their simpler fabrication and lower cost with
respect to traditional inorganic materials, polymer dielectrics are extruded into thin films
or sheets and are widely used as capacitors, gate dielectrics in transistors, electrical cable
wraps, and microelectronic encapsulation. Opposite charges accumulate on both sur-
faces of the dielectric film after a high electric field is applied on a dielectric polymer
film and an electrostatic attraction force builds up between the opposite charges where
the like charges on the same electrode repel each other. In stage, the synergistic effect of
the two forces presses the polymer film in the direction of the electric field and stretches
in the orthogonal directions which cause it to shrink in thickness and expand in the area.
The phenomenon has been named after James Clerk Maxwell, as Maxwell stress or
Maxwell pressure, with the expression as shown in Eq. 6:

P ¼ e0 eE2 (6)

where e0 is the vacuum permittivity, e is dielectric constant of the dielectric material,

and E is the electric field applied across the material thickness. This equation is only
valid on the assumption that e does not change in its value along with the applied
electric field, the stress or strain in the material. Maxwell pressure is a phenomenon
to avoid in usual capacitor industries where even slight shape changes will crack the
thin-film metal electrodes used in capacitors and prevent the device from function-
ing. In addition, localized thinning of the dielectric sheet may lead to drastic charge
and electric field localization where an ultimate outcome is that the device is most
likely to be shorted. The phenomenon has been observed in a number of dielectrics
including using polyethylene and polyisobutylene [70–80, 122].

7.1 Dielectric Fluoropolymers and their Copolymers

Fluorinated polymers are very attractive for their interesting properties and have
applied for various high-tech applications. In this connection, two families of
fluorinated polymers are briefly discussed here. Of these two, the first one corre-
sponds to those where the fluorinated groups are located in the polymer backbone,
which are chemically inert, thermally stable, and have low refractive index and low
dielectric constant. The polymers or copolymers having crystalline structures with
large dipole moments can exhibit high piezoelectricity when their main chain shows
an all-trans conformation, for instance, the poly(vinylidene fluoride) (PVDF) partic-
ularly β-type conformation, the crystalline copolymers of vinylidene fluoride and
trifluoroethylene, and the terpolymers of vinylidene fluoride, trifluoroethylene, and
chlorotrifluoroethylene. There are reports on novel ferroelectric polymers based on
PVDF and its copolymers with hexafluoropropene which was proposed for high
256 S. M. R. Billah

electric energy storage and low loss performance have been reported. The second
family concerns the polymers with a fluorinated dangling group which improves the
surface properties and also exhibits low dielectric constant. Several fluoroalkyl
acrylate and methacrylate polymers have been developed, and their physical prop-
erties have been rigorously studied. Dielectric relaxation studies have been carried
on a series of poly(fluoroalkylmethacrylate)s where the α relaxations above Tg and γ
relaxations below Tg have been reported and assigned to reorientation of segments
and local molecular motion of fluoroalkyl side groups. In advanced electronic
devices, the use of high dielectric constant polymers is a crucial component, for
example, memory and gate dielectrics for integrated circuits, stationary power
generation, and miniature capacitors for telecommunication. Polymers with cyano
groups directly attached to the main chain are of potential interest for these devel-
opments due to the high dipole moments that can be induced along the macromo-
lecular chain. For instance, vinylidene cyanide (or 1,1-dicyanoethylene, VCN) has
often been employed in the preparation of high-polar polymers as a useful starting
monomer [79–108, 122].
Other polymers based on commercially available cyano monomer, for example,
acrylonitrile, (AN) have been used, and the dielectric behavior of polyacrylonitrile,
PAN, in its pristine and cyclized states, has been reported. In addition, a soluble
organic PAN material was studied for its potential applications as gate dielectric
material. Functional transistors have been reported by using PAN along with poly
(3-hexylthiophene) as a semiconductor material. Poly(acrylonitrile-ter-methyl meth-
acrylate-ter-indene) terpolymers have been synthesized and rigorously studied by
isochronal dielectric tests which illustrated their glass-rubber transition values (Tg)
are highly dependent on the composition. In addition, there are reports on the
measurements of the pyroelectric constants of these copolymers which provided a
good approximation for a piezoelectric behavior. Advances in portable electronic
devices, stationary power systems, and hybrid electric vehicles create a great need
for low-cost, compact, and high-performance electrical energy storage devices. The
development of dielectric polymers (capacitor systems) which have high energy
density is governed by the dielectric constant of the materials that separate the
opposite static charges [79–108, 122].

7.2 Dielectric Polymer Composites

Typically, a composite material is a mixture of two or more component materials

behaving like one system with combined characters of multiple constituents. Certain
types of polymer composites can be used as dielectric materials, such as ferroelectric
ceramics. However, dielectric materials (e.g., ferroelectric ceramics and polymers)
have a number of drawbacks that limit their integration as high-k materials in certain
applications. For example, high-k ceramics frequently lack stability that allows very
low-voltage operation, whereas low-k polymers offer low leakage currents and high
stability but require higher operating voltages [109–130]. Different methods are
usually employed for preparing ultra-high k materials from conductive filler/polymer
7 Dielectric Polymers 257

composites which are suitable to be used in embedded capacitors. Ultrahigh-k values

have been investigated with conductive filler/polymer composites when the concen-
tration of the conductive filler approaches the percolation threshold that can be
explained by the percolation theory for conductor-insulator percolation system.
For conductive filler/polymer composites, the effective electrical properties
approaching to the percolation threshold are determined by the scaling theory that
can be demonstrated in Eq. 7 through Eq. 9.

σ ¼ σM ðf  fcÞ t f > fc (7)

σ ¼ σD ðfc  f Þ  q f < fc (8)

e ¼ eD= j f  fc j q ¼ eD ðσM =σM Þs (9)

Here, σM and σD are the electrical conductivity of conductive filler and polymer,
respectively; f and fc are the concentration and the percolation threshold concentra-
tion of the conductive filler within the polymer matrix, respectively; eD is the
dielectric constant of the polymer matrix; and q, s, and t are scaling constants,
related to the material property, microstructure, and connectivity of the phases in
the conductive filler/polymer system. In addition, sometimes, the effective dielectric
constant of the metal-insulator composite could be three or four orders higher than
the dielectric constant of the insulating polymer matrix. This phenomenon can be
stated in terms of a “supercapacitor network” with very large area and small
thickness. In addition, when the concentration of the metal is close to the percolation
threshold, large amount of conducting clusters are in proximity to each other;
however, they are insulated by thin layers of dielectric material. Besides this, the
percolative approach needs much lower volume concentration of the filler compared
to traditional approach of high-k fillers in a polymer matrix. As a result, this material
option shows advantageous characteristics over the conventional ceramic/polymer
composites, particularly ultrahigh-k with balanced mechanical properties including
the adhesion strength. In addition, various metal particles or other conductive fillers,
for example, silver (Ag), aluminum (Al), nickel (Ni), and carbon black, have also
been used to synthesize the polymer conductive filler composites or three-phase
percolative composite systems. High dielectric loss, low dielectric strength, and
narrow processing window are technical barriers for this category of materials. In
addition, because the highly conductive particles are easy to form, a conductive path
in the composite as the filler concentration approaches the percolation threshold.
Recently, much work has been engaged with solving these problems of the conduc-
tive filler/polymer composites, and much progress has been achieved [109–130].

7.2.1 Ferroelectric Ceramic/Polymer Composites

As a major material candidate for embedded capacitor applications, different studies
on ferroelectric ceramic/polymer composites with high-k values have been rigor-
ously investigated. In these studies, the methodologies of different approaches
have been used for combining the advantages of the polymers which meet the
258 S. M. R. Billah

requirements for the low-cost organic substrate process. Some of these advantages
include (a) low-temperature processibility, (b) mechanical flexibility, and (c) low
cost. These materials show easy processing capability since the high temperature
steps required to reach high-k from the ferroelectric phase can be executed in
advance of application to the organic substrate. Additionally, almost any high-k
ferroelectric material can be produced in quantity as submicron powders. These
high-k particles can be mixed with a polymer resin at up to 60 to 80% loading by
volume which can be screen printed, spun on, or stenciled onto the substrate and the
polymer phase that can be cured at temperatures tolerable to organic boards.
However, there are still some challenging issues related to these polymer composites
for high-k applications, for example, limited dielectric constants and capacitance
density and low adhesion strength which results in air gaps and lowers capacitance.
The k of the final composite will be much closer to that of the low-k material. This is
generally the polymer with a k of about 3 to 5 according to the mixing rules for a
two-phase combination of two materials with different k. Similarly, most of the
k values of ceramic/polymer composites developed to date are between 10 and 50 at
room temperature, and the corresponding film can be made in thickness of around
8 μm pinhole free by screen printing and delivers specific capacitance (up to
approximately, 5 nF/cm2). Polar polymers can increase k of the composites at low
frequencies, whereas the presence of polar groups in the polymer matrix also
increases dielectric losses especially within the intermediate- and high-frequency
ranges. Besides this, the k values of ceramic/polymer composites can be effectively
enhanced using polymer matrix with relatively high-k which is mainly due to
k values of polymer matrix that shows very strong influence on the k of the final
composites. For example, Pb(Mg1/3Nb2/3)O3-PbTiO3/P(VDF-TrFE) composites
exhibit k values above 200. Additionally, lead magnesium niobate-lead titanate
(PMN-PT) + BaTiO3/high-k epoxy system (effective k: 6.4) composite shows
k value around 150, in which ceramic filler loading is as high as 85% by volume.
Different investigation demonstrated that the k of 0–3 connectivity type composite is
dominated by the matrix, and as a result, a relatively large volume fraction of high-k
ferroelectric inorganic phase is required. The high filler loading of ceramic powders
is still the technical barriers for real application of ceramic/polymer composites in
the organic substrate. It shows a poor dispersion of the filler within the organic
matrix and shows no adhesion toward other layers in PWB as well because of the
low polymer content [131–170].

7.2.2 Dielectric Character of All-organic Polymer Composites

The composites fabricated by dispersing an organic filler material have very high
dielectric constant in a polymer matrix which can show high-k as well. Copper-
phthalocyanine (CuPc) oligomer based organic semiconductor materials exhibit
higher k value (i.e. 105) and when they are dispersed in P(VDF-TrFE) matrix to
prepare a composite they show higher k value (such as, 225) and a loss factor of
0.4 at 1 Hz. In this case, the high dielectric loss can be attributed to the long-range
intermolecular hopping of electron. In addition, there are reports that chemically
modified copper phthalocyanine (CuPc) can be bonded to the backbone of
7 Dielectric Polymers 259

P(VDF-TrFE) in order to improve the dispersion of CuPc in polymer matrix.

However, as a direct impact of chemical modification CuPc/P(VDF-TrFE) compos-
ites, there can be a reduction of dielectric loss and weakening of dielectric dispersion
(over a particular frequency). A k value above 1000 (@ 1 kHz) has been reported for
an all-polymer high-k percolative material-based composite which has been fabri-
cated by a combination of conductive polyaniline (PANI) with a poly(vinylidene
fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFECTFE)] terpolymer
matrix (k > 50). However, further rigorous studies are a prerequisite in order to
realize all-organic based composites with high-k values suitable for their uses in
capacitors [171–191].

7.2.3 Dielectric Polymer Composite for Energy Storage

Particular type of polymer composites with required dielectric properties can cater
the need for pulse power energy storage systems with high energy density by
combining the scope of processibility and breakdown field strength of the polymer(s)
along with materials of high dielectric constants (such as ceramic fillers). In typical
sense, the fillers are used to enhance the effective dielectric constant of the composite
system avoiding the loss of the high inherent breakdown strength of specific poly-
mers. In addition, one of important points is that any improvement in the effective
dielectric constant should be realized avoiding any type of higher compromise in
dielectric loss (such as energy dissipation). In practical consideration, it is very
difficult to achieve various objectives like (a) high dielectric constant, (b) high
breakdown field strength, and (c) low dielectric loss; however, a suitable compro-
mise is one of the best solutions. As a result, a lion share of research in this area is
mostly focused to boost targeted electrical and other required properties of polymer
composite materials using a sound understanding of the physical phenomena that
have impact on composite dielectric permittivity and breakdown field strength. The
behavior of the polymer-filler interface is directly related to the chemistry and
structure of dielectric composites. In this respect, in some recent studies, for enhanc-
ing dielectric permittivity of dielectric polymer composites, different types of metal
oxides are popularly used; some of these metal oxides include Pb(Zr,Ti)O3, Pb
(Mg0.33Nb0.77)O3-PbTiO3, and BaTiO3. For example, it is highly attractive to
boost the dielectric constant of a dielectric polymer composite in the order of
hundreds or even thousands by using suitable inorganic fillers in accurate propor-
tions. But there are different challenges to realize these practical expectations, some
of which include the following: (a) when the filler with higher level of permittivity in
comparison to that of the polymer matrix is incorporated in the system, it causes an
increase in the effective dielectric constant comes through an increase in the average
field in the polymer matrix that allows relatively little energy storing capacity in the
high permittivity phase; (b) there are chances that the large contrast in permittivity
between two phases can lead to highly inhomogeneous electric fields; and (c) it is
also possible to cause a loss in compatibility between the organophilic polymer
matrix and the hydrophilic metal oxide filler that may contribute to poor level of
homogenous composite. As a result, the modification of the inorganic filler surface
260 S. M. R. Billah

to achieve suitable compatibility of the inorganic filler with the polymer matrix is
one of the main focal points of current research in this area [191–201].

7.3 Dielectric Polymer Nanocomposites

The interfaces between the polymers and the nanoparticles have critical influence in
order to control the dielectric properties of polymer nanocomposites. For example,
polymer-ceramic nanocomposites are promising dielectric materials for many elec-
tronic and power devices that can effectively combine the high dielectric constant of
ceramic particles along with the high dielectric breakdown strength of a polymer. In
addition, it has been reported that as the size of filler particles decreases to the
nanometer scale, the properties of the polymer-filler interface becomes dominant
over the bulk properties of the constituents [107]. This concept goes beyond the
modification of the filler surface to achieve better dispersion of the dielectric filler
particles. In a true nanocomposite dielectric (simply, nano-dielectric), the unique
properties of the interface are amplified by the high surface area of the filler
[107–111, 202–225].

7.3.1 Current Trends in Dielectric Polymer Nanocomposites

Nanocomposite materials are composed of multiple constituents in particular com-
binations which have nano-dimensional phases with distinct differences in structure,
chemistry, and properties. Generally, nanocomposites contain inorganic components
in organic hosts or vice versa. Otherwise, they may also have two or more inorganic/
organic phases in some combinatorial forms with the constraint that at least one of
the phases or features in the nanosize. Nanocomposites show unique combinations
of mechanical, electrical, optical, electrochemical, catalytic, and structural properties
compared to those of each individual component to make this composition. In
addition, their micron-size filled counterparts have a few advantages such as differ-
ent structure, composition and properties of their constituents [109–225].

Nanofillers
Nanofillers are fillers with sub-100 nm size in at least one dimension. One of the
main objectives for the application of nanoparticle instead of micron-scale traditional
fillers is the impact of particle size on their properties. Due to the incorporation of
nanofillers into nanocomposite structures, they can achieve some unique and excel-
lent properties, some of which include (a) electrical, (b) magnetic, (c) optical,
(d) catalytic, (e) mechanical, and (f) chemical or biological properties. For example,
due to the incorporation of carbon nanotube into a nanocomposite structure, it may
achieve ultrahigh modulus and conductivity of carbon nanotubes. As a result,
nanocomposite materials provide the scope of enhancing functionality in contrast
with their single-component counterparts. For instance, nanocomposites with mod-
ified electrical or mechanical properties that retain their optical clarity can be
obtained due to the fact that very small nanoparticles incorporated into their structure
do not scatter light significantly. In addition, nanoparticles are less likely to create
7 Dielectric Polymers 261

large stress concentrations and thus can avoid the compromise of the material
ductility while they contribute to improvement of other mechanical properties.
Nanoparticles have a much higher surface area per unit volume than larger particles,
and they also possess a much greater interface with their surroundings. As a result
when nanoparticles are incorporated into nanocomposite structures as fillers, the
small size of the fillers leads to an exceptionally large interfacial area in the
nanocomposites. The interface has a significant impact in controlling the degree of
interaction between the nanofiller and the polymer matrix which eventually controls
the properties of the nanocomposites. The method of preparation sometimes influ-
ences the size and characteristics of the nanoparticles. The nanoparticle size depends
on the kinetics of nucleation and growth from a supersaturated solution as well as
processes, for example, (a) coarsening, (b) oriented attachment, and (c) aggregation.
Because of the reduction of lattice constants, the large surface energy and thermo-
dynamic instability resulted from the large ratio of the surface to interior atoms exert
great challenges to stabilize nanoparticles. One way to prevent the nanoparticles
from growth in size is to reduce the surface energy by insertion (such as adsorption
and bonding) of surface active components into the particle surface. Synthesis of
nanoparticles in confined geometries and structured reaction media can contribute to
yield anisotropic and size-controlled nanoparticles. A basic understanding is very
important in order to tailor and optimize properties by controlling the size, shape,
volume fraction, interface, and degree of dispersion or aggregation of nanoparticles
to guide enhanced development. In addition, the ability to manipulate the size,
morphology, and arrangements of nanoparticles in such a fashion that their unique
properties (such as, optical, electrical, and magnetic) can be utilized for different
applications remains a challenge [109–151].

Processing of Polymer Nanocomposites

One of the main limitations in the commercialization of nanocomposites is their
processing which involves with a major difficulty relating to proper dispersion of the
nanofillers in the polymer matrix. This is mainly due to the impact of nanoparticles
which are aggregated or agglomerated very easily due to the interparticle surface
forces (e.g., van der Waals forces, capillary forces, and electrostatic forces) which
often leads to undesirable materials properties. The processing of polymer nano-
composites has different type of impacts on the state of the arrangement of nanofiller
in the nanocomposites that can be understood from the distribution and dispersion.
The quality of nanofiller dispersion in the polymer matrix directly correlates with its
effectiveness in the improvement of mechanical, electrical, thermal, impermeability,
and other characteristics. In addition, the natures of a composite are also closely
related to the aspect ratio and surface-to-volume ratio of the filler. Three general
methods generally are involved with dispersing nanofillers in polymers, and they are
(a) direct mixing of the nanoparticle and the polymer either as discrete phases or in
solution phase, (b) in situ polymerization in the presence of the nanoparticles, and
(c) in situ formation of the nanoparticles and in situ polymerization simultaneously.
However, hybrid nanocomposites are prepared by the intimate mixing of the two
phases ((a) + (b)) [109–225].
262 S. M. R. Billah

Direct Mixing
Direct mixing of the nanoparticle and the polymer can be carried out in different ways,
such as in discrete phases or in solution phase. Polymer processing techniques (such as
melt mixing or elastomeric mixing through roll mill, twin screw extruder, Brabender
high-shear mixer, or thermal spraying) can be applied for direct mixing of the nano-
fillers and the polymer as discrete phases. For instance, nano silica (SiO2)/polypropyl-
ene, nano alumina/poly(ethylene terephthalate) (PET) or low-density polyethylene
(LDPE), and nanoparticle-filled nylon can be prepared using some of these techniques.
However, the rapid increase of the viscosity in addition to significant volume fractions
of nanofiller limits the viability of the processing technique. Solution-phase mixing is
related to dissolving or dispersing the polymer and the nanoparticles in solution, and
using solvent evaporation or precipitation technique, the nanoparticle/polymer solution
can be cast into a film or can be isolated from solution. This technique allows to modify
the particle surface without drying which reduces the chances of particle agglomeration
and thereby helps to overcome some of the limitations of direct mixing.
For example, electrically conductive graphene/polymer nanocomposites were syn-
thesized by solution-phase mixing of the exfoliated phenyl isocyanate-treated graphite
oxide sheets with polystyrene, followed by their chemical reduction [151–177].

In Situ Polymerization
In situ polymerization refers to the dispersion of the nanofillers in the monomer or
monomer solution followed by standard polymerization of the resulting mixture.
Some examples include (a) nano SiO2/nylon 6, titania (TiO2)/polymethylmethacrylate
(PMMA), and calcium carbonate (CaCO3)/PMMA. The potential feasibility to graft
the polymer onto the particle surface is one of the main advantages of this method. One
of the main points of this technique is the appropriate dispersion of the filler in the
monomer which often relates to the modification of the nanoparticle surface. It is due
to the settling process which is more rapid in a liquid than in a viscous melt although
dispersion is easier. [109–121, 178–188].

In Situ Nanoparticle Processing/Formation

In situ nanoparticle processing or formation is another type of technique to produce
nanoparticle-filled polymers. Ceramic/polymer composites can be synthesized using
an in situ processing of the SiO2 and TiO2 in a range of polymer matrices by mixing
SiO2 or TiO2 precursor with a polymer followed by the sol-gel reaction. There are
reports on the processing of metal/polymer nanocomposites via an in situ formation
of metal nanoparticles in the polymer matrix from suitable metal precursors where
the presence of the protective polymer can prevent the agglomeration and limit the
size of the nanoparticles. For example, the parameters which affect the size, stability,
and morphology of as-formed nanoparticles have been reviewed. Primary parame-
ters that control the nanoparticle size include the choice of metal precursor and the
metal-polymer interaction. The nanoparticle size tends to reduce when the polymer
has a stronger interaction with the metal precursor (since the precursors are pre-
vented from phase separation) [129–157, 189–211]. Spherical micelle formation
from amphiphilic block copolymers or crosslinked/gelled matrices have some
7 Dielectric Polymers 263

particular control over nanoparticle size and morphology. In this case, metal pre-
cursors either penetrate into the micelles or stabilize in the micelle corona, and thus
metal nanoparticles can form either within the micelles or in corona after the addition
of reducing agent which contributed to produce various morphological structures.
Various conductive, semiconductive, or magnetic nanoparticles (such as gold, silver,
palladium, platinum, semiconductors, and metal oxides) can be formed using this
method which provides tremendous opportunity to tune the properties of these
nanocomposite systems [158–179, 211–231].

Modification of Nanoparticle Interfaces

The interfacial region within the polymer matrix has properties significantly different
from those of the bulk polymer. In addition, the local chemistry, degree of cure, chain
mobility, chain conformation, and degree of chain ordering or crystallinity can vary
continuously from the filler/polymer matrix boundary to some point in the bulk
polymer. Nanofillers have many controlling effects on the resultant behaviors of
polymer composites. Additionally, a specified size and shape that is controlled by the
surface chemistry of nanoparticles is often needed to understand the special advanced
functionalities for various studies and uses of polymer composites. The encapsulation
of nanoparticles gives them important characters which are not usually present in the
uncoated nanoparticles. For example, organic or inorganic coatings on metal or other
inorganic particles improve compatibility with organic ingredients, protect particle
surfaces from oxidation, and thus improve dispersibility, chemical stability, and so
on. As a result, nanofiller interface modification is also essential [180–192, 232–243].

Modification of Nanoparticles by Organic Coatings

In this case, two principal techniques in order to modify the surface of inorganic
nanoparticles with organic molecules are either connecting a short chain molecule
onto the surface via grafting or strong hydrogen bonding or applying a polymer
coating onto the surface via polymerization. Usually these coatings contribute to
have the control over the compatibility of the modified nanoparticles with the
polymer matrix and the strength of the interaction in between. For example, in the
first method, hydroxyl groups on the metal and metal-oxide nanoparticle surface can
react with a silane coupling agent, and the large variety of functionalities attached to
the silanol modifies the nanoparticle surface with long or short, hydrophilic or
hydrophobic, and linear or bulky chains. As a result, the strength of the interaction
between the filler and the polymer matrix can be controlled from covalent bonding to
repulsion, leading to increases or decreases in glass transition temperature, modulus,
or other properties of nanocomposites. Many research activities are engaged with the
control of the size and the degree of aggregation of nanoparticles. In addition, the
coating layer with reactive sites on the nanoparticles can be used to bond particles
together and also to control aggregation of the nanoparticles. Monomer adsorption
and subsequent polymerization on the nanoparticle surface have been illustrated on
micrometer-scale filler surfaces. In addition, another method involves the grafting on
an initiator and then polymerizing a grafted polymer onto the nanoparticle surface.
Besides this, a multilayer structure can be achieved on the nanoparticle surface by
264 S. M. R. Billah

self-assembled polymer layers by the use of layer-by-layer (LbL) colloid templating

strategy. LbL assembly has the advantages of simplicity, universality, thickness control
in nanoscale, low cost, and being environmentally friendly, and uniform multilayers
can be formed by this approach on a number of 3D objects because of the conformal
nature of the polyelectrolyte adsorption process besides the 2D surfaces. The buildup
of polyelectrolyte multilayers on colloidal surfaces ranging in size from several
micrometers down to nanometers has been illustrated. A frequently utilized method
to create nanoparticle-loaded thin-film coatings on colloidal particles is via layer-by-
layer assembly of a polyelectrolyte and preformed nanoparticles of an opposite surface
charge, and this approach provides a simple route to create core-shell [109–119].

Inorganic Coatings
Inorganic coatings have also been applied to nanoparticles via precipitation or
deposition of the inorganic species onto the particle surfaces by a sol-gel type
process; for example, SiO2, TiO2, titanium nitride, and zirconia have been coated
on nanoparticles, usually metal oxides, in this way [109–119].

Nanodielectrics
Nanodielectrics are a new class of dielectric material which emerges with the increased
enthusiasm and activity toward the research on the nanotechnology, and it is also
anticipated that nanocomposites are highly promising nanodielectrics. Dielectric poly-
mer nanocomposites based on nanoparticles are a category of nanocomposites that
provide a potential solution in order to meet the present and future technological
demands, some of which are (a) the good processibility and (b) synergistic properties
(such as mechanical properties of polymers combined with the unique electrical,
magnetic, or dielectric properties of nanoparticles) of polymer nanocomposites. The
heterogeneous inclusions although they are nonpolar sometimes cause heterogeneous
dielectric polarization due to the accumulation of a virtual charge at the interface of two
media with different permittivities or conductivities. Additionally, nano-sized particles
are preferred for high-k dielectric composite materials due to the fact that they could
help achieve thinner dielectric films leading to a higher specific capacitance. As a result,
there is recent progress on the introduction of more nanoparticles of ceramic, metallic,
or even organic semiconductor to prepare high-k dielectric materials [119–170].

8 Performance Enhancement of High-k Nanocomposites

8.1 Filler Size Effect

Several issues of nanoparticle-based dielectric composite materials require to be

addressed. In this case, inner particle size is needed in order to obtain a thin dielectric
film and also to increase the capacitance density. For example, in the case of
ferroelectric ceramics, extremely fine particles may lead to the change of crystal
structure from tetragonal that results from the high permittivity which is cubic or
pseudo-cubic [109–131].
7 Dielectric Polymers 265

8.2 Micron-Sized Nanoparticles

BaTiO3 powders disappear finally when the particle size decreases to approximately
100 nm and 60–70 nm, respectively. For example, there are reports on the synthesis
of BaTiO3/epoxy composite embedded capacitor films (ECFs) with average
particle size of 916 nm (P1) and 60 nm (P2); the k values of ECFs made of P1
were higher than those made of P2. As a result, the coarser particle is more useful
than the finer particle to obtain high-k of ECFs using unimodal powder in this
case. However, by adopting bimodal fillers, fine nanoparticle can effectively
improve the k values by maximizing packing density and removing the voids
and pores formed in the dielectric films. A dielectric constant of about 90 was
obtained at a frequency of 100 kHz by using these two different sizes of BaTiO3
powders [109, 119–131].

8.3 Controlled Dispersion

Uniform dispersion of nanoparticles in nanocomposite materials is very impor-

tant since nanoparticles have the capability to agglomerate which may lead to
undesirable electrical or materials properties. Thus, the dispersion of nano-
particles is an extremely important contributor in order to achieve improved
dielectric properties and reproducibility. Similarly, addition of surfactant or
dispersant such as phosphate esters can enhance the dispersion of nanoparticles
in polymer matrix in order to improve the overall film quality and dielectric
performance of the nanocomposites. Chemical modification of nanoparticles is
also a useful method to enhance the dispersion of nanoparticles. For example,
surface modification of BaTiO3 and related perovskite-type metal oxide nano-
particles with phosphonic acid ligands leads to well-dispersed BaTiO3/polymer
nanocomposite films with high dielectric strength. This methodology is straight-
forward and easily adapted to a wide range of systems by using appropriate
ligand functionality [109, 119–135].

8.4 Control of Dielectric Loss for Conductive Filler/Polymer

Nanocomposites

Conductive filler/polymer nanocomposites have been identified as a promising

method in order to meet the material requirements for embedded capacitors. How-
ever, the dielectric loss of this type of materials is very difficult to control since the
highly conductive particles are easy to form a conductive path in the composite as
the filler concentration approaches the percolation threshold. Recently much work
has been devoted to the control of the dielectric loss of this system to solve this
drawback. In addition, the direct contact of the conductive metal fillers will lead to
high dielectric loss or even conduction for the conductive filler/polymer composites
at or above percolation threshold. Thus, core-shell structured fillers have the
266 S. M. R. Billah

potentials to be used as fillers instead of using conductive filler directly. It is due to

the fact that the nonconductive shell can serve as electrical barrier between the
conductive cores in order to form a continuous interparticle barrier layer network in
order to achieve high-k and low loss [111–167, 243–248].

9 Dielectric Elastomers

Elastomers are polymers which show high degree of flexibility and low modulus when
crosslinked and exhibit significant reversible deformations under applied mechanical
stress. Elastomers are generally dielectrics with dielectric constant ranging from about
2 to 25. Cross-linked elastomers, alone or together with other compounding ingredi-
ents, are referred to as rubbers. Rubbers more frequently studied for dielectric elastomer
actuator (DEA) applications include silicone (PDMS), polyacrylate, and polyure-
thane. Moreover, different pieces of research have been conducted on DEAs utilizing
acrylonitrile-butadiene rubber (NBR), natural rubber (NR), chloroprene (CR),
ethylene-propylene-diene (EPDM), fluorinated rubbers, and polyester-based elasto-
mer [243–257]. Table 6 briefly shows the actuation response and particular features of
some selected commonly used dielectric elastomers [257].

Table 6 Different particular features of some commonly used dielectric elastomers [257, 259–265]
Elastic
Electric Coupling Young’s energy
Dielectric Dielectric field, efficiency Strain, modulus, Pressure, density,
elastomer constant V/μm % % MPa MPa J/cm3
Silicone nusil 2.8 235 54 32 1.0 1.36 0.22
CF19–2186
Silicone DC 2.8 72 64 41 0.125 0.13 0.026
HS3
Silicone DC 2.8 144 54 32 0.7 0.51 0.082
Sylgard 186
Polyurethane 7.0 160 21 11 17 1.6 0.087
Deerfield
PT6100S
Fluorosilicone 6.9 80 48 28 0.5 0.39 0.055
DC 730
Fluoroelastomer 12.7 32 15 8 2.5 0.11 0.0046
Lauren
L143HC
Isoprene natural 2.7 67 21 11 0.85 0.11 0.0059
Rubber
SEBS161 1.7–2 133 80 Areal 0.007–0.163 – 0.151
Copolymer 180
5–30w%
Midblock
7 Dielectric Polymers 267

9.1 Bioinspired Dielectric Elastomers

Nature provides ideas how to create new functional materials resembling those
already existing in the biosphere where the bioinspired and biomimetic materials
have recently gained a huge interest in the scientific community. It looks impossible
to surpass the creations of Mother Nature; however, many recent pieces of research
aim to develop artificial muscles for many potential industrial exploitations. In this
context, artificial muscle is synonymous to muscle-like material, and such materials
have been developed for non-biomedical applications rather than replacing natural
muscles. Some of the possible applications of artificial muscles include (a) refreshable
braille displays, (b) robotic arms and other moving parts, (c) loudspeakers, (d) optical
zoom lenses, (e) active damping and force-feedback systems, and (f) energy genera-
tors. In addition, dielectric elastomers are currently investigated for their uses as smart
materials for their potential applications in muscle-like actions. To a good extent,
dielectric elastomers have some attractive features suitable to resemble the natural
muscles, and some of the important features are (a) strain, (b) actuation pressure,
(c) density, (d) efficiency, and (e) response speed. Compared to other electroactive
polymers, dielectric elastomers are attractive because of their overall desired features
like their high strains and relatively cheaper cost. Thus, rigorous current researches in
this area are focused on their cost-effective multipurpose high-tech applications
[226–236, 243–257].

9.2 Different Aspects of Dielectric Elastomers

Dielectrics work as insulators which can be polarized when subject to an electric

field. Among the dielectric polymers, dielectric elastomers fall in one of the
important category of dielectric polymers which are soft electroactive materials
that can be developed as electromechanical transducers and convert energy from
one form to another. Dielectric elastomers which transduce electrical energy to
mechanical energy when they act on actuator mode can also convert mechanical
energy to electrical energy in a reverse mode (such as generator mode). Dielectric
elastomers are usually crosslinked above the glass transition temperature of
polymer materials which have lower shear moduli (a few kilopascal) and more
mechanical compliance compared with the stiff or hard dielectrics with moduli of
a few gigapascal and achievable strains typically less than 1% (like piezoelectric
crystals and ceramics) [226–236]. Dielectric elastomers are capable of undergoing
a large voltage-induced deformation and have other characteristic properties,
some of which include high energy density, softness, and flexibility. These
materials have been used and also explored for many applications including in
(a) artificial muscles, (b) programmable haptic surfaces, (c) conformal loudspeakers,
(d) energy harvesters, (e) tunable lens, (f) soft robots, (g) sensors of force and
pressure, (h) active noise control devices, (i) oscillators, and (j) resonators and
adaptive optical elements [226–236, 257–260].
268 S. M. R. Billah

9.3 Large Deformation Capability and Typical Failure Modes

of Dielectric Elastomers

Dielectric elastomers (DEs) have many advantages (such as large deformation

capability), but this voltage-induced deformation capability of dielectric elasto-
mers is strongly affected by multiple failure modes. The actuation of DEs is also
limited by electrical breakdown (EB) failure similar to any other dielectric mate-
rials. The material rapture and the electrical breakdown because of the electric field
induced by the applied voltage sometimes can exceed the dielectric strength
of the material. The determination of the dielectric strength of dielectric elastomers
presents many challenges due to the impacts of a number of influencing factors
[237–246]. The dielectric strength of dielectric elastomers monotonically
increased with the increasing stretch ratio while decreased with the increasing
thickness. The dielectric constant of dielectric elastomers is non-monotonic to the
temperature. The configuration of the electrodes on the dielectric elastomers and
the loading rate of the applied voltage have significant effect on the dielectric
strength of dielectric elastomers [247–251]. A constant dielectric strength is
commonly assumed in the theoretical analysis on dielectric elastomers, because
the mechanisms related to these phenomena are not well understood. The compli-
ant electrodes coated on the dielectric elastomer membrane exert no constraint to
both the top and bottom surfaces, when an electric voltage is applied to the
electrodes. The induced electric field along the thickness direction forces the
unconstrained dielectric elastomer membrane to contract in thickness and stretch
in area. The thickness reduction of the dielectric elastomer membrane in turn
causes a higher electric field under the same applied voltage which results in a
higher attractive electrostatic force to further thin down the dielectric elastomer
membrane. This feedback mechanism may lead to excessive thinning of the
dielectric elastomer and results in the electromechanical instability (EMI)
(or pull-in instability), at a particular level of the applied voltage. This excessive
thinning may cause a premature electrical breakdown or result in a desirable large
deformation which depends on the dielectric strength of the dielectric elastomer.
As the advantages of dielectric elastomers mainly present in their capability of
undergoing large deformation, much effort has been devoted in order to tackle the
EMI to improve the actuation performance or even to harness the EMI for giant
voltage-induced deformation of dielectric elastomers [252–256].

10 Dielectric Breakdown of Other Polymers

Dielectric breakdown is the catastrophic failure of an insulating material under an

external applied field resulting in mechanical damage and electrical conduction,
depending upon the defect density of a solid material or a dielectric polymer.
Electrical breakdown testing of polymers for insulator applications has long been a
subject of interest. Table 7 is a selective compilation of the dielectric strengths of
some commonly used polymers [257, 259–269].
7 Dielectric Polymers 269

Table 7 List of dielectric strengths of insulating polymers [257, 259–265]

Polymer Dielectric strength (V/μm)
Polyester 300
Polyimide 280
Polycarbonate 252
Polyethylene 200
Polypropylene (biaxially oriented) 200
Polytetrafluoroethylene 88–176
Epoxy resin 25–45

10.1 Dielectric Breakdown Behavior of Polymer Composites

and Nanocomposites

Active current research activities are focused on enhancing dielectric properties of

composites and nanocomposites based on a wide range of polymers and other
materials (such as inorganic fillers and organic-inorganic hybrid systems). For
example, in a study, inorganic filler has been added to polymers in order to increase
the effective dielectric constant and energy density [269]. Typically used filler
particles in conventional composites are very little in size (such as micron-sized or
larger). However, the addition of micron-sized fillers has often had a negative impact
on breakdown strength which may be due to aggregation of filler particles which
may introduce defect centers that distort and enhance the local electric field that
results in reduced breakdown strength [269]. This type of field distortion is mainly
due to the difference in permittivities of the filler and the polymer matrix under
alternating current (AC) conditions and may also be due to differences in conduc-
tivities under direct current (DC) conditions. Similar types of results are also
observed in related other studies [269–278].

11 Recent Trends in Dielectric Polymer Applications

Dielectric polymers have wide range of applications including in (a) electrical

insulation, (b) dielectric capacitors, and (c) electromechanical actuators. Some
dielectric polymers show large strain deformations when exposed to electric field
(also called dielectric elastomers, as already stated in a previous section) due to their
relative low modulus, high elongation at break, and outstanding resilience charac-
ters. Dielectric elastomers can be used as actuators which have many advantages
over traditional transducers, some of which include – (a) large strains, (b) high
energy densities, (c) high coupling efficiency, (d) quiet operation, and (e) light
weight. There are many applications of dielectric polymers and a growing interest
has recently been shown on fluorinated materials which show the desired character-
istics. Advanced pulsed power and power conditioning technologies for power
generation/regulation and all electric vehicles/ships need a capacitor material in
order to achieve a high discharged electric energy density as well as low loss
270 S. M. R. Billah

performance. Besides this, advanced dielectric applications including power condi-

tioning, electric launch platform, and all electrical or hybrid vehicles require a polar
material, because of their large effective dielectric constants and in turn high
electrical energy storage [279–289]. For example, PVDF is very popular among
commercially available polymer capacitor films, due to its high dielectric constant
and high dc breakdown strength. Electrical and electronic applications and future
trends of fluoropolymers based on vinylidene fluoride (e.g., jacketing of cables for
plenum areas including signaling, communication, and power lines, insulating
compounds for jacketing wires and cable assemblies, cathodic protection, industrial
power control systems, high temperature wiring, and wire and cable sheathing) are
worth to mention here. Fluorinated materials prepared from different polymorphisms
and crystallite sizes have been achieved in PVDF and P(VDF-stat-HFP) (HPF,
hexafluoropropene) films, and the practical applications of ferroelectric polymers
for advanced high energy density dielectric film capacitors have been reported
[122–132]. A significantly reduced ferroelectric loss and relatively high discharged
energy density were investigated due to this antiferroelectric-like behavior even at
high poling fields. Most recently, there are reports on multilayer films for high
energy density storage. The 65-layer poly(carbonate)/poly(methyl methacrylate)/
Poly(VDF-co- HFP) (PC/PMMA/ Poly(VDF-co-HFP)) system showed a 25%
enhanced dielectric breakdown strength, 50% higher energy density, 40% decreased
hysteresis loss energy density, and slower ion migration behavior. The improved
dielectric properties were attributed to the high interactivity between PMMA layers
and both PC and poly(VDF-co-HFP) layers. In addition, cyano polymers bearing CN
groups are interesting as dielectric materials. Piezoelectricity of the poly(VCN-alt-VA)
copolymer, stimulated investigations on the copolymerization of cyano-containing
monomers with various vinyl and diene comonomers. Electrical characteristics of
copolymers based on acrylonitrile have also been reported. Polar polymers
containing C–F and C–CN (alternating copolymers of VCN, block copolymers of
PVDF, and random copolymers of AN) are a potential candidate as dielectric
materials and find many applications in the field above [290–302].

11.1 Microelectronic and Dielectric Polymers

Microelectronic industry uses a variety of polymers, some of which include

(a) epoxies, (b) silicones, (c) benzocyclobutenes (BCB), and (d) polyimides (PI),
and can be applied different techniques such as by spin on or various coating
methods followed by a moderate temperature cure. As a result, these polymer
dielectrics are similar to the organic printed wiring board (PWB) manufacture.
Usually, polymers have low dielectric constant in the range of 2 to 5 (e.g., approx.
2.5 for polystyrene, approx. 2.65 for BCB, approx. 2.7 for parylene, approx. 2.72 for
silicone, and approx. 3.5 for epoxy and polyimide). These modest k values combined
with relatively thick layers in 5–50 μm result in specific capacitances which are
usually from only 0.07 to 0.3 nF/cm2 that make polymer materials useful to embed
only the smallest valued capacitors into the board. It is possible to deposit polymer
7 Dielectric Polymers 271

dielectric layers which are from 2 to 5 μm through coating and curing liquid resins
that can contribute for a significant increase of their specific capacitance up to around
1.5 nF/cm2. Due to para-electric nature of some polymers, the resultant capacitance
is stable with regard to temperature, frequency, and the like. In addition, the
dissipation factor of polymers is also very low which is usually much lower than
ferroelectric ceramics. Epoxy resins have been of particular interest for embedded
capacitor applications due to its compatibility with PWB manufacturing process. In
addition, an epoxy system is basically composed of epoxy resin which works as
hardener and catalyst as well as the adjusting nature of the dielectric constant of
epoxy which can be tailored the components of epoxy system. For instance, the
dielectric constant of epoxy system can be enhanced to a significant extent from 3.2
to 5.0 by proper choice of the catalyst (e.g., metal acetylacetonate). Due to polar
backbone of ferroelectric polymers compared to conventional polymers, these poly-
mers can have higher k values (which may be above 10). For instance, at 1 kHz and
25  C, pure poly(vinylidene fluoride) (PVDF) polymer shows a k value of about 11.
Besides this, poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) copolymer
is a type of relaxor ferroelectric which can have a relatively high-k around 40 at room
temperature after irradiation treatment. For example, a report stated the method
of synthesis of polyvinylidene fluoride–trifluoroethylenechlorotrifluoroethylene
[P(VDF-TrFE-CTrFE)] terpolymers in order to obtain a similar structure as irradi-
ated P(VDF-TrFE) copolymer by introducing CTrFE block in the polymer (which
done to avoid the requires of irradiation process that needs expensive and compli-
cated equipment). It was reported that P(VDF-TrFE-CTrFE) terpolymer with VDF:
Tr-FE:CTrFE molar ratio of 65:35:9 showed a high-k of about 60 (@ 1 kHz) at
33  C, and its dielectric loss tangent was about 0.1. In addition, its dielectric constant
can be as high as 320 (@ 10 kHz) at 145  C, whereas the abovementioned high-k
polymers have non-conjugated backbones. Besides this, in the case of a conductive
polymer with conjugated backbone the k value can be even higher [290–302].

12 Challenges for Embedded Capacitor Materials

and Dielectric Polymers and Composites and Future
Perspectives

Different states of progress in the field of high-k materials for embedded capacitor
applications have been briefly presented in the previous sections. In usual terms,
certain types of high-k materials show different properties which make them suitable
for a variety of applications. Some of these properties include (a) high dielectric
constant, (b) low dissipation factor, (c) high thermal stability, (d) simple process-
ibility, and (e) good dielectric properties over broad frequency range. However, there
is no such ideal materials that satisfy all of the abovementioned properties realized
till today. In this connection, polymer nanocomposites present the most promising
features which have been studied extensively, and efforts to enhance the overall
dielectric performance of these nanocomposites have been focused in order to
maximize the dielectric constant and also to suppress the dielectric loss. In order
272 S. M. R. Billah

to enhance dielectric property of high-k nanocomposites, new insights into the

unique properties of the nanoparticle filler, filler modification, and the dispersion
between filler and polymer matrix are anticipated. In specific terms some of the
required knowledge and technology which have been used in this direction include
(a) optimizing dielectric materials with high filler loading of high-k ceramics for
ceramic-polymer nanocomposites and appropriate loading level of conductive fillers
in the neighborhood of percolation threshold for conductive filler-polymer nano-
composites; (b) improving microstructure of dielectric materials (which include filler
size and distribution, morphology, degree of aggregation, packing, and dispersion in the
polymer matrix); (c) enhancing k values of nanocomposites by using high-k polymer
matrix; and (d) modifying the filler interface in order to facilitate dispersion in the
polymer matrix and also to suppress the dielectric loss of the composite materials.

13 Conclusions

Dielectric polymers work as insulators which implies that no current will flow
through the polymer when a voltage is applied to it although certain changes do
happen at the atomic scale. For instance, when a voltage is applied across a dielectric
polymer, it becomes polarized where the polarization is an effect which slightly
shifts electrons toward the positive voltage due to the fact that atoms are made of a
positively charged nucleus and negatively charged electrons. These charges do not
travel far enough to create a current flow through the dielectric material, because the
shift is very tiny, however the effect is very significant particularly when they are
used in capacitors. In addition, when the voltage source is removed from the
material, it either returns to its original nonpolarized state or stays polarized if the
molecular bonds in the material are weak. The distinction between the term dielectric
and insulator is very thin, for example, all dielectric materials are insulators;
however, a good dielectric is one which is easily polarized. When a certain voltage
is applied to an object, it influences the amount of electrical energy and it also causes
to generate the amount of polarization which is stored in the electric field, typically it
is termed as the dielectric constant of the material. Due to ever-growing requirements
of miniaturization, increased functionality, high performance, and low cost for
microelectronic products and packaging, new and unique solutions in integrated
circuits (IC) and system integrations (e.g., system on chip or SOC, system in
package or SiP, system on package or SOP) have been the topics of current active
research interests. In addition, embedded passives are one of the key emerging
techniques for realizing the system integration. In this case, as an alternative to
discrete components, embedded passives offer various advantages some of which
include (a) higher component density, (b) increased functionality, (c) improved
electrical performance, (d) increased design flexibility, (e) improved reliability, and
(f) reduced unit cost. Additionally, novel materials for embedded capacitor applica-
tions are in great demand, for which a high dielectric constant (k), low dielectric loss,
and process compatibility with printed circuit boards (PCBs) are some of the most
important prerequisites. However, to date, it is very difficult to find materials which can
7 Dielectric Polymers 273

satisfy all desired requirements. In this context, conductive filler/polymer composites

are very promising materials which can demonstrate a dramatic increase in their
dielectric constant close to the percolation threshold. One of the major challenges for
this type of high-k composites is the high dielectric loss inherent in these systems. As a
result, there have been many investigations to designed and developed nanocomposites
based on nanoparticles with controlled parameters in order to fulfill the balance
between sufficiently high-k and low dielectric loss, which satisfied the requirements
for embedded capacitor applications. This chapter selectively and briefly stated differ-
ent features of dielectric polymers (both pristine polymers and composite polymers
doped or coated with inorganic dielectric materials) and their applications and related
aspects. It also briefly stated different aspects of dielectric elastomers and their appli-
cations along with the different applications of dielectric polymers, in general. Detailed
explanation and in-depth analysis of various topics related to dielectric polymers and
their specific application mechanisms in different devices are beyond the scope of this
chapter, so interested readers are advised to consult related books and references, some
of which are included in the reference section.

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Dendrimers
8
Balappa B. Munavalli, Satishkumar R. Naik, Anand I. Torvi, and
Mahadevappa Y. Kariduraganavar

Contents
1 An Overview of Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
2 Classifications of Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
2.1 Simple Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
2.2 Hybrid Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
2.3 Peptide Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
2.4 Multilingual Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
2.5 Amphiphilic Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
2.6 PAMAM Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
2.7 PAMAMOS Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
2.8 Tecto Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
2.9 Chiral Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
2.10 Fréchet-Type Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
2.11 PPI Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
2.12 Metallo Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
2.13 Micellar Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
2.14 Liquid Crystalline Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
3 Synthetic Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
3.1 Divergent Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
3.2 Convergent Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
4 Properties of Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
4.1 Structure and Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
4.2 Reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
4.3 Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
4.4 Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
4.5 Ionic Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
4.6 Compressibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
4.7 Polydispersity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
4.8 Host–Guest Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315

B. B. Munavalli · S. R. Naik · A. I. Torvi · M. Y. Kariduraganavar (*)

Department of Chemistry, Karnatak University, Dharwad, India
e-mail: [email protected]; [email protected]; [email protected];
[email protected]

© Springer Nature Switzerland AG 2019 289

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_9
290 B. B. Munavalli et al.

4.9 Catalytic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317

4.10 Degree of Branching (DB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
4.11 Melt Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
4.12 Electrochemical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
4.13 Biocompatibility and Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
5 Applications of Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
5.1 Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
5.2 Engineering Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
5.3 Miscellaneous Dendrimer Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
6 Future Prospects and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334

Abstract
Dendrimers are the new class of materials, characterized by the combination of
compact molecular assembly and high number of functional groups, which can
make them potential candidates in both medical and engineering applications.
Thus, this chapter presents an overview of dendrimers, which includes the
classification of dendrimers, different methods employed for the syntheses of
dendrimers, and properties and applications of dendrimers. An attempt was also
made to discuss the progress made in the variety of dendrimeric materials.
A special attention was made in discussing the properties of dendrimers and
their structures, which play predominant role in deciding the applications of
dendrimers in various fields. During the review, we came to know that dendrimers
can also demonstrate as novel carriers for drug delivery across the cell membranes
and organ barriers such as blood-brain barrier (BBB) and have a host of applica-
tions in treating tumors and cerebral gliomas and delivery of drugs for specific site
of a brain. This anticipates that a new era of research on the dendrimers would
focus on the development of dendrimers-clusters to form multifunctional thera-
peutic systems, which could subsequently open a new path for clinical applica-
tions. At the end, while concluding, we have also discussed the future prospects
of dendrimers for various applications. To compile this chapter and to provide
adequate information to the readers, we have explored all the possible ways, such
as research articles, reviews, books, book chapters, and Google sites.

1 An Overview of Dendrimers

Dendrimers are highly branched, globular, monodispersed, radially symmetric,

and well-defined homogeneous structures [1]. The dense architecture of the
dendrimers originates from the monomer compositions and their arrangement.
These are highly ordered artificial macromolecules, which are characterized by
the combination of compact molecular structure and high number of functional
groups [2]. These contain uniform branching segments built around a small
molecule or a linear core [3, 4].
The term dendrimers derived from Greek words; “dendros” means “tree” or
“branch” and “meros” means “part.” These were first synthesized by Fritz Vogtle
8 Dendrimers 291

in 1978 and Donald Tomalia and co-workers in 1980s. During the same time,
Newkome and his group [5] independently synthesized the similar macromolecules
and called as “arborols.” The word “arbor” means a tree in Latin.
A dendrimer is classically symmetric around the core and often adopts a three-
dimensional globular structure. In dendritic polymers, generally there are four main
subgroups which are closely related to one another: hyperbranched polymers,
dendronized polymers, dendrigrafts, and dendrimers. These subgroups have the
same concept of synthetic protocols, but the difference lies in the amount of
branching units. Hyperbranched and dendronized polymers are statistically ordered
polymers with polydispersity index (PDI) ranging from 1.5 to 10. Dendrigrafts are
the semi-controlled polymers with PDI values range between 1.1 and 1.5. On the
other hand, dendrimers present unprecedented control over the addition reaction
with the PDI values occurred between 1.0 and 1.05.
Dendrimers consist of three main architectural components, such as core,
interior, and end-groups. The core is positioned at the center, while the branched
wedges (dendrons) are attached at the core. The size of dendron depends on the
number of monomer layers built and each layer is called as a generation (G). The
interior consists of monomers branching that have ABx functionality, where
x
2. From the central core, the dendrons are grown through different synthetic
protocols [6, 7]. The interior part of the dendrimer is traditionally dormant and
not accessible for post modifications. But in some cases, dendrimers are allowed
to functionalization by treating with super acids or super bases to generate active
sites within the interior.
Macromolecular architectural are traditionally classified as linear, crosslinked,
and branched structure to generate polydispersed products of different molecular
weights. However, the synthetic dendrimers offer the chances of generating
monodispersed and structure-controlled macromolecular architecture. Upon
functionalization of the end groups, the physicochemical properties of the
dendrimers can be altered [8–13]. The globular shaped, nanoscale sized struc-
tures with low intrinsic viscosity could be generally obtained with dendrimers of
larger structures. Consequently, branched materials are being attracted both in
material research and in industry. Any deviation during the dendrimer synthesis
generally creates structural defects, and thereby the purification process becomes
tedious or sometimes it is impossible. As a result, the need of good chemistry
background is crucial to achieve high efficiency in dendrimer synthesis. In spite
of this, dendrimers are still seen as tedious, time consuming and expensive
materials to synthesize. Though it is synthetically more challenging, the dendritic
molecules can be tailor-made to include the functional domains so as to achieve
the desired physical and chemical properties.

2 Classifications of Dendrimers

Generally, dendrimers can be classified based on their shapes, structures, branchings,

chirality, etc. They are:
292 B. B. Munavalli et al.

2.1 Simple Dendrimers

These have been made with simple monomer units. The convergent synthesis
of monodispersed dendrimers is based on symmetrically substituted benzene
tricarboxylic acid ester groups. The resulting dendrimers comprise of 4, 10,
22, and 46 benzene rings linked symmetrically with a molecular diameter of
45 Å [14].

2.2 Hybrid Dendrimers

These dendrimers have been obtained by complete monofunctionalization of the

peripheral amines of a “zero-generation” polyethyleneimine dendrimer and thus
provide structurally diverse lamellar, cubic, and columnar self-organized lattices
that are less readily available from other modified dendritic structures [15]. These
dendrimers possess the characteristic properties of both linear and dendritic poly-
mers [16]. Preparation of linear and dendritic polymers can be made in hybrid block
or graft copolymer form which makes them suitable to use as surface active agents,
compatibilizers, or adhesives, for example, hybrid dendritic linear polymers
[14]. The supermolecular hybrid dendrimers (SHDs) exhibit characteristic properties
such as well-defined nanostructure, fluorescent signaling, and arginine-rich peptide
corona. Bio-inspired supramolecular hybrid dendritic systems stimulate for biomed-
ical applications both in vitro and in vivo as shown in Fig. 1. In addition, bio-inspired
supramolecular hybrid strategy largely intensifies the gene transfection efficiency of
SHDs around 50,000-fold as compared to single peptide dendrons (PDs) at the same
reserves-to-production ratio [17].

2.3 Peptide Dendrimers

Peptide dendrimers are radial or wedge-like branched macromolecules consisting of

a peptidyl branching core and/or covalently attached surface functional units. These
dendrimers contain amino acid as branching or interior unit as illustrated in Fig. 2
[18]. The multimeric nature, unambiguous composition, and the ease of production
make these type of dendrimers well suited for various biotechnological and bio-
chemical applications, generally diagnostic purpose and vaccine delivery [19]. In
addition, peptide dendrimers can also be used as contrast agents for magnetic
resonance imaging (MRI), magnetic resonance angiography (MRA), fluorogenic
imaging, and sero diagnosis.

2.4 Multilingual Dendrimers

Multilingual dendrimers are built with multiple copies of a particular functional

group on their surface [16].
8 Dendrimers 293

Fig. 1 Schematic illustrations for self-assembly and biomedical applications of SHDs. (a) Chem-
ical structure of the dual functionalized PDs, (b) self-assembly of PDs onto quantum dots through
the coordination interactions, (c) SHDs with hierarchical nanostructures for biological tracking and
gene delivery in vitro and in vivo. (Adopted with kind permission from Ref. [17] from © ACS)

2.5 Amphiphilic Dendrimers

Amphiphilic dendrimers are the class of globular dendrimers made with two segre-
gated sites of chain end. These have one half that is electron donating site and
another half is electron withdrawing site as illustrated in Fig. 3 [20]. These
dendrimer structures have asymmetrical but highly controlled division of chain
294 B. B. Munavalli et al.

Fig. 2 Synthesis of peptide dendrimer: TMA[β-Ala-TRIS[(Gly-Pro-Nleu)6-OMe]3]3. Poly(propyl-

ene imine) (PPI) dendrimers are available as Astramol™. (Adopted with kind permission from Ref.
[18] from © ACS)

O(CH2)21CH3

O(CH2)21CH3
O
O(CH2)21CH3
O
O O(CH2)21CH3

O O OOC(CH2)2COO O O(CH2)21CH3
62 O
O(CH2)21CH3
O
O(CH2)21CH3

O(CH2)21CH3

Fig. 3 Molecular architecture of extended amphiphilic dendrimer. (Adopted with kind permission
from Ref. [20] from © ACS)

end chemistry. The orientation of these structures at the interface form interfacial
liquid membranes for neutralizing aqueous organic emulsion [14].

2.6 PAMAM Dendrimers

Poly (amido amine) (PAMAM) dendrimers are ellipsoidal or spheroidal in shape. These
are most studied macromolecules and are commercially available [21]. The divergent
8 Dendrimers 295

method is used for their synthesis using ammonia or ethylenediamine as a starting

material. The high solubility and reactivity of these dendrimers is due to the presence
of a number of functional end groups and empty internal cavities [22–24]. PAMAM
dendrimers contain high amino group density than the conventional macromolecules
[21]. They are commercially available as methanol solutions and in generation G0-10
with 5 different core type and 10 functional surface groups [25, 26].

2.7 PAMAMOS Dendrimers

Polyamidoamine organosilicon (PAMAMOS) dendrimers were discovered by Petar

Dvornic and his colleagues at Michigan Molecular Institute in 1990. These are
inverted unimolecular micelles consist of hydrophilic, nucleophilic polyamidoamine
interiors, and hydrophobic organosilicon (OS) exteriors as shown in Scheme 1.

H(2-y) OCH3
N CH2-CH2-COO-(CH2)3-Si-CH3
H2O
y
OCH3
z H(2-y) OH
N CH2-CH2-COO-(CH2)3-Si-CH3
y
OCH3
z

Gx
H3CO
Si
O CH3
OCH3 -MeOH
Gx Si CH3
H3C Si
O CH3 OCH3
CH3
Si
Gx Si O
Gx
OCH3 CH3
CH3 CH3 Si
O O
CH3
Si O Si Si
Gx O Si CH3
O O
CH3 Gx
Si Si Si
Si Gx
O O O
H3C O CH3 CH3
Si Si CH3
H3C
OCH3

Scheme 1 Formation of honeycomb-like nano-domained PAMAMOS dendrimer networks from

alkoxysilyl functionalized PAMAMOS dendrimers. Circular shapes represent PAMAM dendritic
domains of generation Gx. (Adopted with kind permission from Ref. [27] from © ACS)
296 B. B. Munavalli et al.

Fig. 4 Schematic
representation of a core-shell
tecto-(dendrimer) molecule in
solution. (Adopted with kind
permission from Ref. [28]
from © ACS)

The excellent networks regularity and their ability to complex and encapsulate
various guest species offer unprecedented potentials for new applications such as
nanolithography, electronics, photonics, chemical catalysis, and useful precursors
for the preparation of honeycomb like networks with nanoscopic PAMAM and OS
domains [27].

2.8 Tecto Dendrimers

These are made up of core dendrimer which is surrounded by other dendrimers as

shown in Fig. 4 [28]. Each dendrimer performs a specific function leading to a smart
therapeutic system which can simultaneously diagnose the diseased state and deliver
API to the recognized diseased cell [16].

2.9 Chiral Dendrimers

The chirality of the dendrimers is based upon the construction of constitutionally

different but chemically similar branches to chiral core [29], for example, chiral
dendrimers obtained from pentaerythritol (Fig. 5) [30]. They are potentially used as
chiral hosts and chiral catalysts for enantiomeric resolutions and asymmetric syn-
thesis, respectively.

2.10 Fréchet-Type Dendrimers

These are the hydrophobic dendrimer types having carboxylic acid groups as surface
groups, serving as a good anchoring point for further surface functionalization as
8 Dendrimers 297

Fig. 5 Racemic form of the

chiral dendrimer (The
chirality is based on a
pentaerythritol core with four
dendrimer substituents of
different generation).
(Adopted with kind
permission from Ref. [30]
from © ACS)

shown in Fig. 6. The polar surface groups increase the solubility of these dendrimers
in polar solvents or aqueous media [31].

2.11 PPI Dendrimers

The poly(propylene imine) (PPI) dendrimers shown in Fig. 7 made of diamino

butane with tertiary–propylene amines as interior and primary amines as the end
groups [32]. These are commercially available up to generation G-5 and are chosen
as potential molecules in material science and biology.

2.12 Metallo Dendrimers

These dendrimers attached with the metal ion to form the complexation either in the
interior or on the peripheral, thus named as metallo dendrimers. Currently, the
incorporation of metal centers into macromolecules to develop well-defined mole-
cules with new advantageous properties is one of the most active areas of research in
chemistry. The schematic representation of metallo dendrimer is shown in Fig. 8
[33]. The ruthenium bipyridine complex-based dendrimer exhibit both electrochem-
ical and luminescence properties. Thus, the introduction of metals into dendritic
structures results in highly ordered materials with attractive magnetic, electronic, and
photo-optical properties [34–44].
298 B. B. Munavalli et al.

COOK COOK COOK COOK

COOK
KOOC
COOK
KOOC O O O O
KOOC O
O COOK
KOOC O COOK
O
OO O O
O O
O O
O O O O COOK
KOOC O O
O
O O O O COOK
KOOC O O
O
O O O O
KOOC O
O O O O COOK
O
KOOC O O
O O O O COOK
O O
O O
OO O O O
KOOC O COOK
KOOC O COOK
O O O O
KOOC O
COOK
KOOC
COOK
COOK COOK COOK COOK

Fig. 6 Structure of G3-Fréchet-type dendrimer. (Adopted with kind permission from Ref. [31]
from © RSC)

2.13 Micellar Dendrimers

These are the water-soluble dendrimers with unimolecular micellar arrangement

forming a collection of aromatic polymeric chain. Because of micellar structures,
these are able to generate an environment for the complex formation with small
organic molecules in water [14].

2.14 Liquid Crystalline Dendrimers

These are made of mesogenic monomers. For example, mesogen functionalized

carbosilane dendrimer. Functionalization to the end group of carbosilane dendrimers with
36 mesogenic units can be attached through a C-5 spacer and leads to liquid crystalline
dendrimers that form broad smectic phase in the temperature range of 17–130  C [14].

3 Synthetic Approaches

Dendrimers can be developed by two major synthetic approaches, namely, divergent

and convergent. In the divergent approach, the synthesis starts from the core of the
dendrimer to which the arms are attached by step-wise addition of building blocks.
8 Dendrimers 299

H2N NH2 NH2

H2N H2N
H2N N
N
H2N N
N NH2
H2N N N
N NH2
H2N
N NH2
H2N N N N
N N NH2
r.u. N NH2
H2N N
N NH2
N
core
N N NH2
NH2 N N
N NH2
N NH2
N N NH2
N
NH2 N
NH2 N N NH2
N
NH2 NH2
NH2 NH2 NH2 NH2 NH2

PPI-G4
r.u. = repeating unit propylene imine

Fig. 7 Poly(propylene imine) PPI-G4 with surfaces of amine groups modified by attaching
maltotriose. (Adopted with kind permission from Ref. [32] from © RSC)

However, in the convergent approach, synthesis starts from the exterior, beginning
with the molecular structure that finally becomes the outermost arm of the formed
dendrimer.

3.1 Divergent Approach

The divergent synthesis of dendrimers is done by Fritz Vögtle in 1978 [45] for the
first time and is followed by Denkewalter from Allied Corporation in 1981 [46],
Donald Tomalia from Dow Chemicals in 1983 [47], and George Newkome in
1985 [5].
In this approach, monomers are added to a multifunctional core which allows
radial growth of dendrimers outwards layer by layer, resulting in approximately
doubled molecular weight. Since the partially substituted dendrimers are very similar
to the perfect structure both chemically and in size, it is crucial to obtain full
substitution of the end-groups. Through the careful monitoring of the reaction
using analytical methods, such as matrix assisted laser desorption ionization time
of flight (MALDITOF) and nuclear magnetic resonance (NMR), partially substituted
dendrimers can be avoided if a large excess of monomer is used in the addition step.
300 B. B. Munavalli et al.

Fig. 8 Schematic representations of the mono-, bis-, and tris-Ru-based systems. (Reproduced with
consent from Ref. [33] from © RSC)

Divergent synthesis is generally initiated with a multifunctional core molecule

like ethylenediamine (EDA), then four arms are added on nitrogen of EDA with the
help of Michael type addition reaction (two arms possible on each nitrogen). In the
second step, EDA is again reacted with the resulted four arms through the amidation
reaction as shown in Scheme 2 [48].
8 Dendrimers 301

NH2
H2N
OMe

O O
MeO O
OMe
N
N
MeO
O OMe
O
H2N NH2CH2CH2NH2
O NH2
HN O
NH
N
N
HN
O NH
H2N O
NH2
O
OMe
MeO O
O OMe
N
O N
MeO HN O
O NH OMe
N O
O N
MeO HN O
O NH OMe
N O
N
MeO
O OMe NH2
H2N NH2CH2CH2NH2 O
O NH
O
HN

N H
H N O N
N O NH
HN O NH2
H2N O N NH2
H2N N O
O NH NH
HN HN O
O N
N
NH
HN O
O NH2
H2N

Scheme 2 Synthesis of dendrimer through the divergent approach. (Reproduced with consent
from Ref. [48] from © ACS)
302 B. B. Munavalli et al.

These two steps can be repeated multiple times so as to form different generations
of dendrimers. In each generation, the number of arms is doubled than the previous
generation. The excess amount of Michael donor (EDA) is used to avoid the
structural defects at higher generations. This divergent route is advantageous to get
higher yield of dendrimer with lower purity or we can say that the purity is
compromised for getting higher yield. Therefore, this approach of synthesis is
used worldwide in commercial scale for the production of dendrimers. The purity
of the dendrimers is less basically due to one of the reasons: intramolecular and
intermolecular cyclization, Retro Michael reaction, or hydrolysis of ester.
Although the divergent approach is conceptually straight forward, there are some
synthetic problems. As the size of the dendrimers increases, the number of surface
functionalities will also increase. Therefore, to reach the subsequent generation of
dendritic molecule, an exponentially increasing number of reactions need to be
performed on a single molecule, but it is quite challenging even with highly efficient
reactions. The separation of the required product from the by-products is difficult as
the mass, size, and properties of bi-products are often very close to the structurally
perfect dendrimer. Well-known dendrimers which are synthesized using the diver-
gent approach are: poly(amidoamine) PAMAM, poly(propylene imine) POPAM,
and 2,2-bis(methylol) propionic acid (bis-MPA) dendrimers.

3.2 Convergent Approach

The synthesis of dendrimer through the convergent approach was first introduced by
Jean Fréchet in 1990 [49]. In this approach, dendrons that end up to terminal groups
are synthesized first and these are linked together to a core molecule in the final step
for getting complete dendrimer structure.
Convergent approach of dendrimer synthesis overcomes the purity and structural
defect issues of divergent synthesis. With this approach, more uniform and symmet-
ric dendrimers can be synthesized but with lower overall yield. In other words, yield
is sacrificed for purity. This approach is generally used for laboratory scale
dendrimer synthesis. The dendrimer synthesis is initiated from small molecules
that end up at the surface of the sphere and the reactions proceed inward building
and are finally attached to a core. This method makes it much easier to remove
impurities and shorter branches along the way, so that the final dendrimer is more
monodisperse. The dendrimers synthesized by this way are not as large as those
synthesized by divergent methods, because the convergent approach does not allow
the formation of high generations due to the steric hindrance in the reactions of the
dendrons and the core molecule.
A variety of convergent syntheses have been developed in the past decade by
introducing a wide range of functionalities. The most widely used convergent
dendrimer syntheses include: poly(phenylene), poly(alkyl ester), poly(aryl alkyne),
poly(aryl alkene) poly(alkyl ether), poly(aryl ether) dendrimers. Some of these
syntheses will be described more in detail below.
8 Dendrimers 303

3.2.1 Poly(aryl ether) Dendrimers

Poly(aryl ether) dendrimers were developed by Hawker and Fréchet in 1989–1990
[50]. The synthesis makes use of 3,5-dihydroxybenzyl alcohol as the monomer 1 and
two phenolic groups of this monomer were coupled to the benzylic bromide 2, in the
presence of K2CO3 and 18-crown-6, producing the two new ether linkages of the second
generation benzylic alcohol 3 as shown in Scheme 3. Through the reaction with carbon
tetrabromide and triphenyl phospine, the focal benzylic alcohol functionality was then
activated for the next coupling step affording brominated dendron 4. The coupling step was
then repeated using two equivalent of activated dendron and one equivalent of the
monomer, resulting in the third generation benzylic alcohol 5. The Williamson coupling
and bromination steps were repeated subsequently to yield the sixth generation dendron 11.
The synthesis method utilized Williamson coupling reaction between a highly nucle-
ophilic phenolate and a highly activated benzylic bromide, ensuring exceptional yields
during all the generation growth steps. The elimination side reactions were prevented by
the benzylic substrates that frequently accompany nucleophilic displacements.

3.2.2 Poly(phenylene) Dendrimers

The convergent approach for the synthesis of a family poly(1,3,5-phenylene)
dendrimers [4, 51] was reported by Miller and Neenan soon after the report of the
poly(benzyl ether) dendrimer [52].
In the preparation of these polyphenylenes and their fluorinated analogs, aryl
boronic acids 2 or 3 undergo Suzuki coupling with the monomer 1, 3,5-dibromo-1-
(trimethylsilyl)benzene as shown in Scheme 4. Further coupling to the monomer is
initiated owing to the conversion of the trimethylsilyl (TMS) protecting group of
products 4 and 5 to the boronic acid functionality in 6 and 5. This procedure results
in the preparation of dendrons up to third generation 13–16. The rigid repeat units
provide well-defined shapes and diameters of these dendritic structures. Recently,
Mullen et al. have reported the synthesis of poly(phenylene) dendrimers by the
convergent approach [51] similar to the divergent [4 + 2] cycloaddition route
reported previously [52] as shown in Scheme 3.

3.2.3 Poly(alkyl ester) Dendrimers

The convergent syntheses of Poly(alkyl ester) dendrimers was reported by Hult and
co-workers utilizing a repeat unit based on 2,2-bis-(hydroxymethyl)propanoic acid
as shown in Scheme 5 [53]. The two alcohol moieties of the benzyl 2,2-bis
(hydroxymethyl)propanoate monomer 1 undergo coupling with an activated acid
chloride end-group 2 followed by the removal of the focal benzyl ester by
hydrogenolysis. The carboxylic acid could be transformed to the corresponding
acid chloride 4, in nearly quantitative yields using oxalyl chloride. The repeating
coupling deprotection procedure results in the fourth generation dendron 7. Due to
ether or hydrocarbon linkages, these polyesters do not exhibit the chemical stability
of other dendritic macromolecules, but as their ester functionalities are shielded from
nucleophilic attack by the neighboring quaternary carbon, the dendrons show rather
high stability to acidic conditions. The efficient [54] and versatile [55] synthesis of
analogous dendrimers is reported recently by Ihre et al.
304 B. B. Munavalli et al.

BnO BnO

BnO O O
Br BnO BnO
i ii
91% 93% BnO Br
BnO OH
BnO O O

3, [G-2]-Br
2, [G-2]-OH OBn BnO
BnO
i 88%
Reagents BnO
HO O 4, [G-3]-OH
Br OBn
i).
ii
HO O 90%
BnO
K2CO3, 18-C-6 BnO O
Br
ii). CBr4, PPh3
O
BnO O

BnO
O 5, [G-3]-Br

i 92%
BnO
6, [G-4]-OH
OBn BnO
ii
OBn 95%
BnO
BnO
OBn OBn
O O OBn
BnO
BnO O
O OBn
O OBn
BnO O O O
BnO O
O O OBn
O
O O
BnO 7, [G-4]-Br

Br

i ii i ii
8, [G-5]-OH 9, [G-5]-Br 10, [G-6]-OH 11, [G-6]-Br
85% 83% 78% 72%

Scheme 3 Convergent approach for the synthesis of poly(aryl ether) dendrimers. (Reproduced
with consent from Ref. [50] from © ACS)
8 Dendrimers 305

Scheme 4 Convergent approach for the synthesis of poly(phenylene) dendrimers. (Reproduced

with consent from Ref. [52] from © ACS)

3.2.4 Poly(alkyl ether) Dendrimers

The convergent approach for the synthesis of an aliphatic analogue of the poly
(benzyl ether) dendrimer was recently developed by Fréchet and coworkers as
shown in Scheme 6 [56]. The synthesis was initiated by coupling the end groups
to the monomer 1, 3-chloro-2-chloromethyl-propene using the Williamson ether
coupling of a bis-protected triol 2 or 3, with the allylic chloride functionalities of
the monomer [57].
During the synthesis, the double bond of the resulting product 4 or 5 was
converted to the corresponding primary alcohol 6 or 7 via hydroboration/oxidation,
thereby enabling further coupling and this procedure could be repeated in high yields
through fifth generation dendrons 16–19. Although the more demanding purification
of these compounds will likely prevent them from replacing the poly(benzyl ether)
family for many applications, they allow a wide range of chemical modification. For
example, the peripheral ketal and benzyl ether protecting groups can be quantita-
tively removed by acid-catalyzed hydrolysis or palladium-catalyzed hydrogenolysis
exposing multiple peripheral hydroxyl groups capable of further modification by
alkylation or esterification [58].
Since the poly(alkyl ether) dendrons did not interfere with the N-bromosuc-
cinimide bromination of the pendant oligothiophene or subsequent Stille couplings,
306 B. B. Munavalli et al.

Scheme 5 Convergent approach for the synthesis of poly(alkyl ester) dendrimers. (Reproduced
with consent from Ref. [53] from © ACS)

they were selected as solubilizing scaffolds for otherwise intractable oligothiophenes

[59, 60]. Also, the significant polar backbone, similar to poly(ethylene glycol),
of these compounds may prove useful in macromolecular catalysts or biomedical
applications.
8 Dendrimers 307

Scheme 6 Convergent approach for the synthesis of poly(alkyl ether) dendrimers. (Reproduced
with consent from Ref. [56] from © ACS)

3.2.5 Other Convergent Dendrimer Syntheses

Convergent approach has been developed for the preparation of dendritic poly
(amides) [61–68], poly(esters) [69], poly(urethanes) [70, 71], poly(carbonates)
[72], poly(arylamines) [73–76], poly(aryl ketones) [77], poly(aryl alkynes) [78],
308 B. B. Munavalli et al.

poly(aryl methanes) [79], poly(arylammonium) salts [80], poly (thioureas) [81],

poly- (ether imides) [82], poly(keto ethers) [83–85], poly(amine ethers) [86], poly
(amino esters) [87], etc.

4 Properties of Dendrimers

The properties such as well-defined size, shape, molecular weight, monodispersity,

and unimolecular micellar nature make the dendrimers a smart choice for drug
delivery application and enhance the solubility of poorly soluble drug. Despite
several advantages, dendrimers-based drug delivery is still in its infancy even after
three decades of discovery [88].
The typical architecture of a dendrimer has consequences for its physical behav-
ior. The research in the past decade revealed the true nature of dendrimers, regarding
their appearance and physical characteristics. Since many of the proposed uses of
dendrimers rely on the availability of the large amount of functional groups, the
localization of the end groups in dendritic systems is the crucial requirement. The
properties of dendrimers are deviating as compared to their linear macromolecular
counterparts and encompass the transition in physical properties when a sequence of
dendrimer generations is considered. This nature results in the unexpected confor-
mational features for dendritic molecules. Thus for the intended use in applications
such as drug delivery, biocides, gene transfer, catalyst supports, energy, and pro-
cessing aids controlling the molecular architecture of dendrimers is crucial [89–91].

4.1 Structure and Shape

Dendrimers are the type of dendritic molecules with two or more dendrons attaching
to a multivalent core molecule. A dendron is a highly branched sector with surface
groups at the periphery, branching units, and a focal point.
Dendrimers of lower generations (G-0, G-1, and 2) have highly asymmetric shape
and possess more open structures as compared to higher generation dendrimers. For
example, rotaxanes have a linear dumbbell-shaped component bearing bulky
end-groups or stoppers around which one or more macrocycles are trapped [92–95].
As the chains growing from the core, molecule becomes longer and more
branched (in 4 and higher generations) and the dendrimers adopt a globular structure
[96]. Gradually, the dendrimers become densely packed and they extend out to the
periphery, forming a closed membrane-like structure. When a critical branched state
is reached, because of a lack of space dendrimers cannot grow further. This is termed
as the “starburst effect” [21]. For example, in case of PAMAM dendrimer synthesis,
it is observed after the tenth generation. The rate of reaction drops suddenly and
further reactions of the end groups will stop. The tenth generation PAMAM contains
6141 monomer units with a diameter of about 124 Å [97]. In addition, the increasing
branch density with generation is also believed to have striking effects on the
8 Dendrimers 309

structure of dendrimers. They are characterized by the presence of internal cavities

and large number of reactive end groups.
Generally, owing to steric crowding, the structures of dendrimers changed from
the extended form to the globular conformation with increasing generations
[98–100]. Their properties also vary based on the functionalities attached at surface
groups, interiors or cores/focal points, polarities of dendrons/dendrimers, branching
multiplicities (AB2 versus AB3), etc. [31, 101]. The subsequent dendrimer organi-
zations and assemblies can furnish secondary dendritic structures [102–107]. These
characteristics make the use of dendrons/dendrimers feasible in various applications
such as nanomedicines [108], catalysis [109–111], light-harvesting [112], and nano-
capsules for drug or gene deliveries [113].

4.2 Reactivity

The interaction of dendrimers with their environment depends largely on the func-
tional groups. The design of molecular interactions such as hydrogen bonding and the
control of polymer architecture strengthened the interfaces between different poly-
mers or between polymers and other surfaces. To encapsulate reactive sites or provide
highly controlled surfaces and interfaces, three dimensional synthetic dendrimers
have been fashioned. For example, Hoover et al. [114] demonstrate that PAMAM
dendrimers can be used to template bimetallic Pt-Cu nanoparticles with controlled
metal stoichiometries in solution as shown in Scheme 7. Active supported bimetallic
nanoparticle catalysts can be formed by the deposition of nanoparticles onto a high
surface-area oxide support and the thermal dendrimers removal process. The surface
dilution of Pt in Cu is indicated by Infrared spectroscopy of adsorbed CO and
suggested only weak electronic donation from Cu to Pt. Importantly, the stoichiom-
etry set in the initial solution syntheses of the nanoparticles has a direct influence on
the activity of the resulting catalysts. This offers new opportunities for studying
particle composition effects for a variety of catalytic reactions.

4.3 Solubility

Due to the hydrophobicity, the solubility of drugs and bioactive compounds in

water reduces and significantly diminishes their activity in vivo [115, 116]. Only
60% of drug compounds reach the patients, whereas the remaining 40% of
compounds are eliminated during the screening owing to their poor bioavailabil-
ity, low water solubility, and low permeability through biological membranes
[117–120]. Therefore, a thorough understanding of solubility enhancement is the
fundamental task of drug delivery. Dendrimers are a novel type of materials with
a unique structure and properties which are suitable for drug delivery and
solubilization. The solubilization facilitated by dendrimers is based on the
ionic interactions, hydrogen bonding, and hydrophobic interactions. Generally,
hydrophobic interior core of dendrimers is responsible for the encapsulation of
310 B. B. Munavalli et al.

Scheme 7 Synthesis of dendrimer-templated Pt-Cu nanoparticles. (Adopted with kind permission

from Ref. [114] from © ACS)

hydrophobic drugs and the hydrophilic shell of the dendrimers (e.g., carbohy-
drates) involved in interactions with water and solubilization [118–120].
The presence of many chain-ends offers high solubility, miscibility, and high
reactivity to the dendrimers. The nature of surface groups strongly influences the
solubility of dendrimers. Dendrimers terminated with hydrophilic groups and hydro-
phobic groups are soluble in polar and nonpolar solvents, respectively. In tetrahy-
drofuran (THF), the solubility of dendritic polyester was found remarkably higher
than that of analogous linear polyester and also a marked difference was also
observed in chemical reactivity. Single-walled carbon nanotube (SWNT) is a nano-
carrier of bioactive molecules in aqueous solution. Surface modification of SWNT
with a series of dendritic galactopyranosides and mannopyranosides as illustrated in
Fig. 9 improves its solubility in water. Generally, sugars with higher branching were
more effective in solubilization of SWNT [121].
8 Dendrimers 311

Fig. 9 Carbon nanotubes functionalized with Gal-, Man-, or their dendrons. (Reproduced with
consent from Ref. [121] from © ACS)

4.4 Viscosity

Dendrimer solutions are significantly less viscous than the linear polymers.
Molecular weight (MW) and degree of branching (DB) strongly influences the
viscosity of dendrimers. However, the intrinsic viscosity of dendrimers in solu-
tion shows several anomalous behaviors that have hitherto not been explained
within the existing theoretical frameworks. Lu et al. [122] proposed a simple
two-zone model for a dendrimer based on the radial segmental density profile as
illustrated in Fig. 10a, b, which suggests a combined Zimm and Rouse descrip-
tion of the intrinsic viscosity.
312 B. B. Munavalli et al.

a 2.0 b
MD
DD
1.5 TD

1.0
r

0.5

0.0
0 2 4 6
R

Fig. 10 The two-zone model representing the radial segmental density profiles. (a) The radial
segmental density profile of monodendron (MD), didendron (DD), and tridendron (TD). (b) A
schematic of the two-zone model: the balls inside and outside the dotted circle belongs to the dense
part and thin part, respectively; the distorted lines denote the flow field around the structure.
(Adopted with kind permission from Ref. [122] from © RSC)

Based on this simple model, the intrinsic viscosity of the dendrimers can be
calculated using Einstein’s intrinsic viscosity formula for solid spheres assuming the
contributions of dense zone and thin zones the viscosity as additive [97].
ð1
N 1 ðG Þ ¼ ρðR,GÞ4πR2 dR (1)
Rc

The intrinsic viscosity is then,

10π ½RC ðGÞ3 þ kN 1 ðGÞσ 3 

½ηðGÞ ¼ (2)
3N ðGÞM 0

where σ is the radius of a monomer, M0 is the mass of a monomer, k is the ratio

between the total effective volume of the segments in the thin zone and their real
volume termed as coefficient of correlation, and N(G) is the total number of mono-
mers in the dendrimer calculated from the equation below.
 
where N ðGÞ ¼ 1 þ j 2Gþ1  1 (3)

where j = 1, 2, 3. . ., for monodendron, didendron, tridendron, etc.

For classical polymers, the intrinsic viscosity increases continuously with molec-
ular mass. In case of polyether dendrimers, it is found that the intrinsic viscosity
increases up to fourth generation and then decreases [123, 124]. Such behavior is not
found in linear polymers. These properties differ significantly in some of the
dendrimers. For example, for polyamidoamine (tridendrons) synthesized by the
divergent approach, a maximum intrinsic viscosity as a function of generation has
been reported [125]. On the other hand, lysine-based monodendrons have intrinsic
viscosities equal to 0.025 dL/g for all generations [126]. A possible reason for this
8 Dendrimers 313

difference lies on the different density profiles, depending on the length and flexi-
bility of spacers and the interaction between monomer units.

4.5 Ionic Conductivity

The unique properties of dendritic polymers such as the possibility of obtaining

tailored made barrier properties, as well as the introduction of crosslinking points
and other functional groups to a dendritic polymer by end-group modification,
suggest that they have potential as proton exchange membrane fuel cell (PEMFC)
components. Several research groups have been investigated the possibility of using
dendritic polymers as possible electrolyte materials in lithium-battery applications
[127]. Dendritic polymers are highly branched polymers based on ABx type mono-
mers introducing potential branching points in every repeating unit. The presence of
numerous end-groups results in the extensive branching in few entanglements,
giving a globular shape and properties. However, there are only a very few publi-
cations on dendritic polymers-based proton-conducting membranes in PEFC. Taylor
et al. have studied the effect of sulfonated poly(propylene imine) dendrimers in
Nafion on morphology and methanol cross-over [128]. Similarly, the development of
sulfonated poly(3-ethyl-3-(hydroxymethyl)oxetane) (sPTMPO) by end-capping the
hydroxy-groups in the poly-TMPO with 1,4-butane sultone was reported by Gode
et al. [128]. Furthermore, the potential use of the dendritic polymer as the acidic
component in proton-conducting membranes is explored. Chu et al. [129] developed
anhydrous proton-conducting membranes by in situ crosslinking of polymerizable
oils containing poly(amido amine) (PAMAM) dendrimer-based macromolecular
protic ionic liquids (PILs). Minimal correlation of height observed in AFM images
shown in Fig. 11b, d indicates that phase-lag images (Fig. 11a, c) are unlikely to be
an artifact of surface roughness. One can observe that the macromolecular PIL
droplets with the diameter of 30 nm (dark areas) are dispersed in a continuous
polymeric matrix (bright areas) as shown in Fig. 11a. In Fig. 11c, 20–35 nm size of
PIL with long and winding channels can be seen. The conductivity of the composite
membranes enhances due to the formation of proton transport channel created by
homogenous distribution and continuous PIL networks.

4.6 Compressibility

The inverse osmotic compressibility of the poly(propylene imine) dendrimers in

deuterated methanol as a function of concentration with small-angle neutron scat-
tering was measured by Rietveld et al. [130]. As increasing the concentration, the
scattering intensity of fourth and fifth generations does not increase anymore or
increases less than the second and third generations. This effect clearly indicates that
the inverse osmotic compressibility was increased as a function of volume fraction
as shown in Fig. 12a, b. Zhang et al. [131] for the first time characterized the
modification of surface interactions by adsorbed dendrimers of fifth-generation
314 B. B. Munavalli et al.

2.0

2.0
1.5

1.5
1.0

1.0
um

um
0.5
0.5

0
0

0 0.5 1.0 1.5 2.0 0 0.5 1.0 1.5 2.0

um um
2.0

2.0
1.5

1.5
1.0
um

1.0
um
0.5

0.5
0

0 0.5 1.0 1.5 2.0 0 0.5 1.0 1.5 2.0

um um

Fig. 11 AFM phase (a, c) and height (b, d) images of the fracture cross-section of polymer
composite membranes containing PAMAM dendrimer. (Adopted with kind permission from Ref.
[129] from © Elsevier)

poly(propylene imine) by exposing the low energy methyl groups on its outer
surface. The experiment results in decrease of compressibility as the dendrimers
are progressively compressed.

4.7 Polydispersity

The properties such as low polydispersity index, highly regular branching pattern,
and a well-defined number of peripheral groups can be achieved by the stepwise
synthesis of dendrimers [5, 132]. In addition, the reproducible pharmacokinetic
behavior is resulted due to low polydispersity of dendrimers in contrast to that of
some linear polymers containing fractions with vastly different molecular weight
within a given sample [133]. The hydrodynamic volume controls the rate of renal
filtration. Larger the molecules slower will be the elimination [9]. The synthetic
preparation of well-defined high-generation dendrimers is time consuming and the
globular architectures of the dendrimers increase the hydrodynamic volume moder-
ately. Figure 13a–c illustrates an alternative approach for the preparation of hybrids
8 Dendrimers 315

Fig. 12 Inverse osmotic compressibility as a function of volume fraction for generations (a) 2 to
4 and (b) 4 and 5. (Adopted with kind permission from Ref. [131] from © Academic Press)

of polyester dendrimers and PEO star polymers with an increase in molecular weight
to 22,000 [9]. PEO was chosen for renal filtration considering its high biocompat-
ibility [134] and low polydispersity of 1.02.

4.8 Host–Guest Chemistry

Several research groups are inspired by host–guest chemistry to prepare dendrimers

with specific functionalities at the core. Thus, molecular systems are created in
316 B. B. Munavalli et al.

Fig. 13 Polyester dendrimer-linear polymer hybrids. (a) Hybrid of PEO star polymer and
polyester dendrons in which the multivalent dendron can carry several copies of drug and the
linear PEO provide solubility. (b) “Bow-tie” hybrid of polyester dendrimers and PEO. (c)
Polyester dendronized linear polymer. (Adopted with kind permission from Ref. [9] from ©
Elsevier)

which certain functionality is surrounded by a particular satirically congested

structure and the functionality is isolated at a specific site. In dendrimers the ions
or neutral molecules can be hosted inside the internal cavities [135]. Such an
important property of dendrimers can potentially be exploited for a variety of
purposes, such as catalysis, drug delivery, and light harvesting. An advantage
shown by such host–guest systems in contrast to dendrimers with a luminescent
core is that the wavelength of the sensitized emission can be tuned by changing
the guest hosted in the same dendrimer. Dendrimers of the poly(propylene amine)
family functionalized with fluorescent dansyl units at the periphery have been
chosen as hosts for fluorescent dye molecules [136]. Due to their molecular
design, polyphenylene dendrimers create a lot of empty space in their interior,
giving rise to unique host–guest interactions, which can be explored in sensor
fabrication [41, 137, 138]. Especially porphyrin-based dendrimers have attracted
a lot of attention in this research area and they play an essential role as photo-
active, redox, guest-binding, and catalytic entities. Diederich et al. have extrap-
olated the concept of a site-isolated functionality by preparing mimics for
cytochrome c, an electron-transferring protein, and have acquired water soluble
dendritic iron porphyrins by using peripheral triethyleneglycolmonomethyl ether
(PEG-like) moieties (Fig. 14) [41].
Cyclodextrins (CDs), one of the most widely used hosts in the study of
host–guest chemistry as well as in the synthesis of rotaxanes are shown in
Fig. 15 [139–142].
8 Dendrimers 317

Fig. 14 A dendritic water-soluble heme analog. (Adopted with kind permission from Ref. [41]
from © ACS)

4.9 Catalytic Properties

The combined features of dendrimers particularly nanoscopic dimensions and the

ability to molecular solvation make them suited to fill the gap between homo- and
heterogeneous catalysis. In other words, dendrimers will combine the advantages of
homo- and heterogeneous catalysts, if soluble dendrimers with defined catalytical
sites are developed that can be removed from homogeneous reaction mixtures by
simple separation techniques (i.e., ultrafiltration or dialysis) [143]. In the catalytic
dendrimer systems, the active center is located at the core. The exterior functional-
ities of dendrimers can be used to accommodate many catalytic sites on one
molecule, possibly resulting in anomalous and favorable catalytic behavior. Brunner
has been one of the first authors to report on branched molecules containing internal
catalytic sites. He introduced the word “dendrizymes” for the presented molecules
considering the resemblance of the produced structures to prosthetic groups in
318 B. B. Munavalli et al.

Fig. 15 Schematic diagram of preparation of a β-CD polyrotaxane via photodimerization.

(Adopted with kind permission from Ref. [139] from © ACS)

enzymes [144]. The reported first generation dendrizymes are formed in situ by
adding Cu(I) triflate to the chiral compounds. Fréchet-type wedges with a chiral
pyridyl alcohol at the focal point have been used by Bolm et al. [145] as catalysts in
the enantioselective diethylzinc addition to benzaldehyde. Click nonaxylose
dendrimers stabilized platinum nanoparticles and were catalytically active in olefin
hydrogenation in water at room temperature as shown in Scheme 8 [146].

4.10 Degree of Branching (DB)

Degree of branching has been well studied in systems that involve the direct conden-
sation reaction between bifunctional A2 monomers, such as diacids and trifunctional
B3 monomers, such as glycerol, in the presence of lipase and chemical catalysts to
form hyperbranched polymers [147, 148]. To identify the potential applications,
understanding the relationship between percentage of DB and the physical and
chemical properties of hyperbranched polymers is necessary. Degree of branching is
a structural property that is determined by the concentration of linear (L), terminal (T),
and dendritic (D) units within the polymer matrix.
The degree of branching can be regarded as the ratio of branched units in the
polymer to those in a perfect dendrimer. Thus, the limiting values are DB = 0 for
linear polymers and DB = 1 for a perfect dendrimer. Various definitions of DB have
been given. If we do not take into account the vinyl group or initiator unit (core unit),
the DB is defined as

ðnumber of branched unitsÞ þ ðnumber of terminal unitsÞ  1

DB ¼ (4)
ðtotal number of unitsÞ  1

Here, one unit has been subtracted from the numerator and the denominator to
take into account that even a linear polymer has one initiating and one terminal unit.
From the topology of branched systems with trifunctional branch points, for any
given molecule the number of branched units is equal to the number of terminal unit
minus one. Thus, Eq. 4 can be further simplified as:
8 Dendrimers 319

Scheme 8 Synthesis of the glycodendrimer 3 in two steps from the nona-azide core 1. (Adopted
with kind permission from Ref. [146] from © Elsevier)

2  ðnumber of branched unitsÞ

DB ¼ (5)
ðtotal number of unitsÞ  1

Alternatively, the fraction branch points can be defined as

number of branched units

FB ¼ (6)
ðtotal number of unitsÞ  ðnumber of monomersÞ
320 B. B. Munavalli et al.

In the semi-batch system, DB is slightly affected by the presence of polyinitiator

and is mostly governed by the comonomer content. The calculations are also applied
to polymerizations from surface-bound initiators.

4.11 Melt Properties

The viscoelastic or rheological behavior of polymer melts governed by the size of the
macromolecules and their topology is strongly related to their industrial applications.
For melts of linear monodisperse chains, the viscoelastic spectra provide information
about both segmental and chain relaxation times, which, through known scaling
dependences, allow for a determination of the macromolecular sizes of test samples.
The situation is more complicated for the macromolecules with nonlinear topologies
for which the scaling dependences are different. Systems in which both the sizes and
the topologies of molecules are not precisely known and can vary in an undefined
way seem to be especially difficult. This seems to be the case for the broad
distribution of sizes of highly branched but poorly defined molecular topologies
[150, 159]. Both linear and branched molecules can be represented by scaling power
laws, but with remarkably different scaling exponents. For the melts of linear chains,
the exponent 3.39 is observed, which is closed to the typical value of 3.4. However,
the fractions of the branched polymer exhibit considerably lower exponent of 2.61. It
is interesting to note that the value of the normalized chain relaxation time for the
feed polymer with the broad molecular weight distribution (MWD) fits nicely into
the data for the fractions with narrow MWDs. This seems to indicate that conclu-
sions can also be drawn from a series of hyperbranched polymers with broad MWDs
as shown in Fig. 16 [149].

Fig. 16 Molecular weight 6

dependences of the
normalized chain relaxation
time, tc/ts, for branched 5 τ∼M3.39
fractions (●), linear polymers
(□), and branched feed
log (τc /τs)

polymer (+). (Adopted with 4

kind permission from Ref. τ∼M2.61
[149] from © ACS)
3

1
3,5 4,0 4,5 5,0
log Mw
8 Dendrimers 321

4.12 Electrochemical Properties

Since redox-active organometallic units play a key role as multielectron-transfer

mediators in electrocatalytic processes of biological and industrial importance, the
incorporation of such molecules at well-defined locations within dendrimeric structures
is an important objective. In particular, the ferrocene moiety is an attractive organome-
tallic redox center to integrate into dendritic structures as illustrated in Scheme 9
[151–153]. This system is not only electrochemically well behaved in most common
solvents undergoing a reversible one-electron oxidation, but also such electron removal
commonly does not involve fragmentation of the original molecular framework. The
techniques such as cyclic voltammetry, differential pulse voltammetry, and bulk cou-
lometry have been used to study the redox behavior in solution of the peripherally
functionalized ferrocenyl dendritic macromolecules [154–156, 170–173].

4.13 Biocompatibility and Toxicity

In the field of drug delivery, dendrimers have brought the tremendous advances.
A great optimism is expected regarding their potential in biomedical field owing to

R2
R2 R2
R2 Si O Si
O O
Si O Si
O O
CH2-CH O O
Si O Si
Fe R2 O O R2
Si O Si
R1 R2 R2
R1 Si O
R1
Si
R1
8 equiv 2
O O
Si O Si
O O Toluene 25°C

O O Karstedt cat.
Si O Si R1
R1 O O R1 R2
Si R1
O Si CH2-CH R1 Si O Si
R1 R1 O O
Si O Si
1 Fe O O
O O
1 equiv Si O Si
R1 O O R1
Si O Si
R1 R1
CH3 CH3 3
R1= O Si H R2= O Si CH2 CH2
CH3 CH3
Fe

Scheme 9 Synthesis of ferrocenyl monosubstituted octasilsesquioxane. (Adopted with kind

permission from Ref. [151] from © ACS)
322 B. B. Munavalli et al.

their nanometric size lies between 1 and 100 nm. Therefore, they may interact
effectively and specifically with the components of cell such as plasma mem-
branes, cell organelles (endosomes, mitochondria, nucleus), and proteins such as
enzyme, as all these cellular components are themselves in nanometer in size range
[157, 158].
Closely related terms toxicity and biocompatibility of dendrimers are important
for biomedical applications. Dendrimers should be devoid of toxicity and immuno-
genicity. The pharma companies mainly applied the concept of toxicity for the
description of adverse effects to cells, organs, or patients. The second concept of
biocompatibility belongs to the field of biomedical materials as an extent of their
compatibility with the studied system. One can say that biocompatibility and toxicity
are inversely proportional, i.e., more is the biocompatible lesser be the toxicity.
Therefore, understanding of the precise context of material usage is needed to
describe biocompatibility of a material. However, clinical expertise with dendrimers
is still in its infancy and thus it is difficult to specify any chemistry insistently
biocompatible or toxic [116, 159–161].
The electrostatic interactions between the negative charges of most cell mem-
branes and the amino surface groups of dendrimers significantly influence the
stability and permeability of membranes. Also, dendrimer–membrane interactions
are responsible for their high cellular uptake by endocytosis. However, G3 and
higher generations of amino terminated dendrimers have a destructive interaction
with the membrane, which causes cellular lysis and high cytotoxicity. Obviously,
negatively charged dendrimers repulse with negatively charged membranes and
therefore do not have generation-dependent cytotoxicity. For noncharged
dendrimers, their cytotoxicity is influenced by polarity of surface groups. For
instance, polar groups like PEG do not induce a toxic behavior. On the contrary,
nonpolar groups like lipids could invade the membranes by hydrophobic interac-
tions thus resulting toxicity in dendrimers. Lipids can act as immune stimulators
and positively influence the cells. The particle size is a key player for
biodistribution, clearance, and toxicity of dendrimers. The clinical applications
of PAMAM dendrimer in drug delivery are restricted due to their inherent toxicity,
reticuloendothelial system uptake, and hemolysis [162]. Regardless of the exten-
sive pharmaceutical and biomedical applications of dendrimers, toxicity due to
terminal-NH2 groups and multiple cationic charges limits their clinical applica-
tions [163–165]. Dendrimers like PPI, PAMAM, and poly-L-lysine (PLL) exert
significant in vitro cytotoxicity due to their surface cationic groups [166, 167]. Evi-
dence regarding dendrimer safety is conflicting [168]. There are reports of con-
centration and generation-dependent toxicity of free peripheral amine groups
[169]. The cytotoxicity of cationic melamine dendrimers having surface groups
like amine, guanidine, carboxylate, sulphonate, or phosphonate was reported by
Chen et al. Their study concluded that cationic dendrimers were much more
cytotoxic than anionic or PEGylated dendrimers. Not only dendrimers but also
cationic macromolecules in general cause destabilization of the cell membrane and
thus result in cell lysis [170–172].
8 Dendrimers 323

5 Applications of Dendrimers

The unique structural characteristics like nanoscopic size, spheroidal surface, high
branching, cavernous interior and the exciting properties such as low viscosity, high
solubility, high reactivity make dendrimers a good candidate for broad number of
prospective applications in various fields. The emerging role of dendritic macromol-
ecules for anticancer therapies, diagnostic imaging, and nanoscale delivery devices
is remarkable. These integrated medicinal and diagnosis applications include gene
therapy and chemical sensors drug delivery system. In addition, these special classes
of materials also have applications for adhesive and coatings, light harvesting
material, catalyst, electronic applications, separating agents, and many more. The
illustration of various applications of dendrimers is shown in Fig. 17.

5.1 Biomedical Applications

5.1.1 Drug Delivery

Oral Drug Delivery

Among the many drug delivery routes, the oral route is preferred because of its
significant advantages such as less fluctuating plasma drug level with the controlled
drug delivery systems. This is because the drug released slowly from the dosage

Drug delivery
Contrast
Cosmetics Imaging
agents

Energy storage
Catalyst
Devices

Light
Harvesting Sensors
material
Water purification

Fig. 17 Various applications of dendrimers

324 B. B. Munavalli et al.

continuously and thus maintains the constant blood level in the body. Because of
ease of production, low cost, convenience of ease of administration, and flexibility in
designing of dosage, this has received more attention in the pharmaceutical field.
Also, it is the most convenient administration route with good patient compliance,
especially in the patient opinions. In spite of these benefits, defects of oral delivery
route are also obvious. The issues such as less solubility in the aqueous solutions and
low penetration across intestinal membranes are common in oral drugs delivery.
Currently, to overcome these problems, researchers focus on several strategies in
which drugs are loaded into oral drug carriers. The absorption and distribution of
drugs in such systems mainly depended on the properties of these macromolecular
carriers. Through the modification of these macromolecular structures, minimization
of the side effects can be achieved. The ability to protect the drugs from degrading is
the main requirement for an ideal macromolecular carrier for orally administrated
drugs. They might reduce nonspecific interactions with food proteins and enhanced
the absorption across the intestinal epithelium. Dendrimers with featured properties
may act as potential candidates for orally controlled release systems by conjugating/
encapsulating the drug molecules. They can simplify dosing schedules as they
maintain the drug concentrations within the therapeutic range at the injured regions.
Also, the dendrimers can significantly increase the solubility of these orally admin-
istrated drugs and even the stability of drugs in biological environments. PAMAM
dendrimers are expected to have potential applications in enhancing the solubility for
drug delivery systems [110, 173]. The unimolecular micelle nature of dendrimers is
because of the presence of hydrophilic exteriors and hydrophilic interiors. Solubili-
zation behavior is due to the formation of covalent and noncovalent complexes with
drug molecules and hydrophobes [174]. Studies on Caco-2 monolayers, as models of
intestinal epithelial barrier, show that it is possible to minimize toxicity while
maximizing transepithelial transport by engineering surface chemistry of PAMAM
dendrimers [175]. The effect of dendrimer generation and conjugation on the
cytotoxicity, permeation, and transport mechanism of PAMAM dendrimer investi-
gated by D’Emanuele and his research group [176] suggests that, as the concentra-
tion and generation increased, cytotoxicity and permeation of dendrimers increased.
However, it is observed that conjugation with lauryl chloride resulted in reduction in
cytotoxicity.

Ocular Drug Delivery

Drug delivery to the eye has been the most challenging tasks to the pharmaceutical
scientists. Drug delivery to the eye can be generally classified into anterior and
posterior segments based on ocular application [177]. Conventional drug delivery
systems, including eye drops, suspension, and ointments, are not effective enough to
meet the requirements in the treatment of ocular diseases [178]. However, more than
90% of the marketed ophthalmic formulations are in the form of eye drops and most
of them target the front of the eye termed as anterior segment eye diseases [179]. The
precorneal loss factors such as solution drainage, lacrimation, tear dynamics, tear
dilution, tear turnover, conjunctival absorption, transient residence time, and low
permeability of the corneal epithelial membrane cause poor bioavailability of drugs
8 Dendrimers 325

from ocular dosage forms and thus act as the major challenges to the drug delivery.
A supreme ocular drug delivery system must be nonirritating, biocompatible, sterile,
isotonic and biodegradable, improved bioavailability of drugs, increased retention
time, reduced side effects, cellular targeting, better patient compliance, and provid-
ing extended therapeutic effects [180]. Dendrimers can offer unique solutions to
such complex delivery problems like ocular drug delivery.
Vandamme et al. [181] have evaluated several series of (PAMAM) dendrimers for
controlled ocular drug delivery. The residence time of pilocarpine nitrate and
tropicamide was found to be longer for the anionic dendrimer solutions. Results of
a “miotic activity test” on albino rabbits showed that these PAMAM formulations
enhance pilocarpine nitrate bioavailability and also prolonged the reduction of
intraocular pressure (IOP), indicating increased precorneal residence time. Durairaj
et al. [182] studied the dendrimeric polyguanidilyated translocators (DPTs), which
are a class of dendrimers with tritolyl branches and surface guanidine groups as
potential ophthalmic carriers for gatifloxacin, a “fourth generation fluoro quinolone”
approved for conjunctivity treatment. The results have indicated that the DPT forms
stable gatifloxacin complexes allowing once a day dosing with enhanced solubility,
permeability, antimethicillin resistant Staphylococcus aureus (MRSA) activity, and
in vivo delivery of gatifloxacin and thus seems like a potential delivery system.
Shaunak et al. [183] synthesized dendrimer-glucosamine (DG) and dendrimer-
glucosamine 6-sulfate (DGS) using carboxylated PAMAM dendrimer (G3.5) and
then these were, respectively, conjugated with immuno-modulatory and anti-
angiogenic properties. To increase the long-term success after glaucoma filtration
and prevent scar tissue formation, these two conjugates were used together in a
validated and clinically relevant rabbit model of wound healing. By subconjunctival
injection, DG (60.30 mg/animal) and DGS (30.15 mg/animal) were administered.
Bleb survival was evaluated as the primary efficacy end point of treatment.
The results showed that the long-term success of the surgery increased from 30%
to 80% and inhibited the pro-inflammatory and pro-angiogenic responses for the
combination of subconjunctival treatment with DG and DGS. Minimal scar tissue
formation was observed for DG and DGS treated rabbits as compared to placebo-
treated animals. Furthermore, during the entire experimental period, no clinical,
hematological, biochemical toxicity, or microbial infections were observed in all
animals. The results thus suggested that ocular administration of DG and DGS might
be effective, reasonable, and safe routes in clinical practice.

Transdermal Drug Delivery

Drug delivery through a skin to achieve a systemic effect of a drug is commonly
known as transdermal drug delivery. The human skin is a readily accessible surface
for drug delivery. Generally, for the patients who cannot tolerate oral dosage forms
and who are nauseated or unconscious, transdermal drug delivery system (TDDS) is
an alternative route of administration. On the other hand, transdermal delivery of
drug has some limitations due to the slow rate of delivery. Thus, the use of
transdermal enhancers is the most common method to improve drug penetration
through the skin. Various organic solvents act as an effective transdermal enhancers
326 B. B. Munavalli et al.

as they can directly react with the skin and thus cause transient increase in their
permeability and induce immune responses in the skin. Also, the polymeric
enhancers with hydrophilic and hydrophobic properties have gained tremendous
interest. Particularly, PAMAM dendrimers with hydrophilic outer shells and hydro-
phobic interiors can improve either the water solubility or stability of hydrophobic
drugs, which are expected to act as effective penetration enhancers. PAMAM
dendrimer complex with nonsteroidal anti-inflammatory drugs such as Ketoprofen
and Diflunisal are very effective for the treatment of acute and chronic rheumatoid
and osteoarthritis and could improve the drug permeation through the skin as
penetration enhancers. The model drugs Ketoprofen and Diflunisal were conjugated
with G5 PAMAM dendrimer [184].
The utilization of polyhydroxyalkanoate (PHA) and G3 PAMAM dendrimer was
reported by Wang et al. [185] as a novel TDDS. PHA used in this experiment was
composed of 3-hydroxyhexanoic acid (8%) and 3-hydroxyoctanoic acid (92%).
Both the model drug tamsulosin hydrochloride and PHA were mixed together and
laid on the transdermal delivery patches before the in vitro permeation experiments
performed on snake skins. They pretreated the snake skin with PAMAM dendrimer
solution for 24 h to determine the effect of the PAMAM dendrimer on in vitro
penetration efficiency of tamsulosin hydrochloride. However, permeation amount of
the model drug could not enhance significantly. The penetration amount of
tamsulosin in the PAMAM dendrimer containing PHA matrix was 24.0 mg/cm2/
day, but for the dendrimer-lacking PHA matrix it is 15.7 mg/cm2/day. Note that the
required amount of this drug in clinical trials is 20 mg/cm2/day. Thus,
PHA-dendrimer matrix reached the clinical aim and could be developed as a useful
delivery system for clinical TDDS.

Pulmonary Drug Delivery

Pulmonary drug release is the best alternative to the noninvasive administration for
systemic delivery of therapeutic agent (mainly proteins and peptides) due to the fact
that lungs could provide a large absorptive surface area up to 100 m2 but extremely
thin (0.1–0.2 mm) absorptive mucosal membrane and good blood supply.
Dendrimers have been reported for pulmonary drug delivery also [186]. The study
indicates that the relative bioavailability of pulmonary drug delivery of Enoxaparin
was increased by 40% by the positively charged PAMAM dendrimers (G2 and G3
generation). Thus, for Enoxaparin pulmonary delivery, the positively charged
dendrimers are the best suitable carriers.

Controlled Drug Delivery

Controlled drug delivery is one which delivers the drug at a predetermined rate, for a
specified period of time. In this drug delivery system, therapeutic agents may be
released for long periods of time, ranging from days to months from drug-
encapsulating devices at controlled rates. Advantages of such systems over tradi-
tional methods of drug delivery include tailoring of drug release rates, protection of
fragile drugs, and increased patient comfort and compliance. The drug molecule is
encapsulated inside the cavity of dendrimers from which the drug released slowly.
8 Dendrimers 327

Thus, these macromolecules are used to control the release of drug. Encapsulation of
Ketoprofen with dendrimer and sustain release of the drug both in vitro and in vivo
was demonstrated by Man et al. [187] that extended pharmacological response. As
indicated by the in vivo bioavailability evaluation study, PAMAM dendrimers could
be considered as a potential drug carrier of Ketoprofen with sustained release
behavior under suitable conditions.

Targeted Drug Delivery

Targeted drug delivery is a system that delivers a certain amount of a therapeutic
agent to a targeted diseased area within the body for a prolonged period of time.
Through this drug delivery system, required plasma and tissue drug levels
maintained in the body, and thereby preventing any damage to the healthy tissue
via drug. Presence of wide variety of surface functional groups makes dendrimers
highly potential for drug delivery applications. If one of these segments is attached
with active drug molecule, the other can be highlighted as targeting group. Due to
this double functional group, the plasma level of the drugs maintained at desired
level for longer period of time with increasing pharmaceutical efficiency [188–190].
Patri et al. [191] synthesized G-5 PAMAM dendrimer conjugates with folic acid
and modified surface to give, respectively, a hydrophilic, neutral, hydroxyl surface.
Methotrexate inclusion complexes were formed in water and their cytotoxicity was
compared with Methotrexate (MTX) covalently conjugated by an ester linkage that
mediates release of the active drug through hydrolysis. The study showed that the
activity of MTX is proportional to the number of MTX molecules in the inclusion
complex, and all the covalently coupled drug–dendrimer conjugates were stable in
both water and phosphate buffered saline (PBS) buffer solution. This suggests that
drug complex with dendrimer as an inclusion complex improves its aqueous solu-
bility. Thus, a cleavable, covalently linked dendrimer conjugate is suitable for
targeted drug delivery as it does not release the drug prematurely in biological
conditions.

5.1.2 Diagnostic Applications

The multiplicity of reactive chain ends of dendrimers make them well suited for the
medical imaging applications. This allows introduction of large number of contrast
agents onto a single molecule in a controlled manner, thereby enhancing the imaging
sensitivity. Magnetic resonance imaging (MRI) is a well-developed technique that
permits organs, blood vessels, or tissues to be visualized in the human body.
Injection of contrast agents containing paramagnetic metal ions could significantly
reduce the relaxation time of the water protons in the targeted organ. Some of the
dendrimers combining with certain kinds of compounds act as imaging reagents in
clinical detection [192, 193]. Recently Raymond’s group reported significant
enhancement of the relaxivity, solubility, and biocompatibility of MRI contrast
agents connecting PAMAM dendrimer with 1,4,7-triazacyclononane TACN-Gd
complex. The relaxation times of Gd T1 and T2 have increased and the toxicity of
PAMAM dendrimer is less than small molecule complexes. Thus, it could provide an
effective alternative imaging reagent for early diagnosis of cancer [194].
328 B. B. Munavalli et al.

Dendrimers are under investigation as potential polymeric X-ray contrast agents.

Various organometallic complexes such as bismuth and tin are used as potential
dendritic X-ray contrast agents to obtain a high resolution X-ray image
[195]. Because of their distinct morphology and unique characteristics, dendrimers
are fascinating molecules to use as molecular probes. For example, to the generation
of an integrated molecular probe, the immobilization of sensor units on the surface of
dendrimers is a very efficient way, owing to their large surface area and high density
of surface functionalities [196].

5.2 Engineering Applications

5.2.1 Sensors
Development of dendrimer-based sensors has received special attention, in view of
their several unique features that could improve optical sensor performance. For
dendrimers to be used in sensor applications, they must react with the analyte and the
resulting interaction such as absorption, reflectance, luminescence, lifetime, refrac-
tive index, scattering, diffraction, and polarization must change quantitatively.
Development of electrochemical biosensors using dendrimers for analytical appli-
cations has been reported in number of studies [197] for the detection of different
types of analyte, such as uric acid, ascorbic acid, dopamine, phenols, glucose, and
hydrogen peroxide. Dendrimer-modified sensor surfaces have revealed remarkable
stability, even after numerous cycles of regeneration for deoxyribo nucleic acid
(DNA) hybridization and antigen-antibody assays. These matrices have been
found stable in various types of regeneration system, such as urea stripping [198],
glycine-HCl stripping [199], thermal stripping [200], and alkaline stripping.
The high stability of the dendrimer film is attributed to the attachment of each
bioreceptor molecule by forming multiple bonds with several functional groups on
the sensor substrates, as well as the higher holding capacity of the bioaffinity groups.
Immobilization of dendrimers on electrode surfaces and bulk materials can be
achieved using polyvalent interactions, such as adhesives, surface coatings, or
polymer crosslinking [201].
Recently, glucose biosensor preparation based on an Au/AuNP/(FeSH+Cyst)/
PAMAM/GOD system was described by Karadag et al. [202] as shown in Fig. 18.
The biosensor proposed by this group was successfully applied for glucose analysis
in beverages.
Dendrimers conjugated with multiple functional molecules are being explored for
usages within a wide variety of biomedical applications. The targeted drug delivery
system could also serve as a sensor delivering a cytotoxic drug into the desired cells
and thereby monitoring the real-time apoptotic effect of the drug. Myc et al. [203]
reported the synthesis and in vitro apoptosis-sensing function of a bifunctional
G5.0-PAMAM-based dendrimer nanodevice, in which folic acid (FA) was used as
the targeting agent as well as the fluorescence resonance energy transfer (FRET)
reagent.
8 Dendrimers 329

GOX Gluconic
N acid
N
N
GOX Glucose

H 2O 2 O 2
N
N N

N N

+2e
Fe
GOX N N C=C N N GOX

N N Glutaraldehyde
N
N
N

N Cysteamine

S S
S
S

SH

Fe 6-(ferrocenyl) Glucose
hexanethiol Oxidase Au NP
PAMAM

Fig. 18 Preparation of biosensor made of Au/AuNP/(FeSH+Cyst)/PAMAM/GOx system.

(Adopted with kind permission from Ref. [202] from Elsevier)

5.2.2 Light Harvesting Material

Dendrimers are perfectly branched synthetic macromolecules with numerous chain
ends all emanating from core and are used as an interesting scaffolds for light
harvesting applications. Light harvesting is the conversion of light energy into
photon energy or into chemical energy by trapping energy via peripheral chromo-
phores. The tree-like structure of dendrimers could potentially act as an energy
gradient for the funneling process. The periphery of dendrimers can be functionalized
with multiple light absorbing chromophore units that gives a high probability to
capture light. The relatively short through-space distance from the periphery to the
core, due to back folding, allows for high efficiency energy transfer.
The π-conjugated dendrimers based on truxene and thienylethynylene synthe-
sized by Nantalaksakul et al. [204] have shown intrinsic energy gradient from
periphery to the core along with broad absorption in the UV-vis range and proficient
energy transfer to the lower energy center. They are highly potential as light
harvesting materials.
330 B. B. Munavalli et al.

Dendrimer backbones themselves can also be used as the energy donor. The
conjugated dendrimers such as phenylacetylene chains were mainly selected for
these applications. By controlling over the conjugation length of dendritic branches
in these dendrimers, rapid and directional energy transport could be obtained to
achieve an efficient energy transfer. The synthesis of phenylacetylene dendrimers by
Xu et al. [205] showed an efficient, unidirectional energy transfer to a single core
chromophore. The robust, high-yielding synthesis allowed for the preparation of
high-generation (G-n) molecules up to G-6. A strong UV absorption features in the
range of 250–350 nm observed for these cross-conjugated structures and that is
double than the increasing generation. Also, these dendrimers exhibit emission in the
range of 350–450 nm. An energy “sink” was introduced into the system by
functionalizing the core of these structures with the lower band gap, perylene
chromophore. Hence, the phenylacetylene monomer units act as the peripheral
energy donors and perylene acts as the central energy acceptor.

5.2.3 Catalyst
Dendrimers are potential candidates in the field of catalysis, as they will retain the
benefits of homogeneous catalysts such as high activity, good reproducibility, high
selectivity, accessibility of the metal site, and so on. Unlike most other polymeric
species, they will be readily recoverable after reaction. In principle, dendrimers are
the most promising candidates that can meet the needs for an ideal catalyst: persis-
tent and controllable nanoscale dimensions, chemically reactive surface, favorable
configuration in which all the active sites would always be exposed towards the
reaction mixture so that they are easily accessible to migrating reactants and soluble
but can be easily recovered by filtration. These properties of dendrimers, or some
combination of them, make them so useful for their application in catalysis. Till
today, many reports have revealed the designing and application of dendrimer-based
catalyst for various reactions [81, 99, 108, 206–212]. It is well recognized that the
properties such as well-defined structures and small sizes typically 10  15 Å make
the homogeneous catalysts more selective and effective catalysts. The controlled
molecular size and shape of dendrimers and the disposition of functional groups are
highly attractive as scaffold of polymer catalysts.
The leaching of metal from the particle can be achieved through the multipoint
binding sites on the surface of dendritic polymers. Therefore, it is worth noting that a
high catalytic activity can be obtained using dendrimer-templated bimetallic nano-
particle catalysts, which is hardly achievable in the case of monometallic nano-
particles. In view of this, Zhao et al. [213] have synthesized dendrimers encapsulated
with Pt and Pd nanoparticles and found an excellent catalytic activity for the
electron-deficient alkenes and hydrogenation of simple alkenes. Such catalysts
were simply prepared by the incorporation of metal ions into hydroxy-terminated
PAMAM dendrimers followed by reduction with BH2. The intradendrimer metal
nanoparticles are quite monodispersed and stable before, during, and after hydroge-
nation reactions as observed from high resolution transmission electron microscopy
(TEM). It is observed that the fourth generation dendrimer-encapsulated Pd40
nanoparticles showed high catalytic activity for the hydrogenation of allyl alcohol
8 Dendrimers 331

and N-isopropyl acrylamide. Interestingly, the generation has its control over the
hydrogenation rates. For higher generation dendrimers, the hydrogenation rates were
significantly slow, probably due to their less porous surface.

5.2.4 Energy Storage Devices

Dendrimers are the macromolecules with controlled shape and size connected from
branches to a central core. The electron conducting nature resulted from the presence
of internal voids and cavities inside the dendrimers offers them energy storage device
applications. Till date, only few reports are available for dendrimer-based energy
storage devices. The synthesize of a 10-arm NH2 terminated polyamidoamine
dendrimer with a diethylenetriamine core and a redox center reported by Chandra
et al. [214] is presented in Scheme 10. This dendrimer is further used to develop
dendrimers with functionalized magnetic nanoparticles (Fe3O4@D-NH2), which are
potential electrode materials for electrochemical supercapacitors. The electron charge
transfer mechanism between core and the branched surface of the dendrimers is ideal
for energy storage process. The large surface area, diversified composition, unique
porous structure, and excellent electronic conductivity resulted from the combined
advantages of both dendrimers and iron oxide nanoparticles make porous Fe3O4@D-
NH2 a potential electrode material for electrochemical supercapacitors.
Dendrimers special structural characters also find application in fuel cells.
Dendrimers have also been used to encapsulate the electrocatalysts [215] to modify
the proton-conducting membranes [216, 217] and as components in the electro-catalytic
ink [218]. It is worthy to mention that in all these cases, polyamidoamine dendrimers
have been used due to the presence of amino and amidic groups that can interact with
ionic metal precursors, besides amino group allows a subsequent functionalization,
which expands its application potential. Recently, Alvarez et al. [219] have synthesized
and characterized composite of Nafion and PAMAM (G4OH) dendrimer membrane.
Methanol crossover and permeability measurements showed that the dendritic molecule
as modifiers of Nafion membranes acts as a barrier hindering the methanol access. This
result could be attributed to the affinity with methanol of peripheral groups of PAMAM

Scheme 10 Dendrimer functionalized magnetic nanoparticles (Fe3O4@D-NH2). (Adopted with

kind permission from Ref. [214] from Elsevier)
332 B. B. Munavalli et al.

(G4-OH) dendrimer. This proves the potential application of dendrimer-based compos-

ite membrane to be used in the direct methanol fuel cells (DMFC).

5.3 Miscellaneous Dendrimer Applications

5.3.1 Cosmetics
Dendrimers have wide range of applications in cosmetics such as UV sunscreens,
hair treatment, and an oxidant. Due to UV radiation absorbing nature of dendrimers,
these are used in sun screen preparations. A variety of hair grooming compositions
including permanent shaping composition, hair care compositions, hair bleaching
composition, oxidative after-treatment compositions, and hair fixing compositions
will be composed of these dendrimeric derivatives [220]. Polyamine macromole-
cules are used as an antioxidant agents and film forming agents containing disulfide-
functionalized polymers and dendrimers in cosmetics.

5.3.2 Water Purification Process

Various critical physicochemical properties of dendrimers offer an excellent separa-
tion and reaction media for water purification. Dendritic nanopolymers can be used
for the encapsulation of a broad range of solutes in water including anions (e.g.,
perchlorate, nitrate, and phosphate), cations (e.g., copper, silver, gold, and uranium),
and organic compounds (e.g., pharmaceuticals and pesticides). Dendritic nano-
polymers also find its applications as nanoscale reactors and catalysts. They can
bind and deactivate bacteria and viruses [221]. As compared to linear polymers, it is
easier to filter dendrimers because of their globular shape and larger size. Exploring
these unique properties, Diallo and coworkers [222, 223] developed enhanced
microfilteration (MF) and ultrafiltration (UF) techniques for recovering dissolved
cations and anions from aqueous solutions.

5.3.3 Additives, Printing Inks, and Paints

Due to highly ordered and branched structure, dendrimers or hyperbranched poly-
mers offer numerous commercial applications. They have been widely used as
additives in ink formulations (0.5–2% level) to enhance adhesion to a variety of
substrates. They also provide excellent film color characteristics while maintaining
good ink formulation stability and reliable printer operation. The lower “generation”
PAMAM dendrimers are particularly effective for such applications. Their Newto-
nian viscosity characteristics in solution, amorphous, noncrystallizing nature, and
their solubility in polar solvents (tailorable) provide them formulation flexibility and
reproducible ink application characteristics. In fact, their molecular uniformity and
highly functional “Molecular Velcro” surface facilitate their applications even in
micro- and nano-lithography. The modification of surface functional groups of
PAMAM with polyethyleneoxy-side chains could also improve the ink latency
[224]. In addition, dendrimers can also be used for radiation-curable ink formula-
tions in order to achieve good adhesion, water resistance, and humidity resistance
[225, 226].
8 Dendrimers 333

Polyurethane paints made of dendritic polymers are widely used in furniture and
automotive industries because of some beneficial characteristics such as surface
hardness, chemical resistance, light fastness, scratch resistance, and weathering
resistance. Through the use of dendrimer as additives, it is easy to alter the surface
characterization of thermoplastic resin after the molding process. For examples,
polycarbonates are widely used as an engineering thermoplastic for providing a
unique combination of stiffness, toughness, high softening temperature, and
processibility.

6 Future Prospects and Conclusions

Dendrimers are highly defined artificial macromolecules, characterized by high

number of functional groups and compact molecular assembly, which make them
hopeful candidate for various applications. Since last two decades, significant
developments are being occurred in dendrimer research for the establishment of
synthetic procedures and investigation of various properties of the novel class of
macro- and micromolecules.
Today, dendrimer research has created great excitement and immense interest
among the scientific community. This has resulted in tremendous progress into a
synthesis, fabrication, and in arriving potential applications of dendrimers in a wide
variety of technologies. The progress made in the discovery and commercialization
of dendrimers are bound to have the impact on the chemical, energy, electronics, and
space industries in addition to medicine and health care areas. Particularly, in drug
delivery systems, dendrimers research provides an excellent platform for the attach-
ment of drugs and their release to explore the use of dendrimers for various
applications in transdermal, ophthalmic, oral, and gene delivery. Dendrimers can
be designed to improve the properties of some drugs in topical and transdermal
formulations, in delivering the drug to its destination [227–229].
Dendrimers demonstrated as novel carriers of drugs across cell membranes and
organ barriers such as blood-brain barrier (BBB) and have a host of applications such
as treating tumors, cerebral gliomas, and for brain specific delivery of drugs. A new
era of research in dendrimers is the development of dendrimer cluster to form a
multifunctional therapeutic system, which will open a new path for clinical
applications.
The controlled synthesis and purification process of dendrimers is required to
facilitate further research in dendrimer for the specific applications [230]. The low
polydispersity of dendrimers is beneficial to predict its pharmacokinetic behavior in
biological systems. Due to their nanometric scales and the properties similar to
proteins, dendrimers gain attention in studies of their biomimetic properties
[231]. The dendrimers architecture can be monitored by molecular engineering, to
construct structure resembling to enzymes, antibodies, and globular proteins.
Furthermore, there are different areas of biological chemistry where dendrimer
systems found its diverse applications. Some of the significant and fascinating areas of
dendrimer research ongoing include highly sensitive analytical devices [232, 233],
334 B. B. Munavalli et al.

magnetic resonance imaging contrast agents [234], prion research [235], burn
treatment [236], and electron paramagnetic resonance (EPR) imaging with spin-
labeled dendrimers [237–240], etc.
As dendrimer holds great potential adding value in various fields like pharma-
ceutical, therapeutics, and diagnostics, future development in dendrimer technology
must be focused on various aspects, which include:

(i) Reducing the cost of synthesis so as to achieve extensive use of dendrimers as

membranes in various fields.
(ii) Enlarging application of hyperbranched polymers for membrane applications
in the fields of resources and environment.
(iii) Reducing the cytotoxicity of dendrimers by careful surface engineering.
(iv) Multistep synthesis still requires great effort.
(v) Purity aspects of dendrimers and dendrons must be continuously considered
and carefully checked.
(vi) Monitoring the nature of functional groups to control the solubility, related
biological properties, enhanced penetration, and retention effect.
(vii) The applications of dendrimer-based drug delivery systems in cancer treat-
ments are still not acceptable due to difficulty of maintaining clinical grade
purity during synthesis.
(viii) The clinical trial demands detailed investigations of the polymeric carriers
including the incorporated drug and linkages.

To conclude, dendrimers offer various advantages including design, type, and

mode of reactions. At the same time, some of the issues such as complex synthetic
routes, structure-property relationship, biocompatibility, and processability need to
be resolved.

Acknowledgments Authors sincerely thank the DST, New Delhi, for providing the financial support
under DST-PURSE-Phase-II Program. The authors particularly Balappa Munavalli and Satishkumar
Naik thank the UGC, New Delhi, for awarding (RFSMS) fellowship to pursue Ph.D. degree.

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Surfaces and Interfaces
9
Manfred Stamm

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
2 Specific Aspects of Polymer Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.1 Chain Conformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.2 Surface and Interfacial Tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
2.3 Functional Polymer Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
3 Interfaces in Blends, Copolymers, and Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
3.1 Interfaces Between Homopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
4 Characterization Techniques of Polymer Surfaces and Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . 375
4.1 Surface and Interfacial Tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
4.2 Scanning Force Microscopy (SFM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
4.3 Ellipsometry (ELLI) and Surface Plasmon Spectroscopy (SP) . . . . . . . . . . . . . . . . . . . . . 379
4.4 Scanning and Transmission Electron Microscopy (SEM, TEM) . . . . . . . . . . . . . . . . . . . 379
4.5 X-Ray Photoelectron Spectroscopy (XPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
4.6 Electrokinetic Methods (Zeta Potential) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
4.7 Infrared Spectroscopy (ATR-FTIR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
4.8 Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
4.9 X-Ray and Neutron Reflectometry (XR, NR, GISAXS) . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
4.10 Secondary Ion Mass Spectrometry (SIMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
4.11 Ion Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
4.12 Optical Microscopy Techniques (OM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
4.13 Indentation, Adhesion, Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
4.14 Inverse Gas Chromatography (IGC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
5 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386

M. Stamm (*)
Institute of Physical Chemistry and Physics of Polymers, Leibniz-Institut für Polymerforschung
Dresden e. V., Dresden, Germany
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 347

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_10
348 M. Stamm

Abstract
Polymer surfaces and interfaces are present with all polymer materials. They
determine many properties like optical appearance, wetting, and adhesion, but
with blends and composites also for instance toughness, hardness, modulus, and
elongation at break. A short outline of polymer surfaces at molecular scale is
given with reference to special aspects of chain conformation and surface dynam-
ics. The surface tension as a fundamental property of a surface is discussed and
surface functionalization in particular by grafting of polymer brushes onto sur-
faces described. In this way, a very versatile surface functionalization and even
responsive polymer brush surfaces can be obtained. They may be used to control
wetting, adhesion, bio-functionality, catalytic activity, and sensing ability. The
interface between polymers can be formulated on the basis of mean-field theory
with introduction of an effective interaction parameter, which is related with
interface width and fluctuations at the interface. Polymer blends, copolymers as
compatibalizers, and composites are discussed as examples, where interfaces play
an essential role. Several techniques for surface and interface characterization
including scanning force and electron microscopy, photoelectron and IR/Raman
spectroscopy, as well as x-ray and neutron reflectometry or scattering techniques
are critically reviewed. Guidelines for resolution and typical information obtained
are provided. The importance of surface and interface design for future high-tech
devices and advanced materials is highlighted.

Keywords
Surfaces · Interfaces · Wetting · Blends · Copolymers · Composites ·
Functionalization · Brushes · Analysis · Characterization · Surface tension ·
Contact angle · Electron microcopy · X-ray scattering · Neutron scattering ·
Reflectometry · Scanning force microscopy · XPS · SIMS · Ion beam techniques

1 Introduction

The surfaces and interfaces of polymers are important for many properties of
polymeric materials, and their design can introduce interesting functionalities.
This is for instance true for polymer blends, where the interface between incom-
patible polymers strongly influences the mechanical properties, or for the appli-
cation of lightweight composite materials in cars or airplanes, where adhesion
between the reinforcing fibers and the soft polymer matrix plays an essential role.
Very special properties can be achieved with polymer nanocomposites, where
functional nanoparticles are dispersed in a polymer matrix or with thin smart
polymer brush layers as coatings on surfaces, which allow control of wetting and
adhesion properties. Looking on everyday polymeric parts in household, cars, or
sports, one could ask questions like “how do they feel” or “how do they look,”
which in many cases will critically influence the decision for the purchase of a
product. The appearance depends on “the surface,” and the optical or mechanical
properties but also corrosion or scratch resistance depend largely on surface
9 Surfaces and Interfaces 349

composition and structure. A thin functional layer at the surface can influence
those properties significantly. This is in particular the case, when even functional
or smart surfaces or interfaces are used, which can provide biocompatibility,
switching or adaptive properties. The characterization of polymer surfaces and
interfaces in many cases requires special or adapted techniques, and often only a
combination of different techniques will provide necessary information. A careful
characterization is however the prerequisite for the understanding and dedicated
design of materials properties [1, 2].
One should be aware of the fact that one may understand quite different aspects
when talking about polymer surfaces and interfaces. Depending on the properties
under consideration, the surface or interfacial region may extend from sub-
nanometers to micro- or even millimeters, which covers a range of more than 6 orders
of magnitude [1–10]. If one is looking at individual polymer chains (Fig. 1), the
surface and interfacial region will typically range over one chain, where a measure of
the chain size, the radius of gyration, is of the order of 3–30 nm depending on
molecular weight. On the other hand, very different microscopic properties or in
general a combination of them could be important to achieve a particular surface
macroscopic property or appearance. So for instance, for the wetting of a smooth
surface by a liquid, the composition of the outermost surface layer will be important
for the wetting behavior and one has to consider the composition of the first atomic
layer even at subnanometer scale. When on the other hand the optical properties of a
surface are important, one is dealing with a surface layer in the range of the
wavelength of light, that is typically several hundred nanometers large, while for
the adhesion between two sheets of polymeric materials a plastic deformation region
in the vicinity of the interface of up to millimeters may be important because a large
part of the deformation energy is dissipated in this plastic zone. Thus, different
applications require different approaches with respect to desired surface or interface
modifications as well as the use of different characterization techniques, and one
needs a careful definition of the problem before looking for details of surfaces
and interfaces.
A compilation of some common surface and interface analysis techniques is
presented in Tables 1 and 2 indicating typical information that can be obtained
utilizing a particular technique as well as its typical minimal information depth. With
most techniques, the sample preparation and proper adoption of the technique is of
particular importance. The parameters indicated will in most cases depend on the
mode used, the sample system, the available contrast, the addition of, e.g., fluores-
cent dyes, and some quantities cannot be obtained completely independent from
each other. Thus for instance, there exist several different optical microscopy
techniques ranging from simple dark and bright field to differential interference,
fluorescent, or phase measurement interference techniques. For those different
optical microscopy techniques, the available information is quite different from
each other. This is similarly true for scanning force microscopy, electron microscopy,
etc., where always techniques are improved, extended, and further developed. So
these tables can only be seen as a rough guide for selection of particular techniques
and of course are far from being complete.
350 M. Stamm

Fig. 1 Schematics of
polymer surfaces and
interfaces, (a) homopolymer
surface, (b) blend surface with
surface enrichment of one
component, and (c) interface
between polymers with no
interdiffusion. (From Ref. [3])

There are plenty of reviews and books available which cover polymer surfaces
and interfaces (see [1, 2, 4, 5]) as well as particular aspects and characterization (see
[3, 6–11]). In the following, we cover briefly some basic aspects of polymer surfaces
and interfaces including some ways for particular functionalization and shortly
outline some important analytical techniques from Tables 1 and 2.
We distinguish in Tables 1 and 2 between surface and interface analysis tech-
niques, while this distinction is not rigorously true [3]. So several techniques are
applicable for both surface and interface analysis (e.g., x-ray reflectometry, SIMS,
optical techniques, etc.), when they are used in different modes of application. Also
the optimal sample requirements are different from one technique to the next, and the
surface might be facing air, liquid, vacuum, or even a polymer solution. For a
particular technique, the choice and the information content will depend of course
very much on this environment, and therefore one has to be very careful, to analyze
9 Surfaces and Interfaces 351

Table 1 Most common techniques for surface characterization

Smallest
information
depth/width
Technique Probe in/out lateraly (nm) Information Comments
Surface tension/ Liquid drop 0.1/– Surface energy Easy to use,
contact angle ST molecular
information difficult
Scanning force Cantilever 0.05/1 Surface Atomic resolution.
microscopy SFM topography, Many different
composition, modes
toughness etc.
Ellipsometry Polarized 0.1/300 Thin surface Molecular
ELLI light layer interpretation
difficult
Scanning electron Electrons 1/1 Surface Vacuum technique
microscopy SEM topography
X-ray X-rays/ 5/2000 Chemical Quantitative, vacuum
photoelectron electrons composition, technique, lateral
spectroscopy binding state imaging possible
XPS
Electrokinetic Voltage 0.1/– Surface charge Measurement in
measurements/ aqueous medium
zeta potential
Infrared Infrared 2000/2000 Surface Specific ATR-crystal
attenuated total light composition, needed
reflection binding state
ATR-FTIR
Raman Light 0.5/300 Surface Resonance
spectroscopy/ composition, enhancement with
microscopy RS binding state metal clusters
(resonance
enhanced)
X-ray X-rays 0.5/2000 Surface Flat surfaces required
reflectometry XR 0.5/0.1 roughness, thin
Grazing incidence surface layers,
x-ray small angle lateral structure
scattering GISAX
Focused ion beam Ions 2/10 (1 with Imaging, Nanomanipulation
FIB (electrons) SEM) cutting, possible, often in
deposition combination with
SEM
Scanning Cantilever 0.05/1 Tunneling Surface conductivity
tunneling current required
microscopy STM
Optical Light 0.1/300 Surface Many possibilities,
microscopy/ roughness, good height
interferometry structure resolution with
OM interference
techniques
Surface plasmon Light/ 0.1/300 Thin surface Metallic layer on
spectroscopy SP plasmons layers prism necessary
(continued)
352 M. Stamm

Table 1 (continued)
Smallest
information
depth/width
Technique Probe in/out lateraly (nm) Information Comments
Secondary ion Ions 0.1/1000 Surface “Static” mode,
mass composition, vacuum technique
spectroscopy contaminations
SIMS
Micro-indentation Cantilever 100/200 Surface Quantitative
MI hardness, interpretation
module difficult
Neutron Neutrons 0.5/2000 Surface Deuterated
reflectometry NR roughness, compounds needed
enrichment
layer
Auger Electrons 0.2/100 Electronic Surface conductivity
spectroscopy AS 1 excitation, needed
High-resolution surface Vacuum technique
electron energy composition
loss spectroscopy Vibration
HREELS spectrum
Scanning near Light 1/50 Vibrational Local optical
field optical modes, spectroscopy
microscopy fluorescence, possible
SNOM orientation
Inverse gas Gas 0.1/– Gas adsorption, Measurement on
chromatography surface powder
IGC functionality,
energetics

the true materials behavior and not artifacts. On the other hand, one could also just be
interested in a thin contamination layer at the surface, which can change surface
appearance of materials quite significantly. Also resolution does depend on many
parameters and is sensitive in particular on sample conditions and on preparation, so
only “typical” values for favorable conditions are given in the tables. With those
comments, one should be aware that in this short review not all aspects of polymer
surfaces and interfaces can be discussed, and many techniques have elegant ways to
focus on particular aspects and can overcome some of their shortages.

2 Specific Aspects of Polymer Surfaces

2.1 Chain Conformation

Polymers are very long molecules with specific properties, which are determined by
conformational aspects as well as by chemistry given by the constitution of mono-
mers. The architecture of the molecules, i.e., linear, branched, crosslinked, or even
9 Surfaces and Interfaces 353

Table 2 Most common techniques for interface characterization

Typical
smallest
Probe information
Technique in/out depth (nm) Typical information Comments
Pendent drop Liquid 0.2 Interface tension Indirect technique
Transmission Electrons 0.5 Absorption/ Cut perpendicular to
electron reflection of interface, staining
microscopy electrons, interface
TEM width
Focused ion Ions 10 (1 with Concentration Cut perpendicular to
beam FIB (electrons) SEM) profile, element interface with ions,
distribution, imaging with SEM
interface width
X-ray X-rays 0.2 Interference fringes, Contrast of heavy
reflectometry interface width/ elements
XR roughness
Secondary ion Ions 20 Element Dynamic
mass distribution, (destructive)
spectrometry interface width technique
dynamic SIMS
Neutron Neutrons 0.2 Interference fringes, Contrast by
reflectometry interface width/ deuteration
NR roughness
Scanning force Cantilever 0.2 Interface width/ Cut perpendicular to
microscopy roughness/ interface/etching,
SFM topography dissolution/hard
tapping
4
Elastic recoil He/1H, 20 H/D distribution, Contrast by
2
detection ERD H (H, D) interface width deuteration
Forward recoil
spectroscopy
FRD
Nuclear reaction 15N/γ 12 H/D distribution, Contrast by
analysis NRA (4.4 MeV) interface width deuteration
3
He/4He
4
Rutherford He/4He 30 Backscattering Contrast from heavy
backscattering from heavy atoms, atoms
RBS interface width
Small angle X-rays 1 Porod analysis, Bulk sample possible
x-ray scattering electron density
SAXS variation, interface
width
Nuclear Magnetic 1 Spin diffusion from Bulk sample possible
magnetic field species, interface
resonance NMR width
Fluorescence Light 0.3 Quenching of Fluorescence tagging
quenching donor/acceptor of molecules
molecules necessary
354 M. Stamm

star-like or H-shaped, plays a major role on the properties. At the surface, chain
conformations are specific, and various chemical surface modifications are possible.
So the surface properties can be largely modified by surface functionalization caused
for instanced by surface enrichment of components, adsorption, or grafting of chains
at the surface or coating of a thin film. In that way, surface properties can be tuned
independently from bulk properties, and also switching of surface properties is
possible. Those aspects are addressed below, and we first discuss some basic
properties of linear homopolymers at surfaces connected with chain conformations,
topography, and structure. Because of the wealth of possibilities, we will concentrate
on homopolymer surfaces, while many of the polymer surface topics are covered by
books and reviews [1–11].
A long, flexible polymer chain possesses a huge number of internal degrees of
freedom which is the origin of conformational entropy [10, 12–14]. This property
related with the length of polymer chains is the key for the understanding of
polymer behavior and distinguishes polymers from small and stiff molecules. It
leads to unique properties also at surfaces. The simplest model for a flexible
polymer molecule in melt, glassy state and in solution is the Gaussian chain.
The chain is artificially subdivided into segments, whose directions are
uncorrelated in space. These segments, so-called statistical or Kuhn segments,
typically consist of several chemical repeat units of the real chain. The size of the
segments corresponds to the persistence length of the chain, i.e., the distance over
which orientation correlations between monomers decay. Chemical details of the
original chain are mapped into the actual length of the statistical segment and into
(effective) interaction parameters between pairs of such segments. For instance,
the statistical segment length of polyethylene corresponds to about 5 CH2 units
which is about half a nanometer.
The size of a polymer chain is characterized by the average distance between the
chain ends R or the radius of gyration Rg (average distances of segments from the
center of mass of the chain). For an ideal chain we have.

< R2 >¼ a2 N ¼ 6 < R2g > (1)

Here, a denotes the statistical segment length and N the number of segments
(repeat units). The brackets indicate the statistical average. It is obvious that the size
of the (statistical) coil formed by a polymer chain is much smaller than its contour
length: R « Na. Typically, the size of synthetic polymer chains is in the range
between a few nanometers up to some tens of nanometers. Long stiff biological
polymers such as DNA can have a size in the range of several micrometers.
To discuss specific properties of polymer chains in solution at solid surfaces, we
have to distinguish the cases, here the surface has attractive (absorbent) or repulsive
character with respect to the monomers. Free surfaces, i.e., surfaces formed against
air (or vacuum) are considered as a special class of repulsive surfaces where the
surface tension of the polymers is the characteristic property. If we consider a chain
close to a surface, its conformational degrees of freedom are reduced by the
geometrical constraints and so is the chain entropy.
9 Surfaces and Interfaces 355

In order to keep a polymer chain in a dilute solution close to the surface, an

energetic compensation is necessary. This leads to a phase transition scenario for
attractive surfaces: Above a critical temperature of adsorption Tc or below a critical
adsorption strength of the surface, the polymer chains avoid the surface and form a
depletion zone, while below Tc, polymer chains are adsorbed and conformations
change into “pancake-like,” quasi two-dimensional shape [15–17]. This is in partic-
ular true if individual chains are adsorbed on a flat surface from highly diluted
solution. In case of strong adsorption at a flat surface, the chain conformation in the
adsorbed state can be directly measured by atomic force microscopy [17]. Under
special conditions, it is expected that the adsorbed chain conformations reflect the
ones in solution which allows the direct visualization of those chain conformations.
In this way, for instance, conformational phase transition in polyelectrolytes can be
followed in detail [18].
When the bulk phase is dense (melt, glassy state), the layer close to the surface is
densely filled independently on substrate interactions. In computer simulations,
evidence can be found for changes of chain conformations in the vicinity of the
free surface at a scale related to Rg but also deviations on smaller length scales. This
includes an enrichment of chain ends at the surface [20] and a flattened chain
conformation in direct vicinity at the surface [19]. However, the contribution of
chain ends to the free energy and surface tension is rather weak (neglecting chemical
effects), typically of the order 1/N. Despite the problem of free energy and surface
tension, a solid surface influences the chain conformations in other subtle ways. This
regards the interpenetration or entanglements between the chains close to the surface
[22]. As a consequence of neutral boundary conditions, the chain volume is
squeezed if chains are located close to the surface. Therefore, the number of other
chains penetrating the volume of a chain close to the surface is reduced. Conserva-
tion of monomer number (dense melt) leads to a reduction of entanglements by a
factor of 1/2 for long chains close to the surface. Since entanglement properties are
essential material properties which determine dynamic properties of polymers, this
effect can be important. Experiments give indication for such a reduction of the
entanglement density [23]. Generally, it is difficult to observe individual chain
conformations close to the surfaces experimentally, but some experiments are
available in thin films. From neutron scattering experiments, where the radius of
gyration is measured in very thin films, it is concluded that the chain conformation in
confined dimensions flattens and Rg changes as much as 50% [19, 24] (Fig. 2).
One has to take into account that neutron scattering averages laterally over a
certain region. Taking those effects into account, one can conclude that surface
effects on the conformation extend over several Rg. So there is a quite good
agreement between experiment and theory. In that range, also entanglement effects
are expected (but not directly measured), where entanglements should be reduced in
the vicinity of the free surface.
As a trivial effect, there is however also a surface tension connected with capillary
waves at polymer melt surfaces. In comparison to low-molecular-weight samples,
the capillary waves depend not only on surface tension and temperature but also on
viscoelastcity [16] and reflect entanglement effects [25]. With polymers, the surface
356 M. Stamm

Fig. 2 Measurement of the

radius of gyration by small-
angle neutron scattering
SANS in thin films of
polystyrene of different
molecular weights. When the
film thickness d approaches
6Rg0, the flattening of the
chains is observed. Rg0 is the
radius of gyration in the bulk
film, while Rgǁ denotes the
radius of gyration in the
plane of the film measured in
the experiment. (Data from
Ref. [19])

structures are however in many cases not at equilibrium, but frozen-in into the glassy
state from preparation. Upon heating, one then can observe formation of surface
roughness due to development of capillary waves at larger scales as well as smooth-
ening at small length scales [26, 27].
The presence of an interface or a solid surface influences also dynamical pro-
cesses. Since reptation requires strong interpenetration of chains, close to a surface
reptation dynamics should be accelerated. However, it is rather difficult to measure
dynamical effects in the surface region (some nm above the surface only). Computer
simulations gave first indications for surface effects on entanglement properties [28].
Polymers below the glass-transition temperature Tg display solid-state mechanical
properties. Here, fluctuations are frozen on larger time scales. The temperature Tg is
specific for each polymer. With the growing interest in thin polymer films, also
measurements of the glass-transition temperature has been carried out for polymers
under various geometrical constraints (thin films, pores, with or without substrate).
The results obtained are controversial. Based on the previous discussion of dynamics
in polymer melts, one might expect a higher mobility of polymer chains close to the
surface and thus a decrease of Tg. In fact, such results have been reported experi-
mentally for free-standing polystyrene films where a reduction of Tg of about 70 K
has been observed [67]. Other authors found a strong dependence of the substrate/
polymer interaction on the change of Tg [29] and reported an increase of Tg close to
the surface. Part of the controversy may be due to the fact that different experimental
methods and sample preparation techniques are used in different publications. There
are recent results that surface effects on dynamics are only minor [30]. Also from
neutron reflectivity experiments, one can conclude that chain dynamics is only
influenced in a region of the order of Rg [31] (Fig. 3). In this case, the interdiffusion
between two films is measured at a temperature close to Tg, where the thickness of one
film is varied from d = 0.3 to 4.6 Rg. The interdiffusion is sensitive on the region close
to the surface, where a slight increase of dynamics at film thicknesses smaller than Rg
is observed. This is reflected by an increased interdiffusion width σ at given interdif-
fusion time τd between two films, where one film has thickness smaller than Rg.
9 Surfaces and Interfaces 357

Fig. 3 Determination of chain mobility in thin films of thickness d via neutron reflectometry. The
interdiffusion width σ after interdiffusion of time τ equal to disentanglement time τd is determined
for polystyrene films as function of film thickness d. (From Ref. [31])

This could be attributed to effects of entanglements, which are expected to be

reduced close to the surface, and chain ends, which should be enriched at the surface.
One therefore can conclude that surface effects on chain conformation and chain
dynamics are restricted to a region of the order of Rg.

2.2 Surface and Interfacial Tension

The most common way to obtain a picture of the surface properties [3, 8, 9, 11, 32,
33] and to measure the surface energetic state is the determination of the surface
tension. It is determined by the outermost layers of atoms and therefore by a surface
region of typically 0.2 nm. It arises from the asymmetric surrounding of atoms at
the surface, where an atom at the surface is missing some of its neighboring
atoms and consequently experiences a force due to the remaining asymmetric
interactions (Fig. 4).
The surface tension turns out to be a very fundamental property of solids and
liquids [3, 8], since it reflects directly the strength of the bonding within the bulk
material which is schematically shown in Fig. 4. There are very different binding
forces, and hard solids (covalent, ionic, metallic) typically reveal “high-energy”
surfaces (surface tension ~ 500 to 5000 mJ/m2), which is in contrast to weak
molecular solids and liquids (soft matter) with their “low-energy” surfaces (surface
tension <100 mJ/m2). It is clear that most polymers belong to the second class of
materials and interactions between the chains are dominated typically by van der
Waals forces, and in some cases by hydrogen bonds. Surface tension however also
depends on surface roughness and will be influenced by surface segregation of
358 M. Stamm

Fig. 4 Schematics of a G
molecule in bulk (liquid) and
at the surface (interface liquid/
gas) showing neighboring
molecules and interaction
forces [33]
L

components (surfactants, antioxidants, etc.) and in particular by contaminations

(catalyst, solvent, etc.). Therefore, in many practical cases, it may not reflect the
properties of bulk material but of a thin surface layer or even end groups which may
also segregate to the surface. Using surface tension measurements provides infor-
mation on surface composition and structure only in a very indirect way, while it is
relatively easy to measure in the lab and may provide helpful practical information
for application.
In applications, surface and interfacial tensions of polymers are quite important
such as in wetting and coating processes, in blending of polymers, in biocompati-
bility, and in adsorption and corrosion processes. The adhesion, and friction as well
as behavior of colloidal dispersions (paints, cosmetics, etc.) are influenced by surface
and interface tension. The interrelationships between interfacial aspects and mate-
rials properties are despite of their importance still poorly understood. The measure-
ment of surface tensions of polymers is usually performed by determination of the
contact angle, where a liquid drop is positioned on the sample surface. The equilib-
rium contact angle Θ for such a drop on a homogeneous smooth surface depends on
corresponding interfacial tensions as expressed by the Young equation [8, 32]:

γLV cos Θ ¼ γSV  γSL (2)

γLV denotes the surface tension of the liquid with its saturated vapor, γSV the surface
tension of the solid with the saturated vapor, and γSL the interfacial tension between
solid and liquid. It is a consequence of the equilibrium of interfacial forces at the
three-phase boundary at the edge of the drop. While the contact angle between drop
and sample surface is typically measured at the drop edge, also drop profile analysis
techniques may be used which enhance the sensitivity. The drop volume can be
continuously enlarged (advancing contact angle) or decreased (receding contact
angle), and measurements may be performed in a dynamic way. For inhomogeneous
9 Surfaces and Interfaces 359

Fig. 5 Scheme of contact

angle measurement. A drop is
put on a solid substrate via a
syringe and the contact angle
Θ at the edge of the drop is
measured

and rough surfaces, one often observes that the advancing and receding contact
angles are significantly different from each other. Dynamic measurements are
performed with the goniometer sessile drop technique where the drop is deposited
on the surface by a motor-driven syringe, and the volume is increased or decreased at
given speed to measure dynamic advancing and receding contact angles (Fig. 5).
With the so-called ADSA technique (axisymmetric drop shape analysis), a silicon
wafer with a small hole is used where the polymer to be investigated is deposited as a
thin film [3]. From below the wafer, the liquid is put via the hole onto the wafer with
a motor-driven syringe at constant speed and the increasing drop is monitored by a
video camera. By computer analysis of the drop profile, the advancing contact angle
is determined. Then the volume of the drop is decreased at constant speed via the
syringe, and the receding contact angle is determined. Those contact angles will in
general depend on the speed and possibly reach after some initial time a constant
value, but in most cases advancing and receding contact angles are different from
each other. For ideal surfaces, they should coincide. One has to be in particular
careful to avoid influence of surface contaminations like antioxidants, catalyst, etc.,
which may be enriched at the surface and where already small amounts can influence
the contact angle significantly. Also the liquid used (in most cases water) has to be
inert to the surface material. If the surface interacts or swells with the liquid, one can
use the captive air bubble technique, where in an inverted setup, the surface is
constantly covered with the liquid and the syringe introduces from the top an air
bubble via a small hole in the silicon wafer. There are several other techniques used
(e.g., Wilhelmy balance technique with a plate or capillary penetration/Washborn
technique with a powder) and several types of commercial instruments are available
to measure contact angles accurately. If disperse and polar contributions to surface
tension are obtained from measurements with several liquids of different polarity, the
free surface energy can be calculated [8].
The contact angle of a surface against water is of particular interest. One distin-
guishes between hydrophobic surfaces, where the contact angle Θ is larger than 90 ,
and hydrophilic surfaces, where the contact angle Θ is smaller than 90 . Here the
polarity of the surface plays a major role. Very interesting is the so-called
360 M. Stamm

ultra-hydrophobic behavior, where the contact angle Θ is even larger than 150 and
water is strongly repelled. This is achieved by a combination of surface roughness
with a hydrophobic surface [3, 8, 34], where the roughness causes an amplification
effect for the contact angle. Ultra-hydrophobic surfaces are observed in many cases
in nature (wing of butterfly, Lotus leaf, etc.) and often also show self-cleaning
properties, i.e., dirt is easily removed by water.
The interfacial tension is measured between different polymers or between a
polymer and a substrate. In general, it is much more difficult to determine than the
surface tension and therefore it only has been measured for specific examples [3].
The reason is that high viscosities of the polymeric materials, long time scales for the
achievement of equilibrium, and sample decomposition make measurements for
high-molecular-weight polymer materials quite difficult. The determination of inter-
facial tension, however, allows determination of interface width and compatibility of
polymer materials using model assumptions (mean field theory) [1]. In practical
cases, typically the pendant or rotating drop techniques are used.

2.3 Functional Polymer Surfaces

The fascinating aspect of functionalization of surfaces is that a very thin nanoscopic

surface layer can completely change appearance and functionality of a material while
bulk properties are essentially unchanged. This can include wetting, color, hardness,
biocompatibility, conductivity, adhesion, friction, corrosion resistance, and many
more properties [1–5, 7, 34–37]. It is even possible to generate switching, adaptive,
or smart surfaces, which change their properties according to a stimulus. There are
various ways to generate functional polymer surfaces. They have in common that a
thin layer of a functional material is put at the surface. This can be achieved by
chemical bonding, physical adsorption, or segregation of components from the bulk
to the surface. It includes the deposition of a coating to the surface which again can
be achieved in different ways. This is a wide field and it is hardly possible to cover
here all aspects. Several reviews exist [34–37] and we will focus in the following on
the particular way of surface functionalization by polymer brushes which form a
stable nanoscopic thin layer that is chemically attached to the surface.
With polymer brush layers, one can nicely tune surface properties of materials
[34–43]. They can be tightly attached to most materials by the choice of suitable
chemistry. With mixed brush layers, it is possible to achieve switching or adaptive
properties of the surface. Similarly, one can introduce multifunctionality at the
surface by attachment of different chains, nanoparticles, and by incorporation of
chemical functional groups.
For this reason, their use has grown over the last years, and polymer brush layers
are adopted in several areas of application. This includes for instance flat substrates,
but similarly colloidal particles, fibers, or rough surfaces. A big area of application is
related to bio-interfaces, where blood interaction, cell growth, or protein adsorption
is investigated [36, 41, 43]. This happens in aqueous environment and in many cases
water soluble or polyelectrolyte brushes are utilized [38]. Other areas of application
9 Surfaces and Interfaces 361

include coatings, where wetting, adhesion, friction, local sensing, or the reflection
and emission of light is controlled. Some examples will be discussed below.
We should first define in more detail, what we mean with polymer brushes. The
rigorous definition of Alexander and de Gennes [44–46] assumes that brushes are
end-attached polymer chains, which are grafted to the surface at high grafting density
where the chains are significantly stretched due to mutual interactions. There are much
more than one chain in a volume which an unperturbed chain would adopt at the surface
(grafting density Σ  1). It has been shown theoretically and experimentally that chains
are highly stretched chains under those conditions and show properties that are
significantly different from unperturbed chains [46]. One example is the autophobicity
of a so-called dry brush, where free chains cannot penetrate into the brush layer, which
even leads to the dewetting of chains of the same kind on top of the brush layer.
We will however not use this rigorous definition, and call already chains with
some stretching a brush layer [43, 46]. So we only assume that there are more than
one chain in a volume that an unperturbed chain would adopt at the surface (Σ > 1).
The reason is that already this layer can shield the surface nearly completely and that
it can be achieved much easier experimentally. There is still sufficient chain mobility
left to allow mixed layers to switch and to rearrange their conformation on response
to external stimuli. In the following, we will in particular concentrate on mixed brush
layers, which can switch and adapt their properties in response to external stimuli.
If we graft two different polymers onto a solid surface, this surface may adopt
the properties of one or the other material or in between which can be tuned by
external stimuli ([34, 35, 43] and references therein). It even allows to achieve
intermediate or new properties. The scheme of switching is schematically illustrated
in Fig. 6. Two polymers are attached by covalent bonds to the surface either by

In a non-selective solvent

In a solvent selective for the In a solvent selective for the

polymer A polymer B

Fig. 6 Scheme of switching of surface properties with polymer brushes with selective solvents
[43]. (Reprinted from Ref. [48] with permission from Elsevier)
362 M. Stamm

grafting-to or by grafting-from techniques. One assumes that they are statistically

distributed on the surface. The blue polymer could be hydrophilic (e.g., poly(2-vinyl
pyridine)) and the red polymer then would be hydrophobic (e.g., polystyrene). In
most cases, the two components would be incompatible with each other, but like a
copolymer, they only phase segregate at the scale of their molecular dimension. In a
solvent selective for the blue polymer (e.g., acidic water), the blue chains are
swollen, while the red chains would be collapsed at the surface. There is a complex
interplay of lateral and perpendicular phase segregation at molecular level [34],
which results in a nanoscopic phase segregation in the surface plane, while the blue
polymer might be enriched at the surface. After dying of the film, one might expect
hydrophilic behavior, since the wetting is determined by the outermost hydrophilic
layer. A water drop on such a surface thus will show a low contact angle.
Exposing this surface to a nonpolar solvent (e.g., toluene), now selective for the
red polymer, the situation reverses. The red polymer is typically enriched at the
surface, and the dried film might exhibit hydrophobic behavior. The contact angle of
water then will be high. This switching is achieved entirely by a conformational
change, and therefore is completely reversible. The covalently attached chains
cannot perform changes at long range, and they are neither dissolved nor removed,
as it could be the case for purely adsorbed molecules. Also intermediate states are
possible if one applies less selective solvents.
The situation is however more complex as it might appear at first glance. One
definitely needs some chain mobility to achieve switching; chains should be not
too short to be able to form a complete upper layer, while they should not be too
long to assure reasonable switching times for conformational readjustment. The
solvent should partly penetrate the other (upper) component, since otherwise it
might not reach the lower layer to cause swelling. Swelling is also difficult, if the
grafting density is too high. So there are some limitations and requirements to
achieve reasonable switching. Those details of course will largely influence the
switching times.
The timescales of switching can vary over a wide range, and have to be adjusted
with respect to the application. So switching can be fast (less than seconds),
the surface may be called adaptive. A hydrophobic surface then may immediately
switch to hydrophobic behavior with exposure to water – and vice versa. For a
raincoat, on the other hand, this would not be suitable, and a water repelling brush
layer should be stable upon exposure to water and keep the hydrophobic properties.
This can be achieved, when the upper brush layer is thick, quite immobile (e.g., in
the glassy state), and if this layer is mostly impenetrable to water. The switching
times then should be very large (possibly days) and the brush coating is constantly
water repelling.
A significant enhancement of the switching effect can be achieved by a combi-
nation of surface chemistry and surface topography. The amplification effect causes
so-called ultra-hydrophobicity, which is observed at a particular surface roughness.
Combining binary brushes with a particular high surface roughness results in a water
contact angle that can be switched between virtually 0 and 150 degrees! This is then
simply achieved by attaching brushes to a surface with appropriate roughness. In a
9 Surfaces and Interfaces 363

model experiment (Fig. 7a), a rough PTFE surface is obtained by etching with
plasma. Roughness values can be up to several micrometers. From plasma treatment,
one also generates functional groups at the surface, and the mixed polymer brush can
be attached by grafting-to technique. After acidic water treatment, the contact angle
is close to 0, while exposure to 1,4-dioxane or toluene switches the contact angle
to 150 degrees (Fig. 7h). We should note that contact angles of corresponding
smooth surfaces switch only between 70 and 90 degrees, and that roughness pro-
vides the amplification to smaller and larger contact angles, respectively [43]. In the
ultra-hydrophobic state of the brush also the contact angle hysteresis is not observed,
which is another criterion for ultra-hydrophobicity.
Using mixed polymer brushes, a wettability gradient can be generated in one or
two directions [43, 47]. These brushes are generated by grafting in a temperature
gradient which results in a composition gradient. With a linear temperature gradient,
the first homopolymers is grafted, and the second polymer is then put into the
remaining reactive sites at the substrate. Those gradient brushes can for instance
be created with polystyrene PS and the incompatible polyelectrolytes (poly(acrylic
acid) PAA, and poly(2-vinyl pyridine)) P2VP. The corresponding binary gradient
brush shows a gradient of wettability in response to different pH values (Fig. 8). At
pH = 2, the wettability gradient proceeds along the P2VP content in the brush. In
neutral media, the gradient is essentially “switched off,” whereas it appears again at
pH = 9–10 in opposite direction along with increasing PAA fraction. So direction
and amplitude of the wettability gradient of a binary polyelectrolyte brush is tuned
by pH. These properties may be used for microfluidics or for transport of liquids and
particles. Gradient surfaces can similarly be used for separation of binary liquid
mixtures. In a lab-on-a-chip [68] device with an integrated FET sensor, the separa-
tion of a fluid mixture was achieved.
For many analytical applications, the development of chemical and biological
sensors is of interest which includes monitoring of environmental and industrial
processes, quality control of nutrition and water, as well as medical and security
applications. So the change of fluorescence of organic dyes or the plasmon reso-
nance of inorganic nanoparticles in different environments can be used to detect
chemical substances and ions. In this respect, the combination of the responsiveness
of polymer brushes and the special properties of nanoparticles turns out to be very
interesting for fabrication of thin film sensors (Fig. 9) [43]. As an example, gold
nanoparticles may be immobilized via hydrogen bonding on end-functionalized
polystyrene brushes (Fig. 9). The presence of the Au nanoparticles on polystyrene
brushes was visualized by AFM, XPS, and UV-VIS spectroscopy. By the solvent
responsiveness of the polystyrene brushes, the detection of nanoscale optical
changes was possible based on localized surface plasmon resonance (LSPR) of the
immobilized Au nanoparticles. The change of the proximity of the immobilized Au
nanoparticles as a consequence of the solvent-induced reversible swelling-
deswelling of polystyrene chains is the basis of the sensing mechanism. The shift
in plasmon resonance band caused by variation in the surrounding media is used for
sensing, and a chemical nanosensor for the detection of a variety of organic solvents
could be demonstrated.
364 M. Stamm

5 µm

a b

c d e

Water

2.
5
µm µm
5
2.
1,4-dioxane
f g
0 0
advancing contact angle,°

160
140
120
100
80
60
40
20
0
ne ol ne ol ne ol ne ol
o l ue than olue than olue than olue than
t e t e t e t e
Wettability switching of a P S/P2VP brush
grafted to: flat Si, rough PTFE
by selective solvents.

Fig. 7 Two-level structure of a self-adaptive surface: switching of surface properties by a combi-

nation of a rough surface morphology and binary brush on a PTFE surface (a–e) where (b) shows
the SEM image of the PTFE surface after 600 s of plasma etching. The rough surface is covered by
covalently grafted mixed polymer brushes that consist of hydrophobic and hydrophilic chains as
shown schematically in (c–e). By the interplay between lateral and vertical phase segregation, the
morphology and composition of the surface is switching upon exposure to selective solvents.
9 Surfaces and Interfaces 365

Another sensor works with amino-functionalized CdTe quantum dots that are
covalently bonded with carboxylic groups of polyacrylic acid brushes via amide
bonding. AFM images show a change in surface morphology and roughness before
and after the immobilization with NPs. Covalent linkage between the nanoparticles
and polymer brushes was investigated with XPS. Photoluminescence spectroscopy
and fluorescence microscopy show that the quantum dots retain their optical prop-
erties even after the immobilization. The swelling and collapse of the polymer brush
layer with nanoparticles attached in different solvents resulted in an intensity
modulation of emitted light of the nanoparticles due to interference effects that can
be used to detect the swelling of the brush and in this way perform local sensing of
solvent quality [49].
Thus, it was demonstrated that the fabrication of straightforward and highly
sensitive solvent and pH nano-sensors is possible, based on solvent and pH-induced
swelling of polymer brushes coupled with surface plasmon resonance of Au (or Ag)
nanoparticles, respectively. The change in plasmon absorption band of immobilized
Au/Ag nanoparticles can be detected via UV-VIS absorption spectroscopy where
sensitivity is of comparable level as for more complex techniques. Particles have a
good adhesion to the polymer support, which minimizes their leakage even after
multiple uses and the P2VP-Ag NPs system is quite stable at lower pH. This
approach is quite versatile and can be used for the fabrication of nano-sensor
devices based on temperature, pH, and ionic strength responsive polymer brushes.
Surfaces with polymer brushes can also be used to control catalytic activity
[50]. Catalytically active Pd and Pt NP in P2VP brushes can be synthesized by
adsorption of either Pd2+- or PtCl2
6 -ions to the polymer and subsequent reduction to
NP by sodium borohydride (NaBH4). The amount and distribution of nanoparticles
on the surface depends strongly on the employed concentrations and length of
adsorption and reduction steps. Parameters have to be selected carefully to achieve
high surface coverage and ensure the fine dispersion of nanoparticles at the same
time. Both Pd and Pt NP show high catalytic activity, which can be switched by use
of PNIPAM brushes. The stimuli-responsive catalytic coatings are fabricated by in
situ synthesis of metallic nanoparticles in binary PNIPAM–P2VP (poly(N-isopropyl
acrylamide)–poly(2-vinyl pyridine)) brushes (Fig. 10). The amount of immobilized
nanoparticles is controlled by the polymer ratio, since solely P2VP interacts with the
nanoparticles. To investigate the temperature-dependent catalytic activity of the
nano-assemblies, the reduction of 4-nitrophenol to 4-aminophenol by NaBH4 was
monitored by UV-VIS spectroscopy as a model reaction. The peak at 400 nm, owing

Fig. 7 (continued) In corresponding solvents, the individual polymers preferentially move to

the top of the surface (c and e), while in a common solvent both polymers are present at the surface
(d). In f and g, AFM images of the different morphologies after exposure to selective solvents are
shown. The amplification effect for contact angle switching for untreated (back) and functionalized
(orange) surfaces is shown in (h) [34]. (Reprinted with permission from Ref. [34]. Copyright 2003
American Chemical Society (a–e) and from Ref. [48] with permission from Elsevier (h))
366 M. Stamm

Fig. 8 Scheme of the

switching of a wettability
gradient obtained from a
polyelectrolyte gradient
mixed brush (P2VP mixed
with PAA) by pH
[43]. (Reprinted with
permission from Ref.
[47]. Copyright 2004
American Chemical Society)

Fig. 9 Sensing by nanoparticles attached to polymer brushes: (a) carboxy-functionalized gold

nanoparticles are attached on end-functionalized PS brushes and (b) scheme of hydrogen bonding
between carboxy-functionalized Au NPs and hydroxy end groups of PS chain ends [43]
9 Surfaces and Interfaces 367

NO
2 NH 2 NO
2

O- - O-
O
T>Tc

Fig. 10 Scheme of stimuli-responsive catalysis of nanoparticles deposited on binary polymer

brushes; the temperature-induced collapse of PNIPAM chains (green) at Tc is proposed to lead to
a diffusion barrier blocking the access of reactants to the catalyst (red) [50]

to 4-nitrophenole, decreases and the peak at 300 nm increases with time which
indicates the reduction of 4-nitrophenol to 4-aminophenol. Control of the catalytic
activity by the temperature-induced deswelling of PNIPAM at Tc is observed, which
is explained by the formation of a barrier layer of PNIPAM with increasing temper-
ature. In this way, diffusion of components to catalytic active sites is controlled.
Functional polymer brush layers can be used in various ways to control
bio-activity [36, 41]. So adsorption or desorption of proteins as well as cell growth
and cell attachment can be performed with polymer brushes. As an example, it was
shown that functionalized substrates exhibit cell-guiding properties based on incor-
porated bioactive signaling cues [41]. The surface was functionalized by polymer
brushes made of poly(acrylic acid) PAA, which were functionalized with hepatocyte
(HGF) and basic fibroblast growth factor (bFGF) either by physisorption or chem-
isorption (Fig. 11). The GF release kinetics shows a high initial burst followed by a
constant slow release in the case of both physisorbed HGF and bFGF. In contrast,
chemisorbed HGF remained bound to the brush surface for over 1 week, whereas
50% of chemisorbed bFGF was released slowly. These GF-functionalized PAA
brushes produce a measurable effect on human hepatoma cell lines (HepG2) and
mouse embryonic stem cells (mESCs) and can be used as bioactive cell culture
substrates to tune cell growth and differentiation.

3 Interfaces in Blends, Copolymers, and Composites

The interfaces between polymers in blends and copolymers as well as between

polymers and mostly solid components of composites (typically particles and fibers)
determine to a large extend the properties of the materials [1–5]. The interfacial
region, which is formed between phases of an immiscible polymer blend, will
influence the mechanical behavior of the blend under stress. Similarly the adhesion
368 M. Stamm

Fig. 11 Grafting of pol(acrylic acid) PAA as brush on solid substrates: Bio-functionalization

of PAA brush with growth factor (red squares) through physisorption or chemisorption (left).
Interaction of GF-modified PAA brush with HepG2 cells (for HGF-PAA) or mESCs cells (for
bFGF-PAA) (right) [41]

between particles or fibers and the polymer matrix of a composite will influence the
strength of the composite. So we first shortly discuss the theoretical background and
then provide some examples. The investigation of interfaces inside of bulk materials
turns out to be much more complicated than the investigation of surfaces. We discuss
some experimental techniques in Sect. 4.

3.1 Interfaces Between Homopolymers

When two polymer sheets are put together in the melt, an interface is forming. The
width of this interface depends on the chain compatibility and determines for
instance the adhesion between the sheets [1–5, 8–10, 12, 13]. If the two polymers
are compatible, they will interdiffuse with each other and depending on diffusion
time and diffusion coefficient at given temperature, an interface will form. This is
typically controlled by Ficks law. The situation is however more complicated at short
interdiffusion times and if the two polymers are chemically different or possess
9 Surfaces and Interfaces 369

Fig. 12 Interface profile

between the phases of a
blend of two incompatible fB2
polymers. The concentrations
of the polymers in the blend
are ΦB1 and ΦB2, respectively,
and are determined by the f
phase diagram. Z is a
spatial coordinate across
the interface [51]

fB1

different mobility (e.g., different molecular weight). Taking chain reptation into
account with different diffusion laws at different time scales and the enhancement
of chain ends at the surface, a different interdiffusion behavior is expected at small
diffusion times. Similarly the situation becomes more complicated, if mobilities of
the two polymers are different. The mean position of the interface will move and an
asymmetric profile will form. For the development of adhesion, the formation of
entanglements during interdiffusion is important. There are plenty of investigations
of those effects. At longer diffusion times, the compatible polymers will intermix
and at thermodynamic equilibrium form a homogeneous blend.
Most polymers are however incompatible with each other and blends of polymers
will be inhomogeneous in nature [10, 12, 13, 51]. Phase segregation between
components will occur and only small interfaces between the phases will form.
These interfaces between incompatible polymers are typically in the range of
2–50 nm, depending on compatibility. We first will provide a short introduction to
mean field theory of interface formation and interfacial tension, and then present
some specific examples. Experimental methods employed for the investigation of
polymer interfaces are important to gain an understanding and will be discussed in
the following Sect. 4 with respect to their accuracy and advantages, with emphasis
on neutron- and X-ray reflection, electron microscopy, ellipsometry, interfacial
tension, and nuclear reaction analysis techniques.
For most incompatible materials, the interface is not very wide depending on
compatibility [3, 10, 12, 13, 51]. A typical interface profile is shown in Fig. 12.
When two incompatible polymers are put into contact, segments will move if the
materials are heated above the glass transition, and some interpenetration will occur.
Therefore the interface width increases with time and reaches an equilibrium value,
which is determined by the Flory-Huggins interaction parameters χ according to
mean-field theory. The quantity χ expresses polymer compatibility, while it is not
completely understood on a molecular basis. In practice, it is often used as an
empirical parameter and then allows a thermodynamic description of phase separa-
tion for a particular polymer pair within mean-field theory. Besides equilibrium
thermodynamic effects, other factors originating from sample preparation and
370 M. Stamm

experimental conditions also influence interface formation. When two films are put
together to form an interface, there is the influence of initial surface roughness, surface
composition, contaminations, and chain conformation at the surface of the films, which
may largely depend on sample history. In specific cases, it is difficult to reach equilib-
rium, for instance, when segment mobility is slowed down by the glass transition Tg.
When comparing experimentally determined interface widths with calculated ones,
e.g., from interfacial tension data, one must be cautious, because there are influences
from end-group effects, molecular weight distributions, chain orientation, capillary
waves, or initial interface roughness that are not very well understood. We also assume
that additives like antioxidants or plasticizers are not present, since those materials
might migrate to the surface or interface even if present only in trace amounts.
The description of phase behavior in polymer blends is of fundamental interest in
polymer research [10]. A first approach is based on Flory, Huggins, and Staverman
(FHS) theory. Using a lattice model, a simple form for the free energy of binary
polymer blends including the interaction parameter is derived

F FHS ϕlnϕ ð1  ϕÞlnð1  ϕÞ

¼ þ þ χ ϕ ð 1  ϕÞ (3)
kT N1 N2
N1 and N2 are the degrees of polymerization and Φ the volume fraction of one of
the polymers. The interaction parameter χ is related to the interactions between
segments. It is on the other hand an effective interaction parameter, which takes into
account the difference between interactions of the same and different segments of the
blend. So it typically is very small quantity although the actual interaction energies
are much larger. Many theories have been derived to describe the interaction
parameter as a function of temperature to reproduce phase diagrams observed in
different experiments. For complicated phase diagrams, it may be necessary to
introduce a Φ-dependence of χ in addition. Equation 3 now contains first the entropic
terms, which are small at large N, and second the enthalpic term with χ, which
includes the interaction energies and which dominates the free energy. As a conse-
quence, most polymers are immiscible with each other.
In order to discuss the problem of an interface between two polymers [10],
Equation 3 has to be extended by the so-called quadratic gradient term κ(∇ϕ)2
introduced by Cahn and Hilliard to take fluctuations into account. This allows the
derivation of the equilibrium volume fraction profile. An analytical solution for the
volume fraction profile can be calculated for the case of infinite degrees of polymer-
ization (χN » 1), which is equivalent to strong segregation,

1
z 
ϕð z Þ ¼ 1 þ tanh (4)
2 l
with

a
l ¼ pffiffiffiffiffi (5)
6χ
9 Surfaces and Interfaces 371

a is the mean characteristic segment length of the polymers. So even for strong
segregation, the two components interpenetrate over some distance. In the same
approximation also the interfacial tension γ depends on χ
kT
χ 2
γ¼ 2 (6)
a 6
A simple way to estimate the influence of finite chain length is possible for the
case of two polymers with the same degree of polymerization N

a
l ¼ sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 ffi (7)
2
6 χ
N

As a result, the interface width l and the interfacial tension γ are directly related to
the Flory Huggins Stavermann effective interaction parameter χ. For the experimen-
tal determination of l, one has to be careful, however, since besides this intrinsic
interface width also lateral fluctuations are depending on interfacial tension and
consequently on χ. In many cases, it is difficult to distinguish between “intrinsic
interface” and capillary wave effects. This is reflected in computer simulations where
both effects contribute to the apparent interface width and a correction of the
measured interface width with respect to capillary waves is necessary.
As mentioned before, the interface width may be determined by neutron reflec-
tometry [51, 52], if one of the components has been deuterated and a contrast at the
interface has been generated. Two highly smooth films are put on top of each other
and after annealing in the melt the interface width is determined.
One of the most intensively studied incompatible blend systems is poly(styrene)
PS versus poly (methyl methacrylate) PMMA. Values of interface widths l determined
with different techniques are of the order of l = 1.3 nm [51]. The most accurate value
has been obtained with neutron reflectometry from a blend system and has been
confirmed from studies of diblock copolymers, where the interface width between
lamellae is found to be of the same size. Also, temperature-dependent ellipsometry
investigations and TEM yield similar results within error bars. A serious discrepancy,
however, arises when the interface width is calculated from interfacial tension data on
the basis of meanfield theory. Those interface widths are approximately a factor of two
smaller than the measured ones. This might indicate that capillary wave effects might
significantly contribute to experimental values, which may contain “intrinsic” and
capillary wave effects as discussed above. Of course also other effects could contribute
like end-group effects, conformational changes or surface contaminations.
Several other systems have been investigated including interfaces between com-
patible polymers [51, 52]. Theory predicts at initial stages of interdiffusion a special
behavior due to reptation effects. In reptation theory one assumes that initially chains
diffuse across the interface mostly via chain ends, which results in a particular time
dependence of the growth of the interface width. Other studies deal with partially
compatible polymers or blends, where one of the components is in the glassy state.
372 M. Stamm

The blend system of PS and the statistical copolymer poly(styrene-statpara bromo

styrene) PBrxS1x [51] was chosen for systematic investigations of the dependence
of interface width on compatibility. Here compatibility between components can be
adjusted between completely compatible to highly incompatible by a change in
degree of bromination x. Since materials can be obtained by bromination of poly-
styrene with narrow molecular weight distribution, where the degree of bromination
can be high, the contrast between components may be sufficient also for X-ray
reflectivity experiments. However, at low degree of bromination, deuterated PS has
to be utilized, and NR experiments are performed. The results from all experiments
are shown in Fig. 13. At low x, the interface width diverges because the system
becomes compatible at xc. The functional form is fitted empirically by a
composition-dependent χ-parameter, which contains the concentration-weighted
individual segment-segment interaction parameters of the components. Values at
large χ can be compared to other X-ray and neutron reflectivity data. There is good
agreement between different data sets and theory, where mean field theory is used to
calculate the interface width at different compatibility. Also, the influence of the
glass transitions on the interface width has been studied, since the glass transition
also increases with degree of bromination. If the sample is annealed between the
glass transitions of the components, segment interdiffusion is strongly reduced. In
this temperature regime, the interface width depends strongly on temperature until
both components become mobile and the glass transition temperature also of the
second component is reached. At higher temperatures, dewetting phenomena are
observed that are a consequence of the strong incompatibility of the components.
Copolymers are also used for compatibalization of incompatible polymer blends,
where a small addition of a diblock copolymer can significantly improve the
mechanical properties of the blend [3, 53, 54]. This is due to the fact that the diblock
copolymer might be enriched at the interface and provides a mechanical bridge

Fig. 13 Dependence of
interface width l on degree of
bromination x for the blend
system PS versus PBrxS1x.
The system becomes strongly
incompatible at large x, while
it is compatible for x < xc [51]
9 Surfaces and Interfaces 373

between the segregated phases of the two components where interface width and
mutual interpenetration otherwise are small. It has been predicted by theory [53] that
the diblock copolymer will be enriched at the interface and that the interface is
broadened by addition of the copolymer. It is assumed that the two blocks are
compatible with the corresponding homopolymers of the blend. With neutron
reflectometry or nuclear reaction analysis, those predictions can be tested [54] by
utilizing dedicated contrast generation by deuteration: (i) the enrichment of the
copolymer at the interface can be visualized if the copolymer has been deuterated
with otherwise nondeuterated homopolymers, and (ii) the broadening of the interface
is resolved if one of the homopolymers and the corresponding block of the copol-
ymer have been deuterated with otherwise nondeuterated components.
Thin films of copolymers are used in various ways for generation of nanostructures
at surfaces [55–57]. The two incompatible blocks phase segregate at the scale of the
molecules and form nanoscopic ordered morphologies. The interface to the substrate is
important for adhesion but also for alignment of the nanostructured films, while the
surface to air determines the wetting behavior and other properties. A particular example
are structures formed by a supramolecular approach (SMA) with diblock copolymer thin
films of polystyrene, poly(4-vinyl pyridine) PS-b-P4VP and 2-(40 -hydroxybenzeneazo)
benzoic acid HABA, which is a low molar mass additive associated with one of the
blocks by noncovalent interactions [56–58]. This low molar mass additive is removed
easily by selective dissolution from the P4VP phase to obtain a nanoporous ordered thin
film. SMA with block copolymer self-assembly is a simple and powerful technique for
fine tuning of block copolymer morphologies, and has been successfully used in bulk
and in thin films. Figure 14 shows the schematic representation of the formation of
nanotemplates by this technique. A solution of PS-b-P4VP block copolymer and HABA
was spin cast on to a silicon wafer as a thin film. A cylindrical morphology was observed
either with the cylinder axis parallel or perpendicular to the substrate where orientation

Fig. 14 Generation of ordered nanotemplates with diblock copolymer thin films: the supramolec-
ular assembly SMA of PS-b-P4VP block copolymer and HABA (a) is formed by solvent casting.
Depending on the solvent, perpendicular (c) or parallel (b) alignment of the structure is achieved.
The nanotemplate (d) is prepared by dissolution of HABA. The empty cylinders can be filled by
electrodeposition with nickel, and the polymer matrix removed by dissolution in toluene (e) [56].
(Reprinted with permission from Ref. [59]. Copyright 2003 American Chemical Society)
374 M. Stamm

depends on the solvent. By exposure to different solvent vapors, the orientation of the
cylindrical microdomains of P4VP(HABA) could also be switched. Annealing in
chloroform results in parallel, and annealing in 1,4-dioxane results in perpendicularly
oriented cylinders. HABA can be removed from the SMA thin films by immersing in
ethanol to transform the block copolymer thin film into a nanotemplate [59]. Due to
specific interactions, the P4VP material is enriched both at the surface and at the interface
to the silicon wafer. The nanotemplate may be further processed and for instance filled
with nickel by electrodeposition. After removal of the polymer matrix the ordered nickel
nanorods are left over.
The combination of block copolymers with nanoparticles can add additional func-
tionalities to those coatings. The first commonly used way to prepare hybrid polymer/
inorganic nanocomposites is to directly mix presynthesized and suitably functionalized
nanoparticles with block copolymers and then allow the whole system to self-assemble
[7, 56–61]. Nowadays, nanoparticles of various chemical compositions can be synthe-
sized in solution with precise control over size and shape. The nanoparticles should be
stabilized against aggregation and coalescence either electrostatically or sterically by
coating with ligands that bind to or adsorb onto the NP surfaces. These ligands might be
small molecules, functional (co)polymers, polyelectrolytes, or biomolecules that con-
trol interfacial interaction. Such core-shell particles are combined with block copoly-
mers, e.g., by dissolving in common solvent and allowing solvent to evaporate. In
particular cases, annealing steps might be required to bring the whole system to an
equilibrium state. To achieve domain-selective localization, the particle/polymer inter-
actions are tuned such that particles prefer one block copolymer domain over another.
Hydrophobic, electrostatic, or hydrogen bond interactions between monomer units or
functional groups can promote domain-selective nanoparticle localization. Various
types of inorganic nanoparticles stabilized with small organic molecules can be incor-
porated in different domains of block copolymers matrices using direct mixing
approach. As an example, iron oxide nanoparticles stabilized with oleic acid were
selectively segregated into PMMA domains of self-assembled PS-b-PMMA matrix
[57], but many other examples are reported.
So one can fabricate highly ordered arrays of nanoscopic palladium dots and wires
(Fig. 15a) by the direct deposition of presynthesized palladium nanoparticles in
aqueous solution [56]. As mentioned before, the cylindrical morphology observed in
thin films of PS-b-P4VP can be switched from parallel to perpendicular and vice-versa
by annealing in vapor of appropriate solvents. By immersion into ethanol, a good
solvent for P4VP and a nonsolvent for PS, surface reconstruction of the films was
observed with a fine structure. Perpendicular cylinder alignment resulted in a nano-
membrane with hexagonal lattice of hollow standing cylinders, and parallel cylinder
alignment produced nano-channels. Figure 15b shows AFM height images of nano-
pores and nano-channels after surface reconstruction. In these templates, the pore or
channel walls are formed by functional P4VP chains. A subsequent stabilization of the
polymer matrix by UV-irradiation followed by pyrolysis removes the polymer matrix
material and produces highly ordered metallic nanostructures. Figure 15c shows AFM
height images of palladium nano-dots and nanowires after the removal of the polymer
matrix. This method provides a facile approach to fabricate a broad range of
9 Surfaces and Interfaces 375

Fig. 15 (a) Schematic diagram of the fabrication process of ordered arrays of nanoscopic palladium
dots and assemblies using block copolymer template. (b) AFM height images of PS-b-P4VP nano-
templates with perpendicular and parallel arrangement of nanostructures obtained after surface recon-
struction in ethanol. (c) AFM height images of palladium nanodots and linear assemblies obtained after
the polymer matrix removal [56]. (Reprinted from Ref. [60] with permission of Elsevier)

nano-scaled architectures with tuneable lateral spacing, and can be extended to systems
with even smaller dimensions. One can also pattern noble metal nanoparticles such as
gold, platinum, and palladium. It is also possible to deposit differently functionalized
nanoparticles in or respective on top of the different phases of block copolymer thin films
[58]. Also ordered arrays of nanoparticles can be produced inside of the confined space of
block copolymer cylindrical phases [60, 61] and nano-objects formed by selective
solution [7]. Glass and carbon fibers are widely used for mechanical reinforcement to
achieve lightweight materials with good mechanical properties, and oxydic, metallic, or
semiconducting nanoparticles are applied for optical, electrical, magnetic, catalytic, or
sensing applications. Dispersion and contact of fibers or nano-particles with the sur-
rounding polymer matrix are again highly important, which are determined by the
interface between them. The analysis of those interfaces is particularly difficult because
properties of the organic and inorganic components are very different.

4 Characterization Techniques of Polymer Surfaces

and Interfaces

The characterization of polymer surfaces and interfaces is a difficult task and needs
dedicated techniques [1, 3, 11, 20, 32, 51, 52, 62–67]. This is in particular true for the
characterization of interfaces, which are hidden inside of the material. To get a
376 M. Stamm

Fig. 16 Schematics of
some surface characterization
techniques where different
types of radiation are used
for incident and outgoing
beam [3]

reasonable picture, usually a combination of different techniques is necessary. Some

of the most common techniques are schematically depicted in Figs. 16 and 17 and
listed in Tables 1 and 2, where also typical resolution and information obtained is
provided. Those data are however only rough guides and resolution for instance can
be much worse or better depending on sample preparation and particular instrumen-
tation used. As an example, for a polymer blend surface, the wetting properties are
determined by contact angle measurements, which may provide already a hint on
surface composition or segregation of components, the roughness, and lateral nano-
structure is determined by scanning force microscopy, the detailed surface compo-
sition by x-ray photoelectron spectroscopy, the morphology in the vicinity of the
surface by x-ray reflectometry or in more detail by grazing incidence x-ray scatter-
ing, and mechanical properties of the surface by nano-indentation. One might of
course not need all this information, and characterization techniques have to be
carefully chosen for a particular question. Several other and more dedicated tech-
niques are available, which may provide better resolution or additional information,
but mostly require more dedicated instrumentation and in many cases also special
sample preparation.
From the time dependence of interface formation, one can learn about segment
mobility and interdiffusion mechanisms. Techniques are needed that can resolve
details of the interface between polymeric components at nanoscopic level. Since the
interface width for incompatible polymers is typically much smaller than 50 nm, the
resolution of the technique has to be adapted for a determination of such small
interface widths. To achieve good resolution, a suitable contrast between compo-
nents has to be present in order to “see” the interface between the components. Such
a contrast can be generated for neutron reflectometry (NR), for example, by deuter-
ation of one of the components [1, 3, 52]. So in multicomponent systems, one
particular component and its interfaces with other components can be made visible
for neutrons. The application range may be limited by the particular sample geom-
etry needed. Other techniques include ellipsometry, small angle scattering, ion
techniques, electron microscopy, and measurements of interface tension.
9 Surfaces and Interfaces 377

Fig. 17 Schematics of several surface and interface analysis techniques: (a) Rutherford
backscattering (RBS), (b) nuclear reaction analysis (NRA), (c) dynamic secondary ion mass
spectrometry (DSIMS), (d) transmission electron microscopy (TEM), (e) x-ray (XR) and
neutron reflectometry (NR) as well as ellipsometry (ELLI), and (f) surface plasmon spectros-
copy (SP) [3]
378 M. Stamm

4.1 Surface and Interfacial Tension

The measurement of surface tension is still one of the easiest and most common
techniques for a first surface characterization [3, 8, 32]. Experimental techniques and
problems have been discussed in Sect. 2.2. For a detailed surface analysis, other
techniques should be used in addition.
The measurement of interfacial tension of polymers is much less straightforward
and is determined mostly only in special cases of low-molecular-weight materials.

4.2 Scanning Force Microscopy (SFM)

Scanning force microscopy has been developed as a very versatile technique with
many modes for a variety of applications [3, 62, 63]. It provides nanoscopic
resolution both in width and height at the surface of a film or substrate, and for
instance single polymer molecules adsorbed on a smooth solid substrate have been
resolved. Available operation modes include contact, noncontact, hard/soft tap-
ping, materials, adhesion, phase, friction or chemical contrast, indentation, soft or
force-distance mode, use of tunneling current, electrostatic, electro-chemical or
magnetic interactions, it can be operated in different environments including
vacuum, air, liquid or inert/humid atmosphere, and offers various fascinating
and versatile possibilities. Nanoscopic resolution of different aspects of a surface
can be obtained. So one can measure and visualize the surface with respect to
topography, surface hardness, friction, adhesion, conductivity, electrostatic
charge, or magnetism. By different operation modes ranging from noncontact to
hard tapping, the strength of the interaction of the tip with the substrate can be
controlled. To perform depth profiling, the surface can be removed by etching or
dissolution techniques, and in this way structures inside the sample and at hidden
interfaces may be resolved.
With the tip, individual molecules and atoms at the surface can be manipulated,
and for example single atoms may be positioned on a solid surface by the tip. It
therefore may not only be used as an analytical but also as a nano-manipulation tool.
Its strength comes from the fact that a lateral image can be obtained relatively easily
at nanoscopic resolution by different modes, while surface properties at quantitative
level are not easy to obtain with this technique. It can be combined with other
techniques. Tip-enhanced Raman spectroscopy provides local chemical information,
where by plasmon effects at the AFM-tip a local signal enhancement up to a factor of
1010 may be achieved, which allows measurement of Raman signals from nano-
scopic small spots. An analogous technique is nano-IR, where the local thermal
expansion by an IR-beam is detected at nanoscopic level.
A similar technique is scanning tunneling microscopy where the tunneling current
between tip and surface is measured and used for tip control. It requires however
conductive samples like metals or semiconductors, while nonconducting polymers
have to be covered with a conductive layer for measurement. Spectroscopic infor-
mation is obtained with scanning near-field optical microscopy, SNOM, where a
9 Surfaces and Interfaces 379

particular optical fiber is used as a light guiding tip to illuminate the sample. The
emitted or absorbed light is then analyzed.

4.3 Ellipsometry (ELLI) and Surface Plasmon Spectroscopy (SP)

Ellipsometry can be used to measure the thickness and index of refraction of a thin
layer on a substrate with high precision (the thickness resolution can be better than
1 nm depending on optical contrast) and as a function of time. The change of the
polarization state of reflected light from the surface is determined, which provides
information on the optical properties of the reflecting medium (Fig. 17) [3, 62]. For
very thin films, however, the thickness and index of refraction cannot be measured
independently and the so-called optical thickness is determined. For thicker films the
technique then reveals thickness and index of refraction of the layer independent
from each other (thickness typically larger than 10–20 nm), and may provide
information on anisotropy and roughness. By direct ellipsometric imaging (micros-
copy) or scanning techniques, lateral information on thickness or index of refraction
variations at micrometer scale can be resolved too. Problems and limitations may
occur from correlations of thickness and index of refraction, low optical contrast in
multilayer samples, but also from ambiguities in the evaluation of data in more
complex situations, where due to limited experimental data detailed information on
the system is difficult to extract. Then spectroscopic or variable angle ellipsometry
provides additional information and may help in determination of system parame-
ters. Measurements can be performed under various environmental conditions
including for instance the adsorption kinetics of molecules in solution at a solid
substrate which may be measured in-situ with a liquid cell. IR ellipsometry can be
performed by use of IR radiation from a synchrotron source, which can even provide
chemical information in monolayer polymer films or elemental composition.
Surface plasmon spectroscopy (SP) is a very similar technique (Fig. 17) while it
uses surface plasmons in a thin metal layer, which are excited by the incident light.
The plasmon resonance is influenced by the adjacent polymer layer, which in this
way can be analyzed with respect to polymer film thickness and index of refraction.
Information content of SP is comparable to ellipsometry, but requires a metallic layer
for the excitation of the plasmons.

4.4 Scanning and Transmission Electron Microscopy (SEM, TEM)

Scanning electron microscopy (SEM) [3, 62, 64] is used in scanning and reflection
mode for surface investigations. SEM reveals an image of the surface typically at
nanometer lateral resolution, and contrast is obtained by electron scattering, absorp-
tion, or emission. An image of the element distribution is achieved for instance by
electron energy loss (EELS) or x-ray fluorescence spectroscopy (EDX). With
organic materials, the sample degradation by the electron beam has to be considered
(but also can be used for contrast generation and electron lithography). Contrast and
380 M. Stamm

resolution may be improved, when the surface is covered by a thin conducting film,
sputtered at an angle with respect to the surface normal to obtain shading effects. In
most cases, quantitative analysis of SEM images is however difficult.
Transmission electron microscopy (TEM), may be used to investigate bulk
materials and interfaces where typically a 50 nm thick slice (Fig. 17) is prepared.
This slice can be cut with a microtome (using a diamond knife, possibly under cryo-
conditions) or with an ion beam (FIB, see below). After staining or other contrasting
methods, the interface between materials may be resolved. Limits of resolution arise
from intrinsic TEM resolution, but also from preparation, where artefacts and
smearing of the interface may occur. Chemical and elemental resolution is obtained
using inelastic electron scattering (electron energy loss spectroscopy, EELS) or x-ray
emission (EDX). The sample has to withstand ultra-high vacuum during measure-
ment and electron beam damage. For liquid or sensitive samples, cryo-techniques are
adapted where the sample slice is shock-frozen and cooled during the experiment.
With special setups, experiments at atmospheric conditions or in liquid state
are feasible, but require dedicated sample environment with thin windows. TEM
however needs in all cases a very special sample preparation, which may be time
consuming and difficult to achieve.

4.5 X-Ray Photoelectron Spectroscopy (XPS)

X-ray photoelectron spectroscopy (XPS) can be used to characterize the chemical

composition of polymer surfaces. Due to limited electron emission depth, with
polymers typically a depth of up to 7 nm is probed [3, 62, 65]. In some cases the
acronym ESCA for electron spectroscopy for chemical analysis is used indicating
the possibility of chemical analysis as well as the combination of photoelectron
and Auger electron peaks in observed spectra (electron spectroscopy). Electrons
from the inner shells or valence bands of the sample are excited and ejected by the
incident soft X-rays. The number of photoelectrons which are leaving the sample
surface is measured as a function of incident energy. The emission depth of the
electrons from the sample is limited, which determines the depth resolution. The
measured energy spectrum of the electrons then is characteristic for elemental
composition and binding state of atoms of the sample. One can quantitatively
determine the surface composition and binding of different species. Measurements
are performed under vacuum, and with nonconducting surfaces surface charging
has to be avoided.
With conventional scanning XPS instruments, the lateral resolution is typically
not better than several micrometers. It may be significantly improved using X-ray
photo electron emission microscopy (XPEEM), where an electron microscope is
used to image the outgoing electrons. Here the lateral resolution may be of the order
of 10–30 nm, when soft x-rays from a synchrotron source are used. Similarly a
synchrotron source is needed for transmission x-ray microscopy (TXM), which
utilizes the absorption of soft x-rays in a thin film sample for lateral imaging of
chemical composition at similarly good resolution.
9 Surfaces and Interfaces 381

4.6 Electrokinetic Methods (Zeta Potential)

The preferential adsorption of cations or anions, the dissociation of surface groups,

the adsorption of polyelectrolytes, the isomorphic substitution of cations and anions,
and the accumulation or depletion of electrons determines the electrokinetic poten-
tial on the surface of a solid in contact with a polar medium (usually water) [3].
Usually, one assumes the presence of an electric double layer consisting of two
regions of charge distribution at an interface: first a fixed layer and second a diffuse
layer. A “surface of shear” or “slipping plane” is located between these two layers.
An externally applied electric or mechanic force causes a relative movement
between the fixed layer and the diffuse layer. The electrokinetic or zeta (ζ) potential
is the potential at this surface. The electrokinetic potential can be measured by
applying an external electric field, which results in relative movement of the solid
and liquid phases (electrophoresis, electro-osmosis), which generates an electric
potential or produces an electric current (called streaming potential/streaming cur-
rent, sedimentation potential). This can be measured with several experimental
techniques, but with planar surfaces often the streaming potential is determined.

4.7 Infrared Spectroscopy (ATR-FTIR)

Infrared spectroscopy provides chemical information and is used for surface and thin
film investigations in reflection or attenuated total reflection mode (ATR-FTIR)
[3]. Quantitative determination of composition or binding states via vibrational
modes is possible. So it is a powerful analytical tool for detection of dynamics at
solid/liquid or solid/air interfaces. ATR-FTIR utilizes multiple reflections from a
large smooth crystal. The reflecting plane between crystal and surrounding medium
is investigated. The IR beam is totally reflected at this interface, but still an
evanescent wave penetrates the surrounding medium. Molecules can be distin-
guished by their IR-spectrum, and deuteration is sometimes used to differentiate
between different constituents. The evanescent wave typically penetrates of the order
of the wavelength into the other medium, and therefore probes a depth of several
micrometers. Utilizing an IR-microscope the lateral resolution similarly can be
several micrometers. With an IR array detector, spectroscopic information can be
obtained at high speed and spatial resolution. IR synchrotron radiation again
enhances time resolution, and allows use of IR ellipsometric imaging techniques
for measurement of composition, thickness, orientation, and index of refraction of
surfaces and thin films [66].

4.8 Raman Spectroscopy

With Raman spectroscopy also the chemical composition at the surface may be
detected [3]. In contrast to IR spectroscopy, those vibrational and rotational states
are detected where the polarisation is changing. Since the energy shift of the
382 M. Stamm

scattered light is detected, the observed signal is not so strong and powerful lasers are
needed for the investigation of surfaces. With surface enhanced Raman spectroscopy
(SERS) the surface signal however can be enhanced by many orders of magnitude.
The plasmonic enhancement from metallic nanoparticles (preferentially Ag) is
used which are deposited on the surface, and Raman spectroscopy becomes sensitive
to the direct environment of those particles [69].

4.9 X-Ray and Neutron Reflectometry (XR, NR, GISAXS)

X-ray and neutron reflectometry techniques (XR, NR) use the fact that x-rays and neutrons
are reflected at interfaces (Fig. 17) when a suitable contrast is present [1, 3, 52].
The difference in electron density between materials provides a contrast for x-rays,
and x-rays are in particular sensitive for the surface of thin films against air or
vacuum. The electron densities between polymers are in most practical cases not
very different, and XR cannot easily resolve the interface between two polymer
films. The contrast for neutrons on the other hand can be generated by deuteration of
one component, i.e., all hydrogens are replaced by deuterium, which chemically is
essentially identical to hydrogen, and the interfaces between polymers can then be
resolved at nanometer resolution. Both techniques however cannot easily distinguish
between lateral fluctuations of the interface (generated by thermal fluctuations,
surface roughness, or capillary waves) and the “true” interface (generated by inter-
diffusion between components). Since both quantities can be in the nanometer range,
a quantitative interpretation of reflectometry data in terms of interface width may be
difficult (see Sect. 3.1). A separation between interdiffusion and lateral fluctuations
may not be necessary however in many cases. Both techniques can on the other hand
provide valuable information on film thickness, surface and interface roughness,
capillary waves, surface segregation and profile of components in a blend, interdif-
fusion, interface width and asymmetry etc. The sample should be smooth and flat,
and extend laterally typically over several cm. XR and NR can provide information
even at sub-nanometer resolution if the quality of the sample (smoothness) is perfect.
For Grazing Incidence Small Angle X-Ray Scattering (GISAXS), two techniques
are combined: Grazing Incidence Diffraction (GID), which uses reflection geometry
to obtain diffraction from the surface and near surface region, and Small Angle X-ray
Scattering (SAXS), which obtains electron density fluctuations and structures at
1–100 nm length scales typically in normal transmission mode. Experiments are
carried out close to the critical angle for total external reflection, which results is a
considerably enhanced surface sensitivity. The full potential of GISAXS is obtained
when it is performed with synchrotron radiation and an area detector. GISAXS is a
nondestructive structural probe like other reflectivity and scattering techniques and
does not require a conducting surface or special sample preparation. With flat
samples GISAXS yields excellent sampling statistics and averages over macroscopic
regions while it provides information on lateral nanostructures close to the surface,
size distributions, particle geometry, and spatial correlations. Similarly neutrons
9 Surfaces and Interfaces 383

can be used at grazing angles (GISANS), but this technique requires high flux
neutron sources.
A careful analysis of the decay of the small angle x-ray or neutron scattering
(SAXS, SANS) in transmission allows for a determination of the interface width in a
two phase system of a bulk sample (Porod law). Because of weak scattering this
measurement is only possible with high scattering contrast between components and
a strict two component system has to be assumed. An x-ray microbeam (0.05–20 μm
in diameter) from a hard x-ray synchrotron source is used for so-called scanning
x-ray microscopy where the beam is scanned over the sample to determine at each
spot a full x-ray small or wide angle scattering pattern with an area detector.
Structural information at micro- to nanometer level is obtained, spatially resolved
at different locations of the sample.

4.10 Secondary Ion Mass Spectrometry (SIMS)

Secondary ion mass spectrometry (SIMS) may be used to determine the chemical
composition of surfaces and interfaces at high resolution [3, 63, 65]. Secondary ions
are generated by bombardment of the sample surface with an ion beam under
vacuum. Those generated ions from the sample are analyzed in a mass spectrometer.
The organic characteristic fragments are used for identification of the composition
(fingerprint technique). In the “static” mode of operation at low ion flux, only a
monolayer is removed from the surface (static SIMS). This mode is used for surface
investigations and allows for instance very sensitive investigations of surface
contaminations.
At high incident ion flux in the “dynamic” mode (Fig. 17), the sample material is
continuously sputtered away, and by monitoring the secondary ion flux one gener-
ates a depth profile of elements and fragments (dynamic SIMS). At constant sputter
rate also interfaces between polymers may be investigated, and depending on sputter
rate a depth resolution as small as 12 nm may be achieved.

4.11 Ion Techniques

Several techniques use ions as probes for interface analysis besides SIMS (Figs. 16
and 17) [3]. They require dedicated equipment and are usually applied under ultra-
high vacuum. Typically an ion accelerator in the appropriate energy range as well as
corresponding ion sources and detectors are needed. Deuteration of one component
is again a technique for contrast generation between polymers [54]. While the
resolution is reasonably good, ion techniques are quite helpful for interface width
determination of polymers. Elastic Recoil Detection/Forward Recoil Detection and
Nuclear Reaction Analysis are typical and well-developed techniques. When heavy
atoms are present in the sample, Rutherford Backscattering can be used.
A common lab technique uses scanning of a focused ion beam (FIB) for imaging,
but in a cross beam set-up is often utilized in combination with a SEM for micro-/
384 M. Stamm

nano-machining of a sample (cutting, milling, etching, ion deposition). The ion

beam can etch deep cuts into the sample, which then are investigated by SEM or
TEM further. In this way, hidden interfaces may be visualized, and the ion beam is
also able to cut soft/hard interfaces, which otherwise may be difficult to achieve.
Many possibilities for nano-machining, ion-beam lithography and nano-pattern
generation exist, but one should be aware that after FIB treatment there is always a
thin surface layer which contains some incident ions and has been modified by the
ion beam. By FIB machining, structures may be generated down to the range of
10 nm. The combination of FIB and SEM in commercial instruments offers the
possibility of simultaneous imaging of the treated region with the SEM at high
resolution, while the ion beam is machining the surface. With added nano-
manipulators for instance conductivity measurements can be performed. Various
materials like Pt, W, SiO2, etc. may be locally deposited on a sample surface in the
FIB using ion-beam-activated deposition by local decomposition of molecules from
a directed gas flow. The FIB in this way can be considered as a nano-lab.

4.12 Optical Microscopy Techniques (OM)

If nanoscopic resolution is not required, optical microscopy techniques provide easy

possibilities of lateral imaging of the surface under atmospheric conditions and in
some cases also at an interface of the sample. In standard operation, lateral resolution
is limited by the wavelength of light, which ranges typically from 300 nm to
micrometers. With a tiny waveguide, the lateral resolution can be enhanced to
some nanometers (SNOM). Interference techniques improve the sampling depth,
and it is enhanced for instance with phase measurement interference microscopy to
0.5 nm. Fluorescence techniques can also reach nanoscopic resolution. Several
microscopic techniques are available at different level of sophistication to be used
for surface and interface characterization:
Light microscopy in reflection or transmission mode with dark field or differential
interference contrast for lateral inhomogeneities, Brewster-angle, ellipsometric, or
surface plasmon microscopy for thickness determination, phase measurement interfer-
ence microscopy for surface topography with subnanometer height resolution, fluores-
cence microscopy with labeled molecules for distribution and movement of molecules
also at nanoscale, IR, or Raman microscopy for lateral distribution and identification of
molecules, as well as confocal laser scanning microscopy for lateral and depth sensi-
tivity in sub-micrometer range. The resolution limit of fluorescence microscopy has
recently been significantly reduced by specific techniques, which allow for instance
measurements of cells and bio-objects at resolution in the nano-range.

4.13 Indentation, Adhesion, Mechanical Properties

A classical mechanical surface characterization is the hardness determination [3].

A hardness measurement is done by indenting a well-defined diamond stylus at a
9 Surfaces and Interfaces 385

certain load into the surface measuring the depth of the indent. The test was miniatur-
ized for the investigation of thin layers and anisotropic materials (micro-hardness test).
Here a small diamond stylus of well-defined geometry is used, and both indentation
depth and indentation load are simultaneously recorded as function of time. From an
analysis of the load-displacement data, both the hardness and the Young’s modulus can
be calculated. Hardness as well as stiffness images of a surface are obtained by scanning
the surface. With appropriate tips nano-indentation experiments are performed with a
scanning force microscope. The surface can be deformed elastically, and knowing the
cantilever stiffness a stiffness image of the surface is obtained. However, quantitative
stiffness values are difficult to obtain and the technique is usually used only in a
qualitative way to obtain a stiffness contrast between components for lateral imaging.
This is similarly performed for friction and adhesion of the tip at the surface and
corresponding images are obtained. Here the adhesion of the cantilever tip to the
surface is determined, but also colloidal particles may be attached to the cantilever
for example. Tests of adhesion of films deposited on a surface are essentially fracture
tests. Adhesion of those films is most commonly measured by peel tests, but may
also be determined from blister or double cantilever beam tests. Adhesion tests
should be performed in view of the desired application, since values depend in
most cases on the measurement technique used. This is similarly true for friction
between two solid samples, which can be measured at macroscopic and microscopic
level utilizing different techniques and local probes. One should keep in mind that
mechanical properties at the surface and interface can be very different from the
bulk, and a detailed understanding is still missing.

4.14 Inverse Gas Chromatography (IGC)

From a measurement of the adsorption of test gases (and vapors of liquids) at surface
of a material one can get interesting information on surface activity, composition,
and phase transitions. While gas chromatography is aiming at the characterization of
the adsorbing gas, inverse gas chromatography is aiming at the characterization of
the surface of the filler material, which can be a polymer powder or fiber. Specific
gases (“probes”) of known properties are utilized to determine the interaction
behavior, to provide surface characteristics and functionality of the filler material.
A commercial gas chromatographic apparatus can be used, and the method is
relatively cheap and easy to apply.
As mentioned before, we cannot cover details of the surface and interface
characterization techniques because of the wealth of techniques used. In addition,
there is fast technical development in many areas and resolution depends largely on
experimental conditions and samples, which have to be prepared in a dedicated way
to achieve optimal resolution or contrast. The conclusions given above therefore
have to be taken with care. One always should keep in mind that the choice of a
suitable and optimal technique for a particular problem is of crucial importance and
should consider aspects like sample preparation, necessary spatial and depth reso-
lution, contrast generation, as well as environmental conditions needed.
386 M. Stamm

5 Summary and Outlook

Polymer surfaces and interfaces are important for nearly all polymer materials and
determine many properties. In this chapter a short outline of polymer surfaces at
molecular scale is given with reference to special aspects of chain conformation and
surface dynamics. In this respect, the surface tension as a fundamental property of a
surface is discussed. Surface functionalization can change appearance of a material
very significantly. In particular, the grafting of polymer brushes onto surfaces is
described as a very versatile tool, where even responsive polymer brush surfaces can
be obtained and wetting, adhesion, bio-functionality, catalytic activity and sensing
ability controlled. From the theoretical side, the interface between polymers can be
formulated on the basis of mean-field theory with introduction of an effective
interaction parameter, which is related with interface width and fluctuations at the
interface. Examples are polymer blends, copolymers as compatibalizers and com-
posites, where interfaces play an essential role. Important for surface and interface
characterization are dedicated techniques, which include scanning force and electron
microscopy, photoelectron and IR/Raman spectroscopy as well as x-ray and neutron
reflectometry or scattering techniques. For their efficient use, guidelines for resolu-
tion and typical information obtained are provided.
Polymer surfaces and interfaces and the functionalization in their vicinity are
becoming more and more important with the development of more complex and
nanoscale devices and materials. So requirements for functional coating are getting
more and more challenging, and self-cleaning, multifunctional, responsive or adap-
tive coatings are desired. Similarly nanocomposites with dedicated properties
require particular functionalization of the surface of the nanoparticles for good
dispersion and interfacial adhesion. In microelectronics industry the design of
nanoscopic thin and structured multilayer films provides a challenge to interfacial
design concerning adhesion, wetting, roughness, electron transport and optical as
well as mechanical properties of polymers used for the design and fabrication of the
nano-electronic devices. This becomes even more demanding with the introduction
of flexible devices, where typically a flexible polymer film is used as a support. So
there are plenty of problems and questions connected with surfaces and interfaces in
the design of future advanced devices and materials. They require a good funda-
mental understanding of surface and interface properties, which is only possible with
highly advanced characterization techniques. So this area will also in the future be
under constant development.

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Membrane Surface Modification
and Functionalization 10
Syed Mohammed Javaid Zaidi, Kenneth A. Mauritz, and
Mohammad K. Hassan

Contents
1 Polyethylene Glycol Grafting Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
2 Plasma-Induced Surface Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
3 UV-Induced Surface Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
4 Zwitterionic Polymer Grafting Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
5 Layer-by-Layer Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
6 Chemical Vapor Deposition Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
7 Oxidative Stability of Surface Modification and Practical Aspects . . . . . . . . . . . . . . . . . . . . . . . . 407
8 Conclusions and Future Prospective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412

Abstract
Surface functionalization of membranes is one of the efficient techniques that can
bestow these membranes with novel properties and transform them into valuable
finished products. It has been widely applied to polymeric membranes in many
fields and has progressed rapidly in recent years. The modified membranes have
been widely used in various applications, such as in separation processes for
liquid and gaseous mixtures (gas separation, reverse osmosis, pervaporation,
nanofiltration, ultrafiltration, microfiltration), biomaterials, catalysis (including
fuel cell systems), and “smart” membranes. In this chapter, various approaches to
the surface modification and functionalization of polymeric membranes are
highlighted and reviewed. Also, the applications of the modified membranes

S. M. J. Zaidi (*) · M. K. Hassan

Center for Advanced Materials, Qatar University, Doha, Qatar
e-mail: [email protected]; [email protected]
K. A. Mauritz
School of Polymers and High Performance Materials, The University of Southern Mississippi,
Hattiesburg, MI, USA
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 391

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_11
392 S. M. J. Zaidi et al.

will be discussed from the aspect of environmental stimuli-responsive gating

membranes, antifouling membranes, adsorption membranes, pervaporation and
reverse osmosis membranes, membranes for energy conversion, gas separation
membranes, and biomedical membranes. A detailed overview of the usage of
polyzwitterions and oxidative stability of surface modifiers to alter membrane
surface charge will be outlined. Finally, recent advances and developments in
surface modification techniques such as layer-by-layer assembly and chemical
vapor deposition will be discussed.

Surface modification of membranes allows better performance and even to imple-

ment new functionality. Modifications render better performance in liquid and
gaseous mixtures separation (gas separation, reverse osmosis, pervaporation, nano-
filtration, ultrafiltration, microfiltration), biomaterials, stimuli-responsive gating, and
energy conversion systems.
Membranes for water separation and purification are among the materials that
widely use surface treatment due to the fouling phenomena. Fouling in this case
originates from microbial growth on membrane surface followed by the production
of extracellular polymeric secretions (EPS) containing proteins, glycoproteins, lipo-
proteins, polysaccharides, and other biomacromolecules [1]. Foulants are typically
adsorbed to the membrane surface via hydrophobic interaction, van der Waals
attraction, hydrogen bonding, Lewis acid-base interaction, and electrostatic repul-
sion. Many strategies have been used to exclude or reduce membrane fouling
including surface hydrophilicity enhancement, surface roughness reduction, and to
alter membrane surface charge [1–6]. Hydrophilic surface modifiers are highly
permeable thin-film coating such as crosslinked poly(ethylene glycol) (PEG)
[7–10] or grafted chains of PEG brushes [11, 12] or zwitterionic polymers [13, 14].
This chapter presents an overview of the most common strategies and methods
used for surface modifications of the membranes in order to eliminate fouling or
attain new function and better performance. Also, a detailed overview of the usage of
polyzwitterions to alter membrane surface charge will be outlined. Finally, we will
cover some of the recent advances in surface coating modification techniques such as
layer-by-layer and chemical vapor deposition. Our specific focus on water desalina-
tion and cleaning membranes modifications arises from their technological impor-
tance as well as abundance in the literature.

1 Polyethylene Glycol Grafting Strategy

Surface grafting and surface segregation are two leading methods for antifouling
membrane fabrication. Surface grafting is one of the most commonly used methods
to mitigate issues like fouling or to introduce additional functionality to the mem-
brane. Grafting typically happens through one of the two widely used strategies
“grafting from” or “grafting to” (Fig. 1) [15]. In the “grafting from” method, active
functional groups that exist on the membrane surface are used to initiate
10 Membrane Surface Modification and Functionalization 393

Fig. 1 Surface modification methods using the “grafting from” and “grafting to” approaches.
(Figure from [15], with kind permission of Elsevier)

polymerization of monomers from the surface. While in the “grafting to,” polymers
carrying reactive groups at their chain ends or on a chain are covalently linked to the
membrane surface [16]. Grafting to method became more competent with the recent
development of various “click” chemistries. However, the grafting from is proven to
be more flexible and useful as a big range of grafting densities and chain lengths can
be realized [17]. Overall, grafting has a big advantage over other ways of surface
modification as it includes covalent attachment of polymer chains on membrane
surface, thus preserving the long-term chemical stability of the modified surface [2].
Polyethylene glycol (PEG) is one of the most widespread modifiers for surface
grafting and segregation. Due to its hydrophilicity, neutral charge, and high hydra-
tion capacity via hydrogen bonding with water, PEG can help membrane to greatly
resist non-specific adhesion of protein and other natural organic materials [1].
Fan et al. used PEG as a surface modifier and pore-forming agent for poly-
ethersulfone (PES) membrane matrix and in the presence of m-trihydroxybenzene
(MTB) as a hydrogen bond donor [18]. As a common pore-forming agent [19] and
during the non-solvent-induced phase separation (NIPS) process, PEG can migrate
from the hydrophobic PES membrane matrix to the coagulation bath due to its
solubility in water. Therefore, PEG will postpone the solidification of the membrane
matrix and promotes fully developed macropores besides its role as hydrophilic
surface modifier. Furthermore, MTB mediates the hydrogen bonding interaction
between PES and PEG to manipulate the surface segregation behavior of PEG
(Fig. 2) [18]. The antifouling performance of PES/PEG-MTB membranes was
ominously improved as indicated by the increase in flux recovery ratio from
74.3% to 98.4% and the residence stability of PEG on membrane surface [18].
Furthermore, Liu et al. revealed that using an amphiphilic modifier, consisted of
crosslinked hydrophobic melamine formaldehyde (MF) backbone and hydrophilic
polyethylene oxide (PEO), helped to reduce the thermodynamic stability of the
394 S. M. J. Zaidi et al.

Fig. 2 MTB role in forming

hydrogen bonding interaction CH2 CH2 O PEG
between PES and PEG. n
(Figure from [18], with kind
permission of Elsevier) OH
HO
MTB

OH
O
S O PES
O n

casting solution and resulted in PES membranes with high porosity during the NIPS
process [20]. Crosslinked hydrophobic MF segments were more compatible with the
hydrophobic PES matrix and introduced large diffusion hindrance, due to entangle-
ments with PES chains, which would decrease loss of the amphiphilic modifier
during operation. The membranes showed durable antifouling properties after three
cycles of ultrafiltration experiment, and the FRR values of the three cycles were
bigger than 95% (Fig. 3) [20].
Polydopamine (PDA) represents another attractive strategy for membrane surface
hydrophilization and even better when grafted with poly(ethylene glycol) mono-
amine (PEG-NH2). It can be easily deposited on almost all types of surfaces from
buffered, aqueous dopamine solution under, and it greatly influences hydrophilicity,
charge, and surface roughness of the substrate [21–29]. Moreover, simplicity and
non-specificity of the PDA deposition process enable improved fouling resistance
and enhanced recovery of commercial membrane modules via filling feed side of the
module with buffered dopamine solution [30].
Many researchers reported improved fouling performance for different mem-
branes modified with polydopamine, polydopamine-g-poly(ethylene glycol), and
polydopamine-g-polyvinyl alcohol. Modified membranes exhibit good mechanical
stability, better chemical stability for the grafted layer under acidic and alkaline
conditions, and improved antifouling ability [31–34]. In addition, PDA deposition
highlighted the importance of applying modifications to membranes with bigger
pores than targeted, as surface treatment will effectually reduce the membrane pore
size [31]. Figure 4 shows the fouling behavior of modified and unmodified poly-
sulfone ultrafiltration membranes, under constant permeate flux and with a
1500 ppm soybean oil emulsion feed. This operational mode maintains fixed per-
meate flux while the transmembrane pressure (TMP) increases with time to over-
come membrane fouling. It is identical the industrial membrane purification systems
which operate at constant permeate flux to guarantee a steady rate of clean water for
a particular membrane area [31]. All membranes exhibit similar initial permeances;
however, this trend did not last for long as the PDA- and PDA-g-PEG-modified
membranes eventually showed lesser TMP comparing to that of the unmodified
PS-10 membrane. This result demonstrated the fouling alleviation of the PDA and
10 Membrane Surface Modification and Functionalization 395

Fig. 3 Chemical structure of the amphiphilic modifier (MF-g-PEGn) (left) and time-dependent flux
of PES/MF-g-PEG2000 (0.36 wt %) in the three cycles of ultrafiltration operation (right).
(Figure from [20], with kind permission of Elsevier)

PDA-g-PEG coatings and also the effectiveness of the strategy of using membranes
with larger pores to avoid blockage due to surface modifications.

2 Plasma-Induced Surface Treatment

Plasma-induced grafting is a fast, safe, and low cost method that attracted more
attention from researchers to modify the membrane surface [35–37]. Ju et al. used
low-pressure plasma source, with a radio frequency of 13.56 MHz, to induce surface
396 S. M. J. Zaidi et al.

Fig. 4 Constant flux fouling

of modified and unmodified
polysulfone membranes
exposed to a 1500 ppm
soybean oil emulsion feed.
The membranes had a pure
water permeance of
570 LMH/bar and fouling
performed at 55 LMH. Feed
pressure, 2.1 barg, and
crossflow velocity, 0.18 m/s.
(Figure from [31], with kind
permission of Elsevier)

grafting of poly(vinylidene fluoride) (PVDF) membrane with poly(ethylene glycol)

diacrylate (PEGDA) [38]. FTIR spectra of the grafted samples revealed the presence
of O–C=O absorption from PEGDA and indicate that growth of grafted PEGDA
polymer is linked to the increase in the PEGDA monomer concentration. Scanning
electron microscopy (SEM) images of samples’ cross-section show a uniform
microporous structure that consists of spherical particles having roughly the same
size. Contact angle of the PEGDA-treated membranes dropped from about 110
to
0
for all the PEGDA monomer concentration used. This instantaneous drop was
thought to be due to occupying the PVDF porous rough surface with hydrophilic
PEGDA chains, according to the Wenzel model [39]. Moreover, the tensile strength
of the PVDF membrane improved after PEGDA modification. The PVDF-g-
PEGDA membranes showed high separation efficiency and high fluxes, under
ultralow pressure, for different oil-in-water emulsions including colza oil, lubricating
oil, and soybean oil (Fig. 5) [38].
Wu et al. also reported grafting of crosslinked collagen on porous PVDF mem-
brane with the aid of low-temperature plasma treatment [40]. Glutaraldehyde was
used as a crosslinker for the collagen coated on the membrane surface. This
crosslinker has the advantages of high reaction activity with protein, stability of
crosslinking points, and the ability to keep the molecular structure of protein chains
in space. Glutaraldehyde concentration, crosslinking time, and temperatures were
shown to have a great impact on membrane contact angle and pure water flux.
Permeability and adsorption capacity of bovine serum albumin as well as cell
culture ability of the membrane indicated that they possess good hydrophilicity and
biocompatibility [39].
10 Membrane Surface Modification and Functionalization 397

Fig. 5 Images of the lubricating oil-water emulsion (10%, w/w) separation process from PVDF-g-
PEGDA-20 membrane. (Figure from [38], with kind permission of Elsevier)

3 UV-Induced Surface Treatment

Graft polymerization induced by UV irradiation is a commonly used surface treatment

method due to its high efficiency, low operation cost, simplicity, and distribution of
grafted chains near the surface without damaging the bulk polymer [41, 42]. Pan et al.
used UV light and benzophenone photoinitiator to graft the hydrophobic polypropylene
(PP) surface with acrylic acid [42]. The photoinitiator typically abstracts the active
tertiary hydrogen in polypropylene to forming surface radicals which react with the
monomer to form acrylic acid chains on the surface. Thin-film composite (TFC) mem-
brane was then formed on the hydrophilic PP surface through interfacial polymerization
of piperazine (PIP) and trimesoyl chloride (TMC) monomers [42]. Membranes’ separa-
tion performance experiments were conducted with methyl orange and fast green (FCF)
solutions in the feed. Membrane rejection to both TFC and methyl orange increased,
while the flux decreased with increasing the acrylic graft degree (GD). Rejection of FCF
solution was higher than that of the methyl orange, while its permeation flux was lower
comparing to the methyl orange solution, due to difference in molecular weights of the
organic solutes, (Fig. 6a, b). Increasing the GD caused the polyacrylic surface layer to
become denser, as indicated by the SEM pictures of Fig. 7, therefore increasing mem-
brane rejection to FCF and methyl orange from the feed solution [41].
Wang et al. highlighted the importance of having membranes with both hydro-
philic and antibacterial characteristics in order to reduce biofouling [43]. In their
work, UV photo-grafting method proved very effective in introducing both capsaicin
derivative (N-(4-hydroxy-3-methoxy-benzyl)-acrylamide, HMBA) and itaconic acid
(IA) to the polyethersulfone (PES) membrane surface, in a single reaction step as
shown in Fig. 8 [43]. Organic antibacterial compounds, like capsaicin, chitosan,
halamine, polycations, and graphene oxide, can be covalently attached to the
membrane surface to avoid the drawbacks of the inorganic antibacterial modifiers
398 S. M. J. Zaidi et al.

Fig. 6 Separation performance of the TFC membranes with FCF and methyl orange solutions in
the feed, showing (a) flux and (b) rejection. (Figure from [42], with kind permission of Springer)

[42, 44, 45]. These drawbacks include inevitable release of inorganic modifier metal
ions into feed solution and shorten the lifetime of the antibacterial material [46].
Results showed that grafting of HMBA and IA on PES membrane surface caused
significant reduction for the membrane permeability due to the decrease in
10 Membrane Surface Modification and Functionalization 399

Fig. 7 SEM pictures of neat polypropylene TFC membrane (a) and the membrane after grafting degrees
of (b) 6.46 and (c) 13.71 wt%, respectively. (Figure from [42], with kind permission of Springer)

membrane pore size; however, BSA rejection rate increased from 90.1% to 96.4%
(Fig. 9a) [43]. Meanwhile, pristine PES showed a massive drop of about 77% for the
water flux during 150 min of operation in the presence of significantly high BSA
concentration of 1.0 g/L in the feed. Drop of water flux for the modified membranes
under the same condition ranged from 7.7% to 42.7% depending on the molar
concentration of IA in the grafting solution (Fig. 9b) [43]. Antibacterial activity of
the membranes increased considerably with increased UV irradiation time with a
slight drop as IA concentration increases. This slight degradation in antibacterial
activity was ascribed to dilution of the HMBA density on membrane surface with
addition of the IA monomer and thought to be acceptable considering improvements
of the antifouling performance of the membranes [43].

4 Zwitterionic Polymer Grafting Strategy

Polyzwitterions (PZs) are antifouling polymer chains, having positively and nega-
tively charged functional groups, which received rising attention due to their great
hydration ability and outstanding anti-protein and bacterial adhesion characteristics
[47, 48]. Unlike PEG chains, localized charges on PZ chains bind strongly to H2O
400 S. M. J. Zaidi et al.

Fig. 8 Schematic diagram of the UV surface modification procedure. (Figure from [43], with kind
permission of Elsevier)

molecules forming electrostatically induced hydration layer, which physically swell

the polymer and inhibit protein or bacteria attachment to its surface [49, 50]. Poly
(sulfobetaine methacrylate) (polySBMA) is a common PZ, and it was utilized to
modify the surfaces of membranes for hemocompatible medical devices and reverse
osmosis [51, 52].
The “grafting from” approach was used to grow polysulfobetaine brushes on
polyamide membranes coated with polydopamine for reverse osmosis desalination, as
shown in Scheme 1 [48]. This approach generated PZ chains of narrow molecular
weight distribution at relatively mild polymerization condition and enabled higher
polymer densities on membrane surface comparing to the “grafting to” method
[47, 53, 54].
The hydrophilic, zwitterionic coating on membrane surface increased water flux
by 17% over that of the unmodified polyamide commercial membrane and without
significant loss of the salt rejection performance. Meanwhile, the modified mem-
branes displayed considerable suppression of protein and bacterial adhesion of 69%
and 88%, respectively, compared to untreated membrane as shown in Fig. 10. Strong
repulsive force of polysulfobetaine brushes, to the hydrophobic protein and bacteria,
arises from the anionic sulfate and cationic quaternary ammonium groups that form a
hydration layer through electrostatic interaction as well as hydrogen bonding [47].
Yu et al. introduced a novel approach to graft alkyne-terminated polyzwitterions
onto polyamide (PA) surface using click chemistry in two-step reaction. First,
they introduced azide functional group onto polyamide using SN2 nucleophilic
10 Membrane Surface Modification and Functionalization 401

Fig. 9 (a) Pure water flux a 100

and BSA rejection rate for
600
neat and modified membranes

BSA rejection rate (%)

under fixed applied pressure 500 95

PWF (L.m–2.h–1)
of 0.1 MPa, BSA solution
concentration of 1.0 g 400
dissolved in 1 L of phosphate 90
buffer (pH = 7.4). (b) 300
Normalized water flux for the
same set of samples operated 200 85
with three cycles of BSA in
the feed solution. Samples 100
marked as PES-g-mHnI, 80
PES S-g-1H01 S-g-1H11 S-g-1H51
where m:n is the molar ratio of PE PE PE
HMBA and IA, respectively.
(Figure from [43], with kind b 1.2 PES membrane PES-g-1H01
permission of Elsevier) PES-g-1H11 PES-g-1H51
1.0
Normalized Water flux

0.8

0.6

0.4

0.2

0.0
0 20 40 60 80 100 120 140 160
Time (min)

substitution on nitrogen atom, a reaction that was facilitated by the adjacent electron-
withdrawing C=O and benzene groups. Then, the alkyne groups of PZ were grafted
to azide groups of polyamide via an azide-alkyne cycloaddition click reaction as
shown in Fig. 11 [55]. In this context, click chemistry offers the benefits of greater
site selectivity, almost quantitative conversion under mild conditions, no side reac-
tions or by-products, and stable aromatic triazole ring that makes grafted chains
strongly attached to the substrate [56–59].
Forward osmosis mode testing of the membranes indicated that neither the flux
nor the NaCl rejection was significantly affected by PZ grafting. Fouling experi-
ments were conducted using humic acid as model foulant. The flux declines signif-
icantly for neat polyamide membranes, while the PZ-grafted showed negligible
decline after addition of the foulant (Fig. 12a) [55]. To check for fouling reversibility,
all membranes were cleaned using 20 mM NaCl cleaning solution after the fouling
experiments. After cleaning, water flux of unmodified polyamide showed only
ffi 77% of its original flux, while grafted membranes reserved its original flux before
fouling (Fig. 12b) [55]. These excellent antifouling characteristics of surface
402 S. M. J. Zaidi et al.

Scheme 1 Steps of the “grafting from” approach to grow polysulfobetaine brushes on polyamide
membrane surface coated with PDA. (Scheme from [48], with kind permission of the Royal Society
of Chemistry)

modified membranes were attributed to combined influences of reduced specific

binding, strong hydrophilic repulsion, and steric repulsions of the long flexible PZ
chains as illustrated in Fig. 12c [55].

5 Layer-by-Layer Technique

Layer-by-layer (LbL) technique has been used as an effective surface modification

method for membranes used in desalination of brackish and seawater, reclamation of
wastewater, and membrane bioreactors (MBR) [60–63]. Gao et al. employed a LbL
10 Membrane Surface Modification and Functionalization 403

Fig. 10 Normalized fluorescence intensity of surface modified and unmodified polyamide mem-
branes, showing the extent of bovine serum albumin adherence to membrane surface. Values
normalized to fluorescence of the untreated PAM, which was given an intensity of 100. Error
bars are standard deviation over three replicates. (Figure from [48], with kind permission of the
Royal Society of Chemistry)

O
S S N
O n O N
N3 C12H25
S S N
N S
C12H25 n O O O N
O C
S
O O C
+ O
+
N
+
N

O S O
O S O – +
O + +
– +
+
−

O +
−

−
−

N N
−
−

+ + −
+ + − N N
+ − − −
−

+
−

+ N3 N3 + −
−
−

+ + +
−

+
−

− N
− − N + +
− − + + +
− + + +
−

+ + +
−

+
−

N N
−
−

− − N N
− − + −
+ −
+ + + +
Alkyne-PZ Azide-PA PZ-PA

Fig. 11 Cycloaddition click reaction between alkyne-PZ and the azide-polyamide (PA) membrane.
(Figure from [55], with kind permission of Elsevier)
404 S. M. J. Zaidi et al.

Fig. 12 Performance of grafted PA-PZ comparing to unmodified PA membranes in a forward

osmosis system with (a) humic acid fouling experiments and (b) extent of flux recovery after
membrane cleaning. The flux data are normalized by the membrane flux prior to the fouling
experiments. (c) Schematic diagram of the antifouling characteristics of the PZ-grafted membrane.
(Figure from [55], with kind permission of Elsevier)

method to consecutively deposit TiO2 nanoparticles and GO nanosheets on a

commercial porous ultrafiltration polysulfone membrane, followed by partial
reduction of GO via ethanol-UV treatment as shown in Fig. 13 [60]. TiO2 is a
very common photocatalyst for decomposing organic pollutants in water to CO2
and water [64]. Its superior efficacy originates from its high removal efficiency,
effective cost, chemical stability, and low toxicity [65]. Combining effective
photocatalysts with membrane porosity could ominously improve the separation
performance if the catalyst can effectively work in the UV and visible light
regions [66]. However, TiO2 has low photoactivity in visible sunlight due to
high band-gap energy (3.2 eV) which requires UV light for the activation of its
electron-hole pairs [67]. GO has the ability to expand TiO2 efficiency to the
visible region due to its electron-transferring character and therefore can greatly
10 Membrane Surface Modification and Functionalization 405

Fig. 13 Illustration (a) and reaction schemes (b) involved in the layer-by-layer method to modify
surface of porous polysulfone membrane with the TiO2-GO photocatalyst. (Figure from [60], with
kind permission of Elsevier)

increase the lifetime of electron-hole pairs [68–72]. In addition, GO’s large

surface area (2630 m2/g) establishes closer and longer contact between organic
pollutant and the photocatalyst [73].
The photocatalytic activity of the membranes in removing methylene blue
(MB) is presented in Fig. 14, where C and C0 are MB concentrations during and
at the beginning of the filtration experiment, respectively. Unmodified PSf
membrane did not show any photocatalytic activity under dark, UV, or sunlight
(Fig. 14a). Coating a single layer of TiO2 or GO on the PSf membrane did not
show more than 10% removal of MB in dark. Under UV light, both TiO2 and GO
are more photocatalytically active than under sunlight as both have a semicon-
ductor character and seem to have similar band-gap energy (Fig. 14b, c). The
TiO2-GO double layer exhibits highly improved and similar photocatalytic per-
formance in presence of either UV or sunlight irradiation (Fig. 14d). That
performance was also much better than a single layer of each photocatalyst
under same irradiation. Incorporating TiO2 with GO decreased the band-gap
energy for each semiconductor so that lower energy sunlight irradiation was
capable of activating more electrons in the semiconductors and led to improved
photocatalytic activities [60]. In addition, ethanol-UV treatment of the TiO2-GO
membrane further improved the MB degradation kinetics as such treatment
partially reduced GO and enhanced the ability of GO to conduct more electrons
from TiO2 nanoparticles. Besides, the TiO2-GO-grafted membrane showed
enhanced flux increased under UV due to photo-enhanced hydrophilicity and
MB degradation. Therefore, surface grafting of TiO2-GO provides a very encour-
aging route to fabricate high-performance photocatalytic PSf membranes for
viable water treatment technology [60].
406 S. M. J. Zaidi et al.

Fig. 14 Methylene blue removal by virgin polysulfone (a) and the membrane after surface
modification with (b) TiO2, (c) GO, and (d) TiO2-GO, respectively. (Figure from [60], with kind
permission of Elsevier)

6 Chemical Vapor Deposition Technique

Initiated chemical vapor deposition (iCVD) is a solvent-free method in which

thin-film deposition of various polymers occurs on virtually any substrate.
Monomers volatilization, their combination to form long chain polymers, and
film deposition happen concurrently at modest vacuum and low temperature.
Distinctive features of the iCVD technique include long-term stability,
conformality, full functional retention, scalability, and ability to control thickness
at the nanometer level [74–76].
Electrospun fibrous poly(trimethyl hexamethylene terephthalamide) (PA6(3)T)
membrane surface rendered hydrophobic by depositing poly(1H,1H,2H,2H-
perfluorodecyl acrylate) (PPFDA) using the iCVD technique [77]. Membrane
10 Membrane Surface Modification and Functionalization 407

Fig. 15 MD performance
showing the permeate flux for
the PA6(3)T surface-treated
fiber membranes with
different fiber diameters.
(Figure from [77], with kind
permission of the American
Chemical Society
Publications)

distillation (MD) performance revealed that decreasing fiber diameter increased

the liquid entry pressure and permeate flux (Fig. 15). This trend was linked to
variations in tortuosity rather than difference in membrane thickness or porosity.
Porosity typically decreases as fiber diameter decreases and membranes had
negligible variation in their thickness. However, this study reported increased
curling of the electrospun mats with smaller fiber diameter reflecting high levels
of tortuosity. In addition, surface diffusion could also help to enhance flux as
smaller diameter for the fiber means high specific surface area [77].
Zaidi et al. copolymerized and deposited hydrophilic hydroxyethyl methacrylate
(HEMA) and hydrophobic perfluorodecyl acrylate (PFDA) on commercial RO
membranes using the iCVD technique [76, 78]. The iCVD has a unique feature of
controlling deposited amphiphilic poly(HEMA-co-PFA) film in a real time, which
was then confirmed by SEM as depicted in Fig. 16 [78]. Bacterial adhesion tests
showed great reduction in cell attachment on coated membranes comparing to that of
the bare membranes (Fig. 17) [76]. The membrane having amphiphilic character
(with 40% PFDA) gave the highest resistance to bacterial attachment, which indi-
cates the importance of compositional heterogeneity of amphiphilic chain in
rejecting the foulants. Meanwhile, water permeation flux decreased with increasing
the PFA content, while the coating chemistry did not affect the NaCl solution salt
rejection [78].

7 Oxidative Stability of Surface Modification and Practical

Aspects

Oxidative stability of the coat or grafted polymer chains and brushes is crucial
for membrane performance over long term. Water treatment and separation
environments are very complicated and highly corrosive as it contains harsh
408 S. M. J. Zaidi et al.

Fig. 16 Cross-section SEM images of unmodified membrane (a) and the membranes after surface
treatment with poly(HEMA-co-PFA) films containing 40% of PFA comonomer. Deposited film
thickness was measured to be (b) 48  5, (c) 70  5, and (d) 96  3 nm, respectively. (Figure from
[78], with kind permission of Elsevier)

chemicals like seawater especially at high temperatures. In addition, oxidative

solutions like NaClO and H2O2/Cu+2 are periodically used to clean fouled
membranes. Although the chemical and oxidative stabilities are very important
aspects for extended membrane lifetime, only few researchers reported such
studies [79–82].
In an effort to understand the oxidative stability of some common surface
modifiers, Ren et al. conducted a very interesting study on a UV-induced surface-
grafted polypropylene microfiltration membrane (PPMM). They used two
typical surface modifiers with good antifouling capability, poly(sulfobetaine
10 Membrane Surface Modification and Functionalization 409

Fig. 17 SEM picture of

bacterial colonies on surface
of unmodified (a) and the
surface after modification with
the amphiphilic poly
(hydroxyethylmethacrylate-
co-perfluorodecylacrylate) (b)
using the iCVD technique.
(Figure from [76], with kind
permission of Elsevier)

methacrylate) (polySBMA) and poly[oligo(ethylene glycol) methyl ether meth-

acrylate] (polyOEGMA) [81]. Modified membranes were immersed in NaClO
and H2O2/Cu+2 oxidants solutions, and their stability was evaluated via moni-
toring change in remaining mass of graft polymer over extended time periods
(Fig. 18). Surprisingly, polySBMA-grafted membranes lost their grafting mass
more quickly than the polyOEGMA-grafted ones. PEG chains were in fact
reported to be more susceptive to oxidative degradation in the studied solutions.
Meanwhile, there was no apparent change in the polySBMA-grafted membrane
morphology although it lost about 70% of grafted polymer mass [81]. The
authors used the time-of-flight secondary ion mass spectroscopy (TOF-SIMS)
to understand the mechanism of the rapid oxidation of the polySBMA chains.
Results suggest that hydroperoxide and hydroxyl radicals formed in the Cu2+
catalyzed H2O2 solution are responsible for the attacks on the polySBMA chains
410 S. M. J. Zaidi et al.

Fig. 18 Remaining mass

ratios of polyOEGMA-
(hollow circle) and
polySBMA-grafted (solid
triangle) PPMMs after
oxidation in (a) 0.1 mM Cu2+
with 0.01 mM H2O2 and (b)
6.7 mM NaClO solutions.
(Figure from [81], with kind
permission of Elsevier)

(Fig. 19). They could cause complete detachment of the grafted chain via ester
linkage hydrolysis and also breaking the C-N bonds resulting in elimination of
the quaternary amine group [81, 83]. Electrophilic character of the quaternary
ammonium group was also thought to accelerate the radical attack and resulted in
rapid oxidative loss of polySBMA [81]. Introduction of amide group in the
polysulfobetaine chain, instead of the ester bond, made it more stable to NaClO
solution [82].
Another aspect of practical importance is to simplify and scalability of the
modification processes. Zhou et al. reported a simple one-step co-deposition of
dopamine and PSBMA on the surface of microporous polypropylene membranes.
Dynamic protein filtration tests confirmed the excellent antifouling property of the
modified membranes [84].
10 Membrane Surface Modification and Functionalization 411

Fig. 19 Hydroxyperoxide and hydroxyl radicals formation in the Cu2+/H2O2 solution (a) and
(b) mechanism of oxidative degradation polySBMA chains on membranes. (Figure from [81], with
kind permission of Elsevier)

8 Conclusions and Future Prospective

Surface modification has been used as an effective method to modify the surface of
the membranes to tailor it for a specific application. One of the most important
surface modification purposes is to protect the membrane from direct exposure to
harsh environment such as chlorine or oxidants content in water, foulants, and pH of
the water at which the membrane life will be shortened. This technique has been
found very effective in reducing the fouling of the membranes in water desalination
and treatment, which is a major problem facing the industry today. Among various
techniques, such as grafting, plasma treatment, UV treatment, zwitterionic coating
on membrane surface, layer-by-layer (LbL) assembly and chemical vapor deposition
(CVD), and plasma CVD, are getting more popular as an effective method to
fabricate the membranes especially for water treatment and energy applications.
They have the better control of the thickness of the surface layer at the nanoscale and
are more stable. Moreover, the nanoparticles and various macromolecules can be
incorporated into the membrane surfaces. Relatively new technologies, LbL assem-
bly and plasma CVD, offer flexibility and great control over the film properties,
which are key to overcome problems, associated with other surface modification
techniques. Recently, graphene oxide (GO), a single sheet functionalized graphene
with oxygen-rich functional group, has attracted attention from researchers in the
field of water treatment. This material provides fast water transport, hydrophilicity,
as well as excellent chemical stability.
One of the advantages of these relatively new techniques, LbL assembly and
CVD, that has not been thoroughly observed was the flexibility and applicability of
412 S. M. J. Zaidi et al.

this technique to create ultrathin film from various materials. To the best of our
knowledge, most of the works are still focused on polyelectrolyte. Although some
people have started introducing nanomaterial such as silver nanoparticles, graphene
oxide, and clay, but still there is a gap available to do research in terms of membrane
material modification. There were many polymers that have never been investigated
because no appropriate technology was applicable to prepare ultrathin film using
those polymers; now there is an opportunity to advance the research using these
recent techniques. Using LbL assembly, one can create the film either from the
polymer itself or from the monomers. One can also combine organic and inorganic
material with nano-level control easily to fabricate highly resistant membrane toward
chlorine and foulants at the same time giving high flux and high rejection or
selectivity, for instance. Tailoring the film properties is one of the strengths and
advantages of LbL assembly and CVD that has not been thoroughly investigated yet.

Acknowledgments The authors would like to acknowledge the support of the Center for
Advanced Materials (CAM), Qatar University, for this work.

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Fiber-Reinforced Composites
11
Ajithkumar Manayan Parambil, Jiji Abraham,
Praveen Kosappallyillom Muraleedharan, Deepu Gopakumar, and
Sabu Thomas

Contents
1 Macro Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
1.1 Synthetic Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
1.2 Natural Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
1.3 Fiber Size and Length . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
2 Nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
2.1 Synthetic Nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
2.2 Polymer Nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
2.3 Carbon Nano Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
2.4 Carbon Nanotube Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
2.5 Metal Oxide Nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
3 Nanoscale Bio-Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
3.1 Nanocelluloses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
3.2 Nanochitin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
3.3 Starch Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
3.4 Bio-Nanofillers as Reinforcement for Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . 439
4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441

A. Manayan Parambil · J. Abraham · D. Gopakumar · S. Thomas (*)

International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi
University, Kottayam, Kerala, India
e-mail: [email protected]; [email protected]; [email protected];
[email protected]; [email protected]
P. Kosappallyillom Muraleedharan
International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi
University, Kottayam, Kerala, India
Department of Mechanical Engineering, Saintgits College of Engineering, Kottayam, Kerala, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 417

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_14
418 A. Manayan Parambil et al.

Abstract
Fiber-reinforced composites (FRC) are widely used in spacecraft, helicopters,
aircraft, ships, boats, automobiles, chemical processing equipments, biomedical
devices, sports items, buildings, bridges infrastructure, etc. Nowadays, more and
more exciting development on advanced forms of FRC materials are happening
across the world. Development of high-performance resin systems, incorporating
carbon nanotubes and other nanoparticles, are one among them. Polymer fibers
have numerous imperative applications apart from using as reinforcement in
composite materials. They are widely used in packaging, flooring, rope, textile
industries, etc. In this context, the study on fiber-reinforced composites is very
much important and the chapter gives an insight on the fiber-reinforced compos-
ites from macro to nanoscale.

Composite materials do exist naturally and synthetically. They are synthetically

made from two or more constituent materials having considerable difference in
chemical and physical properties that will always remain discrete in their structure.
Composites are composed of fibers in a matrix and should be strong and stiff with
low density. Thermosetting polymers like epoxy and polyester resins are widely used
matrices in a composite. This is due to the flexibility in molding after initial
fabrication. Similarly, glass and carbon fibers are usually used fibers in composites.
The use of metals and ceramics as matrixes for composites are not widely used
because of the high manufacturing cost and intricacy in the addition of fibers.
Fiber-reinforced composites are composites having fibers as reinforcement which
form the main source of strength and matrix which join and arrange all the fibers
together. Matrix transfers the stresses between the reinforcing fibers. Fillers or
modifiers are being used to impart special properties and make the process smooth.
They are composed of axial particulates embedded in a matrix material. The
interfacial bonding is important for fiber-reinforced composites. Aligned, random,
and woven fibers are the common geometries for fiber-reinforced composites [1].
Aramid, carbon, glass, boron, alumina, silicon carbide, and natural fibers are the
fibers being used in this class of materials.
Fiber-reinforced plastics (FRP) consist of fibers in a polymer matrix, where fibers
are the intermittent or disseminated phase and polymer matrix are the continuous
phase. They are stout, stiff, have high strength-to-weight ratio and stiffness-to-
weight ratio. When compared to unreinforced plastics, they possess ameliorate
fatigue resistance, superior toughness, and upper creep resistance. Reinforced plas-
tics are relatively easy to design, fabricate, and repair. Interestingly, they are com-
posed of the combined properties of its constituents. The percentage of fiber by
volume ranges from 10% to 60% in reinforced plastics. Similarly, the ratio of fiber
integrated in a matrix is constrained by the distance between nearby fibers. It is
investigated that higher weight percentage of fibers usually results in poor structural
properties. The highest practical fiber content is reported to be 65%.
Generally, hybrids have better properties than single-fiber composites and are
more costly. The composites are called a hybrid when more than one type of fibers
11 Fiber-Reinforced Composites 419

are used in reinforced plastics. For higher temperature applications, glass or carbon
fiber-reinforced hybrid plastics are developed that ranges about 300
C. When hybrid
fibers are exposed to atmosphere, they showed brittleness, abrasiveness, lack of
toughness, and chemical degradation. It is also seen that the fiber properties is signif-
icantly influenced when the quality of the material and processing method is varied.

1 Macro Fibers

1.1 Synthetic Fibers

The use of synthetic fibers as reinforcement in plastics is due to well-developed

manufacturing base and good mechanical properties. Synthetic fibers used as rein-
forcement in polymer composites are glass fiber, Kevlar fiber, graphite fiber, boron
fiber, and carbon fiber. Table 1 shows the typical properties of synthetic reinforcing
fibers. Synthetically designed FRP satisfy the properties required to meet the struc-
ture and durability of the materials for numerous application. The different types of
synthetic fibers are discussed below.

1.1.1 Glass Fibers

Glass fibers stand as the least expensive fiber and are widely used. The material
which is made out of these fibers are called glass-fiber-reinforced plastic (GFRP).
These materials contain 30–60% of glass fibers by volume. Glass fibers can also be
classified to continuous fibers and discontinuous or staple fibers. Glass is a chemical
form of silicon dioxide (SiO2). Various surface treatments like silane treatment
(a silicon hybride) are generally espoused. The different kinds of glass fibers
are E, S, and E-CR-type fibers. Calcium aluminoborosilicate glass is the universally
employed E-type fiber. Magnesia aluminosilicate is an S-type glass fiber which
offers high strength and stiffness. But they are costly. E-CR-type is the one which
offer higher resistance to elevated temperatures and are known to be high-
performance glass fibers. They are even more resistant toward acid corrosion than
E-type glass fibers. The refractive index of S-glass fibers is high to that of resin

Table 1 Properties of synthetic reinforcing fibers [2]

Fibers Characteristics
Glass High strength and density, low stiffness, and cheaper, e.g., calcium
aluminoborosilicate and magnesia aluminosilicate
Carbon High modulus/strength, less dense compared glass, used with CNTs in
combination and are cheaper
Boron Higher strength, stiffness, density, contains tungsten filament at its center, and
are expensive
Aramids Higher strength-to-weight ratio and expensive
(Kevlar)
Other fibers: Nylon, silicon, silicon carbide, boron nitride, tantalum carbide, steel, tungsten,
molybdenum
420 A. Manayan Parambil et al.

matrix and they offers high tensile strength than other glass fibers. In case of resin
composites, the flexural properties can be significantly improved by incorporating
discontinuous S-glass fibers. Moreover, these fibers will not affect the curing
properties of the composites [3].
The main advantage of using glass fibers are the low cost and high strength of the
material. These fibers are extensively used in recreational vehicles in order to save
weight and for durability [4]. They are extensively used in dentistry as fixed partial
dentures, root canal post systems, orthodontic fixed retainers, and periodontal splints [3].
When compared to the organic polymer matrixes, glass fibers have meager wetta-
bility. But these properties can be improved by salinizing these fibers with amino
propyl tri-methoxy silane [5].

1.1.2 Carbon Fibers

Being more expensive than glass fibers, carbon fiber combines the properties of low
density, high strength, and high stiffness. Based on the nature of carbon, these
composite material are called as carbon-fiber-reinforced plastic (CFRP) and graphite-
fiber-reinforced plastic (GFRP). Carbon and graphite are differentiated based on the
purity and processing temperature of the material. Carbon fibers have 90% amor-
phous carbon while graphite fibers have 99% crystalline carbon. Due to superior
mechanical properties, composites containing carbon fibers are used in aeronautical,
marine, automobile, sporting equipment, and mechanical engineering applications
[6–8]. Carbon fibers show more stiffness, lesser weight, lesser density, lesser coeffi-
cient of thermal expansion, lesser abrasion, improved electrical conductivity, vibrat-
ing damping, inert to chemicals, elasticity to failure at thermal temperature, higher
fracture strength, creep resistance, and biocompatible [9]. Carbon fiber composites
are resistant to corrosion and fire and have higher fatigue life [10]. Reduced produc-
tion cost and shorter composite manufacturing time make carbon-fiber-reinforced
epoxy polymer composite a good candidate for automotive application [8]. Carbon
fiber-reinforced composites showed optimal biocompatibility and are appropriate for
the design of materials for implant sustained full arch dentures [9]. When compared to
glass fibers, carbon fibers showed improved stiffness and strength.
The physical interlocking and interfacial adhesion of carbon fiber and polymer
matrix can be improved by treating with HNO3. This will remove the impurities on
the surface and increase the roughness of carbon fiber. Moreover, this may increase
the oxygen functional group on the surface, thus improving the properties [7]. The
need of the enhancement of electrical and thermal conductivity of reinforced plastic
components leads to the development of conductive graphite fibers. The fibers are
smeared with metal incessantly by electroplating. The conductive fibers obtained as
chopped or continuous form are incorporated directly into injection-molded plastic
parts. These type of fibers finds suitable for electromagnetic and radio frequency
shielding and lightning strike protection [11].

1.1.3 Ceramic Fibers

Nextels is a ceramic fiber which contains alumina, silica, and boric acid and has oval
shape in cross section. These fibers are resistant to chemicals and have very less
11 Fiber-Reinforced Composites 421

elongation and thermal conductivity. They are suitable for high temperature appli-
cations. Polyborosilazane fibers (SiBN) can be developed using multistep polymer-
ization and melt spun of hexamethyldisilazane, HSiCl3, BCl3, and CH3NH2 [12]. As
the temperature increases, the fiber diameter decreases and the tensile strength
improved. Using low-temperature CVD process, boron nitride-coated alumina fibers
can be developed [13]. Pyrolysis of cured SiC fibers at different environment
resulted in SiC fibers having different electrical resistivity, good mechanical
strength, and high temperature performance [14]. SiBNC ceramic fibers were devel-
oped using one pot synthesis of polyborosilazane and melt spinning. Similarly,
electron beam irradiation of green fibers infusible was also used to develop SiBNC
ceramic fibers [15].

1.1.4 Polymer Fibers

Aramid, rayon, and nylon are the source for polymer fibers. Aramids are the most
commonly used fibers. In aramid fiber family, Kevlar showed very high specific
strength and are toughest among aramid fibers. This is because it undergoes plastic
deformation prior to fracture. However, the absorption of moisture and the resulting
degradation of properties limit its applications. Similarly, spectra is another polymer
fiber which show improved abrasion and flexural fatigue resistance. This fiber
belongs to polyethylene polymer fiber which has increased molecular chain orien-
tation and molecular weight. Moreover, their specific strength and stiffness are
higher than aramid fibers. This can be attributed due to their lower density. In spite
of these benefits, these fibers have meager adhesion and low melting point which can
be considered as its major drawbacks.

1.1.5 Boron Fibers

Boron fibers are prepared by depositing boron on tungsten fibers by CVD. They are
stronger, stiffer, and resistant to higher temperature. Due to the use of tungsten, these
fibers have high density and are very expensive. Boron fibers can also be developed
using laser-assisted chemical vapor deposition [16]. By reacting liquid magnesium
with boron fibers, superconducting Mg2B2 fibers can be developed [17]. Aluminum
matrix composites can be reinforced with boron fiber [18]. Low molecular weight
and excellently spinnable born nitride fiber can be fabricated by preceramic
method [19].

1.1.6 Other Fibers

Sapphire, steel, tungsten, molybdenum, and tantalum carbide are other fibers used in
composites. Whiskers also are used as reinforcing fibers. Whiskers are single crystal
with needle-like structure having diameter ranging from 1 to 10 μm and 100 to
15,000 nm aspect ratio. They are free of imperfections, and imperfections do not
significantly affect their strength. This is due to their small size. The elastic moduli
and tensile strength are observed to vary with material. The tensile strength was
observed 15–29 GPa and elastic moduli ranging from 400 to 700 GPa. Multiple
shear band formation result in compressive strain to failure and effect in plastic
deformation of tungsten fibers/ZrAl-NiCuSi bulk metallic glass composite [20].
422 A. Manayan Parambil et al.

Tungsten fiber-reinforced tungsten composites can be used as plasma facing material

for future fusion reactors [21]. Further, intercalated graphene/molybdenum disulfide
hybrid fiber is developed for capacitive energy storage application [22].

1.1.7 Production of Synthetic Fibers

Polymers are made in to semisolid polymer fibers with continuous filament like
arrangement by extruding through spinneret. These fibers are extensively used in
plastic reinforcement. The extruder has many holes which allow the polymers to pass
through and form fiber. The process starts by converting liquid polymer to rubbery
form and later solidifying when the filaments begin to flow through the holes of the
spinneret. This process is termed spinning.
The polymer molecules should be oriented in the direction of the fiber. In order to
make the direction similar, significant stretching has to be induced. This orientation
influences the strength of the fibers and possesses high strength. Thus, this process
forms the most important steps during fiber formation. This can be performed soon
after extrusion and during pliable stage of the polymer. About 800% strain can be
persuaded. Synthetic fiber-reinforced polymer matrix composites have proved their
viability in the fabrication of many components in various applications.

1.2 Natural Fibers

As the name points, these fibers are generated from animals, plants, and minerals.
The structural performance of the plants is also influenced by these fibers. It also
showed significant reinforcement property when it was used in plastic. Further, plant
fibers are classified into bast, leaf, seed, fruit, wood, grasses, and reeds. Similarly,
animal fibers are classified into animal hair, silk, chicken feather, and avian fibers. In
addition, mineral fibers are classified into asbestos, ceramic, and metal fibers.
Natural fibers are complex and three dimensional. Their walls are enclosed with
hydroxyl ion-containing polymers like cellulose, hemicellulose, pectin, and lignin.
Natural fibers consist of mainly cellulose fibrils (fibers) embedded in lignin matrix
(resin). Apart from the polymers, organic with low molecular weight and inorganic
matters are also present in lesser ratio in these fibers. The decay resistant, color, and
smell are influenced by these extractives. The composition of few natural fibers is
given in Table 2 [23]. The use of natural fibers enhances the mechanical properties
(strength and stiffness) of plastic or polymer composite. It has to be noted that the
density as well as cost is not much influenced by the use of natural fibers. These
materials can be effectively employed in automobile industry due to its lighter
weight which reduces fuel consumption.
Natural fibers are recyclable, which is their main advantage. There are few
technical concerns which have to be addressed for incorporating natural fibers in
polymer composites [24]. The fiber properties should be homogenized and the
degree of polymerization should be understood before reinforcing natural fibers in
polymer composites. Similarly, their crystallization, adhesion property, and flame
retardant nature should be known.
11 Fiber-Reinforced Composites 423

Table 2 Composition of natural fibers [23]

Cellulose Ligin Hemicellulose Pectin Wax Moisture
Fibers (wt %) (wt %) (wt %) (wt %) (wt %) content (wt %)
Jute 61–71.5 12–13 13.6–20.4 0.4 0.5 12.6
Hemp 70.2–74.4 3.7–5.7 17.9–22.4 0.9 0.8 10
Kenaf 31–39 15–19 21.5 – 1.7 –
Flax 71 2.2 18.6–20.6 2.3 0.3 10
Ramie 68.6 0.6–0.7 13.1–16.7 1.9 0.4 8
Sunn 67.8 3.5 16.6 0.3 2 10
Sisal 67–78 8–11 10.0–14.2 10 – 11
Cotton 82.7 – 5.7 – – –
Kapok 64 13 23 23 – –
Coir 36–43 41–45 10–20 3–4 – 8
Banana 63–67.6 5 19 – – 8.7
Palf 70–82 5–12 – – – 11.8

The structural constitution of natural fiber is shown in Fig. 1. One primary layer
and three secondary layers are arranged outside and inside, respectively, for each cell
wall. The inner secondary layer has more cellulose content than the outer primary
layer. But the primary layer has more lignin content than the secondary layer. Within
each layer, microfibrils of cellulose are found to be parallel to each other. Around the
longitudinal direction, they are observed to be spiral. The angle between the axis and
the fibril of the fiber is called microfibrillar angle/spiral angle. Each layer has
different angles of spiraling. The hemicellulose and lignin together holds the cellu-
lose microfibrils in each layer. The properties of fibers are influenced by their
chemical components and complex chemical structure [25].
The properties of the fibers can be tailor-made by controlling the structure,
microfibrillar angle, cell dimensions, defects, and the chemical composition of
fibers. The mechanical properties are summarized in Table 3.
The cellulose content also influences their mechanical properties. Young’s modulus
and tensile strength was found to increase as the cellulose content increase. Similarly, the
structure and morphology are greatly affected by the lignin content of the fiber. The
wettability and adhesion of the fibers depend on the waxy substance of the natural
rubber. They have more potential to serve as substitute for artificial fiber composite. So
the rising global energy crisis and environmental threats can be addressed by carrying
out extensive research in this area. Accordingly, extensive studies on the natural fibers
with thermoplastic and thermosetting composites were carried out [26].

1.3 Fiber Size and Length

Comparatively, small cross section and orientation of molecules in the longitudinal

direction make the fibers robust and stiff in tension. Thus, chance of forming
424 A. Manayan Parambil et al.

Fig. 1 Structural constitution

of natural fiber

Table 3 Mechanical properties of natural fibers [23]

Density Diameter Tensile strength Youngs Elongation at
Fibers (g/cm3) (μm) (Mpa) modulus (GPa) break (%)
Jute 1.3–1.45 25–200 393–773 13–26.5 1.16–1.5
Hemp – – 690 – 1.6
Kenaf – – – – 2.7
Flax 1.5 – 345–1100 27.6 2.7–3.2
Ramie 1 – 400–938 61.4–128 1.2–38
Sunn – – 1.17–1.19 – 5.5
Sisal 1.45 50–200 468–640 9.4–22 3–7
Cotton 1.5–1.6 – 287–800 5.5–12.6 7–8
Kapok – – – – 1.2
Coir 1.15 100–450 131–175 4–6 15–40
Banana – – 1.7–7.9 – 1.5–9
Palf – 20–80 412–1627 34.5–82.5 1.6
11 Fiber-Reinforced Composites 425

significant defects with in the fiber is negligible. The tensile strength of glass
fiber is comparatively higher than that of the bulk form up to 4600 MPa. Fibers
are usually continuous and discontinuous which are generally long and short,
respectively. For short fiber, the average fiber length is increased resulting in their
improved mechanical properties. The aspect ratio typically ranges from 20 to
60 for a short fiber and 200 to 500 for long fiber. Reinforcing materials could also
exist in the form of shredded fibers, flakes, continuous roving fibers, woven
fabric, yarn, and mats of various combinations. Bringing the size of these fibers
down from macro to micro level is expected to give several amazing properties to
the reinforced polymers.
Composites were fabricated using different polymer processing techniques and
fibers with varied length to diameter ratio (L/D). This ratio and size play a crucial
role in their strength [27]. Fiber L/D ratio influences the mechanical properties and
water absorption characteristics. Low L/D ratio induces stress concentration and may
lead to decrease the strength [28]. The use of long fibers increases the mechanical
strength of WPC when processed with injection molding technique [29, 30]. Both
beneficial and limited or no effects of fiber length on mechanical properties using
extrusion were reported [31–33].

2 Nanofibers

2.1 Synthetic Nanofibers

Nanofibers are defined as fibers with diameters less than 100 nanometers and length
about some micrometers. These can be synthesized by melt processing, interfacial
polymerization, electrospinning, antisolvent-induced polymer precipitation, and
electrostatic spinning [34]. Nanofibers have extreme high aspect ratio which attri-
butes to their special properties when compared to nonwovens. Properties like lower
density, huge surface area to mass, tight pore size, and improved pore volume make
them ideal candidates for a wide range of filtration applications. The extensive study
on one-dimensional structures of nanofibrous compounds and their physical prop-
erties points the use of these materials in semiconductors, optical, sensors, electronic,
polymer fillers, and nonwoven porous membranes. Basic representation of the
nanofibers is given in Fig. 2.

2.2 Polymer Nanofibers

The diameter of polymer nanofibers is in nanometer. The surface area per unit mass
is larger and thus the surface can be easily functionalized. This property makes the
materials suitable for tissue engineering, clothing, sensors, etc. These fibers can also
be employed as reinforcement in composite materials. Electrospinning, phase sep-
aration, template synthesis, and self-assembly can be adopted for developing
426 A. Manayan Parambil et al.

Fig. 2 Basis representation

of nanofibers

polymer nanofibers. A large variety of polymers can be converted to nanofibers by

electrospinning technique. Mass production can be achieved through this process
[35]. Various applications of polymer nanofibers are depicted in Fig. 3.

2.3 Carbon Nano Fibers

Carbon fibers are developed using anisotropic carbon having carbon content of about
92–100%. Initially, they were prepared by carbonizing bamboo or cotton. Carbon
nano fibers are found to be promising candidates in areas such as reinforcement of
composites, energy storage, energy conversion, and self-sensing devices. Size is the
major difference between conventional carbon fibers (CCF) and carbon nano fibers
(CNF). Diameter of CCF is around micrometers and CNF is around 50–200 nm. The
typical CCFs were developed from high-strength polyacrylonitrile or meso-phase
pitch. Similarly, CNFs were prepared by catalytically vapor deposition growth and
electrospinning. The cup-stacked CNF and the platelet CNF can be prepared by
catalytically vapor deposition. Polymer fibers were used as precursors for the synthesis
of CNF via electrospinning technique, and the final properties of CNF depend on the
characteristics of polymer solution and processing parameters [36] (Figs. 4, 5, and 6).
Posttreatment approaches and production procedures highly influence the prop-
erties of the CNF [38]. The excellent properties of CNF include impressive creep
11 Fiber-Reinforced Composites 427

Fig. 3 Various applications of polymer nanofibers

Fig. 4 Difference between

CNF and CCF [37]
428 A. Manayan Parambil et al.

Fig. 5 Cup-stacked CNF structure formation (a–c) and platelet CNF structure (d) [37]

Fig. 6 Electrospinning setup for CNF fabrication [37]

resistance, high tensile strength of ~7 GPa, low density of 1.75–2.00 g/cm3,

improved modulus of <900 GPa, high thermal conductivity (1950 W/mK), and
excellent electrical conductivity. The resisting power of these materials against
oxidizing agents is very little, but is impervious to other chemicals. Within
aluminum or magnesium alloys, metal matrices, CNF showed extraordinary physical
properties. Thus, unique composites having astonishing thermal properties are
possible to fabricate. The theoretical calculation of the thermal coefficient of expan-
sion and the thermal conductivity reveal the potential of this material. Because of
these properties, CNFs can be used as reinforcing agents in polymer matrix, and
these novel materials have applications in military, aerospace, construction, medical,
and sporting goods [39].
11 Fiber-Reinforced Composites 429

2.3.1 Preparation of CNF Composites

In carbon nano fibers, individual fibers show tendency to form agglomerates due to
van der waals force of attraction between them. It will affect the overall performance
and final properties of the composites. Proper and uniform dispersion of CNFs is a
challenging task to obtain composites with improved properties. So, the dispersion
technique has a vital role in fabricating CNF composites. Polymer composites based
on CNF can be prepared either by melt mixing process or sonication process in low
viscosity solutions. Among these, melt mixing is the widely used method because of
its simplicity, less expensiveness, and convenience. Extrusion or roll mill, Haake
torque rheometer, and mini-max molder belong to the melt mixing method [40, 41].
All these methods involve shear mixing for getting proper dispersion of CNF. So it is
very important to find out low shear mixing technique to preserve the structure of
CNF. Surface treatments for CNF are another strategy to get proper dispersion of it in
polymer matrix. Here, compatibility between polymer matrix and surface functional
groups is the important parameter which predicts the final properties of the compos-
ites [42]. This will improve the dispersion and wetting properties of the nanofibers
which will also enhance the property of composite materials. This can even be
observed even at considerably reduced loads. The conductive filler surface can
even be functionalized or grafted. But depending on the thickness and functiona-
lization layer transport properties, the composite transport properties may reduce. So
certain parts of conductive layer should be selectively functionalized.

2.3.2 Properties of CNF Composites

Poly(ether ether ketone) nanocomposites incorporated with vapor-grown carbon
nanofibers (CNF) were fabricated by typical polymer processing techniques. Inves-
tigation of mechanical properties of the composite exposed a steady rise in tensile
stiffness and strength with nanofiber filling portions up to 15 wt% without negatively
affecting material’s ductility [43]. Multiscale fiber-reinforced composites (MFRCs)
were fabricated using vacuum-assisted resin infusion molding (VARIM) which
contains CNF and epoxy [44]. Similarly, by adopting very low fiber-loaded nano-
phased matrices, mechanical and thermal properties can be enhanced. During the
fabrication, nanoparticles can be trapped within the fiber preform mesh in inter-tow
regions which can be considered as its drawback. MRFs are the acceptable method
for developing carbon nanofiber/fiber-reinforced polymer composites. The surface
functionalization of CNF using amine and carboxylic acid groups improve compres-
sive strength and interlaminar shear strength (ILSS) [44]. Core-shell nanofibers were
electrospinned for interfacial toughening and self-healing of carbon-fiber/epoxy
composites [45]. The ultrathin self-healing fibers were contrived through electro-
spinning, where a core shell of dicyclopentadiene (DCP)-poly acrylonitrile (PAN)
nanofibers is formed in which liquid DCPD was enwrapped into PAN. The interface
of the carbon fiber fabrics neighbor to each other was integrated with these core-shell
nanofibers. After resin infusion and curing, they form ultrathin self-healing inter-
layers prior to resin infusion. Interfacial damages in composite laminates are self-
repaired using core-shell DCPD/PAN fibers. Vapor-grown carbon nanofibers were
found to be interesting additive for polymers in tribological applications since it acts
430 A. Manayan Parambil et al.

as a solid lubricant. Several studies have been reported on the effects of various filler
concentrations on the tribological and mechanical properties of various polymer
composites [46, 47]. Surface treatment of carbon nanofibers on the mechanical
behavior of polymer composites were investigated by several researchers. The
improved mechanical performance of the composites is due to the enhanced disper-
sion and interfacial attachment among fibers and the matrix [48, 49]. In addition,
decrement in the mechanical properties is also observed in some other cases [50].
Rheological study on polyethylene composites reinforced with vapor-grown
carbon nanofiber exposed the impact of temperature, frequency, and concentration
of nanofiber (up to 30 wt %) on the rheological properties of the composites
[51]. Nanofilled epoxy dispersions structure is highly sensitive to the rheology and
is evidenced from the relationship between the morphology and rheology [52]. Stud-
ies based on the correlation between electrical and rheological behavior of
CNF-filled composites was done by Paleo et al. [53]
Electrical properties, especially percolation threshold of CNF-based polymer
nanocomposites, depend on several aspects including CNF aspect ratio, dispersion,
distribution, alignment, and conductivity. Similarly, the crystallinity, surface tension
of polymer matrix, processing methods, and conditions also influence their electrical
properties. Several strategies are developed to diminish the percolation threshold in
polymer composites [54]. Table 4 summarizes the percolation threshold concentra-
tions that have been reported so far. It has been shown that posttreatments of CNFs
improve the electrical conductivity of composites. These treatments include carbon-
ization, graphitization, etching in air around 400–600
C, and soaking in nitric acid,
sulfuric acid, or sulfuric/nitric acid. Polymer showed improved interaction with
nanofibers after surface treatment. Moreover, different dispersion, distribution, wet-
ting, and final aspect ratio of nanofiber after compounding can be observed. The
CNF intrinsic conductivity may reduce the percolation threshold. Several other
parameters also play major role in improving the conductivity of composites. For
determining the conductivity of the composite, CNF surface area and morphology
are considerably significant than the intrinsic conductivity [55] Moreover, better
EMI shielding capability depends on the surface area of CF for their polymer
composites [56].
Compounding or molding instruments available are mini-max molder (MMM),
melt mixing in Haake mixer (MM-H), melt mixing in Brabender twin screw kneader
(MM-BTS), melt mixing in twin screw extruder (MM-TSE), in situ polymerization
(ISP), melt mixing in DACA mixer (MM-DACA), mechanical stirring (MS), mixed
in Brabender (MB), melt mixing in a two-roll mill (MM-TRM), heterocoagulation
(HT), solution processing (SP), melt mixing in chaotic mixer (MM-CM), and mixing
in thinky mixer (M-TM). Similarly, molding methods are injection molding (IM),
compression molding (CM), curing (C), and casting (CS).
Polymer nanocomposites containing carbon fibers have been broadly studied in
an effort to overcome the deficiencies of metal-based protections to prevent electro-
magnetic radiations. Carbon nanofibers can be used to raise the permittivity of neat
resin so as to attain enhanced radiation absorption in the frequency range 8–12 GHz.
Better dielectric properties were obtained at lower filler concentration by using CNF.
11 Fiber-Reinforced Composites 431

Table 4 Percolation threshold of different polymer composites containing CNF [54]

Polymer Fiber type Percolation threshold Compounding/molding
PP VGCNF 5.6 vol % MMM/IM
VGCNF 3 vol % MMM/IM
VGCNF 2.47 vol % MMM/IM
VGCNF 5.2 vol % MMM/IM
VGCNF 4.97 vol % MMM/IM
VGCNF 0.5 vol % MMM/IM
VGCNF 9–18 wt % MM-H/CM
VGCNF 18 wt % MM-BTS/CM
VGCNF 7.5 wt % MM-BTS/CM
VGCNF 4–5 vol % MM-TSE/IM
MWNTs 0.05 vol % MM-H/CM
MWNTs 8 wt % MM-H/CM
CB 9.5 wt % MM-H/CM
CB 3 phr MM/CM
PC VGCNF 6.3 wt % ISP/CM
VGCNF 7.5 MM-DACA/CM
MWNT 1–1.5 wt % MM-DACA/CM
VE 2 wt % MS/C
4 wt % MB/C
PE VGCNT 2.5 phr MM-TRM/CM
PA-6 MWNT 4–6 wt % MM-TSE/IM
P(S-co-BuA) MWNT 1.5 vol % HTCS
PS VGCNF ˂1 vol % HT/CM
VGCNF 1 wt % SP/CS
PMMA VGCNF 8 phr MM-TRM/CM
6 wt % MM-BTS
2 wt % MM-CM
Epoxy 0.5 wt % SP/C
VGCNF 2.5 wt % M-TM
SWNT 0.0052 vol % SP/C
SWNT 0.062 wt % SP/C
MWNT 0.022–0.04 wt % SP/C

The investigation of the influence of filler aspect ratio on the electromagnetic

properties of epoxy-amine resin reinforce with carbon nanofibers confirmed the
role of filler aspect ratio. The study suggest to choose nanofibers with higher value
to design conductive lightweight materials with reduced cost, lower filler amounts,
and improved electrical properties [57]. Carbon nanofibers-reinforced conductive
foam structures are very promising for the use in lightweight EMI shielding mate-
rials. Electromagnetic absorbers (EMA) are now attaining ample attention particu-
larly in the field of microwave frequencies applications. CNF/epoxy composites and
the effect of carbon nanofibers dispersion on their microwave absorbing properties
was investigated by Nanni et al. [58] Two different dispersion techniques are used to
432 A. Manayan Parambil et al.

prepare the composites. Different absorbing performance is obtained for different

mixing strategies at same filler loading and sample thickness. It was proved that the
absorbing performance and the electromagnetic properties are severely influenced by
the material microstructure. So, much care should be taken during material prepara-
tion. Similarly, repeatability has to be ensured for reliable practical application.
Carbon nanofibers can be used to improve the thermal conductivity of the
polymer composites. It was noted that for the thermoplastics, the use of carbon
nanofibers increase the working temperature range by 100
C. Upon the addition of
nanofibers, the rate of polymer crystallization get increased with negligible change in
the mechanism of nucleation. This was evidenced from the Avrami method [59, 60].
It was found that dispersion of CNF and the formation of percolated network of CNF
in polymer matrix have a significant effect on the thermal conductivity of polymer
composites [61]. BN/VGCNF/rubbery epoxy hybrid composites can be used for
fabricating thermal interface materials (TIMs) having thermal conductivity and
electrical insulating property. At thick bond lines, hybrid composites offer improved
interfacial thermal transport. This was studied from their thermal contact resistance
measurements. Here, thermal conductivity was imparted by CNF. So, as the CNF
content is increased, the property is enhanced [62]. Self-assembled multilayered
carbon nanofiber nanopaper was used for enhancing electrical actuation of shape
memory polyurethane nanocomposite [63]. Bio-based polyester reinforced with
vapor-grown carbon nanofiber is employed for electroactive shape memory perfor-
mance [64]. Life cycle energetic effect concomitant with the production and use of
polymer nanocomposites (PNC) reinforced with carbon nanofiber (CNF) is investi-
gated by Vikas et al. [65] The use of PNCs reinforced with CNF and CNF-GF in the
automobile body panel exposed the use of lower CNF-loaded PNCs. These com-
posites show potential to save the net life cycle energy when compared to steel. This
owes to the enhanced fuel economy benefits.

2.4 Carbon Nanotube Fibers

CNT arrays, films, and fibers can be conveniently utilized than individual CNTs.
Individual CNTs provide extraordinary physical and mechanical properties to man-
ufacture these high-performance macrostructures. CNT fibers showed greater spe-
cific strength and modulus than polymeric and carbon fibers. This is due to axially
aligned and highly packed CNTs along the fibers [66]. Moreover, they require high
energy to break and are flexible compared to commercial fibers. Furthermore, they
show reasonable thermal and electrical conductivities. Flexible medical devices,
transmission lines, biosensors, high-performance composites, and microelectrodes
are the expected area of application for CNT fibers [67]. CNT fibers are fabricated
through spinning processes. Some are lyotropic liquid crystalline suspension of
nanotubes, MWCNTs previously grown on a substrate, aerogel of SWCNTs and
MWCNTs. Polymer infiltration and surface modification are very important post-
treatment process. Chemical bonding and polymer infiltration can be obtained by
introducing abundant amount of functional groups [68]. Figure 7 represents various
11 Fiber-Reinforced Composites 433

2
Polymer Press
matrix

Woven
3
cloth

CNTs

Constant pressure
Prepreg ply
Aligned
CNT forest Roller

Silicon substrate

Fig. 7 (I) Representation of laminated composite fabrication: (1) fiber cloth aligned with nano-
tubes; (2) stacking of fiber cloth grown with matrix-infiltrated CNT; (3) hand lay-up fabrication of
nanocomposite laminates. (II) Transfer-printing of vertically-aligned CNTs to prepreg: (A) transfer-
printing process demonstration; (B) CNT forest fully transplanted to the surface of a Gr/Ep prepreg
ply from its original silicon substrate; (C and D) CNT forest SEM images, indicating the CNT
orientation after transplantation

manufacturing routes to produce CNT fiber-reinforced composites to get improved

properties [69, 70].
CNT fiber stretchable conductors can be fabricated with modest prestraining –
then buckling approach [71]. A thin layer of liquid PDMS is coated on to CNT fibers
434 A. Manayan Parambil et al.

before transferring to the prestrained substrate. The fiber-PDMS substrate interfacial

bonding can be thus enhanced and facilitate the buckling formation.

2.5 Metal Oxide Nanofibers

Metal oxide nanofibers are produced by the combination of electrospinning and sol
gel methods. Metal oxide precursors are first mixed with polymer solution and
calcinated at high temperature. During this process, the polymer is removed and
metal oxide nanofibers are obtained. Silica is the most common filler used to
improve thermomechanical properties of polymers in microelectronic devices.
This is because of its electrical insulation properties, low CTE, good mechanical
propertie,s and low cost. But micron-sized particles are needed in order to get
desirable mechanical properties. This can be achieved by the synthesis of nanosized
silica fibers. Enhancements in the thermal conductivity and coefficient of thermal
expansion were observed in silica nanofibers-filled epoxy when compared to silica
nanoparticle-filled epoxy at low filler loadings. This high aspect ratio-filled epoxy
has the potential to be used as a new generation of high-efficiency electronic
encapsulation and underfill material [72].

3 Nanoscale Bio-Fillers

Science and technology now focus on producing more sustainable and environmentally-
friendly materials due to the problems involved in plastic recycling and scarcity of the
petroleum-based materials [73]. Nanoscale bio-fillers have engrossed plentiful attention
in practical applications and academic research because of its excellent reinforcing
capability to the polymer matrix. Bio-nanofillers, due to its greater aspect ratio, superior
surface area, and exceptional properties, show substantial applications in various arenas.
The use of nanocomposites with bio-nanofillers offers novel technological and com-
mercial opportunities in automotive, electronics, and biotechnology industries.
We can classify the biomass-based nanofillers into three types:

1. Nanocellulose
2. Nanochitin
3. Starch nanocrystals

The development in the production of bio-fillers like cellulose, chitin, chitosan,

and starch at the nanoscale attain abundant potential to diminish most of the
sustainability issues. They are biodegradable and renewable. In this perspective, it
is essential to generate more knowledge regarding the potential use of these
bio-based fillers in various industrial applications. The use of bio-fibers as fillers is
a growing trend nowadays and is attracted by many manufactures. The high specific
stiffness, low cost, and flexibility during polymerization make them suitable for
reinforcing in polymer composites.
11 Fiber-Reinforced Composites 435

3.1 Nanocelluloses

Nowadays, scientists are focused on the isolation and characterization of novel forms
of cellulose: various forms are nanocrystals, whiskers, nanofibrils and nanofibers.
Nanocelluloses are cellulosic materials having one dimension in nanometer. Chem-
ically, cellulose is composed of D-glucose units linked with unbranched β (1–4)
glycosidic bond [74]. Natural fibers consist of lignin matrix embedded with cellulose
fibrils and can be considered as natural composites. The crystallinity and cellulose
nature influence the reinforcing efficiency of natural fiber. Chemical compositions of
some typical cellulose-containing materials are shown in Table 5. Nanocelluloses
have drawn much attention due to their unique properties, like high tensile strength,
surface area to volume ratio, Young’s modulus, and low coefficient of thermal
expansion [75, 76]. All of these excellent properties make nanocellulose as a
promising and potential material for the reinforcement in polymer nanocomposities
[77] Nanocelluloses can be classified into cellulose nanofibers (CNFs), cellulose
nanocrystals (CNCs), and bacterial nanocellulose (BNC). The CNCs have nano-
dimensions in both length and diameter wise, whereas the CNFs have diameter at
nanoscale and length up to several micrometers. Moreover, CNFs have both amor-
phous and crystalline region. But CNCs only have crystalline phase as shown in
Fig. 8. Normally CNFs and CNCs have been extracted via chem mechanical
treatments and strong acid hydrolysis, respectively. In the acid hydrolysis process,

Table 5 Chemical compositions of some typical cellulose-containing materials. (Copyright 2012

[78]. Modified with permission from Elsevier)
Source Cellulose (%) Hemicellulose (%) Lignin (%)
Hard wood 43–47 25–35 16–24
Soft wood 40–44 25–29 25–31
Bagasse 40 30 20
Coir 32–43 10–20 43–49
Corn cobs 45 35 15
Corn stalks 35 25 35
Cotton 95 2 1
EFB 50 30 17
Flax(retted) 71 21 2
Flax (unretted) 63 12 3
Hemp 70 22 6
Henequen 78 4–8 13
Jute 71 14 13
Kenaf 31 26 18
Ramie 76 17 1
Sisal 73 14 11
Sunn 80 10 6
Wheat straw 30 50 15
Banana fibers 63–64 19 5
436 A. Manayan Parambil et al.

Fig. 8 Representation of fabrication of cellulose nanomaterials from different sources [79]

strong acid like sulfuric acid have been employed for the reaction and it destroys the
amorphous portions (disordered region) and lead to the nanocrystal structure.
Many procedures are reported for the extraction of cellulose nanofibers (CNFs).
Steam explosion coupled with the mild acid hydrolysis is generally employed as an
efficient method to extract cellulose nanofibers. Fortunati et al. [80] reported the
extraction of the cellulose nanofibers (shown in Fig. 9) from the sunflower stalks by
the steam explosion process in an autoclave. Chirayil et al. [81] employed the steam
explosion process for extracting cellulose nanofibers from isora fiber in an autoclave.
This techniques involved alkaline treatment, bleaching, acidic steam treatment, and
homogenization. The prepared cellulose nanofibers have nanofibrillar network-like
structure with high crystallinity and good thermal stability. High-intensity ultrasonic
treatment is the technique for the extraction of cellulose nanofibers.
Nanocellulose fibers were prepared by pretreating cellulose in NaOH/urea/thiourea
solution. The fibers were then defibrillated by ultrasonication. They achieved high yield
of 85.4% [77]. The obtained nanocellulose fibers were about 30 nm in diameter having
cellulose II crystal structure. Cryocrushing is an alternative method for producing
nanofibers. During the process, the frozen fibers are subjected to high impact forces
where the ice crystals exert pressure on the cell wall leading them to rupture and form
microfibrils. Nanofibers were isolated from soybean stock using cryocrushing together
with a high-pressure fibrillation process. The fibers were having diameters in the range
50–100 nm. Grinding is the process for the extraction of cellulose nanofibers from
11 Fiber-Reinforced Composites 437

Fig. 9 TEM image of the

cellulose nanofibers [80]

microcrystalline cellulose [82]. Cellulose nanofibers were obtained with uniform width
of 15 nm from wood by the grinding in an undried state [83].
CNCs are typically prepared by acid hydrolysis of the macrocellulose including
cotton linters, wood pulp, and microcrystalline cellulose. A strong acid treatment to the
amorphous region in the cellulose microfibrills helps to extract the highly crystalline
part. The subsequent rod-like crystals after the acid hydrolysis are known as cellulose
nanocrystals and their diameter usually ranges from 5 to 20 nm. The size depends on the
nature of the cellulosic source and condition of acid hydrolysis.
Danial et al. [84] extracted CNCs from waste paper by acid hydrolysis using 60%
(V/V) H2SO4 solution at 45
C with constant stirring. CNCs with length ranged in
100–300 nm, as shown in Fig. 10, were obtained and also observed that newspaper
can serve as a precursor for the effective production of CNCs. Similar results were
reported by Kargarzadeh et al. [85], using H2SO4 acid hydrolysis of kenaf fibers.
They extracted the CNCs from kenaf bast fibers by mechanical stirring using 65 wt%
of H2SO4 at various reaction times.

3.2 Nanochitin

Chitin can be considered as the abundant naturally occurring polymer next to

cellulose. They are observed in the cell wall of yeast, fungi, and exoskeleton of
arthropods as their structural constituent. Chitin and cellulose are similar type of poly-
saccharides where cellulose have hydroxyl group and chitin have acetamide group.
Chitin has high molecular weight with β (1-4) (N-acetyl-D-glucoamine) as shown in
Fig. 11. The high crystallinity and mechanical strength of nanochitin make it as a suitable
438 A. Manayan Parambil et al.

candidate for reinforcement in polymer nanocomposites. Chitin is natural, nontoxic,

nonallergic, antimicrobial, and biodegradable and is insoluble in water.
Several literatures have been reported about the extraction of nanochitin from
different sources. Acid hydrolysis is the well-known procedure to extract nanochitin
from sea food wastes. Chitin nanowhiskers were successfully extracted from crab
shells and squid pens by hydrochloric acid hydrolysis [86].
Similarly, Gopalan et al. [87] prepared protein-free chitin whiskers suspensions
via hydrolyzing the purified chitin sample with 3N HCl at the boil for 90 min under
stirring. Chitin nanowhiskers had aspect ratio close to 16 which is shown in Fig. 12.

3.3 Starch Nanocrystals

Starch has established substantial attention during the past two decades due to its
high strength and biodegradability. Amylose and amylopectin together form starch.

Fig. 10 TEM image of cellulose nanocrystals [84]

Fig. 11 Chitin chemical

structure with β-1,4 linkage CH3

OH O NH

HO
O
O
O
O
HO
NH OH

O CH3
n
11 Fiber-Reinforced Composites 439

Amylose is a linear or slightly branched (1 ! 4)-α-D-glucan and amylopectin is a

highly branched (1 ! 4)-α-D-glucan short chains linked through α-(1 ! 6) linkages
[88]. Figure 13 illustrates the inner structure of the starch granule and chemical
structure of amylopectin. Chen et al. [89] extracted starch nanocrystals from potato
starch granules having width of 10–20 nm and length of 40–70 nm (Fig. 14). They
dispersed 36.725 g of potato starch granules in 250 mL 3.16 M sulfuric acid aqueous
solution by stirring for 5 days at 40
C.

3.4 Bio-Nanofillers as Reinforcement for Polymer

Nanocomposites

Abundant reports are there about the reinforcing effect of the bio-nanofillers like
cellulose nanocrystals, cellulose nanofibers, chitin nanocrystals, and starch nano-
crystals. Cellulose nanocrystals or cellulose nanowhiskers are used as reinforcement

Fig. 12 TEM images of

chitin whiskers [87] (inset:
typical electron diffractogram
of chitin fragments)

Fragment of OH
crystalline lamellae Amorphous O
material HO OH
HO OH O
O OH
Amylopectin HO OH O
lamellae OH
O n
O
HO HO OH
OH
O
HO OH O
O
HO OH O
Hilum
Om OH
HO OH O
O OH
Amorphous growth ring Crystalline growth ring
HO OH

Fig. 13 Representation of starch granule structure and amylopectin molecule [90]

440 A. Manayan Parambil et al.

Fig. 14 TEM image of starch

nanocrystals from potato
starch granules [89]

in plastic and rubber matrices. Nanocellulose are also used as reinforcement for
various polymer including poly(propylene), poly(styrene), and high density poly
(ethylene) [91]. Similarly, cellulose nanowhiskers showed strong reinforcement
capability [92, 93]. Cellulose nanowhiskers are derived from tunicate and reinforced
with styrene and butyl acrylate copolymer latex. Even at low cellulose nanowhisker
loading, the nanocomposites had significant enhancement in mechanical properties
than the neat polymer in its elastomeric effect.
Cellulose nanofibers can be isolated from soybean source via combined mechan-
ical and chemical treatments. The addition of cellulose nanofibers will significantly
change the stress-strain behavior of the composites. There will be improvement in
the thermal properties of poly(vinyl alcohol) PVA when cellulose nanofibers is added
[82]. Cellulose nanofibers-reinforced PLA nanocomposite can be prepared by twin
screw extrusion. The tensile modulus and strength were increased for nano-
composites with 5 wt% cellulose nanofibers from 2.9 GPa and 58 MPa to 3.6 GPa
and 71 MPa correspondingly [94].
Colloidal suspension of chitin nanowhiskers and latex of both unvulcanized and
prevulcanized NR can be used to prepare chitin nanowhisker-reinforced NR nano-
composites. The solid nanocomposite films were developed by casting and evapo-
rating methods. Evaporated samples of chitin whiskers having nano size are
observed to form a three-dimensional rigid network. These observations were
based on the bound rubber content, diffusion coefficient, and relative weight loss
values [87]. On carrageenan polymer matrix, the chitin nanofibers are well dispersed
and thus form smooth and flexible composite films. Carrageenan film modulus and
tensile strength increase significantly ( p < 0.05) after reinforcement with chitin
nanofibers (up to 5 wt%). Moreover, they were prominent against the growth of
Gram-positive foodborne pathogen [95]. The tensile testing of the chitin nano-
whisker films prepared by using ionic liquid 1-allyl-3-methylimidazolium bromide
(AMIMBr) in polyvinyl alcohol (PVA) matrix indicates mechanical property
enhancement with increase in the ratio of PVA to chitin [96]. The mechanical
performance were studied for starch-based composite reinforced with novel chitin
11 Fiber-Reinforced Composites 441

nanoparticles prepared by blending glycerol plasticized potato starch (GPS) and

chitin nanoparticles (CNP) by casting and evaporation [97]. CNP showed uniform
dispersion in the GPS matrix at low loading levels. In GPS/CNP composites, the
filler and matrix were having impressive interaction. This results in improving the
glass transition temperature, tensile strength, storage modulus, and water vapor
barrier properties. But aggregation of CNP occurs at higher loading (greater than
5 wt %) by negatively affecting their properties. The mechanical properties of the
cross-linked carboxylated SBR composites reinforced with chitin nanocrystals were
water-responsive. The swollen composites exhibited decreased strength and modu-
lus. The significant reinforcement effect of chitin nanocrystals on cross-linked
carboxylated SBR was attributed to the unique structure of chitin nanocrystals and
their interfacial interactions in the composite [98]. The prominent improvement of
mechanical performance of starch nanocrystals developed from potato starch gran-
ules is ascribed to persistent stress of rigid starch nanocrystals and stress transferring
interceded with robust interaction on the interface between starch nanocrystals
nanofiller and waterborne poly urethane matrix [89]. Pullulan film reinforced with
starch nanocrystal nanocomposites can be prepared using an amorphous matrix of
sorbitol-plasticized pullulan with aqueous suspension of starch nanocrystals as the
reinforcing phase. Because of the starch nanocrystals interaction and filler-matrix
interaction, there is restriction of the mobility of pullulan chains. These conse-
quences in increasing the amount of nanocrystals and higher temperature shift of
glass transition temperature. For the samples conditioned at different environments,
the strain at break in the samples are drastically decreased by enhancing the tensile
strength and the Young’s modulus. This can be attributed to the addition of the
nanocrystals [99].

4 Summary

The profuse use of various fiber-reinforced composites in different areas shows the
importance of studying and investigation about them. Different types of fibers offer
different properties and can be applied in variety of areas. From macro to nanoscale,
these materials showed fantabulous changes in their properties. Knowledge on fibers
and fillers used in fiber-reinforced composite is very important to tailor-make new
materials having superior properties. Development of new composite indeed needs
better understanding on fiber-filler interaction. So, studies on these materials show
exceptional importance nowadays.

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Composites and Nanocomposites
12
Shah Mohammed Reduwan Billah

Contents
1 General Aspects of Composites and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
2 Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 450
2.1 Different Types of Microcomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
2.2 Basic Compositions and Selected Features of Composites . . . . . . . . . . . . . . . . . . . . . . . . . 454
3 Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
4 Types of Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
4.1 Zero-Dimensional Nanocomposites (Such as Nanoparticles Based Systems) . . . . . 458
4.2 One-Dimensional Nanocomposites (Such as Nanotubes and Nanowires) . . . . . . . . . 459
4.3 Two-Dimensional Nanocomposites (Nanolayers Based Systems) . . . . . . . . . . . . . . . . . 459
5 Selected Features of Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
5.1 Crack Pinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
5.2 Crack Deflection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
5.3 Immobilized Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
5.4 Debonding and Plastic Voids Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
6 Discussion on Different Types of Selected Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . 461
6.1 Polymer/Carbon Nanotubes Based Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
6.2 Polymer/Metal Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
6.3 Polymer/Clay Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
7 Designing Composites and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
8 Processing of Composites and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
8.1 Melt Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
8.2 Solution Mixing or Solvent Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
8.3 In Situ Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
8.4 Electrospinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
8.5 Layer-by-Layer Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471

S. M. R. Billah (*)
University of East London, Stratford Campus, London, UK
CCIRA UK Limited, Galashiels, UK
Department of Chemistry, Durham University, Durham, UK
School of Textiles and Design, Heriot-Watt University, Galashiels, UK
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 447

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_15
448 S. M. R. Billah

9 Environmental Stimuli-Responsive and Functional Polymer Composites

and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
10 Selected Behaviors of Composites and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
10.1 Reinforcement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
10.2 Electrical Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
10.3 Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
10.4 Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
10.5 Glass Transition Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
10.6 Barrier Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
10.7 Antiflammibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478
11 Challenges for Composites and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478
12 Bio-composites, Green Composites, and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
12.1 Biocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
12.2 Cellulose Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
12.3 Cellulose Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
12.4 Stimuli-Responsive Smart Cellulose Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
12.5 Bio-inspired Stimuli-Responsive Mechanically Dynamic Composites . . . . . . . . . . . 482
13 Single Polymer Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
14 Future Directions in Composites and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
15 Conclusion and Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488

Abstract
In general, a composite is usually made up of two or more materials having two or
more phases with heterogeneous characters, where at least one is in a microscopic
scale. In addition, a composite can be classified as a nanocomposite when at least
one of the reinforcement dimensions is in the nanometer range (from 10 to 200 nm).
Both composites and nanocomposites have many promising mechanical, thermal,
electrical, optical, and other interesting properties that make them a field of current
active research interest both in academia and industry. This chapter selectively
covers both fundamental and applied research involved mostly with polymer-based
composites and nanocomposites along with a brief discussion on the future research
directions for further improvements on high-performance composites and nano-
composites for a variety of conventional and high-tech applications.

A composite is usually made up of two or more materials having two or more phases
with heterogeneous characters (where at least one is in a microscopic scale). They can
be of different types. For example, a fiber-reinforced composite contains fibers of high
strength and modulus, with dimensions on the order of microns, embedded in or
bonded to a matrix with distinct interfaces between them. In this system, both fibers
and matrix can retain their distinctive physical and chemical characters; however, in
the resultant composite system, they produce a combination of properties that cannot
be achieved with either of the constituents acting alone. Additionally, a composite can
also be classified as a nanocomposite if at least one of the reinforcement dimension is
in the nanometer range (10–200 nm). A nanocomposite illustrates many great prom-
ises not only in terms of superior mechanical performances, but also in terms of
superior thermal, electrical, optical, and other properties. Usually, these properties are
12 Composites and Nanocomposites 449

manifested, at relatively low-reinforcement volume fractions. Some of the main

reasons for such highly improved properties are (a) the properties of nano-
reinforcements are considerably higher than the reinforcing fibers in use; (b) the
ratio of their surface area to volume is very high, which provides a greater interfacial
interaction with the matrix. Additives used in the production of polymer nano-
composites can be of different types, such as (a) one-dimensional (e.g., nanotubes
and fibers), (b) two-dimensional (such as layered minerals like clay), (c) zero-
dimensional (e.g., spherical particles). Over the past two decades, both micro- and
nanocomposites have been successful to attract active research interests both in
academia and industry because of their fantastic properties, such as outstanding
mechanical properties (such as improvement in elastic stiffness and strength by adding
only a small amount of the nanoadditives). These advantages can be contributed to the
large surface area to volume ratio of nanoadditives when compared to the micro- and
macroadditives. Some significant and superior characteristics of polymer micro- and
nanocomposites include (a) barrier resistance, (b) flame retardancy, (c) scratch/wear
resistance, (d) optical, magnetic, and electrical properties. This chapter covers both
fundamental and applied research involved mostly with polymer-based micro- and
nanocomposites, also presents possible directions for further improvements on high
performance micro- and nanocomposites. Additionally, micro- and nanocomposites
can also contain a huge variety of materials (such as functional materials, environ-
mental stimuli-responsive materials, materials with specific target applications) with
potentials for many conventional and high-tech industrial applications. So, this chapter
also briefly covers selective aspects of different types of functional and environmen-
tally responsive micro- and nanocomposites along with their particular current and
potential applications.

1 General Aspects of Composites and Nanocomposites

Continuous academic and industrial research and development activities in the field
of micro- and nanocomposites and their profound impacts on the designs and
applications in materials used in various sectors involved with our everyday life
and have an impact in our ever changing life-styles. Traditional materials are being
gradually replaced by composite materials for attaining higher technical perfor-
mances with cost-effectiveness. Composites are practically in use for ages, such as
(a) concrete (which is basically a mixture of stones held together by cement) is a
familiar material for building; (b) some particular natural composites (which are
made of wood and bone) have been known to human civilization for a long time.
However, during the last 40 years, the production of synthetic composites has been
rapidly increased where one can link the spur of this rapid expansion over the last
few decades with the development of carbon fibers (in the UK) and boron fibers
(in the USA) in the early 1960s. These new fibers have high elastic characters which
provide significant increase in the stiffness of composites (due to high modulus-to-
weight and stiffness-to-weight ratio presented by these composites) which are
suitable for a variety of applications [1–10]. For example, highly ordered polymer
nanocomposites are complex materials which show sound morphological characters
450 S. M. R. Billah

due to their variations in compositions, structures, and properties on a nanometer

length scale. Polymer nanocomposites are of different types. Metal-polymer nano-
composites are one of the important class and they are attractive due to their potential
applications in low cost, high metal surface areas. A wide range of metals used in
polymer nanocomposites are mostly involved with their one of the main application
focused on catalytic systems which particularly use specific metals (such as Pt, Ni,
Co, and Au, with known catalytic activities). Some of the most frequently utilized
techniques usually used to prepare polymer/CNT and/or polymer/clay nano-
composites are (a) melt mixing, (b) solution casting, (c) electrospinning, and
(d) solid-state shear pulverization. Variety of high-tech and conventional applica-
tions of nanocomposites make them a matter of current active research item and
some of the potential applications of polymer/CNT and/or polymer/clay nano-
composites include (i) photovoltaic devices, (ii) optical switches, (iii) electromag-
netic interference (EMI) shielding, (iv) aerospace and (v) automotive materials,
(vi) packaging, (vii) adhesives, and (viii) coatings [11–32]. This chapter covers a
broad range of topics mostly related to polymer based micro- and nanocomposites
(such as polymer/carbon nanotubes, polymer/metal nanospheres, polymer/clay
nanoplatelets micro- and nanocomposites). This chapter also presents different
issues involved with the general overview, synthesis, and applications of micro-
and nanocomposites in order to provide a general understanding on the fundamental
features of these materials for both conventional and high-tech advanced materials.

2 Composites

Composites are made from two or more constituent materials with significantly
different physical or chemical properties which have the capability to provide superior
and unique characteristics different from their individual components [1]. Micro-
composites are essentially a type of composites and people made and used composite
for many centuries, for example, the earliest uses of composites date back to the 1500s
B.C. when early Egyptians and Mesopotamian civilizations used a mixture of mud and
straw to create strong and durable buildings. Fiber reinforced composites are another
type of example which is the most common configuration for composite system. In
addition, the modern era of composites begins with the development of synthetic
polymers, such as plastics (such as vinyl, polystyrene, phenolic, and polyester) that
were developed in early 1900s. These plastics alone could not provide enough strength
for structural applications, as a result reinforcement was needed in order to provide the
strength and rigidity. In this context, the easy processing character provides the great
potential as composite matrix materials for these polymeric materials. As for instance,
Owens Corning introduced the first glass fiber in 1935 and later the glass fiber was used
to reinforce plastic polymers as the pioneer work of the Fiber Reinforced Polymers
(FRP) industry as we know it today. When a reinforced polymer is prepared by the
combination of a plastic polymer, it gives an incredibly strong structure and also
lightweight materials. Different wars incubated the seeds for many of the greatest
advancements in composites. The fiber reinforced polymer industry was brought into
12 Composites and Nanocomposites 451

real production from laboratory and developed extremely fast due to the need of
lightweight applications in military aircraft during the World Wars. Due to the light-
weight and strength of the composites, the engineers used these materials for various
diverse range of applications. For instance, it was discovered that fiberglass composites
were transparent to radio frequencies, and then the material was applied in sheltering
electronic radar equipment. People began to try to fit composite into other markets in
order to overcome the lower demand for military products when time elapsed into the
peaceful times. As for instance, in the 1970s the composites industry began to mature
and better plastic resins and improved reinforcing fibers were developed. A further
example include the development of an aramid fiber known as Kevlar by Du Pont and
carbon fiber was also developed around this time and these new fibers with improved
properties brings more choice for the fiber reinforced composites [1]. At present, the
current focus on the composite industry is on various functional applications of
composite in different advanced areas, for example, in the areas of renewable energy.
In addition, corrosion chemical resistant composites are highly resistant to chemicals
and will never rust or corrode and boats made with fiberglass can stay in the highly
corrosive salt water without any rusting. Composites with conductive particles dis-
persed in polymers have the capability to provide tunable conductivity and are widely
used in industry as a type of conducting polymers. In most recent scientific studies,
composites utilize even better fibers and resins and many of which incorporate nano-
materials to provide nanocomposites [2, 3]. Composites are often carefully designed for
specific uses which are unlike many natural and artificial materials that are usually
applied by chance only after they have been discovered or invented for particular
applications. These composites have now been used for a wide range of products (such
as from stealth bombers to smart cars and from bridges to oil rigs) although they were
originally developed as light and strong materials for the aerospace industry in the
mid-twentieth century [2–5, 8–15, 23–35]. Composites are usually synthesized by the
combination of two or more natural or artificial materials in order to maximize their
useful properties and minimize their weaknesses. Glass-fiber reinforced plastic (GRP)
is one of the oldest and well-known composites which is made by the combination of
strong and brittle glass fibers with flexible plastic to provide a composite material that is
tough but not brittle. For example, composites have many typical applications in place
of metals due to their similar strength but much lighter than metals. Most composites
have fibers of one material which are tightly bound into another material that is termed
as matrix. Similar to adhesive, the matrix binds the fibers together and makes them
more resistant to external damage; however, the fibers make the matrix relatively
stronger and stiffer and provide the desired resistance to cracks and fractures in the
composite. For fiber-reinforced composites, in usual practice, different types of mate-
rials are used as fibers and matrix (although single polymer composites are also
developed for various purposes). Typically used materials as fibers include (a) glass,
(b) carbon, (c) silicon carbide, (d) asbestos. Examples of generally used materials as
matrix include (a) different types of polymers (such as natural and synthetic polymers),
(b) metals (e.g., gold, aluminum, silicon, platinum), (c) ceramic materials [36–47].
They are useful for the production of many conventional and high-tech composites
widely used in a variety of industrial applications [1, 2, 48–55].
452 S. M. R. Billah

2.1 Different Types of Microcomposites

As already stated above that microcomposites are a type of composites, so the divisions
of microcomposites are closely aligned with the types of composites. As a result, for a
better explanation, different types of matrix which are used in various applications in
order to produce common types of composites are briefly described here.
Polymer matrix composites – GRP (Glass Reinforced Plastic) is a well-known
example of this type, where ceramic fibers are commonly used in a combination with
a plastic matrix. There are other hundreds of examples of polymer matrix composites
where different polymer matrices are used along with different additives.
Metal-matrix composites (MMCs) – this type of composite typically embed
silicon carbide fibers in an alloy matrix (made of aluminum and magnesium).
However, other matrix materials, for example, titanium, copper, and iron, are also
used. There are many applications of MMCs some of main applications include
(a) in sports items, (b) in missile guidance systems.
Ceramic-matrix composites (CMCs) – it is another major type composites. For
instance, silicon carbide fibers fixed in a matrix made from a borosilicate glass. The
ceramic matrix provides them a required suitability for their useful applications in light-
weight, high-temperature components, such as parts for airplane jet engines [1–14].

2.1.1 Fiber-Reinforced Composites (FRCs)

A fiber-reinforced composite (FRC) is a mixture of two or more distinct constituents
on a microscopic scale with different properties (e.g., the fiber/fabric reinforcement
and the matrix) [1]. The reinforcement can be in either in a continuous or discon-
tinuous form. Additionally, fiber-reinforced composites can be classified based on
the nature of reinforcement as shown in Table 1.
The orientation of the reinforcement can be designed to give the correct level of
mechanical properties where needed. The matrix can be of different types including
polymer, ceramic, metals, etc. Polymers are the most common matrix for composite
materials [1]. The mechanical properties of different classes of matrix material vary
considerably. In addition, the processing techniques of different types of composites
also have differences in some aspects which are shown in Table 2.
Another possible classification can be made according to the nature of the
additional phase included within the composite structure, so that it is possible to
identify two different classes of composite materials.

2.1.2 Nanoreinforced Composites

Nanoreinforced composite systems are based on the embodiment of nanoscaled
fillers and nanomodification represents a reliable and solid procedure in order to
produce next-generation of composites since small quantities are needed for enhanc-
ing their mechanical properties and modifying thermo-electrical behavior. Nano-
scaled reinforcing can be in the form of nanoparticles, nanoplatelets, or nanotubes
which are usually used by reinforcing both thermoset and thermoplastic polymers.
More complex systems can be prepared by applying the nanoreinforced polymers as
matrices for preparing multiscaled composites. These systems are characterized by
 12

Table 1 Classification of fiber-reinforced composites

Composites and Nanocomposites

Composites
Fiber reinforced Particle reinforced Structural
Single layer Multilayer Random Preferred Laminates Sandwich
Continuous fiber reinforced Discontinuous fiber Laminates Hybrids orientation orientation panels
reinforced
Unidirectional Woven Random Preferred
reinforcement reinforcement orientation orientation
453
454 S. M. R. Billah

Table 2 A general classification of composite processing. [33–36]

Composite Processings
Processing of thermoset composites Processing of thermoplastic composites
Short-fiber based Continuous fiber based Short-fiber based Continuous fiber
composites (such as composites (e.g., lay- composites (for based composites
injection, compression up, filament winding, instance, injection (e.g., thermoforming,
and liquid molding, liquid molding, and compression lay-up, compression
spray-up) pultrusion) molding) molding)

enhanced properties emerged from the superimposition of the nanoeffects provided

by the nanofillers and the traditional effects of the traditional microsized long fibers
[1, 2, 56–71].

2.1.3 Hybrid Composites

Hybrid composites are prepared including particular engineered phases within the
traditional composite structure and by employing specific properties of such com-
ponents. However, it is possible to enable extra reinforcement mechanisms or
activate nonstructural features. For example, components of hybrid composites
include metals and nanofluids through thickness reinforcements, optical fibers, and
piezoelectric materials [1, 2, 33, 72–88].

2.2 Basic Compositions and Selected Features of Composites

Every major technical and scientific revolution always takes place in accompany of
radical transformations in the field of material science which is clearly observed form
the study of scientific history. At present microcomposite technology has an impor-
tant role in modern engineering which is usually used to replace the traditional
metallic materials in several industrial applications (e.g., aerospace, automotive, and
shipping industry) in order to improve mechanical properties and reduce structural
weight. One of the particular advantages of this kind of material include the
possibility of using this for tailoring the properties of a specific part for meeting
the requirements of different specific applications [89–120]. This opportunity has the
capacity for leading to a material specifically designed and manufactured for that
application by avoiding the problem of sophisticated designing [121–133]. In prin-
ciple, a microcomposite is usually prepared by using two or more components that
differ in form or composition on a macroscopic scale and are characterized by
complementary properties. For example, the main difference with a traditional
alloy is that in case of microcomposites each constituent does not dissolve or
merge completely into another phase that retains its identity and results in a material
characterized by better properties than the ones of the single components considered
separately. In addition, a particular role among the large composite materials group is
played by fibrous composite materials which are characterized by having a very thin
and sharp macroscopic interphase between the different components of which they
are made of (e.g., matrix and reinforcement material). It actually acts as another
12 Composites and Nanocomposites 455

phase within the material which is characterized by its own properties. Structural
composites usually have bi-phasic systems based on the multiple presence of a
mainly fibrous reinforcement and a matrix in which the first behaves as the source
for key structural properties, while the latter serves as binder to shape the material
structural identity. In order to analyze more in depth their unique mechanical
properties and fully understand where these properties come from, it is important
to focus our attention on the role played by each of these components within the
composite structure and how they act both as a single phase and a complex system
[134–154].
Materials and structures are two vital elements when a composite has to be
defined. However, in this context, it is really difficult to define a material and a
structure, although many people try to define a material as a homogeneous thing
when it can be seen with bare eyes and a structure is a inhomogeneous material
structure that is made up of a fixed geometry or mixing of materials. For example, an
alloy is a material even though it contains two or more components; however, a
honeycomb core built up of two different components is a structure. Materials are
often divided into the six broad classes – (a) metals, (b) ceramics, (c) glasses,
(d) elastomers, (e) polymers, and (f) composites [161–181].
Research laboratories around the world are working diligently to find out ways to
exploit these materials. One of the limiting factors towards mass customization is
that there is little data available on the long-term results of many high-performance
materials along with their relatively higher initial cost which retards the potential
customers to use this types of materials. As already stated, most of these high
performance materials have potentials to use them in the production of high-
performance advanced composite materials using many conventional and high-
tech methods for a wide range of applications [182–197].
Many challenges are usually observed during the production of high-quality
polymer composites, some of which include (a) uniform dispersion of the
materials, (b) physical compatibility of different components, (c) ensuring
robust technical performances, (d) lightness, (e) cheaper in production cost,
(f) inserting required properties (both conventional and functional) [1–3,
198–208]. Manufacturing micro- and nanocomposites with outstanding required
technical properties along with strictly maintaining the sustainability by meeting
environmental concerns and also ensuring productivity and price compared to
the competitor materials are some the very fundamental challenges for micro-
and nanocomposite materials. In addition, designing micro- and nanocomposites
by incorporating variety of conventional and functional materials suitable for
various types of conventional and high-tech industrial exploitations in terms of
producing functional intelligent materials and devices with complex structures,
high level of integration and miniaturization, recyclability with minimum envi-
ronmental load are still some way to proceed with in order to utilize the new
opportunities and benefits out of these materials. Many pieces of current active
research activities are focused in pioneering laboratories around the world in
order to address different aspects and issues of advanced micro- and nano-
composites for various applications [1, 2, 33, 50, 209–228].
456 S. M. R. Billah

3 Nanocomposites

Nanocomposites can be defined as a class of materials where one or more phases

with nanoscale dimensions (such as zero-, one-, two-dimensions) are embedded in a
matrix (such as polymer, metal, ceramic). For example, polymer nanocomposites
have at least two-phase systems consisting of polymers and fillers of which at least
one dimension is in the nanometer range (1–100 nm) [18–21]. The nanofillers can be
one-dimensional nanotubes or nanofibers, two-dimensional clay platelets, or three-
dimensional spherical particles. The advantage of nanoparticles is that, because of its
high specific surface area, already at low concentrations major effects on the
macroscopic properties can be obtained. Over the past years, polymer nano-
composites have attracted considerable interest in both academia and industry, but
one of the outstanding problems is to control the state of dispersion of the nano-
particles, which is highly determined by the preparation method. As already stated
elsewhere, nanocomposites have many applications where some of which include
(a) reinforcement of polymers/structural materials, (b) thermal conductivity,
(c) electrical conductivity, (d) light emitting diodes/field effect transistors/actuators,
(e) hydrogen storage, (f) absorption of radar waves, (g) dissipation of electric
discharge, (h) shielding of electromagnetic radiation [18–31].
Highly ordered polymer nanocomposites exhibit distinct morphological char-
acter due to their variations in a number of areas including (a) composition,
(b) structure, (c) properties on a nanometer length scale [61–64]. Novel physical
characters of soft and bulk polymer nanocomposites are highly influenced by the
nature of supramolecular organization of the nanostructures [65]. A typical idea to
add a nanoscale second phase is to create a synergy between the various novel
constituents with desired properties capable to meet or exceed achievable design
expectations. In that case, the properties of nanocomposites depend on a number of
variables (more particularly related to the matrix material) with various characters
including (a) nanoscale dimensions, (b) loading, (c) degree of dispersion, (d) size,
(e) shape, (f) orientation of the nanoscale second phase, (g) interactions between
the matrix and the second phase. The presence of the nanoparticle and the inter-
action of the polymer with the particle, as well as the particle orientation in a
dispersed fluid composition may cause to produce a variety of ordered composite
materials in the bulk or film [66–68]. When metals are incorporated into polymer
matrices, they show unique optical, magnetic, and dielectric properties at the nano-
and macroscale in nanocomposites, apparently because of the surface and confinement
effects of the nanoparticles [69–75]. The preparation of magnetic nanocomposites
which are comprised of polymer shells and magnetic nanoparticles constitutes
fascinating approach as the modular nature of polymeric materials facilitates the
design of a wide range of hybrid nanocomposites of different compositions
[70–73]. Additionally, the inherent dipole moment in ferromagnetic colloids enables
the one- and two-dimensional assembly of such materials into novel meso-
structures. The development of magnetic assemblies from ferromagnetic and super-
paramagnetic nanoparticles on supporting surfaces has been reported where some
of the structures that have been shown to occur due to the impact of magnetic
12 Composites and Nanocomposites 457

assembly which include (i) one dimensional chains [16], (ii) flux closure rings [77],
(iii) two dimensional super-lattices of closed packed nanocrystals [78], and (iv) three
dimensional labyrinth-like supra-structures [78, 79].

4 Types of Polymer Nanocomposites

From structural consideration, a nanocomposite is a material that contains compo-

nents which are usually very little (>100 nm in scale) in dimension. In this context,
components of a nanocomposite can be divided into three categories – (a) zero-
dimensional (nanoparticles, such as metal oxide and ceramic oxide nanoparticles);
(b) mono-dimensional (nanotubes and nanowires, such as carbon dot, titanium oxide
nanotubes); and (c) bi-dimensional (nanoplatelets, such as layered silicates, nano-
clays, and graphene). However, from a design context, nanocomposites can be
divided into two classes, such as (a) biphasic nanocomposites (polymer matrix +
nanoreinforcement) and (b) triphasic composites (polymer matrix + fibrous rein-
forcement + nanoreinforcement). Additionally, the specific relationship which
relates the structure of the nanoreinforcement with its specific characters is one of
the most important morphological features [80–126]. It can be illustrated with the
ratio between the surface area and the volume of the little component well within
specific nanometer range (Fig. 1).
In specific terms, the variation of the dimensions (or length in case of nanowires
and thickness in case of nanoclays) of particle sizes from micrometer scale to
nanometer scale, this ratio is usually improved by several orders of magnitude.
This type of modification is generally responsible to change the nature of the
interphase between reinforcement and matrix that contributes to generate new
properties (which control the impressive characteristics of nanocomposites). For a
general understanding (within the limited framework of this current chapter), differ-
ent selected aspects of different types of nanocomposites are included here.

Fig. 1 A schematic representation of surface/volume ratio for various type of nanoreinforcements

458 S. M. R. Billah

4.1 Zero-Dimensional Nanocomposites (Such as Nanoparticles

Based Systems)

Nanocomposites reinforced with nanoparticles are one of most widely used mate-
rials for various industrial applications. These nanoparticles are generally incorpo-
rated into the systems for improving various desired properties of the
nanocomposite systems (e.g., enhancing mechanical properties of the matrix,
such as elastic modulus, tensile strength and fatigue resistance). For instance,
Cho et al. [20] studied the behavior of polymeric composites reinforced with
spherical particles made of alumina and glass (of different dimensions from
0.5 mm to 15 nm) and their different impacts on mechanical properties of the
nanocomposite systems. Singh et al. [21] analyzed the fracture toughness of
polymeric thermoset resins doped with micron- and nanometer-sized aluminum
particles and observed that both particles size and volume fraction significantly
influenced the composite toughness and fracture behavior and also contributed to
enhance the mechanical response of the material when the volume fraction was
increased and the particle dimensions were decreased. They also noticed that the
incorporation of normal aluminum reduced the strength of the composite system,
while after a treatment with organosilicates, fracture toughness was significantly
enhanced. Lopez et al. [22] investigated the nature of nanocomposites prepared by
embedding alumina nanoparticles in a vinylester resin at different percentages and
reported similar type of results that established a linear increase of the modulus as
the percentage of nanoparticles within the composite structure was raised to higher
levels. But these values were relatively lower than the modulus recorded for pure
resin which were be attributed to the presence of alumina aggregates within the
polymer. Zhang et al. [23] studied the effect of nanosilica particles in epoxy based
composite and observed their mechanical properties at various selected tempera-
tures and noticed that the presence of a homogeneously dispersed nanometric
phase contributed to improve elastic modulus, impact resistance, and fracture
toughness when the volume content was increased. Besides this, the analytical
models revealed that the nanoparticles induce an improvement of the local
deformability around the crack tip. In addition, the effect of nanosilica on the
fracture behavior was strongly influenced by the temperatures which contributed in
the activation of different mechanisms at various test temperatures. For a better
understanding of the mechanisms involved with these improvements, some authors
investigated the interactions between polymer chains and nanoparticles using
molecular dynamic simulations [24, 25]. They observe that when the polymer-
nanoparticles interaction strength is relatively higher compare to that of polymer-
polymer one, the elastic modulus is improved with reduction in the dimensions of
the nanoparticles. Besides this, a key factor is the density of polymeric chains that
surround the nanoparticles this is significantly influenced by the nanoparticles
dimensions that create a stiff layer around the reinforcement and contribute to
enhance energy absorption rate. Vlasveld et al. studied a multiscaled hybrid system
to investigate the mechanical properties of a three phasic system obtained from
embedding nanoscaled mica particles in a woven glass fibers reinforced PA6
12 Composites and Nanocomposites 459

matrix [26]. They observed that the nanomodification contributed to increase the
matrix modulus and enhance matrix-dominated flexural and compressive strength
by more than 40%. Another research group also observed similar behavior (a 40%
increase of the tensile strength in the transverse direction as a result of an exper-
imental campaign on a three phase composite produced by the modification of a
conventional epoxy resin with silica nanoparticles and then using it with E-glass
fibers to obtain a multiscaled system) [27]. Nanoparticles are generally used to
modify the mechanical character of a composite. However, nanoparticles can also
be used to activate particular nonstructural functions. For example, Kagawa
reported a unique effect of nanoparticles on nanosilica reinforced epoxy resin
and established a relationship of the optical properties of these nanoparticles [28].

4.2 One-Dimensional Nanocomposites (Such as Nanotubes

and Nanowires)

Typically, a nanotube is a nanoscaled structure synthesized by a sequence of atoms

which are arranged in a long thin cylindrical structure. Several materials such as
TiO2, silica, silicon carbide, particular type of carbon materials can be used for the
synthesis of nanotubes [34–37]. In general terms, a CNT can be defined as a series of
carbon atoms arranged in a tube-like shape formed by at least one layer of graphite.
Based on the number of layers that form the single CNT structure, it is possible to
obtain two different categories of nanotubes, which are: (a) single walled carbon
nanotubes (SWCNT), (b) multiwalled carbon nanotubes (MWCNT). Both SWNT
and MWNT have been widely used for improving the properties of many composite
and nanocomposites for a wide range of applications [80, 99, 108–124].

4.3 Two-Dimensional Nanocomposites (Nanolayers Based

Systems)

Nanoplatelets (usually based on phyllosilicates) based nanocomposites have very

thin (several nm in thickness) layers embedded within the polymeric matrix [29]. In
addition, phyllosilicates mainly composed of alumina and silica which are organized
in layered structures where each layer has a sequence of tetrahedric and octahedric
type very thin silica sheets that can be dispersed within a polymer in two different
ways – (a) tactoids (piled silica/alumina sheets) and (b) intercalated/exfoliated layers
(resin-separated layers) [29]. A principal distinction between these two structures is
the dispersion of tactoids in a resin that can give rise to classical microcomposite;
however, when detached nanoplatelets are used, it is possible to produce nano-
composites. Different structures reinforced with nanoplatelets (typical examples
include montmorillonite, saponite, and hectorite) have been rigorously studied and
the results indicate significant improvements of tensile strength, tenacity and impact
properties [30, 31]. In a separate study, Okada and Usuki observed that the doping of
nylon 6 with a small amount of montmorillonite contributed to improve stiffness and
460 S. M. R. Billah

enhance Young’s Modulus (structural features) and also to decrease water absorption
rate (nonstructural feature) [32]. Tsai and Wu used a multiscaled hybrid system to
study and analyze the mechanical behavior of a three phase system obtained by
embedding nanoscaled organoclay in glass fibers reinforced epoxy. They noticed
that the presence of the nanoscaled phase contributed to improve both tensile
strength (+74%) and Young’s modulus (+67%) [33]. Besides this, another type of
2D nanocomposites is based on the inclusion of graphene layers within the structure
of traditional materials [322–343]. Graphene, a carbon allotrope, made by a single
planar sheet of carbon atoms densely packed in a honeycomb crystal lattice, has been
rigorously studied and used in producing composites and nanocomposites for a wide
range of potential and practical applications [1, 344–360].

5 Selected Features of Polymer Nanocomposites

Many studies have been conducted throughout last couple of decades to produce
physically and chemically robust nanocomposites for a wide range of industrial
applications. For example, reinforcements are one of them which have many impacts
on the overall properties of nanocomposites. When the impact of a reinforcement is
reduced, it may lead to an increase of the surface area in contact with the polymeric
matrix and generates nanoeffects within the nanocomposite structure. Additionally,
the fundamental difference with microscaled reinforcement is that the reinforcement
dimensions are of the same magnitude of the radius of gyration of the polymer chains
that form the matrix. This relationship may lead to complete new intermolecular
interactions which are different from what generally happens in classical micro-
reinforced composites that contributes to induce the formation of a polymer inter-
phase layer characterized by its own set of properties.
Mechanisms involved with the strengthening of nanocomposites can be divided
into two categories, they are (a) in plane mechanisms (such as crack pinning or
bowing and crack deflection) and (b) out of plane mechanisms (for instance,
immobilized polymer layers and debonding/plastic voids growth).

5.1 Crack Pinning

In 1970 Lange originally postulated this effect where microreinforced composites

showed this type of effect even at lower intensity [46–48]. Crack pinning effect is
related with dispersion hardening (which usually occurs when the particles act as
pinning points during cracks propagation). In this context, the crack is stretched out
and forms a secondary nonlinear source, whereas the main one stays pinned at the
position where it encounters the particle. A higher energy level is needed to
propagate as the dislocation energy is function of its length and this effect could
be amplified by reducing the distance between different particles or by using smaller
particles since it contributes to the opening of multiple nonlinear cracks in order to
dissipate more energy.
12 Composites and Nanocomposites 461

5.2 Crack Deflection

Crack deflection takes place when the crack tip arrives in the proximities of a stiffer
particle and is deflected after being forced to turn around it. In that situation, the
crack shows twisting or tilting from its plane of propagation by increasing its total
surface area thus absorbing more energy. Besides this, the crack changes its mode of
propagation from normal mode to a superposition that includes contributes from
other modes [49].

5.3 Immobilized Polymer

Polymer immobilization relates the creation of a layer of immobilized polymer

between the reinforcement particles [50]. This layer can be dislocated throughout
the structure in order to create an interphase network that strengthens the composite
due to their small size (e.g., several nm). But this substructure alters the chemical
natures of the material and changes the glass transition temperature and also can
affect other mechanical characters (e.g., storage modulus or damping).

5.4 Debonding and Plastic Voids Growth

The debonding is a toughening effect which is activated by particles embedded

within the composite structure that are debonded from the matrix. This process
absorbs just a small amount of energy (compared with energies involved in matrix
plastic deformation or the other mechanisms); it can reduce the constrains on the
crack tip in order to support a subsequent growth of voids that allows larger
deformations [51].

6 Discussion on Different Types of Selected Polymer

Nanocomposites

6.1 Polymer/Carbon Nanotubes Based Nanocomposites

Recent developments in the fields of nanotechnology, carbon nanotube (CNT)

reinforced polymer composites, and related areas have experienced tremendous
advancements and they are the most studied polymer nanocomposites due to their
potential applications. Carbon nanotubes have the ability to improve the properties of
the resultant materials several orders of magnitude relative to the unfilled polymers
when these CNTs are finely dispersed within different polymer matrices. In this context,
some of the enhanced properties include (a) tensile behavior, (b) strength, (c) toughness,
(d) stiffness, (e) electrical and thermal conductivity, and (f) crystallization kinetics. This
section briefly provides some information on various selected aspects of polystyrene/
CNT and polyethylene/CNT nanocomposites. References have been provided for detail
462 S. M. R. Billah

information on other selective polymer nanocomposites based on carbon nanotubes.

Some of these polymers include (i) polystyrene, (ii) poly(ethylene oxide), (iii) poly
(ε-caprolactone), (iv) polypropylene, (v) various nylons and poly(ethylene terephthal-
ate), and (vi) particular types of elastomers.

6.1.1 Polystyrene/Carbon Nanotubes Composites

A method using electrostatic assembly has been reported to synthesize polystyrene
(PS)-carbon nanofibers (CNF) via a bottom-up method [57]. In this method a home-
made PS latex has been mixed with an aqueous suspension of oxidized CNF to
obtain the nanocomposites through the electrostatic interaction of the cationic PS
with the anionic CNF. It shows that the molding temperature has an important effect
on the morphology and electrical conductivity of PS-CNF composites, where the
optimal temperature and pressure are 185  C and 25 MPA, respectively. This
technique also exhibits a percolation threshold below 2 wt%. This study also
shows the thermal analysis in the presence of the CNF that demonstrates an increase
in the onset and the thermo-oxidative temperature by 60  C. The CNF have little
impact on the alteration of the glass-transition temperature (Tg) of the polymer.
Another research group also reported similar results from their investigation in order
to prepare a composite of syndiotactic PS (sPS) filled with carbon nanocapsules
(CNC) using a solution-blending method coupled with ultrasonication [58]. They
also observed that the addition of filler had no impact on the Tg of the polymer;
however, it led to an increase in the melt-crystallization temperature of the β–form
sPS. In this case, the presence of the filler triggered a fast crystallization of the sPS
that induced either by melt quenching or by slow cooling of the molten state which
was attributed to the existence of a profound primary nucleation density. CNCs have
been used as high quality nucleating agents in order improve crystallinity and
thermal stability of sPS. For example, in a report CNFs have been used as nucleating
agents to produce PS microcellular nanocomposite foams with uniform size distri-
butions [129]. It also observed that addition of a small amount of CNFs has the
pronounced effect in order to reduce the composite’s cell dimensions and increase
the cellular density. Additionally, the favorable surface and geometrical characteris-
tics of CNFs have excellent nucleation efficiency when used as fillers. Electrically
conductive composites were produced by incorporating single-wall carbon nano-
tubes (SWCNT) into polystyrene matrices which have good rheological and
mechanical properties [130]. In this case, a contiguous SWCNT cellular-structure
was synthesized by coating PS pellets with SWCNTs and pressing them afterwards
at elevated temperatures [130]. The novel SWCNT cellular-structures showed better
electric conductance and lower electrical percolation threshold when compared to
nanocomposites with well dispersed SWCNTs. Chang et al. investigated PS com-
posites after dispersing SWCNTs in the polystyrene matrix using a variety of
concentrations of SWCNTs and studied morphological, electrical, and mechanical
properties of the resultant nanocomposites. They noticed that composites influenced
by annealing treatment and annealed composites demonstrated relatively higher
electrical conductivities than the raw composites. However, even after annealing,
the SWCNT/PS composites showed lower electrical conductivities compared to the
12 Composites and Nanocomposites 463

PS/SWCNT cellular-structures. It was also observed that usually it is difficult to

disperse SWCNTs in polymers because of the energy of mixing is endothermic up to
nanotube diameters of 2.2 nm [132]. Polystyrene and carbon nanotube based
composites have a wide range of applications [132–139].

6.1.2 Poly(Ethylene Oxide)/Carbon Nanotubes Composites

There is a range of reports on the synthesis of poly(ethylene oxide) (PEO) nano-
composites containing SWCNTs which have many attractive application potentials
[130–140].
Additionally, carbon nanotubes have been extensively used for the synthesis of
CNT based composites using different types of polymers such as (a) polystyrene,
(b) poly(ethylene oxide), (c) poly(ε-caprolactone), (d) polypropylene, (e) nylon,
(f) poly(ethylene terephthalate), (g) biopolymers and natural polymers [25, 90–99,
106, 117–128, 192–200, 228–373].

6.2 Polymer/Metal Nanocomposites

Functional materials with special properties and/or combinations of unique properties

have been constantly getting evolved since the advanced technologies keep develop-
ing by the day. Materials based on nanosized metal particles may assist to meet many
of the requirements. This section briefly and selectively presents different pieces of
work on the synthesis and characterization of polymer/metal nanocomposites and their
applications. Metal containing materials show excellent mechanical properties and/or
exceptional electrical or electromagnetic characteristics suitable for a variety of
applications. Metal polymer nanocomposites can be synthesized using various types
of metals, some of the metals include (a) platinum, (b) cobalt, (c) nickel, (d) silver,
(e) palladium, (f) gold, (g) other metals (such as copper, zinc, titanium) [1–2, 10, 13,
17, 20–23, 69–80, 100–107, 210, 217, 226, 294]. Metal-polymer nanocomposites are
highly popular for their potential advanced applications with significant industrial
scale exploitations which require quite a number of features including low cost, high
metal surface areas. For example, catalytic systems are widely investigated along with
various metals for the synthesis of polymer nanocomposites. In this context, metals
such as Ag, Pt, Ni, Co, and Au are well known for catalytic activities. Metal
nanoparticles and conductive polymer matrices are usually embedded for producing
electrically active devices for a variety of electronic applications. In addition, metal-
polymer nanocomposites are also popular for their uses in optically active devices and
magnetically active products. From a muscle like structure to bioactive nano-
composites, these materials provide promising improved characters over the original
components that help to expanse their usage envelope. In terms of synthetic perspec-
tive, currently researchers have developed highly specific pathways in order to
produce materials with well-defined tailored properties. Highly cost effective and
generally applicable synthesis pathways have been reported by different research
groups. Such methods are well suited for a wide range of metals and show the
capability to deliver nanoscale metal-polymer composites with significantly enhanced
464 S. M. R. Billah

characters over the starting materials. Some methods of these types sometime use
unique chemical bonds and/or treatments that help compatibilize metal surfaces with
the organic matrices. Other methods also utilize steric effects similar to mechanical
wrapping of the polymers around metal nanospheres to produce metal-polymer
nanocomposites. Moreover, compounding techniques to mechanically insert metal
particles in polymer substrates are also practiced occasionally to produce metal-
polymer nanocomposites [108–125].

6.3 Polymer/Clay Nanocomposites

Polymer and clay nanocomposites are widely investigated for various academic and
industrial researches for their potential applications. For example, the exfoliation,
intercalation, and aggregation of clays in PEO nanocomposites have been extensively
studied in the past. The reality is that the functionality of each component is sometime
changed by addition of another, although in complicated multicomponent systems it is
difficult to draw conclusions if too many parameters are varied. In addition, all the
constituents must be considered at once because of the fact and for a more complete
picture of how a system behaves in a real environment. More specifically, in order to
examine the polymer-clay interactions a combination of methods is used [108–125].
Different techniques have been extensively used by different researchers some of
which include (a) microscopic techniques (such as SEM, TEM, AFM, CLSM),
(b) scattering (e.g., WAXS, SAXS) techniques for studying structure and providing a
measure of size, shape, and interfacial polymer conformation. Besides this, rheology and
mechanical testing are much utilized techniques as they can sufficiently distinguish
between properties of chemically versus physically cross-linked polymer-clay materials.
In this section only specific selective information on polymer nanocomposites based on
laponite and montmorillonite is provided, since these two clays are among the most
studied and reported. Laponite and montmorillonite are popular for producing clay
composites when they are used in combination with a number of polymers which
include (a) poly(urethane urea), (b) poly(methyl methacrylate), (c) polystyrene,
(d) poly(ethylene oxide), (e) diblock and triblock copolymers, (f) polyurethane,
(g) poly(ε-caprolactone), (h) polylactic acid and/or poly(lactic-co-glycolic acid),
(i) poly(ethylene oxide), (j) polypropylene [117–128, 199–200, 260–410].

7 Designing Composites and Nanocomposites

Similar to previous sections, information on different aspects of composites has been

provided in terms of the information on composite materials. In the context of
research conducted on hybrid composites (primarily based on intermingled carbon
and glass fiber fabrics) can be traced back to the early 1970s. However, in view of
prospective use as lightweight load bearing composite structures, different pieces of
work of Bunsell and Harris in the year 1974 or Summerscales and Short in the years
1978 and 1980 are sometimes considered as the first pieces of research work on the
12 Composites and Nanocomposites 465

mechanical properties of various material combinations [214–216]. A wide range of

combinations emerged since then to prepare fiber reinforced polymer (FRP) com-
posites of viable architectures.
Many reviews primarily focused on polymer-based hybrid composites. For
example, in one of the review, Ashby (in the year 2003 and 2011) defines hybrid
materials as the combinations of two or more materials assembled in such a way as to
have attributes not offered by either components one alone [217, 218]. Additionally,
he stated the ingredients to be used in hybrid material design (including the choice of
materials to be combined, their configuration, their relative volume fraction, and the
scale length of the structural unit). Generally, there are three types of hybridization
architectures which are (a) interlayer, (b) intralayer, and (c) intrayarn. In that case,
the interlayer hybridization implies reinforcement mixing on the layer level, while
the intralayer configurations within each layer. The first architecture is the most
general configuration as it is handy to be prepared and the latter is rather difficult to
be produced but proved to yield improved mechanical characters [219, 220].
In the light of above, numerous combinations emerged and studied by different
investigators from property prediction point of view, cost, and performance, behav-
ior under various loading conditions and application potential based on different
features. In 1987, Kretsis at first reviewed hybrid composites and focused particu-
larly on hybrid composites based on epoxy resins reinforced with synthetic fibers,
carbon, and glass, especially continuous and unidirectional orientation with effective
mechanical characters [221]. Various composites were found to pose challenges in
terms of environmental benefits. Thus, natural products were preferred to promote
environmental issues [222–224]. One of the primary parameters in the hybrid
polymer composites design is the hybrid ratio that has a direct significant control
over the overall performance of structure which is intimately related to the hybrid
effect. Morom et al. defined the hybrid effect in 1978 and observed that the deviation
from linear rule of mixtures can be modified to be used to predict a large spectrum of
mechanical properties in addition to the failure strain [225]. Consequently, positive
and/or negative hybrid effects obtained from these predictions may be useful to
quantify the examined property. This rule is known as the linear rule of hybrid
mixtures, but the accuracy of this rule is debated [226]. Many factors have influences
on the hybrid effect. For example, high performance composites are expected to
show outstanding returns from their individual reinforcement and matrix constitu-
ents. Additionally, without limiting the influencing factors, some important ones
such as the nature, distribution, amount, layering pattern, and individual features of
the composite constituents have strong effective influence on the different properties
of the composite. Subsequently, material selection is a significantly important to
tackle different issues of the composite made with different constituents since in
many cases they share an important part in the composite design. Additionally, other
parameters, for example, fiber-matrix interface, interlaminar strength, and fracture
toughness, have considerable influences of the hybrid effect of the composite.
Theoretical predictions developed in order to address microstructure-property con-
nection have a long and venerable history and have been successful to attract the
attention of some of the luminaries of science, including Maxwell, Rayleigh, and
466 S. M. R. Billah

Einstein. Since their very early work on the characters of heterogeneous materials,
there has been a huge upsurge of effective contributions in the literature on this
subject. For example, one of the outstanding contributors is Torquato [227]. In the
most typical sense, the overall characters of heterogeneous materials can be pre-
dicted using expressions developed by utilizing various ways including
(a) variational principles, (b) local and homogenized solutions to the problems,
(c) phase-interchange relations, (c) exact solutions using effective medium approx-
imations, (d) analyzing rigorous bounds and cross-property relations. These signif-
icant advances have enabled investigators to overcome the limitations of the models
and also allow them to compute property estimations that depend on other require-
ments imposed real materials. Tailoring composites with unique spectrum of prop-
erties depends primarily on the systematic approach to relate the effective characters
to the microstructure using accurate expressions. It is possible to relate changes in
the microstructure quantitatively due to changes in the macroscopic property.
Major developments in hybrid composites are mainly due to increasingly new
industrial demands as well as pressures. Material designers and manufacturers
constantly engaged with searching novel combinations to meet desired objectives
which allow faster structural optimization based on different things including (a) cost
minimization, (b) high performance and lightweight condition, (c) easy manufactur-
ing feasibility. The main development of hybrid polymer composites mostly based
on thermosetting resins that range from epoxy to polyester and poly vinyl ester. For
example, epoxy resins and derived blends have been rigorously studied due to their
versatility in applications with all manufacturing technologies, good compatibility
with almost all types of fibers, both synthetic and natural.
Market demand effectively controls the consumption of composites (either ther-
moplastics or thermosetting). However, the capability to adapt these materials to
economic and technical market requirements depends on the innovation in terms of
both materials and processes that can be supplemented by adaptability to the
environmental constrains (such as circular 3R concept – recycling, reusing, and
remanufacturing) [228]. Composites have many application areas, for example, they
have some engineering applications. Civil and automotive engineering, marine and
aerospace, biomedical and sensing devices have several application domains of
modern composite materials [229–233]. In addition, a balance in cost and perfor-
mance can be sized behind each material design. Particularly, the study of hybrid
composites is a multidisciplinary effort that overlaps with various branches of
material science, engineering, applied mathematics, and others. The ability to tailor
hybrid composites with a unique spectrum of characters depends on microstructure
and correlation of experimental retrieved data with theoretical predicted values,
bounded by certain processing conditions.
Important material characteristics of a polymer microcomposite depend on a
number of things including (a) volume fraction of reinforcements, (b) geometrical
parameters (such as length, shape), (c) orientation and layering type, supplemented by
interface interactions with the matrix system. The overall characteristic of the resultant
composite is defined by each and every components present in the composition
[234–236].
12 Composites and Nanocomposites 467

A proper control in thermal expansion is highly required for a polymer micro-

composite suitable to be used in structural applications. In order to mitigate the effects,
different components of the composite should be carefully selected to ensure proper
matching with the thermal expansion coefficients at interfaces or at least control the
variation within an allowable limit [239–244]. Thermal expansion coefficients of the
components used in the composites, particularly particle reinforced composites which
are usually used in electronic applications (such as energy harvesting, power elec-
tronic, electronic packaging, sensing devices, actuators), need to be controlled ade-
quately in order to ensure high product quality [245–256].
Electrical properties of composites are significantly important criteria for the
designs of different types of composites, most particularly composites targeted for
electronic applications [257]. In many cases, electrical properties of composites are
desired to exhibit required electromagnetic properties along with distinct levels of
thermal, and/or mechanical behavior while maintaining structural integrity [258,
259]. As a result, required electronic character along with specific physical and
coupling behaviors is also needed to meet certain industrial requirements. For
example, electrical properties of particular types of composites can be tailored in
order to meet specific industrial applications, such as (a) composites for electronic
packaging (e.g., printed circuit boards, thermal interface materials), (b) composites
for microelectromechanical systems (MEMS) and BioMEMS where their functions
are multifold (both active sensing and housing) [260–270]. In addition, many
challenges are usually encountered during the design and development of high-
performance composites using different materials, some of which include (a) method
of proper combinations and sustaining structural integrity, (b) issues relating to
synthesis, (c) characterizing and property modeling or simulation, (d) ensuring
higher technical performances at a lower cost [214–238]. In this regard, reflections
on the overall behavior, interferences, and synergies with direct consequences on
their balanced properties need careful consideration in order to produce high-quality
composite structures. Currently, synthetic materials have predominance over natural
or 3R materials (such as recycled, reused, recovered), so scientists are focused on
producing hybrid composites to ensure many desired industrial needs as well as
meeting environmental requirements. In this connection, in order to mitigate the
usual challenges in existing and future trends need comprehensive interdisciplinary
studies to overcome many issues and produce high-quality composites that can fulfill
desired industrial exploitations [259–270].

8 Processing of Composites and Nanocomposites

Designing and processing are critical to produce most sustainable, cost-effective,

and environmentally viable micro- and nanocomposites for a wide range of appli-
cations. The final characters of micro- and nanocomposites rely on the processing
methods and conditions where some of most commonly used method include
(a) melt processing, (b) solvent processing, (c) in situ polymerization,
(d) electrospinning, and (e) layer by layer (LBL) assembly.
468 S. M. R. Billah

8.1 Melt Blending

Melt blending, a popularly used to prepare composites where the compounding, is

usually carried out in a single- or twin-screw extruder by heating the polymer and the
nanoparticle mixture in order to form a melt. The mixer provides the required shear
and elongational stress to the process for breaking apart the filler agglomerates and
dispersing them uniformly in the polymer matrix. This technique is one of the
popular techniques to produce composite materials. For example, carbon nanotubes
(both Single Wall Nanotube or SWNT and Multi-Wall Nanotube or MWNT) along
with different polymers are frequently used to produce conductive polymer com-
posites, where better dispersion is usually achieved with MWNT rather than with
SWNT [321]. The extruder, a versatile device, allows to have better control on shear
and mixing simply by changing the screw configurations where a higher shear rates
generally provides better dispersion and production rates as well as material through-
puts in a continuous extrusion process can be high. An important advantage of melt
processing is that no organic solvents are needed during processing and the
compounded nanoparticle-polymer composite can be processed using various
polymer-processing techniques (e.g., injection molding, profile extrusion, blow
molding). However, a number of variables (such as temperature, screw-speed,
residence time, and shear stress) are directly involved with the mixing process and
these parameters should be optimized in order to produce high-quality composite
materials because a variation in these parameters usually produce composites with
differences in their properties (e.g., agglomerate structure, packing density, length to
diameter ratio, dispersion uniformity of the fillers, such as carbon nanotubes in
composite polymeric matrix). Besides this, the polymer matrix (particularly, the
melt viscosity) also affects the degree of dispersion and the shear forces generated
in most mixing equipment are not large enough to break and disperse the fillers in the
polymer matrix efficiently. In addition, special mixers where shear rates are an order
of magnitude higher than usually obtained from a typical screw-extruder are often
used to ensure better dispersion with improved properties, although the high shear
has the potential for degrading both the polymer and the filler used in the composite
production. A wide range of polymers are popularly used in composite productions
using melt blending technique, some of which include low density polyethylene,
high density polyethylene, polypropylene, polystyrene, poly methyl methacrylate,
polyamide, polyesters, and polycarbonate and a brief details of these can be found in
different reviews [293, 306, 313, 322–324].
Melt processing has shown to enhance mechanical properties of composites to
some extent [324]. A study reveals that the intensity in the mixing section improves
dispersibility over the kneading section and the polymers containing functional
groups can react with functional groups on fillers (such as carbon nanotubes) in
order to improve dispersions [326]. Another study observes that the extensional flow
gives better dispersion of nanotubes compared to that observed from shear flows
[327]. For example, several studies on the melt blending of graphene and polymers
demonstrate the low thermal stability of most chemically modified graphene and the
low bulk density of graphene create difficulties in using melt processing technique.
12 Composites and Nanocomposites 469

Additionally, some studies have been carried out where high shear melt mixing
technique has been used for the fabrication of graphene based nanocomposite with
poly lactic acid [328], polyethylene terephthalate [329], polypropylene [330], nylon
6 [331], polycarbonate [332], polystyrene [333], and elastomers [334] although high
shear forces have the tendency to cause buckling, rolling, or shortening of graphene
sheets and thus cause a reduction in aspect ratio of a graphene composite.
Melt mixing of clay with polymer has been shown to produce polymer micro- and
nanocomposites with improved properties [335–354]. For example, a variety of
polymers have been effectively melt compounded using clay to provide various
degrees of exfoliation. Additionally, the intercalation during melt processing of clay-
polyethylene oxide enhanced further by microwave irradiation [354]. Liu et al. [355]
reported an exfoliated composite by compounding organic clay and nylon 6 using a
twin-screw extruder. Typically, due to nylon’s excellent affinity for the silicate
surface, the degree of exfoliation between nylon 6 and clay is quite high [303]. In
addition, stresses generated during melt blending can break up the clay aggregates
and with an increase in the affinity between the clay and the polymer, the dispersion
of the individual platelets in the polymer matrix also increases.

8.2 Solution Mixing or Solvent Casting

Micro- and nanocomposites are also frequently produced by using solution mixing
or solvent casting technique which involves the agitation of the filler (such as CNT,
nanoparticles) in a polymer that is dissolved in a solvent prior to casting in a mold
and then the solvent is removed by evaporation. Both thermoplastic and thermoset
polymers have been used to prepare composites using this technique. For example,
polymers like PMMA, poly(vinyl alcohol) [358], polyhydroxyaminoether [359], PS
[360], PE [361], PEO [362], and epoxy [363–365] with CNTs have been used to
prepare composites using solution mixing or solvent casting technique. Polymer
solution of lower viscosity (when dissolved in a proper solvent, in contrary to a melt
condition) coupled with agitation by mechanical stirrer or ultra-sonication contrib-
utes to a better dispersion of nanoparticles in the polymer matrix. Different types of
solvents (such as aqueous or organic) are usually used in solution mixing or solvent
casting of polymer composites; however, there are environmental implications
which are involved with the removal of organic solvents from the casted composites.
Solution mixing and solvent casting techniques have been reported to prepare
different polymer composites using modified graphene and a range of polymers,
some of which include (a) PVA, (b) PMMA, (c) PP, (d) PS, (e) LLDPE, (f) nylon,
(g) epoxy, (h) PANI, (i) PU [410–430].

8.3 In Situ Polymerization

It is one of the popular techniques to produce micro- and nanocomposites. For

example, different polymer composites (particularly based on carbon nanotube and
470 S. M. R. Billah

polymers) have been synthesized by using in situ polymerization technique. It is

possible to use this technique for producing both thermoset and thermoplastic
materials. For instance, during the production of CNT based polymer composites,
the nanotubes are dispersed in the monomer which is then polymerized and the
dispersants may be added to assist in the de-agglomeration of the nanotubes. Besides
this, functionalization or polymer adsorption techniques have been reported to assist
in the dispersion process where the polymerization is initiated with the increase of
temperature and by the addition of a chemical initiator to start the reaction (or by
mixing the monomers). Microwaves have been utilized for inducing polymerization
reaction as the nanotubes have the capability to absorb microwave that increase
temperature which allows the grafting of polymer molecules on to the walls of the
nanotubes. The method can be used to make CNT composites with polymers that are
insoluble in most common solvents or are thermally unstable which limits the scope
of melt processing [102, 362–378, 421–430].

8.4 Electrospinning

Electrospinning, an established and experimentally straight forward technique, has

the potential to produce virtually continuous lengths of submicron width fibers, from
a wide range of materials that includes many polymers (such as natural polymers like
cellulose, synthetic polymers like polystyrene) and their blends. Electrospun fibers
have the potential for different types of applications, some of which are
(a) production of novel composites, (b) biomedical applications, (c) filtration,
(d) textiles, (e) tissue engineering, (f) optical and electronic devices, (g) sensing
applications [41–45]. A significant enhancement on the functional properties of
electrospun polymer fibers can be achieved by the incorporation of functional
materials such as quantum dot, polymer (e.g., to make a blend), metal complexes,
nanoparticles, carbon nanotubes, dye molecules, dye loaded zeolite crystals, or
proteins. In a typical electrospinning process, a high voltage (kV) is applied to a
metallic capillary through which the polymeric solution is fed and the charges
induced on the surface of the pendant polymer droplet act in opposition to the
surface tension of the fluid. When the repulsive Coulombic interacts above a critical
voltage, it overcomes surface tension in order to cause an acceleration of electrified
polymer jet from the apex of the droplet towards a grounded collector (such as a
metal sheet, e.g., a Cu sheet) which usually kept at certain distance from the metal
capillary (Fig. 2). The polymer jet is elongated into a long, thin filament as the
solvent evaporates and is deposited onto the collector in the form of fibers and based
on the nature of collection, fibers may be collected in random mats or in more
ordered assemblies (such as aligned mats). The elongational flow of the polymer
exhibits some degree of orientation of the macromolecular chains in the fibers and
also shows interesting behaviors of uniaxial properties (such as birefringence). The
morphologies and dimensions of electrospun fibers depend on the complex inter-
relationship between intrinsic polymeric and solution properties, processing param-
eters, and also on ambient conditions where electrospinning is carried out. There are
12 Composites and Nanocomposites 471

Fig. 2 Schematic diagram of a typical electrospinning rig

reports of using electrospinning technique for producing electrospun nanofibers

doped with advanced materials for a variety of applications. For example, one
study exhibited the procedure of incorporating cadmium sulfide quantum dots that
were co-electrospun with polyethylene oxide for the production of fluorescence
nanofiber composite in order to transfer optical properties from quantum dots to
polyethylene oxide nanofibers. In addition, the iron oxide nanoparticles were
co-electrospun with poly vinylidene fluoride tetrafluoro ethylene to produce electro-
spun nanocomposite to incorporate strong super paramagnetic properties. Both of
these two ways devise a practical method to produce nanostructured which can be
extended toward a cellulose-polyethylene oxide-quantum dot nanocomposite by
using electrospinning technique. Figure 2 illustrates a schematic diagram of a
commonly used typical electrospinning rig for nanofiber production.
Electrospinning technique is also widely used to produce electrospun composites
and nanocomposites using a wide range of fillers and polymers for a variety of
applications [41–45, 389–407].

8.5 Layer-by-Layer Deposition

Layer-by-layer (LBL) deposition technique is also another popular method for

producing micro- and nanocomposites, which involves as immersion process to
charge the substrate either negatively or positively using an oppositely charged
polyelectrolyte that is adsorbed onto the substrate. In this case, when equilibrium
is achieved, the substrate becomes ready to remove for rinsing followed by drying
and immersing in a negatively charged polyelectrolyte solution. This process is
repeated and continued for achieving required film thickness on the substrate
which depends on a number of factors including (a) the concentration of polymer
472 S. M. R. Billah

in the solution, (b) ionic strength, (c) molecular weight of polymer, (d) temperature
during assembly, (e) ionic strength, (f) pH. In addition, in case of an irreversible
polyelectrolyte absorption, the charge overcompensation can cause charge reversal
at the surface. This technique allows to insert different materials between layers as
long as they have the opposite charge. For example, when a negatively charged
substrate is immersed in the solution of positively charged polyelectrolyte, the latter
forms a submonolayer on the surface of the substrate that can switch the surface
charge to positive which is then immersed in the dispersion of negatively charged
polyelectrolyte or nanoparticles after rinsing with water in order to form a new layer
that can switch the surface charge to negative again. This whole cycle is usually
repeated for a number of time to achieve the expected result. There are many benefits
of LBL assembly, one of which include during this process a high level of dispersion
of nanoparticle into a composite that occurs as a result of direct absorption of
nanoparticle from a solution to a solid state shows no a phase segregation. Besides
this, the typical concept of LBL assembly is a useful versatile method in order to
combine various materials (e.g., carbon nanotubes, clays, nanoparticles, polymers,
proteins) to produce a wide range of micro- and nanocomposites. This method also
allows to control the morphology at nanoscale to provide desired compact and
ordered structures relative to other solution-based techniques. LBL assembled thin
films have a wide range of applications in various areas, some of which include in
(a) producing transparent conducting films, (b) field effect transistors,
(c) supercapacitors. However, a slow deposition speeds and cumbersome assembly
process are some of the principal limitations of this technique [1, 2, 33, 50].

9 Environmental Stimuli-Responsive and Functional

Polymer Composites and Nanocomposites

Materials responsive to surrounding environmental conditions (such as light, pH,

temperature, magnetic, and electric fields) are attractive for current intensive funda-
mental scientific research for their multiple conventional and high-tech applications.
In this context, the responsive materials of interest are composite and nano-
composites. A wide range of materials (such as photo-, thermo-, pH-, magnetic,
electrical, enzyme-responsive materials or molecular switches) have the potentials to
be used with different matrices for producing variety of composites and nano-
composites. Additionally, shape memory polymers or materials, self-healing mate-
rials, materials used in different functional applications (such as electromagnetic
shielding, electronic applications, energy storage) are widely studied for their appli-
cations in particular types of composites and nanocomposite production targeting
specific industrial applications [41–51]. Nanocomposites are in the forefront of study
due to the fact that when very low load levels (<5%) of the filler are introduced into
the nanocomposite structure, they provide a dramatic impact on the final properties
of nanocomposite matrices. This is attributed to fact that there is an increase in
interfacial interaction of the 1D nanomaterials with the polymeric matrix. Respon-
sive nanocomposites have an impact on a wide ranging areas, including biomedical
12 Composites and Nanocomposites 473

applications, energy, security, and military applications. For instance, polymeric

materials used in gasket seals have the potential adaptation in order to differ
temperatures and humidity in such a way which can maintain an optimal degree of
functionality regardless of climate variations [41–51].
The production of responsive nanocomposites is directly involved with a greater
understanding on the nature and the interactions of nanomaterials with other poly-
meric materials or the matrices they are applied in order to realize a specific or
multiple objectives. The diverse nature of the effective utilization of responsive
nanocomposites multidisciplinary approaches are required in order to investigate the
cross-over understanding needed to make the quantum leaps necessary to realize the
successful uses in various fields and also on their potential industrial scale applica-
tions. Successful applications of nanoparticles and different computational models
have been developed by different research groups in order for effective incorporation
into responsive nanocomposites. Different research groups have synthesized various
metal, semi-conductor, and ceramic nanomaterials and introduced into responsive
polymer matrix to produce responsive nanocomposites. Different methods have
been investigated for producing responsive nanocomposites some of which include
(a) electrospinning, (b) soft templating and photocatalytic nanostructuring,
(c) interfacial assembly, (d) inkjet technology, (e) coating, (f) layer by layer depo-
sition. In order to determine the structure of functionalized nanoparticles in solution
and also to resolve the interactions between them, different research groups have
used large-scale atomistic molecular dynamics simulations for producing responsive
nanocomposites. Additionally, simulations have also been used to investigate the
effect of nanoparticles on the flow and processibility of polymer nanocomposites for
different application purposes. Various methods have been reported for the
functionalization of nanocomposites and also to produce responsive nanocomposites
for specific as well as multiple application potentials. Some of these methods include
(a) electrospinning, (b) templating, (c) layer-by-layer deposition, (d) inkjet technol-
ogy. Many efforts have also been focused on discovering what effect the existing
materials interactions with the polymer matrices have and refining their functiona-
lization strategies for specific or multipurpose applications potentials [41–51].

10 Selected Behaviors of Composites and Nanocomposites

10.1 Reinforcement

When composites and nanocomposites are reinforced with nanofillers, they usually
show enhanced mechanical properties. However, excellent properties of nanofillers are
yet to be realized (particularly, in the cases of higher volume fractions), when used in
composite formulations. In a study, a modulus improvement by a factor of six is
predicted at 0.01 filler volume fraction for an aspect ratio of 1000 for 1D nanotubes or
2D platelets using the Halpin-Tsai equation [235]. Additionally, molecular simulations
predict similar reinforcing potentials for aspect ratio of approximately 100 as well as
relative enhancements in modulus may be much higher than the increase in tensile
474 S. M. R. Billah

strength [236]. There is usually a decrease in strain at break when loaded with nano-
fillers. For example, when nanotubes are doped or incorporated into micro- and nano-
composites, there is typically an increase in certain properties with an increase with the
nanotube content at low volume fractions but there is a decrease at higher fractions due
to issues related to dispersions and agglomeration [237–255]. When carbon nanotubes
are used as fillers in nanocomposite fabrications, usually modulus of graphene filled
nanocomposites shows an increase with an increase in loading fraction which illustrates
that the strength of the interface is critical to the improvement of the mechanical
properties. An increase in modulus is more pronounced for elastomeric matrices because
of their lower intrinsic modulus. Different investigations also confirm that the mechan-
ical reinforcement of graphene is superior over some other fillers (e.g., carbon black,
single wall nanotube) [255]. For example, in graphene based epoxy polymer composite,
functionalized graphene sheets provide higher fracture toughness, fracture energy
stiffness, strength, and fatigue resistance at lower loading fractions as compared to
nanotubes [253]. Besides this, normally, there is an increase in tensile strength with
increase in graphene content (with some exceptions) [254] and reduction in elongation
or remain unchanged. However, for the case of carbon nanotube based composites, the
level of mechanical enhancement observed to be relatively lower than the theoretical
predictions. Similar trends of mechanical properties of nanoclay are reported for carbon
nanotube or graphene based polymer composites which in an addition of this type of
fillers increases modulus and tensile strength while decreases elongation at break.
However, with clay, the relative reinforcement [256, 292] for a given volume percent
of filler in the composite is markedly lower compare to that of graphene based [255] or
carbon nanotube based composite [257]. The tensile modulus of a polymeric material
shows an increase when nanocomposites are formed with either pristine or organically
modified clays, for instance, for nylon 6 based composite shows an increase in tensile
strength by 42% and modulus by 90% [257, 258]. In this case, there is an increase in
stiffness for an increase in the molecular weight of the matrix at any given loading, even
though all the moduli of the neat nylon 6 are almost similar [257–259].

10.2 Electrical Conductivity

Polymer composites and nanocomposites provide an excellent potential to produce

electrically conductive materials by incorporating electrically conductive materials
(such as carbon nanotubes, graphene, conductive metal oxides) as fillers into their
structures or by other suitable means. These types of conductive materials are useful for
a wide range of applications including (a) conductive adhesives, (b) antistatic coatings,
(c) conductive films, (d) electronics, (e) packaging, (f) electrical appliances. In all these
cases, methods of loadings and dispersions of conductive materials have critical
importance. For example, in percolation threshold (the critical loading point) when
the composite shows a transition from an insulator to a conductor due to the formation
of a continuous conducting network, it must be properly controlled to produce desired
level of conductive nature. Because, under the percolating threshold, the electrical
properties are usually dominated by the dielectric matrix and thus the composite
12 Composites and Nanocomposites 475

exhibits nonconductive character, the fillers are unable to form a continuous network in
order to ensure flow of electrons. In contrast, beyond the percolation threshold, only a
tiny increase in loading with conductive fillers contributes to cause a significant
improvement in conductivity, and because of the increase in filler contents, they
begin to form a contact with each other. In addition, at percolation threshold, conduc-
tion paths are created in the insulating matrix to cause an increase in conduction,
although beyond a certain level of filler concentration a plateau in conductivity is
reached and some of the main controlling factors which have direct influences on the
percolation threshold are (a) aspect ratio, (b) nature of functionalization, (c) method of
processing, (d) nature of the polymer matrix, (e) nature of dispersion [292–300].

10.3 Thermal Conductivity

Thermal conductivity of certain types of polymer composites and nanocomposites is

sometimes highly desired for their specific applications in particular areas (such as
electronic devices, protective applications). Thermal conductivity of polymer com-
posites and nanocomposites depends on a variety of determining factors which include
(a) the nature of the polymer matrix and fillers, (b) nature of dispersion of conductive
fillers in the polymer matrix. Currently, thermal conductive polymeric composites are
being increasingly used in different areas to meet specific application targets. Ther-
mally conductive polymer composites are usually produced by using thermally
conductive fillers into composite structures. For example, the polymers filled with
the thermally conductive fillers effectively dissipate heat generated from electronic
components where the management of heat is directly related to the lifetime of
electronic devices. As already mentioned, to improve thermal conductivity of com-
posites, fillers with excellent thermally conductivity (such as metal oxides, CNT,
graphene) are popularly employed because they provide several advantages, some
of which include (a) easy processibility, (b) low cost, (c) corrosion resistance to certain
extend. In this context, carbon-based 1-dimensional nanomaterials (for instance,
carbon nanotube, carbon nanofiber) exhibit different useful properties, some of
which are (a) high thermal conductivity, (b) corrosion resistance, (c) low thermal
expansion coefficient compared to metals. As a result, CNT based polymer compos-
ites are highly attractive as thermally conductive materials are suitable for various
applications. It has been reported that functionalized nanotubes usually contributed to
offer higher thermal conductivity compared to unfunctionalized tubes because of
higher dispersion capability [301]. A significant number of studies relating to the
thermal conductivity of graphene/polymer composites have been reported [302–303].

10.4 Thermal Stability

Thermal stability of both micro- and composites is an important factor which is mainly
designed based on the final use of micro- and nanocomposites. As already stated both
micro- and nanocomposites are fascinating materials made from two or more distinct
476 S. M. R. Billah

components with different chemical, physical, and mechanical properties, but when
combined, possess better properties than those of each individual components used
alone. Composites materials have many advantages, such as (a) high specific strength
and modulus, (b) ease of fabrication, (c) high design flexibility, (d) resistance to fatigue and
corrosion, (e) desirable thermal expansion characteristics, (f) economic efficiency. Due to
these interesting properties, the composites materials are widely used in different indus-
tries, some of which include (a) aerospace industry, (b) military industry, (c) automobile
industry, (d) construction materials and other engineering applications. At present there is
a thrust towards the compaction of electrical power equipment with enhanced insulation
electrical stress levels which requires new electrical insulating materials. It is interesting to
note that in past few decades, some particular polymeric materials with excellent desired
criteria (such as light weight, robust mechanical properties, low cost, and some with
unique nonwetting surface characters) have been successful to surpass insulation behav-
iors of conventional porcelain and glass materials. However, despite these suitable
properties, polymeric materials are unable to withstand the high heat from surface arcing
that is instigated by the synergism of different factors, such as (a) pollution, (b) moisture,
(c) voltage. In addition, surface arcing causes material loss because of different reasons
such as (i) heat ablation, (ii) electrical tracking of polymers. In order to overcome these
types of problem, inorganic fillers are popularly used along with base polymers for
improving various characters which include (a) resistance to surface discharge activities,
(b) other technical performances within a cost-effective approach. Usually polymers show
higher thermal expansion compared to metals and by adding fillers (such as clay, carbon
nanotubes, graphene), this thermal expansion of polymers can be reduced by imposing
restriction on the movement of a significant volume of polymer chains due to their
interaction with the fillers. However, graphite has a positive thermal expansion coefficient
and when incorporated into polymers does not cause a reduction in the expansion of
polymers. In contrast, a reduction in thermal expansion was observed when reduced
graphene oxide or SWNTs were incorporated into the structure of resins [304]. Fillers
with negative thermal expansion coefficients (such as graphene oxide, single walled
carbon nanotube) when used in composites fabrication contribute to increase thermal
stability by decreasing the thermal expansion coefficient of the composite system. For
example, in a study, it was observed that the degradation temperature of PS increased
from 400  C to 450  C when impregnated with graphene sheets [304–305]. In addition,
the thermal stabilities of graphene based PMMA composite system are reported to be
higher than that of PMMA. Besides these evidences, there are also reports on clay
nanocomposites prepared by using injection molding technique exhibited anisotropy
where the expansion coefficient in the flow direction was observed to be relatively
lower than in the perpendicular direction which was attributed to the orientation of
platelets in the respective direction. Similar types of results were observed when MMT
was aligned using magnetic or electric field [304–308].

10.5 Glass Transition Temperature

Methods of preparation and nature of the micro- and nanocomposite structures have
pronounced impacts on the glass transition temperature of the composite systems
12 Composites and Nanocomposites 477

which are almost all cases different from the individual components of the composite
systems. Many factors have direct impact on the Tg of composite system; one of the
main reasons include the capability of the fillers to impede the motion of polymer
chains due to the interfacial interaction between the polymer and the filler. For
example, different investigations have observed that both Tg and the breadth of
the transition are usually affected by the presence of fillers in composite structures
[304, 309–310]. Other important factors that influence Tg include (a) thickness [304,
311–312], (b) methods of preparation and measurement [313], (c) nanoparticle
dimension [309–314], (d) chemical structure of the polymers [315]. Besides this,
the interaction of the filler with the surface is significantly important as it can play a
role to influence the degree of change of Tg and it is also observed that surfaces that
interact strongly with the polymer contribute to improve Tg [304, 316–317]. In
contrast, the unadsorbed material may have the same or lower Tg compared to the
bulk depending on the nature of the adsorbed layer. Besides this, hydrogen bonds at
the polymer-substrate interface may also contribute to enhance Tg relative to bulk
values [304, 313, 317]. Graphene platelets with particular characters (such as higher
aspect ratio, higher surface roughness) when dispersed uniformly within a composite
polymer matrix can improve Tg of the composite. For example, in a study it was
noticed that solvent and melt blending processes cause insignificant changes in the
Tg of polymer-graphene or polymer-GO composites, while in situ polymerization
with unmodified graphene or solvent blending with chemically modified graphene or
GO helped to enhance Tg of the composite matrix due to the covalent bonding
between the graphene and the polymer. The nature of polymers used in composite
structure is also a vital factor to control the glass transition temperature of the
composite. For example, nanospherical silica showed an increase in Tg with PVP,
decrease in Tg with PMMA, while Tg was unchanged with PS [304, 318]. When a
polymer is mixed with a carbon nanotube, the resultant mixture usually shows an
increase or a decrease on its glass transition temperature depending on the nature of
surface functionalization of nanotubes used in the mixture [304, 319–324].

10.6 Barrier Properties

The structural compositions of micro- and nanocomposites are significantly

influenced when they are incorporated with fillers that have large aspect ratios and
can show various properties including impeding and changing the diffusion path of
penetrating molecules (such as well-dispersed fillers can create a tortuous path for
permeants to travel). For example, in a study a decrease in gas permeability
(independent of the type of gas) was reported for clay reinforced composites,
while in another study a 1% loading of clay in PET showed a two-fold reduction
in oxygen gas permeability. Different reports observed a decrease of water vapor
permeability of PCL clay nanocomposites over neat PCL. In addition, a decrease in
water vapor permeability with an increase in the aspect ratio of the platelets has been
reported. Gas molecules find it too difficult to permeate defect-free graphene sheets
which provide an opportunity for graphene based polymer composites films to apply
as protective elements in electronics and fuel cells (which are sensitive to the
478 S. M. R. Billah

presence of gases, e.g., oxygen and moisture). Additionally, GO conjugated polymer

nanocomposite films have the capability to reduce the level of oxygen and carbon
dioxide permeation. For example, in different investigations graphene polyimide
composite films have been reported to exhibit high moisture barrier characters and
some other polymers based composite films also observed similar results [80–99,
108–124, 304, 324–328].

10.7 Antiflammibility

Polymers show low fire resistance compared to metals or ceramics. When a polymer
is burnt, it decomposes and releases gaseous products. Micro- or nanocomposite
matrices having well-dispersed nanoplatelet/nanotube in the structures assist to form
continuous networks that contribute to form protective layers on the surfaces and
finally exhibit relatively more resistance to fire compared to pristine polymers which
are used in this composite matrices. Alternatively, this protective layer that provides
heat shielding contributes to prevent the gaseous degradation products from diffus-
ing through it and reacting with the oxygen in the air. A micro- or nanocomposite
impregnated with a filler (such as carbon nanotube, graphene, nanoclay, SiO2)
illustrates a significant reduction in the maximum heat release [329] compared to
neat polymer although the total heat release remained unchanged. In addition, aspect
ratio of dispersed silicate layers and the processing method have a robust influence
on the antiflammability characters of composite matrices [304, 330–338].
Besides these selected behaviors, there are many important behaviors (such as
physical characters, rheological properties, responsive natures to certain stimuli in
the cases of stimuli-responsive composites and nanocomposites, functional proper-
ties in case of functional composites) need to be considered properly for realizing
desired application potentials from micro- and nanocomposites.

11 Challenges for Composites and Nanocomposites

Different challenges are observed during productions and also dealing with micro- and
nanocomposites during practical applications. For example, carbon based nanofillers are
relatively at an early stage of development in comparison to nanoclay based nanofillers
which are widely used in composites formulations and have met with more relative
success. However, several fundamental challenges are required to be addressed in order
to achieve full potentials on the uses of nanofillers in polymer composites [304]. Uniform
and balanced dispersions of fillers into composite structures are critically important in
order to realize the desired full potentials from micro- and nanocomposites. Some of
popular techniques used in composite processing are not economically viable, while
some other frequently used techniques, such as solvent processing, LBL assembly, and
electrospinning although useful for better dispersions of fillers into composite structure
but show less cost-effectiveness. In this context, melt processing is one of the most
widely used economically viable processing methods which sometimes provides
12 Composites and Nanocomposites 479

inadequate dispersion of filler in the composite system to produce poor optimal prop-
erties [1–2, 33, 304]. Mechanical reinforcement of melt processed composites exerts
many challenges. For example, (a) SWNT shows agglomeration at higher volume
fractions, (b) MWNTs require to be disperses at much higher loading. An increase in
interfacial area with decrease in easy tube diameter is usually observed. For example, at
0.5 wt% of nanotubes MWNT has 70% of the interfacial area of SWNT, as a result,
SWNT lose their intrinsic advantage of higher aspect ratio. Additionally, composites at
higher loading do not perform at a similar way when loaded at a lower level; thus, it
influences the magnitude of reinforcement. Improvement and ensuring the quality of
polymer composites with different fillers (such as CNT, graphene, or clay) depend upon
a number of factors, some of which include (a) nature of filler (such as CNTs, MWCNT
or SWCNT), (b) layers of graphene or clay, purity, length of CNTs, diameter and length
of CNT (aspect ratio), (c) loading of nanofillers, (d) dispersion in the matrix,
(e) alignment (tough to align graphene or nanoclay), (f) interaction between the polymer
and the nanofiller, (g) nature of the polymer, (h) method of fabrication [304, 333]. In the
published pieces of work on composites, in most of the cases, a single type of nanofiller
in a polymer matrix has been used, however, simultaneous incorporation of different
nanofillers may have some significant impacts on the characters of the composite
matrices. The impact of synergy in properties between multiple nanofillers is yet to be
investigated. As for instance, 1D fillers may interfere with the stacking of 2D platelets,
so the incorporation of CNTs into glass fiber composites inhibits crack formations
because of the large density of nucleation sites provided by CNT [1, 304, 334].
Load transfers between nanofillers and polymers are usually obtained by both
noncovalent and covalent modifications with functional groups. The introduction of
covalently functional bonds disrupts the conjugation of CNTs and graphene which
sometimes lead to a negative effect on the electrical properties of the resulting
composites. In an investigation, it was observed that a combination of noncovalent
and covalently fuctionalization on CNT contributed to enhance compatibilizer-
polymer interaction leading to better mechanical and electrical properties [304]. As
a result, it is very important to have a better understanding of the interface between the
noncovalently functionalized CNT/graphene and the polymeric matrix in order to
enable simultaneous improvement of both mechanical and electrical characters of the
composites [304, 335–336].
Additionally, selectively some important aspects of biocomposites, green com-
posites and nanocomposites, single polymer composites, stimuli-responsive com-
posites are very briefly covered in the next sections and interested readers are
advised to consult relevant references for more detail information [437–458].

12 Bio-composites, Green Composites, and Nanocomposites

Similar to microcomposites and nanocomposites that have been successful to draw

active current research interests all over the world due to their wide range of
conventional and high-tech industrial applications, biocomposites, green compos-
ites, and nanocomposites are widely studied for a huge plethora of potential
480 S. M. R. Billah

industrial applications. Many natural polymers (such as cellulose, chitin, gelatine,

collagen) can be used for bio-based composites and nanocomposites which are
highly attractive due to the natural abundance that are also renewable in nature.
Biopolymers (such as cellulose) have many truly impressive range of diverse
properties which can be accessed from the raw resources like cellulose. Cellulosic
nanocomposites are usually produced by different techniques commonly applied in
nanotechnology where the cellulose component may work as the polymeric matrix
or it can also work as a nanoparticle and/or the nanometer-scale constituent (such as
cellulose nanocrystals) or can be doped with advanced materials (e.g., quantum dots,
functional materials) for functionalization. Since the most abundantly available
natural polymers, they can be used to produce environmentally friendly biocompat-
ible renewable material which are focal points for many conventional to high-tech
advanced applications [434–455].

12.1 Biocomposites

Environmental concerns along with the development of bio-based composite materials

for different industrial applications have been successful to draw active current
research interests on biomaterial based composites and nanocomposites (such as
cellulose based bio-nanocomposites). For example, many investigations are focused
on the use of natural fibers in composites as an alternative to conventional synthetic
fillers, which are traditionally used to reinforce thermoplastic matrices. The develop-
ment of such composite materials using the bio-based and biodegradable reinforcing
agent (such as nanofibrillated cellulose) has been thoroughly investigated by different
researchers. Additionally, the use of bio-reinforced composites in automotive, con-
struction, packaging, and medical applications also increasingly focused to mitigate
specific the requirements for environmental sustainability. So, at present there are quite
a lot of interest on green polymer based polymer nanocomposites. Green polymer
based nanocomposites have unique characteristic properties for combining the advan-
tages of natural fillers and organic polymers. In this regards, plant fibers are found
suitable to reinforce polymers [434–455]. As a result, in this current section cellulose
based composites and nanocomposites are briefly described.

12.2 Cellulose Nanocomposites

Cellulose, the most abundant natural biomass possesses very promising properties,
some of which include mechanical robustness, hydrophilicity, biocompatibility, and
biodegradability. Cellulose based composites have many applications (e.g., in drug
delivery systems, hydrogels, electronic active papers, sensors, shape memory mate-
rials, and smart membranes) and also offer interesting potential improved properties
and new functionalities. Cellulose based stimuli-responsive smart materials have
many advantages, some of the most important ones include regulation of stimuli-
responsive behaviors during the reactions with the environmental stimuli and wide
12 Composites and Nanocomposites 481

application potentials of this smart materials in different fields (e.g., as biomaterials).

There are different ways to incorporate different stimuli-responsive materials into the
structures of cellulose composites to regulate different properties of the bulk com-
posite structures. Although environmentally stimuli-responsive cellulose composites
have many conventional and high-tech applications, there are quite a lot of chal-
lenges in order to produce high-quality stimuli-responsive cellulose composites and
there are ways how to mitigate these challenges [41–51].

12.3 Cellulose Composites

At present cellulose-fiber-reinforced polymer composites is a very attractive

research topic due to their attractive properties, some of which include (a) low
density, (b) nonabrasive, (c) combustible, (d) nontoxic, (e) low cost, and
(f) biodegradable properties. There are different active current research activities
all over the world on the efficient use of cellulose fibers as reinforcing materials for
the preparation of various types of composites. However, the use of cellulose-fiber-
reinforced composites is relatively less attractive due to a number of reasons, such
as (a) relatively less interfacial adhesion, (b) low melting point, and (c) lower
hydrophilicity. Different techniques are used to overcome these drawbacks. For
example, pretreatments of the cellulose fibers can be used to modify the fiber
surface (e.g., influencing moisture adsorption process using chemical functiona-
lization and improving surface roughness techniques). There are different methods
of producing cellulose composites; one of the important methods is the use of
micro- and nanofibers produced by using electrospinning technique. The produc-
tion of cellulose based electrospun macro- and nanofibers has been successful to
attract increasing interest due to different reasons including (a) high strength and
stiffness, (b) biodegradability and renewability, (c) relative ease in the production
of high-quality composites using these fibers. The development of electrospun
cellulose micro- and nanofibers based composites is relatively a new area of
research and these fibers can be used as reinforcement in composite materials
due to their contribution in the improvement of mechanical, thermal, and biodeg-
radation properties of composites. Cellulose fibers are hydrophilic in nature and
thus important to increase their surface roughness for the development of compos-
ites with enhanced properties. There are different methods of the surface modifi-
cation of cellulose fibers for their applications in the synthesis of high quality
nanocellulose and cellulosic composites. For example, a reduction of amorphous
parts of fibers obtained from natural plants to cause a break down in the hierarchi-
cal structure of the plant into individualized nanofibers of high crystallinity is one
of these types of usually used approach. As already mentioned, different advan-
tages of cellulose fibers (e.g., abundantly available, low weight, biodegradable,
cheaper, renewable, low abrasive nature, good mechanical properties) have made
them attractive reinforcing materials although they have some disadvantages (e.g.,
moisture absorption, quality variations, low thermal stability, and poor compati-
bility with the hydrophobic polymer matrix) [41–51, 434–444].
482 S. M. R. Billah

12.4 Stimuli-Responsive Smart Cellulose Composites

Despite specific interesting features of cellulose composites for value additions along
with the aim of applying cellulose materials for both conventional and high-tech
applications, cellulose composites can be used to fabricate environmental stimuli-
responsive smart materials, which will show intelligent behaviors when exposed to
specific environmental stimulus. Environmentally stimuli-responsive smart cellulose
composites show change in their features (such as morphology, mechanical strength,
wettability, color, thermal property, electrical or magnetic property) in a controlled
manner in response to the introduction of a predetermined external stimulus. These
types of environmentally stimuli-responsive smart cellulose composites are produced
by incorporating environmental stimuli-responsive materials into the structure of
cellulose composites to make them environmentally responsive. These stimuli-
responsive materials are usually used to generate desired controllable changes on
the cellulose composite to produce and control a specific alteration on different
properties, such as shape, mechanical rigidity/flexibility, opacity, porosity. Environ-
mentally stimuli-responsive smart cellulose composites have great potential in many
applications, especially as biomaterials and drug carriers. [41–51, 430–435, 445–455].

12.5 Bio-inspired Stimuli-Responsive Mechanically Dynamic

Composites

Polymer nanocomposites which show stimuli responsive changes in their morphol-

ogy and mechanical behaviors have wide potential applications in the production of
smart protective devices or the development of adaptive biomaterials. For example,
there are a few reports on the development of bio-inspired stimuli-responsive
mechanically dynamic composite materials based on the dermis of sea cucumbers.
In this case, a percolating cellulose nanofiber network has been used as reinforce-
ment to a low-modulus matrix polymer. The cellulose nanofibers display strong
interactions between themselves which contributed for an even dispersion of perco-
lating nanocomposites to display a high stiffness due to the abundance of surface
hydroxyl groups. This study showed that the nanofibers–nanofibers interactions
were largely switched off by the introduction of a chemical regulator which allowed
a competition in hydrogen bonding and thus caused a significant decrease in the
stiffness of the material. They developed nanocomposites which showed three orders
of magnitude modulus changes by using a host polymer with a thermal transition
with a specific regime [41–51, 446–451].

13 Single Polymer Composites

Environmental regulations relating to safe production and final applications of compos-

ites and nanocomposites play provided one of the important impetus to develop single
polymer based composites and nanocomposites. As a result, a usual interest to improve
12 Composites and Nanocomposites 483

the recyclability of composite and nanocomposite materials has recently emerged and
for complying with the environmental regulations and other new requirements, a
possible strategy has recently been developed which termed as single polymer compos-
ite where both matrix and reinforcement have the same chemical composition. One of
the principal advantages of single polymer composites is that, unlike traditional hetero-
geneous composites (such as glass- or carbon reinforced polymer composites), they can
be totally melted down at the end of the product life for recycling. Additionally, life
cycle assessment does not produce favorable results for conventional reinforced com-
posites, although high-quality mechanical performances have been achieved to some
extent. One of the main reasons behind this is the use of energy-intensive techniques
usually used in the production of the reinforced composites and limited recyclability of
the corresponding composites. For example, glass fibers are one of the principal
component in polymeric matrix composites (PMCs) and this type of reinforcement is
severe challenge during both mechanical and thermal recycling. Natural fibers are
popularly introduced as reinforcement in order to overcome this problem. Natural fibers
are usually renewable in nature which can be thermally recycled, but difficulties arise
during recycling because of their low thermal stability. This practical challenge was one
of the main impetus to a search for alternative recycling-friendly homocomposites, such
as single polymer composites which represent a valuable alternative to the traditional
fiber reinforced composites where the matrix and the reinforcement are from the same
chemical composition that facilitates an ease in recyclability. Additionally, advantages of
single polymer composites include (a) the possibility of manufacturing lightweight parts
and structures in comparison with traditional composites because of lower density of
polymeric fibers compared with traditional reinforcements (such as glass fiber, carbon
fibers, basalt, talc, and silica); (b) better interfacial adhesion fiber-matrix, in comparison
with traditional composites, because of a full compatibility with single polymer com-
posites. However, the main challenge on the production single polymer composites is
the small difference in melting temperatures of the matrix and reinforcement where both
constituents have the same chemical composition. However, there are scopes to expand
this processing windows by using polymers with same chemical composition but
different chemical structure (e.g., high density polyethylene, low density polyethylene,
different types of polylactic acids and their structural homologs) or changing the
chemical structure of the polymers. A vast series of single polymer composites has
already been reported for a wide range of industrial applications [1–10, 30–79,
456–461].

14 Future Directions in Composites and Nanocomposites

Both micro- and nanocomposites are very wide fields of research where almost
everyday there are some notable progresses being made by dedicated research
groups from all around the world because micro- and nanocomposites have their
applications in a wide range of areas including (a) material sciences, (b) biological
sciences, (c) engineering and technologies, (d) electronics, (e) other areas life and
physical sciences. As a result, it is almost impossible to cover all areas; however,
484 S. M. R. Billah

very precisely recent trends of current research activities from different selected
fields are briefly stated here. Both the micro- and nanocomposites are focused on
high-quality, cost-effective, and technically performing environmentally benign
products development where one of the main thrust is biocompatibility with cost-
effective environmentally friendly product developments [1–10, 33, 304].
The higher strength-to-weight ratios of nanocomposites have made them novel
materials to replace metals in applications which requires high material performance
(e.g., windmill blades, aircraft components). Nanofiller-reinforced polymer nano-
composites are usually formed by dispersing strong and stiff nanoparticles in various
polymeric matrices, and much of the recent work on nanocomposite mechanics only
focuses on improving the reinforcement phase (such as the dispersion of nanofillers).
However, the design of high-performance nanocomposites requires polymeric matri-
ces with superior mechanical properties and versatile techniques for tailoring these
matrices. Additionally, suitable polymeric nanoscale building blocks for advanced
composite matrices have been prepared from conventionally strong materials. For
instance, a high performance polymer poly-paraphenylene terephtalamide (also
known as Kevlar or aramid polymer) has been used as a matrix material in the
form of nanoscale building blocks for nanocomposites. Besides this, the synthesis of
reactive aramid nanoscale structures has addressed the limitations in the field of
synthetic nanocomposites that traditionally relied on a set of polymeric building
blocks with low reactivity and of limited variability. Reactive nanoscale aramid
structures have been prepared to bond with various moieties to form aramid net-
works with tailored nanostructures, morphologies, and mechanical properties.
Kevlar based metal (such as gold) nanocomposites have been shown to provide a
combination of stiffness, strength, and strain to failure due to the reinforcement
effect of the metal particles (such as gold nanoparticles) through their bonding with
the aramid matrix [1–10, 33, 50–89, 304].
A structure-property relationship has been established by a systematic tailoring
and optimizing the mechanical properties of these advanced aramid nanofiber/gold
nanoparticle composites. The workers showed the first demonstration of the possi-
bility for aramid nanoscale fibers to form versatile nanosized building blocks that can
then be crosslinked or conjugated to fabricate composite structures involving mate-
rials that offers a new generation of nanostructured aramid materials. Besides this,
the Kevlar/gold nanocomposites synthesized based on aramid nanostructures have a
higher strain energy density than that of a commercial plain-woven Kevlar mat tested
along its strongest axis which indicates their potential as high performance materials
to resist extreme high rate loadings (e.g., blasts). A wide variety of materials have
been investigated for producing technically robust high-performance composites and
nanocomposites for a huge range of applications. For example, recently, growing
prospects of clay (such as layered hydrous aluminosilicates) based nanocomposites
have renewed further interest in understanding the fundamental elastic and plastic
properties of hydrous aluminosilicates [1–10, 33, 50–89, 304].
In the last two decades, polymer-clay nanocomposites have been successful to
attract active research interests due to their significant improvement capability in
mechanical and physical properties with minute amount of nanofiller which provide
a promise to avoid the typical compromise that exists between properties and
12 Composites and Nanocomposites 485

processability of composite materials. However, their success has so far been limited,
despite the expectations created by nanoclays in the academic and industrial commu-
nities for their huge application potentials. Some of the reasons behind these setbacks
include (a) poor dispersion of nanoclays in polymer matrices, (b) weak interfacial
interaction with polymers, (c) limited control of nanoclay-orientations. As a result,
more pieces of continuous research activities are targeting improve these nanoclay-
polymer interactions. These are some examples of current trend of research in a tiny
area of composites and nanocomposites. As already mentioned in different earlier
sections that both composites and nanocomposites are widely used in a huge range of
areas, so the current research and developments in these areas are continuously going
on for different reasons, including (a) high-tech and cost effect product developments,
(b) incorporating new features on existing products according to customer demands,
(c) mitigating environmental concerns, (d) addressing other issues that arise with the
change of time, situation, supply, demands, advents of new methods, and scientific
tools, (e) incorporating new functionalities [1–10, 33–189, 304–407].
There are increasing trends in using lightweight, high-strength, fiber-reinforced
composites for producing different parts of electric cars, aerial vehicles and wind
turbines. However, one of the principal limitations is the use of these new materials
cause different level of microcracks which can lead to catastrophic failures which are
often hard to detect and repair. In this context, a solution to this problem is to use
materials with self-healing capability in order to repair themselves in case of any
cracks and restore their mechanical properties automatically. It is interesting to note
that research on this self-healing capabilities of certain materials has been carried out
for over a decade and have been successful to produce self-healing composites
capable to recover properties (e.g., interlaminar fracture toughness with over 100%
efficiency). As a result, some particular types of current self-healing polymers offer a
new route toward safer, longer-lasting, fault-tolerant products and components
across a broad cross section of industries (such as coatings, electronics, transporta-
tion, energy, security, printing, textiles). Some particular types of composites, such
as lightweight ballistic composites, have many applications in defense sectors (e.g.,
in military and law-enforcement applications). Ballistic composites can be designed
in various ways and sometimes they can be designed and produced to give superior
properties (in some particular areas) compared to particular type of conventional
materials usually used for ballistic purposes. Since they are light weight and have
durability against environmental conditions (such as moisture, chemicals, gases,
heat) with high performance (e.g., high strength, impact and ballistic resistance,
damage tolerance), they have huge range of applications in different areas. For
instances, lightweight ballistic composites are widely used in various areas including
(a) light weight vehicles, (b) watercraft and aircraft armor giving high performance
and light weight protection against bullets and fragments. Additionally, they also
show high-quality insulating properties in high temperature environments. There are
continuous developments in this area to overcome many existing limitations as well
as incorporating more desired properties into the composite structures based on
customer demands (mostly from defense and law-enforcement applications).
Composite based textiles are increasingly used in various industrial sectors (e.g.,
car seats, carpeting). However, the term textile composites is often used to describe a
486 S. M. R. Billah

limited narrow range of materials which are mostly based on three-dimensional

reinforcements generally produced by using specialist pieces of equipment. There
are intensive research activities on a broad range of polymer composite materials
with potentials for textile reinforcements, for example, (a) woven and noncrimp
commodity fabrics, (b) high performance 3D textiles.
Increasing environmental regulations along with more customer demands with
sustainable and environmentally friendly natures from different products are other
important impetus to increase current industrial and academic research interest on
green composites. Scientists and engineers are increasingly focused on minimizing
the environmental impact on the production of polymer microcomposite and nano-
composites. For example, lifecycle assessment is highly important at every stage of a
product’s life, such as (a) from initial synthesis through to final disposal, (b) safe
handling of materials and environmentally friendly processing methods to ensure a
sustainable society. Leading researchers all around the world are actively engaged
with research and development activities in this area to produce green composites by
using different techniques (including using suitable natural and environmentally
benign polymers with environmentally sustainable and safe processing techniques)
[1–5, 66–93, 304–407].
In addition, current other trends in main industrial applications of composites and
nanocomposites include (a) aerospace industry (for producing wings, fuselage,
radomes, antennae, tail-planes, helicopter, blades, landing gears, seats, floors, inte-
rior panels, fuel tanks, rocket motors cases, nose cones, launch tubes);
(b) automobile industry (for making body panels, cabs, spoilers, consoles, instru-
ment panels, lamp-housings, bumpers, leaf springs, drive shafts, gears, bearings);
(c) maritime industry (for the preparation of boats hulls, decks, masts, engine
shrouds, interior panels); (d) chemical industry (for producing pipes, tanks, pressure
vessels, hoppers, valves, pumps, impellers); (e) domestic applications (such as for
making interior and exterior panels, chairs, tables, baths, shower units, ladders),
(f) electrical and electronic industries (for producing panels, housings, switchgear,
insulators, connectors, packaging); (g) leisure industry (for making motor homes,
caravans, trailers, golf clubs, racquets, protective helmets, skis, archery bows,
surfboards, fishing rods, canoes, pools, diving boards, playground equipment);
(h) health and security; (i) sensoric applications; (j) other branches of material,
polymer, and life sciences including engineering and technologies [1–33, 50–96,
236–298, 346–389, 456–466].

15 Conclusion and Perspectives

Composites and nanocomposites are some of the most important topics in modern
nanoscience and nanotechnology due to their practical and potential exploitations in
industrial and academic studies for ever-growing enormous applications in everyday
life. If we look forward to most important focal points of industrial and academic
researches for the twenty-first century, both micro- and nanocomposites are some of
these fields which will contribute to high level of scientific and technological
12 Composites and Nanocomposites 487

developments. Both conventional and functional hybrid composites will play a

major role in the development of advanced materials for high-performance materials
for advanced high-tech and also cost-efficient applications. Current continuous
research in both composite and nanocomposites (including conventional and func-
tional hybrid systems) is being carried by the growing interest of chemists, physi-
cists, biologists, and materials scientists in order to fully realize the potential
opportunity to create high-tech cost-effective advanced materials as well as conven-
tional materials with desired criteria. For example, for hybrid composite systems
they provide the opportunity to incorporate different components into the structure
which can be designed for a simultaneous benefit from the best of the three realms –
(a) inorganic, (b) organic, and (c) biological features. In addition, composites also
provide the opportunity to use bio-inspired strategies for mimicking the growth
processes that occur in biomineralization and design innovative multiscale structured
hybrid systems (from nano- to millimetric scale) which are hierarchically organized
in terms of structure and functions. Besides these effects, the high versatility in
chemical and physical properties and shaping, hybrid nanocomposites offer signif-
icant opportunity in order to facilitate integration and miniaturization thus open up to
golden door for many promising applications in a variety of areas including
(a) optics, (b) electronics, (c) ionics, (d) mechanics, (e) membranes, (f) functional
and protective coatings, (g) catalysis, (h) sensors, (i) biology, (j) medicine,
(k) biotechnology, (l) security, (m) structural applications. Many conventional and
hybrid composite based materials have been continuously appearing in the market
either as prototype or commercial products, during the past decades where attempts
were made to discuss the applications of some of these composites within this
chapter but they only represent a small fraction of the tip of the iceberg.
In addition, currently, molecular approaches of solid state chemistry and nano-
chemistry have reached a very high level of sophistication where chemists have the
tools for taking practical steps to tailor-make any molecular species (e.g., molecules,
clusters, nanosized particles, nanolamellar compounds, nanotubes) and also to
design new functional hybrid materials with improved technical performances. As
a result, at this level of knowledge and understanding in nanoscience and nanotech-
nology and also following strict rules of environmental issues imposed by the current
society, for manufacturing composite based high-tech materials and devices with
complex structures, high level of integration and miniaturization is just a question of
scientist’s imagination and of making industries aware of their opportunities and
benefits. In this context, one can bet that advanced composite materials will play a
major significant role in oncoming future to shape everyday life.
This chapter covers a broad range of aspects and issues of micro- and nano-
composites and briefly covers different areas of polymer-nanocomposites known to
date which include (a) polymer/carbon nanotubes, (b) polymer/metal nanospheres,
and (c) polymer/clay nanoplatelets composites. This chapter also presented different
issues involved with the general overview, synthesis and applications of micro and
nanocomposites in order to provide a general understanding on the fundamental
features of these materials for both conventional and high-tech advanced applica-
tions. However, besides all these efforts, it is beyond the scope of this current chapter
488 S. M. R. Billah

due to space limitation to cover all important features of micro- and nanocomposites
emerging almost everyday because of intensive research in this field. So interested
readers are suggested to consult the references provided along with this chapter for
more in-depth information and current and future issues of related journals, books,
and conference proceedings cited in the reference section to have most update
current information on micro- and nanocomposites.

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Polymer Blends
13
Ibrahim Khan, Muhammad Mansha, and
Mohammad Abu Jafar Mazumder

Contents
1 History of Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
2 Classification of Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
2.1 Completely Miscible Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
2.2 Completely Immiscible Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
2.3 Partially Miscible Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
3 Compatibilization Strategy for Good Dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
4 Methods of Polymer Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
4.1 Melt Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
4.2 Mill Mixing and Fine Powder Mixing Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
4.3 Solution Casting Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
4.4 Freeze Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
4.5 Latex Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
4.6 Mechanochemical Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
4.7 Interpenetrating Polymer Network Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
5 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
5.1 Spectroscopic Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
5.2 Energy-Dispersive X-Ray Spectroscopy (EDX) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
5.3 Scanning Electron Microscopy (SEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529
5.4 Transmission Electron Microscopy (TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
5.5 X-Ray Diffraction (XRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
5.6 Tensile Tester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
5.7 Differential Scanning Calorimetry (DSC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531
5.8 Dynamic Mechanical Analysis (DMA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532
5.9 Thermogravimetric Analysis (TGA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532
5.10 Rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533
5.11 Miscellaneous Characterization Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533

I. Khan · M. Mansha · M. A. Jafar Mazumder (*)

Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
e-mail: [email protected]; [email protected]; [email protected]

© Springer Nature Switzerland AG 2019 513

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_16
514 I. Khan et al.

6 Properties of Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 534

6.1 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 534
6.2 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
6.3 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
6.4 Optical and Glass Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
7 Applications of Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
7.1 Nanocomposites and Other Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
7.2 Electronic Device and Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
7.3 Membrane and Plastic Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
7.4 Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542
7.5 Miscellaneous Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543
8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545

Abstract
In this chapter, we have presented different aspects of polymer blends, from
fundamentals to the synthesis, physical and chemical properties, and applications.
Polymer blends are made from the combination of two or more polymer compo-
nents, having staggering and incredible applications in numerous fields due to their
advanced properties. A brief introduction of the polymer blends about its origina-
tion and development is presented in the first part of this chapter; then important
polymer blend types and synthesis methods are summarized with a brief discussion
about their thermodynamic properties. Different characterization techniques were
also discussed which can be used to determine the morphological, structural,
chemical, and mechanical properties of these materials. The thermal, mechanical,
and electrical properties of different polymer blends are discussed considering some
recent applications of polymer blends in different industries.

Keywords
Polymer blends · Copolymer · Miscibility · Morphology · Compatibilization ·
Rheology

Abbreviations
ABS Acrylonitrile butadiene styrene
ATRP Atom transfer radical polymerization
BHJ Bulk heterojunction
BSA Bovine serum albumin
CAB Cellulose butyrate
CAGR Compound annual growth rate
CMCA/CA Carboxymethyl cellulose acetate/cellulose acetate
CPs Conjugated polymers
DEC Diethylene carbonate
DIM Direct injection molding
DMA Dynamic mechanical analysis
13 Polymer Blends 515

DMC Dimethyl carbonate

DSC Differential scanning calorimetry
EBA Ethyl butyl acrylate
EC Ethylene carbonate
EDLC Electrochemical double-layer capacitor
EDX Energy-dispersive X-ray spectroscopy
ELSD Evaporative light scattering detector
EPDM Ethylene propylene diene
EVA/SAN Poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile)
GO Graphene oxide
GPC Gel permeation chromatography
HDPE High-density polyethylene
HPLC High-performance liquid chromatography
IPN Interpenetrating polymer network
LDPE Low-density polyethylene
LLDPE Linear low-density polyethylene
MMMs Mixed matrix membranes
MMT Montmorillonite
MW Molecular weight
NC Nitrocellulose
NMR Nuclear magnetic resonance spectroscopy
OCP Open circuit potential
P(VDF-co-HFP) Poly(vinylidene fluoride-co-hexafluoropropene)
PA Phosphoric acid
PA 6,6 Polyamide 6,6
PA12 Polyamide-12
PANI-PVC Polyaniline-polyvinylchloride
PBI Polybenzimidazole
PBT Poly(butylene terephthalate)
PCE Power conversion efficiency
PCL/PLA Poly ε-caprolactone/poly lactic acid
PDA Photodiode array detector
PDMAEMA N,N-dimethylamino-2-ethylmethacrylate
PE Polyethylene
PEDOT Poly(3, 4-ethylenedioxythiophene)
PEGF Polyethylene glycol fumarate
PFCE Partially fluorinated copolyester
PIM-1 Polymer of Intrinsic Microporosity-1
PIPN Pseudo-interpenetrating polymer networks
PL Photoluminescence
PLLA Poly(L-lactide)
PMMA Poly(methyl methacrylate)
PMMA/EVA Poly(methyl methacrylate)/ethylene-co-vinyl acetate
PNMPy Poly(N-methylpyrrole)
516 I. Khan et al.

PS Polystyrene
PSCs Polymer solar cells
PSF Polysulfone
PSI Polydispersity index
PV Pervaporation
PVA Poly vinyl alcohol
PVB Polyvinylbutyral
PVC/EVA Poly(vinyl chloride)/ethylene-co-vinyl acetate
PVC/SAN Poly(vinyl chloride)/poly(styrene-co-acrylonitrile)
PVdC-AN Poly(vinylidene chloride-co-acrylonitrile)
PVDF Polyvinylidene fluoride
PVDF-HFP Poly(vinylidene fluoride-co-hexafluoro propylene)
PVOH Poly(vinyl alcohol)
PVPh Poly (4-vinylphenol)
SBR Styrene butadiene rubber
SDCDPS Disodium 3,30-disulfate-4,40-dichlorodiphenyl sulfone
SEM Scanning electron microscopy
SFPAE Sulfonated fluorinated poly(arylene ether)
SIPN Semi-interpenetrating polymer network
SPEEK Sulfonated poly(etherethereketone)
SPPU Sulfonated polyphenylene sulphone
SRNF Solvent resistance nanofiltration
TEM Transmission electron microscopy
TGA Thermogravimetric analysis
THF Tetrahydrofuran
TMPC Tetramethyl bisphenol-A polycarbonate
UF Ultrafiltration
UTM Universal testing machine
VRFB Vanadium redox flow battery
XLPE Cross linked polyethylene
XRD X-ray diffraction
ZIF Zeolitic imidazolate framework

1 History of Polymer Blends

Since the introduction of nitrocellulose (NC), first synthetic polymer to be used in

energetic material formulations, prepared by Braconnot in 1833, has opened a new
era in the world of science. No doubt, the polymer industry nowadays is one of the
most developing industries in the world and has brought evolutionary changes in
everyday life. It is very difficult to consider our daily life without their influence and
impacts of these polymeric materials [1]. Considering industrially synthesized
available polymers, the scientists started to modify the structure of these materials
in different ways to make them suitable for different target applications. One of
such modifications of these materials is polymer blending. Polymer blend is a
13 Polymer Blends 517

homogenous or heterogeneous mixture of at least two polymers/copolymers. In

some cases, it is also referred as polymer mixture. These polymers can interact
chemically or physically depending on their structural properties, and their physical
properties obviously differ from their parent components [2].
The history of the polymers is set dates back to 3000 BC, when shellac (natural
polymer) was used as varnish in India [3, 4]. When Christopher Columbus discov-
ered the new world in 1495–96, he brought an important product with noticeable
elastic properties, called rubber. Gutta percha was introduced in seventeenth century.
But the first synthetic polymer available industrially was nitrocellulose (in 1833). In
1850s, Charles Goodyear patented ebonite, which is a hard rubber prepared by the
vulcanization of natural rubber or related polymers into more durable materials by
the addition of variable amount of sulfur (e.g., 25% to 80%) [3].
In 1846, the first polymer blend patent, prepared from gutta percha and natural
rubber, was claimed by an artist Alexander Parkes [3]. That patent was the start of
this amazing technology, which has grown so rapidly, and the number of polymer
blend patents approached to 3000 within a year. In the recent times, the focus to the
polymer blends industries is tremendously increased due to their magnificent appli-
cations in every aspect of life [4, 5].
The most important unit of operations in the polymer industry are blending and
mixing, which mostly follow the criterion discussed below [3, 5]:

1. Selection of suitable polymers, which can be mixed to a certain extent to form

polymer blend. The polymer structure and chemical properties play an imperative
role in this case.
2. Selection of a suitable solvent, as a reaction medium for raw polymers. It is
pertinent for the polymer components to have some solubility in the solvent for
good blending. In certain cases, surfactants can also be used for good mixing.
3. Addition of a copolymer whose one part is soluble in one phase, and other part is
soluble in other phase.
4. Addition of a large amount of core-shell (co)polymer.
5. If needed, stabilizers/plasticizers are also added.
6. Provide proper conditions and medium for reaction to occur.

Over the period of time, certain devices have been designed for the purpose of
polymer synthesis and its blending. Hancock patented first internal mixer in early
1830s [5], which was improved by Freyburger to a more efficient counter-rotating twin
shaft machine in 1876–1877 [6]. Chaffee patented two-roll mills screw extruder in
1836 [7]. In the late nineteenth century, the electric extruders were developed in
Britain, while in the early twentieth century, specifically during World War I and II,
the world developed Myriad polymer industry to fulfill its need. Following the
development of polymer technology, the rapid advancements were observed in the
polymer processing devices such as co-extruders, film blowers, crosshead dies,
filament extruders, breaker plates, screen packs venting, and two-stage screws in
extruders. In the beginning of the 1980s, computer devices came into the picture,
which made the polymer blending an ultimate choice for many industrial,
518 I. Khan et al.

agricultural, medicinal, and domestic applications [8], and turns out as a huge
industry. It constitutes approximately 36 wt% of the total polymer consumption,
and their applicability continues to increase with industrial development. Nearly 65%
of polymer alloys and blends are produced by polymer manufacturers itself, 25% by
some related companies, and the remaining 10% by other sources. The expected
market growth of polymer blends is tabulated in Table 1, and the diagrammatic
representation is shown in Fig. 1. The worldwide market in volume for polymer
blends was estimated to be more than 22 billion pounds in 2012, which is expected to
increase to 28 billion pounds by 2018 assuming the increasing rate at 4.4% [at a
5-year compound annual growth rate (CAGR)] (Table 1). Asia being the leading
polymer market occupied nearly 55% of the total market, followed by Europe and
America [9, 10].
The major objective of polymer blending is to achieve cheap, readily available, and
commercially viable products with unique properties. Polymer blending is a vast and
unlimited subject of interest that requires highest attention theoretically and experi-
mentally. From the literature, it was found that polymer blends have superior prop-
erties compared to its component polymers. Blending of different polymers is one of
the most important industrial tools to get more efficient and attractive product for
various applications. Some characteristics of polymer blending are mentioned below:

1. Provide materials with desired properties at the lowest possible expense, which
are within the limit of an ordinary people.
2. It can be used to extend the engineered resin performance that is essential in large-
scale applications.
3. Depending on its applications, one can easily design polymer blends of unique
properties, e.g., improving specific properties by increasing impact strength or
solvent resistance.
4. Polymer blends are suitable for recycling and biodegradation.
5. Blending technology offers striking opportunities for salvage and recycling of
polymer wastes, which is impossible in case of their pure component.
6. Polymer blending greatly improved processability, product consistency, and scrap
reduction of the primary targeted polymer.

Table 1 Global engineering resin and polymer alloy/blend market by resin type, through 2018
($ millions)
CAGR%
Resin 2012 2013 2018 2013–2018
Polycarbonates 8000 8280 10,476 4.8
Polyamides 6000 6279 7883 4.7
Polyacetals 2500 2593 3110 3.7
PBT 2100 2193 2722 4.4
Other ETPs (i.e., PET, PPS, LCPs, 997 1033 1237 3.7
polysulfones, etc.)
Alloys/blends 2575 2673 3209 3.7
Total 22,172 23,051 28,637 4.4
13 Polymer Blends 519

12,000
10,000
Million lbs.

8,000
6,000
4,000
2,000
0
2012 2013 2018

Polycarbonates Polyamides Polyacetals

PBT Other ETPs (1) Alloys/blends

(1) Includes PET, PPS, polysulfones, LCPs, polyketones and others

Fig. 1 Expected market growth of polymer blends. (Source: BCC Research Report (2013) global
engineering resin and polymer alloy/blend market by resin type, 2012–2018 ($ millions)

7. Polymer blending is an appropriate method for swift formulation changes, e.g.,

yearning applications.
8. Considering environmental issues, the polymer blends also increases the life time
of the parent polymer.

2 Classification of Polymer Blends

The miscibility of individual polymer is always considered to be a key factor for

classifying polymer blends. By definition, miscibility is the capability of a mixture
that form a single phase over certain range of temperature, pressure, and composi-
tions. The miscibility term describes the homogeneity of polymer mixtures at a
particular temperature. It can be influenced by various factors such as morphology,
intermolecular interaction, crystalline phase, and surface tension. The polymer blend-
ing miscibility can be judged by various factors such as chemical structure, molecular
weight distribution, and molecular architecture of the components that can be con-
firmed by light scattering, X-ray scattering, and neutron scattering. By using the
second law of thermodynamics, one can comment about the miscibility or immisci-
bility of two polymers considering a factor of entropy involved in it by Eq. 1 [11].

ΔGM ¼ ΔH M  T ΔS M (1)

where ΔG = change in free energy, ΔH = change in enthalpy, ΔS = change in

entropy, T = absolute temperature, and M = mixing.
For a homogeneous miscible blend, the ΔGM requires a negative value. For high-
molecular-weight polymer blends, the gain in entropy (S) is negligible. Hence, ΔGM
520 I. Khan et al.

can only be negative if the ΔHM is negative, which means that the mixing must be
exothermic. The system usually requires specific interactions between the blend
components. These interactions may range from strongly ionic to nonbonding and/or
weak bonding that includes hydrogen bonding, ion–dipole, dipole–dipole, and
donor–acceptor interactions. Thus, for complete miscibility of the polymer blends,
the following conclusion can be drawn [11, 12]:

Condition 1. Thermodynamically Gibbs free energy of mixing must be negative.

ΔGAB < ΔGA þ ΔGB (2)

Or

ΔGM < 0 (3)

Condition 2. The enthalpy of mixing must also be negative.

ΔH M  T ΔS M < 0 (4)

As enthalpy depends on pressure, the increasing pressure will increase miscibility

as indicated in Eq. 4.

Condition 3. The second derivative of Gibbs free energy of mixing (ΔGM) with
respect to volume fraction (φ) must be greater than zero, i.e., positive.
 2 
Δ@ ΔGM =Δϕ2 > 0 (5)

The phase diagram, depicted in Fig. 2, can be used to decide the phase behavior of
the polymer blends [11–13]. In Fig. 2, the binodal separates miscible and metastable
regions from each other, while the spinodal separates two phase regions from
metastable.
Considering above discussion, Fig. 2 can also be related with Fig. 3 that explain
the miscibility of polymer blends. Figure 3 showed the relationship between Gibbs
free energy of mixing (ΔGM) and composition of the components in terms of volume
fraction (φ) for binary mixtures [14]. In Fig. 3, miscible mixture, which has positive
ΔGM value between starting point and end point, indicated the component in this
blend systems are fully immiscible. The case is reverse for curve immiscible
mixture, in which all conditions are applicable and the components are fully
miscible. For curve partially miscible mixture, there are two minima, and amorphous
phase is observed to its right and left, so partial miscibility can be observed.
Considering the applicable conditions and miscibility of the blend systems, the
following three types of blend can be explained:
13 Polymer Blends 521

Fig. 2 Phase diagram for

liquid mixtures, showing
upper critical (UCST) and
lower critical solution
temperature (LCST)
[12]. (With kind permission
from Springer)

Fig. 3 Gibbs free energy of mixing for binary phases

2.1 Completely Miscible Polymer Blends

As discussed above, the Gibbs free energy and enthalpy of mixing are negative
for miscible blends. The homogeneity is achieved at least on a nanometer scale, if
not on the molecular scale. The glass transition temperature (Tg) plays an
important role in miscible blend. The parent component has their own Tg values
that alter and appear with a new value after mixing with other polymers; e.g.,
polystyrene and poly(phenylene oxide), poly(ethylene terephthalate) with poly
(butylene terephthalate), and poly(methylmethacrylate) with poly(vinylidene
fluoride) are some important fully miscible polymer blend systems. It is worth
to mention that the important chemical and physical compatibilities should be
recognized and have an idea before mixing any polymer component to get fully
miscible polymer blend products [15, 16]. Table 2 provides some examples of
fully miscible polymer blends with their Tg values [17–21].
522 I. Khan et al.

2.2 Completely Immiscible Polymer Blends

The most distinct features of these blends are their different morphology and
inhomogeneous matrix composition. These blends have a sharp interface, coarse
morphology, and poor adhesion between the blending component phases. Thus,
to make them suitable for different applications, compatibilization is very impor-
tant, which can be carried out with the help of a specific compatibilizer for a
particular system. The compatibilization makes the blending system much stable,
and better blended phase morphology is attained by inducing better interactions
between two immiscible polymers. One of the important concerns in this kind of
blends is the glass transition temperature (Tg). The Tg is not sharp, and usually
found more than one values. In binary polymer blends, there are two Tg values, as
the components are immiscible so they somewhat retain their own Tg values.
Examples of fully immiscible polymer blends systems include polystyrene/poly-
butadiene, poly(ethylene terephthalate)/poly(vinyl alcohol), and polyvinylidene
fluoride/polylactic acid blends [22]. Some typical immiscible polymer blends and
their Tg values are listed in Table 3 [23–27]. In these products, one can clearly
identify the phases of both components as they are not miscible, though their
physical properties are somewhat different from original one. Figure 4 shows the
two components of immiscible polymer blend systems in which component A is
in small proportion as compared to component B. Therefore, it will be separated
as small spheres and the larger component will form a sea (Fig. 4a). After suitable
treatment, the component A and B will assume a shape, which can be easily
distinguished from each other (Fig. 4b).

Table 2 Some reported miscible polymer blend system with Tg values

S. no Components (Tg  C) Component % Polymer blend Tg value References
1. PB (100) SBR (15) 25:75 60 17
2. PBT (40) PET (81) 25:75 51 18
3. PVDF (40) PMA (16) 25:75 6 19
4. PS (96) PPO (216) 20:80 113 20
5. ABS (105) PLLA (60) 30:70 73.5 21

Table 3 Some reported fully immiscible polymer blend system with Tg values
S. no Components (Tg  C) (Component %) Polymer blend Tg value ( C) References
1. PS (96) PB (100) 30:70 103 23
2. Nylon Nylon 20:80 49 24
6 (54) 612 (46)
3. PA-6 (50) SEBS (95) 50:50 60 25
4. PET (82) PC (149) 20:80 123 26
5. PS (87) PC (146) 20:80 134 27
13 Polymer Blends 523

Fig. 4 Immiscible polymer

blends: (a) before mixing and
(b) after mixing

2.3 Partially Miscible Polymer Blends

The nature of the partially miscible polymer blends can be depicted from curve C in
Fig. 3, which represent two regions. These regions specify the existence of some
intermediate miscible phase, recognized as partially miscible polymer blend region.
The partially miscible blends exhibit properties in between miscible and immiscible
polymer blends. In these polymer blends, a small portion of one of the blending
components is dissolved in other blending component. These polymer blends are
normally compatible and blend phases are homogeneous with their own Tg. But the
Tg values are shifted from the neat components to the blend components. Typical
example of partially miscible polymer blend is the PC/ABS blends, in which PC and
ABS are partially dissolved in one another. The resulted interface is wide and the
interfacial adhesion was found to be noble [16, 28–30].

3 Compatibilization Strategy for Good Dispersion

Compatibility is a wide and intriguing arena of research [31–35]. Figure 5 presents

some common compatibility strategies for polymer blending [36, 37]. In many cases,
particularly in immiscible polymer blends, compatibilization is very useful tool for
improving the disparity components in the reaction matrix. It successfully reduces
interfacial tension, assist dispersion, and stabilizes the morphology of the combining
reactants against offensive stresses and strains (arising out of processing). It enhances
adhesion between different phases and improves the overall mechanical properties of
the polymer blends. Gravity and interfacial tension are the two important driving
forces for the phase segregation of the polymer blend components. The rate of
de-mixing greatly depend upon the interfacial tension, density, and viscosity [38, 39].
Various approaches can be used to reduce the interfacial tension in the melted state
and improve the adhesion between the immiscible phases in solid states. The selection
of the most appropriate blending technique is very important. It could be helpful
obtaining continuous or interpenetrating phase morphology that may result in direct
load sharing. The addition of a third homopolymer or even block or graft copolymer
524 I. Khan et al.

Fig. 5 Compatibility Compatible

strategies of polymer blends Polymer Blend
Immiscible Polymer
Polymer Blend Alloy

Homogeneous
Immiscibility
Polymer Blend
Polymer
Isomorphic Blend
Macromolecule
Polymer Blend

Visibility and
Morphology
Miscibility
Constituents

or small molecular active compounds, which is miscible in either of the two phases,
called nonreactive compatibilization can also be used. In addition, functionalization
can also be successfully used for reactive compatibilization [11]. Noted that in
physical compatibilization, the compatibilizing agent is added prior to initiate the
reaction. This added agent is capable to reduce the interfacial tension between the
blending components which provide emulsification effect and promoting adhesion
between the reaction phases [40, 41]. Beside these degradation, coupling and grafting
can also be used as an efficient method for achieving compatibility.

4 Methods of Polymer Blending

Several methods can be used to synthesize and/or prepare polymer blends [42]. Each
method has their own merits and demerits. Short summary of some feasible polymer
blends preparation techniques are presented below.

4.1 Melt Blending

This is one of the most widely used contamination-free techniques for the preparation
of polymer blends [42]. Special devices that include different extruders (Fig. 6) and
temperature controller devices are used to process and melt individual component.
The raw materials are introduced to a special chamber containing extruders to have
uniform mixture of all raw materials. Temperature is elevated to a desirable limit and
all added materials are consequently melted. Besides the composition of the compo-
nents, process conditions such as blending duration, operating temperature, and
pressure are also important to achieve desirable properties of the blend. This method
is usually considered to be a good technique except considering the fact that sometime
it appears to be too expensive and the obtained polymer blend might not be uniform
(if it is not properly handled) and results mechanically less efficient products [42].
13 Polymer Blends 525

barrel temperatures material

feeder output spectrum pressure
feed rate
output
feed rate motor
input

screw speed die

input motor

torque screw speed barrel temperatures material

output input temperature

Fig. 6 Twin extruder [42]. (With kind permission from Springer)

4.2 Mill Mixing and Fine Powder Mixing Technique

A simple straightforward method in which the blending components are mixed

through milling and grinding. Different kinds of milling devices and grinder are
used for this purpose. The raw materials are grinded to achieve the finest powder
which are then mixed together to achieve uniform mixing at micro level. The product
is then subjected to additional operations to get the desired polymer blend products
[43, 44]. Bunbury mixer, which is also known as Master Mixer, is extensively used
for mechanical mixing of the polymer ingredients and thus suitable for synthesis of
polymer blends [44].

4.3 Solution Casting Method

This is one of the simplest available techniques and very common among the users.
In this method, the blend is casted from a common solvent, and this method
comprises the following steps:

1. The desired component polymers are selected for blending.

2. The selected polymers are dissolved in a specific solvent. It is noted that the
solvent selection is very important and plays an important role in solution casting
method.
3. The solution mixture keep stirring for a certain period of time to get the homog-
enous solution.
4. The binders and compatibilizers are added if required.
5. The resulted product is collected at the end of the process and characterized.
526 I. Khan et al.

The only limitation of this method is the incompatibility of the component

polymer and separation of the solvent from the product, because residual solvent
can distress the bulk properties of the blend [45, 46].

4.4 Freeze Drying

Quenching is a well-known method in any chemical laboratory operations, also used in

freeze-drying method. In freeze-drying, the component polymers are quenched down to
a suitable (normally very low) temperature, and the solution got frozen. The component
polymers will have a very least chance to agglomerate and thus all frozen solvent can be
collected very easily. The solvent is then removed by the application of sublimation.
This method is the best when symmetrical solvents are used in the solution [47–49].

4.5 Latex Blending

A latex is an important word and carry specific meaning in polymer industry. It is

used for a stable dispersion (emulsion phase) of polymer particles at micro level in
any specific aqueous medium. Thus, the latex blending is a special technique for
polymer blending and other polymerization techniques. This method produced
rubber-toughened plastic blends. To achieve such blends, the contributing polymers
should be in the latex or in the emulsion form, which is followed by mixing. The
mixing process is very important since this will provide micro-sized homogenous
latex, and distribution of discrete phases [50, 51].

4.6 Mechanochemical Blending

In this method, polymer blends are given by a specific polymeric system in which long-
chain monomeric sequences of type one is linked chemically with similar long-chain
monomeric sequences of the other kind (Fig. 7). This connection may be axial or in cross

Fig. 7 IPN polymer blend formation

13 Polymer Blends 527

direction. This connection may be axial or in cross direction that produced either block or
graft kind of copolymer system. Following this step, crosslinking occurred either by
selective or random fashion that leads to inter-crosslinking or graft crosslinking which is
termed as mechanochemical polymer blends. This polymer system is appeared as a
special network which is interpenetrating in nature. Therefore, it is also called
interpenetrating polymer network (IPN). Like other polymer blends, this system also
possesses unique mechanical, thermal, and optical properties [52–54].

4.7 Interpenetrating Polymer Network Technology

This is closely related to mechanochemical technique, but uses without external

mechanical force in this system. The polymer blend system is highly penetrated into
each other, and for separation it requires high energy to break the chemical bonds
[2, 54]. In these systems, the components are grown in such a way that they are
entangled into each other but not by chemical bond. Thus, special techniques are
usually required to produce such polymer systems, as simple mixing will not be
enough to get interpenetrating polymer network (IPN). The semi-interpenetrating
polymer network (SIPN) is comprising one or more polymer networks that includes
linear or nonlinear branch polymer. This system is characterized by embedding at
least one network into the polymer at a molecular scale. In this case, the polymer part
can be separated from the network without damaging any chemical bond [2]. On the
other hand, pseudo-interpenetrating polymer networks (PIPN) are prepared by the
partial penetration of polymer into the network system. Thus, the polymer and
network parts are distinct, and their properties are retained in greater extent, and
their separation is relatively easier than the SIPN [2].

5 Characterization

Characterization of materials provide valuable information about their structure and

properties. Variety of characterization techniques can be used to determine the exact
nature of the polymer blends [13, 55]. The characterization techniques that usually
used to characterize the polymer blends are discussed below.

5.1 Spectroscopic Techniques

The spectroscopic techniques are frequently used for the structural determination of
any kind of molecular compounds including polymer blends. Mass spectroscopy
provides information about the molecular weight and surface concentration of the
polymer blends [56]. In specific operational condition, it also provides information
about the propagating chain length at different interval of time. Fourier-transform
infrared spectroscopy (FT-IR) has numerous applications in polymer blends, espe-
cially in qualitative and quantitative analysis. By comparing the FT-IR spectrum of a
528 I. Khan et al.

neat component and blends, the chemical information about the functional groups
and other properties of the blended polymers can easily be determined. If there is any
chemical interaction taking place, some signal would be lost, shifted, or appeared in
the polymer blends final spectrum. In addition to chemical information, useful
physical information can also be obtained from peak broadening or shifting. FT-IR
is also valid for determining hydrogen bonding in polymer blend system. Moreover,
FT-IR spectra provide significant information regarding the phase separation of
polymer blends [57]. Nuclear magnetic resonance spectroscopy (NMR) can also
help deducing the structural properties of polymer blends. In addition to the tradi-
tional 1H and 13C NMR, solid-state NMR technique is also well known for elucida-
tion of certain properties of polymer blends [58].
Typically, the spectroscopic techniques comprise three basic units: (1) The light
source, such as neon, xenon, or argon lamps, mercury lamps, etc.; (2) Sample
chamber, which is specific for each spectral technique; and (3) The detector, which
is also different for different spectroscopies. The date interpreter evaluates the results
and transformed them into an individual spectra. Figure 8 shows the schematic
representations adopted for various spectroscopies.

5.2 Energy-Dispersive X-Ray Spectroscopy (EDX)

EDX is also called energy-dispersive X-ray analysis (EDXA) or energy-dispersive

X-ray microanalysis (EDXMA). This spectroscopic technique primarily relies on an
interaction of X-ray excitation and a sample. EDX is helpful in determining the

Fig. 8 Schematic representation of basic components used in various spectroscopic techniques

13 Polymer Blends 529

atomic ratio and elemental composition of the components atoms. Moreover, EDX
can also be used to determine the contaminants in the mixture of polymer blends. In
the recent past, Kindgren investigated the bright spots in different polymer blends
consisting of ethyl butyl acrylate (EBA), low-density polyethylene (LDPE), linear
low-density polyethylene (LLDPE), high-density polyethylene (HDPE), cross-
linked polyethylene (XLPE), poly amide 6 (PA6), and polyamide 6,6 (PA6,6)
using EDX. The results showed that the iron and aluminum oxide traces exist in
the mixture as contaminants, which came from the processing unit [59].

5.3 Scanning Electron Microscopy (SEM)

Phase morphology of polymer blends is normally characterized by this technique. It is a

type of microscopy that generates images of a sample by scanning its surface with a
beam of electrons. The electrons interact with the atoms in the sample, producing
various signals that is detected and converted into image by computer called micro-
graph. The micrograph contains valuable information about the sample’s surface
topography and composition. In the case of polymer blends, this technique assists
researcher to predict the distribution of components. Moreover, the homogeneity of
phase can also be predicted. In this technique, the samples are cryogenically fractured by
immersing the samples in liquid nitrogen. A brittle fracture is obtained avoiding large
deformations in the surface to be examined. This technique can be modified depending
on the kind of polymer blends. Wang et al. prepared PBT/PFCE polymer blend to study
the morphology and structural properties of the polymer components and their distri-
bution [60]. They used different ratios of PFCE polymer to achieve more effective
polymer blend having good mechanical and thermal properties. They used SEM images
to study the external and internal morphology, properties, and distributions of the
PBT/PFCE polymer blend components (Fig. 9). The sample was fractured under
nitrogen environment and the brittle portion was used for the analysis. The fractured
portion showed homogeneous spherical drop-like distribution of PFCE in PBT matrix
(Fig. 9a), which is supported by the backscattered micrograph (Fig. 9b). The uniform

Fig. 9 SEM micrographs of PBT/PFCE polymer blend. (a) Cryofractured portion of the blend
system. (b) The backscattered electron micrographs [60]. (With kind permission from ACS)
530 I. Khan et al.

distribution of mixed phases is very important for better and efficient polymer blend, as
it determines the final physiochemical properties of the blend system [59, 60].

5.4 Transmission Electron Microscopy (TEM)

TEM is an optical technique in which a beam of electrons is transmitted through an

ultra-thin specimen (sample) and provides a good deal of characteristic information
about the sample. To extract the information, the TEM image can be magnified and
focused onto an imaging device and the assimilated information regarding polymer
blend can easily be achieved. In general, the TEM sample preparation procedure is
similar to the SEM. Typically for TEM analysis, some thin portions of the polymer
blends were cut with the help of UC6 microtome supported diamond knife. Gold
coating is usually applied to most of the polymer blend samples as they are relatively
weak conductors. Wang et al. studied the PBT/PFCE polymer blend for the mor-
phology and structural properties of the polymer components by SEM as discussed
above [60], and compared the findings obtained by TEM analysis. The results were
in good agreement as they obtained in their SEM study, i.e., the polymer matrixes
were fully mixed and the phases were uniform.

5.5 X-Ray Diffraction (XRD)

This is one of the most viable characterization techniques for the determination of
crystallinity in the polymer blends. In XRD, the ordered atoms cause to deflect the
beam of incident X-ray in many specific directions, from which the angles and
intensities are obtain in the graph, called crystallograph. This crystallograph provide
an excellent information about the crystal lattice and the unit cell. From the electron
density, the mean positions of the atoms in the crystal, their chemical bonds,
disorder, and various other information can also be determined. In a recent study,
Lv and coworkers used XRD technique to study the crystalline properties of the
PCL/PLA polymer blend. They determined two extra XRD peaks, which were
accountable for PLA along with the characteristic PCL peaks. In addition, they
also observed decrease in intensity of PCL X-ray peaks, attributed to the immisci-
bility of both polymers [61].

5.6 Tensile Tester

The mechanical properties of polymer blends are the most desirable aspects in
blending. These days, research scientists are tapping much efforts to produce
mechanically strong products. The mechanical strength of the products can be tested
by the tensile tester. A tensile tester, universal testing machine (UTM), generally
works on the stress and strain principle, and young modulus can be obtained from
thermographs that determine the mechanical strength. The tensile properties of
13 Polymer Blends 531

PLLA was reported in a study [62], in which they found that the block copolymer
(5 wt% PEOPBO)/PLLA blends showed significant increase in mechanical prop-
erties after blend formation. Beside this technique, differential scanning calorimetry
(DSC), dynamic mechanical analysis (DMA), and rheology can also be used to
determine the mechanical properties of polymer blends.

5.7 Differential Scanning Calorimetry (DSC)

DSC is one of the prominent thermo-analytical characterization techniques for

polymers and their blends. In this technique, the difference in the amount of heat
required to increase the temperature of a sample and/or reference is calculated as a
function of temperature. During the experiment, the temperature of the reference
and/or sample should linearly increase with time at a specific ramping rate. It is
worthwhile to mention that the reference sample should be scanned over the range of
temperatures for a well-defined heat capacity. DSC contribute experimental result in
the form of a DSC graph as a function of heat flux versus temperature or time. This
technique is the best to identify the transition glass temperature (Tg) and enthalpies
(H ) of the system. Moreover, the depression in the achieved melting point indicated
by DSC can be used to determine the miscibility of the blend system. Similarly, the
polymer/polymer interaction values can also be judged from the DSC graph [63].
Rady et al. used DSC to investigate the phase-changing behavior of granular
composites. They devised simple protocol for DSC (Scheme 1) to obtain accurate
results based on the estimation of the thermal resistance between the sample and its
enclosure [64].

Css
Tss
DSC schematic diagram

Furnace qss Rss

Sample Reference
container container Cps Cpr
Tps Tpr
Sample Reference
Cooling Rods
Tss qs Rps Rpr qr
empty

Tps Tpr Ts Tr
Sample Reference Cs Cr
Ts plate plate Tr
Cooling Ring Rs Rr
TF
Furnace TF

DSC thermal model

DSC furnace and calorimeters

Scheme 1 Differential scanning calorimetry (DSC) device (left) with schematic representation
(right) [64]. (With kind permission of Tech Science)
532 I. Khan et al.

5.8 Dynamic Mechanical Analysis (DMA)

Viscoelastic properties of polymers are of great interest to the researcher, and can be
studied by DMA. In DMA, a stress is applied on a polymer blend system in sinusoidal
form. Due to the stress, some changes take place in polymer blends from which the
strain is calculated, and eventually complex modulus is determined. The DMA can also
be used to calculate Tg of the specific material. Beside this, thermo-mechanical analysis
(TMA) is also helpful finding transitions analogous to certain molecular motions. Nair
et al. prepared polymer blends with different cross-linking density using variable
amount of ethylene propylene diene (EPDM) and styrene butadiene rubber (SBR),
and studied their crosslinking density by DMA. This study suggested that changing the
composition of one of the monomers can lead to difference in Tg and Tc [65].

5.9 Thermogravimetric Analysis (TGA)

Thermal analysis of polymer blends can also be carried out with thermogravimetric
analysis (TGA). The thermograph obtained from TGA shows the relationship
between physical or chemical changes with temperature. Alongside the temperature,
time or mass loss can also be used to get information about the polymer blend
[66]. Justin and Guiseppi used TGA to study the thermochemical properties of P
(Py-co-PyBA) hydrogel, and found that the inherent and the modified hydrogel-P
(Py-co-PyBA) were stable in the range of 25–300  C. The thermograph indicated
intense decomposition at ~400  C. The comparative Tg result also indicated that the
modified hydrogel is more stable than the original one [67].
Thermogravimetric analysis (TGA), shown in Scheme 2, was utilized to study the
interface of H3PO4 and steam with the polybenzimidazole (PBI) and pyridine-bearing

Scheme 2 Schematic diagram of the TGA experimental set up. MC mixing chamber, MFC mass
flow controllers [68]. (With kind permission from RSC)
13 Polymer Blends 533

aromatic polyether (TPS) systems. It is determined that the evaporation rate is by a

factor of two lower than that of the pure phosphoric acid under the same steam partial
pressure [68].

5.10 Rheology

Rheology is the flow of matter in response to an applied force. It can be applied to a

variety of materials, especially to macromolecules and polymer blend systems. This
technique is entirely dependent on the elasticity and plastic properties of the polymer
blend systems. Rheological properties of polymer blends require extensive investi-
gation to understand the basic principles involved in this technique. Yang and Han
studied different polymer miscible blend systems constitute of PVPh. They are
capable of forming hydrogen bonds due to the presence of active hydrogen and
electronegative groups. Various characterizations in addition to rheology indicated
that the blend systems are soluble in THF at lower temperature but the solubility
decreases at elevated temperature indicating the cross-linking phenomenon takes
place in PVPh specimen [69].
Badino et al. [70] indicated that online rheology produced much reasonable data
compared to conventional rheological techniques after proper calibration. They
further suggested that the impeller is useful for online rheological measurements
as in the case of Aspergillus awamori. The typical protocol for the online rheology is
given in Scheme 3.

5.11 Miscellaneous Characterization Techniques

In recent years, the gradient HPLC techniques, such as gradient polymer elution
chromatography (GPEC) are used to find out the compositional drift of copolymers

190RPM

peristaltic %TORQUE measuring

60.2

pump head
microcomputer
air
sterile
air
on-line
rheometer

gas
separator
peristaltic
bioreactor pump

Scheme 3 Schematic representation of online rheometer apparatus [70]. (With kind permission
from Scielo)
534 I. Khan et al.

or the scrutiny of polymer additives as a form of composition of the polymer blends.

With the choice of the selected columns and the gradient conditions, separations are
achieved that depend on molecular weight, adsorption mechanism, or kinds of
precipitation. The use of a special detector allow researcher to get specific informa-
tion about the material. For example, an evaporative light scattering detector (ELSD)
allows one to perform solvent gradients with a universal mass detector and observe
both UV-absorbing and non-UV-absorbing polymer samples without baseline dis-
turbances. The addition of a photodiode array detector (PDA) allows compositional
analysis across the molecular weight distribution of many copolymers, can be useful
for the identification of components in a polymer blends, and also invaluable for the
quantitation of polymer additives and other small molecules in traditional reverse
phase separations. The gradient gel permeation chromatography (GPC) is also used
to determine the composition and structural information about the polymer blends
[71]. Gomez et al. studied the thermodynamics of binary and ternary polymer blend
systems by a theoretical approach, and compared the results with experimental
calculations obtained from GPC [72]. They theoretically computed the viscosimetric
parameters and compared with the experimental data. It was found that their
computed values of intrinsic viscometric parameters are in good agreement with
experimental results.

6 Properties of Polymer Blends

Depending on the structure and compositions, the polymer blends have certain
physical and chemical properties. The properties can be controlled by using an
appropriate composition of polymer components. Following are some of the most
important properties of polymer blends, which needs to be considered for a particular
application.

6.1 Electrical Properties

Polymers have distinct electrical and conducting properties that depend on the
behavior of the overall structure of the polymer. These properties can be changed
with a modification of pure polymer. These modifications can be obtained by adding
a filler, i.e., making its nanocomposite or making their blends with other polymer,
though many other approaches can also be employed to get the desired product.
Therefore, researchers are trying hard to build suitable polymer blends, which can be
used as polymer blends in electrical industries. The temperature dependence of direct
current (DC) conductivity was studied by S. Ameen et al. [73], in which various film
samples were prepared from polyaniline-polyvinylchloride (PANI-PVC) blends.
They doped polyaniline by adding different concentrations of sulfamic acid in
aqueous tetrahydrofuran (THF) solution. The blended films were prepared by
varying the amount of doped PANI, where PVC amount was kept constant. The
sample films were used to determine the effect of sulfamic acid (dopant) in the
13 Polymer Blends 535

temperature ranges from 300 to 400 K. In order to evaluate the effect of the dopant
on PANI-PVC, the conductivity-derived parameters such as pre-exponential factor
(σ o) and activation energy (ΔE) were calculated first. The structural changes of
PANI-PVC blended films were characterized by FTIR spectroscopy from which it
was derived that the suitability of the dopant is good in the chemical doping process.
They concluded that the conductivity of the blends increased regularly as the percent
amount of doped PANI increased in the polymer blend.

6.2 Mechanical Properties

Mechanical strength of polymer blends is the most important aspect in any robust and
tangible applications. Normally, polymer blends leads to enhanced mechanical prop-
erties. There are certain parameters that includes tensile strength, bulk modulus, young
modulus, ductility, hardness, plasticity, and yields strength which are required to
calculate determining the overall mechanical strength of the polymer blends. Generally,
researcher uses different parameters, and correlate them with the mechanical toughness
to evaluate their product [74]. The most recent article published by Aranburu et al.
studied the change in the mechanical properties of the constituent’s polymer after
blending [75]. They synthesized polypropylene/polyamide-12 blends with the help of
direct injection molding (DIM), and found that on the gradual cooling crystallization of
polypropylene, the nucleating effect of polyamide-12 (PA12) takes place, thus leading
to the modification of crystalline morphology. This modification can be attributed to the
interaction between the two polymers. Crystallinity of PA12 drops slightly, while that
of polypropylene increased to greater extent. This increase in crystallinity is directly
proportional to the enhancement in the mechanical properties. Chung and Green
reported the synthesis of thin polymer blend film (nanoscale thickness) of miscible
polymer blends from polystyrene (PS) and tetramethyl bisphenol-A polycarbonate
(TMPC) and determined their elastic moduli and stiffness. They concluded that by
varying the composition of the component and the thickness of the nanoscale films, the
elastic properties and stiffness behavior alter significantly [76].

6.3 Thermal Properties

Thermal stability of polymer blends is an important marker for thermal industrial

applications. For example, thermal aging of certain materials is observed due to their
less resistant to solar light and other heat discharging materials. Certain polymeric
materials are incapable to resist heat even at very low temperature, deform quickly,
and release certain chemical to the object in contact. There are various parameters
that can be used to compare the thermal stabilities of different polymer blend
systems, i.e., critical temperature, glass transition temperature, heat of fusion, heat
of vaporization, flammability, solidus, thermal expansion, thermal conductivity,
softness, etc. All these factors are equally important and can be correlated to each
other. Lizymol and Thomas investigated the thermal properties of three polymer
536 I. Khan et al.

blends systems, i.e., PVC/EVA, EVA/SAN, and PVC/SAN, using thermogravimetric

methods. It was found that PVC/EVA system was completely miscible, and thermal
stability improved significantly [77]. Kim et al. showed that a polymer blend made
up of two polymeric components having high miscibility and a suitable linker
structure can produce a very homogeneous and dense thermal network, which
enhanced mechanical properties of immiscible blend system [23].

6.4 Optical and Glass Properties

The optical properties of polymer blends are also considered as one of the basic and
important properties that helps obtaining variety of information of the blends. Optical
property of any substance can be described as the interaction of radiations with the
substance mostly in the visible region. In addition to other techniques, UV and
photoluminescence (PL) are the two main techniques used to study the interaction of
radiations with the substance. Takahashi et al. studied the optical properties of PMMA/
EVA polymer blend system [78]. The system showed great transparency (~100%) at
room temperature since the refractive index difference for both components were
found to be very small at that temperature. They also reported that increasing the
temperature significantly decrease the transmittance. Similar observation has been
reported in the literature using varieties of other polymer blend systems [79].

7 Applications of Polymer Blends

Polymer blends can be used in numerous applications that include synthesis of

nanocomposites for improved chemical and mechanical properties, catalysis, med-
ical applications, electronics, and membranes, and are depicted in Fig. 10. Some
important applications are discussed below.

Fig. 10 Applications of
polymer blends Nano-
Industry

Medical Electronic
applications device and
Batteries

Applications

Membrane
Catalysis and plastic
industry

Sensors
13 Polymer Blends 537

7.1 Nanocomposites and Other Nanomaterials

The melt extrusion method was used to prepare thermoplastic starch/poly(vinyl

alcohol) (PVOH)/clay nanocomposites that exhibited the intercalated and exfoliated
structures. These nanocomposites were investigated to realize the effect of clay
cation, water, PVOH, and clay contents on clay intercalation and mechanical
properties. The taguchi experimental design method was applied on montmorillonite
(MMT) having three types of cations or modifiers (Na+, alkyl ammonium ion, and
citric acid). It was observed that the tensile strength and modulus were increased for
nanocomposite samples with 10%, 5%, and 4% (by weight) of water, PVOH, and
clay loading, respectively [69]. Sodium alginate/poly(vinyl pyrrolidone) polymers
were used to make nanocomposite membranes by varying concentrations of
phosphotungstic acid (H3PW12O40) (PWA) using pervaporation (PV) method
(Scheme 4). PV performance of the membranes was evaluated in terms of separation
factor, and flux was evaluated by considering the effects of filler concentrations,
temperature, and feed water surface. It was found that the membrane performance
was reduced by increasing the feed water composition due to swelling. Moreover,
the membranes showed significantly low Arrhenius activation energies for water
than ethanol, suggesting efficient dehydration of ethanol [80].

Scheme 4 Polymeric blend nanocomposite membranes for ethanol dehydration – effect of

morphology and membrane–solvent interaction [80]. (With kind permission from Elsevier)
538 I. Khan et al.

7.2 Electronic Device and Batteries

Transport studies were carried out using PVA-chitosan blended polymer on electro-
lyte system and in proton battery. The electrolyte was prepared by solution casting
method. The blend consisting of PVA (36 wt%) and chitosan (24 wt%), doped with
NH4NO3 (40 wt%), exhibited highest conductivity at the room temperature. Differ-
ent amount of ethylene carbonate (EC) was used as plasticizer to further enhance the
conductivity of the blends. It was found that 70 wt% of EC give the highest
conductivity value (1.60  103 Scm1) of the studied sample. The fabricated
polymer blends doped with EC is used as electrolyte in the fabrication of
Zn + ZnSO47H2O/electrolyte/MnO2 cells. The open circuit potential (OCP) of the
polymer blends was found to be in the ranges between 1.6 and 1.7 V [81]. Similarly,
polyvinylidene fluoride (PVDF) and cellulose butyrate (CAB) blends supported
membrane with polyethylene (PE) were used for gel polymer electrolyte of lithium
ion battery. The ratio of PVDF and CAB found more effective in 2:1, which
appeared to be the largest ionic conductivity (2.48  103 Scm1), and good
compatibility for anode and cathode of lithium ion battery [82].
The electronic properties of thermoplastic polyurethane/poly(ethylene oxide)
(TPU)-based polymer blends were found useful in the cathode materials of Li-ion
batteries. The results show that the addition of TPU to the blend polymer results in
loss of the crystallinity of PEO and improves the dissolution of lithium salts into the
solid polymer electrolyte (SPE) matrix. TPU can also improve the mechanical
stability and the electrochemical properties. Among the TPU/PEO blend electro-
lytes, the TPU/PEO = 1:3 based electrolyte presents an ionic conductivity of
5.3  104 S cm1 with electrochemical stability above 5 V (vs. Li+/Li) at 60  C.
The preparation of TPU/PEO blend polymer solid polymer electrolytes (SPEs) is
provided in Scheme 5 [83].
Proton-exchange membrane (PEM) was developed by polybenzimidazole (PBI)
with poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) blend for
conducting proton in high temperature fuel cell. The loading of phosphoric acid

Scheme 5 The preparations of TPU/PEO blend SPEs [83]. (With kind permission from Elsevier)
13 Polymer Blends 539

(PA) controlled the hydrophobicity of PVDF-HFP, and supposed to be responsible

for low water uptake as compared to pristine PBI. The fluorine atom presence in
PVDF-HFP in the blend membranes results higher proton conductivity and also
enhances stability. The PA doped blend showed good mechanical stability [84].
Due to high ionic conductivity and leak proof capabilities, the polymer gel
electrolytes play potential role in lithium ion batteries. Poly(vinylidene chloride-
co-acrylonitrile) (PVdC-AN) and poly(methylmethacrylate) (PMMA) electrolyte
blends showed good mechanical properties, less reactivity towards lithium electrode,
amorphous in nature, and produces favorable passivation of ions. This polyelectro-
lyte blend system not only helps in electron pair formation through C  N, C=O,
and C  O  C but also result in the formation of polymer salt complexes with
cations of lithium salt, which provide a base for ionic conduction. Solvent casting
technique has been used to prepare PVdC-AN based electrolyte. The ionic conduc-
tivity of 0.398  106 Scm1 was achieved by using EC plasticizer (60 wt%) to
PVdC-AN/PMMA blend, and increases the ionic conductivity with increasing the
temperature in a linear fashion. It was also found that the plasticizer helps lithium
salts remained in the amorphous region of the polymer. FT-IR and thermal analysis
also confirmed the presence of complexes and their compositions [85].
The salt leaching method was opted to synthesize microporous polymer mem-
brane of poly(vinylidene fluoride) (PVDF)/sodium hydrogen carbonate (NaHCO3).
The microporous polymer electrode was synthesized by dissolving all the compo-
nents in a mixture of solvents consisting of dimethyl carbonate (DMC), propylene
carbonate (PC), and diethylene carbonate (DEC) in the presence of salt, lithium
trifluoromethane sulfonate (LiCF3SO3). The lithium salt containing membranes have
AC conductivity of 1.34  105 Scm1 (GPE100). The stability of the electrolyte
was observed at extreme potentials with insignificantly small currents, e.g., 35 μA/
cm2 at 4.0 V vs. Li/Li+. The potential window in the range of 3.0–4.0 V have shown
no peaks [86]. The transport phenomenon has been studied for the polymer blend
PVA-chitosan in proton batteries. The preparation of the electrolyte was carried out
by solution casting method. It is seen that PVA (36 wt%), chitosan (24 wt%) blend
was doped in NH4NO3 (40 wt%) showed the highest conductivity at room temper-
ature. The observed conductivity was around 2.07  105 Scm1. Further enhance-
ment in conductivity was observed by the addition of plasticizer EC to the 60 wt% of
PVA-chitosan and 40 wt% of NH4NO3, and the highest conductivity was found to be
1.60  103 Scm1.

7.3 Membrane and Plastic Industry

Moghareh Abed et al. prepared graft copolymers containing poly(vinylidene fluo-

ride) with poly(oxyethylene methacrylate) (PVDF-g-POEM) using atom transfer
radical polymerization (ATRP). The hydrophilic blends of PVDF hollow fibers
produced by 5 wt% of the copolymer in PVDF spinning dope solution that resulted
a pure water flux of approximately 130.5 Lm2 h1 having molecular weight cut-off
200 kDa (Scheme 6). The hydrophilic nature and antifouling characteristics of the
540 I. Khan et al.

Scheme 6 Synthesis of graft copolymers poly(vinylidene fluoride) with poly(oxyethylene meth-

acrylate) (PVDF-g-POEM) [87]. (With kind permission from Elsevier)

hollow fiber tested by flux recovery method [87]. The sorption and permeation
properties were studied for mixed matrix membranes (MMMs) formed by the
polymer of PIM-1 and the zeolitic imidazolate framework ZIF-8 (Fig. 11). McBain
sorption microbalance and GC gas permeation apparatus was used in self-supported
films of ZIF-8, and He, H2, O2, N2, CO2, and CH4 gases were used for the
permeability coefficients. It was found that increasing the amount of ZIF-8 nano-
particles into PIM-1 results increasing the free volume due to increasing cavities and
loosely packed polymer chains [88].
A composite membranes prepared by varying the amount of poly(vinylidene fluoride-
co-hexafluoropropene) (P(VDF-co-HFP)) and sulfonated fluorinated poly(arylene ether)
(SFPAE), and explored in vanadium redox flow battery (VRFB) application. The SFPAE
and P(VDF-co-HFP) showed good compatibility with each other, and P(VDF-co-
HFP) enhanced thermal, mechanical, and proton selectivity. The life time of the cell in
VRFB increased by 44% with an addition of 10 wt% P(VDF-co-HFP). Thus, the
blend made up of SFPAE and P(VDF-co-HFP) is considered as an excellent material
for producing low-cost and high-performance VRFB membranes [89].
A three membered ultrafiltration membrane has been formulated by a carboxy-
methyl cellulose acetate (CMCA)/cellulose acetate (CA) in the presence of 2.5 wt%
polyethylene glycol through phase inversion process. The surface roughness of the
CA/CMCA blend membranes were analyzed by SEM and AFM, and observed large
pore sizes in upper layer and porous structures in cross-sectional area. This novel
13 Polymer Blends 541

Fig. 11 (a) Magnified and (b) [1 1 1] stacking structure of ZIF-8, with tetrahedral Zn sites in blue,
and the N and C atoms in green and black, respectively. (c) Molecular structure and (b) Molecular
model of PIM-1

blend membrane appeared with greater ultrafiltration and low contact angle. During
the introduction of rejection by blend membrane to bovine serum albumin (BSA), the
fouling resistance ability was studied. It was found that this modification has positive
influence [90]. A blended film of a copolymer prepared from chitosan/polyethylene
glycol fumarate (chitosan/PEGF) was prepared for the evaluation of composition
influence on the blending properties as wound dressing material. It is observed
that blending chitosan with PEGF removed the brittleness of neat chitosan film, and
AFM showed the increase of roughness on the film. Water vapor transportation rates
observed in the range of 904–1447 g2 day1 on the wounds. These membranes on
wounds show powerful antibacterial activity against Pseudomonas aeruginosa and
Staphylococcus aureus (> 99.76  0.16%). The film composition comprising 80 wt%
chitosan and 20 wt% PEGF is considered to be a suitable candidate for biomedical
applications particularly as a wound dressing material [91].
Polysulfone (PSF) ultrafiltration (UF) membranes modified by PSF based
block copolymer with an inclusion of additive poly(N,N-dimethylamino-2-
ethylmethacrylate) (PDMAEMA) blocks were prepared. PDMAEMA-b-PSF-b-
PDMAEMA block polymerization was carried out by condensation and ATRP
process. The copolymer and the resin were blended by traditional phase inversion
process to synthesize UF membranes as shown in Scheme 7. The modified polymeric
chains structured on the membrane surface and pore walls, and the contact angle
measurements were carried out. The result showed that the surface hydrophilicity and
542 I. Khan et al.

Scheme 7 Synthesize of UF membranes by blending copolymer with PSF resin [92]. (With kind
permission from Science Direct)

fouling resistance significantly increased. The platelets adhesion experiments results

showed that there is a remarkable improvement in hemocompatibility that can lead to
the potential applications of blood separation and proteins isolation [92].

7.4 Supercapacitors

Plasticized chitosan and starch blends doped with LiClO4 have been used as polymer
electrolytes for the supercapacitors. Furthermore, the ionic conductivity of non-
plasticized blended chitosan/starch was found to be below the Tg of chitosan. The
use of plasticizer in the biodegradable polymer increases the amorphous nature and
enhances the conductivity of the blend [93]. Electrochemical double-layer capacitor
(EDLC) is an inimitable device for the storage of electrical charge. It works on the
principle of double-layer capacitance at the electrode/electrolyte interface where
electric charges are accumulated on the electrode surfaces and ions of opposite
charges are arranged on the electrolyte side. It has the ability to store considerable
charge, high power density, lower charging time, long durability as well as environ-
mental friendly features in comparison with the conventional capacitors [94–96]. In
2008, Li et al. reported starch-derived activated carbon electrodes as a promising
material for EDLCs [97]. This study not only discussed the effect of temperature on
biodegradable blend polymer electrolytes but also discussed the pore size effect of
activated carbon for a virtuous carbon based supercapacitor. The blend ratio
containing chitosan (60 wt%) showed the conductivity of 3.7  104 Scm1. The
activation energy measured through the Arrhenius plot was found to be
0.52–0.75 eV. The fabricated supercapacitors have shown reasonably good electrical
performance at room temperature like energy density and specific capacitance of
133 Fg1. It is evident from the galvano static studies that the different current
density has a significant impact on charge – discharge time. The capacitance of the
capacitor is dependent on the affinity of electrolyte towards salt, electrode material
under different temperature and ionic conductivity [98].
13 Polymer Blends 543

The multilayer materials were prepared by electrodeposition technique using

layer by layer (LbL) deposition of poly (3, 4-ethylenedioxythiophene) (PEDOT)
and poly(N-methylpyrrole) (PNMPy). This multilayer capacitor showed high ability
to store charges and electrochemical behavior in comparison to individual polymeric
capacitors. It was seen that the synergistic effect produced by the favorable interac-
tions of PEDOT and PNMPy at the interfaces, and increase in number of layers
resulted to enhance charge storage efficiency. It has also been experimentally proven
that ml-PEDOT/PNMPy is acting more appropriate capacitor electrodes than the
individual PEDOT and PNMPy [99].

7.5 Miscellaneous Applications

Forward osmosis (FO) membranes supported on thin film composite are formed
by the sulfonated polyphenylene sulphone (sPPSU) and 2.5 or 5 mol% of 3,30-
disodiumdisulfate-4,40-dichlorodiphenyl sulfone (sDCDPS) monomers. The hydro-
philic and sponge-like structures facilitate the membranes with characteristics to
transport more water and exhibit anti-fouling properties. This new membrane
enhances water flux by 4.4-fold under pressure-retarded osmosis [100].
Mollá et al. prepared sulfonated poly(etherethereketone) (SPEEK) material that has
the ability to conduct good proton at higher degrees of sulfonation, and attained glass
transition temperature near 200  C. The higher amount of sulfonation also resulted in
excessive swelling and dissolution in water at higher temperature which leads to limit
its use in direct methanol fuel cell. Therefore, as a remedy the stable desired membrane
was prepared by the addition of sulfonated blend with polyvinyl alcohol (PVA). The
inclusion of PVA (more than 25 wt%) in the modified mebrane resulted the stablity in
hot water and increase methanol permeability. While inclusion of hydrophobic poly-
mer, polyvinylbutyral (PVB) (above 30 wt%) the resulted blend appeared to be
extrememly stable in boiling water but lower the proton conductivity [101].
Graphene oxide (GO) membrane was prepared from polysulfone (PSf) using wet
phase inversion method. The hydrophilic properties of the membranes were studied
by measuring the surface wettability and swellability. SEM analysis showed that the
presences of large spaces while contact angle measurements indicate the membrane
is moderate hydrophilic in nature. GO doped (2000 ppm) membranes (Scheme 8)
showed improvement in Na2SO4 salt rejection up to 72% at 4 bar pressure. It was
also found that the salt rejection phenomenon dependent on the pH and rejection
efficiency increases with increase in pH [102]. Solvent Resistance nanofiltration
(SRNF) membranes were also prepared from the polysulfones (PSf) which obtained
from different sources via immersion precipitation. The performance of the synthe-
sized asymmetric membranes was studied considering the effect of purity, polydis-
persity index (PSI) and molecular weight (MW) [103].
Solar cells based on conjugated polymer bulk heterojunction (BHJ) prepared from
conjugate polymer constituted of monomers N-9-(heptadec-9-yl)-2,7-bis(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CzB), 3,9-bis(4,4,5,5-tetra-
methyl-1,3,2-dioxaborolan-2-yl)-5,11-di(N-heptadec-9-yl)indolo[3,2-b]carbazole (ICzB),
544 I. Khan et al.

Casting solution (PSF+GO+NMP)

GO Platelets

Phase inversion

Water NMP

GO

Water coagulation bath Polymer rich phase

Polymer thin phase

Scheme 8 Schematic diagram of GO doped membrane for usage of salt rejection [102]. (With
kind permission from Science Direct)

and 2,5-di(4-(5-bromo-4-octylthiophen-2-yl)-2,1,3-benzothiadiazol-7-yl)thiophene
(DTBTTBr2), attracted huge attention owing to their flexibility, easy manufacturing,
low-cost, and light weight [104]. They are composed of a mixed blend of an electron-
donating conjugated polymers and an electron-deficient fullerene derivatives which is a
source of renewable and clean energy. In the last decades, the power conversion
efficiency (PCE) of polymer solar cells (PSCs) has rapidly improved, which benefited
from the design and synthesis of novel conjugated polymers (CPs), the optimization of
the device fabrication process and modifying the morphology of the active layer.
Polymer complex was formed by solution casting process using the copolymer of
methyl methacrylate (90 wt%) and ethyl methacrylate (10 wt%) with an incorporation of
sodium iodide. By addition of sodium iodide, the ionic conductivity (5.19  106 Scm1)
and Tg of the polymer complex increases up to 20%. However, the further increase in
sodium iodide led to decrease in conductance due to cross-linked effects. LSV analysis
showed that copolymer electrolytes were stable electrochemically up to voltage 2.5 V,
and the efficiency of this material was found to be only 0.65% [105].

8 Conclusion

A polymer blend is a mixture of two or more polymers that usually blended together
by a readily available and cheap polymer blending process to create a new material
with different physical properties. In this review chapter, we have provided a com-
prehensive overview on history, types, miscibility, phase separation, morphology,
application, and other fundamental properties of polymer blends, using a wide range
13 Polymer Blends 545

of state-of-the-art techniques. These days’ different polymer blend systems received

huge importance in industrial and domestic applications due to their unique mechan-
ical, electrical, and optical properties.

Acknowledgments The authors would like to gratefully acknowledge King Fahd University of
Petroleum & Minerals (KFUPM) for providing excellent research facilities, and Deanship of
Scientific Research, KFUPM, Saudi Arabia for financial assistance to carry out this research
through internal grant project No. IN161036.

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Conducting Polymers and Composites
14
Abd Almonam Baleg, Milua Masikini, Suru Vivian John,
Avril Rae Williams, Nazeem Jahed, Priscilla Baker, and
Emmanuel Iwuoha

Contents
1 Nature of Conducting Polymer Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 552
2 Conducting Polymers and Their Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 552
2.1 Electronic Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
2.2 Band Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
3 Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
3.1 The Hopping Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560
3.2 Solitons, Polarons, and Bipolarons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
4 Synthesis and Characterization of Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
4.1 Polypyrrole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
4.2 Polythiophene and Its Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565
5 Principal Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
5.1 Polypyrrole (PPy) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
5.2 Polythiophene (PTh) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
5.3 Poly(3,4-ethylenedioxythiophene) (PEDOT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
5.4 Polyfuran (PFu) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
5.5 Polyaniline (PANI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
6 Conducting Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
6.1 Conducting Star Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
6.2 Dendrimer Star Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
7 Conducting Polymer-Based Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581

A. A. Baleg · M. Masikini · S. V. John (*) · N. Jahed

Department of Chemistry, University of the Western Cape, Bellville, South Africa
e-mail: [email protected]
A. R. Williams
Department of Biological and Chemical Sciences, The University of the West Indies,
Cave Hill, Barbados
P. Baker · E. Iwuoha (*)
SensorLab, Department of Chemistry, University of the Western Cape, Bellville, South Africa
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 551

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_17
552 A. A. Baleg et al.

7.1 Polyaniline–Carbon Nanotubes Composites (CNCs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581

7.2 Synthesis of the Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
7.3 Interactions Between PANI and CNT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
8 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589

Abstract
Conducting polymers (CPs) characteristically form polarons, bipolarons, or sol-
itons and exhibit low band-gap energies. These properties make them to be
suitable materials for applications in sensors, semiconductors, anticorrosion
coatings, batteries, and display devices, among others. This chapter focuses on
the electronics, electrochemistry, and processability of some commonly used CPs
in the recent past – namely, polyaniline (PANI), polypyrrole (PPy), polythiophene
(PTh), poly(3,4-ethylenedioxythiophene) (PEDOT), and polyfuran (PFu). Also
included in the chapter are conducting dendritic star copolymers and polymeric
nanocomposites incorporating single-walled and multiwalled carbon nanotubes.

1 Nature of Conducting Polymer Materials

Since the early 1970s, researchers have been focussed on the task of identifying organic
solids that exhibit remarkable conducting properties. These organic compounds, with the
ability to effectively transfer charge, can be divided into three main groups: radical-ion salt
charge-transfer complexes, carbon-based small molecules, and conjugated conducting
polymers (CPs). Conducting polymers (more commonly termed synthetic metals) are
organic polymers that exhibit highly reversible redox behavior and demonstrate the
properties of both metals and plastics. CPs gained in popularity owing to their interesting
electrical and optical properties, which had previously only been observed in inorganic
systems. One of the most remarkable features of CPs is their ability to be nanostructurally
tailored for more specialized applications, through innovatively manipulated synthetic
transformations. This flexibility has resulted largely in the replacement of traditional
inorganic conducting materials with CPs, which, through blending or composite forma-
tion, have introduced improved processability, mechanical properties, and stability. These
enhancements have allowed CPs to have practical application in various fields, including
electromagnetic shielding and microwave absorption [1, 2], static electricity dissipation,
heating elements [3], membrane materials [4], paint coatings for anticorrosion protection
[5, 6], sensor materials, and molecular devices [7]. This chapter provides an examination
of CPs and composites — their properties, synthesis, and applications. In addition,
conducting star copolymers, dendritic star copolymers and dendrimers are also explored
as they are inextricably connected to their progenitor molecules (the CPs).

2 Conducting Polymers and Their Properties

Conducting polymers (CPs) typically contain a linear backbone of repeating conjugated

monomers as the fundamental structural unit, as exemplified by polyacetylene (PAC),
polypyrrole (PPy), polyaniline (PANI), and polythiophene (PTh) [8, 9]. Two general
14 Conducting Polymers and Composites 553

types of conducting polymers exist. The first is a composite material (with dimensions in
the nanometre range) that engages a polymer to hold together conductive filler-like
metal flakes [10]. Typical examples of conductive components used to prepare this type
of CP include conducting solids (carbon black, carbon fibres, aluminium flakes, stainless
steel fibers, metal-coated fillers, metal particles, etc.) and conjugated conducting poly-
mers. The latter can be had via polymerization at an electrode (anode) surface coated
with a nonconducting polymer film [11]. These conducting nanocomposites (CNCs) can
be synthesized from a variety of metals and conjugated polymers as well as oligomers
and have attracted considerable interest because of the possibility of using them to create
suitable materials for electrocatalysis, microelectronics, and chemical sensors [12]. The
second group of CPs consists of a set of polymers whose backbones constitutionally
propagate charge, making the polymer itself conductive [13]. The conductivity arises
from the chemical bonding which produces an unpaired π-electron per carbon atom in
the backbone of the polymer. The carbon atoms are π-bonded in an sp2pz hybridized
configuration, where the orbitals of successive carbon atoms overlap, providing for
delocalization of the electrons along the polymer chain [14]. Consequently, charge
mobility is exerted along the polymer backbone, introducing properties such as electrical
conductivity, low-energy optical transitions, low ionization potential, and high electron
affinity. During doping (addition of known quantities of chemical species) and poly-
merization of CPs, the π-bonds are highly susceptible to chemical and electrochemical
oxidation and/or reduction processes leading to the formation of nonlinear defects,
namely, solitons, polarons, and bipolarons, all of which contribute to the electrical
conduction in these polymeric materials [15–18].
CPs like PPy, PAC, PTh, and PANI have undergone extensive development over
the past 25 years. Thus, organic conducting and semiconducting polymers can now be
synthetically bespoke to optimize desirable properties such as melting point, melt
viscosity, solubility, electrical and thermal conductivity, etc. Although found in
oligomers of 4–10 repeating units, enhanced electrically conductive properties are
frequently observed in polymers (e.g., CPs) with hundreds or thousands of repeating
units by virtue of the long range ordering of the polymer chains in the solid state [19].
For CPs to be useful in multifarious applications, they need to have excellent
electrical and mechanical properties, solution or melt processability, and high envi-
ronmental stability. Conducting polymer composites (CPCs), resulting from the
blending of an insulating polymer matrix with an electrical conductive filler (carbon
black, carbon fibers, metal particles), show many interesting features owing to their
electrical resistivity variations with temperature [20–22]. For instance, changing the
nature of the positive temperature coefficient (PTC) effect, i.e., transition tempera-
ture and amplitude, allows for the adjustment of the CPC properties, thereby
potentially giving access to a wider range of applications. As such, self-regulated
heating can be coerced in a CPC with a sharp positive temperature coefficient effect.
Moreover, these materials have the ability to withstand corrosion and can be
prepared using common plastics processing techniques such as extrusion or injec-
tion. A list of CPs widely in use today are shown in Fig. 1 and include the well-
known PAC, poly(3-alkyl-thiophene), PPy, and PANI [23].
Since the early 1990s, CPs have been reported to function as thin films for
batteries, capacitors, light-emitting diodes, ion-selective electrodes, and solid-state
554 A. A. Baleg et al.

NH S
n n
n

Polyaniline Poly paraphenylene sulfide Polyparaphenylene vinylene

S n N n S n
H
Polythiophene Polypyrrole Poly(3-alkyl-thiophene)

O O
O
O
S n
S n n
Polyisothiophene Polyethylene dioxythiophene Polyfuran

n
Polyacetylene

Fig. 1 Chemical structures of common conducting polymers (CPs)

devices [24, 25]. Recently, the application of CPs has extended to include sensors,
actuator components in microsurgical tools, controlled drug delivery systems, correc-
tive implantable aids, lifelike prosthetic limbs, actuators, and artificial muscles [26].
It is worth noting that a change in emphasis in the area of materials science and
chemistry has opened the doorway to new approaches in analytical sensing, which
influences the design of sensors, particularly those that employ electrochemical or
spectroscopic transduction methods. Specifically, conducting polymers are fre-
quently used in environmental monitoring and clinical diagnostics to achieve fast
detection, high sensitivity, small size and specificity for investigation of a particular
analyte through the use of electrochemical sensors [27] and biosensors [28].

2.1 Electronic Classification

Electrons are essential for conductivity and can be loosely categorized into one of
four groups. The first type – core electrons – primarily exists close to the nucleus and
are rarely removed owing to the relatively large magnitude of the effective nuclear
charge felt by these electrons.
14 Conducting Polymers and Composites 555

Fig. 2 Binding energy levels

of σ, π, and n electron states d - antibonding
for organic molecules.
(Redrawn from Ref. [29])

p - antibonding

BINDING ENERGY
n - non-bonding

p - bonding

d - bonding

σ-Electrons constitute the chemical bonds that are responsible for maintaining the
structural integrity of the molecule. Nonbonding or n-electrons are usually associated
with the lone pairs present on the atoms of some elements and can influence the
susceptibility of a bond to reaction. Weaker and less-localized connections than the
internuclear bonds of σ-electrons are also present upon the birth of molecules. These
entities, known as π-electrons, are likewise involved in bonding but are often thought of
as being “free” (delocalized) and hence require the least amount of energy to jump to the
next energy state (Fig. 2). This π-electron “cloud” enables conduction and polymers that
contain π-electrons, through double bonds, are known as conjugated polymers.

2.2 Band Theory

Band theory is widely used to explain electrical conductivity as it describes the

energy states of electrons. When two identical atoms, each having a partially-filled
orbital, are brought together, the two atomic orbitals interact to produce two new
(molecular) orbitals – one of lower energy and one of higher energy. Two electrons
occupy the lower energy orbital. The (now-filled) orbital of lower energy is a
bonding orbital and the higher energy (empty) orbital is an antibonding orbital.
The magnitude of the energy difference between the highest of the low-energy
orbitals (highest occupied molecular orbital – HOMO) and the lowest of the high-
energy orbitals (lowest unoccupied molecular orbital – LUMO) is called the energy
band gap (Eg).
556 A. A. Baleg et al.

Fig. 3 The origin of band structure in polypyrrole. (Redrawn from Ref. [30])

As shown in Fig. 3, for the PPy system [30], molecular orbital perturbation effects
lead to energy states that are comparable. As the length of the polymer chain
increases progressively from one to infinity, the occupied valence orbitals form
continuous bands called valence bands (VBs), and the empty orbitals coalesce into
continuous bands referred to as conduction bands (CBs).
In other words, Eg is the energy difference between the highest energy eigenstate of
the valence band (VB) and the lowest energy eigenstate of the conduction band (CB) and
represents the minimum energy that is required to excite an electron up into the
conduction band where it can participate in the conveyance of charge (Fig. 3). To
maintain conductivity, valence electrons must move to the CB through this gain in energy.
In band theory, depending on the size of the energy gap (Eg), the material can be
an insulator or a semiconductor (Fig. 4). An insulator has electrons in the valence
band that are separated by a large band gap from the conduction band. Hence, these
electrons are prevented from participating in conduction. Semiconductors, whose
conductivities can range from 103 to 10–9 S.cm–1, usually have energy gaps
l
eV. They are mainly inorganic, crystalline solids, and the magnitude of the energy
gap is such that electrons may be thermally excited across it into the empty upper
band, where they can conduct, leaving holes in the lower band, which can also
contribute to conductivity [31].
Contrastingly, a conductive material such as a metal has overlapping of the
conduction and valence bands. This means that orbitals are freely available and
electrons are “free” to move into the conduction band, increasing the possibility of
transference of charge. Metals generally have conductivities of order of magnitude
of 106 S.cm–1, while insulators are at the other end of the conductivity gamut with
magnitudes around 10–22 S.cm–1 owing to their very large band gap which renders
thermal excitation impossible.
14 Conducting Polymers and Composites 557

Highly conjugated CPs can display semiconductor properties without the inor-
ganic, crystalline structure. The difference between band energy levels in these
materials is such that the bands may be regarded as being continuous, and the
electrons can adopt any energy that falls within the upper and lower boundaries of
the bands. Both inorganic solids and CPs can be doped using charged chemical
species [32, 33] to increase the conductivity (Fig. 5); however, the concentration of
dopant is the discerning factor; in the case of semiconductors of the crystalline type,
concentrations usually lie in the parts per million (ppm) order of magnitude while the
polymer type can have dopant constituents, the concentration levels of which are as
high as 50% (relative to the weight of the polymer).

CONDUCTION BAND
CONDUCTION BAND
ENERGY

Eg
Eg CONDUCTION BAND

VALENCE BAND VALENCE BAND VALENCE BAND

INSULATOR SEMICONDUCTOR CONDUCTING
SUBSTANCE (METAL)

Fig. 4 Energy gap representation of an insulator, a semiconductor, and a metal

Fig. 5 The conductivity of log10 (S/cm) (CH)2 PANI PPy PTh Others
various conducting polymers
at 24  C. (a–e) forms of [CH
(I3)]x, (f–k) forms of PANI, 6
5 a q
(l, m) PPy doped with PF6, (n) b
4 c
PPy (TSO), (o, p) forms of f l
3 o r
PTh, (q) PPV (H2SO4), (r) 2 g h m
d n s
PPP (AsF5), (s) Kr-implanted 1 e i p
poly(phenylenebenzobisoazole), 0
(t–z) undoped versions of the -1
respective polymers [32] with -2 jk
kind permission of Cambridge -3
University Press. -4 t
-5 w
-6
-7
-8 x
-9 u v yz
-10
-11
-12
-13
-14
-15
558 A. A. Baleg et al.

2.2.1 Band Theory of Conductive Polymers

While traditional band models have prevailed, for the most part, in explaining the
semiconductor physics of inorganic crystalline materials, they have tended to break
down when applied to CPs. Although it has been postulated [34] that conducting
polymers and conducting inorganic crystalline materials have similar properties,
fundamental differences lie in how the electrons move from one location to another.
For instance, oxidation or reduction of CPs creates structural deformations along the
polymer backbone, where transmission of charge will most likely occur.
When an electron in the valence band of a conducting polymer is exposed to a
stimulus that causes it to become excited, a polaron forms. Generally speaking, a
polaron is a spin-bearing charge-carrier that is typically linked with radical cations or
radical anions. It is thought to consist of two defects – a charged defect (ion) and a
neutral defect (radical) (Fig. 6a). Instead of the energized electron leaving a
completely empty hole, partial delocalization occurs to offset the new energy level
created by the excited electron. This deconfinement of the electrons means that the
surrounding monomer units become anatomically distorted – a polaron [35]. Further,
conductivity is influenced by the number of polarons (or other quasiparticles such as
bipolarons or solitons) generated in the material and their movement across the mass
of the material. Doping can, therefore, influence the conductivity of a material as
defects in the form of radical cations or anions are introduced.
At low doping levels, charges are stored as polarons and bipolarons (Fig. 6) and so
beget an electrically conductive partially filled band. For most conducting polymers
such as PPy, bipolarons (pairs of defects) are created when two polarons form on the
same polymer chain [38] and since PPy is a highly disordered polymer there are as
many as one defect for every three rings [37]. Polarons and bipolarons can also hop to
nearby chains to carry the electric current. In single polaron hopping, only one electron
moves back and forth between two defect states whereas in bipolaron hopping, two
electrons migrate simultaneously between two randomly created defect states. When

a
H H H H
N N N N
N N N N
H H H H
b
H H H H
N N N N
N N N N
H H H H
c
Deformation
coordinate

Fig. 6 Schematic of (a) a polaron and (b) a bipolaron on a PPy chain. (c) The bottom schematic
represents the deformation of the polymer lattice created from the charge defect. (Redrawn from
Refs. [36, 37])
14 Conducting Polymers and Composites 559

PPy is oxidized and becomes more conductive, it is a polycation with many of these
delocalized positive charges (defects) on its backbone, countered by dopant anions.

3 Conductivity

The conductivity of polypyrrole (PPy) can range from nothing tangible (~ 10–5
Ω–1cm–1) as found in insulators, to 100 Ω–1cm–1 [37]. Electrical conductivity in
conducting polymers (CPs) involves movement of positively charged carriers or
electrons along polymer chains and hopping of these carriers between chains. It is
generally believed that the interchain hopping resistance is much greater than the
intrachain transport resistance. PPy is conductive because of the ability of electrons
to hop along and across the polymer chains owing to the π-conjugating bonds. In
spite of these simple generalizations, conductivity within conducting electroactive
polymers is a complex issue. A polymer that can exhibit conductivity across a range
of some 15 orders of magnitude, most likely utilizes different mechanisms under
different conditions. In addition to the electronic conductivity exhibited by
conducting electroactive polymers, ionic conductivity, owing to the solvent/electro-
lyte incorporated during synthesis, is also a contributing factor [39].
Doping ions help to decrease the band gap (Eg) between the energy levels and hence
increase conductivity (Fig. 7). As such, by using small counter anions that are coplanar
with the polymer chains, the conductivity can be boosted [40]. Hydrogen peroxide,
polyethylene oxide, and dodecylbenzenesulfonate, among others, have all acted as
doping ions [41–43]. In addition to the introduction of dopants, conductivity and
stability have been reported to result from lower temperatures and plating potentials
(as well as degree of roughness of the plating surface), higher concentrations of
monomer, electrolyte, and water together with longer deposition times [40, 44, 45].

Fig. 7 Band structure a b c d

representation of PPy and how
Eg is modified with doping:
(a) no dopant, (b)
intermediate doping level –
bipolarons are noninteracting
at this point, (c) 33% dopant
per monomer, and (d) 100%
dopant per monomer. The
material has changed from an
4.0 eV 1.4 eV
insulator with a band gap of
4.0 eV to a semiconductor
with full doping at l.4
eV. (Redrawn from Ref. [46])
560 A. A. Baleg et al.

3.1 The Hopping Process

Conduction via localized electrons implies discrete jumps across an energy barrier
from one site to the next. In other words, if two molecules are separated by a potential
barrier, a carrier on one side can move to the other side via two mechanisms – either
by tunnelling through the barrier or by moving over the barrier via an activated state.
The latter process is called hopping. This carrier mobility is the main reason for the
transport of the charges in CPs. The mobility of the charge carriers can be restricted
as the degree of overlapping decreases at molecular or atomic levels. However, as the
electronic states become increasingly localized, transport of the particles escalates
through the hopping process. The relative importance of the two mechanisms
depends on the shape of the barrier and on the availability of thermal energy, the
latter resulting in a thermally activated type of mobility that increases with an
increase in temperature and is mainly found in the hopping process. We can learn
a lot about the conduction process by determination of the carrier mobility, e.g., its
temperature dependence provides a good criterion by which we can distinguish band
and hopping types of mechanisms. Though polymers are amorphous materials, a
short-range order prevails. Hence, the theory that is used to explain the electronic
band structure in a crystalline phase can also be applied to amorphous polymers. If
the spatial fluctuations in the interatomic distances are large, the correspondingly
large and random fluctuations in the height or depth of the potential wells may lead
to the localization of states below a certain critical and well-defined energy. Accord-
ingly, when the carrier mobility is low, and the mean free path is comparable with the
interatomic distance, conduction can be expected to take place by a hopping process
in the localized states. In order to obtain conduction through hopping, it is necessary
to have an insulating or semiconducting material exhibiting a few intrinsic thermal
free carriers, at least over a limited energy region, thereby establishing a large
density of sites through which charge transfer can take place. There are three
principal pathways that ensure carrier mobility – single chain or intermolecular
transport (intrachain), interchain transport, and interparticle contact [47]. The
intrachain movement depends on the effective conjugation of the polymer, while
the interchain hopping is determined by the stacking of the polymer molecules. In a
hopping mechanism, only those carriers with an energy kT, where k is the Boltzman
constant and T is the temperature, below the Fermi level have a significant proba-
bility of hopping. Mott showed that for strongly localized states, the conductivity at
low temperatures must follow a relationship of the form
 
B
δ  exp
T =4
1

where δ is the conductivity and B is a constant related to the hopping mechanism.

At high temperatures, deviations from T1/4 occur, which can be understood in terms of
interchain hopping [48]. A carrier trapped in a chain, after detrapping through large
energy input, may drift along the same chain or may hop onto an adjacent chain. As
such, in amorphous polymers, the conduction occurs due to two distinct processes: a
14 Conducting Polymers and Composites 561

temperature-dependent trap hopping and a comparatively less temperature-dependent

interchain hopping.

3.2 Solitons, Polarons, and Bipolarons

Polymer doping leads to the formation of conjugational defects – solitons, polarons,

and bipolarons – in the polymer chain. The presence of localized electronic states of
energies less than the band gap, arising from changes in local bond order – including
the formation of solitons, polarons, and bipolarons – has led to the possibility of new
types of charge conduction [8]. The ground state structure of such polymers is twofold
degenerate, thus the charged cations are not bound to each other by a higher energy
bonding configuration and so can freely separate along the chain. The effect of this is
that the charged defects are independent of one another and can form domain walls
that isolate two phases of opposite waveform with identical energy (solitons).
Solitons are subdivided into three categories: a neutral soliton, positive soliton,
and negative soliton. An interesting observation is that charged solitons have no
spin; however, neutral solitons have spin but no charge. A positively charged soliton
occurs when an electron is removed from a localized state of a neutral soliton by
oxidation. A negatively charged soliton is produced when an electron is inserted by
reduction (Fig. 8). Solitons produced in polyacetylene (PAC) are believed to be
delocalized over about 12 CH units, with the maximum charge density existing next
to the dopant counterion (A–). The bonds closer to the defect show decreased bond
alternation compared with those further away from the center. Soliton formation
results in the creation of new localized electronic states that appear in the middle of
the energy gap. At high doping levels, the charged solitons interact with one another
to form a soliton band, which can eventually merge with the band (VB and CB)
edges (Fig. 8) to create true metallic conductivity [49–51].
A neutral polymer has full VB and empty CB, separated by the band gap. Formation
of polarons and bipolarons generates new energy levels located at mid-gap. Bipolarons
and polarons are self-localized particle-like defects associated with characteristic dis-
tortions of the polymer backbone and with quantum states deep in the energy gap owing
to strong electron–lattice coupling. Polarons are obtained through a combination of a
neutral and a charged soliton existing on the same polymer chain. Two mechanisms
have been put forward to explain the transition from polaron to bipolaron states: polaron
recombination into bipolarons [52–54], where the bipolaron is generated when polarons
of the same electric charge meet each other; and single-polaron to bipolaron transitions
[55–57], where the polaron structure is transformed by the addition of one extra charge.
Oxidation causes additional polarons to form and eventually the unpaired electron of the
polaron is removed, or two individual polarons combine to form a dication or bipolaron
(Fig. 9) [58]. A polaron has a spin 1/2 and an electric charge e, whereas a bipolaron
is spinless with a charge 2e and is of lower energy than the two distinct polarons from
which it was created. For example, the bipolarons are located symmetrically with a band
gap of 0.75 eV for PPy. With continued doping, continuous bipolaron bands form [59],
and the band gap also increases as newly formed bipolarons are made at the expense of
562 A. A. Baleg et al.

NEUTRAL CHAIN

POLARON

A A

SOLITONS

A A

CONDUCTING
BAND

VALENCE
BAND

NEUTRAL CHAIN POLARON SOLITONS SOLITON BAND

Fig. 8 Soliton structures of polyacetylene

the band edges. For a very heavily doped polymer, it is conceivable that the upper and
the lower bipolaron bands will merge with the CBs and the VBs, respectively, to
produce partially filled “conducting-like” bands rendering metallic-like conductivity
to the polymer, as shown in Fig. 9. Conjugated polymers, e.g., PPy, with a degenerate
ground state exhibit a slightly different mechanism. However, in either case, polarons
and bipolarons are produced upon oxidation [60]. Indeed, density functional theory
calculations showed that the charge carrier in oxidized polypyrrole are bipolarons [61].
The oxidative doping of polypyrrole (PPy) proceeds in the following way. An
electron is removed from the π-system of the backbone, producing a free radical and a
spinless positive charge. The radical and cation are coupled to each other through local
resonance of the charge and the radical, via a sequence of quinoid-like rings, the
number of which is limited by the prohibitive amount of energy required for the
creation and separation of the defects. For the polaron state of the PPy, it is believed
that the lattice distortion extends over four pyrrole rings and can be either a radical
cation or radical anion thereby creating a new localized electronic state in the gap, with
the lower energy states being occupied by a single unpaired electron. The polaron state
of PPy is symmetrically located about 0.5 eV from the band edges [59, 60, 62].
14 Conducting Polymers and Composites 563

H H H
N N N NEUTRAL CHAIN
N N N N
H H H H
A
H H H
N N N POLARON
N N N N
H H A H H
A

H H H
N N N
BIPOLARON
N N N N
H H A H H
A

CONDUCTION BAND

VALENCE BAND

NEUTRAL POLYMER POLARON BIPOLARON BIPOLARON BANDS

Fig. 9 Formation of polarons and bipolarons for polypyrrole (PPy)

A consistent description of the dynamics of the mechanism of creation, stability,

and transition of polarons, and bipolarons constitutes a critical problem in the
understanding of these materials. The polaron–bipolaron transition problem was
explicitly addressed by Čík et al., in poly(3-dodecyl thiophene) in connection with
temperature changes [52]. They found that when the sample was heated and subse-
quently cooled, there was an amplification of the diamagnetic inter- and intrachain
bipolarons. Kaufman et al. studied PPy [53] using optical absorption spectroscopy
and electron spin resonance and found that the metastable states possess spin, while
the stable states do not. Their data revealed a slow transition, consistent with the
diffusion rate limited by the mobility of the dopant.

4 Synthesis and Characterization of Conducting Polymers

It is well known that the conductivity of a polymer is influenced by a number of

factors including polaron length, conjugation length, overall chain length, and by
charge transfer to adjacent molecules, most of which can be influenced by the
method of preparation. Conducting polymers (CPs) are synthesized, either
564 A. A. Baleg et al.

chemically or electrochemically. Each method has advantages and disadvantages, as

summarized in Table 1 [9].
Chemical synthesis includes the usual methods of condensation polymerization (i.e.,
step growth polymerization) or addition polymerization (i.e., chain growth polymeri-
zation). The standard CPs  PPy, PTh, PANI, and poly(3,4-ethylenedioxythiopene)
(PEDOT)  can be polymerized both chemically and electrochemically [62]. With
chemical synthesis of polymers, it is feasible to synthesize CPs that are currently not
possible with electrochemical synthesis. However, because the latter method is rela-
tively straightforward and reproducible [9, 64], it is rapidly becoming the preferred
alternative for making CPs and consists of dissolving a monomer in a solvent/electro-
lyte medium followed by the electrodeposition of a polymer film onto an electrode
surface using pulse, galvanostatic, potentiostatic, or sweeping techniques [65]. One
advantage associated with the electrochemical polymerization of conducting polymers
is that the reactions can be performed at room temperature, either by varying the
potential or current for specified periods of time, thereby permitting the thickness of
the film to be monitored and controlled. CPs such as PTh, polycarbazole, polyindole
polyazulene, and PPy can all be synthesized using this technique [66].

4.1 Polypyrrole

Polypyrrole (PPy), as a model for the CPs, can be obtained chemically or electro-
chemically. The electrochemical polymerization of pyrrole (Py) has been extensively
studied since it is easily obtained in the form of freestanding films and has good
environmental stability and conductivity. Electrochemical polymerization is
performed using a three-electrode configuration (working, counter, and reference)
in a solution of the monomer (Py), appropriate solvent, and electrolyte (dopant)
(Fig. 10).
Current is passed through the solution and electrodeposition occurs at the posi-
tively charged working electrode or anode. Monomers (Py) at the working electrode
surface undergo oxidation to form radical cations that react with other pyrrole mono-
mers or radical cations, forming insoluble polymer chains on the electrode surface

Table 1 Comparison of chemical and electrochemical CP polymerization

Polymerization
approach Advantages Disadvantages
Chemical Larger scale production possible Thin films inaccessible
polymerization Postcovalent modification of bulk Complicated syntheses
CP possible
More options to covalently
modify CP backbone
Electrochemical Thin film synthesis possible Difficult to remove film from
polymerization Ease of synthesis electrode surface
Entrapment of molecules in CPs Postcovalent modification of
Doping is simultaneous bulk CP is difficult
14 Conducting Polymers and Composites 565

Fig. 10 Three-electrode
setup for electrochemical
synthesis of conducting
polymers – reference
electrode, working electrode,
and counter electrode

(Scheme 1) [67]. A number of important variables, including deposition time, tem-

perature, solvent system (water content), electrolyte, electrode system, and deposition
charge need be considered. Each of these parameters has an effect on film morphology
(thickness and topography), mechanics, and conductivity, which are properties that
have a direct impact on the utility of the material for specific applications [63].

4.2 Polythiophene and Its Derivatives

In its doped oxidized state, a poly(3,4-ethylenedioxythiophene) (PEDOT) layer/film

shows exceptional stability, transparency, and high conductivity (300 S.cm–1) [68].
The electrosynthesis of polyalkylenedioxythiophenes was carried out in 1994 by the
anodic oxidation of 3,4-ethylenedioxythiophene or 3,4-trimethylenedioxythiophene.
This resulted in polymers that were extraordinarily stable during charging and
discharging, owing to a narrow band gap [69]. The electropolymerization process
may also be executed through in situ polymerization of 3,4-ethylenedioxythiopene
(EDOT) or via oxidative means [70].
Polymerization of PEDOT is typically carried out in acetonitrile, employing
LiClO4 as electrolyte, which results in a sky-blue doped PEDOT layer containing
ClO4– as counter ions. Oxidative polymerization, with iron(II) chloride, has been
demonstrated to be a satisfactory method of synthesizing neutral, fully undoped
566 A. A. Baleg et al.

H N H
-e H
N N N N N
H H
H H H H
- 2H+
H
N
H -e
H N H + N N N N
- 2H
H n H H H H

N N N N N N
H H H H H H
n n

Scheme 1 Mechanism for heterocycle polymerization via electrochemical synthesis. This path-
way is initiated by the oxidation of a monomer at the working electrode to give a cation species,
which can then react with a neutral monomer species or radical cation oligomeric species to
generate the polymer, redrawn from Ref. [67]

molecules with considerable yield [70]. PEDOT (Scheme 2) is an intermediate in the

preparation of doped, highly conductive PEDOT and can be isolated through the
adjustment of selected reaction conditions.

5 Principal Conducting Polymers

5.1 Polypyrrole (PPy)

Polypyrrole, composed of a number of connected pyrrole rings, has been lauded for
its conductivity (resulting from interchain hopping) and high stability. In addition,
the ease of oxidation and availability of its monomer, pyrrole, ensured that it would
be extensively studied and characterised by thermal analysis and electrochemical
techniques that include cyclic voltammetry (CV) and impedance spectroscopy. The
chemical synthesis of polypyrrole, through the oxidation of pyrrole, was first
accomplished in the early twentieth century. Pyrrole itself is ubiquitous in nature,
making appearances in the building blocks of chlorophyll, hemoglobin, bile pig-
ments, and mold metabolites, among others. Much later, the first electrochemical
deposition of PPy was accomplished in 1968 [71]. Since then, PPy has been
prepared by the electropolymerization of pyrrole onto a variety of conductive sub-
strates, for example, stainless steel, nickel, and platinized silicon wafers, with
promising results [72–76]. The properties – physical, chemical, and electrical – of
14 Conducting Polymers and Composites 567

O O O O O O
O O
FeCl3 S FeCl3 S S
S S S
S
O O O O O O

FeCl3

O O O O O O
S S S
S S S
O O O O O O
n

FeCl3

O O O O O O
S S S
S S S
Cl- O O Cl- O O O O
n

Scheme 2 Synthesis of poly(3,4-ethylenedioxythiophene) and doped poly

(3,4-ethylenedioxythiophene)

H A- A-
H H H
N N N N
N N A- N N
H H H H

Fig. 11 Polypyrrole (PPy), with counter ions (A–) to balance charge. (Redrawn from Ref. [81])

electrochemically deposited PPy (Fig. 11) can be reshaped through doping and
changeable plating conditions [41, 42, 77–80] thereby increasing its versatility.
The easy alteration of these properties, through the judicious choice of dopants,
places PPy in a very select group of conducting polymers, increasing its attractive-
ness for application in biosensor technology, among others.
PPy exhibits good electrical conductivity and high air stability (its conductivity
decreases by only 20% per year in an exposed environment) and, by its very nature,
has been used in a variety of technological applications in various research areas,
namely, secondary batteries [82–85], electrochromic display devices [86, 87], light-
emitting diodes [88, 89], capacitors [90–92], sensors, [93–97] membranes [98], and
568 A. A. Baleg et al.

enzyme electrodes [99–101]. It has been reported that the electrical conductivity is
stable even at 200  C [36, 102]. Consequently, conducting polymeric materials [103,
104], such as PPy, have become an area of increasing research interest as they show
great potential for application in solid-state devices [105].
The ability to control polypyrrole’s surface properties, such as charge density and
wettability, holds promise for effective interaction between biological tissue and the
polymer [106–109]. However, polypyrrole itself reveals rather poor properties in
terms of electrochromic behavior [110], and often, further enhancement through
doping and sensitizing with various dyes is required to obtain good optical properties
[109–114]. Additionally, the syntheses of conducting star, graft, and block copoly-
mers are some of the ways to effectively improve electrical and mechanical proper-
ties of conducting polymers and polypyrrole is no exception. In order to make
conducting polymers processible, several approaches have been developed, one of
which is to prepare graft and block copolymers with desired end groups like pyrrole
or thiophene [115–118].

5.2 Polythiophene (PTh)

Polythiophenes (PThs) are an important representative class of π-conjugated poly-

mers that exhibit a sought after combination of high environmental/thermal stability,
processability, and electrical conductivity. PTh has been used in a variety of appli-
cations such as electrical conductors, nonlinear optical devices, light-emitting
diodes, transistors, electrochromic or smart windows, photoresists, antistatic coat-
ings, sensors, batteries, electromagnetic shielding materials, artificial noses and
muscles, solar cells, microwave absorbing materials, new types of memory devices,
nanoswitches, imaging materials, and polymer electronic interconnect batteries
[119–121]. PThs have a regular polymeric backbone (Fig. 12) which can be modified
by varying the nature of the dopant and through facile ring modifications. Owing to
their chemical and electrochemical stability, high conductivity upon doping, and
nonlinear optical properties, PThs are among the most widely studied conjugated
organic polymers, experimentally and theoretically. However, polythiophene is gener-
ally insoluble in common organic solvents and decomposes readily, thereby limiting its
use in practical applications. The real interest in this class of CPs was sparked when it
was realized that three-carbon substitution of the thiophene ring yielded a wide variety
of versatile CPs. The substituted PThs, namely, poly(3-methylthiophene) and poly

R R R R

S S S S
S S S S

R R R R n

Fig. 12 Structure of polythiophene (PTh) where R = H, poly(3-methylthiophene) where R = CH3

and poly(3-hexylthiophene) where R = C6H13
14 Conducting Polymers and Composites 569

(3-hexylthiophene), etc., all exhibit good solubility in common organic solvents with
the latter finding importance as a benchmark hole conductor in organic photovoltaics
[122]. The chemical method for the synthesis of PTh is used in bulk production while,
electrochemically, very thin and better-ordered films can be prepared. Chemically
synthesized PThs are produced in their undoped state and can be doped chemically
or electrochemically to increase conductivity [123].

5.3 Poly(3,4-ethylenedioxythiophene) (PEDOT)

The first synthesis of PEDOT was successfully done by scientists at the Bayern A G
Laboratories in the late 1980s. The commercial name, Baytron, was given to PEDOT
following the chemical polymerization of 3,4-ethylenedioxythiophene [70]. PEDOT
[124] has been of interest in numerous studies because of its high transparency, high
conductivity, excellent environmental stability, and relatively low band gap
[125]. These unique properties make PEDOT an excellent material for utilization
in electrochromic devices, antistatic coatings, biocorrosion coatings, light-emitting
diodes, sensors, and synthetic textiles [126–129]. PEDOT has also been reported to
be excellent for the synthesis of nanostructured materials and devices whose elec-
trical, electronic, magnetic, and optical properties are comparable to those of metals
or semiconductors. Compared to other unsubstituted PThs and derivatives, PEDOT
exhibits a distinctly low oxidation potential and a small band gap in the oxidized
state [130, 131]. It has been revealed that undoped PEDOT has a band gap energy
of –1.6 eV and can be electrochemically cycled between its reduced and oxidized
states. This superior electrochemical stability may be attributed to the presence of the
ethylenedioxy binding group at the α and β position of the thiophene ring in EDOT
(Fig. 13), which blocks coupling along the backbone, making the resulting polymer
regiochemically defined [130, 132].
Conducting polymers may be employed in their unmodified state or they may be
doped to enhance their electrical capability; PEDOT is one of the few examples
within the conjugated polymer family which is both p- and n-dopable [133]. It is
acknowledged that upon electrochemical p-doping or n-doping, conducting poly-
mers undergo a redox process which involves ion transport into and out of the
polymer matrix to balance the electronic charge, resulting not only in an increase in
electronic conductivity but also structural transitions which give rise to spectral
changes [134–137] which allowed for their exploitation in the field of sensors.

Fig. 13 Structure of poly

(3,4-ethylenedioxythiophene)
O O O O O O
(PEDOT)
S S S
S S S
O O O O O O
n
570 A. A. Baleg et al.

Indeed, Nien et al. [138] used PEDOT as the matrix to fabricate an amperometric
glucose biosensor; the biosensor showed a detection limit and sensing sensitivity of
0.13 mM and 12.42 mA cm2 M1, respectively. Other incorporations of PEDOT in
sensors include a direct detection DNA sensor, that quantifies the targeted single-
strand DNA [139], and a self-absorbing piezoelectric sensor consisting of
conducting PEDOT [140]. In addition, an amperometric sensor coated with
PEDOT for the measurement of chromate ions and an enzyme modified biosensor
entrapped by PEDOT for the detection of phenolic compounds, with high catalytic
activity have been reported [141]. Moreover, it was found that the increased surface
area of the polymer led to a high rate of electron transfer between the electrode and
p-benzoquinone, when the latter was employed as an electron mediator.
Electrochemical polymerization is widely used to construct conducting polymer
films, but the option of using a conducting substrate from which a conducting
polymer is formed may limit practical applications [142]. Recently, the incorporation
of nanomaterials into a polymer matrix and the study of nanoparticles-matrix inter-
actions have been of interest to material scientists [143]. Polymers are considered a
good choice as host matrices for composite materials, because they can easily be
designed to yield a variety of bulk physical properties [144, 145]. PEDOT coatings
prepared by electrochemical polymerization in aqueous solution allows the direct
incorporation of water-soluble anions [146], into its matrix. Xiao et al. developed an
adenosine 5’-triphosphate (ATP) doped PEDOT for neural recording devices that
displayed great stability and biocompatibility [147]. Balamurugan et al. [124] dem-
onstrated a silver nanograins (AgNGs) incorporated PEDOT modified electrode for
electrocatalytic sensing of hydrogen peroxide. The modified electrode exhibited good
electrocatalytic activity towards the reduction of hydrogen peroxide without an
enzyme or mediator immobilized on the electrode. It showcased a detection limit of
7 μM and a response time of 5 s. Vasantha et al. disclosed the electrochemical
synthesis of a poly(3,4-ethylenedioxythiophene)-(PEDOT)|ferricyanide film modi-
fied electrode by cyclic voltammetric and chronoamperometric techniques, for the
determination of ascorbic acid in aqueous solution with a detection limit of 5  105
M [148]. Olowu et al., in 2010, constructed an aptasensor for the detection of
17β-estradiol, an endocrine disrupting chemical, based on a poly(3,4-ethylenediox-
ythiopene)-gold nanocomposite platform; the detection limit was 0.02 nM [149].

5.4 Polyfuran (PFu)

Furan is one of the five-membered heteroaromatic ring compounds that can be

converted into a conducting polymer by both chemical and electrochemical methods
in aqueous and organic media. It is lesser known than pyrrole and thiophene because of
its high oxidation potential. Polyfuran (Fig. 14), through chemical synthesis, has found
application in industry as an insulator and is very sensitive to humidity – its electrical
resistivity decreases considerably and reversibly upon contact with moisture.
Ali et al. [150] studied the dispersion of normal modes in polyfuran and this
conducting polymer was used in optoelectronic devices, as upon doping the color
14 Conducting Polymers and Composites 571

O O O O
O O O O
n

Fig. 14 Chemical structure of polyfuran (PFu)

Fig. 15 General polymeric

structure of polyaniline H H
N N N N
y 1-y

changes from yellow-brown to black-brown [151, 152]. Meanwhile, Galal et al.

developed a promising electrochemical biosensor to determine dopamine, epinephrine
and norepinephrine, ascorbic acid, and paracetamol. The sensor was fabricated via
electrodeposition of palladium nanoclusters on a polyfuran film modified platinum
electrode and saw exceptional improvement in the detection limit. Moreover, diffusion
coefficient measurements confirmed the fast electron transfer kinetics of the electro-
chemical oxidation of the analyte molecules at the sensor/solution interface [153].

5.5 Polyaniline (PANI)

Polyaniline (Fig. 15) has been studied extensively as an important conducting

material owing to its promising electronic and optical properties [65, 154]. It has
also generated considerable interest because of the many synthetic pathways avail-
able to scientists, its chemical stability, good environmental stability, low cost, and
ease of redox doping [155]. Although PANI boasts good environmental stability and
conductivity, processing of the polymer into useful products has been problematic
because of its insolubility in common nontoxic organic solvents and the fact that its
ready decomposition before melting. PANI is unique among inherently conducting
polymers such as PPys and PThs because its N heteroatom can directly participate in
the polymerization process and in the conjugation of the conducting form to a greater
extent than the N and S heteroatoms in PPy and PTh.
PANI can be synthesized by either chemical or electrochemical oxidation of
aniline under acidic conditions. The most widely used technique is oxidative cou-
pling, involving the oxidation of the monomers, to form radical cations which couple
to form dications. Repetition of this propagation step leads to the polymer. Electro-
chemical synthesis is preferred to chemical synthesis because of the accessibility to
thin films and better ordered polymers. The best films are reported to be produced
from electrochemical techniques using three electrode systems [156]. The film can
be deposited at the working electrode through electropolymerization of monomeric
aniline from a suitable medium that limits the dissolution of the substrate. This
electropolymerization process is preferably conducted in acidic media at a pH < 1
[157, 158]. PANI-coated electrodes, as components of sensors, presents some
572 A. A. Baleg et al.

advantages such as acceleration of electron transfer reactions, immobilization of

biological compounds, amplification of signal, and elimination of electrode fouling.

5.5.1 Polyaniline Derivatives

Similar to unsubstituted PANI, polyaniline derivatives are also synthesized by
chemical or electrochemical oxidative polymerization of the respective substituted
aniline monomers in acidic solution, although some other approaches such as plasma
polymerization [159, 160], electroless polymerization [161], solid-state polymeriza-
tion [162, 163], enzyme-catalyzed polymerization, and photochemically initiated
polymerization [164] have also been reported. Conditions related to the formation of
PANI and its derivatives, such as the type of supporting electrolyte, monomer
concentration, applied potential, the type of solvent, and pH of the electrolyte
[158, 164], as well as the influence of anions on the electrodeposition of polyaniline
and on polyaniline redox reactions, have also been extensively described in literature
[165, 166]. These factors are known to dictate the morphology and properties of the
generated polyaniline.
It is well known that the low solubility of PANI, in common organic solvents,
ultimately restricts processability. To overcome this challenge, substituted PANI was
investigated and polymerization of a typical derivative of aniline resulted in a soluble
conducting polymer. The substituent groups present in the units of the polymer chain
are thought to contribute to a decrease in the stiffness of the polymer chain resulting
in better solubility. Unfortunately, substitution of the phenyl ring or the N-position of
polyaniline units has been shown to decrease the conductivity [167]. However, poly
(2,5-dimethoxyaniline) (PDMA), bearing anilines substituted with two methoxy
groups (2,5-dimethoxyaniline), has been reported to be a soluble polymer (Fig. 16)
with a conductivity similar to PANI [168, 169] though the redox transitions occur at
lower potentials in comparison with PANI (0.70 V for PANI and 0.27 V for
PDMA) [170].

5.5.2 Oxidation States of Polyaniline

Polyaniline has the general formula [(―B―NH―B―NH)n (―B―N=Q=N―)1n]m,
in which B and Q are the rings in the benzenoid and quinonoid forms, respectively.

Fig. 16 Structures of (a) O

2,5-dimethoxy aniline and
(b) PDMA
H2N O
A

O O O
H H
N N N
H
O O O
n
B
14 Conducting Polymers and Composites 573

PANI can be rapidly converted between the base and salt forms by treatment with acid or
base, thus, the general polymeric structure shown in Fig. 15 is now accepted by the
scientific community.
PANI can exist in three basic forms depending on the existing oxidation state,
which ranges from the fully reduced (y = 1) leucoemeraldine state to the half
oxidized (y = 0.5) emeraldine form to the fully oxidized (y = 0) pernigraniline
configuration. Reduction of the emeraldine salt to leucoemeraldine and oxidation
to pernigraniline both see a decrease in conductivity [171]. In fact, the fully
oxidized and fully reduced states of PANI are insulators, although they possess
other interesting physical and chemical properties. Beside changes in oxidation
levels, different forms of PANI are also characterized by a change in color
[172]. For instance, the emeraldine salt obtained by electrochemical polymeri-
zation in acidic media is green in color and can be converted into the dark blue
form by further oxidation to the fully oxidized pernigraniline salt and even
further into the violet pernigraniline through treatment in basic media. It can
also be reduced to colorless leucoemeraldine or further converted into the blue
nonconducting form of emeraldine in basic media [173] (Scheme 3). Interest-
ingly, the two blue forms of PANI – pernigraniline salt and emeraldine – are of
different shades [172].
Among the three oxidation states of PANI, the emeraldine salt is the one that
displays the highest conductivity, by doping or protonation of the emeraldine base
[174] – and is composed of an alternating sequence of three benzenoid units and one
quinonoid unit. Further, it consists of amine (–NH–) and imine (=N–) sites in equal
proportions [175]. The imine sites are protonated by acids to the bipolaron (dication
salt) form. However, further rearrangement occurs to form the delocalized polaron
lattice, which is a polysemiquinone radical-cation salt and is responsible for the high
conductivity of PANI [164].

6 Conducting Copolymers

Practical use of polypyrrole and other conducting electroactive polymers

are limited by their brittle structure, insolubility and poor mechanical and
physical properties, all of which restrict their processability [176]. Improvements
to the processability of conducting polymers can be had by copolymerizing them
with other monomers resulting in star, graft or block copolymers [177,
178]. Copolymerization permits the chemical linking between the insulating
matrix (end groups) and the conjugated polymer [179]. Structural modification
of conducting polymers via copolymerization has been used to obtain materials
with a broad range of electronic, optical, and mechanical properties [180]. Thus,
electrochemical syntheses of pyrrole copolymer films with substituted pyrroles,
[181], thiophene [182], terthiophene [183], and other combinations of aromatic
compounds [184, 185], have been reported. The resulting copolymers have
properties different from those of the homopolymers of the constituent
monomers.
574 A. A. Baleg et al.

6.1 Conducting Star Copolymers

Star copolymers are a class of branched macromolecules that have a central core to
which multiple linear polymer chains are attached – the core consists of a moiety
with multiple branching points (Fig. 17). The cores may be formed from

Scheme 3 Different oxidation states of PANI. Redrawn from Ref. [166]

Fig. 17 Representation of a
star copolymer

Multifunctional centre
Polymer arm
14 Conducting Polymers and Composites 575

hyperbranched polymers, dendrimers, or other symmetric or semi-symmetric mole-

cules which have multiple attachment sites. The three dimensional (3D) structure,
with extended conjugated linear polymer chains, gives star copolymers properties
that are different from the typical two-dimensional, linear polymers [19].
Conducting star copolymers are used in their undoped state for applications in
which the conductivity requirements are not too high, for example, static dissipation,
or where the optical property of the polymer coating is of chief importance as in
a pigment or reflective layer. Materials with conductivities in the range of 10–6 to
1 S.cm–1 are suitable for these purposes. Furthermore, the conducting chains sur-
prisingly can provide sufficient intermolecular overlap to give solid materials with
electrical conductivities higher than the corresponding linear, non-star conducting
polymers [19, 186–188].
The regular 3D structure of star copolymer gels combines the properties of
hardness and flexibility and is being investigated as materials that are hard without
being brittle [19]. The combination of star copolymer and conducting polymer
structures realises an approach to make materials that possess the favorable proper-
ties of both – improved processability and electrical conductivity. The former results
from the spheroidal structure of hyperbranched, dendrimeric, and starburst poly-
mers. A conducting star copolymer may be constructed in which two or more
different conjugated arms radiate from the central core [86]. Doping of the
conducting star copolymers, to increase the electrical conductivity, may be achieved
using methods applicable to the conjugated radiating chain moieties. For conjugated
chains based on pyrrole, thiophene units or their derivatives, doping may be
achieved by treatment with oxidizing agents such as iodine, ferric chloride, ferric
tosylate, gold trichloride, and antimony chloride. If the polymer side chains are
composed of polyaniline, doping can be brought about by treatment with hydro-
chloric acid [189]. Doping can also be obtained electrochemically by confining the
polymer to an electrode surface and subjecting it to an oxidizing or reducing
potential in an electrochemical cell.

6.2 Dendrimer Star Copolymers

Dendritic copolymers (Fig. 18) are a specific group of dendrimers. These exist as two
different types of copolymers – segment-block dendrimers built with dendritic
segments of different constitution, obtained by attaching different wedges to one
polyfunctional core molecule and layer-block dendrimers consisting of concentric
layers around the central core. Hawker and Fréchet [190] synthesized a layer-block
dendrimer as well as a segment-block dendrimer which consisted of one ether-linked
segment and two ester-linked segments. The inner two generations were ester-linked
and the outer three ether-linked.
Dendrimer-star copolymers [191] are a novel type of molecular architecture, in
which many linear homo- or block copolymer chains are attached to the dendrimer.
They have been developed because they combine the properties of star copolymers
with those of dendrimers [192–197]. Two general methods have been used to prepare
576 A. A. Baleg et al.

Fig. 18 Copolymers: (a) segment-block dendrimer and (b) layer-block dendrimer

the dendrimer-star copolymers – one is to link monofunctional linear polymers onto the
dendrimer surface [192, 196–198] and the other is to grow armed polymer chains from
the surface of the dendrimer by “controlled/living” polymerizations, such as anionic
polymerization [199], ring-opening polymerization (ROP) [200], and atom transfer
radical polymerization (ATRP) [201]. Synthesis of a hybrid dendrimer-star copolymer,
through the reversible addition-fragmentation transfer (RAFT) polymerization process,
has been reported by Zheng et al. [202]. Wang et al. discussed a conducting star-shaped
copolymer, consisting of a regioregular poly(3-hexylthiopene) arm attached to a
polyphenylene dendrimer core [203]. Miller and Tomalia announced the conductivities
of polyamidoamine (PAMAM) dendrimers modified with cationically substituted
naphthalene diimides; the study showed that the conductivity increased with increased
humidity, to as high as 18 S.cm–1 at 90% relative humidity. The conductivity was, in all
cases, electrical and isotropic [204].
In 2011, Baleg et al. reported on the synthesis and characterization of a star
copolymer based on a PPI dendrimer core (generations 1–4) and polypyrrole [205]
(Fig. 19). In the same year, a star copolymer which involved the electro-
copolymerization of (3,4-ethylenedioxy thiophene) (EDOT) with G2PPT was devel-
oped by Olowu et al. [149, 206].
Poly(propylene imine) (PPI) dendrimers are highly branched macromolecules
having terminal amino groups which exhibit a number of interesting characteristics.
The dendrimer can be used as a hydrogen donor because of the high density of amino
groups; many of the properties of dendrimers are strongly influenced by these
terminal groups [207–209].
The use of dendrimer-oligothiophene hybrid macromonomers for the preparation
of a soluble, highly conducting PTh, having only dendritic substituents, has been
communicated [210]. Roncali et al., in 1999, described electrogenerated poly
(dendrimers) containing conjugated poly(thiophene) chains. In his approach, an
electroactive conjugated polymer was synthesized by electropolymerization of
increasing generations of dendrimer derivatives by a bithiophene group [211].
Deng and others described the synthesis and application of amine-terminated
14 Conducting Polymers and Composites 577

H H
N N H H
N N C N N CH N N
N H
H H H N N N
n H H H
n

H H N
N N N H H
N N C N N CH N N
N H
H H H N N N
n H H H n
N N

H H H H
N N N N N
C N N CH
N N N H N N N N
H H H H H H
n
n

H H H H
N N N CH N N
N N C N
N H N N N
H H H H H H
n n

Fig. 19 Poly(propylene imine)-co-polypyrrole

fourth-generation PAMAM dendrimers functionalized with thiophene dendron

jackets and their roles in the preparation of dendrimer-encapsulated nanoparticles
for energy-transfer and fuel cell application [212]. A series of star-shaped copol-
ymers, using first generation (G1) to the fifth generation (G5) PPIs as the core,
were prepared [213, 214] in order to investigate their miscibility properties with
linear polystyrene. The unsaturated end groups of polyisobutylene were converted
into anhydride termini by Alder-ene reaction with maleic anhydride, and the
product was reacted with the PPI dendrimers to generate PPI-polyisobutylene
star copolymers [215]. The formation of dendritic stars with conducting polymers
such as PANI, PTh, and PPy saw an increase in the conductivity which was
attributed to a nanostructural change in the product owing to elongation of the
conjugation chains and unhindered π-stacking of the polymer molecule with the
dendrimer [205, 212, 216].
Dendrimer-like star-branched polymers have recently appeared as a new class of
hyperbranched polymers and are recognized as nano-ordered globular macromole-
cules. Based on their architectures which bear many characteristic structural features
such as hierarchical hyperbranched structures, generation-based radial architectures,
differing branch densities between core (inside) and shell (outside), and many
junction points and end-groups [217, 218].
It is also possible to synthesize a variety of dendrimer block copolymers by
introducing different polymer segments at each dendrimer branch. Interesting
morphologies and nanostructured materials have been reported by several research
groups [219–226]. Thus, dendrimer-like star-branched polymers and block copol-
ymers are promising specialty functional materials with many possible applica-
tions as drug, vaccine, and gene encapsulated delivery devices, surface modifiers,
functional nanosize spheres and micelles, surfactants, molecular recognition sys-
tems, and microelectronic materials to name a few. Yoo et al. [227] synthesized a
series of dendrimer-like star-branched polystyrenes by developing an iterative
578 A. A. Baleg et al.

methodology based on the “arm-first” divergent approach. This resulted in high-

generation and high-molecular-weight polystyrenes with narrow molecular weight
distributions [227].

6.2.1 Poly(propylene imine)-co-polypyrrole Dendritic Star Copolymer

Synthesis of novel star copolymers based on the PPI dendrimer core (generations 1–4)
and PPy shell was rendered via a condensation reaction (Scheme 4) between the PPI
surface amine moieties and 2-pyrrole aldehyde to give the pyrrole-functionalized PPI
dendrimer (PPI-2Py). Subsequently, the pyrrole units on the dendrimer backbone
underwent chemical oxidative copolymerization, using ammonium persulfate as an
oxidant, providing the conducting star copolymer with polypyrrole side chains in 75%
yield. Electrochemical synthesis was achieved via cyclic voltammetric scans of a
PPI-2Py drop-coated platinum electrode (Scheme 4). In both cases, the resulting star
copolymer, poly(propylene imine)-co-polypyrrole, exhibited higher conductivity than
the pristine pyrrole and improved thermal stability over PPI-2Py [205].

H2N NH2

N N + OHC N
H
H2N NH2

MeOH / 48h / RT

C N N C
N H H N
H N N H

C N N C
N H H N
H H

(NH4)2S2O8.H2O / CHCl3 / RT
N
H

H H
N N N N
n H C N N C H n
H H
N N

H C N N C H
N N H H N N
H H
n n

Scheme 4 Chemical synthetic procedure for poly(propylene imine)-co-polypyrrole – a dendritic

star copolymer. Redrawn from Ref. [205]
14 Conducting Polymers and Composites 579

6.2.2 Dendritic Poly(propylene thiophenoimine)-co-poly(3,4-ethylene

dioxythiophene) Dendritic Star Copolymer
In another development, Olowu et al., in 2011 [149], also synthesized a star copolymer
which involved the electrocopolymerization of 3,4-ethylene dioxythiophene (EDOT)
with a G1 poly(propylene thiophenoimine) (G1PPT) modified gold electrode
using cyclic voltammetric techniques (Scheme 5) to produce a generation 1 poly
(propylene thiophenoimine)-co-poly(3,4-ethylene dioxythiophene) dendritic star
copolymer (G1PPT-co-PEDOT) for use in the detection and quantification of the
endocrine disrupting compound, 17β-estradiol. Electrochemical impedance spec-
troscopy confirmed the more desirable conductive behavior of the star copolymer
over PEDOT.

6.2.3 Dendritic Poly(propylene thiophenoimine)-co-poly(-3-

hexylthiophene) Dendritic Star Copolymer
Novel star copolymers based on a G3 PPI dendrimer core and a poly
(3-hexylthiophene) shell were prepared by Makelane et al. [228]. The synthesis of

H2N NH2

N N

H2N NH2
PPI DENDRIMER

MeOH / 48h
OHC S
S S
C N N C
H H
N N

C N N C
S H H S
G1PPT

O O
O O
O DCM O
S S
S
S S S S
O O
n O C N N C O n
H H
N N

O C N N C O
O H H O
S S S S
G1PPT-co-PEDOT
S S
n O O
O O n

Scheme 5 Synthetic pathway to poly(propylene thiophenoimine)-co-poly(3,4-ethylene

dioxythiophene) dendritic star copolymer. Redrawn from Ref. [149]
580 A. A. Baleg et al.

the G3 poly(propylene thiophenoimine) (G3PPT) dendrimer was carried out by

condensation of PPI with 2-thiophene carboxaldehyde. The thiophene units on the
dendrimer backbone were polymerized electrochemically, in the presence of
3-hexylthiopene on a gold electrode coated with G3PPT using cyclic voltammetry
(Scheme 6) resulting in the poly(propylene thiophenoimine)-co-poly(3-hexylthiophene)
dendritic star copolymer.

NH2 CH N N HC
NH2 S S
NH2
N HC
CH N S
NH2 S N N
N N
NH2 CH N N HC
H2 N 2-thiophene- S S
carboxaldehyde N
N N N N N N
N
Methanol
CH N
H 2N NH2
48 h S N HC
S
N N N N
NH2
N HC S
H 2N S CH N
N N N N N N
N N

NH2 N HC
H2N CH N
N S S
N N
NH2 N
H2N N HC
S
S CH N
H2N NH2
N HC
CH N S
S
ne
G3PPI Dendrimer
phe
io
lth
xy
he
3-
C6H13 C6H13

S n
S
n S S C6H13
C6H13 S CH
HC S
N C6H13
N
C6H13 n
n S
S S
S
N HC
CH N S C6H13
C6H13 S N C 6H 13
C6H13 N
S S
S
CH N N HC n
n S
S S
C6H13 N C6H13
N N N C6H13
C6H13
S CH N
S n
S N HC S
S
n S
C6H13 N N C6H13 C6H13

C6H13 N HC
S n
S CH N S S
S
C6H13
n S
C6H13
N N N N
C6H13

S
C6H13
S CH N N HC n
S S S
N N
S N HC C6H13
n C6H13 S S
CH N
S C C6H13
S 6H
N H 13
C6H13 N C S
C6H13 CH
S S S n
S C C6H13
6H
S
n C6H13
13
S
C6H13
S n
G3PPT-co-P3HT
n

Scheme 6 Synthesis of generation 3 poly(propylene thiophenoimine)-co-poly(3-hexylthiophene)

dendritic star copolymer. Redrawn from Ref. [228]
14 Conducting Polymers and Composites 581

7 Conducting Polymer-Based Composites

Conducting polymers and their composites have been extensively utilized in the
fabrication of sensors and other technology that necessarily warrant materials that
are responsive in nature. However, as previously mentioned, conducting polymers
on their own suffer from low processibility and sensitivity as well as fouling
[229]. The expansion of the field of CP-based composites, whose robustness and
high detection limits, provided a means of overcoming these challenges associated
with neat CPs, expanded.

7.1 Polyaniline–Carbon Nanotubes Composites (CNCs)

The discovery of carbon nanotubes (CNTs) in 1991 [230] led to an explosion of

interest in nanoscience and nanotechnology research. Although there were initial
high expectations of the potential of the CNTs, it soon became apparent that working
with the carbon allotrope in its natural form presented some challenges. One
response to facilitate the utilization of CNTs and their extraordinary properties in
real-world bulk applications was the development of CNT/polymer nanocomposites
(NCs). There now exists ongoing research into new combinations of traditional stock
as hybrid materials, blends, and NCs and exploitation of their complementary
properties [231, 232]. In this context, the development of conducting polymer–CNT
composites, as novel futuristic materials, has attracted the curiosity of investigators
because the blending of the two constituents offers the possibility to observe and
capitalize on synergistic effects.
Some studies have emerged in the literature explaining that certain discrete
properties of the components of conjugated polymer–CNT composites are enhanced,
relative to the individual units, therefore validating their suitability for selected
technological applications [233–235]. Incorporating CNT as fillers into conducting
polymers results in NCs that possess much higher electrical conductivities than CPs.
The CNT has been shown to behave as a transport bridge between the conducting
domains of CPs, thus enhancing the electrical conductivity of the CP and by
extension, the nanocomposite [236]. Currently, the construction of polymer com-
posites is the biggest area of application for CNTs owing to the nanocomposite’s
high durability, high strength, light weight, design, and process flexibility. The
successful utilization of carbon nanotubes in the assembly of the composite depends
heavily on the homogenous dispersion of CNTs individually and uniformly through-
out the matrix, without negatively affecting their structural integrity or reducing their
aspect ratio [237]. Additionally, the enhanced mechanical properties of the nano-
composites require good interfacial bonding to achieve significant load transfer
across the CNT–matrix interface [238]. Therefore, careful processing of the com-
posites is of utmost importance. In the next section, we will discuss the different
processing techniques and properties of a polyaniline/carbon nanotube (PANI–CNT)
nanocomposite as a benchmark model.
582 A. A. Baleg et al.

7.2 Synthesis of the Composites

Various methodologies have been developed for chemically and electrochemically

[239] preparing PANI–CNT composites, with two of the most common being direct
solid-state mixing [240] and dispersal of CNTs in PANI solutions [241, 242]
(Scheme 7a, b). However, a cursory scan of the literature reveals that in situ

1. DIRECT MIXING

a. Solid-State Mixing

Mechanical Blending
PANI + CNT PANI-CNT
(Powder) (Powder) (Solid)

b. Solution Mixing
Sonication /
PANI + CNT Mechanical Blending PANI-CNT
(Powder) (Powder) (Dispersion)

2. IN SITU CHEMICAL POLYMERIZATION

(NH4)2S2O8 + 1M HCl
Aniline + CNT PANI-CNT
(Dispersion) 0 ºC (Solid)

3. ELECTROCHEMICAL POLYMERIZATION

Aniline, HCl / H2SO4, pH ~ 1

-0.2 V to 0.9 V vs Ag/AgCl

or 0.75 V vs SCE

GCE-CNT PANI-CNT (film)

Aniline, CNT, HCl / H2SO4, pH ~ 1

-0.2 V to 0.9 V vs Ag/AgCl

or 0.75 V vs SCE

GCE PANI-CNT (film)

Scheme 7 General preparative methods of PANI-CNT composites

14 Conducting Polymers and Composites 583

polymerization (Scheme 7c) is the most favored synthetic method for PANI-CNT
NCs as it enables grafting of polymer molecules onto CNT, leading to better
dispersion coefficients and augmented interactions between the CNT and the poly-
mer matrix. Arguably, the in situ polymerization of aniline or substituted aniline in
an acidic dispersion of multiwalled or single-walled carbon nanotubes, in the
presence of an oxidant at low temperatures, is the simplest method reported so far
[239, 243, 244]. Nevertheless, several approaches have been successfully adopted to
obtain intimate mixing of nanotubes with polymer matrices in general, and poly-
aniline in particular, including dry powder mixing, solution blending, melt mixing,
in situ polymerization, and surfactant-assisted mixing.

7.2.1 Solution Processing of Composites

Solution casting, which involves mixing of carbon nanotubes and the polymer in a
suitable solvent, is the most common technique used in the preparation of CNTs/
polymer. One benefit is easy deaggregation and dispersion of carbon nanotubes
through agitation of the CNTs with the polymer in a solvent. This method consists of
three steps:

(a) Dispersion of carbon nanotubes in either a suitable solvent or polymer solution

(b) Mixing of carbon nanotubes and the polymer
(c) Recovery of the nanocomposite by precipitation or casting of a film

The synthesis of nanocomposite CNT/polymer can be done either through an

organic or aqueous medium and the choice of solvent is usually dependent on the
solubility of the polymer. Lau et al. [245] revealed the influence of solvents on
carbon nanotubes dispersion and the thermal and mechanical properties of the
composites. Their results demonstrated that, contrary to the general belief that only
small traces of CNTs are needed to strengthen the epoxy composites, the choice of
solvent used in the dispersion of CNTs cannot be ignored. They concluded that only
the acetone-dispersed nanocomposites displayed improvements in flexural strength
over the pure epoxy. Ethanol and dimethylformamide (DMF) actually countered the
benefits of CNTs in the resulting nanocomposites. Subsequently, thermogravimetric
characterization (TGA) proved the existence of remaining solvent in the resulting
nanocomposites bringing to the fore the importance of considering the boiling points
of solvents in the interest of improving the purity of products. Further study [246]
provided evidence of the solvent influence, using Fourier Transform Infrared (FTIR)
spectroscopy, on the molecular structure of the final nanocomposite. The presence of
remaining solvent altered the reaction mechanism by restricting the nucleophile–
electrophile interaction between the hardener and epoxy, thereafter affecting the
degree of cross-linking and degrading the transport and mechanical properties of the
cured structures.
In general, dispersion of carbon nanotubes can be done by magnetic stirring,
shear mixing, reflux or most commonly, ultrasonication. The latter technique can be
executed in two ways – mild sonication in a bath or high-powered sonication.
Unfortunately, the use of high-powered ultrasonication for long periods of time
584 A. A. Baleg et al.

can cause shortening of the carbon nanotubes, i.e., reduce the aspect ratio, which is
detrimental to the composite [247].
One resolution to this problem has been to disperse higher loadings of nano-
tubes, through the use of surfactants [246, 248, 249]. As an alternative to the
covalent functionalization of CNTs, this approach preserves the integrity of the
nanotubes without disrupting the extended π-conjugation [236]. When CNTs
are dispersed in aqueous solutions containing surfactants, each individual nano-
tube (or small bundle) is encased in its own micelle-like envelope with the
hydrophobic substituents of the surfactant oriented toward the nanotube and the
hydrophilic groups oriented toward the solution. The insertion of aniline in
the hydrophobic region within the micelle/CNT hybrid template guides the growth
of PANI on the CNT surface. The utilization of surfactants including, anionic sodium
dodecylsulfate (SDS) [250], dodecylbenzene sulfonic acid sodium salt [251],
dodecylbenzene sulfonic acid (DBSA) [252], cationic cetyltrimethyl ammonium
bromide (CTAB) [253], non-ionic poly(ethylene glycol) mono-p-nonyl phenyl
ether (Oπ-10) and polyvinyl alcohol [254, 255], during the micelle/CNT
hybrid template directed synthesis of CNT/PANI have produced composites with
coaxial nanostructures. In such cases, cationic and nonionic surfactants are not
incorporated into the CNT/PANI composites, unlike anionic surfactants that
generally are integrated into the composite as a dopant. Zhang et al. [256] reported
the template-directed synthesis, characterization, and electrical properties of
single-walled carbon nanotube (SWNT)-based coaxial nanowires; that is, core
(SWNT)shell (conducting polypyrrole and polyaniline) nanowires in which an
aqueous solution containing the cationic surfactant cetyltrimethylammonium
bromide (CTAB) or the nonionic surfactant poly(ethylene glycol) mono-p-nonyl
phenyl ether (Oπ-10) was employed. The results revealed that the micellar
molecules could affect the surface morphologies of the resulting coaxial nanowires
(SWCNT/polymer composite) but not the molecular structures of the corresponding
conducting polymers.
In solvent blending, a slow evaporation step often leads to CNT aggregation. The
research groups of Laplaze [257] and Chauvet [258] suggested spin-casting on
substrate or drop-casting on a hot substrate CNT/polymer suspension to expedite
the evaporation step and hence alleviate the aggregation problem. The solution
processing method in the case of PANI/CNT composites generally consists of
mixing PANI (Emeraldine Salt or Emeraldine Base) and CNT solutions or disper-
sions together in an appropriate solvent. Solvents, such as N-methyl-2-pyrrolidone
(NMP), dimethylformamide (DMF), or N,N-dimethyl propylene urea (DMPU) are
good solvents for the emeraldine base (EB) and are preferred solvents for the
preparation of EB–CNT composites [259]. Water processing of emeraldine
salt–carbon nanotube (ES–CNT) composites utilize CNT functionalized with hydro-
philic moieties, such as carboxylic acid groups [260, 261], and/or hydrophilic PANI
(sulfonated [262, 263] or boric acid [264–266]), or self-doped PANI. These modi-
fications are to ensure that the CNTs are properly dispersed in the water. Water
processing also refers to the ex-situ processing of ES–CNT composites reported in
the literature [242, 260, 262, 267]. The external doping of PANI is important in the
14 Conducting Polymers and Composites 585

preparation of stable aqueous colloids of ES, which leads to the nanofiber nanoscale
structure of PANI [242, 268].
The classic surfactant-free method for the preparation of CNT/PANI compos-
ites consists of mixing aniline with an oxidant such as ammonium peroxydisulfate
[269], ferric chloride [270], polyphenylene sulfide [271], etc. in an aqueous
acidic dispersion [272] of MWCNT or SWCNT in concentrations ranging from
2 to 70 wt% either at low temperatures (0–4  C) [173, 273] or at room temperature
[274]. Among the available surfactant-free preparation methods that have been
proposed to facilitate the dispersion of hydrophobic nonfunctionalized CNTs in
aqueous media, addition of ethanol to the aqueous reaction medium [274], or
refluxing in aniline [275], are generally accepted as being the most efficient.
Another approach is to chemically modify the carbon nanotube surface so as to
disrupt the rope structure and add reactive species to the nanotubes thereby
improving interfacial bonding in CNT/PANI composites. Carboxylic acid
[276–278] and amine-functionalized [278–280] CNTs are also frequently used
for the same purpose. The oxidation of amino groups, covalently linked to CNT in
aminobenzoyl functionalized CNT, generates radical cations that initiate polymer-
ization on the surface [281].
The morphology of CNT/PANI composites depends on the content of CNT
[282]. For instance, the morphology of neat PANI is comparable to that of
MWCNT/PANI formed as individual nanofibers when MWCNT loading is at
2.7 wt%. However, when the MWCNT loading increases to 10 wt%, granular
nanofibers are obtained. Greater than 20 wt% results in a continuous porous
matrix formed from the cross-linked smooth-surface nanofibers and increasing
the content of PANI to 80 wt% in the composites leads to full encapsulation of the
carbon nanotubes by polyaniline [236]. Furthermore, Li and Kim [283] found
that the use of a high mass ratio of aniline/MWCNT (4:1) can lead to the
formation of nanofibers, with diameters between 10 nm and 15 nm, through in
situ polymerization.

7.2.2 Melt Processing of Composites

Solution processing is an important technique for both carbon nanotubes disper-
sion and nanocomposite formation; it is less suitable for industrial scale processes.
To facilitate large-scale production for commercial applications, melt processing is
the better alternative and the most commonly used method for industrial purposes
owing to the low cost and simplicity of process. This technique makes use of the
fact that thermoplastic polymers soften when heated. Melt mixing generally
requires high temperatures to decrease the viscosity of the substrate and high
shear forces to disperse the nanofillers, such as CNTs. Thus, composites of
different shapes can be fabricated by techniques such as compression molding,
injection molding, or extrusion. While melt blending is presented as a very simple
method [284–287], the use of high shear forces and high temperatures can cause
deterioration of the nanocomposite structure. To overcome these problems during
melt processing, optimization of the processing conditions is required, not only for
the different nanotube types but also for the entire range of polymer–nanotube
586 A. A. Baleg et al.

combinations [288]. For instance, high shear force is required to achieve CNT
dispersion but this can lead to CNT fragmentation. Therefore an optimum shear
stress is required to achieve the desired dispersion with the least amount of damage
to the CNTs. On the other hand, high temperatures enhance CNT dispersion by
lowering the viscosity but excessively high temperatures lead to loss of the
intrinsic properties of the polymer. Studies have suggested that these challenges
can be curtailed through modifications in melt compounding. Haggenmueller et al.
[289] combined solution and melt blending by subjecting a solvent-cast SWCNT/
polymer film to several cycles of melt pressing. Jin et al. [290] introduced polymer-
coated MWCNTs (rather than pristine MWCNTs) into the polymer melt to max-
imize compatibility.

7.2.3 In-situ Polymerization Processing of Composites

In addition to the previously mentioned two methods, which combine nanotubes
with high molecular weight polymers, in situ polymerization utilizes CNTs and
monomers. In situ polymerization has advantages over other composite fabrica-
tion methods, for example a stronger interface results owing to the facile intimate
interactions between the polymer and nanotubes during and after the growth stage
[291]. The main advantage of this method is that it enables grafting of polymer
macromolecules onto the walls of CNTs. In addition, this processing technique
allows for the preparation of NCs with high nanotube loading and very good
miscibility. It is particularly useful when insoluble and/or thermally unstable
polymers are desired, especially when processing by solution or melt processing
is not possible. A simple in situ chemical polymerization of aniline, in an acidic
dispersion of multiwall carbon nanotubes (MWCNTs) or single-wall carbon
nanotubes (SWCNTs), in the presence of an oxidant at low temperature, has
been reported by Cochet et al. [243, 244]. Saini et al. [292] described the
fabrication process for a highly conducting PANI–MWCNT NC via an in situ
polymerization. Carbon nanotube-polyaniline hybrid materials were successfully
prepared using in situ emulsion polymerization and an in situ inverse micro-
emulsion route (Scheme 8) [251, 293]. In situ polymerization has also been used
for the preparation of composites of substituted PANI in the presence of either
SWCNTs or MWCNTs. These include poly(o-anisidine) [294], poly(N-
methylaniline) [295], poly(diphenylamine) [296], and poly(aminobenzoic acid)
[297–299].
Another practical approach for the preparation of PANI–CNT composites is
electrochemical deposition. Early attempts included the direct electrochemical poly-
merization of aniline on individual CNT whiskers [299] and an aqueous dispersion
containing aniline and CNT [300]. In the latter example, the aniline functionalized
CNT was sometimes dispersed in the electrolyte [301], while at other times,
substituted PANI was grafted to SWCNT by oxidative coupling during
electropolymerization [302, 303]. In 2014, PDMA multiwall carbon nanotubes
(PDMA-MWCNTs) nanocomposite films were synthesized by in-situ electrochem-
ical polymerization of a well-dispersed solution of DMA and multiwall carbon
nanotubes (MWCNTs) [304].
14 Conducting Polymers and Composites 587

Scheme 8 In situ synthesis of MWCNT/PANI core-shell nanowires using inverse micro-

emulsion [279]

7.3 Interactions Between PANI and CNT

Electrical, thermal, and mechanical properties observed in PANI–CNT composites

are intermediate between pure PANI and CNT and is dependent on CNT content and
the extent of its integration with PANI. Thus, electrochemical properties of
PANI–CNT composites are enhanced compared with the two individual compo-
nents. For instance, electrochemical growth, redox, and capacitive currents of the
composites are several-fold higher than the pure PANI [239, 305]. The same
behavior is also observed in composites of CNT with substituted PANI derivatives,
but the extent of the current increase depends on the nature of the substituent present
on the aniline ring [239]. Such a remarkable current enhancement appears to be
unique to PANI–CNT composites and has not been observed for any other conju-
gated polymer–CNT composite. The augmented properties are a direct result of the
intimate interactions between PANI and carbon nanotubes.
There exists various possibilities for interactions between PANI and CNT in the
composites. One of the first suggestions was the attachment of aniline radicals,
generated during electrochemical oxidative polymerization, onto the CNT lattice
especially at defect sites [239]. However, it was also postulated that the carboxylic
acid sites on the acid-treated CNTs were the most likely sites of interaction with the
588 A. A. Baleg et al.

Led Photocopiers

Display Devices
Photoconducting
Frequency Doubler

Plastic Batteries Josephson

Electrochromism Juction Computer
Logic High Field
Magnetic Non-Linear Magnet
Recording Optical Generators
Metal
Phenomena
Ferromagnetism
Super Conductors

Solid CONDUCTING POLYMERS

State
Conductive
Surface
Piezoelectric EMI/ESD
Solid State Conducting
SENSOR Photochemical Composites
Reactions

Transducers
Optical Storage Super Capacitor
Connectors

Fig. 20 Applications of conducting polymers

aniline monomer [305]. PANI can interact either with functionalized or with
nonfunctionalized CNT.

8 Conclusions

CPs are characterized by a conjugated structure of alternating single and double

bonds (extended π-orbital system) through which electrons can move from one end
of the polymer to the other. Hence the electrons become delocalized over the whole
and are shared by many atoms.
Conducting polymers (CPs) are mainly used in environmental monitoring and
clinical diagnostics to achieve fast detection, high sensitivity, small size, and spec-
ificity for investigation of a particular analyte through the use of electrochemical
sensors and biosensors. Conductivity values for conducting polymers vary from
10-10 to 106 S.cm-1, covering the range associated with semiconductors and conduc-
tive filler composites, at the lower end, to metals at the higher end. Polymers with
electrical conductivity and semiconductivity are of interest as lightweight replace-
ments for inorganic metals and semiconductors. CPs have electrical and optical
properties similar to those of metals and inorganic semiconductors but also exhibit
14 Conducting Polymers and Composites 589

the attractive properties associated with conventional polymers such as ease of

synthesis and processing.
In addition, conducting polymers have the potential to replace metal coatings
and may be applied more economically utilizing nonvacuum processes from
solution or from the melt. There are also clear signs that the effectiveness of
conducting polymers in transferring electrical charges can be exploited for the
preparation of nanocomposites (NCs) in the construction of sensors and in molec-
ular devices. Likewise, organic semiconducting polymers may be synthetically
tailored to optimize desirable properties such as melting point, melt viscosity,
solubility, electrical and thermal conductivity. Conducting polymer composites
(CPCs), resulting from the blending of an insulating polymer matrix with electri-
cal conductive fillers (carbon black, carbon fibres, metal particles), show many
interesting features including the variation in their electrical resistivity with
thermal solicitations.
The use of pyrrole in the electrochemical synthesis of conducting polymers has
proven important in allowing the development of new polymeric materials with
worthwhile electrical properties. Recent studies have shown that conducting poly-
mers  namely, PPy, PANI, and PEDOT  all have good biocompatibility and are
promising alternatives for use in the development of new biodegradable conduits for
restoration function of injured peripheral nerves or in the regeneration of a nerve gap
by using in situ electrical stimulation.
Synthesis of conducting star, graft, or block copolymers of the conducting
polymer permits chemical linkage between the insulating matrix (end groups) and
the conjugated polymer. The new materials formed in this manner possess enhanced
processability and chemical stability. Electrochemical copolymerization can produce
a variety of conducting materials with different optical, electrical, morphological,
and electrochromic properties.
Overall, these unique polymers (CPs) and their derivatives showcase a wide range
of specific industrial applications (Fig. 20).

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Shape-Memory Polymers
15
Magdalena Mazurek-Budzyńska , Muhammad Yasar Razzaq,
Marc Behl , and Andreas Lendlein

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
2 Shape-Memory Effect (SME) in Polymers According to Fixation of
Temporary Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
2.1 SME Based on Physical Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
2.2 SME Based on Reversible Covalent Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
3 Triple/Multiple-Shape Effect (TSE/MSE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
4 Temperature-Memory Effect (TME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
5 Reversible SME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
5.1 Reversible Shape-Memory Effect (rSME) Under Constant Stress . . . . . . . . . . . . . . . . . . . 635
5.2 Reversible Bidirectional Shape-Memory Effect (rbSME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
6 Magnetically Triggered SMPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
7 Shape-Memory Hydrogels (SMH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
8 Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654

Abstract
Shape-memory polymers (SMPs) are stimuli-sensitive materials capable of
changing their shape on demand. A shape-memory function is a result of the
polymer architecture together with the application of a specific programming
procedure. Various possible mechanisms to induce the shape-memory effect
(SME) can be realized, which can be based on thermal transitions of switching

M. Mazurek-Budzyńska · M. Y. Razzaq · M. Behl

Institute of Biomaterial Science, Helmholtz-Zentrum Geesthacht, Teltow, Germany
e-mail: [email protected]; [email protected]; [email protected]
A. Lendlein (*)
Institute of Biomaterial Science, Helmholtz-Zentrum Geesthacht, Teltow, Germany
Institute of Chemistry, University of Potsdam, Potsdam, Germany
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 605

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_18
606 M. Mazurek-Budzyńska et al.

domains or on reversible molecular switches (e.g., supramolecular interactions,

reversible covalent bonds). Netpoints, which connect the switching domains and
determine the permanent shape, can be either provided by covalent bonds or
by physical intermolecular interactions, such as hydrogen bonds or crystallites.
This chapter reviews different ways of implementing the phenomenon of pro-
grammable changes in the polymer shape, including the one-way shape-memory
effect (1-W SME), triple- and multi-shape effects (TSE/MSE), the temperature-
memory effect (TME), and reversible shape-memory effects, which can be
realized in constant stress conditions (rSME), or in stress-free conditions (revers-
ible bidirectional shape-memory effect (rbSME)). Furthermore, magnetically
actuated SMPs and shape-memory hydrogels (SMHs) are described to show the
potential of the SMP technology in biomedical applications and multifunctional
approaches.

Abbreviations
1-W SME One-way shape-memory effect
AD Actuator domains
Alg Alginate
AMF Alternating magnetic field
BA n-Butyl acrylate
BD 1,4-Butanediol
BHECA N,N-bis(2-Hydroxyethyl) cinnamamide
BM 1,10 -(Methylenedi-p-phenylene)bismaleimide
CA Cinnamic acid
CAA Cynnamylidien acetic acid
CD Cyclodextrine
CIE Crystallization-induced elongation
CLEG Copolymer network from PCL with grafted PEG segments
CMF Cavitation-based mechanical force
cPEVA Covalently crosslinked poly[ethylene-co-(vinyl acetate)]
CTB Carboxyl-terminated polybutadiene
DA Diels-Alder reaction
DETA Diethylenetriamine
DMPA Dimethylolpropionic acid
Gly Glycine
H Magnetic field strength
Hdef Deformation magnetic field strength
HDI Hexamethylene diisocyanate
HEA-CA Ethyleneglycol-1-acrylate-2-CA
HEMA Hydroxyethyl methacrylate
Hhigh High magnetic field strength
Hlow Low magnetic field strength
H-NC Hybrid nanocomposite
Hsw Switching magnetic field strength
Hσ,max Magnetic field strength at maximum stress generated
15 Shape-Memory Polymers 607

IPN Interpenetrating polymer network

IR Infrared
LU Low frequency ultrasound
MACL Copolymer of PCL and poly(cyclohexyl methacrylate)
MDI 4,40 -Diphenylmethane diisocyanate
MIC Melting-induced contraction
MME Magnetic-memory effect
MNP Magnetic nanoparticles
MSE Multi-shape effect
PBA Poly(butylene adipate)
PCHMA Poly(cyclohexyl methacrylate)
PCL Poly(e-caprolactone)
PDC Multiblock copolymer from PPDO and PCL
PEG Poly(ethylene glycol)
PEGDA Poly(ethylene glycol) diacrylate
PET Poly(ethylene terephthalate)
PEU Poly(ester-urethane)
PEVA Poly[ethylene-co-(vinyl acetate)]
PHEG-Cn Poly[N5-(2-hydroxyethyl) L-glutamine] with alkyl side chains
-CnH2n+1
PLA Polylactide
PLLA Poly(L-lactide)
PPDL Poly(ω-pentadecalactone)
PPDL-PCL Multiblock copolymer from PPDL and PCL
PPDO Poly( p-dioxanone)
PPGDMA Poly(propylene glycol) dimethacrylate
PS Polystyrene
PSVP Poly[styrene-co-(4-vinylpyridine)]
PTMG Poly(tetramethylene glycol)
PUR Polyurethane
PVA Poly(vinyl alcohol)
Qef Deformation fixation efficiency
rbSME Reversible bidirectional shape-memory effect
r-DA Retro-Diels-Alder
Rf Shape fixity ratio
Rh-PCBs Rhodium-phosphine coordination bonds
rmag-SME Magnetically controlled rSME
Rr Shape recovery ratio
rSME Reversible shape-memory effect
S/V Surface-to-volume ratio
SAXS Small-angle X-ray scattering
SGD Shape shifting geometry domains
SME Shape-memory effect
SMH Shape-memory hydrogel
SMP Shape-memory polymer
608 M. Mazurek-Budzyńska et al.

sNP Silica-coated iron oxide nanoparticles

Tact Actuation temperature
Td Deformation temperature
Tenv Environmental temperature
TFX Polyetherurethane prepared from MDI, BD, and PTMG
Tg Glass transition temperature
THF Tetrahydrofuran
Thigh Highest temperature in the course of shape-memory programming
Tlow Lowest temperature in the course of shape-memory programming
Tm Melting transition temperature
TME Temperature-memory effect
TMPA Temperature-memory polymer actuator
Tperm Highest thermal transition temperature of a thermoplastic material
at which the domains acting as physical crosslinks melt
TSE Triple-shape effect
TSP Triple-shape polymer
TSPC Triple-shape polymeric composites
Tsw Switching temperature
Ttrans Thermal transition temperature
Tu Unloading temperature
Tσ,max Temperature determined at the maximum of recovery stress
UPy 2-Ureido-4-pyrimidinone
UV Ultraviolet
ZnCTB Zinc salt of carboxyl-terminated polybutadiene
ZnOl Zinc oleate
β-CD β-Cyclodextrin
ε0 rev Reversible elongation
em Maximum deformation
ep Strain of the sample after recovery to the permanent shape
eu(N ) Free state deformation after cooling
λ Wave length
σ max Recovery stress

1 Introduction

Shape-memory polymers (SMPs) are a class of stimuli-responsive polymeric mate-

rials in which on demand shape changes can be implemented by tailored programming
procedures [1]. The most prominent among the reported shape-memory capabilities of
polymers is a one-way, thermally-induced shape-memory effect (1-W SME).
A general requirement of polymers capable of 1-W SME is a chemically or physically
crosslinked network structure, which could be both, amorphous or semicrystalline in
nature. Initially the 1-W SME was realized in γ-radiated polyethylene, which until now
is applied in heat-shrinkable tubes for insulating electronic wiring or heat-shrinkable
15 Shape-Memory Polymers 609

films for packaging labels. Furthermore, shape-memory polyurethanes have been

commercialized for automotive applications as well as for smart textiles and fabrics.
Degradable SMPs containing ester moieties are an example of multifunctional
polymers and address biomedical applications, such as biodegradable implants and
controlled drug release systems [2–5]. SMPs have many advantages compared to
metallic shape-memory alloys such as lightweight and capability of much higher
deformations. Moreover, according to the broad potential variation of structure
architecture, they can be easily tailored for specific applications [6]. Furthermore,
by combining the shape-memory capability with other functionalities (hydrolytic
degradability, self-healing, drug-release etc.), multifunctional polymers can be
obtained [7]. It is important to note that the SME in polymers is a function of a
polymer resulting from a combination of the polymer structure and morphology,
together with the applied processing and programming [1]. In addition to 1-W SME,
the phenomena of programmable changes in shape of polymers can be realized in
different manners, including triple- and multiple-shape effect (TSE/MSE),
temperature-memory effect (TME), as well as SMEs with reversible shape changes.
The latter include the reversible shape-memory effect (rSME) and the reversible
bidirectional shape-memory effect (rbSME), in which polymer samples can switch
between two shapes under constantly applied stress or under stress-free conditions,
respectively. All of them will be discussed in this chapter with the emphasis on the
switching mechanisms and examples of polymer systems, in which those concepts
are realized.

2 Shape-Memory Effect (SME) in Polymers According

to Fixation of Temporary Shape

In this part, general concepts and mechanisms of SMEs will be introduced based on
examples of SMPs exhibiting 1-W SME. The phenomena described will be classi-
fied according to the types of molecular switching mechanisms. The permanent
shape of shape-memory networks is defined by the netpoints, which can be realized
by covalent bonds or physical interactions (e.g., crystallites, glassy hard domains,
hydrogen bonds, ionic assembly). However, it has to be noted, that netpoints basing
on physical interactions are in general not as strong as covalent bonds. Therefore,
thermoplastics are more prone to undergo unintended and irreversible changes in a
shape-memory cycle, which lead to incomplete shape recovery.
Several polymer architectures have been identified as suitable for exhibiting a
SME. The most basic one is a covalently crosslinked polymer network, in which the
switching segments create linkages between net points (Fig. 1a). Covalently
crosslinked polymer networks can also contain side groups able to form a segregated
phase (Fig. 1b) or to cleave covalent bonds reversibly (Fig. 1c). SMPs have been also
realized in triblock copolymers able to form multiphase morphologies (Fig. 1d), or
copolymers containing liquid-crystalline (Fig. 1e) switching domains [8]. SMP
systems, in which the netpoints and the switching domains are not covalently
connected to each other, can be realized as interpenetrating polymer networks
610 M. Mazurek-Budzyńska et al.

Fig. 1 Examples of polymer network architectures suitable for exhibiting an SME (molecular
switches: red; netpoints: gray): (a) switching segments linking netpoints, (b) side chains as
switching segments, (c) functional groups as molecular switches capable to reversibly form a
covalent bond, (d) ABA triblock segments linking netpoints, (e) liquid-crystalline domains
enabling the fixation, (f) ionic switching segments and ionomers containing ion-rich domains as
netpoints. ((a–d) taken from Ref. [6] Copyright © 2009, Springer-Verlag Berlin Heidelberg, (e–f)
reproduced from Ref. [8] with permission from The Royal Society of Chemistry. https://doi.org/
10.1039/c2sm27077c)
15 Shape-Memory Polymers 611

(IPNs) or polymer blends. Furthermore, netpoints related to physical interaction,

such as crystallites, hydrogen bonds, or ion-rich domains (Fig. 1f) can be utilized
in SMPs.
Depending on the different architectures of SMPs, various stimuli might be used
to induce the shape recovery from the temporary to the permanent shape. Typically,
SMPs respond to changes of temperature, ion concentration, pH, IR irradiation,
alternating magnetic fields, or ultrasound applied. Examples of various mechanisms
of molecular switching based on physical or chemical interactions utilized in SMPs
will be described in the following sections.

2.1 SME Based on Physical Interactions

The most commonly utilized switch to induce the shape recovery is a thermal
transition temperature (Ttrans) associated to a melting (Tm) or a glass transition
temperature (Tg) of the switching domains [9]. Furthermore, supramolecular inter-
actions related to hydrogen bond formation, ionic, or metal-ligand interactions
enable reversibly crosslinked networks capable of a SME [2, 10].

2.1.1 SME Based on Thermal Transition of Switching Domains

Depending on the polymer architecture and the temperature range of interest for the
particular application, a glass transition temperature (Ttrans = Tg) or a melting
transition temperature (Ttrans = Tm) can be chosen to serve as a Ttrans. The flexibility
of chains below Ttrans is at least partly limited, whereas upon heating above Ttrans the
mobility of molecular chains increases, resulting in softening of the material. When
Ttrans = Tm, the temporary shape is programmed by stretching the material at
T > Ttrans, followed by cooling, whereby the crystallization of the switching segment
is initiated. The crystalline domains formed prevent the polymer chain segments
from immediate recoiling, and by this fix the temporary shape. In case of Ttrans = Tg,
the fixation of temporary shape is related to the transition from the rubber-elastic or
viscous state to the glassy state, in which the flexibility of the entire segment is
limited. The recovery of the original shape is driven by regaining the entropy, which
was lost during the orientation of polymer chains [11]. The molecular mechanism of
thermally-induced SME, including programming the temporary shape and recover-
ing of the permanent shape, is schematically shown in Fig. 2. Three shape-memory
systems are presented: (a) a thermoplastic, linear multiblock copolymer, and cova-
lently crosslinked polymer networks with (b) Ttrans = Tm and (c) Ttrans = Tg,
respectively.
The thermally-induced SME is typically quantified by cyclic, thermomechanical
investigations [12]. In most of the cases, it is performed with a conventional tensile
testing machine equipped with a thermochamber, which enables temperature control
during mechanical deformation of the specimen according to specific temperature
protocols. Besides the cyclic, thermomechanical tests various methods of the char-
acterization of SME have been applied, such as bending tests, compression tests or
three-point flexural test [13, 14]. In a schematic representation in Fig. 3, the different
612 M. Mazurek-Budzyńska et al.

Fig. 2 Schematic a
representation of the
molecular mechanism of the extension
thermally-induced SME for Ttrans and
(a) a multiblock copolymer cooling
with Ttrans = Tm, (b) a
covalently crosslinked
polymer with Ttrans = Tm, and
Ttrans
(c) a polymer network with
Ttrans = Tg. At T > Ttrans of the
switching segments, these
segments are flexible (shown
in red) and the polymer can be Ttrans heating
deformed elastically. The
temporary shape is fixed by
cooling below T < Ttrans
(shown in blue). If the
temperature is raised again, b
the permanent shape is extension
recovered. (Reprinted from and
Ref. [1] with permission, © Ttrans
cooling
WILEY-VCH Verlag GmbH,
69,451 Weinheim, Germany,
2002)
Ttrans

Ttrans heating

c
extension
Ttrans and
cooling

Ttrans

Ttrans heating
15 Shape-Memory Polymers 613

Fig. 3 Three basic methods to quantify the thermally-induced SME by cyclic thermomechanical
tests. (A) Tensile test; (B) Bending test; (C) Compression test. The black curve shows a full cycle
starting with the programming step at Thigh > Ttrans (indicated by the red point and arrow) and the
recovery under stress-free conditions. The recovery under constant strain conditions is highlighted
by the solid gray curve for thermoplastics (physical netpoints). (Taken from Ref. [13], reprinted
with permission (Taylor & Francis Ltd., http://www.tandfonline.com))
614 M. Mazurek-Budzyńska et al.

cyclic testing methods can be overviewed, including the resulting changes in

shape during programming and recovery, as well as the related stress-temperature-
strain diagrams.
The macroscopic changes of the sample during the cyclic, thermomechanical
investigations can be described by two values: the shape fixity ratio (Rf) and the
shape recovery ratio (Rr). Rf measures the ability to fix the mechanical deformation
applied during the programming process (Eq. 1), whereas Rr quantifies to which
extent is the shape recovered in the Nth cycle (for N > 1) with respect to the
recovered shape of the previous (N1)th cycle (Eq. 2).

eu ðN Þ
Rf ¼  100% (1)
em
εm ðNÞ  εp ðNÞ
Rr ¼  100% (2)
εm ðNÞ  εp ðN  1Þ

Different test protocols can be applied with various programming procedures. A

typical test protocol is as follows: first, the sample is heated up to a temperature
Thigh > Ttrans and stretched to the certain strain (em), which is typically a maximum of
the strain before the break of the sample. In the next step, the sample is cooled to
Tlow < Ttrans, which enables the fixation of the temporary shape (eu). This step can be
performed in two different ways – in stress-controlled or in stress-free conditions.
Afterwards, the sample is heated to Thigh, whereby it recovers to the permanent shape
(ep) and the next cycle can begin. The switching temperature (Tsw), at which the
recovery to original shape is the fastest, is determined at the inflection point of the
elongation/temperature curve at the maximum of the absolute value of Δe/ΔT.
An important group of thermoplastic SMPs are linear block copolymers. The
mechanism of SME induction is based on formation of a phase-segregated morphol-
ogy. The phase with the lower thermal transition provides switching domains and the
other phase (with higher thermal transition Tperm) provides domains defining the
permanent shape. In case of Ttrans = Tm, a relatively sharp thermal transition is
observed, whereas the glass transition is always related to a broad temperature range.
The most intensively investigated linear block copolymers utilizing Tm = Ttrans
constitute thermoplastic polyurethanes, polyolefins, polyethers, polyesters, copoly-
mers containing poly(ethylene terephthalate) (PET) and poly(ethylene glycol)
(PEG), copolymers of polystyrene (PS) and polybutadiene, or triblock copolymers
ABA of poly(2-methyl-2-oxazoline) and poly(tetrahydrofuran) [1, 15–17]. Low
melting point aliphatic polyesters, mainly poly(e-caprolactone) (PCL) [18], are the
most frequently used building-blocks for the switching segments in the polyure-
thane, polyamide or polyaramide shape-memory systems [19, 20]. Also polymer
blends were demonstrated to exhibit a thermally induced SME [21–25].
The second group of thermally-induced shape-memory block copolymers consti-
tutes materials with Ttrans = Tg; however, for this group, the shape change is
relatively slow [1, 26, 27]. The most expanded class of these materials are poly-
urethanes, in which the switching segments are mostly realized by mixed phases, and
15 Shape-Memory Polymers 615

are typically based on soft segments from PCL, poly(tetrahydrofuran), PEG or

copolymers of lactide and glycolide [1, 28, 29]. Due to their amorphous structure,
these shape-memory polyurethanes are more prone to biodegradation.
Thermoplastic elastomers like polyurethanes or polyesters feature excellent pro-
cessability, however, the lack in chemical crosslinks leads to lower stresses during
recovery and lower cyclic recoverable strains [30]. Therefore, covalently crosslinked
systems based on linear or branched polymer precursors were designed to be capable
of thermally-triggered SME. Netpoints can be created according to two main
strategies: during the synthesis step or by post-processing methods (crosslinking
by radiation; UV- or γ-radiation, e-beam, neutrons) [1]. The first strategy is realized
mainly by the (co)polymerization or (co)polycondensation of monomers, among
which at least one is trifunctional or of a higher functionality [31]. An example are
poly(tetrahydrofuran)- based polyurethane networks with tailorable switching tem-
peratures synthesized by the precursor method, utilizing 1,1,1-trimethylolpropane as
a crosslinking agent [32]. Highly crosslinked networks exhibiting Rr of 96–98%
were obtained based on poly(butylene adipate), diphenylene diisocyanate, and
hyperbranched polyester Boltorn H30 [33]. Ring-opening polymerization of e-
caprolactone initiated by trifunctional glycerol, followed by polyaddition with
4,40 -diphenylmethane diisocyanate (MDI) and 1,6-hexanediol, resulted in shape-
memory networks with Rf and Rr of 92% and 99%, respectively [34]. A very
important group of crosslinked SMPs constitutes AB networks synthesized by
copolymerization of monofunctional telechelic monomers with bifunctional
crosslinkers. This type of systems can utilize both, Tm or Tg as Ttrans. In case of
(meth)acrylate-based covalently crosslinked SMPs, most is based on Ttrans = Tg of
the switching segment [10, 35, 36]. One of the examples utilizing Ttrans = Tm are
various crosslinked copolymers of semicrystalline oligo[(e-caprolactone)-co-
glycolide]dimetacrylate with a n-butyl acrylate. These SMPs were capable of
Rf > 82% and Rr > 97%, in which Ttrans could be adjusted in a temperature range
between 23  C and 52  C [37]. A photopolymerized network containing oligo(e-
caprolactone)diacrylate with polyhedral oligosilsesquioxane moieties in the middle
of the chains exhibited Rr of 99% when heated to Ttrans = 80  C [38]. AB polymer
networks based on various acrylates containing amorphous poly[(L-lactide)-ran-
glycolide]dimethacrylate with Ttrans = Tg in the range of 9–45  C exhibited SME,
with Rf and Rr values above 97% and 98%, respectively [39]. The group of (meth)
acrylate-based SMP networks is very important according to potential biomedical
applications due to their biodegradability and biocompatibility [10, 35, 36].

2.1.2 SME Based on Reversible Hydrogen Bonds

Two moieties exhibiting hydrogen bonds, pyridine and ureidopyridine units, have
been widely studied in SMP systems. Pyridine moieties can be implemented into
polymer (typically polyurethane) structure in the form of grafted side chains
[40–42]. Reversibility of pyridine-based hydrogen bonds is achieved according to
sensitivity to temperature, presence of carboxylic acid, or humidity. In the presence
of the latter ones, the hydrogen bonds between the pyridine units in polymer chains
616 M. Mazurek-Budzyńska et al.

are substituted by the hydrogen bonds between pyridine units and acid or water
molecules, resulting in cleavage of crosslinks [43, 44].
Furthermore, 2-ureido-4-pyrimidinone (UPy) units can be incorporated into
the main polymer chains. They increase the strength of intermolecular interac-
tions as the UPy units are capable of quadruple-hydrogen bonds formation
[45–47]. In the first step, UPy was functionalized with a polymerizable group
and afterwards copolymerized with acrylates or bisacrylates [48, 49]. Supramo-
lecular shape-memory elastomers were synthesized from n-butyl acrylate, tri-
methylolpropane trimethacrylate, and the UPy-substituted ethyl methacrylate
monomer. Based on the cyclic, thermomechanical analysis, Rf of about 90%
and Rr of about 100% were determined [48]. In poly(vinyl alcohol) (PVA)
supramolecular networks crosslinked by UPy dimers, thermo- and water-induced
shape memory behavior with a Rr of nearly 99% was demonstrated. UPy dimers
defined the permanent shape of the samples, whereas the PVA chains provided
the switching domains enabling the fixation of a temporary shape [50]. Biode-
gradable, supramolecular SMPs containing an elastic poly(glycerol sebacate)
backbone and multiple hydrogen-bonding UPy grafts (Fig. 4) were designed.
The dynamic supramolecular interactions within those multifunctional elasto-
mers enabled also tunable mechanical properties as well as the capability of self-
healing [51].
Poly[(methyl acrylate)-co-(acrylic acid)] networks were reported to show excel-
lent shape-memory properties (Rr > 99%) due to the combination of hydrogen
bonding and controlled crosslinking density [52]. A self-assembling, H-bonding
polymeric system containing a polystyrene backbone and polyacrylate amide
brushes was designed. The amide formed polyvalent clusters of H-bonds capable
of reversible self-assembly and cleavage [53]. A SME based on hydrogen bonding
could also be realized in IPN systems [54]. A semi-interpenetrating polymer network
based on poly[(methyl methacrylate)-co-(N-vinyl-2-pyrrolidone)]/poly(ethylene
glycol) was capable of SME with Rr of 99%. The PEG-poly(N-vinyl-2-pyrrolidone)
complexes served as switching domains, whereas covalent netpoints defined the
permanent shape [55, 56]. The temporary shape was fixed at pH = 10, whereas the
permanent shape was recovered at pH = 1.3. The mechanism of these pH-induced
SME is based on the formation of a hydrogen bond interaction between the nitrogen
atom of the pyridine ring and the urethane group in neutral or alkaline environment.
Under acidic conditions, due to the protonation of the pyridine ring, cleavage of the
intermolecular hydrogen bonding takes place resulting in the recovery of permanent
shape (Fig. 5). Furthermore, the obtained system could be applied in the drug-
delivery field [57].
Poly(carboxylic acid)s can form intermacromolecular complexes with PEG
by the hydrogen bonding between the carboxyl groups of poly(carboxylic acid)s
and the ether oxygen atoms of PEG. The formation of these hydrogen-bonded
complexes is highly sensitive to a change in the temperature. The shape-memory
behavior of H-bonded complexes of poly[(acrylic acid)-co-(methyl methacrylate)]
networks with PEG of varying molecular weight was reported with Rr of 99%
[58]. In poly[(acrylic acid)-co-acrylonitrile]-based systems, the complexation
 15
Shape-Memory Polymers

Fig. 4 Schematic presentation of supramolecular SMPs obtained based on poly(glycerol sebacate) backbone and reversible multiple hydrogen-bonding
ureidopyrimidinone (UPy) grafts. (Reprinted from Ref. [51], Copyright 2016, with Permission from Elsevier)
617
618 M. Mazurek-Budzyńska et al.

Fig. 5 Schematic representation of the pH-induced SME in PEG-based polyurethane (PUR)

containing N,N-bis(2-hydroxylethyl)isonicotinamine (BIN) units. The pyridine rings in PUR are
protonated resulting in distortion of the hydrogen bond in acidic condition. Once the pyridine rings
are deprotonated under neutral or basic conditions they enable a reversible switching between
two shapes. (Reproduced from Ref. [57] with permission of The Royal Society of Chemistry.
https://doi.org/10.1039/c4py00474d)

occurred through H-bonding of carboxyl group of acrylic acid with ether group of
poly(tetramethylene oxide) (PTMO) enabling a SME with Rr > 93% [59].

2.1.3 SME Based on Ionic Interactions

Usage of ionic interactions as a method to induce an SME was demonstrated by the
neutralization of sulfonated polymers with zinc salts [60–62]. SMPs were prepared
from mixtures of the zinc salt of a sulfonated poly[ethylene-co-propylene-co-(5-eth-
ylidene-2-norbornene)] ionomer and zinc oleate (ZnOl). Physical netpoints based on
intramolecular ionic interactions provided the permanent network structure. Strong
dipolar interactions between the ionomer and a dispersed phase of crystalline ZnOl
enabled a fixation of a temporary shape (Fig. 6) [62].
Biodegradable poly[oxyethylene-b-(butylene adipate)] ionomers, synthesized by
bulk polymerization of adipic acid, bis[poly(oxyethylene)] sulfonated dimethyl
fumarate, and 1,4-butanediol, exhibited a SME, with a Rr in the range of 81–95%
at 40  C [63].
15 Shape-Memory Polymers 619

Fig. 6 Schematic
representation of SMP based
on the zinc salt of a sulfonated
poly[ethylene-co-propylene-
co-(5-ethylidene-2-
norbornene)] ionomer and
zinc oleate (ZnOl). (Reprinted
with permission from Ref.
[62]. Copyright 2011
American Chemical Society)

Fig. 7 Schematic diagram of metallosupramolecular interaction exemplarily for poly[(n-butyl

acrylate)-co-(methyl methacrylate)] bearing a side group of the ligand 2,6-bis(10-methylbenzi-
midazolyl)pyridine. The ligand can be reversibly crosslinked by the zinc trifluoromethanesulfonate
upon temperature increase. (Reproduced from Ref. [64] with permission of The Royal Society of
Chemistry. https://doi.org/10.1039/c4ra02843k)

2.1.4 SME Based on Metal-Ligand Interactions

Another approach to achieve reversible bonds in SMPs is the incorporation of
metal-ligand interactions into polymer system. The change of shape is realized by
the thermally-triggered association and dissociation of metal-ligand complexes.
Structure organization on molecular level is schematically shown in Fig. 7,
exemplarily for poly[(n-butyl acrylate)-co-(methyl methacrylate)] bearing a
side group of the ligand 2,6-bis(10-methylbenzimidazolyl)pyridine. The ligand
reversibly crosslinks with the zinc trifluoromethanesulfonate when the temperature
620 M. Mazurek-Budzyńska et al.

is increased, and therefore enables a shape-memory as well as self-healing

capability [64].
High-molecular-weight SMPs capable of supramolecular interactions with metal
ions were obtained based on europium salts and low molecular weight polybutadiene
functionalized with 4-oxy-2,6-bis(N-methylbenzimidazolyl)pyridine ligands. The
addition of a tetra-functional thiol and a photoinitiator, followed by photo-
crosslinking via the thiolene reaction, resulted in formation of SMP networks. In
the solid state the metal ligand complexes formed a separated phase and served as a
switching phase enabling the fixation of the temporary shape. The recovery of the
permanent shape could be induced under various stimuli such as heat, UV-light or
presence of solvents (for example methanol) (Rr > 80%, Rf > 97%) (Fig. 8) [65].
Blends of zinc-neutralized carboxyl-terminated polybutadiene and poly[styrene-
co-(4-vinylpyridine)] were tightly bound by the metal coordination interactions
between Zn2+ ions (Fig. 9). The obtained elastomers were capable of large defor-
mations and exhibited good shape-memory properties with Rr up to 81% in the first
and 97% in the following cycles [66].
The phenomenon of ultrasonic cavitation enabled the stimulation of the SME in
covalently crosslinked polymer networks containing coordination bonds [67]. In this

Fig. 8 The solution-cast non-crosslinked films can be fixed into various permanent shapes; (a) a
strip of non-crosslinked film is wrapped around a cylinder into a spiral shape; (b) irradiation with
low intensity UV-light initiates photo-crosslinking to get the permanent spiral shape. (Reprinted
with permission from Ref. [65]. Copyright 2011 American Chemical Society)
15 Shape-Memory Polymers 621

Fig. 9 Scheme of the metal coordination interactions in the blend of zinc salt of carboxyl-
terminated polybutadiene (ZnCTB) and poly[styrene-co-(4-vinylpyridine)] (PSVP). The ZnCTB
chains crosslink PSVP nanodomains by supramolecular bonds between one zinc ion and two
pyridine groups. As indicated in the scheme, some ZnCTB chains may form bonds with the same
PSVP nanodomain (CTB loops), resulting in no contribution to growth of the network. (Reprinted
with permission from Ref. [66]. Copyright 2016 American Chemical Society)

SME, which is independent of heat, the sonification creates small vacuum bubbles or
voids in the liquid medium. When the bubbles attain a volume at which they can no
longer absorb energy, a violent collapse takes place resulting in shock waves with
a velocity around 100 m • s1. These shock waves generate a strong mechanical
force near the solid-liquid boundary. For this ultrasound cavitation-induced SME,
the key challenge was the design of an appropriate polymer system, which enabled
the effective permeation of the mechanical force throughout the bulk polymer
sample. Furthermore, selection of suitable mechanoresponsive molecular switches
to fix the temporary shape was critical as well. Therefore, interconnected macro-
porous systems based on poly(n-butyl acrylate), diphenylphosphinostyrene, and
poly(propylene glycol) dimethacrylate (PPGDMA) (Fig. 10a) were designed.
Rhodium-phosphine coordination bonds (Rh-PCBs) served as mechanically sensi-
tive molecular switches, which were able to fix the temporary shape and to control
the recovery to permanent shape. The interconnected macroporous structure with
thin porous walls provided a large specific surface area and allowed the penetration
of the ultrasound waves through the pores. Water captured within the pores acted as
an ultrasound transporting medium, whereby the collapse of the cavitation bubbles
inside the macropores induced the energy input efficiency from the ultrasound
source to the polymer. Rhodium-phosphine complexes formed a separated micro-
phase and provided aggregates, which could be reversibly dissociated under ultra-
sonic cavitation-based mechanical force (CMF). Furthermore, the CMF accelerate
the ligand exchange rate of Rh-PCBs. As a result, once the deformed sample is
treated by low frequency ultrasound (LU), the topology of molecular switches is
capable to undergo a rapid rearrangement, enabling the deformed polymer chains to
622 M. Mazurek-Budzyńska et al.

Fig. 10 (a) Chemical structure of rhodium coordinated interconnected macroporous polymer

network. (b) Schematic illustration of the ligand-exchange of rhodium-phosphine coordination
bonds. (c) Schematic illustration of proposed shape-memory mechanism of the rhodium coordi-
nated interconnected macroporous polymer network. (Reprinted from Ref. [67] with permission,
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

relax the stress and fix the temporary shape (Fig. 10b). Subsequent LU treatment
again causes an increase of the ligand exchange rate of Rh-PCBs and the dissociation
of the microphase segregated morphology takes place, resulting in the recovery to
the permanent shape (Fig. 10c) [67].
15 Shape-Memory Polymers 623

2.2 SME Based on Reversible Covalent Bonds

A fixation of a temporary shape to obtain a SME can also be achieved when

reversible crosslinking reactions are used as a switch [68]. The first group of
SMPs containing reversible covalent bonds utilizes photodimerization, Diels-Alder
reaction, or redox reactions of mercapto groups. The advantage of this concept is the
formation of very strong temporary crosslinks, resulting in high Rf. However,
optimization of Rr is still a challenge due to the low efficiency of reversibility of
these reactions [2].
The most frequently utilized reversible covalent bonds in SMP are based on
Diels-Alder (DA) and retro-Diels-Alder (r-DA) reactions. However, it has to be
noted that DA reaction is not an on-off switch, but always exists in a dynamic state,
in which the temperature change only shifts the equilibrium [69]. In DA-based
systems, typically furan derivatives as terminal groups [70–76], pendant groups
[77, 78], or as a part of main chains of the polymer [79, 80] are reversibly crosslinked
with bismaleimides. For example, PLA and star-shaped PCLs were functionalized
with furan moieties. The subsequent crosslinking with bismaleimides resulted
in polymer networks exhibiting SME [72–74]. Bio-based polyesters with efficient
shape-memory properties were obtained from a furan-diol after polycondensation
with succinic acid and crosslinking with bismaleimides [79]. Polyketons
functionalized with furan pendant groups and crosslinked with 1,10 -(methylenedi-
p-phenylene)bismaleimide (BM) resulted in SMP networks with Ttrans = 50  C [78].
Besides DA reaction, redox reactions of the mercapto group can also be utilized to
create reversible covalent bonds in SMPs [81, 82]. For example, cellulose containing
mercaptoic acid terminal groups could be functionalized by dimethylsulfoxide to
obtain disulfides capable of gel-sol transition when oxidation/reduction reactions
were performed. However, Rr decreased with each redox treatment due to side
reactions, which reduced the number of mercaptoacetyl groups [81].

2.2.1 Light-Induced SME

The photodimerization of cinnamic acid (CA) or cynnamyliden acetic acid (CAA)
formed the basis for the first light sensitive SMP. These photoresponsive units are
able to undergo a reversible [2 + 2] cycloaddition reaction stimulated by light of
different wavelength ranges (Fig. 12c). The programming cycle consisted of defor-
mation of the samples to em followed by irradiation with UV-light of λ > 260 nm. In
this way, new covalent bonds between CA molecules were formed and the tempo-
rary shape (em) could be fixed. When the sample was irradiated with the UV-light
of λ < 260 nm, the newly formed covalent bonds were cleaved and the
permanent shape was recovered (Fig. 11). Two different molecular architectures
were explored: a graft-polymer and an interpenetrating polymer network (IPN). The
polymer network with the grafted light-sensitive group was realized by a copoly-
merization of n-butyl acrylate (BA), hydroxyethyl methacrylate (HEMA), and
ethyleneglycol-1-acrylate-2-CA (HEA-CA). Poly(propylene glycol) dimethacrylate
(Mn = 560 g mol1) was used as a crosslinker. In this system, Rf up to 52% and Rr up
to 95% could be realized. The IPN system was obtained by copolymerization of BA
624 M. Mazurek-Budzyńska et al.

Fig. 11 SME of photoresponsive polymers. (A): a film of grafted polymer; (a) permanent shape;
(b) temporary shape; (c) recovered permanent shape. (B): an IPN polymer film. (a) permanent
shape; (b) corkscrew spiral temporary shape; (c) recovered shape obtained by irradiation with UV
light. (C): Molecular mechanism of SME of the grafted polymer network: the chromophores (Δ) are
covalently grafted onto the permanent polymer network (●), forming photoreversible crosslinks (♦).
(Reproduced from Ref. [83]. © 2005 Nature Publishing Group)

with 3.0 wt% poly(propylene glycol)-dimethacrylate (Mn = 1,000 gmol1) as a

crosslinker, followed by mixing with about 20 wt% star-poly(ethylene glycol)
containing CAA terminal groups. The light-induced SME with Rf up to 33% and
Rr up to 98% was observed [83]. A light-induced SMP, in which the light-sensitive
CA groups were incorporated in the main chain, could be obtained based on
α,ω-hydroxyl polyesters (PLA, PCL, PEG). Again based on the [2 + 2] cycloaddition
reaction, the reversible gelation of polyesters was achieved by irradiation with UV
light [84]. Multiblock biodegradable poly(ester-urethane)s (PEUs) containing pen-
dant cinnamamide moieties were synthesized via a two-step polyaddition reaction
using N,N-bis(2-hydroxyethyl) cinnamamide (BHECA), α,ω-hydroxyl PLLA, and
PCL. Hexamethylene diisocyanate (HDI) was used as a coupling agent. The Rf
reached 50% at a BHECA content of 20 wt%, whereas the Rr reached >95% at a
PLLA content of 50 wt% [85]. Similar PEUs containing pendant photoresponsive
moieties (diethyl 2,20 -[cinnamoylazanediyl]diacetate and diethyl 3-[cinnamoyloxy]
pentanedioate) were reported to show Rf in the range of 70–85%, and Rr in the range
of 40–70% [86].
Also coumarin groups are capable to undergo a reversible [2 + 2] cycloaddition,
and therefore they can be used in photo-induced SMP [87–89]. PCL with a
pendent coumarin group was prepared by solution polycondensation of
7-(3,5-dicarboxyphenyl) carbonylmethoxycoumarin dichloride and α,ω-dihydroxy
terminated PCL (Mn = 1250, 3000, and 10,000 g • mol1). These photosensitive
polymers underwent a rapid, reversible photocrosslinking when exposed to
15 Shape-Memory Polymers 625

irradiation with alternating wavelengths (280/254 nm) without an additional photo-

initiator. Obtained networks provided the shape-memory properties, in which both Rf
and Rr values were between 88% and 100% for tensile strains of 100–500%. The
shape-memory ability strongly depended on the degree of the crystallization of PCL
segment and the crosslinking density of the polymers [87].
The light-sensitive shape change can also be driven by photoisomerization
reactions, typically utilizing azobenzene moieties [10, 90, 91]. Azobenzenes can
be switched reversibly from cis to trans conformations by exposure to light of
appropriate wavelength ranges (Fig. 12a). The interconversion between these two
photoisomers linked to polymer chains can induce macroscopic changes in the
polymeric material. However, this effect was studied more in the context of revers-
ible shape changing of polymeric systems, and not as conventionally understood
SME [92–96]. Similarly, changes in the polymer shape were observed in the systems
containing triphenylmethane leuco [97, 98] (Fig. 12b) or spiropyran derivatives [99,
100], which dissociate into ion pairs upon exposure to UV light. The recombination
reaction of the ion pair occurs thermally in the dark.

3 Triple/Multiple-Shape Effect (TSE/MSE)

Triple-shape polymers (TSPs) are capable to memorize two temporary shapes (A and
B) in addition to the original shape (C). TSPs require a polymer system containing at
least two phase segregated domains characterized by two transition temperatures
Ttrans,A and Ttrans,B [101–103]. The original shape (C) is defined by covalent
netpoints and constitutes a permanent shape. Temporary shapes A and B are created
by a two-step programming process. Physical or chemical crosslinks associated to
the highest transition temperature (Ttrans,A) determine shape A, whereas shape B is
related to the second highest transition temperature (Ttrans,B). In the recovery process,
upon application of the external stimuli, the TSP switches back from the intermedi-
ate shapes (A and B) until the permanent shape C is achieved [8]. Typical chemical
structures of TSPs and the processes occurring at the molecular level during the
triple-shape change are shown in Fig. 13 [8]. Further increase of the number of phase
transitions raises the number of temporary shapes and results in multi-shape effects
(MSE). The MSE was realized in thermoplastic polymers providing broad switching
transition, covalently crosslinked networks, IPNs, and polymeric multi-material
systems [68, 104].
Methods to quantify the efficiency of SME in TSPs are similar to the ones used
for 1-W SME. Cyclic, thermomechanical measurements are performed, from which
Rf and Rr of each shape can be calculated. Examples of typical cyclic, thermo-
mechanical experiments performed for TSP and the macroscopic changes in the
polymer shape are shown in Fig. 14A and B, respectively [108]. The sample is
stretched at Thigh from eC (shape C) to e0B. Cooling under the stress determined at e0B to
Tmid results in eB,load. Unloading after 30 min leads to eB (shape B). The sample is
further stretched to e0A and cooled to Tlow under the stress determined at e0A, whereas
626 M. Mazurek-Budzyńska et al.

Fig. 12 Schematic illustration of light-induced isomerization and photochemical reactions.

(a) Trans–cis photoisomerization of azobenzene groups. (b) Photoinduced ionic dissociation of
triphenylmethane leuco derivatives. (c) Photodimerization of the cinnamic acid (CA) group. (Reprinted
from Ref. [90] with permission, © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

the elongation decreases to eA,load. Shape A, corresponding to eA, is obtained by

unloading after 20 min. The recovery process of the sample proceeds during
reheating from Tlow to Thigh under stress-free conditions. The sample contracts to
shape B at eB,rec, and further to shape C at eC,rec (Fig. 14A, a). In the second protocol
presented in (Fig. 14A, b), the sample is stretched at Thigh from eC (shape C) to e0B .
15 Shape-Memory Polymers 627

Fig. 13 Chemical structure as well as schematic representation of the changes in the polymer
network at the molecular level of selected examples of TSPs. (a) CLEG network [105], (b) side-
chain liquid crystalline polymer networks [106], and (c) UPy network [107]. The switching
segments related to Ttrans,B are colored in red. The switching segments related to Ttrans,A are
shown in blue. The segments in light color represent that they are amorphous (flexible), while the
segments in dark color represent that they are solidified to form temporary netpoints. The gray dots
represent the permanent netpoints, and the gray lines visualize the amorphous polymer chain
segments. (Reprinted from Ref. [8] with permission from The Royal Society of Chemistry.
https://doi.org/10.1039/c2sm27077c)

Cooling to Tlow under the stress determined at e0B results in eB,load. Subsequently the
sample is unloaded for 10 min, heated to Tmid and after passing Ttrans,A with some
additional time for equilibration at Tmid eB (shape B) is reached. The sample is
further stretched to e0A and cooled to Tlow under the stress determined at e0A, whereas
the elongation eA,load is achieved. Shape A, corresponding to eA, is obtained by
unloading after 10 min. By reheating from Tlow to Thigh under stress-free conditions
the recovery process of the sample to shape B at eB,rec and further to shape C at eC,rec
is monitored.
The first examples of polymer networks capable of a triple-shape effect (TSE)
were realized in two multi-phase polymers. The first one, named MACL, was a
copolymer obtained from PCL (Tm = 50  C) and poly(cyclohexyl methacrylate)
(Tg = 140  C). The second one, named CLEG (Fig. 13a), was a copolymer obtained
from PCL (Tm = 50  C) and grafted PEG segments (Tm = 34  C) introduced as side
chains. Both systems were synthesized by photoinduced copolymerization of poly
628 M. Mazurek-Budzyńska et al.

A Programming Recovery B a
160
a 100 0 Thigh
εA 140
εAload εA 120
80
Elongation (%)

Temperature / °C
100
60 ε0B 80
Tmid
60
40
εBrec 40
εBload
εB
20 εCrec 20
b
εC 0
Tlow
0 –20
0 40 80 120 160 200 240 280
Time / min

b Programming Recovery

100 0 εAload 70 Thigh

εA
εBrec 60
εBload εA
80
Elongation (%)

Temperature / °C
εu,1 50 c
ε1ts εB Tip
60 0 40
εB Tmid
30
40
20

20 εCrec 10
εC
0 Tlow
0
0 40 80 120 160 200 240
Time / min

Fig. 14 (A) Example of cyclic, thermomechanical experiment; the strain (solid line) and temper-
ature (dashed line) as a function of time. ((a). Reprinted from Ref. [105], Copyright 2006 National
Academy of Sciences. (b) Reprinted from Ref. [109], Copyright 2005, Materials Research Society,
Warrendale, PA). (B) Series of photographs illustrating the triple-shape effect. (a) Temporary shape
(A) at room-temperature, (b) second temporary shape (B) around Tmid, and (c) permanent shape
(C) at Thigh. (Reproduced from Ref. [108] with permission from The Royal Society of Chemistry.
https://doi.org/10.1039/b922992b)

(PCL)dimethacrylate [105]. Another example describes a maleated-polystyrene-b-

poly(ethylene-co-butylene)-b-polystyrene block copolymer with two Tms related
to poly(ethylene-co-butylene) (EB) (55–65  C) and polystyrene segments
(105–115  C). EB segments contained maleic anhydride reactive groups, which
enabled the grafting of polybutylene succinate to the main polymer backbone.
Therefore, the obtained polymer system was capable of TSE based on two melting
transitions related to EB and polystyrene segments [110]. Furthermore, a liquid-
crystalline polymer network providing two transition temperatures related to a glass
transition (80  C) and an isotropic-nematic transition (150  C) was realized by
an unsaturated, liquid-crystalline polyester, which was further crosslinked
with dicumylperoxide [111]. Another crosslinked, glassy network containing
15 Shape-Memory Polymers 629

Fig. 15 Schematic representation of PCL-PPDO IPNs capable of TSE. (Reproduced from

Ref. [54], with permission of The Royal Society of Chemistry. https://doi.org/10.1039/c3py01476b)

liquid-crystalline side chains was synthesized via ring-opening methathesis poly-

merization followed by radical crosslinking. Two Ttrans were correlated to the
thermal transitions of the domains related to the main network chains and the grafted
side chains (Fig. 13b) [106, 112].
Triple-shape poly(e-caprolactone)/poly( p-dioxanone) (PCL/PPDO) IPN was
synthesized via crosslinking 2-ureido-4-pyrimidinone-functionalized PCL and
PPDO. The PPDO network was obtained by coupling a star-shaped PPDO precursor
with 1,6-hexamethylene diisocyanate. The PCL network was formed through the
quadruple hydrogen bonds between 2-ureido-4-pyrimidinone ligands (Fig. 15).
Melting transitions of PCL and PPDO served as Ttrans of switching domains resulting
in TSE with Rf,A–B of 99%, Rf,B–C of 82%, Rr,C–B of 59%, and Rr,C–A of 92% [54].
A TSE could also be obtained in systems, in which polymers providing the
thermal transitions are macroscopically separated in a bilayer system. For example,
two epoxy thermoset layers with two separated Tgs were used to create a macrophase-
separated TSP composite with two Ttrans [113]. Similarly, two-layer shape-memory
PUR crosslinked with silica nanoparticles have shown two separated Tgs and
exhibited TSE [114]. Non-woven thermoplastic PCL fibers were incorporated into
630 M. Mazurek-Budzyńska et al.

Fig. 16 (a) Schematic illustration of the typical temperature-dependent dynamic mechanical

behavior of triple-shape polymeric composites (TSPCs). (b) Photographs showing the sequential
recovery of TSPCs from temporary shape A (A), to temporary shape B (B), and to permanent shape
C (C). Here the TSCP consists of nonwoven thermoplastic PCL fibers incorporated into a matrix of
an epoxy-based SMP. (Reprinted from Ref. [115] with permission, © 2010 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim)

shape-memory epoxy matrix. Two well-separated thermal transitions (Tm,PCL = 55  C

and Tg,epoxy = 20–45  C) were utilized to fix two temporary shapes (Fig. 16) [115]. The
TSE was also realized in polymeric composites containing small liquid-crystalline
molecules (such as cholesteryl isonicotinate or 4-hexadecyloxybenzoic acid), which
constituted separated phase and provided additional transition temperature [116, 117].
Instead of multiple discrete thermal transitions, a new approach based on a single
broad thermal transition was discovered [118–120]. A thermoplastic copolymer of
tetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (trade
name Nafion ®) exhibiting a broad Tg (55–130  C) was capable of a triple- and
quadruple-shape effect (Fig. 17) [118, 121]. This broad single thermal transition
enabled the programming of two temporary shapes at two deformation temperatures.
Furthermore, it was found that Nafion® could remember the temperature, at which
the deformation was programmed. This effect is referred to the temperature-memory
15 Shape-Memory Polymers 631

Fig. 17 Quadruple-shape-memory properties of PFSA (Nafion ®). (a) Macroscopic demonstration

of the quadruple memory effect. S0: permanent shape; S1: first temporary shape (Td1:140  C); S2:
second temporary shape (Td2: 107  C); S3: third temporary shape (Td3: 68  C); S2rec: recovered
second temporary shape (Tr1: 68  C); S1rec: recovered first temporary shape (Tr2: 107  C); S0rec:
recovered permanent shape (Tr3: 140  C). (b) Quantitative thermal mechanical cycle. Rf(S0 ! S1):
58.7%, Rf(S1 ! S2): 57.1%, Rf(S2 ! S3): 96.1%, Rr(S3 ! S2): 100.0%, Rr(S2 ! S1): 99.6%,
Rr(S1 ! S0): 93.0%. (Reprinted by permission from Macmillan Publishers Ltd.: Nature Ref. [118]
copyright 2010)

effect (TME) (further explained in Sect. 4). Another strategy for preparing tunable
SMPs assumes utilization of fillers to adjust polymer behavior. Graphene oxide
nanocomposite sheets can act as a physical crosslinker and significantly change
the thermomechanical behavior of poly(propylene carbonate), enabling a MSE and
TME in the investigated composites [122].
Similarly to 1-W SME, various molecular switching mechanisms based on
reversible bonds can be utilized in TSPs. In one of the studies, TSPs were prepared
based on amorphous (meth)acrylate copolymers containing grafted UPy capable of
reversible hydrogen bonding at Ttrans around 60  C [107]. Polyurethanes capable of
exhibiting TSE were synthesized through solution polymerization of PEG,
dimethylolpropionic acid (DMPA), and MDI. The Tg of PEG chains, together with
the association and disassociation of carboxylic dimers, acted as two switches to
632 M. Mazurek-Budzyńska et al.

control the TSE (Fig. 18). The hydrogen bonding interaction between NH and C=O
in urethane groups formed permanent netpoints [123]. Furthermore, a photo-
responsive hyperbranched polymer system was obtained based on diester monomer
containing 4-hydroxycinnamic acid (coumaric acid) with conjugated double bonds
and succinic acid for coupling. Reversible crosslinking was related to photo-
dimerization of cinnamic double bonds (Fig. 12c) [124].

Fig. 18 Shape fixity ratio (a), shape recovery ratio (b), the procedure (c), and the mechanism
(d) of TSE. When the sample is heated to 80  C, the hydrogen bonds between NH and C=O of
urethane groups fix the permanent shape. When cooled to 40  C, the hydrogen bonds between
carboxylic dimmers fix the temporary shape B. Upon further cooling to 0  C, PEG segments
transform from the rubber state to the glassy state, fixing the temporary shape C. When the
sample is reheated to 40  C and 80  C, the sample recovers shape B and shape A, respectively.
(Reproduced from Ref. [123] with permission of The Royal Society of Chemistry. https://doi.
org/10.1039/c5py02010g)
15 Shape-Memory Polymers 633

4 Temperature-Memory Effect (TME)

Temperature-memory polymers (TMP) are capable of memorizing temperatures, at

which they were previously deformed. This temperature-memory effect (TME)
provides a flexible approach of adjusting thermosensitivity to certain temperatures
without the need of changing their chemical composition [122, 125–128]. TME
requires a broad transition temperature ΔTtrans, which can be both a Tg or Tm. This
broad thermal transition can be considered as an infinite number of thermal transi-
tions Ttranss, which can be utilized as separated switching domains. In this way,
the temporary shape is fixed only by a fraction of polymer chains associated to
certain Ttrans.
The TME was reported for polymer networks as well as for thermoplastic
polymers. Poly(ester-urethane)s with poly(ω-pentadecalactone) as hard segments
and PCL segments acting as crystallizable switching units were reported.
Response temperatures could be systematically adjusted by variation of the
deformation temperature in the range of 32–65  C [129]. Polymer networks
with crystallizable switching domains were formed by blending two poly[ethyl-
ene-co-(vinyl acetate)]s (PEVA) differing in their comonomer ratio, resulting in
very broad melting temperature ranges (ΔTtrans = 0–100  C). The recovery under
stress-free conditions as well as under constant stress was observed. It was
demonstrated that three different parts of the same material piece can be pro-
grammed at different Tprog, and therefore show the recovery under different Ttrans
of 40  C, 60  C, and 80  C (Fig. 19) [125].
Poly(vinyl alcohol) (PVA)/carbon nanotube (CNT) nanocomposites showed a
TME because of their confined structure. In these nanocomposites, the CNTs
favor the stabilization of crystalline domains. Therefore, by increasing the stiff-
ness of the polymer, CNTs enable more energy to be absorbed and restored. It has
also been shown that significant gradients of Tg can be developed at the interface of
nanoparticles. Amorphous polymer shells around the CNTs or around crystalline
domains largely overlap and percolate. This results in a distribution of polymer-CNT
or amorphous polymer-crystallite distances ranging from molecular contact to sev-
eral nanometers. This distribution causes a wide broadening of the glass transition
[130, 131].
The influence of unloading temperature (Tu) upon the strain and stress recovery
was studied in phase-segregated poly(ester-urethane) with crystallizable switching
segments of poly(1,4-butylene adipate) (PBA). A novel route of sample program-
ming was explored. An uniaxial stretching and unloading were performed at the
same temperature (Td = Tu), followed by specimen cooling below crystallization
transition of switching segments (PBA). Independent of the programming route, a
maximum tensile strain em of 100% was applied at Td (Fig. 20a). Almost linear rises
of the switching temperatures (Tsw) and Tσ,max with Td were observed. Remarkably,
the onset temperatures Tsw,on and Tσ,on, which marked the beginning of strain
decrease and stress increase, strongly depended on Td (Fig. 20b). This illustrates
that a temperature-memory onset programming could be achieved over a broad
temperature range [132, 133].
634 M. Mazurek-Budzyńska et al.

Fig. 19 Photograph series of three different TME demonstration devices prepared from
crosslinked PEVA. (a–d) TME shaped temperature-memory demonstrator with three different
Tsw, here each character was deformed at a different Tprog = 40  C (T), Tprog = 60  C (M), and
Tprog = 80  C (E). Heating at 5 K min1 led to three subsequent shape changes. (a) T = 0  C,
t = 00:00 min; (b) T = 57.7  C, t = 11:48 min; (c) T = 73.4  C, t = 15:06 min; (d) T = 93.2  C,
t = 19:00 min. (Reprinted from Ref. [125] with permission, Copyright © 2011 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim)

5 Reversible SME

Unlike the 1-W SME, in reversible SMEs, polymers can switch between two
memorized shapes upon heating and cooling without the requirement of a
re-programming step. In reversible shape-memory effect (rSME) [134, 135], an
external stress is required to induce the shape shifting of a polymer sample. In
contrast to rSME, the reversible bidirectional shape-memory effect (rbSME) enables
the polymer sample to change between preprogrammed shapes under stress-free
conditions [136, 137]. A development of this revolutionary capability of SMPs
enables new and more advanced applications of smart polymeric materials.
15 Shape-Memory Polymers 635

Fig. 20 (a) Engineering

stress-strain curves of poly
(ester-urethane)s at different
temperatures (strain
rate = 300% min1). The
corresponding Young’s
moduli were 1341 MPa
(60  C), 1145 MPa
(50  C), 746 MPa (40  C),
483 MPa (30  C), 282 MPa
(20  C), 217 MPa (10  C),
156 MPa (0  C), 144 MPa
(10  C), 116 MPa (20  C),
103 MPa (30  C), and 43 MPa
(40  C). (b) Temperature-
memory properties: the
evolution of Tsw, onset
temperatures Tsw,on, Tσ,on, and
temperature related to
maximum recovery stress
σ max (Tσ,max) with Td.
(Reprinted with permission
from Ref. [132], Copyright
2014 American Chemical
Society)

5.1 Reversible Shape-Memory Effect (rSME) Under Constant

Stress

A reversible actuation under constant stress could be observed in semicrystalline

polymer networks containing at least one crystalline switching domain. An rSME
bases on crystallization-induced elongation (CIE), in which switching segments of
polymer chains are oriented by application of constant stress under cooling to
Tlow < Tm, followed by the melting-induced contraction (MIC), which occurs at
Thigh > Tm. Stretching of the sample results in preorientation of polymer chains.
During subsequent cooling oriented chain segments serve as raw nuclei in the
direction of applied load and induce subsequent epitaxial growth of lamellae of
semicrystalline domains. The melting of crystallites while heating to Thigh under
applied stress enables polymer chains to form random coils and contract to original
elongation [135, 138]. Similarly to 1-W SME, the cyclic, thermomechanical
636 M. Mazurek-Budzyńska et al.

measurements are performed to quantitatively analyze the rSME. Firstly, the

sample is programmed by elongation at Thigh, whereby polymer chains become
preoriented. The temporary shape A, with the elongation of eact,CIE, is achieved as
a result of CIE occurring under the direction of load. Reheating to Thigh under ϭc
causes MIC, whereby the shape B (erev,MIC) is obtained. When the temperature is
changing between Tlow and Thigh, a reversible switching between elongated and
contracted shapes under ϭc is observed. Two parameters are quantified based
on the cyclic, thermomechanical measurements – the shape change during CIE
(Ract,CIE) (Eq. 3) and the recovery ratio due to MIC (Rr,MIC) (Eq. 4) for each of
N cycles.

eact ðN Þ  erev ðN  1Þ
Ract,CIE ¼ (3)
erev ðN  1Þ

eact ðN Þ  erev ðN Þ
Rr,MIC ¼ (4)
eact ðN  1Þ  erev ðN  1Þ

One of the first examples of polymeric systems capable of rSME was

crosslinked poly(cyclooctene), in which Tms could be adjusted by the crosslinking
density [135]. Later on a rSME was also found in the other semicrystalline
crosslinked polymers such as PEVA [139], PCL [134, 137, 140] or poly(ω-
pentadecalactone) (PPDL) [141, 142]. The approach was even extended to TSE,
in which a rSME was shown over two transition temperatures, with a reversible
switching under stress between three shapes (A, B and C) (Fig. 21) [138]. The
strategy to achieve a reversible TSE under tensile load was to design a multiphase
polymer network containing two different semicrystalline segments showing two
separated and fully reversible CIE (Fig. 21, cooling from II to III and further IV)
and MIC (Fig. 21, heating from IV to III and further to II). Similarly to two-way
rSME, the CIE was induced by the crystallization promoted along the uniaxial
loading stress.

5.2 Reversible Bidirectional Shape-Memory Effect (rbSME)

For decades, researchers have been trying to enable a stress-free, fully reversible
shape shifting of polymer systems to overcome the necessity of a re-programming
step and the requirement of external stress application. This challenge could be
solved by polymers capable of a rbSME, which possesses a tremendous potential for
further application [136]. In such a system, a polymer sample can undergo a
reversible change of the shape upon cooling and heating without application of an
external force. Polymers exhibiting rbSME contain two crystallizable domains. One
is associated to the higher melting transition (Tm,SGD) and it determines the shape
shifting geometry. The second one is related to the lower melting transition (Tm,AD)
and is responsible for actuation of the reversible shape shifting (Fig. 22a). The
first reported polymer network capable of a rbSME was a poly(ester-urethane)
15 Shape-Memory Polymers 637

Fig. 21 Polymer network synthesis from star-shaped precursors and the mechanism of reversible
TSE under constant stress; I: network synthesis; II: shape (Crev) after application of the constant
stress σ c at Thigh; III: shape (Brev) at Tmid after PCL-related CIE; IV: shape (A) at Tlow after PPDL-
related CIE. (Reprinted from Ref. [138] with permission, Copyright © 2010 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim)

containing PPDL and PCL blocks, which provided the shape shifting geometry
determining domains and the actuation domains, respectively [136]. The pro-
gramming step, leading to fixation of the temporary shape B, consists of defor-
mation of the original shape C at Treset > Tm,PPDL by applying an external force,
then cooling the sample to Tlow < Tm,PCL followed by releasing the stress. Shape
A was achieved when the sample was heated to Thigh (Tm,PCL < Thigh < Tm,PPDL).
Reversible switching between shape A and B was observed under stress free
638 M. Mazurek-Budzyńska et al.

Fig. 22 (a) Scheme of the rbSME for copolymer networks: After deformation at Treset the shifting
geometry determining domains (red) are crystallized by cooling (programming). The rbSME is
triggered by the reversible crystallization and melting of oriented actuation domains (green). Black
dots: crosslinks. (b) Photograph series showing rbSME of a polymer ribbon from PPDL-PCL(75).
The sample was reprogrammed by Treset into an open shape (new shape A), which could be shifted
reversibly to a folded shape (new shape B). (Reprinted from Ref. [136] with permission, Copyright
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

condition when the temperature was changed between Tlow and Thigh. Reheating
to Treset caused recovery of the original shape C (Fig. 22b).
The rbSME is quantified by cyclic, thermomechanical tensile tests, in which two
parameters, the reversible elongation e0 rev, and the deformation fixation efficiency
Qef, can be determined according to Eqs. 5 and 6, respectively (Fig. 23).
15 Shape-Memory Polymers 639

Fig. 23 The rbSME of PPDL-PCL(75) quantified in cyclic, thermomechanical tensile tests.

(a) Elongation as function of temperature, reversible shape change between shape A and B.
(b) Four reversible cycles, e (black) and T (red) versus time plot. (c) The deformation fixation
efficiency (Qef) and the reversible elongation (e0 rev) as a function of the PCL weight content.
(d) Structural changes occurring during the rbSME determined by SAXS recorded for shape A
and shape B in subsequent reversible cycles. (e) Changes of long periods schematically shown for
PPDL-PCL during rbSME. (Reprinted from Ref. [136] with permission, Copyright © 2013
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
640 M. Mazurek-Budzyńska et al.

lB  lA
e0rev ¼ (5)
lA
eA
Qef ¼ (6)
eprog

Shape-switchable microparticles based on a crosslinked polymer network,

containing well-defined six-arm poly(ethylene glycol)-poly(e-caprolactone), were
elaborated to provide a concept of dynamically shape-switching carriers for drug
delivery. These polymer particles have the ability to reversibly change the shape
between spherical and elliptical, either extracellularly or intracellularly, when cycli-
cally heated and cooled between 43  C and 0  C under stress-free conditions [143].
Recently, a mechanism for rbSME of PCL-based aliphatic polyurethanes (HPL)
has been proposed based on molecular flipping and temperature-induced structural
changes. PCL domains served as actuating domains, whereas the hard domains,
consisting of HDI and 1,4-butanediol, served as shifting geometry determining
domains. During heating above Ttrans, the local reorganization of hard segments in
molten soft segment phase is facilitated because the local environment of soft
domains became liquid and the interactions of polymer chains within the soft segment
are limited. The resulting consolidation of hard segments leads to formation of a more
stable pseudohexagonal crystalline phase within the hard domains. During cooling,
hard domains in the near of the actuation domains foster the recrystallization by
providing the heterogeneous nucleation sites. A “spring model” of the resultant
structure was presented, in which two actuation domains acting as springs are
chemically attached between two geometry determining domains (Fig. 24b), leading
to increase and decrease of the cluster size during the cooling and heating, respec-
tively (Fig. 24c). Therefore, upon the temperature change between 5  C and 50  C,
the polymer sample was able to exhibit the rbSME by extension and contraction on
the macroscopic level, between shape A and B, respectively (Fig. 24a) [144].

5.2.1 Temperature-Memory Polymer Actuators (TMPAs)

In crosslinked copolymer networks exhibiting a broad melting temperature range
(ΔTm), the concept of interchangeable skeleton-forming and actuation domains was
realized. These temperature-memory polymer actuators (TMPAs) implemented a
temperature-memory with bidirectional actuation. By variation of the parameter
called Tsep, the actuation temperatures Tact of TMPAs can be adjusted. Tsep divides
ΔTm into an upper Tm range (Thigh > Tsep), which constitutes the skeleton-forming
domains, and a lower Tm range (Tlow < Tsep), which provides the actuation domains
and enables the temperature-controlled bidirectional actuation by CIE and MIC.
Reversible shape changes are realized in the polymer network by crystallization/
melting of oriented segments in the actuation domains between Tlow and Tsep
(Fig. 25) [127]. In covalently crosslinked poly[ethylene-co-(vinyl acetate)]
(cPEVA) containing crystallizable polyethylene (PE) segments, repeating units of
vinyl acetate contribute to a broad melting transition of PE crystallites and were used
for both, the skeleton-forming and actuation function [127].
15 Shape-Memory Polymers 641

Fig. 24 (a) Photograph series demonstrating rbSME of HPL with a plot showing 10 repeating
cycles of rbSME; Opening (shape A) and closing (shape B) of the ring upon heating to 50  C and
cooling to 5  C. Full recovery to permanent shape at 90  C. (b) Proposed spring models to
demonstrate rbSME in HPL through molecular flipping. (c) Models showing changes in cluster
size with the temperature change from 5  C to 50  C. (Reprinted with permission from Ref.
[144]. Copyright 2016 American Chemical Society)
642 M. Mazurek-Budzyńska et al.

Fig. 25 Working principle of

the programmable
temperature-memory polymer
actuator. (A) Programming
step: amorphous, chemically
crosslinked sample is
deformed at Tprog (● chemical
crosslinks) (right). At Tsep the
crystallization of the internal
skeleton-forming domains
takes place (marked in orange)
(center). Actuation: reversible
shape changes of the polymer
sample by crystallization/
melting of oriented
polyethylene segments in the
actuation domains (green)
between Tlow and Tsep (left).
(B) Thermal and
thermomechanical
investigations of cPEVA.
(Reprinted from Ref. [127])

6 Magnetically Triggered SMPs

Thermally-induced SME can also be triggered indirectly, by application of light

(IR irradiation), radio frequency, or microwaves [8, 145]. Controlled heating on
demand can be realized by introduction of nano- or microfillers sensitive to electrical
current or alternating magnetic fields [7, 146]. In case of utilizing an IR irradiation,
nanofillers such as carbon nanotubes or gold nanorods were incorporated to enhance
the heat transfer [147, 148]. Furthermore, addition of gold nanoparticles results in
local control of the shape recovery according to poor thermal conductivity of the
filler [149]. Electrical conductivity of polymeric materials can be enhanced by
incorporation of carbon black, carbon nanotubes, carbon nanofibers, or metal pow-
ders [7, 147, 150–152]. Examples of mechanisms of response to external stimuli in
shape-memory composites are presented in Fig. 26.
A remote actuation of the thermally-induced SME without the need of a direct
contact has been realized by the incorporation of magnetic nanoparticles (MNP) into
15 Shape-Memory Polymers 643

Fig. 26 Examples of mechanisms of response to external stimuli in shape-memory polymeric

composites: (a) a matrix dominated response after energy is transferred from the nanofiller to the
matrix, (b) a change in the overall matrix–filler interaction, (c) a filler dominated response in which
the filler–filler interactions are switched “on” or “off.” (Reproduced from Ref. [151] with permis-
sion of The Royal Society of Chemistry. https://doi.org/10.1039/c0jm02383c)

the SMP matrix and subsequent triggering of the SME by alternating magnetic fields
(AMF) [153]. The MNP dissipate heat in an AMF by hysteresis/or relaxation loss
mechanisms. This heat spreads into the polymer matrix and is triggering the shape
recovery process. The first example was polymer matrix of an aliphatic poly(ether-
urethane) (TFX) obtained from methylene bis( p-cyclohexylisocyanate),
1,4-butanediol, and polytetrahydrofuran. Another system was a biodegradable multi-
block copolymer (PDC) with poly( p-dioxanone) as hard segment and PCL as
switching segment containing MNP based on iron(III)oxide core with silica shell
(sNP). This silica shell improved the compatibility of the nanoparticles with polymer
matrix and helped to gain a homogenous distribution of particles in the polymer
matrix. In this composite, the sNP content varied between 0 and 10 wt%. When the
sample was placed in the AMF ( f = 258 kHz, H = 7–30 kA • m1), the bulk
temperature of the composite rose by inductive heating of the nanoparticles. Within
few minutes the temperature determined at the sample surface reached a constant
level (Tmax), in which the sample was in the thermal equilibrium with the environ-
ment. Tmax increased strongly with increasing sNP concentration and magnetic field
strength. When Tmax exceeded Tsw in the bulk of the composite, the shape recovery
occurred. A reduction in the frequency and in the magnetic field strength required for
triggering the SME was observed when magnetite particles in the range of 9 μm were
used [146]. Furthermore, when a near single crystal metal alloy comprising of
terbium, iron, and dysprosium-d of nominal composition Tb0.3Dy0.7Fe1.92 was
embedded in an epoxy thermoset, radio frequency could be used to indirectly heat
SMP. Here, the radio frequency triggered the magneto-electroelastic effect, which
generated the indirect heating [154]. In addition, the indirect magnetic actuation of
644 M. Mazurek-Budzyńska et al.

thermosets could be achieved by the incorporation of nickel zinc ferrite particles into
commercial ester-based thermoset polyurethane [155].
By using a polymer matrix with two switching domains, a magnetically con-
trolled TSE could be realized [156]. In this case, the composite consists of sNP
incorporated into a multiphase polymer network named as MACL (see Sect. 3,
TSE/MSE). MACL-based composite was prepared by thermally-initiated copoly-
merization of PCL dimethacrylate and cyclohexyl methacrylate in the presence of
sNP. The network composite exhibited two distinct, well separated thermal transi-
tions: a melting transition assigned to the crystalline PCL domains in the range of
41–48  C, and a glass transition associated to the amorphous PCHMA domains in
the range of 131–156  C. By stepwise increasing the magnetic field strength, a
two-step recovery of shapes B and C could be obtained, with the best triple-shape
properties achieved for nanocomposites containing 40 wt% of PCL (Fig. 27). In this
way, the triple-shape effect could be characterized by two distinct switching mag-
netic strengths Hsw,1(A ! B) and Hsw,2(B ! C), which correspond to the switching
temperatures determined in cyclic, thermomechanical tensile tests. In addition, the
magnetically controlled TSE of multiphase polymer networks named CLEG, with
two crystallizable switching segments based on PEG side chains and PCL crosslinks,
was also demonstrated [156].
Instead of using a multi-phase polymer system with two distinct Ttrans, a hetero-
geneous geometry of a polymer composite with one switching domain could also
enable a TSE. This geometrically controlled TSE was based on the concept that the
composite samples with identical chemical composition but with a higher specific
surface area to volume ratio (S/V) required a higher Hsw and vice versa. This increase
in Hsw was attributed to the higher heat transfer to the environment during endog-
enous heating of the composite by exposure to AMF. In contrast, during exogenous
heating (environmental heating), the kinetic of the heating rate could be controlled
by the control of the S/V ratio of the sample. Based on these findings, a device
having two segments differing in their S/V ratios was fabricated by using a
crosslinked PCL + sNP (10 wt%) nanocomposites. Such a composite had shown a
dual-shape effect with a shape-recovery exceeding a relatively small temperature
interval (ΔTrec  10  C). After programming by bending and subsequent cooling,
the device was exposed to an environmental heating. Here, the segment of the device
with the higher S/V ratio was recovered first, while the other segment with lower S/V
ratio required a longer time period to recover to the original shape. During
magnetically-induced experiments, this sequence of the recovery was reversed.
Here, the segment with lower S/V ratio recovered first at lower magnetic field
strength (Hlow), while for the observation of the recovery in the segment with higher
S/V ratio, the applied H needed to be increased to Hhigh. This geometrical design
enabled a precise control over the shape change process of the two segments. It was
speculated that by combining different heat sources (e.g., IR light and Tenv or
microwaves and Tenv), complex movements from a thermo-sensitive composite
can be achieved [157].
Magnetic fields could also be used to generate a magnetic-memory effect (MME)
in polymer composites. The MME is defined as the ability of magneto-sensitive
15 Shape-Memory Polymers 645

Fig. 27 Images obtained for a triple-shape composite polymer network obtained from cyclohex-
ylmethacrylate, poly(e-caprolactone) dimethacrylate and 12.5 wt% silica coated iron(III)oxide
nanoparticles during recovery at a magnetic field strength H of (a) 0 kA • m1, (b)
14.6 kA • m1, and (c) 29.4 kA • m1. (Reproduced from Ref. [156] with permission from The
Royal Society of Chemistry. https://doi.org/10.1039/b923000a)

materials to remember the magnetic field strength (Hdef), at which they were
deformed recently [158]. To enable MME in polymer composites, MNPs were
incorporated into TMP matrices with broad thermal transitions (ΔTg or ΔTm),
associated to the switching domains. The MME requires programming (and recov-
ery) of the composite during application of AMF. Therefore, specific magneto-
mechanical programming experiments were designed to demonstrate and quantify
the MME. A setup consisting of an inductor coil equipped with tensile tester with
plastic clamps was used to deform the samples to em, while being exposed to Hdef.
The recovery of the composites was carried out under stress-free or strain-control
conditions by stepwise increasing the applied H. Under stress-free conditions, the
composites recovered their initial shape at a switching magnetic field strength Hsw
646 M. Mazurek-Budzyńska et al.

close to Hdef, while under constant strain conditions they respond by building up
stress with a peak maximum at Hσ,max. While on the one hand the MME required
more defined conditions as compared to the TME (such as sample dimension or
environmental temperature), on the other hand, the MME enabled a remote actuation
with a significantly shorter actuation interval.
Compared to environmental heating, magnetic heating is an endogenous heating
process and occurs significantly faster. However, adding MNP adversely affects
other material properties, e.g., crystallinity and elasticity of the SMPs. Another
important issue in the preparation of such composites is the suppression of nano-
particles aggregation and segregation from the polymer matrix [159]. A potential
solution for this challenge is the covalent integration of the MNP into the polymer
chain segments, which leads to a cooperative motion of both, the continuous and the
dispersed phase. Such a covalent bonding of the MNP in a polymer network has
been used to develop hybrid composites, which could enable a magnetically con-
trolled rSME (rmag-SME). The hybrid nanocomposite (H-NC) consisted of oligo(ω-
pentadecalactone) (OPDL) matrix crosslinked by OPDL-coated mNP with the usage
of diisocyanates. Similar to the magneto-mechanical programming procedure
designed for MME exploration, programming of the H-NC in an AMF by stretching
was carried out. The H-NC (5 wt% mNP) sample was kept in the center of the
inductor coil with the help of plastic clamps, while the deformation em = 50% at
Hhigh in stress-controlled mode was carried out. Subsequently, the magnetic field was
switched “off” to Hlow = 0 and the cooling to ambient temperature took place. As a
result, the sample elongated quite dramatically at the point of crystallization from em
to eact  85% in the direction of applied stress. The effect was reversible, therefore,
after applying Hhigh again, the sample contracted back to the original strain erev
(Fig. 28). The reversible length changes could be explained by a directed crystalli-
zation of the crystalline lamellar perpendicular to the load direction when the H-NC
cools to ambient temperature. The rmag-SME was quantified by determining the
relative increase in strain (Ract,CIE = 65%) between the sample dimensions at Hlow
and at Hhigh [141].

7 Shape-Memory Hydrogels (SMH)

A relatively new group of smart materials, which are capable of combining several
functions constitute shape-memory hydrogels (SMH). These highly water-swellable
polymer networks have been extensively investigated for drug delivery, cell culture,
separation, and sensing applications. SMHs combine stimuli sensitivity with their
unique softness, high hydrophilicity, biocompatibility, and ability of rapid diffusion
of molecules [68]. Stimuli-sensitive hydrogels are typically crosslinked materials
containing hydrophilic and hydrophobic fractions. Hydrophilic components enable
swelling in water, whereas a hydrophobic part provides the reversible change of
the structure from ordered to disordered under variation of certain external stimuli
such as temperature [59, 160–164], pH [165–168], ultrasound [163], or content of
ions [169–172].
15 Shape-Memory Polymers 647

Fig. 28 (a) Formation of the hybrid nanocomposite using iron(III)oxide tetrahydrate nanoparticles
with tethered hydroxyl-terminated groups, trifunctional hydroxyl monomers, and 1,6-hexane
diisocyanate (HDI) linker. (b) Cartoon depiction of the nanocomposite network. The inclusion of
the trifunctional hydroxyl monomer allowed for adjustable elasticity and MNP content in the film.
(c, d) Illustration of the setup used to perform magnetic shape-memory cycles under a constant
stress provided by a weight (300 g). (e) A plot showing the changes in strain resulting from a pulsed
magnetic field. (Reprinted from Ref. [141] with permission, © 2013 WILEY-VCH Verlag GmbH &
Co. KGaA, Weinheim)

One of the first hydrogels with programmable, thermally triggered SME was a
covalently crosslinked copolymer of acrylic acid, stearyl acrylate, and methylenebi-
sacrylamide used as a crosslinker [173, 174]. The acrylic acid constituted the
hydrophilic part, which swells in water, whereas the hydrophobic, crystallizable
stearyl side chains of Tm = Tsw = 50  C served as switching segments. Heating
above Tsw was related to significant decrease of the hydrogels’ stiffness (from 10 to
0.1 MPa) [175]. In another example, the thermally-triggered SMH was based on
648 M. Mazurek-Budzyńska et al.

Fig. 29 Schematic representation of the shape-memory mechanism of crystalline shape-memory

gel and PHEG-Cn hydrogel. (a) Alkyl chains are in the molten state at high temperature. (b) In the
shape-memory gel, alkyl chains are in crystalline state after cooling. (c) In the PHEG-Cn hydrogel,
alkyl chains are in non-crystalline state but segregated at low temperature. (Reprinted from Ref.
[176], Copyright 2012, with permission of Elsevier)

polypeptides with hydrophobic alkyl side groups. The fixation of the temporary
shape was related to segregation of side groups instead of conventional fixation
based on a solidification by a phase transition of constituent polymers (Fig. 29)
[176, 177]. The segregated hydrophobic alkyl chains fix the temporary shape only
partially, and its segregation strength weakened gradually with an increase of the
temperature [176]. A similar ability to remember multiple shapes at various
recovery temperatures was reported for shape-memory ionomers with broad phase
transitions [118].
A double-network hydrogel combining the thermally-induced shape-memory
and mechano-responsive shape-changing effects was reported [178]. SMHs
based on a crosslinked N-vinyl-2-pyrrolidone network containing oligomeric
side chains of PPDL acting as switching segments have shown dual-shape
memory effect. Independently of the wt% of PPDL, Rf > 95% and Rr > 92%
were achieved. Furthermore, a degree of swelling of investigated hydrogels was
almost independent of the temperature [179]. Similarly, SMHs consisting of the
15 Shape-Memory Polymers 649

Fig. 30 Recovery process of an OPDL-SA-based triple-shape hydrogel and the molecular

mechanism. (Reprinted with permission from Ref. [181]. Copyright 2016 American Chemical
Society)

hydrophilic poly(N-vinyl-2-pyrrolidone) segment, crosslinked by the oligo(eth-

ylene glycol) dimethacrylate, and grafted crystallizable oligotetrahydrofuran was
reported to show SME with Ttrans around body temperature [180].
Furthermore, a thermally-induced triple-shape-memory hydrogel was obtained
by introducing two different hydrophobic crystallizable switching segments (PPDL,
THF) in a form of grafted side chains into the hydrophilic poly(N-vinyl-2-
pyrrolidone) polymer network. In the presented study, a permanent shape C was
folded to shape B and further to shape A. Upon heating from Tlow to Thigh in the
water bath, the subsequent recovery to shape B and then shape C were observed
according to sequential melting of semi-crystalline switching segments related to
shape A and shape B (Fig. 30) [181].
Considering the limitations of heat as a trigger to recover the original shape, non-
covalent interactions such as metal-ligand binding, dynamic covalent bonds and
guest-host interactions have been recently investigated as a new way of realizing the
SME [65, 68, 169, 182–186]. Furthermore, in comparison with solid SMPs, the
presence of water in hydrogels enables new opportunities regarding a shape-memory
capability based on molecular switches sensitive to other stimuli than those realized
in solid SMPs.
650 M. Mazurek-Budzyńska et al.

Fig. 31 Schematic presentation of the mechanism of TSE of the hydrogels in response to

concentration of zinc ions: (a) In 30% ZnCl2 solution, formation of CN–CN dipole pairing and
Zn–CN linkage, (b) In pure water, only CN–CN dipole-dipole interactions are present, (c) in 50%
ZnCl2 solution, both CN–CN pairs and Zn–CN linkage are dissociated. (Reprinted from Ref. [172]
with permission, © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Molecular switches based on metal ions-organics complexation can realize a

SME in hydrogels by controlling the oxidative state of the metal ions [169–172,
187]. One example of such a system was achieved in a chemically crosslinked
copolymer of acrylonitrile and 2-methacryloyloxyethyl phosphoryl choline. The
TSE was triggered by the dynamic association and dissociation of dipoledipole
pairs of the cyano groups in response to the presence or absence, as well as
concentration of zinc ions (Fig. 31) [172, 187].
Similarly, ion-responsive hydrogels (PVV) strengthened by hydrogen bonding,
synthesized by the copolymerization of 2-vinyl-4,6-diamino-1,3,5-triazine (VDT),
poly(ethylene glycol) diacrylate (PEGDA), and 1-vinylimidazole (VI) were
reported. The introduction of zinc ions further increased the mechanical properties
of PVV hydrogels and enabled the fixation of a variety of temporary shapes due to
the strong coordination of zinc with imidazole [188, 189]. Also, copper-containing
hydrogel materials possess shape-memory functionality. A SMH based on cova-
lently crosslinked PEGDA network with incorporated copper ions was able to
change its’ shape from A to B under the oxidation process. Figure 32 shows the
macroscopic changes of the sample, which can be realized in a solution of sodium
metabisulfite or by the exposition to air. The temporary shape is formed by the
oxidized Cu2+ ions, which serve as a crosslinking agent by coordination with
pyridine. The material properties of hydrogels containing Cu2+ (blue and rigid)
are significantly different from those of hydrogels containing Cu+ (yellow and
soft) [171].
A supramolecular hydrogel, able to respond to two independent stimuli (ion
concentration and change of pH) was reported to show TSE. Initially,
the hydrogel sample was deformed and the temporary shape I was fixed by
soaking in CaCl2 solution, whereby Alg–Ca2+ complexation occurred. Then the
sample was heated to 90  C, deformed again, and immersed into glycine–NaOH
15 Shape-Memory Polymers 651

Fig. 32 (a) Conversion of Cu+-doped hydrogel to Cu2+ in air. (b) Demonstration of shape-memory
for copper-crosslinked hydrogels. (Reprinted with permission from Ref. [171]. Copyright 2013
American Chemical Society)

aqueous solution (pH = 10.6), whereby the second temporary shape (II) was
fixed. The recovery from shape II to shape I proceeds due to the breakage of
PBA-diol ester bonds, whereas the permanent shape would be recovered due to
the disassociation of the Alg–Ca2+ crosslinks upon immersion into K2CO3
solution (Fig. 33) [190].
Supramolecular physical crosslinking based on a host-guest complex has been
used as molecular switch to enable SME in hydrogels. Cyclodextrins (CDs), which
consist of a hydrophilic external surface and a hydrophobic cavity, can be utilized as
host compounds. A pH-sensitive, biodegradable and biocompatible SMH was pre-
pared by crosslinking the β-cyclodextrin modified alginate (β-CD-Alg) and
diethylenetriamine modified alginate (DETA-Alg). The pH-reversible β-CD-DETA
complexes served as a switching phase, whereas the crosslinked alginate chains
served as a fixing phase (Fig. 34). A temporary shape was fixed at pH = 11.5
whereas a recovery to the initial shape occured at pH = 7. The Rr of 95.7  0.9% and
the Rf of 94.8  1.1% were achieved [167]. Addition of free β-cyclodextrin
molecules to poly(N-isopropylacrylamide)-based hydrogel network containing
β-cyclodextrin-adamantane temporary linkages leaded to disassociation of temporary
netpoints and increase of swelling capacity [191].
A physically crosslinked SMH with two kinds of hydrogen bonds was recently
reported. The stronger H-bonding between poly(vinyl alcohol) (PVA) and tannic
652 M. Mazurek-Budzyńska et al.

Fig. 33 (a) TSE at the macro-scale. (b) TSE behavior at the micro-scale, microscope images of the
original hydrogel and two temporary shapes. (c) The mechanism of the TSE: the original hydrogel can
fix its temporary shape I in CaCl2 solution and memorize temporary shape II in Gly–NaOH solution at
pH = 10.6. By immersion in Gly solution (pH 6) the temporary shape I can be recovered, and further by
immersion in K2CO3 solution, the hydrogel can recover to the original shape. (Reprinted from Ref.
[190] – Published by The Royal Society of Chemistry. https://doi.org/10.1039/c6sc02354a)

acid (TA) served as the permanent netpoints, whereas the weaker H-bonding
between PVA chains were able to reversibly break and act as temporary netpoints.
The hydrogel samples were able to recover their original shapes when immersed in
water at 60  C, or at 125  C in time periods shorter than 3 min [192].
15 Shape-Memory Polymers 653

Fig. 34 Molecular
mechanism of the pH-induced
SME in β-cyclodextrin Bending
modified alginate SMP.
(Reprinted from Ref. [167] Acid
with permission, © 2012
WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim) A: pH 11.5
B: pH 7.0
Base

Bending
Acid

D: pH 7.0
C: pH 11.5
β-CD DETA ICs Alg Fix crosslinks

8 Conclusions and Outlook

Different concepts to realize the phenomena of programmed changes in polymer

shapes were described. Although conventional SMEs were briefly introduced, the
emphasis was placed on new mechanisms as well as new shape-memory concepts.
The capability of SME in polymers, enabling a temporary fixation of a new shape,
can be realized by physical interactions within the polymer structure utilizing the
thermal transition of switching domains, formation of hydrogen bonds, or ionic and
metal-ligand interactions. Furthermore, reversible covalent bonds were utilized as
molecular switches. In this approach, a photodimerization of cinnamic acid, Diels-
Alder reaction, or redox reactions of mercapto groups were capable of fixing a
temporary shape. The creation of multiphase polymer systems, polymers with
broad phase transitions, and multimaterial systems resulted in the development of
novel SMEs such as reversible bidirectional SME or multiple-shape effect, which
highly extend the range of potential applications of SMPs [193].
The creation of multifunctional materials based on SMPs is a further focus of
recent research. Depending on the molecular design, shape-memory functionality
can be combined with other functions such as biodegradability, self-healing, or drug-
release capability [182, 188, 194, 195]. Furthermore, shape-memory hydrogels, due
to their soft nature, architecture, and capability of gathering the large amounts of
water, were found to be promising candidate materials for multifunctional, biomed-
ical approaches. Much attention was paid to magnetically-induced SME, which
plays an important role in applications, in which a direct heating by increasing the
environmental temperature is not feasible [141, 153].
654 M. Mazurek-Budzyńska et al.

An important motivation driving the field of shape-memory and actively-moving

polymers is the broad application potential for these materials. Thermally-induced
SMPs already reached the mass market in the area of textiles and packaging
applications [196], however the technology platform of existing materials is moving
towards some highly sophisticated applications such as in the field of aerospace or
active medical devices. The field of biomedical applications was one of the major
driving forces in the past, and due to the tunable properties of SMPs (e.g., soft
material, switching around the body temperature, biocompatibility, biodegradability,
drug-release capacity, etc.), it will be a strong motivation in the future as well
[10]. The most promising areas are self-deployable stents and minimally-invasive
surgeries [129, 197]. The first potential applications of SMP-based implants [198] or
active prosthesis were already demonstrated [199–201]. The application require-
ments in the medical field are very complex, therefore, a trend toward the develop-
ment of multifunctional materials can be seen [7, 202]. With all the progress
achieved in the development of new SMPs and corresponding mechanisms within
relatively short time periods, we envisage that the progress of SMP research will
even intensify in the near future.

Acknowledgments This work was financially supported by the Helmholtz-Association through

programme-oriented funding.

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Self-Healing Polymers: From Biological
Systems to Highly Functional Polymers 16
Stefan Zechel, Martin D. Hager, and Ulrich S. Schubert

Contents
1 From Nature to Synthetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
2 General Mechanism and Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
3 Functional Polymeric Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 692
4 Characterization of Self-Healing Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
5 Comparison with Other Material Classes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 701
6 Commercial Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 701
7 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 704
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705

Abstract
The self-healing phenomenon is well-known from nature. Since the last 15 years,
several approaches were developed in order to transfer this behavior into syn-
thetic materials and to enable the preparation of multifunctional polymers. The
following chapter summarizes the different polymers and their corresponding
healing mechanism and provides an overview of the current state of the art.
Additionally, the healing of functions as well as the characterization of the self-
healing behavior is provided. Furthermore, a short comparison between polymers
and other material classes is presented. Finally, the first commercial available
systems are summarized showing the way for future developments in this area.

S. Zechel · M. D. Hager (*) · U. S. Schubert

Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena,
Jena, Germany
Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Jena, Germany
e-mail: [email protected]; [email protected]; [email protected]

© Springer Nature Switzerland AG 2019 665

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_19
666 S. Zechel et al.

Abbreviations
Cp Cyclopentadiene
DA Diels-Alder
DCPD Dicyclopentadiene
EHM Eisenberg-Hird-Moore model
ENB 5-Ethylidene-2-norbornene
hDA Hetero Diels-Alder
IR Infrared spectroscopy
Mebip 2,6-Bis(methylbenzimidazolyl)pyridine
NMR Nuclear magnetic resonance spectroscopy
PEG Poly(ethylene glycol)
PIB Poly(isobutylene)
PPG Poly(propylene glycol)
RAFT Reversible addition-fragmentation chain transfer
ROMP Ring-opening metathesis polymerization
SAXS Small angle X-ray scattering
TDCB Tapered double cantilever beam
TEMPO 2,2,6,6-Tetramethylpiperidinyl-1-oxy

1 From Nature to Synthetic Materials

In the early human history, the usage of materials was limited to natural materials
(e.g., stone, wood, fur, etc.). Later on, humans became capable of fabricating
synthetic materials resulting in a large variety of different materials utilized nowa-
days. In recent years, the design of novel materials is increasingly based on natural
archetypes. Despite our capability to synthesize and prepare almost every imagin-
able material, some natural examples are still outstanding and unrivalled, to name
just a few examples, gecko feet, which are capable to “stick” to almost every material
allowing the reptile to run on the ceiling, [1] spider silk outperforming almost every
synthetic fiber [2], as well as natural composites (e.g., nacre) featuring mechanical
properties far beyond those properties from the single components [3]. Consequently,
a biomimetic material research is ongoing providing a novel blueprint for material
design. Important lessons from nature are the hierarchical structuring of materials
(e.g., up to seven levels in bone) as well as their ability for repair – some materials
are even continuously remodeled (e.g., bone) [4, 5]. In particular, the ability of
nature to repair damage and to restore the original properties as well as functions is
intriguing. This feature is generally not found in common synthetic materials:
Damage will sooner or later lead to the complete failure of the material. In nature,
a cut in the finger will be healed; typically 70% of the maximum load and maximum
stiffness will be restored within several days [6]. Even a more severe damage/injury
can be healed: a broken bone [7]. Depending on the fracture, even full recovery is
achieved within a few weeks [8]. Additionally, self-healing is also present at the
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 667

Fig. 1 (a) Photograph of an

axolotl and (b) schematic
representation of the
regeneration of a limb.
(Reprinted with permission
from Ref. [11])

molecular level, for instance, the healing of DNA [9] and the repair cycle of the
photosystem II [10]. A masterly performance is the regeneration of whole limbs by
the axolotl (Ambystoma mexicanum) (see Fig. 1) [11, 12].
These examples provide the basis for the bioinspired design of self-healing
materials [13–15]. Important lessons from nature include bleeding (i.e., transport
of material to the damage location, mobility for closure of the damage), vascular
networks corresponding to our vascular blood system providing transport also after
damage, hierarchical structures enabling outstanding material properties, and revers-
ibility (e.g., the constant remodeling of bones or the reversible interaction of
molecular building blocks).

2 General Mechanism and Classification

The biological systems described above are very complex, and nature is the expert
for the design of materials with self-healing properties. However, the question of
what we can learn from nature arises at this point. In general, the strategy of self-
healing can partly be adapted from nature [16]. An injury at our finger will subse-
quently lead to bleeding, which represents the generation of a mobile phase resulting
in a filling of the wound. However, the blood would stream out and no real closure,
and, thus, self-healing could take place without an immobilization of the mobile
668 S. Zechel et al.

Fig. 2 Schematic representation of the healing of mechanical damage: A scratch occurs and results
in a damage of the material (a). The generation of a mobile phase (b) leads to a closure of the crack
(c) and to a regeneration of the original mechanical properties (d). (Adapted with permission from
Ref. [17])

phase, which is in that case the coagulation. This basic mechanism results in a crack
closure and partial restoration of the function. However, nature goes further and
substitutes the healing materials (the coagulated blood) with the original material
(the skin). This general healing mechanism can also be found in synthetic polymeric
materials and consists of the crack propagation, the generation of a mobile phase,
and the immobilization (see Fig. 2) [17].
Nevertheless, this general healing mechanism can be achieved in many different
ways. Since polymers and polymer composites are easy to functionalize, many
different healing strategies were already developed. These approaches can be
divided by two different classifications [17]. The first differentiation divides the
strategies according to the requirement of an external stimulus. Thus, on the one
hand autonomous healing takes place without the utilization of an external trigger
like light or heat. Nonautonomous self-healing materials must be activated in order
to obtain the mobile phase, which can be obtained in the simplest case by heating to a
certain temperature (i.e., the healing temperature). This classification is quite con-
troversially discussed in literature since the final application and the conditions in
which the material is used define the final influences [18]. Thus, a material can be an
autonomous self-healing material in temperate climate zones, whereas it will be
nonautonomous in the Arctic Circle.
A more useful classification divides the self-healing materials into extrinsic and
intrinsic [17]. Extrinsic healing requires the presence of an additional self-healing
agent. This healing agent is embedded into the polymer matrix (by encapsulation
into capsules or the utilization of vascular networks) and is released when the scratch
occurs resulting in the formation of the mobile phase [19, 20]. Intrinsic self-healing
materials, on the other hand, can heal mechanical damage by itself without any
further additives/embedded healing agents. This behavior is realized by the utiliza-
tion of a specific polymer design and by the incorporation of functional groups,
which can provide a certain kind of reversibility in order to later activate the
formation of the mobile phase [21]. A general overview of the already used
polymeric self-healing materials and the resulting properties as well as the
corresponding healing conditions is provided in Table 1. Furthermore, selected
examples of intrinsic self-healing polymers are depicted in Fig. 3. Additionally, it
can be mentioned that the mechanical properties for extrinsic self-healing systems
strongly depend on the matrix. In the case of intrinsic systems, the molecular design
and the functional moieties are crucial for the mechanical properties.
Table 1 Summary of selected self-healing polymers and their properties with a comparison to biological systems
16

Mechanical data Healing conditions and

Classification Self-healing mechanism Chemical compounds Polymer class (E-modulus,etc.) efficiencies References
Extrinsic self- The healing is based on DCPD/ENBa Epoxy Fracture load up Bulk healing; [22]
healing the release of healing to 200 N autonomous healing at
agent when a crack RT, 100% efficiency
occurs. The healing Polystyrene-block- Tensile strength Bulk healing; healing at [23]
agent is encapsulated polybutadiene- 4 MPa RT for 24 h, 80%
into capsules or vascular block-polystyrene efficiency
networks Siloxanesa Epoxy No values Bulk healing; healing at [24]
providedb RT for 24 h, 50%
efficiency
Epoxy-vinyl ester Fracture load up Bulk healing; [25]
to 37 N autonomous healing at
RT, 50% efficiency
Poly(dimethyl No values Bulk healing; [26, 27]
siloxane) providedb autonomous healing at
RT, 100% efficiency
Epoxya Epoxy Young’s Bulk healing; healing at [28]
modulus up to 130  C, up to 50%
15 GPa efficiency
Failure load Bulk healing; healing at [29]
68 N 80  C for 48 h, up to
80% efficiency
Amine-epoxya Epoxy Critical load Bulk healing; healing at [30–32]
Self-Healing Polymers: From Biological Systems to Highly Functional. . .

130 N 30  C for 48 h, up to
100% efficiency
Thiol-epoxya Epoxy Young’s Bulk healing; healing [33–36]
modulus above 150  C within
3.7 GPa minutes; 100% efficiency
(continued)
669
 670

Table 1 (continued)
Mechanical data Healing conditions and
Classification Self-healing mechanism Chemical compounds Polymer class (E-modulus,etc.) efficiencies References
Thiol-enea Epoxy No values Bulk healing; healing at [37]
provided RT for 3 to 5 days, 100%
efficiency
Thiol-isocyanatea Epoxy Peak load 84 N Bulk healing; healing at [38]
RT for 1 to 5 days, 100%
efficiency
Azide-alkynea Poly(isobutylene) Storage Bulk healing; healing at [39]
modulus 2 MPa 60  C for 5 days, 100%
efficiency
Acylhydrazine/ Epoxy Elastic modulus Bulk healing; [40]
methacrylatea 1.8 GPa autonomous healing at
RT; up to 100%
efficiency
Glycidyl methacrylatea Epoxy Fracture Bulk healing; healing at [41]
toughness 25  C for 72 h, 100%
0.68 MPa m1/2 efficiency
Maleinimidea Epoxy Flexural Bulk healing; healing at [42–44]
strength 3.3 GPa RT for 1 to 20 days, up
to 80% efficiency
Isocyanatea Epoxy Young’s Bulk healing; [45]
modulus autonomous healing at
3.3 GPa RT
Polyurethane Fracture Bulk healing; healing RT [46]
toughness for 24 h, 100%
0.02 MPa m1/2 efficiency
S. Zechel et al.
 16

Cyanoacrylatesa Epoxy Compression Bulk healing; [47]

strength autonomous healing at
180 MPa RT
Polyester Stiffness Bulk healing; [48]
0.87 Nm2 autonomous healing at
RT, 97% efficiency
Vinyl estera Epoxy and vinyl No values Bulk healing; [49]
esters providedb autonomous healing at
RT
Unsaturated polyestera Epoxy No values Bulk healing; [50]
providedb autonomous healing at
RT
Intrinsic based (Retro-) Diels-Alder Furan-maleimide Network based on Compression 150  C for 24 h; up to [51, 52]
on covalent DA-units modulus: 57% efficiency
bonds 3.1 GPa
Epoxy No values Scratch healing; healing [53]
provided at 140  C for 30 min
Polyurethane No values Scratch and bulk [54, 55]
providedb healing; healing at
120  C for 5 min, up to
80% efficiency
Block copolymer Indentation Scratch healing; healing [56]
modulus at 155  C for 4 h; up to
1.8 GPa 100% efficiency
Methacrylate Indentation Scratch healing; healing [57–59]
Self-Healing Polymers: From Biological Systems to Highly Functional. . .

modulus at 120  C for 1 h; 100%

1.5 GPa efficiency
Anthracene-maleimide Poly(ethylene Tensile 100  C for several days; [60]
adipate) modulus: up to 55% efficiency
26 MPa
(continued)
671
 672

Table 1 (continued)
Mechanical data Healing conditions and
Classification Self-healing mechanism Chemical compounds Polymer class (E-modulus,etc.) efficiencies References
Cyclopentadiene- Network based on Compression 120  C for 20 h; up to [61]
cyclopentadiene Cp-units modulus: 1560 110% efficiency
to 1759 MPa; E-
modulus
>3 GPa
Fulvene-cyanoolefine Network based on No values 10 s at room [62]
DA-units with provided temperature; no
small PEG spacers efficiency provided
(Retro-) Hetero-Diels- Dithioesters- Network based on No values Heat press for 10 min. at [63]
Alder cyclopentadiene hDA-units providedb 120  C; over 100%
efficiency
[2 + 2]-Cycloaddition Coumarin based Polyurethane No values Scratch healing; lighting [64, 65]
providedb for 1 min. with
254 nm + 90 min. with
350 nm
Cinnamate based Network based on Flexural Lighting for 10 min. [66]
cinnamate groups strength: 42 to with λ > 280 nm; ca.
50 MPa 20% efficiency
[4 + 4]-Cycloaddition Anthracene based Polyglycerol No values Scratch healing; lighting [67]
provided for 15 min. with
254 nm + 24 h at RT
Acylhydrazones Acylhydrazones Methacrylate No values Scratch healing; heating [68]
crosslinker provided for 24 h at 100  C; 100%
scratch closure
Imines Dialdehyde and Network based on Tensile strength Scratch healing; heating [69]
multivalent imine imine units 4 MPa at 35  C
S. Zechel et al.
 16

Disulfides Disulfide crosslinkers Epoxy based on No values Bulk healing; heating for 1 [70–72]
PEG and PPG providedb h at 60  C; 65% efficiency
Tensile strength Bulk healing; healing for [73]
0.23 MPa 24 h at RT; 90% efficiency
Polyurethane Tensile strength Bulk healing; healing for [74, 75]
0.81 MPa 24 h at RT; 95% efficiency
Acrylate Young’s Scratch healing; applying [76]
modulus 20 kPa force using an AFM tip at RT
Thiuram-disulfide Polyurethane Young’s Bulk healing; visible [77]
crosslinkers modulus light irradiation at RT for
12 MPa 24 h; 100% efficiency
Polysulfides Tetrathiol and Organic and No values Scratch healing: heating [78]
tetrasulfide as inorganic network providedb for 10 min at 70  C;
crosslinkers based on silicone 100% efficiency
Urea Urea crosslinks Poly(urethane-co- Young’s Bulk healing; healing for [79]
urea) modulus 24 h at 37  C; 87%
1.22 MPa efficiency
Alkoxyamine Alkoxyamine Polystyrene No values Scratch healing; heating [80, 81]
crosslinker providedb for 30 min at 125  C
Polyurethane No values Healing for 150 min at [82]
based on PEG providedb 80  C; 70% efficiency
Diarylbibenzofuranone Diarylbibenzofuranone Poly(propylene No values Healing for 24 h at RT; [83]
crosslinker glycol) providedb 98% efficiency
Transesterification Carbonic acids Epoxy-co- Force at break Healing for several hours at [84, 85]
Self-Healing Polymers: From Biological Systems to Highly Functional. . .

polyesters 15 N RT; up to 80% efficiency

Boronic acids Network based on No values Healing for 3 days at RT [86]
boronic esters and providedb and 85% humidity; up to
thiol-ene adducts 90% efficiency
Polycyclooctene No values Healing for 16 h at 50  C; [87]
providedb up to 90% efficiency
673

(continued)
 674

Table 1 (continued)
Mechanical data Healing conditions and
Classification Self-healing mechanism Chemical compounds Polymer class (E-modulus,etc.) efficiencies References
Supramolecular Hydrogen bonds Thymine Poly(isobutylene) No values Bulk healing; healing at [88]
intrinsic healing provided (for 20  C for 72 h
rheology see
Ref.)
Hamilton wedge Poly(isobutylene) No values Bulk healing; healing at [89]
provided (for RT for 48 h
rheology see
ref.)
Poly(styrene- Young’s Bulk healing; healing at [90]
block-butyl modulus 30  C for 24 h; 95%
acrylate) 12 MPa efficiency
Amide Poly(methyl Young’s Bulk healing; healing at [91]
methacrylate) modulus RT for 24 h; 80%
brush polymer 32 MPa efficiency
Methacrylate No values Scratch healing; healing [92]
provided at 50  C for 30 min
Polystyrene brush Young’s Bulk healing; healing at [93]
polymer modulus RT for 24 h; 90%
35 MPa efficiency
Ureas Poly No values Bulk healing; healing at [94]
(dimethylsiloxane) providedb RT for few hours
Network based on No values Bulk healing; healing at [95, 96]
ureas providedb RT for 3 h
S. Zechel et al.
 16

Ureidopyrimidone Poly(butyl No values Bulk healing; healing at [97]

acrylate) provided RT for 50 h; 100%
efficiency of adhesion
recovery
Poly(lactic acid)- Young’s Scratch healing; lighting [98]
alt-poly(ethylene- modulus from 4 for 20 min with UV light
co-butylene) to 150 MPa
Poly(styrene- Young’s Bulk healing; healing at [99]
block-butyl modulus up to 45  C for 18 h; 75%
acrylate) 40 MPa efficiency
π-π- Interactions Pyrene-naphthalene Polysiloxane No values Scratch healing; heating [100]
diimide provided at 120  C
Poly(propylene Tensile modulus Healing for 240 min at [101, 102]
oxide) and 3  105 pa 100  C; up to 95%
polybutadiene efficiency
Ionomers Surlyn ® Poly(ethylene-co- No values Healing induced by [103–107]
methacrylic acid) providedb ballistic impact; healing
at different temperatures
possible
Copolymers acrylate Acrylates No values Scratch healing; healing [108, 109]
and acrylic acid provided at temperatures between
RT and 100  C for some
hours; up to 100%
efficiency
Elastic moduli Bulk healing; healing [110]
Self-Healing Polymers: From Biological Systems to Highly Functional. . .

of 1 MPa with magnetic-induced

heating for 15 min;
100% efficiency
(continued)
675
 676

Table 1 (continued)
Mechanical data Healing conditions and
Classification Self-healing mechanism Chemical compounds Polymer class (E-modulus,etc.) efficiencies References
Metallopolymers Terpyridine ligands Methacrylates Indentation Scratch healing; heating [111–113]
modulus of for several hours at
2 GPa temperatures between
60  C and 150  C
depending on metal salt
Mebip ligands Poly(ethylene-co- No values Scratch healing; UV- [114, 115]
butylene) providedb light irradiation 60 s
Histidine ligands Methacrylates Indentation Scratch healing; heating [116]
modulus of for several minutes to
2 GPa hours at temperatures
between RT and 150  C
depending on metal salt
Imidazole ligands Graft copolymers No values Healing for 3 h at RT; [117]
out of styrene and providedb 100% efficiency
butyl acrylate
Host-guest interactions Crown ether based Acrylate No values Scratch healing; healing [118, 119]
providedb for 3 min at RT
Methacrylate No values Scratch healing; healing [120]
providedb for 20 min at RT
Cyclodextrin Methacrylate No values Scratch healing; healing [121]
provided for 24 h using 1.5 V at
RT
Acrylate Maximum stress Bulk healing; healing for [122–124]
at break 73 kPa 24 h at RT; 84%
efficiency
Selected biological systems
S. Zechel et al.
 16

Skin Wound healing by Protein Elastic modulus Bulk healing; [125]

bleeding 66 MPa autonomous healing at
37  C; healing time
depends on wound size;
100% efficiency
Bone Transport of new Calcium-phosphate Mineral Elastic modulus Bulk healing; [126, 127]
minerals to the broken 20 GPa autonomous healing at
part 37  C within 4 to
6 weeks; 100%
efficiency
Mussel byssus Interaction between Zinc(II)-histidine and Protein Young’s Bulk healing; healing at [128]
threads dopamine and iron(III) iron(III)-dopamine modulus 37  C within 168 h; up to
and zinc(II) and histidine 500–900 MPa 100% efficiency
General comment: Efficiencies for the scratch healing tests were not provided only if a 3D analysis of the scratches were performed; furthermore, hydrogel
(organogel)-based systems are not listed due to their dependency of the water (or organic solvent) content; the maximum healing efficiency is 100%, and higher
values (in particular in the case of extrinsic systems) are normalized to that value.
a
These mentioned chemistries were adopted from reference [20], and a more detailed overview of the specific chemistry behind the healing is presented in this
excellent review article.
b
In these cases the exact values are not provided; however the graphs of the mechanical testing can be found in the publications.
Self-Healing Polymers: From Biological Systems to Highly Functional. . .
677
678 S. Zechel et al.

1012

Natural polymers and

Calcite polymer composites
1011 Hydroxyapatite
Covalent polymers
Mollusc shell
Diels Alder networks (51, 52)
1010 Dragline silk Reversible urea-networks (79)
Young‘s modulus (Pa)

Diels Alder thiourethane thermosets (63)

Cocoon silk
Tendon
Diels Alder anthracene-maleimide(60)
109 Imine-based-polymers (69)

Supramolecular polymers
Hydrogen bonding blocks (99)
108 Viscid silk
Hydrogen bonding brushes (93)
π-π polymers (101)
Natural elastomers
Cork Ionomers (110)
107
Metallopolymers (114)
Metallopolymer-cellulose composite (115)

106
105 106 107 108 109 1010 1011
Strength (Pa)

Fig. 3 Schematic representation of the mechanical properties of selected examples of intrinsic self-
healing polymers and a comparison to biological materials. (The biological values are adopted from
Ref. [3])

In the following paragraph, a more detailed description of each healing mechanism

is provided. Firstly, extrinsic self-healing systems will be discussed. Most of the
extrinsic self-healing polymers are based on the pioneering work of White and
coworkers [22]. The authors incorporated microcapsules filled with dicyclopentadiene
into an epoxy resin. When a crack occurs, the capsules are broken and the liquid
monomer is released resulting in a filling of the crack. The mobile phase is immobilized
by the ring-opening metathesis polymerization (ROMP) of the dicyclopentadiene
induced by the contact with the embedded Grubbs catalyst (see Fig. 4).
The basic system could be further improved and different parameters were
optimized. Thus, the healing agent, the catalyst (which is not always required), the
polymeric matrix, as well as the capsules (composition as well as size) were varied in
order to achieve a more robust and better healing system. A summary of the different
systems is given in Table 1, and for a detailed overview of the underlying chemistry
in capsule-based systems, the interested reader is referred to an excellent review of
Du Prez and coworkers [20].
However, the first developed synthetic self-healing systems featured same draw-
backs. The most important one is the limited multiple healing behavior at the same
position. If the capsules are empty due to a previous healing event, another crack at
the same position cannot be healed anymore since no healing agent is present. In
order to overcome this problem, several groups focused on the development of
vascular networks, which are inspired by the human skin [129, 130]. The blood
system in humans is responsible for the delivery of the “healing agent” to the wound.
This basic principle was transferred into synthetic materials as depicted in Fig. 5
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 679

Fig. 4 Schematic
representation of the self-
healing principles of capsule-
based materials: (a) A crack
occurs; (b) the crack leads to
the rupture of the capsules
resulting in a release of the
liquid monomer, which is
subsequently polymerized (c)
leading to a filling of the crack
and the restoration of the
original mechanical
properties. (Reprinted with
permission from Ref. [22])

a Cut

Epidermis
b Epoxy coating

Capillaries
Acoustic
emission
Microvascular sensor
Dermis
dv essels substrate
r bloo
Large

Fig. 5 Schematic presentation of the healing of the human skin (a) and the adopted synthetic
material using hollow fibers as transport ways for the healing agent (b). (Reprinted with permission
from Ref. [129])

[129]. For this purpose, hollow fibers were incorporated into a polymeric material,
and these were utilized for the transport of healing agents [131]. This setup has two
advantages compared to the capsule-based system. On the one hand, the transport of
the healing agent to the crack is enhanced, and, furthermore, a healing at the same
position can be obtained as shown by Toohey et al., who measured a healing
efficiency of approximately 50% after seven healing cycles [129]. Furthermore,
the microvascular system was further improved by varying the polymeric matrix,
the healing agent, the catalyst, as well as the fibers [31, 32, 132–134]. One recent
680 S. Zechel et al.

development in the context of vascular network-based self-healing materials was the

possibility to heal large volume damage [40]. For this purpose a two-stage mecha-
nism was required since the healing agent itself is too less viscous and would flow
out. Thus, a previous gel formation by the reaction of a bis-acylhydrazine and a
trialdehyde was required increasing the viscosity of the healing agent. Afterward, the
real immobilization by polymerization was obtained resulting in healing of a round
crack with a diameter of 35 mm.
The extrinsic self-healing stills lacks in healing over a longer period of time. The
vascular networks still lose their mechanical properties during time and a reduced
self-healing efficiency after several healing cycles were observed [129]. Thus,
further optimization of the flow of the healing agents is required in order to obtain
long-term healing and to enable application.
Another concept, which is more promising in terms of healing of a long period of
time, is intrinsic self-healing [21]. In this case, the healing is not based on an external
healing agent. Instead the material itself has a special design, which offers the
possibility to generate a mobile phase. The mussel byssus threads are the most
prominent biological examples of such system, [128] which will be discussed in
the section about self-healing metallopolymers.
In general, intrinsic self-healing polymers are based on a kind of reversible
linkage. This reversible character offers the switching between the solid,
non-healing, and the mobile phase. Thus, a smart design of such materials would
offer both: high mechanical performance and excellent self-healing properties
[21]. However, the realization of the perfect combination is quite difficult, and
most intrinsic self-healing materials still lacks in mechanical stability or autonomic
self-healing behavior without any external trigger. The reversible character of
intrinsic polymeric systems can be generated in many different ways and requires
a special molecular process, which can be triggered by an external stimulus and,
furthermore, is reversible resulting in the original molecular state. The most useful
classification of intrinsic self-healing polymers is the classification into covalent-
based [135] and supramolecular-based systems [136].
Firstly, the dynamic covalent system will be discussed in detail. Most of the
investigated systems belong to reversible covalent-based self-healing that describes
the utilization of cycloadditions [135]. These processes are ring formation reactions,
which are, under specific circumstances, reversible. In particular, three different
cycloadditions have been utilized for the design of self-healing polymers: Diels-
Alder reactions and [2 + 2]- and [4 + 4]-cycloadditions (see Fig. 6). In all three
cases, the cycloaddition is reversible and can be switched between the closed state
(cycloaddition adduct) and the open state, which is required for the generation of a
mobile phase. Whereas the Diels-Alder reaction is thermally reversible, the other two
cycloadditions can be switched by light irradiation. However, photo-switchable sys-
tems have not often been utilized so far for self-healing polymers, and the [4 + 4] was
used, to the best of our knowledge, only once [67]. For the [2 + 2]-cycloaddition, two
different structures were incorporated into polymers in order to realize self-healing
materials. On the one hand, cinnamate derivates were utilized [66, 137–139], and the
other possibility is the application of coumarin systems [64, 65].
 16

Diels Alder reaction

R1
a) O O H b) O H c) d) NC COOH e) S
N N
+ + + + +
O O R
S CN
NC CN

O O
NH CN NC S
R
COOH
NH S
O CN

O CN

[2+2]-Cycloaddition [4+4]-Cycloaddition

f) g) h)
O
+
+ O + R
R O
O O
O
O O

O O

R
Self-Healing Polymers: From Biological Systems to Highly Functional. . .

O O

O O
R

O O

Fig. 6 Schematic representation of the utilized cycloadditions for the design of self-healing polymers: Diels-Alder reaction (a–e), [2 + 2]-cycloaddition
(f and g), as well as [4 + 4]-cycloaddition (h)
681
682 S. Zechel et al.

The by far most investigated class of cycloadditions for self-healing polymers is

the Diels-Alder reaction. In that case the reversible retro-Diels-Alder reaction pro-
ceeds under thermal treatment, and the temperature strongly depends on the chosen
dienophile as well as diene and ranges from room temperature up to 200  C
[140]. The diversity of the utilized systems is depicted in Fig. 6. The most promising
as well as the most investigated system is the maleimide-furan system. The cyclo-
addition between these two compounds proceeds even at room temperature, whereas
the retro-Diels-Alder temperature happens at temperatures above 100  C [141]. Fur-
thermore, furan as well as maleimide can easily be functionalized in order to
incorporate them into polymeric materials. The pioneering work on this system
was performed by the group of Wudl, who were able to design a polymer network
consisting of multifunctional furan and maleimide units [51, 52]. During thermal
treatment the network opens due to the retro-Diels-Alder reaction enabling the
generation of a mobile phase. This process leads to a healing, and during cooling
the network is reformed again recovering the excellent mechanical properties
(E-modulus of 3.1 GPa). Besides the network based only on furan and maleinimide
units, also copolymers containing the Diels-Alder units were investigated like epoxy,
[142] polyesters [143, 144], or methacrylates [57, 58, 145]. A recent development
was the incorporation of this self-healing strategy into block copolymers. Thus,
Barthel et al. were able to synthesize a diblock copolymer consisting of poly
(ethylene glycol) as well as a furan-glycidyl ether (FGE) [56]. The crosslinking
with a low molar mass bismaleimide was performed resulting in a polymer network,
which was able to heal scratches within 3 h at 155  C (see Fig. 7).

a 0.0 mm 5.0 b 0.0 mm 5.0 c 0.0 mm 5.0

0.0 90.0 μm 0.0 90.0 μm 0.0 90.0 μm
70.0 70.0 70.0
2.0 60.0 2.0 60.0 2.0 60.0
50.0 50.0 50.0
4.0 4.0 4.0
40.0 40.0 40.0
6.0 30.0 6.0 30.0 6.0 30.0
20.0 20.0 20.0
8.0 10.0 8.0 10.0 8.0 10.0
0.0 0.0 0.0
10.0 –10.0 10.0 –10.0 10.0 –10.0

Fig. 7 Schematic representation of the self-healing behavior of a PEG-b-PFGE copolymer

crosslinked by a low molar mass bismaleimide: (a) Film before scratching, (b) scratch, and
(c) self-healing after 3 h at 155  C. (Reprinted with permission from Ref. [56])
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 683

The reversible cycloadditions are not the only utilized reversible covalent inter-
actions, which have been used for the design of self-healing polymers. Di- and
polysulfides are other important substance classes in this context. However, the exact
molecular mechanism is still not fully understood, and several explanations are
provided [135]. Thus, the healing can be based on a reversible metathesis like
reaction between two functional groups [70] or the homolytic cleavage of the S-S
bond, [146] which can also be promoted by the addition/generation of radicals. Other
possibilities are the exchange reaction between a free thiol [71] and the disulfide or
the reduction of the S-S bond [147]. All mechanisms are described in literature and
can potentially contribute to the overall healing mechanism of disulfide-based
materials. Besides disulfides also polysulfides could be utilized for such an
approach. For instance, the group of van der Zwaag presented a hybrid material
containing inorganic as well as organic compounds [78]. Furthermore, tetrasulfides
were incorporated in order to achieve healing. During thermal treatment, the con-
centration of S-S bonds in the network decreases, resulting in a (partial)
decrosslinking and finally healing at 70  C. This mechanism could be studied
using several techniques like IR spectroscopy or rheological measurements.
As already shown with the previous examples, the reversibility or the dynamics of
a system is crucial for the self-healing process of intrinsic healable polymers. These
dynamic processes were summarized by Lehn and coworkers under the term
“dynamers,” which include several substance classes [148]. For instance, imines
and acylhydrazones are named in this context since both are able to perform dynamic
exchange reactions or cleavage of the covalent bond [149–152]. However, most of
the investigations were performed in solution, and the transformation of this knowl-
edge into the solid state is rather difficult. Nevertheless, it was possible to utilize
polymers containing these dynamic groups for the preparation of self-healing mate-
rials. In particular, the acylhydrazone-based polymers featured self-healing proper-
ties, which can either be based on the cleavage of the bonds (at low pH values and in
the presence of water) or the dynamic exchange between two functional units. For
hydrogels, Deng et al. could report a self-healing process at very low pH values
resulting in a depolymerization of the network [153]. However, the healing at high
pH values was not possible, but the limitation can be overcome with a double
network structure using disulfide bonds as a second reversible element [154]. Chang-
ing from hydrogels to solid materials, the healing mechanism changes as reported by
Kuhl and coworkers [68]. Therefore, the authors designed a methacrylate-based
polymer network crosslinked by acylhydrazone functions and could show the
healing ability of these materials. However, a rather low tendency for healing was
observed, and higher temperatures were required, which could be explained by the
reduced flexibility in the solid state (i.e., bulk polymer) compared to the hydrogels
(see Fig. 8). Furthermore, mechanistic investigations were performed using IR and
solid-state NMR, revealing that the healing is presumably based on the exchange
reaction between two functional groups. Besides the acylhydrazones, also imines
were utilized for the design of self-healing polymers, but to a lesser extent [69]. Nev-
ertheless, an impressive example was recently presented by Liu and coworkers
[155]. The authors presented the healing of a protein-based hydrogel which was
684 S. Zechel et al.

Fig. 8 Representation of the self-healing behavior of a methacrylate-based acylhydrazone net-

work: (a) polymer film, (b) inflicted scratch, and (c) healing after the scratch after 64 h at 100  C.
(Reprinted with permission from Ref. [68])

obtained by the crosslinking of a protein with a dialdehyde. The formation of imine

bonds introduced a reversible element, which was further opened by the generation
of protons due to an enzymatic process. Thus, healing of the gel at room temperature
was observed.
Comparable self-healing phenomena could be obtained for ester crosslinked
polymers. Also in these materials a dynamic exchange between functional groups
is responsible for the healing mechanism. This so-called transesterification could be
found for carboxylic [84] as well as boronic esters [87]. The healing mechanism is
based on the exchange between two ester functions, which can be enhanced by the
addition of Lewis acids [84].
The last possibility to design self-healing polymers based on reversible interac-
tions is the utilization of stable radicals as well as the corresponding adducts. A
typical and well-known stable radical in polymer science is the 2,2,6,6-tetra-
methylpiperidinyl-1-oxy (TEMPO), which is utilized in the nitroxide-mediated
polymerization [156] or organic radical batteries [157]. This concept was also
transferred into self-healing polymers. For this purpose, polymer networks
crosslinked by a TEMPO unit were prepared, and the self-healing was studied in
detail. Firstly, the group of Zhang studied polystyrene-based systems, and these
systems revealed a self-healing behavior at 125  C [80]. Furthermore, the molecular
mechanism was studied using various techniques, in particular by ESR [81]. Thus,
the authors could demonstrate that the healing is based on a crossover reaction
between two functional groups. Additionally the basic principles could also be
transferred into polyurethane systems revealing a lower healing temperature of
80  C due to an increased flexibility of the polymer backbone [82].
Another radical-based concept is the utilization of diarylbibenzofuranon (Fig. 9).
In this particular case, the healing is based on the dissociation of the adduct into two
stable radicals [83]. The equilibrium between the two species is more dynamic than
the TEMPO-based one, and, thus, a healing process at room temperature could be
observed.
The class of covalently crosslinked system is investigated in detail, and a wide
range of reactions are already applied for this purpose. Furthermore, there are also
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 685

a) b)

R
O

Fig. 9 Schematic representation of the utilized stable radicals for the production of self-healing
materials: TEMPO (a) and diarylbibenzofuranon (b)

supramolecular interactions available, which feature also a kind of reversibility. The

advantage of these secondary interaction is the simple tunability of the strength and,
consequently, of the properties of the material [136]. However, this feature makes it
somewhat challenging to design materials offering both self-healing abilities and
distinguished mechanical properties [158]. Thus, a high degree of reversibility leads
to excellent self-healing properties, but it goes hand in hand with poor mechanical
performance. Despite this tightrope walk, it was possible to utilize several supramo-
lecular motifs for the design of self-healing materials, which will be discussed in
detail in the following paragraph: hydrogen bonds, ionic interactions, metal-ligand
bonds, π-π interactions, as well as host-guest complexes [136].
Hydrogen bonds are by far the most investigated supramolecular interactions in
terms of self-healing properties [159]. For this purpose, several structural motifs
have been studied, e.g., ureas, ureidopyrimidone or nucleobases. An impressive
example of hydrogen-based self-healing polymers was presented by Leibler and
his group [95, 96]. The authors synthesized a polymer network containing urea
functions, which were responsible for the crosslinking and, additionally, for the self-
healing behavior. The authors claimed that the healing of the material is based on the
formation of unbound hydrogen bond units at the crack due to the damage event and
that these free moieties reform hydrogen bonds if the two parts are placed together.
Thus, healing at room temperature could be obtained within minutes. However, if the
material parts are kept away from each other and the healing process was started after
several hours, an insufficient healing was obtained and the mechanical properties
were not restored. This phenomenon was explained by the reassembly of the freshly
formed hydrogen bonds, and, thus, no sticking of the polymer was possible anymore.
After the first development of hydrogen bond-based self-healing materials, sev-
eral other systems were studied in detail. One important moiety is thymine, which is
686 S. Zechel et al.

also a natural building block of the DNA. The utilization of thymine in polymeric
materials mostly requires a complementary partner, which can be, e.g.,
diaminotriazine [160]. However, it is also possible to utilize thymine without any
additional partner as shown by Binder and coworkers [88]. In that case, the authors
functionalized poly(isobutylene) (PIB) with thymine functions and constructed
another network by alkyne-azide click chemistry. The very polar thymine units
lead to aggregates within the copolymer, and during a scratch free supramolecular
moieties are obtained, which are reformed by the contact of two freshly cut surfaces
resulting in a healing. However, the effect of phase separation seems to be more
important for the self-healing than the contribution of the reversible hydrogen bonds
itself.
One very similar moiety compared to thymine and one of the most frequently
investigated molecular units in the context of self-healing materials is barbiturate.
Mostly, this system is used with the corresponding Hamilton wedge as shown in
Fig. 10 [161]. The rather strong hydrogen bonds as well as the simple functiona-
lization procedure allow a broad range of potential polymer structure. Thus, Herbst
et al. were able to end functionalize PIB with either one or two hydrogen bonding
motifs [89]. A mixing of the corresponding polymers led to a network formation via
clusters since the highly polar functional groups segregated from the unpolar
polymer backbone. Furthermore, the healing ability at room temperature was stud-
ied, and a healing after 48 h could be obtained. An improvement was reported

Fig. 10 Schematic representation of the supramolecular pair based on barbiturate and the
corresponding Hamilton wedge (left) and the self-healing ability of block copolymers based on
these interactions (right). Healing of the block copolymer containing only barbiturate (A and C) and
the adduct of the block copolymer containing barbiturate as well as a Hamilton wedge containing
polymer (B and C). (Reprinted with permission from Ref. [90])
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 687

3 years later by the same group. Therefore, the group prepared block copolymers
with the hydrogen bonding (barbiturate) units localized in the hard block (polysty-
rene) [90]. These materials also featured a healing ability after 24 h at 30  C as
shown in Fig. 10. However, the utilization of α,ω-difunctionalized polyisoprene with
two Hamilton wedges and the block copolymer resulted in weaker mechanical
properties, but also cracks could be healed at room temperature.
However, the main disadvantage of all the investigated hydrogen bonding-based
self-healing polymers is the weak mechanical performance. Thus, only very soft
materials were obtained. In order to overcome this problem, Guan and coworkers
developed a multiphase phase system offering both mechanical stability and self-
healing properties [93]. For this purpose, the authors prepared a polystyrene-based
copolymer which featured brushes containing a polyacrylate with an amide function.
This function enables hydrogen bonds and, thus, crosslinking. Furthermore, a
phase separation was obtained between the hard and the soft block. Although the
introduction of non-flexible hard blocks, the copolymer still featured a self-healing
ability at room temperature and good mechanical properties (E-modulus of up to
35 MPa).
π-π Interactions represent another important class of supramolecular interactions
utilized for self-healing materials. In order to obtain such an interaction, an electron-
rich as well as an electron-poor aromatic compound is required [162]. As electron-
accepting unit, only naphthalene diimide was utilized, and it was incorporated into
polymers as end groups or as repeating units. Furthermore, electron-rich aromatic
systems are required, and mostly two different systems were used up to now:
perylene [163] and pyrene [100–102, 164]. If both polymers are combined, second-
ary interaction takes place (see Fig. 11) resulting in crosslinking of the polymer as
well as a chain folding. The obtained polymeric materials feature the ability to close
cracks during thermal treatment since the thermal activation of the π-π interaction
leads to a disassembly and, finally, to mobility, which is required for closing the
crack. During cooling, the π-π interactions are reformed, and the original properties
of the polymer can be reobtained. Firstly described in 2009, the π-π interaction was
already used several times for the preparation of self-healing materials [100]. In the
first approach, a polysiloxane containing two pyrene units as end groups were mixed
with a naphthalene diimide containing copolymer resulting in the formation of a
supramolecular network. This material is able to heal cracks at temperatures above
90  C. The basic principles could also be transferred into other systems, and, thus,
other copolymers for the naphthalene diimide containing part were utilized such as
poly(propylene oxide) [101, 102, 164]. Furthermore, polybutadiene was used as
building block for the pyrene block [101]. Additionally, the mechanical performance
could be enhanced by the utilization of cellulose nanocrystals [165]. Finally, also
perylene was incorporated into a polymeric structure resulting in a π-π interaction
[163]. In that case, healing after 40 min at 70  C or after 14 min at 125  C could be
observed.
Ionomers are a very important class of supramolecular healable materials
[136]. These copolymers reached already the industrial scale and are sold by DuPont
under the trade name Nucrel ® poly(ethylene-co-methacrylic acid) or Suryln ®
688 S. Zechel et al.

O O

N N R

O O O

O O O
O O
N N R
N N R
O O
O O O

O O
O O O
N N R
N N R
O O O
O O

O O O

N N R

O O

Fig. 11 Schematic representation of the formed complexes by π-π interaction starting from a
naphthalene diimide derivates and pyrene (red) and perylene (green). (Adopted from Ref. [163])

(different salts of poly(ethylene-co-methacrylic acid)) [166, 167]. These copolymers

feature excellent mechanical properties and are used as packing materials or top
layers for, e.g., golf balls [167]. The commercial availability leads to several
publications reporting the self-healing ability of Nucrel ® and Suryln ®. However,
the self-healing effect of those polymers is up to now not used on an industrial scale.
Nevertheless, the self-healing phenomenon is studied by several groups and will be
described in the following paragraph.
Generally, ionomers are defined as polymers containing a certain amount of ionic
groups (1% to 15%), which leads to a special behavior since a phase separation of the
ionic groups within the nonpolar backbone is obtained [168]. These so-called multi-
plets aggregate further to ionic clusters according to the Eisenberg-Hird-Moore model
(EHM) [169]. Furthermore, the ionic clusters lead to a crosslinking of the polymer
and to a reduced mobility at room temperature. During thermal treatment the order of
the ionic clusters itself is destroyed, which can increase the mobility of the polymer
chains. In the case of Suryln®, further thermal treatment would lead to a melting of the
polyethylene parts, which are crystalline at room temperature (Fig. 12) [170].
Most investigations on the self-healing behavior of ionomers is focused on the
testing of the healing abilities after a ballistic impact [103, 105, 171]. For this
purpose, a polymer film was penetrated with a bullet resulting in a hole within the
polymer. Furthermore, this kind of damage leads to heating of the polymer, which
surrounds the generated hole [171]. Thus, parts of the polymer become sufficiently
mobile to close the crack and to heal the damage. Kalista and coworkers investigated
this behavior further at different temperatures [104]. The authors could show that the
temperature of the film has a crucial influence on the healing abilities. However, the
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 689

Increased temperature

Ti Tm
relaxational
process

Tc

Ordered state Disordered state Molten state

(ionic crystallites)

Fig. 12 Schematic representation of the thermal behavior of ionomers (in particular of Suryln ®):
The ordered state at room temperature with crystalline polyethylene as well as ionic cluster
undergoes two thermal transitions; disorder of the ionic clusters and melting of the polyethylene.
(Reprinted with permission from Ref. [170])

most important parameter is heating of the surrounding polymer, and, consequently,

the heating has to be stronger if the polymer film is cooled before the penetration.
Additionally, lower temperatures can cause a kind of brittleness of the film resulting
in non-healing of the ionomer. This behavior can be in particular observed for low
degrees of neutralization of Nucrel ®. Despite all the ballistic tests, it still requires the
access to a shooting place to perform these experiments, and in order to overcome
this problem, Varley and van der Zwaag developed a similar method to test the same
behavior without a gun [106]. For this purpose, they constructed a hydraulic tensile
testing apparatus, which also resulted in hole formation.
The ballistic penetration is not the only method which was reported to test the
self-healing capacity of ionomers. Exemplary, Bose et al. studied the scratch healing
behavior of ionomers. Furthermore, the utilized copolymers were not based on
Suryln or Nucrel. Instead they prepared a copolymer consisting out of tert-butyl
acrylate and n-butyl acrylate [108, 109]. In a second step, the tert-butyl ester was
cleaved off and the obtained acid was neutralized using different metal salts, i.e., zinc
(II) and cobalt(II) acetate as well as sodium hydroxide. Furthermore, the ionic
content was varied, and the synthesized materials were investigated using rheology
as well as microscopy in order to follow the healing behavior of the scratches. The
authors could show that these ionomers are also able to heal scratches, even if they
were not generated by high impact damage. Furthermore, a correlation between the
mechanical properties and the self-healing abilities was obtained since the crossover
frequency of the storage and the elastic modulus obtained by rheology goes hand in
hand with the mechanical and self-healing properties. Therefore, the authors could
reveal the optimal design principle for having both mechanical stability and self-
healing behavior [108, 109].
690 S. Zechel et al.

Metallopolymers are another important class of materials in terms of self-healing

and are in some points comparable to the previous mentioned ionomers [172]. Meta-
llopolymers are polymers featuring additionally a metal complex (i.e., a complex
consisting of a metal ion and the corresponding ligands). This secondary interaction
can influence the properties significantly, and interesting features can be obtained.
Thus, metallopolymers were already utilized for special optical, shape memory, or
certain biomedical applications [173]. However, the design of metallopolymers is
rather challenging since the metal complex as well as the rest of the polymer influences
the properties, respectively. The right combination can also lead to self-healing poly-
mers. For this purpose, two basic mechanisms are described in literature: reversible
opening of the metal complex or the formation of ionic clusters in analogy to ionomers
[172]. The first one is already known in solution but strongly depends on the chosen
metal ion-ligand combination. The second possibility requires a phase separation
within the formed polymer of the metal complexes, which are mostly charged, from
the rest of the polymer. Which contribution is the predominant one depends on the
special design (the metal complex, the polymer backbone, the counterion, etc.).
The first self-healing metallopolymer film was described by the groups of Weder
and Rowan in 2011 [114]. For this purpose, the authors synthesized a poly(ethylene-
co-butylene) α,ω-end functionalized with 2,6-bis(methylbenzimidazolyl)pyridine
(Mebip) ligand. Subsequently, the ligand-containing copolymers were mixed with
either zinc(II) or lanthanum(III) bistriflimide resulting in metallopolymers. The
healing was studied by inducing a scratch into the polymer film and irradiation
with UV light. The lighting leads to a decomplexation resulting in flexibility.
However, a secondary effect of the high-power UV light was the heating of the
polymer film up to 220  C, which further enhances the mobility. Thus, a healing was
obtained within seconds. The mechanical properties could be enhanced by the
utilization of cellulose nanocrystals, and the obtained composite materials featured
E-modulus values up to 100 MPa [115]. Another optical healable metallopolymer
was reported by Wang and Urban [174]. The authors used a poly(ethylene imine) and
incorporated copper(II) complexes. These complexes undergo a geometry change
during lighting, resulting in a volume change and, finally, in self-healing properties.
Metallopolymers are multi-stimuli-responsive materials, and, therefore, these
polymers can be addressed by several external triggers [173]. The most frequently
utilized one in terms of self-healing is temperature. The first thermal-induced self-
healing of metallopolymers was reported by the Schubert group in 2013 [112]. The
authors synthesized different methacrylate copolymers containing terpyridine moi-
eties in the side chain via RAFT polymerization (see Fig. 13). Crosslinking with iron
(II) sulfate resulted in metallopolymers which featured self-healing depending on the
chosen copolymers. Whereas copolymers based on methyl methacrylate have a too
high glass transition temperature, copolymers with lauryl methacrylate show self-
healing abilities at 100  C. Furthermore, the healing mechanism was investigated
using Raman spectroscopy as well as theoretical calculations revealing that the
healing process is presumably based on the partial decomplexation [175].
However, the required temperatures were rather high, and a follow-up study of
the same group could show that it is possible to reduce the required energy input. For
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 691

NC S
k l
O S
O O O O O
3
O + O
RAFT R
5
N O 70°C,DMF
N O
N R

N N
N

Fig. 13 Schematic representation of the synthesis of a terpyridine-containing copolymer, which

can later be utilized for the complexation of different metal ions resulting in metallopolymer
networks (Adapted from Ref. [113])

Fig. 14 Self-healing behavior of a metallopolymer network crosslinked by terpyridine-manganese

(II) chloride complexes. Self-healing at 70  C (a–c) and partial healing at 50  C (d–f). (Reprinted
with permission from Ref. [113])

this purpose, cadmium(II) acetate was used resulting in a weaker crosslinking since
acetate-bridged complexes were formed [111]. Thus, healing at 70  C within minutes
was possible. Additionally, the required temperature could be further reduced to
60  C by the utilization of manganese(II) chloride (Fig. 14) [113]. Finally, the
Schubert group also presented a general predication of the healing ability of meta-
llopolymers showing that rheology can be utilized as a prediction tool. If a crossover
of the storage and the elastic modulus at a certain temperature is found, the material
692 S. Zechel et al.

reveals self-healing. However, the film-forming properties are also important for the
healing process, and thus, in the case of brittle films, the general correlation is not
useful anymore.
The results in the field of synthetic self-healing metallopolymers are promising.
However, these are far away from that what nature can do. Mussel byssus threads are
also able to heal mechanical damage [176]. This behavior is found under living (harsh)
conditions in an ocean at low temperatures [128]. Responsible for that behavior are
iron(III)-dopamine as well as zinc(II)-histidine interactions [177, 178]. These interac-
tions lead on one hand to mechanical stiffness and furthermore to the possibility to
stick on the surfaces of rocks (mostly the iron(III)-dopamine interaction is responsible
for this behavior) [179, 180]. Additionally, the partly opening and the reorganization
of the metal complex can lead to a self-healing in mussel byssus threads (Fig. 15)
[181]. This impressive behavior was tried to mimic also with synthetic materials.
However, no approach comes close to nature so far. Nevertheless, more insights in the
behavior of the mussel can be obtained, which can lead to novel materials with
outstanding properties in the future.
Thus, iron(III)-dopamine or zinc(II)-histidine units were incorporated into poly-
meric materials or hydrogels revealing in self-healing abilities [116, 182, 183]. The
weak interaction between those moieties led to a healing behavior at room temperature
or slightly increased temperature. Furthermore, in the case of iron(III)-dopamine, it
was also possible to utilize the pH value as trigger for the self-healing since a lower pH
value led to a protonation of the dopamine [183]. Similar to the zinc(II)-histidine
interaction, also zinc(II)-imidazole can be utilized for such an effect [117].
Host-guest interactions are the last important class of supramolecular self-healing
materials. For the preparation of such polymers, a host (typical for self-healing
polymers: cyclodextrin or crown ethers) interacts with a guest, e.g., ferrocene or
ammonium salts. The non-covalent interactions are reversible and can be triggered
by temperature or, in the case of ferrocene, by oxidation. The reversibility is the
crucial aspect for the design of self-healing materials. The pioneering work in this
field was performed by Harada and coworkers [122]. The authors could successfully
synthesize a cyclodextrin- and ferrocene-containing polyacrylate, which crosslinks
due to the host-guest interactions. The oxidation of the obtained gel led to an opening
of the interactions resulting in mobility and the ability to self-heal (Fig. 16). Besides
the interaction with ferrocene, cyclodextrin can also interact with, e.g., adamantane
or azobenzene [123, 184]. Additionally, the host molecule can be changed toward
crown ethers, which are more responsible for ammonium salts. This interaction can
be triggered by several stimuli like temperature, pH value, or chemicals (e.g., other
competing ions) [118]. These special features could already be utilized for the design
of self-healing materials, and further development in this area is expected.

3 Functional Polymeric Materials

Most research on self-healing materials was and is still focused on the healing/
restoration of mechanical properties. In this context, several mechanisms have been
developed, which provide a regeneration of the mechanical properties under specific
 16

(C) stretched (ε = 50%)

(B) stretched (ε = 20%) phase II
phase I and II
(A) native; phase I

first first
loading loading

(E)
second
loading
His
Flank
(E) healing
top view of top view of preCol
Proximal preCol 6+1 bundle Monomer
(D) unloaded; phase II
unloading

(B) (C)
byssus
thread (F)

2 – 5 cm
Distal (E)
Collagen domain
(A)
Self-Healing Polymers: From Biological Systems to Highly Functional. . .

extensible domain;
Plaque phase I
extensible domain;
(D) phase II

Fig. 15 Schematic representation of the healing mechanism of mussel byssus threads. (Reprinted with permission from Ref. [181])
693
694 S. Zechel et al.

Fig. 16 Schematic representation of the self-healing healing process of polymer networks

crosslinked by ferrocene-cyclodextrin interactions and the reversible opening induced by the
oxidation of the ferrocene. (Reprinted with permission from Ref. [122])

conditions. Compared to nature, synthetic polymeric materials are still at the begin-
ning of the development to multifunctional materials. Thus, nature can repair the
mechanical performance as well as the function. For instance, a scratch in the human
skin leads to a loss in both mechanical stability and function (e.g., as barrier against
substances from the outside). After the scratch occurs, bleeding starts resulting in a
closure of the crack. Up to this point, this behavior can also be found in synthetic
materials. However, nature goes further and initiates a second healing step in which
new skin is reformed having the same properties as before. Thus, the barrier function
or the ability to sweat is reformed. This complex behavior is still influencing the
research efforts in developing new materials, which feature both reparation of the
mechanical performance and the regeneration of additional functions. The following
paragraph will shortly demonstrate which functions can already be healed/restored in
functional materials. For a more detailed description, the interested reader is referred
to the literature [185].
The two most frequently investigated functions are conductivity as well as optical
properties. Furthermore, it is also possible to restore special functions of coatings
like superhydrophobicity.
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 695

Conductivity can be repaired in different ways, and several strategies have been
developed in the past. First of all, it is possible to introduce reversible bonds into a
conjugated polymer backbone. In this context, Williams et al. reported a conjugated
polymer containing carbene metal complexes, which are able to be reversibly opened
at higher temperatures in the presence of DMSO vapor [186]. Furthermore, the
polymer featured electric conductivity comparable to silicon. However, the authors
only studied the scratch healing behavior, which could be observed at higher temper-
ature, and not the restoration of the conductivity, which has to be improved first.
Another possibility for the generation of self-healing conductors is the embedding
of conductive material into a self-healing polymer. Thus, the group of Bao explored
several combinations and could show the healing of the function as well as the
mechanical stability by utilizing the polymer which was investigated by Leibler
[95]. Firstly, the incorporation of nickel microparticles into that polymer matrix led
to a material featuring a conductivity of 40 S cm 1, which is a rather high value
[187]. After a mechanical damage, 90% of the conductivity could be regenerated
within seconds, and the complete recovery of the mechanical properties was
obtained after 10 min. However, this basic principle could also be transferred into
batteries. In lithium ion batteries, the main challenge is to increase the capacity. One
possibility to increase the capacity of the anode is the utilization of silicon anodes.
However, these electrodes are mechanically not stable due to a large volume change
during charging/discharging, resulting in crack formation (see Fig. 17). However,
Bao and coworkers could overcome this problem by the utilization of self-healing
polymer, which holds the anode material together and enables the fabrication of a
lithium ion battery with a capacity of nearly 3000 mAh g 1 over 20 cycles.
The third possibility to enable healing of conductivity is the utilization of the
extrinsic healing concept, i.e., the encapsulation a conductive material in cap-
sules. The first approach toward this healing strategy was presented by the

Fig. 17 Schematic representation of the self-healing property of a silicon anode compared to a

normal one: Charging of the battery leads to a lithiation and to a volume change of the battery
resulting in crack formation and to a total failure of the anode (above) or by the utilization of a self-
healing binder (red) to a stable electrode. (Reprinted from Ref. [188])
696 S. Zechel et al.

Moore group in 2009 [189]. The authors were able to encapsulate carbon
nanotubes. However, an addition of a nonpolar solvent is required in order to
enhance the release. This basic principle could later be used for the reparation
of silicon anodes [190]. For this purpose, carbon black as well as o-dichloro-
benzene was incorporated into microcapsules. However, the addition of a core
thickener was required leading to the restoration of the conductivity. Further-
more, it is also possible to utilize liquid metals (alloys) for this process like
eutectic gallium indium [191, 192].
The healing of optical properties is still in its infancy, and only very few
publications focus on the healing of optical active polymeric systems [185]. How-
ever, these properties can range from absorption to emission or in the simplest case to
transparency. The latter one is a typical phenomenon known in the daily life. A clear
top coating is scratched resulting in worse aesthetics due to the visible scratch.
Healing of the scratch requires for certain applications (e.g., as clear top coating in
cars) not only the disappearing of the scratch. Furthermore, it is required to obtain
afterward again a clear coating, which has the same optical properties as before. One
approach toward the solution of that problem was presented in 2011 by Braun and
coworkers [193]. The authors tried to overcome scattering phenomena from the
encapsulated capsules as well as from the healed polymer. For this purpose, dibutyl
phthalate was encapsulated into a PMMA matrix. During crack propagation the
capsules are ruptured resulting in a release of the dibutyl phthalate. Thus, a swelling
is observed, which leads to healing of the crack and a regeneration of the
transparency.
Furthermore, it can be possible to heal also other functions of optical active
polymers like absorption or emission, which would be interesting, e.g., for solar cell
applications. However, a self-healing polymer featuring this property does not exist
so far. Nevertheless, first attempts were created like the utilization of a transport of
fluorescent dyes through a polydimethylsiloxane matrix [194].
The last discussed function to be self-healed is the reparation of the surface
properties of a polymer coating. One very impressive approach was presented
from Esteves and coworkers [195–197]. The authors utilized the so-called self-
replenishing of a coating. For this purpose, poly(e-caprolactone) was prepared
containing perfluoro-chains as well. These chains phase separate from the rest of
the polymers and are moved to the top of the coating, leading to very hydrophobic
properties. After the top layer of the coating is removed, the hydrophobicity is lost
but is regenerated during time due to a subsequent phase separation process. This
effect is schematically shown in Fig. 18.

4 Characterization of Self-Healing Polymers

The characterization of self-healing polymers represents a crucial part of the inves-

tigation of such materials. The major task is the investigation of the self-healing
phenomenon itself and to quantify or at least to visualize the self-healing effect
[198]. Furthermore, the material properties are of significant interest, which allow a
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 697

Fig. 18 Schematic representation of the self-replenishing effect of polymer coatings utilizing

perfluoro-chains. (Reprinted with permission from Ref. [197])

comparison of the properties to materials without any healing ability. For this
purpose, mostly standard mechanical tests are utilized. Additionally, the healing
mechanism, in particular for intrinsic systems, should be studied in detail in order to
analyze the molecular changes and to understand the basic principles of the self-
healing process. Finally, the healing of functional materials, in which specific
functions besides the mechanical properties are healed, requires the investigation
of the corresponding property like conductivity (see Sect. 3). In the following part,
the different methods of the investigation for self-healing processes as well as for the
study of the molecular processes will be presented in detail.
The investigation of the self-healing properties can be realized by different tests.
Tensile testing, tapered double cantilever beam, and scratch healing are the most
common methods to analyze the healing ability. Furthermore, the healing after
ballistic impact or the determination of the fracture mechanics was also utilized for
this purpose [198]. However, a standardized testing of the self-healing properties is
not available at the moment and has still to be developed. The problem behind the
standardization of healing quantification is that the testing method strongly depends
on the later application. Thus, materials, which will be utilized as coatings, should be
studied via scratch healing analysis, whereas bulk material applications require the
determination of the mechanical properties before and after the healing event [198].
698 S. Zechel et al.

The tensile test is the one of the most frequently utilized methods in terms of self-
healing materials. The method allows the determination of the mechanical properties
of the material, like E-modulus, tensile strength, or elongation at break. Furthermore,
these properties can also be studied temperature-dependent. Finally, virgin and
healed samples can be compared, and the healing efficiency can easily be deter-
mined. However, several parameters were utilized in the literature for the calculation
of the healing efficiency. Some examples are elongation at break [199], the maxi-
mum load at failure [42, 52], or the recovery of the yield point stress [200]. The
limitation of this method is the exact determination of the healing efficiency. During
the healing event, the surface of the broken tensile specimen has to have contact.
However, depending on the hardness of the material, this requirement is difficult to
fulfill, and nonoptimal healing events take place resulting in a lower healing
efficiency [198, 201]. Nevertheless, the method is widely utilized since it is easy
to perform and both the healing process and the mechanical properties of the healed
material can be analyzed. The method can also be applied for biological samples
since threads can also be investigated by this technique. Thus, Harrington et al.
studied the healing of mussel byssus threads using such testing equipment
(Fig. 19) [128].
The tapered double cantilever beam (TDCB) represents another possibility to test
the mechanical properties as well as the healing efficiency [202]. During the testing a
load-displacement curve is generated which can also be utilized for the

Fig. 19 Schematic representation of the healing within mussel byssus threads within three cycles
of tensile testing. Cycle 1 describes the original mechanical properties, and cycle 2 was directly
measured after the first cycle with no rest in between. The third cycle represents the healing of the
mechanical properties of such a thread after 1 h at ambient conditions. (Reprinted with permission
from Ref. [128])
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 699

50
Virgin
Healed
40
Load, P (N)

30

20

10

0
0 5 10 15 20 25 30
Crack-opening displacement, δ (mm)

Fig. 20 Schematic representation of the data obtained by a TDCB for capsule-based healing
system (dicyclopentadiene encapsulated into capsules in an epoxy resin with a Grubbs catalyst).
The original material (solid black line) as well as the healed sample (dotted black line). (Reprinted
with permission from Ref. [204])

determination of the healing efficiency. The fraction toughness is a useful parameter

for this purpose [203]. The TDCB is mostly utilized for extrinsic self-healing
systems. Thus, the capsule-based healing system (dicyclopentadiene encapsulated
into capsules in an epoxy resin with a Grubbs catalyst) could be studied using this
method, and typical curves revealed from this measurement are depicted in
Fig. 20 [204].
A relatively similar approach compared with the TDCB is the testing of the
fracture mechanics [198]. Also within this method, the crack propagation is ana-
lyzed, and healing efficiency as well as mechanical data can be obtained. However,
this kind of testing is not often utilized for the determination of the healing ability of
polymers although it seems to be quite promising for the investigation of soft
materials [201, 205].
A completely different method for the analysis of the self-healing behavior is the
utilization of the scratch healing tests. In this case, no mechanical properties will be
analyzed and will also not be utilized for the determination of any kind of efficiency.
This testing method focuses more on the ability of the material to close scratches on a
surface and is of particular interest for materials utilized later as coating [198]. How-
ever, most of the publications simply utilize the optical imaging of the scratch as well
as analyze the presence and disappearance of a scratch during healing. This method
can just be utilized to show the general healing ability of newly developed system;
quantification is not possible. For this purpose, a 3D imaging of the crack is required,
which allow the determination of the crack volume, the healing speed, as well as the
percentage of healed volume (corresponding to a kind of healing efficiency). Thus,
700 S. Zechel et al.

Fig. 21 Schematic representation of the quantification of the scratch healing behavior by the
analysis of the residual volume of the scratch. (Reprinted with permission from Ref. [206])

also kinetic studies of the healing process itself would be possible. Such a
system was developed by Garcia and coworkers [206]. This procedure requires the
utilization of an indenter in order to induce defined cracks, which can later be utilized
for the healing studies. Furthermore, the volume is measured using a confocal
microscope, and the sample is placed on a heating stage, which enables the simula-
tion of the required healing circumstances (Fig. 21). During the time the scratch is
closed as well as the residual volume can be measured and be utilized for
the analysis of the healing kinetics and the determination of the healing efficiency.
This method was already used for different polymeric systems like ionomer [206],
Diels-Alder crosslinked copolymers [57], tetrasulfide [78], or acylhydrazone-based
networks [68].
Besides the investigation of the self-healing behavior itself, the characterization of
the molecular processes, which enables this phenomenon, is a general important topic
[198]. In particular, the behavior in the solid state is of great interest and cannot be
simply transferred from solution investigations. Therefore, certain techniques are
available which allow the analysis of the materials under healing conditions. The
most efficient testing methods seem to be spectroscopic analysis like IR and Raman
spectroscopy [198]. Both techniques were already utilized for such investigations,
e.g., Raman spectroscopy was used for the analysis of the self-healing mechanism of
metallopolymers [175]. The advantage with this kind of analysis is the specific study
of molecular fragments which are responsible for the healing process. Thus, Bose et al.
were able to follow the Diels-Alder units during thermal treatment and could show the
opening of the Diels-Alder adduct at higher temperature [57]. This process is respon-
sible for the generation of a mobile phase and finally for the healing process itself.
Both techniques are the most utilized methods for the understanding of the
molecular dynamics. Furthermore, solid-state NMR [111] or scattering techniques
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 701

like small angle X-ray scattering (SAXS) can be utilized to determine the behavior in
the solid state [112]. Recently, a new method for the investigation of the self-healing
phenomenon was presented by Garcia and coworkers [207]. The authors utilized
broad dielectric spectroscopy in order to evaluate the flow behavior of the material.

5 Comparison with Other Material Classes

Self-healing materials are by far not limited to polymeric materials. Also other
material classes have been investigated within this context. However, polymers are
still the by far most studied self-healing material class. This fact can be related to the
wide variety of different polymers available as well as the “easier” access to self-
healing properties for polymeric materials compared to other systems. Considering
the general mechanism, a mobile phase has to be generated. Within a typical
polymeric material, the mobility can be provided by (liquid) healing agents as well
as by elevated temperatures (ca. 100  C). Metals as well as ceramics require much
higher temperatures (close to 1000  C) [17]. Particularly the former material class
features another intrinsic drawback: The mobile species will be atoms compared to
large polymer chains or segments.
Nevertheless, comparable approaches have been investigated for the other mate-
rial classes. Self-healing metals are still the least studied material class [208]. One
approach utilizes the precipitation of hard materials in growing voids (e.g., boron
nitride). Similar to metals, most of the approaches for the healing of self-healing
ceramics are based on high temperature processes [209]. Comparable to the above
described encapsulation of healing agents, also oxidizable compounds (e.g., SiC,
TiC) have been encapsulated within ceramics [210, 211]. A crack can be closed by
heating resulting in the oxidation of the healing filler material resulting in the
formation of an oxide, which closes finally the crack. Moreover, a special ceramic
material, MAX phases, has been investigated. These materials can also form oxides
upon heating resulting in a healing process [212–214]. Interestingly, concrete mate-
rials feature a similarly broad spectrum of different approaches for self-healing
properties like polymers. The applied mechanisms range from the encapsulation,
the design of damage-tolerant concretes combined with the “natural” ability of
concrete for healing, to the encapsulation of bacteria, which can close the crack by
precipitation of minerals [215–218].

6 Commercial Systems

The previous illustration of the wide variety of different self-healing polymeric

materials sets expectations for further industrial/commercial applications of these
materials. The field of smart polymers, particularly self-healing polymers, will
strongly grow in the next years resulting in a market volume of 2.7 billion $ in
2020 [219].
702 S. Zechel et al.

However, not only the offered possibilities as well as the large versatility will
determine the success of self-healing polymers, the “real” demands considering the
corresponding applications will decide on the success. There are still some chal-
lenges to be solved to enable a commercial application of self-healing polymers:

• Costs – Many approaches are not based on the common commercial monomers
as well as basic chemicals, resulting in higher costs of the resulting polymers.
There is still a debate how much more expensive a self-healing material can be
compared to the financial benefit which arises from the healing ability. For
instance, the double lifetime of a self-healing polymer does not necessarily
mean that the double price will be accepted. In fact, in certain application areas,
the self-healing ability would be considered as additional asset of the next
generation, which should come to the same (or even) lower price. Therefore it
is not surprising that the current research on self-healing materials was mainly
focused on areas which are not prize sensitive, i.e., aerospace and military.
• Long-term stability/lifetime – Many research studies show that the healing is
possible multiple times. However, the calendrical lifetime is mostly neglected.
Will the material still heal after 5 years?
• Real-life applications – The section on the characterization of self-healing poly-
mers illustrated the importance for the selection of the right test/characterization
method. Within the scientific community, there is a quest for more standardized
test in order to enable a comparison of the performance of different materials.
However, real-life applications would require a testing under the specific
parameters.
• Acceptance – Interestingly, the field of self-healing polymers is easily comprehen-
sible to the general public, e.g., terminology inspired by science fiction: terminator
polymers [220]. Nevertheless, the fact that a (totally) new material was developed
might hamper the application in more conservative industrial sectors.
• Material properties – Admittedly, many of the above described examples do not
feature material properties relevant to typical applications. Future developments
are required to achieve self-healing polymers with usable properties. Particularly,
the supramolecular systems (as well as the highly reversible polymers) might
feature an inherent disadvantage. The materials will show creep under load.
• Need – In the last years, polymeric materials have developed from plastics –
sometimes synonymous used for material inferior quality – to high performance
materials challenging other material class. For instance, the new generations of
airplanes consist of >50% polymer composites as structural parts. Polymers have
superseded metals. Considering the possibilities already offered by polymers as
well as polymer composites, self-healing might currently be degenerated to a nice
add-on instead of being a real asset. However, with a broadened view, self-healing
is one aspect of smart materials. Different other properties as well as abilities
(e.g., stimuli-responsiveness, shape memory, adaptive materials) will be inherent
in the next generation of the materials we use.

Several of the above described general principles have been already utilized in
commercial systems – extrinsic as well as intrinsic self-healing polymers have been
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 703

utilized. The prime example, i.e., the capsule-based approach, has been commer-
cialized by a company providing solutions for thermosets, coatings, as well as
elastomers [221]. Hydrogen bonding self-healing polymers are offered by two
companies: Arkema [222] as well as Suprapolix [223]. Another commercial supra-
molecular polymer is the ionomer Surlyn. The healing capability after ballistic
impact is utilized in self-healing targets at shooting grounds [224].
The most common approach for commercial systems is self-healing polyurethane
coatings, which are based on a network with a relatively low glass transition
temperature. A scratch in the coating can be healed at elevated temperatures (e.g.,
warming by sunlight) due to the reflow of the material (see Fig. 22). These systems
have been commercialized by several companies, including Covestro (formerly
Bayer Material Science), Nissan, as well as Rühl. Besides the application as car
coating, also the interior of cars (e.g., wooden steering wheel) is covered with this
self-healing coating [225].

Fig. 22 Schematic representation of self-healing polyurethane coating. (a) Damage of the polymer
network leads to deformation and gentle heating the restoration of the network. (b) Initial scratch is
vanishing within few minutes. (Reprinted with permission of Covestro)
704 S. Zechel et al.

7 Conclusion and Outlook

Fifteen years ago, self-healing was introduced as a bioinspired research theme. Since
this time, researchers aimed for the design of novel materials which feature this
outstanding property. However, the comparison between natural and synthetic
polymeric materials still is in strong favor for the biological systems; nature had
several million years to perfect these materials. Nevertheless several new approaches
have been studied in the last decade, and one can expect that the development will
continue on a high level.
However, still some important challenges have to be solved. First of all the
typical problems of both approaches (extrinsic and intrinsic) are in the main focus.
Thus, the extrinsic systems will be developed toward longer stability against
cracks enabling more healing cycles. For this purpose, the vascular networks
will be of particular interest. However, a continuous flow of the healing agents
even after several cracks has to be obtained. On the other hand, the intrinsic
systems must be improved toward better mechanical properties. As it can be seen
in Table 1, the most intrinsic self-healable materials feature poor mechanical
properties with very low E-modulus values. Only the covalent systems based on
the Diels-Alder reaction reported by Wudl and coworkers resulted in high moduli
[51, 52]. Thus, the intrinsic systems and, in particular, the supramolecular mate-
rials have to focus on the combination of high mechanical stability and excellent
self-healing properties.
Furthermore, the development toward multifunctional self-healing systems will
be a major trend in the next years. Thus, the healing of functions and not only of the
mechanical properties will be advanced. Additionally, the combination of both
seems to be very promising, and some first results show the high potential of this
research topic [185]. Nevertheless, the healing of specific functions is still in its
beginning, and new general approaches will be studied in order to go the next steps
to self-healing materials.
The development of new materials goes hand in hand with their characterization.
However, a standard technique for the investigation of the self-healing phenomenon
is still not available, and each material is tested differently [198]. Thus, it is hard to
compare different types of polymers in terms of their ability to heal, but also
regarding their mechanical properties. Nevertheless, the characterization has to be
also suitable for the later application. For instance, the utilization as coating requires
scratch healing, whereas bulk healing must be tested by tensile measurements.
Therefore, the standardization of the characterization is required and further tech-
niques must be developed.
The next years will provide more self-healing materials, which are based on their
natural archetypes. Nature can still provide plenty of inspiration [226].

Acknowledgments The authors thank the Deutsche Forschungsgemeinschaft (DFG, SPP 1568)
for financial support.
16 Self-Healing Polymers: From Biological Systems to Highly Functional. . . 705

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Drug Delivery: Polymers in the
Development of Controlled Release 17
Systems

Scott Campbell and Niels Smeets

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 720
1.1 Brief Overview of Traditional Delivery Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 721
1.2 Importance of Concentration and Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
1.3 Device Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
1.4 Drug Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729
2 Polymeric Systems for Controlled Drug Release . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
2.1 Polymeric Implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
2.2 Hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
2.3 Nanomedicines: Nanoparticles, Microgels, and Micelles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740

Abstract
This chapter comprises an overview of the basic elements that one must take into
account when developing a new drug delivery system. It begins with an outline of
traditional methods to deliver drugs, relating these to important considerations
that must be taken into account when developing a drug delivery system, includ-
ing the importance of controlling the drug concentration and location, and the
properties of the device and the therapeutic. This chapter then continues by
describing various types of polymeric delivery systems, including implants,
hydrogels, and nanoparticles, microgels, and micelle nanomedicines. This chap-
ter then concludes with a brief perspective on the potential of nanomedicine drug

S. Campbell (*)
Department of Chemical Engineering, McMaster University, Hamilton, ON, Canada
e-mail: [email protected]
N. Smeets
EcoSynthetix, Burlington, ON, Canada
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 719

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_20
720 S. Campbell and N. Smeets

delivery systems; a much more thorough perspective can be found in Chap. 27,
“Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer
Systems.”

Abbreviations
BA Bioavailability
BMA Butyl methacrylate
CLRP Controlled-living free radical polymerization
CMC Carboxymethyl cellulose
DPA Hydrophobic block
DPB Hydrophilic block
EPR Enhanced permeability and retention
FDA US Food and Drug Administration
GI Gastrointestinal
HA Hyaluronic acid
IM Intramuscular
IR Infrared
IV Intravenous
MPS Mononuclear phagocyte system
NIPAM N-isopropyl acrylamide
PBA Phenyl boronic acid
PEG Poly(ethylene glycol)
PGA Poly(glycolic acid)
PLA Poly(L-lactic acid)
PLGA Poly(lactic acid-co-glycolic acid)
PMMA Poly(methyl methacrylate)
PNIPAM Poly(N-isopropyl acrylamide)
POEGMA Poly(oligoethylene glycol methacrylate)
PVA Polyvinyl alcohol
RGD Arginine-glycine-aspartic acid
SC Subcutaneous
SPIONs Superparamagnetic iron oxide nanoparticles
Tg Glass transition temperature
Z Aggregation number

1 Introduction

Achieving better control over drug release is essential to improving the effectiveness
of a wide range of therapies targeting specific ailments and diseases throughout the
body. The development of drug delivery methods that can deliver controlled,
sustained amounts of drug to specific locations while still being tolerable to the
body would drastically enhance how healthcare is provided globally. Such a release
system could improve the efficacy of the therapeutic, the safety of the treatment, the
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 721

duration of the treatment, minimize resistance to medication, patient compliance,

decrease the amount of times a treatment is administered, and eventually even be
personalized for the treatment to specific individuals [1, 2].
Advancements in the field of polymer synthesis and functionalization have
proven essential in the development of better drug delivery technologies. Indeed,
the maturation of the field of polymeric drug delivering biomaterials has led to the
improved capability in controllably producing polymers with precise molecular
weights, structures, and functionalities. This is not to say that it is solely these fields
that are linked. In fact, drug delivery as a whole is wildly multidisciplinary; the
evolution of improved controlled delivery devices has required advancements in a
wide variety of other areas of research to get to where it is today, such as biology,
imaging technologies, drug discovery, and gene therapy, to name a few. Once an
understanding of the biological response to foreign materials has been acquired, how
to maximize the effectiveness of a given drug for a specific therapy (i.e., dosage,
duration of treatment, localization, etc.) and the rate at which the drug will be
eliminated from the body (the pharmacokinetics) is established, an optimal con-
trolled release system can be designed. This is where the innovations in polymer
synthesis technologies come into play. The deft use of polymeric biomaterials can be
used to match the ideal release characteristics for a specific drug and therapy,
resulting in significant improvements over current conventional clinical methods.
This chapter highlights the use of such polymeric biomaterials as controlled drug
delivery systems that are currently commercially available or extensively researched.
This chapter first discusses the importance of knowing the characteristics of the
therapeutic intended to be released and releasing the correct amount of this thera-
peutic in the correct location for treatment. We will then delve into the types of
polymeric systems that are often used to develop drug releasing materials (polymers
in inorganic implants, micro/nanoparticles, micelles, polymeric capsules, and
hydrogels).

1.1 Brief Overview of Traditional Delivery Methods

To understand the benefits of controlled release systems, we must first briefly discuss
traditional delivery methods. The majority of drugs are intended to ultimately reside
in the blood stream, circulating systemically to perform their treatment. This lack of
localization of most drug systems is the source of the lengthy list of side effects
seen with most therapeutics, with exception to only the safest drugs. Of these
systemically delivered drugs, 90–95% are delivered either orally or injected/infused
parenterally [3].
Oral dosage forms are incredibly common as they have fairly consistent transit
times in the body, are easy to use, and are socially acceptable, leading to good patient
compliance [4]. However, oral administration is the least efficient and a highly
variable delivery mechanism as the drugs have to transit through myriad of hostile
environments on their way to being passed into the systemic blood stream. The
majority of drug absorption occurs in the small intestines, so the drugs must first pass
722 S. Campbell and N. Smeets

through the low pH and enzyme-containing environment of the stomach. The time
the drug spends in the stomach, and consequently drug absorption overall, depends
on whether the delivery system is solid or liquid (liquid forms pass through
more rapidly), the size of the delivery vehicle, and the amount of food in the stomach
[5, 6]. The drug then comes into contact with bile salts in the large intestine that can
emulsify fats or lipids to allow them to be absorbed, but ~15–20% of bile salts are
ultimately excreted as waste if this is the intended mechanism of drug absorption.
The drug then reaches the small intestine and must pass through negatively charged
mucus, which readily entraps cationic drugs, to get absorbed by the villi in the small
intestine. The absorption is facilitated by the high surface area of the villi and the
short distance between the surface of the villi and the blood capillaries that lead to
the portal vein. After all of this, the drug still has to pass through the biggest
challenge it faces to reach the blood stream, as the liver stands in the way between
the portal vein and the systemic blood stream. The liver, the metabolic engine of the
body, is able to metabolize a wide range of drugs and severely limits proteins and
peptides from being delivered in simple dosage forms [6–8]. The fact that the drugs
must pass through the liver before reaching the bloodstream is known as the hepatic
“first-pass effect,” which is the primary cause of the inefficiency and low bioavail-
ability (BA), the fraction of the administered dosage that reaches systemic circula-
tion, of oral dosage forms [4, 7].
Intravenous (IV) injections, on the other hand, are the most efficient way to get
material into the blood stream. The bioavailability for IV injections is 100%, which
allows for any drug to be delivered via this mechanism with a rapid onset of action.
There are several disadvantages to these injections: there is a risk of infection; it
presents as a shock to the system, where delivering excessive dosages is often not be
a recoverable mistake; it requires a professional; they generate medical waste; there
is a risk of disease transmission via needle reuse; and the drugs have a short half-life
in the blood stream [9]. Intramuscular (IM) and subcutaneous (SC) injections are
slightly safer in terms of the degree to which they are a shock to the system, as the
drug must diffuse through the tissue and into capillaries to reach systemic circula-
tion. This leads to a lag in the onset of action, as it accumulates in the circulatory
system at a slower pace, and bioavailabilities that are <100%. These tissues are more
acidic than most tissues, and the diffusion rate is largely dependent on the drug’s
size. Larger drugs that are less sensitive to acidic environment can exhibit slower,
more sustained release with this method.
Another delivery method that is largely dependent on diffusion is transdermal
delivery. If a drug reservoir or a topical solution is applied to the skin, the drug must
diffuse through the stratum corneum, which is the hardest layer to pass through and
the rate limiting step, the viable epidermis, and the epidermis to partition into
circulation [9]. The stratum corneum is particularly thick (10–20 μm) and most
drugs are transported on a tortuous lipidic intracellular pathway through this region
[10]. A proportion of the absorbed drug is then subject to the first-pass effect,
depending on the capillaries that the drug is absorbed into. These factors limit this
form of delivery to low molecular weight, potent drugs that can be delivered slowly
over prolonged amounts of time, which is particularly beneficial for the treatment of
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 723

chronic pain, glaucoma, hypertension, contraception, attention deficit hyperactivity

disorder, and smoking cessation, among others [10].
Buccal (inner cheek) and sublingual (under the tongue) are two common delivery
methods that take advantage of highly vascularized tissues with a relatively thin
epithelial lining [11]. These methods have high bioavailabilities with rapid onset of
action that can be comparable to injections, as administered drugs can readily diffuse
through the tissue and reach circulation via the jugular vein that avoids the first-pass
effect [10]. High bioavailabilities can be achieved via this route for small molecules
(15–70%) and, importantly, for peptides as well (<25%). Adhesive tablets, gums,
lozenges, and lingual sprays have been commercialized and used to deliver drugs
suitable for acute, patient-administered therapies, such as pain management, insom-
nia, smoking cessation, diabetes, etc. [10]. However, these tissues have low surface
areas, the region markedly limits the dosage that can be applied, and the taste can
present as a major inconvenience for the patient (particularly if long time scales are
required) [11].
Intranasal delivery has similarly high bioavailabilities to buccal and sublingual
delivery for many of the same reasons: a thin epithelial lining (even thinner than
buccal delivery) that is highly vascularized and relatively leaky in nature in com-
parison to other mucosae that can allow drugs to bypass the first-pass effect
[10, 12]. Nasal tissues also possess high surface area amenable to efficient delivery.
The primary inhibiting factor that decreases the BA via this delivery method is the
viscous, enzyme-containing mucous that coats this region. This mucous is capable of
trapping larger drugs that cannot diffuse rapidly through it. It is also highly anionic
and has a pH of 5.5–6.5, which can affect the diffusion and activity of certain drugs.
Despite this, the nasal route has proved clinically useful for peptides and small
molecules, including lypressin, progesterone, insulin, vitamin B-12, calcitonin, etc.,
as they have higher viabilities using this route (~10%) than via other strategies
(1%) [10, 12]. Small, lipophilic, nonionic drugs tend to possess greater bioavail-
abilities via this route.
The pulmonary route also possesses a large available surface area (>100 m2),
combined with an extensive blood supply with only a thin membrane separating the
air from the blood and systemic circulation; however, it is difficult to ensure that the
drug reaches this site [10]. The particles must be of an optimal size (~0.5–5 μm) to be
delivered to tissues deep within the lung with still highly variable efficiencies
between 30 and 60% in the lungs [10, 13]. Some of the drug that does reach the
site can also be trapped by the thick mucus layer that is present, which is carried by
cilia toward the trachea by what is known as the mucociliary escalator [10]. The fact
that low proportions of the drug reach the lungs leads to variable (low) BAs and
provided doses. These disadvantages have led to the focus for many pulmonary
systems being placed on the treatment of local diseases or conditions, such as
congestive obstructive pulmonary disease, asthma, and respiratory infection [10].
The last of the more common delivery routes are rectal, vaginal, or urethral. Of
these, rectal is most commonly used, often when the patient is vomiting, immobile,
unconscious, or has difficulty swallowing [10]. It is also a highly vascularized region
with few layers of epithelial cells with a mucosal layer that can trap materials similar
724 S. Campbell and N. Smeets

Table 1 Advantages and limitations of common delivery routes

Route Pros Cons
Oral Convenient Lowest BA
Consistent transit time First-pass effect, gut exposure
Good compliance No protein/peptide delivery
Most commercialized dosage
route
Intravenous 100% BA Inconvenience
(IV) injections Rapid onset of action Infection risk
Short half-life
Overdosing is a major concern – no
time to recover
Intramuscular (IM)/ Good BA Inconvenience
subcutaneous Avoids gut exposure Requires a professional
(SC) injections Slower, more sustained Infection risk
release compared to IV
Transdermal Convenience Limited to low molecular weight,
Good compliance potent drugs
Skin resistant to damage Toughest barrier
Buccal/sublingual Good BA Inconvenience – taste
Several dosage forms Limited size of drugs, device
amenable to small molecules/ Clearance by saliva
peptides Selective permeability
Avoids first-pass effect, gut Local toxicity of adhered dose
exposure
Easy to access, good
compliance
Intranasal Good BA Limited size of drugs
Quick onset of action Mucous limits types of drugs that
Avoids first-pass effect, gut can penetrate through, can clear
exposure drugs
Convenience, good Taste and sensory liability
compliance
Pulmonary Convenience Unpredictable BA
Large surface area for Limited dose, dose volume,
absorption applications
Well perfused with blood Clearance by mucociliary escalator
vessels
Rectal Better BA than oral route Inconvenient
Portion avoids first-pass Erratic absorption
effect Sociocultural stigma

to aforementioned mucosal layers. It also has a better BA than oral administration as

~50% of the drug typically bypasses the first-pass effect. Of course, this route is
inconvenient, has patient compliance issues, and sociocultural stigma and sensitiv-
ities associated with it [10].
All of these typical administration methods are outlined in Table 1 with their
primary advantages and disadvantages. Controlled release systems are designed to
overcome or alleviate many of the shortcomings listed in this table by mediating the
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 725

precise amount of drug being released once they are in the body and/or spatially
controlling where the drug is released after it is administered.

1.2 Importance of Concentration and Location

The goal of controlled release is to extend the time frame that the drug is in active use
for in a given treatment in comparison to traditional delivery techniques and to
improve the efficacy of treatment in the process [3]. For each particular treatment
type, there is a minimum drug concentration above which the drug can successfully
treat the given malady and below which the concentration is inadequate to effec-
tively treat the condition, termed the minimum effective dose. Simultaneously, there
is another concentration above which the amount of drug is toxic to the body known
as the toxic limit [14]. The range of concentrations in between the minimum
effective dose and the toxic limit is called the therapeutic window, and this is the
target region for clinical therapy. A schematic of typical drug concentrations deliv-
ered by various different methods after the time of administration is shown in Fig. 1.
Intravenous (IV) injections go directly into the blood stream with the concentra-
tion generally above the toxic limit initially. As the drug is rapidly cleared from the
blood stream (often renally, however this largely depends on size and hydrophobic-
ity of the drug), it traverses through the therapeutic region until its concentration
reaches the minimum effective dose. Extravascular delivery methods, such as oral,
pulmonary, and topical treatments take longer to be initially introduced to the blood
stream, and their concentration slowly increases until it reaches into the therapeutic
window. Once in the blood stream, the drug will be cleared in a similar manner to the
IV injections, but the rate of drug supplied to the blood stream should overcome the
rate that it is being cleared at for a short time frame before the drug concentration

Fig. 1 Representative figure of drug concentration over time for various forms of release. This
figure shows the advantage of local delivery over traditional methods: the drug’s systemic blood
concentration remains below toxic limit (upper dashed line) while persisting above the minimum
effective dose for the region (lower dashed line) for a longer period of time
726 S. Campbell and N. Smeets

plateaus, ideally still within the therapeutic window, and ultimately falls below the
minimum effective dose concentration.
Controlled release systems are often intended to slowly release drugs such that
they will slowly head into the therapeutic window, similar to extravascular drug
delivery systems, but then persist in this region by continuing to deliver drugs over a
much longer time frame while they are therapeutically effective [14, 15]. This is
possible because their controlled release capabilities allow them to be loaded with
much more drug initially and, if designed correctly, they will slowly deliver their
payload without reaching a toxic level of drug concentration. Upon the expulsion of
the majority of their payload, their release rate will dip below that of the clearance
rate of the drug from the bloodstream until the drug is no longer effective. The
pharmacokinetics of controlled release devices could allow for more effective
treatment, while lowering the frequency and number of administrations that are
required for a given treatment, which could be much more convenient for the patient
and, consequently, improve patient compliance.
These benefits could be further enhanced by advances in drug delivery technol-
ogy which have led to the development of controlled release devices with the ability
to deliver drugs in a pulsatile manner [16]. The idea for these is to be capable of a
drug release profile similar to controlled release devices initially, but then also have
the ability to deliver further pulses of release after it initially leaves the therapeutic
window, leaping the drug concentration back into the therapeutic window when
desired/required by the patient. This type of mechanism is aiming to mimic how
cells, the smartest delivery vehicles, supply growth factors, cytokines, and extracel-
lular matrix materials when necessary based on signals from their surround envi-
ronment in vivo [3]. These more advanced release systems would be particularly
relevant as replacements for treatments that require frequent injections (i.e., pain
management, diabetes) and could also allow for more personalized clinical treat-
ments where the variations in response that different individuals have to various
treatments can be offset by real-time dose management [17, 18].
Note that while Fig. 1 refers to the drugs concentration in the blood, this primarily
refers to drugs intended for systemic therapy. An analogous figure could be made for
locally focused therapy where the drug concentration in the therapeutic region of
interest is the primary consideration (and the label of the y-axis).

1.3 Device Considerations

Much of the initial commercialized controlled release work involved orally delivered
systems were improved by using advances in polymer technology to protect the drug
as it passes through the gastrointestinal (GI) tract and deliver the drug payload once it
reaches the intestines, where the drug can be absorbed into the blood stream [19]. An
example of this would be polymer-based capsules that are stable at the low pH of the
stomach and then release drug in the higher pH environment of the intestines by the
capsule degrading, dissolving, or swelling and bursting [20]. These technologies do
not stop a large portion of the drug from being metabolized in the hepatic first-pass
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 727

effect but can significantly enhance the bioavailability of the systemic drugs they are
delivering.
Greater improvements over current therapies take advantage of one of the clear
major benefits of many controlled release systems: the ability to direct delivery at a
particular, preordained site in the body. This can be achieved by two major mech-
anisms: by using a macroscale system that is implanted or injected at the specific site
of interest, such as degradable polymers or a polymer as a semi-permeable mem-
brane within a drug-loaded implant, or injectable hydrogel delivery systems; and the
use of nanoscale systems that are designed to travel through the circulatory blood
stream and accumulate in a specific location via a ligand-targeting mechanism, the
enhanced permeability and retention (EPR) effect (the theory that the extra blood
supply required by tumorous tissues results in leaky vasculature that promotes the
preferential accumulation of certain nanoparticles at these tumorous sites), and/or
externally-mediated targeting (i.e., magnetic guidance of metallic nanoparticle-poly-
meric nanocomposites). If the device can be successfully localized at the desired
location, the number of systemic side effects should be limited, the treatment could
occur over a longer time frame with any given dosage, and efficacy of treatment can
be improved by the fact that the bioavailability of the drug to the target site will be
improved [14].
Any foreign material that is placed in the body, particularly foreign materials that
are intended to remain located at a specific site for a longer length of time, will be
subjected to an immune response from the host. A key parameter in the design of
controlled release systems is minimizing this response to negate the removal of the
delivery vehicles from the body and/or the formation of a fibrous capsule that can
affect the pharmacokinetics of drug release.
For therapeutic delivery using nanoparticles that circulate in the blood stream, the
major limitation is the nonspecific uptake of the nanoparticles in healthy organs that
prevents the accumulation of enough nanoparticles at the disease site to allow for the
concentration of drug to reach therapeutic levels [21]. This is due to the mononuclear
phagocyte system (MPS), a system of largely macrophages in the liver, spleen, and
lymph nodes, sequestering nanoparticles rapidly postinjection. The cascade begins
with what is known as the opsonization of the nanoparticles, where plasma proteins
adsorb onto the surface of the nanoparticles, which can also mask targeting ligands
on the particles [22]. These proteins promote the attachment of the nanoparticles to
specific receptors on phagocytes, which then internalize the particles and transport
them to phagosomes which fuse with lysosomes. This process is vital to consider,
because if the nanotherapeutic device accumulates in alternative tissues, it can cause
undesired release and undesired effects, particularly if the drug or delivery material
is toxic in heightened quantities in the tissue it has accumulated in.
Importantly, the initial formation of the protein corona around the nanoparticles is
dependent on the nanoparticle’s size, surface charge, rheology, hydrophobicity, and
surface chemistry, which can all now be engineered fairly well due to advances in
materials and polymer science at the nanoscale. To ensure suitable circulation half-
lives for nanotherapeutic delivery systems, there size should generally range from
~5 nm to 200 nm, and particles of 50–100 nm are generally long-lasting in circula-
tion and have been shown to accumulate in tumors via the EPR effect [22]. This is
728 S. Campbell and N. Smeets

because particles <5 nm are rapidly removed from circulation via renal clearance,
and particles >200 nm are larger than the cell slits of the spleen [22]. Larger particles
2–5 μm readily accumulate in the capillaries of the lungs [10]. In terms of surface
charge, cationic materials tend to adsorb negatively charged serum proteins, leading
to nonspecific accumulation and rapid clearance from circulation. Nanoparticles
with neutral and negative surface charges have longer circulation half-lives, as
they reduce the adsorption of serum proteins, and negatively charged materials
have been shown to experience lower accumulation in the liver and spleen [21].
The rheological properties of the nanoparticles also is important, as softer, more
deformable, nanogels have been shown to experience longer circulation half-lives
and are less prone to accumulating in the spleen, as they are able to deform and
squeeze through the interendothelial slits in the spleen [22]. Highly deformable
nanogels that accumulated in the spleen were also shown to migrate back into the
circulatory system over time. Similar nanogels have been shown to deform enough
to pass through other difficult barriers in the body, such as the blood-brain barrier,
which has a cut-off of ~400–550 Da.
The hydrophobicity of the nanotherapeutic delivery system is also highly impor-
tant, with proteins attaching to anything that is not hydrophilic enough. The most
widely used method to shield nanoparticles from protein adsorption is PEGylation,
where the highly hydrophilic poly(ethylene glycol) (PEG) is densely grafted onto the
surface of the nanoparticles [22]. The PEG forms strong associations with water
molecules, forming a hydrating layer that inhibits protein adsorption. Similar hydro-
philic polymers, such as polyvinyl alcohol (PVA) and polysaccharides, can also
extend the circulation lifetime of nanoscale vehicles in a similar manner.
Macroscale devices that are injected/implanted into the body will not be rapidly
cleared from the body but face some of the same issues as nanoscale circulating
systems initially with regards to their biocompatibility. When a foreign material is
implanted/injected into the body, it disrupts the anatomic continuity of the tissues,
and the wound healing response is triggered [3]. This begins again with proteins
adhering to the surface of the biomaterial and platelet cells adhering to these attached
proteins and releasing clot-forming proteins, a stage known as hemostasis. This
initiates the inflammation stage, where cytokines are released to recruit inflammatory
cells (neutrophils, monocyte, lymphocytes, and macrophages) that initiate phagocy-
tosis, the digestion of tissue and biomaterial debris, and release growth factors
[3]. The growth factors stimulate the proliferation of cells that can recreate the
damaged tissue and may form a tight, fibrous capsule around the biomaterial, a
process known as fibrosis, effectively isolating it from the native tissues. The
thickness of the fibrous capsule is governed by extent of the foreign body response
[3]. Since this fibrous capsule can affect the kinetics of drug release and prevent the
integration of the biomaterial with host tissues, which is essential for degradable
and/or wound healing systems, limiting the extent of the inflammatory response is
often critical for delivery systems.
While one can limit protein adsorption onto these materials, as is done for
circulating nanomedicines, it is difficult to stave off protein adsorption entirely for
materials that will be present in the body for extended amounts of time. Making the
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 729

biomaterial hydrophilic and anionic rather than cationic will limit the extent of the
immune response, but the best way to limit this response as much as possible is to
mimic the native tissues as much as possible. For example, hydrogels are water-
swollen crosslinked networks of water soluble polymers that, with current polymer
engineering, are highly tunable such that they can be developed to be mechanically
and physiochemically and similar to extracellular matrix of soft tissues [23]. As a
result, many hydrogel-based biomaterials have been injected or implanted and are
well-tolerated by the body. One must consider the rheology, surface charge, hydro-
philicity, and density of the environment of treatment site and compliment these
properties as best as possible with the implanted device.
The size and shape of macroscale biomaterials and their components may influ-
ence fibrosis and other factors that may be essential to the effectiveness of a
biomaterial. For example, surface porosity has been determined to be important
parameter influencing angiogenesis in tissue engineering with the strongest angio-
genic response occurring with pore sizes of 30–40 μm, much larger than initially
believed [24]. While it was not the case for this particular biomaterial, a similar
biomaterial could be used to simultaneously release growth factors for tissue engi-
neering or wound healing. A similar finding was seen when observing how the
geometry of several materials affected the host recognition and foreign body
immune response. It was found that spherical materials, including hydrogels,
glass, stainless steel, and latex and natural polymers, were the most biocompatible,
but, notably, spheres greater than 1.5 in diameter markedly mitigated foreign
reactions and fibrosis [25]. Both of these results showed that cells seem to prefer
surprisingly large, well-contoured smooth surfaces.
Ideally, the material can also slowly degrade into nontoxic components that can
be phagocytosed and naturally removed from the body over time [21, 26]. If the
material cannot be degraded, it will ultimately be surrounded by a fibrous capsule
unless it is surgically removed prior to the formation of the capsule. Biodegradable
hydrogels can be used to entrap and hide micro- and nanoscale polymer delivery
vehicles, effectively hiding them from the immune response, improving their bio-
compatibility, while they deliver their payload until they are slowly released as the
hydrogel degrades [27]. Degradation might also generally be an important factor of
the delivery of the therapeutic if that is how the drug is released. The degradation and
subsequent release rate can be controlled by altering the chemistry by which the
material degrades in the environment conditions of the desired disease site. Many
polymeric release systems utilize enzymatic and hydrolytic degradation to either
degrade the polymer by surface erosion to slowly release the therapeutic or to
degrade a covalent link between the vehicle and the drug to control release and
limit the burst release that is often associated with diffusion-based systems [27].

1.4 Drug Considerations

While considering all of the above factors, it is important to develop the device so
that it can be easily delivered to the disease site and to match the properties of the
730 S. Campbell and N. Smeets

device with the appropriate drug for treatment to optimize the compatibility between
the two. The drug can be associated with the device via charge, hydrophilicity, or
even be covalently attached. Generally, the greater the affinity that exists between the
drug and the vehicle, the greater the loading efficiency and the cumulative drug
loaded is. Improvements in the drug-carrier compatibility can be achieved by
altering the carrier, covalently tethering the drug to the carrier, or by drug derivati-
zation, to adjust the drug’s hydrophobicity or miscibility with the carrier [28]. The
device can also be used to effectively conceal the drug from the body until it is used.
However, if the drug is attached such that it is exposed to the external environment,
the effects that this may have on protein adsorption and the biocompatibility of the
device must be considered [28].
Drug-carrier compatibility is greatly influenced by the hydrophobicity of both
components. The better these hydrophobicities match up, the easier it generally is to
load drugs into these materials. A wide range of delivery vehicles are designed to
slowly deliver hydrophobic drugs, as these are difficult to deliver via traditional
methods, particularly with any sort of spatiotemporal control. For example, hydro-
phobic drugs will preferentially partition into the hydrophobic domains of delivery
devices. These hydrophobic domains could consist of a more hydrophobic pocket or
region within a hydrogel or capsule to the hydrophobic core of nanoparticles
stabilized with a hydrophilic shell. Hydrophilic drugs can also be delivered from
delivery vehicles, but they will partition into the generally hydrophilic environment
of the body at a more rapid rate.
If ionic interactions are to be used to partner the drug with the delivery vehicle,
control of the distribution of charge in the vehicle can also influence where the drug
will preferentially be located in the vehicle. For example, distributing the charge
such that the majority of charge is located near the center of a nanogel can hide the
majority of an oppositely charged drug in the center region of the hydrogel [29].
Anionic drugs could also be loaded into similar zwitterionic nanogels with a cationic
core to hold the drug and an anionic surface to repel proteins in circulation. The
control of distribution of charge in this manner could be used for a wide variety of
systems.
When the drug is intended to diffuse out of the release device, the size of the drug
can also be an integral factor. With all other parameters constant, smaller drugs will
diffuse out more rapidly than larger drugs. The passive Fickian drug diffusion rate
can be altered by adjusting properties of polymeric carriers, such as the porosity,
hydrophilicity, average molecular weight, surface charge, and for hydrogel-like
material, crosslink density [30–32]. Particularly for hydrophobic systems, the better
the drug-carrier affinity, the slower the diffusion rate will be, as the drug will not be
as inclined to partition into the relatively hydrophilic environment of the body.
Drugs can be covalently conjugated to their delivery vehicle to slow or mediate
their release, either through a degradable linkage that will release the drug over time
or by immobilizing the drug on the surface of the vehicle, as is done for numerous
nanomedicines. For this latter scenario, the effects of immobilizing a specific drug
entity on its biological activity must also be considered [3]. For proteins in particular,
the immobilization of certain proteins to the polymeric delivery vehicle could lead to
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 731

conformational changes that expose the active portion of the protein and enhance its
activity. On the other hand, the opposite could also occur and all biological activity
might be lost. Even if the proteins could be released from their associated polymer,
their free activity may be adversely affected by the immobilization process. There-
fore, choosing the appropriate chemistry for immobilization can be critical.
The stability of the drug-carrier interaction can be critically altered in the in vivo
environment. This effect has been evident in the use of nanoparticle carriers that
carry chemotherapeutics in their hydrophobic cores, either by physical entrapment or
covalent attachment. The bioavailability of these systems to the target site is often
lower than expected not only due to less than optimal biodistribution but also
because the blood components can act as competing drug acceptors [28]. The
resulting drug leakage, where a significant amount of the drug being delivered is
released prior to the device reaching its target site, can be reduced by drug deriva-
tization to improve the drug-carrier interaction. For these systems, altering the drug’s
chemistry so that it is more hydrophobic or so that it is more miscible with the core
material have been shown to improve the drug-carrier compatibility enough to limit
drug leakage [28]. The derivatization of drugs could be used to similarly improve
drug-carrier interactions for a wide range of vehicles, provided that the activity of the
therapeutic is not negatively affected.
While tuning the characteristics of the drug and delivery vehicle are integral to
developing polymeric controlled release systems, a wide range of different types of
polymeric systems that were alluded to above, including polymeric capsules, nano-
particles, and hydrogels, can be used for these purposes. Choosing the right poly-
meric system to suit the therapeutic purpose can be highly important. In order to
make this important decision, a deep understanding of the characteristics and
synthesis of, and mechanisms of release from these different types of polymeric
systems is required.

2 Polymeric Systems for Controlled Drug Release

The diversity of tissues within the human body virtually eliminates the possibility of
a “silver bullet” for controlled drug delivery. Consequently, many different poly-
meric systems have been developed to deliver drugs in a targeted and controlled
manner to various tissues. These polymeric systems can be categorized based on
their dimensions, ranging from macroscopic (1–10 mm, e.g., polymeric implants and
contact lenses) to microscopic (1–100 μm, e.g., hydrogels) and finally nanoscopic
(1–100 nm, e.g., polymer nanoparticles, capsules, and micelles) [33]. The design of a
polymeric device to deliver a specific therapeutic to a target tissue is governed by the
nature of the tissue and the ease and method by which that tissue can be reached. For
example, polymeric implants are preferred for delivering therapeutics to the body’s
exterior organs, such as the skin and eye, or for tissues located directly under the skin
that are easily accessible using minor surgical methods. However, for cancerous
tissues or delicate internal organs such as the heart and brain, nanoparticles or
injectable hydrogels are preferred as these can be administered using minimally
732 S. Campbell and N. Smeets

invasive surgical methods such as catheters and injections which reduce patient’s
level of discomfort and the risk of infection. Irrespective of the type of polymeric
drug delivery device selected for the intended application, any device has to be
sufficiently stable under physiological conditions, biocompatible, degradable (or at
the very least clearable), and should not trigger an adverse immune response from
the host. Furthermore, the therapeutic payload should be released at the desired
location and, ideally, for a prolonged period of time with a sustained concentration
within the therapeutic window. Despite all these requirements, many successful drug
delivery devices have been developed and a selected number have found their way
into the clinical application [34]. Current developments are now moving towards
more sophisticated polymeric devices that can either autonomously respond to
queues (e.g., change in the physiological temperature or pH or the presence of
specific biomolecules) presented in vivo or respond to external stimuli (e.g., mag-
netic fields or near-infrared (IR) irradiation) to trigger on-demand release of the
therapeutic at the desired location.

2.1 Polymeric Implants

The medical community relies heavily on implantable medical devices to treat a

variety of diseases such as the vascular stent to preserve blood flow or the acetabular
cup that lines acetabulum in a hip replacement. These polymeric devices also hold
great potential for the controlled release of therapeutics and have consequently been
used, for example, for glaucoma treatment using contact lenses [35] or to treat
restenosis using drug eluding stents [36]. There is great diversity in the design,
shape, and size of polymeric implantable drug delivery devices, but essentially they
consist of a drug reservoir and a polymer matrix that the drug has to diffuse through
to become bio-available and deliver its therapeutic effect. The rate at which the drug
is released from the polymer matrix is predominantly controlled by the pore size or
void space between adjacent polymer chains that make up the matrix.
Implantable polymer drug delivery devices are generally divided into passive and
active delivery systems [37]. The principle of passive delivery systems is that release
of the therapeutic is predetermined by the choice of the materials, fabrication
methods, or drug formulation and cannot be altered once the device in implanted
in vivo. The simplest example of a passive delivery system are the earliest drug
eluding contact lenses, where the contact lens was soaked in a drug containing
eye-drop solution followed by diffusional release once applied onto the postlens tear
film [38]. More sophisticated designs are based on poly(lactic acid) (PLA), poly
(glycolic acid) (PGA), or poly(lactic acid-co-glycolic acid) (PLGA) [39], which are
US Food and Drug Administration (FDA) approved, biocompatible, and biodegrad-
able polymers. PLGA-based implants are bioerodible under physiological conditions
[40], and the rate at which they erode, and consequently release the therapeutic, can
be controlled to great extent. Conversely, active delivery systems provide a means to
control release after implantation using external stimuli, requiring an additional level
of sophistication in terms of the polymer design. For polymeric devices, this often
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 733

results in the use of responsive polymers that exhibit a physiochemical change due to
changes in the temperature or pH. Ibuprofen release was triggered externally from an
implantable device by heating the poly(methyl methacrylate (MMA)-co-butyl meth-
acrylate (BMA)) matrix above its glass transition temperature (Tg) [41, 42]. Heating
was achieved by embedding superparamagnetic iron oxide nanoparticles (SPIONs)
that can be selectively heated when placed in an alternating magnetic field. Another
example, also utilizing SPIONs, was reported where “on-demand” drug delivery was
realized by embedding temperature responsive poly(N-isopropyl acrylamide)
(PNIPAM) microgels into an ethyl cellulose membrane covering a drug depot.
Heating of the SPIONs causes a reversible discontinuous phase transition of the
PNIPAAm polymer which results in deswelling of the microgels and, consequently,
release of drug from the encapsulated depot [43].
Recent developments in the synthesis of polymeric materials, combined with
novel fabrication techniques for polymeric devices (e.g., microfluidics or 3D print-
ing), has resulted more complex and more sophisticated designs [33]. Ultimately,
it is the expectation that these complex microfabricated devices can deliver drugs
“on-demand,” by coupling sensors to measure local concentrations of bioactive
molecules and responding autonomously. Currently, this is only under clinical
investigation for implantable devices that can measure blood glucose levels and
release appropriate amounts of insulin to treat diabetes [44, 45].

2.2 Hydrogels

Hydrogels are water-swollen polymer networks that are formed as a result of

physical or chemical cross-linking of water-soluble polymers [46]. Hydrogels pos-
sess high water content, excellent biocompatibility, controllable porosity, and
mechanical and (potentially) compositional similarity to native soft tissues [47],
and have consequently been of interest for drug delivery applications [23], However,
the hydrophilicity of hydrogels combined with their high water content and high
porosity results in low affinity for hydrophobic drugs and fast release kinetics
generally ranging from a few hours to a few days [23]. Furthermore, the inherent
elasticity of these materials often necessitates surgical implantation. Successful
clinical application of hydrogels for drug delivery has yet to reach the market and
their biomedical application therefore currently remains limited to contact lenses,
hygiene products, and wound dressings [20].
Much of the foundational work on the relationship between the physical hydrogel
structure and the drug release kinetics [48] was reported on hydrogels prepared from
a “bottom-up” approach, i.e., the polymerization of water-soluble monomers and
cross-linker(s). Contact lenses are a good example of “bottom-up” hydrogels [49]
and their composition can be easily adjusted by incorporating functional monomers
to improve drug affinity and positively affect the release kinetics [38]. A particularly
promising approach is the use of functional monomers in combination with imprint-
ing to form high affinity cavities within the hydrogel matrix, as was for example
demonstrated by using methacrylic acid in combination with a timolol (cationic drug
734 S. Campbell and N. Smeets

used in glaucoma treatment) [50]. Wound dressings are another example where
“bottom-up” hydrogels are used to deliver antimicrobials, growth factors, and/or
supplements to the wound [51]. A range of hydrophilic monomers have been used to
prepare such hydrogels, often including biopolymers such as hyaluronic acid (HA),
collagen, or chitosan [51]. Similar to contact lenses, drug release in wound dressing
is also governed by molecular diffusion and faces many similar challenges in terms
of achieving prolonged drug release. The use hydrogels for in vivo drug release often
is paired with the use of poly(ethylene glycol)-based polymers and/or macro-
monomers to improve biocompatibility and mask the hydrogel from the host’s
immune system [52].
A major drawback to the use of “bottom-up” hydrogels is that their synthesis
conditions often are incompatible with in vivo conditions. Hydrogels fabricated from
a “top-down” provide a promising route towards clinical in vivo application of
hydrogels, as these materials are prepared by physical or chemical cross-linking
of presynthesized polymer chains [53–55], especially given the extensive range of
biorthogonal (click) reactions available for hydrogel synthesis [56]. Furthermore,
these hydrogels can be injected into the patient’s body (avoiding invasive surgery)
which also enables effective molding of the hydrogel shape in situ to fit existing
cavities or defects in the native tissue which increases bioavailability of the drug.
Our laboratory has reported extensively on injectable poly(oligoethylene glycol
methacrylate) (POEGMA) hydrogels for in vivo drug delivery applications
[57–60]. These hydrogels are prepared by coextruding two oppositely reactive
POEGMA polymers (i.e., a hydrazide and aldehyde functionalized polymer, which
react in a biorthogonal manner to form a reversible hydrazine bond) [61, 62] using a
double barrel syringe with a 25 gauge hypodermic needle. The “top-down” approach
provides significant advantages as the hydrogels can be easily injected subcutane-
ously [58], are fully degradable [60], and can be readily functionalized with hydro-
phobic moieties to increase affinity for hydrophobic drugs [63]. Another interesting
example is the use of oxime cross-linking chemistry [64, 65], which has been used to
deliver a PEG hydrogel to the ventricular wall of Sprague Dawley rats by means of a
catheter [66]. One major advantage of using the “top-down” approach for hydrogel
fabrication is that the resulting hydrogel networks are much more uniform [67, 68],
which is a very important physical property that ultimately controls the drug release
kinetics [52].
Current research efforts are focusing on the use of extending the use of various
biorthogonal cross-link chemistries to achieve even better control over the unifor-
mity of the hydrogel network and associated physiochemical properties such as the
mechanical strength, degradation, and release kinetics, as well as to improve the
biocompatibility of these materials during and after injection. Furthermore, there is a
lot of emphasis on “smart” hydrogels that offer the possibility of a change in drug
release kinetics as a response to a change in the environmental conditions
[23, 69]. Ultimately, it is expected that hydrogels can reach a level of sophistication
that will allow them to mimic natural systems that are able to release drugs
on-demand in a self-regulated manner [70]. Some promising first steps are being
made in this direction by fabricating hydrogels for self-regulated insulin delivery
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 735

[71, 72] and hydrogels that can self-regulate flow in microfluidic channels [73]
(which can ultimately be used to control the release rate of therapeutics). Further-
more, many of these hydrogel materials are now being further functionalized with
specific cell markers, such as the arginine-glycine-aspartic acid (RGD) peptide [57,
74, 75], to stimulate cell proliferation and tissue regeneration [76].

2.3 Nanomedicines: Nanoparticles, Microgels, and Micelles

Nanomedicine is broadly defined as the use of nanoscale or nanostructured materials

in medicine that, due to their structure, have unique medical effects [77]. In light of
this chapter, we focus on polymeric colloidal nanoscale materials including nano-
particles, microgels, and micelles. There is a lot of interest, both from academia and
industry, for drug delivery applications for these materials, accounting for roughly
75% of the research activity in the nanomedicine market [77]. The increasing interest
in these nanomedicine materials can be explained by four paradigm shifting prop-
erties [78]: (1) “scaffolds” to build upon: nanomedicines display excellent colloidal
stability, even in complex fluids like the blood, and their surface can be easily
modified with specific ligands to allow for cell-specific targeting or covalent bonding
of drugs [79]; (2) high surface to volume ratio: vitally important property for
optimizing drug loading, drug release, and colloidal interactions [78]; (3) shape:
many different shapes of nanomedicines have been fabricated (e.g., nanospheres,
nanorods, nanoshells, nanocubes, etc.) [80], which has been shown to affect cellular
uptake [81–83], where these materials accumulate in the body [84], as well as the
cellular responsive in vivo [85]; and (4) unique optical properties. Polymeric nano-
medicines, whether they are solid or porous nanoparticles, microgels, or micelles, all
display these advantageous properties.
From a biological perspective, there are additional important considerations for
nanomedicines. The success of any nanomedicine in vivo is dependent on its blood
circulation time [86]. Any foreign nanoscale material is actively removed from the
plasma by the reticuloendothelial system (macrophages) and renal filtration (urinary
excretion) [87]. Small nanoparticles (< 10 nm) [88, 89] are quickly removed by
renal filtration, which is purely size driven and controlled by the endothelial pores in
the glomerular capillaries the kidney (~8 nm). Larger particles are eliminated from
the plasma by phagocytosis, with increasing efficiency as their size increases
[90, 91]. Independent of size, any nanomedicine is first marked by opsonin proteins
(opsonization) to trigger an immune response that ultimately results in phagocytosis.
Protein adsorption increases with increase size, which in turn results in faster
macrophage uptake and elimination from circulation [92]. However, the effects of
opsonin adsorption can be reduced by imparting the nanomedicine with the ability to
evade the immune system (so-called “stealth” properties), by functionalizing the
surface with PEG (known as PEGylation) [93–95], or other hydrophilic polymers
such as PVP [96] or dextran [97]. Consequently, nanomedicines of 100 nm and
smaller are generally preferred [98], although the size may vary depending on the
target tissue. The efficacy of nanomedicines can be further improved by
736 S. Campbell and N. Smeets

functionalizing the surface with specific ligands (e.g., small molecules, polypeptides,
protein domains, antibodies, and nucleic acid-based aptamers) [99] which possess
inherent ability to direct selective binding to cell types or states and, therefore, confer
“smartness” to nanoparticles [100]. However, this may not always be necessary as
some tissues can be targeted solely by the enhanced permeability and retention
(EPR) effect [84]. Finally, the nanomedicine should be biocompatible, nontoxic,
and clearable from the body.

2.3.1 Nanoparticles
Nanoparticles have been under investigation as nanomedicines for drug delivery
since the 1970s [101, 102], when it was established that dispersions of solids
particles could be safely administered intravenously. Polymeric nanoparticles are
solid, porous, or hollow particles ranging from 20–500 nm that consist of hydro-
phobic polymers. These nanoparticles are generally fabricated using a dispersed
phase free radical polymerization techniques such as (mini)emulsion polymerization
or dispersion polymerization. The fabrication technique used for the synthesis of the
nanoparticles governs whether nanospheres (matrix-type nanomedicines) or nano-
capsules [103] (reservoir-type nanomedicines) are obtained [101]. Poly(alkyl cya-
noacrylate) nanoparticles synthesized via heterogeneous polymerization techniques
[104], for example, can be obtained as nanospheres or as nanocapsules and have
been investigated as potential nanomedicines for cancer treatment [105]. Alterna-
tively, nanoparticles can be fabricated using a solvent evaporation process, based on
the principle that a solid polymer particle forms as the solvent evaporates from a
solvent in oil emulsion. PLA and PLGA nanoparticles are typically prepared this
way [39] and have been investigated for the controlled release of therapeutics
targeting, e.g., cancer, inflammatory diseases, and cardiovascular disease [106].
An early limitation for nanoparticle drug delivery vehicles was that the polymers
used were not biocompatible nor biodegradable. Consequently, the majority of
nanoparticles are now prepared from biocompatible and/or biodegradable polymers
such as poly(alkyl cyanoacrylates) [104], poly(lactic acid-co-glycol acid) [39], or
poly(ε-caprolactone) [107, 108]. Furthermore, these hydrophobic nanoparticles are
prone to opsonization and require modification of their surface with hydrophilic
polymers such as dextran [109] and PEG [110]. As a result, PEG-PLGA nano-
particles have become the benchmark polymer nanoparticles for drug delivery
applications [39]. Often PEG-PLGA nanoparticles are further modified with specific
cell targeting ligands such as lectins [111] or folic acid/folate [112, 113] to increase
their targeting efficacy. Another important consideration is the drug loading and drug
release kinetics. Drug loading of solid nanoparticles (i.e., matrix-type nano-
medicines) is hampered by slow diffusion of the drug into the matrix. One potential
strategy circumventing slow diffusion is by preparing the nanoparticles in the
presence of drug, a process referred to as molecular imprinting [114]. For example,
poly(methyl methacrylate-co-methacrylic acid) nanoparticles were imprinted with
paclitaxel, which resulted in a 12 times higher drug affinity and slow controlled
release kinetics when compared to conventional nanoparticles [115]. Naturally, it is
important that the drug molecule is not altered or degraded by the polymerization
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 737

chemistry. Reservoir-type nanoparticles are generally loaded during the solvent

evaporation process or interfacial polymerization [116], which alleviates potential
chemical modification or degradation of the drug [117]. This was shown by the
group of Vauthier [118], who demonstrated that poly(isobutylcyanoacrylate) nano-
capsules formed by interfacial polymerization did not affect insulin and the insulin-
loaded nanocapsules induced a reduction of the glycemia to normal levels in
steptozotocin diabetic rats. Ultimately, the release kinetics is governed by the
diffusion of the drug through the polymer particle or capsule wall. However,
degradable polymers (such as PLA or PLGA) erode which may have beneficial
results for the release kinetics [39].
Although many nanoparticle-based nanomedicines have been investigated for a
broad range of illnesses, currently available nanoparticle nanomedicines have not
been able to improve the activity of a great number of drugs [101]. Generally,
nanoparticles suffer from poor drug loading (usually less than 5% by weight),
which results in low effective doses insufficient to reach the pharmacologically
active concentration, or substantial amounts of polymer that may cause inflammation
or other toxicological effects. Furthermore, the drug release kinetics are generally
too fast (i.e., “burst release”), which causes leaching of the drug prior to reaching the
target tissue, a small pharmacologically active window, or substantial side effects if
the drug concentration exceed the toxic threshold [101].

2.3.2 Microgels
Microgels are water-swollen discrete particles ranging from 20 nm to 50 μm that
consist of cross-linked water-soluble polymers [119]. Microgels have been widely
recognized for their potential as a nanomedicine for drug delivery, largely due to ease
with which responsiveness stimuli can be incorporated into their design
[120–122]. Such responsive microgels (also referred to as “smart” microgels) are
generally synthesized through free radical precipitation polymerization [123],
although many other synthetic routes have been reported (e.g., inverse miniemulsion
polymerization [124], polymerization-induced self-assembly [125], or the use of
covalent dynamic bonds [126]). Temperature responsive microgels are most com-
monly used for drug delivery applications as these microgels can undergo a distinct
shrinking response, which causes the microgel to deswell and expel water (and other
molecules such as drugs) from their interior.
Microgels offer many advantages as a nanomedicine “scaffolds” as these particles
can be fabricated over a broad size range and with excellent control over the
morphology, internal structure [127, 128], and distribution of functionality
[29]. These properties are particularly important as both the swelling/shrinking
responses of microgels as well as the drug release kinetics are governed by
the homogeneity of the microgel structure [29, 127]. Furthermore, desired function-
alities for drug complexation, chemoligation for cell-specific targeting and internal-
ization, or PEGylation can be readily introduced into the microgel structure during
synthesis [29]. From a biological perspective, microgels are highly hydrophilic and
have low interfacial energy which reduces opsonization and increases bioavailability
and biocompatibility. These materials are also highly deformable [129] which may
738 S. Campbell and N. Smeets

make these materials excellent candidates for drug delivery that require crossing
tight junction barriers such as the blood brain barrier [130]. The potential for drug
delivery comes from the high void fraction and the potential to load relatively high
amounts of drugs, released under sustained or burst kinetics. The stimuli respon-
siveness and the ability to release drugs on-demand, as was mentioned earlier, is
probably the main reason why microgels have generated the significant amount of
academic interest we see today.
However, despite the many advantages that microgels offer as nanomedicines and
the maturity of the microgel field from a chemistry point of view, no microgel-based
drug delivery therapies are currently in clinical trials [131]. Furthermore, even in
academia relatively few microgel drug delivery vehicles are designed and tested
specifically for in vivo applications [34, 46]. Clinical application of microgels is in
part hampered by the toxicity of the monomers that are used for their synthesis (often
N-isopropylacrylamide (NIPAM) which is a neurotoxin) and the fact that elaborate
chemistry is required to render microgels degradable (obviously this only holds true
for synthetic microgels). Furthermore, there is currently no solid understanding how
the phase transitions observed in vitro correlate to those in vivo once the microgels
are subjected to the inherent complexity blood and both intercellular and intracellu-
lar environments [120]. A minor shift of these transitions has the potential to
completely alter the predetermined release kinetics. Finally, further improvement
over the release kinetics of hydrophobic drugs is required to provide microgels with
the ability to offer prolonged drug release capability. The use of covalently bound
drugs which are released based on degradation of the microgel or in response to a
change in the environmental conditions provides a step in the right direction [16].

2.3.3 Micelles
Amphiphilic block-copolymers consisting of a hydrophilic and a hydrophobic
block assemble in water to form micelles ranging from 10 to 100 nm. The advent
of controlled-living free radical polymerization (CLRP) [132] in the early 2000s
has greatly simplified polymer synthesis and enabled the design of amphiphilic
block-copolymers with excellent control over the number-average molecular
weight, dispersity, and the relatively length of the respective blocks. The latter is
especially important as the ratio of the degree of polymerization of the hydrophobic
block (DPA) and the degree of polymerization of the hydrophilic block (DPB)
governs the aggregation number (Z ) as well as the critical micelle concentration
(CMC) [133]. The significant interest in micelles for drug delivery applications
arises from their particle morphology, consisting of a hydrophobic core that offers
loading of hydrophobic drugs surrounded by a water-swollen hydrophilic shell that
offers colloidal stability and masks the particle from the host’s immune system
[134, 135].
The effectiveness of micelles as nanomedicines arises from the extent to which
distribution and temporal control can be achieved [136]. The excellent control over
the molecular weight and block length ratios result in excellent control over the size
and the morphology of the micelle. Furthermore, the low polydispersity of the
17 Drug Delivery: Polymers in the Development of Controlled Release Systems 739

block-copolymers translates into micelles with a very narrow size distribution.

These size aspects are very important as they control both the blood circulation
time and the biodistribution [84], especially when the EPR effect is used as the
mode of targeting. The CLRP chemistries used to prepare the block-copolymers
offers additional advantage that the functional chain ends can be used to couple cell
targeting ligands [137, 138], such as aptamers onto the surface of the micelle [139,
140]. This modification in particular has made micellar nanomedicines a promising
tool for intercellular drug delivery [141]. Many of the current research efforts are
focused on achieving improved temporal control over drug delivery, exploiting
responsive block-copolymers that assemble into micelles able to release their
payload once exposed stimuli that are unique to the diseased tissue or the
intercellular environment that is targeted [142, 143]. Intercellular drug delivery
can be triggered through the presence of increased concentrations of certain bio-
molecules or existing pH gradients, whereas drug release in cancerous tissue can be
triggered through the slightly acidic pH (~6.8) or the abnormal temperature of
cancerous tissues [144]. Regardless of the stimuli, the physical (e.g., cloud point
transition) or chemical change (e.g., protonation/deprotonation) that occurs affects
the solubility of the hydrophilic block, causing the micelle to accumulate, disas-
semble, and release its payload. Alternative approaches focus on the use of phenyl
boronic acid (PBA)-modified micelles that are glucose-responsive for the release of
insulin [145, 146] or the disulfide cross-linked micelles that can be disassembled in
the presence of glutathione [147–149].
Although micelle-based nanomedicines have, most probably, been established
the most promising drug delivery vehicles, due to the great synthetic versatility that
can be achieved within their design, clinical application of micelle-based formula-
tions is largely limited to PEG-PLA based systems. This is largely due to the fact that
many of the more advanced micellar designs contain block-copolymers that are not
yet FDA approved and often require multistep synthesis to be prepared. Further-
more, assembly and long-term stability of these micelles is based on their CMC.
Once injected into the bloodstream, the micelles are diluted to the point where the
concentration of their components could fall below the CMC, causing the micelles to
disassemble and release their payload before the target tissue is reached. Although it
should be noted that this can be largely avoided by synthesizing cross-linked
micelles [150].

2.3.4 The Overall Potential of Nanomedicines

Nanomedicines offer enormous potential for clinicians to improve the outcome of
treatment (e.g., higher therapeutic index due to localization in the diseased tissue) as
well as the quality of treatment (e.g., nonsurgical administration, lower doses reduce
unwanted side-effects). However, complete understanding of the relationship
between the physiochemical properties of nanomedicines (size, shape, surface
chemistry, targeting ligands) and their biological properties (circulation time,
immune response, biodistribution, penetration of tissues) will be necessary before
nanomedicine-based therapies will become commonplace.
740 S. Campbell and N. Smeets

3 Conclusions

The development of strategies capable of improved control of drug release could

drastically advance patient safety and outcomes, and the healthcare system overall.
Prior to the development of novel controlled release strategies, it is important to
consider the properties of the drug, the optimal location of release, and the desired
release rate of the drug to achieve the intended outcome. This chapter briefly
discussed these important considerations, as well as the wide array of potential
delivery routes of a drug or drug delivery system and various general methodologies
to produce polymeric systems (from macroscale implants to nanomedicines) that can
be utilized for drug release. It is of extreme importance to complement a potential
controlled delivery device with the drug characteristics, route of delivery, and
location of release. In many cases, the best method may be to localize the delivery
to a specific local in the body to simplify the process.
▶ Chap. 27, “Drug Delivery: Localized and Systemic Therapeutic Strategies with
Polymer Systems” will build on the ideas that were introduced in this chapter to
concentrate on a variety of strategies for localized delivery to various regions in the
body and the systemic delivery of nanomedicines for the treatment of cancer. This
chapter will conclude with a perspective on the direction that the drug delivery field
could trend towards in the near future and highlights the major challenges that must
be overcome to effectively transition more controlled delivery systems from the
benchtop to the clinic.

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Conjugated Organic Polymers for
Optoelectronic Devices 18
Shahid Pervez Ansari and Farman Ali

Contents
1 Organic Molecules in Optoelectronic Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750
2 Benefits of OLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
3 Electronic Structure of Conjugated Organic Molecules and Luminescence . . . . . . . . . . . . . 752
4 Energy Transfer in Guest-Host Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 753
5 Working of an OLED . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754
6 Materials for OLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 756
6.1 Anode Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 756
6.2 Hole Injection Materials (HIM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
6.3 Hole Transport Layer (HTL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
6.4 Electron Transport Layer (ETL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758
6.5 Cathode Interfacial Materials (CIM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758
6.6 Cathode Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
6.7 Light-Emitting Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
7 Performance Parameters of OLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
8 Conjugated Polymers in LED . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
9 Chemical Synthesis of Optoelectronic Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
9.1 Soluble Precursor Route . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
9.2 Dehydrohalogenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762
9.3 Transition Metal-Catalyzed Coupling Polymerizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
9.4 Condensation Polymerizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
10 Blue, Green, Red, and White Light-Emitting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
10.1 Blue-Emitting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
10.2 Green-Emitting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773
10.3 Red-Emitting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 776
10.4 White Light-Emitting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
11 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 782
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 782

S. P. Ansari · F. Ali (*)

Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim
University, Aligarh, India
e-mail: [email protected]; [email protected]; [email protected]

© Springer Nature Switzerland AG 2019 749

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_21
750 S. P. Ansari and F. Ali

Abstract
Organic Light-Emitting Devices (OLEDs) have received much attention in the
past two decades. The possibility of cost effective production of large area
devices is the main attraction for doing research in this area. There has been a
considerable progress in the development of materials and the device engineering
for improving the efficiency of OLEDs. These significant developments have
resulted in their commercialization. In this chapter we describe OLEDs. We
discuss their working principles and the measurements that are normally made
in these devices. We also discuss the different types of conjugated polymers
which are used for specific purposes in these devices.

Keywords
Electroluminescence · Conjugated polymers · OLEDs · PLEDs

1 Organic Molecules in Optoelectronic Devices

Optoelectronic devices have been the focus of investigation in physics and chemistry
for more than 50 years. The electroluminescence (EL) was first observed by
Bernanose in 1950s, where he applied a high-voltage alternating current (ac) field
to the crystalline thin films of acridine orange and quinacrine [1, 2]. Pope and his
co-workers demonstrated the direct current (dc) driven EL using a single crystal of
anthracene [3]. In the initial stages of development organic EL devices, the driving
voltage was as high as 100 V in order to obtain significant light output [4–6].
A significant decrease in the operating voltage (~30 V) was observed with thermally
evaporated film of anthracene [7]. Optoelectronic properties were studied mainly in
the academic institutions due to low efficiency of these devices. The breakthrough in
EL efficiency was first observed by C. W. Tang and Vanslyke at Eastman Kodak
Research Laboratories (USA) by making a bilayer device [8]. This demonstration
highlighted the potential of using organic thin films for a new generation of opto-
electronic devices.
The motivation for doing research in organic-based optoelectronic devices comes
from the possible cost-effective production of large area devices. Also the physical
and chemical properties of organic molecules can be tailored according to the
requirement of application by modifying the molecular structure. For example,
color of emission of organic molecules can be adjusted by increasing or decreasing
the pi electron conjugation. The synthesis of a large number of new organic
molecules with the desired colors was reported, which emit different colors with
good quantum yield. They are promising materials for multicolor displays and
flexible devices.
Organic thin films have found to be useful in a number of applications, which are
now getting commercialized [9, 10]. Organic light-emitting device (OLED) is the
most successful application. Significant progresses have also been made in the thin
film transistors and the organic solar cells. Organic light-emitting transistors and
18 Conjugated Organic Polymers for Optoelectronic Devices 751

Table 1 History of major developments in OLEDs

Discoveries and
S. No. developments Year References
1. Blue light emission 1953 A.B. Bermose, M. Comte, P. Vouaux, Blue
from LED on Li emission from LED based on lithium complex,
complex J. Chem. Phys. 50 (1953) 64–69 (in French)
2. EL reported in 1963 M. Pope, H. Knllmann, P. Magnante,
anthracene crystals Electroluminescence in organic crystals, J. Chem.
Phys. 38 (1963) 2042–2043
3. EL reported in tetracene 1976 J. Kalinowski, J. God lewski, R. Singnerski,
Electroluminescence in tetracene crystals, Mol.
Cryst. Liq. Cryst. 33 (1976) 247–259
4. EL reported in PVK 1983 R.H Partridge, Electroluminescence from
polymer polyvinylcarbazole films, Polymer. 24 (1983)
733–762
5. Double layered OLED 1987 Tang, Van Slyke, U.S. Patent (1979) 4,164,431.
U.S. Patent (1982) 4,356,429. Van Slyke, Organic
electroluminescent diodes. 51 (1987) 913–915
6. Single layered PLED 1990 R.H. Friends, J.H. Burroughes, D. Bardleywo,
U.S. Patent 90/13148(1990)
7. Double layered PLED 1993 N.C. Greenham, R.H. Friend, in Solid state physics
(Academic, New York/London 1995), pp. 2–150
8. Flexible OLED 2007 M. Hack, R. Hewitt, K. Urbanik, A. Chwang,
technology J.J. Brown, Full colour top emission AMOLED
displays on flexible metal foil, in Proceedings of
IMID/IDMC’06, Gigest conference (Daegu, 2006),
pp. 305–307

photodetectors have also attracted attention [11, 12]. We may also see organic
materials in many more applications such as lasers, super capacitors, and memories
in future [13].
This brief overview of organic electronics is not a comprehensive review of the
entire field. Rather, it is intended to justify the current enthusiasm in exploring
organic materials for various applications. In the latter sections of this chapter, we
will describe concepts which will be useful to understand conjugated organic poly-
mers for various applications. We will review the development of new conjugated
polymers for OLEDs. A glance of discoveries in OLEDs are given in Table 1.

2 Benefits of OLEDs

The energy policies of present encourage maximum energy saving technologies.

OLEDs are very competent in the light of these policies. OLEDs possess many
advantages compared to both LCDs and LEDs, some of these are listed below [14]

• OLEDs are highly economical.

• OLEDs offer flexibility of processing.
752 S. P. Ansari and F. Ali

• OLEDs provide a greater range of colors and brightness.

• OLEDs also offer color tuning.
• OLEDs possess high energy saving potential.
• OLEDs are Mercury-free.
• OLEDs possess high luminous efficiency.

3 Electronic Structure of Conjugated Organic Molecules

and Luminescence

The conjugated organic molecules are used in organic electronics. These organic
molecules have π-bonds in an alternate fashion. The overlap of atomic pz orbital
leads to the formation of π-bond. The π-electrons in conjugated organic molecules
are delocalized throughout the molecular backbone. Figure 1 shows a schematic of
π-conjugated molecules.
A π-bond is formed after the σ-bond. The electrons in the π-molecular orbitals have
higher energy than the electrons in σ-orbitals. Therefore the highest occupied molec-
ular orbital (HOMO) is a π-molecular orbital in conjugated molecules. The ground
state of molecules is a singlet as the number of π-electrons in the HOMO is even. It is
these π-electrons in HOMO which participate in electronic transitions. The various
photophysical processes, absorption, and emission of light in a conjugated organic
molecule can be explained with the help of Jablonski diagram (Fig. 2). The HOMO of
the molecule has two electrons with paired spin in the ground state and this state is
shown as S0. When an electron is promoted from HOMO to the lowest unoccupied
molecular orbital (LUMO), it becomes the excited state of the molecule. In the excited
state, the electron in the LUMO can have its spin paired or unpaired with the spin of
the electron in the HOMO. Thus the excited state of the molecule can be singlet (S1) or
triplet (T1). The radiative electronic transitions from S1 to S0 and T1 to S0 are known
as fluorescence and phosphorescence, respectively. The non-radiative transition
between the states of same spin multiplicity like S1 to S0 is known as internal
conversion (IC). Intersystem crossing (ISC) is a non-radiative transition between the
states of different multiplicity. Figure 2 also shows the typical time scale for these

Fig. 1 π-conjugated
molecules; formation of
π-bond occurs due to the
overlap of atomic pz orbitals
18 Conjugated Organic Polymers for Optoelectronic Devices 753

Fig. 2 Jablonski diagram of

energy levels in π-conjugated
organic molecule
IC
ISC

ISC

processes. The intensity of molecular fluorescence or phosphorescence is a conse-

quence of interplay between different processes. The band gap in organic molecules
depends upon the extent of π-electrons delocalization. The band gap may vary
between 1 and 4 eV. Thus, depending upon the band gap the organic molecules
may absorb and emit photons anywhere from near-infrared to near-UV region.
For emission to occur, the molecule needs to be in electronically excited state.
One way of getting the excited state of a molecule is by absorption of light. The
excited state can also be formed by a simple electron transfer reaction between anion
and cation radical pair. This principle is used to obtain the chemiluminescence [15]
and electrochemiluminescence [16] in solutions. The physical movement of cation
and anion radicals in a solvent medium is important to form the excited state of
molecules. Light emitting electrochemical cells using gels and polymers [17] are
gaining attention but cells using liquids are less attractive for practical applications.
A solid state analogue of this process is OLED. In OLEDs, the electrons and holes
are pumped in to the LUMO and HOMO levels, respectively, to form the excited
state. These electrons and holes then recombine to give electroluminescence.

4 Energy Transfer in Guest-Host Systems

Energy transfer from host donors to guest acceptors via Forster/Dexter mechanism is
utilized to tune the color of emission and improve efficiency in OLEDs. Forster
energy transfer is a long-range mechanism (up to ~10 nm) due to dipole-dipole
coupling between donor and acceptor [18]. Dexter energy transfer is a short-range
mechanism (typically ~1 nm) and it involves intermolecular electron exchange
process [18]. Energy transfer from singlet to singlet can either be Forster or Dexter
or involve both mechanisms. The triplet-triplet energy transfer is always through
Dexter mechanism only. Figure 3 shows the schematic of light emission processes
and energy transfer in guest-host systems of phosphorescent emitting layer in
OLEDs.
754 S. P. Ansari and F. Ali

Fig. 3 Schematic of energy Energy transfer

transfer and light-emission S1
processes in host-guest S1
systems in phosphorescent T1
OLEDs
ISC
Energy transfer T1

Phosphorescence
S0
S0
Host Guest

Hole Electron
transport transport
layer layer
Cathode

Cathode LUMO
LUMO
Anode
Anode HOMO HOMO

Luminescent
guest molecules

Fig. 4 (a) Schematic diagram of a single layer OLED, and (b) bilayer OLED. Hole transporting
layer is a diamine and electron transporting layer is Alq3

5 Working of an OLED

The electrical energy is converted into light energy in an OLED. Figure 4a shows the
schematic energy level diagram of the single layer OLED. Cathode and anode injects
electrons and holes into the LUMO and HOMO of organic thin film, respectively.
These injected electrons and holes move towards each other under the influence of
applied electric field and when they meet on to the same organic molecule, that is,
hole in the HOMO and electron in LUMO, it becomes the excited state of organic
molecule. The excited state may diffuse to other molecules if it is long lived (e.g.,
triplet), and its properties are conserved during the diffusion. In other words, the
excitation of organic molecule behaves like a quasi-particle and this is termed as an
exciton. The exciton binding energy in organic molecules is of the order of
0.5–1.0 eV [19]. The electron and hole in the excited molecule may recombine
radiatively by emitting a photon. The emission so obtained is called electrolumines-
cence (EL). The energy of the emitted photon depends on the band gap energy of the
excited organic molecule.
18 Conjugated Organic Polymers for Optoelectronic Devices 755

The recombination of injected electrons and holes gives high electroluminescence

efficiency in OLED. In case the injected carriers do not meet each other than the EL
efficiency of OLED is less or even zero. In organic molecules, the mobility values of
electron and hole are very different. As a result, one of the injected carriers (e.g.,
hole) moves faster than the other carrier (e.g., electron) and reaches the opposite
electrode without recombination. This is normally the case in single-layer device. An
efficient strategy to prevent the leakage of injected carriers was first demonstrated by
Tang and Vanslyke in 1987 [8]. They fabricated a bilayer device with hole transport
layer (HTL) and electron transport layer (ETL). Figure 4b shows the schematic
energy level diagram of a bilayer device. In this device, diamine functions as HTL
and tris(8-hydroxyquinolinato) Al(III) (Alq3) as a ETL. The injected carriers move
towards the diamine/Alq3 interface and are not able to cross over the interface
because of high energy barrier. They pile up at the interface and form the molecular
excitons which emit light. The interface may also be doped with other low band gap
guest molecules for harvesting the excitons [20]. The other advantage of this bilayer
structure is that excitons are formed away from the conductive contacts which are
known to quench the excitons. This particular demonstration has highlighted the
importance of using multilayer architectures in order to improve the EL efficiency of
the OLEDs. Nowadays, functionally distinct organic layers such as hole inducing
(HIL), hole transporting (HTL), hole blocking (HBL), electron transporting (ETL),
electron blocking (EBL), emissive layers, etc. are used in OLEDs to improve the
overall EL efficiency [21]. Table 2 shows the different components of a multilayer
OLED. Figure 5 shows the schematic of a multilayer OLED. It also shows the

Table 2 The different components of a multilayer OLED, their function and representative
examples
S. No Component Functions/properties Materials
1. Substrate Provides support for PLED Glass/plastic foil
2. Anode A transparent anode with good Indium tin oxide
electrical conductivity, high work
function suitable for hole injection
in HOMO of organic layer
3. Hole Smooth surface over ITO, supports PEDOT:PSS, PVK, cross-linked
Transport efficient hole injection by reducing conjugated polymers
Layer energy barriers in case of red-green
(HTL) emitting polymers
4. Emissive Light emitting polymers PPV, MEH-PPV, CN-PPV,
Layer Derivatives of Polythiophene,
(EML) Polyfluorenes, poly
(1,4-phenylenes) etc.
5. Electron Provides balanced injection of 1,3,4 Oxadiazole
Transport charge carriers
Layer
(ETL)
6. Cathode Facilitates electron injection in Li, Ba, Ca, Al etc
polymeric materials
756 S. P. Ansari and F. Ali

Al -2.30
LiF (1nm) -2.80 e-
BCP (6nm) -3.0 LiF/Al N
EBL N
P2NHC (40nm) & BCP
TPD (40nm) ITO h+ HTL ETL
F4TCNQ (3nm) & N

ITO -5.24 -5.40 HBL

-5.0 N
glass
TPD -5.74 TPD
HIL -6.5
ITO : transparent electrode (anode) P2NHC
BCP
HTL : hole transporting layer NC CN
EL : emissive layer F F
HBL : hole blocking layer F F
ETL : electron transport layer -8.34 NC CN
Al : aluminium (cathode) F4TCNQ F4TCNQ

Fig. 5 The schematic of an high efficiency multilayer structure OLED, its corresponding schematic
energy level diagram, and the molecular structure of the molecules used

schematic energy level diagram and the molecular structure of the organic molecules
performing different functions.
The multilayer OLED is complete in all functional aspects. It has 2,3,5,6-
Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ)/N,N0 -diphenyl-N,N0 -
bis(3-methylphenyl)-1,10 -biphenyl-4,40 diamine (TPD) at the anode which effi-
ciently injects and transports holes and 4,7-diphenyl-1,10-phenanthroline
(BCP)/LiF/Al as a composite cathode which injects and transports electrons to
the P2NHC (emissive layer). TPD and BCP layers also separate the emissive
layer from the anode and cathode, respectively, as a result of which the electro-
luminescence of 3,6-dipyrenyl-N-hexylcarbazole (P2NHC) does not get
quenched due to electrodes. TPD and BCP layers also confine the injected
electrons and holes in the P2NHC layer. The device exhibit high electrolumi-
nescence efficiency at low turn-on field due to efficient hole and electron
injection accompanied by exciton formation and radiative recombination.
In the later sections we discuss functionally distinct organic layers which are used
in the high efficiency OLED.

6 Materials for OLEDs

6.1 Anode Materials

The function of anode is to inject holes into the HOMO level of organic molecules
and therefore high work function materials are desirable for efficient injection of
holes into the HOMO level. Indium Tin Oxide (ITO) coated on glass is the most
popular anode material because it has the following advantages: (a) transparent in
18 Conjugated Organic Polymers for Optoelectronic Devices 757

the visible region, (b) can make “contact” with the organic molecules, and (c) high
work function for efficient hole injection. The work function of ITO is typically
4.5 eV, which can be increased up to 5.1 eV by UV ozone treatment [9]. The other
materials which can be used for the anode, besides ITO, are Poly (3,4-ethylene
dioxy-2,4-thiophen)-polystyrene sulfonate (PEDOT:PSS) [22], noble metals like
gold and platinum [23]. PEDOT:PSS is a conducting polymer and its thin films
are transparent to the visible spectrum. Thin films (<1 nm) of gold and platinum
are also transparent to the visible spectrum. The work function of gold and
platinum are 5.1 eV and 5.6 eV, respectively [9].

6.2 Hole Injection Materials (HIM)

An efficient OLED requires a multilayer device architecture, therefore the interfacial

structure at the organic-metal and organic-organic interfaces play an important role in
devices. A thin film (~1–2 nm) of HIL acts as an interface connection layer between
the anode and the HTL. It improves the film forming property and facilitates efficient
hole injection from anode to the HTL [24]. As a result, the operational voltage
decreases and less amount of heat is generated inside the device. The frequently
used HILs are PEDOT:PSS, copper phthalocyanine (CuPc), or various inorganic
buffer layers like TiO2 [25]. CuPc layer on ITO has proved to be an effective HIL
[23]. PSS-rich PEDOT:PSS was also used as HIL [23]. The exact mechanism of
“modification” by PEDOT:PSS is still unclear but the most accepted one is the
creation of interfacial dipoles on surface of PEDOT:PSS that helps the injection of
holes to the HTL [26]. The surface of bare ITO is undesirably rough and spikes on
bare ITO normally shunt the device. Coating of ITO with PEDOT:PSS layer helps to
avoid these problems. However, the commercially available PEDOT:PSS solutions
have unpredictable short shelf-life (nearly 6 month). An electron acceptor molecule
(F4TCNQ) is also used as HIL on ITO anode [23]. More recently, inorganic com-
pounds like ZnO have also been used as thin buffer layer between ITO and HTL [27].

6.3 Hole Transport Layer (HTL)

The use of HTL with thickness (40–100 nm) on top of ITO with or without HIL
serves the following functions: (a) gives an interface with the emissive layer
(b) provides energy barrier for electron and confines them to the emissive layer,
and (c) transport holes to the emissive layer for the exciton formation.
The general requirements for organic molecules to be used in as HTL are: (a) high
hole mobility, (b) their HOMO level in the thin film should be close to the work
function of the anode in order to facilitate easier hole injection, (c) high glass transition
temperature, (d) high stability of its cation radical, and (e) large optical band gap in
order to avoid the absorption of visible light as emitted by the emissive layer.
The frequently used small molecules in HTL are N,N0 -diphenyl-N,N0 -bis
(3-methylphenyl)-1,10 -biphenyl-4,40 diamine (TPD), N,N0 -diphenyl-N,N0 -bis
758 S. P. Ansari and F. Ali

O O

N
S n n
n n
N C8H17 C8H17

n N N
SO3–

PEDOT:PSSPVK Poly-TPD PFN

Fig. 6 Molecular structure of polymers used at the interfaces in OLEDs

(1-naphtylphenyl)-1,10 -biphenyl-4,40 -diamine (NPD), and copper phthalocyanine

(CuPc). The polymers used as HTL are PEDOT:PSS, poly-N-vinylcarbazole
(PVK), poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), etc. [23, 28] (Fig. 6).
The mobility values for holes in small molecules TPD and NPD are 2  103 and
3  104 cm2 V1 s1, respectively [9]. The mobility values for holes in polymers
PVK and poly-TPD are 2.5  106 and 1  104 cm2 V1 s1, respectively. These
molecules have low electron affinity (2–2.5 eV), and hence they also function as
electron blocking layer.

6.4 Electron Transport Layer (ETL)

The use of ETL with thickness (~6–10 nm) between the emissive layer and cathode
facilitates electron injection during the device operation. The ETL also helps to
confine holes within the emissive layer due to its large work function. The general
requirements for organic molecules to be used as an electron transporting layer are:
(a) the energy of LUMO level is close to the work function of cathode for easier
electron injection, (b) high mobility values for electrons for efficient transport into
the emissive layer, (c) high glass transition temperature, (d) high stability of anion
radical, and (e) large optical band.
The frequently used small molecules in ETL are tris(8-hydroxyquinolinato) Al
(III) (Alq3), 4,7-diphenyl-1,10-phenanthroline (BCP), 2,9-dimethyl-4,7-diphenyl-
1,10-phenanthroline (Bphen), 1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene
(TPBI), and Oxidazole derivatives [9]. The mobility value of electron in Alq3 is
1.4  106 cm2 V1 cm1 [9] and hole is 2  108 cm2 V1 s1 [9]. The value
electron mobility of BCP and Bphen is in the order of 105 cm2 V1 s1 [29].

6.5 Cathode Interfacial Materials (CIM)

The electron injection from the cathode can be improved by decreasing the work
function of cathode. The use of a thin layer (~1 nm) of a CIM in contact with the
cathode decreases the work function of the cathode (e.g., Al) and facilitates electron
injection. The popular materials used in CIF are LiF, CsF, and Li2O [23]. The barrier
to electron injection has been shown to decrease by 0.4 eV in the case of Alq3/LiF/Al
18 Conjugated Organic Polymers for Optoelectronic Devices 759

than Alq3/Al [30]. The mechanism of lowering in work function using CIM is
debated. It was speculated that free Li atoms are formed at the Alq3/LiF/Al interface,
which in turn forms Alq3 anion [31]. However, the use of CIM along with Al
(4.2 eV) is equivalent to using low work function cathodes like Ca (2.87 eV) and
Mg (3.66 eV) [9]. Water/alcohol soluble conjugated polymers poly [(9,9-bis(30 -(N,
N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9–dioctylfluorene)] (PFN) have
also been used as a cathode interfacial layer in organic devices [32].

6.6 Cathode Materials

The function of cathode is to supply electrons into the LUMO. The requirements for
cathode materials are as follows: (a) low work function to facilitate efficient electron
injection into the LUMO, (b) wetting properties to ensure good contact with adjacent
organic layers, (c) stable to ensure long lifetime of device, and (d) transparent when
used in “top-emitting” OLEDs.
The most popular cathode material is Al (4.2 eV). The other materials which are
commonly used for cathode are LiF/Al (3.6–3.8 eV), Ca/Al, Mg/Ag (2.9 eV), and
Ba/Al (2.6 eV) [21, 23]. Very low work function materials such as Cs, Ca, etc. need
to be capped with another stable metal film such as Al, Ag to avoid oxidation.

6.7 Light-Emitting Materials

The material that gets the most value in OLED is the one used in emissive layer. The
organic molecules to be used in the emissive layer must have high photo-
luminescence quantum yield in the thin solid film. The other requirements of a
light emitting materials are as follows: (a) compatible HOMO and LUMO for
efficient carrier injection from electrodes or adjacent organic layers, (b) good film
forming property, (c) large stokes shift, (d) high glass transition temperature,
(e) good solubility in suitable solvents is essential for polymers as they can only
be deposited via spin coating, and (f) efficient energy transfer from the host, if used
as a guest (dopant).
The emitting layer may also be doped with another highly luminescent guest
molecule. Energy transfer from the host (primary exciton) to guest (secondary
exciton) makes possible to change the color of emission. This strategy is widely
used in harvesting triplets excitons in phosphorescent OLEDs [23].
The color of emission of an OLED is decided by the band gap of the polymer used
in the emissive layer. If a blue-emitting polymer is used in the emissive layer then
electroluminescence spectrum of the device will also be blue. To make a display like
television, we require white light emission. For an organic molecule, it is difficult to
emit such a broad spectra. The way white light easily generated is by mixing blue,
green, and red emitters in suitable ratio in the active layer. The synthesis of white
light-emitting polymers is little difficult but has been done. In the later section, we
review the polymers synthesized and used in fabricating blue, green, red, and white
light-emitting OLEDs.
760 S. P. Ansari and F. Ali

7 Performance Parameters of OLEDs

The performance of an OLED is measured in terms of various parameters. They are

current efficiency (cd/A), brightness (cd/m2), power efficiency (W/W), lifetime, and
internal and external quantum efficiency. The internal quantum efficiency (ηint) is the
number of photons generated in the device per injected carrier, and it can have a
maximum value of 100%. External quantum efficiency (ηext) is the number of
photons emitted out of the device per injected carrier in the forward or viewing
direction. The light out-coupling efficiency (ξ) of device is limited by absorption
losses and guiding of electroluminescence within the device and its substrate.
For a refractive index of the emissive medium n, ξ for a flat interface is given by:
ξ  1/(2 n2) [9].
Internal quantum efficiency is determined by various factors. Charge balance
factor (γ) accounts for the ratio of electrons and holes injected (ideally 1) into the
device and the probability of their recombination (ideally 1). Spin statistics predicts
the formation of triplet and singlet state in the ratio of 3:1 from the uncorrelated
electron and hole recombination. The emission from these states depends upon the
quantum yields of fluorescence (φF) and phosphorescence (φP). In ground state,
most organic molecules have a total spin of S = 0, and during the course of
electronic transition, the spin remains conserved. The fluorescence quantum yields
close to 1 have been reported for many organic molecules [23]. The electronic
transitions involving a change in spin multiplicity are spin forbidden. Therefore
the phosphorescence from the S = 1 (triplet) state to the singlet state is generally
inefficient and almost all energy is lost to the non-radiative processes. Transition
from the triplet state is partially allowed in certain heavy metal complexes, such as
Iridium (Ir), due to mixing of metal orbitals. Heavy metal complexes of iridium and
platinum have high phosphorescent quantum yield and they are used to harvest the
triplet excitons formed in the emitting layer [10].
Taking into all the above factors, external quantum efficiency (ηext) can be written
as


ηext ¼ ξ γ rs φFþ rt φP . . . (1)

where rs and rt are singlet and triplet state formation efficiencies. Figure 7 shows the
various processes that follow electron-hole recombination in OLEDs. Internal quan-
tum efficiency of nearly 100% and external quantum efficiency of 19.0  0.5% have
been demonstrated using a heavy metal (Ir) complex [33].

8 Conjugated Polymers in LED

The EL in conjugated organic polymers based on poly(N-vinyl carbazole) (PVK)

and doped with luminescent dyes was first reported by Partridge [34]. Friend and co-
workers described an EL device based on conjugated poly(p-phenylenevinylene)
18 Conjugated Organic Polymers for Optoelectronic Devices 761

h+ e−

γ
h+ -e− pair
rs
rt
Singlet exciton Triplet exciton
φF φP

thermal T-T anhilation Phosphorescence

Fluorescence deactivation
Delayed fluorescence
ξ
External emission thermal
Internal dissipation deactivation
ηext

Fig. 7 Schematic of the external quantum efficiency

(PPV) [1]. The EL efficiency and low turn-on voltage of this device projected
conjugated polymers as promising candidates for commercial application. Since
then a number of polymers with different emission color have been synthesized
and tested. In the following sections we first describe the popular chemical reactions
adopted to synthesize conjugated polymers and then we review the development of
most promising polymers for blue, green, red, and white light emission.

9 Chemical Synthesis of Optoelectronic Polymers

There are many polymerization techniques to prepare light emitting polymers. The
synthesis of different light emitting polymers as reported in literature exploited
mainly four important C–C bond forming techniques. These include soluble precur-
sor polymer route, dehydrohalogenation reactions, transition metal-catalyzed cou-
pling polymerizations, and condensation polymerizations. In this section, we present
representative examples of all the above mentioned reactions.

9.1 Soluble Precursor Route

This is the most extensively used strategy for the synthesis of PPV and its deriva-
tives. The polymer produced by this method possess very high molecular weight,
and their films are highly oriented by stretching during conversion of the precursor
polymer to its conjugated form (Scheme 1) [35]. The conversion temperature can be
reduced to 100  C by using bromide derivatives instead of chlorides, thus enabling
the fabrication of flexible devices [36].
762 S. P. Ansari and F. Ali

– + + –
CIH2C CH2Cl + (CH3)2S Cl(H3C)2SH2C CH2S(CH3)2Cl

+ Cl–
NaOH S
+ (CH3)2S + HCl
n n

Scheme 1 The Wessling-Zimmerman precursor route to PPV

NaH/DMF
CIH2C CIH2Cl
n

Scheme 2 Synthesis of PPV using dehydrohalogenation reaction

OH
O
Methanol/Sodium methoxide HCl/Paraformaldehyde
2-ethylhexy lbromide Dioxane/80°C
MeO reflux/N2
MeO

O
O
Cl KOtBu, THF, 24h.

N2
Cl n
MeO
MeO

Scheme 3 Glich polymerization of MEH-PPV

9.2 Dehydrohalogenation Reactions

These reactions are employed to synthesize different PPV derivatives. Unsubstituted

PPV is synthesized by the dehydrohalogenation of dichloroxylene in the presence of
sodium hydride and DMF solvent [37] (Scheme 2).
Glich polymerization is most widely used for the synthesis of PPV derivatives.
Mainly alkyl or alkoxy substituted PPV derivatives are synthesized using this
method [38, 39] (Scheme 3).
18 Conjugated Organic Polymers for Optoelectronic Devices 763

Pd catalyst
X + (HO)2B
Base

X = Br, l, Cl, sulfonyl

O
O O
O B
O N O
I
MeO Pd(dppf)Cl2.DCM
+
KSAc. DMF MeO
N
Br
O O Br

Scheme 4 Representative examples of Suzuki-Miyura Coupling reaction

O
O OH
N
B Pd(dppb)Cl2 HN
NH + HO N
Na2CO3, Toluene, N
N 150°C, 15 mins
Cl
MW

Scheme 5 Representative example of microwave assisted Suzuki-Miyura Coupling reaction

9.3 Transition Metal-Catalyzed Coupling Polymerizations

9.3.1 The Suzuki-Miyaura Coupling

The Suzuki coupling reactions are mainly for the cross-coupling reaction of
organoborons with organohalides. The organoboron are present in the form of a
boronic acid or ester. These reactions offer very high tolerance toward various
functional groups and by-products containing boron can easily be removed. These
reactions are most commonly used to form aryl-aryl bonds and are very effective for
the synthesis of highly substituted conjugated aromatic products. Suzuki coupling
has found extensive use for the preparation of alternating copolymers [40, 41]
(Scheme 4).
In presence of microwaves, Suzuki reactions get accelerated (Scheme 5).
This reaction can also be used to obtain aromatic alkylations. C-H insertion
negates the necessity to begin with an aryl halide, improving the atom efficiency
of the process (Scheme 6).
Nehls et al. synthesized thiophene-naphthalene oligomer via microwave-assisted
Suzuki coupling of the appropriate bromo and boronic acid derivative [42]
(Scheme 7).
764 S. P. Ansari and F. Ali

O O
HO Pd(OAc)2, KH2PO4
+ B
OH OH
OH Ag2CO3, Benzoquinone
tBuOH, 100°C

Scheme 6 Representative example of Suzuki-Miyura Coupling reaction

OC 8H 17
OC8H17
Br Pd catalyst S S C6H13
+
C6H13
S S O Br MW/KOH/THF S
B
OC8H17 S OC8H17
O
C6H13

Scheme 7 Synthesis of thiophene-naphthalene oligomer via microwave assisted Suzuki-Miyura

Coupling reaction

Scheme 8 Synthesis of benzothiadiazole-cyclopentadithiophene (BTZ-CDT) copolymers via

Suzuki polycondensation

9.3.2 Suzuki Polycondensation

Suzuki polycondensation reaction was discovered in 1987. Since then, it has been
utilized for the synthesis of polyarylenes as a powerful tool. A typical procedure for
Suzuki polycondensation [43, 44] (Scheme 8).
Advantages of Suzuki Reactions:

• Mild reaction conditions.

• Availability of common boronic acids.
• Inorganic by-products are easily removed from reaction mixture.
• Stereoselective.
• Less toxic than other competitive methods (i.e., Boronic acids are environmen-
tally safer and less toxic than organostannanes.).
• Reaction will take place in the presence of other functional groups.
• Protecting groups are not always necessary.
• Relatively cheap reagents, easy to prepare, and GREEN.
18 Conjugated Organic Polymers for Optoelectronic Devices 765

9.3.3 The Stille Coupling

This is a very versatile reaction and an excellent alternative to the Suzuki reaction. In
this reaction, organostannanes are used instead of organoboron. The tin atom bears
four functional groups; therefore, it is very important to have very good understand-
ing of the rates of transmetallation reaction of each group. Relative rate of
transmetallation:

Alkynyl > Vinyl > Aryl > Allyl  Benzyl >> Alkyl

The main attraction and advantage of the Stille coupling reaction is the use of
organostannanes which are easily prepared, purified, and stored. An important
benefit of these reactions is their tolerance (better than Suzuki Coupling) to many
functional groups and can also be carried out in neutral conditions. Compounds like
aromatic ketones, biaryl derivatives, and styrenes can be synthesized using this
reaction [45, 46] (Scheme 9).
Carsten et al. polymerized thiophene containing monomers with stannyl groups via
microwave-assisted Stille coupling reaction [47]. Stille reactions are very versatile and
are widely used to synthesize functional/multifunctional light emitting polymers.

9.3.4 Heck Coupling

The Heck reaction is a cross-coupling reaction of an organohalide with an alkene
to make a substituted alkene using palladium as a catalyst and a base. Heck
coupling reaction can be described as a palladium-catalyzed C–C formation
between aryl/vinyl halides and activated alkenes in presence of a base. The
reaction starts with the oxidative addition of aryl halide to the palladium atom,
which is followed by coordination and migratory insertion of the olefin to the
palladium. Bond rotation then places the two groups trans to each other to relieve
the steric strain and subsequent β-hydride elimination results in a trans final
product. Base-mediated reductive elimination regenerates the palladium(0) cata-
lyst. The Heck reaction is of great importance, as it allows substitution reactions
on planar sp2-hybridized carbon atoms. Another advantage of this reaction is its
excellent trans selectivity [48, 49].
Heck method is not suitable for the preparation of PPV homopolymers, but
this method is more useful for the preparation of PPV-related block copolymers
(Scheme 10). Heck reaction yields the same regular copolymer regiochemistry and
double-bond configuration with a much higher yield, better purity, and also high
luminescence efficiency.

9.3.5 Yamamoto Coupling

In Yamamoto coupling, C–C bonds of aryl halogenides are formed by mediation
from a transition metal as catalyst, like bis(cyclooctadiene)nickel(0), Ni(cod)2. In
Yamamoto coupling, only a single halogen functionalized monomer is required,
offering diversity in monomers and simple reaction procedure.
Yamamoto polymerization of a dihaloaromatic compound (AA-type monomer)
gives a polymer. The main advantage of Yamamoto polymerization is that AA-type
766 S. P. Ansari and F. Ali

Pd(0)
R X + R' SnR"3 R R'

Pd2(dba)3, P(2-Fur)3
+ SnBu3 MeCN, 80°C
N Br N
34717 35000 Cl
Cl OEt Pd2(dba)3, P(2-Fur)3
+ N O
N SnBu3 DMF, 75-80°C N
N Cl

MeO
MeO SnBu3
Pd(PtBu3)2
+
CsF, dioxane
Cl 60-100°C

Br Br
Bu3Sn Pd(ppH3)4
+ N
N Br SnBu3 DMF, 50°C
(0.5 equiv) HH-Py2V Br

Bu3Sn Pd(PPh3)4, LiCl N

HH-Py2V +
NMP, 115°C
SnBu3
N n
(1.0 equiv)
HH-Py2V(MW = 8.3 kDa)

C8H17 C8H17C8H17
PdCl2(PPh3)2
S Br + S *
Br S Me3Sn S SnMe3 * S
P(o-tilyl)3, PhCl S
MW 200°C, 10 min n
C8H17

Scheme 9 Representative examples of Stille coupling reaction

monomers are straightforward to work with. For example, poly(9,9-bis

(2-ethylhexyl)fluorene) was prepared by Yamamoto- type polycondensation of a
2,7-dibromofluorene with bis(COD)nickel and bipyridine [50, 51]. However, this
method usually requires stoichiometric amounts of catalyst. Investigations on
Ni-catalyzed reductive polymerization of 2,7- dibromofluorenes with excess zinc
dust as a reductant led to the synthesis of highly conjugated and processable PFs
(Scheme 11).
Lee and Hsu synthesized green-emitting polymers using Yamamoto coupling
reaction by end capping N-aryl- 1,8-naphthalimide and 1,8-naphthoilenearyli-
midazole derivatives into polyfluorene [52].
18 Conjugated Organic Polymers for Optoelectronic Devices 767

R3 R3
Cat. Pd(0) / Ligand R1
R1 X + H R4 R4
R2 base R2

OCH3 H3CO
C6H13
O (CH2)6 O
C6H13
H3CO H3CO

Pd(OAc)2, P(o-tolyl)3

Et3N, DMF, Δ

C6H13
OCH3 H3CO
l
O (CH2)6 O
H
C6H13
H3CO H3CO n

Br
PdCl2(PPh3)2
N
N Et3N, NMP
N n
HT-PPyV

Scheme 10 Representative examples of Palladium catalyzed Heck coupling reaction

9.4 Condensation Polymerizations

9.4.1 Wittig Reaction

Wittig reaction is one of the most versatile methods for the synthesis of alkenes in
which electrophilic carbonyl compounds such as aldehyde and ketone are attacked
by a phosphorus ylide. Phosphoniumylides are readily formed by the addition of a
suitable base to the corresponding phosphonium salt. Wittig polycondensation route
was used for the preparation of well-defined alternating copolymers. Here we present
one of the example related to PPV, Blau et al. synthesized poly(mphenylenevinylene-
co-2,5-dioctyloxy-p-phenylenevinylene) by Wittig reaction [53] (Scheme 12).

9.4.2 Horner-Emmons Condensation

Horner-Emmons condensation is a practical modification of Wittig reaction that is
used for the synthesis of PPV related alternating copolymer [54]. Wittig polymers
have high molecular weight and it contain certain amount of cis-vinylene double
bonds. Horner-Emmons condensation has some advantages over Wittig reaction
768 S. P. Ansari and F. Ali

Scheme 11 Nickel catalyzed Yamamoto coupling

OC8H17 OHC CHO

+ OC8H17
CH2PPh3
+ Br–
Ph3PH2C
Potassium tert-Butoxide/Toluene
Br– OC8H17 n
OC8H17

Scheme 12 Synthesis of PPV derivative by Wittig reaction

O
O THF
+ OHC CHO
(C2H5O)2OPH2C CH5PO(OC2H5)2 K+OBu
H3CO n
H3CO

Scheme 13 Synthesis of Poly(MEHPV-alt-PV) by Horner-Emmons condensation

such as, newly formed double bonds are purely trans in nature, it shows good
regioselectivity, high degree of conversion, and finally good yield [55]. Kim et al.
prepared poly (MEHPV-alt-PV) by using Horner-Emmons condensation is
displayed in Scheme 13. The reaction consist of substituted phosphonate ester
reacted with terephthaldehyde under the presence of potassium tert-butoxide to
produce alternating copolymer [55].

9.4.3 Knoevenagel Coupling Route

Emissive polymers containing vinylene linkages are also prepared by using
Knoevenagel coupling reaction, in which carbon-carbon double bonds are formed
between respective monomers. Knoevenagel condensation based on the reaction
between aldehyde groups with active methylene species requires strong electron
withdrawing substituent groups (CN, for example) [55]. Employing Knoevenagel
condensation numerous PPV-related homo and copolymers with CN containing
vinylene units have been synthesized. Hanack et al. prepared cyano substituted
poly(2,6-naphthylenevinylene) (CN-2,6-PNV) by using Knoevenagel condensation
reaction between two monomers, namely, 1,5-bis(hexyloxy)-2,6-naphthalenediace-
tonitrile and 1,5-bis(hexyloxy)-2,6-naphthalenedicarbaldehyde in the presence of a
strong base is shown in Scheme 14.
18 Conjugated Organic Polymers for Optoelectronic Devices 769

H 13
OC 6 CN
OC6H13 OC6H13
OC6H13
CHO KtOBu
CN n
+
OHC NC
CN OC6H13
OC6H13 OC6H13 OC6H13

Scheme 14 Synthesis of poly(2,6-naphthylenevinylene) by Knoevenagel condensation

Fig. 8 Molecular structures

of different families of blue-
emitting polymers
n
R R
n n
S
1 2 3

10 Blue, Green, Red, and White Light-Emitting Polymers

10.1 Blue-Emitting Polymers

The fluorophores that are responsible for blue light emission typically contain
phenyl, or fluorene, or heterocycles such as thiophene, etc. in their chemical struc-
ture. Figure 8 shows the molecular structures of different families of blue-emitting
polymers. These flourophores may be present in the main chain of polymer or as its
side chain. The presence of side chain play an important role and its function is to
increase interaction, decrease planarity for color shift in the emission spectrum, and
to enhance solubility of polymers [56].
Poly(p-phenylenes) (PPPs) is an important class of blue-emitting polymers.
Figure 9 shows the molecular structures of different PPPs derivatives. PPPs
can make neat thin films which emit at ~460 nm. Electrochemically polymerized
Poly(p-phenylene) (PPP) was also observed to exhibit light-emitting properties
[56, 57]. It was found that the reaction condition for polymerization affect the
light-emitting properties. The polymers obtained electro-reductively with charges
of 50 and 100 mC/cm2 show EL maxima in the region between 450 and 550 nm
while that with a charge of 1 mC/cm2 falls at about 600 nm [58, 59]. PPPs have poor
solubility and low quantum efficiency (QE) which made them less attractive for blue
OLED. The issue of poor solubility was addressed by attaching the alkyl chains in
the polymer backbone. Many PPPs derivatives were synthesized. Monoalkoxy
substituted PPPs, poly[2-(60 -cyano-60 -methylheptyloxy)-1,4-phenylene] (CN-PPP)
(6), poly(2-decyloxy-1,4-phenylene) (DO-PPP) (5), and poly[2-(20 -ethylhexyloxy)-
1,4-phenylene] (EHO-PPP) (4) are soluble in organic solvents [60, 61]. The three
polymers show nearly identical PL spectra, with PL and EL maxima at 420 nm. A PL
quantum yield for the polymers in a 1% solution is 85% and the yields in films
770 S. P. Ansari and F. Ali

O O

n n n
1 4 5

O
O CN O
n
n n O
6 7 8

O
O
n
n O
O

9 10

Fig. 9 Molecular structures of PPV polymers

ranges from 35% to 46%. The best external QE for LEDs with a structure of
ITO/PVK/PPPs/Ca are 3.0, 2.0, and 1.4% for 4, 5, and 6, respectively, where PVK
is poly(N-vinylcarbazole).
Poly(2-benzoyl-1,4-phenylene) (PBP) (7) is soluble in common organic solvents
and thermally stable up to 400  C [62]. The polymer film having thickness of 15 nm,
when photo excited at 390 nm exhibit PL maximum at 433 nm, slightly less than that
of PPPs but higher than that of alkoxy substituted PPPs. Quantum yield of PBP in
chloroform was measured to be 15%. A LED having a structure of ITO/PVK-PBP
(3:1) blend/PBD-PMMA (3:1) blend/Ca/Al exhibits an EL maximum at 446 nm with
an EQE of 0.17%, where PBD and PMMA are 2-(4-biphenyl)-5-(4-tert-
butylphenyl)-1,3,4-oxadiazole and poly(methyl methacrylate), respectively.
Photophysical properties of dialkoxy substituted PPVs (8, 9, and 10) have also
been studied [62]. The absorption spectra are reported to be similar and unaffected
by the length of the alkyl chain or isomeric structures. The peak absorption wave-
length is at about 336 nm. Degree of polymerization, length of alkoxy substituent,
and preparation methods affects the absorption maxima of the resultant molecules.
The intensity of absorption changes with the length of the alkoxy groups. Poly
(2,5-dibutyloxy-1,4-phenylene) (8) in methylene chloride shows an extinction coef-
ficient 6.4  106 cm2/mol whereas poly[2,5-bis(30 -methylbutyloxy-1,4-phenylene)]
(9) shows an extinction coefficient 3.8  106 cm2/mol. The PL maxima of 8, 9, and
10 in chloroform appear at 410 nm. Poly(2,5-diheptyloxy-1,4-phenylene) (10) when
synthesized by oxidative coupling using anhydrous FeCl3 as a catalyst has a band
gap of 3.5 eV and a PL maximum for a film at 400 nm with a strong secondary peak
18 Conjugated Organic Polymers for Optoelectronic Devices 771

at 500 nm [63]. The result suggests that during the preparation of the polymer some
defects would have been produced which leads to the secondary emission.
Thiophene-based polymers can also give blue emission. The band gap of poly-
thiophenes can be controlled by steric hindrance via bulky side chain substituents on
the thiophene unit [64]. Poly(3-cyclohexyl-4-methylthiophene) (PCHMT) (2)
(Fig. 8) possesses large band gap. The PL maximum of 2 in chloroform was
observed at 460 nm. The bilayer device of 2 with PBD as an electron transporting
layer sandwiched between ITO and Ca gives an EQE of 0.6% and an EL maximum
at 460 nm. It is also reported that single-layer device of polythiophene with crown
ether unit attached to positions 3 and 4 (11) gives an EL maximum at 470 nm
[65]. Poly(dioctylthiophene) (12) in toluene shows a PL maximum at 470 nm [66].
A LED with a structure of ITO/12/In also shows EL maximum at 470 nm. The stereo
interactions between the alkyl chains is likely responsible for short chain length and
blue color in polythiophenes. However, the QE values of all LEDs prepared with this
material are not promising (Fig. 10).
The fluorine-based polymers is other important family of blue-emitting polymers.
Figure 11 show the molecular structures of typical fluorene derivatives such as
polyfluorenes (PFs, 3),5,6polyindenofluorenes (PIFs, 13),7,8 and ladder-type poly-
phenylenes (LPPPs, 14). In solution, they emit blue to blue-green which gets

Fig. 10 Molecular structures O

of poythiophenes
O O

O O
H17C8 C8H17

S n S n S n

2 11 12

Fig. 11 Typical fluorine based blue-emitting conjugated polymers

772 S. P. Ansari and F. Ali

red-shifted with increasing rigidity of the polymer chain with emission maxima of
420 nm for 3, 430 nm for 13, and 450 nm for 14. The first PLED for blue color
emission was made in 1991 [67]. A layer of poly(9,90 -di-n-hexylfluorene)(PDHF)
(3) was formed by spin-coating its solution in chloroform onto ITO glass and a layer
of magnesium-indium alloy on the polymeric layer was vacuum-deposited. The EL
spectrum of PDHF exhibited the emission maximum at 470 nm with a shoulder at
420 nm and a FWHM of ~200 nm. In the solid state broad emission bands at longer
wavelengths ~530 nm also appears [68–71]. The cause of long-emission band for 3,
13, and 14 has been correlated to the emission from the ketonic defects which get
incorporated in the polymer backbone as 9-fluorenone units [72–77].
Craig et al. purified the monomers used in the synthesis of polyfuorenes to ensure
reduced levels of fluorenone defects in the corresponding polyfuorenes. The syn-
thesized polymer demonstrated pure blue and more stable electroluminescence when
exposed to high temperatures [78]. Green EL was suppressed by incorporating a
novel buffer layer of tetrakis(4-(5-(α,α,α-trifluoromethylphenyl))-2-oxidiazolyl)phe-
nyl)methane (CF3OXD) between emissive layer and the Ca/Ag or Ba/Ag cathode
[73]. The problem of ketonic defects in fluorene-based polymer was also addressed
by replacing the alkyl groups in the methine bridges with the aryl substituents
(Fig. 12). The greater stability of blue emission in molecule 15, 16, and 17 arises
due to high resistance to oxidation and a reduction in excimer diffusion to a ketone
defect sites. Efficient, stable blue-emitting LEDs have been fabricated using the
polymers 15, 16, and 17 [79, 80].
The other important strategy adopted to avoid long-wavelength emission in
polyfuorenes was replacing the vulnerable C-9 carbon in polyfluorene by a hetero-
atom, such as silicon. Many new polymers were synthesized. The optical properties
of polymer poly(9,9-dihexyl-2,7-dibenzosilole) (18) were similar to that of poly

Fig. 12 Stable blue-emitting polyfluorenes

18 Conjugated Organic Polymers for Optoelectronic Devices 773

(9,9-dioctyl-2,7-fluorene) (PFO) [81]. Thin film of P27SiF show photoluminescence

(PL) emission maxima at 425 nm and has two vibronic sidebands at 449 and 482 nm.
The PL efficiencies of 18 and PFO were also similar ~60%. Of the two polymers, 18
was found to be more thermally stable and maintained its color purity even after
annealing at 250  C for 16 h whereas films of PFO degraded as indicated by the
appearance of a broad green band centered at 535 nm. The electroluminescence
emission spectrum measured on a single layer device in the configuration
ITO/PEDOT/18/Ba/Al showed emission maxima at 431 and 451 nm and efficiency
slightly superior to that of the corresponding device fabricated with a single layer of
PFO. The copolymerization of 3,6-silafluorene unit into the 2,7-silafluorene gave
P36-27SiF90(19) [82]. The copolymer did not show undesirable long wavelength
emission and it was thermally stable. The device of the copolymer with a configu-
ration of ITO/PEDOT:PSS/PVK/19/Ba/Al exhibited an external quantum efficiency
of 1.95%, a luminous efficiency of 1.69 cd/A, and a maximum brightness of
6000 cd/m2. Homopolymers and copolymers of spirofluorene were also found to
give stable blue emission [83]. Fluorene-9,90 -(20 ,70 -di-n-octyloxyxanthene)](PSFX)
(20) have high quantum efficiency of close to 1 in solution and 0.92 in thin film. Its
optical properties were found similar to PFO. An OLED fabricated using PSFX as
the emitting layer ITO/PEDOT/20/TPBI/Mg:Ag/Ag exhibits an efficient, stable blue
emission and a maximum external quantum efficiency of 1.74%. The EL spectrum
remains unchanged even at high brightness (103cd/m2). High PL quantum efficien-
cies of fluorene-based polymers and their good performance in devices make them
promising candidates for OLEDs.

10.2 Green-Emitting Polymers

In the photoluminescence (PL) spectrum, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-

phenylenevinylene] MEH-PPV as a solid thin film emits yellowish-red light with
λmax at 593 nm and shoulder peaks at 640 nm and 707 nm. Nguyen et al. have blue
shifted this emission of MEH-PPV by blending MEH-PPV with poly
[9-vinylcarbarzole] (PVK) and TiO2 nanoparticles [84]. The single layer devices
based on the blended polymer films were fabricated in the configuration ITO/(PVK:
MEH-PPV) + TiO2/Al have shown green electroluminescence. The optical proper-
ties of PPVs were also found to depend on the substitution pattern of the alkoxy
groups in the polymer backbone. 2,3-dialkoxy substituted PPVs as synthesized by
Holmes and co-workers have shown significant blue-shift in the emission maximum
and they were also having high PL and EL efficiency in the solid state [85–87]. The
di-butoxy-PPV shows green emission with λmax at 530 nm and a PL efficiency of
40%. Bigger alkyl groups increases the steric constraints as in (23) leads to a further
blue-shift in the emission with λmax at 513 nm and a drop in PL efficiency to 28%.
The PL efficiency of MEH-PPV was only in the range of 15%–20% [88–89].
Benzothiadiazole is an electron deficient monomer unit which was used in copo-
lymerization with fluorene to red-shift the blue emission of polyfuorenes (PFs) to
green region [90]. The polymer Poly(9,9-dioctylfluorene-alt-benzothiadiazole)
774 S. P. Ansari and F. Ali

(F8BT, 24) synthesized shows PL emission peaks at 545 nm and has a shoulder peak
at 576 nm and a long wavelengths tail that extends up to 750 nm [91]. Single-layer
device with the configuration ITO/ZnO/Cs2CO3/F8BT/MoO3/Au containing thick
layer of F8BT as the emissive layer shows excellent current efficiency of more than
20 cd/A at a brightness of ~1000 cd/m2 [92]. The peak external quantum efficiency
(EQE) of the device was close to 7% (Fig. 13).
Yong Cao and coworkers synthesized green-emitting poly[2,7-silafluorene-co-
benzothiadiazole)]PSiF-BT10 (25) by incorporating 2,1,3-benzothiadiazole
(BT) into the backbone of blue-emitting poly(2,7-silafluorene) (PSiF) [93]. The
peak emission wavelength and PL quantum efficiency of PSiF-BT10 as a solid
thin film were measured to be 530 nm and 0.52, respectively. This λmax is very
close to that of a similar fluorene derivative (PFO-BT10) for which λmax is 533 nm.
The PL quantum efficiency of PFO-BT10 was 0.68, a little higher than PSiF-BT10.
The polymer LED with the configuration of ITO/PEDOT:PSS/PVK/PSiF-BT10/Ba/
Al showed the maximum EQE of 3.81% and current efficiency of 10.6 cd/A.
Yu et al. (2013) synthesized green-emitting PPF-SO-BT (26) polymers containing
9,9-bis(4-(2-ethylhexyloxy) phenyl)fluorene (PPF), dibenzothiophene-S,S-dioxide
(SO), and benzothiadiazole (BT) units with varying ratios [94]. Of these polymers,
PPF-SO15-BT1 exhibited highest fluorescence quantum yield (~0.67) and good
thermal stability. Light-emitting diodes (LEDs) using PPF-SO15-BT1 as the emis-
sive layer in the device configuration ITO/PEDOT:PSS/PVK/PPF-SO15-BT1/CsF/
Al have shown green electroluminescence. The maximum brightness and the max-
imum current efficiency measured in this device are 30,314 cd/m2 and 17.6 cd/A,
respectively.

RO OR

n
21, MEH-PPV 22,R = C4H9, 23, R=2-ethylhexyl 24, F8BT

R R

S
O O N N
S

x y

25, PSiF-BT10 26, PPF-SO-BT 27, PCPPBTs

28

Fig. 13 Molecular structures of different green-emitting polymers

18 Conjugated Organic Polymers for Optoelectronic Devices 775

The BT units were also copolymerized with cyclopenta[def]phenanthrene deriva-

tives to give poly(4,4-bis(2-ethylhexyl)-4H-cyclopenta[def]phenanthrene)-co-poly
(2,1,3-benzothiadiazole) (PCPPBTs, 27) [95]. The introduction of BT unit resulted
red-shifted emission. The color of emission was found to be varying with the amount of
BTs. The PL spectra were having two emission peaks at around 410 and 530 nm in thin
films. The polymer LEDs of combination (ITO/PEDOT/polymer/Ca:Al) of PCPPBTs
exhibited emissions λmaxat 508–528 nm. Among all the devices fabricated, the best
device was the one with PCPPBT10, which showed the highest luminous efficiency of
1.25 cd/A and the highest brightness of 1170 cd/m2. This study established that PL
efficiency can be improved by randomly copolymerizing the BT into the PCPP.
Fluorene and benzothiazolylpyrazoline units were copolymerized to give Poly
(9,9-dihexylfluorene-alt-benzothiazolylpyrazoline, 28) [96]. This polymer possessed
good thermal stability. As a solid thin film, the polymer emits green light (λmax at
501 nm) with high (PL) quantum yield of 47%. Polymer light-emitting diode
(PLED) fabricated with the configuration of ITO/PEDOT/PVK/polymer/Ba(4 nm)/
Al(160 nm) emit green light with λmax at 501 nm. The maximum brightness and the
maximum EQE achieved were 1726 cd/m2 and 1.59%, respectively.
Lee et al. synthesized a series of polyfluorenes (P1-P5) which were end-capped
by N-aryl-1,8-naphthalimide and 1,8-naphthoilenearylimidazole derivatives in an
attempt to red-shift the blue emission of (PFs) into the greenish region [96]. The
color of emission was tuned by controlling the content of 29–33. The electrolumi-
nescence (EL) spectra of polymers (34–38) exhibit greenish-blue, bluish-green, pure
green, and yellowish-green emission with the corresponding peak emission (λmax) at
465 nm (for 35), 490 nm (for 34 and 36), 500 nm (for 37), and 545 nm (for 38). Of
these polymers, 37 could give pure green emission in the device. The maximum
brightness achieved for this polymer was ~6500 cd/m2 with a current efficiency of
0.56 cd/A (Fig. 14).

O N N C8H17 C8H17
O N O O N N
Ar Ar

Br n
Br Br

29, X=H 32 33 34-38,

where Ar = 29-33
30, X=OCH3
31, X=CN
Fig. 14 Molecular structures of green-emitting polymers
776 S. P. Ansari and F. Ali

10.3 Red-Emitting Polymers

Gurge and co-workers studied the asymmetrically substituted, “push-pull” family of

PPVs, i.e., poly(2[5]-chloro-5[2]-(n-hexyloxy)-1,4-phenylenevinylene) and poly(2
[5]-bromo-5[2]-(n-hexyloxy)-1,4-phenylenevinylene), 39 and 40, respectively
(Fig. 15) [97]. These polymers gave strong EL emission in the ~620 nm (orange-
red to red) spectral region even without fine-tuning of emission characteristics.
Single-layer LED of configuration ITO/39/Ca exhibited an output brightness of
~20 cd/m2 at 30 V pulsed input voltage using 1 mA of current [97].
Lo and Burn synthesized polymer (41) (Fig. 15) by incorporating a red-emitting
porphyrin as a side chain to the PPV unit by a rigid phenylacetylene linker [98]. Red
emission with λmax at 604, 653 nm were observed in PL studies which suggest that
the red emission originated from the porphyrin chromophore. But the EL device
performance was rather poor.

Fig. 15 Molecular structures of red-emitting polymers

18 Conjugated Organic Polymers for Optoelectronic Devices 777

Morin and Leclerc synthesized 2,7-carbazole-based light-emitting homopolymers and

copolymers [99]. Wherein, poly(N-(2-ethylhexyl)-2,7-carbazole-alt-3,30 ,4000 ,30000 -tetra-
methyl-300 ,400 -dihexyl-2,20 :50 ,200 :500 , 2000 :5000 ,20000 -quinquethiophene-100 , 100 -dioxide)
(PCPTO) (42) (Fig. 15) emits red light with λmax at 638 and 671 nm. The fluorescence
quantum yield in chloroform solution was measured to be 25% for PCPTO.
Manjunatha and co-workers synthesized narrow band gaped donor-acceptor type
polymer from cyanovinylenepoly{3,30-(3,4-ditetradecyloxythiene-2,5-diyl) bis
[2-(thiophen-2-yl)prop-2-enenitrile]}(43) (Fig. 15) [100]. The polymer exhibited
red-fluorescence in solution as well as in solid state. The peak emission wavelength
of polymer in solid thin film was measured to be 647 nm. The PL efficiency of the
polymer was determined to be 43%.
Fluorenone and dialkylbithiophene were copolymerized to give regioregular,
alternate copolymer poly[(5,50 -(3,30 -di-n-octyl-2,20 -bithiophene))-alt-(2,7-fluoren-
9-one)] (PDOBTF) (44) (Fig. 15) by different preparation methods [101]. The
photoluminescence studies showed that PDOBTF emits red light with λmax at
643 nm in the solid state.
Kim and co-workers synthesized an alternating copolymer poly(PTZV-alt-TV)
(45) (Fig. 15) using Wittig polycondensation between 10-(2-ethylhexyl)-phenothia-
zine-3,7-dicarbaldehyde and thiophene bis(phosphonium) salt [102]. The PL emis-
sion of poly(PTZV-alt-TV) as a thin film was having λmax at 584 nm.
Electroluminescent device was fabricated in an ITO/PEDOT/poly(PTZV-alt-TV)/
Ca/Al configuration which showed maximum brightness of 140 cd/m2 and a lumi-
nous efficiency of 1.3  102 cd/A. However, at different voltages emission at
650 nm was also observed. The EL emission spectrum of the device showed a broad
emission range (500–800 nm).
Cho and co-workers were able to tune the color of emission of polyfuorenes by
copolymerization of fluorene with different comonomers. They were able to synthe-
size pure red-emitting poly{9,9-dioctylfluorene-2,7-diyl-alt-2,5-bis(2-thienyl-2-
cyanovinyl)-1-(20 -ethylhexyloxy)-4-methoxybenzene-500 ,500 -diyl} (PFR4-S) (46)
by doing Suzuki coupling of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-
yl)-9 0 ,9 0 -dioctylfluorene and 2,5-Bis{2-(40 -bromothienyl)-2-cyanovinyl}-2-
(20 -ethylhexyloxy)-5-methoxybenzene [103]. The PL and EL emission peaks of
PFR4-S as a solid thin film were at 674 nm. Single-layer LED devices fabricated
from this polymer emitted pure red light. The CIE coordinate values x = 0.66,
y = 0.33 of the device was almost identical to the standard red (x = 0.66,
y = 0.34) as demanded by the National Television System Committee.
Peng and co-workers synthesized a series of red-light-emitting copolymers
(47–49) using fluorene and 2-pyran-4-ylidenemalononitrile (PM) [104]. The PL
emission of these polymers in thin films emit red color with λmax around
641–662 nm and additional peaks in the range 704–712 nm. The absolute PL
quantum yields of the polymer as solid thin films were measured to be about
4–7%. The PLEDs fabricated with the configuration of ITO/PEDOT/polymer/Ba/
Al emit red light with EQE of 0.21–0.38%.
Ying and co-workers copolymerized 3,6-dibromo-N-alkylcarbazole having
red-emitting Iridium complex in the alkyl chain with fluorene to give poly
778 S. P. Ansari and F. Ali

NC CN

CN O
O
S
S
R
H3CO NC n
x
C6H13 C6H13

46, PFR4-S 47: R=H, 48: R=OC6H13, 49: R=OC12H25

N N x n

O O

lr

50 N

Se Se
H17C8 C8H17 H17C8 C8H17
x N N y m
X
51: PFO-SEBT: X=S, 52: PFO-SeBSe: X=Se

Fig. 16 Molecular structures of red-emitting copolymers of fluorene

(fluorene-alt-carbazole) (50, Fig. 16) based copolymers [105]. Iridium complex in

the ratio of 1 mol% to that of host polymer was sufficient to completely quench the
emission of host polymer. The polymer PFCzIrBpz-1 in the device configuration
ITO/PEDOT:PSS/polymer+PBD/Ba/Al gave an orange-red emission. The phospho-
rescent polymer light-emitting diodes (PhPLEDs) showed a maximum luminous
efficiency (LE) of 5.58 cd/A and a maximal luminance of 8625 cd/m2.
Yang and co-workers synthesized a series of copolymers, using alkyl-substituted
fluorene and 4,7-diselenophen-20 -yl-2,1,3-benzothiadiazole (SeBT), or 4,7-diselenophen-
20 -yl-2,1,3-benzoselenadiazole (SeBSe) as the comonomers (51, 52, Fig. 16) [106]. The
PL emission peaks as solid thin films were found to depend upon the content of
comonomer. The PL and EL is dominated by narrow-band-gap species and peaked
at 670–790 nm. The double layer devices made from these two types of copoly-
mers in the configuration ITO/PVK/polymer/Ba/Al reached an EQE of 1.1% and
0.3%, respectively.

10.4 White Light-Emitting Polymers

Single polymer which can emit white light can be synthesized by incorporating two
chromophores (blue and orange) or three chromophores (blue, green, and red) into a
18 Conjugated Organic Polymers for Optoelectronic Devices 779

polymeric chain. It is very difficult to synthesize the latter; however, it offers better
color quality while synthesis of the former type of white light-emitting polymer is
easy. Tu and co-workers developed two component polymers for white light emis-
sion. They incorporated 1,8-naphthalimide (orange emissive) unit as dopant into
polyfluorene (blue-emitting polymer) with varying dopant ratio [107]. A novel
single-component polymer system (53) with 0.05 mol% of dopant showed white
light emission. A white polymeric light-emitting diode (WPLED) fabricated with the
configuration ITO/PEDOT:PSS/53/Ca/Al showed a current efficiency of 5.3 cd/A
and a power efficiency of 2.8 lm/W at 6 V [107].
Sun and co-workers synthesized a series of copolymers by incorporating orange-
emitting 2,3-dimethyl-5,8-dithien-2-ylquinoxaline (DDQ) unit in the backbone of
PFO with varying mole ratio [108]. White emission could be obtained by carefully
controlling the DDQ unit (~0.02 mol%) in the PFO backbone. The two distinguished
emission peaks (blue and orange red) leading to white light emission were observed
in the polymer PFO-DDQ002 (54) due to incomplete energy transfer from the PFO
to DDQ. A WPLED fabricated with the configuration ITO/PEDOT/PVK/PFO-
DDQ/54/Ba/Al showed high EQE and current efficiency of 2.64 and 4.1 cd/A,
respectively. The CIE coordinates remained stable for different voltages.
Lee et al. synthesized a series of copolymers by incorporating 2-(2,6-bis-{2-
[1-(9,9-dihexyl-9H-fluoren-2-yl)-1,2,3,4-tetrahydro-quinolin-6-yl]-vinyl}-pyran-4-
ylidene)-malononitrile as the orange unit into a polyfluorene main chain as the blue
host [109]. The polymer (F6DCM005) having 0.05 mol% of orange-emitting
comonomer (DCMF) was found to emit white light with peak emission at
423/450 nm (blue) and at 580 nm (orange). The PLED fabricated in the configura-
tion ITO/PEDOT:PSS/55/Ca/Al showed white light emission with CIE coordinates
(0.33, 0.32). The maximum brightness and current efficiency achieved in the device
were 1180 cd/m2 and 0.60 cd/A, respectively [109].
Hsieh and co-workers synthesized copolymers (56, Fig. 17) by incorporating
orange emitting chromophore 2,5-dihexyloxy-1,4-bis(2-thienyl-2-cyanovinyl) ben-
zene in the mole ratio (0.1 and 0.025 mol%) into the polyfuorenes for getting white
electroluminescence [110]. The PL peaks of copolymer films ~428 and 570 nm were
due to fluorene unit and the orange chromophore unit respectively. The PLEDs of the
copolymers PFR1 and PFR2 showed white light emission with CIE coordinates
(0.36, 0.35) and (0.32, 0.30), respectively, which are close to white light emission
(0.33, 0.33). The maximum EL brightness achieved with PFR1 and PFR2 were 5419
and 3011 cd/m2, respectively [110].
Lee and co-workers copolymerized 2-{2-(2-[4-{bis(4-bromophenyl)amino}
phenyl]-vinyl)-6-tertbutylpyran-4-ylidene}malonitrile (TPDCM) (red emitter),
{4-(2-[2,5-dibromo-4-{2-(4-phenylaminophenyl)vinyl}phenyl]-vinyl)phenyl}-diphe-
nylamine (DTPA) (green emitter), and a 2,7-dibromo-9,9-dihexylfluorene (DHF)(blue
emitter) in suitable ratios to get white light-emitting polymer [111]. White emission
was observed in the polymer PG3R2 (57, Fig. 18) having the comonomers compo-
sition as 3 mol% of DTPA and 2 mol% of TPDCM. The WPLED device fabricated in
the configuration ITO/PEDOT:PSS/polymer/Ca/Al showed white light emission with
CIE coordinated of (0.33, 0.35). The peak luminance and current efficiency achieved
were 820 cd/m2 and 0.1 cd/A, respectively [111].
780 S. P. Ansari and F. Ali

N C8H17 C8H17
1-x xn
C8H17 C8H17
y S S x
N N
O N O
C10H21 H3C CH3
53 54

N N
X y
O

NC CN

55: F6DCMF

O NC S

S CN O

56: PFR

Fig. 17 Molecular structures of white-emitting copolymers

Tokito and co-workers were able to get white light emission by blending red
phosphorescent polymer (RPP) (58) and blue phosphorescent polymers (BPP) (59)
[112]. The RPP and BPP when mixed with the ratio of 10:1 in a PLED having the
configuration ITO/PEDOT:PSS/58 + 59/Ca/Al showed white EL with CIE coordi-
nates of (0.34, 0.36). The EQE of white emission was measured as 4.5%.
Xiong et al. fabricated polymer white light-emitting diodes based on the blend of
poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]-end capped with polysilsesquioxane
(PFO) and poly[(9,9-bis(30 -(N,N-dimethylamino)propyl)-2,7-fluorene-alt-2,7-
(9,9-dioctylfluorene))-co-[2,7-(9,9-dioctlyfluorene)-alt-5,5-bis(2-(4-methyl-1-naph-
thalene) pyridine-C2,N) iridium (III) acethylacetonate]] (PFN-NaIr05) (60)
[113]. The PLED of the configuration ITO/PEDOT/PVK/PFO: PFN-NaIr05/Al
with 5% PFN-NaIr in the blend showed white light emission having CIE coordinates
of the (0.34, 0.35).
Xu et al. demonstrated white light emission by doping a blue-emitting oligomeric
silsesquioxane-terminated poly(9,9-dioctylfluorene) (PFO-poss) (61) with green
18 Conjugated Organic Polymers for Optoelectronic Devices 781

Fig. 18 Molecular structures of some other white-emitting copolymers

emitting fac-tris[2-(40 -ter-butyl)phenylpyridine]Iridium (III) [Ir(Bu-ppy) 3] and

red-emitting bis-(1-phenylisoquinolyl)Iridium(III)(1-trifluoro)acetylacetonate
[(Piq)2Ir(acaF)] [114]. The electroluminescence spectrum was found changing
with the concentration of the guests. The WPLED with the configuration
ITO/PEDOT:PSS/PVK/PFO-poss+62+63/Ba/Al and with the doping concentrations
of 0.14 wt% for 62 and 63. TheCIE coordinates of WPLED was around (0.33, 0.33).
The maximum brightness achieved in the device was ~10,200 cd/m2.
782 S. P. Ansari and F. Ali

White light emission has also been reported by utilizing excimer or exciplex
formation. Chao and co-workers reported WPLED which utilized the exciplex
formation between poly(N-vinyl carbazole) PVK (64) and poly(2-dodecyl-p-phen-
ylene) (C12O-PPP) (65) [115]. A broad EL spectrum having emission from 400 to
700 nm was observed. The exciplex emission was arising from the recombination of
the electron in the lowest unoccupied molecular orbital (LUMO) of C12O-PPP and
the hole in the highest occupied molecular orbital (HOMO) of carbazole groups
in PVK.
Lee and co-workers reported white light emission from a single-layered system
based on oxadiazole and phenylenevinylene copolymer having ether linkage
[116]. The emission spectrum of the above was found to be composed of red and
blue-green components from different species, i.e., red component originated from
the new excited dimer while blue-green component from an individual lumophore
and excimer. The excited dimer generated in the above system was reported to be
different from excimers/exciplex, typically observed in electro- and photo-
luminescence and could not be produced during these processes and could be seen
only in the system under high electric field.

11 Conclusion

Herein, the various components of making an efficient OLED are discussed. We first
described the electronic transitions and energy transfer processes involved in con-
jugated polymers. The working of different types of device architectures, their
efficiencies, and the measurement that are normally made in OLEDs are also
presented. The various types of materials and their functional requirements as
needed in the making of multilayer OLEDs are discussed. Several categories of
blue, green, red, and white light-emitting polymers have been highlighted. Conju-
gated polymers have established their importance for optoelectronic device applica-
tions. They give high electroluminescence efficiency in OLEDs. The improved
efficiencies of these devices are facilitating the commercialization of these devices.

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Electrochromic Polymers for Solar Cells
19
Suru Vivian John and Emmanuel Iwuoha

Contents
1 Introduction to Electrochromism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790
1.1 Classes of Electrochromic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 791
1.2 Operating Principle of an Electrochromic Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 791
2 Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 793
2.1 Conjugated Polymers as Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 793
3 Charge Carriers in Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
4 Electronics of Conjugated Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 804
5 Electrochromism in Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
5.1 Electrochromism in Poly(aniline) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
5.2 Electrochromism in Poly(thiophene) and Its Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . 808
5.3 Electrochromism in Triphenylamine Containing Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . 811
6 Electrochromic Devices with Optically Transparent Polymer Layer . . . . . . . . . . . . . . . . . . . . . . 812
7 Electrochromism and Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817

Abstract
Electrochromic materials have attracted a lot of research interest for their fasci-
nating spectro-electrochemical properties and commercial applications. A large
number of inorganic and organic electrochromic materials ranging from transition
metal oxides, metal coordination complexes, viologen systems, and conducting
polymers are available. Electrochromic conducting polymers are exciting new

S. V. John (*)
Department of Chemistry, University of the Western Cape, Bellville, South Africa
e-mail: [email protected]
E. Iwuoha
SensorLab, Department of Chemistry, University of the Western Cape, Bellville, South Africa
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 789

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_22
790 S. V. John and E. Iwuoha

class of electronic materials with a huge potential in the rapidly growing area of
plastic electronics due to their electronic and optical properties, ease of pro-
cessing, low-power consumption, flexibility, and low processing cost. They
consist of vibrant colors and can be processed under simple ambient temperature.
In this chapter, the general field of electrochromism is introduced, with cover-
age of the classes, operating principle, the experimental methods used in their
study, and applications of electrochromic materials. Some of the most impor-
tant examples of the major classes of electrochromic conducting polymers are
highlighted. It surveyed electrochromic conducting polymers with a focus on
their chemistry, electrochemistry, stability, and ability to enhance the perfor-
mance of solar cell device.

Abbreviations
DEG Diethylene glycol
ECD Electrochromic device
Eg Band gap
EPR Electron paramagnetic resonance spectroscopy
FTIR Fourier transform infra red spectroscopy
HOMO Highest occupied molecular orbital
ITO Indium tin oxide
LUMO Lowest unoccupied molecular orbital
MVRH Mott variable range hoping
NIR Near infra red spectroscopy
NMP N-methylpyrrolidone
PB Prussian blue
PDMA Poly (2,5-dimethoxyaniline)
PEDOT Poly(3,4-(ethylenedioxy)thiophene)
PET poly(ethylene terephthalate)
UV-Visible Ultra violate visible spectroscopy
VTECWs Variable transmission electrochromic windows
WO3 Tungsten oxide

1 Introduction to Electrochromism

Chromism is a general term for reversible color change in material due to response to
external stimuli. This change is generally named based on the type of external
stimuli. The color change can be as a result of exposure of the material to light
(photochromic), vapor (vapochromic), solvent (solvatochromic), heat (thermo-
chromic), or oxidation/reduction of the chemical specie (electrochromic). The
reversible change of absorption with distinct electronic (UV-Visible) absorption
spectra following an electrochemical (oxidation/reduction) reaction is termed
electrochromism. It is the switching between redox states which results in the
generation of various visible to near infra red (NIR) electronic absorption [1, 2].
19 Electrochromic Polymers for Solar Cells 791

It results in the reversible and visible change in the transmittance and/or reflectance
of a material due to electrochemical oxidation or reduction. Usually, a color change
between a transparent or bleached state and a colored state or between two colored
states is observed. On the other hand, cases exist where more than two redox states
are electrochemically available. In such cases, the electrochromic material may
likely display more than two colors. This is termed polyelectrochromism.
Electrochromic materials, therefore, are chemical species that can be electrochem-
ically switched between different colors. They exhibit reversible and highly stable
changes of their optical properties upon oxidation or reduction by the passage of an
electrical current which takes place as a result of an applied voltage [3, 4]. They have
the ability to reversibly change the optical properties (refractive index n, extinction
coefficient k) upon insertion and extraction of small charges by application of voltage.
Basically, materials are considered to be electrochromic when noticeable visible color
changes are observed under illumination. Nevertheless, chemical species have shown
possibility for modulation of radiation in the near infrared (NIR), thermal infrared, and
microwave regions [5–7]. In this case, “color” can mean response of detectors to these
electromagnetic regions, not just the color noticed by the human eye [8].

1.1 Classes of Electrochromic Materials

Synthetic chemistry has produced a number of materials for electrochromic appli-

cations. Chemical species such as transition metal oxides, metal coordination com-
plexes, viologen systems, and conducting polymers show electrochromic properties
[1, 3, 5, 9–14]. They can be classified as either inorganic, organic, or hybrid.
Inorganic electrochromic materials are in the form of transition metal oxides such
as tungsten trioxide, oxides of molybdenum and vanadium [15, 16], and transition
metal complexes like Prussian blue systems [17, 18]. Viologen derivatives [19, 20]
and conducting polymers, e.g., poly(aniline), poly(thiophene), are examples of
organic electrochromic materials while hybrid systems are formed by the complex-
ation of metal ions with organic ligands or polymers bearing coordination sites.

1.2 Operating Principle of an Electrochromic Device

The operating system for the study of electrochromic materials with very few
exceptions is a two-terminal electrochemical cell configuration and all employ at least
one optically transparent electrode. Materials to be applied for electrochromic device
are first studied either as an electro-active solute or surface film under potentiostatic or
galvanostatic control and an absorption measurement medium [1]. Conventional elec-
trochemical techniques such as cyclic voltammetry (CV), coulometry, or chronoam-
perometry [21] are employed. The potentiostat or galvanostat is usually connected to a
spectrophotometer and in situ spectroscopic measurement is carried out during the
passage of current [22, 23]. Three-electrode circuitry can be employed for testing of
materials to investigate their electrochromic parameters [1], while a simple
792 S. V. John and E. Iwuoha

two-electrode system comprising of the working electrode and the counter electrode can
be employed for practical electrochemical device investigations. Basically, the two
electrode system involves a working electrode (the primary/electrochromic elec-
trode) and a counter electrode (the secondary electrode) in a sandwiched config-
uration (Fig. 1). The working or electrochromic electrode is typically made of
glass or flexible plastic (mainly poly(ethylene terephthalate) (PET))sheet, coated
with an optically transparent electrically conducting film, e.g., tin doped indium
oxide (ITO) on which the electrochromic material is deposited. A solid (often
polymeric), gel, or liquid electrolyte is sandwiched between the primary electrode
and the charge-balancing secondary electrode in the electrochemical cell to
separate both electrodes. Upon application of an appropriate electrical potential,
the electrochemical cell becomes charged/discharged and the device undergoes
color switch which takes place at the working electrode. After the decay of the
resulting current pulse and color change effected, the new redox state persists,
with little or no power input. During this time, the optical response is monitored
and recorded by in situ spectroscopic measurement.
The active electrochromic material can be WO3, MoO3, V2O5, Prussian blue [PB,
iron(iii) hexacyanoferrate(ii)], viologen systems, e.g., 1,l0 -disubstituted-4,
40 -bipyridylium salts, conducting polymers or a complexation of organic and inor-
ganic material. This chapter focuses on conducting polymers and their application as
the active electrochrome in electrochromic device.
Fig. 1 Schematic
representation of the operating
principle and testing of an
electrochromic material
19 Electrochromic Polymers for Solar Cells 793

2 Conducting Polymers

Conducting polymers are conjugated polymers that conduct electricity. They are
organic macromolecules which consist of at least one backbone chain of alternating
double- and single-bonds. This is due to the conjugation which occurs as a result of
the overlap of a p-orbital with another across an intervening σ – bond. The system
usually comprises of a region of overlapping p-orbitals bridging the adjacent single
bonds and allows delocalization of π-electrons across all p-orbitals aligned adjacently
[24]. The π electrons do not belong to a single bond or atom, but rather to a group of
atoms. A conjugated compound may be cyclic, acyclic, linear, or mixed. Systems
with the largest form of conjugation are graphite, carbon nanotubes, grapheme, and
conductive polymers. They have a unique characteristic which is the conjugated
molecular structure of the polymer main chain where the π-electrons delocalize over
the whole polymer chain and can result in interesting and useful optical and electronic
properties. Generally, conducting polymers can either be ionically or electronically
conducting. Polymer electrolytes are classified as the ionically conducting polymers
while conjugated conducting polymers and the insulating polymers blended with
conducting materials are classified as electronically conducting polymers. In this
chapter, the conducting polymers are limited to conjugated conducting polymers.
Although known for many years, conjugated polymers did not attract significant
research interest until the mid-1970s due to their intractable nature. Research papers
based on conjugated polymers were rare and the research was usually not done according
to a fixed plan or system as the chemical nature and mechanism of their conductivity was
not known. For decades, after the demonstration of polymers by Hermann Staudinger in
1920 as long chain molecules which led to his Nobel Prize in Chemistry in 1953, the
general perception about polymers is that they were insulators, until the conductivity of
polyacetylene was reported by Shirakawa, McDiarmid, and Heeger in 1977. This report
brought about a change in the research in this field of polymers. They showed that poly
(acetylene) can be made conductive by reaction with halogen vapors [25]. The reaction
was proven to occur by the modification of neutral polymer chains to polycarbocation
and concurrently inserting the corresponding halogen anion between the polymer chains
in order to neutralize the positive charge on the polymer chain which was induced by
doping [26]. They also showed that after doping polyacetylene with electron-
withdrawing AsF5 the conductivity increased, reaching the order of 103 S/cm
[25, 27]. Extensive research into the chemistry and physics of this field including well-
defined methodology both for the doped and undoped forms began after this discovery.
Table 1 presents major organic conducting polymers according to their composition. The
well-explored classes are written in bold and the less well explored in italics.

2.1 Conjugated Polymers as Semiconductors

2.1.1 Basic Characteristics

Poly(acetylene), the simplest conjugated polymer, and the prototype of other conju-
gated polymers exist in two isomeric forms. The structures can either be trans- or
794 S. V. John and E. Iwuoha

Table 1 Major organic conducting polymers according to their composition

Heteroatom present
Components of No hetero-atom Nitrogen-containing
the main chain present Sulfur-containing Polymers Polymers
Double bonds Poly(acetylene)s
(PAC)

Poly(heptadiyne)s

Double bonds Poly(p-phenylene

coupled with vinylene) (PPV)
aromatic cycles

Aromatic cycles Poly(phenylene) Poly(thiophene)s Poly(aniline)s

only (PANI)

Poly(fluorine)s Poly
(3,4-ethylenedioxythiophene) Poly(pyrrole)s
(PEDOT) (PPY)
Poly(azulene)s)

Poly(carbazole)s
Poly(isothianaphthene)

Poly(indole)s)

Poly(paraphenylene sulfide)

cis- based on the locations of the hydrogen atoms on the double bond carbons.
Trans-poly(acetylene) has the two hydrogen atoms located on the opposite sides of
the double bond carbons, while cis-poly(acetylene) has the hydrogen atoms located
on the same side of the double bond carbons (Fig. 2a, b). Each carbon atom of poly
(acetylene) is sp2 hybridized and can therefore be handled as a one-dimensional
analogue of graphite. Nevertheless, the C-C bond in poly(acetylene) are not equal
(Fig. 2d). This is known as the Peierls distortion or Peierls effect. The Peierls effect
has an important effect on the electronics of poly(acetylene) and by extension, other
conjugated polymers. It modifies the properties of a polymer by opening a gap
between the highest occupied molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO) [28, 29]. This occurs when the pz-orbitals of the polymer
align perpendicular to the polymer backbone creating an enabling environment for
electronic interaction between the double bonds, an interaction that results in
delocalization, improving the conductivity of the conjugated system [30]. A periodic
19 Electrochromic Polymers for Solar Cells 795

bond alternation and variation in charge density occurs within the chains due to
variation in the delocalization of the double bonds (Fig. 2c).
The π-conjugated system of poly(acetylene) and most polymers is formed by the
overlap of carbon pz orbitals. However, in some systems like that of poly(aniline),
the pz orbitals of nitrogen also take part. The main chain structure of poly(aniline) is
in a way complicated compared to other conjugated polymers. The presence of basic
centers of amine and imine nitrogens in the conjugated backbone of poly(aniline) makes
it show a different chemistry compared to other poly-conjugated systems. Generally,
poly(aniline) exists in three main structural forms, namely, leucoemeraldine, emeraldine
base, and pernigraniline depending on the level of reduction or oxidation. The
neutral or most reduced form of poly(aniline) is leucoemeraldine. It consists of
rings of phenylene joined together by amine nitrogens. The completely oxidized
form of poly(aniline) is pernigraniline. It consist of benzenoid and quinoid type of
bonds and rings in the ratio 1:1 with imine nitrogens in between the ring, while the
partially oxidized form – emeraldine base – consists of equal numbers of imine and
amine nitrogens with benzenoid and quinoid rings in the ratio 3:1 (Fig. 3).

Fig. 2 Structure of various a b

forms of poly(acetylene) H H H H H H H

n n
H H H H H H H H
Trans-poly(acetylene) Cis-poly(acetylene)
c d

Total delocalization of Bond length alternation of short

the double bonds double bonds and long single
bonds (the Peierls distortion)

H H
N N

N N Leucoemeraldine
H H n

H
N N

N N n
Emeraldine Base
H

N N

Pernigraniline
N N n

Fig. 3 Structure of tetrameric repeat units of the three forms of poly(aniline)

796 S. V. John and E. Iwuoha

The conductive ability of a polymer largely depends on the band gap (Eg). The
band gap is defined as the energy difference between the highest occupied molecular
orbital (HOMO) or valence band and the lowest unoccupied molecular orbital
(LUMO) or conduction band [31]. According to the energy difference, materials
are classified into three groups as shown in Fig. 4: conductors, semiconductors, and
insulators. For conductors, band gap does not exist as the highest energy level of the
HOMO combines with the lowest energy level of the LUMO (no energy gap between
the HOMO and LUMO). As a result, the electrons easily migrate to the LUMO from
the HOMO. Some examples of good conductors are Fe, Cu, Al, Au, Ag, etc.
Semiconductors and insulators on the other hand have defined band gaps. For an
insulator, the difference in energy between the HOMO and the LUMO energy level is
large; thus, the promotion of electrons from the HOMO to the LUMO in principle is not
possible. Due to the large band gap between the HOMO and LUMO of insulators, they
do not conduct electricity. Examples of insulators are mainly saturated polymers,
Bakelite, rubber, and wood. The band gap for saturated insulated polymers is higher
than 10 eV [32]. This hinders the promotion of electrons from the HOMO to the LUMO
and therefore prevents conductivity. For conjugated semiconducting polymers, the
energy of delocalized HOMO is increased, while that of the LUMO is decreased due
to delocalization through the polymer chain. Their conductivity falls in between those
of metals and insulators with moderate band gaps. The gap between insulators is
usually larger than that of semiconductors as can be seen in Fig. 4. They absorb light
with an energy that is equal to or higher than the gap between their HOMO and LUMO.
Examples of semiconductors are GaAs, ZnO, conjugated polymers, etc.
When light of certain energy (equal to or higher than the band gap) is absorbed by
a semiconductor, electrons are transferred from π to a π excited state. This phe-
nomenon is known as excitation and it is represented in Fig. 5 [33].
Conductivity of polymeric materials can be intrinsic or induced (doped). The
conductivity of intrinsic conducting polymers ranges from 1011 to 105 S/cm,
while the conductivity of doped conjugated polymers generally ranges from 103
to 103. Conjugated undoped polymers conduct electricity only in the lower

Fig. 4 Representative energy level diagram of energy gap in conductor, semi-conductor, and
insulators
19 Electrochromic Polymers for Solar Cells 797

semiconducting region. For conjugated polymers to be applied as electrochemically

active materials, improving the conductivity is vital. This can be achieved by doping
of the polymer materials. Doping lowers the band gap and increases the polymer
conductivity up to a range of 105–105 S/cm (Fig. 6) [34].

2.1.2 Doping in Conjugated Polymers

Doping in inorganic semiconductors is generally due to the incorporation of holes in
the valence band or addition of electron in the conduction band. Doping in

Fig. 5 Orbital diagram of an unsaturated material. i) Ground state. (ii) Energy is absorbed and an
electron is excited from the π orbital to the π orbital (excited state)

Conductivity increases with increased doping

Ag, Cu Doped trans-poly(acetylene)

106
SEMICONDUCTORS METALS

Fe (105 S/cm)
Mg
104 Doped poly(aniline)
In, Sn
INCREASING DOPING LEVELS

102 (103 S/cm)

100
Ge
10–2
10–4 trans-poly(acetylene)
Si (10–5 S/cm)
10–6
AgBr
10–8
Glass Polyaniline
10–10
INSULATORS

Diamond (10–10 S/cm)

10–12
Nylon 10–14
Quartz 10–16

Fig. 6 Conductivity of electronic polymers. (Reprinted from Curr. Appl. Phys., 1, Alan
G. MacDiarmid, “Synthetic metals,”: a novel role for organic polymers (Nobel Prize 2000 Lecture),
269–279, Copyright (2001), with permission from Elsevier.)
798 S. V. John and E. Iwuoha

conjugated polymers is however different. The mechanism in this case, in addition to

electron acceptance or release, involves the simultaneous insertion of counter ions
into the polymer matrix. The doped polymers are considered as polymeric organic
salts and the oxidizing or reducing agents used for the doping are known as dopants
or doping agents. Doping of conjugated polymers can be achieved in two ways.
They are:

• Redox type doping

• Acid-base doping

Redox Type Doping

Redox type doping is the doping of conjugated polymers by an applied voltage.
Conducting polymers can either be p-type doped or n-type doped. In p-type doped
polymer, the main chain of the polymer is oxidized by counter-anions leaving holes
in the chain. For n-type doping, the polymer main chain is reduced by counter-
cations leaving electrons on the main chain.

p-Type Doping
Oxidative or p-type doping can be defined as the loss of electrons by the valence
band, i.e., from HOMO of conjugated polymer to the oxidizing agent. The oxidiz-
ing agent accepts the electrons and becomes reduced. It leaves the polymer main
chain with positive charges. It involves the oxidation of the polymer chains to
polycarbonium cations and concurrently inserting a suitable amount of anions
between the polymer chains to neutralize the polycarbonium cations charge. The
oxidizing agent is termed the p-type dopant. Examples of oxidative or p-type
dopants are Br2, I2, AsF5, H2SO4, SO3, FeCl3,PF3, SF6, CH3F, NO2F, NO2,
NO+SbCl6, HClO4, BCl3, etc. In oxidative doping, the oxidants gain electrons
from the polymer and become the counter-anion according to the reaction
represented by Eq. 1


CP þ 3=2 I 2 ! CPþ ðI 3  Þ (1)

where CP denotes conducting polymers.

The p-type doping can be carried out both chemically and electrochemically on a
variety of conjugated polymers like poly(acetylene), poly(aniline), poly(pyrrole),
poly(p-phenylene), poly(thiophene), etc.

n-Type Doping
The n-type doping on the other hand is the transfer of an electron from a reducing
agent to the empty conduction band, i.e., to the LUMO of conjugated polymer. In
n-type doping, the conjugated polymer accepts electrons from the dopant (the
reducing agent), an ionic complex is formed having negatively charged conjugated
polymer chain and counter cations, and the polymer becomes reduced. The reducing
agent in this case is termed the n-type dopant. The n-type dopants are
19 Electrochromic Polymers for Solar Cells 799

electron-donating substances. Due to the electron rich nature of conjugated polymers

as a result of their π-system, strong reducing agents such as alkali metal are required
for n-type doping. The process leaves the polymer main chain with negative charge
carriers, and the dopant loses electrons and become the counter-cation. The reaction
is represented by Eq. 2

CP þ Naþ ðC10 H 8 Þ ! CP ðNaþ Þ þ C 10 H 8 (2)

As a result of the electron rich nature of conducting polymers and the strength of
the reducing agent required for their n-type doping, there are relatively a small
number of reports available on the n-type doped conjugated polymers.

Acid-Based Doping
Conjugated polymers possessing strong basic centers in their backbone can be doped
by acid-base doping methods in addition to redox doping method. The emeraldine
base form of poly(aniline), for example, undergoes protonation in an adequate
amount of strong protonic acid to give the corresponding emeraldine salt. The
protonation involves the imine nitrogens and they are preferentially protonated in
a two-step transition from isolated, doubly charged, spinless bipolaron to a polaronic
metal (Fig. 7). The first step of the protonation gives the product with the charge
stored as bipolarons (Fig. 7ii); then due to instability on the polymer chain, redis-
tribution of charge (internal redox process) occurs and transforms the bipolarons into
polarons (Fig. 7iii). The polarons then undergoes a second step by separating to
form a polaron lattice (Fig. 7iv).
Generally, the doping process involves charge transfer to or from the π-system of
conjugated polymers, while the σ-system is kept unbroken. Although the structural
identity of the individual chains of doped polymers is maintained, the electronic,
vibrational, supramolecular structure and other properties of the polymer are altered.
The doping process increases the polymer conductivity by several orders of magni-
tude and in some cases reach the conductivity of metals [35–39].

2.1.3 Doping Methods

There are two main doping methods employed for the doping of conjugated polymers.

• Electrochemical doping
• Chemical doping

Electrochemical Doping
Oxidative or reductive doping can be achieved by electrochemical oxidation or
reduction of conducting polymers on an electrode surface. In the electrochemical
oxidation or p-doping process, the main chain of the polymer loses an electron and
becomes oxidized according to Eq. 3 below

CP  e þ A $ CPþ ðAÞ (3)

800 S. V. John and E. Iwuoha

Fig. 7 Preferential H
protonation of emeraldine N N
base form of poly(aniline).
i) Before protonation, (ii–iv) i) N N n
after protonation, (ii) H
formation of bipolarons, (iii)
2H+ Protonation
formation of polarons), and
(iv) formation of polaron H H
lattice N N
+
+
ii) N N n
H H

Internal redox

H H
N N
.+
.+
iii)
N N
H H n

Polaron separation

H H
N N
.+ .+
iv)
N N
H H n

where A represents the anions in the solution, CP+(A) represents the oxidized
conducting polymer and doped counter-anion. In the reduced systems, the main chain
of the polymer accepts electrons and becomes reduced according to Eq. 4 below

CP þ e þ M þ $ CP ðM þ Þ (4)
Generally, electrochemical doping is conducted in a nonaqueous electrolyte
solution having quaternary amine salts of mono-valent anions either at constant
current or constant potential. In most cases, the monomer is used and it undergoes
both polymerization and doping simultaneously. The supporting electrolyte supplies
the ions and dopes the conjugated polymer by coupling ionically with the monomer.
The dopant anions generated from the electrolyte are inserted into the polymer
matrix and oxidation takes place concurrently. A variety of supporting electrolytes
are available for electrochemical doping and poor nucleophilic aprotic solvents (e.g.,
acetonitrile, benzonitrile) are employed. Other aprotic solvents such as dimethyl
formamide, dimethyl sulfoxide, hexamethyl phosphoramide, and hydroxylic, with
nucleophilic character can also be used. The nucleophilicity of this second class of
aprotic solvent is reduced by the addition of a suitable protic acid for their applica-
tion as solvent for electrochemical doping. Quaternary ammonium salts of the form
R4NX (where R = Alkyl, Aryl group and X = Cl, Br, I, PF6, CF3SO3, ClO4,
BF4, CH3C6H4SO3) are commonly used supporting electrolytes that are soluble
in aprotic solvent [40].
19 Electrochromic Polymers for Solar Cells 801

Electrochemical doping of conjugated polymers has been extensively

employed. In electrochemical doping, polymers are obtained from the monomers
by electropolymerization and this results in a doped polymer; they therefore do
not require additional doping [41]. Nevertheless, if a different dopant is needed,
the polymer can be electrochemically reduced to its neutral form before
re-doping with the anion of interests either chemically or electrochemically.
The polymer can be deposited from a polymer solution on an electrode surface
by spin coating or drop coating. In most cases, electrochemical doping is carried
out using cyclic voltammetric electrochemical method and the accompanying
spectroscopic changes can be monitored. This is usually made possible by the use
of spectro-electrochemical methods where a spectroscopic instrument is coupled
with an electrochemical instrument, e.g., UV-Vis/CV [42–44], EPR/CV [45–48],
FTIR/CV [49–52], Raman/CV [53, 54].

Chemical Doping
The first report on doping of conjugated polymers was on the use of halogens
(Br2 and I2) and arsenic pentafluoride (AsF5) as doping agents for poly(acetylene)
[25, 27]. Equation 5 shows the chemical reaction describing the doping of poly
(acetylene) with halogen
h
 i
ðC 2 H 2 Þx þ 3=2 yx X 2 ! ðC 2 H 2 Þy þ X 
3 y (5)
x

The doping process involves the conversion of the doping agents into linear
polyhalogen anions (I3, Br3) which are then inserted into the polymer matrix.
The mechanism for the doping of poly(acetylene) with Br2 is slightly delicate. In
the case of Br2 oxidative doping, the reaction involves the addition of bromine to
the double bond and this breaks the conjugation and converts parts of the poly
(acetylene) into insulating poly(dibromovinylidene). To avoid this, doping with
Br2 is conducted in very mild conditions. Arsenic pentafluoride can be used to
achieve both redox and acid-base types of doping. Transition metals with oxi-
dizing properties, e.g., FeCl3 [55, 56], strongly or mildly oxidizing acids such
as HClO4 and H2SO4 [57] arsenates or antimonates (NO2+XF6, where X = P,
As, Bi), nitrosonium salts (NO+XF6, where X = P, As, Bi), and nitronium salts
of hexafluorophosphates can be used for the doping of a good number of
conjugated polymers. Chemical doping of conjugated polymers is a useful
method of doping of conjugated polymers. However, in this technique, control
over the doping level is somewhat poor and complete doping to the optimum
concentrations often results in inhomogeneous doping.
Doping brings about a six- and ninefold increase in the conductivity of conju-
gated polymers. Conducting polymers shows temperature dependence conductivity
similar to that of semiconductors. It obeys the Mott variable range hoping (MVRH)
model. MVRH is a model that describes low-temperature conduction in strongly
disordered systems with localized charge-carrier states [58]. The MVRH has a
characteristic temperature dependence represented by
802 S. V. John and E. Iwuoha

1=
σ ¼ σ o e ð =T Þ
To 4
(6)

For n- space dimension of the material, MVRH is given as

1
=ðnþ1Þ
σ ¼ σ o e ð =T Þ
To
(7)

where σ is the prefactor, n is the space dimension number of the material. The
prefactor is independent or weakly dependent on temperature.
The degree of ordering and doping of conjugated polymers plays a huge role in
their conductivity.

3 Charge Carriers in Conducting Polymers

The charge carriers in conjugated polymers are solitons, polarons, or bipolarons.

Solitons are interesting type of excited states which have kinks in the bond alterna-
tion. They can exist in the neutral or redox state. The neutral soliton can lose an
electron and be oxidized to form a positive soliton or gain an electron and be reduced
to form a negative soliton. Neutral soliton So has a spin of ½ while charged soliton is
spinless. Polarons, on the other hand, are radical ion associated with a lattice
distortion. The positively charged and negatively charged polarons formed from
oxidation and reduction of the polymer main chain are denoted as P+ and P,
respectively, and they possess a spin of ½. The coupling of two positively charged
polarons or two negatively charged polarons on the main chain of a conjugated
polymer results in bipolaron. It is a pair of like charges (dication) associated with
strong local lattice distortion. It is formed when the concentration of the polaron is
high on the polymer main chain. It is thermodynamically more stable than two
polarons and it is spinless.
The major charge carriers in conducting polymers, however, are polarons. For
n-type doping of poly(acetylene), neutral chains of the polymer are either chemically
or electrochemically reduced to polycarbonium anions and cations are inserted into
the polymer chain simultaneously. In such instance, negatively charged spinless
solitons are the charge carriers. Figure 8 shows the schematic representation of the p-
and n-type doping process of poly(acetylene). The p-type process starts by the
removal of an electron from the π-system of the polymer resulting in the formation
of a radical cation (polaron). It is followed by the removal of a second electron
resulting in a second radical cation which recombines or couples with the first to give
spinless dication (bipolaron). The spinless dication can further be oxidized to
solitons [59].
For polyheterocyclic systems, the removal of an electron from the π-system
results in the emergence of a radical cation called polaron. The presence of the
polaron creates a domain of quinine-type bond sequence within the aromatic bond
19 Electrochromic Polymers for Solar Cells 803

Polyene
a
+ e–
+ A+
A– Polaron
b (radical cation)
e–
A+
A– Bipolaron
A– (dication)
c
recombination of free
radicals to spinless
solitons

A– A–
Soliton pair
d

p-Type doping of poly(acetylene)

Polyene
a
+ e–
+ C+
C+ Polaron
b (radical anion)

+ e–
+ C+

C+ Bipolaron
C+ (dianion)
c
recombination of free
radicals to spinless
solitons

C+ C+
Soliton pair
d
n-Type doping of poly(acetylene)

Fig. 8 Schematic representation of p- and n-type doping of poly(acetylene). A = anion,

C+ = cation

sequence of the polymer chain. Removal of a second electron may either lead to the
formation of another polaron or a spinless bipolaron [60]. The bipolaron in this case
is a dication separating the quinine bond domain from the aromatic bond domain in
the polymer chain (Fig. 9).
804 S. V. John and E. Iwuoha

a S S S S
S S S S n

– e–
+ A–

b S S S S
S + S S S n

– e–
+ A–

A–
S S S + S
c S + S S S n
A–

Fig. 9 Schematic representation of p- type doping of poly(thiophene)

4 Electronics of Conjugated Polymers

The absorption spectra of conjugated polymers can be used to distinguish between

intrinsic conducting and doped conducting polymers. For doped conducting poly-
mers, strong absorption maximum peak in the visible to near-infrared (NIR) region
of the electromagnetic spectrum is generally observed. This is brought about by the
presence of polarons and bipolaron in the main chain of the conjugated polymers.
Figure 10 [61], for example, shows the absorption spectra of poly
(2,5-dimethoxyaniline) (PDMA) in different doping states at different applied poten-
tials (0.3 V, 1.0 V, and 0.5 V) in 0.001 M HCl as supporting electrolyte. The spectra
show three absorption bands at 370, 470, and 690 nm. The peak at 370 nm
corresponds to the fully reduced leucoemeraldine state of PDMA (yellow). Upon
partial oxidation, the peak disappears and a peak at 470 nm is observed. The peak at
470 nm is the intermediate or partially oxidized form of polyaniline (emeraldine)
which is green in color. The peak disappears upon full or complete oxidation and
another peak which corresponds to the completely oxidized form of polyaniline
(pernigraniline) which is blue-violet to purple in color appears at about 690 nm. The
doped poly(aniline) can be reduced to its intrinsic conducting form by dedoping of
the polymer. In such case, the absorption band which corresponds to the oxidized
form of polyaniline is weakened and finally disappears.
The band gap values are estimated from spectroscopic and electrochemical
measurements. For spectroscopic measurements, the onset absorption is estimated
from the tangential position where the absorption begins to level to a straight line as
shown in Fig. 11.
19 Electrochromic Polymers for Solar Cells 805

1.4 Yellow peak at 370 nm Blue peak = 690 nm

Green peak at 470 nm

1.2 0.3 V
Absorbance

1.0
1.0 V

0.8

0.6
0.5 V
0.4

0.2
300 400 500 600 700 800 900
Wavelength (nm)

Fig. 10 UV-VIS spectra of the PDMA film recorded at different applied potentials to distinguish
doping levels. (Adapted with permission from Ref. [61])

Fig. 11 Representation of
onset absorption

From the onset of the absorption, the band gap is calculated using Eq. 8

1240
g ¼
E op ðeVÞ (8)
λonset

g is the optical band gap and λonset is the onset absorption in nm.
where Eop
806 S. V. John and E. Iwuoha

For the electrochemical measurements, the HOMO and LUMO energy levels of
the polymers are estimated from the cyclic voltammetric onset oxidation and onset
reduction potentials of the polymer or material, respectively. The electrochemical
band gap of conjugated polymers can be calculated using the linear correlation
between the ionization and oxidation potential with the electron affinity and reduc-
tion potential derived by Bredas and co-workers [62] on the basis of a comprehen-
sive comparison between the valence effective Hamiltonian (VEH) theoretical
results and experimental electrochemical data (Eqs. 9, 10, and 11)


I p ¼  Eox
onset þ 4:4 eV (9)


Ea ¼  E red
onset þ 4:4 eV (10)

And E elg ¼ I p  E a (11)

where E ox red
onset and E onset are onset oxidation and reduction potentials (determined at the
position where the current starts to differ from the baseline) Fig. 12.
Conducting polymers are intrinsic semi-conductors with band gaps which depend
on the chemical composition of the conjugated backbone as well as the substituent
on the main chain. Their optical and electronic properties can therefore be varied
resulting in the fabrication of various types of electronic devices. The conductivity of
conducting polymers increases by several folds due to doping. They not only show
high conductivity but also impart interesting optical and mechanical properties. They
have fascinating properties like good scalability, mechanical strength, flexibility,

Fig. 12 Representation of electrochemical onset oxidation and reduction

19 Electrochromic Polymers for Solar Cells 807

unique optical properties, ease of processing, long shelf life, and low cost for device
integration [63, 64]. They therefore find applications as semiconducting materials, in
electronics, optoelectronic, and other semiconducting materials. Interestingly, these
π-conjugated polymers also possess electrochromic properties like diverse colors,
high optical contrast, fast switching speed, and good processability for electro-
chromic device applications, such as smart windows, mirrors, and displays
[64–71]. Also, in addition to having the electronic and optical properties of metals
and inorganic semiconductors, conducting polymers have intriguing electrochemical
redox properties. They can exhibit more redox states and generate multiple colors
unlike their inorganic counterparts [1].

5 Electrochromism in Conducting Polymers

Electrochromism occurs in conjugated polymers when the polymer is induced by

redox processes. This results in the modification of the electronic properties of the
polymer, giving rise to changes in the color. Upon oxidation or reduction (doping),
the gap between the highest occupied molecular orbital (HOMO) and lowest unoc-
cupied molecular orbital (LUMO) potentials (band gap) is modified and color
changes. The color changes lead to the ability of such electrochromic materials to
exhibit various colors. The energy band between the HOMO and the LUMO
determine the intrinsic optical properties of conducting polymers. They are doped
with counter anions when oxidized (p-doping) and contain delocalized π-electron.
Reduction removes the dopant to give the undoped (neutral) electrically insulating
form. The color can be controlled by structural modification of the main-chain of the
polymer structure, nature of the monomer substituent, side chains, the pendant
group, or the length of the polymer chain. All conducting polymers therefore are
potentially electrochromic in nature due to redox switching which give rise to new
optical absorption bands and colors together with transfer of electrons/counter
ions [72].

5.1 Electrochromism in Poly(aniline)

Poly(aniline) has received considerable attention due to its broad range of tunable
properties derived from its structure flexibility. It exists in three distinct oxidation
states and can be switched between oxidation states by chemical or electrochemical
means through the conversion of some of the amine nitrogen(s) to imine nitrogen(s).
The reduced form of poly(aniline), leucoemeraldine, is yellow. By chemical or
electrochemical doping, poly(aniline) shows reversible transitions to its intermediate
oxidized form of blue emeraldine base form(EB), while further oxidation to
pernigraniline state renders the material purple [73, 74]. The emeraldine base
form can be protonated to its green conducting emeraldine salt.
Generally, poly(aniline) is known for insolubility resulting in intractability.
With the recent breakthroughs in the synthesis of conducting polymers with
808 S. V. John and E. Iwuoha

nano-dimensional control, the challenge of poor processability of poly(aniline) has

been overcome. The nanosphere mixture of poly(aniline) with poly(sodium4-
styrenesulfonate) (PSS) is highly dispersed in aqueous solution as the emeraldine
salt and the electrostatic interaction between poly(aniline) and the surfactant makes
this nano-dispersion stable [75, 76]. Figure 13 shows the chemical oxidation of
polyaniline with the blue emaraldine base and green emeraldine salt form [75]. Due
to high conductivity and rapid redox switching, nano-sized poly(aniline) has poten-
tial advantages in electrochromic application.

5.2 Electrochromism in Poly(thiophene) and Its Derivatives

Poly(thiophene), a polyheterocyclic system, has received wide research interest for

applications in organic electronics (organic photovoltaic cells, organic light emitting
diodes, organic field effect transistors) and other applications. A good number of
publications on organic electronics are based on thiophenes. The success of this
group of polymers in organic electronics, particularly in organic photovoltaics, is
huge. Its unique properties prompted the research for it possible application as the
active material in electrochromic device. The potential of poly(thiophenes) for
electrochromic applications was first reported in 1983 [77, 78]. Unsubstituted poly
(thiophene) was electrochemically polymerized, and its redox properties were inves-
tigated and reportedly revealed a red to blue switch on p-type doping. This corre-
sponds to the bleaching of its π-π* transition in the visible region with simultaneous
emergence of infrared charge-carrier optical transitions. Electrochemical n-type
doping of the unsubstituted poly(thiophene) resulted in a color change of red to
black-green [79].
The thin films of polythiophenes are blue in their doped state with a maximum
wavelength of 730 nm (oxidized state) and 470 nm in their undoped (reduced) state

Fig. 13 Schematic diagram and photograph of preparation of PANI/PSS-NPs. (Reprinted from

Electrochemistry Communications, 12, Sung Jong Yoo, JoonHyuk Cho, Ju Wan Lim, Sun Ha Park,
Jyongsik Jang, Yung-Eun Sung, High contrast ratio and fast switching polymeric electrochromic
films based on water-dispersible polyaniline-poly(4-styrenesulfonate) nanoparticles, 164–167,
Copyright (2010), with permission from Elsevier.)
19 Electrochromic Polymers for Solar Cells 809

[80]. Monomer modification can significantly alter optical response. For example,
the positions of methyl groups or alkoxy substituents on the polymer backbone of
polymer films prepared from 3-methyl-thiophene-based oligomers strongly deter-
mined the color [81]. The colors varied from pale blue, blue to violet in the
oxidized form and purple, yellow, red to orange in the reduced form. This
variation in color is ascribed to changes in the effective conjugation length of
the polymer chain. Reynolds’ group reported a series of alternating conjugated
donor–acceptor polymeric hybrids containing 3,4-dioxythiophenes, 2,1,3-
benzothiadiazole, and unsaturated spacers (ethynylene or trans-ethylene).The
presence of trans-ethylene spacers induced narrowing of the energy gaps
affording various tones of greens, a color not common to achieve in the field of
π-conjugated polymers [82]. The polymer showed excellent optical and redox
stabilities to repeated switching of over 3000 cycles, demonstrating the potential
of this polymer for electrochromic device applications.
Poly(3,4-(ethylenedioxy)thiophene)s an analogue of poly(thiophene) is a unique
electron-rich polymeric material possessing high oxygen content. It was designed in
the late 1980s at the Bayer AG research laboratories in Germany to address the lack
of processability exhibited by the more conventional unsubstituted poly(thiophenes).
Compared to its unsubstituted poly(thiophenes) parent, neutral deep blue PEDOT
shows a relatively stable and highly transmissive sky blue oxidized state. In Fig. 14,
the onset of the optical absorption of neutral PEDOT lies in the near-IR region of the
electromagnetic spectrum. This excellent transmissivity of PEDOT has attracted
significant research attention and has been the focus of a considerable number of
publications [81, 83].
Havinga and Reynolds et al. [67, 85] introduced solubilizing alkyl side chains to
the alkylenedioxy bridge of PEDOT, to produce the first neutral-state solution
processable PEDOT derivatives (Fig. 15a). They investigated the electrochemical
performance of these materials and compared the response to that of the
unsubstituted PEDOT. In addition to the direct effect of this structural modification
on the energy gap of the subsequent analogues, which depends on the length and
bulkiness of the substituted pendant group (1.75–1.8 eV), the substitution was found
to enhance the switching properties of PEDOT and a more effective depletion of the
neutral-state optical absorption was observed on full oxidation. Hydrophobic ana-
logue exhibiting particularly high contrast ratios, rapid switching times along with
the same dark blue to transmissive sky blue switch on electrochemical oxidation and
narrow band gap of 1.65 eV, has been reported for the perfluoroalkyl ester-
functionalized derivative PEDOT-F (Fig. 15b) [86].
The electrochromic properties of PEDOT and its derivatives have revealed
contrast ranging from 45 to 62% and a fast response time of ~10 s in their
maximum wavelength of absorption [87–91]. Considering the ease of functiona-
lization and structure controlled optical properties of poly(thiophene) and its
analogues, they have attracted research attention as conducting polymer active
electrochromes. Various possibilities of fine tuning the colored neutral state
taking full advantage of the different substitution-induced backbone conforma-
tions have been proposed.
810 S. V. John and E. Iwuoha

Fig. 14 Spectroelectrochemistry of a thin film of PEDOT at different oxidation states with inset
pictures of variation in the blue color on application of different biases. (Reprinted (adapted) with
permission from Ref. [84], Copyright (2004) John Wiley and Sons)

Fig. 15 Structure of PEDOT derivatives

19 Electrochromic Polymers for Solar Cells 811

5.3 Electrochromism in Triphenylamine Containing Polymers

Triphenylamine containing polymers are readily soluble aromatic polyamides. They

show interesting redox properties that are useful for electrochromic application. The
preparation and characterization of a series of novel electrochromic aromatic poly-
amides have been reported. The electrochromic properties of a series of polyamides
with pendent triphenylamine units based on N,N-bis(4-aminophenyl)-N0 ,
N0 -diphenyl-1,4-phenylenediamine exhibited two reversible oxidation redox couples
at different applied potential ranging from 0 to 0.85 V. They revealed color change
from pale yellow to green and then blue at 0.85 and 1.25 V, respectively [92]. Liou
reported several triphenylamine containing electrochromic polymers with interest-
ing color transitions that showed good electrochromic reversibility in the visible
region and near infrared range [93–96]. However, despite the interesting properties,
majority of the polymers only reveal less than two stages of electrochromism due to
challenge of increasing electroactive nitrogen atoms within triarylamine-
containing structures. In a recent work, the Liou group designed and synthesized
a series of novel near infrared electrochromic starburst triarylamine-based materials
with the incorporation of electron-donating substituents at the para-position of
phenyl groups [97]. This is believed to be able to prevent the coupling reactions
by affording stable cationic radicals and lowering the oxidation potentials
[98–104]. In the neutral form (when no voltage was applied), the film of one of
the reported polymers exhibited strong triarylamine absorption around 346 nm with
almost transparent response in the visible region. At an applied voltage of 0.55 V,
the intensity of the absorption peak at 346 nm decreased while a new peak at
447 nm and broad intervalence charge transfer absorption around 1170 nm was
observed. The broad absorption at 1170 nm was due to the intervalence charge
transfer absorption excitation between states in which the positive charge is cen-
tered at different nitrogen atoms. The applied voltage was varied between 0.55 V
and 1.45 Vand the response showed different spectro-electrochemical behavior and
colors as shown in Fig. 16.
The electron-donating substituents reportedly stabilized the radical cations and
lead to good solubility and film forming property of the polyamide in addition to
good thermal stability. The report by Beaupre´ et al. of electrochromic polymers
containing a 4-butyltriphenylamine (BuTPA) unit on the main chain shows the
color transition of these polymers as shown in Fig. 17 [105]. The copolymers show
promising optical and electrochemical properties for military camouflage needs
with color transition from pale yellow to green, transparent to khaki, or pale green
to reddish-brown. The copolymers PC(BuTPA) and PCC(BuTPA) are colorless in
their neutral states and show reversible color transition from colorless to khaki fits
either desert or forest background for military camouflage. Relatively good electro-
chromic characteristics such as high contrast ratio both in the visible range and
near infrared region, low switching times, high coloration efficiency, and highly
electrochromic/electroactive reversibility are reported for these novel polymers.
This suggests a good potential for practical applications in both visible and near
infrared region.
812 S. V. John and E. Iwuoha

OMe
i OMe

N N
O O
Ar:
N N N Ar
H H
n O
99%
N

MeO OMe

ii
Ox. Ox. Ox. Ox.

Re. Re. Re. Re.

0 729
346 1100
(e)729
20
1079
Transmittance (%)

40 447 (d) 1170

Transmittance (%)

0
583 20
60
40
(c)
60 1.4
80 80 1.2

l)
(b)
C
1.0 Ag
(a) 100
0.8
g/
.A

100 400 0.6

vs

600
800 0.4
V

Wa
l(

400 600 800 1000 1200 1400 1600 vele 1000 0.2
ia

ngt
h (n 12001400 0.0
nt
te

Wavelength (nm) m)
Po

Fig. 16 i) Structure of the aromatic polyamide and the appearance of the flexible film; (ii)
Electrochromic behavior (left) at applied potentials of (a) 0.00, (b) 0.55, (c) 0.80, (d) 1.10,
(e) 1.45 (V vs. Ag/AgCl), and 3D spectroelectrochemical behavior (right) from 0.00 to 1.45
(V vs. Ag/AgCl) of polyamide thin film (~120 nm in thickness) on ITO-coated glass substrate in
0.1 M TBAP/CH3CN. (Reprinted (adapted) with permission from (Ref. [97]), Copyright (2011)
American Chemical Society)

6 Electrochromic Devices with Optically Transparent

Polymer Layer

The replacement of ITO (an optically transparent electrically conducting material)

by a polymer in an electrochromic device setup is referred to as an “all-polymer”
electrochromic device. PEDOT-PSS in otherwise all-plastic designed device architecture
has resulted in a strictly “all-polymer” electrochromic device [106]. In this case, a film of
poly(3,4-(ethylenedioxy) thiophene)–poly(styrene sulfonate) (PEDOT–PSS) served as
19 Electrochromic Polymers for Solar Cells 813

O O

N N
S S

C4H9 C4H9
PT(BuTPA) PE(BuTPA)

N
C8H17 N
C4H9
PC(BuTPA)
C4H9
3
N N
H 3O C8H17 C8H7
PCC(BuTPA)
C6H3
C6H13

C4H9
PF(BuTPA)

Fig. 17 Chemical structure and color transition of some triarylamine-containing copolymers.

(Reprinted (adapted) with permission from (Ref. [105]), Copyright (2006) American Chemical
Society)

the electrically conducting material film and was spin-coated on commercial

transparent plastic. The prototypes were made from PEDOT-PSS and mixed
with N-methylpyrrolidone (NMP) or diethylene glycol (DEG) additive by incor-
poration into the aqueous casting solutions of PEDOT-PSS [106]. Devices which
exhibited excellent relative luminance change values as high as 51% with con-
trast nearly as high as that obtained when using ITO-coated glass electrodes
(56%) have been reported [70]. About 51% transmittance change at 540 nm upon
switching and high stability with only a few percent contrast loss over more than
30,000 switches was demonstrated by Argun et al. [106].

7 Electrochromism and Solar Cells

It is a well-known fact that the most abundant source of renewable energy is solar
radiation. Researchers in the field of renewable energy are working tirelessly and
making frantic efforts to make photovoltaic technology an alternative source of
energy. As promising and interesting as this may sound, solar radiation is also one
of the main causes of energy consumption in buildings (both residential and com-
mercial) through increased cooling demands when the heat generated is high.
Increases in the energy consumption of buildings can be mainly attributed to the
desire to be comfortable and free from thermal discomfort arising from too high or
too low perceived temperatures, while in the building by occupants.
814 S. V. John and E. Iwuoha

The energy consumed by buildings for heating, cooling, lighting, and ventilation
accounts for about 30–40% of the global primary energy [107]. The energy lost
through inefficient window stock accounts for ~30% of the heating and cooling in
buildings in the USA [108]. It is estimated that 41% of the energy consumed in the
USA in 2009 was in the commercial and residential buildings, a 48% increase in the
1980 estimate [109]; 19% of this value is attributed to cooling and lighting and 37%
attributed to space heating and the remainder to water heating and consumer electronics/
appliances [109]. There is a considerable high energy demand for cooling systems in
Europe with electrically driven air conditioning dominating the peak power during
summer in parts of Europe as well as in the USA. Therefore, in more extreme climates,
the electrical power may be entirely dominated by air conditioning.
A potential technology for reduction in both lighting and cooling energy use
through modulation of transmitted light and solar heat is variable transmission
electrochromic windows (VTECWs) [110, 111], popularly known as “smart win-
dows.” Smart windows are used in the control of the incident daylight and glare in
buildings and automotive applications [112–114]. This technology can modulate the
solar energy entering a building as well as other see-through devices by application
of an applied voltage. They can be switched from 62% visible transmittance, 0.47
solar heat gain coefficient to a fully tinted state with 2% visible transmittance and
0.09 solar heat gain efficiency [110]. Their ability to modulate solar energy trans-
mittance keeps the heat from the sun out and provides substantial total energy
savings. They offer tunable shading which allows light energy use savings of up to
48–67%, while bringing down annual peak cooling loads to as low as 19–26% when
compared to efficient low-e windows [115]. As a result, shade or blinds are not
necessary for reduction of glare in buildings and the comfort of building occupants
can be significantly enhanced with comfortable working or living environment and a
clear view and link to the outdoors.
VTECWs combine electrochromism and light-harvesting ability for power gen-
eration. They require an external power source offsetting some of the energy savings.
They can be self-powered switchable devices only or can be used as power sources
for different applications. This can be achieved by the integration of an electro-
chromic device with a photovoltaic device. The integration results in so-called self-
powered or photo-electrochromic device [116–120]. The photovoltaic component or
device is externally incorporated to the periphery of the electrochromic windows
[117–120] as part of the device stack. The device is typically based on low band-gap
a -Si or dye-sensitized solar cells as the power-generating component and transition
metal oxides, metal coordination complexes, viologen systems, or conducting poly-
mers as the active electrochrome. The combination of solar cell and electrochromic
device results in improved efficiency while saving energy. VTECWs are now
preferred over the low e-windows as a result of the awareness of reductions in
glare, reflections on the computer monitor, and window luminance. Sbar et al. [110]
modeled the performance of commercial office buildings in three US climate zones
and demonstrated that electrochromic windows can notably reduce building energy
consumption compared to current static glazing systems. Lee et al. summarized the
findings from a 15-month monitored pilot demonstration of WO3 large-area
19 Electrochromic Polymers for Solar Cells 815

electrochromic windows with automated controls in a west-facing conference room

in Washington DC [121]. The electrochromic windows were automatically con-
trolled in an on–off, fully clear, or fully tinted mode with a dimmable lighting system
installed as shown in Fig. 18.

Fig. 18 (a) Interior view of the conference room with upper and lower control zones and (b)
Signage instructing occupants on how to switch the windows. (Reprinted from Energy and
Buildings, 47, E.S. Lee, E.S. Claybaugh, M. LaFrance, End user impacts of automated electro-
chromic windows in a pilot retrofit application, 267–284, Copyright (2012), with permission from
Elsevier)
816 S. V. John and E. Iwuoha

Electrochromic materials find applications for transmittance modulation of

sunlight control window glazings used in cars and buildings (smart windows),
protective eyewear for the military, optical displays, antiglare car rear-view
mirrors, controllable aircraft canopies, and storage devices [3, 65, 69, 122]. Mate-
rials for electrochromic device applications must possess characteristics such as
long-term stability, rapid redox switching, multiple colors within the same
material, high coloration efficiency (CE), and high optical transmittance change
(Δ%T). These characteristics play a huge role in electrochromic device performance
and it is therefore crucial to obtain a good combination of these characteristics.
Usually, the photogenerated current triggers the color of the electrochromic layer
[123, 124]. Photo-electrochromic devices using the dye-sensitized solar cell (DSSC)
approach have been fabricated based on metal complexes (e.g., Prussian blue) or
metal oxide (e.g., WO3) [116, 125]. The DSSC acts as the solar power generating
material while the electrochromic material acts as the active electrochrome in the
device. Inorganic materials like WO3 are the major players in the design of electro-
chromic devices. They have been extensively studied and found commercial
application.
Organic electrochromic devices in which the active electrochromes are poly-
mers have also been reported. Xu et al. reported in a patent, the synthesis, and
application of poly(3,4-propylenedioxythiophene) as the active electrochrome in
electrochromic devices [126]. Wudl and co-workers reported EDOT derivative
which exhibited high coloration efficiency and stability after 5000 switching
cycles but only with a contrast ratio of 57% [127, 128]. Ho et al. described the
first photo-electrochromic device based on electrochromic polymer PEDOT. The
device consists of dual ECD/DSSC all-in-one device. In this device, WO3 (the
conventional metal oxide active electrochrome) was replaced by a film of
PEDOT (Fig. 19) [129]. The device reportedly possessed much larger coloration
efficiency values than those of other materials like WO3. The same group recently
reported on alkyl substituted analogue of the parent PEDOT (PProDOT-Et2
(Fig. 15c))-based photo-electrochromic device with enhanced contrasts (~34%
transmittance attenuation) [130].
Despite the fact that inorganic materials have been extensively studied for
electrochromic devices and have found commercial application in this field,
conducting polymers have become a recent focus of researchers in this field.
This is basically due to the fact that all electroactive and conducting polymers are
potentially electrochromic materials, more processable than inorganic electro-
chromic materials, and offer the advantage of a high degree of color tailorability [131].
They have several advantages such as processability, high coloration efficiency, fast
switching ability, and multiple colors within the same material over inorganic
materials. Inorganic materials offer limited color variation and their use involves
complicated processing. The improved advantage of conducting polymers over the
inorganic materials for electrochromic device is achieved through the modification
of various polymer systems via monomer functionalization and copolymerization
[132–135] which result in significant improvement or change in the spectral property
and electrochromic response.
19 Electrochromic Polymers for Solar Cells 817

e– e–

Glass Coloring
Glass

hu I–
(Visible) e–
e–

I3– ClO–4
electrolyte

I–
Ru-dye
molecules
I3– e–

ClO–4

Bleaching
ITO ITO
TiO2 fine PEDOT
particles

Fig. 19 Photo-electrochemical cell described by Ho et al. (Adapted with permission from

Ref. [129])

8 Conclusion

Considering the extent of recent progress in the design of conjugated conducting

polymer electrochromes, the current interest of these materials for electrochromics
and organic electronics is not unexpected. They have witnessed a surge of interest for
their applications in electrochromic devices in the past decade due to their ever-
improving physical properties. Given the ability to manipulate the polymer band gap
by modifying the molecular structure of its repeat unit and the opportunity to
simultaneously tune the colors, ambient-stable materials operating over tens to
hundreds of thousands of switching cycles can be achieved. Due to their process-
ability, environmental stability, wide range of colors and spectral properties, electro-
chromic conducting polymers are on the path to commercialization.

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Textile Coatings
20
Shah Mohammed Reduwan Billah

Contents
1 General Aspects of Textile Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
1.1 Advanced Functional Coated Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 828
1.2 Coated Textiles for Conventional and High-Tech Applications . . . . . . . . . . . . . . . . . . . . 829
2 Textile Fabrics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
3 Different Types of Coatings and Application Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 831
3.1 Knife Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 831
3.2 Pad Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
3.3 Screen Printing/Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
3.4 Digital Coating Using Inkjet Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
3.5 Other Coating Techniques Usually Used in Textile Coatings . . . . . . . . . . . . . . . . . . . . . . 835
3.6 Recent Technological Advancements and Their Impacts on Textile Coatings . . . . . 837
4 Film Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 843
5 Polymers and Additives for Typical Textile Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
5.1 Selected Characters of Commonly Used Polymers in Textile Coatings . . . . . . . . . . . . 845
5.2 Thermoplastic Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 846
5.3 Thermosetting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
5.4 Rubbers and Their Uses in Textile Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
6 Textile Coating Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
7 Functional Coatings on Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
8 High Thermal-Resistant Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
9 Fire Retardant Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
9.1 Application of Flame Retardant Finishes by Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
10 Silicones in Textile Fabric Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
10.1 Surface Active Agents and Chemical Softeners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 851
11 Scratch- and Abrasion-Resistant Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852

S. M. R. Billah (*)
University of East London, Stratford Campus, London, UK
CCIRA UK Limited, Galashiels, UK
Department of Chemistry, Durham University, Durham, UK
School of Textiles and Design, Heriot-Watt University, Galashiels, UK
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 825

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_30
826 S. M. R. Billah

12 Self-Healing Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853

13 Antibacterial Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
14 Antifouling Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
15 Enzymatic Biocoatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
16 Antimicrobial Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
17 Microencapsulation in Coating and Finishing of Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856
18 Conductive Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856
19 Self-Assembled Nanophase Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
20 Coated Breathable Fabrics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
21 High-Tech Superhydrophobic-Coated Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 859
21.1 Design, Development, and Evaluation of Superhydrophobic Coatings . . . . . . . . . . . 860
22 Powder Coating Technology and Coated Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 862
22.1 Epoxy Powder Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
22.2 Hybrid Powder Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
22.3 Polyester Powder Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
22.4 Acrylic Powder Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
22.5 UV-Curable Powder Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
23 Photonic Coatings on Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 865
24 Textile Finishing and Textile Coatings in Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 865
24.1 Main Influencing Factors for Future Developments in Textile Coating
and Finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
25 Conclusion and Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 868
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 868

Abstract
Textile coatings usually provide material layers which adhere to the textile
structures. A typical textile coating formulation generally contains polymeric
binder(s) along with other additives (such as colorants, adhesion promoter,
biocide, plasticizers, etc.) which are applied in the form of a solution or a
dispersion or a paste or a similar fashion using a spreading technique onto a
textile fabric. Different types of techniques are commonly used for textile coat-
ings, for examples, spray coating techniques, the application of nanoscale tech-
nologies, biotechnology, and plasma technology. Certain coating technologies
including digital coating technology have many industrial potentials in order to
produce higher performance coated textiles with a variety of conventional and
functional properties. Textiles with multifunctionalities are increasingly
demanded as a part of advanced and future marketing strategies, for instance,
garments and technical textiles for outdoor environments can have novelty and
durable self-cleaning properties at the same time. Various ways are usually used
to impart novelty and functionality into coated textiles. For example, sol–gel
chemistry is one of many techniques which can be used to produce super-
hydrophobic coated textiles suitable for many high-tech and general application
purposes. This chapter provides selective pieces of information on different types
of popular textile coatings and related specific features which have pronounced
impacts on the behaviors of coated textiles. It also briefly provides some selective
pieces of information on different advancements in textile coatings in
20 Textile Coatings 827

consideration to the applications of new advanced techniques as well as fre-

quently used general coating techniques (such as spraying, padding, etc.) to
produce high-performance coated textiles for conventional and high-tech
applications.

1 General Aspects of Textile Coating

Textile coating is one of very highly important topics for aesthetic as well
as functional modification of the textile surface in order to produce high-quality
textiles and their products suitable for various applications. Additionally, the devel-
opment of conventional and functional coated textiles with multiple properties
have potential applications in different areas including – (a) protective and casual
clothing, (b) security, (c) mobility, (d) lightweight construction, (e) geotechnology,
(f) environmental technology, (g) health, (h) communication and emotion, (i) fashion
and designs, (j) automobile, and (k) filtration. Besides these, coated textiles have
diverse range of other applications as well. For example, a military tent can be made
of a material that combines nylon fabric with a neoprene coat, whereas a urethane-
coated polyester cloth can be used to make the inflatable chutes installed at the
emergency exits from the aircrafts. For textile coatings, different types of coating
formulations are used. For example, typical textile coating formulations usually
contain polymeric binder(s) along with other additives (such as colorants, adhesion
promoter, biocide, plasticizers, etc.). Generally, a coating formulation is applied onto
the textile surface in the form of a solution or a dispersion or a paste or a similar
fashion using a suitable spreading technique [1–3]. In addition, during different
textile coating formulations, a wide range of polymers are practically in use for a
variety of purposes. For a typical textile coating based on a polymeric system, two or
more layers are usually applied on textiles where at least one of the layer is a textile
fabric and the other is the thin continuous polymeric layer along with other additives.
The nature of each layer and their combined characters determine the overall prop-
erties of the coated system. In this context, the textile substrate provides the required
strength (such as tear and tensile strengths), elongational, and dimensional properties
of the system. The polymer coat provides different desired properties, some of which
include – (a) the required resistance to penetration and impermeability (to liquids,
gases, and dust particles), (b) improving fabric abrasion, (c) providing other required
character on the coated textile surfaces, (d) increasing conductivity, (e) providing
shielding from electromagnetic interference/radiofrequency interference (EMI/RFI),
(f) introducing antimicrobial properties, (g) modifying the appearance for decorative
purposes [2–5]. The layers within the coated textiles are bonded to each other in situ
by the adhesive properties of the layers in order to produce “coated fabrics,” or
additional adhesives which are sometimes also used to produce “laminated fabric.”
Besides this, coating on textiles can be carried out in a variety of ways. For example,
in order to produce a typically coated textile, different steps can be used successively,
828 S. M. R. Billah

which include – (a) direct spreading of the thick liquid layer of coating formulation
or paste of polymer in liquid form over the textile surface, (b) evaporating the thick
liquid layer or liquid in the polymer paste to leave the polymer on the fabric (for
solvent-based system), or (c) allowing the transformation into a coat in the case of
plastisol- or dispersion-based system (both of these processes are usually carried out
in special dryer or ovens). In addition, required level of crosslinking of the polymer
coat is achieved during this drying step (also called curing) which helps to enhance
durability to abrasion and resistance to solvents (and water). Advantages of this
processing type include the production of coats without mechanical or thermal
stresses. However, removing large amounts of solvent or dispersion medium involve
time and energy which are often very expensive and not environmentally friendly
[5–14].

1.1 Advanced Functional Coated Textiles

Textiles are a ubiquitous part of human life which can be incorporated with a
number of functional materials in order to provide new useful functional and high-
tech application properties. In order to produce advanced functional coated textile,
a wide range of functional materials and polymers can be used for textile coatings.
Some of these functional materials include – (a) environmentally responsive
materials (such as photoresponsive, thermally responsive, electrically responsive,
magnetically responsive, biologically responsive materials), (b) chromic sensoric
materials (such as photochromic, thermochromic, ionochromic, electrochromic,
piezochromic, mechanochromic materials), and (c) other sensoric matertials or poly-
mers. For example, photonic materials are widely used in advanced textiles for many
high-tech applications [1, 2]. Photonic coatings have the capability to provide some
important functional features on photonic-coated textiles useful for various applica-
tions, such as in electronic textile applications. The combination of textiles with
electronics for producing electronic textile systems provides many potentials in
new emerging application fields. The development of photonic polymer coatings
can change their volume or surface topology in a reversible, dynamic fashion
when exposed to an external stimulus. For instance, topographic response can be
established by using hydrogels or liquid crystal polymer networks by the change of
the surface corrugation in response to light (by which, various functional coating
characters can be modulated, for example, wettability and/or mechanical friction).
Similarly, volume changes in photonic coatings can be produced by different stimuli
that can lead to a change in light reflection [1–4, 8–20].
Polymer coatings as well as textile coatings have a significant importance
in our everyday life which protect everyday objects from environmental influences.
In addition, coatings are also widely used for aesthetic purposes which include –
(a) adhesion-promotion/reduction and (b) antireflection or antifouling. These
functional characters are often determined by the surface topography. Currently,
extensive research interests are focused on the improvement in the design or
formulation of stimulus-responsive polymer-based coating systems which are
20 Textile Coatings 829

mostly dynamic in nature rather than on their static properties. In this type of coating
systems, the changes in characteristic properties in response to an external stimulus
(where the functional properties can be adjusted autonomously) depend on user
needs or on environmental changes. These types of smart coatings have important
potentials in meeting social challenges in many areas including – (a) sustainable
energy, (b) health, (c) food safety, (d) sensors, (e) electronics, (f) communication.
For instance, the photo-induced dimensional or structural change has many attractive
appealing features since it can be done locally without contact and without changing
the immediate chemical environment of the polymer coatings or the integration
of electrodes. Photoexposure has the potential in order to lead to the structural
modification of a polymeric network to generate a change in the surface topography.
Additionally, photo-induced changes in the surface roughness or the hydrophilicity
of materials are highly attractive because they can alter their wettability and/or also
can controllably change in their nature of adhesion. Photoresponsive coatings are
sensitive to sunlight, and they have the potential to develop sun-tracking materials or
materials with self-cleaning properties involving structural changes [1, 2, 5, 18–35].

1.2 Coated Textiles for Conventional and High-Tech Applications

Coated textiles have huge application potentials. Polymer coating on textiles can
be on one or both side(s). Textile coatings are very important on different types
of applications of textile substrates, some of which include – (a) specific textile
products usually used in aerospace, automotive (e.g., airbags), (b) chemical pro-
cessing, (c) E-textiles, (d) geotextiles, (e) military textiles, (f) filtration and heating,
venting and air conditioning applications, (g) textile products used in carpeting,
(h) protective clothing, (i) fuel cells, (j) home furnishing applications, (k) inflatable
boats, (l) folding kayaks, (m) gloves, (n) snowshoes, (o) tents, and (p) fuel tanks.
Overall properties of a polymer-coated textiles dependent on a number of things
including on the nature of textiles, polymers used in coatings along with the nature
of additives and application techniques used. The nature of textiles plays a very vital
role on the performance of polymer-coated textiles. Some of the usually used textiles
for coating with polymers include (a) natural textiles (such as cotton, wool, silk,
hemp, jute, linen); (b) synthetic polymer-based textiles (for examples, polyester,
nylon, viscose, acetate/triacetate, acrylic/modacrylic, aramid); and (c) other poly-
meric substrates, such as elastomeric, fluoropolymer, polyamide, olefin, polyolefin,
polyester, polyethylene, Rayon, styrene acrylonitrile, and polyvinyl chloride.
Certain type of fiber glass-based substrates (such as fibers of glass, fiberglass,
E-glass, S-glass, rock wool, slag wool, ceramic, boron, carbon, graphite, silica,
metallic fibers, and zirconia-based fibers) can also be coated with particular types
of polymer-coating systems. In all of these cases, polymers play a dominating part
for textile coatings [27, 36–66].
As a result, a solid background and knowledge of polymer science and technol-
ogy in addition to knowledge of textile technology and the principles of chemical
engineering is very important for producing highly viable and robust textile coating
830 S. M. R. Billah

formulations suitable for different industrial scale exploitations. However, a detail

discussion on all of these areas is beyond the scope of this current chapter; it only
provides selected brief information on the components of the textile coating systems
as well as short discussions on different types of textile coatings, chemistry and
technology involved with these methods, along with their applications in textile
coatings.

2 Textile Fabrics

The nature of a textile fabric where the textile coating is applied is one of the main
determinant on the characters of coating system. A variety of coating techniques are
practically in use for textile coatings, for example, conventional, continuous coating
methods use substantial tension on textile fabrics, more specifically woven textiles
need more applied tension as they show relatively more dimensional stability.
Fabrics made from staple fibers, especially cotton, are the most commonly used
textile substrate for coating for a long time [4, 43, 60]. However, at present fabrics
made from synthetic filaments are most predominant for their use in textile coatings
mainly due to their strength and easy processing. Figure 1 illustrates three basic
types of textile constructions which are – (a) a woven, (b) a weft-knitted, and (c) a
warp-knitted textile fabric. In a plain-woven fabric construction, each weft yarn goes
between every warp yarn, where every other weft insertion takes the opposite sides
of the warp yarns. This is also the most dimensionally stable woven construction as
this system locks every yarn in place. The density of the fabric depends on the
thickness (such as dtex) of the yarns and how tightly the yarns are packed, and it also
has a control on the rigidity of the fabric. Weft-knitted fabrics can be produced by
using flat- and circular-knitting techniques. In principal, a single yarn bobbin can be
used as it is made to form loops (held by needles) into which new loops of the same
yarn can be formed and the yarn is led from side to side in flat-knitting and circularly

Fig. 1 Illustration of plain textile constructions: (a) woven structure, (b) knitted wept structure,
(c) knitted warp structure
20 Textile Coatings 831

upwards in circular knitting. Particularly, knitted fabrics and plain weft-knits have
tendency to show deformation which makes the fabrics easy to fit onto a human
body; however, this property may be a drawback when stability and rigidity is
required. Warp knitting is an intermediate between weaving and weft knitting, but
it is probably the most versatile construction technique of textile fabrics where the
fabrics can be anything from the finest lace to the most robust automotive interior.
In this case, yarns are vertically placed side-by-side, similar to the warp yarns
in weaving and placed in guiders in order to allow them to be interlocked with
each other horizontally. Additionally, the fabrics often mechanically outshine
woven- and weft-knitted fabrics. Synthetic filaments are mainly required for this
type of construction for avoiding entanglements. Many noble characters can also be
incorporated with this system according to end uses. This makes them ideal for many
high-tech applications, some of which include – (a) sports items, (b) products for
automotive interior, personal protective equipment, and (c) geo and greenhouse
fabrics [4].

3 Different Types of Coatings and Application Methods

Coatings are protective and/or decorative compositions that dry to a cohesive,

adherent, tack-free film when applied to a substrate (such as textile substrates).
Textile coatings contain polymeric binders along with other additives (such as
colorants, adhesion promoter, biocide, plasticizers, etc.). Based on the nature
of components used in the coating formulations and also on the objectives of the
coated surfaces where they are applied, textile coatings can be of different types. For
examples, hydrophobic and hydrophilic coatings; organic and inorganic coatings;
aesthetic and functional coatings; conventional and technical coatings; and metallic
and nonmetallic coatings. Coating mechanisms also depend on the nature of coating
formulations and also on the nature of the substrates [4, 57]. Various types of coating
techniques are usually used in textile coatings where main types include – (a) pad
coating, (b) direct coating or knife coating, (c) inkjet coating technology, (d) atomic
layer deposition, (e) chemical and physical vapor deposition, (f) UV coating,
(g) plasma coating, (h) magnetron sputtering, (i) screen printing, (j) sol–gel coating,
(k) coating by using evaporation techniques, (l) coating by layer-by-layer deposi-
tion, and (m) coating by using general or specific spraying technique [4, 56–59].

3.1 Knife Coating

Knife coating, or direct coating, is one of the most widely used technique for textile
coatings. In principle, a blade is used to smear out a thickened polymeric formulation
across a moving textile substrate. When the substrate rests on a roll beneath the blade
the technique is called knife-over-roll (Fig. 2). Other setups include – knife-over-air
(or floating knife) and knife-over-blanket. Different setups mainly deal with the
penetration of the coating into the textile substrate where the knife-over-roll yields
832 S. M. R. Billah

Fig. 2 Schematic illustration of knife-over-roll coating

Fig. 3 Schematic illustration of pad (or pad-mangle) coating

the highest degree of penetration and floating knife causes the lowest. In this case,
blade angle, gap height, coating speed, and the shear viscosity of the formulation are
also important for the degree of penetration which, in turn, affect the adhesion
of the coating to the substrate. These parameters are affected by other forces related
to textile coatings some of which include – (a) tension, (b) air flow, (c) pressure,
(d) temperatures, (e) time, and (f) relative humidity [4, 57].

3.2 Pad Coating

Pad coating (also known as impregnation) is a dipping procedure where excess

formulation is squeezed out by the rollers from the textile fabrics. A typical pad
coating arrangement is demonstrated in Fig. 3. The method allows coating to pene-
trate into the interstices in the textile fabric and between the fibers in the yarn. In this
case, the coating is on the entire fabric, whereas in most other cases, coating methods
lead to a more one-sided coating. The amount of applied material to the fabric
depends on coating viscosity as well as the speed by which the fabric moves through
20 Textile Coatings 833

the coating liquid and the time the fabric is in the liquid is referred to as dwell time.
From a fluid-mechanical consideration, the pad-mangle coating process is viewed
as a combination of dip coating and a forward two-roll coating process (Fig. 3). Main
governing factors in the dip coating process include – (a) nature of the textile
substrate, (b) substrate speed, (c) surface tension and viscosity of the formulation
(with water as solvent, the effect of drying during the process is negligible), (d) nip
pressure of the roll coater, (e) roller speed, and (f) rheological properties (such as
viscosity, surface tension, flow behavior). Sometimes, it is difficult to control the
shear forces applicable during the entire process because of the great number of
process parameters [4, 57].

3.3 Screen Printing/Coating

Rotary screen printing is considered as one of the most common printing techniques
in the textile industry since it provides many advantages over other techniques, some
of which include – (a) efficiency and (b) fast and versatile in character, especially
when compared to older methods (such as engraved roller printing and flat-bed
screen printing). The basic principle behind both rotary and flat-bed screen printing
is that the printing formulation is pressed through a screen onto the textile substrate.
Usually, the screen is printed with the inverse of the desired pattern with an
UV-curable ink, then with an open screen mesh. Rotary screen printing usually
contains a cylindrical screen often made of perforated nickel, whereas the screen is
flat in flat-bed screen printing and often made out of polyester mesh. During
industrial rotary screen printing, the fabric rests on a rubber mat that moves the
fabric forward under the rotating screen. As the friction between the fabric and
screen is low, the method is suitable even for delicate, stretchable, lightweight textile
substrates with uneven surfaces. A magnetic table is used beneath the substrate and
a squeegee or a metal rod is placed over the screen on the top of this table which is
used to squeeze out the print through the cylinder. Rotary screen printing allows
continuous printing operation without having to move the screen exactly into a new
place which is essentially required during flat-bed screen printing process. However,
the flat-bed technique still has industrial applications in printing of individual textile
products (such as t-shirts and table cloths), and it is also popular for laboratory-scale
textile coating using screen coating technique [4, 54–62].

3.4 Digital Coating Using Inkjet Technology

Inkjet technology have many wide range of applications including in digital dyeing,
printing, and coating of textile substrates. Inkjet printing, a noncontact printing
technology, allows deposition of ink droplets on various substrates, such as textiles,
paper, leather, ceramic, glass, and also on many other substrates for different pur-
poses. It is capable to meet the market demand for producing samples and product
within a very short time compared to screen printing technology. This technique is
834 S. M. R. Billah

also suitable for mass customization along with the scope of adaptation to unlimited
design possibilities with respect to repeat size and color range. Inkjet printing
techniques can also be used for the digital dyeing of textiles using a very innovative
technique where the colorants and related additives can be applied on the substrates
in the form of a jettable ink disposing through the inkjet printhead which is commonly
used for inkjet printing technology. Inkjet printing techniques are increasingly
gaining the momentum to produce very high-quality printed substrates using a
wide variety of materials, including, conventional dyes, functional dyes, pigments
to meet the demand for a wide variety of colored substrates for their different
applications. All inkjet technologies are basically precise microdisposal techniques
which digitally control the fluid droplet (e.g., the ink) ejection from the printhead onto
a substrate. Various techniques can be used for a digital control on the fluid droplet
ejection from the printhead to the substrates which are sometimes used as a basis
for the classification of inkjet printheads. For example, continuous inkjet printing
technique or drop-on-demand inkjet printing technique are two mostly used terms for
a broader classification of industrial inkjet printing technology (although there are
variants within each class). Recently, inkjet technology has been rigorously explored
for digital coating of textiles for both conventional and high-tech coated textiles with
immense industrial application potentials. There are many advantages of using inkjet
technology for digital coating of textiles. For example, using inkjet technology, fluid
deposition can be precisely controlled and placed in an exact location. It is particu-
larly beneficial for applications that require multiple coatings on a single substrate
(such as coated textile for outdoor work wear). Inkjet technology can also be used
for functional coatings on textiles using different types of inkjet printheads. These
techniques can also be used for high-throughput productions on both rigid and
flexible substrates. In addition, inkjet coating can be used for functional finishing of
textiles which may provide different benefits including – (a) fast turnaround time,
(b) maximum customization, (c) reduced wastage, and (d) improved energy savings.
Table 1 provides a comparison on the benefit of using digital inkjet coating technique
along with other usually used coating technique [1, 2].

Table 1 A comparison of digital inkjet coating with other selective coating techniques
Name of Nature of
coating Film Nature of Type of material
technologies quality productivity Applicability Scalability process waste
Spray-coating Low High Polymer/ High Subtractive High
or doctor small molecule
blade
Screen Low Very highInorganic/ Medium Subtractive Medium
printing/ polymer/small
padding molecule
Inkjet coating Medium High Inorganic/ High Additive Low
technology polymer/small
molecule
Evaporation High Low (batch) Inorganic/small Low Subtractive Medium
molecule
20 Textile Coatings 835

3.5 Other Coating Techniques Usually Used in Textile Coatings

A range of other techniques are also popularly used during textile coatings.
During particular types of textile coatings, many nanomaterials are applied on textiles
using different advanced coating techniques, such as (a) chemical vapor deposition,
(b) physical vapor deposition, (c) atomic layer deposition, (d) electrodepos-
ition, (e) spray coating (both plasma and thermal), (f) self-assembling monolayers,
(g) plasma coating, (h) sol–gel coating, and (i) nanotechnology. Sometime it is very
difficult to separate one technique from another due to the fact that very often a total
coating package come with a combination of more than one technology. For example,
nanotechnology is widely used to engineer and modify the characters of different
ingredients used in textile coating formulations, and sometimes these ingredients are
used by other coating techniques. Additionally, there are many versatile and widely
used processes for the applications of nanoparticles. Nanotechnology is usually used
to provide the tools to control three prominent parameters which are essential to
ensure the performances of thin films. These three main parameter are – (a) chemical
composition (and crystalline structure at nanosized domains), (b) thickness,
(c) topography (including nanoscale patterning of the surfaces of the thin films).
These techniques can be used to produce coated textiles with a diverse range of
properties [4, 8, 28, 29, 67–150] and some of which have been mentioned in different
parts of this chapter (both previous and successive sections).

3.5.1 Chemical Vapor Deposition and Physical Vapor Deposition

These techniques involve heating the material in order to convert the material into
the gas phase and also deposit it onto the textile surface by using chemical reactants
for triggering the deposition process. For depositing the thin film material, several
techniques are widely used, some of which include – (a) thermal evaporation,
(b) magnetron sputtering, and (c) pulsed laser deposition [4, 57–62].

3.5.2 Electrodeposition
It is a coating process that uses the electric current in order to produce metallic
coatings on textile substrates, and there are different ways to apply this technique.
For example, in one method, the deposition is achieved by negatively charging the
substrate to be coated and by immersing it into a solution containing a salt of the
metal to be deposited [4, 60–64].

3.5.3 Spray Coating

Primarily two methods such as (a) plasma spray coating and (b) thermal spray coating
are frequently used in spray coating along with other spray coatings for advanced
textiles. During plasma spray coating (also termed as – plasma arc plating, plasma arc
spraying, and plasma coating), powders are introduced in a cavity that contains the
gas stream of a plasma gun, and after being melted, the powders are projected onto the
surface of the substrate (under coating operation, such as textile surface). Thermal
spraying coating system contains a feed stock material (powder or wire) for heating
and accelerating it to high velocity using a gas stream. Then the particles strike the
836 S. M. R. Billah

surface of the textile substrate and the particles deform and freeze onto the substrate,
and the collision speed is an essential element that have direct control on different
coating properties [4, 57, 60, 65–68].

3.5.4 Plasma Coating

Originally, plasma coating was developed for coating on the clothing mainly used
by the military or for protective applications for saving the wearer from chemical
agents. However, at present, it is generally used for producing very high hydrophobic
nature on coated substrates (such as bioinspired or lotus effect type hydrophobic
nature on coated substrates). In addition, continuous research on this type of tech-
nique has been successful to find ways to reduce the amount of functional additive
required for the production of nonwovens for the hygiene industry. Plasma, a fourth
state of matter, is usually used for modifying textile surfaces during textile coating
using plasma treatments. Two main groups of plasma treatments are – (a) degradative
surface treatments (such as cleaning, etching, sterilization) and (b) addition treat-
ments, (for examples, activating by temporarily increasing the surface energy,
functionalizing by permanently introducing chemical groups, and deposition or
coating). Plasma treatments have many advantages where one of which is that it is
a dry alternative method of textile processing. Plasma treatments under low pressure
(~0.01 kPa) or subatmospheric pressures (~1 kPa) can be used to provide uniformity
of treatment combined with flexibility, but this type of batch treatments use expensive
plasma equipment. In addition, the in-line, high-speed continuous plasma processing
systems at atmospheric pressure (~100 kPa) are less flexible and are influenced by
the environment. To produce different desired characteristic properties on textiles, the
effective use of plasma technologies in order to functionalize fiber surface is an
important step. Plasma treatments are usually carried out on textile for a number of
reasons, some of which include – (a) imparting hydrophilicity to polypropylene and
polyester; (b) increasing adhesion of coatings; (c) pre-treatment for water, oil- and
stain-repellent finishes; (d) pre-treatment for ultra-hydrophobicity/self-cleaning fin-
ishes; (e) pre-treatment for printing wool; (f) pre-treatment for inkjet printing;
(g) enhancing fiber dyeability; (h) modifying electrical conductivity or antistatic
finishes; and (i) application of antimicrobial and flame retardant finishes. Another
important area for developing textile finishing is the introduction of plasma-
polymerization processes, some of which are – (a) plasma-induced polymerization
processes directly on the fiber surface; (b) surface grafting of polymers; (c) functional-
ization of the fiber surface to accept the deposition of polymers and reaction with the
fiber surface; (d) cold plasma discharge synthesis of new polymeric structures to
impart novel effects on the fibers surfaces. Besides this, the use of plasma technol-
ogies for the production of higher easy-care performance through the production
of ultra-hydrophobic finishes in order to produce self-cleaning fabrics with water-,
oil-, and stain-repellent characters [4, 57, 58].

3.5.5 Self-Assembling Monolayers

Self-assembling monolayers are one-molecule thick thin layers spontaneously
formed by a substance that have many potential applications including scratch-
resistant coatings and also producing coated self-cleaning textile surfaces. Crucial
20 Textile Coatings 837

dimension in self-assembling monolayers is the thickness perpendicular to the

plane of the monolayer where this dimension and the composition along this axis
can be influenced (simply at the scale of 0.1 nm) by controlling the structures of the
molecules which are used to make up the monolayer. As for instance, self-
assembling monolayers can also be used to provide tailor-made functions by chang-
ing the structures of the organic molecules in simple ways where interfacial free
energies can be controlled [4, 57, 67, 68].

3.5.6 Atomic Layer Deposition

Atomic layer deposition technique has many uses including producing ultrathin and
conformal thin film structures for many semiconductor and thin film device appli-
cations. This technique is also used for sequential self-limiting surface reactions
in order to control film growth in the monolayer or submonolayer thickness regime.
It has many potential applications in advanced electronic devices. In addition, it has
many advanced applications, for example, this can be used to control the film
structure in the nanometer or subnanometer scale which is useful for coating textile
substrates with complex surface topographies [4, 57, 68].

3.6 Recent Technological Advancements and Their Impacts

on Textile Coatings

Ongoing progresses in different areas of science and technology have been contin-
uously influencing the nature of textile coatings. However, due to limitation of space,
only a few selective scientific achievements on nanotechnology and its impacts of
textile coatings are briefly and selectively covered here in this chapter and sol–gel
technology is also discussed separately.

3.6.1 Nanotechnology in Textile Coatings

Nanofinishing technique is also used for nanocoating of textiles. Nanotechnology
is sometimes used to impart novel qualities on fabric which can repel water and oil
without any loss of natural breathability and comfort of the fabric. Nanotechnology
has been popularly used to improve molecular organization in order to give fibers
and fabrics advanced performance characteristics without losing the original soft-
ness, durability, and breathability. Basic principles of designing a breathable fabric
involve proper selection of different important things, some of which include –
(a) film and coating, (b) fabric substrate, (c) lining material, (d) garment designing,
and (e) nature of additional finish.
In addition, nanotechnology has been successful to open up new horizons in the
production of high-quality coated textiles along with other multiple application in
textile products. For example, nanoscale emulsions are popularly used for chemical
finishing of textiles to achieve uniformity and precision onto the textile surface if this
technique is used during textile coating. During the use of this method, finishes
are usually emulsified into nanomicelles, made into nanosols or wrapped in nano-
capsules in order to attach them to textile substrates for uniform coating in particular
cases. Many high-quality coated textiles for various applications can be used using
838 S. M. R. Billah

this technique. Many nanomaterials are widely used in textile coating formulations.
Generally, the term nanoscale refers to the size range from 100 nm down to 1 nm
(ISO 2010). Nanomaterials have a much larger surface area per unit mass and hence
they become more reactive at the nanoscale. As the nanomaterials decrease in size
towards the molecular and the atomic scale (such as approximately 0.2 nm), the
optical, electrical, and magnetic properties become increasingly dependent upon
quantum effects, as a result characteristic changes in properties can be observed.
Nanoscale technologies encompass a number of enabling technologies (incorporat-
ing materials, manufacturing, measurement, and integration techniques) which result
in products normally embedded into a larger scale component or system rather than
products in their own right. In this case, first generation nanoscale technologies refer
to passive technologies (for example, antimicrobial coatings, nanocomposites) and
second generation refer to active nanoscale technologies (for instance, controlled
release drugs, multifunctional sensors) whereas the third generation refer to active
systems of nanoscale technologies (such as where more than one active nanoscale
technology is present within a system). In particular types of textile coatings,
nanosized particles are applied by coating onto the textile for providing specific
specialist performance properties. In this context, textile coating techniques incor-
porate nanotechnology and the coated textiles produced by using these techniques
are useful for variety of advanced applications including in medical textiles (such as
antimicrobial or antiviral textiles which usually meet biocidal requirements).
Nanotechnology is widely used to produce inkjet inks which can be delivered on
textile surfaces by different techniques including inkjet coating technique. Inkjet
coating on textiles involves the application of chemical coatings onto a textile
substrate by using the similar method which is usually used for digital inkjet printing
technique. Both conventional and advanced functional or technical coated textiles
can be produced by using this inkjet coating technique. For examples, specific
developments in inkjet-coated fabrics include – (a) textiles with dirt repellency and
self-cleaning attributes, (b) stimuli-responsive color changing textiles, (c) rubber-
like fabrics which are impermeable to toxic chemicals, (d) stain-resistant fabrics,
and (e) waterproof fabrics. In addition, during chemical finishing, it is possible to
incorporate different types of nanoscale materials, which are – (a) with one dimension
in the nanoscale (for example, thin film coatings or nanocoatings), (b) with
two dimensions in the nanoscale (such as nanotubes), and (c) with three dimensions
in the nanoscale (for instance, nanoparticles, nanocapsules). There are different
types of nanoscale materials which include – (a) nanoparticles, (b) nanowires,
(c) nanocomposites, (d) carbon nanotubes (single wall, multiwalled),
(e) nanocapsules, (f) quantum dots, (g) nanoporous materials, (h) coatings and
surfaces, (i) nanofibers, (j) graphene, (k) fullerenes, and (l) nanostructured materials.
Nanofibers and nanotechnology in textiles covers a wide range of materials including
textile finishing. In order to impart different functionalities on textiles using different
techniques including coating, nanocomposites can be used to utilize different nano-
particles for incorporation into a polymeric matrix. Nanocomposites have many
potentials for a wide range of textile applications and also to functionalize the textile
substrates for particular set of applications, some of which include (a) UV protection,
20 Textile Coatings 839

(b) biocompatibility, (c) superhydrophobic, self-cleaning finishes, (d) electrical

conductivity, (e) water-, oil-, and soil-repellency, (f) flame retardancy,
(g) antimicrobial activity, (h) antistatic properties, (i) biocatalysts, (j) abrasion resis-
tance, (k) moisture management, and (l) hydrophilic finishes. In addition, nano-
capsules can be used to encapsulate different products, for examples, fragrances,
enzymes, catalysts, oils, adhesives, polymers, nanoparticles, biological cells, vita-
mins, and provitamins. Besides this, nanocoatings can be carried out using a variety
of other techniques, where some prominent techniques include – (a) physical vapor
deposition, (b) chemical vapor deposition, (c) sol–gel treatments, (d) spin coating,
and (e) inkjet technology [4, 57, 58, 69–82]. Nanomaterials are also used for a number
of reasons including – (a) producing self-cleaning fabrics, (b) imparting water-,
oil-, and soil-repellency, (c) providing antibacterial and antifungal finishes,
(d) photocatalytic coatings for detoxifying or color removal, and (e) applying abra-
sion resistant finishes. In addition, sometimes plasma technologies are used for
surface functionalization prior to nanocoating or before the incorporation of chemical
finishes. Moreover, the exploration of nanoscale technologies for application of
nanofinishes can be used to introduce novel finishes for smart textiles and also to
extend the end uses of other type of textiles. However, there are also some potential
risks associated with the use of nanoscale materials (for examples, nanoparticles,
carbon nanotubes) which may limit the full utilization of nanomaterials and more
extensive research is needed to address all these issues [58, 83–99].

3.6.2 Sol–Gel Technology in Textile Coating

Sol–gel technology is popular for particular types of textile coatings. In typical
sol–gel coating formulation, the precursor used in the sol–gel process is usually
dissolved in a solvent in order to form a sol or gel which depends on the reactor
conditions and also to cause precipitation because of chemical reactions. Four basic
steps in the sol–gel process are – (a) hydrolysis, (b) condensation and polymerization
of particles, (c) growth of particles and agglomeration, and (d) formation of net-
works. Practically, sol–gel technology has been popularly used for a long time where
inorganic materials are used along with other components in the coating formula-
tions. Inorganic components of sol–gel coating compositions are usually used
to enhance different desired properties including strength and wear resistance to
obtain important effects on thin coated layers. This technique is widely used in many
industrial applications including in textile coating. However, there are some issues
which limit the wider applications of this technique in textile coatings and some of
which include – (a) the use of highly acidic solutions and predominance of organic
solvents and (b) high process temperatures and long process sequences. Inorganic
sol can be synthesized from various nanopowders of metal oxides (for instances,
TiO2, ZnO, Fe3O4, Al2O3, and SiO2). Coated textiles with hydrophilic or hydropho-
bic surfaces have been reported by using sol–gel techniques [28, 92, 99–122].

Sol–Gel Coatings for the Functionalization of Textiles

Sol–gel technology is popular for the functionalization of textile in order to achieve
better physical maintenance and improvement of particular properties with potentials
840 S. M. R. Billah

of various industrial exploitations. During sol–gel coating, textiles are chemically or

physically modified with used sols (with particle diameters <50 nm or nanosols)
in the coating formulation and change the physico-mechanical, optical, electrical,
and biological properties of the coated textiles. In addition, sol–gel coating protects
coated textiles from destruction and creates new desired functionalities on coated
textiles, some of which include – (a) water, oil and soil repellency, (b) antimicrobial
resistance, and (c) improvements on different technical performances (such as
abrasion resistance, washfastness, lightfastness). This chapter briefly provides
some basic information on the core development on the recent functionalization
methods for producing multifunctionalized textiles by coatings and similar other
techniques which use modified silica nanosols.
Multifunctional textiles have significant potentials to meet future challenges and
also benefit from future changes in overall textile and apparel industries. Functional
textiles have vivid application potentials which are sometimes designed to meet
consumer demands in terms of comfort, easy care, health, and hygiene and also to
protect against mechanical, thermal, chemical, and biological attacks. Besides
these, functional textile coatings have significant contributions in order to develop
performance and durability for technical textiles (such as in automotive, railroad
and aviation engineering, in construction and for home textiles). Coated functional
textiles demonstrate particular characteristic properties, some of which are –
(a) enhanced stability against mechanical, chemical, photochemical or thermal
destruction, (b) strong water-, oil-, and soil-repellence characters, (c) shifting
light absorption and emission properties from the UV up to the IR region, in
particular cases, (d) enhanced electric conductivity (such as for antistatic and
electromagnetic protective effects), (e) immobilization and controlled-release of
active species (for instances, with biocidal, therapeutic, and well-being effects).
Simultaneously, important textile properties (for example, appearance, feel and
durability to laundering) should be maintained as additional feature to newly
incorporated functionalities on the coated textiles to make them suitable for their
uses as high-tech or smart textiles. In usual terms, the textiles can be functionalized
not only by using new production technologies (for example, 3D structures) but
also by improving fiber materials or modifying the fiber surface. Principles related
to selected methods of textile functionalization using different modification tech-
niques include:

(a) Incorporating functional additives (such as organic or biological compounds,

inorganic particles, polymers) into the polymer melt or polymer solution before
spinning. High permanence is a clear advantage, although low flexibility is a
drawback whereas the high nontextile portion, and also the procedure is not
practically suitable for natural fibers.
(b) Direct chemical grafting of additives on the textile fiber surface or by using
linkers on textile surfaces. In addition, this method produces excellent perma-
nent effects; however, it is restricted to reactive fibers and additive structures.
(c) Post-treatment of textiles using functional coatings. This technique is flexible
with regard to coating technology and shows productive capacity which is
20 Textile Coatings 841

Reducing
Resistance to inflamation
abrasion

Water, oil and soil

Application in repellent behaviour
dyeing

Electrical Nanosol Enhacing UV

conductivity coating protection

Controlled release
Providing Biocatalytic or oil and flavours
biocompatibility characters Enhancing
antimicrobial
characters

Fig. 4 Various uses of nanosol coatings and their applications on textiles

largely independent from fabric type that requires low quantities of additive and
enables the combination of different functionalities in a simple way.

Besides this, textile functionalization by using coating techniques is widely

involved with the applications of inorganic sols which are usually produced from
modified silica and other metal oxides. Many reasons are usually considered behind
the use of inorganic sol coatings for the functionalization of textile surfaces some
of which include – (a) sols based on modified silica and other metal oxides (particle
size <50 nm) usually form transparent oxide layers on textiles which show good
adhesion property; these metal oxide layers also exhibit stability against light,
heat, chemical, and microbial attacks; (b) these layers also contribute to enhance
the mechanical behaviors of the textiles (for examples, high mechanical strength,
wear, and abrasion resistance while offering possible methods of varying the surface
characteristics); (c) the oxide coatings can act as carrier for embedded functional
additives, such as organic or biological compounds, inorganic particles, and poly-
mers since it is easy to control layer porosity and the degree of immobilization of the
embedded compounds; (d) this technique also allows the coating formulations at
room temperature and normal pressure using conventional coating devices usually
applied for textile finishing (for example, padding, exhaust processing techniques,
dip-coating, spraying) [4, 28, 57, 92, 99–122]. Figure 4 illustrates different uses of
nanosol coatings and their applications on textiles.

Improved Stability Against Mechanical or Thermal Destruction

Many reports are focused on the modification of textile materials using silica
particles in a sol–gel process to produce ceramic-like composites with higher density
and enhanced mechanical characters. Treating textiles using inorganic nanosols can
be applied in order to enhance abrasive resistance since the inorganic coating
improves solidity. As for instance, the coating of polyester sieves used for paper
842 S. M. R. Billah

production with alkyl modified silica nanosols has the potential for enhancing
their abrasion characters. Moreover, enhancement in abrasive resistance and tensile
strength after nanosol treatments have been reported for other textile substrates (for
examples, cotton, polyamide, and glass fibers). For example, when cotton is treated
with pure silica sols modified by adding epoxysilanes (such as glycidylpropyloxy-
trimethoxysilane or GPTMS), it exhibits a significant improvement in, adhesion
property of nanosol coating to the fiber which eventually contributes to enhance the
mechanical stability of the coated textile substrates. In addition, this enhanced
adhesion property of the nanosol coating on textile is attributed to the chemical
bonding which generates from the opening of the epoxy ring of GPTMS and the
reaction of the hydroxy groups on the cotton surface. There are many applications
for antiabrasion coated textiles, some of which include – the applications of polyes-
ter sieves in paper production and for home textiles (such as furniture or carpets),
knife- and bullet-proof protective clothing. In addition, nanosol coatings are also
popularly used to improve the fire and heat resistance of wooden materials, which
usually use silica nanosols modified with phosphorus compounds (for example,
diethylphosphite or phenylphosphonic dichloride). On the contrary, only a few
reports deal with the improvement of fire resistance of textiles by using nanosols
(though for instance, the use of simple silica sol coatings modified with fluorinated
silane compounds has been reported to improve the flame resistance of nylon-based
carpets). Additionally, the use of SiO2–TiO2 or SiO2–Al2O3 nanosols to textile filters
can contribute to improve heat resistance up to a particular temperature (such as
300
C). Besides this, the flame retardant characters of wool can be enhanced by
using hydrolyzed TiCl4–NH4HF2–dicarboxylic acid solutions. Enhanced heat and
flame resistances have been reported where phosphorus-containing flame-retardants
have been embedded into the nanosol coatings on textile fibers [8, 28, 29, 123–132].

Improved Water, Oil and Soil Repellency

Textiles with repellent characters are significantly important because of a broad
range of prospective uses (for examples, water-repellent textiles as rainclothes
and tents, or easy-to-clean oil-repellent fabrics). Coating with modified nanosols
helps to cover the full range between hydrophilic and hydrophobic textile characters.
Coating textiles with silica nanosols based on perfluoroalkyl compounds contributes
to enhance the hydrophobicity, oleophobicity, and soil repellence of fibers. Addi-
tionally, when alkylsilane compounds without fluorine substituents are used in
nanosol-based coating formulations, they also help to improve water-repellent
characters of the coated textiles [91, 133–135].

Advances in Sol–Gel Coatings for Smart Textiles

In order to meet the increasing demands for comfortable, aesthetic, durable,
functional, and safe textile products with advanced characteristic properties, the
development of new techniques for processing and designing textiles are highly
required. As a result, nanotechnology has been successful to attract its application
on various features of textiles in recent years. Nanoscale manipulation and com-
position are usually used to improve desired properties and to include new func-
tionalities for all kinds of textiles (for examples, self-cleaning, sensing, healing,
20 Textile Coatings 843

decorating, actuating, and communication). The inorganic sol–gel matrix produced

by using coating with nanoparticle sols can be combined with organic systems to
obtain required characters onto textiles (for instances, good mechanical, thermal,
and photochemical stability). These coatings also demonstrate improved adhesion
properties to different types of substrates (for examples, paper, textile, and polymer
sheets), and the matrices are toxicologically and biologically inert, and their
porosity can be controlled. As a result, compounds can be embedded in these
matrices and released in a controlled way into the adjacent gaseous or liquid phase.
In addition, sols and derived coatings can be synthesized based on ambient
conditions using conventional coating processes for textile finishing. In different
ongoing research activities, textiles have been functionalized with new functional
materials. For example, in different reports biosensors integrated within textiles
have been developed using various techniques (for example, incorporating
functionalized optical fibers into fabric structures). Sol–gel coatings have been
designed for the encapsulation of reactive biological entities to deposit on the
optical fiber core and specific interactions with target analytes in order to induce
changes in the color of embedded dyes for detection purposes by using light-guided
optical fibers. These materials are suitable for various applications including –
(a) professional clothing, (b) biomedical textiles, (c) high-tech sportswear, and
(d) technical textiles. Additionally, sol–gel technology provides some promising
application potentials for tailoring surface characters on the coated substrates and
also to combine different functionalities in a single material. For example, the
nanoparticulate sols can be applied using commonly used techniques in textile
industry for fabrication and functionalization of the textile fibers. Moreover, new
functional fibers can be generated by using extrusion and electrospinning tech-
niques from hybrid organic-inorganic sols. The combination of innovative sol–gel
materials, specific functionalization, and casting and deposition techniques pro-
vides the scope for new perspectives in smart textiles with protection, healing, and
comfort by drug delivery mechanisms, wetting, decorative, and sensing properties
[20, 135–193].

4 Film Formation

When a coating formulation is applied on a textile substrate, usually the film is

formed over the surface after the drying and annealing of the coating formulation.
For simplicity, this film formation may be divided into four stages:

(a) Firstly, the particles are randomly distributed in the medium.

(b) Secondly, water or solvent evaporates from the formulation and the polymer
particles are packed together.
(c) Thirdly, the polymer particles deform for a more thermodynamically favored
structure.
(d) Fourthly, the inter-diffusion of polymers across particle boundaries (and some-
times they are chemically crosslinked).
844 S. M. R. Billah

Fig. 5 Schematic diagram for the illustration of different stages of film formation

Since stages two and three are often referred to as drying in an industrial
context, the last stage may thus be called curing or annealing, although these terms
are highly dependent on the place and main objectives of their uses. Drying is
normally performed at a lower temperature for ensuring the solvent evaporation
which should not cause irregularities in the coating. However, the annealing oper-
ation is performed in higher temperatures for enhancing the inter-diffusion or,
when possible, because it is used to catalyze the chemical reaction necessary for
crosslinking. For waterborne coatings, the film formation process is often the most
energy demanding step in the production [4, 57, 158, 180, 183]. Figure 5 demon-
strates the schematic diagram of different stages of film formation process.

5 Polymers and Additives for Typical Textile Coatings

A wide range of polymers are generally used in textile coatings and they perform
various activities and also have significant control on the final characteristics of
coated textiles. Based on the nature of polymer and other additives used in the textile
coating formulations many final characters of the coated textiles can be effectively
controlled. These characters could be related to the aesthetic or technical or any other
types. For examples, there are different functional characters, where one or more
than one final characters may be desired from a functional coated textiles. Some of
these functional characters include – (a) chemical resistance, (b) solvent resistance,
(c) acid resistance, (d) alkali resistance, (e) flame resistance, (f) water repellancy
or resistance, (g) oil resistance, (h) increased rigidity, (i) abrasion resistance, (j) tear
resistance, (k) good ability to stretch, (l) high or low friction, and (m) specific
response to particular surrounding environment. Using proper selection of polymers,
additives, and textile substrates, many of these desired characters can be realized on
coated textiles. A wide range of additives are used along with polymers to control
many of these desired characters. Some of which have been selectively and briefly
discussed in different sections of this chapter.
Compatibility of the nature of the polymer with a particular type of textile is an
important issue to select a specific polymer for a particular type of textile coating
20 Textile Coatings 845

formulation. In this case, textile surfaces may denote any material intended for
textile use, some of which include – (a) loose staple fibers, (b) filaments, (c) yarns,
(d) braids, and (e) nonwoven, woven, and knitted fabrics of both organic and
inorganic origins. Textile coatings can also add or change the functionality of textile
(a character of a textile that does not form covalent bonds or adhere to the fabric on
its own). Polymeric binders usually used in textile coatings are sometimes designed
to form enough secondary bonds for adhesion with the textile surface. Additionally,
polymers used in textile coatings may also exhibit functional characters (such as
hydrophobicity or increased rigidity). Sometimes the polymeric binders generally
used in waterborne coating come in the form of waterborne dispersions, into which
functional materials and auxiliaries are added. The coating binders can be any types
of polymers which have enough adhesion property; however, compatibility with the
coating method and the end-use purpose is an essential requirement. Usually used,
polymeric binders include – (a) rubbers, (b) polyvinyl chloride, (c) silicones,
(d) acrylates, and (e) polyurethanes [4, 20, 57, 166–184].
Textiles coated with polymers can work as flexible composites, and they contain
polymer coatings and the textile substrates which adhere together through specific
coating processes and provide additional properties for the coated substrates. Mostly
high molecular weights polymers are usually used in polymer coatings of textiles.
Both natural (such as gelatine, casein, biopolymers), and synthetic polymers can be
used in textile coatings. Synthetic polymers can be mainly categorized in three types
based on their thermal responses, such as – (a) thermoplastic polymers, (b) thermoset
polymers, and (c) rubbers. Thermoplastic polymers are mostly reprocessable with
long chain which can be softened with temperature. Thermosets polymers have
strong three-dimensional networks where individual long chain molecules are
interconnected to each other by strong covalent bonds (or chemically crosslinked).
Thermosets are hard and glassy at room temperature, and they cannot be softened by
heat and they are not reprocessable. Rubbers have highly flexible networks, and they
are soft and elastic at room temperature. Physical entanglements in rubber act as
physical crosslinks between the chains. Both thermoplastics and rubbers are widely
used as coating materials [20, 57, 178–183].

5.1 Selected Characters of Commonly Used Polymers in Textile

Coatings

Several types of thermoplastics (for examples, polyvinylidene chloride, polyvinyl

acetate, polyurethanes, acrylics) and most of the natural and synthetic rubbers are
commonly used for textile coatings. Different properties of thermoplastic polymers
are suitable for textile coating due to their hot-melting and thermally induced
welding characters. Selection of polymers for textile coatings depend on the partic-
ular natures of the polymers (such as melting points, glass transition temperature,
molecular weight, mechanical and chemical properties). Table 2 illustrates selected
behaviors of some commonly used polymers in textile coatings. Most frequently
used thermoplastic polymers in textiles coatings include – (a) polyvinylchloride,
846 S. M. R. Billah

Table 2 Selected behaviors of some commonly used polymers in textile coatings

Type of polymer Glass transition temperature (
C) Melting temperature (
C)
Low density polyethylene 120 115
Polypropylene 20 165
Polyvinylchloride 85 220a
Polyvinylidenechloride 17 185–200
Polyvinylaceate 29 –
Polystyrene (amorphous/atactic) 100
High density polyethylene 135 130
Polyethylene terepthalate 69 265
Polyamide 50 215
Polycarbonate 145 295a
Polymethylmethacrylate 105
(amorphous)
Polyacrylonitrile 90
Polytetrafluoroethylene 20 327a
Polyetheretherketone 145 335
Thermoplastic polyurethane 230
Polyisoprene (natural rubber) 73
Polybutadiene <90
Styerene-butadiene-rubbers 25–75 55
Polyisobutylene (butyl rubber) 70 0
Polydimethylsiloxane (silicone 125 55
rubber)
a
Decomposing

(b) polyvinyledene chloride, (c) polyvinylacetate and acetate copolymers,

(d) acrylics, (e) polyurethanes, and (f) different types of rubbers and particular
types of thermosetting polymers [4, 20, 57, 177–192].

5.2 Thermoplastic Polymers

Four main types of thermoplastic polymers include – (a) polyethylene,

(b) polypropylene, (c) polyvinyl chloride, and (d) polystyrene. Sometimes, these
polymers are also termed as commodity thermoplastics. Engineering thermoplastics
have better mechanical properties compared to commodity thermoplastics. Some
of these engineered thermoplastics include – (a) polyethylene terephthalate,
(b) polybutylene terephthalate, (c) polyamides (or nylons), (d) polycarbonate,
(e) polymethyl methacrylate, and (f) polyetheretherketone. These polymers show
high strengths, with high stability performances in continuous use at temperatures
>100
C. In addition, engineering thermoplastics are produced and used on a small
scale and have prices higher than those for commodity thermoplastics. Specialty
plastics are also popularly used thermoplastics in textile coatings which have specific
20 Textile Coatings 847

properties some of which include – (a) high heat-resistance and (b) exceptional
mechanical properties. These polymers are relatively more expensive. Poly-
tetrafluoroethylene is considered to be a specialty plastic with unique low-friction
properties. Microstructure-based thermoplastics usually show amorphous glassy
or semicrystalline solid behavior and amorphous thermoplastics are glassy up to a
specific temperature (the glass transition temperature) above which they transform
into a more rubbery structure without a distinct melting point. In addition, semicrys-
talline thermoplastics are two-phase materials comprising an amorphous phase with
the certain glass transition temperature and a crystalline phase with a specific melting
temperature [4, 20, 57–60, 178–183].

5.3 Thermosetting Polymers

Most of the thermoset polymers are hard, rigid, and brittle, with high temperature-
and chemical-resistances, and they are popularly used as matrices for reinforced
composites. These type of thermoset polymers are usually used to provide good
adhesion when used along with other additives during textile coatings. Some
thermosets (for examples, epoxy, phenolics, and polyester resins) are mainly used
as the matrices for fiber-reinforced composites, whereas amino resins are mainly
used for bonding chipboard. If the number of branch points in a polymer system is
progressively increased, long branched molecules with infinite “tree molecules” are
initially formed and ultimately a 3D network system is obtained. In addition, a
single-tree molecule (also called as the “gel point”) forms, when most of the polymer
becomes nonsoluble, and a swollen gel forms if a solvent is added to the system
[4, 57, 185–192].

5.4 Rubbers and Their Uses in Textile Coatings

Rubbers are crosslinked amorphous polymers and their glass transition temperatures
are characteristically below 25
C. In these systems, no rigid groups (for instance,
phenyl rings) present in the chain or as side groups, and no polar groups are available
that can increase intermolecular forces. Rubbers are dominated by commodity
types (for example, natural rubber and styrene-butadiene copolymer rubber) which
are mostly used for tire production. For this and many other applications (such as
conveyor belts, pressure hoses), rubber systems reinforced by fibers are used. The
rubber matrix allows flexibility in bending, whereas the fabric reinforcement limits
the in-plane stretching of the product. Raw rubber shows plastic-like deformation
which behaves like an elastomer (for examples, a material that can undergo large
elastic deformations which are reversible) only after crosslinking by vulcanization.
There are also specialty rubbers which have certain properties. For example, butyl
rubbers have low air permeability, nitrile rubbers have good oil resistance, and
silicone rubbers have low temperature-resistance. Some of these rubbers are also
used in textile coatings [4, 57, 185–192].
848 S. M. R. Billah

6 Textile Coating Formulations

Textile coating compositions are of different types which can be very simple
to enormously complex in nature based on a number of factors relating to the
main objectives of the coating formulations. In general, a typical coating formulation
contains three main components which are – (a) colorants, (b) vehicle, and
(c) additives. Colorants (such as dyes or pigments) provide the required shade or
carry out other functions, while the vehicles (sometimes also termed as binders) act as
the adhesive to stick colorant particles to substrate or to each other. Additives are
auxiliary chemicals which are used to modify the properties of the coating in fluid or
solid state. The chemical and physical properties of organic coatings are directly
controlled by a number of main factors some of which include – (a) the nature
of main ingredients used in the organic coating formulations, (b) the nature of the
substrate where they are used, (c) mode of application of the coatings on the sub-
strates, (d) surrounding environments, (e) drying system used, and (f) nature
of pre-treatments on the substrates or post-treatments on the coated substrates.
Technological advances on the coating techniques along with recent developments
of nanomaterials and their applications on organic coatings for a wide variety of
application areas are in the way to achieve many high performance organic coating
systems for different technical performances in various coated substrates [4, 8, 28, 29,
57, 95, 108–150, 184]. Generally, textile coatings are applied as multilayered systems
which have different coating layers, such as – (a) primer and (b) topcoat. However, in
some cases (such as automotive coatings), there can be a number of coating layers
depending on the nature of final uses of the coated products. In this case, each coating
layer is applied to perform certain specific functions, though its activities are
influenced by the other layers in the system. In addition, the interactions among
different layers and the interfacial phenomenon play a significant role in the overall
performance of the multicoat systems and particular characters of coatings are usually
associated with specific parts of a coating system [4, 57, 185–195].
Different types of coatings are usually used for producing functional advanced
coated textiles for specific applications some of which are briefly and selectively
discussed in the successive sections along with a number of other particular items
with specific textile coating applications.

7 Functional Coatings on Textiles

Generally, coatings are applied on surfaces to provide decorative, protective,

or functional characters or a combination of these properties. Functional coatings
provide additional functionality besides the usual characters of a coating formulation
and depending on the actual application of a coated substrate, additional function-
ality may have diverse features. Some particular examples of functional coatings
include – (a) self-cleaning, (b) easy-to-clean (anti-graffiti), (c) antifouling, (d) soft
feel, (e) antibacterial, (f) flame retardancy, and (g) antimicrobial. In addition, func-
tional coatings are sometimes designed to provide certain specific characters, some
20 Textile Coatings 849

of which include – (a) durability, (b) reproducibility, (c) easy application and
cost effectiveness, (d) tailored surface morphology, and (e) environmental friendli-
ness. Based on functional characteristics of functional coating formulations, this
coating system can be of different types. Functional coatings provide the functional
character using different means, such as – (a) physical means, (b) chemical means,
(c) mechanical means, and (d) thermal means. For example, chemically active
functional coatings perform their activities either at film–substrate interfaces
(such as anticorrosive coatings), in the bulk of the film (for example, fire-retardant
or intumescent coatings), or at air–film interfaces (e.g., antibacterial, self-cleaning)
[20, 57, 142–181, 195–247]. Selectively, some specific types of functional coatings
along with their certain applications on textile coatings are briefly discussed here.

8 High Thermal-Resistant Coatings

High thermal-resistant coatings are required for a wide variety of thermally resistant
textiles for both conventional and high-tech specific applications. Some of these
coated textiles include (a) certain types of technical textiles; (b) textiles for fire
fighters, coats for extreme environments; and (c) textiles for certain types of auto-
motive applications. Thermal- and fire-resistant coating formulations usually con-
tains fluorine- or silicon-based products to produce a high thermal-resistance for
the coated textile products. However, all fluorinated coatings are not suitable for
high-temperature applications as they degrade above ~300
C and produce toxic
by-products. Although currently silicon containing coatings dominate the textile
coatings, there are also other binders (for examples, phenolic or epoxy resins)
which are also popularly used to formulate high thermal-resistant textile coatings.
Silicon-containing polymers provide better thermal resistance as it takes very high
level of energy in order to cleave silicon bonds compared to carbon bonds in
analogous molecules. For example, recently developed silicon-based coatings
which exhibit thermal resistance up to a very high temperature (such as 1000
C).
Silicon derivatives (for example, silicone resins like siloxanes or inorganic silicates)
are commonly used for high-temperature resistance textile coating applications.
Silicon containing materials are usually expensive, but copolymers or blends of
silicones with acrylate, epoxy or urethanes are very often used to reduce costs.
Many investigations have been reported innovative ways to design thermal-resistant
coatings; for instance, titanium esters in combination with aluminum flakes have
been incorporated into binders which can show resistance to high temperatures
[20, 176–179, 181–183].

9 Fire Retardant Coatings

Fire retardant coatings are highly important for producing particular types of cloth-
ing, tents, automotive textiles, or similar other types of materials based on coated
textiles. Different types of materials used in fire retardant coating formulations.
850 S. M. R. Billah

For example, when phosphorus containing compounds are used in fire coating
formulations, these materials form a protective layer as a glassy surface barrier
coating. However, halogen- and antimony-based fire retardants are toxic in nature
and not eco-friendly. Additionally, intumescent coatings form an expanded carbo-
naceous layer which acts as a protective barrier against heat transfer and hinders the
diffusion of combustible gases and melted polymer to the site of combustion. Fire
retardant textile coatings usually composed of three main components which are –
(a) an inorganic acid (dehydrating agent), (b) a carbonaceous char-forming material,
and (c) a blowing agent. Coating performances of the intumescent system depend on
the choice of the ingredients and their appropriate combination. Expandable graph-
ites are popular as fire retardant agents since they contain different compounds
including acids which are entrapped with different carbon layers. When exfoliation
of the graphite takes place, it provides an insulating layer to the substrate during
exposure at higher temperatures. Polyurethanes and phosphates are widely used in
the fire-retardant intumescent system whereas the nature of solubility of phosphates
in water sometimes causes migration problem. Using proper techniques (such as
microencapsulation of phosphates like diammonium hydrogen phosphate within
a polyurethane shell) can limit this problem to certain extent. Currently, silicon
or inorganic hydroxide-based fire-retardant coatings are very popular for variety of
industrial applications including textile coatings. Additionally, polymer clay (lay-
ered silicates) nanocomposites have been successful to attract current active research
due to their potential use as fire retardants in industrial applications including in
textiles [20, 176–179, 181–184].

9.1 Application of Flame Retardant Finishes by Coating

Flame retardant finishes are applied on textiles by using a variety of techniques

including spray coating, padding, impregnation, and inkjet coating technology.
There are different ways to realize flame retarding character of textiles where some
of which include – (a) removal of heat, (b) enhancement of fiber decomposition
temperatures, (c) decreased formation of flammable volatiles and increase in char,
(d) decreased access to oxygen or flame dilution, and (e) interference with flame
chemistry and/or increase in fuel ignition in fuel ignition temperature.

10 Silicones in Textile Fabric Coatings

Silicones are widely used in different steps of textile and other types of fiber
processing which range from wet processing to finishing. They are also widely
used in textile coatings for a diverse application range comprising fashion wear
(for example, women’s stockings) to technically demanding air bags applications in
the car. These applications are based on cross-linked silicone polymers or elastomers
that are usually used to formulate crystal-clear coatings that produce either soft and
flexible film or hard and rigid film. All such coatings may have nearly similar
20 Textile Coatings 851

compositions and share common raw materials for up to 70% of their formulation
technique. These formulations can exhibit better thermal stability (over a wide range
of temperatures) than organics. For example, liquid silicone rubbers (LSR) are
popularly used material for such fabric coatings due to their ease of use and rapid
cure when exposed to elevated temperatures (there is an exception to this statement
relating to one-part Room Temperature Vulcanisable or RTV elastomers used in
women’s stockings). Addition of SiH functional polymers to SiVi functional poly-
mers using a platinum catalyst cross-linking is usually used to prepare these elasto-
mers. These liquid silicone rubbers similar to other silicone elastomers contain fume
silica in these structures because these fillers can dramatically improve mechanical
properties. Silicone polymers are used in textile coatings for a variety of purposes
where one of the prime applications is to provide some form of protection from
exposure to high temperatures (as in conveyor belts), low temperatures (as with
many outdoor goods), or exposure to stress over long periods of time (as in air bags
or compensator bellows) since silicones are more stable than other elastomers.
Typical applications and key properties of silicon elastomer based textile fabric
coatings can be divided two categories which are – (a) soft coatings and (b) hard
coatings. Main application areas for silicone elastomer-based soft coatings (whose
key properties are given in the bracket) include – hold-up stockings (where key
properties are – ease to process, crystal clear, soft, nonslip/high elongation):

(i) Outdoor clothing and tents (where key properties are – adhesion, flexible,
thermal stability, thermal stability, colorless, and hydrophobicity)
(ii) Air bags (where key properties are – strength, adhesion, slip, and stability at
elevated temperature)

Similarly, main application areas for silicone elastomer based hard coatings
(whose key properties are given in the bracket) include:

(i) Conveyor belt coating (where key properties are – adhesion, nonslip/abrasion
resistance, thermal stability, and food grade)
(ii) Compensator bellow (where key properties are – adhesion, flexible,
chemical/thermal stability, and abrasion resistance)
(iii) Medical protective wear (where key properties are – hydrophobic, auto-
clavable, adhesion) [8, 28, 29, 121–177, 197–219]

10.1 Surface Active Agents and Chemical Softeners

Generally, a soft luxurious handle significantly improves the aesthetic appeal of

a cloth, particularly, at the point of sale; however, it equally contributes to the
thermopsychological comfort of a garment during wear. In this context, the perfor-
mance requirements for chemical softeners which function as fiber lubricants have
impacts on the decreasing nature of fiber/fiber and fiber/metal frictions which may
vary according to the end-use. Additionally, this performance requirements may vary
852 S. M. R. Billah

in a number of specific cases, some of which include – (a) soft, luxurious

handle, (b) high durability to machine washing (and dry cleaning), (c) antistatic
(protection against garment cling), (d) minimum effects upon color/color fastness,
(e) non-yellowing in the presence of heat, sunlight (UV radiation), and atmospheric
pollutants (for examples, oxides of Nitrogen, NOx), and (f) compatible in
co-application with other finishes. Different types of chemical softeners are available
based upon anionic, nonionic, cationic, pseudo-cationic and amphoteric compounds.
Some of the most important softening agents are the cationic aminosilicone deriv-
atives, particularly, aminoethylaminopropyl polysiloxanes. These softeners can be
modified in various ways in order to enhance their hydrophilic characters which
are important in modern moisture management control systems used in many forms
of clothing (such as sportswear, activewear, outdoor performance wear). Epoxy-
functional and carboxy-functional silicone softeners can provide yellowing resis-
tance, hydrophilic properties, and soil-release characters. However, softer handling
fabrics can be achieved using terpolymers with amine and polyether functionality,
while epoxy- and glycol-functional siloxanes can be regarded as durable hydrophilic
softeners. Aminosiloxane softeners have been widely used for the preparation
of microemulsions but nanoemulsion-based softeners are now being produced
with particle sizes down to 10 nm, creating a more luxurious softness. In this
case, for multifunctional finishing softeners are usually chemically designed for
co-application with other finishes as well as not impairing the overall performance
of the finished fabric.

11 Scratch- and Abrasion-Resistant Coatings

Some particular types of textile coatings are designed to show scratch and abrasion
resistance.
The consumer prefers to retain the aesthetic appearance of coated textile sub-
strates, so clear coats used on particular coated textile substrates (such as coated
textile for automobile applications) are expected to show good scratch and abrasion
resistance. Scratches have the tendency to cause damage to the underlying substrate
which is an additional problem. There are ongoing research projects around the
world to mitigate the challenge of producing scratch resistance coating with little or
no adverse impact on other desired properties. Generally, scratch resistance can be
obtained by incorporating a greater number of cross links in the binders used for
coating formulations although it is a known fact that highly cross linked binders
often produce hard films which have poor impact resistance because of less flexi-
bility. However, a less-cross linked binder usually produces soft film and shows
better performance with regard to other properties (such as antifingerprint and impact
resistance) but shows less scratch and abrasion resistances. As a result, a proper
combination of hardness and flexibility is a prerequisite in order to ensure optimal
scratch resistance. Clearly, organic-inorganic hybrid films are relatively popular
for developing scratch-resistant coatings in this context, and recent progresses in
nanotechnology also have significant role in developing scratch-resistant coatings.
20 Textile Coatings 853

For example, the use of siloxane encapsulated SiO2 nanoparticles has been reported
to develop scratch- and abrasion-resistant coatings. In similar type of studies in
industrial scale, coating industries have developed scratch-resistant coatings using
different techniques including – (a) by incorporating SiO2 nanoparticles into an
organic matrix that can migrate to the surface and (b) by enhancing the enrichment
of nanoparticles near the coating surface. In different studies, coatings with
good abrasion- and scratch-resistant properties have also been reported [52, 81–87,
91, 137, 167–175].

12 Self-Healing Coatings

Self-healing coatings try to replicate the lesson from the mother nature which often
termed as biomimicry. It is a coating technique which deals with special type of
polymers along with other additives to produce self-healing effect on the coated film.
Self-cleaning coatings provide a special functional property which also frequently
termed as “lotus effects” or self-cleaning effects. In this type of coating on textiles
or a textile product, manual cleaning is not required because a shower of rain is
sufficient to carry out the cleaning process, these surfaces can be soiled though.
There are reports that the self-cleaning property of lotus leaves could be attributed
to their specialized surface morphology and hydrophobic character. Since the high
hydrophobic character of lotus leaves provides pronounced water-repellence to
produce special type of surface morphology for these leaves which eventually
deny the dirt or the soiling materials any chance to form an intimate contact with
the surface; as a consequence, when the water droplets roll onto the leaf surface, they
carry along the contaminants or dirt or soiling materials. Different research groups
have attempted to mimic lotus effect by developing self-cleaning using different
techniques including coating techniques (and detailed discussions on self-cleaning
coating surfaces can be found elsewhere, which is beyond the scope of this current
chapter). Recent interests to mimic nature using different advanced techniques have
produced a huge amount of successful results in various areas of science and
technology. For example, in this context, during the past few years, self-cleaning
coatings using photocatalytic titanium dioxide (TiO2; particularly the anatase crys-
talline form) have attracted significant research interests in academic and industrial
sectors. In addition, when photocatalytic TiO2 particles are irradiated with an
ultraviolet light source (for example, sunlight), electrons are seen to be promoted
from the valence band to the conduction band of the particle which generates a
region of positive charge (h+), holes, in the valence band and a free electron in the
conduction band. These charge carriers can either recombine or migrate to the
surface where the holes can react with the hydroxyl or adsorbed water molecules
on the surface and produce different radicals (for examples, hydroxyl radicals and
hydroperoxy radicals). On the contrary, the electrons combine with the oxygen and
produce superoxide radicals. Photoproduced radicals of this kind usually show
strong oxidizing capability in order to cause the deterioration of organic contami-
nants or microbials pieces on the particle surface. Besides this, TiO2 can also be used
854 S. M. R. Billah

to produce superhydrophilic behavior (such as, so called, water sheathing effect)

which allows contaminants to be washed away relatively easily with water or rainfall
if the coatings are applied onto external surfaces. The underlying mechanisms
photocatalysis and hydrophilicity are completely different in nature although they
occur simultaneously [57–60, 114, 150].

13 Antibacterial Coatings

Antibacterial coatings on textiles and other flexible matrices have been successful
to attract active current research interests due to their wide range of application
potentials in different areas of science and technology. Antibacterial coated textiles
have been reported to contribute in the protection from microbial attacks. Microor-
ganisms (for example, bacteria, fungi, or viruses) exert potential threats and there
are limitation of producing antibacterial-coated textile substrates including –
(a) problems of aesthetics (discoloration of the coating), (b) risks to health and
hygiene, (c) bed smells, and (d) biofilm development or microbial corrosion in the
case of metallic substrates. Different types of coating formulations are usually used
in textile coatings, and they show different level of antimicrobial resistance when
formulated using antibacterial or antifungal chemicals (e.g., biocide and fungicide)
into the coating formulations. For example, organic coatings are susceptible to
microbial attack and the nature of the coating composition also have direct impact
on this. When biocides or fungicides are used in the textile coating formulations,
they have different level of control on the growth of microbial organism on the
coated substrates. Two typical types of phenomena are usually observed, they are –
(a) inhibition of the growth of microorganism and (b) killing the microorganism.
Developing biorepulsive (without killing) antibacterial coatings are quite popular
nowadays due to new legislations and pressures from environmental agencies [4, 57,
114, 150, 200–203].

14 Antifouling Coatings

The accumulation of unwanted materials on the surface of a material is sometime

termed as antifouling. Fouling materials could be of different types – (a) living
organisms (biofouling) and (b) nonliving substances (such as inorganic or organic
materials). Fouling is usually due to the adhesion of proteins, polysaccharides, and
bacteria on a surface (such as textiles), and biofouling is a problem associated with the
maritime industry (for instances, ships, cables, aquaculture nets, maritime textiles).
Both outdoor and indoor textile substrates are subject to organic and inorganic material
depositions which reduce the utility and durability of the fabrics. Different techniques
are usually used to protect from fouling where coating is one of them. For examples,
both biocidal and nonbiocidal coatings are used to prevent foulings. In this case,
biocide-based antifouling coatings reduce leaching of the incorporated biocides into
the coating. Biocides are toxic, and there are strong legislation in order to restrict the
20 Textile Coatings 855

use of biocides; for instance, tributyl tin is a highly efficient marine biocide, but it is no
longer in use biofouling coatings due to its toxicity [4, 57, 58, 60, 92].

15 Enzymatic Biocoatings

Biological coatings have a wide range of potentials for industrial exploitations,

including in coating of medical textiles or similar biomedical applications of the
textiles which are required to show biodegradability for specific applications.
The range of enzymes available for textile applications is growing by the day. It is
possible that many of these enzyme can be used for different treatment on textiles
(such as pre-treatment, post-treatment, modification of certain properties) using
different techniques including in – coating techniques, padding, and inkjet coating
technology. Continuous research and development on smart materials and biomate-
rials containing enzymes or enzyme substrates and enzyme immobilization on fabrics
have been successful to produce novel sophisticated functionalities which are useful
for textiles usually used in medical, protective, and defense applications. For exam-
ples, textiles incorporated with wound healing, self-cleaning or self-detoxifying
properties, or various antimicrobial effects sometimes use oxidoreductases and
hydrolases where enzyme immobilization in polymers are usually achieved by
using entrapment, covalent attachment, and adsorption bonding. In addition, smart
materials can respond to triggers (such as enzymes) in order to allow a controlled
release of active agents (for example, drugs, perfumes, antibiotics, and antimicrobial
substances) for high-tech textiles for high added-value products [57, 189].

16 Antimicrobial Coating

Microbial growth on textiles or usually used clothing (such as casualwear, sports-

wear, and activewear) when exposed to certain environmental conditions such as
prolong exposure to moisture or damp conditions or perspirations exerts a real
problem on health and safety to the users due to a number of reasons including
bacterial growth and body odors. Additionally, prolong uses of technical textiles in
outdoor environments where bacteria, fungi, and algae may grow on the textile
materials may cause a number of problems, such as (a) physical deterioration,
(b) rotting, and (c) the growth of unsightly stains. To avoid this type of problem,
antimicrobial finishes can be applied in order protect the textile substrates from these
microbial attacks and also to make the clothes to smell fresh and increase their life
strength. Antimicrobial finishes can be applied by using different techniques where
coating is one of them. Antimicrobial finishes of various kinds have been developed
which work in various ways some of which include – (a) controlled release of the
antimicrobial agent or provide a barrier/blocking action using inert films/coatings to
physically block bacteria, (b) provide films/coatings with direct surface activity
against bacterial growth, and (c) regenerate active antimicrobial agents, which
are regenerated by bleaching during laundering or using ultraviolet radiation.
856 S. M. R. Billah

In addition, there could be a number of other ways to incorporate antimicrobial

agents or similar types of materials on textiles or their products. For example,
durability to washing treatments can be increased by a number of approaches,
some of which include – (i) insolubilization of the antimicrobial agent either in or
on the fiber; (ii) fiber treatment with resins, condensates, or fiber cross-linking
agents; (iii) microencapsulation of the antimicrobial agent and durable bonding of
microcapsules to the fiber surface; (iv) coating of the fiber surface; (v) chemical
modification of the fiber by covalent bond formation; (vi) use of graft polymers,
homopolymers, and/or copolymerization on the fiber. Textiles usually used in
healthcare or biomedical application require protection against microorganisms
where different types of antimicrobial agents are used, some of the most commonly
used ones are – (a) metals and metal salts (such as silver, copper based salts),
(b) quaternary ammonium compounds (for example, 3-trimethoxysilylpropyl-
dimethyloctadecyl ammonium chloride), (c) polyhexamethylene biguanide,
(d) triclosan (or 2,4,40 -trichloro-20 hydroxyphenol ether), (e) chitosan (β(1,4)-2-
amino-2-deoxy-D-glycopyranose), and (f) N-halamine and peroxyacid. Additionally,
some metal-complex dyes also show antimicrobial activity; however, metal-free
dyestuffs are now more preferred due to environmental pollution caused by metal-
complex dyes [4, 57, 114, 150, 200–203].

17 Microencapsulation in Coating and Finishing of Textiles

Microencapsulation is a type of micropackaging where different types of materials

(such as cyclodextrins, urea, preformed synthetic polymers, biopolymers) can be
used to work as a container or a cage in order to encapsulate the materials used in the
core. The containers or the cages usually worked as a shell for the materials used in
the core. For example, for thermoregulation, phase-change materials have been quite
widely used in performance clothing.
Macroencapsulation are also popular in a number other areas of textile
finishing, some of which are – (a) aromatherapy or controlled fragrance release,
(b) antimicrobial finishes or deodorizing finishes, (c) insect-repellent or insect-resist
treatments, (d) skin moisturizing or skin cooling finishes, (e) controlled release of
vitamins or provitamins, (f) chemical protection, (g) application of UV-absorbers,
(h) enzymetic actions, and (i) microclimate control in clothing, especially for ther-
moregulation of garments [4, 30, 57, 189–191]. Some of these microcapsules can also
be used during textile coating formulations in order to realize specific application
properties from particular types textiles coated with these microcapsules along with
other additives present in the coating formulations.

18 Conductive Coatings

Conducting polymers are widely used for nanocoating on textiles for their various
application potentials including their attractive electrochemical properties and their
applications in advanced and conventional applications. Nanocoatings are usually
20 Textile Coatings 857

used in host matrices in various composite films. In addition, organic or inorganic

particles can be mixed with or incorporated to conductive polymers to modify their
behaviors, such as – (a) morphology, (b) conductivity, and (c) different physical and
chemical properties, which depend on their target applications [15, 64].

19 Self-Assembled Nanophase Coatings

Conventional sol–gel method includes hydrolysis condensation processes which

proceed through condensation polymerization upon film application on the substrate.
In this case, the evaporation process results in voids and channels throughout the
solid gel and cannot provide adequate corrosion protection because of high crack-
forming tendency. Sol–gel technology is limited by the fact that the maximum
attainable coating thickness using this technique is typically lower than 2 mm.
However, different studies establish that incorporation of nanoparticles to the sol
can make it possible to increase the coating thickness, without increasing the
sintering temperature [5, 31–42, 68, 87–97].

20 Coated Breathable Fabrics

Coated breathable fabrics are mostly engineered composite materials which can be
produced by a combination of a textile fabric and a polymer coating onto the fabric
surface. Polymer materials (such as resins or polymer pastes) can be used for coating
textiles during the coating process. The polymer coating provides new properties on
the coated fabric. Polymers can also be applied to a fabric in terms of polymer
membranes or they can be laminated to the fabric afterward in a separate process.
Different processes and classes of adhesive and machinery are used during laminat-
ing process. Producing a strong bond using lamination technique is relatively simple;
however, there are practical challenges when original properties of the fabric are to
be preserved. But using flexible lamination technique some of the desired objectives
such as appearance, handle, and durability can be preserved to some extent
[4, 16–29, 57, 108]. Breathable fabric can be divided into various groups based on
fundamental principles and design of the nature of waterproof character and breath-
ability of fabrics. Some of these include – (a) closely woven fabrics, (b) microporous
membranes and coating, (c) hydrophilic membranes and coating, (d) combination of
microporous and hydrophilic membranes and coating, (e) retroreflective microbeads,
(f) smart breathable fabrics, and (g) biomimetics. Differences in underlying mech-
anisms have significant influences on the vapor regulation of these fabrics which
varies widely. In addition, some of the high-performance products mentioned are
more expensive than normal waterproof fabrics. For a variety of applications,
the technology is continuously evolving in the areas of a cost-effective manufactur-
ing process to produce cost-effective breathable textiles. This technique uses quite
a lot of methods to reduce the price, some of which are – (a) improving material
formulation to enhance the properties of film and coating material, (b) controlling
pore sizes and their distributions, (c) improving characteristics of hydrophilic solid
858 S. M. R. Billah

membrane, and (d) developing new technology combining new required methods
(such as biomimetrics, smart breathable fabrics) [4, 16–29, 57, 108].
Methods of Incorporation of Membranes and Their Applications in Textile
Coatings When microporous fragile films are applied on fabrics, it causes to lose
cloth-like feels. So, the incorporation of this type of films onto textile should be
done in such a way that can maximize the high-tech function without adversely
affecting the classical textile properties, such as handle, drape, and visual impres-
sion. Four major techniques are usually used to incorporate membranes onto
textiles, they are – (a) laminating membrane and outer fabric, (b) liner or insert
processing, (c) laminating membrane and lining fabric, and (d) laminating outer
fabric, membrane and lining. Development of an improved and cheaper method
(Reifenhauser) for producing breathable waterproof film/nonwoven laminates by
a combined film extrusion and lamination process have been reported in different
research studies. There are ways of incorporating coating by an electrostatic
process rather than by using mechanical pressure. So, a careful selection of
lamination process is vital to ensure the breathability of the laminate to maintain
at a high level. The membrane has to be laminated with at least one substratum in
order to serve varied applications of breathable fabrics. The nature of lamination
of particular substrates depends on the final applications, some of which include –
(a) woven for garments and wound dressing, (b) nonwovens for wound dressing,
inserts/lining, roofing membranes and (c) foams for upholstery. For a number of
reasons, nonwovens are usually more cost effective than traditional fabrics.
MediSoft (Polymer Group Inc., the Netherlands) is a blend of spunmelt and
spunlace which provides enhanced softness and breathability. DuPont Acturel
(a product of DuPont) is made of three layers which are – (a) a polyester based
nonwoven inner layer, (b) Dupont Hytrel as a breathable membrane layer, and
(c) spun-bonded polypropylene as an outer layer. In this case, the first two layers
are formed by an extrusion coating process, and the final outer layer is attached to
the layer of Hytrel by an adhesive lamination process. Similarly, different type of
nonwoven fabrics are made into breathable fabrics. In usual term, most of coated
fabrics are treated with coating materials on the outer face sides. The conventional
method of applying coating onto the fabric is by the direct application of the knife-
over-roller technique. Sometimes textile coatings consist of several layers. Thin-
ner coatings are applied on flexible fabrics (such as coating onto warp knitted,
nonwoven, open weave, and elastic fabric) are sometimes achieved by using
transfer coating technique. Transfer coating process applies a film by using
casting technique on a release paper, which subsequently adhered to the fabric
to make laminates. Some commercial products produced by using this transfer
coating process include – (a) Cyclone (Carrington), (b) Entrant (Toray), and
(c) Keelatex. Transfer coated and laminated fabrics are more permeable compared
to direct-coated fabrics of the same fiber type for a particular polymer coating
weight due to the blocking of the interstices by coating material in the latter case
[4, 16–29, 57].
20 Textile Coatings 859

21 High-Tech Superhydrophobic-Coated Textiles

Durable non-wetting fabrics and their preparation and liquid transport function
for high-tech applications. Recently, intensive research interests are focused on
superhydrophobic textiles for a variety of application potentials. For example,
air-permeable, super-liquid-repellent fabrics exhibit strong resistance to various
liquid fluids and have self-cleaning, anti-sticking, and anticontaminating character-
istics which have huge industrial application potentials for high-tech textile and
textile products. However, most of the liquid-repellent fabrics are not strong enough
and sometimes limit the application potentials. In this context, different related
current research activities are focused on developing durable super-liquid-repellent
fabrics and exploring novel property of liquid-repellent fabrics [8, 20, 125–128,
137–166, 169–185, 200–228].
Typical elastomeric nanocomposites are used for the coating of superhydrophobic
textile fabrics. For examples, polydimethylsiloxane filled with functionalized
silica nanoparticles and fluorinated alkyl silane is popular for producing a super-
hydrophobic coating on fabrics (such as polyester, cotton, wool). In certain cases, the
coated fabrics showed water contact angles higher than 170
and sliding angles
lower than 5
. In addition, some coated textiles exhibited remarkable durability
against strong acid, strong alkali, repeated machine washes, boiling water, and
severe abrasion damages while retaining its superhydrophobic character. Besides
this, durable, self-healing superamphiphobic fabrics can be prepared by elastomeric
fluoropolymer containing nanoparticle and fluorinated alkyl silane. Many research
groups have reported durable, self-healed coated fabrics which can show significant
hydrophobic character. For example, a new coating system has been reported which
can be used to produce fabrics with a durable self-healed superamphiphobic surface
using elastomeric fluoropolymer containing nanoparticle and fluorinated alkyl silane
with a two-step wet-chemistry coating technique. In that technique, the coating
consists of a commonly used, commercially available fluoro-containing polymer,
poly(vinylidene-fluoride-hexafluoropropylene), a fluorinated alkyl silane, and a
surface modified silica nanoparticle. Besides this, different studies demonstrated
that the treated fabrics showed remarkable liquid repellency (with water contact
angle as high as 170
, and a contact angle above 150
to many oil fluids, such as
soybean oil and hexadecane). When self-healing polymers are used in the coating
formulations, they can show self-healing ability during any chemical damage and
can restore their super liquid-repellent properties simply by a short-time heating
treatment or room temperature ageing. Superhydrophobic-coated textile substrates
have significant uses in various areas. For examples, wetting and non-wetting of
fabrics have been involved with various applications. Superhydrophobic textiles
(a textile surface with a contact angle larger than 150
to water) using coating
techniques or other useful techniques have many applications in self-cleaning
and anti-sticking abilities and potential uses in a variety of decontaminations.
Significant progress has been reported to improve superhydrophobic fabrics
860 S. M. R. Billah

although most of the superhydrophobic fabrics show low durability to wash and poor
abrasion fastness. Superoleophobic surfaces exhibit contact angle more than 150

with organic liquids having very low surface tensions and low contact angle hyster-
esis. They have huge application potentials in antifouling, anticrawling, decontam-
ination, and microfluidics areas. Superoleophobic surfaces naturally show
superhydrophobic characters when liquid repellency is based on a low surface
energy (LSE) surface [169, 202–228].

21.1 Design, Development, and Evaluation of Superhydrophobic

Coatings

Nanosol coatings are popular for producing hydrophobic-coated textiles where

inorganic sols prepared from ordinary metal oxides, such as SiO2, TiO2. These
metal oxides are chemically or physically modified with suitable hydrophobic
additives during coating formulations. Some of the usually used hydrophobic addi-
tives are – (a) monomeric alkylsilane compounds, (b) polysiloxanes with hydropho-
bic groups (the chemical structures are shown in Scheme 1), and (c) fluorinated
compounds (such as perfluorooctyltriethoxysilane).
However, for the preparation of water-repellent textiles, fluorinated compounds
exert some practical limitations due to their high cost and potential risks to human
health. Long-chained monomeric alkylsilane compounds can be used in the place
of fluorinated compounds to produce hydrophobic nanosols for textile coatings.
Additionally, with the increase of chain lengths of alkylsilane additives, the hydro-
phobicity of coated textiles shows a considerable increase. In addition, sol–gel
coatings on textiles have been frequently used for functionalizing and refining the
desired characters of coated textiles. Coating solutions can be applied onto the textile
substrates using high speed spraying or other conventional coating methods. Very
tiny (such as diameter less than 50 nm) size of the sol particles when used in the
coating formulations along with other required additives contributes to improve
adhesion properties and other mechanical as well as chemical properties of the
coated textiles. The application of specially made nanosol solutions on coated
textiles also enhance other properties some of which include – (a) abrasion resis-
tance, (b) hydrophobic characters, (c) soil-repellent behaviors, and (d) modification
of optical and biological properties. Additionally, it also provides the opportunity for
the preparation of multifunctional coatings, for examples – multifunctional and
bioactive coatings. A detail discussion on these multiple application methods and
their synthetic techniques are beyond the scope of this current chapter. Special type

CH3 CH3
HO CH2 Si O CH2 OH Si O
m n m n
CH3 O CH3 O

Scheme 1 Polysiloxanes for hydrophobic modification of nanosols

20 Textile Coatings 861

of sol–gel coated superhydrophobic coated textile have many applications, some of

which include – (a) antiadhesive wound dressing, (b) leaching behavior of embedded
dyes, (c) photobleaching behavior, (d) UV protection, (e) improved electric conduc-
tivity of textiles, (f) immobilization and controlled release of bioactive species, oils,
and flavors, (g) antimicrobially finished textiles, (h) photoactive nanosol coatings,
(i) nanosol coatings containing nondiffusible antimicrobial additives, (j) nanosol
coatings with controlled-release embedded biocides, and (k) oil and flavor released
coatings of textiles [5, 8, 18–29, 31–47, 104–141, 151–170]. Besides this,
superhydrophobic surfaces are topics of active current research interest both in
academic and industrial arena for their many practical applications including –
(a) contamination prevention, (b) self-cleaning, (c) antifouling surface designs,
(d) anti-icing coatings, (e) corrosion resistance of metals and their alloys, and
(f) biomedical and biological applications. By controlling the topographic features
and surface energies, coated hydrophobic surfaces can be fabricated. In addition,
a surface’s water repellency is an important phenomenon in natural and technolog-
ical processes and a superhydrophobic surface is termed by a water contact
angle (WCA) greater than 150
and a sliding angle (SA) lower than 5
. Examples
of superhydrophobic surfaces prevail in nature which include – (a) lotus leaves,
(b) butterfly wings, (c) duck feathers, etc. Based on bioinspiration from nature,
superhydrophobic surfaces can be derived by using two kinds of approaches
which are – (a) firstly, the solid surface that is chemically modified with a low-
surface-energy material and (b) secondly, nano- and microscale structures which are
created on the substrate to prevent water from completely being in contact with the
surface. In this method, the water droplets sit mostly on the air and the water droplets
on superhydrophobic surfaces can be nearly spherical and therefore have a tiny
liquid–solid contact area that leads to easy roll off. Cassie’s law states how simply
roughing up a substrate can increase the apparent contact angle of a surface to
form appropriate surface patterns on hydrophobic surfaces in order to lead to a
general change in their wettability for increasing the contact angle substantially.
On this theme, an extensive research has been carried out in order to understand
the formation of superhydrophobicity on various substrates. For example,
organic/inorganic hybrid coatings have been extensively studied based on the
sol–gel technique to produce a simple and cost-effective method in order to
functionalize different surfaces. The presence of aliphatic hydrocarbon or perfluoro
chains in the sol–gel precursors can substantially decrease the surface energy
of the derived coatings. In addition, the mechanical properties of the films and
adhesion strength to the substrate can be improved by crosslinking the silanol groups
in the matrix and introducing chemical bonding between the coating and the
substrate [219–268].

21.1.1 Self-Cleaning Fabrics: Superhydrophobic Finishes for Water-,

Oil-, and Stain-Repellency
The revolution in this area involves the use of biomimetics to mimic the microstruc-
ture and nanostructure of the surface of the lotus leaf (also called “lotus effect”)
which essentially provides the lotus leaf with self-cleaning characters where the
862 S. M. R. Billah

contact angle of water on a lotus leaf can reach up to 170
due to the nature of the
surface roughness generated by the wax layer. In addition, the water droplets rest
on the outermost points of the minute wax mounds with air underneath the droplets
so that the surface area contact is as low as 7%. By mimicking this similar idea,
researches use nanotechnology approach in order to replicate the “lotus effect” on
coated textile surfaces by engineering the micro- and nanoscale surface features
of fibers and fabrics using nanomaterials or other suitable materials or techniques.
Similarly, fluorochemical-based finishes have been developed that can provide
superhydrophobic performance with extremely high water contact angles (>150
)
which allow water droplets to roll off at slight inclination. In addition, a novel water
shedding angle method has been developed in order to evaluate the water-repellent
characters of superhydrophobic surfaces [173–177].

21.1.2 Application of Polymer Nanocomposites for Producing

Superhydrophobic, Self-Cleaning Textiles
Different types of technique (for examples, sol–gel methods, self-assembly of
polymer layers, plasma treatments, and laser etching) are popularly used for incor-
porating nanoparticles to create a nanoscale surface roughness to meet different
required specifications for particular products (such as highly water proof or soil-
resistant textiles). Using specific types of polymers and nanoparticles, now it is
practically possible to produce multifunctional properties on coated textiles (such as
self-cleaned coated textiles), where such fabrics can exhibit higher levels of easy
care, but the durability of the effect (particularly oil-repellent character) should
preferably persist throughout the wear life of the textile product. Besides this, this
area of research in chemical finishing and coating has been successful to emerge as
a new vistas in textile finishing. The higher fabric performance along with desired
functionality may open up new consumer markets and outdoor technical textile
markets in near future. For example, the incorporation of nanoparticles (such as
anatase type titanium dioxide) during textile coatings or other suitable operations
may contribute to photocatalytically decompose fabric stains (such as certain type
of stains) due to the action of ultraviolet radiation from sunlight [20, 176–179,
181–184].

22 Powder Coating Technology and Coated Textiles

Mostly for composite textiles, powder coating technology has some appealing
application potentials. In addition, powder coatings have many attractive features
which also make them popular day by day. In principle, coatings from solid
components are melt mixed during the application of powder coatings on suitable
substrates where the insoluble components (such as pigments are dispersed in
the matrix of the binder components). In addition, the formulation is pulverized on
a substrate and finely fused to become a continuous film; binders for thermosetting
powder coatings consist of a mixture of the primary resin and a cross-linker
[67–74]. For example, semicrystalline urethane groups containing polymers without
20 Textile Coatings 863

Table 3 Different types of thermosetting powder coatings

Coating types Usually used binders Popular cross-linkers
Epoxy coating Bisphenol A epoxy Polyamines
Novolac epoxy Anhydrides or phenolics
Hybrid coatings Polyesters with COOH end groups Triglycidylisocyanurate
Polyesters with OH end groups Block isocyanates
Acrylic coatings Epoxy functional acrylics Dicarboxylic acids
Hydroxy functional acrylics Blocked isocyanates
UV-curable coatings Acrylate functional resins Free radical
Epoxy functional resins Cationic

using isocyanates or phosgene can be used for powder coating resins. The new
development in polyurethane chemistry is generally promoted by the use of non-
isocyanate and phosgene free routes [67–75]. Powder coatings are of different types
some of which are selectively described in Table 3.

22.1 Epoxy Powder Coatings

Epoxy resins are popularly used in powder coatings which is the largest in pro-
portions in terms of use from the class of thermosetting powder coatings. Addition-
ally, in an epoxy coating, a bisphenol A or a novolac epoxy resin is cross-linked
with polyamines or anhydrides. Bisphenol A (BPA) epoxies are usually prepared by
reacting BPA with epichlorohydrin to incorporate glycidyl ether end groups. Epoxy
resins are prepared from the reaction of o- or p-cresol-formaldehyde novolacs with
epichlorohydrin and the resulting novolac epoxy resins are useful in applications
where more than two epoxy groups per molecule are expected. Epoxy powder
coatings exhibit attractive sound mechanical properties (such as adhesion, and
corrosion protection), and they have many potential uses, some of which include –
decorative applications in institutional furniture, shelving, and tools. In addition,
protective epoxy coatings include various applications for pipes, electrical equip-
ment, primers, and automotive underbody parts [67–73].

22.2 Hybrid Powder Coatings

Polyesters with carboxylic acid end groups are cross-linked by an epoxy cross-linker
during their use in hybrid coatings, and these type of coatings are intermediate
between epoxy and polyester coatings. Usually, polyester resins are derived from
neopentyl glycol and terephthalic acid with a small amount of other monomers in
order to adjust the glass transition temperature and also to introduce branching which
increases the functionality above two. This type of coating exhibit color retention
and UV resistance than epoxy powder coatings and also used in many applications
(such as water heaters, fire extinguishers, radiators, and transformer covers). In
864 S. M. R. Billah

addition, powder coatings containing carboxylic acid terminated polyesters have

poorer flow behaviors compared to hydroxy terminated polyesters [67–73].

22.3 Polyester Powder Coatings

Triglycidylisocyanurate (TGIC) is a popular cross-linker for carboxylic acid-

terminated polyesters with basic catalysts (with a solid trifunctional epoxy cross-
linker) where the presence of three functional groups results in higher cross-link
density than obtained with BPA epoxy resins. Typically used binders generally
contain 4–10 wt% TGIC and 90–96 wt% of carboxylic acid-terminated polyesters.
Additionally, the generally used polyesters are less branched compared to those used
in hybrid coatings due to their higher functionality of TGIC than BPA oxides. TGIC-
based powder coatings have good exterior stability and mechanical characters which
are useful for different applications including in – (a) outdoor furniture, (b) farm
equipment, (c) fence poles, and (d) air conditioning units. However, TGIC is
considered to be toxic in nature. Tetra(2-hydroxyalkyl)bisamides were introduced
as cross-linking agents for carboxylic acid-terminated polyesters in exterior durable
coatings, and these coatings also have good mechanical character and flow behav-
iors. Usually, blocked isocyanates are also used as cross-linkers with polyesters
containing hydroxy end groups, and this type of isocyanate-polyester powder coat-
ings typically exhibit better flow compared to most powder coatings due to the
unreacted cross-linkers or blocking agents released upon unblocking are good
plasticizers. They are usually used for coating different items, some of which include
– (a) automobile wheels, (b) lighting fixtures, (c) garden tractors, (d) fence fittings,
and (e) playground equipment. In this context, derivatives of isophorone
diisocyanate, bis(4-isocyanatocyclohexyl) methane, and tetramethylxylidene
diisocyanate are selective examples of blocked isocyanates which show solid phys-
ical characters [67–73].

22.4 Acrylic Powder Coatings

The epoxy or hydroxy functional acrylic binder is cross-linked with dicarboxylic

acids (such as dodecanedioic acid (HOOC(CH2)10COOH)14, or blocked isocya-
nates) during in acrylic coatings. Usually, acrylic powder coatings exhibit superior
detergent resistance and are useful for applications in different types of coatings
(such as coating washing machines) [67–73].

22.5 UV-Curable Powder Coatings

Polymers with acrylic functional groups or epoxy functional groups (which are cross-
linked within the polymer network through free radical or cationic mechanism) are
widely used in UV-curable coatings. Radiation curable coatings are cross-linked
through reactions initiated with radiation rather than heat, and they exhibit relative
20 Textile Coatings 865

stability during the storage in the absence of radiation where the crosslinking takes
place at ambient temperature when exposed to radiation. In powder coatings, it is very
important to control the balance of binder glass transition temperature, molecular
weight, and reactivity. When the glass transition temperature of a binder used in the
coating formulation is high enough, it provides an option to avoid the sintering
operation. However, low glass transition temperature contributes to promote coales-
cence and levelling at the lowest possible temperature. But the short baking times at
low temperatures are possible when the resins are highly reactive and the baking
temperature is well above the glass transition temperature of the final cross-linked
film. This type of compositions may exhibit crosslinking during extrusion and a rapid
increase in viscosity as the particles fuse in the oven limits the ability of the coating to
coalesce and level. Different factors have controlling effect on glass transition tem-
perature which include – (a) chemical composition and (b) molecular weight. In
addition, it has been reported to use higher molecular weight to ensure more flexibility
within the resin systems since these may have adequate package stability and also flow
more easily during baking than a low molecular weight resin of similar glass transition
temperature that has more rigid chains. Moreover, differential scanning calorimetry is
one of the powerful tools to determine glass transition temperature and curing and cure
response, and this technique is also often used to study powder coatings [67–73].
All these types of powder coatings have many potentials in different particular
types of textiles for specific applications.

23 Photonic Coatings on Textiles

In this type of coatings, usually photonic materials (such as photonic metal oxides, a
photoresponsive material or similar other type of materials) are incorporated in the
coating formulations for producing certain types of functional coated textile sub-
strates. For example, when a photochromic dye is used as a photonic material in
the coating formulation, the textile substrate coated with this formulation shows
photoresponsive behavior when exposed to UV light or sunlight. In this case,
the dye isomerizes into a different form when exposed to actinic radiation (such
as sunlight, UV light). For producing photoresponsive-coated textiles, different
types of photochromic dyes are most commonly used, some of which include –
(a) azobenzene derivatives (which undergo cis–trans isomerization), (b) hydrophobic
spiropyran derivatives (which isomerize into the hydrophilic merocyanine form),
(c) spirooxazines, (d) fulgides, and (e) diarylethenes. Isomerization of the photochro-
mic dye can change the functional characters of the coated textile substrates to cause
change in topological behaviors [1, 2, 79, 80, 188–192, 204–209, 218].

24 Textile Finishing and Textile Coatings in Future

Textile finishing processes including textile coatings are changing with time and also
with the evolution of new environmentally friendly materials (such as polymers,
dyes, pigments, additives) and techniques (such as nanocoating technologies, plasma
866 S. M. R. Billah

coating, inkjet coating, and other advanced coating techniques). Different ground
breaking noble achievements have recognizable significant impacts on textile sectors
that have been realized almost in every decades since 1920 to current age. To keep
pace with this evolutions in different areas, there are relative changes in order to
adopt these new methods and techniques during the production of finished textile
products including the coated textile substrates. Different external factors have
significant influences on this textile finishing as well as textile coating sectors. For
example, changes in global macroeconomics, politics, global resources (such as
sustainable uses and availability of different resources including fibers, energy,
water), possible climate change and initiatives towards more environmentally and
cost-effective production targets, as well as the growth of domestic developing
economies have immense impact on different processing techniques and methods
usually used for the production of textile and allied products in the future. The textile
finishing (including textile coating) sector is a type of service sector, and it requires
to be responsive to the changing market demands where incremental changes are
usually apparent. In addition, in almost every decade, some technical developments
have been reported which very often bring about quantum changes in textile
finishing as well as in textile coatings. For example, textile finishing as well as
textile coating sectors have encompassed three main revolutions (which are –
mechanical, chemical, and electronic revolutions) which are on the verge of
fourth revolution due to their necessary competence with on-coming technological
revolution with the advent of the state of art new technologies (some of which
include – nanotechnology, biotechnology, plasma technology, other advanced coat-
ing technologies, and inkjet technology). Current developments in these areas of
textile finishing (including textile coatings) and also in the areas of easy care, durable
press, and wrinkle-free finishes and antimicrobial and flame-retardant finishes;
softening techniques are worth to mention here. In addition, developments in
microencapsulation and also in self-cleaning fabrics with superhydrophobic finishes
for water-, oil-, and stain-repellency have significant achievement in these areas to
produce high-quality textile products for specific targeted applications. In this
context, novel application technologies for chemical finishing which significantly
decrease water and energy consumption have also made some very striking notable
progresses which have the potentials to shape these industries.
Coating technique is one of many techniques which can also be used for applying
easy care, durable press, and wrinkle-free finishes onto the textiles. Significant
progresses have been made in the field of textile finishing to produce easy
care, durable press, and wrinkle-free textiles using different techniques. Addition-
ally, notable improvements have been realized by giving chemical cross-linking
treatments on cotton and other cellulosic fibers and their blends with synthetic fibers.
For example, for textile finishing, mainly self-cross-linking resins (such as urea-
formaldehyde) have been replaced with NN0 1,3-dimethylol-4,5-dihydroxyethylene
urea (DMDHEU) and other derivatives, where the release of formaldehyde is
significantly reduced by the use of methylated or glycolated DMDHEU derivatives
which show improved stability compared to DMDHEU. The use of such products in
along with a formaldehyde acceptor (such as urea or diethylene glycol) can be
20 Textile Coatings 867

applied to minimize formaldehyde generation from the resin finished fabric. Besides
this, zero formaldehyde resins (such as DHDMI, or DMeDHEU, or 1,3-dimethyl-
4,5-dihydroxyethylene urea) have also been developed; however, a less uniform
cross-linked distribution with a reduced easy-care performance is one of the limiting
effects of this type of resins. In addition, a higher amount of this type of resin is
usually required in order to produce a satisfactory performance, and the curing
temperature and cure times are comparatively higher than for DMDHEU. Poly-
carboxylic acids based other formaldehyde-free resin finishes, for examples, citric
acid, malic acid, 1, 2, 3, 4-butanetetracaroboxylic acid or polymaleic acid derivatives
have been reported for their usefulness in wrinkle-free finishing, but their durable
press performance is relatively inferior to that of DMDHEU. In addition, ultra-low
formaldehyde resins are very popular in this regard for meeting targets set by the
legislation on residual formaldehyde levels in finished fabric. Continuous research
activities are going on for a chemical breakthrough to produce new cross-linking
agents which are formaldehyde-free and also to prepare new catalysts that can ensure
cross-linking of cellulosic and cellulosic blend fabrics cured in considerably short
period of time and also at low temperatures [238–288].

24.1 Main Influencing Factors for Future Developments in Textile

Coating and Finishing

Textile finishing (as well as textile coatings) in future depends on a number of things
where the currently available techniques and methods as well as the future devel-
opments in this area needs to satisfy different competing criteria including the
consumer demands, innovation, change in process due to environmental causes
and sustainability, as well as new product functionalities. In this context, the main
drivers of change in textile finishing (including textile coatings) are required to
concentrate on a number of areas including in – (a) fashion (such as aesthetics,
appearance, image, or prestige), (b) consumer demands (for examples, comfort,
changing demands, or lifestyles), (c) environmental causes (such as legal, ecological,
care, REACH, BPD), (d) safety requirements (for instance, legal, health, or protec-
tion), (e) technical specifications (for instance, innovation, new applications, smart
textiles, wearable technologies), (f) meeting sustainability (such as supply chain
sustainability, maximizing performance with minimum use of fibers and all utilities
like energy, water, chemicals and also incorporating recycling possibilities), and
(g) other demand (such as aftercare). Here, REACH stands for registration, evalu-
ation, authorization, and restriction of chemicals, whereas BPD stands for biocidal
products directive.
The global market for chemical finishes is increasingly becoming very discerning
and is demanding comparatively more technical input from both chemical suppliers
and textile wet processors in order for providing more innovations and develop-
ments. In addition, there are incremental demands from both the retailers and also
from consumers on novel finishes, greater added value, enhanced comfort, protec-
tion, and performance from the finished textiles or coated textiles and their products
868 S. M. R. Billah

which they purchase. The continual expansion of technical textile sector with a range
of textile applications and end uses involves continuous research in the areas on
chemical finishes for self-cleaning textiles and abrasion-resistant textiles, among
many other performance-driven criteria which are creating challenges for chemical
manufacturers and textile finishing companies as well as industries which are mainly
focused on textile coatings.

25 Conclusion and Perspectives

Coated textile fabrics have a wide variety of applications, for examples, their uses in
protective clothing to architectural materials. Typically used textile coating technol-
ogies use a wide variety of materials (such as elastomers and silicones, polyurethane,
polytetrafluoroethylene) for the applications of coating formulations using different
techniques which include – direct coating, transfer coating, digital or inkjet coating,
and extrusion coating. Recent advances on coating textiles using advanced tech-
niques are enormous, some of which include – (a) plasma coating, (b) nanocoating,
(c) inkjet coating with the aim to improve functionality, reduce the costs, and also
improve environmentally sustainable manufacturing operations. The chapter has
briefly discussed different important topics and items usually used for conventional
and advanced textile coatings. For example, it has briefly described the methods and
approaches in order to design hydrophobic or superhydrophobic coatings based on
sol–gel chemistry by incorporating hydrophobic moieties and controlling surface
morphology. It has also provided a brief account of various types of coatings
and methods which are usually used in textile coatings. At the end, it has briefly
discussed the recent trends in textile coatings and the nature of advanced technolo-
gies which are focused in most current progresses and trends in future developments.
It is beyond the scope of this current chapter to provide a detail explanation of all the
methods and coating systems stated in this chapter, so readers are advised to consult
the references for more detailed information.

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Anticorrosive Coating
21
Mazen K. Nazal and Mohammad Abu Jafar Mazumder

Contents
1 Basis of Corrosion Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 884
2 Corrosion Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 886
3 Materials for Anticorrosive Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 887
3.1 Metallic Coating Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 888
3.2 Inorganic Coating Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
3.3 Organic Coating Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
4 Mechanism of Anticorrosion Protective Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
5 Performance Testing and Evaluation of Anticorrosion Coating Materials . . . . . . . . . . . . . . . . . 899
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 906

Abstract
Protection of construction tools such as bridges, rails, ships, cars, engines, cargo,
and storage containers against corrosion is significant. The scale-up of corrosion
in a system can be prevented or at least minimized by altering the environment,
changing the material properties, and/or protective coating. The main objective of
this book chapter is to present and describe the different types of corrosion control
methods in addition to the materials (organic, metallic, and inorganic) used as

M. K. Nazal
Centre for Environment and Water (CEW), King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
e-mail: [email protected]
M. A. Jafar Mazumder (*)
Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 883

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_24
884 M. K. Nazal and M. A. Jafar Mazumder

anticorrosive coatings and discuss the mechanism of different classes of anti-

corrosion protective coating (i.e., barrier, sacrificial, and inhibitive coating).
Furthermore, some anticorrosive coating evaluation methods using outdoor expo-
sure and laboratory tests have been discussed.

Keywords
Anticorrosion · Coating · Pigments · Inhibitors · Controlling corrosion

Abbreviations
ACAT Amine-capped aniline trimer
aq Aqueous
Cd Capacitance of double layers
CPE Constant phase element
DMDES Dimethyldiethoxysilane
EMF Electromotive force
FGNP-TPP Functionalized graphite nanoplatelets modified with
tripolyphosphate anion
FHWA Federal Highway Agencies
GPTMS Glycidoxypropyltrimethoxysilane
HEE Hydrophobic electroactive epoxy
l Liquid
MAPTS Methacryloxypropyltrimethoxysilane
MTES Methyltriethoxysilane
n Power of the diffusion impedance
PAAMPS Poly-acetamide-acetoxyl methyl-propylsiloxane
PANI shell with AuNPs Polyaniline-modified gold nanoparticles
PANI–MWCNT Multiwall carbon nanotube–polyaniline
RGO Reduced graphene oxide
Rp Polarization resistance
Rs Electrolyte solution resistance
s Solid
SEPI Superhydrophobic electroactive polyimide
TEOS Tetraethoxysilane
W Warburg impedance
Y0 Admittance constant
χ2 Chi square
ω Frequency

1 Basis of Corrosion Protection

Corrosion is the phenomenon of destruction and consumption of materials chemi-

cally, electrochemically, and/or biologically with the environment [1]. The corrosive
environment includes but not limited to air, humidity, and different types of water
(i.e., marine, salt, fresh, and distilled), natural atmosphere, ammonia, hydrogen sulfide,
21 Anticorrosive Coating 885

acids, and fuel gases. Based on the exposure, these environments are divided into three
different types: (a) atmospheric (i.e. industrials, rural, and marine), (b) splash zone, and
(c) immersion (i.e., in soil, seawater, and freshwater). Consequences of corrosion are
loss of industrial efficiency, insulation of heat exchanger pipelines, loss of products,
and contamination and shutdown of plants, which imply inconvenient increase of cost,
destroy the economy, and deplete the resources. Table 1 shows the annual cost of
corrosion studies at some countries. In addition, a study conducted by Federal
Highway Agencies (FHWA), USA [2], C. C. Technologies Inc., USA [3], and
National Association of Corrosion Engineers [4] found that the corrosion is covered
by around 3.1% of the national gross domestic product with an approximate cost of
$276 billion. In the United States, the corrosion cost of gas and liquid transportation’s
pipelines exceeds $7 billion and is expected to be very high in the future due to the
highly corrosive environment in gulf countries. Also, the United States spends around
10% of the maintenance of aircraft on corrosion remediation [4].
Corrosion science and corrosion engineering cannot be separated; virtually they
go hand-in-hand. The corrosion science describes classification of different forms of
corrosion in addition to the mechanism and rate. On the other hand, the rules and
principles established from corrosion science are used in the corrosion engineering.
Corrosion engineering concerns on designing of materials and coating of struc-
tures to prevent corrosion. Basic science such as chemistry, physics, and biology and
different disciplines of engineering such as mechanical, civil, metallurgical, and
electrical engineering contribute to the theme of corrosion and anticorrosion. The
following functions affect corrosion and deserve to be considered in corrosion science
and engineering: (a) impermeability, (b) mechanical strength, (c) dimensional integ-
rity, (d) physical properties, (e) contaminations, and (f) damage to equipment. Con-
sider the following points and abovementioned direct and indirect hindrance that
intrigue and motivate us to study anticorrosion:

(i) The importance of materials such as iron, aluminum, copper, manganese, and
titanium as resources to life.
(ii) Corrosion may contaminate stored products such as food and water.

Table 1 Overview of Country name Annual cost Year

cost of corrosion studies
United States $ 5.5 billion 1949
at some countries
in selected year United States $ 70 billion 1975
United States $ 276 billion 2002
Japan $ 9.2 billion 1974
West Germany $ 6 billion 1967
United Kingdom £ 1.365 billion 1970
Australia $ 2 billion 1982
Kuwait $ 1 billion 1987
India $ 320 million 1960
Finland $ 54 million 1965
886 M. K. Nazal and M. A. Jafar Mazumder

(iii) Fully understand the engineering corrosion to provide better design and con-
struction knowledge for industrial process and transportation medium.
(iv) Prevent the disaster caused by corrosion, such as crushing civil and military
constructions and explosion of oil pipelines and oil tanks.
(v) Complete understanding of corrosion science is required for designing an
efficient artificial tool that can be implemented in the human body.

Corrosion resistance and developing anticorrosion materials depend on many

factors such as effect of oxygen, effect of oxidizing materials and conditions,
temperature, corrosive concentration, metallurgical factors, velocity of corrosion,
and galvanic coupling [5]. A powerful solution that dealt with corrosion and
preventing failure occurring in industries and constructions is the main motivating
force in the development of anticorrosive coating materials such as alloy, compos-
ites, metals, polymers, and ceramics with advanced chemical, physical, and mechan-
ical properties better than the surfaces to be covered. In the last decades, many
anticorrosion materials (i.e., metallic, inorganic, and organic materials) were devel-
oped and investigated based on corrosion type and their mechanisms in protecting
different types of environment such as industrial atmosphere and immersed marine
seawater. In recent years, a number of anticorrosive coating materials which showed
significant improvements in the resistivity of materials’ surface against corrosion
have been explored for protection against corrosion, and many of them have
appeared with significant advancement. These advanced materials offer better resis-
tant, cheap, more efficient operation, reduction in contamination of products, and
highly pure and eco-friendly environment. However, despite very promising and
encouraging outcome from anticorrosion research, unraveling of the complex mech-
anism and/or nature of corrosion has become the impediment in designing new
anticorrosive coating materials and methods.

2 Corrosion Control

The pricey damage caused by corrosion could have been reduced by the application
of corrosion control. A wide range of methods have been used to protect materials
from corrosion. Some of the most common methods are listed below:

1. Alteration of environment: In this method, the corrosion can be reduced by

reducing aeration, eliminating moisture, pumping an inert gas, reducing the
flow of turbulence, and/or decreasing the surrounding temperature.
2. Introducing inhibitors: The inhibitors are generally added less than 0.1% by
weight to the respective system. Consequently, the inhibitors protect the metals
by adsorbing on to the metal surface and forming a protective film or eradicating
the corrosion agent from the surface.
3. Cathodic protection: It is based on galvanic action, where the metal surface is
protected by making it a cathode of an electrochemical cell. The metal protection
21 Anticorrosive Coating 887

can be achieved by sacrificial metal to act as the anode or impressed electromotive

force (emf) methods.
4. Anodic protection: It is relatively new compared to the cathodic protection. The
corrosion is controlled by keeping an active-passive metal or alloy in the passive
region by an externally applied anodic current. It has many advantageous prop-
erties over the cathodic protection, namely, (i) it requires low current, (ii) it
reduces the corrosion rate largely, and (iii) it is applicable to some strong acids
and other highly corrosive media. However, this type of corrosion control
possesses some limitations which are as follows:
(a) The coating metals must have passivity such as stainless steel, nickels, and
chromium and their alloys.
(b) This type of protection cannot be used if the media contains chloride ions,
because the formed film can be attacked by those ions and be destroyed.
5. Selection of proper materials and design for equipment: The corrosion can be
minimized in this method by designing a system with a complete drainage of
liquid, eliminating cracks, avoiding direct contact between two different metals
specially if there is a large gap in their electrochemical activity, and making the
equipment easy to be cleaned, inspected, and maintained.
6. Lining and coating: There are many methods that can be used to apply the coat or
line on top of the surface or inside the pipelines such as electroplating, cladding,
and organic coating.

As a whole, the chance for corrosion of a certain type can primarily be prevented
by a careful choice of suitable materials and the building or machine design.
Typically, the scale-up of corrosion in a system can be prevented or at least
minimized by altering the environment, changing the material properties, and/or
protective coating. This protective coating is particularly important because it
includes all the corrosion prevention methods such as barrier effect (inhibition),
materials selection (conducting polymers), and cathodic/anodic protection.

3 Materials for Anticorrosive Coating

Protection of the surface of metallic materials or steel is achieved by one or

multilayered system using anticorrosive coating materials. These materials can
be classified in three major groups [6]: (i) metallic, (ii) inorganic, and (iii) organic
coating materials. Many types of materials or elements can be used in each class,
as illustrated in Fig. 1.
Corrosion inhibitors, whether inorganic or organic, retard the corrosion rate by
affecting the anodic reaction or cathodic reactions or both. For inhibition of anodic
reaction, the reaction rate of anodic dissolution turns out to be slow, and/or a thin film
over the anode is formed by the produced reaction products. However, in cathodic
reaction inhibition, the flow of electrons from the anode to the cathode is disrupted
and/or the produced reaction products adsorbed selectively at the cathode sites.
888 M. K. Nazal and M. A. Jafar Mazumder

Coating Materials

Metallic

Organic Inorganic

Thermoplastics Conversion Porcelain Inorganic

Cement Linings
coatings enamals Zinc/Silicates
Elastomer (Rubber)

Thermosetting
Chromate Portland cement

Zinc-Rich coatings
Phosphate Potassium Silicate

Anodizing Modified Potassium

Silicate

Calcium
Aluminates

Fig. 1 Classification of materials and methods used in coating

The corrosion inhibitors work on one or more of the following factors:

• Increasing the anodic or cathodic polarization behavior

• Increasing the electrical resistance or the metallic surface
• Adsorbing themselves on the metallic surface and forming a film
• Reducing the movement or diffusion of ions to the metallic surface
• Interacting with the metallic surface or the environment near it

3.1 Metallic Coating Materials

Many metals (such as nickel, alumina, lead, zinc, copper, etc.) and their alloy composites
are used as coating materials [7]. These metals are less noble than stainless steel;
therefore, the main role of such coating is to form a barrier to protect the active metal
(stainless steel) surface. Other factors should also be considered in the selection of
metallic coating: (i) the metals should resist direct attack of the environment, (ii) they
should be hard, and (iii) they should be nonporous. There are number of methods used to
coat the metal surface by anticorrosive coating materials such as hot dipping (galvaniz-
ing), electroplating, thermal spray (metal in powder form), cladding stainless steel and
weld overlaying are used to coat the stainless steel metal surface. The quality of coating
is affected by many factors, such as (1) thickness uniformity, (2) porosity and continuity
of coating, (3) its adherence, and (4) the average thickness of coating.
21 Anticorrosive Coating 889

3.2 Inorganic Coating Materials

Chromate, potassium silicate, phosphate, modified potassium silicate, calcium alu-

minate, and zinc/silicate compounds are used as an inorganic coating (Fig. 1).
Inorganic coating is achieved or formed by chemical conversion, spraying, or
diffusion [6]. It is worthwhile to mention that the metallic and inorganic coating
materials should form a barrier without defects (brittleness and very low porosity).
Otherwise these defects can accelerate localized corrosion of the coated metals
instead of coating due to galvanic effect.

3.3 Organic Coating Materials

Better coating can be formed by organic coating materials. These organic materials
coat the active metal surface by formation of thin film of paint, varnish, and lacquer.
Most organic material coatings adhere to the metal surface by two mechanisms: the
first one is the mechanical adhesion which is common in porous materials, where a
large surface area of metal is used and the organic coat is anchored on the surface
physically. The second mechanism is the chemical adhesion. In this mechanism, the
organic coat is bound to the surface through a covalent, ionic, hydrogen bonding,
dipole-dipole, and/or van der Walls interactions [8]. To obtain good organic coatings,
the following three steps should be considered: (i) suitable surface preparation,
(ii) selection of proper priming coat, and (iii) top coat. It is noted that without proper
surface preparation, the priming coat does not have a good adherence. As a result,
the top coat will not be firmed and may peel off any time.
The first and most important step in assuring good coat performance is surface
preparation. If there is oil or grease contamination in the surfaces, the oil and grease
should be removed first by the solvent or vapor degreasing, for example, a chlori-
nated hydrocarbon, by alkali or emulsion cleaning, and so forth. The degreased
surface can then be sandblasted or pickled.
Painting is one of the long-established methods of corrosion control. Paint
consists resin or plasticizer as binder materials, in addition to organic materials as
a coloring and protective coat [9]. If the environment can be effectively excluded,
paint can do its proposed job. It takes good user technique to be sure a paint works
properly otherwise it can be a wastage of money. The main target of painting is to
furnish a barrier coating that will exclude the environment and prevent its premature
adverse reaction with the substrate. All paint systems fail eventually, but avoidance
of premature failure is needed to minimize the cost.
Paint failure normally involves a combination of oxidation and ultraviolet light.
Due to the oxidation and/or ultraviolet light, there may be a change in appearance,
such as loss of glass, or reduction in the film thickness. Premature failure is usually
characterized by a loss of adhesion, either with the substrate or between successive
paint layers. Loss of adhesion to the substrate also can be a secondary process
resulting from corrosion. To avoid these problems, adequate cleaning must be
done to remove greasy oils of various kinds, poorly adherent prior coatings,
890 M. K. Nazal and M. A. Jafar Mazumder

corrosion product salts, and solid corrosion products, such as mill scale. Primers that
are to be top coated must be completely cured; manufactures are tempted to
underestimate the time required for this coat. Topcoats on primers or other existing
coatings must be compatible. As a general rule, two paint coats will be compatible if
the plots of their solubility parameters versus their hydrogen bonding index are
appropriately close.
The correlation between solubility parameter and hydrogen bonding, which can
be used to judge on the suitability of polymeric paints and the compatibility between
resin and solvent system or between an existing polymeric coating and a paint. In
general, the existing coating should be swelled somewhat by the solvent system of
the topcoat and should not be completely soluble [10].
Two classes of painting should be recognized. The first class is cosmetic painting
for noncorrosive indoor applications, whereas a solvent wipe may be the only
justified pretreatment, and the coating thickness is not important, for example,
painting on fire mains for identification purposes. The second class is intended to
protect from corrosion; here the pretreatment is necessarily expensive and extensive.
Thickness is also important for optimum performance and should be thin (3–12 mils)
for air-dried coatings, depending on type of coating used and the intended
service [10].
Three steps should be followed for obtaining the best performance of protective
coatings using paints. Firstly, the applied coat of paint at the steel surface produce
high quality finishing surface. Secondly, the applied coat helps prompting weldable
priming usually by pigmented iron oxide. The resultant prime should be hard enough
to withstand handling on the way to the assembly site with minimal damage. Lastly,
a hard thin top coat can be applied prior to protect a softer primer. When old paint is
recoated, it is necessary to remove the loose and nonadherent layers on the surface.
Note that pickled or sandblasted steel usually rusts rapidly. Therefore, a superficial
oxide is replaced with a phosphate which acts as a good paint base. Alternatively, a
combination paint called Etch primer from phosphoric acid and specialized primer
can be used [10].
Protective coating using organic materials are applied to a surface in liquid form
and dried to give a prolonging solid film. Drying process usually involves chemical
reactions and polymerization or merely consists of solvent evaporation [11].
Polyaniline conducting polymer is commonly used as common materials for
organic protective coating, which can easily be prepared as a cheap product, and
it has a good tunable properties and thermal stability [12, 13]. It is not like
traditional polymeric coating materials which require multilayer coating to protect
a metal’s surface against corrosion. The main advantage of this material is that it
can be used as single-layer coat [14]. The polyaniline nanostructure composites
(i.e., nanospheres, granules, nanotubes, and nanofibers) demonstrated an improve-
ment in their application as anticorrosive coating materials [15–18]. Different
kinds of polyaniline nanostructure composites are depicted in Fig. 2. Moreover,
there are different methods utilized for preparation of polyaniline such as self-
assembling, electrochemical polymerizations, and heterophase interfaces which
could easily provide different kinds of structures with tunable properties. Table 2
21 Anticorrosive Coating 891

Fig. 2 Schematic illustration of nucleates and monomer of aniline to produce different types of
PANI nanostructures [18]. (With kind permission from RSC)

shows different polyaniline nanostructure composites classified based on their

structures’ morphologies.
One of the important classes of corrosion inhibitors is organic adsorption inhib-
itors (e.g., primary amine, amide, imidazoline, and polyethoxylated amines). The
organic adsorption inhibitors adsorb and form thin film onto the metal surface. The
effectiveness of adsorption inhibitors depends on the electrical potential of metals,
chemical structure, size, and shape of inhibitor molecules. On the other hand, the
inorganic adsorption inhibitors are classified into (i) cathodic inhibitors, such as
carbonate, sulfate, and hydrazine, and (ii) anodic inhibitors such as silicate, bicar-
bonate, phosphate, chromate, or nitrite compounds. These inhibitors are usually
added in small amount (
0.1%) to the corrosive media and are able to stop or
slow down electrochemical corrosion reaction on the metal surface.
892 M. K. Nazal and M. A. Jafar Mazumder

Table 2 Examples on different PANI nanostructure composites

Composition of
PANI-based Methods of
corrosion composition Corrosion
# Structure inhibitor preparation Substrate medium Ref.
1 Nanospheres PANI shell with In situ Zinc 1 M KCl [19]
AuNPs polymerization
and dispersion
mixing
2 Granules ND–PANI In situ Steel and HCl [20]
polymerization aluminum
PANI–CN Ultrasonic Carbon 3.5% [21]
oxidative steel NaCl
polymerization
3 Nanotubes PANI–MWCNT In situ Mild steel 3.5% [22]
polymerization NaCl
PANI Emulsion Mild steel 3.5% [23]
polymerization NaCl
4 Nanofibers ZnO–PANI In situ Carbon 3.5% [24]
polymerization steel NaCl
PANI Direct mixed Aluminum 0.6 M [17]
reaction alloy NaCl
PANI Three different Mild steel 3.5% [25]
types of NaCl
reactions
5 Other HEE and SEPI Nanocasting Cold-rolled 3.5% [26]
nanocomposites synthesized technique steel NaCl
from ACAT
Urchin-like Emulsion – – [27]
PANI polymerization
and in situ
polymerization

4 Mechanism of Anticorrosion Protective Coating

Corrosion of metals causes a significant shortage in the function of the technical

system as a result of the destruction of the metals. The metals are destroyed by
converting them to oxides or other form of corrosion products. Consequently,
understanding the mechanism and thermodynamic of corrosion is significant for
controlling corrosion. Mechanism of corrosion is classified to three main types:
(i) physical, (ii) chemical, and (iii) electrochemical corrosion. Chemical corrosion
involves chemical reaction and takes place in dry conditions on homogeneous or
heterogeneous surface by direct contact with chemical compounds. While physical
corrosion occurs by a combination between a corrosive environment and tensile
loading cracks resulting in multiple branching cracks such as the corrosion that
happens in stainless steel pressure vessels. In electrochemical corrosion, exposing
21 Anticorrosive Coating 893

two different surface structure or composition in different operational environments

causes of evolving an electrical potential. This system of corrosion consists of three
elements as shown in Fig. 3. The corrosion site (anode), the corrosion media (electro-
lyte), and the metals, which are active in the system but do not corrode (cathode), are the
main components in the electrochemical process. The process usually occurs through a
coupled electrochemical half-cell of anodic and cathodic reaction.
In this process, the metals lose an electron in the anodic reaction thus increasing
their oxidation number. For example, as shown in Eqs. 1, 2, and 3, Fe, Cu and Cr lost
2, 2, and 3 electrons, respectively, whereas the first two reactions are considered as a
corrosion reaction but the third one is not.

FeðsÞ ! Fe2þ ðaqÞ þ 2e (1)

2CuðsÞ þ H2 Oðl Þ ! Cu2 OðsÞ þ 2Hþ ðaqÞ þ 2e (2)

Cr3þ ðaqÞ þ 4H2 O ! CrO4 2 ðaqÞ þ 8Hþ ðaqÞ þ 3e (3)

where s, aq, and l represent the state of solid, aqueous, and liquid, respectively.
In the third reaction, there is a loss of electrons from Cr+3 and a charge transfer in
the solution without a phase change. Therefore, the corrosion reaction should have a
mass transfer in addition to the electron loss from metals.
In cathodic reaction, the electrons are consumed, whereas the metals gain elec-
trons, and their oxidation number is decreased. For example, in acidic media, the
predominant cathodic reaction is the reduction of two hydrogen ions at a metal
surface and formation of hydrogen gas, as shown in Eq. 4:

Fig. 3 Corrosion process of steel that leads to the creation of small holes in metal [28]. (Permission
for unrestricted use under creative commons attribution license)
894 M. K. Nazal and M. A. Jafar Mazumder

2Hþ ðaqÞ þ 2e ! H2 ðgÞ (4)

In case of availability of the metal surface in a neutral or basic media, the cathodic
reaction includes reduction of the dissolved oxygen molecules to hydroxyl ions as
shown in Eq. 5:

O2 ðg Þ þ 2H2 O þ 4e ! 4OH (5)

Coupling of both electrochemical reactions (cathodic and anodic) at the same

metal surface occurs at different sites because of the heterogeneity of metal surface
or metals containing impurities. For example, in the acidic environment, the iron
atoms at metal surface act as anodic half-cell, released two electrons and appear as
Fe+2. These released electrons from iron (Eq. 1) is consumed by two hydrogen ions,
and got reduced at another sites as cathodic half-cell on the same metal surface.
For the electrochemical corrosion, the protection types can be classified based on
their protective mechanism to three main classes, galvanic effect (coating sacrificial),
barrier effect, and inhibitive effect. The anticorrosion mechanism by barrier coating is
achieved through its role as a barrier to oxygen and water from the environment by
forming an ionic impermeability interface with high electrical resistance [29–31].
This leads to very low conductivity which in turn minimizes transferring the corro-
sion current between the anodic and cathodic side at the substrate [32]. Table 3 shows
some of those materials used in protective coating. Because of heat and chemical
resistance of SiO2, it improves the acidic corrosion and oxidation resistance of metal

Table 3 Various protective coating materials

Thickness
Substrate Coating composition Coating method (um) Reference
Carbon steel SiO2 Dip-coating 0.15 [34]
Mild steel ZrO2 Dip-coating 0.3–0.6 [36]
Aluminum SiO2 Dip-coating N/A [38]
Aluminum Epoxysilane-epoxy Spraying 30–50 [39]
Aluminum TEOS-GPTMS- Spin-coating N/A [40]
PDMS
Carbon steel TEOS-MAPTS Brushing N/A [41]
Galvanized steel TEOS-MTES Dip-coating 4.0 [42]
Stainless steel CaO-P2O5 Spin-coating 1.0 [43]
Aluminum ZrO2-TEOS-MAPTS Spin-coating 1.9–7.5 [44]
Carbon steel PAAMPS polymer Dip-coating 2.1–2.5 [45]
containing a cerium (Ce)
Stainless steel Cerium-TEOS-MTES Spin-coating 1.9–2.0 [46]
Aluminum MTES Electrodeposition 0.16–0.18 [47]
AISI 304 stainless MTES and DMDES Deposition 0.58–0.76 [48]
steel
Metal substrate of Strontium aluminium Roll bar coater 5 [49]
zinc 5% aluminium polyphosphate
21 Anticorrosive Coating 895

substrate at different temperatures; as a result it has been used efficiently as a

protective coat for stainless steel [33, 34]. Zirconium oxide ZrO2 has a good chemical
stability as well as it can minimize the cracking of metal substrate due to its high
expansion coefficient that is close to the variety of bulk metal substrates [35, 36].
Recently, the reduced graphene oxide (RGO) has been developed as a protective
coating material. A monolayer defect-free RGO with high-barrier properties was
synthesized to prevent water and oxygen gas molecules and even strong acids such
as hydrofluoric acid (HF) to reach the surface of substrate and cause corrosion
[37]. The main challenge for defect-free RGO barrier coating is its synthesis with
a large surface area.
The second type of protective coating mechanism is called sacrificial or galvanic
coating. In this type, the metallic substrate is protected by another electrochemically
more active metal or alloy. In another words, the sacrificial metal or alloy dissolves
favorably to protect the substrate metals. This type of coating is unlike the first type
of protection mechanism. Since its protection mechanism depends on the electrical
conductivity, the coat must be in direct contact with the metal substrate; therefore, it
is only applied as a primer. As shown in the electrochemical activity series in Fig. 4,
there are some metals that might be used as sacrificial coat such as zinc, aluminum,
and chromium on metal substrate. For example, zinc (Zn) is used as primer to protect
the metal substrate by forming an anodic site active coat [50]. The cathode protection
mechanism using Zn sacrificial coat is illustrated in Fig. 5.
For further improvement of the performance of zinc-rich sacrificial coat, many
composites of zinc with other nanoparticles such as aluminum oxide [51], silicon

Fig. 4 Galvanic series

896 M. K. Nazal and M. A. Jafar Mazumder

Water
droplet

O2
Sacrificial anode Zn2+ (aq)

e–

Zinc Iron
(anode) (cathode)

Zn Zn2++ 2e– O2 + 4H+ + 4e– 2H2O

Fig. 5 Scheme illustrates the mechanism of sacrificial coat for cathodic protection

dioxide [52], and titanium dioxide [53, 54] were investigated. In 2011, Khan
et al. [55] prepared a zinc-silica nanocomposites coat with different functionalized
silicas. They found the functionalized silica with thiol group can interact strongly
with zinc metal and form an efficient coating on the surface of metal substrate. To
improve the incorporation of sacrificial coat furthermore with surface of metal
substrate, recently, Camargo et al. [56] enhanced the electrodeposition of zinc-
titanium dioxide coat on steel substrate using ultrasonication method. They reported
that using high-speed electrodeposition under ultrasound sonication reduces the
titanium dioxide particle agglomeration and forms smaller particle size in addition
to its better distribution in zinc sacrificial matrix. Consequently, as a result of
enhancement of the hardness of sacrificial coat, it improve the corrosion resistivity.
The main challenge for sacrificial coating is to keep its conductivity as high as
possible without compromising the hardness as well as the adhesion and cohesion
properties on the metal substrate.
Figure 6 shows the setup of anodic protection, where it is used as an example for
protection of a steel storage tank for acidic solution. To achieve successful anodic
protection, it requires a controlled potential current and formed insoluble film in
aggressive solution. In the anodic protection, many factors influence the protective
potential such as the chloride ion concentration as well as the temperature. As shown
in Fig. 7, the protective potential is inversely proportional to the current, whereas the
metallic coating resistance decreases due to the effect of chloride concentration and
temperature [57]. The low current density for anodic corrosion rate is due to the
limited ionic mobility in the formed insoluble film at the protected surface.
The third protection type based on the anticorrosion mechanism is inhibitive
coating. The corrosion inhibitor materials used in this type initially diffuse from bulk
solution to the surface of metal, and then their molecules start condensation at the
21 Anticorrosive Coating 897

Fig. 6 Schematic illustration

for anodic protection [57]. DC Power (+)
(With kind permission from Source
(–)
Springer) V
Anode

Coated Steel
Storage Tank
(+)

Solution

AE RE

Fig. 7 Polarization curves for

the effects of chloride
concentration and temperature
on the passive region [57].
(With kind permission from
Springer)

surface followed by the adsorption to form monolayer or multilayer protective

coating on the metal surface [58]. The schematic representation of adsorption of
inhibitor molecules on metal surface is shown in Fig. 8.
The inhibitor material adsorbs on the surface of metal and forms monolayer or
multilayers mainly through one of the following interaction mechanisms:

1. Electrostatic interaction between the charged molecules and the surface.

2. Interaction of the nonbonding or the π-electrons with the empty orbitals available
in the surface chemical structure.
3. A mixed mechanism includes both of the above.
898 M. K. Nazal and M. A. Jafar Mazumder

Fig. 8 Schematic representation of adsorption of inhibitor molecules on metal surface from bulk
solution [58]. (Permission for unrestricted use under creative commons attribution license)

The main advantages of this type of protection are that (i) it is cheaper than
sacrificial zinc-pigmented coatings and (ii) it works in most environments. However,
the inhibitive coating is not applicable for coating the immersed structure and must
have low water permeability to work effectively. The inhibition coat composition
must contain soluble constituent which can react with metal surface. Therefore, it is
mainly applied as a primer for substrates exposed to the atmospheric environments
such as industrial environment [59]. In inhibitive coating, the substrate passivates the
materials’ coat that consists mainly of insoluble metallic compounds to protect the
surface of the substrate from the aggressive species. The inhibitive coat contains low
percentage of slightly water-soluble inorganic salts such as phosphate [60], silicates
[61], chromates, and molybdates [62]. These inorganic salts dissolve partially once
they are permeated with water, and then the dissolved components are moved to the
surface of the metal substrate which reacts with it and form protective products that
passivate the metal substrate. Therefore, the inhibitive coat should consist of enough
soluble inorganic salt pigments to insure sufficient leaching from the coat to passiv-
ate the surface of substrate but not too high to prevent occurrence of blistering [63].
This indicates a balance has to be obtained between compounds which work as a
barrier and those as inhibitive inorganic salts.
Generally, molybdates, silicates, and chromate salts are used as an inhibitive
pigment in the inhibitive organic coats. However, in Europe, phosphate salts are
mainly used [59]. In regard to phosphate salt-based pigments, they can be classified
into four generations, namely, (i) pigments which contain only zinc phosphate salt,
which has weak inhibitive properties due to its low water solubility [64];
(ii) modified zinc phosphate salts with aluminum, iron, molybdenum, potassium,
or sodium [65]; (iii) zinc polyphosphates and zinc tripolyphosphate; and (iv) zinc
phosphate which contains organic compounds [66].
Recently, Mohammadi et al. [67] synthesized functionalized graphite nano-
platelets modified with tripolyphosphates anion (FGNP-TPP) to improve the anti-
corrosion coating performance of epoxy by dispersing the nanoparticles on it. Their
results indicate high coated steel substrate resistivity for corrosion. The proposed
mechanism is illustrated in Fig. 9. Tripolyphosphate anions close to the surface of
metal substrate are released from the epoxy coating after its exposure to moisture
from the environment. Polyphosphate anions compared to chloride anions have high
competitive and binding strength to ferric and ferrous oxide at the surface of the
21 Anticorrosive Coating 899

Fig. 9 Illustration for inhibition mechanism using FGNP-TPP epoxy coating composite [67].
(With kind permission from Elsevier)

substrate. Therefore, a stable and dense protective ferric and ferrous phosphate layer
is formed.
The organic inhibitors have the ability to form an efficient protective film on the
surface of metals which might be exposed to media with high hydrocarbon contents.
Therefore, the most widely used inhibitors in the oil and gas industry are the organic
inhibitors [68]. There are many organic inhibitors that have showed excellent
performance as corrosion inhibitors. As shown in Table 4, they have been used as
corrosion inhibitors for different metal surfaces immersed in basic or acidic media.
They belong to different organic families, such as isoxazolidines [69], pyridines
[70–72], fatty amides [73, 74], imidazolines [75–79], and polymers [80].
As a summary, the chart in Fig. 10 shows the main three types of anticorrosion
protection, where they are applied, and their advantages and disadvantages.

5 Performance Testing and Evaluation of Anticorrosion

Coating Materials

Characterization of anticorrosive coating materials is very important. To characterize

a coating material, sample development process, point of interest and evaluation
criteria of the coating materials should be taken into consideration. There are many
outdoor and laboratory tests which have been used to evaluate the performance of
coating materials. The outdoor exposure method is the most reliable way to test the
suitability of certain coating materials for certain substrate in specific environment.
In this approach, the coated substrate is exposed to real environmental conditions in
900 M. K. Nazal and M. A. Jafar Mazumder

Table 4 Chemical family groups of organic inhibitors for anticorrosive coatings

Organic inhibitors
(Chemical family) Structure Surface Media
Isoxazolidines Carbon steel Acidic

Imidazolines Carbon steel Acidic

R,R’ = alkyl, aryl; X = NH2,

NHR, OH
Nitriles Alkylnitriles Carbon steel Acidic
C17H35  CN
Aromatics

Pyridines Carbon steel Acidic

X = CH3, Br, OR
Oximes Alkyloximes Carbon steel Acidic

Aromatics

Primary and secondary Cycloalkylic Carbon steel Acidic

amines

Aromatic (X = H, NO2, CH3,

Cl, COOH)

Benzilamines

Imidazoles Copper alloy and Basic

carbon steel
R = alkyl, aryl
Ureasy Thioureas Copper alloy and Acidic
carbon steel

X = O,S, R = alkyl, aryl

(continued)
21 Anticorrosive Coating 901

Table 4 (continued)
Organic inhibitors
(Chemical family) Structure Surface Media
Triazoles Copper alloys Basic

Tetrazoles Copper alloys Basic

R = alkyl, aryl
Amides and thioamides Amides Carbon steel Acidic

Thioamides

R,R’ = alkyl
Polyvinyls Carbon steel Acidic

R, R’ = alkyl, aryl heterocyclic

Polyesters R – (OCH2CH2)n Carbon steel Acidic
R = alkyl, aryl

a long-term study where it will be finally used [81]. Therefore, the outdoor exposure
test provides a good representation results for the degradation of the anticorrosive
coating materials in specific environment, which consider the main advantage of this
test method. However, it has many disadvantages, for example, degradation of
coating materials in real environment takes a very long time (>10 years). In addition,
the variability of environmental conditions makes obtaining consistence corrosion
rate and mode not possible, which affects the accuracy of concluding result [82].
On the other hand, the second approach, where tests are done in the laboratory,
can provide reproducible results on the performance of coating materials in a shorter
time at different environmental conditions. This approach includes accelerated tests
such as salt spray tests, cyclic testing, and advanced cycling testing. The coated
surface is evaluated later by visual methods exposing them to outdoor or laboratories
corrosion environmental conditions. It is based on translation visual signs of corro-
sion on the surface that lead to useful conclusion, which depends heavily on the
operators’ capability and experience. Therefore, combining the previous visual
method to an electronic method is very beneficial to understand the mechanism of
corrosion and the quality of coating materials.
Since corrosion is mainly an electrochemical process, using electrochemical
techniques is considered the best strategy for characterization and evaluation of the
anticorrosive coating materials’ performance. Particularly, the electrochemical
impedance spectroscopy (EIS), which is relatively fast, accurate, and reproducible,
902 M. K. Nazal and M. A. Jafar Mazumder

Fig. 10 Types of anticorrosion protection coating with their advantages, disadvantages, and area of
applications

has been widely used in studying the performance of coating materials to understand
the mechanism of corrosion reaction at the coated surface-solution interface. In
addition, the EIS is a well-established and powerful technique for the characteriza-
tion of coating materials. However, the EIS has some practical limitations, and it
requires skilled persons and experts to personally perform data analysis.
Figure 11 shows the illustration for the simplest electrical characteristic of
electrode surface-electrolyte solution interface which can also be called Randle
electrochemical circuit. This interface mainly consists of (i) a thin film capacitor
(double layer capacitance (Cd)) which is divided into two planes, inner and outer
Helmholtz planes, (ii) resistivity of charge transfer which is expressed by polariza-
tion resistance (Rp), and (iii) another resistor electrical component which expresses
the resistivity of electrolyte solution (Rs). In some cases, another electrochemical
component appears which is called Warburg impedance (W) due to the impact of
neutral and charged species diffusion from and to the surface. The inductive effect is
not usually appearing in the electrochemical equivalent circuit, therefore, the more
common electrical component is presented in the electrochemical circuit [83].
Generally, the EIS results can be interpreted by one of two approaches: funda-
mental approach and phenomenological approach. For the fundamental approach, a
physico-electrochemical model accounting the processes which take place in the
measurement system is required to formulate a mathematical representation includ-
ing all the parameters and express the relationship between the input and the output
21 Anticorrosive Coating 903

Fig. 11 A simple electrified interface, in which the vertical dotted lines in (a) are represented by
the electronic components in (b) [83]. (With kind permission from ACS)

of the tested system to fit the measurement data and then get an information about the
reaction mechanism. The main drawback of this approach is that it requires a fully
understood reaction mechanism to formulate the model since the electro- chemical
system sometimes appear as complex to get a useful model. Therefore, the second
approach is often used to analyze the EIS data by using a well-defined electrical
equivalent circuit as a physical model that contains electrical parameters, such as
resistors and capacitances, and simulates the EIS measured data. The starting model of
the most probable equivalent circuit can be constructed based on the following points:

1. It is usually derived based on other research results.

2. Starting with a simple electrical circuit includes resistors, capacitors and constant
phase elements, Warburg, and inductor (their symbols and impedance expression
are represented in Table 5) extracted from analysis. The graphical information in
the Nyquist and Bode plots (typical examples) are shown in Fig. 12.
3. The number of electrical elements should be as low as possible in the proposed
equivalent circuit. Any additional element added to the circuit has to decrease the
chi square (χ2) value and enhance the goodness of fit.
4. The ordered electrical elements in the equivalent circuit should be selected with a
theoretical meaningful model.
5. The EIS data should be validated using Kramers-Kronig (KK) transforms.
6. When logical changes happen in the tested system, a systematical change should
be shown with time for the calculated values of electrical elements in the circuit.
904 M. K. Nazal and M. A. Jafar Mazumder

Table 5 Some of the impedance elements’ symbols and expression

Graphical Impedance
# Electrical element Symbol symbol expression Unit
1 Resistor R Z=R [Ωcm2]
2 Capacitor C Z = 1/jωC [F or s/Ω]
3 Constant phase element Q Z = 1/( jω)n Yo [Sn
(CPE) Ω1cm2]
4 Warburg W Z = 1 / ( jω)0.5 Yo Ω s1/2

a
-1000

-800
y
nc
Z ″(ω) (Ω)

ue

-600

Low
req
hf

frequ
Hig

-400

-200 ency
Rs RS+RP
0
45°

0 500 1000 1500 2000 2500 3000

Z ′ (ω) (Ω)

b
200k
Phase shift (degrees) Amplitude (Ω)

3k
RS+RP
2k

1k
RS
0
1m 10m 100m 1 10 100 1k 10k 100k 1M 10M

–30

–60

–90
1m 10m 100m 1 10 100 1k 10k 100k 1M 10M
Frequency (Hz)

Fig. 12 A typical EIS result. (a) Nyquist and (b) Bode magnitude and phase shift [83]. (With kind
permission from ACS)
21 Anticorrosive Coating 905

6 Conclusions

Regardless of the detailed discussions in the aforementioned sections of

this chapter, there are a number of coating technologies and/or methods and
materials which are available for protecting metal surface from corrosion; how-
ever, so far, to date, no single coating technology has been developed to ade-
quately protect the metallic surface from corrosion in harsh environment. The
current coating schemes are complex, multilayer systems that incorporate many
different technologies and must be conducted very carefully in order to achieve
optimum results. There are a number of factors to be considered when developing
a coating process for an industrial application. Significantly some of them are
listed below:

1. Development of new inhibitors as a green chemical to replace the existent toxic

organic and inorganic inhibitors
2. Development of a new surface treatment for better coating and new corrosion
inhibitors to substitute some of the non-environmentally friendly inorganic
inhibitors
3. Replacement of toxic chemicals such as chromium and other toxic metals in a
new composition of stainless steel
4. Environmental concerns with the use of solvent-borne organic coatings but the
development of water-borne and powder coating technologies
5. Employing the fundamental knowledge and understanding of corrosion mecha-
nism to develop alloys with better surface corrosion resistance
6. Development of smart organic inhibitors and coatings that may detect and rebuild
automatically a breakdown in the coated stainless steel surface
7. Development of the concern over waste disposal, capital investment, ease of
manufacturing, coating performance, and environmental issues
8. Combining two or more inhibitors to make their solubility lower or higher to get
long-term or short-term protection, respectively, via sustained release or
passivation
9. Adding other components such as pigments, organic inhibitors, or additives to
increase the efficiency of anticorrosive coating and reinforce their impermeability
with extenders as well as keep the corrosive ions out

Above all, a great deal of research is still required to be done to develop better,
simpler, and cheaper coating technologies so that we can take advantage of the
economically feasible, environmentally friendly, and excellent mechanical proper-
ties of this material.

Acknowledgments The authors would like to gratefully acknowledge King Fahd University of
Petroleum and Minerals (KFUPM) for providing excellent research facilities and Deanship of
Scientific Research, KFUPM, Saudi Arabia, for financial assistance to carry out this research
through internal grant project No. IN131047.
906 M. K. Nazal and M. A. Jafar Mazumder

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Conducting Polymer Nanocomposites as
Gas Sensors 22
Mohammad Omaish Ansari, Sajid Ali Ansari, Moo Hwan Cho,
Shahid Pervez Ansari, Mohamed Shaaban Abdel-wahab, and
Ahmed Alshahrie

Contents
1 General Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
2 Commonly Used Conducting Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
3 Factors Affecting the Gas Sensing Response in Conducting Polymer
Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
3.1 Electrical Conduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915

M. O. Ansari (*)
Center of Nanotechnology, King Abdulaziz University, Jeddah, Saudi Arabia
School of Chemical Engineering, Yeungnam University, Gyeongbuk, South Korea
e-mail: [email protected]
S. A. Ansari
Department of Energy and Materials Engineering, Dongguk University, Seoul, Republic of Korea
e-mail: [email protected]
M. H. Cho
School of Chemical Engineering, Yeungnam University, Gyeongbuk, South Korea
e-mail: [email protected]
S. P. Ansari
Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim
University, Aligarh, India
e-mail: [email protected]
M. S. Abdel-wahab
Center of Nanotechnology, King Abdulaziz University, Jeddah, Saudi Arabia
Materials Science and Nanotechnology Department, Faculty of Postgraduate Studies for Advanced
Sciences, Beni-Suef University, Beni-Suef, Egypt
e-mail: [email protected]
A. Alshahrie
Center of Nanotechnology, King Abdulaziz University, Jeddah, Saudi Arabia
Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 911

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_25
912 M. O. Ansari et al.

3.2 Doping Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915

3.3 Undoping Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
3.4 Surface Area Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
3.5 Role of Environmental Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918
4 Polyaniline and Its Nanocomposites as Gas Sensing Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . 919
4.1 Effect of Nanoparticles in the Sensing Properties of Pani Nanocomposites . . . . . . . . . 921
4.2 Effect of Dopant in Sensing Properties of Pani Nanocomposites . . . . . . . . . . . . . . . . . . . . 921
4.3 General Sensing Mechanism for Pani-Based Nanocomposites . . . . . . . . . . . . . . . . . . . . . . 922
5 Polypyrrole and Polythiophene Nanocomposite as Gas Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . 925
6 Polythiophene-Based Optical Gas Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927
7 Functionalized Conducting Polymers in Gas Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930
8 Conclusion and Future Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 933
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 934

Abstract
The great concerns regarding environmental and living beings protection together
with the widespread requirements for highly accurate process monitoring have
highlighted the need for the development of new and sensitive sensors.
Conducting polymers and their nanocomposites have been used widely as sens-
ing materials owing to their special redox chemistry. The electrical properties can
be controlled easily by doping and undoping processes resulting into the gener-
ation of conducting and nonconducting states, respectively. The electrical con-
ductivity also depends on the type and amount of filler (nanosize filler in some
cases) used which produces the positive or negative carriers responsible for the
conduction. Any type of interaction of these polymers that affects the number and
movement of charge carriers affects the conductivity and is the main principle
behind the gas sensing characteristics. Advances in nanotechnology allows for
the fabrication of various conducting polymer nanocomposites using different
techniques. Conducting polymer nanocomposites have high surface area, small
dimension, and show enhanced properties, making them suitable for various
sensor devices. This chapter presents the different types of gas sensors based on
the conducting polymer (polyaniline, polypyrrole, and polythiophene)-based
nanocomposites, their progress, and future scope of ongoing research in this
research area. The factors that affect the performance of the gas sensors and the
chemistry of the sensing process are also addressed.

1 General Overview

With the publication of the paper entitled “Synthesis of Electrically Conducting

Organic Polymers: Halogen Derivatives of Polyacetylene, (CH)x” in “Chemical
Communications” in 1977, a new field of chemistry, “Electrically Conducting Poly-
mers,” was born [1]. The new concept that the plastics or polymers can conduct
electricity became an exciting area of research and the work in this field has made
significant advances. Later, many other conjugated polymeric materials and their
22 Conducting Polymer Nanocomposites as Gas Sensors 913

derivatives were found to possess electrical conductivity [2–9]. Of these polymers,

polyaniline (Pani), polypyrrole (PPy), and polythiophene (PTh) have attracted the
highest attention of researchers owing to their wide range of electrical conductivity
from insulating to metallic, unique redox properties, good stability, low cost, ease of
synthesis, and promising applications in various fields such as corrosion protection,
energy storage, supercapacitors, gas sensors, etc. [4–15]. The use of conducting
polymers to form conducting nanocomposites has been achieved successfully and
has been an area of interest over the past few years. A nanocomposite is generally
defined as a two-phase system, in which the dimensions of at least one of the phases
are in the order of nanometers. One of the most promising nanocomposite systems is
the hybrids based on organic Pani, PPy, or PTh, nanoparticles such as metal oxides
(ZnO, TiO2, etc.) and carbonaceous materials (CNT, graphene (GN), etc.)
[16–18]. These nanostructured particles combined with conducting polymers can
give rise to the polymer nanocomposites with interesting properties to be the
potential materials for newer and novel applications. The resulting nanocomposites
can be produced in the form of nanofibers, nanorods, thin films, etc. [19–21].
Pani, PPy, and PTh are used widely as the sensing materials due to their redox
nature [22–26]. The electrical conduction can be controlled easily by a doping or
undoping process resulting into the generation of conducting and nonconducting
states, respectively. The electrical conductivity of these polymers depends on the
type and amount of dopant used which produces the charge carriers responsible for
electrical conduction. Any interaction with the polymer that affects the number and
movement of charge carriers along the chain or by the hopping of charge carriers
between chains will affect the conductivity of the doped polymer. This is the main
and basic chemical principle that enables them to be used as the chemical-vapor
sensing materials. In comparison, conducting polymer-based sensors have high
sensitivity and short response times and these features are mostly observed at
ambient temperatures [27–29].
The main problems associated with the conducting polymers are their poor
stability, low surface area, low sensitivity at room temperatures, and comparatively
low conductivity in comparison to metallic conductors. In this regard, the nano-
composite of conducting polymers with metal oxides (TiO2, ZnO, SnO2), metals
(Ag, Au, Zn), carbonaceous materials (CNT, GN), etc., is expected to effectively
promote gas sensing and make sensor operational at low temperature [30]. In the first
place, the interaction of polymers with n-type semiconducting particles such as TiO2,
SnO2 will lead to the formation of p-n heterojunctions at polymer-metal oxide
nanoparticle interfaces. Thus, depletion regions may appear at polymer-metal
oxide nanoparticle interfaces and when the composite is treated with deprotonating
gas (e.g., amines), the width of depletion regions increases, which accounts for the
sensing response [31–33]. Apart from this, the nanoparticles also affect the surface
area of the polymers composites, which is directly related to the sensing response.
The generation of mesoporous structures or coating of polymers on nanoparticles
effectively increases the overall surface area of the polymer nanocomposite thereby
resulting in better sensitivity [34–36].
914 M. O. Ansari et al.

As a result of the large number of publications on the research and develop-

ment of conducting polymer nanocomposites within a short span of time, the main
purpose of the present chapter is to outline the status of the applications of these
nanocomposites in different fields. The work selected here is far from complete
and fully exhaustive of the numerous works published over the last few years but
it is meant to highlight some specific important features and furnish a represen-
tative scenario of the advances and progress in this field. For convenience, the
discussion is divided into a few categories depending on the field of their
applications.

2 Commonly Used Conducting Polymers

Polymers that is plastics, we know behave somehow the opposite of metals. They are
used as insulators as they do not conduct electricity. Electric wires are coated with
polymers to protect us from short circuits.
This view of polymers was changed with the discovery of polyacetylene which
can be made conductive almost like a metal by Alan J. Heeger, Alan G. MacDiarmid,
and Hideki Shirakawa [1]. For this discovery, the Royal Swedish Academy of
Science awarded the Nobel Prize in Chemistry for the year 2000 to these three
scientists who have revolutionized the development efforts in the field of electrically
conducting polymers.
Conducting polymers have extended π-systems and are quite susceptible to
chemical or electrochemical oxidation or reduction. Therefore, the electrical and
optical properties of these polymers could be altered precisely by carefully control-
ling the process of oxidation and reduction. Because these reactions are often
reversible, it is possible to control the electrical and optical properties systematically
and a great deal of precision switching from a highly conducting state through
semiconducting to an insulating state and vice versa [37]. Therefore, conducting
polymers can be perceived as macromolecules with a fully conjugated sequence of
bonds along the backbone which acquires positive or negative charges by the
oxidation or reduction process, respectively. With the advent of many more discov-
eries in the field of conducting polymers, there is a wide variety of polymers that
exhibit electrical conductivity. Figure 1 presents the structures of some of the
conducting polymers.

3 Factors Affecting the Gas Sensing Response in Conducting

Polymer Nanocomposites

To develop the basic concept of gas sensing by conducting polymer nanocomposites,

it is important to understand the phenomenon of doping, undoping, and the effect of
the addition of nanoparticles on the surface area and electrical properties of the
polymer and its nanocomposites.
22 Conducting Polymer Nanocomposites as Gas Sensors 915

H
n N
n
Polyacetylene Polyaniline

N n S n
H
Polypyrrole Polythiophene

n n
Poly(phenyl vinylene) Poly(p-phenylene)

O O
n
R R
S n
Poly(3,4-ethylene-dioxythiophene), PEDOT Polyfluorene

Fig. 1 Common conducting polymers

3.1 Electrical Conduction

Conjugated polymers can be oxidized or reduced more easily than conventional

polymers. Because of the presence of the π-conjugated structure, the electrical
conduction is obtained through “doping” leading to the generation of charge-carriers
in the form of free electrons or holes. The charge carriers are usually delocalized over
the conjugated polymer chain [38].
To conduct, a polymer must have a conjugated backbone for the easy movement
of charge carriers. On the other hand, when conjugated polymers do not contain any
intrinsic charge-carriers, charge-carriers need to be provided extrinsically, typically
by a charge transfer process, generally known as “doping” as a very poor analogy to
silicon technology. Polymers have the electronic profiles of either insulators or
semiconductors. Therefore, the band gap in a fully saturated chain such as polyeth-
ylene is ~ 5 eV and decreases to approximately ~1.5 eV in the fully conjugated
system of polyacetylene. The respective intrinsic conductivities are ~10
17 Scm
1
and ~10
8 Scm
1 which is very low in both the cases [39].

3.2 Doping Process

The role of the dopant is to either remove or to add electrons to the polymers. These
dopants acts as charge transfer agents. The electrical conductivity can be increased
916 M. O. Ansari et al.

by “doping” i.e., p-type doping (oxidation) or n-type doping (reduction) increase the
electrical conductivity by many orders of magnitude. The doping reaction can be
represented in the generalized form as:

Oxidation: P þ n Xþ A
! ½P : nXþ  ½nA
 ðp
type dopingÞ (1)

Reduction: P þ n Xþ A
! ½P : nA
 ½nXþ  ðn
type dopingÞ (2)

where P is the part of the polymer chain. The soliton or a polaron (cation or anion)
formation is the first step which may be followed by second electron transfer
leading to the formation of dication or dianion also called as bipolaron. Thus this
charged segment can interact with neutral polymer segments to give polymer
segments of variable lengths. The general principles can be illustrated best by
examining specific examples, particularly polyacetylene, which has been studied
intensively. The reactions between conjugated polymers and oxidants ( p-type
doping by an acceptor) or reductants (n-type doping by a donor) have been
observed to cause a dramatic increase in electrical conductivity. The commonly
used oxidants ( p-type dopant) include HClO4, FeCl3, AsF5, I2, NH4BF4, SO3CF3,
HCl, HNO3, H2SO4, and H3PO4 whereas the reductants (n-type dopants) include
Li, K, and Na. A general equation for doping of a conjugated polymer may be
expressed as [40, 41]:

P þ 2n FeCl3 ! ½Pþn ½n FeCl4
 þ n FeCl2 ðp
type dopingÞ (3)

P þ n Na ! ½P
n ½n Naþ  ðn
type dopingÞ (4)

3.3 Undoping Process

Another important aspect of doping is its reversal, called undoping or dedoping or

compensation or electrical neutralization of a doped polymer in which, for exam-
ple, a p-type doped polymer reacts with some reducing agent and regains its
insulating state. The undoping agent diffuses into the polymer matrix and neu-
tralizes the charges of the system via a charge-transfer reaction. The process may
involve chemical reactions between the undoping agent and carbonium ion or/and
dopant leading to neutralization by charge-transfer. The undoping agents gener-
ally used for p-type doped conjugated polymers include ammonia, water, hydra-
zine, etc., and the chemistry of the process may be given by the following
equations.

8NH3 ! 6NH4 þ þ 6e
þ N2 (5)

6H2 O ! 4 H3 Oþ þ 4 e
þ O2 (6)

ðπ
polymerÞnþ þ n e
! ðπ
polymerÞ (7)

22 Conducting Polymer Nanocomposites as Gas Sensors 917

Undoping may also be affected by thermal treatments as observed in the case of

PTh. The kinetics of undoping may be studied by several methods such as electrical
conductivity measurements, x-ray diffraction, optical spectroscopy, etc.

3.4 Surface Area Aspects

The functional groups on the surface of the polymers are generally responsible for
the sensing signal. The intercoiled or compressed polymeric structure will give a
poor response due to the fewer unexposed functional sites, while porous or meso-
porous structures will have large number of exposed functional groups and hence
show stronger response. The inclusion of nanomaterials in the polymeric system
greatly affects the surface area of the overall polymeric nanocomposite. The elec-
trochemical deposition of conducting polymers may introduce porosity and increase
the surface area while solution-cast films of conducting polymers typically exhibit
low porosity [42, 43]. The in situ polymerization technique for the formation of the
polymer nanocomposites under optimal conditions generally leads to the wrapping
of nanomaterials by the polymer thereby increasing the surface area (Fig. 2).
The simultaneous in situ formation of nanocomposites alongside the polymer
chain results into the formation of mesoporous structures which can have great
applications in gas sensing due to the large surface area. Nazish et al. [11, 44]
reported the formation of the nanocomposite of Pani with TiO2 where Pani chain
formation and formation of TiO2 from the respective precursor occurred simulta-
neously. The TiO2 precursor trapped inside the weak growing Pani network upon
hydrolysis subsequently broke the Pani chain and made it porous resulting into the
generation of mesoporous structures. Figure 3 presents a schematic of this synthesis
process.

Large number of exposed

functional sides
Exposed unexposed (buried)
functional sides inside the
polymer lump CNT
CNT
Same
Polymer coating on
polymer can
Polymer nanoparticles
CNT be coated on
large
number of
nanoparticles
which fully
exposes its
surface area

Nanoparticle

Fig. 2 Effect of nanomaterials on the surface area of polymer nanocomposite

918 M. O. Ansari et al.

Fig. 3 Schematic diagram of the polymerization mechanism leading to the formation of meso-
porous Pani@TiO2 nanocomposite. (Reprinted with permission from Ref. [44]. Copyright (2015)
American Chemical Society)

Hard template-assisted synthesis of Pani and thereafter final removal of the

template has also shown to give Pani and its composites with highly ruptured surface
morphology which eventually increases the surface area.

3.5 Role of Environmental Conditions

The temperature and humidity are also important factors that play very crucial role in
sensing property of conducting polymer-based sensors [45]. Increase in the conduc-
tance of the conducting polymers occurs with the rise in temperature and humidity.
As most of the sensors are based on chemiresistors, therefore, any change in the
temperature or humidity will also affect its conductance [46, 47].
The process of sensing involves two main steps: adsorption of analyte molecules
on sensing surface of the film followed by reaction between them. The temperature is
able to influence both steps. As adsorption prefers low temperature, any temperature
22 Conducting Polymer Nanocomposites as Gas Sensors 919

increase will shift the equilibrium and analyte desorption will become favorable. As
the adsorption/desorption are the important steps, sensitivity will decrease with
increase in temperature [48, 49]. While the sensitivity of the sensors based on
redox reactions increase with the increase of temperature because of the increased
reaction rate [50].
As a matter of fact, there are many sensors which are quite sensitive to humidity
itself, and here the water vapor becomes analyte. Therefore, the data of sensing
property may be misleading in the presence of humidity which may be due to the
similar response of the sensing material towards the analyte gas and humidity [51].
When humidity is present while sensing an analyte molecule, the adsorption
becomes competitive between water and the analyte molecule. Consequently,
water molecules will occupy some active sites, therefore, the sensitivity sensor
for the analyte decreases with increase in humidity [48]. However, few cases of
cooperative effect analyte and humidity have also been found in sensing film [52].
Sometimes, pressure also affects the sensing property, for eg. with change in
pressure, phase transition may occur in PPy, causing alternation of conductivity
and thereby its sensing of analyte [53].

4 Polyaniline and Its Nanocomposites as Gas Sensing

Materials

Considerable work involving Pani doped with different organic and inorganic acids
has been done in the field of chemical vapor sensors. Koul et al. [54], Ayad et al.
[55], Pinto et al. [56] used Pani as chemical vapor sensor for sensing alcohols,
ammonia, and some derivatives of ammonia and reported Pani to be a good material
for their sensing. Redox reactions of PPy and PTh also occurs with volatile organic
compounds (VOCs), also making them suitable for gas sensing applications [57, 58].
Nanocomposites of these polymers are expected to give an enhanced sensing
response due to the higher surface area, as discussed above.
Several studies found that the reaction of Pani nanocomposites with VOCs is
reversible. Tai et al. [59] examined the sensing behavior of Pani:TiO2 composite
films towards NH3 and CO and reported that Pani@TiO2 films were more sensitive
to NH3 than CO. The good reproducibility towards NH3 was explained based on
NH4+ being formed upon exposure to ammonia which decomposes to gaseous
ammonia and a proton added to Pani when exposed to ambient air and results in
the restoration of the initial level of doping. The thickness of the films and poly-
merization temperature also affects the sensing behavior. Thin films show better
response due to the better adsorption and desorption during sensing and the films
prepared at the optimal temperature are superior to those prepared at other temper-
atures in terms of the response properties [60].
Ma et al. [61] showed that Pani does not have any specific character to distinguish
between different gases and the sensing response, either strong or weak, will be
recorded for most chemicals. On the other hand, some gas sensor arrays can be
used to identify different gases with aid of an artificial neural network system.
920 M. O. Ansari et al.

They reported gas-sensitivity of Pani and TiO2 composite film towards tri-
methylamine, triethylamine, ethanol, formaldehyde, acetone, and toluene vapors.
The results showed different sensitivity and recovery time for different gases. The
sensitivity and the response time of triethylamine were much lower than that of
trimethylamine, and hence the composite film can be used to distinguish between
trimethylamine and triethylamine. In addition, the composite film showed little
response to ethanol, formaldehyde, acetone, and toluene.
Therefore, it can be concluded that Pani-based nanocomposites are the excellent
sensor for organic bases such as ammonia or ammonia derivatives or other base-
based chemical compounds due to the change in electrical conductivity upon
interaction with bases and the response and recovery time can be an important
parameter for distinguishing between different types of gases. Many other reports
on different sensors such as humidity, carbon monoxide, nitrogen oxides, carbon
dioxide, etc., also work on the same principle [62, 63]. In general, the sensitivity is
lower in these cases due to the smaller change in electrical conductivity upon
exposure to these compounds compared to ammonia and ammonia derivatives.
The sensing of ammonia-based derivatives can be done at much lower concentra-
tions such as below ~0.5 ppm while for H2, ethanol, methanol, and acetone, etc., a
much higher concentration is required [64]. A comparative study of the sensing
response towards CO, methane, and liquefied petroleum gas (LPG) at room temper-
ature by a Pani/Co3O4 nanocomposite showed high selectivity towards CO at a very
low ppm concentration while in the case of methane and LPG, a very small or no
response was recorded even at 100 ppm [65]. This suggests that both methane and
LPG consisting of hydrocarbons cannot affect the conductivity of Pani/Co3O4
significantly. Therefore, a very small response was recorded in their case while a
sharp increase in conductivity was observed in the case of CO gas suggesting an
increase in charge carriers in Pani. The resonance structure of CO withdraws a lone
pair of electrons from the amine nitrogen in Pani resulting in the transfer of a positive
charge from the carbon of CO to the amine nitrogen of Pani which results in an
increase in the number of holes and consequently an increase in its conductivity. In
contrast to the above findings, the Pani@CdSe and Pani@γ-Fe2O3 sensing response
was attributed to the sensor’s modified depletion layer and the detection of LPG is
due to an increase in the depletion depth caused by the adsorption of gas molecules at
the depletion region of the p-n heterojunction [66, 67].
The electrical properties of Pani and Pani-based nanocomposites in the doped
states are sensitive to water which provides a basis for their potential applications as
humidity sensors. Humidity affects the resistivity for two reasons; the adsorbed water
molecules dissociate at the imine nitrogen centers and the positive charge migrates
through the Pani or Pani-based nanocomposites [68]. Jain et al. [69] and other workers
[70] reported that the increase in conductivity of Pani films in humid conditions is due
to proton exchange between the polymer and the water adsorbed on the surface of
Pani. NMR spectroscopy showed that proton transfer takes place in Pani in the
presence of water. This transfer can be described by the following redox reaction:

> NH2 þ þ H2 O !> NH þ H3 Oþ (8)

22 Conducting Polymer Nanocomposites as Gas Sensors 921

4.1 Effect of Nanoparticles in the Sensing Properties of Pani

Nanocomposites

Different types of nanoparticles in Pani nanocomposites respond differently to

different gases which may be due to a synergistic effect. The Pani@TiO2 nano-
composite shows superior NH3 gas-sensing characteristics in comparison to
Pani@SnO2 and Pani@In2O3 films. Pani being a p-type polymer and the metal
oxide being n-type interact to form a p-n junction resulting into the formation of a
positively charged depletion layer on the surface of the inorganic nanoparticles
which results in a lowering of the activation energy and enthalpy of physisorption
for NH3 gas. This leads to a higher gas sensing response compared to that of Pani.
The lowest unoccupied molecular orbital (LUMO) of Pani and the conducting band
of TiO2 compared to SnO2 and In2O3 matches well, leading to better sensing
characteristics of Pani@TiO2 [71].
Gong et al. [72] showed that the p-n heterojunctions between TiO2 and Pani
nanoparticles acts as an electric on-off current switch when NH3 gas is absorbed by
Pani. The change in bulk resistance of Pani and the combination of the p-n depletion
layer functions as a current switch which turns on the current circuit by absorbing H+
and turns off the current circuit by adsorbing NH3 gas. Dhawale et al. [73] proposed
a similar sensing mechanism where the heterojunctions showed the maximum
response of 63% upon exposure to 0.1 vol% LPG at room temperature. Figure 4
shows a schematic diagram of a nanosized p-n heterojunction as a switch to control
the electric current flow.
Nanoparticles have also been observed to act as catalyst for the redox reactions of
Pani. Methanol detection by the Pani@Pd nanocomposite revealed a very strong
response in the order of ~104 magnitudes. The Pd acts as a catalyst for the reduction
of imine nitrogen in Pani by methanol [74]. Choudhury et al. [33] reported a similar
catalytic influence of Ag nanoparticles in ethanol detection by the Pani@Ag nano-
composite. A faster protonation-deprotonation of Pani was observed upon exposure
to ethanol in the presence of Ag nanoparticles.

4.2 Effect of Dopant in Sensing Properties of Pani

Nanocomposites

Pani or its nanocomposites doped with different types of dopants generally

respond differently to various VOCs. Song et al. [75] showed that in the case of
Pani doped with HCl, HNO3, H2SO4, and organic protonic acids (e.g.,
sulfosalicylic acid), the resistance increased upon exposure to ammonia
irrespective of the acid used. The noticeable difference is that the recovery and
response time of Pani doped with H2SO4 was longest while the shortest response
and recovery times were recorded for a sulfosalicylic acid-doped Pani. In another
study, it was proven that HCl-doped Pani showed superior gas sensing character-
istics to p-toluenesulfonic acid ( pTSA)-doped Pani because HCl effectively
922 M. O. Ansari et al.

l1 Metal
l l

TiO2 l2
TiO2

Dedoped
P-N P-N PANI
H+ doped
junction junction
PANI
l1 P
NH3-H2O l1 P
I I X
N
N
l2 l2 TiO2
TiO2

R1 R2 R3 R1 R2 R3
l1 l1
I I

l2 l2
R4 R4

Fig. 4 Schematic diagram of the nanosized p-n heterojunction as a switch to control the electric
current flow in TiO2 microfibers. (Reprinted with permission from Ref. [72]. Copyright (2015)
American Chemical Society)

improved the conductive properties of Pani in a wide range of concentrations and

pTSA in a narrow range of concentrations [76].
The optimal dopant concentration for high gas sensitivity is generally required
with a bulky dopant such as camphor sulfonic acid (CSA). For high concentrations
of CSA, the number of Pani–H+ reacting with NH3 would not make up a high
proportion of all Pani–H+ within certain limits and steric hindrance would reduce the
chance of NH3 being absorbed by Pani (Fig. 5). As a result, their ammonia sensing
performance was degraded although the high concentration CSA-doped Pani com-
posite showed better conductivity [77].

4.3 General Sensing Mechanism for Pani-Based Nanocomposites

The gas sensing response can be summarized as a combination of the absorption-

desorption phenomenon as well as electrical compensation, as a side reaction. The
main reasons for the gas-sensitivity should be attributed to the interaction between
Pani and the adsorbed gas through strong interactions such as chemical bonding and
weak interactions, such as hydrogen bonding, van der Waals forces, etc. Recovery is
very difficult in the case of strong interactions while it is much easier for weak
interaction systems [61]. This might be due to the formation of weak complex of
22 Conducting Polymer Nanocomposites as Gas Sensors 923

B
+
H

CSA concentration increased

Pani chain B B
B Base + CSA +
H H
B B B
CSA CSA
CSA + + +
H H H

CSA CSA CSA

Fig. 5 Effect of the CSA concentration on the sensing of NH3 by CSA-doped Pani composite

C7H7SO3
NH4+ and after desorption, resistivity slightly higher than the original
value is observed [78]. Many workers suggested that the deprotonation reaction
causes the conductivity of the Pani to decrease for low concentrations of base
[79–82].
In these reports, at low concentrations, the reversible interaction occurs,
whereas at high concentrations, the irreversible interaction occurs for short expo-
sure to ammonia vapors [83]. For pTSA doped Pani@TiO2, the interaction of
ammonia is similar to the acid/base interaction and at higher concentration of
ammonia, the neutralization of the dopant acid occurs rapidly leading to the
formation of nonconducting emeraldine base. However, at low concentrations of
ammonia, the chemisorption of ammonia molecules occurs on the positively
charged nitrogen atoms as proposed in the mechanism. This process is largely
reversible but neutralization reaction is also partially involved as discussed above
leading to the undoping of Pani. During the chemisorptions, the ammonia mole-
cules interacts by its lone pair with positively charged nitrogen atoms of Pani,
thereby decreasing the hole mobility which results in a decrease in electrical
conductivity. By this interaction, the nitrogen slightly acquires pentavalent con-
figuration and becomes unstable (nitrogen does not show pentavalency because of
the absence of d orbitals). Thus favorable desorption of ammonia occurs upon
exposure to an ambient atmosphere. Figure 6 presents a schematic representation
of the sensing mechanism.
Therefore, Pani and the Pani-based nanocomposites can serve as excellent sensor
for a variety of gases such as ammonia or their derivatives, water vapor, carbon
monoxide, or carbon dioxides. The sensing generally involves redox reaction in all
the cases with a combination of chemisorption and desorption. The more undoping
of Pani or its nanocomposites takes place, the lower the cyclic stability while high
desorption under ambient conditions or inert atmosphere will provide better sensors.
In addition, a higher operating temperature (~90  C) is unsuitable for the gas
sensitivity because it may damage the linear structure of the polymer and hinder the
migration of charge carriers [84]. Figure 7 shows a typical resistivity based sensor of
Pani and its nanocomposites [85].
924 M. O. Ansari et al.

Fig. 6 Schematic sensing mechanism of Pani involving the chemisorption-desorption phenome-

non and electrical compensation. (Adapted from Ref. [83] with permission from Elsevier)
22 Conducting Polymer Nanocomposites as Gas Sensors 925

OVG-4 gas generator Sensing chamber

dry N2+NH3

dry N2
Carrier gas

MFC - 1
Sensor
stage

N2

USB interface to computer Agilent Multimeter

Fig. 7 Schematic illustration of the experimental setup used for gas sensing evaluation. (Adapted
from Ref. [85] with permission from Elsevier)

5 Polypyrrole and Polythiophene Nanocomposite as Gas

Sensors

Like Pani, PPy and PTh also show similar gas sensing characteristics due to
the similar conjugated structures. The derivatives of PTh such as poly
(3-hexylthiophene) (P3hT) have been used widely because of its better stability
and processability. PPy and P3hT in the doped state behave like p-type semicon-
ductor and can interact readily with different gases. Owing to the basic structural
similarity of PPy and P3hT with Pani, the sensing reaction also takes place similarly
while the response and recovery times can vary widely.
Undoped PPy does not show any gas sensitivity but shows high sensitivity in
doped PPy depending on the dopant anion [43]. The gas sensing response of
PPy@WO3 reported by Geng et al. [86] was observed to be different when exposed
to 1000 ppm NH3, H2S, and NOx at room temperature. The response time for NH3,
H2S, and NOx was 54 s, 135 s and 124 s, respectively. The recovery time of PPy to
NH3 and H2S was very long and PPy showed irreversibility when exposed to NOx
gases. PPy is a p-type semiconductor whose carrier is a hole while WO3 is p-type
semiconductor whose carrier is an electron. The irreversibility towards NOx may be
due to the blocking of PPy interaction sites by NOx. The sensing mechanism of
PPy@WO3 towards H2S can be explained by the co-effects of the proton doping
process and the effects of the n-type semiconductor. Similar to ammonia sensors,
926 M. O. Ansari et al.

PPy being p-type reacts with reducing gases such as NH3 leading to a decrease in
charge carrier density and the conductivity decreases once the mobility of the charge
carrier decreases as observed in the case of the Pani-based nanocomposites [28]. PTh
also responds in a similar manner to redox reactions and upon doping the PTh film
with halogens such as iodine, the electrons are removed from the rings of PTh
(protonation reaction) thereby increasing the hole density leading to an enhancement
of the electrical conductivity. Upon exposure to ammonia, the molecules are
physisorbed and undoping takes place. Higher concentrations of ammonia lead to
a higher carrier density and consequently a better sensor response. The process of the
change in electrical resistance is partially reversible under ambient or inert atmo-
spheres as observed in the case of Pani and PPy-based nanocomposites [87].
Alcohols such as methanol and ethanol upon exposure to PPy nanocomposites
increase the conductivity which is in contrast to the reducing gases such as H2S and
NH3 or their derivatives. The conductivity of PPy changes with the change in the
doping level and PPy is a p-type semiconductor. Therefore, exposure to electron-
donating gases such as alcohol will cause an increase in resistance [88–90]. Chang
et al. [91] reported that PTh responds to alcohol with high reversibility. This is in
contrast to the inorganic sensors which are poisoned by alcohol. Another interesting
report by Goncalves et al. [92] revealed the swelling behavior of P3hT films which
affects the interchain spacing thereby affecting charge transport and hence the
conductivity. The highest response for tetrahydrofuran (THF) in their case was its
polar nature, which imparts high levels of swelling to the P3hT films and enlarges the
spacing between the polymeric chains resulting in lower conductivity. The poor
response to methanol which is not a solvent for P3hT is due to the absence of its
swelling effect.
Li et al. [93] reported that PPy shows high sensitivity towards humid conditions
and plenty of works have been done on the low temperature humidity sensing on
PPy-based composites [94]. Sun et al. [95] reported that the sensing phenomenon
involves an ionic conduction mechanism. Under humid conditions, a layer of water
molecules begins to form at the polymer surface and polymers containing hydro-
philic groups such as –COOH, –SO3H, –NH2, etc., ionize and produce conductive
ions i.e., charge carriers. The concentration of conductive ions increases with
increase in relative humidity and the resistance of the sensing materials decreases.
The PTh humidity sensor also works in a similar manner, the presence of surface
water affects the PTh conduction that occurs through the overlap of adjacent π-bonds
and surface water enhances the overlap of π-bonds [96]. Hoshina et al. [97]
explained the generation of holes in the film in the vicinity of adsorbed H2O due
to its large dipole. H2O is expected to adsorb only at the surface and grain boundaries
and so the holes induced by H2O provide conduction paths.
Akbarinejad et al. [98] prepared a 3D PPy film with very high porosity and coated
it over copper interdigital electrode by electrospinning of soluble PPy nanoparticles.
The coated system was studied for its sensing properties as gas sensor proved to be
an excellent material for aliphatic amines with high sensing response, low detection

limit, and good repeatability at operating temperature upto150 C. In addition, it also
showed extremely high sensitivity and selectivity to n-butylamine. The sensitivity
22 Conducting Polymer Nanocomposites as Gas Sensors 927

toward n-butylamine was observed to be approximately three orders of magnitude

higher than that of other aliphatic amines. The detection limit was 0.42 ppm and
linear range for determination of n-butylamine was 10.54–21.08 ppm.
Kamble et al. [99] synthesized nanofibrous PTh on glass substrate through a
simple chemical bath deposition method. The film was tested for its sensing prop-
erties toward different gases. Out of these different gases like CO, H2S, LPG, NH3,
NO2, and SO2, the highest selectivity of the PTh film for NO2 was seen. The
morphology, concentration of monomer, and thickness of the deposited film plays
significant role in the sensing properties of the film. The film deposited at 0.5 M
monomer concentration showed the highest NO2 gas response of 47.58% at room
temperature. These results also showed that initial concentration of monomer plays
an important role as the deposition parameters to control the morphological and gas
sensing properties of the chemical bath deposited PTh film.
Liao et al. [58] on studying the mechanism of gas sensing on derivatives of PTh
films proposed that change in the thickness of films occurs on exposure to vapors
which large defines the sensitivity. The X-ray reflectivity, analytical technique can be
used to study the structure of films is extremely accurate in measuring film thickness
with Angstrom resolution and the swelling and de-swelling of PTh films on exposure
to vapors can be easily measured by X-ray reflectivity. The change in the thickness
can be characterized to estimate the different amounts of vapor as well as for
exposures in a saturated chamber of amines, alcohols, etc. In order to establish the
change in thickness as related to vapor exposure, the deswelling of films was also
observed in situ. The advantage of X-ray reflectivity measurement is that the insitu
characterization of the physical interaction between the PTh and vapors can be easily
studied. The thickness change and its relation to the uptake of analyte by the PTh
films can be easily studied. Figure 8 shows the reflectivity changes of poly-
butylthiophene films on interaction with analyte, and a definite swelling of films is
observed. Further examining the desorption process, the thickness of poly-
butylthiophene films was monitored after desorption of acetone from the film. The
scans in Fig. 8 show the fringes shifting to the right, as a result of the decrease in film
thickness. Thus the X-ray reflectivity measurements confirms the physical interac-
tion between the analyte species and the PTh films and the analytes diffuse to the
interface and interacts with the charge carriers, effecting reducing the drain current at
a given voltage. It can also be concluded that the physical interaction between the
analyte and PTh film results in a few Angstroms increase in the film thickness. This
effect must be accounted for any mechanistic model proposed for the sensing
response.

6 Polythiophene-Based Optical Gas Sensors

PTh has also been studied as an optical sensor and several studies have utilized the
absorbance, reflectance, fluorescence, and refractive index properties, both intensity
and wavelength of absorbance and fluorescence are used as a measure of the gas
sensing response [100]. Solis et al. [101] examined the absorption and refractive
928 M. O. Ansari et al.

Fig. 8 X-ray reflectivity scan depicting the baseline drift (control) and the clear shift due to analyte
exposure (exposed). (Adapted from Ref. [58] with permission from Elsevier)

index change for the detection and high sensitivity and a rapid response time was
observed. A small change in the side chain of PTh also induces significant changes in
the responses of the optical sensors and the sensors responded differentially towards
P3Th and poly(3-dodecylthiophene) suggesting that using PTh with different
side chains is a good method for obtaining sensors with better selectivity. The
sensing behavior can be due to the physical interactions between the gas and PTh
causing swelling of the polymeric films. The redox reaction can also occur but
oxidation–reduction reactions are not possible in the case of a neutral gas [102].
The swelling behavior increases the pore volume, accelerates the dilution of chro-
mophores (polymer chains), and results into the decrease in the absorbance which
can also affect the aggregation state of the polymer chains changing their confor-
mation and interchain interactions. The change in absorbance affects all the optical
parameters and can be a good measure of the sensor performance. Goncalves et al.
[103] reported that different types of PTh as an active layer can be used in optical
sensors for the detection of n-hexane, toluene, tetrahydrofuran, chloroform,
dichloromethane, methanol, and water vapor in concentration range of
500–30,000 ppm. On the other hand, the major drawbacks are the poor signal
response and either the sensitivity to VOCs needs to be improved or amplifying
systems will be needed for future commercial applications [104].
The typical simplest fabrication of sensor involves coating of PTh-based com-
posite on substrate which works as electrode for the sensing purpose. The coated
substrate such as silicon wafer/glass coated PTh-based composite results in high
22 Conducting Polymer Nanocomposites as Gas Sensors 929

Fig. 9 (a) Bare sensor and (b) poly(3-hexylthiophene) (P3hT) film-based sensor. (Taken from Ref.
[105])

effective charge carrier mobility and is directly related to the sensing characteristics.
Figure 9 shows the bare sensor and P3hT film-based sensor [105].
In summary, there are various factors which affect the sensing response, i.e., the
thickness of polymer films, side chains attached to the polymer unit, and band gap of
polymer. The transition from the conducting state to the insulating state changes the
optical properties of the PTh derivate. The nonconducting undoped state of poly
(3-octylthiophene) which is dark red in color becomes light blue on doping; similarly
the neutral state of poly(N-methylpyrrole) is transparent which becomes brown on
oxidation and blue to colorless change on oxidation occurs for poly(ethylenediox-
ythiophene). In insulating state, the materials possess a characteristic π–π* transition
in the visible region and the extent of which is governed by the band gap and length
of conjugation [106]. The exposure of these polymers and their composite to gases
results in the change in the structure due to weak interactions, doping-undoping,
compensation as observed in their optical spectra, and this is also accompanied by a
change in conductivity [107].
Besides their sensing toward the metallic ions, these polymers also exhibit good
sensitive to acidic vapor. The changes observed in these cases are reversible and thus
offer very promising prospects and application in various fields of application. Deep
colored solutions (from violet to yellow) are formed by the reaction of poly(thio-
phene-3-propionic acid) or poly(thiophene-3-octanic acid) with 1 equivalent alkali
metal hydroxide or tetraalkylammonium hydroxide per carboxylic acid group
depending on the size of the counter ion. It could be explained on the basis of
varying size of counter ions in the carboxylate polymer which affect the stereo-
chemistry of the polymer. Smaller cations favor planar ( p-stacked purple phase)
while larger cations prevent planarity and self assembly (isolated yellow phase)
(Fig. 10). When exposed to HCl vapor, the polymer films quickly changed from red,
orange, or yellow (depending on the cation) to purple. It is attributed to the
protonation of the carboxylate groups in the polymer, which allows the polymer
930 M. O. Ansari et al.

Fig. 10 PTh zipper sensors: analyte driven disassembly and self-assembly. (Adapted from Ref.
[108] with permission from Elsevier)

chains to attain a relaxed conformation from a twisted to a violet p-stacked confor-

mation with H-bonding, therefore, zipped phase of polymer is an ordered phase.
However, when the polymers are left in air, they reverted back to their original color.
Thus, a promising future of these polymer and their special stereo structures could be
anticipated [108].

7 Functionalized Conducting Polymers in Gas Sensing

Apart from the main stream conducting polymers, functionalized or derivatives of

main conducting polymers are also utilized for the sensing purposes. The aim to
develop sensors based on the functionalized conducting polymer is solely to remove
the specific drawback concerned with the particular conducting polymer. For exam-
ple, Poly(N-alkylanilines) are soluble in common organic solvents while main
conducting polymers are insoluble in these solvents. The introduction of bulk
alkyl groups into the polymer backbone can be used to dissolve it in common
solvents which makes their processing easy [109]. There are numerous reports of
gas sensing properties of substituted or functionalized conducting polymer. Patil
et al. [110] reported excellent sensing properties of poly(o-anisidine)/tin oxide
nanocomposites towards the LPG. These nanocomposites possess better sensing
properties toward LPG detection than pure poly(o-anisidine). The nanocomposite
behaves as p-type semiconductor and its resistance increases on exposure to LPG,
and this feature is employed for the measure of the sensing characteristics. Ratole
and Khadayate [111] reported gas sensing properties of poly(o-anisidine)/TiO2 and
found higher response than the pure poly(o-anisidine). These films of poly
(o-anisidine)/TiO2 nanocomposites when exposed to NH3 not only showed better
response than that of poly(o-anisidine) but also possessed faster gas desorption from
22 Conducting Polymer Nanocomposites as Gas Sensors 931

the surface as compared to poly(o-anisidine) itself. Valentini et al. [112] prepared and
studied CNT/poly(o-anisidine) nanocomposites. The poly(o-anisidine) deposition
onto the CNTs imparted higher sensitivity to the sensor based on these nano-
composites. On exposure to HCl, CNT/poly(o-anisidine) nanocomposites showed
higher sensitivity than CNT alone. The increased sensing capability for inorganic
vapors is attributed to direct charge transfer with electron hopping effects on
intertube conductivity through physically adsorbed poly(o-anisidine) between
CNT. Casalbore-Miceli et al. [113] electropolymerized 4-(Ferrocenylmethylidene)-
4H-cyclopenta[2,1-b:3,4-b]-dithiophene for its humidity sensing properties.
Tanaka et al. [114] studied electrical and optical characteristics of poly
(3-octyloxythiophene). Because of higher energy of valance band originated from
electron donating alkoxy group, poly(3-octyloxythiophene) exhibits more stable
doped state and strong interaction with electron accepting molecules and offers its
nature to be utilized for gas sensing application. There were reversible changes in its
electrical properties on exposure/absence of organic gases. It also exhibited linearity
against gas concentration. Other derivatives of Pani, poly (o-toluidine), poly
(N-methylaniline), poly(N-ethylaniline), poly (2,3 dimethylaniline), poly (2,5
dimethylaniline) were found to be good sensor for alcohol vapors [115].
Surwade et al. [116] studied poly-o-toluidine as gas sensor, herein this study they
suggested good and reversible sensing properties of poly-o-toluidine toward NO2
gas in the concentration range 10–100 ppm using UV irradiation at room tempera-
ture. They also found that solvent used for casting the film with dipolar aprotic
solvents yields the conducting polymer films showing a strong response. The choice
of solvents also affects the morphology of the polymer film which is attributed to the
chain conformation in the solutions that is preserved in the solid state, i.e., polymer
film and it opens a new line to control the sensing and selectivity response of
the polymer. Aussawasathien et al. [109] used electrospinning technique to prepare
poly(o-toluidine) (POT)–polystyrene composite fibers doped with CSA in the form
of nonwoven mat on Au substrate as chemical vapor sensor. Owing to the different
nature of different sensing gases, the response of the electrospun fiber was also
varied. The composite fiber sensor responded to volatile chemicals in different ways,
depending on the polarity of sensing chemicals. The change in electrical response
with chemical vapor was noticeable even at low amount of fibers. This can be
attributed to large specific surface area, high fiber aspect ratio, and high
interconnecting network of composite fibers. It was also observed that the surface
morphology of the electrospun fibers was unaffected after gas sensing.
As far as substituted pyrrole is concerned, its derivatives have also been utilized
as sensor. Poly (N-methylpyrrole) was found to be sensitive toward various organic
vapors [117, 118]. Costello et al. [119] developed chiral poly(3-substituted-pyrrole)
sensor to detect chiral molecules in vapor phase. The polymers were fabricated into
chiral sensors by coating the chiral monomer onto poly(vinylidene) difluoride
membrane and polymerizing within the membrane structure using ferric chloride
oxidant. The sensors exhibited significant chiral discrimination properties, exhibited
differential changes in electrical resistance and mass when exposed to different
enantiomers in the vapor phase (e.g., (R)- and (S)-menthol, 2-butanol, limonene,
932 M. O. Ansari et al.

and carvone). Preliminary results obtained in their work proved that chiral
conducting polymers have opened up a new approach for detection of gaseous
analytes. Paul et al. [120] developed a rapid carbon monoxide detection system by
electrochemically functionalizing PPy with ferrocenylmethyl trimethylammonium
iodide as a co-dopant which exhibited very high sensitivity to ppm levels of carbon
monoxide gas and fast recovery under normal dry room temperature conditions.
Iron-based complexes are expected to provide sensitivity for carbon monoxide
detection due to the preferential interaction with iron moiety [121]. However, such
complexes would have to be modified to suit electrochemical polymerization of
conducting polymers. Paul el al [120] synthesized a new dopant derived from
ferrocene attached with tetramethylaminoiodide group so that it can be used during
electrochemical polymerization and also dope PPy with the same. These have been
then tested for sensitivity and found to be rapidly responsive to ppm levels of carbon
monoxide. They functionalized PPy with 5,10,15,20-tetraphenyl-21H,23H-porphy-
rin iron(III) chloride to detect presence of carbon monoxide gas in ppm level.
Controlled functionalization of PPy was done by incorporation of various concen-
trations of porphyrin. The redox properties of the PPy matrix can be altered strongly
by the linkage of electroactive species, especially with coordination compounds.
Thus, pyrrole-based polymers containing redox sites of adequately designed transi-
tion metal complexes like porphyrin, phthalocyanine, etc., have been prepared by
chemical as well as electrochemical methods. The polymerization of these pyrrole
substituted complexes has produced interesting polymers aimed at catalyzing redox
and organic reactions but not mainly for gas sensor applications. In another research,
Paul and Joseph [122] reported NO2 sensing capacity of PPy functionalized with
iron(III)phthalocyanine-4,4,4,4-tetrasulfonic acid monosodium salt. The increase in
conductivity of the functionalized PPy was found on exposure to NO2 at room
temperature. This material exhibited excellent stability, reversibility, and reproduc-
ibility. Thuwachaowsoan et al. [123] synthesized perchloric acid doped Poly
(3-thiopheneacetic acid), P3TAA, by oxidative polymerization methodology, and
later prepared its composite with zeolites (zeolite L, zeolite modenite, zeolite beta)
by random dry mixing. The type of zeolites affected the sensitivity and zeolite beta
(composite with 20% (v/v) of zeolite beta) showed the highest electrical conductivity
and sensitivity due to the lowest amount of Al which leads to large number of
available active sites of positive charges on the polymer chain. These positive
charges (polaron or the bipolaron) can easily interact with H2 hence giving the
sensing response.
Krondak et al. [124] reported the chemoresistivity of 4,40 -dibuthoxy-2,20 -
bipyrrole and 4,40 -dimethoxy-2,20 -bipyrrole for electrical and sensing characteris-
tics. These polymers were synthesized by cyclic voltametry and showed high
sensitivity for HCl in the ppm range. These polymers also sensed the presence of
NH3, NO, and oxygen, however, less sensitivity than towards HCl. The electrical
conductivity of the polymers was observed to be pH dependent; in comparison to
4,4-dibuthoxy-2,2-bipyrrole, the conductivity of the methoxy-2,2-bipyrrole shifted
to acidic range. This behavior also offers their utilization in the advancement of
enzymatic biosensors with pH transducing.
22 Conducting Polymer Nanocomposites as Gas Sensors 933

Lange et al. supported that presence of ozone changes the oxidation and proton-
ation states of Pani and m-chloro-Pani which could be seen as change in optical
absorbance between 500 and 800 nm. The higher sensitivity of Pani and m-chloro-
Pani in comparison to N-methyl- Pani is probably caused by their ability to be
oxidized to pernigraniline [125].
Torsi et al. [126] studied alkoxy and alkyl substituted regiochemically defined
polyterthiophenes as active layers in sensing organic thin films transistors. The
active layers possess polycrystalline morphology and the substituent chains on it
bear different associated dipole moments. VOCs carrying moieties that are chem-
ically homologous to the selected polymers’ side chains are used as analytes. Both
electrical and quartz crystal microbalance sensor responses are evaluated and a
rationale for the sensing mechanisms involving weak polar/polar-type interactions
is proposed. In another report, Torsi et al. [127], utilized dipentoxy-substituted
PTh thin film in configuring an organic thin film transistor. Sensing response of
the film was found to be very fast for 1-hexanol and ethanol and sensitive as low
as 0.7 ng/ppm.
Xu et al. [128] synthesized SnO2 hollow spheres and further its composite with
PTh, the resulting PTh hybrid composite showed good synergistic interaction
between SnO2 and PTh. The hybrid possessed higher thermal stability than pure
PTh. Gas sensing properties (sensor response and selectivity) of these hybrids were
found to be good toward NO2 at temperature below 100  C. The increased sensing
performance of the hybrids is attributed to the large surface area of the hybrids and
the p–n heterojunction formed between p-type PTh and n-type SnO2 hollow spheres.
Pirsa and Alizadeh [129] studies gas sensors based on sulfonte ion doped PPy and
found rapid response and lowest detection limit for DMSO among different VOCs.
These sensors were fast, reversible, and reproducible. Therefore, these hybrids can
be utilized for detection of DMSO and other VOCs in the atmosphere or at work
place.
Organic field effect transistors based on P3hT and CuII tetraphenylporphyrin
composite were studied for sensing behavior toward nitro-based explosive com-
pounds. For example, 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 2,4,6-
trinitrotoluene (TNT) and dinitrobenzene. Sufficient changes, suitable for sensing
were observed in transistor on current and conductance on exposure [130].

8 Conclusion and Future Challenges

Overall, nanocomposites of Pani, PPy, and PTh offer the safe detection of a wide
variety of gases at room temperature. Room temperature sensing gives high stability
and prevents structural changes such as polymer deformation. Conducting polymer-
based gas sensors have potential applications in different contexts such as industries,
household emission, vehicle emission control, environmental monitoring, and bio-
sensors. Sensors are inexpensive, easy to fabricate, and operate at room temperature
with very little power consumption. Future works may include the introduction of
different chemical moieties and chemically modifying the polymer structure to
934 M. O. Ansari et al.

customize the properties and enhance the selectivity for different gases. Finally, new
strategies will be needed to fully understand the underlying mechanism involved in
analyte sensing by conducting polymers and its nanocomposites which will assist in
the fabrication and commercialization of highly selective sensors for specific agents.
Pani, PPy, and PTh nanocomposites have high potential in the field of gas sensing
and can be used in wide variety of applications. On the other hand, major drawbacks
limit their commercialization due to the following demerits:

1. Alan MacDiarmid, one of the pioneers in conducting polymer research, stated

that “there are as many different types of polyaniline(s) as there are people who
make it!” [72]. Therefore, different reaction setups even with a slight change in
the reaction parameters may yield a polymer product with a completely different
set of properties. In the case of Pani, PPy, and PTh, optimized conditions are
needed to obtain a controlled nanostructure because pH, time of synthesis, and
temperature affect the final polymer product considerably.
2. The dopant also plays an important role, and the quantification of dopant by chemical
synthesis is a tedious job. Different amounts of dopant may remain in the final product
due to the different amount of losses of dopant during filtration which depends on
many factors such as suction pressure, filtration time, washing, etc.
3. The shelf life of doped Pani, PPy, and PTh is relatively short due to the undoping
reaction which might take place upon exposure to reducing conditions.
4. Such sensors in contrast to metal oxide sensors do not work at high temperatures
because polymer degradation is often the competing reaction.
5. The sensor response towards a large number of nanocomposites is influenced by
humidity which may cause the false response. Therefore, the development of
Pani, PPy, and PTh nanocomposites impervious to humidity will be one of the
great challenges of the future.

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Polymeric Membranes for Natural Gas
Processing: Polymer Synthesis 23
and Membrane Gas Transport Properties

Jimoh K. Adewole and Abdullah S. Sultan

Contents
1 Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 943
2 Natural Gas Processing Using Membrane Separation Technology . . . . . . . . . . . . . . . . . . . . . . . . 943
3 Functional Polymeric Membranes for Natural Gas Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . 945
4 Classification of Membrane Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
5 Theoretical Background of Gas Separation in Polymeric Membranes . . . . . . . . . . . . . . . . . . . . 950
6 Synthesis, Preparation, and Transport Properties of Functional Polymeric Membrane
for Natural Gas Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955
6.1 Thermal Rearrangement and Cross-Linking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955
6.2 Grafting of Polymer Backbone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 966
6.3 Template Polymerization Technique and Use of Porogens . . . . . . . . . . . . . . . . . . . . . . . . . . 966
6.4 Sulfonation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 967
6.5 Technique for Preparing Polymers of Intrinsic Microporosity (PIM) . . . . . . . . . . . . . . . . 969
6.6 Membrane Preparation Using 3D Printing Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . 970
7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 970
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 971

Abstract
Polymers are macromolecules made up of repetition of some simpler units called
monomers. To the general public, polymers are used as consumer products in the

J. K. Adewole
Center for Integrative Petroleum Research, College of Petroleum Engineering and Geosciences,
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
e-mail: [email protected]
A. S. Sultan (*)
Department of Petroleum Engineering, College of Petroleum Engineering and Geosciences, King
Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Center for Integrative Petroleum Research, King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 941

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_26
942 J. K. Adewole and A. S. Sultan

forms of plastics, fibers, rubber, adhesive, paints, and coatings. Today, new areas
of applications of polymers have emerged due to the continuous growth of new
classes of polymers. Varieties of functional polymers have been developed for
various applications including organic catalysis, separation, biotechnology, medi-
cines, optoelectronics, photographic, building, and fuel. Natural gas separation using
functional polymers is a new area of application where not much information is
available. This work seeks to present an overview of the synthesis, preparation, and
separation performance of functional polymers in natural gas separation.

Abbreviations
6FDA 2,20 -bis(3,4-Dicarboxyphenyl) hexafluoropropane dianhydride
APTMDS bis(3-Aminopropyl)-tetramethyldisiloxane)
BAS bis(Aminopropyl) polydimethylsiloxane
CD Cyclodextrin
CH4 Methane
CMS Carbon molecular sieve
CO2 Carbon dioxide
DADE Diamino diphenyl ether
EDA Ethylene diamine
GPU Gas permeation unit
HPAAc Hydroxyl poly (amic acid)
HPI Hydroxyl ployimide
MDI 4,4-Metylenediphenyl diisocyanate
NG Natural gas
PBO Polybenzoxazoles
PBT Polybenzothiazoles (PBT)
PDMC Propane-diol monoesterified cross-linkable polyimide
PEG Polyethylene glycol
PEO Polyethylene oxide
PHA Polyhydroxyamide
PIM Polymers of intrinsic microporosity
PIOFG Ortho-positioned functional groups
PPG Poly(propylene glycol)
PTMS Poly[1-(trimethylsilyl)-1-propyne]
S-PEEK Poly(ether ether ketone)
TCDA 2,3,5-Tricarboxy cyclopentyl acetic dianhydride
THF Tetrahydrofuran
TR Thermal rearrangement/thermally rearranged
TR-PBI Thermally rearranged microporous polybenzimidazole
XLPEGDA Cross-linked poly(ethylene glycol diacrylate)

List of Symbols
DD Gas diffusion coefficient by Henry modes of sorption
ED Activation energy of diffusion (kJ/mol)
EP Activation energy of permeation
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 943

DH Gas diffusion coefficient by Langmuir modes of sorption

ΔHS Enthalpy of the gas
kD Henry’s law constant
b Langmuir affinity constant
0
CH Langmuir capacity constant
L Membrane thickness (dense-selective layer thickness)
P Permeability
αAB Permselectivity or selectivity or separation factor of component A from B
DA0 Pre-exponential factor
SA0 Pre-exponential factor
PA0 Pre-exponential factor
A or B Gas components (or permeated and rejected component, respectively)
D Diffusivity coefficient
R Universal gas constant, 8.31 J/mol
S Solubility coefficient
T Temperature, K

1 Natural Gas

Currently, the world cleanest, safest, and most efficient energy source is natural gas
[1–3]. The carbon dioxide emission factor of commercial natural gas is 26% lower than
that of oil and 41% lower than the emission from coal during combustion [4]. Natural
gas is often found in crude oil or gas reservoirs, condensate wells, and coal beds [2] with
methane (CH4) as its primary constituent [5]. In addition, natural gas contains some
heavier hydrocarbons, water (in the form of vapor), mercury, nitrogen, helium, and acid
gases [6]. Table 1 contains a detailed composition of a typical raw natural gas. It is
important to note that natural gas composition varies from place to place [7]. The
composition shown in Table 1 is the range obtained for Eleme (Nigeria), Alberta
(Canada), Western Colorado (USA), Miskar (Tunisia), Southwest Kansas (USA), Rio
Arriba County (New Mexico), and Bach Ho (Vietnam). In the present global economy,
natural gas is indeed one of the fastest growing primary sources of energy [2, 8–10]. In
2012, it constitutes about 24% of the global energy mix and it is expected to rise to
28 by 2040 (Fig. 1). The natural gas world market is estimated as US$22billion per
annum [11]. Clearly, for natural gas to maintain its position as one of the world’s most
sought after energy sources, alternative cheaper and energy efficient means of pro-
cessing technique (such as the membrane) is needed.

2 Natural Gas Processing Using Membrane Separation

Technology

Today, membrane gas separation technology is a commercially available process for

gas separation and purification. This include separation of nitrogen from air (oxygen
enrichment), recovery of hydrogen from process streams, dehydration of gas
944 J. K. Adewole and A. S. Sultan

Table 1 Natural Component Composition range (mol%)

gas compositions
Helium (He) 0.0–1.8
[8, 12–14]
Nitrogen (N2) 0.21–26.10
Carbon dioxide (CO2) 0.06–50.00
Hydrogen sulfide (H2S) 0.0–3.3
Methane (CH4) 29.98–90.12
Ethane (C2H6) 0.55–14.22
Propane (C3H8) 0.23–12.54
Butanes (C4H10) 0.14–8.12
Pentanes and heavier (C5H12 +) 0.037–3.0

a 7% 2% b
4% 7%
33% 7% 26%
5% 1 Oil
2 Natural Gas
3 Coal
4 Hydro
5 Nuclear
30%
27% 6 Other
24% 28%

Fig. 1 Forecast of changes in the global energy mix. (a) 2012. (b) 2040. (Copied from
Kontorovich et al. [15] with permission from Elsevier)

streams, recovery of vapors from gases, and natural-gas processing [16–18]. The
composition of crude natural gas displayed in Table 1 clearly reveals that the raw
natural gas needs further treatment in order to meet a specified quality standard. The
standard that is specified by pipeline transmission and distribution companies is
shown in Table 2. Membrane separation is one of the major separation techniques
that are used in natural gas purification [1, 9, 19]. In membrane natural gas pro-
cessing, research attention has been focused more on the removal of CO2 due
to its abundance in the raw gas than H2S. The removal of CO2 will enhance the
calorific value (energy content) of the natural gas, significantly reduce the volume
of gas to be transported through pipeline and cylinders, prevent atmospheric pollu-
tion, and reduce the susceptibility of the pipeline to corrosion [11, 20]. Presently,
commercially available CO2 separation techniques include adsorption, cryogenic
distillation, and membrane [21].
For many reasons, membrane separation has witnessed a much more rate of
growth than other separation techniques [17]. This is particularly due to some of
the special features of membrane separation technique which distinguishes it from
others. Advantages of membrane gas separation include higher separation efficiency,
faster separation, simplicity, and high space economy [7, 23–26]. The use of an
efficient gas processing technology for producing a cleaner source of energy will
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 945

Table 2 Natural gas Major components Mol% range

specifications for
Methane 75
various applications
[8, 13, 14, 22] Ethane 10.0
Propane 5.0
Butanes 2.0
Pentanes and heavier 0.5
Nitrogen and other inerts 3.0
Carbon dioxide 2.0–5.0
Total diluents gases 4.0–5.0

constitute an excellent approach in addressing environmental issues that are associ-

ated with greenhouse gas emission at relatively lower cost.

3 Functional Polymeric Membranes for Natural Gas

Processing

Review of available literature on membrane gas separation techniques revealed that

current research efforts in improving the competitiveness of membrane gas separation
with other gas separation processes can be classified into two: namely [27], engineer-
ing, which deals with the design and optimization of membrane modules, and
materials, which involves the design and development of novel membrane materials.
In materials development, research efforts are twofolds:

(i) Synthesis of new novel polymers for preparation of new membranes.

(ii) Modification of existing commercial polymers to improve their gas separation
properties.

In both cases, the synthesis of functional polymers and functionalization of

existing polymers have dominated research endeavors. Functional polymers are
macromolecules which contain specified chemical groups or polymer that has certain
specific physical, chemical, and biological properties. The selection of such poly-
mers for certain application depends on the presence of the functional groups it
contains. Usually, the properties of such polymers are determined by the presence of
functional groups which are different from those of the backbone chains [28]. The
polymers can be based on simple linear backbones, three-dimensional (such as
stars, hyperbranched polymers) or dendrimers (tree-like structures polymers). All
these polymers have been used in the preparation of membrane materials for gas
separation. For example, CO2 has an affinity to amine, polar ether oxygen linkages,
and other functional groups. Thus, polymers which bear any of these functional
groups are often preferred for preparing membrane materials for CO2 removal from
natural gas. Table 3 showed commercial membranes that are presently being used in
industrial gas plants. Also, the performance of other commercially available
946 J. K. Adewole and A. S. Sultan

membranes in CO2 removal from CH4 is shown in Fig. 2. These membranes are
made from polymers that contain one or more functional groups.
The presence of these functional groups in a polymer will enhance the solubility
and solubility selectivity of such polymers with respect to CO2. In addition, the
presence of the functional groups could also enhance the diffusivity of the natural
gas component in membrane especially when they are positioned as branches within
the polymer matrixes. The presence contributes seriously to intrasegmental rotational
mobility and intersegmental chain packing of polymers [32]. For instance, Table 4
shows two membrane samples, one with ether functional group and the other without.
It can be observed that the one with ether has higher solubility as compared to the
other one. Also, the second without ether has higher diffusivity which is a result of the
gap created by the presence of H2 branching
 2 that
 is not3 available in the first one.
ðSTPÞ
The unit of P is Barrer; S is 108 cms , D is cm3 ðcm
polymer Þ-atm .
The effect of substitution of the bulkier functional groups (such as tri-
fluoromethyl) in place of the methyl groups has also been investigated for iso-
propylidene moiety of the diamine. The results shown in Table 5 revealed once

Table 3 Commercial Membrane Selectivity CO2/CH4

membranes used for CO2
Cellulose acetate 10.0–28.0
removal from natural
[7, 16, 29–31] Polysulfone 22.0
Polyimide 32.5

Fig. 2 Gas separation (CO2/CH4) performance of some commercial polymeric membranes. (Cop-
ied from Adewole et al. [4] with permission from Elsevier)

Table 4 Comparison of effect of functional groups on gas transport and separation properties of
polymers [3]
Name Structure P S D Permselectivity
4,4-Oxydianiline 23 4.89 3.58 60.5
(4,4-ODA)

Methylenedianiline 19.3 3.96 3.70 44.9

(MDA)
 23

Table 5 Comparison of effect of bulkier functional groups on gas transport and separation properties of polymers at 10 atm and 35  C [32]
Name Structure Solubility Diffusivity
6FDA-ODA 4.89 3.58

6FDA-MDA 3.96 3.70

6FDA-6FpDA 4.72 10.3

Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . .
947
948 J. K. Adewole and A. S. Sultan

again that the polymer with ether oxygen linkage has the highest CO2 solubility than
other polymers. This is majorly due to the interaction between the ether linkage and
CO2. Moreover, polymers with bulkier functional groups (placed as branches) have
higher diffusivity. For instance, the diffusivity of 6FDA-MDA with H branch is
about 64% lower than 6FDA-6FpDA which contains bulkier functional group units
as branches. This is because the substitution of the bulkier central moiety for less
bulky ones leads to simultaneous disruption in intermolecular packing and suppres-
sion of intrarotational flexibility in the diamine segment
 2  of polyimides [32].
3
ðSTPÞ
Permeability unit (Barrer); solubility unit 108 cms , cm3 ðcm
polymerÞ-atm .
The main aim of this work is to provide an overview of the method of synthesis
and transport properties of polymers that are presently being used for natural gas
processing. Particularly, the writing will be limited to functional polymers for
separation of major components of natural gas which include helium, nitrogen,
carbon dioxide, hydrogen sulfide, methane, ethane, propane, Butanes, pentanes,
and heavier hydrocarbon. In addition, functional polymeric membrane gas transport
properties in terms of permeability, solubility, diffusivity, and selectivity will be
considered. Polymeric membrane materials are often subdivided into two classes,
namely, rubbery and glassy polymers. Rubbery polymers are those that are above the
glass-transition temperature while glassy polymers are those below the glass-
transition temperature [1]. The glassy polymers often possess high selectivity but
their permeability are low [33]. Moreover, the permeability may deteriorate over
time as a result of polymer aging. In the contrary, the rubbery polymers are known to
be highly permeable but their selectivity and plasticization resistance properties are
low. Herein, attention has been given to both classes of polymers.

4 Classification of Membrane Materials

Polymeric membranes have been applied in a verity of areas such as filtration

(microfiltration, nanofiltration, and ultrafiltration), reverse osmosis, pervaporation,
desalination, membrane distillation, membrane crystallization, dialysis, gas and
vapor separation, and so on. The classification of membrane materials is carried
out based on many factors. Membrane materials can be either synthetic or natural.
Natural membrane materials are those polymers that are often found in animals and
plants. Examples include polysaccharides and rubbers [34]. Synthetic membranes
can be further classified into organic (polymers), inorganic (such as ceramic, metals,
zeolites, and carbon [35]), or mixed-matrix (containing both organic and inorganic
materials). Figure 3 depicts a pictorial representation of membrane material classi-
fication. Moreover, both the synthetic and natural polymers can be used in gas
separation in the form of solid or liquid membranes.
In terms of morphology, membrane materials can be classified into porous
and nonporous membranes. The scanning electron microscope (SEM) surface
images of porous and nonporous membranes are shown in Fig. 4. According to
the cross-sectional structure, membranes can be isotropic (symmetric membranes)
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 949

Membrane
Materials

Natural Synthetic

Biomaterials e.g. Organic

Inorganic
Cellulose (Polymer)

Glassy Rubbery Ceramic Glass Metals Zeolite

Fig. 3 Membrane material classification for gas separation

Fig. 4 Surface images of porous and nonporous membranes. (a) Nonporous membrane. (b) Porous
membrane

or anisotropic (asymmetric membrane with a thin porous or nonporous selective layer

that is supported by a much thicker porous substructure) [34]. Asymmetric mem-
branes are commonly prepared in such a way that they are integrally anisotropic.
Dual-layer (or composite) membrane is an example of asymmetric membrane
(Fig. 5). The dual-layer technique provides the opportunity to separately optimize
the performance of the selective layer and the porous support. The top selective layer
could be a barrier with pores in the nanometer range or a nonporous polymer. The
porous sublayer provides the mechanical support that is needed during operation.
During operation, all the membrane materials are often packed within a certain
housing called modules. There are two major types of membrane modules: the
hollow fiber module (containing hollow fiber membranes) and the spiral wound
module (housing flat sheet membranes). The two types of module are shown in
Figs. 6 and 7, respectively. Majority of the large-scale membrane gas separation
plants are operated based on these two modules. A photograph of membrane CO2
separation plant is shown in Fig. 8.
950 J. K. Adewole and A. S. Sultan

Fig. 5 Cross-sectional images of dual-layer polymeric membranes. (a) Flat sheet dual-layer.
(b) Hollow fiber dual-layer. (Reprinted from [36] by permission from Elsevier)

Permeate Gas

Feed Gas
Reject Gas

Hollow-Fiber Membrane

Gas A + B Gas B

Gas A

Fig. 6 Hollow fiber membrane module. (Reprinted from [37])

5 Theoretical Background of Gas Separation in Polymeric

Membranes

Theoretically, the permeation of gas through nonporous dense polymeric membranes

is commonly described using the Solution-diffusion mechanism. Based on this
mechanism, gas molecules are first sorbed by the membranes at the upstream
(high-pressure) interface, the sorbed gas then diffuses through the membrane, and
it is later desorbed at the downstream (low pressure) chamber [39–41]. A schematic
illustration of a gas permeation setup is shown in Fig. 9. Gas molecules movement
through polymeric membranes is controlled by diffusivity coefficient (D) and solu-
bility coefficient (S). The solubility coefficient is thermodynamic in nature and is
determined by the following factors:
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 951

ion
olut
dS
Fee

Perforated Central Tube

Anti-telescoping Feed Channel

Device Spacer
Membrane

ate
me
Per
te
ntra
nce
Co Permeate Collection
Material
Membrane
Feed Channel Spacer
Outer Wrap

Fig. 7 Schematic representation of spiral wound membrane module. (Copied from [38])

Fig. 8 Photograph of a CO2 separation plant. (Reprinted from [7] with permission from Elsevier)

(i) The inherent condensability of the penetrant

(ii) Polymer–penetrant interactions
(iii) The amount of excess volume existing in the glassy polymer

Diffusivity coefficient, D, is a kinetic parameter which determines the mobility of

individual molecules through the polymer chains [42]. It is determined by packing
and motion of the polymer segments and by the size of the penetrant molecule.
952 J. K. Adewole and A. S. Sultan

P Tubing
Pressure Switch
Wiring
P

Polymer sample holder

Heating Jacket

ISCO Pump Upstream chamber Downstream chamber

Gas reservoir

Pt-100

Data
Acquisition

Fig. 9 Schematic diagram of a permeation setup for measuring gas permeability. (Copied from
Adewole et al. [43] with permission from Springer)

Increasing the diffusivity or the solubility or both for a particular gas by structural
modification of the polymer allows one to raise the gas permeability. Moreover, such
modification could also lead to improvement of the permselectivity of a desired gas
over an undesired one [4].
The permeability (P), which provides information about the ability of the mole-
cules to pass through a membrane, is therefore defined as the product of diffusivity
coefficient and solubility coefficient:
P ¼ DS (1)

The commonly used unit of permeability in membrane gas separation is the

barrer. Conversion from barrer to other unit can be done using the given expression:
1 barrer = 1  1010cm3(STP)cm/(cm2scmHg) = 7.5005  1018m2s1Pa1 [44].
The ability of a membrane to separate a gas A from a mixture of gases (A and B)
referred to as the selectivity (αAB).
PA
αAB ¼ (2)
PB

The Eq. (2) above is used for calculating selectivity involving single (pure) gas
permeation through a membrane. For the permeation of mixed gases, the selectivity
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 953

(which is referred to as mixed gas selectivity or the separation factor) is calculated

using the following equation [20, 45, 46]:

   
Composition of A Downstream yA
Composition of B Downstream y
Separation factor ¼   ¼  B (3)
Composition of A Upstream xA
Composition of B Upstream xB

where A is the gaseous component which permeated through the membrane. B is

the gaseous component which was retained or rejected from permeating through
the membrane. The x is the mole fraction of the gaseous component which is
present in the feed while y is the mole fraction of the gaseous component in the
permeate. It is important to note that the type of the permeation experiment
(either pure or mixed gas permeation) needs to be mentioned while reporting
the selectivity. By combining Eqs. (1) and (2), it is possible to express the
selectivity as:

DA S A
αAB ¼  (4)
DB S B
The DDB is often referred to as the mobility selectivity or diffusivity selectivity.
A

Also, the SS AB is referred to as the sorption selectivity or solubility selectivity [40].

A parameter that is used for expressing membrane performance depends on the
type of membrane module. For hollow fiber membranes, the separation performance
is commonly expressed in term of permeance. The permeance of a hollow fiber
membrane to gas A is the permeability of the membrane (PA) divided by the
membrane thickness (L ). Mathematically,

PA
Permeance ¼ (5)
L
For dual-layer hollow fiber, L is the dense-selective layer thickness and can be
determined as follows [47]:

PAðdens_e_filmÞ
L¼ (6)
ðP =L ÞAðdual-layer_hollow_fiber_membraneÞ

Accordingly, the selectivity is expressed as:

ðP =L ÞA=
αAB ¼ ðP =L ÞB (7)

The permeance is commonly expressed using the gas permeation unit (GPU) (1GPU
is equivalent to 1  106cm3(STP)/(cm2scmHg) or 7.5005  1012ms1Pa1)
[47, 48]. It is a common practice to use Eq. 7 for asymmetric membranes especially
when the thickness of the active layer is not known.
954 J. K. Adewole and A. S. Sultan

The relationship between the operating temperature and the gas diffusion coeffi-
cient in polymeric membrane can be represented by the Arrhenius equation [40]:
 
E D
DA ¼ DA0 exp (8)
RT

where DA represents the diffusion coefficient (cm2/s) of gas A. DA0, ED, T, and R are
the pre-exponential factor, the activation energy of diffusion (in kJ/mol), the tem-
perature (in K), and the universal gas constant, respectively. Here, the value of the
R is 8.31 J/mol.
Similarly, the solubility as a function of temperature can be expressed by the van’t
Hoff equation:
 
ΔH S
S A ¼ S A0 exp (9)
RT

SA0 and ΔHS are the pre-exponential factor and the enthalpy of solution of the
gas A, respectively.
The gas permeability can therefore be expressed as a function of temperature by
combining Eqs. 8 and 9 substituting them into Eq. 1 as follows:
 
E P
PA ¼ PA0 exp (10)
RT

E P ¼ E D þ ΔH S (11)

PA0 and EP are the pre-exponential factor, and the activation energy of perme-
ation, respectively.
Gas transport through polymeric membrane is also affected by the upstream (feed)
pressure as well as downstream (permeate) pressure of membrane module. The effect
of pressure on gas transport properties of the two major classes of polymeric
membrane is very much distinguishable. For example, in rubbery polymers, the
well-known solution-diffusion model is used to describe gas transport behavior as a
function of feed pressure. On the other hand, gas transport behavior in glassy poly-
mers is more complicated and other equations are needed. Changes in gas perme-
ability as a function of pressure is often explained using the dual-mode model and
partial/total immobilization models [40]. In this model, solubility is expressed as:

FC 0H b
S ¼ kD þ (12)
1 þ bp

where kD, C 0H , and b are constants referred to as Henry’s law constant, the Langmuir
capacity constant, and the Langmuir affinity constant, respectively. In the case for
total immobilization model, F is set to 1.
Using a modified form of Eq. 12 allows the permeability of gases to be expressed
using the dual-sorption model as follows [16]:
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 955

C 0H bDH
P ¼ k D DD þ (13)
1 þ bp2

where DD is the diffusion coefficient for gas molecules absorbed by Henry sorption
mode and DH the coefficient for gas molecules absorbed Langmuir mode of sorption.
Equation (1) provides a better measure of the gas transport properties and
separation performance of polymer because all the parameters included in these
equations are experimentally measurable. Therefore, all these parameters will be
used as indices of the degree of natural gas purification capability of the functional
polymers in this discussion.

6 Synthesis, Preparation, and Transport Properties

of Functional Polymeric Membrane for Natural Gas
Processing

6.1 Thermal Rearrangement and Cross-Linking

High thermal property and chemical resistance are some of the properties that are
needed for polymers to be used for separation NG components. Aromatic polymers
such as polybenzoxazoles (PBO) and polybenzothiazoles (PBT) are two excellent
types of polymers with these properties. However, the high chemical resistance
(to common solvents) makes it difficult for them to be used in membrane prepara-
tion. This challenge was overcome by using thermal rearrangement method which
involves a postfabrication polymer – modifying reaction. The process is carried out
by thermally rearranging the aromatic polyimides containing functional groups
(PIOFG) such as –OH and –SH in order to obtain a dense PBO and PBT membrane
[49]. The whole procedure is a two-stage procedure:

(i) Synthesis of hydroxyl-containing polyimides: Polyimides containing ortho-

positions functional groups (PIOFGs) were prepared via a two-step process.
First, formation of hydroxyl-containing poly(amic acids). Then thermal
imidization.
(ii) Synthesis of thermally rearranged membrane: Thermal treatment was done at
varying temperature (300 to 450  C) and time 1 to 3 hours under argon gas in a
quartz tube furnace.

A schematic of the proposed scheme for thermal rearrangement is shown in

Fig. 10.
The transport properties of TR membranes were evaluated with respect to per-
meability, solubility, and diffusivity. Results of these properties showed that gas
transport properties depend on the final heat treatment temperature and the method of
imidization used for preparing the polyimide. Previous reports [50] showed that
thermal rearrangement of polyimide was triggered at around 350  C and at 450  C,
full conversion of polyimide to thermally rearranged polymer occurred. At the
956 J. K. Adewole and A. S. Sultan

temperature between 350  C and 450  C, TR membranes were believed to contain

both unchanged segments and thermally rearranged segments. Usually, polyimide
shows higher H2 permeability than CO2 permeability. This is in consistent with the
order or increasing kinetic diameters of penetrant molecules. This means that the
diffusion selectivity plays a major role. On the other hand, TR polymer treated at
450  C has permeability in the order: CO2 > H2 > He>O2 > N2 > CH4 with high
gas permeability values. By increasing the treatment temperature, the gap between
the permeabilities of CO2 and H2 reduces and at 450  C the order of the permeability
values for these two gases are completely reversed. The change in behavior suggests
that CO2 solubility is higher in TR polymer than H2 solubility and this contribute to
the higher value of CO2 permeability as compared to that of H2. Table 6 shows the
comparison of gas transport properties of polyimides made from two imidization
methods. The gas selectivity decreases with increase in treatment temperature;
however, TR polymer still looks promising because it has higher CO2 permeability
with corresponding high CO2/CH4 selectivity than other conventional polymers such
as cellulose acetate and polyimides.
The huge success recorded on the use of thermal rearrangement method for the
synthesis of TR-PBO membranes encouraged researchers to further dig into inves-
tigating the thermally rearranged polymers. Importantly, a detailed fundamental
understanding of the behavior of the TR polymers is needed in order to develop a
better procedure for the design and synthesis of these polymers.

Fig. 10 Proposed thermal rearrangement mechanism from hydroxyl-containing polyimide to

polybenzoxazole. (Taken from Park et al. [49] with permission from Elsevier)

Table 6 Gas transport properties of polyimide obtained by various imidization methods [49, 51]
Method of imidization CO2 permeability (Barrer) CO2/CH4 selectivity
Chemical imidization 17 62
Thermal imidization 6 43
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 957

Wang and Chang [52] carried out a systematic investigation on the evaluation
of the physicochemical and gas transport properties of a representative thermally
rearranged polymer (polyhydroxyamide (PHA)) with respect to temperature. The
study was aimed at providing solid evidence that will help to elucidate
the fundamentals of thermal cyclization and provide molecular illumination of
the temperature-induced chain rearrangement. Therefore, the effect of thermal
cyclization temperature on the thermal rearrangement process was investigated.
The effect of the temperature on the chemical structure transformation, thermal
stability, physical properties, gas separation performance, and gas sorption prop-
erties of the resulting membranes were evaluated. Results revealed that the
thermal cyclization temperature is a factor that affects the degree of thermal
conversion, influences the thermal history of polymers, and causes thermal
cross-linking.
Table 7 shows the effect the temperature has on gas separation performance of the
resulting membrane. Membranes that are cyclized at higher temperature exhibit
better performance. According to the authors, the superior performance recorded
for these membranes is due to the fact that a higher thermal cyclization temperature
caused the suppression of polymer chain segmental rotation, resulted in lower chain
packing density, and enhanced the formation of microvoids.
The work carried out by Wang and Chang [52] on TR polymers involved the use
of PHA as processors owing to its high rate of conversion at relatively lower
temperature. Wang et al. [53] used another similar polymers but with a higher
number of functional groups. The authors employed poly(hydroxyl amic acid)
(PHAA) as a precursor to synthesize PBO. PHAA comprises of hydroxyl and
carboxyl functional group giving room for the exploration of different stages of
thermal cyclization of PHAA in a stepwise manner. The first step involved the
transformation of PHAA to poly(imide benzoxazole) (PIBO) at temperature up to
300  C. During the second step, PIBO was finally transformed to polybenzoxazole
(PBO) at 400  C. This was followed by a systematic investigation of the resulting
evolution of the structure and gas separation performance of the ensuing membrane.
The results of the physicochemical and gas transport properties are shown in Table 8.
It was concluded that gas separation efficiency of polymer membrane can be tailored
by the use of appropriate thermally induced structure transformation and polymer
chain rearrangement.

Table 7 Effects of cyclization temperature on gas transport properties

Cyclization Permeability Ideal selectivity

Membrane temperature FFY CO2 CH4 N2 CO2/CH4 CO2/N2
PHA – 0.134 5.76 0.13 0.24 43.0 24.2
PBO 1 300 0.195 44.7 1.56 2.28 28.6 19.6
PBO 2 350 0.198 84.2 3.48 4.42 24.0 18.9
PBO 3 425 0.202 183 8.53 10.10 21.4 18.1
PBO 4 450 0.220 532 28.9 30.30 18.4 17.6
958 J. K. Adewole and A. S. Sultan

Table 8 Gas transport properties of poly(benzoxazole) membranes prepared from poly

(hydroxyamide amic acid) via stepwise thermal cyclization
Permeability Ideal selectivity
Membrane Temperature d-Spacing CO2 CH4 N2 CO2/N2 CO2/CH4
PHAA 130 5.28 2.12 0.05 0.10 21.1 40.2
PIBO 200 5.39 5.06 0.10 0.24 21.1 49.4
PIBO 220 5.48 9.65 0.20 0.46 21.0 48.5
PIBO 300 5.63 30.2 0.69 1.53 19.8 43.6
PBO 350 5.77 113 3.43 5.73 19.7 33.0
PBO 400 6.16 456 17.4 23.8 19.2 26.2

It is worth mentioning that the authors observed a bimodal distribution for

temperatures 350  C and 400  C. A detailed explanation of these results can be
found in the original article [53].
Various research articles have been published on alternative approaches to
molecularly design advanced membrane materials using thermal rearrangement.
The conversion of hydroxyl-containing imides to PBO was reported by Tullos
et al. [54]. This> method was used by many researchers to synthesize membranes
for gas separation purposes [49, 55]. Another approach for producing highly
permeable polymeric membrane is by controlling the free volume cavities via
the synthesis of poly(benzoxazole-co-imide) [56] and the incorporation of het-
erocyclic compound (such as pyrolone or ether) during copolymerization [57].
Thus thermally rearranged poly(benzoxazole-co-pyrrolone) was reported by
Choi et al. [57] while thermally rearranged poly(ether-benzoxazole) membrane
was reported by Calle et al. [58].
Similarly, the change in the intrinsic properties of TR-PBO as a result of the
incorporation of a cardo moiety was investigated by Yeong et al. [59]. The work
resulted into the synthesis of sets of new copolyimide with different composition of
cardo-copolybenzaxole membranes with enhanced gas transport properties. Sanders
et al. [60] employed polycondensation method to prepare thermally rearranged
polyimide membranes. The authors used HAB and 6FDA as precursors. A new
synthesis route which involves alkaline hydrolysis of carbonyl-group of poly-
pyrrolone and thermal treatment was investigated by Han et al. [61]. Highly perme-
able thermally rearranged microporous polybenzimidazole (TR-PBI) membrane was
produced using this method. A new copolyimide was prepared by Lu et al. [62]. This
polymer was subsequently thermally treated in air and N2 atmosphere to attain
thermal oxidative and thermally rearranged membranes, respectively. Table 9 con-
tains the summary of the gas transport properties of these polymers.
The thermal rearrangement method has not been limited to flat sheet membrane.
Some articles have been published on thermally rearranged hollow fiber membrane
as well. The first TR hollow fiber membrane was reported by Kim et al. [63]. The
membrane was fabricated by spinning hydroxyl poly(amid acid) (a soluble precursor
polymer) via a phase separation process. A hollow fiber membrane (with a high
permeability) was produced by thermal imidization and subsequent thermal
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 959

Table 9 Gas transport properties of polyimides prepared by thermal oxidative and thermal
rearrangement procedure
Permeability Selectivity
CO2 CH4 N2 CO2/N2 CO2/CH4
TO 31.22–653.93 3.83–13.42 3.04–15.15 43.16–94.74 48.73–75.20
TR 24.54–5087.49 16.62–245.45 20.44–212.78 15.37–34.65 20.73–42.62
TO thermal treatment in Air, TR thermal treatment in nitrogen

rearrangement of hydroxyl polyimide. The effect of thermal treatment parameter

(time from 10 to 60 mins and temperature from 450  C to 500  C) on gas separation
performance of the membrane was also investigated. An optimum treatment param-
eter of 500  C and 10 mins was found to produce a membrane with the highest
selectivity of CO2/CH4 of 22. The membrane has a permeance of 2326 and 105 GPU
for CO2 and CH4, respectively. Various other reports and description of thermal
rearrangement procedure for polymers have also been published on the use of
thermal rearrangement [64–68].
A cross-link is a formation of intermolecular connections through chemical
bonds. It is used to develop materials with superior resistance to swelling and
plasticization. The possibility of swelling and plasticization phenomenon is very
high when using a polymeric membrane to separate natural gas with a high concen-
tration of CO2 or separation at high feed pressure. Cross-linking methods that have
been reported in the literature for developing plasticization resistant membranes
include chemical, thermal, and photochemical cross-linking [3, 69, 70].
The mechanism of cross-linking shown in Fig. 11 has been employed
in a variety of ways to produce membranes with better gas separation perfor-
mance. For example, esterification, cross-linking, mono-esterification, trans-
esterification reaction, imide ring opening reactions, thermal cross-linking by
decarboxylation, and chemical cross-linking using diamino compounds are some
of the methods that have been used successfully prepare membranes with better
plasticization resistance properties [71–73].
Cross-linking often results in a reduction in chain mobility and increase in Tg.
It has been successfully employed for producing membranes with superior perfor-
mance at high pressure. When a polymeric membrane is cross-linked, its plasticiza-
tion pressure increases, consequently, the cross-linking processes helps in stabilizing
the membrane at a higher partial pressure of CO2 [74]. Membranes with higher
packing density, smaller free volume, better resistance to CO2-induced plasticization
phenomenon, and higher Tg has been produced using thermal annealing.
Staudt-Bickel and Koros [75] carried out cross-linking in order to determine
its effect on the reduction of swelling and plasticization. The work was focused on
simultaneous inhibition of chain mobility and intrasegmental packing by changing
the backbone structure of the polymer. Polyimides with strong polar associating
functional groups were synthesized. In addition, cross-linking polyimides and
copolyimide were also synthesized in the study. Gas permeability and perm-
selectivity of CO2/CH4 were investigated. It was observed that the presence of
 960

O H3C CH3
O O
H2NH2C CH2NH2
N N

O H3C
O
Matrimid p-xylenediamine

O H3C CH3
O H3C CH3 O O
O O
NH N
N N O
O H3C
O O H3C NH

CH2

CH2

NH O H3C CH3
O
O
NH N

O H3C
O

Fig. 11 Mechanisms of chemical cross-linking modification of Matrimid with p-xylenediamine. (Taken from Tin et al. [70] with permission from Elsevier)
J. K. Adewole and A. S. Sultan
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 961

-C(CF3)- linkage and polar carboxylic group enhanced the CO2/CH4 perm-
selectivity of the polyimides. The effects of cross-linking degree were evaluated
using chemical and thermal cross-linking approach. Plasticization and swelling
properties were investigated up to 41 atm feed stream pressure using pure CO2 as
feed gas. The authors concluded that cross-linking of polyimide can enhance the
plasticization resistance properties of the cross-linked membrane. However, such
enhancement is often accompanied with reduced gas permeability.
Copolymer membranes were synthesized and evaluated for natural gas pro-
cessing by Wind et al. [5]. The authors used cross-linked polyimides copolymers
(6FDA-DAM,DABA and 6FpDA,DABA). Transport properties of natural gas com-
ponents (used as 50/50 CO2/CH4 mixtures and multicomponent mixtures) were
investigated at 35  C and an upstream pressure up to 55 atm. The cross-linking
procedure was performed at a range of temperature (220  C to 295  C) and
1,4-butylene glycol and 1,4-cyclohexanedimethanol were used as cross-linking
agents. Posttreatment annealing was done at temperatures between 130  C and
295  C. In order to ensure a clearer interpretation of the results, the effect of various
treatments (such as thermal treatment and chemical cross-linking) were decoupled
with respect to separation performance of the membrane. The composition of the
multicomponent gas mixtures is CO2 (30.01–30.02), CH4 (61.0–62.95), C2H6
(3.99–4.0), C3H8 (2.99–3.0), C4H10 (2.01), and toluene (0.0299) (in mol%) while
the mixed gas is 50 mol% each of CO2 and CH4. The results obtained on the
performance analysis of the membrane were compared with membranes made of
commercially available polymers (such as Matrimid and cellulose acetate). It was
observed that the resulting membranes from these studies have better transport and
penetrant-induced plasticization properties than the commercially available poly-
mers. The summary of the results of transport and plasticization resistance properties
are shown in Table 10. It can be observed from the table that by covalently cross-

Table 10 Gas separation and plasticization resistance properties of cross-linked copolyimides

membrane [4]
α Plasticization
Polymer T P (CO2) CO2/ pressure
membrane Method ( C) (Barrer) CH4 (atm)
6FDA-DAM: Annealing 130 135 28 20–25
DABA 2:1 220 115 33 >22.5
295 95 30 35
Cross-linked with butylenes 220 40 26 >55
glycol monoester 295 150 30 >30
Cross-linked with 295 43 37 33
benzenedimethanol
monoester
6FDA-6FpDA: Cross-linked with ethylene 220 24 47 27
DABA 1:2 glycol monoester
6FDA-DAM: Annealing 220 47 23–28 >40
DABA 2:1 50–55 23–27 >10
962 J. K. Adewole and A. S. Sultan

linking, its plasticization resistance property can be improved. The table also
revealed that thermal annealing can serve as an effective tool for suppressing CO2-
induced plasticization challenges.
In a similar study by Omole et al. [76], separation capability of an asymmetric
hollow fiber membranes made from propane-diol monoesterified cross-linkable
polyimide (PDMC) was investigated. The ability of PDMC to effectively separate
CO2 from gas mixture was studied under aggressive operating conditions. The cross-
linked membranes showed a good separation performance for CO2 and CH4.
A selectivity value of about 49, CO2 permeability of 161 barrer, were obtained
under the operating condition of 65 psia, 35  C, and 10% CO2. The membranes also
showed good resistance to CO2-induced plasticization at a CO2 partial pressure up to
400 psia. Thus, plasticization was effectively suppressed. The improved plasticiza-
tion resistance was however accompanied by a decline in membrane permeability.
The accompanied deterioration of the permeability was as a result of densification of
the selective top layer during the annealing process.
High temperature cross-linking is a common procedure for modifying polyimide.
There is, therefore, a need to develop a low-temperature protocol in order to
reduce the cost of membrane preparation. Liu et al. [77] developed a simple
low-temperature (room temperature) chemical cross-linking technology for
membrane preparation. The authors tested this technology using 6FDA-durene
cross-linked with a p-xylenediamine methanol solution. Gas (such as N2 and
CO2) permeation properties of the cross-linked polyimides were investigated at
35  C and 10 atm. Low-temperature chemical cross-linking was also applied by
Tin et al. [70] for the modification of a commercially available polyimide
(Matrimid ® 5218). Pure and mixed gas permeation properties of the membranes
were performed using CH 4 and CO2 gases. Moreover, the authors also studied the
effect of cross-linking on plasticization resistance properties of the membrane.
The outcome of the studies showed that plasticization resistance increased
significantly. The plasticization pressure was found to increase from 15 atm to
32 atm following a 7-day polymer cross-linking. This is more than 100%
increment. Unfortunately, the increase in plasticization resistance property was
accompanied by 45% decrease in permeability. There was no significant change
in the ideal selectivity.
A critical observation on the side effect of cross-linking revealed that cross-
linking is often accompanied by a reduction in permeability. To solve this problem,
rapid quenching was introduced into membrane cross-linking procedure. The use of
rapid quenching was used for solving the challenge of permeability reduction with
no compromise to the plasticization resistance properties of the membranes. In some
cases, improved plasticization resistance property was recorded. For instance,
decarboxylation-induced cross-linking was utilized by [74] to improve the plastici-
zation resistance of 6FDA-DAM:DABA (2:1) copolyimides. Two sets of membrane
samples were employed for the studies. One set of membrane samples was annealed
while the other set was rapidly quenched from above its Tg. Gas permeability and
solvent dissolution tests were performed on both samples. The sample that was
subjected to rapid quenching was observed to exhibit better plasticization resistance
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 963

property. The plasticization pressure was observed to increase from 28 atm to more
than 49 atm. The results of these plasticization resistance properties are shown in
Table 11. In addition, the normalized CO2 permeability was found to be stable up to
49 atm. Also, the samples did not dissolve in solvents such as cyclohexanone, THF,
and NMP which were well-known solvents for dissolving polyimides. In fact, the
quenched membranes did not dissolve after boiling in NMP for 18 hr. It was
concluded that both responses that were observed are due to cross-linking which
occurred in the polyimide.
The outcomes of many investigations on the use of chemical cross-linking
indicate that the technology is promising in developing plasticization-resistant
membrane. However, the use of chemical cross-linking has its own challenges.
Some of these challenges include the formation of ester linkages when diol is used
as cross-linking agents. It is highly possible for the linkages so formed to be
hydrolyzed when a membrane is used in the presence of aggressive acid gas feed
streams. The hydrolysis is known to be capable of reversing the effects of the cross-
linking, reduce the membrane separation efficiency, and make it (the membrane) to
be more susceptible to penetrant-induced plasticization [74]. For this reason, a new
method of cross-linking which does not cause formation ester linkages was devel-
oped. The new cross-linking approach involves the use of a high-temperature
decarboxylation process. The decarboxylation of the acid pendant (at high temper-
ature) will create free radical sites that are capable of initiating the cross-linking
process in the absence of a diol cross-linking agent.
Clearly, the use of decarboxylation approach has a variety of advantages and
disadvantages. One of the major concerns of the high-temperature decarboxylation
as a cross-linking technique is the possibility of causing the collapse of the transition
layers as well as the substructure of asymmetric hollow fiber membrane that was
developed using decarboxylated materials. In order to address this challenge, an
attempt was made to investigate the possibility of carrying out thermal cross-linking

Table 11 Plasticization properties of polyimide membrane prepared using thermal treatment and
chemical cross-linking [4]
Treatment Cross-linking P (CO2) Plasticization
temperature agents/method Polymer (barrer) pressure (atm)
Noncross-linked 6FDA-mPD 9 5–7
35  C Ethylene glycol in 6FDA-DABA 7.5 24
DMAc
Noncross-linked 6FDA-mPD / 7 15
DABA (9:1)
35  C Ethylene glycol in 6FDA-mPD / 11 36
DMAc DABA (9:1)
220  C, 23 h Decarboxylation 6FDA-DAM: 0.65a 25-32
DABA (2:1)
220  C, Rapid quenching 6FDA-DAM: 0.64a >49
23 h + Quenching from above Tg DABA (2:1)
a
The normalized permeability which was calculated as a ratio of the measured permeability to the
initial permeability that was measured at 2 atm
964 J. K. Adewole and A. S. Sultan

at a temperature below the glass transition temperature. Consequently, a new thermal

cross-linking method was reported by Qiu et al. [72]. Using this method, a glassy
polymer can be easily cross-linked at a temperature that is lower than the glass
transition temperature of such a polymer. The sub-Tg method of cross-linking is a
promising method that could facilitate a large-scale method of fabricating asymmet-
ric membranes. The sub-Tg method was used to develop a polyimide (6FDA-DAM:
DABA (3:2)) membrane for application in CO2 separation. The properties of the
resulting membranes were evaluated using solubility, thermal, and permeation tests.
The gas transport properties and gas separation performance tests were performed
using aggressive gas mixtures as feed streams at high feed (upstream) pressure. The
feed streams consist of both the pure and mixed gases of CO2 and CH4. The results
of the permeation tests revealed that there was significant improvement in the
plasticization resistance properties of the membranes. Tested membrane samples
showed no sign of plasticization at feed pressure as high as 48 bar and 69 bar for pure
and mixed gas permeation tests, respectively. The results of the solubility test were
used to corroborate the increment in the plasticization resistance properties. It was
observed that some membranes did not dissolve in hot solvents such as NMP at
100  C when soaked in the hot NMP for 1 week. The authors also carried out further
studies to discover the range of temperatures at which cross-linking occurred. It was
observed that there was no cross-linking at a temperature below 300  C [72].
Diamino-organosilicone (bis(3-aminopropyl)-tetramethyldisiloxane)), APTMDS)
is another cross-linking agent that was investigated by Chen et al. [78]. The authors
employed two different routes to accomplish the cross-linking and the preparation
of two different cross-linked polyimide membranes. In addition, both routes were
implemented at ambient temperature. The results of gas separation performance
of the resulting membranes are shown in Tables 12 and 13. From these tables, it
can be observed that both methods produced membranes with enhanced gas sepa-
ration properties.
Research focus on CO2 separation has targeted polymeric materials with rela-
tively higher CO2 selectivity. Interestingly, the rubbery polymers constitute the most
promising materials in this respect [16]. Outstanding rubbery polymers such as those

Table 12 Gas separation performance of cross-linked polyimide membranes [78]

P (CO2) Ideal Separation
Polymer Cross-linking method (barrer) selectivity factor
6FDA-ODA Original sample 19 53 49
Immersion in APTMDS/ 12–17 66–90 39–62
methanol
Direct mixing of APTMDS in 12–14 71–82 55–64
polyimide solution
6FDA-ODA Original sample 57 15 14
TemMPD Immersion in APTMDS/ 18–54 15–41 14–40
(50/50%) methanol
Direct mixing of APTMDS in 24–33 19–24 15–24
the polyimide solution
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 965

Table 13 Gas transport and plasticization resistance properties of cross-linked polyimide mem-
branes [78]
CO2 permeability Plasticization
Polymer (barrer) pressure (atm)
6FDA-ODA 15 20–24
Cross-linked 6FDA-ODA 8 >41
6FDA-ODA(50%)-TemMPD (50%) 48 14
Cross-linked 6FDA-ODA (50%) -TemMPD 12 >41
(50%) (direct mixing)

containing polyethylene oxide (PEO) segments have better solubility selectivities

due to their molecular interaction with the CO2 quadrupole. On the other hand, PEO
is crystalline. Therefore, to achieve useful gas separation performance from poly-
mers in which PEO has been incorporated, the PEO crystallization must be
suppressed. This will give room to achieving high fluxes and retard swelling.
Some of the means by which this could be accomplished include cross-linking,
polymer blending, or block-copolymerization [16]. A comprehensive description of
polyethylene glycol can be found in Adewole et al. [4]. Within the polyether family,
PEO is as an outstanding membrane forming material particularly suitable for
processing and purification of gas mixtures containing polar gases (such as CO2
and H2S) and nonpolar ones (such as H2, N2, and CH4) [79, 80]. This is due to its
polarity and CO2 affinity [81]. PEO contains an ether oxygen functional group which
favorably interacts with CO2 at the molecular level which then result in increase in
selectivity toward the gas [82].
One of the strategies that can be used to improve the gas separation capability of
PEO-based membrane is to destroy the crystalline nature of PEO and make it to
become more amorphous. A family of cross-linked poly(ethylene glycol diacrylate)
(XLPEGDA) was prepared by Lin and Freeman [80]. The effect of cross-linking on
the crystallinity and gas permeability of XLPEGDA was investigated. The results
revealed that the cross-linking have successfully disrupted the crystallinity. No
significant effect was observed with respect to the permeability and diffusivity.
Expectedly, it was observed that the solubility selectivity for the CO2/CH4 gas pair
increased due to the interaction of PEO functional group with CO2. Lin and
Freeman [83] also measured the permeabilities of CO2 and CH4 through
XLPEGDA membrane as a function of temperature and feed fugacity. The authors
observed that permeability of CH4 is independent of feed fugacity while that of CO2
increased with increasing fugacity. Therefore, it can be inferred that the cross-
linking have no significant effect on the plasticization resistance behavior of the
polymer. During the permeation test, the significant quantity of CO2 sorbed into the
polymer caused an increase in polymer chain flexibility as well as an increase in
fractional free volume.
Li et al. [84] prepare a series of poly(urethane-urea)s polymers using
4,4-metylene diphenyl diisocyanate (MDI), various types of polyether diols, and
ethylene diamine (EDA). Membrane produced using the prepared copolymers were
966 J. K. Adewole and A. S. Sultan

subjected to pure gas permeation tests using CO2 and CH4. The data obtained from
the permeability measurements revealed that the CO2 permeability increased instan-
taneously with increase in feed pressure for all the samples. Such type of transport
phenomenon is commonly associated with rubbery polymers. Usually, rubbery
polymers always exhibit a high tendency for CO2 sorption. Mixed as well as pure
gas permeation tests results of highly permeable poly(ethylene) oxide [85], cross-
linked poly(ethylene) oxide [86], and blend of polyimide-b-ethylene oxide)/poly-
ethylene glycol [87] membranes did not show any promising performance with
respect to plasticization resistance. Therefore, it can be concluded that polyether-
based polymers are not suitable for high-pressure removal of CO2 gas from CH4.
Studies on how the plasticization pressure of these class of highly permeable poly-
mers can be improved are recommended for further research. Other new membranes
and thermal treatment methods have been reported. Details of these can be found in
the literature [54, 88–95].

6.2 Grafting of Polymer Backbone

The performance properties of polymeric membranes can be improved by the

incorporation or the substitution of small functional groups onto the rotating unit
of the polymers. This simple method has been applied by some researchers to
enhance the permeability and selectivity of membranes. Pixton and Paul [96] studied
the gas transport properties of 2,2-(4-hydroxy-phenyl) adamantane polysulfone and
1,3-(4-hydroxyphenyl)adamantane polysulfone membranes and compared the
results with that of bisphenol A-based polysulfone. The results of the pressure-
dependent permeability tests that was carried out on the membranes (with a thickness
in the range of 50–75 μm) revealed that both polymers can resist CO2-induced
plasticization up to a pressure of 20 atm. It is worth mentioning that 20 atm is the
maximum pressure of the experiment. Therefore, there is every possibility for the
plasticization pressure to be more than 20 atm. The recorded improvement in the
plasticization suppression properties is, however, dependent on the thickness of the
membrane. This became evident from the studies that were later carried on ultra-thin
film polysulfone membranes where the plasticization pressure was found to be lower
[19]. To date, varieties of new and more advanced grafting techniques have been
reported for modifying polymers that are used for applications in gas separation.
Some of these techniques can be found in the open literature [97–99].

6.3 Template Polymerization Technique and Use of Porogens

Template polymerization is a concept that was derived from natural polymerization

processes. The process mimics the polymerization techniques that are found in
nature. Examples include DNA replication and biosynthesis of proteins [100]. Tem-
plate polymerization the technique provides scientists with the opportunity to control
and tune polymer properties during polymerization [101]. It is a versatile process
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 967

that can be employed in synthesizing ultrathin polymeric membranes. It can be made

to proceed in various ways such as template polycondensation, ring opening poly-
merization, polyaddition, and ionic or radical polymerization [100, 101]. The pro-
cess is a convenient way of producing poly complexes, poly complex composites,
and polymer blends.
The term “porogen” is an acronym for “pore generator” [102]. The mechanisms
of porogen-induced pore formation have been investigated by a number of authors.
Traditionally, this method is used for the preparation of porous materials for appli-
cations in dielectric industries [103, 104]. The porogenation process can be
performed via a sacrificial thermal decomposition of the porogens in the range of
350  C and 400  C [103–105]. Marti et al. [106] provided a detailed description of
another new approach for using porogens for membrane preparation. Recently, this
approach has been found to be very useful in developing membranes with better
resistance to plasticization phenomenon. The techniques of template polymerization
and use of porogens can be traced back to the preparation of carbon molecular sieve
(CMS). A comprehensive explanation of CMS and its preparation are presented in
Mohamed [107], Kita [108], and Williams and Koros [109].
Aromatic polyimides have been used as polymer precursors for the preparation of
CMS membranes due to their excellent balance of productivity and separation factor
or ideal selectivity [110]. CMS membranes are fabricated by heating up the poly-
imides to a temperature range of 700–900  C. The high-temperature heating process
often results in polyimides degradation [110]. Relatively low-temperature pyrolysis
was therefore proposed. Islam et al. [111] and Weiliang et al. [112] employed
low-temperature pyrolysis for preparing flexible pyrolytic membranes. Sulfonated
polyimides were pyrolyzed at a temperature range of 370  C and 450  C to produce
dense flat sheet membranes. The membrane contains a large number of microvoids
which were caused by “template-like effect” of SO3H groups. Gas (CO2) perme-
ability of the membranes was found to have increased by 378 barrer in comparison
with the polymer precursor.
Similar approach has been used by other authors such as Xiao and Chung [113]
(using beta-cyclodextrin thermal labile molecule with large dimensions) and Chua
et al. [114] (using thermal labile saccharide units with different molecular weights
and structures: glucose (180 g/mol), sucrose (342 g/mol), and raffinose (504 g/mol)).
Based on the permeability of CO2, membrane prepared using cyclodextrin, porogens
was found to be the best membrane (Table 14). A further investigation into the
plasticization behaviour of polyimide containing cyclodextrin porogens was
performed by Askari et al. [69, 115]. A summary of the plasticization properties of
the membrane developed using the copolyimide is displayed in Table 15.

6.4 Sulfonation Method

Sulfonation involves the replacement of a hydrogen atom of an organic compound

with a sulfonic acid (-SO3H) functional group. It is often accomplished reaction of
the organic compound (such as a polymer) with sulfuric acid at high temperatures.
968 J. K. Adewole and A. S. Sultan

Table 14 Gas transport properties of partially pyrolyzed polyimide membranes using various
porogens [4]
α
Porogens Temperaturea ( C) P (CO2) CO2/CH4
Sulfonic group 370–450 145–380 –
Carboxylic acid 425–475 39.1–94.8 60–47
Cyclodextrin 300–450 56–8000 31–17
Saccharides 200–425 533–1389 24.9–26.9
a
This is the temperature of partial pyrolysis

Table 15 Penetrant-induced plasticization properties of 6FDA-Durene/DABA co-polyimides with

α, β, and γ-cyclodextrin [69]
Polymer Treatment temperature ( C) Plasticization pressure (atm)
Original polyimide 200 5–10
300 10–15
425 15–20
Polyimide grafted with- α-CD 200 7–10
300 10–15
425 25
Polyimide grafted with β-CD 200 7–10
300 10
425 >30
Polyimide grafted with γ-CD 200 10
300 10
425 >30

Sulfonation is one of the new methods that have been proposed for modification of
gas transport properties of polymers. Sulfonated polymeric membranes usually
exhibit enhanced separation performance than the original ones. Studies on
structure–properties relationship of sulfonated polymers was conducted by Piroux
et al. [116] for a large series of sulfonated copolyimides. The copolyimides were
synthesized with a naphthalenic dianhydride, a sulfonated diamine, and various
nonsulfonated diamines. It was observed that the contribution of the dispersed
sulfonated phase to the gas transport greatly depends on the structure of the non-
sulfonated diamine.
Previously, polymer structures are commonly modified by postsulfonation.
Unfortunately, the practice of postsulfonation lead to lower thermal and mechanical
stabilities of the polymers compared with the original polymer. In addition, it very
difficult to achieve a high degree of sulfonation using postsulfonation process. To
overcome this problem, sulfonation of monomers prior to polymerization was
proposed. Khan et al. [117] prepared a series of sulfonated poly(ether ether ketone)
(S-PEEK) membranes by the sulfonation of its monomers. Commercial-scale appli-
cation of the membranes (that were prepared from the S-PEEK) for CO2 separation
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 969

Table 16 Transport and plasticization properties of S-PEEK with sodium ions [117]
Degree of CO2 permeability Plasticization pressure
Polymer sulfonation (barrer) (bar)
S-PEEK-Na-1 0.44 8 11
S-PEEK-Na-2 0.76 10.5 32
S-PEEK-Na-3 1.10 14.5 >40

from gas mixtures was investigated. The authors also investigated the effects of
various degree of sulfonation and the presence of different types of ions (H, Na, Li,
Mg, Ba, and Al) on the gas separation performance of the membranes were inves-
tigated. Results obtained for the plasticization pressure and CO2 permeability are
displayed in Table 16.

6.5 Technique for Preparing Polymers of Intrinsic Microporosity

(PIM)

Percentage crystallinity is one of the major morphological properties which

determine the transport properties of polymers that are used for making membrane.
Less crystalline (amorphous) are commonly recommended candidate for mem-
brane applications. A successful synthesis of nanoporous polymers was reported
by Budd et al. [118]. The new set of polymers were prepared from certain
microporous networks of functional units including phthalocyanine, porphyrin,
and hexaazatrinaphthylene. Due to the microporous nature of the starting mate-
rials, the resulting polymer from this synthesis protocol is often called polymers of
intrinsic microporosity (PIMs) [119].
PIMs are nanoporous (0.4–0.8 nm), soluble, solution proccessable, and thermally
stable (initial decomposition at around 460  C) polymers. They have very high
surface areas (of ~800 m2/g) and free volume [119, 120]. A detailed description of
the concept of PIMs can be found in Budd et al. [118]. Following the pioneering
article that was published on PIMs synthesis, the polymers have been further
investigated for a variety of applications [120]. In gas separation application, PIMs
have high permeability as well as high selectivity that are above the Robeson’s upper
bound for a number of gas pairs. Table 17 shows the separation performance results
of PIMs in separating CO2 from CH4. Phthalazinone-based copolymers with intrin-
sic microporosity (PHPIMs) was reported by [121]. A high temperature aromatic
double nucleophilic subcondensation polymerization method was used to synthesize
the polymer. Gas separation performance of membrane prepared from the polymers
was investigated. The effect of the stiffness of the phthalazinone unit was investi-
gated in order to explore the possibility of using this property to design a new high-
performance membrane for gas separation. The results of the investigation showed
that the introduction of phthalazinone moiety resulted into amorphous glassy copol-
ymers which exhibit excellent thermal stability and gas separation properties.
970 J. K. Adewole and A. S. Sultan

Table 17 Gas transport properties of PIMs [4]

Experimental parameters Permeability (Barrer)
Feed Temperature
Membrane pressure ( C) CO2 CH4
PIM-1a 0.2 bar 30 23,000 125
PIM-7b 0.2 bar 30 1100 62
Polybenzodioxane- PIM-1 1 atm 25 4390 310
Thioamide-PIM 1 bar 25 1120 56
Carboxylated PIMs 50 psig 25 620–6715 –
Cross-linked PIMs 3.4 atm 30 1291–2345 52.6–192
PIMs (Trifluoromethyl and 50 psig 25 731–3616 –
Phenylsulfone groups
a
Prepared using 5,5,6,6-tetrahydroxy-3,3,3,3 tetramethyl-1,1-spirobisindane and tetrafluoroterephthalonitrile
b
Prepared using 5,5,6,6-tetrahydroxy-3,3,3,3 tetramethyl-1,1-spirobisindane and 7,7,8,8-tetra-
chloro-phenazyl-3,3,3,3-tetramethyl-1,1-spirobisindane

6.6 Membrane Preparation Using 3D Printing Technologies

Three-dimensional (3D) printing is a new technology whose applications have been

extended into almost all aspects of research and development. The technology is also
referred to as additive manufacturing or rapid prototyping. It involves a layer-by-
layer building of materials to create materials of various geometries from 3D image
data [122, 123]. The 3D technology has been recently applied for membrane
materials fabrication. It is a technology that is expected to revolutionize membrane
materials and modules fabrication. In membrane technology, the applicable additive
manufacturing techniques can be grouped into four: namely, photopolymerization,
powder, material extrusion, and lamination [124, 125]. The most promising among
these is the photopolymerization. It is the curing of photoreactive polymers (photo-
polymers) with a laser, UV, or light [124].
Presently, the majority of the polymeric membranes produced by 3D printing
technology have been evaluated for liquid. Thus, very few publications can be
found on gas separation. Polymers that have been investigated for membrane fabri-
cation include polydimethylsiloxane membrane for use as gas-liquid contactor
[126–128], m-phenylene diamine [129, 130], polyamide-12 using selective laser
sintering [131] and photocurable formulation of diurethane dimethacrylate
(DUDA), poly(ethylene glycol) diacrylate (PEGDA), dipentaerythritol penta-/hexa-
acrylate, and 4-vinylbenzyl chloride [125].

7 Conclusion

Advances in the method of synthesis and gas transport properties of functional

polymeric membrane materials were reviewed. The transport properties of both
rubbery and glassy polymeric membranes that were prepared by these methods of
23 Polymeric Membranes for Natural Gas Processing: Polymer Synthesis and. . . 971

synthesis were described in terms of permeability, solubility, diffusivity, and selec-

tivity. It was generally observed that the presence of functional groups such as polar
ether oxygen linkages, hydroxyl, and amine enhances the separation efficiency of
polymeric membranes. The intermolecular interaction of these functional groups with
CO2 enhances its solubility within the membrane matrix and hence the solubility
selectivity of the membrane is improved. The size of such functional groups contrib-
utes in the enhancement of CO2 diffusivity and hence diffusivity-selectivity of the
membranes. It was also revealed that porogens such as sulfonic, carboxylic acid,
cyclodextrin, and saccharides could be excellent candidates for improving the sepa-
ration properties of polymeric membranes. Therefore, the introduction of any of these
functional groups or similar ones into the polymer backbone is one of the promising
methods for producing membranes with superior natural gas separation performance.

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Proton Conductions
24
N. Awang, Juhana Jaafar, A. F. Ismail, T. Matsuura,
M. H. D. Othman, and M. A. Rahman

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 978
2 Proton Transport in Cation Exchange Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 980
3 Types of Proton Conductive Membrane Materials for Fuel Cell Applications . . . . . . . . . . . 981
3.1 Perfluorinated Ionomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 983
3.2 Partially Fluorinated Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 983
3.3 Nonfluorinated Aliphatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 985
3.4 Nonfluorinated Membranes with Aromatic Backbones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 986
3.5 Acid–Base Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991
4 Enhancing Proton Conductivity by Electrospinning Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
5 Electrospun Polymer-Based Nanofiber Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996
6 Current Studies and Future Directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1000
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1000
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001

N. Awang · J. Jaafar (*) · A. F. Ismail (*) · M. H. D. Othman · M. A. Rahman

Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia,
Johor Bahru, Malaysia
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia,
Johor Bahru, Malaysia
e-mail: [email protected]; [email protected]; [email protected]; [email protected];
[email protected]; [email protected]
T. Matsuura
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia,
Johor Bahru, Malaysia
Department of Chemical Engineering, University of Ottawa, Ottawa, ON, Canada
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 977

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_27
978 N. Awang et al.

Abstract
The importance of proton conductivity is enormous for biological systems and in
devices such as electrochemical sensors, electrochemical reactors, electro-
chromic devices, and fuel cells. In the book chapter, the phenomenon of proton
conductivity in materials was discussed with a special emphasis on five different
types of conductive materials, namely, perfluorinated ionomers, partially fluori-
nated, aromatic polymers, acid-base complexes, non-fluorinated ionomers, and
hydrocarbon. In a fuel cell, the proton exchange membranes (PEMs) have a
profound influence on its performance. Many researchers have investigated the
functionalization methods to solve the methanol crossover problem and to obtain
low electronic conductivity, low electroosmotic drag coefficient, good mechan-
ical properties, good chemical stability, good thermal stability, and high proton
conductivity. The way forward of developing high-performance proton-conduc-
tive polymeric membrane via electrospinning for as fuel cells was also
addressed.

1 Introduction

Proton conductivity plays an important role in many processes; for example, the
production of electricity in a hydrogen fuel cell and the photosynthesis in green
plants. Proton is the main ion which has no electron shell. In this way, it strongly
interacts with the electron density of its surroundings, which then takes some of the
H (1s) characters [1, 2].
However, in nonmetallic compounds, proton strongly interacts with the valence
electron density of only one or two nearest neighbors. If this is a single oxygen,
being well separated from other electronegative species resulted in the formation of
O-H bond which is less than 100 pm in length compared to
140 pm for the ionic
“radius” of the oxide ion. The proton finds its equilibrium position deeply embedded
in the valence electron density of the oxygen (Fig. 1a). For medium distances
between oxygen and another oxygen (
250–280 pm), the proton may be involved
in two bonds: a short, strong bond with the so-called proton donor and a longer, weak

a b c

Fig. 1 A schematic representation for different cases of proton binding in a nonmetallic environ-
ment where the proton is coordinated to one or two preferentially basic species. Note that the given
potential surfaces correspond to the electronic structure of the indicated proton positions [1]
24 Proton Conductions 979

bond with a proton acceptor. This is the case for an asymmetrical hydrogen bond
(O-H•••O) which is directional in character (Fig. 1b). For extremely short oxygen
separations (
240 pm), a symmetrical hydrogen bond may be formed, i.e., the
proton is involved in two equivalent bonds (Fig. 1c) [3, 4].
Hydrogen bond is a type of interaction which involves proton conduction pro-
cess. The stronger the covalent or ionic bonds, the hydrogen bonds have the
tendency to fluctuate less [3]. For proton conduction process, distance between
proton acceptor and proton donor is important in defining strong hydrogen bond
and proton conductivity. It is clear that the compounds with the highest proton
diffusivity are hydrogen-bonded liquids (for instance, dilute aqueous solutions of
acids) or solids in which weak or medium hydrogen-bond interactions are not or just
marginally confined by the vicinity of other sorts of bonds. An essential feature of
hydrogen bond is to give a path to proton transfer from a proton donor to a proton
acceptor and the part as proton conductor is played by materials which can be a
proton conductor especially for ion exchange membrane [4].
Ion exchange membranes are thin films or sheets of ion exchange materials which
can be used to allow the transportation of anions or cations and separate the ions [5].
In the 1950s, ion selective membranes in sheet form with high selectivity, low
electrical resistance, good chemical stability, and high mechanical strength were
observed [6]. In the 1970s, DuPont has invented a cation exchange membrane from
sulfonated polytetrafluoroethylene which is chemically stable, known as Nafion ®.
The Nafion ® is used for the application of energy storage system in the chlor-alkali
production industry and energy conversion (fuel cell) [7].
Owing to high electrochemical property as well as chemical resistance, Nafion®
still widely applied as the fundamental membrane for fuel cell [8]. The poly-
tetrafluoroethylene backbone in Nafion ® has been made with perfluorinated vinyl
ethers pendant side chains which are terminated by a sulfonate ionic group
[9, 10]. Since a nanophase separation occurs between hydrophobic matrix and
hydrophilic ionic domains in the hydrated Nafion ® due to the amphiphilic compo-
sition (water-soluble group attached to a water-insoluble nonpolar hydrocarbon
chain), the membrane has to be fully hydrated for good proton conductivity in
order to operate at temperatures below 80  C. Other than that, the operating
temperature must be increased above 100  C for transportation and to limit the
poisoning of anode catalysts by traces of CO, and thus enable high-energy-con-
sumption applications [11].
Nafion® membranes, however, show drawbacks and dramatic alteration which
are caused by water evaporation. So, at these temperatures, Nafion ® has weak
conductivity performance and the effect can be related to the dehydration of initial
ionic domains. Therefore, commercially available Nafion® membranes nowadays do
not fulfill the specification of a fuel cell that can be applied above 100  C and
hydrated swollen membranes are desirable at elevated temperatures for the purpose
of maintaining mechanical properties and proton conductivity [12].
There are two principal mechanisms that portray proton diffusion in a manner
that the proton stays shielded by some electron density along the whole diffusion
path. One of the well-known principal mechanism is the principal situation where
980 N. Awang et al.

“vehicles” show to claim local dynamics yet dwell on their destinations, the protons
being exchanged inside of the hydrogen bonds from one “vehicle” to another. Extra
redesign of proton environment involves reorientation of individual species or
significantly more expanded gatherings, then resulted in the formation of continuous
trajectory for proton migration. This mechanism is often termed as Grotthuss
mechanism.

2 Proton Transport in Cation Exchange Membrane

The transport of proton in cation exchange membrane is greatly affected by the

presence of water molecules. Water molecules provide a probe for the local envi-
ronment, and the hydrogen bond network dynamics of water is confined in the
hydrophilic region of cation exchange membrane materials. Therefore, water pro-
vides a better medium for protons to freely move than other common ions environ-
ment. This is the result of the fact that proton in water does not take place through
normal diffusion, but via a process where the hydrogen bonds between water
molecules are converted into covalent bonds and vice versa [13].
The movement of proton in hydrated state occurs in two processes which are free
solution-diffusion process (Fig. 2a) and proton hopping process (Fig. 2b). Proton
diffuses into water phase explained the first process while the movements of protons
in sequential steps involving the formation and breakage of hydrogen bonding of
a series of water molecules explained the proton hopping mechanism. In Grotthuss
mechanism, the original proton that enters the membrane is not the proton that comes
out of the membrane. This is because, it is not the proton itself that is transported;
only the charge of the proton is transported, and not its mass. The charge is basically
passed on from one water molecule to another water molecule [14].
Proton transport through a hydrated ion exchange membrane can, in principle,
occur via the two processes mentioned above. The approach to explain the transport
in ion exchange membrane is that the water in an ion exchange material can be
understood as bound (or “nonfreezable,” “associated”) water and free (“freezable,”
“bulk-like”) water. The free water resembles bulk water with hydrogen bonds as the
major interactions.
Bound water molecules are in the vicinity of the materials while the free water is
further away. The strength of bonding between the bound water molecule and
the materials is more prominent than that of hydrogen bonding in free water. The
free water is bulk-like but the bound water is thought to be a part of the materials.
The free solution diffusion of a proton through a hydrated membrane can, in
principle, include both free and bound water. On the other hand, the free diffusion
is much slower in bound water. Then again, the proton hopping or the Grotthuss
mechanism can happen in both free and bound water. This transport phenomenon in
ion exchange membrane clarifies the ion transport in polyelectrolyte membranes
[15]. Figure 3 illustrates the domain distribution of proton, water, and methanol
transport in polyelectrolyte membranes.
24 Proton Conductions 981

Fig. 2 Proton transport via (a) free solution diffusion and (b) proton hop mechanism (Grotthuss
mechanism) [15]

3 Types of Proton Conductive Membrane Materials for Fuel

Cell Applications

The materials which represent the majority of all-known fast proton conductors
applied in the synthesis of polymer membranes can be generally classified into five
different groups: perfluorinated ionomers, partially fluorinated polymers, non-
fluorinated hydrocarbons, nonfluorinated membranes with acid-base complexes,
and aromatic backbones [16]. Figure 4 shows the categories of membranes based
on the materials applied [17].
982 N. Awang et al.

Fig. 3 An illustration of domain distribution in sulfonated polymer electrolyte membranes [16]

Classification of
membrane materials

Partially Non-fluorinated
Perfluorinated Non-fluorinated Acid-base
fluorinated membranes with
lonomers hydrocarbons complexes
polymers aromatic backbones

PFSA PTFE-g- NPI Supported

TFS SPEEK/PBI/P4VP composite
PFCA membrane
BAM3G
PVDF-g- SPEEK/PEI poly-AMPS
PFCI PSSA
SPEEK

Gore- SPEEK/PSU(NH2)2
SPPBP
select

MBS-PBI SPSU/PBI/P4VP

SPSU/PEI

SPSU/PSU(NH2)2

PVA/H3PO4

Fig. 4 The categories of membranes based on materials [17]

24 Proton Conductions 983

The most highest proton conductivity happens at 100% relative humidity. Other
than the disadvantages of the membrane, proton conductivity which depends on the
humidity of Nafion ® constrains the utilization of Nafion ® as a membrane in a fuel
cell. Other than this, since the fuel that is utilized as a part of the fuel cell framework,
for example, alcohol-based fuels and hydrogen are dissolvable in water over a wide
range of compositions, this raises an issue based on the fact that not just water
diffuses through the polyelectrolyte membrane (PEM) but the fuel as well. Hence-
forth, the reaction focuses on the cathode which alludes to mixed potential. Appar-
ently, decreasing the water uptake can promptly diminish the methanol crossover
issue. Lamentably, decreasing the fuel crossover all this while yields proton con-
ductivity [189].
Based on these disadvantages, analysts have attempted to imagine a low fuel
permeability and high conductivity membrane from hydrocarbon polymer and
partially perfluorinated ionomer that can dismiss the current inadequacies as of
now, and the membranes are utilized in low- and high-temperature operation.

3.1 Perfluorinated Ionomers

Nowadays, perfluorinated polymers have been intensively studied due to special

characteristics which are high electronegativity of fluorine atom with C–F bond,
small in size, and low polarization capacity [18]. The membranes usually apply
the incorporation of a moiety of a molecule more than sulfonic group (CF2SO3H)
that can be further treated into the membranes either anionic or cationic way [19].
Owing to good chemical and thermal stability, this type of polymers is also used as
part of a chlor-alkali process in producing proton exchange membranes for fuel cell
application.
Perfluorinated polymers have been commercially manufactured by three major
companies which are DuPont (Nafion ®), Asahi Glass (Flemion ®), and Asahi Chem-
ical (Aciplex-S ®). Nafion ® was widely applied compared to others commercialized
membranes due to high proton conductivity, high mechanical strength, and good
synthetic stability [20]. The Nafion ® chemical structure is shown in Fig. 5.

3.2 Partially Fluorinated Polymers

Over the past 20 years, there are several studies that have been attempted to
produce novel proton exchange membranes by utilizing partially fluorinated poly-
mers as the main materials [21]. Few approaches were discovered for instance
grafting porous PTFE with partially fluorinated sulfonated poly(arylene ether
ketone), sulfonating poly(arylene ether sulfone)s containing fluorophenyl pendant
group, and blending polybenzimidazole with a fluorinated polymer [21, 22]. The
results have shown several improvements not only mechanically but also
984 N. Awang et al.

Fig. 5 Chemical structure of F F F F F F F F F F F

Nafion ®
C - C- C - C- C - C -C -C -C - C - C
F F F F F O F F F F F
F C F

F C F

O
F C F

F C F

O S O

OH

chemically. This significant improvement in membrane properties can be related

to C–F bond strength (460 kJ/mol) which is greater than that of C–H bond
(410 kJ/mol) [23].
Further modification of better PEM was done by Kerres’ group by arranging
the of fractional oxidation of sulfonated polysulfone (PSU) and consequent cross-
linking of the remaining sulfonate groups with a,ω-diiodoalkanes by utilizing
sodium hypochlorite (NaOCl) [24–27]. The advantages of the process are: (1) no
side reaction occurs during oxidation process, (2) the partially oxidized polymer is
stable at ambience environment, and (3) the desired oxidation degree is easily
balanced. The study found that the application of swelling ratio and water uptake
weaken the membrane mechanical and is the using of different types of cross-linker
chain length and the difference of oxidation degree in sulfonated polymer.
Eventhough the method successfully improve the desired properties, desired proton
conductivity still cannot be achieved due to the cross-link interaction that brings
down the quantity of free –SO3H groups in the cross-linked membranes
[25]. Another characteristic which is marked as failure in this study is the compat-
ibility issue between Nafion ® bonded anode and cross-linked hydrocarbon
membrane.
To date, a research on reinforced partially fluorinated membranes proved to
have superior properties than fluorinated hydrocarbon membranes. The membranes
demonstrated high water uptake, low interfacial resistance, and high mechanical
strength [28–30]. Besides, reinforced composite membranes from partially fluori-
nated membranes also showed better dimensional stability and low cost [31–35]. In
any case, the execution of PTFE composite membrane is profoundly reliant on the
combination of state polymer and porous PTFE substrate [36].
The combination of α, β, and β-trifluorostyrene monomer was then discovered
to improve the fuel cell properties [37, 38]. Figure 6 shows the chemical structure of
24 Proton Conductions 985

a b
(CF CF2 CF CF2)n (CF CF2 CF CF2)n

SO3H
SO2

(CF CF2)m

Fig. 6 (a) Linear poly(trifluorostyrene) and (b) cross-linked poly(trifluorostyrene)

the polymer. The observation was done using the optimization of reaction of ion
exchange capacity with multiple equivalent weights from both cross-linked and
linear α, β, β-trifluorostyrene. The outcomes showed that the beta coordinating
impacted the perfluorinated polyalkyl group attached to the aromatic ring and caused
a great problem in the sulfonation of poly-α, β, β-trifluorostyrene. The problem in the
sulfonation procedure was due to the meta-coordinating impact of the perfluorinated
polyalkyl group attached to the aromatic ring as shown in Fig. 6

3.3 Nonfluorinated Aliphatic Hydrocarbons

Nonfluorinated aliphatic hydrocarbons are one type of membranes that is used

to synthesize proton exchange membranes [39, 40]. The polymer materials can
be aromatic or aliphatic in bulk pendant groups or in a polymeric backbone of
a membrane. Nowadays, the best technique to deliver a high proton conductor
electrolyte membrane is by utilizing hydrocarbon polymers as the polymer
backbones [41].
Hydrocarbon membranes offer few advantages over PFSA membranes such as
less cost, economically accessible, and their structure permits the introduction
of pendant groups from the polar site. Hydrocarbon polymers comprise of polar
groups which restrict the absorption of water to polar groups of polymer chain and
have high water uptake over a large range of temperature. A certain degree of
appropriate molecular design can be disintegrated due to the decomposition of
hydrocarbon polymers. Likewise, hydrocarbon polymers are effectively reused by
ordinary strategies. The chemical structure of the hydrocarbon is shown in Fig. 7.
Table 1 shows the summary of previous studies regarding the synthesis of
nonfluorinated aliphatic hydrocarbon materials. Figure 8 shows the prominent
structure under this category.
986 N. Awang et al.

Fig. 7 Poly(butadiene [CH2-CH]x [CH2-CH2]y [CH2-CH]n1 [CH2-CH]n11

styrene) block copolymer
CH2

CH3

SO3H

Table 1 Modification of aromatic polymers

No. Types of membrane (category) Design methodology
1 Sulfonated poly(4-phenoxybenzoyl-1,4- Formulated from poly( p-phenylene) and
phenylene) (SPPBP) particle course of action fundamentally like
poly ether ether ketone (PEEK). Direct
sulfonation created a highly proton
conductive polymer [42]
2 Cross-linked/non-cross-linked (SPEEK) Direct sulfonation of PEEK in corrosive
sulfuric acid resulted in high thermal
stability alongside proton conductivity [42]
3 BAM3G membrane (Ballard advanced Polymerization of α, β, β-trifluorostyrene
material of third generation membrane) incorporated the monomer screened from a
group of substitution α,β,β-trifluorostyrene
[43]
4 Membrane of base-doped with Presentation of natural inorganic Bronsted
S-polybenzimidazoles (PBI) bases to sulfonated PBI [44]
5 Methylbenzenesulfonate These alkylsulfonated aromatic polymer
PBI/methylbenzenesulfonate poly( p- electrolytes have extremely brilliant proton
phenylene terephthalamide) membranes conductivity and thermal stability when
compared to PFSA membranes, even above
80  C [21]
6 Imidazole-doped sulfonated Complexation with imidazoles to
polyetherketone (SPEK) accomplish high proton conductivity
Methylbenzenesulfonate PBI/ [4]. These alkylsulfonated aromatic polymer
methylbenzenesulfonate poly( p- electrolytes have extremely brilliant proton
phenylene terephthalamide) membranes conductivity and thermal stability when
compared to PFSA membranes, even above
80  C [21]
7 Imidazole-doped sulfonated Complexation with imidazoles to
polyetherketone (SPEK) accomplish high proton conductivity [4]
8 Imidazole-doped sulfonated Complexation with imidazoles to
polyetherketone (SPEK) accomplish high proton conductivity [4]

3.4 Nonfluorinated Membranes with Aromatic Backbones

Thermal stability of a proton exchange membrane can be improved by applying

these two major approaches: (a) modification of polymers with bulky groups in the
backbone of the aromatic polymer to give them relevant protons conduction and
(b) incorporation of aromatic hydrocarbon specifically into the hydrocarbon polymer
24 Proton Conductions 987

Fig. 8 Grafted membranes CH3

(a) FEP main and a
(b) sulfonated polystyrene
side chain (CF2-CF2)n (CF2-CF2)m

b CF2

HC SO3–

backbone [45]. Owing to bulky and inflexible aromatic groups, polyaromatic hydro-
carbon is an essential material in enhancing stability due to high glass temperature
(Tg) which is above 200  C [46]. Besides, the aromatic rings offer the probability of
nucleophilic substitution and also electrophilic. Polyether ketones (PEKs) with a
diverse number of ether and ketone functionalities (for instance, PEEK, PEKEK, and
PEKK), polyesters and polyimides (PI), polyether sulfones (PESF), and poly(arylene
ethers) are a percentage of the pertinent samples of main chain polyaromatics or
polyarylenes.
Past researchers have discovered that polyesters must be forestalled since the
ester group does not give enough support in the aqueous acid, while polyaromatics
are much of the time decided for fuel cell operation on account of their high thermal
stability. The particular polymer components in fitting modification do not just
demonstrate the stability in oxidizing, decreasing, and acidic situations additionally
thermally stable [47]. Table 2 displays the summary of efforts made in designing the
information of membranes that is considered as the distinct options for PSFA.
Another diverse methodology has been carried out. A cross-linked 3 wt%
quaternized polyvinyl alcohol (QAPVA) was adjusted with 2 wt% chitosan and
2 mL gluteraldehyde per 20 mL mixture as the cross-linked reagent. The composite
membrane was found to have high proton conductivity and low methanol
permeability at a lower water content of 8%. One of the studies is the correlation
performance of two membranes at higher temperatures: direct synthesized
sulfonated polybenzimidazoles and Nafion ® [62–65]. The results showed
that sulfonated polybenzimidazoles delivered higher performance than Nafion ® at
high temperature. The creators asserted that sulfonated polybenzimidazoles demon-
strated better performance because direct sulfonated polymidazole expands the
asymmetry backbones and thus inclined to have low dimensional swelling, more
rigid moieties, and more selectivity.
Another study is poly(aryloxyphosphazene)s functionalized with sulfonimide
units and phenyl phosphonic acid units [43]. The investigation discovered the
polymer as proportional candidate materials for fuel cells application. Radiation
and blending cross-linking of polyphosphazenes were added in order to lessen
the methanol permeation and water swelling from these ionomers [44]. Schuster
et al. have shown that imidazole-terminated ethylene oxide oligomers can achieve
988 N. Awang et al.

Table 2 Findings of electrospun fiber polymer-based membrane for fuel cell application [48]
Ion
Proton exchange
conductivity capacity
No. Membrane type (mS cm1) (meq/g) Modification information
1 Sulfonated polysulfone – 2.16 Synthesized by utilizing
intricate sulfur trioxide-triethyl
phosphate as the sulfonating
operators. Excellent mechanical
properties and generally high
IEC were obtained [49].
2 Sulfonated – 2.22 SPES was covalently cross-
polyethersulfone linked and integrated by
(SPES) utilizing substituted diamine-
sulfone to bring high proton
conductivity and mechanical
quality for operations above
100  C [50].
3 Styrenic system of – 3.65 Sulfonated naphthalene type
styrene divinyl benzene polyimides were combined to
(SDVB) poly(arylene) accomplish low water/methanol
permeability, high proton
conductivity, and coefficients
different from PFSA [51].
4 Styrenic system of – 2.15 SDVB and poly
styrene divinyl benzene (fluoroethylene-co-
(SDVB) hexafluoropropylene) (FEP)
were combined, trailed by
sulfonation by achieving
membranes extremely
indistinguishable to PFSA [52].
5 Sulfonated polyether 10.00 – PPBP and PEEK were
ether sulfonated by utilizing
ketone (SPEEK) and concentrated sulfuric acid.
sulfonated poly Thermal stability up to at least
(4-phenoxy benzoyl- 200  C was obtained. A
1,4-phenylene) conductance of around 102 S/cm
at 65 mol% of sulfonation in the
event of SPPBP was observed
while SPEEK showed a lower
conductance for the same mol%
of sulfonation [53].
6 Sulfonated poly [bis 9.20 1.40 The base polymer and sulfur
(3-methyl phenoxy) trioxide were sulfonated by
phoszene] yielding higher proton
conductivity, cross-linking,
lower water, and methanol
diffusion synthetic mechanical
stability when contrasted to
Nafion ® [54]
(continued)
24 Proton Conductions 989

Table 2 (continued)
Ion
Proton exchange
conductivity capacity
No. Membrane type (mS cm1) (meq/g) Modification information
7 Sulfonated polyimide 29.00 – PI was sulfonated by utilizing
(PI) sulfur trioxide to obtain
properties proportionate to
Nafion 117 [55].
8 Hydrogenated poly 54.00 1.43 Polystyrene was sulfonated by
(butadiene-styrene) utilizing acetyl sulfate as the
(HPBS) sulfonated sulfonating specialists. To
polystyrene expand the sulfonation, ionic
conductivity was equipotential
to Nafion ® (103 to 102 S/
cm). In any case, discontinuity
in the properties at 15%
sulfonation was noted [56]
9 Hydrogenated poly – 1.00 Incorporated by heterogeneous
(butadiene-styrene) sulfonation of poly (butadiene-
(HPBS) styrene). Mixed with
polypropylene as an
improvement in both proton
conductivity and thermal
properties [57]
10 Poly 58.00 0.99 Aryloxyphosphazenes bearing
[aryloxyphosphazene] bromo-phenoxy side groups
polymers were treated with
t-butyllithium, continued with
diphenylchlorophosphonate by
converting to phenyl
phosphonic acid groups [58]
11 Sulfonated polyaryls 23.00 – Polyetherketones were
recustomized by mixing it with
polymers including
immobilized heterocycles; for
instance pyrazole, imidazole, or
benzimidazole as the proton
solvating species to accomplish
high proton conductivity. Water
crossover was definitely
reduced while proton
conductivity was kept high [59]
12 Impregnating fleeces 0.07 – Polysulfone, micro glass fiber,
on polyte-trafluoro and a composite grid
ethylene (PTFE) matrix constituting both fleeces were
impregnated on a PTFE matrix.
Different from the two
impregnated fleeces, the
composite membranes did not
show similar or lower resistance
than Nafion 117 [60]
(continued)
990 N. Awang et al.

Table 2 (continued)
Ion
Proton exchange
conductivity capacity
No. Membrane type (mS cm1) (meq/g) Modification information
13 Sulfonimide compound 60.00 0.99 Cross-linking sulfonimide was
integrated by applying the
macromolecular substitution
method to deal with the
phosphazene bearing pendant
sulfonimide gatherings
produced to obtain high proton
conductivity [58]
14 Polystyrene graft 11.00 1.07 Cross-linking sulfonimide was
polymerSulfonimide integrated by applying the
compound macromolecular substitution
method to deal with the
phosphazene bearing pendant
sulfonimide gatherings
produced to get high proton
conductivity [56]
15 Polystyrene graft – 3.40 Cross-linking styrene/
polymer acrylonitrile was acquired from
N-vinylpyrrolidone/
2-acrylamide-2-methyl-1-
propane sulfonic acid graft
polymer by applying
divinylbenzene and kept it in
order to acquire a better
stability in an oxidative domain
[61]

conductivity up to 10–5 Scm1 at 120  C [58]. The structures of nonfluorinated

membranes with aromatic backbones classification are shown in Fig. 9.
Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is a hydrophobic polymer with
a high glass transition temperature (Tg = 210  C), excellent hydrolytic stability, and
high mechanical strength. Eventhough PPO chemical structure is simple compared
to other aromatic polymers, it permits many modifications on both benzyl and aryl
positions, characteristics of PPO meet most of the requirement for PEMFCs appli-
cation. The PPO chemical structure also favored for fuel cell application due to their
stability in acidic medium and thermally stable: (1) nucleophilic substitution of
bromomethylated PPO, (2) electrophilic substitution on benzene ring, (3) coupling
and capping of terminal hydroxyl groups in PPO chains, (4) metalation of PPO with
organometallic compounds, and (5) radical substitution of hydrogen from methyl
groups [42].
24 Proton Conductions 991

Fig. 9 Structures of H3C CH3

a O O
(a) SPSU, (b) SPEEK, and
(c) SPPBP C S

O O
SO3H

b O

O O C

n
SO3H

SO3H
c

C O

3.5 Acid–Base Complexes

Acid-base complexes are well known as low-cost and practical substitution for
proton exchange membranes. The materials are proved to maintain highly proton
conductive in elevated temperatures. The acid-base complexes normally involve the
process of incorporating acid component into alkaline polymer base to activate
proton conduction [16]. The chemical structures of acid-base complexes polymers
are shown in Fig. 10.
Currently, the most outstanding system for high-temperature PEMFC under
ambient pressure is phosphoric acid-doped polybenzimidazole (PBI/H3PO4) mem-
brane. Different studies have used polybenzimidazole (PBI/H3PO4) for various
applications, for example, fuel cell technologies, physicochemical characterizations,
and membrane casting. Many researchers have focused on acid-doped PBI mem-
branes. High-temperature PEMFC effectively appears at temperatures of up to
200  C under ambient pressure, and related fuel cell technologies have been created.
992 N. Awang et al.

H3C CH3
H2N O O e H 3C CH3 O O
NH2
S
a C S O

O O
O O
SO3H

b
f O
O O C
N
c H SO3H
N N
H

N
d
N
N
H
N
H

Fig. 10 Structure of basic polymers (a–d) and acidic polymers (e and f)

The upside of the membrane is mandatory for gas humidification which allows the
elimination of complicated humidification system in contrast and Nafion ® cells.
Other exceptional working elements of PBI are simple control of cell temperature
and air flow [66].
The acid-base membranes comprise of basic polyetherimide (PEI) and sulfonated
polymers (aPBEK, sPPENK, and sPPESK). All the membranes mentioned have
been studied and have shown thermostability, oxidative resistance with highly
proton conductivity, hydrolysis resistance, and excellent resistance to swelling.
From the observation of every attribute, they are anticipated as high potential proton
exchange membrane materials later on [67].
As of late, the improvement of membranes selection with sensible cost and great
performance, fuel cells have been broadly concentrated on. Acid-base polymer
blends are said to be highly potential materials because of the interactions in the
middle of polymers and acid, for instance, hydrogen bonding bridges and ionic
cross-linking (electrostatic forces) increase the membrane swelling control without
reducing the flexibility. Thus, these membranes have high mechanical flexibility and
strength, high proton conductivity, low water uptake, great thermal stability, and
decrease crossover [46, 68–74].
The mixture of acid-base polymer membranes were prepared by blending
sulfonated poly (2, 6-dimethyl-1, 4-phenylene oxide) (sPPO) with (3-aminopropyl)
triethoxysilane (A1100) by utilizing a sol-gel process for fuel cell application.
Analyses have shown that acid-base interaction enhances membrane homogeneity
and thermal stability as well as flexibility and mechanical strength [57, 75, 76].
Poly (2, 21-(m-phenylene)- 5, 51-bibenzimidazole)/phosphoric acid (PBI/H3PO4)
complex is both promising and captivating. It has demonstrated high potential for
24 Proton Conductions 993

a b O O
H2N H2N
C C
+ Pho OPh
H2N NH2
H2N

H H OH
N N
+ 2 + 2H2O
N N
n

Fig. 11 Structure of (a) tetraaminobiphenyl, (b) diphenyl isophalate, and (c) poly
[2,21–(m–phenylene)–5,51 bibenzimidazole]

fuel cell applications at medium temperature and subsequently numerous inves-

tigations have been made to optimize and understand this specific system.
A broad observation on the PBI complexes has been completed at Case Western
Reserve University. The structure of the reactants and the PBI item are shown in
Fig. 11.
A research conducted on blending of sulfonated polysulfones and doped H3PO4 –
PBI [77, 78]. PBI acid-base membranes are known for their excellent attributes in
fuel cell applications (with improvement in conductivities above 102 S/cm 160  C
at 80% relative humidity which is higher than acid-doped PBI membranes under the
same condition). However, their long-term stability of doped PBI membranes has yet
to be found and proven.
Acid-base complex membranes (PBI/H3PO4) do not depend on humidity.
The materials are highly sensitive to the doping level of complex. As the doping
level increases, the proton conduction of the materials increases. A research proved
that the conductivity of PBI membrane was about 4.6  102 S/cm at a tempera-
ture of 165  C at 450% doping. It has been shown that conductivity could reach
0.13 S/cm at extremely high doping level around 1600%. The situations occur when
the doping constantly increases, the anion moieties support the proton hopping
between imidazole sites and the distance between the clusters of acid sites decreases.
The significant effects of applying high-temperature specialty polymers are not only
for thermal stability purpose but also to promote stability in oxidative, reducing, and
acidic environments [28, 79–84].
A study has supported proton hopping mechanism which is called Grotthus
mechanism for PBI membrane doped with phosphoric acid as acid-base complex
(PBI/H3PO4) [85]. The research has been carried on a doped PBI/H3PO4 membrane
at 190  C under atmospheric pressure and produced a current density of 1.2 A/cm2
and a power density of 0.55 W/cm2. Conductivity data of doped PBI at temperatures
below glass transition temperature and the relatively high change in entropy (which
994 N. Awang et al.

could be related to the molecular rearrangements that is essential for Grotthus

mechanism) showed that Grotthus mechanism is possible. At such elevated temper-
atures, the poison tolerance of the electrode catalysts was significantly improved
compared to that at lower temperatures [86].
There are several polymers from the acid-group complex type that have been
tested for fuel cell performance [87]. The research on poly(4-vinylimidazole)-H3PO4
complexes has shown that the complexes of amorphous polyamide with H3PO4 have
high conductivity but low mechanical strength and lack chemical stability at tem-
peratures above 90  C [88]. Another research that synthesized synthesized a new
protonic conductor gel (PVAL/H3PO2/H2O) using prime chemicals which were
H3PO2 (hypophosphorous acid) and PVAL (polyvinyl alcohol) showed improve-
ment in mechanical property. The study reached the highest electrical conductivity at
ambient and sub-ambient temperatures in this type of material reported up to now
in the literature (in the order of 101 Scm1). In addition, the variation of electrical
conductivity with temperature and acid concentration was studied. The highest open
fuel cell voltage measured at 23  C was 435 mV. The performance of the fuel cell
improved when it was fed with humidified hydrogen [89].
SPEEK/PBI membranes which comprised of poly(benzimidazole) PBI as the
basic compound and sulfonated poly(etheretherketone) SPEEK as the acidic com-
pound have been reviewed by Kerres et al. [90]. The membranes exhibited high
thermal stability (decomposition temperatures more than 270  C), excellent proton
conductivity at ion-exchange capacities IEC of 1, and showed good performance
when tested in H2 membrane fuel cell.
Despite these selected polymers have been studied as membrane and have
achieved high proton conductivity, some studies regarding the fabrication of poly-
mer are still rare. Hence, the technique needs to be further investigated in order to
improve the mass transfer and solve the methanol crossover problem. One of the
suggested fabrication methods is electrospinning. The method is believed able to
improve the pathway and provide better characteristics for DMFC membranes.

4 Enhancing Proton Conductivity by Electrospinning

Technique

Electrospinning is one of the most straightforward, adaptable, and advanced pro-

cessing technique in delivering nanofibers [91]. The process is grouped into a couple
of strategies, for instance, magneto-electrospinning vibration-electrospinning, bub-
ble electrospinning, and siro-electrospinning. The principal patent of electrospinning
has been issued by Formhals in October 1934 [92]. In spite of the fact that the
procedure has been generally connected for just about 70 years, the utilization of
electrospun nanofibers as a part of delivering membrane for fuel cells is still new. In
this manner, the situation leads electrospinning process to end a subject of interest
for several years [91].
Actually, the electrospinning process became widely known in the sixteenth
century prior when William Gilbert recorded the first electrostatic attraction of
24 Proton Conductions 995

a liquid. In 1846, highly nitrate cellulose was delivered by Christian Friedrich

Schonbein. In 1900, the first electrospinning patent was filled by John Francis
Cooley. John Zenely has distributed the work on fluid droplets qualities towards
the end of metal capillaries in 1914. His exertion started the endeavor to simulate
a model that conduct fluid mathematically under electrostatic forces [92].
In addition, the majority of work presented by Formhals and Zenely were
specifically connected to the polymer. Compared to conventional techniques, for
example, melt spinning, wet spinning, and dry spinning, electrospinning can create
smaller pore size and larger specific surface area with the diameter of fiber ranging
10~1000 nm, while the conventional system can only deliver fiber with a diameter in
the range of 5~500 μm [91].
In the electrospinning method of polymers, high-voltage electrostatic field is
connected to the charged surface of the polymer solution bead and subsequently
will prompt the ejection of a liquid jet through a spinneret. Due to the current
circumstances, the electrostatic force conquers the surface tension of the bead and
the formation of Taylor cone occurs when the solution is leaving the tip of the
spinneret and thus prompting the charged jet in the long run [20, 93–103]. The
formation of Taylor cone is proportional to the connected voltage, the voltage
continues to expand until the equilibrium condition is obtained between the surface
tension and the electrostatic force (Fig. 12). The electric field controls the course of
charge jet and the solidified spun fiber is gathered on the turning or stationary
conductive collector [20, 93–102, 104, 105]. A setup for electrospinning is shown
as in Fig. 13.
Other than electrospinning process, template synthesis, drawing, phase separa-
tion, and self-assembly are the other methods that can be used in developing
nanofibers [98, 99]. However, due to the versatility possessed by electrospinning
process, it becomes more favorable to be used in developing highly porous, pat-
terned, and nanofibrous polymeric materials nanofibers [100].

a b c

Polymer
solution

Taylor cone

Pendant Induced charges

drop from electric field

Jet initiation

Fig. 12 Formation of Taylor cone. Voltage is increased until the equilibrium between surface
tension and electrostatic force is achieved as in Fig. 11c [97]
996 N. Awang et al.

Syringe Solution Needle Jet

Pump Tylor cone

High Voltage Collector

Fig. 13 Electrospinning setup

5 Electrospun Polymer-Based Nanofiber Membranes

As aforementioned, the work presented by Formhals and Zenely were only

connected to the polymer and this turns the initial move towards expanding the
improvement of electrospun nanofibers from different kinds of polymers. Nanofibers
have been created from hundreds kinds of polymers [48] and just a few concentrates
on the impact of polymer-based membrane electrospun fibers in fuel cell application.
The following are a few polymer-based membranes that have been mainly utilized
lately to make nanofibers for fuel cell application.
Nafion ® has been economically utilized as a polymer electrolyte membrane and
it has demonstrated high performance in proton conductivity [92] which is essential
for fuel cell. Another direction for Nafion has been induced being developed of
Nafion nanofibers by Dong et al. [102]. A total of 0.1% of high molecular weight
carrier polymer, poly (ethylene oxide) PEO (Mw = 8000 kg/mol), was utilized as a
part of their study. They effectively acquired higher purity for Nafion ®, Nafion
nanofiber and higher proton conductivity with a magnitude of 1.5 Scm1 compared
to bulk Nafion ®, Nafion film. The reduction in diameter of the fiber from 500 nm to
400 nm was found to enhance the proton conductivity of the fuel cell.
The ionic morphology of polymer-based membrane (the morphology of a poly-
mer is based on the impact of proton conductivity) is another essential trademark for
improving proton conductivity. The orientation of ionic domains along the fiber
pivot direction can be obtained due to the application of shear force during electro-
spinning process. Figure 14 shows the image of 400 nm wide Nafion nanofiber. The
picture portrays the request of magnitude (aligned structure) higher than that of bulk
business nafion the aligned electrospun fibers bring higher conductivity and this
orientation can be extended if the utilized of shear forces increment as a part of
parallel with diminishing the fiber diameter [106].
Tamura and Kawakami [103] have synthesized membrane electrolytes containing
sulfonated polyimide nanofibers and sulfonated polyimide for proton exchange
24 Proton Conductions 997

Fig. 14 SEM image of

99.9 wt% Nafion nanofiber

membrane fuel cell. They found that the polyimides inside the nanofiber were
fundamentally oriented when electrospun. This membrane demonstrated a change
in stability by expanding the measure of aligned nanofiber while the gas crossover
permeability diminished when contrasted with membrane without nanofibers
because of the total structure inside the nanofibers. Moreover, the proton conductiv-
ity of the membrane in parallel direction demonstrated a higher value when
contrasted with membrane in perpendicular direction and sulfonated polyimide
membrane without nanofibers that was prepared through solvent casting technique.
Pan et al. [104] in their study has concentrated on adding nanowire-based superior
in the application of smaller scale fuel cells. Nafion/poly (vinyl pyrrolidone) (PVP)
nanowires (NPNWs) were blended by electrospinning. 1.27 g of Nafion (E.I.DuPont
Company, identical weight (EW) = 1100), 0.26 g of PVP (Sigma, MW~1300 000),
and 2.1 mg tetramethylammonium chloride (Sigma) in 0.7 g ethanol were prepared
as the antecedent polymer for electrospinning. Plastic syringes with stainless-steel
needle used and the 10 cm separation between the needle tip and the collector was
connected. The voltage connected was 16 kV. The use of PVP as a part of this study
was devoted to the high subatomic weight of PVP. It was kept in mind that the end
goal was to effectively electrospin the Nafion with no commitment on proton
conductivity [120–125].
Electrospun Nafion itself is difficult to create alone because it is not soluble in
most normal solvents and thus will inevitably lead to the arrangement of micelles
which diminish the chain entrapment [105]. Pan et al. [104] have utilized the
authority which is made of two conductive substrates (silicon) isolated by a void
gap. The study found that the transportation of protons to reach the cathode in
NPNWs turned out to be more effective, hence the proton conductivity of NPNWs
was found to be bigger corresponding to the diminishing measurement because of
the increment in the level of the “texture” coming about because of special orienta-
tion [126–139]. They uncovered that the proton conductivity can be upgraded by
adjusting the distance across the NPNWs below 2.3 μm. The other findings on the
998 N. Awang et al.

Table 3 Findings on electrospun fiber polymer-based membrane for fuel cell application [48]
Proton
conductivity
Based polymer Filler/carrier polymer (mS cm1)
Poly(vinyl alcohol) Nafion ® 22
Polyvinylidene fluoride Nafion ® 2
Sulfonated polyethersulfone Nafion ® ~85
Sulfonated random copolyimide Sulfonated polyimide Up to 370
Bromomethylated sulfonated Sulfonated poly(2,6-dimethyl-1,4- 30–80
polyphenylene oxide (BPPO) phenylene oxide) (SPPO)
3 M perfluorosulfonc acid PEO 55
polymer
Nafion ® 5 wt% PVA or PEO 8.7–16
3 M perfluorosulfonc acid PAA 498
polymer
Polymerized ionic liquid Poly(MEBIm-BF4), PAA 7.1  10–4
Sulfonated poly(ether ether None 37 (solvent
ketone ketone) DMF)
41 (solvent
DMAc)
Sulfonated poly(arylene ether None 86
sulfone) sulfonated polyhedral oligomeric 94
silsesquioxane
(sPOSS)
Sulfonated copolyimide ~100
Polyvinylidene Phosphotungstic acid (PWA, up to ~0.4
12.8 wt%)
AquivionTM PEO (Mw 1x106) 66
Sulfonated Zro2 PVP, poly(2-acrylamido-2- 240
methylpropanesulfonic acid)
(pAMPS)

electrospun fiber polymer-based membrane for fuel cell application are outlined in
Table 3.
As concerned, most of the previous studies have been focusing on polymer
reinforce composite proton exchange membranes and the resulting membrane per-
formance is dominant for proton conductivity rather than fuel barrier properties.
A direct methanol fuel cell especially had shown a significant drawback on power
density and efficiency, if it is compared to a polymer exchange membrane fuel cell
which operates with hydrogen due to the methanol crossover from anode to cathode
[100, 105, 107].
The latter approach (Table 4) which concerns the preparation of new electrolyte
composite membrane based on proton conducting materials has been investigated in the
past few years for its good proton conductivity as well as the methanol barrier properties.
These new electrolyte composite membranes consist of dispersion fillers, such as silica,
heteropolyacid, zirconium phosphate, etc., within the polymer [140-145].
24 Proton Conductions 999

Table 4 Studies on modification of PEM based on proton conducting materials [108]

Approach Purpose
1. Modifying perfluorinated ionomer To improve water retention properties at high
membrane/preparing acid-base blends temperature (>100  C)
2. Modifying ionomer membrane To improve conductivity
3. Preparing new electrolyte composite To improve the properties of polymer electrolyte
membranes based on proton conducting membrane as desired properties, especially the
materials barrier properties and mechanical stability of the
two components which can be combined into
one composite

Hydrophilic property is important for a membrane to keep the membrane

hydrated for proton conduction purpose [109]. Sulfonated polyetherketones
(PEEKK and PEEK) are suitable candidates which believed to have high durability
that can withstand the fuel cell operation for more than thousand hours [110]. The
introduction of inorganic material which is clay into sulfonated poly ether ether
ketone (SPEEK) has proved a few improvements notably in reducing methanol
permibility [111].
Bafna [112] has proved the advantages of clay composite over other nano-sized
filler like nanofibers. They found that the surface area to volume ratio (A/V) for nano-
fibers was two times higher than that of clay layer. This means that the nanofiber
would have a higher surface area of filler exposed to the polymer matrix, and thus
would have higher reinforcing ability compared to the clay layers [146–155].
However, when it is oriented strongly in a particular direction in the composite,
the ability is served to the clay layers to reinforce the composite biaxially. In
preventing the transport of gasses or fluid through a particular composite direction,
a large amount of filler surface area is required, and for this highly oriented filler, the
area would be significantly larger in a clay composite. This gave a reason for Bafna
[112] to prepare a polyethylene-clay nanocomposite in their work. Depending on the
clay quantity and the dispersion state, clay can act as a nucleating agent as well as an
obstacle to the polymer mobility. But electrospinning process favors the elongation
of the chains and the ordering of the polymer [113].
Smectites, which are a family of both montmorillonite (MMT) and hectorites, are
a valuable mineral for industrial applications due to its high cation exchange
capacity, high surface area, high surface reactivity, and high barrier property com-
pared to others natural clays [111]. Organoclay Cloisite 15 A ® is the material
prepared from montmorillonite (MMT) and cation di-tallow as mentioned. Tallow
is the mixture of octadecyl (>60%), hexadecyl, and tetradecyl. Cloisite is a very
crucial additive in polymer nanocomposite membrane since it has been modified
from MMT and the possibility in enhancing the compatibility with the organic
polymers is expected to occur [105].
Since exfoliated structure is a desirable morphology, a new fabrication method
need to be further discovered. Electrospinning is one of the techniques that could
provide an exfoliate matrix mixture of SPEEK and Cloisite 15A ®. The electro-
spinning process not only can create a smaller path for methanol to permeate but also
1000 N. Awang et al.

improve proton conductivity due to good dispersion of cloisite 15A ® within the
membrane which can retain more water for proton conduction purpose [107].

6 Current Studies and Future Directions

The incorporation of modified clay, cloisite 15A ®, and compatibilizer which is 2,4,6-
Triaminopyrimidine (TAP) has proved the ability of membrane to conduct more
proton and reduce methanol permeability. However, swelling at high degree of
sulfonation may reduce the performance of DMFC still mark as an issue for this
study. Owing to halfly exfoliated surface structure, the study propose the further
application of SPEEK with closite 15A ®. There are several modifications that need
to be studied to curb the swelling aspects in SPEEK such as:

I. Providing bridging links to the reactive sulfonic groups by using thermal

activation and cross-linking of polymer chains by polyols [114].
II. Introducing hydrophobic-hydrophilic block for SPEEK in different ratios [115].
III. Applying blending technique for SPEEK. The compatible blends occur between
SPEEK-polyether sulfone (PES), SPEEK- polyether imide (PEI), and poly-
benzimidazole (PBI) [116–118].

Methanol permeability in SPEEK can be reduced by incorporating dispersive

fillers, for instance, silica [119]. Apart from this approach, it is vitally essential to
note that membrane morphology is an important element in providing methanol
path. Thus, it is highly recommended for a PEM to possess exfoliated surface
structure. The structure is ideal in creating path which can reduce methanol perme-
ability. One of the solution to create this morphology is by electrospinning
[156–168].
Electrospinning is a new method in fuel cell research field. It is said to be an
advance method in reducing size of filler which promote better dispersion of fillers in
polymer matrix without agglomeration. A filler can act as an obstacle to the polymer
mobility as well as a nucleating agent depending on the dispersion and loading of the
clay itself [24].

7 Conclusions

Significant amount of research works have been conducted to solve two major
problems faced by PEM which are methanol crossover and low proton conductivity.
It has come to a conclusion that functionalization of polymeric material selection
is important in improving PEM properties. Among all types of membranes, SPEEK
has shown outstanding characters to replace commercial Nafion ® membrane.
Several modifications have been done on SPEEK, and it proved to have several
potential as a good PEM. Nevertheless, there are few weaknesses need to be
improved notably on morphology. The exfoliated morphological structure is
24 Proton Conductions 1001

important in providing winding methanol route to alleviate the crossover. Hence,

fabrication of the functionalized SPEEK by electrospinning is suggested since it is
believed to provide exfoliated morphology. Besides, it is the best solution to develop
high-performance membrane for DMFC.

Acknowledgment The author (Nuha Awang) is thankful to the Ministry of Higher Education
(MOHE) and Ministry of Science, Technology & Innovation (MOSTI) for the financial support
under vote number of R.J130000.4F157, R.J130000.05H25, and R.J130000.4S057), and also to the
Research Management Centre (RMC), UTM for research management activities, and Zamalah
scholarship provided by School of Graduate Study (SPS), UTM.

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Desalination
25
Rasel Das, Syed Mohammed Javaid Zaidi, and
Sayonthoni Das Tuhi

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
2 Polymers for Membrane Fabrications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1017
2.1 Synthetic Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1018
2.2 Biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1027
2.3 Nanomaterial for Mixed-Matrix Polymeric Membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033
3 Conclusion and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1036
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1037

Abstract
Polymeric membranes are currently extensively investigated for water purifica-
tion. Strong motivations behind this are due to their unique structural charac-
teristics such as high mechanical, thermal, and chemical stabilities. They are
also flexible in nature in such a way that one can easily fold them into hollow
fiber or flat sheet. Based on such features, an excellent pollutant selectivity
and permeability of water have been observed; thereby a remarkable separation
capacity is expected. This chapter covers a comprehensive discussion on the
fabrication of both synthetic and biopolymeric membranes for water desalination.
Fundamental knowledge on structures, types, functionalizations, and optimiza-
tions of different advanced polymer-based membranes, especially microfiltration

R. Das (*)
Chemical Department, Leibniz Institute of Surface Engineering, Leipzig, Germany
e-mail: [email protected]; [email protected]
S. M. J. Zaidi
Center for Advanced materials, Qatar University, Doha, Qatar
e-mail: [email protected]
S. D. Tuhi
Department of Microbiology, University of Chittagong, Chittagong, Bangladesh
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 1011

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_28
1012 R. Das et al.

(MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO), were
discussed in details with their synthesis procedures. MF and UF membranes are
suitable to retain larger organic and inorganic molecules, whereas NF and RO are
popularly used to purify salty water. MF is usually prepared by cellulose acetate,
polysulfone, poly(ether sulfone), and poly(vinylidene fluoride). Secondly, UF
membrane is made by polysulfone, poly(ether sulfone), poly(vinylidene fluoride),
poly(acrylonitrile), and poly(etherimide). Thirdly, polysulfone, polyamide poly
(vinylidene fluoride), chitosan, and aquaporin are the major building blocks for NF
membranes. Finally, cellulose acetate, polysulfone, and aromatic polyamides are
the major constituents of RO membranes. Carbon nanotube is highlighted as a part
of polymers’ composites membrane with respect to improved or novel perfor-
mance, and the potential implications of those developments for future membrane
technology are discussed. Finally, some of the research gaps and future prospects
of polymeric membrane technologies are also highlighted.

Keywords
Polymers · Structures · Functionalization · Water purification · Desalination

Abbreviations


C Degree Celsius
ABA Triblock copolymer with a hydrophobic B segment flanked
by two identical hydrophilic A segments
AQP0 Mammalian aquaporin 0 isoform
AQP1 Mammalian aquaporin 1 isoform
AQP3 Mammalian aquaglyceroporin 3 isoform
AQP4 Mammalian aquaporin 4 isoform
AqpZ Bacterial (E. coli) aquaporin Z isoform
CA Cellulose acetate
cm3/cm2/s Cubic centemeter per centemeter square per second
CNT Carbon nanotube
CNT Carbon nanotube
COD Chemical oxygen demand
CTA Cellulose triacetate
DOPC 1,2-Dioleoyl-sn-glycero-3-phosphocholine
DOTAP 2-Dioleoyl-3-trimethylammonium-propane (chloride salt)
g/mol Gram per mol
GFD Gallons per square foot per day
GO Graphene oxide
GS Gas separation
kDA Kilo Dalton
kg h1 m2 Kilogram per hour per meter sqaure
kg/m3s Kilogram per cubic meter second
L m2 h Liter per meter square hour
L m2 h1 bar1 Liter per meter square per hour per bar
L m2 h1 Liter per meter square per hour
25 Desalination 1013

L/hm2 Liter per hour meter square

L/m2h Liter per meter square per hour
L/min Liter per minute
m/s Meter per second
m2 s1 Meter square per second
m3 m2 day1 Cubic meter per meter square per day
MF Microfiltration
mL/cm2s Mililitre per centemeter square per second
mm Millimeter
MM Mixed matrix
MMCNT Mixed matrix carbon nanotube
MPa Megapascal
mPa1 s1 Meter per pascal per second
MW Molecular weight
MWCNT Multiwalled carbon nanotubes
NF Nanofiltration
NIPS Nonsolvent-induced phase separation
nm Nanometer
ppm Parts per million
PVDF Polyvinylidene di(fluoride)
RO Reverse osmosis
SPES Sulfonated polyethersulfones
SWCNT Single-walled carbon nanotubes
TFC Thin film composite
TIPS Thermally induced phase separation
UF Ultrafiltration
VA Vertically aligned
VACNT Vertical aligned carbon nanotube
VIPS Vapor-induced phase separation
WP Water permeation
μm Micrometer

1 Introduction

Global warming causes severe climate changes that increase ice-melting and sea
level. It submerges the available fresh water resources and makes them saltier.
Therefore, future water shortage is a must, and the lack of cost-effective sea and
brackish water desalination technology has further aggravated the crisis for the
rapidly growing population. This paves the way for a big threat to human develop-
ment, health, sustainability, and social and economic progresses.
In order to secure pure water availability, many water treatment technologies
under the category of primary (screening, filtration, centrifugation, separation, sed-
imentation, coagulation, and flocculation), secondary (aerobic and anaerobic treat-
ments), and tertiary (distillation, crystallization, evaporation, solvent extraction,
1014 R. Das et al.

oxidation, precipitation, ion exchange, membrane filtration technologies) have been

proposed [1]. Among them, membrane technologies such as microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO) [2] are commonly
used for water purification. Membrane can be simply defined as a thin barrier which
allows a very selective mass transport. Although both the organic (e.g., polymers) and
inorganic (zeolites, ceramic, etc.) materials have been used, organic polymers are
popularly examined for commercial membrane fabrications. Table 1 shows some
important commercial organic polymers corresponding to their membrane processes.
The major advantage of membrane technologies are high throughput, high pollutants
rejection ability, high selectivity, high mechanical strength, and spent media regen-
eration [2]. In order to make an effective membrane, one needs to ensure these
advantages for high water flux and pollutants rejections with low biofouling (long
life-span) effects. For manufacturing purpose, membrane needs to be reproducible,
low capital costs for packaging.
Membranes are usually classified based on few factors such as nature of
the polymers, morphology, geometry, preparation method, separation regime, and

Table 1 Polymers used for industrially established separation membranes [5]

Morphology
Barrier Membrane
Polymer barrier type Cross section thickness (mm) process
Cellulose acetates Nonporous Anisotropic ~0.1 RO
Mesoporous Anisotropic ~0.1 UF
Macroporous Isotropic 50–300 MF
Cellulose nitrate Macroporous Isotropic 100–300 MF
Cellulose Mesoporous Anisotropic ~0.1 UF
Polyacrylonitrile Mesoporous Anisotropic ~0.1 UF
Polyetherimides Mesoporous Anisotropic ~0.1 UF
Polyethersulfones Mesoporous Anisotropic ~0.1 UF
Macroporous Isotropic 50–300 MF
Polyethyelene Macroporous Isotropic track- 6–35 MF
terephthalate etched
Polyamide (aliphatic) Macroporous Isotropic 100–500 MF
Polyamide (aromatic) Mesoporous Anisotropic ~0.1 UF
Polyamide (aromatic) Nonporous Anisotropic/ ~0.05 RO,NF
composite
Polyether (aliphatic) Nonporous Anisotropic/ ~0.05 RO,NF
composite
Polyethylene Macroporous Isotropic 50–500 MF
Polyimides Nonporous Anisotropic ~0.1 GS,NF
Polypropylene Macroporous Isotropic 50–500 MF
Polysiloxanes Nonporous Anisotropic/ ~0.1 < 1–10 NF
composite
Polyvinylidenefluoride Mesoporous Anisotropic ~0.1 UF
Macroporous Isotropic 50–300 MF
25 Desalination 1015

processes [3]. Figure 1 shows the permeability of solutes through several polymeric
membranes, such as NF, UF, MF, and RO. Among them, RO has been extensively
used for desalination and around 19% of the world’s desalination plants have
successfully installed the RO membrane [4].
Classification of membrane depends on several factors as shown in Fig. 2 [6]. It
reveals two forms of membrane (a) flat sheet and (b) hollow fiber based on its
geometry. Based on structural variations, two types of membranes are classified
(a) symmetric or isotropic and (b) asymmetric or anisotropic, as shown in Fig. 3. It
shows symmetric membranes are uniform in structure (homogenous) throughout the
whole membrane body which controls overall separation performances. On the other
hand, the gradient structure in asymmetric membrane is controlled by densest part of
the membrane.
Symmetric membranes are synthesized by vapor precipitation and phase inver-
sion processes [7, 8]. Porosity of the membrane is controlled by using the concen-
tration of polymers and the phase compositions. At low polymer with high humidity
concentrations, it is possible to synthesize highly porous membrane and vice versa as
shown in Fig. 4. Thermally-induced phase inversion process has also found effective
to get symmetric porous membrane structure. On the other hand, different types of

Fig. 1 Major polymeric membranes for water purification

1016 R. Das et al.

Geometry Bulk Structure Production Method Separation Regime Application

Stretched films Dialysis

Nucleation track Porous Ultrafiltration
Phase inversion Microfiltration

Symmetric

Extrusion
Non-porous Gas separation
Solution casting
Hollow-fiber
Flat-sheet
Dialysis
Ultrafiltration
Phase inversion Porous Microfiltration
Asymmetric
Solution coating
Non-porous Reverse osmosis
Interfacial polymerization
Pervaporation
Plasma polymerization
Gas separation

Fig. 2 Classification of synthetic membranes. (Adapted with permission from American Chemical
Society [6])

Symmetric Membranes

porous cylindrical porous web-or sponge dense polymer film

Asymmetric Membranes
a

integrally-skinned integrally-skinned thin-film composite

(porous skin layer) (non-porous skin layer) a) selective coating layer
a) selective skin layer (material A)
(material A) b) microporous support
b) microporous support (material B)
(material A)

Fig. 3 Structural representation of symmetric and asymmetric membrane structures. (Adapted with
permission from American Chemical Society [6])
25 Desalination 1017

Fig. 4 Effects of polymer concentrations on membrane morphology: (a) membrane resulting from
polymer-rich and (b) polymer-poor phases. (Adapted with permission from American Chemical
Society [6])

asymmetric membranes are synthesized by different production methods. For exam-

ple, phase inversion method is suitable for porous integral membrane. The mem-
brane has directly been used for UF and MF processes. However, dense integral
membrane is more suitable for RO and gas separations.

2 Polymers for Membrane Fabrications

Ideal polymers are the major building blocks for a membrane which should have
high mechanical, thermal, and chemical stabilities. In addition, it should also be
flexible in such a way that one can easily fold them into hollow fiber or flat sheet.
In general, synthetic organic polymers such as cellulose, cellulose acetates, cellulose
acetate butyrate, cellulosic ester, cellulose nitrates, polycarbonate esters, ethyl cellu-
loses, polyacetylenes, polyacrylonitrile, polyamides, polyamide esters, polyamide-
hydrazide, polyamideimides, polyaryletherketone, polyetherketones, polycarbonates,
poly(phenylene oxide) polyesters, polyestercarbonate, polyethers, polyetherimides,
polyetherketones, polyethersulfones, polyethylenes, polyhydrazides, polyimides, poly-
phenylene oxides, polyphenylene sulfide, poly(phthalazine ether sulfone ketone),
sulfonated poly(phthalazine ether sulfone ketone), polypropylene, polysiloxanes, poly-
sulfones, sulfonated polysulfones, polytetrafluoroethylene, poly(trialkylsilylacetylenes),
poly(trimethylsilylpropyne), polyureas, polyurethanes, polyvinylalcohol, poly-
vinylchloride, polyvinylidene fluorides, and so on have been used to fabricate
different membrane processes [9]. But all polymers are not commonly practiced
industrially. Here we will only highlight those polymers which are commonly
used for membrane fabrications. Firstly, both the MF and UF membranes are
usually made by poly(vinylidene fluoride), polysulfone, poly(acrylonitrile), and
poly(acrylonitrile)-poly(vinyl chloride) copolymers. MF membranes also utilized
1018 R. Das et al.

the cellulose acetate and cellulose nitrate blends, nylons and poly(tetrafluoroethylene)
[10, 11]. Secondly, poly(ether sulfone) is a major building block for UF membranes.
Thirdly, NF membranes are made by polyether, polyimide, polyamide, and polyester.
Finally, RO membranes are usually prepared by cellulose acetate or polysulfone
coated with aromatic polyamides. Although same polymers could be used to fabricate
multiple membranes, there are huge physicochemical differences along with their
performances for water purification as we summarized in Table 2.

2.1 Synthetic Polymers

Man-made polymers have been synthesized by taking in to account their commercial

utility in various sectors and are commonly classified as thermoplastics, thermosets,
elastomers, and synthetic fibers. Although most of the synthetic polymers have long-
chain structures, they are different in either main or side chain variations. Most of the
membranes made by synthetic polymers have been commercialized for industrial or
domestic uses. The synthetic polymers for membrane fabrications such as cellulose
acetate, polysulfone, polyethersulfone, polyacrylonitrile, polyvinylidene fluoride,
polyetherimide, polyamide, and polyimide are widely studied due to their mechan-
ical strength, flexibility, and chemical stability. Here we discussed these polymers in
detail including their structure, types, and modification strategies in the subsections
below, and also highlighted their applications for water purification in Table 3.

2.1.1 Cellulose and Cellulose Acetate

Cellulose is a naturally abundant polymer and its ester form is the so-called cellulose
acetate as shown in Fig. 5a. Cellulose acetate can be obtained from the cellulose
acetylation. The degree of acetylation determines the replacement rates of cellulose’s
OH groups with CH3COO groups. This substitution is important for controlling
membrane properties. Scaling from 0 to 3, where 0 represents unreacted cellulose
and 3 depicts completely substituted cellulose, which is called cellulose triacetate
(CTA) [27]. Higher degree of acetylation brings high salt retention, but low
water permeability. Loeb and Sourirajan [28] used heat treatment to fabricate the
RO membrane using cellulose acetate in 1960. The membrane was so effective for
water desalination than the other existing membranes at that time, which allow its
rapid commercialization in the market. Later, the same fabrication processes were
used to form MF. The degree of acetylation for commercial cellulose acetate-
mediated RO membrane is about 2.7, which postulates a good balance between
salt rejections and permeate flux. Some membranes are prepared by the blending of
cellulose acetate and CTA. It increases the membrane’s mechanical stability and
resistance to hydrolysis, but decreases water permeability. A commercial cellulose
acetate-blended membrane exhibits a flux of 22 GFD at 425 psi (Δp), and an
average NaCl rejection of 97.5% [29]. The membranes are relatively easy to make
and are typically resistant to chlorine attack. It can tolerate up to 5 ppm of free
chlorine which is much higher than the aromatic polyamide-based membranes.
However, cellulose acetate membrane has some disadvantages such as the low
25 Desalination 1019

Table 2 Major differences among some major polymeric membranes

Feature RO NF UF MF Refs.
Definition A process that A separation A process whereby A separation [12]
applies process in which a solution process in which
transmembrane particles and containing a solute particles and
pressure to cause dissolved of >1–100 nm in dissolved
selective movement macromolecules diameter is macromolecules
of solvent against smaller than 2 nm removed from the larger than 100 nm
the osmotic are rejected solvent are rejected
pressure difference
Specific Desalination, water Hardness, heavy Virus and colloid Suspended solids, [2, 5, 13]
application reuse, and ultrapure metals, and removal protozoa, and
water production dissolved organic bacteria removal
matter removal
Materials Organic polymers Organic polymers Polysulfone, Polypropylene, [14–18]
such as, polyamide, like polyamide, acrylic, cellulose, polysulfone,
polysulfone, and polyester, and and others polyurethane, and
polyether sulfone other porous so on
polymers
Pore types Micropores Micropores (<2) Mesopores (2–50) Macropores [5, 19]
and sizes (0.3–0.6) (>50–500)
(nm)
Thickness ~0.1–0.2 ~0.05 150–300 50–100 [20, 21]
(μm)
Water ~3  1012 ~40  1012 ~0.5  1010 – [2, 20]
permeability
(mPa1 s1)
Solute Good Good Moderate Poor [2, 20]
rejection
ability
Self-cleaning Only with Only with Only with Only with [2, 22–25]
capability functionalization functionalization functionalization functionalization
especially at especially at especially at
ceramic-reactive ceramic-reactive ceramic-reactive
membranes membranes membrane
Tunable Mixed matrix only Mixed matrix only Mixed matrix with Mixed matrix with [2]
selectivity ceramic reactivity ceramic reactivity
Membrane Yes Yes Yes Yes [2]
fouling
Pressure uses 30–60 20–40 1–10 <1.0 [26]
(bar)

water flux, weak chemical resistance, and high biodegradability. The membrane
typically tends to hydrolyze over time which decreases their selectivity and sensi-
tivity toward salt molecules. Water pH determines the stability of the membrane
(stable pH: 4–6). Salt rejection of cellulose acetate membranes decreases as temper-
ature increases. Influent water temperature usually should not exceed 35
C
[30]. Therefore, several modifications of the polymer using styrene, poly-
(4-vinylpyridine), phenyl isocyanate, propylene oxide, acrylamide, O-(carboxy-
1020 R. Das et al.

Table 3 Major observations of synthetic polymeric membranes for water purification

Type Synthetic polymers Key features Refs.
MF Polyvinyl alcohol/ Water permeability (WP): 32,346 L/m2 h at [52]
polypropylene 0.24 bar
Smaller avg. pore size than nonwoven
membranes
Poly(vinylidene fluoride) / Enhanced hydrophilicity and improved flux [53]
hydroxyethylmethacrylate
UF Cellulose acetate nanofiber 10 higher flux than commercial [54]
membranes (WP: 3540 L/m2 h)
Polyimide/polyethersulfone WP: 3565–1780 L/m2 h [55]
Enhanced thermal resistance and mechanical
strength
Polyethylene terephthalate WP: 0.1–0.21 mL/cm2 s [56]
Reversible pH-responsive permeation
Polysulfone/poly[2,20 -(m- WP: 355 L/m2 h [57]
phenylene)- Enhanced porosity, hydrophilicity, and
5,50 -dibenzimidazole] thermal stability
Polyvinyl chloride and WP: 52–323 L/m2 h at 0.1 MPa [58]
polyvinyl formal Enhanced antifouling property
Cellulose acetate/polyethylene WP: Max 360 L/m2 h at 0.05 MPa [59]
glycol Antibacterial and antifouling
Concurrent separation
Polyurethane/polyvinylidene WP: 130 L/m2 h [60]
fluoride Six times higher fluxes than the pure PVDF
membranes
Cellulose acetate and its WP: 316–406 L/m2 h [61]
derivatives Hollow fiber, and hydrophilicities cellulose
acetate > cellulose acetate butyrate >
cellulose acetate propionate
Cellulose acetate with the highest antifouling
properties for humic acid and bovine serum
albumin
Polysulfone WP: 227.8 L/m2 h [62]
Mixed with polyethylene glycol methyl ether
(PEGME) as an additive
Decreases contact angle from 71
to 47

Nano-chitin whisker/poly WP: 392 L/m2 h [63]
(vinylidene fluoride) Improved mechanical properties
Antifouling membrane
NF Polysulfone WP: 7.5–8.9 L/m2 h [64]
Gravity-driven membrane filtration
Improved permeate quality in the presence of
biofilm on membrane surface
Poly(acrylic acid-co- WP: 0.794 L/m2 h [65]
polyethylene glycol methyl Hydrophilic surface
ether methacrylate) pH responsive 90% flux recovery ratio after
bovine serum albumin separation
(continued)
25 Desalination 1021

Table 3 (continued)
Type Synthetic polymers Key features Refs.
Cellulose acetate WP: 3540 L/m2 h (10 times greater than that [66]
of most commercial membranes)
71% porous structure
Poly(ethylene glycol) WP: 50–92 L/m2 h [67]
diglycidyl ether/polyamide 99.1 to 99.9% NaCl rejection with >95%
organic rejection
Improved fouling resistance
Polysulfone WP: Max 70 L/m2 h [66]
Cadmium removal 98%
Cellulose acetate WP: 5.09  10–6 m/s [68]
81.7% NaCl rejection
Polyamide WP: 5.67  10–6 m/s [68]
98.3% NaCl rejection
RO Sulfonated polyfuran WP: 0.8 m3 m2 day1 [69]
99.8% NaCl rejection
Polyether-polyfuran WP: 0.5 m3 m2 day1 [69]
99.9% NaCl rejection
Sulfonated polysulfone WP: 0.06 m3 m2 day1 [69]
98% NaCl rejection
Polyamide (aliphatic-aromatic) WP: 0.7 m3 m2 day1 [69]
99% NaCl rejection
Polypiperazine-amide WP: 0.3 m3 m2 day1 [69]
68% NaCl rejection
Poly(vinyl) alcohol via 1.2 L/hm2 [70]
network cellulose 98.9% NaCl rejection
Cellulose acetate/polyethylene WP: 0.35 L/hm2 [71]
glycol-600 81.50% NaCl rejection
Increased hydrophilicity
Polypropylene WP: 0.9 L/m2 [72]
77.9% NaCl rejection
Polysulfone WP: 1.1 L/m2 h [72]
96.4% NaCl rejection
Polysulfone WP: 6.5–32.8 L/m2 h [73]
83–94% NaCl rejection
Polysulfone WP: 0.15–0.24 L/m2 h [46]
79–95% NaCl rejection
Poly(pathalazinone ether WP: 22.9 L m2 h [74]
sulfone ketone) 99.2% NaCl rejection
Poly(pathalazinone ether WP: 270 L/m2 h [75]
amide) >18.2% NaCl rejection
>99% dyes rejection
Polyvinylidene fluoride WP: 0.55–0.25 L/m2 h [46]
2–99% NaCl rejection
1022 R. Das et al.

Fig. 5 Chemical structures of some commonly used synthetic polymeric membrane materials

methyl), O-nitro, and O-(cyanoethyl) groups, and so on have been observed in

fabricating the RO membrane for improving its mechanical strength, salt selectivity,
and water flux [31, 32].

2.1.2 Polysulfone
Compared to cellulose acetate, polysulfone is more thermostable and is so called
thermoplastic polymers and was introduced by Union Carbide in 1965. The poly-
mer is expensive because of its high costs of raw materials. Figure 5b shows
a typical repeating unit of polysulfone having aryl-SO2-aryl subunit. The forma-
tion of polysulfone requires the active reaction between the diphenol (bisphenol-A
or 1,4-dihydroxybenzene) and bis(4-chlorophenyl)sulfone, forming a polyether by
removing of NaCl as shown in Eq. 1. Based on its purity of reactant monomer, one can
achieve to get a high-molecular-weight long polymer.
25 Desalination 1023

nHOC6 H4 OH þ nðClC6 H4 Þ2 SO2 þ nNa2 CO3

! ½OC6 H4 OC6 H4 SO2 C6 H4 n þ 2nNaCl þ nH2 O þ nCO2 (1)

Polysulfone is rigid in structure, but transparent. It can hold its physicochemical

properties in temperature between 100 and 150
C. Polysulfone is highly stable in
a wide range of pH (2–13), so that the membranes prepared by them (UF and MF)
can be easily washable using both acidic and basic solutions to reuse [33]. Autoclave
and steam sterilization of the membrane can also be possible to thwart the microbes
clogging into the membrane pores. But special attention should be paid to see
whether the integrity and pore structure of the membrane should not be changed.
The polymer is popular to use pressure-driven water and gas filtration membranes
because of its high compaction resistance and can withstand at high pressure without
compromising its strength. Polysulfone allows easy membrane fabrications with
the controlled properties (pore sizes and volumes). Yuan et al. [34] synthesized
polysulfone-based NF membrane and achieved high Na2SO4 (>80%), but low
rejection of NaCl (15%). Besides desalination, polysulfone-based membranes also
have huge applications in hemodialysis and gas separation. The membranes are
popular to build the filter cartridges because of ensuring high flow rates at very low
pressures as compared with nylon and polypropylene. Polysulfone can also be used
as a copolymer with others, e.g., sulfonated polyethersulfones (SPES), for highly
durable proton-exchange membranes in fuel cell [35]. Modification of polysulfone
membrane using nanoparticle [36], polyethylene glycol [37], poly(vinyl alcohol),
carboxymethyl cellulose [38], and so on has been well documented to improve NF
membrane’s permeability, selectivity and sensitivity, thermal and solvent resistance,
and also mechanical properties.

2.1.3 Polyethersulfone
Polyethersulfone is an important polymer for separation sciences because of its
high chemical (oxidative and hydrolytic) and thermal stabilities. Compared to poly-
sulfone, polyethersulfone consists of phenyl rings separated by alternate ether and
sulfone linkages as shown in Fig. 5c. Direct sulfonation reactions lead to sulfona-
tion at the ortho position of the ether bond. Since polyethersulfone has sensitivity to
aromatic hydrocarbons or ketones, they are widely used in UF, MF, and dialysis
membranes. Polyethersulfone-based membrane commonly prepared by phase in-
version method and is asymmetric in structure. The two most common
used polyethersulfones are Ultrason E6020P (58) and Radel A-100 (15 kDa). Besides
desalination, the polyethersulfone membrane has also been used for blood pur-
ification. Rastegarpanah and Mortaheb [39] reported that the permeate flux for
polyethersulfone is 1.02  103 as comparable with commercial polytetrafluo-
roethylene membrane 1.07  103 kg/m3s. It helps polyethersulfone to achieve
the overall separation factors >99%. However, the hydrophobic character of
polyethersulfone-based membranes brings difficulty for membrane fouling as
1024 R. Das et al.

compared to polysulfone. So, the membrane has short life span and sensitivity.
Therefore, anchoring of hydrophilic functional groups such as the sulfonated,
pegylated, and carboxylated groups into the polyethersulfone membrane are impor-
tant to increase the surface free energy, thereby reduced fouling effect. Some poly-
mers such as polyvinylpyrrolidone, polyethylene glycol, cellulose acetate phthalate,
Poly(1-vinylpyrrolidone-co-styrene), acrylic acid, and so on have been reported to
increase polyethersulfone-based membrane porosity and polarity. Sometimes nano-
particles such as TiO2, ZnO, SiO2, ZrO2, and so on have been used to fabricate
organic–inorganic hybrid membrane for controlling the asymmetric structure and
membrane porosity [39]. Alternatively, those membranes which are hydrophilic
(having tendency to swell in water) could be strengthened by using hydrophobic
polyethersulfone. Such compromised membrane between the hydrophilic and hydro-
phobic junction especially at pores would give high flux and decrease fouling effects.

2.1.4 Polyacrylonitrile
Polyacrylonitrile is a semicrystalline organic polymer resin, which is also known as
Creslan 61. Acrylonitrile is a major part of this polymer with a linear formula
(C3H3N)n as shown in Fig. 5d. Polyacrylonitrile is synthesized by either the free
radical or anionic polymerizations of acrylonitrile monomer. Besides, vinyl could be
used as comonomer (1–10%), but it depends on special field applications. Polyac-
rylonitrile is popular because of its thermostability (<300
C) and resistance to
organic solvents, bacteria, photoirradiation, and membrane-forming ability. Polyac-
rylonitrile often shows superior performance than polysulfone-based membrane.
Polyacrylonitrile is mainly used to prepare UF and RO membranes and porous
supports of composite membranes using phase inversion process due to its superior
resistance to hydrolysis and oxidation. In spite of having polar group in the backbone
of the polymer, polyacrylonitrile is hydrophobic in its pure state. Hence, during
preparation, it is typically copolymerized with more hydrophilic monomers to
improve its hydrophilicity and processability to make it less brittle [40]. Similar to
other membrane, polyacrylonitrile is also susceptible to foul that decreases its
reusability. Therefore, modification of polyacrylonitrile with various polymers
(amphiphilic) and nanomaterials such as carbon nanotube (CNT), SiO2, TiO2,
Al2O3, and so on is important. Such composite membrane has shown enhanced
water permeability (increased porosity), salt retention, and antifouling property and
stability in real applications. For instance, polyacrylonitrile-based membrane has
shown water flux of about 250, which is further increased to almost 1150 Lm2 h1
upon SiO2 modification [41]. Similarly, graphene oxide (GO)-doped polyacryloni-
trile composite membrane shows a high water flux (65.1 L m2 h1) and salt
rejection rate of about 99.8% [42].

2.1.5 Polyvinylidene Fluoride

Polyvinylidene di(fluoride) also known as PVDF is a semicrystalline polymer
having a repeating unit of –(CH2CF2)n– (Fig. 5e). As like other membranes polymer,
polyvinylidene fluoride has high chemical, mechanical, and thermal stabilities. One
important beauty of this membrane is its longevity (aging resistance), which is one of
25 Desalination 1025

the most important features for a commercial membrane. Because of its smooth-
ness, it can easily be packed as flat sheet or tubular or hollow membrane. Classical
nonsolvent-induced phase separation (NIPS) and thermally induced phase separa-
tion (TIPS) methods are popularly used to fabricate porous polyvinylidene
fluoride membrane. TIPS method has some advantages as compared with NIPS.
Polyvinylidene fluoride synthesized by TIPS typically shows high mechanical
strength and lower antifouling property. But it needs high energy to pump water
through it. So far, MF and UF membranes are commonly prepared by poly-
vinylidene fluoride polymer. The polymer is also used in gas separation, distilla-
tion pump, ion exchange technology, and so on. Many company including Asahi
Kasei Chemicals, Merck Millipore, Koch Membrane Systems, Hyflux, and so on
are now marketing the polyvinylidene fluoride-based membrane commercially.
TIPS is also used for MF, whereas NIPS is useful for UF membrane. But vapor-
induced phase separation (VIPS), solution casting and electrospinning can also be
used to fabricate both membrane types. Xiao et al. [43] fabricated MF using
polyvinylidene fluoride for municipal effluent treatment. The membrane was so
stable and decreases chemical oxygen demand (COD) and develops appropriate
water quality prior to RO treatment. Zhao et al. [44] synthesized UF membranes by
crosslinking chitosan which shows high flux and rejection efficiency and less
fouling effects.
Polyvinylidene fluoride has also been used as a support to develop composite
membranes such as thin film composite (TFC)-based RO and NF membranes.
Although polysulfone was popular at primary level, polyvinylidene fluoride is
now getting popularity because of its high mechanical strength and resistance to
chemicals. Figure 6 shows the polyvinylidene fluoride-based TFC membrane prep-
aration [46]. The composite membrane shows high water flux and salt rejection
abilities as compared with polysulfone as the support. Liang et al. [47] used plasma
treatment for surface functionalizations of polyvinylidene fluoride which would be
acted as anchoring site for coating of inorganic silica nanoparticles in UF membrane
(Fig. 7). This allows improving the hydrophilicity and antifouling properties of
polyvinylidene fluoride membranes.

2.1.6 Polyetherimide
Polyetherimide is an amorphous dense polymer having a repeating molecular unit
(C37H24O6N2) (Fig. 5f ) with MW of about 592 g/mol. It has been commonly used
for UF membrane because of its good thermal and chemical stabilities, excellent
film-forming ability, and low cost polymer. Compared to other polymers, poly-
etherimide is a hydrophobic one and is inadequate to use in membrane fabrication.
Bowen et al. [48] modified polyetherimide using charged polymer called
sulfonated poly(ether ether ketone) and showed that it increases the overall
hydrophilicity of the membrane and enhances water permeability and NaCl rejec-
tion. Other modifiers such as Al2O3, Fe2O3, ZrO2, ZnO, and TiO2 have been used
to achieve more hydrophilic surface, higher specific surface area, and bactericidal
and self-cleaning properties [49].
1026 R. Das et al.

O O

HN HN C C

Hydrophobic PVDF Active

COOH X
polyamide layer

Plasma Surface properties

PVDF-based Polyamide TFC
treatment are changed
depending on
plasma sources Removal and dry
Electron Radical
lon Neutral In situ polymerization
TMC in hexane
at interface
COCI

Hydrophobic PVDF
Hydrophilic PVDF CIOC COCI

Surface
functionalization Interfacial
O2-CH4 plasma polymerization MPD in water
H2N NH2

Hydrophilic PVDF Hydrophilic PVDF

Fig. 6 Preparation of polyamide TFC membrane based on polyvinylidene fluoride. (Adopted with
permission from Elsevier [45, 46])

O OH O O
O O
Air O OH O OH

Argon plasma

PVDF membrane Activated PVDF membrane surface

Surface-tailored Grafted MAA

NH2 NH3+ Copolymerization Monomers
silica nanoparticles

NH3+ NH3+

COOH
COOH COOH
HOOC
O HOOC
O COOH COOH
Binding of nanoparticles O
O

COOH

Functionalized PVDF membrane Surface-grafted PVDF membrane

Fig. 7 Illustration of preparation of argon plasma treatment of polyvinylidene fluoride membrane

followed by its graft copolymerization and nanoparticle binding. (Adapted with permission from
Elsevier [45, 47])
25 Desalination 1027

2.1.7 Polyamide
Polyamide is a naturally occurring macromolecular polymer such as proteins, wool,
silk, etc., where the repeating units are held together by amide bonds (Fig. 5g). It can
also be synthesized artificially to achieve higher durability and strength. Such poly-
amides are nylons, sodium poly(aspartate), aramids, and so on, which have been
commonly used in textiles, automotive applications, carpets, and so on. More than
35% of polyamides are commonly utilized in industry. However, most of the
currently available polyamide-based membranes are RO and NF prepared by inter-
facial polymerization of acyl chlorides and various water-soluble reactants [50]. The
method is popular nowadays, because it is possible to optimize individual feature or
characteristics of a membrane chain. So, one can even optimize the polymeric structure
at the surface which has direct regulatory effects in the water permeability and solute
rejection. Chlorine is a common antifouling agent which has been used in wastewater
treatment processes. But it can attack polyamide chains and damage its physical
structure. In order to increase polyamide’s chlorine stability and antifouling property,
several modification techniques have been observed for polyamides using polyvinyl
alcohol, 3-allyl-5,5-dimethylhydantoin, methylene-bis-acrylamide, and so on [51].

2.1.8 Polyimide
Polyimide is a polymer of imide monomers (Fig. 5h). Polyimide had been in mass
production since 1955 because of their strong heat resistance properties. It was
first synthesized by reacting naphthalene-1,4,5,8-tetracarboxylic dianhydride or
4,49-oxydiphthalic anhydride with 4,49-diaminobiphenyl-2,29-disulfonic acid and
nonsulfonated diamine monomers such as 4,49-oxydianiline. The soluble poly(amic
acid) is first formed by polycondensation of aromatic dianhydrides with aromatic
diamines. Then, poly(amic acid) is shaped into the polyimide product by dehy-
dration step. Based on the main polymeric chain composition, polyimide could
be classified into aliphatic, aromatic, and semiaromatic. In addition, based on
inter–main-chain interactions; polyimide can be categorized into thermoplastic and
thermosetting. Thermosetting polyimide has good thermal and mechanical proper-
ties (very low creep and high tensile strength). Polyimide can hold these morpho-
logical properties up to 452
C. In addition, polyimide is chemically stable in various
solvents ethers, alcohol, esters, hydrocarbons, and so on. Although polyimide is
relatively stable in weak acid, there is a least evidence to use the polymer in higher
alkaline solution.

2.2 Biopolymers

The popularity of synthetic polymers has been decreased because of its stringent
environmental regulations. Therefore, researchers are now replacing the synthetic
polymers by natural biopolymers because of their sustainability and renewability
[76]. Special physicochemical properties of biopolymeric membranes would help
1028 R. Das et al.

to achieve high water permeation and separation, toxic metal capture, toxic organic
dechlorination, and biocatalysts [77]. Most of the biopolymers are typically poly-
saccharides and a few are protein. The following subsections covered some popular
biopolymers that have been used to fabricate current membrane technologies, and
some major evidences of biopolymeric membrane performances for water purifica-
tion are summarized in Table 4.

2.2.1 Chitin and Chitosan

Chitin is an important polysaccharide known as poly(β-(1–4)-N-acetyl-D-glucosamine)
and was first identified in 1884. Because of structural similarity with chitosan, chitin is
often considered as cellulose derivative, but it has acetamide groups at C-2 positions
[78]. Aquatic flora and fauna such as fungi, diatoms, nematodes, arthropods, shrimps,
crabs, lobsters, krill, and squid are the major natural sources of chitin. Similarly,
chitosan is a linear polysaccharide composed of randomly distributed (1–4)-linked
glucosamine and N-acetyl-D-glucosamine [79]. Generally, the physical characteristics
of chitin and chitosan are white, hard, inelastic nitrogenous polysaccharides. Chitosan
can be isolated directly from the cell wall of certain fungi. Moreover, it can be obtained
from chitin by a chemical method or an enzymatic production method [80]. Chitosan is
produced commercially by deacetylation of chitin, which is the structural element in
the exoskeleton of the crustaceans crab and shrimp, and the cell walls of fungi (Fig. 8)
[81, 82]. When the degree of deacetylation of chitin reaches about 50% (depending on
the origin of polymer), it becomes soluble in aqueous acidic media and is called
chitosan [83]. Chitosan membranes have been explored in many uses, such as in
water–ethanol pervaporation, enzyme immobilization and cationic specimen transpor-
tation, protein separation and concentration, controlled ingredient release, and envi-
ronmental applications [26]. Chitosan is applied in RO membrane preparation, where
the degree of acetylation is about 0.3–0.8. Treatment with an organic acid or an acid
anhydride, chitosan is converted to the acetylated form which is stable and useful as an
RO membrane. Moreover, chitosan membrane has excellent thermal and chemical
stabilities and exhibits mechanical strength sufficient for the pressure difference in the
operating condition [84].

2.2.2 Carrageenans and Pullulan

Carrageenan is an anionic polysaccharide extracted from marine red algae, large and
highly flexible molecules that curl forming helical structures (Fig. 9). Chemically, it
is a linear polymer, sulfated galactan, composed of alternating disaccharide repeating
units of 3-linked β-D-galactopyranose (G units) and 4-linked α-D-galactopyranose
(D units) or 4-linked 3,6-anhydro-α-D-galactopyranose (DA units) [85]. Based on
the number and position of sulfate groups, the isomers of carrageenan are known as
kappa, iota, and lambda-carrageenan. Carrageenan is biocompatible, biodegradable,
nontoxic, cheap, gel forming, and its oligosaccharides possess antibacterial activities
against Escherichia coli, Staphylococcus aureus, Saccharomyces cerevisiae, Pseu-
domonas citronellolis, and Mucor species [81, 82, 86, 87]. However, these carra-
geenan films are observed to be very brittle and for this their potential applications
also be hindered.
25 Desalination 1029

Table 4 Biopolymer-based composite membranes

Type Membrane materials Performance/key feature Refs.
UF/NF Chitosan/polyacrylonitrile Water permeability (WP): 1.1 L/m2 h [109]
>99.95% organic waste rejection
Pervaporation Chitosan and WP: 1730 g/m2 [110]
γ-(glycidyloxypropyl) Increased membrane stability
trimethoxysilane
RO Chitosan/poly-N-acetyl WP: 1.67  10–3 cm3/cm2/s [111]
glucosamine 78.8% NaCl rejection
NF N,O carboxymethyl chitosan/ WP: 16 L/min [112]
cellulose acetate 83.40% chromium rejection
72.60% copper rejection
NF 2-Hydroxypropyltrimethyl WP: 2.57 kg h1 m2 [113]
ammonium chloride chitosan/ Order of salts rejection:
poly(acrylonitrile) MgCl2 > CaCl2 > NaCl,
KCl > MgSO4 > Na2SO4 > K2SO4
NF N,O carboxymethyl chitosan/ Nickel sulfate-water (rejection [114]
polyether sulfone 74–80%)
Nickel chloride-water (rejection
57–62%)
NF Trimethylallyl ammonium WP: 6.3 L/h m2 [115]
chloride onto chitosan/poly Rejections trend:
(acrylonitrile) MgCl2 > CaCl2 > MgSO4 > NaCl
> KCl > Na2SO4 > K2SO4
Biopolymeric κ-Carrageenan-pullulan WP: 0.13 g m2 s1 [116]
Increase temperature brings
increased permeate flux
Good dye rejection
NF Aquaporin Z/cellulose acetate WP: 34 L/m2 h [117]
>30% NaCl rejection
High throughput with lesser energy
consumption
– D-block copolymer (poly 60–80% NaCl rejection [118]
(2-vinylpyridine-b- Maximum flux rates at pH 5.5–6.0
methacrylicacid)
RO ESPA/PEBAX 1657 WP: 19.9  2.6 L/m2 h [119]
(polyether–polyamide block 99.0  0.06% NaCl rejection
copolymer)
UF Poly(isoprene-b-styrene-b-4- WP: 24–850 L m2 h1 bar1 [120]
vinylpyridine) triblock Membrane pore densities:
terpolymers 4.53  1014–1.48  1015 pores/m2
NF Aquaporin (AqpZ-DOPC) WP: 3.6 L m2 h1 bar1 [121]
20% NaCl rejection
NF AqpZ-ABA WP: 34.2 L m2 h1 bar1 [122]
32.9% NaCl rejection
NF AqpZ-ABA WP: 8.2 L m2 h1 bar1 [123]
45.1% NaCl rejection
NF AqpZ-DOPC/DOTAP WP: 5.5 L m2 h1 bar1 [124]
75% NaCl rejection
RO AqpZ-DOPC WP: 4 L m2 h1 bar1 [125]
96% NaCl rejection
1030 R. Das et al.

Fig. 8 Production method for chitin and chitosan

Fig. 9 Composite membrane made by cross-linking of κ-carrageenan-pullulan. (Adapted with

permission from Elsevier [92])
25 Desalination 1031

Pullulan is another linear glucan polysaccharide consisting of repeating units of

maltotriose joined by α-D-(1 ! 6) linkages (Fig. 9) [88]. It is an extracellular glucan
intricate by a fungus of the genus Aureobasidium, which is commonly called black
yeast. Due to its capacity to form strong, resilient films and fibers, pullulan gains the
major interest in its own or combined with other thickeners or gelling agents
[89]. Pullulan have a disadvantage for some applications, though this can be
improved by mixing a small amount of another polysaccharide such as carrageenan
or xanthan gum [90, 91]. Combination of κ-carrageenan and pullulan composite
membrane (Fig. 9) shows sufficient mechanical strength for practical use and
excellent mass transfer characteristics, especially for molecular-size screening. The
fraction of κ-carrageenan (FC) typically determines the membrane characteristics
such as mechanical stability and mass transfer effect. Because of its cross-linked
hydrophilic structure, it exhibited high selectivity and high water flux [92].

2.2.3 Alginate
Alginate is a biocompatible, nontoxic, nonimmunogenic, and biodegradable biopoly-
mer. It is composed of guluronic acid (G) and mannuronic acid in its chain structure
(Fig. 10), and typically extracted from brown algae (Phaeophyceae) including Lam-
inaria hyperborea, Laminaria digitata, Laminaria japonica, Ascophyllum nodosum,
and Macrocystis prrifere by treatment with aqueous alkali solution, e.g., NaOH
[93]. Alginates have been traditionally applied in the food industry as thickeners,
suspending agents, emulsion stabilizers, gelling, and film-forming agents. The phys-
ical properties (e.g., viscosity and mean molecular weight) of sodium alginate are
very susceptible to physicochemical factors (e.g., pH and total ionic strength)
[93]. For example, at near-neutral pH, the carboxylic functional groups of sodium
alginates deprotonated and induce repulsive inter- and intramolecular electrostatic
forces and have shown high negative charges [94]. In recent years, alginate mem-
branes have been investigated in diverse ways (e.g., pervaporation, immobilized cell
reactor, and UF), and can be prepared by low concentration cross-linker needed
support matrix (e.g., glass fiber filter) to maintain flat membrane [94].

2.2.4 Aquaporins
Aquaporins are a class of membrane-spanning proteins, responsible for the water
transport across the cell membrane [95]. The first human aquaporin, which was first
demonstrated by Agre and coworkers, was named AQP1. The first aquaporins are
described by their water channel activity, and since then 12 other human/mammalian

Fig. 10 β-D-mannuronic acid COOH

and α-L-guluronic acid O OH
monomers of alginate O OH HO
COOH
HO OH HO
O

β-D-mannuronic acid (M) α-L-gluluronic acid (G)

1032 R. Das et al.

aquaporins have been discovered (named AQP0 through AQP12) with critical physi-
ological functions [96]. Moreover, aquaporins have been found in plants, yeast, and in
the domains of Bacteria and Archaea. Though most of the aquaporins have water
transport functions, solute transport [96] and formation of intercellular junctions
(AQP0, AQP4) have been reported for selective aquaporins [97]. As an example, the
aquaporin obtained from mammalian eye lens, AQP0, is selective for water, nonethe-
less, does not show high permeability, while in case of AQP2, which is present in kidney
tissues and involved in concentrating urine, shows high selectivity and high permeabil-
ity. The E. coli aquaporin AQPZ has high water permeability and no known transport of
solutes [98]. The transport of water in aquaporins is more rapidly than existing RO and
forward osmosis (FO) membranes, since there is a fundamental difference in transport
mechanism. In contrast to the “jump diffusion” mechanism of existing membranes,
water transport in aquaporins occurred through narrow hydrophobic nanochannels
(diameter < 200 nm) by frictionless movement. Briefly, the pore openings around
3 Å of aquaporins are lined with mostly hydrophobic amino acids as shown in Fig. 11
[99]. Here, the large solutes are rejected through size exclusion, as the narrowest part of
the channel is 2.3 Å. A positively charged arginine residue is located at this narrow part
and helps to reject positively charged solutes through electrostatic repulsion [100]. And,
lastly, molecular reorientation of water molecules occurs by hydrogen bonding with a
residue near the pore. This molecular reorientation (water dipole reorientation) breaks
the extensive hydrogen bonding that normally allows rapid H+ transfer in bulk water
and in doing so prevents passage of H+ ions. It is that single aquaporins transfer water
molecules at rates of 2–8  109 molecules per second [100, 101]. However, nowadays,
aquaporin-based membranes are not commercially available due to the difficulties of
attaining large quantities of proteins and producing large areas of membrane material.

2.2.5 Block Copolymers

Block polymers are macromolecules composed of multiple block polymeric species
which have the ability to self-assemble into highly ordered structures (Fig. 12), when
it is placed in a selective solvent [103]. Because of having self-assembly properties,
block copolymer possesses narrow pore size distributions and high porosities. The
property is useful for membrane protein insertion [104]. Block polymers may appear
in different forms due to the self-assembly by varying the concentrations and
conditions, including densely packed cylindrical pores ideal for water separation
membranes [105]. Phase inversion, shear aligning, and controlled substrate–polymer
interactions are the common methods for large-scale production of block polymers.
Theoretically, aligned cylinders can be formed through nanostructuring of block
copolymers, which could enable a fully polymeric analog to aquaporin or align CNT
membranes that may give a chance to take advantage of nanopore performance,
while maintaining ease and economy of large-scale polymeric membrane fabrication
[106]. These block polymers, which are sometimes called amphiphilic block copol-
ymers, can be designed to have hydrophobic and hydrophilic blocks. The amphi-
philic block copolymers are mostly used in biomimetic membranes preparation
because of having some advantages like high mechanical and chemical stability,
customizable properties, and ability to perform end group functionalization
25 Desalination 1033

Size restriction
180H Electrostatic
repulsion

R195
192N

Water dipole
reorientation

N76

Fig. 11 Longitudinal section of AQP-1 water channel. The aqueous pore (blue color) which has a
pre-diameter of 2.8 Å corresponds to the size of water molecules. (Adapted with permission from
Nature [102])

[107]. Block copolymers are typically expensive, so using the polymers with other
membranes as small percentage could provide large cost savings and improved
performances for separation science.

2.3 Nanomaterial for Mixed-Matrix Polymeric Membrane

CNTs are composed of graphite sheets (allotropic form of carbon) rolled up in a tube-
like structure with appearance of latticework fence (Fig. 13). Multiwalled carbon
1034 R. Das et al.

Fig. 12 Assembly of block

copolymer. (Adapted with
permission from Nature [108])

Fig. 13 (Super) structure representations of (a) an MWCNT and (b) an SWCNT. (Adapted with
permission from American Chemical Society [128])

nanotubes (MWCNTs) are composed of multiple layers of graphene sheets

(Fig. 13a), whereas single-walled carbon nanotubes (SWCNTs) have cylindrical
shape consisting of a single graphene shell (Fig. 13b) [126, 127].
CNTs membrane works with low energy consumption because of its frictionless
water transport capability through nanotubes hydrophobic hollow cavity (Table 5).
The membrane is highly sensitive toward multiple pollutants and salts, antifouling,
25 Desalination 1035

Table 5 Potentiality of vertically aligned (VA) and mixed matrix (MM) CNT membranes
Membrane
types Substrate/filler Major observations Refs.
MM Polysulfonate Increased hydrophilicity [131]
Increased water permeability, up to 2 wt%
Decreased solute rejection, up to 2 wt%
Decreased permeability and increased rejection at
4 wt%
MM Polysulfonate Increased surface roughness [132]
Altered surface hydrophilicity
Increased mechanical stability
MM Poly(vinylidene Eliminated E. coli cells (~2 μm) through size [133]
fluoride) exclusion
Inactivated 80% of the bacteria within 20 min
contact time
Removed viruses with great extent
MM Polyamide- Increased water permeability [134]
polysulfone Enhanced bacterial cytotoxicity (60%/h)
Decreased biofouling during operation
MM Polyethersulfone Increased water refluxing capacity [135]
Greater antifouling activity against whey proteins
MM Poly(methyl Increased water flux (62%) with improved [136]
methacrylate) selectivity and sensitivity
Retained Na2SO4 (99%)
MM Polyvinyl-N- Cytotoxic for Gram-positive and Gram-negative [137]
carbazole bacteria (~80–90%)
Removed virus (~2.5 logs)
Cost-effective method
MM Polysulfone Increased fouling resistance [138]
MM Polysulfone Increased water flux (60–100%) [139]
Retained solutes and resistant to protein fouling
MM Polysulfone Enhanced thermal stability [140]
Increased heavy metals rejection
MM Polyethersulfone Increased water fluxing without aggressive chemical [24]
cleaning
Excellent antifouling properties rendered
membranes suitable for recycling use
MM Polysulfone Increased water flux (160%) [141]
MM Polyvinylidene Reduced fouling tendency [23]
fluoride Improved self-cleaning ability
Retained salts (R (Na2SO4) > R (MgSO4) >
R (NaCl))

self-clean, reusable, and good water permeable. CNTs can be doped into existing
engineered membranes or membranes themselves by aligning them together. On the
basis of current fabrication systems, there are two types of nanotube membranes
(i) vertically aligned (VA) CNT membranes and (ii) mixed matrix (MM) CNT
membranes [129]. Figure 14 postulates both membrane prototypes along with their
distinguishable properties. VACNT membranes can be synthesized by aligning
1036 R. Das et al.

Fig. 14 Schematic illustration of the two types of CNT membranes. (a) vertically aligned and
(b) mixed matrix CNT membranes

perpendicular CNTs with supportive filler contents (epoxy, silicon nitride, etc.)
between the tubes (Fig. 14a) [130]. On the other hand, MMCNTs membrane consists
of several layers of polymers or other composite materials (Fig. 14b).

3 Conclusion and Future Perspectives

Polymeric membranes outperform classical water treatment technologies because of

their special physicochemical properties. Different polymer chemistry helps to
fabricate membrane with desired properties which contributes significantly to yield
potable water. Simple operating procedures of membrane-based water treatment
plants at different capacity according to the desired requirements in the given area
make membranes technologies more popular commercially. One important conclu-
sion from the activities highlighted in this chapter is that the synthetic polymers that
have been produced in such a way that packing of these polymeric membranes into
different configurations will not affect membrane’s performances. But most of the
biopolymers depend on their natural macromolecular configurations for water flux
and pollutants retention. Altering their architecture might not be feasible to develop
new biopolymer-based membrane technology. However, among all membrane
25 Desalination 1037

technologies, RO is a popular one to desalinate both brackish and sea water. About
19% of the world’s desalination plants have successfully installed the RO mem-
brane. But energy requirements and fouling problem of the membrane have
remained a big issue to think. The theoretical minimum energy that required for
sea water desalination is 0.81, 0.97, and 1.29 kWhm3 for a water recovery of
25, 50, and 75%, respectively, suggesting research gaps for further improvement of
the technologies. On the other hand, fouling has remained a major problem for
recrudescence and reusability of the membrane. Most of the polymers described here
are hydrophobic in nature which attracts foulant molecules to adsorb onto the
membrane surface. As a corollary, most of the membrane pores become saturated
which ultimately decrease water flux and pollutant-rejection ability of the mem-
brane. In order to overcome these, current polymeric membranes have been deco-
rated with guest compounds and nanomaterials, so that the functionalized membrane
would have high water permeability, high pollutants selectivity, and antifouling
properties for feasible uses. But, there is no evidence to transform these advanced
functionalized membranes commercially which is associated to their scaling-up into
designed products that can be economically mass produced. Therefore, cross-
fertilization between academic research works and industrial research and develop-
ment activities is important to bring a technology from a lab-bench to field level.

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Enhanced Oil Recovery
26
Muhammad Shahzad Kamal and Abdullah S. Sultan

Contents
1 Enhanced Oil Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1047
1.1 Evaluation and Screening Techniques for EOR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049
1.2 Polymer Systems for Enhanced Oil Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
2 Drilling Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
2.1 Classification of Drilling Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056
2.2 Evaluation and Screening Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
2.3 Polymer Systems for Drilling Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059
3 Hydrate Inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
3.1 Evaluation and Screening Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
3.2 Polymer Systems for Kinetic Hydrate Inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1067
4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1068
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069

Abstract
Worldwide energy demand has been increased in last few decades, and it is
expected that it will increase up to 50% by the end of next decade. Oil and gas
were major sources of energy in past, and it is expected that it will remain the

M. Shahzad Kamal
Center for Integrative Petroleum Research, King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
Department of Petroleum Engineering, King Fahd University of Petroleum and Minerals, Dhahran,
Saudi Arabia
e-mail: [email protected]
A. S. Sultan (*)
Department of Petroleum Engineering, College of Petroleum Engineering and Geosciences,
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Center for Integrative Petroleum Research, King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 1045

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_29
1046 M. Shahzad Kamal and A. S. Sultan

primary source of energy in next few decades. Therefore, efforts are being made to
upgrade drilling, completion, workover, and production operations to maximize the
oil recovery at a lower cost. In last few decades, water-soluble polymers have been
extensively used in different gas and oilfield applications. In the present chapter, we
discuss the various types of polymeric systems that have been applied in various
oilfield applications. These applications are mainly enhanced oil recovery, drilling
fluids, and kinetic gas hydrate inhibition. Properties required for each application
are also discussed and related to the chemical structure of the polymer.

Keywords
Polymer · Enhanced oil recovery · Drilling fluid · Kinetic hydrate inhibitors ·
Viscosity

Abbreviations
AAs Antiagglomerates
AM Acrylamide
AMPS 2-Acrylamido-2-Methylpropane Sulfonic Acid
API American Petroleum Institute
ASP Alkali-surfactant-polymer
CEC Cation exchange capacity
CMC Carboxymethylcellulose
EOR Enhanced Oil Recovery
HAPAM Hydrophobically modified polyacrylamide
HEC Hydroxyethylcellulose
HPAM Partially hydrolyzed polyacrylamide
HP-μDSC High-pressure microdifferential scanning calorimetry
HTHS High-temperature high-salinity
IEP Isoelectric point
k Permeability
KHIs Kinetic hydrate inhibitors (), and
ko Permeability of oil
kw Permeability of water
MD Molecular dynamic
PAM Polyacrylamide
PEO Polyethylene oxide
PVCap Poly(vinyl caprolactam)
PVIMA Poly (N-methyl,N-vinylacetamide)
PVP Poly(vinyl pyrrolidone)
sI Structure I
sII Structure II
sIII Structure III
SP Surfactant-polymer
sT Structure T
ta Hydrate plug formation time
THIs Thermodynamic hydrate inhibitors
26 Enhanced Oil Recovery 1047

ti Induction time
VIMA N-methyl,N-vinylacetamide
VP Vinylpyrrolidone
μ Viscosity
μo Viscosity of oil
μw Viscosity of water

1 Enhanced Oil Recovery

Oil is the most important source of energy and it is expected that it will remain a
primary source of energy in meeting future energy demands [1]. Therefore, it is
extremely important to discover new oil fields and/or enhance the production from
existing oil reservoir. Oil from reservoirs is recovered in three different stages,
namely, primary, secondary, and tertiary stages. In the primary stage, oil is recovered
due to natural drive energy available in the reservoir. In secondary recovery, water
and/or gas are used to increase the oil recovery. Only 15–20% oil is recovered using
primary and secondary oil recovery process. About 7,000 billion barrels of conven-
tional and heavy oil could not be recovered using conventional oil recovery methods
[2]. To recover the remaining oil, tertiary oil recovery also called as enhanced oil
recovery (EOR) methods are used. A typical classification of EOR method is given
in Fig. 1. Thermal EOR, gas EOR, and chemical EOR are three main tertiary oil
recovery methods. The worldwide share of each EOR method is given in Fig. 2
[3]. Data show that most of the previous EOR projects were carried out using thermal
injection followed by the gas injection. The share of chemical EOR was not
significant due to low oil prices, unavailability of suitable chemicals, high chemical
cost, and poor understanding of the mechanism. However, chemical EOR could be a
preferable choice in future due to bulk production of EOR chemicals that resulted in
low oil prices. The oil reservoirs are mainly characterized as sandstone and carbonate
reservoirs. The data presented in Fig. 3 show that majority of the EOR projects were
carried out in sandstone reservoirs. A major fraction of the residual oil is present in

EOR

Thermal GAS Chemical

In-situ Electro- Steam Miscible Immiscible Polymer Alkali Surfactant Nanoparti-

Magnetic cles
combustion

ASP SP

Fig. 1 Classification of EOR processes

1048 M. Shahzad Kamal and A. S. Sultan

Fig. 2 EOR projects categories [3]. (© Elsevier, published with the kind permission of Elsevier.)

Fig. 3 EOR field projects in different reservoirs [4]. (© Society of Petroleum Engineers, published
with the kind permission of Society of Petroleum Engineers.)
26 Enhanced Oil Recovery 1049

carbonate reservoirs. Therefore, it is expected that most of the future EOR projects
would be in carbonate reservoirs. Carbonate reservoirs are more challenging com-
pared to sandstone reservoirs due to high temperature high salinity (HTHS) condi-
tions and heterogeneity of carbonate reservoirs.
In chemical EOR, surfactants, polymers, and/or alkalis are used to increase the
displacement efficiency and the volumetric sweep efficiency [5–12]. The ultimate
objective is to increase the capillary number, which is defined as the ratio of viscous
forces to interfacial forces [13–16]. Surfactants are used to lower the interfacial
tension between water and oil. An ultra-low value in the range of 10 3 mN/m is
required to achieve a capillary number higher enough for effective displacement
[17]. In addition to IFT reduction, surfactants also improve the oil recovery via
microemulsification of trapped residual oil, wettability alteration, and improving the
interfacial rheological properties [18–24]. Polymers are used to improve the mobility
ratio by enhancing the viscosity of the displacing phase fluid. Mobility ratio is the
ratio of mobilities of the water to oil (kwμo/koμw). Here k is effective permeability and
μ is viscosity. Subscript w represents oil while o denotes water phase. The eventual
target in any EOR project using polymer is to achieve a mobility ratio of less than
1 [25]. Higher mobility ratio results in viscous fingering due to high mobility of
water. Such a lower mobility ratio is achieved using water-soluble polymers.
Surfactant-polymer (SP) and alkaline-surfactant-polymer (ASP) injections are also
common to have relative advantage of each component.

1.1 Evaluation and Screening Techniques for EOR

The polymers for EOR are screened by comparing their rheological properties,
thermal stability, adsorption, compatibility, chemical stability, injectivity,
coreflooding data, and cost. Ideally, a polymer should have good thermal stability
for longer time at reservoir conditions (few weeks to few months), high resistance to
mechanical degradation (up to 1000 m3/m2/d flux during entering into porous rock),
low adsorption on reservoir rock (<1 mg/g-rock), good compatibility with reservoir
brine and other chemicals, good tolerance to injection and formation brine, high
injectivity, high viscosity, and low cost [26].
As the main purpose of injecting polymer is to achieve and maintain high viscosity,
therefore, it is extremely important that polymer should tolerate harsh conditions. At
high temperature, the polymer can degrade and precipitate by interaction with the
injection of formation brine. The usual expectation from a good polymer is that it
should maintain 50% of its original viscosity for at least 6 months [27]. Polymer
adsorption on reservoir rock is a serious issue, and it should be considered during
screening process due to economic reasons. A high retention on reservoir rock can
lower the viscosity of the flood and affect mobility ratio. Polymer retention is
measured using static adsorption test or dynamic adsorption core flooding test. Static
adsorption tests are performed in sealed aging tubes using a fixed amount of crushed
rock and polymer solutions. The solutions are stirred for a particular time (usually
1 day of stirring and another 1 day for equilibrium) at given conditions of
1050 M. Shahzad Kamal and A. S. Sultan

temperatures. Similarly, dynamic adsorption is determined using analysis of core

samples and polymer solutions before and after flooding. Adsorption density can be
determined by the difference of polymer concentration before and after flooding. An
acceptable polymer for EOR must have adsorption lower than 1 mg/g-rock
[27]. Adsorption of a polymer depends on several factors such as nature and type of
reservoir rock, salinity, and temperature. Adsorption of polymer on the reservoir is
related to the isoelectric point (IEP). At a pH lower than IEP, the surface charge is
positive and vice versa. The IEP of kaolinite and limestone is 4.7 and 8.2, respectively
[28, 29]. It means if pH > 4.7, adsorption of the anionic polymer would be lower
compared to cationic polymer due to electrostatic interactions in sandstone reservoirs. If
pH < 8.2, the adsorption of the anionic polymer would be higher compared to cationic
polymer in limestone reservoirs. Polymers for EOR are supplied in dry powder form;
however, the equipment required to dissolve these polymers are bulky, which may not
found space on offshore platforms. Polymer solutions experience a very high shear rate
that may cause shear degradation in the polymer. A very high initial viscosity of
polymer makes it more difficult to inject into the reservoir. If the polymer solution is
not prepared properly, debris can plug the pore space around the well-bore [30].

1.2 Polymer Systems for Enhanced Oil Recovery

To achieve a favorable mobility ratio, high molecular weight (9–25 million Dalton)
polymers are utilized. High viscosity can be achieved using a low concentration of
high molecular weight polymers. Other factors that affect the viscosity of polymer
solutions are polymer molecular weight, temperature, salinity, and concentration of
divalent ions. Subsequent sections will discuss various types of synthetic and bio-
polymers for EOR applications.

1.2.1 Synthetic polymers

A number of polymers have been investigated in both laboratory and field in last few
decades. The most important polymers used in EOR are acrylamide-based copoly-
mer and terpolymer. Polyacrylamide was among the first polymers that were used as
mobility control agents in EOR. Many attempts were made to modify the polyacryl-
amide by copolymerizing acrylamide with different suitable monomers that are more
tolerant to temperature and salinity.
Partially hydrolyzed polyacrylamide (HPAM) is widely used in EOR applications
[31–36]. The structure of the HPAM is shown in Fig. 4. The aqueous solution of the
HPAM is negatively charged and highly viscous. The presence of negative charges on
the backbone causes a stretching of polymer chain due to electrostatic repulsion. This
stretching results in a high viscosity of the polymer. The fraction of acrylate group (the
Fig. 4 Structure of HPAM
26 Enhanced Oil Recovery 1051

degree of hydrolysis) usually ranges between 25– and 35% [37]. A higher degree of
hydrolysis causes the distortion of flexible chains that can result in viscosity reduction
and flocculation in hard brine. The properties of HPAM can be tuned by changing the
acrylate contents in the copolymer. The negative charges induced due to hydrolysis
increase the viscosity of the polymer; however, the higher percentage of acrylate group
in the HPAM can weaken the tolerance to salinity and hardness [38]. Hydrolysis of
HPAM strongly depends on the pH and temperature [39]. The rate is speedy at high
temperatures compared to low temperatures [40]. Based on the available data, HPAM
is stable up to 70  C in presence of divalent cations; however, without divalent ions,
HPAM found to be stable at 100  C [41, 42]. Therefore, HPAM is recommended only
in the reservoir having the temperature up to 75  C if the divalent concentration is high
in the formation brine. However, if the divalent concentration is less than 200 ppm, its
application can be extended up to 100  C. HPAM exhibit excellent rheological
properties that depend on polymer concentration, temperature, salinity, pH, shear
rate, and the presence of other chemicals such as surfactants and alkalis. Salts cause
a dramatic reduction in the viscosity of the HPAM due to charge screening effect
[43]. Salts bring the cations in aqueous solution, which interact with the anions present
on the polymer backbone. These interactions result in lowering the viscosity of the
polymer. In general, the application of HPAM is limited to the reservoir with low
temperature and low salinity. For HTHS reservoirs, different copolymers have been
developed by incorporating more salt and temperature tolerant monomer. In last four
decades, a number of attempts were made to design the water-soluble polymers for
HTHS reservoirs. These efforts were focused mainly on the development of
acrylamide-based copolymer by incorporating a suitable monomer, hydrophobically
modified polyacrylamide, and thermos-thickening polymers [44–50].
The first category consists of those polymers where acrylamide monomer is
copolymerized with more temperature and salt tolerant polymers. The two most widely
reported polymers include a copolymer of acrylamide (AM) and 2-acrylamido-2-
methylpropane sulfonic acid (AMPS) and acrylamide-vinylpyrrolidone (AM/VP)
copolymer. Sulfonate makes it resistance to divalent and salinity in general. A typical
structure of AM/AMPS copolymer is given in Fig. 5. The AM/AMPS copolymer
showed good thermal stability up to 110  C and no viscosity changes were observed
after 16 days. However, at 120  C, the polymer lost 50% of its original viscosity

Fig. 5 A typical structure of

AM/AMPS copolymer
1052 M. Shahzad Kamal and A. S. Sultan

after 10 days of aging [51]. Other monomers that can polymerize with acrylamide
include: N-phenylmaleimide [52], allylbenzamide [53], sodium vinyl sulfonate
[54], 2-(acrylamido)-2-methylpropyl trimethylammonium chloride [55], sodium
3-acrylamido-3-methylbutanoate [56], carboxymethylcelluloselose [57], ether
carboxylate [58], and sodium (acrylamido) methanesulfonate [53]. Although
some of these copolymers have high thermal stability at harsh conditions com-
pared to HPAM, their cost is higher compared to HPAM.
The second category of the polymers includes hydrophobic associating polymers,
which contain hydrophobic monomer in the main hydrophilic chain. In aqueous solu-
tion, the association among different hydrophobic groups results in the formation of
hydrophobic microdomains [59]. At higher concentrations, the formation of network
structure takes place due to intermolecular associations. The hydrophobic monomer can
be incorporated by grafting on the backbone or by copolymerizing [60]. The viscosity of
HPAM changes gradually by increasing polymer concentration; however, the viscosity
change of hydrophobically modified polymers with concentration is abrupt as a result of
the aggregation of hydrophobic groups [45]. Similarly, the adsorption behavior of
associating polymers is different from the adsorption behavior of the unmodified
counterpart. The adsorption isotherms of associating polymers have different shapes
compared to their unmodified counterpart without any plateau due to multilayer adsorp-
tion as shown in Fig. 6. Multilayer adsorption of associating polymers causes high
adsorption density of associating polymers that result in an abrupt decrease in the
viscosity of the aqueous solution. Although in last few years, the number of publications
on associating polymers has been increased tremendously, their field applications are
limited. One pilot test was performed using associating polymer in China [61].

Fig. 6 Adsorption behavior of polyacrylamide (PAM) and hydrophobically modified polyacryl-

amide (HAPAM) [60]. (© Elsevier, published with the kind permission of Elsevier.)
26 Enhanced Oil Recovery 1053

The third category of modified polymers consists of thermo-thickening polymers that

contain thermo-sensitive hydrophobic monomers as pendant chains on the hydrophilic
backbone. These thermo-sensitive monomers are soluble in water at low temperatures
but show a lower critical solution temperature. By increasing temperature, the hydro-
phobic chains become insoluble in water and associate to form a microdomain [62]. The
viscosity of thermo-thickening polymers increases with temperature after a critical point.
Poly (acrylamide-co-2-acrylamido-2-methylpropane sulfonic acid)-g-poly acrylamide-
co-N-(1,1-dimethyl-3-oxobutyl) acrylamide is typical example of thermo-thickening
polymer [63]. A comparison of viscosity behavior of different polymers is shown in
Fig. 7. This unique behavior of thermo-thickening polymers helps in easy injection due
to the low viscosity at low temperatures. On the other hand, the high temperature inside
the reservoir causes an increase in the viscosity that is a primary requirement for EOR.
Thermo-thickening polymers achieve high viscosity only after critical concentration.
Therefore, use of high concentration makes the process costly.

1.2.2 Biopolymers
Biopolymers have also been used in EOR applications due to their good water
solubility and tolerance to salts. Xanthan gum, guar gum, carboxymethylcellulose,
hydroxyethylcellulose, welan gum are some typical examples of biopolymers [64].
Xanthan gum is an extracellular polymer which is obtained mainly by the
bacterium Xanthomonas [65]. A typical representation of xanthan repeating unit is
given in Fig. 8. Xanthan gum mainly consists of glucose units, mannose units, and
glucuronic units. In addition, side chains of xanthan gum also consist of charged

Fig. 7 Comparison of viscosity of different polymers at different temperatures [44]. (© John Wiley
and Sons, published with the kind permission of John Wiley and Sons.)
1054 M. Shahzad Kamal and A. S. Sultan

Fig. 8 Representation of
chemicals structure of xanthan
repeating unit [65]. (© John
Wiley and Sons, published
with the kind permission of
John Wiley and Sons.)

moieties (acetate and pyruvate). The chain length of xanthan gum is similar to that of
acetate; therefore, it is also being used in different applications such as viscosifier in
food ingredients, in cosmetics, and in pharmaceutical [66–68]. The average molec-
ular weight of typical xanthan gum used for EOR application is between one million
Dalton and 15 million Dalton. Its thermal stability depends on the brine salinity. At a
particular temperature, xanthan gum is thermally stable if it achieves an ordered
structure by addition of salts. However, if it attains a disordered structure by adding
salts, it is not thermally stable at that temperature and salinity. For example, a
xanthan solution was thermally unstable at 90  C when its salinity was 1 g/L
(disordered structure). But a solution with a salinity of 50 g/L was stable at this
temperature (ordered structure) [69]. In summary, the rheological behavior is favor-
able in high salinity conditions; however, it is not thermally stable at high temper-
atures (>90  C) and the addition of a high amount of salts causes the conformational
transition [70, 71]. The adsorption of xanthan gum on different rock surface depends
on rock type, pH, temperature, and salinity. The other issues associated with xanthan
gum are its high cost, biodegradation, biochemical reactions, and difficulties asso-
ciated with injectivity [72, 73]. The issue of biodegradation is usually overcome by
adding a suitable biocide such as formaldehyde [74].
Hydroxyethylcellulose (HEC) is a nonionic hydrophilic polysaccharide and con-
sidered as environmental friendly polymer owing to its properties. HEC have better
injectivity compared to xanthan gum [75]. It can be hydrophobically modified to
improve its viscosity and thermal stability at low concentrations. A typical structure
of hydrophobically modified HEC is given in Fig. 9. Addition of sulfonate also
improves the thermal stability of the polymer. Another neutral polysaccharide
schizophyllan (Fig. 10) was reported for EOR applications [76]. At high salinity,
schizophyllan can maintain viscosity for a long time. A field test conducted using
schizophyllan showed improved oil production after injection.
26 Enhanced Oil Recovery 1055

Fig. 9 Schematic –
O +
representation of modified SO3Na
HEC [77]. (© Elsevier,
published with the kind OH OH
permission of Elsevier.) O

O
HO O

HO O O O O
O

OH OH

O O
n-C16H33

OH
OH
OH
CH2

HO
O

OH
O
CH2 O CH2
HO HO O
O OH
O
OH O
O
HO OH
CH2 O
OH

Fig. 10 Molecular structure of schizophyllan [76]. (© Gao (author), (https://link.springer.com/

article/10.1007/s13202-015-0213-7#aboutcontent), according terms of Creative Commons Attri-
bution 4.0 International License (http://creativecommons.org/licenses/by/4.0/).)

In summary, various biopolymers have been evaluated for EOR applications.

Despite the fact that biopolymers have good tolerance to temperature and salinity,
their poor biodegradation limits their field applications.

2 Drilling Fluids

Drilling of the well bore is the first step in the exploration and recovery of oil
(Fig. 11). Drilling fluids are mainly composed of liquids, solids, and chemical
additives [78]. Drilling fluids are primarily used in the drilling operations to perform
different functions such as removing the formation cutting from the downhole,
stabilizing the downhole formation, preventing loss of fluid, and lubricating the bit
1056 M. Shahzad Kamal and A. S. Sultan

Fig. 11 Schematic diagram

of drilling process
[80]. (© The authors, (http://
www.mdpi.com/1996-1073/
10/4/540), according terms of
Creative Commons
Attribution 4.0 International
License (http://
creativecommons.org/
licenses/by/4.0/).)

and drill string [79]. In any drilling operation, drilling fluids are injected down
through a drill string that returned to the surface in the annulus formed by borehole
wall and bring back the formation cuttings. Before injecting again, the chemical and
physical properties of the fluid are tailored again by adding one or more additives.
The formulation of drilling fluid is very important to preserve the rock integrity and
permeability of the formations during the process. Therefore, the final selection of
drilling fluid additives decided after studying the reservoir rock characteristics. The
performance of drilling through high permeability zones or through shales rocks
(soft rocks) usually results in formation damage. The formation damage occurs
because of the invasion of drilling fluids into the formation. The invasion of drilling
fluids also results in shale swelling.

2.1 Classification of Drilling Fluids

Drilling fluids are classified into various categories based on the phase of fluid,
alkalinity, dispersion ability, and several types of additives used for specific formu-
lations such as pH control agents, weight control agents, viscosity control agents,
fluid loss control agent, and shale inhibition. The careful selection of drilling fluid
additives is very influential on the performance of drilling fluids. The general
selection of drilling fluid is carried out based on petrophysical data, geology, and
previously available drilling field data. Drilling fluids are classified into various
categories (Fig. 12).
Gas-based drilling fluids are employed to transfer rock cuttings from bottom hole
to the surface with high speed along with a minimum fluid loss in the formations. It
was observed that problems occurred with extreme complex formation reservoirs
where the lifting of drilled cutting could not be completely addressed. Shale
26 Enhanced Oil Recovery 1057

Drilling fluid

Gas/Air Foam Liquid

Oil-based Water-based

Fig. 12 Classifications of drilling fluids

reservoirs showed enhanced drilling speed with the gas drilling fluid system. It is
difficult to maintain the balance between formation pressure and column pressure
[81, 82].
Foam-based drilling fluids are formed by embedding gas/air bubbles into liquids
and stabilized by surfactants. Foam-based drilling fluids are mainly used to prevent
lost circulation during the drilling process. Foam-based fluids showed enhanced
drilling performance in terms of quick recovery of drilled cutting towards the
surface. However, the stability of foam-based drilling fluids is complicated towards
the performance of drilling fluids compared to the conventionally used liquid based
drilling fluids [83, 84].
Oil-based drilling fluids are most efficient compared to the all other gas-, foam-,
or water-based drilling fluids. Oil-based fluids show better rheological properties,
thermal properties, and inhibitive properties for water-sensitive shale reservoirs.
However, oil-based drilling fluids are more expensive and toxic compared to other
drilling fluids. Disposal to open surface and environmental concerns on oil base
fluids are restricting their application. Therefore, water-based drilling fluids are
widely recommended for drilling operations [85–88].
Water-based fluids are economical, environmentally friendly, and easily prepared
for required drilling formation. The main components of water-based drilling fluid
formulations are usually water (continuous phase), viscosity builder (clays or poly-
mers), and other organic agents to control the various properties such as rheology
and filtration properties. The water used may be of very high salinity; therefore,
alkalis such as potassium hydroxide are used to maintain the pH at which polymers
and clays work effectively. Some high specific gravity materials such as barite or
hematite are used to attain the required density of drilling fluids. The presence of
additives in water-based drilling fluids enhances the rheological properties (viscos-
ity, gel strength, yield stress), reduces the coefficient of friction, and enhances the
density of drilling fluid which is used to maintain the balance between column and
formation pressure. However, water-based fluids show poor fluid loss properties and
1058 M. Shahzad Kamal and A. S. Sultan

sensitive to shale formations. To avoid fluid loss and inhibit the shale swelling, the
high molecular weight polymers are employed [89–92].
Water-soluble polymers are used in drilling fluids as a viscosity enhancer, floc-
culants, de-flocculants, filtration control agents, and shale stabilizer [79]. Due to
interactions of drilling fluid with clay-bearing shale, borehole instability may occur.
Borehole stability is one of the many functions that a drilling fluid must fulfill. The
water of the drilling fluid formulations can interact with shale and alter the properties
of the exposed subsurface. The shale can swell or become mechanically from soft to
hard which affect the drilling efficiency. Nature of the water is an important and
decisive factor that how it will interact. Freshwater has more effect compared to
saline water. Therefore, some salts like sodium chloride and potassium chloride are
added to reduce the swelling of shale. Polymers can be used as shale stabilizer as an
added electrolyte may not perform effectively. Polymers can be used alone or with
electrolytes. The main selection criterion of the polymer is its compatibility with
other drilling fluids chemical in addition to its performance as shale stabilizer.

2.2 Evaluation and Screening Techniques

Drilling fluids are characterized based on three different classifications: rheology,

fluid loss, and reactivity.
Rheology is a valuable tool for characterization of drilling fluids. Both dynamic
and steady shear analyses of drilling fluids are performed to simulate the behavior in
real field conditions. Steady shear rheological analysis of drilling fluids is carried out
at different shear rates as the polymer may experience a range of shear rates during
circulation. The shear rates experienced by the polymer in drill pipe, in the annulus,
and at bit nozzle are usually 103 s 1, 102 s 1 and 105 s 1, respectively [93]. On the
other hand, dynamic tests are used to investigate different material properties such as
gel strength, gel formation, and low shear viscosity. The creep-recovery test, the
relaxation test, amplitude sweep test, and the frequency sweep test are few examples
of rheological analysis important for drilling fluid evaluation. The creep-recovery
test is important to understand the material response under constant stress. Linear
viscoelasticity is characterized by amplitude sweep test while the frequency sweep
test is used to determine the zero shear viscosity and structural strength [93].
Fluid loss is measured using a set of different techniques such as API filtrate, leak
off, high-pressure high-temperature filtrate, and dynamic filtrate. Filtration test is
performed to evaluate the drilling fluids at different temperature and pressures using
multiple filter press stages [94]. Static filtration test simulates the condition of
filtration process in drilling operations when drill string at rest and no drilling is
carried out, while dynamic filtration test simulates the true filtration process when the
drill bit is rotating at high shear rates [95]. Cation exchange capacity (CEC) is an
important technique to determine the reactivity of drilling fluids and mainly depends
on the pH and types of exchangeable cations in the bentonite used in drilling fluid.
According to API standards, 2 ml of drilling fluid is mixed with sulfuric acid,
hydrogen peroxide, and methylene blue solution with well stirring. The reactive
26 Enhanced Oil Recovery 1059

Fig. 13 FESEM of: (a) CMC, (b) PAM, (c) CMC-g-PAM [104]. (© The authors, (https://www.
sciencedirect.com/science/article/pii/S1110062114200109#!), according terms of Creative Com-
mons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/).)

contents of drilling fluid could be determined by putting a drop of mixture on filter

paper. A green or blue halo was formed around the droplet indicates the end point of
the test. The CEC of drilling fluids is reported in milliequivalents per ml of drilling
fluid [96, 97]. Density measurement of drilling fluid is also important to simulate the
commune pressure in drilling well using density meter. The carefully designed
density of drilling fluid is used to maintain the balance between formation pressure
and column pressure [98].
Bentonite inhibition tests are also used in the characterization of drilling fluids
[99]. This test is used to determine the inhibition capacity of drilling fluid for reactive
shale formations and maintaining low rheological properties. For this test, the
weighted amount of reactive drilled cuttings is dispersed in drilling fluid for 16 h
according to API standards in the hot rolling oven. After 16 h, the remaining weight
of drilled cuttings was measured and percentage recovery of cuttings are reported
[100, 101]. Drilling fluids are characterized to measure chemical contents, solid
contents, pH, and lubricity. Particle size measurement can provide an indication of
flocculation or deflocculation [99].
Zeta potential of drilling fluids is measured using zeta potential analyzer to
determine the stability of drilling fluids and dispersion of drilling fluid additives.
Zeta potential was measured as a function of drilling fluid additives such as pH and
electrolyte concentration. Zeta potential values are reported in positive and negative
magnitude. The lower values of zeta potential represent the low stability of drilling
fluids, while higher values indicate the better stability of drilling fluids [102, 103].
Field emission electron microscope images (Fig. 13) are used to determine the
morphology of polymer and grafted polymers used as drilling fluid additives [104].

2.3 Polymer Systems for Drilling Fluids

Several polymers have been investigated in drilling fluids such as xanthan gum, guar
gum, flaxseed, hydroxyethyl cellulose, carboxymethyl cellulose, and acrylamide-
acrylate copolymers [105]. A polymer with narrow molecular weight range and low
molecular weight acts as fluid loss reducer, while a polymer with high molecular
weight and broader range functions as flocculants and viscosifier [106].
1060 M. Shahzad Kamal and A. S. Sultan

Among synthetic polymers, acrylamide-acrylic acid copolymers with various

ratios are most commonly used polymers for drilling fluid applications. Anionic
partially hydrolyzed polyacrylamide is most reported polymer for drilling fluid
applications. Partially hydrolyzed polyacrylamide is mainly used as flocculants
and shale stabilizers due to its high molecular weight. Acrylamide can be
copolymerized with various other monomers to have improved properties such as
thermal stability. The cationic polymers obtained by copolymerization of positively
charged monomer with acrylates or acrylamide are also used in drilling fluids as
flocculants. Polymer nanocomposites containing different nanoparticles such as
TiO2, ZnO, SiO2, and CuO are also investigated in drilling fluids [89, 107, 108].
Natural and modified natural polymers are also common in the industry. Poly-
saccharides such as xanthan gum, guar gum, and scleroglucan gum are used as a
rheology modifier in drilling fluids. Polysaccharides are complex structures with
high molecular weight and have a high tolerance to salinity. Several grades of natural
polymers are available in the market to be used in drilling fluid formulations.
Another important natural polymer is starch, which is obtained from either corn or
potatoes. It is widely used in drilling fluid formulations as fluid loss control. Among
modified natural polymers, anionic carboxymethylcellulose (CMC) is most com-
mon. CMC is a linear polysaccharide modified with carboxylic acid groups and is
anionic in nature. Depending on molecular weight and degree of the substitution, it
can be used as fluid loss control and rheology modifier in drilling fluid formulations.
Hydroxyethylcellulose (HEC) is nonionic in nature and mainly used as viscosifier.
Carboxymethyl starch is a modified form of starch and has higher thermal stability
compared to starch. It is used in drilling fluid formulations as fluid loss reducer.

3 Hydrate Inhibition

Another interesting application of water-soluble polymers is as kinetic hydrate

inhibitors in gas transmission lines. Gas Hydrates are solid crystalline ice-like
compounds in which gas molecules are trapped in a water cavities at moderate
pressures and low temperatures [109–112]. The gas molecules can be propane,
ethane, isobutene, methane, and CO2. Gas hydrates can be classified as structure
I (sI), structure II (sII), structure III (sIII), and structure T (sT) [113–115]. Formation
of gas hydrate in gas transmission lines is a serious problem and can result in
blockage of pipelines and the explosion of pipelines. The gas hydrates result in
severe economic losses in addition to putting hazard to human safety [116–120].
Different methods are being used in industry to avoid hydrate formation. These
methods include insulation of pipelines, lowering the water level from a gas stream,
changing the operational parameter to keep conditions unfavorable for hydrate
formation, and utilizing chemicals [121–123]. Insulation and removal of water are
not common due to economic issues as they involve huge cost. Injection of
chemicals to delay or prevent hydrate formation is common in the industry. These
chemicals are termed as gas hydrate inhibitors and can be classified as thermody-
namic hydrate inhibitors (THIs), kinetic hydrate inhibitors (KHIs), and
26 Enhanced Oil Recovery 1061

anti-agglomerates (AAs). THIs change the thermodynamic conditions to that values

where hydrate formation is not favored [124–129]. Various organic compounds that
are used as THIs include methanol, monoethylene glycols, and an electrolyte such as
NaCl. The major drawback associated with using THIs is the cost of the process as
high concentrations (10–50%) of the chemicals are required [130, 131]. Storage of
bulk amount of chemicals in the offshore environment is not recommended and
practical. Anti-agglomerates prevent the agglomeration of hydrates but could not
stop the hydrate formation. In presence of AAs, the formation of hydrate takes place
in form of finely suspended slush and gas lines can be cleaned easily
[132–134]. KHIs are usually water-soluble polymers and prevent/delay nucleation
and crystal growth. This way hydrate formation can be avoided due to lesser
residence time the pipelines compared to hydrate formation time. Several explana-
tions were proposed to explain the hydrate inhibition using water-soluble polymers.
One explanation is that KHIs adsorb on the surface while perturbation of water
structure can also inhibit the hydrate formation [135–137]. Another mechanism
suggests that polymer chain interact and interfere with the nucleation and/or crystal
growth. In this way, guest molecules could not enter into the crystal lattice
[138, 139]. The major advantage of using KHIs is that they are used at a very low
concentration (0.1–1 wt%), which results in lower cost and easy handling and
storage of the chemicals.

3.1 Evaluation and Screening Techniques

Potential water-soluble polymers are assessed with the high-pressure autoclave, the
high-pressure microdifferential scanning calorimetry (HP-μDSC), Raman spectros-
copy, nuclear magnetic resonance spectroscopy, the flow loop, the rocking cell,
X-ray diffraction, conductivity measurements, and molecular simulation
[116, 140–143]. Most of the techniques are used to measure either hydrate nucle-
ation temperature or induction time. Types of the test may be either isothermal
(to measure the hydrate induction time) or temperature ramp (to measure the hydrate
nucleation temperature). Details of test methods are provided in subsequent sections.

3.1.1 Autoclave System

Hydrate induction time and temperature can be determined using an autoclave. In
autoclave systems, hydrate formation is inferred when a sudden pressure drop occurs
due to gas uptake into hydrate cages [144–147]. Constant cooling or isothermal
methods can be implemented using an autoclave (Fig. 14). In the constant cooling
method, the cell is cooled at a low cooling rate at a constant stirring speed. A typical
constant cooling plot is shown in Fig. 15. During cooling, pressure drops at a
constant rate due to the decreasing temperature before hydrate nucleation. Due to
the slow cooling rate, hydrate formation is detected as the point of deviation from a
linear decrease in pressure due to gas being used in hydrate formation. Torque data
also indicate hydrate formation with an increase of torque signaling hydrate forma-
tion. Gas consumption data can also give information about hydrate formation as gas
1062 M. Shahzad Kamal and A. S. Sultan

Fig. 14 A schematic diagram

of a high-pressure autoclave
system [148]. (© American
Chemical Society, published
with the kind permission of
American Chemical Society.)

80 25

75
To Ta 20
Pressure [bar]

70
15
Tcell[°C]

65
10
60

5
55
Pressure [Bar]
Temp Cell [°C]
50 0
0 200 400 600 800 1000
Time [min]

Fig. 15 Results of a typical constant cooling test using an autoclave [148]. (© American Chemical
Society, published with the kind permission of American Chemical Society.)
26 Enhanced Oil Recovery 1063

7 9.6
Gas Consumption [bar]
Temp Cell [°C]
6 9.5
Gas Consumption [bar]

5 9.4

Tcell[C°]
4 9.3

3 9.2

2 9.1
ts t1 t3
1 9.0

0 8.9
0 100 200 300 400
Time

Fig. 16 Results of a typical isothermal test using an autoclave [148]. ©American Chemical
Society, published with the kind permission of American Chemical Society

consumption increases suddenly due to hydrate formation. In the isothermal method,

fluids in the cell are subjected to a constant temperature at a constant stirring speed.
A typical isothermal plot is shown in Fig. 16. The time where the first pressure drop
is observed is called the induction time (ti). The total time taken for the formation of
the hydrate plug (ta) can also be measured. The period between ta and ti is known as
the slow growth period.

3.1.2 High-Pressure Microcalorimeter

The high-pressure microcalorimeter consists of multiple high-pressure cells.
HP-μDSC can operate in the temperature ramping or isothermal modes. In the
temperature ramping mode, a constant cooling is applied, and as the crystal
formation is an exothermic process, hydrate nucleation temperature is determined
from the first exothermic peak. A typical temperature ramp plot obtained using an
HP-μDSC is shown in Fig. 17, where the first exothermic peak is observed at
12.5  C. During the heating cycle, hydrate decomposition can be detected using
endothermic peaks. In Fig. 17, the two endothermic peaks are due to the melting of
ice (0  C) and the melting of hydrates (13  C). A typical isothermal plot obtained
using an HP-μDSC is shown in Fig. 18. Hydrate nucleation time is the time taken to
observe the exothermic peak. Hydrate conversion can also be obtained by integrat-
ing the heat output with respect to time [149]. The advantage of HP-μDSC is that it
requires very small amount of inhibitor and the test takes shorter time compared to
other techniques.
1064 M. Shahzad Kamal and A. S. Sultan

15 20
15
10 10
exo
A 5

Temperature (°C)
Heat flow (mW)

0
5
–5
–10
0
–15

Water (gas)
–20
–5 Water (No gas) –25
Temperature (°C)
B –30
–10 –35
0 1 2 3 4 5 6 7
Time (h)

Fig. 17 A typical temperature ramp plot obtained using an HP-μDSC [150]. (© American
Chemical Society, published with the kind permission of American Chemical Society.)

Fig. 18 A typical temperature ramp plot obtained using an HP-μDSC for fresh and memory
solutions [150]. (© American Chemical Society, published with the kind permission of American
Chemical Society.)

3.1.3 Rocking Cell

The rocking cell equipment has several cells and can be used to test the effect of
inhibitors on gas hydrate nucleation, growth, and decomposition. The stainless steel
cells can withstand high pressures. A steel ball is placed inside the cell which rolls
back and forth along the length of the cell to agitate the solution inside. Once the
26 Enhanced Oil Recovery 1065

Fig. 19 Results of a typical temperature ramp test conducted using a rocking cell [151].
(© Elsevier, published with the kind permission of Elsevier)

cells are loaded with the desired solution, they are placed in a cooling bath controlled
by an external refrigerator. The temperature and pressure of the cells are observed by
the data acquisition system. The cells are continuously rocked and the hydrate
formation is signaled when the steel ball can no longer move freely inside the cell.
Just as with HP-μDSC, both constant temperature and ramping experiments can be
performed. The advantage of the latest model of the rocking cell equipment is that
several experiments can be performed at the same time, giving good statistical data
with fewer runs. In the temperature ramping mode, the performance of the inhibitor
is evaluated in terms of the hydrate nucleation temperature. Results of a temperature
ramping test are shown in Fig. 19 and the black solid line is the reference obtained
without rocking. Pressure decreases linearly during cooling and increases linearly
during heating due to thermal contraction and expansion, respectively. In the tem-
perature ramping experiment with rocking (red dashed line), pressure decreases
linearly during cooling due to thermal contraction up to point A. Pressure drops
faster at the onset of nucleation of the hydrate due to high gas consumption during
hydrate formation. Hydrate decomposition can also be studied using the temperature
ramping mode. A Linear increase of pressure (point B) with temperature indicates
complete hydrate decomposition [151]. The strength of an inhibitor can be evaluated
using the time taken for hydrate nucleation at a constant temperature.

3.1.4 Flow Loop Apparatus

The flow loop apparatus has been extensively used in the evaluation and character-
ization of hydrates under a wide range of conditions [152–158]. The laboratory flow
loop apparatus is typically made of stainless steel and essentially composed of a pipe
and a pump with a sight glass and a camera used for visual observation and
1066 M. Shahzad Kamal and A. S. Sultan

recording. Water injection and the flow regime is controlled using pumps. The
temperature is normally controlled using pump-fed water and cooling is achieved
by circulating a coolant such as ethylene glycol. Pressure and temperature inside the
pump, which are used to monitor hydrate formation, is monitored using temperature
and pressure sensors [159]. The flow loop apparatus is typically used by oil compa-
nies to simulate field conditions in the final stages of evaluation. It is relatively
expensive than the high pressure autoclave and the rocking cell equipment. How-
ever, the flow loop apparatus can give much more realistic values and assessment of
the behavior as the tests will be conducted under real field conditions.

3.1.5 Advanced Evaluation Techniques

With the advancement in technology, several novel techniques and methods have
been developed to evaluate the performance of KHIs. Ohno et al. used solid state 13C
NMR to analyze hydrate formation with and without kinetic inhibitors [160]. Lee
et al. also used solid state 13C NMR to analyze hydrate formation behavior of methane
and natural gas in the presence and absence of monoethylene glycol [161]. Daraboina
et al. investigated the formation kinetics of methane/ethane/propane hydrates using
the 1H nuclear magnetic resonance imaging technique in the presence of biological
and commercial inhibitors [162]. The technique is a useful tool particularly for
biological inhibitors, which are available in limited quantities. Yang and Tohidi
used the ultrasonic test technique for the evaluation of KHIs [163]. Karamoddin
and Varaminian investigated the tetrahydrofuran hydrate formation behavior in the
presence of different inhibitors using conductivity measurements [164].

3.1.6 Molecular Simulations

Molecular simulation technique has been utilized in hydrate studies by several
researchers [165–176]. Baez and Clancy [169] used molecular dynamic (MD)
simulations to study crystal growth. A spherical hydrate crystal was implanted in
the melt to monitor the kinetics of growth and dissolution of a hydrate crystal and they
reported slow crystal growth. In another study, Ota and Qi [177] used MD simulations to
investigate the nucleation process of methane hydrates. MD simulations of mixtures of
methane and water molecules placed in a cubic cell were used to determine that the
nucleation process has three stages. In the first stage, gas molecules undergo a dispersive
process followed by water molecules making hydrate cavities in the second stage and
finally the hydrate structure becoming steady in the third stage. Other research groups
have also studied crystal growth of gas hydrates using MD simulations [178, 179].
Anderson et al. [180] projected the hydrate inhibition efficiency of polyethylene
oxide (PEO), PVP, poly(vinyl caprolactam) (PVCap), and poly (N-methyl,N-
vinylacetamide) (PVIMA). They found a correlation between the degree of inhibi-
tion and the free energy of binding between the inhibitor and the hydrate crystal
surface. Experimental data support this conclusion with the most effective inhibitor
(PVIMA) having the highest negative binding energy ( 45.8) and the least effective
inhibitor (PEO) having the lowest negative binding energy ( 0.2). Moon et al. [181]
found a correlation between the inhibition mechanism of PVP and the surface energy
using simulations. They showed that PVP increases the time taken to form the
26 Enhanced Oil Recovery 1067

critical nucleus when the surface energy of the interfacial region is increased. Storr
et al. [182] successfully designed and evaluated quaternary ammonium zwitterions
based on inhibitors using MD simulations. Zheng [183] used MD simulations to
investigate the effects of the molecular weight of hyper branched polyesteramides
and showed that low molecular weight inhibitors inhibit crystal growth but do not
prevent crystal growth. On the other hand, high molecular weight inhibitors desta-
bilize the crystals and prevent further crystal growth.

3.2 Polymer Systems for Kinetic Hydrate Inhibition

Polymer-based KHIs are primarily vinyl lactam polymers, amide polymers, and
natural polymers. Typical examples of vinyl lactam polymers are PVP, PVCap,
poly (N-vinyl piperidone), and vinyl pyrrolidone/vinyl caprolactam copolymers.
Amide polymers are mainly acrylamide-based polymers and vinyl amide polymers.
Natural polymer KHIs are mainly starch, chitosan, and amino acids.
Poly (vinyl pyrrolidone) is most reported KHI in the scientific literature due to its
several advantages such as low cost and availability of literature. The structure of
PVP is given in Fig. 20. Currently, PVP serve as a benchmark to compare the
performance of modern polymeric KHIs. Typical molecular weights of commercial
PVP range from 10,000 to 350,000. Surface adsorption is the main mechanism of
hydrate inhibition using PVP. PVP shows good performance at low subcooling
conditions and it is not an efficient KHI at high subcooling conditions
[184]. PVCap is another important kinetic inhibitor, which has been used in industry
and compared with PVP for its inhibition performance. Under different conditions,
the performance of PVP and PVCap differ and there is no well-defined rule to predict
which inhibitor will be more effective at given conditions. Additional experimental
work is required to understand the inhibition performance at various given condi-
tions. Poly (N-vinyl piperidone) is another less common investigated polymer for
hydrate inhibition applications. Its inhibition performance was found to be interme-
diate between PVP and PVCap [185]. To utilize the relative advantages of different
polymers, several copolymers and terpolymers such as vinyl pyrrolidone/vinyl cap-
rolactam copolymer and vinyl pyrrolidone/vinyl caprolactam/dimethylaminoethyl

Fig. 20 Structure of PVP (a) a b

and PVCap (b)

CH2 CH CH2 CH
n
n O
N
N
O
1068 M. Shahzad Kamal and A. S. Sultan

Fig. 21 Structure of a b
polyacrylamide (a) and poly
H2C CH H2C CH
(N-methylacrylamide) (b)

C O C O

N N
H H H3C H
x x

methacrylate terpolymer with different ratios have been evaluated for inhibition
performance.
Amine-based polymers include acrylamide, vinyl amide, and allyl amide
polymers. Polyacrylamide and poly (N-methylacrylamide) have been investigated
and showed similar mechanism as of vinyl lactam polymers [186]. The structure of
these polymers is given in Fig. 21. N-methyl,N-vinylacetamide (VIMA) is the most
monomer from this class. The copolymer made from VIMA and another suitable
monomer from acrylamides, maleimides, and carboxylate have shown good inhibition
performance in various investigations. VIMA/VCap copolymer has shown higher
subcooling compared to poly (N-methyl, N-vinylacetamide) and PVCap [187].
Besides these classical polymers, research has moved to investigate other classes
of polymers. Three dimensional highly branched dendrimeric compounds are also
being utilized in hydrate inhibition [188]. Commercially available “HYBRANES”
are hyperbranched polyesteramide with a number average molecular weight of 1200
[189]. Fluorinated polymers have also been investigated for hydrate inhibition,
despite the fact they showed low inhibition performance compared to nonfluorinated
polymers [190]. Due to the poor biodegradability of the KHIs, the research has
moved towards the development of natural and biodegradable inhibitors. Starch is a
naturally occurring polysaccharide and importantly is biodegradable and environ-
mentally friendly [191]. Another polysaccharide reported for hydrate inhibition is
chitosan that is produced by deacetylation of chitin. Despite the fact that starch and
chitosan have shown good performance as hydrate inhibitors, their field applications
are limited due to high cost and less availability.

4 Conclusion

Water-soluble polymers have been utilized in several gas and oil field applications.
HPAM is most commonly used polymer in enhanced oil recovery and drilling fluids
due to low cost, high viscosity, and commercial availability. However, its perfor-
mance is limited to only low-temperature and low-salinity conditions. For HTHS
applications, acrylamide copolymers such AM-AMPS with better thermal stability
have been developed. Hydrophobically associating polymers and thermo-
viscosifying polymers have been specially designed for HTHS.
The use of polymeric kinetic hydrate inhibitors has gained attention in last few
years due to their effectiveness at low concentration that makes them economic and
26 Enhanced Oil Recovery 1069

environmentally friendly. Poly (vinyl pyrrolidone) and poly (vinyl caprolactam) are
two most commonly reported kinetic inhibitors in literature. To overcome the
limitations of classical polymers, research has shifted towards development of
cheap, high performance, and environmentally friendly green kinetic inhibitors.
The major drawback associated with green kinetic inhibitors is their unavailability
in bulk and high cost. Despite the fact that laboratory research has moved towards
the development of green kinetic inhibitors, their field application is limited.

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Drug Delivery: Localized and Systemic
Therapeutic Strategies with Polymer 27
Systems

Scott Campbell and Niels Smeets

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1081
2 Strategies for Drug Delivery: Organs and Systemic Diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1082
2.1 The Gastrointestinal Tract: Oral Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1082
2.2 Skin: Topical Treatments and Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1086
2.3 The Lungs: Pulmonary Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
2.4 The Brain: Traversing the Blood-Brain Barrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1096
2.5 The Eye: Ocular Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1098
2.6 Other Common Regions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
3 Systemic Controlled Release Case Study: Cancer Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1107
3.1 What Is Cancer? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1108
3.2 Passive Targeting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1109
3.3 Active Targeting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1112
3.4 Alternative Cancer Therapies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1118
4 Current Understanding/Trends and Future Prospective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1121
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1125

Abstract
This chapter expands upon some of the basic concepts regarding drug delivery
and takes a tour through various regions of the body that are commonly treated
locally with controlled release systems, investigating current research and com-
mercial strategies involving the use of polymeric systems within each region after
briefly describing the biology and the typical biological targets of each region.
This section includes drug delivery throughout the gastrointestinal tract and to the

S. Campbell (*)
Department of Chemical Engineering, McMaster University, Hamilton, ON, Canada
e-mail: [email protected]
N. Smeets
EcoSynthetix, Burlington, ON, Canada
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 1079

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_32
1080 S. Campbell and N. Smeets

skin, lungs, brain, and eye, along with several others. The use of polymeric
materials for systemic controlled release is then briefly described and thoroughly
investigated in a case study on the most common target of systemically delivered
nanomedicines: cancer. The chapter concludes with a perspective on where the
field of drug delivery is headed in the future.

Abbreviations
AMD Age-related macular degeneration
AMF Alternating magnetic field
AMT Adsorptive-mediated transcytosis
APC Antigen-presenting cells
BA Bioavailability
BBB Blood-brain barrier
BCNU 1,3-bis(2-Chloroethyl)-1-nitrosourea
BRB Blood-retinal barrier
CNS Central nervous system
COPD Chronic obstructive pulmonary disease
CPT Camptothecin
DNA Deoxyribonucleic acid
Dox Doxorubicin
DSPE Distearoylphosphatidylethanolamine
EGF Epidermal growth factor
EPR Enhanced permeability and retention
EVA Ethylene vinyl acetate
F(ab0 )2 Dimers of Fabs
Fab Antigen-binding fragments
FDA U.S. Food and Drug Administration
FGF Fibroblast growth factor
GI Gastrointestinal
GM-CSF Granulocyte-macrophage colony-stimulating factor
HA Hyaluronic acid
HGH Human growth hormone
HIV Human immunodeficiency virus
HPV Human papillomavirus
IGF-1 Insulin-like growth factor
IgG Immunoglobulin G
IR Infrared
LbL Layer-by-layer
LCST Lower critical solution temperature
LRP Low-density lipoprotein receptor-related protein
MPEG Methyl ether poly(ethylene glycol)
MPS Mononuclear phagocyte system
MRI Magnetic resonance imaging
NCS Nanotoxicological classification system
NIPAM N-Isopropyl acrylamide
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1081

PAMAM Polyamidoamine
PBA Phenyl boronic acid
PBAE Poly(β-amino ester)
PCL Polycaprolactone
PDGF Platelet-derived growth factor
PDMS Polydimethylsiloxane
PEG Poly(ethylene glycol)
PEI Poly(ethylene imine)
PEM Polyelectrolyte multilayers
PEO Poly(ethylene oxide)
PHEMA Poly(2-hydroxyethyl methacrylate)
PLGA Poly(lactic acid-co-glycolic acid)
PMMA poly(methyl methacrylate)
PNIPAM Poly(N-isopropyl acrylamide)
POEGMA Poly(oligoethylene glycol methacrylate)
PPO Poly(propylene oxide)
Ptx Paclitaxel
PVA Polyvinyl alcohol
RGD Arginine-glycine-aspartic acid
RNA Ribonucleic acid
SC Subcutaneous
scFv Single-chain fragment variables
siRNA Small-interfering RNA
SPIONs Superparamagnetic iron oxide nanoparticles
Tg Glass transition temperature
TGF-β1 Transforming growth factor
UV Ultraviolet
VPPT Volume phase transition temperature

1 Introduction

Some of the basic concepts regarding drug delivery are discussed in ▶ Chap. 17,
“Drug Delivery: Polymers in the Development of Controlled Release Systems.”
These include traditional delivery methods, the importance of drug location and
concentration for release, the necessity to complement the properties of the drug with
that of the delivery system, and various techniques to produce polymeric drug
delivery devices, including polymeric implants, hydrogels, and nanomedicines.
This chapter develops on those ideas and concepts to discuss various strategies
for both localized and systemic controlled drug delivery. For localized treatments,
a tour is taken through various regions of the body, including the gastrointestinal
(GI) tract, the skin, the lungs, the brain, the eye, etc., where there is a brief
description of the important biological aspects of the region, followed by an exam-
ination of current and upcoming controlled release strategies using polymeric
1082 S. Campbell and N. Smeets

systems. Only a handful of controlled delivery devices have been commercialized to

date; so much of this discussion involves the current state of research for each given
section. The systemic portion is a case study on various strategies that are being
studied for the treatment of cancer, mostly via the use of polymeric nanomedicines.
The chapter then concludes with a brief discussion on the current trends and a future
perspective on the drug delivery field. This includes some of the primary challenges
that must be overcome to commercialize new controlled release systems that could
benefit people around the world by enhancing the effectiveness, duration, patient
compliance, and the safety of a given treatment, while decreasing the frequency at
which a given treatment is administered [1, 2].

2 Strategies for Drug Delivery: Organs and Systemic

Diseases

Any therapeutic that is intended to be delivered systemically, via oral administration

or parenteral injection, is subjected to modification by the liver and/or clearance by
the kidney. Orally administered drugs additionally have to traverse the varying harsh
pH environment of gastrointestinal (GI) tract and the first-pass metabolism of the
liver. Despite this, the vast majority of drugs are still delivered by these methods. As
the relatively young field of targeted and controlled drug delivery advances, these
traditional methods of administration will be replaced by smarter technologies with
more consistent pharmacokinetics, less side effects, with high levels of patient
compliance.
This section takes a tour throughout various organs in the body and discuss
strategies to deliver drugs to treat diseases associated with these organs. The
importance of targeting polymeric materials to the desired site of action and the
significant differences in treatment strategies that are present depending on
the location are emphasized in this section. For each location, there will be a
description of the biology of the region of the body, highlighting the principle
obstacles that must be overcome to deliver drugs to the location, examples of specific
current or emerging research strategies using polymer-based therapeutics being
developed to improve how medicine can be delivered to these regions, and com-
mercialized treatments and/or the barriers to broad commercialization to treat dis-
eases in the specific organ/region of interest.

2.1 The Gastrointestinal Tract: Oral Delivery

Oral delivery of small molecules is the most common and widely accepted delivery
method. Oral administration systems are generally easy to ingest, pain-free, versatile
in terms of the variety of drugs that can be administered this way, and have high
patient compliance [3]. However, as mentioned previously, there are a wide range of
obstacles that limit the bioavailability (BA) of orally administered drugs. Both the
acidic gastric environment of the stomach and the constant secretion and recycling of
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1083

the protective mucus lining of the GI tract must be overcome before even reaching
the epithelial lining of the intestine, which is the most vital barrier that must be
overcome to achieve efficient oral drug delivery [4, 5]. Furthermore, the fraction of
the initial drug dose that successfully traverses past this epithelial layer and into
the bloodstream must first come in contact with the portal system, where they are
subjected to the hepatic first-pass effect. As a result, even though the majority of
tablet-based drugs that we take are via oral administration, their bioavailability is
very low with low proportions of drug actually reaching systemic circulation. These
obstacles, along with the plentiful number of proteases, nucleases, and lipases
throughout this journey also means that protein therapeutics are particularly difficult
to administer orally, as GI proteases digest 94–98% of orally taken proteins [5].
Early sustained release approaches focused on taking advantage of the differing
pHs throughout the alimentary canal, developing drug-loaded systems that were
stable at low pH (1–5) to bypass the stomach, but dissolve at neutral to higher
pHs (>7.4) to preferentially release the drug in the small intestines [6]. Acrylic-
based polymers that exhibit pH-dependent swelling have been a major focus in the
development of particles that can prevent the release of therapeutics until they reach
specific locations in the GI tract. For example, poly(methacrylic acid) can be blended
with polymers like polyethylacrylate and polymethacrylate to fabricate particles that
are in a collapsed state at low pHs and swell or dissolve at specific higher pHs that
are associated with certain portions of the intestines [4]. These materials can be used
to coat drug pellets or be used as individual microparticles or nanoparticles that have
spatially controlled delivery based on their pH responsiveness. A promising orally-
delivered system involving pH-responsive chitosan-co-poly-γ-glutamic acid nano-
particles that were loaded with fast-acting insulin was shown to result in comparable
blood glucose responses in reaction to a glucose challenges to standard subcutaneous
(SC) doses in diabetic rat models [7]. This is particularly surprising, as even if the
insulin is delivered locally in the intestines, it still has several barriers to overcome,
including the hepatic first-pass system. This nanoparticle system thus represents an
impressive potential non-invasive alternative to current insulin, and possibly many
other therapeutic, delivery strategies. Despite research like this, no pH-responsive
particle systems have completed human trials. Pellets coated with pH-responsive
materials may also prove ineffective as a treatment for all populations, as variations
in pH between individuals and within an individual’s GI tract could severely limit
solely pH responsive therapies [4].
Particles that shield drugs and are also able to infiltrate the mucous layers could
improve the retention time of the drug-carrying vehicles in the intestines, hopefully
leading to longer-term release from orally-administered materials. In order to design
particles for this, more information on the mucous layer must be known. Mucous,
a complex, shear-thinning hydrogel, has evolved to efficiently trap and rapidly clear
pathogens and foreign particulates. This mucous is constantly secreted and turned
over to remove undesired compounds and lubricate the GI tract. There are two
different layers of mucous throughout the alimentary canal: a firmly adherent
mucous layer that neighbors the intestinal epithelium and a thicker loosely adherent
mucous layer. The firmly adherent layer contains cell bound mucins that allow them
1084 S. Campbell and N. Smeets

to adhere to the epithelial layer, while the loosely adherent mucous is less bound to
the surface and experiences a much more rapid turnover than the adherent layer.
Knowing these properties about mucous, several strategies have been employed
in the engineering of polymeric systems that attempt to improve the retention time
of drugs within these mucous layers or to traverse through the mucous to reach the
underlying epithelial cells. Polymers such as poly(acrylic acid), PLA, PLGA, and
poly(sebacic acid) can adhere to mucous via hydrogen bonding, hydrophobic inter-
actions, polymer entanglements with mucins, or a combination thereof [4]. Particles
can also be designed to have a positively charged surface to obtain mucoadhesive
properties, as electrostatic interactions between these particles and the negatively
charged sugar moieties present on mucins can be quite strong [4]. As a result, PLGA
particles have been coated with chitosan and assessed for their mucoadhesive
enhancement as a result of this coating. Small molecule therapeutics, proteins,
and peptides can be encapsulated and shielded from the harsh gastroenvironment
by mucoadhesive polymeric microsphere and nanoparticles. However, passively-
targeted mucoadhesive systems tend to be rather limited in terms of oral adminis-
tration, as nonspecific mucoadhesion to undesired surfaces can readily occur. It is
thought that this nonspecific adsorption would result in a wide range of these
mucoadhesive systems adhering to portions of the loosely connected mucous layer
and rapidly cleared along with it, effectively eliminating the drug carriers just as
efficiently as foreign pathogens would be.
Alternatively, particles can be designed to be hydrophobic and negatively charged.
These particles are designed to reach specific lymphoid tissues in the intestine, called
Peyer’s patches, that are covered with M cells. M cells provide antigen sampling for
immune surveillance and, as a result, these cells have a particularly high transcytotic
capacity [4]. These areas have much thinner and less dense overlying mucin layers, as
they also do not secrete mucous [5]. Polystyrene particles as large as 1 μm in size
(larger is generally better) [5] have been shown to be transcytosed by these M cells
[4]. Targeting ligands, including bacterial adhesins, lectins, and IgA antibodies, can
also be attached to the polymer surface to enhance their chances of transcytosis past
these M cells [5]. However, the efficiency of these processes are questionable, as
Peyer’s patches make up less than 1% of the surface area of the intestines [4], and
studies using glucan nanoparticles have indicated that a majority of the nanoparticles
are taken up by dendritic cells before reaching the bloodstream [5]. The fact that these
particles are endocytosed by dendritic cells in such large proportions could initiate an
immune response, which could be advantageous for the orally administered vaccines
but would generally be undesired.
Nanoparticles can be designed to penetrate the outer mucous layer to reach the
firmly adherent mucous layer to have longer residence times and deliver the drugs
closer to the epithelium. For alternative systems where the nanoparticles are designed
to be delivered into circulation themselves to later release their contents, the pene-
tration of the mucous barrier is necessary first step to reach the underlying absorptive
epithelial cells in the GI tract. Viruses have evolved to penetrate mucous by being
small enough to not be sterically hindered by the mucin mesh of mucous and
possessing a highly hydrophilic surface that lacks any mucoadhesive hydrophobic
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1085

areas [4]. There are several strategies that have been employed in attempt to develop
mucous-penetrating polymeric systems, to varying degree of successes. While there
has not been in vitro or in vivo proof of successful mucous penetration in the GI tract
[4], coating the surface of the drug carrier with a high density of low molecular weight
poly(ethylene glycol) (PEG) appears to be a promising technique. This coats the
entire surface with highly hydrophilic PEG groups, and the high density ensures that
hydrophobic areas are avoided. While this technique hasn’t been observed in the GI
tract in vivo, it has been in vaginal mucous, which could afford similar results for
intestinal applications [8]. If particles like this could shield therapeutics from the
harsh environments prior to the intestines, as well as the degradative enzymes within
the intestines, and subsequently penetrate the mucous lining to the more adherent
mucous layer, they could be retained longer and slowly release and deliver the
therapeutic for prolonged lengths of time. However, one area of concern is that
penetrating nanoparticles may, in some cases, compromise the integrity the mucous
barrier that is essential for our health, and the effect of these systems on the mucous
that they penetrate through must be studied further [4, 5].
To reach the blood stream drugs have to pass through the epithelial layer of the
intestines. The epithelium is composed of villi that dramatically increase the total
absorptive surface area of the GI tract to be 300–400 m2 [4]. The absorptive nature of
these tissues allows for many small molecule drugs to be taken into the blood stream
by passing in between the epithelial cells via the paracellular pathway. However
larger therapeutics, including cancer drug and biologics like antibodies, enzymes,
growth factors, hormones, nucleic acids, and vaccines, must rely on the transcytosis
pathway, where receptors actively bind and guide these materials through the cell in
endosomes while avoiding the degradation pathway [5, 9]. There are several ways
that small nanoparticle systems (<500 nm) loaded with larger therapeutics could be
transported across the epithelium via the transcyctosis pathway, rather than just the
drugs themselves, to enhance the amount of drug that enters the bloodstream by
shielding and protecting them all the way there [9]. This is achieved by actively
targeting specific receptors that are commonly present on intestinal epithelial cells
that allow for efficient transport via the transcytosis pathways. Notably, polymeric
nanoparticles can be tagged with vitamin B12 and the neonatal Fc receptor (FcRn)
to enhance the transport of nanoparticles across the epithelium of GI tract to reach
circulation and areas like the kidneys, liver, lungs, and spleen to release their
drug [5]. Both of these tags have been used to deliver orally-administered insulin
more effectively, with one study using the FcRn receptor being capable of producing
a 15-h hypoglycemic response with a much lower [10], clinically-relevant initial
dose than what has been used for many studies involving orally delivered insulin
(1.1 U/kg rather than 10–100 U/kg) [11].
Many of these polymeric systems, particularly those involving the delivery of
large molecules and biologics, have yet to be developed in a form that is suitable for
human clinical trials. There are still several hurdles to overcome in terms of
improving orally administered therapeutics, such as further improving the bioavail-
ability of these systems, better understanding the differences between in vivo animal
models and human systems, accounting for patient-to-patient variations, and even
1086 S. Campbell and N. Smeets

variations within the patient depending on their lifestyle [5]. Despite this, many of
these methodologies are improving at a rapid rate to the point that they are nearing
commercialization within the next few decades. There will always be an appeal for
advances in oral delivery, particularly if it can be utilized effectively for a wider array
of therapeutics, due to the convenience, compliance, and flexibility of this treatment
method that has the potential to treat more people while lowering hospital visits and
overall healthcare costs.

2.2 Skin: Topical Treatments and Wound Healing

The skin is the largest organ in the human body, and, as such, it is highly important
in providing immunity, and maintaining homeostasis and sensory feedback [12].
As a large, easy-to-access organ, its convenience alone presents as an attractive
alternative to oral delivery and hypodermic injection if an efficient method of
delivery can be achieved through the skin. Delivering materials transdermally
(across the skin boundary) could be a non-invasive, self-administered method to
get drugs into the body while evading the first-pass effect. Drugs delivered via this
method can also be delivered at a constant rate over long durations, and can be halted
on demand by simply removing the system [13]. The first transdermal system that
took advantage of these benefits was a 3-day patch to treat motion sickness. Since
then there are approximately 20 transdermal systems, including nicotine patches,
which have greatly improved the public acceptance of patches [14]. These patches
often utilize hydrogels in the drug-containing reservoir to keep in moisture and
maintain drug activity, and polymeric membranes to control release.
However, as the first line of defense in preventing foreign compounds from
entering the body, the skin is designed to be impermeable to a wide variety of
materials. Consequently, transdermal delivery has been limited to drugs with molec-
ular masses up to only a couple hundred Daltons. In particular, it has proven difficult
to use the transdermal route to deliver hydrophilic drugs, particularly vaccines,
and macromolecules and peptides, including small-interfering RNA (siRNA) and
DNA [15]. Thus, delivering polymeric nanoparticle carriers transdermally also
cannot be done by traditional means, which do not attempt to increase the perme-
ability of the skin.
For transdermal delivery, drugs must traverse first through the outermost layer,
the stratum corneum (10–20 μm thick) [12]. The stratum corneum barrier is a brick-
like structure, where the bricks are nonliving corneocyte cells bourne in the epider-
mis surrounded by a mixture of lipids that are mostly arranged in bilayers. This is
the most difficult layer for even small drugs to pass through, as hydrophobic and
hydrophilic molecules must travel through a tortuous path around the corneocyte
cells though the lipid tails or head, respectively [16]. This is the rate limiting step for
any drug to be delivered transdermally and the skin structure that primarily limits the
number of drugs that can be delivered via the transdermal route. The drugs must then
traverse the avascular viable epidermis (50–1,000 μm thick) to reach the dermis [12].
The dermis is 1–2-mm thick and possesses a rich capillary bed just below
the dermal-epidermal junction where the drugs can be absorbed into systemic
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1087

circulation. Drugs applied topically can also use hair shaft to reach the dermis with
less resistance, and many topical drug delivery utilize this route to one degree or
another (whether it is designed for or not).

2.2.1 Polymeric Microneedles

Since it was established that penetrating through the stratum corneum is the trickiest
step in transdermal drug delivery, a variety of different strategies have been devel-
oped to improve transdermal delivery that focus on the targeted permeabilization of
this outermost layer of the skin [15]. The emergence of technologies that can locally
disrupt the stratum corneum to facilitate transdermal release with improved safety
and efficacy, including chemical enhancers, electroporation, cavitational ultrasound,
thermal ablation, microdermabrasion, and microneedles, are now medically accept-
able. While many of these techniques do not make use of polymers and are thus
outside the scope of this chapter (they are discussed in much greater detail in an
excellent review article [15]), microneedles are one of the most promising tech-
niques for transporting larger therapeutics across the skin. Microneedle systems are
often comprised of polymers to serve their purpose, mainly due to their low cost and
ease of manufacture over metallic microneedles.
Microneedles present as a simple but elegant solution to getting drugs across the
stratum corneum in a minimally invasive manner. By piercing through the stratum
corneum (and often into the epidermis and/or the superficial dermis) microneedles
can: generate micron-scale pathways into the skin to increase its permeability;
actively transport drugs into the skin via a variety of mechanisms; target the effects
only to the stratum corneum; and do all of this in a manner that is considered painless
and well-tolerated that can also be achieved without any specific training [15]. This
is highly advantageous, as needle phobia and inconvenience (due to the fact that
vaccine injections must be performed by a professional) are significant barriers that
limit vaccination coverage [17]. The costs associated with administration and patient
time are also significant factors that microneedles could significantly influence by
being an inexpensive, self-administered technique.
There are several ways in which microneedles can be used to enhance the
transdermal delivery of therapeutics. Solid microneedles can be used to first pierce
the skin to improve the permeability of a variety of therapeutics from extended-
release patches. Drugs can also be coated on the exterior of microneedles or encap-
sulated within microneedles to deliver drugs across the stratum corneum. Hollow
microneedles can also be used to infuse drug into the skin through the needle,
however, these are generally made from inorganic components [14]. These strategies
can be used to deliver a wide range of small molecules, proteins, DNA, vaccines, and
virus particles transdermally in clinically relevant quantities [15].
Over the last couple decades, advances in microneedle design have transitioned
from expensive, clean room-based development of silicon-based needles to low-cost
methods of fabricating metal and polymeric microneedles. Polymeric needles that
are water soluble and degrade over time (generally in a matter of minutes) have been
used to encapsulate drugs within the polymeric matrix that are released as the
needles degrade, leaving no sharp medical waste after use [15]. The different types
of microneedles are depicted in Fig. 1.
1088 S. Campbell and N. Smeets

Fig. 1 Drug delivery using microneedles. The various microneedles are: (a) applied to the skin and
then (b) are allowed to release drug over a predetermined amount of time via various mechanisms.
Solid microneedles are applied and removed, and then hydrogel-based drug releasing systems are
often applied to efficiently release the drug to the dermis through the void space afforded by the
microneedle. The bioresorbable polymer coating of coated microneedles rapidly disbands from the
microneedle and is left there to release drug upon removal of the system. Dissolving microneedles
contain biodegradable polymer that remains in place to release their encapsulated therapeutics over
time. Hollow microneedles are left in place to continuously inject drug directly into the dermis over
extended periods of time. (Original drawing adapted with permission from Ref. [14])

Polymeric microneedles can be made in several ways but the most common,
cheap, and commercially viable method involves first creating molds to form the
microneedles in. These molds are typically made via photolithography with optically
curable polymers, such as the ultraviolet (UV)-curable SU-8. After this, inverse
molds are generally made with silicone polymers, such as polydimethylsiloxane
(PDMS), by pouring them on the master mold and curing them. Aluminum, poly-
vinyl alcohol (PVA), and silicon have also been used to make molds, but PDMS is
the most prevalent and cheapest. These molds are then filled with softened or molten
thermoplastics, such as polycarbonate or poly(methyl methacrylate) (PMMA) at
elevated temperatures that resulting in non-degradable microneedles upon cooling
[14]. Biodegradable and water soluble polymers, such as PVP, PVA, and PLGA,
with encapsulated drugs can also be fabricated with molds in an analogous manner.
Polymeric microneedles can be coated with drugs to facilitate their delivery by
dipping or spraying the microneedles with a drug solution and letting the material dry
on the surface of the microneedles. A wide range of materials, from very
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1089

small molecules to macromolecules, vaccines, DNA, and micron-scale particles

can be coated onto the surface in this manner. The microneedles can also be
fabricated/coated with ionically charged polymers, which can be used to coat drugs
on the exterior of polymeric microneedles via layer-by-layer (LbL) techniques. These
technique involves repeatedly dipping the microneedles in two oppositely-charged
solutions, such as positively charged polymer and negatively charged protein, to
build up polyelectrolyte multilayers (PEMs) coating the surface of the microneedles,
that, when applied, will slowly dissolve and release the drug of interest. A variety of
materials can be released this way, including negatively charged DNA or protein [18],
and even larger poly(lactic-co-glycolic acid) (PLGA) nanoparticles and cationic
polypeptides [19]. These drugs will then dissolve in the environment of the dermis
to allow for a more facile pathway to systemic circulation. In an interesting example
of this, PLGA microneedles were coated with twenty PEM bilayers of positively and
negatively charged polymers to create an even coating, followed by 24 bilayers of a
hydrolytically degradable cationic polymer poly(β-amino ester) (PBAE) and plasmid
DNA or 4 bilayers of PBAE and PLGA nanoparticles [19]. These microneedles were
shown to deliver these materials to the viable epidermis successfully in vivo, dem-
onstrating that PEMs on the coating of microneedles can be used to potentially deliver
materials for gene therapy or co-deliver multiple therapeutics within PEM layers on
microneedles. The plasmid DNA delivered from these materials was found to be
successfully transfected into dendritic cells in vivo, showing that microneedles could
potentially be used for gene therapy and DNA vaccine delivery [19].
Another area in which polymer microneedles provide additional benefits over
their inorganic counterparts is their capacity to be used to generate degradable or
dissolving microneedles. Numerous polymers that have been traditionally developed
to dissolve or degrade over time to release therapeutics can be used as microneedles
as well. These polymers are typically biocompatible, safe, and are water soluble
in nature, and include carboxymethyl cellulose, dextran, PVP, PVA, PLGA, etc. [14].
These dissolving microneedles can be used simply to improve the permeability
through the skin, but regularly encapsulate controlled amounts drug molecules to
release them as they degrade.
The most common method of producing these microneedles, which was
described above, involves by making a solution of drug and the polymer melt and
allowing the solution to solidify in a prefabricated PDMS mold. It is imperative to
ensure that heat-sensitive therapeutic (i.e., antigens and proteins) should be incor-
porated in conditions such that they will not forfeit their activity in the development
process. One of the primary benefits of this technique is that controlled release can be
achieved for extended time frames (up to months), which means that the biodegrad-
able polymeric microneedles need to remain in the skin for long amounts of time as
well. This can be inconvenient for the patient. One neat solution to solve this issue
involved encapsulating nanogels into the microneedle base that swell when the
microneedles are applied and the microneedles rapidly lose their mechanical strength
and break away to remain in embedded in the skin to degrade on their own [20].
There have been numerous promising studies that have involved the delivery
of multiple small molecules, lidocaine, peptides, protein, DNA, RNA, insulin and
1090 S. Campbell and N. Smeets

vaccines [17]. Polymeric microneedles are particularly amenable to vaccine delivery.

Their low cost, thermostability, ability to dispense consistent doses, and the potential
for them to be self-administered effectively, which has been demonstrated with
metallic microneedles, could allow for a wide range of vaccines, including live,
attenuated, and subunit vaccines, to be administered in a facile manner [17]. This
could ultimately greatly improve vaccination coverage as a result. There is currently
only one vaccine that can be self-administered, which is Vivotif Berna ®, an orally-
delivered typhoid vaccine that has been used at a rate of three million vaccinations
per year [17, 21]. Microneedles, and particularly polymeric microneedles, could
present as a highly beneficial disruptive technology in this market.
Despite the promising release studies involving polymeric microneedles, the fact
that this is still quite a new field combined with the lengthy U.S. Food and Drug
Administration (FDA) approval process associated with the delivery of therapeutics
means that the number of fully commercialized polymeric microneedles is currently
rather limited. There are several metallic microneedles that have been commercial-
ized over the years, mainly for cosmetic purposes, including the Dermaroller ® that
is used for home use to improve skin texture; Soluvia ®, which uses hollow micro-
needles to deliver influenza vaccine; and MicronJet ®, which consists of four hollow
silicon microneedles that have a luer lock adapter to allow it to be attached to
standard syringes [14]. The sole polymeric microneedle is the MicroHyala ®,
which is a patch of dissolving microneedles that contain hyaluronic acid (HA) to
treat wrinkles that is sold in Japan [14]. The relative cost of polymeric microneedles
in comparison to metallic counterparts, combined with the numerous benefits of
microneedles, should afford for its use in many more commercial products over the
next decade.

2.2.2 Wound Healing

A wound to the skin compromises its primary function, increasing the risk of
dehydration and infection, particularly for burns. Wound dressings intended to aid
the process of healing have been used throughout human history, ranging from
primitive applications of plant herbs, animal fat, and honey to tissue engineered
scaffold from polymeric sources [22]. The goal with modern wound dressings has
been to establish and maintain a moist environment around the wound to assist in
wound healing while preventing infection.
Both natural and synthetic polymers play a distinct role in wound dressings, with
the majority of wound dressings making use of natural polymers. The most widely
used wound dressings are hydrocolloid dressings, which are generally colloidal
polymeric materials (often made from natural polymer such as carboxymethyl
cellulose and gelatin) that adhere to both moist and dry sites and form a gel upon
contact with the wound [22]. These dressings become increasingly more permeable
to water and air as the gel forms, but these systems often have an outer cover that
prevent water vapor exchange between the wound and its surroundings, which is not
ideal for wounds that require oxygen to rapidly heal.
Alginate is natural polysaccharide that is commonly used in wound dressings.
Alginates rapidly form hydrogels upon contact with moderate to heavily exuding
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1091

wounds, with calcium ions in the exudate forming the crosslinks between the alginic
acid polymer components [22]. These materials rapidly absorb the components that
the wound secretes and form a protective film that sustains moisture content and
healing temperature while minimizing bacterial contamination. Alginates also can be
removed with less pain than conventional dressings.
There are several other common natural hydrogels that are useful for wound
healing purposes, including collagen, hyaluronic acid, and chitosan. For example,
collagen matrices are a natural component of connective tissues that are widely
known to play a prominent role in the induction of clotting and minimizing the
appearance of scars [22]. Collagen hydrogels also stimulate the formation of fibro-
blasts and enhance the migration of endothelial cells to the wound site. Hyaluronic
acid (HA) is another extracellular matrix component that can be the main component
of naturally biocompatible, safe, and effective dressings that deter immune responses.
Naturally-derived chitosan hydrogels also are effective wound healing materials,
promoting the infiltration of inflammatory cells and tissue granulation and organiza-
tion in the early stages of the wound healing process [23].
Synthetic hydrogels can be applied either as an amorphous gel, which need
a secondary cover to remain in place, or as elastic sheets. Hydrogels are ideal
wound healing materials in terms of their capacity to promote moist healing, be
non-adherent to allow for facile removal, be non-irritating, be permeable to metab-
olites, improve reepithelization, to cool the surface of the wound, and to rehydrate
and remove dead tissues to improve healing [22]. Hydrogels are also highly mallea-
ble, able to heal while reducing the compressive forces on the wound to make the
healing process more comfortable. However, they contain large amounts of water,
which limits the amount of wound exudate that they can absorb, leading to their use
in primarily light to moderately exuding wounds.
Many of these natural components, and several synthetically-designed hydrogels,
are also biodegradable, and will be removed as they promote wound healing and
new tissue formation. More complex, “smart” hydrogels that take advantage of the
advances in the fabrication of biomaterials are an essential part of the development of
a new generation of synthetic hydrogel-based skin substitutes that better mimic the
tissue and normal physiologic responses of the tissue during wound healing and then
ultimately degrade over time. Tissue engineered skin substitutes are often comprises
of these more complex hydrogel materials (either natural or synthetic) and can be
seeded with naturally-derived cells prior to application.
Importantly, these engineered matrices also contain and release molecules that
can inhibit infections and promote and increase the efficacy of wound healing. While
there have only been a few clinical studies performed to date, many modern
dressings could easily be used to deliver drugs to improve wound healing, especially
considering that a large amount of these are polymeric hydrogel or hydrogel-like
materials [22]. Consequently, a wide range of the aforementioned wound dressings
have also been studied for their capacity to release antimicrobials, growth factors,
and genetic material as they protect and encourage the wound healing process.
The drug is initially released from these materials as the fluids that exude from
wounds further hydrate and swell the polymer matrix, enhancing the diffusional
1092 S. Campbell and N. Smeets

release in the process. Solely Fickian release will occur in materials that do not
degrade. However, most materials are designed to degrade so that any drug
remaining in the dressings will be released. This degradation is thought to be the
overriding mechanism in the latter part of most release profiles.
The delivery antibiotics or antibacterial component is intended to resist infec-
tions, particularly for wounds from surgery, accidents, and for diabetic foot ulcers.
Localizing the antibiotics, such as dialkylcarbamoylchloride, minocycline, tetra-
cylcline, and silver, along with the wound dressings rather than systemically allows
for lower antibiotic doses, lower antibiotic resistance, better tissue compatibility, and
reduced interference with the healing process [22]. One of the earlier examples of
antimicrobial-releasing materials was a silicone hydrogel that released ofloxacin
used to prevent infections in human patients with superficial and deep dermal-
depth burn wounds that prevented infection while reducing pain and enhancing
the epithelialization process in comparison to more traditional ointment-laden
gauze [24].
More recent polymeric wound healing systems tend to deliver growth factors, or,
in similar situations described above where infection is a clear risk, releasing growth
factors and antimicrobials simultaneously. Growth factors play an active physiolog-
ical role in various necessary parts of the healing process, including enzyme pro-
duction, protein expression, and cell division, migration, and differentiation [22].
Growth factors are involved in every stage of wound healing by stimulating angio-
genesis and cellular proliferation, which is involved in producing the extracellular
matrix, inflammation, and fibroblast activity. Common growth factors that have been
researched to improve healing are epidermal growth factor (EGF), fibroblast growth
factor (FGF), granulocyte-macrophage colony stimulating factor (GM-CSF), human
growth hormone (HGH), insulin-like growth factor (IGF-1), platelet-derived growth
factor (PDGF), and transforming growth factor (TGF-β1) [22]. These all play a
distinct role in the healing process. For example, GM-CSF is highly important for
rapid wound healing and ensuring the formation of suitable scar tissues [22].
The combination of delivering growth factors alongside has proven to be highly
beneficial in certain situations. EGF has been found to reverse the negative effects of
the antibiotic silver sulphadiazine when delivered from a hydrogel dressing [25].
Another collagen-hydrogel matrix with the antibiotic tobramyacin, FGF, and PDGF
exhibited markedly enhanced wound healing compared to the hydrogel matrix with
only the antibiotic [26]. DNA can also be delivered from similar polymeric dressing
to regenerate tissues as well [27]. A wide variety of materials can be released from
polymeric wound dressing biomaterials that are designed to mimic tissues and
encourage release to restore skin structure and function after injury.

2.3 The Lungs: Pulmonary Delivery

The pulmonary delivery route has been a well-established route for the local
treatment of respiratory diseases. Asthma stands out as a particularly identifiable
and commonly used example, with inhaler treatments having been in use since the
1950s [28]. Other disorders that are commonly treated with pulmonary drug
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1093

administration are pulmonary hypertension, respiratory inflammation, cystic fibro-

sis, chronic obstructive pulmonary disease (COPD), and tuberculosis [29–31]. This
is a common administration route because a high local concentration of drug can
be achieved for the treatment of respiratory diseases and it is a viable option to
non-invasively deliver biologics like peptide and proteins [31–33]. It has also been
developed for use in delivering insulin to the blood stream non-invasively as
this administration method avoids the first pass effect, unlike many alternative
approaches. The downside to this method is that the rapid decay of inhaled drugs
(without an accompanying delivery vehicle) means that multiple daily inhalations
may be required for a given therapy, which is inconvenient for the patient and leads
to low compliance [32]. The effectiveness of inhaled administration can be improved
with the use of polymeric micro- and nanoparticles, once the underlying nature of the
tissues associated with the lung are understood.
The lung consists of two primary sections: the conducting airways and the
respiratory region. The upper airway, consisting of the mouth/nasal cavity, pharynx,
larynx, trachea, bronchi, and bronchioles, is lined with mucous that is propelled
upwards away from the lung, has low regional blood flow, and possesses a small
surface area with thick tissues (>10 μm) compared to the lower lung, resulting in
many barriers to drug delivery in this region of the lung [32]. However the lower
region of the deep lung consists of the respiratory bronchioles and the alveoli, which
accounts for around 95% of the lung total surface area. These alveoli have a large
surface area (70–150 m2) [29], limited quantities of proteolytic enzymes, and a thin
tissue lining (<0.3–1 μm) [32] leading to an extensive blood supply [6, 16]. This
results in the deep lung being particularly suitable as a site for long term systemic
delivery of molecules.
Inhaled drug systems disperse throughout the lungs via three mechanisms:
Brownian diffusion, impaction, and gravitational sedimentation. While these are
dependent upon numerous particle properties, such as charge, surface characteristics,
hygroscopicity, temperature, breathing pattern, and the relationship between the
timing of the aerosol pulse injection with that of the breathing cycle, the principle
factor is generally seen as particle size [31]. Small particles diffuse, based on
Brownian motion, throughout the lungs, while larger particles tend to deposit in
the lower lungs via gravitational sedimentation and inertial impaction [29]. Currently,
most commercial inhalers deliver drug powders into the lungs. These small lone drug
particles (<0.5 μm) are so small that much of it fails reach the lower respiratory
region and >90% of the drug is immediately exhaled or rapidly eliminated by
mucous clearance in the upper airway [29, 32]. Larger particles that are >5 μm
tend to be delivered via impaction, as when they are administered they travel at such
a high velocity that they collide with the respiratory wall and are deposited in the
oropharynx regions [34]. Local delivery to tissues deep within the lung can be
most efficiently achieved with particles that are of an optimal size (~0.5–5 μm)
for gravitational sedimentation to occur [16, 35]. However, prolonged retention in
the deep lung tissues may be difficult in some cases, as many particles that
reach deep lung tissues are generally cleared when they are taken up by an army
of alveolar macrophages, which is highly efficient for particles from 1 to 3 μm in
diameter [30, 32].
1094 S. Campbell and N. Smeets

There are several methods that have been used to engineer materials that could be
delivered to the deep lung while avoiding the lung’s natural clearance mechanisms.
A very significant study found that the aforementioned particle diameter values that
determine which mechanism a given particle will likely be dispersed were not simply
the diameters of the particles, but aerodynamic diameters (dae) [30]. This means that
larger, porous particles could be deposited in the deep lung and be too large to be
rapidly cleared by the alveolar macrophages. This study involved 8.5 μm PLGA
particles with a density of 0.1 g/cm3 that were loaded with insulin, and these porous
particles were ten times more likely to reach deep lung tissues than solid particles
with similar a dae and were shown to deliver insulin for 96 h in diabetic rats, offering
nearly as effective insulin bioavailabilities to subcutaneous (SC) injections (87.5%)
[30]. These porous particles also showed lesser aggregation between particles (owed
to their lower surface area) produced a reduced inflammatory response in compar-
ison to solid microparticles with a similar dae. The porous PLGA particles were also
shown to release significant quantities of testosterone for a prolonged 24-h period
from quite large 20.4 μm porous particles, exhibiting that it is truly the dae that must
be considered to deliver particles to the desired region of the lungs [30]. Similar
PLGA particles are now being pursued in clinical trials by Pulmatrix for the
treatment of chronic obstructive pulmonary disease and similar particles have been
developed for a wide range of drugs, including heparin, deslorelin, anthocyanin, and
more [33]. Porous PLGA particles have also been shown to deliver rifampicin,
an anti-tuberculosis antibiotic, for 8 h in guinea pigs in vivo [36]. While porous
nanoparticles have distinct advantages, they have more rapid release than from solid
nanoparticles. A study showed that the release of isoniazid, an antibiotic for tuber-
culosis, was released over 3 days, 6 days, and 7 weeks for porous, non-porous, and
hardened PLGA microparticles respectively [37]. Regardless of particle type, all
were shown to be more effective at clearing bacteria with a single dose in vivo in a
murine model than the daily administration of free drug [38].
Another method to evade macrophage uptake is to use dry polymeric micropar-
ticles that swell once they become hydrated. Chitosan-functionalized PEG micro-
particles were investigated for this purpose. The particles were initially ~10 μm and
somewhat porous (ρ  0.7 g/cm3) and ballooned to 70 μm upon hydration [39].
These particles were capable of delivering a hydrophilic model drug, sodium
fluorescein, and were very effective at avoiding macrophage uptake in vitro, so
they could potentially be applicable for pulmonary drug release [39]. Nanoparticle-
containing microparticles could also be utilized that take advantage of the ability of
microparticles to reach alveolar tissues and the benefits of nanoparticles to avoid
clearance to deliver therapeutics to the blood stream or to internalize into cells for the
delivery of genes and other biologics. Nanoparticles <100 nm in size are taken up to
a larger extent by the alveolar epithelial cells than macrophages, so this “Trojan
horse” strategy could be an effective method of delivering small nanoparticles to the
deep lung for genetic therapies.
The pulmonary administration of nucleic acids has been investigated treat genetic
and chronic lung disorders. To suit this purpose, PLGA has been modified with
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1095

polymeric gene delivery vectors like poly(ethylene imine) (PEI). PEI can encapsu-
late negatively-charged DNA and siRNA into nanoscale complexes and protect their
degradation by nucleases and is often grafted with PEG to reduce its toxicity [32].
In order to penetrate cells, additional functionalities are required to efficiently deliver
genes. For example, TAT, a cell-penetrating peptide, was coupled to PEG-PEI
to form small 90 nm polyplexes that showed significantly enhanced gene delivery
efficiency in mice in vivo than with PEI alone [40]. Other targeting moieties,
including lactose, lactoferrin, galactose, etc., can also be used to target specific
receptors of cells to promote internalization [32]. These could be coupled with
promising polymeric delivery systems, such as PLGA-based particles,
diethyleneaminopropylamine-co-PVA-co-PLGA particles that have shown efficient
siRNA delivery [41], and chitosan nanoparticles that have shown effective in vivo
siRNA delivery in mice [42] and rats [43].
PLGA nanoparticles have also been surface modified with chitosan to deliver the
peptide elcatonin more effectively than unmodified nanoparticles [44]. Polyelectro-
lyte nanoparticles that self-assemble from siRNA and chitosan to form polyplexes
that were used to deliver this siRNA to human lung carcinoma cells in vitro. These
materials have shown successful in vivo RNA interference in mice, allowing poten-
tial for in vivo lung cancer treatment via pulmonary administration.
Living radical polymerization has been used to develop micelles of PEG and the
hydrophobic distearoylphosphatidylethanolamine (DSPE) for the pulmonary deliv-
ery of paclitaxel (Ptx) to cancerous lung tissues [45]. The localized delivery of this
system would be particularly beneficial for cancer treatments to negate the amount of
systemic side effects associated with lung cancer treatments. The accumulation of
Ptx in the lungs was 45 times higher than intravenously administered Ptx and 3 times
higher than a conventional chemotherapeutic delivered intratracheally [45]. The Ptx
concentration in other tissues was also much lower in the case of the micelles and the
normal lung tissues did not appear to be injured [45]. These micelle-based systems
appear to have great efficacy and could lead to more micelle-based strategies for
treatment of lung disorders or to other polymeric systems delivering chemothera-
peutic agents for lung cancer treatments.
Although vast amounts of research have been performed on polymeric systems
for pulmonary administration, there are few examples of systems that have suc-
cessfully made it to clinical trials. One of the main issues is that the fate of nano- and
micro-materials and their long term effects on the functionality of lung tissues is
still unknown and difficult to determine. While these particles are supposed to limit
the number of required administrations and many of these are biodegradable over
time, the effects of the accumulation of particles in the lung and particularly on the
lining fluid of the lung are unknown [32]. A deeper knowledge of these effects and
an understanding of how best to examine the safety of these materials after in vivo
use must be established before many of these materials lead to commercially used
products. However, the current porous PLGA systems under clinical trials may pave
the way for the rest of the field of pulmonary administered micro- and nano-
systems.
1096 S. Campbell and N. Smeets

2.4 The Brain: Traversing the Blood-Brain Barrier

There are many treatments where the brain is the principal target region for thera-
peutics, including Alzheimer’s disease; Parkinson’s disease; Huntington’s disease;
amyotrophic lateral sclerosis (ALS); schizophrenia; learning impairment; HIV infec-
tion of the brain; protecting tissues after cerebral ischemia, a condition that occurs
when there is an insufficient amount of blood flow to the brain; and brain cancers
[46]. Due to the obvious inherent risks of trying to deliver therapeutics directly to the
brain, the majority of work that focusses neural drug delivery involves transporting
nanotherapeutic carriers from the blood to the brain, through the blood-brain barrier
(BBB). The BBB is one of the strictest barriers in therapeutic delivery. It is a
contiguous layer of the endothelial cells of the cerebral capillaries connected by
tight junctions, <12 nm, that can be 100 times tighter than the junctions of other
capillary endothelium [47, 48]. The barrier is analogous to cell membranes, where,
in general, it allows for the facile transport of lipophilic molecules across the
membrane while restricting the exchange of hydrophilic compounds, small proteins,
and charged molecules between the plasma and the central nervous system (CNS).
Even small therapeutic molecules have difficulty crossing this barrier.
The approaches for delivering therapeutics to the brain can be invasive or
non-invasive. Invasive treatments not only include direct intracerebral/intraventric-
ular injection or intracerebral implantation of the drug/delivery device, but also by
techniques that can temporarily increase the permeability of the BBB, which include
osmotic disruption and focused ultrasound [49]. These techniques, simply due to
their invasive nature, pose the risk of complications, including intracranial infections
and brain edema, and are expensive, complex procedures [46]. Noninvasive tech-
niques to deliver drugs to the brain have thus been the focus of the majority of the
research in this area, often by conjugating specific functionalities on the surface of
nanoscale delivery vehicles.
A wide variety of ligands can be functionalized to the surface of nanosized
polymeric carriers to improve their transport across the BBB. These take advantage
of transporters native to the endothelial cells that deliver essential hydrophilic and
large compounds across the BBB, such as choline, amino acids, and lipoproteins
[47]. Transferrin was one the first ligands discovered for this purpose, as the
transferrin receptor is overexpressed in the endothelial cells that comprise the BBB
[50]. Numerous other ligands have been used to allow nanocarriers to pass through
the BBB, including a wide range of peptides; apolipoproteins that are recognized by
low-density lipoprotein receptors on the surface of the BBB’s endothelial cells; and
even insulin, which targets the insulin receptor and can transport carriers across the
BBB ten times more efficiently [46]. Receptor-mediated endocytosis in this manner
is used to transport many carriers that would otherwise be too large to cross the BBB
into the brain.
To target specific neural diseases, nanocarriers can be designed with functional-
ities that can be used to allow the carrier to travel through the bloodstream and
traverse the BBB and target the disease of interest. This is of particular interest for
the treatment of brain tumors. Cancers of the brain are particularly difficult to treat,
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1097

with patients often having to undergo invasive neurosurgeries to excise the tumorous
tissues. However, many cancers often have overexpressed receptors that may be
utilized for targeting, similar to the BBB.
In fact, some of the overexpressed receptors on glioma cells correspond with
the BBB receptors, including lactoferrin and transferrinproteins [46]. Lactoferrin-
functionalized polycaprolactone (PCL)-b-PEG polymersomes encapsulating doxo-
rubicin (Dox) and tetradrine, a multidrug resistance inhibitor, exhibited a greater
accumulation in brain tumors within an in vivo glioma model in rats relative to non-
lactoferrin-functionalized controls [51]. This particular study highlighted that the
effectiveness of the targeted application of Dox is significantly enhanced by the
combined delivery of a multidrug resistance inhibitor, decreasing the tumor growth
rate and extending long-term survival compared to controls. Dox alone has been
shown to exhibit promising results, including an increase in mice survival time and
a reduction in tumor volume, when targeted in vivo to glioma cells in mice
with similar PCL-b-PEG polymersomes using transferrin as the targeting moiety
[52]. Another common receptor at the BBB and on human glioma cells is the
low-density lipoprotein receptor-related protein (LRP). Similar polymersomes
functionalized with Angiopep-2, a small, LRP-binding peptide, were shown to
penetrate into the brain by receptor-mediated endocytosis and preferentially accu-
mulate in the gliomal bed and in infiltrating gliomal cells to deliver paclitaxel (Ptx),
another common cancer drug.
Alternatively, multiple ligands could be used to treat brain cancers and other
ailments. PCL-b-PEG nanoparticles with covalently conjugated Pep-TGN peptides
and the AS1411 DNA aptamer on their surface was used to selectively target gliomas
cells in the brain. The dense Pep-TGN coating could afford the passage of the
nanoparticles into the brain and, once there, the aptamers decorated on the surface
of the nanoparticles could then bind with the highly expressed nucleotin protein on
gliomas cells, which the aptamers have a very high affinity for [53]. In vivo imaging
confirmed that both particles were needed to best accumulate at the cancerous target,
and this nanomedicine with both Pep-TGN peptides and the AS1411 DNA aptamer
showed improved survival times when loaded with docetaxel (Dtx), another
common chemotherapeutic, in comparison to singly-functionalized nanoparticle
controls.
All of the above studies utilized IV administration to rapidly get the carriers into
the systemic blood in order to traverse the BBB into the brain utilizing receptor-
mediated endocytosis. There are, however, alternative mechanisms. For example,
polycationic molecules can be efficiently internalized by the negatively charged
membrane of the cerebral endothelial cells in the BBB, in a process known as
adsorptive-mediated transcytosis (AMT) [54]. An IV injection of biodegradable
PLGA-trimethylated chitosan nanoparticles loaded with coenzyme Q10 was used
to treat an Alzheimer’s disease animal model using this route, resulting in an increase
in learning ability and a reduction in the escape latency from a water maze compared
to controls.
Another alternative mechanism to internalize carriers in the brain is to use
intranasal administration to allow for the transport of specific functionalized vehicles
1098 S. Campbell and N. Smeets

to the brain from the nasal cavity via the system of nerves that exists between the two
(olfactory and trigeminal nerves) [55]. Lectin-functionalized nanoparticles are able
to bind to the glysolated nasal muscosa to initiate this transport, and a range of
biodegradable nanoparticles functionalized with various lectins have been shown
to utilize this pathway to accumulate in therapeutically significant quantities in
the brain after 2 h [50]. For example, Solanum tuberosum lectin-functionalized
PEG-b-PLGA nanogels loaded with the antipsychotic drug haloperidol were able
to use this pathway, with most of the nanocarriers likely traversing to the brain
directly via the olfactory receptor cells. The lectin-functionalized nanogels accumu-
lated in the brain tissues 1.5–3-fold more effectively than controls. The haloperidol-
loaded nanogel formulations were shown to effectively induce catalepsy, effectively
calming the mice down in the way that this antipsychotic drug for the schizophrenia
treatment should, when delivered intranasally [56]. The downside of this and other
alternative routes of delivery to the brain is that they generally have low bioavail-
abilities (<0.1%) [46, 55].
Despite the extensive research interest in developing nanotherapeutic delivery
vehicles for traversing across the BBB, it is still in its early stages and there are no
clinically available treatments currently. This is due to the difficulty in obtaining
high bioavailabilities to the cerebral site of interest (significant proportions do not
make it past the BBB), the biocompatibility concerns of nanoparticles, and the long
FDA process that it difficult to get through. Therefore, invasive delivery methods,
namely injections and infusions are frequently used for treating only the most severe
ailments. However, there are polymeric brain implants capable of controlled release
the is currently used to treat malignant gliomas [57]. The first one was approved
by the FDA in 1995 and is a wafer composed of a biodegradable polymer, poly
(carboxyphenoxypropane-co-sebacic acid), with the entrapped chemotherapeutic
drug 1,3-bis(2-chloroethyl)-1-nitrosourea (BCNU) that is implanted after a malig-
nant tumor is removed and releases its payload as it degrades over 3 weeks in this
localized treatment regime [57, 58]. The result was a statistically significant
improvement in the survival of the patients. Several other similar bioresorbable
implants were developed and placed in clinical trials since [59], notably resorbable
microchips made from PLA that significantly reduced tumor sizes in an in vivo rat
model via the controlled, localized release of BCNU [60].

2.5 The Eye: Ocular Delivery

The eye is a particularly interesting target tissue for drug delivery as its unique nature
presents numerous anatomical and physiological barriers that makes therapeutic
delivery through traditional means extraordinarily difficult [61]. Drug delivery to
the eye is generally characterized in terms of which of two regions the delivery is
intended for: either the anterior or posterior segment of the eye. These segments
and the overall anatomy of the eye are depicted in Fig. 2. The anterior segment of the
eye is responsible for collecting and focusing light, while the posterior segment is
responsible for detecting this light and transferring this information to the optic nerve
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1099

Fig. 2 The anatomy of the eye: a transverse cross-section of the eye. The different components of
the anterior and posterior segments are separated by the dotted line. (Original drawing adapted with
permission from Ref. [62])

that leads to the brain. The outermost layer of the anterior section is a transparent
collagenous layer called the cornea. The anterior chamber, filled with aqueous
humor, separates the cornea from the iris, the pigmented potion of the eye that
regulates the amount of light that enters the lens, and the lens. This chamber is
enclosed on either side by the ciliary body, which secretes aqueous humor that
provides nutrients to these avascular tissues and maintains the intraocular pressure.
The structure of the lens-iris barrier is what separates the anterior and posterior
portions of the eye [62]. The collagenous outer layer in the posterior segment is an
opaque white color and called the sclera. Between this structure and the retina is a
middle layer called the choroid, which is a network of capillaries that supplies the
inner layer, the retina, with nutrients. The retina detects and transduces the light
signal, and transfers the neurosensory information to the brain via the optic nerve.
The vitreous is the largest part of the posterior segment of the eye, encompassing the
space between the lens and the retina [63]. This region is filled with a hydrated gel
like extracellular matrix called vitreous humor.

2.5.1 Anterior Segment Treatments

Anterior segment diseases, including dry eye, microbial keratitis, giant papillary
conjunctivitis, and vernal keratoconjunctivitis, are treated topically with eye
1100 S. Campbell and N. Smeets

drops/ointments, systemically, or periocularly via subconjunctival injections or

implants [62]. Drugs delivered systemically can reach the aqueous humor, which
provides nutrients to the anterior segment of the eye and is secreted from the ciliary
body, after it passes through the blood-aqueous barrier [64]. However, only small
portions of the drug will partition into the aqueous humor. Thus large amounts of
potent drugs are required to deliver therapeutically relevant concentrations of the
drug to the desired anterior eye site, which can result in numerous undesired side
effects [62].
Of these methods, topical administration is the most common, with numerous
small, moderately-charged drugs being known to penetrate the cornea, conjunctiva,
and sclera to enter the eye. Topical administration via eye drops is only really useful
for anterior segment diseases, particularly for those that can be treated with small
therapeutics [64]. The pharmacokinetics of release in this case are very complex, as
they are impacted by the flow of tears (lacrimation), blood flow, aqueous production,
as well as the physical barriers of the tissues they are trying to penetrate [62]. The
correct administration of eye drops involves proper placement of the eye drop, the
correct number of administrations per day, and the correct time intervals between
multiple dosings or therapeutics [65]. The difficulty in maintaining this procedure
leads to low patient adherence, which is an issue that only increases with age.
Additionally, the majority of each eye drop will be washed away within minutes.
This is the crux of the issue of using eye drops: only a small amount, typically
<1–3%, of small drug compounds reach the aqueous humor site with 75% of
drug lost rapidly via lacrimation and absorbed systemically by the conjunctiva
[64–66]. The degree of permeability steeply drops for larger compounds, meaning
the larger the drug is the lower its bioavailability will be. Thus, for any drug within
eye drops, in order to be effective high concentrations of drug are required, as most
of it will be lost in the process.
There are several strategies that will slightly improve the bioavailability of eye
drops involving polymeric particles. Mucoadhesive nanoparticles, microgels, and
dendrimers that enhance the retention of drug delivering molecules to the surface of
the eye include PEG, poly(acrylic acid), and positively-charged polymers such as
polyamidoamine (PAMAM) [61]. These particles can also be uptaken by the corneal
epithelial cells for treatment and/or prolonged release to other anterior segments.
Viscosity enhancers can also prolong the residence time of an eye drop. For example,
in situ gelling hydrogels have been incorporated into eye drops specifically for the
purpose of increasing the residence time of a given droplet by delaying its removal
via lacrimation.
Injections into the subconjunctival space around the eye have been used to store a
drug depot close to the surface of the sclera. This space can be used to store up to
0.5 mL of a drug containing solution and proteins as large as 145 kDa have been
shown to penetrate the sclera from this region (via the periocular route), affording an
option for both anterior and posterior segment treatments [64]. Most drugs injected
into this space are cleared by the systemic circulation, particularly rapidly with
small drugs, but this still provides as a simple option for the delivery of larger
molecules in particular. An interesting hydrogel-based biomaterial composed of tri
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1101

(ethyleneglycol)dimethacrylate and poly(ethyleneglycol)dimethacrylate containing

three different small molecular weight model drugs with a controlled release cover
made from the same polymers and was implanted in the subconjunctival space [67].
The device was capable of delivering multiple drugs that traverse the sclera at
different controlled rates, depending on the composition of the hydrogel and/or
hydrogel cover (by altering the ratio of the comprising copolymers) [67]. Micro-
spheres composed of polyester have been injected subconjunctivally and studied for
the release of timolol to treat glaucoma, and, promisingly, were shown to be capable
of delivering timolol for more than 3 months in vitro [65]. Another option that is
used for large molecular weight drugs is to inject small reservoirs of drugs into the
densely-packed stromal cells of the cornea. The macromolecules immunoglobulin G
(IgG) were shown to have an exceptionally high half-life of 26 days when injected
intrastromally [68].
Much of the biomaterial strategies that are currently being developed for the
anterior region center around the use of contact lenses as the delivery vehicle, as
these systems are minimally-invasive and should have relatively good compliance.
Contact lens-based delivery systems have great potential for anterior eye segment
treatments, as they provide as a potential drug reservoir that is placed against the
cornea for long time frames and is currently used by a significant portion of the
population in the developed world [69]. Through the advent and consistent improve-
ment of silicone hydrogel-based biomaterials, it is now clinically possible to produce
contact lenses that can be worn for 30 days and could be soaked in a drug of interest
prior to their use [69]. However, more controlled, sustained release is generally
required, resulting in numerous research groups attempting to better control release
from drug-containing hydrogel contact lenses. In the development of novel means to
deliver therapeutics from hydrogel contact lenses, drug have been immobilized on
surface-modified poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels, incorpo-
rated in a colloidal structure dispersed in the lens, electrostatically bound to poly-
meric hydrogels containing ionic functionalities, and molecularly imprinted in the
hydrogel network of contact lens [66]. While none of these materials are commer-
cialized as of yet, contact lenses have the potential to provide as a better solution to
eye drops for a wide range of therapies.

2.5.2 Posterior Segment Treatments

Delivery to the posterior segment of the eye is remarkably difficult due to a variety of
anatomic and physiologic limitations, as all of the barriers to release for the anterior
segment are also present here, but with a much longer required diffusional distance
[62, 69]. Additionally, this region is particularly unique in the body in that it is
largely acellular in nature. However, the development of improved methods of
delivery to the posterior segment of the eye is important as diseases associated
with this region, including age-related macular degeneration (AMD), posterior
uveitis, diabetic retinopathy, and retinitis due to glaucoma, are the primary causes
of vision loss in developed nations [62, 69, 70]. A further complicating factor with
these diseases is that they often need to undergo treatment over the course of years
1102 S. Campbell and N. Smeets

[61]. As a result, alternative strategies are frequently used to deliver drugs to the
vitreous, choroid, and retina.
Notably, systemic delivery is particularly difficult for delivery to the eye, as the
inner and outer blood-retinal barriers (BRBs), which separate the neurosensory
retina from circulation, are known to be similarly exclusive as the BBB [64].
While functionalized nanoparticles delivered intravenously with transferrin or
arginine-glycine-aspartic acid (RGD)-peptide have been shown to result in poly-
meric nanoparticles capable of reaching and treating the eye in a significantly
improved manner over non-functionalized particles, this improvement was rather
small considering that the bulk of the nanoparticles would have not been capable of
crossing the exclusive BRB [61]. As a result, more direct methods of delivery are
typically desired to avoid side effects associated with systemic delivery.
Intravitreal injections are the most common method of conventional treatment
and, from a therapeutic perspective, have been rather successful, particularly for
AMD treatments [64, 69]. These injections are useful for posterior treatments
because the vitreous is central to the tissues of the posterior region and high drug
loads can be applied [61]. However, many treatments require frequent injections,
which greatly increases the risk of complications over time, such as cataracts, vitreal
hemorrhage, endophthalmitis, intraocular hemorrhage, retinal detachment, and
increase intraocular pressure [63, 69, 71]. Many of these complications could result
in permanent vision loss. The injections are also demanding of an ophthalmologist’s
time, and are inconvenient for the patient (leading to low patient compliance).
Frequent intraocular injections are thus only really suitable for treating older patients
with advanced forms of posterior segment diseases, leaving younger patients without
safe and effective treatment options [69]. Drugs that are injected into the intravitreal
space are cleared (with a limited retention half-life of <3 days) via an anterior route
through the aqueous humor or via a posterior route that involves the drug crossing
retinal space and the BRB [64, 72]. Large molecular weight drugs (>500 Da in this
case) have long half-lives in the vitreous from days to weeks and small drugs have
been PEGylated to increase their molecular weight to enhance their retention time
in the posterior segment [73]. Polymeric nano- and micro-particles, micelles, lipo-
somes, hydrogels, and implants can also be used for the controlled release of drugs
over longer time frames in the vitreous.
The main issue is the maintenance of therapeutically-relevant concentration
levels of the therapeutic throughout lengthy treatments, which is difficult to achieve
long-term [65, 69]. Despite this challenge, several commercial devices have
been developed for the delivery of therapeutics to the back of the eye. These
FDA-approved devices are all implants. These implants, along with alternative
implants currently in FDA trials, utilize polymers such as PLGA, polycaprolactone
(PCL), and poly(orthoester) if they are to biodegradable, and silicone, PVA, and
ethylene vinyl acetate (EVA) if they are not degradable in nature [72]. For example,
Retisert ® is a nondegradable device that is surgically implanted in the sclera that can
continuously deliver small amounts of drug to treat posterior uveitis over 2.5 years
[63, 72]. After this time, the device must also be surgically removed. Iluvien ® is a
new commercially available injectable implant (injected in a similar manner to
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1103

typical intraocular injections) capable of long-term delivery of corticosteroids to

treat diabetic macular edema [63]. However, once this material is injected it is not
erodible or degradable, so it remains in the vitreous. Ozurdex ® is an implant that is
capable of sustained release over 1–3 months for treating either posterior uveitis or
diabetic macular edema, but because this implant is composed of PLGA it has
biodegradable properties and is approved by the FDA [61, 63]. There are several
other implantable systems, both degradable and non-degradable, in development that
are currently in the clinical trial process [63].
Commercialized systems that could be facilely injected to the back of the eye,
deliver therapeutically-relevant drug dosages for posterior eye segment ailments
over months, and ultimately degrade would be ideal, but this type of technology is
not currently available and presents as a great market opportunity in the future.
However, as biomedical sciences and biomaterials research advance, new opportu-
nities to improve therapies are emerging for the treatment of posterior segment
diseases.
Iontophoresis has been used to non-invasively drive the permeation of ionized
drugs across the sclera, periocularly, via the application of weak electric currents
[62]. This method can be used to deliver high concentrations of drugs to the choroid
and tissue, and often use hydrogels as the component that is actually in contact with
the sclera due to their soft nature. Transcleral delivery using electrophoresis from
HEMA-co-EGDMA hydrogels has shown to be effective with a two minute appli-
cation and this is a promising method for the delivery of hydrophilic macromole-
cules, like DNA, siRNA, etc., across the sclera [62, 72].
Microneedles for use on the eye have been adapted from previous work on the use
of microneedles to deliver drugs across the skin. These systems have primarily been
explored as an option to deliver drugs through the sclera. Microneedles would
provide as a simple, less intrusive alternative to the surgical implant strategies for
extended release that are currently available on the market. A hollow microneedle
system has been developed that partially penetrates the sclera and would allow for
the slow release of therapeutics (up to 35 μL) into vitreous in a manner that could be
facilely administered in a clinical setting [74]. Microneedles can also be designed
to a specific length such that they can deliver drugs to the suprachoroidal space
for diseases like chorioretinitis, choroidal neovascularization, AMD, and glaucoma
[61]. Hollow microneedles were shown to be capable of injecting polymeric nano-
particles from 20 nm to 10 μm in size into the suprachoroidal space and these
particles remained for over 2 months [75].
Polymeric nano- and micro-particles have been studied for delivering therapeu-
tics topically, periocularly, suprachoroidally, and via intravitreal injections [64]. The
use of biodegradable polymeric particles is particularly important for the eye, as the
degradation of these particles will allow them to be eventually cleared from the eye
in their smaller fragments. The biodegradation of polymers like PLGA can also be
used to mediate drug release in the eye [64]. The difficulty in designing a system that
is stable, can control the release rate, and is made of safe polymeric materials whose
degradation products are also safe has hindered the progress of polymeric particle
formulations being used for ophthalmic drug delivery in the market. Polymeric
1104 S. Campbell and N. Smeets

nanoparticles also could not be injected into the vitreous humor, as they diffract light
and would cloud one’s vision [64]. Larger microparticles would not have this issue,
as they would sink to the bottom of this region of the posterior segment. PLGA
microspheres have been developed that are large enough to sink after vitreal
injection and deliver a growth factor that improves the recovery from ischemic
retinal injuries (brain-derived neurotrophic factor) [65], and anti-transforming
growth factors to limit fibrosis after glaucoma surgeries [76]. These larger particles
also have longer residence times in the subconjunctival space for long term peri-
ocular delivery of therapeutics through the sclera [61]. One of the biggest issues
related to the use of polymeric nanoparticles is that, due to their size, larger surface-
to-volume ratio, and the associated diffusion lengths, they are generally not capable
of the long term delivery of weeks to months that would particularly benefit the
treatment of eye-related disorders (where it is particularly undesirable to have
frequent administrations), even though they may be present for over 4–6 months
[72]. This is the major advantage that the previously mentioned commercial implants
have over polymeric particles. Larger implants can load more drug and deliver the
drug slowly due to their smaller surface-to-volume ratio that allow for prolong
release of up to several months. Larger microparticles have this analogous advantage
over nanoparticles, but to a lesser extent to typical macro-scale implants [61].
Injectable in situ gelling systems are another potential solution that is being
studied, as they can afford long-term release while being capable of being adminis-
tered with a simple injection as opposed to the invasive surgeries required for
implants [64]. These are hydrogels that form upon injection by an increase in
temperature, via thermogelation, as the polymer exceeds its lower critical solution
temperature (LCST) and interacts with itself to form a physically-crosslinked
hydrogels in the vitreous that can later be used to deliver drugs or cells that were in
the pre-gelation solutions [70]. Thermogelling hydrogels present as a safe alternative
to intravitreal injections and are capable of prolonged therapeutic delivery [61].
Verisome, a thermogelling drug delivery system involving an in situ-forming biode-
gradable hydrogel containing lipid forms a spherule upon injection into the vitreous,
and was able to release therapeutic levels of a drug for macular edema, triamcinolone,
for 12 months in early clinical trials [63]. Hydrogels that form via the in situ
crosslinking of two reactive functionalized polymers could also be realized, as recent
developments in injection devices have allowed for the injection of these types of
polymeric systems into the vitreous [77]. These covalently-crosslinked hydrogels can
be similarly biodegradable have tunable crosslink densities that could further slow the
release of drugs contained within them in a controlled fashion, leading to longer term
release from injectable materials [78]. Injectable hydrogels can also be injected into
the subconjunctival space to deliver drugs over longer time frames via the periocular
route to deliver drugs to the posterior segment through the sclera [61].
Several responsive systems whose release rates can be altered have been inves-
tigated as well [63]. These advances generally attempt to take advantage of the fact
that light can be easily transmitted to materials within the eye due to the necessary
transparent nature of the cornea and the lens. Light-responsive systems can be made
from incorporating light sensitive materials that respond to specific wavelengths
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1105

or convert light into heat within polymeric micelles or hydrogels. In the case
of micelles, a chromophore can be attached to the hydrophobic part of the polymer.
When a specific wavelength of light (typically in the visible or near-infrared
(IR) range) is applied the chromophore, it is cleaved and this disrupts the micelle,
causing it to release its drug-loaded contents. This is usually an irreversible process
and a way to deliver bursts of drug using micelles [63]. Verteporfin is a systemically
administered liposome that experiences photodynamic disruption of the lipid bilayer,
releasing its drug contents, and is currently clinically used for the treatment of
subfoveal choroidal neovascularization [61]. Gold nanoparticles (2–3 nm) can also
be embedded in the inner and outer layers of liposomes and near-IR light can be used
to heat these materials and cause them to irreversibly release their contents in a
similar fashion [72]. Hydrogels with reversible photodynamically labile crosslinks
can also be used to regulate drug release, where exposure to a certain wavelength of
light will cause the crosslink to form while another wavelength may be used to
eliminate that same crosslink, affording external control over the crosslink density
and tortuosity of the hydrogel, which can regulate drug release. Near-IR induced
heating of thermosensitive hydrogels incorporated with gold nanoparticles, or other
nanoparticles that transduce near-IR light to produce heat, can also be used to
remotely alter the hydrogel’s swelling characteristics and, consequently, regulate
the associated drug release from the hydrogel networks [72]. Many eye conditions
would benefit from a drug release profile that is in tune with the patient’s needs
associated the state of the condition being treated, all while inhibiting the prevalence
of side effects [63]. Thus, if implemented successfully, such advanced systems
would serve as a new generation of ophthalmic drug delivery strategies that are
capable of altering their drug release kinetics on demand in real time.

2.6 Other Common Regions

There are several other administration methods that can be used to deliver medica-
tions, however these methods are generally utilized to a lesser extent than the
aforementioned methods and/or they have not been explored in drug delivery
research using polymeric particles nearly as readily for a variety of reasons. The
nasal route can be used to rapidly and noninvasively deliver drugs for, for example,
sinus issues or into circulation, as, similar to the lungs, the tissues are fairly facilely
penetrated by therapeutics and this region is highly vascularized. However, signif-
icantly more small particles are lost via the nasal route than in the lungs and it is
difficult to design polymeric particles that will remain in this region for prolonged
lengths of time without being cleared by the mucosal turnover [29]. As highlighted
in the section on delivery to the brain, the nasal route can be used to deliver materials
to the brain [56], but localized delivery by controlled release vehicles has not been
extensively studied in order to pursue simpler and likely more efficacious routes of
delivery to the brain.
Another region of the body that is widely used for traditional drug delivery is
delivery to the anal cavity via suppositories. This region also has tissues that are
1106 S. Campbell and N. Smeets

easily penetrated to deliver drugs rapidly to the bloodstream (with ~50% of the drugs
bypassing the first-pass effect), leading to its widespread use in patients that have
difficulty in taking drugs themselves via alternative means. However, the socio-
cultural stigma, inconvenience, and low patient compliance associated with this
method has led to limited research in the development of controlled release methods
via this route [16]. The anal administration method is generally used for acute rather
than chronic treatments, also leading to little motivation to engineer devices capable
of prolonged release.
Alternatively, localized treatments to the bladder with polymeric devices have
been studied, as delivery to the region is so difficult and inconvenient that prolonged
release is desired to limit the number of administrations. An example of this is the
use of hydrogels for the treatment of bladder cancer. A floating hydrogel made of
the thermosensitive polymer poloxamer 407 was developed that could float in the
bladder to avoid urinary obstruction and irritation while delivering the anti-cancer
drug Dox in vivo [79]. While mucoadhesive hydrogels have also been used in the
bladder [79], another strategy utilized nanocomposite hydrogels with magnetic
nanoparticles to magnetically target the hydrogel to the specific region of the bladder
that has cancer to more effectively treat the diseased region [80]. While there are
several research groups looking into treating the bladder with polymeric release
systems, they are limited to looking into serious ailments of the regions, like bladder
cancer, as the difficulty in delivering materials to this region means localized
delivery will only be performed under dire circumstances.
The vagina is a principle site of infection for many sexually transmitted infections
(STIs). As a result, intravaginal rings composed of extruded polymers, such as
elastomeric polyurethane [81], silicone [82], and PEG [83], have been developed
for their use in the delivery of therapeutics to prevent and treat sexually transmitted
infections and as contraception [6]. These polymeric devices can be used for over
6 months and are periodically removed for 1 week intervals. These systems are also
capable of locally deliver antibodies, microbiocides, and siRNA to protect against
both pregnancy, human papillomavirus (HPV) infection, human immunodeficiency
virus (HIV) infection and many more [6, 84]. Many intravaginal systems have also
been commercialized, including a few intravaginal rings [82, 84]. This can also be
used as a site of administration for systemic acting therapeutics, as the released
materials bypass the hepatic first pass effect and controlled release can take place for
over 30 days in some cases [84].
Drug eluting stents have been used for many years to enhance healing and limit
the inflammatory response after surgeries where stents are utilized to maintain the
structure of the arteries/veins that underwent surgery [85]. These systems often have
crystalline drug coated to the surface of the stent and their drug is generally released
at a fairly rapid rate. A wide range of drugs have been used for this purpose,
including antibiotics, proteins, genes, cardiovascular agents, hormones, and steroids
[86]. The use of bioresorbable polymeric coatings, like PLGA, PLA and PCL, can
offer long term release and improve the long term biocompatibility of stents after
their administration by reducing inflammation [85, 86]. As a very specialized
platform, many of these stents have been commercialized and seen great success
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1107

in treating local issues [86]. These systems are solely suited for localized treatment,
as they are invasive to insert, and, as such, their potential applications are also quite
limited. These limitations have, in a way, simplified the applications and require-
ments of the delivery system to such an extent that they have been successfully
commercialized to a great degree to date (which has yet to be achieved for the
majority of controlled release systems), although there is still room for improvement
in these devices as well.

3 Systemic Controlled Release Case Study: Cancer Therapy

Many biologics, including antibodies, enzymes, growth factors, hormones, peptides,

nucleic acids, and vaccines, are clinically limited to parenteral delivery into blood
circulation [5]. Many of the diseases that are treated by these materials are chronic in
nature [5], meaning short-lived injection treatments must be frequently performed
for long periods of time for treatment. The pain and inconvenience of these treat-
ments leads to reduced treatment efficacies and poor patient compliance. Improving
the release of these drugs that are introduced systemically could drastically improve
healthcare. However, when a disease is not confined to a specific organ in the body,
the best method of treatment can be much more complicated to determine.
As we have seen earlier in this and the previous chapter, many ailments
that can affect the body systemically can be treated by polymer-based delivery
vehicles, which, in turn, may be administered in a wide variety of methods. For
example, insulin-releasing systems can be administered systemically or via the oral,
nasal, transdermal, pulmonary, etc. routes. Glucose-sensitive hydrogels and micro-
gels, normally composed from phenylboronic acid (PBA) or its derivatives, can also
be used to deliver insulin as it is required [6]. Mannan-functionalized PLGA can be
used to aid the delivery of vaccines, as mannan is a natural polysaccharide that binds
with mannose receptors on antigen-presenting cells and this can be used to enhance
the uptake of antigen to elicit improves antigen-specific T-cell responses [50, 87].
Nanoparticles can also be used to access the intracellular environment via
the endocytosis process, and, as such, they are currently being investigated as a
safe substitute to viral gene-delivery [61]. The plasma membranes of cellular barriers
are very restrictive to admission of macromolecules (which are normally hydro-
philic) and hydrophilic small molecules into the cell. It is well established that the
transferrin receptor of cells regularly undergoes internalization and recycling, and, as
such, can be utilized to transport transferrin-functionalized polymeric nanoparticles
into cells [61]. Functionalizing these polymeric nanoparticles with ligands such as
transferrin, deslorelin, and RGD peptide are known to enhance the cell entry of
nanoparticles and consequently also improving the desired therapeutic effect [61].
Polymeric nanocarriers can enhance both gene transfection and its duration by
protecting nucleic acids, such as siRNA and miRNA, from degradation by the
numerous nucleases in the body, reduce the number of off-target interactions of
nucleic acids with cell receptors, enhance the entry of nucleic acids into the target
cells, and sustain this intracellular delivery [61]. Although there have been no
1108 S. Campbell and N. Smeets

clinical success in gene delivery to date [88], approaches that are able to maintain the
stability of sensitive molecules, like proteins, hormones, and nucleic acids, are
integral for new drug releasing systems and are currently a significant focus of
drug delivery research [6]. Similar strategies with functionalized nanomedicines
are being researched for a wide range of drugs and, from blood thinners to painkillers
to allergy medications, and each with its own set of pros and cons, particularly when
considering the drug and disease of interest.
This section in particular will focus on what is one of the most challenging
hurdles that modern medicine is currently grappling with: the treatment of cancer.
The best means of treatment is not a trivial choice in the case of cancer. There are a
wide range of potential directions that could result in a viable treatment option for
a variety of cancers, but selecting the optimal direction to proceed in is far from
obvious at this point in time. It may simply be the case that each form of cancer may
be so different and malleable that individual treatment methods must be applied
to any given cancerous tumor. This section aims to briefly examine the state of
polymer-focused research and medical treatments that are currently being employed
and look at the direction that research in this area may head toward.

3.1 What Is Cancer?

Cancer has provided a persistent challenge to medicine and biomedical research over
the last several decades and its devastating effects are still felt today, as it remains
one of the leading causes of death in the world. Over 8.2 million deaths were
reportedly attributed to cancer in 2012 [88]. The mortality rate of cancer has only
recently started to slightly decline, owing to a deeper understanding of the disease
and extraordinary advancements in the diagnosis and treatment methods. However,
this mortality rate remains high at ~20.2% [88], so there is clearly much that remains
to be discovered. The majority of the research involving the delivery of chemother-
apeutics to tumorous sites has yet to be commercialized, which means that, while
there is still a lot of work that must be done to drastically improve mortality rates
from the disease, there is certainly a reason to be optimistic about the treatment of
cancer in the future.
Cancer represents a large array of diseases that involve abnormal cell growth due
to genetic defects in the regulatory circuits of cells that dictate cell proliferation and
homeostasis [89]. These abnormal cells also have the potential to spread to other
locations in the body. Cancer cells undergo unregulated, malignant growth may take
shape in the form of a mass or lump, but they could also be distributed throughout the
body. This malignant growth can be characterized by six distinct alterations in cell
physiology: (1) the cells independently grow and divide regardless of the growth
signals; (2) their growth is insensitive to growth-inhibitory (antigrowth) signals;
(3) they are able to avoid programmed cell death (apoptosis); (4) they possess
an unlimited number of potential replications; (5) they continually promote angio-
genesis, the formation of blood vasculature; and (6) they are capable of invading
healthy tissues and metastasizing to spread to other organs [89].
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1109

Cancer is currently treated by surgical intervention, radiation, and chemothera-

peutic drugs, often utilizing several different chemotherapeutics to have a better
chance of eradicating the cancerous tissues [90]. The drugs themselves are generally
deadly to cells that quickly replicate and are delivered intravenously, and these
drugs, along with the radiation, often kill healthy tissues and cause toxic side effects
to the patient [90]. This is the primary issue associated with cancer treatment:
the mortality rate of cancer remains high due to the fact that there is currently no
means to which chemotherapeutic drugs can be delivered to tumor sites without also
provoking severe, sometimes lethal, side effects to healthy organs and tissues [88].
Developing methods to effectively target and deliver chemotherapeutics to cancer-
ous tissues could minimize the dangerous side effects associated with chemotherapy
and reduce the mortality rate of cancer as a whole [90–92]. Thus, investigating
systems that could potentially target cancers in a more effective manner has been an
important focus of drug delivery research in recent decades.
An idealized treatment system would be a nanocarrier that is capable of over-
coming the body’s natural biological barriers, parsing through and distinguishing
between cancerous and healthy cells, selectively targeting these malignant tissues,
and recognizing and responding to the heterogeneity and complexity of the tumor
microenvironment in order to deliver an optimal dosage of the therapeutic
on-demand [88]. These can be simplified into four steps: retain, evade, target, and
release [93]. These are certainly lofty goals for an engineered drug-releasing vehicle,
and these systems have consequently been traditionally termed as “magic bullets”
[94]. While delivery science is nowhere close to developing a “magic bullet”
currently, science is taking small steps towards this ultimate goal. The focus in the
last few decades has been to develop systems that can more effectively overcome
biological barriers and target cancerous regions in the body to more effectively
deliver drug to the region of interest (the tumor) while limiting the side effects of
the chemotherapeutic as much as possible. These systems are often polymeric
nanoparticles, which have the beneficial characteristics of preventing premature
degradation of the drug, protecting the bulk of the drug from interacting with the
biological environment before it reaches its target, improving the delivery of poorly
soluble drugs (the majority of chemotherapeutics are hydrophobic), possessing the
ability to load multiple drugs/diagnostic agents, being capable of possessing con-
trollable pharmacokinetic release profiles, and improving the intracellular transport
of the drug [88, 90]. There are two general strategies for systemically delivered drug
delivery nanoparticle systems to target cancers: passive targeting and active
targeting.

3.2 Passive Targeting

Passive targeting exploits the anatomical and physiological irregularities of solid

tumors to target nanoparticles to their location [95]. The rapid growth associated
with solid cancerous tumors with high cell densities relies on these tumors receiving
increasing quantities of nutrients and oxygen to afford their accelerated growth rate
1110 S. Campbell and N. Smeets

[95–97]. As a result, they promote substantial angiogenesis, to the point where they
often promote the formation of leaky vasculature, or gaps between the endothelial
cells of blood vessels that are regularly connected via tight junctions [88]. These
gaps in the tumor vasculature are typically balloon from their normal range of
5–10 nm to 100–800 nm [92, 97]. The defective nature of the vasculature around
tumors results in substantial leakage of blood plasma components into the tumor
tissues. Tumor tissues also tend to have dysfunctional lymphatic drainage which
leads to much of the material introduced to the tumorous region also being retained
in these tissues [95]. Collectively, these phenomena associated with solid tumors are
termed the enhanced permeability and retention (EPR) effect.
Polymeric nanoparticles can exploit the EPR effect to improve their accumulation
at the site of the tumor and if they are effectively retained in the tissue they could
release their payloads in the vicinity of the tumor cells. This passive strategy, which
has been used since the mid-1980s, theoretically should be fairly simple to utilize.
Improving the effectiveness of passive targeting should relate to prolonging the
length of time that the drug-loaded nanoparticles can be retained in the circulatory
system [98]. Polymeric nanoparticles can be engineered to remain stable within the
circulatory system and avoid protein adsorption and eventual clearance by the
mononuclear phagocyte system (MPS) system and be within the optimal size range
for taking advantage of the EPR effect. The accumulation of polymer nanoparticles
that can occur around solid tumors due to the EPR effect is depicted in Fig. 3.
As mentioned previously in the chapter, a proven method to improve the circu-
lation half-life of a nanoparticle (and the most commonplace one) is to functionalize
the target vehicle with PEG. In fact, several of the early nanocarrier-based drugs that
were initially developed to utilize the EPR effect and are currently on the market are
PEGylated drug conjugates or PEG-coated liposomes [90, 99]. It is widely regarded
that brush-like PEG configurations that form a hydrated shell are shown to better
evade protein adsorption and phagocytosis [92]. “Stealth” PEG-functionalized par-
ticles should thus allow for the passive accumulation of these particles at the tumor
site, where they could release their drug outside of the cluster of malignant cells or
enter the cells and release their payload.
Particle size and shape is an important consideration when designing nanoparticle
carriers to target tumors. Particles from 30 to 200 nm in size are generally regarded
as the optimal size range for passive targeting [100]. The large gaps in the vessel
structure around some solid tumors allows large nanoparticles to extravasate into the
tumorous regions (depending on the size and the stage of the tumor), so sizes up to
the cut off size for the spleen (~200 nm) can be utilized [88]. These sizes also relate
to the degree to which the nanoparticles can spread throughout these solid tumors.
This is a diffusion-based process, so smaller nanoparticles have a better chance of
spreading throughout the tissue. However, nanoparticles smaller than 30 nm tend not
be retained at well, as they can diffuse back out into the vasculature network, and
may not accumulate at the target site [88].
If they reach and are retained in the target tissues, nanoparticles generally have a
high intracellular uptake, and anisotropic structures may provide a better configura-
tion for binding with the target cells. Spherical nanoparticles have been shown to
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1111

Fig. 3 The delivery of polymeric nanoparticles, small (20–40 nm) and large (40–200 nm), to solid
tumors via the enhanced permeation and retention (EPR) effect. The angiogenesis that is promoted
by fast-growing tumors enhances the gaps between endothelial cells of blood vessels from 5–10 nm
to 100–800 nm to allow for nanoparticles to extravasate and be retained in the tumorous tissues.
These particles would otherwise remain in the blood stream in vasculature surrounded by healthy
tissues. Small nanoparticles may not be retained as well as large nanoparticles, as they are small
enough to escape from the tumor microenvironment, which is much less likely for larger
nanoparticles

follow a laminar flow pattern, so only the nanoparticles near vessel walls will
extravasate via the EPR effect, whereas anisotropic particles have less regular flow
patterns and could possibly accumulate in greater quantities if they could avoid the
clearance via the MPS [101, 102]. However, these anisotropic structures also
generally have a higher degree of opsonization and phagocytotic uptake [88]. Over-
all, spherical particles are the more popular option for nanocarriers as they are better
at avoiding the body’s natural barriers and they can be facilely and cost-effectively
fabricated in a variety of forms. This is especially true of polymeric nanocarriers,
from nanoparticles to dendrimers to micelles.
The simplicity of passive targeting has led to it forming the basis of many current
clinical therapies [97]. However, relying on the EPR effect alone has not provided a
1112 S. Campbell and N. Smeets

therapeutic option that is anywhere near a “magic bullet”-like treatment option for
cancer. An issue associated with this strategy is the fact that all tumors, even tumors
that are of the same type and at the same stage, are different, with varying degrees of
density, heterogeneity, angiogenesis (and associated vessel leakage, permeability,
and retention capability), etc. In fact, some solid tumors do not exhibit the EPR effect
at all and it is difficult to determine the extent to which a given tumor does exhibit
this effect [90]. Notably, as Bae and Park importantly revealed in 2012, while the
EPR effect may affect the distribution of intravenously injected nanoparticles, in
all studies relying on the EPR effect less than 5% of the desired drug from the
nanoparticles ultimately reaches the tumor site [93]. In this work, they questioned
that if the bulk (>95%) of nanoparticles accumulate in other locations, particularly in
the liver, lungs, and spleen, then is passive targeting really targeting at all? [93]. This
is the primary issue currently facing nanoparticles that are designed to target specific
tissues: they primarily accumulate in undesired locations. Thus, a great deal of recent
focus in the area of improving cancer therapy with polymeric nanoparticles has not
only relied on the EPR effect, but also active targeting strategies.

3.3 Active Targeting

Active targeting involves the binding of the nanocarriers to specific, targeted cells
after they leave the blood stream. This is achieved by functionalizing the nano-
carriers with specific ligands that can recognize and bind to particular receptors
on the surface of the target cells via a range of conjugation chemistries [103], and
these targeting techniques have been attempted since the early 1980s [104]. These
functionalization chemistries are highly dependent on the functional groups present
on the ligand of interest (that can be conjugated without affecting its targeting
efficiency) and the functional groups present on the polymersome, micelle,
dendrimer, or polymer nanoparticle. For example, particles functionalized with
PEG brushes to promote a longer circulatory half live could also be functionalized
with an active targeting ligand via conjugating the ligand with the distal end of the
PEG chains. In this case, if the terminal end of the PEG is functionalized with
a p-nitrophenylcarbonyl group, amino containing ligands, such as antibodies, could
then be readily attached to PEGylated polymer nanocarriers via a carbamate (ure-
thane) bond [103]. Examples such as this exhibit why polymer nanocarriers have a
distinct advantage over many other forms of nanocarriers, as they can be designed to
possess specific chemistries to enable them to be functionalized with active targeting
moieties.
To actively target cancer cells in an effective manner the targeting ligand must
bind with a high selectivity to surface markers (antigens or receptors) that are
uniquely expressed on the target cells [90]. If this occurs, nanocarriers could bind
to these cells and these carriers could be internalized (often via receptor-mediated
endocytosis) to release their payload inside the cell [88]. Generally, most surface
markers that are present on cancerous cells are present on some other native cells in
the body, so exclusively targeting tumors is difficult. However, selective targeting is
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1113

possible if the surface marker is sufficiently overexpressed on the target cell relative
to healthy native cells [90]. For example, to improve the therapeutic efficacy of
delivering liposomes with the anti-CD19 monoclonal antibody to B-cell receptors
[105] and the delivery of doxorubicin-containing liposomes to a breast cancer model
with ErbB2 receptors [106], 104–106 and 105 receptors per cell were required,
respectively. Different receptors are also classified as internalizing (such as the
anti-CD19 receptor) or non-internalizing (the anti-CD20 receptor), and these could
be targeted for different purposes [90]. Internalizing receptors could kill malignant
cells individually, whereas noninternalizing receptors could be used to kill cells via
the bystander effect, where the nanocarrier is attached to a cell within a solid tumor
and releases its contents within range of a wide array of malignant cells [90].
The use of multiple targeting ligands on a single nanocarrier could also improve
targeting capacity, as the collective interactions between a carrier with numerous
ligands with several receptors on a target cell result in much stronger bonding [90].
For example, many cancers are characterized by a marked overexpression of folate
receptors (100–300 times that of healthy tissues), leading extensive amounts of
research to focus on using folic acid as a targeting ligand for a wide range of cancers
[50]. Dendrimers with multiple folate groups on their periphery (which is very
simple to design with dendrimers) target these cancerous cells to a much greater
extent than free folate (2,500–17,000-fold) [107]. However, there are downsides to
targeting with extremely high binding affinities, as carriers that extravasate into
a tumor region may interact with only the first cancerous cells that they come in
contact with, anchoring them to tumor cells in close proximity to the leaky vascu-
lature and limiting their degree of penetration into solid tumors [90]. Thus, if active
targeting is to be effective, a fine balance must be achieved between binding affinity
and other factors that affect the tumor penetration depth of the polymeric nano-
carriers (i.e., size, surface chemistry, etc.).
Active targeting moieties that are often employed include proteins (including
antibodies and antibody fragments), nucleic acids, peptides, vitamins, and carbohy-
drates [90]. These moieties have been studied for targeting since 1981 [104] and the
first ligand-drug conjugate was commercialized in 2000 [90]. The first attempts at
targeting focused on the use antibodies as targeting ligands. Antibodies can be used
to treat cancer alone or can be conjugated to nanocarriers and whole, native anti-
bodies with two binding sites per molecule or antibody fragments can be used for
targeting. Whole monoclonal antibodies can be used alone to treat cancers, as they
have high binding affinities to the surface of cancer cells and immune cells can bind
to the exposed Fc portion of the antibody and subsequently initiate a signaling
cascade to kill the malignant cell [90]. This process may not be sufficiently selective,
as the Fc portion can bind to normal cells and lead to increased immunogenicity and
uptake of the nanocarrier in the liver and spleen. Monoclonal antibodies, due to this
constant Fc region, are also bulky molecules (~150 kDa) that will dramatically
increase the size of the majority of nanocarriers that they are attached to.
Antibody fragments, such as antigen-binding fragments (Fab), dimers of Fabs
(F(ab0 )2), single-chain fragment variables (scFv), and diabodies (dimers of scFvs),
contain the binding components of monoclonal antibodies and a lesser number of
1114 S. Campbell and N. Smeets

redundant amino acids [90]. The resulting fragments are smaller in size, have lower
immunogenicity, and target in a more selective manner [88]. Fusion proteins that
consist of two or more genes can also be engineered to bind to target cells with a high
affinity. These proteins, and small proteins known as affibodies, could be designed to
interact with specific conformations of cell receptors to improve their targeting
specificity. This has been examined in a study that aimed to deliver siRNA to
activated lymphocytes. These white blood cells possess an integrin LFA-1 receptor
whose conformation shifts from a low affinity, non-adhesive form on nonactivated
leukocytes to an adhesive, high affinity form upon activation by the immune system
[108]. Complexes of siRNA and a fusion protein containing a scFv were shown to
selectively deliver the siRNA to activated lymphocytes 10,000-fold more than
nonactivated cells [108]. Taking advantage of the conformation of receptors on
cancerous cells could be exploited in a similar manner to attempt to target cancer
more effectively with antibody fragments.
Aptamers are synthetic, short, single-stranded oligonucleotides that are selected
in vitro from large arrays of random sequences (~1014–1015) to bind to specific
targets. These nucleic acid oligomers can form complex 3D structures that can
specifically bind to cancer cell receptors and can be tethered to polymeric nano-
particles. For example, Farokhzad et al., developed biodegradable PLGA-b-PEG
nanoparticles encapsulating docetaxel that were surface functionalized with RNA
aptamers to treat prostate cancer [109]. These aptamers recognize and coordinate
with prostate-specific membrane antigens, which are situated on the surface of
prostate cancer cells. A murine in vivo treatment with these nanoparticles resulted
in markedly lower toxicity and significantly better treatment outcomes than the
drug alone, which was attributed to the selective targeting capacity of the aptamer-
polymer nanoparticle system [109]. Screening techniques, including newer forms of
high throughput screening, have been employed to attempt to optimize the targeting
efficiency and selectivity of various antibodies and their fragments to various
varieties of cancer, leading to a vast expansion in the library of potential targeting
antibodies and aptamers [99].
Peptides represent another potential targeting ligand. Peptides have a low molec-
ular weight, are easy to produce, lack immunogenicity, and can be facilely (and
densely) fastened to the surface of nanoparticles [88]. Peptides regularly have lower
binding affinities than most other targeting ligands, but they can also be attached in
greater densities than most alternatives to compensate for this relative disadvantage.
A range of differing peptides can interact with receptors on cancer cells and have
been explored as potential targeting moieties on delivery vehicles. The RGD peptide
is one of the peptides that is often used for targeting, as it has an affinity for integrin,
which are often overexpressed by the endothelium during tumor angiogenesis [88].
However, small binding peptides can also nonspecifically bind to healthy cells, as
RGD is known to do with other integrins on normal cells, negating the intent to
selectively target malignant regions [88].
Many of these active targeting strategies still rely on the EPR effect to get within
range of tumor before they can make use of their functionality to target cancerous
cells. Thus, many nanomedicines must be designed to navigate the circulatory
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1115

system for as long as possible while avoiding opsonization and rapid clearance, and
are also functionalized with PEG as a result. However, PEG-functionalization can
also inhibit interactions between the nanoparticle with the target cells, leading to
lower efficacy, especially when active targeting strategies are also being employed
[88]. As a response, strategies exploring the use of biomimetic coatings and or
particles where the PEG structure is removed upon entering the tumor, often using
stimuli-responsive chemistries that interact with the unique qualities of the tumor
environment (i.e., higher temperature, lower pH, etc.), have undergone extensive
development in recent years [88].
Stimuli-responsive polymeric nanoparticles have the potential to provide better
spatial, temporal, and dosage control via on-demand delivery. These nanocarriers
would undergo certain protonations or molecular or supramolecular conformational
changes in response to a change in its local environment (temperature [110–112],
pH [113–115], or solute concentrations [116, 117]), which could be provoked
by an external stimulus [118, 119]. Thermosensensitive “smart” polymers like
poly(N-isopropyl acrylamide) (PNIPAM), poly(oligoethylene glycol methacrylate)
(POEGMA), and, less famously, poly(γ-2(2-(2-methoxyethoxy)-ethoxy)
ethoxy-ε-caprolactone)-b-poly(γ-octyloxy-ε-caprolactone) all have a lower critical
solution temperature (LCST). Thermosensitive polymers become less water soluble
as their local temperature increases above their LCST, causing the polymers to recoil
and take up less hydrodynamic volume. This is a reversible process, such that when
the temperature is subsequently lowered below the LCST, the polymers become
more soluble and return to their original state. Cross-linked networks of these
polymers reversibly deswell (or shrink in size) when their temperature is increased
above their volume phase transition temperature (VPTT, which is normally slightly,
~1  C, above the LCST of their comprising polymers) [112, 118]. These particles
could be utilized in combination with locally-induced hyperthermia treatments,
which is a clinical treatment that involves the targeted short-term exposure of
cancerous tissues to elevated temperatures (39–43  C) that will preferentially elim-
inate the more temperature-sensitive cancer tissues while being safe for normal
tissues [120].
Using microgel nanocarriers composed of these thermosensitive polymers in
conjunction with hyperthermia treatments could be used to alter the local tempera-
ture of these “smart” microgels at the tumour site, and could allow for the drug-
loaded nanocarriers to become insoluble, aggregate, and accumulate as a coacervate
at this site (as they become less hydrophilic and less dispersible in aqueous solutions
when they deswell), and release drug as they deswell and accumulate in tumorous
regions [110, 121]. While this has not been shown for microgels in vivo, thermo-
sensitive liposomes have been engineered to release all of their contained drug at
hyperthermic temperatures, and have undergone clinical trials in a combined hyper-
thermia/chemotherapy treatment for both breast cancer, colorectal liver metastasis,
hepatocellular carcinoma [118, 122].
Hyperthermia can also be induced by the nanocarriers themselves by adding
inorganic nanoparticles to “smart” systems that can produce heat in response to
external triggers. For example, PLGA nanoparticles were designed to have a glass
1116 S. Campbell and N. Smeets

transition temperature (Tg) of 45  C and were half-coated with a gold layer that could
produce enough heat in response to near-IR irradiation to induce hyperthermia,
releasing drug to show antitumor activity in breast cancer models in the
process [123].
Magnetic nanoparticles have also been coated with PEG to stabilize the nano-
particles for hyperthermia treatments, and have become one of the clinical standards
for hyperthermia treatments (and magnetic resonance imaging (MRI)) [124, 125].
When alternating magnetic fields (AMFs) are applied to magnetic nanoparticles like
superparamagnetic iron oxide nanoparticles (SPIONs), the SPIONs generate heat
that can be used for hyperthermia treatments. Combining hyperthermia with che-
motherapy synergistically improves on the cytotoxic effects on cancerous cells
of either therapy alone [124, 126, 127], so achieving drug release concurrent to
localized hyperthermic heating with these particles could prove quite advantageous.
Consequently, numerous core-shell nanoparticles with a magnetic SPION core and
polymer coatings loaded with drug have been developed [128, 129]. The polymer
coating could also be thermosensitive to improve the diffusion of drug upon
hyperthermia heating as well. An example of this is in nanocapsules containing
both SPIONs and poly(styrene allyl alcohol) (PS16PAA10) that were capable of
releasing hydrophilic fluorescently-labeled DNA plasmids and hydrophobic quan-
tum dots on-demand upon heating induced via short AMF applications [130]. Poly-
mer-coated SPIONs like these can have additional functionalities rather than a drug
delivery with hyperthermia alone, but could also be used to generating contrast
in MRI, and could be magnetically targeted to the site of interest [131, 132].
The complexity of the magnetic guidance of sufficient quantities of magnetic
nanocomposite particles and concurrently using hyperthermia treatments have
slowed its clinical application [118], but magnetic nanoparticles are being used for
clinical treatments at present [127], so these intriguing advances might be surpris-
ingly close to being realized clinically.
There is also a slight difference in pH that exists between the extracellular
environment of solid tumors (6.5–7.2) and healthy tissues (~7.4) that can be
exploited for spatially controlled drug release [118]. This disparity is attributed to
the abnormal increase in angiogenesis associated with rapidly growing tumors,
which leads to a deficit in oxygen and nutrients and a glycolytic metabolism that
produces acidic metabolites [118]. This opens the door for the use of pH-responsive
polymeric nanomedicines for cancer treatment, provided that their response is
sensitive enough to experience a transition due to a subtle change in pH. Chitosan
is a pH-sensitive polymer that swells upon the protonation of its amino group
(pKa ~6.3) and hollow chitosan nanospheres were shown to successfully deliver
tumor necrosis factor α (TNF-α) to breast cancer cells upon reaching their slightly
acidic environment to suppress their growth of in a murine model [133].
Polymeric micelles have also been designed to possess sharp pH-dependent
micellation/demicellation transitions around tumoral pH values (6.4) by using a
block copolymer of methyl ether poly(ethylene glycol) (MPEG) and poly(β-amino
ester) (PBAE) [134]. These micelles were shown to deliver the chemotherapeutic,
camptothecin (CPT), to the target breast cancer site in murine models and burst
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1117

due to the low pH of these areas to release an effective quantity of the CPT while
lowering the side effects to other tissues over delivery of the free drug alone [134].
Similar micelles of piperidine- and imidazole-modified PEG-PBAE have since been
used to treat cerebral ischemia, which is when there is insufficient blood flow to the
brain, resulting in a lower pH that can be used to target the therapeutic [135].
These pH-responsive systems can also be combined with inorganic nanoparticles
to provide additional functionality. An excellent example of this are the hollow
superparamagnetic microgels fabricated via supramolecular assembly by Chiang
et al. [132]. These are hollow particles with a pH-sensitive poly(acrylic acid-co-N-
isopropyl acrylamide (NIPAM)) gel shell containing SPIONs that was stabilized
with PEG. The hollow core could be loaded with drug and the particles could be
magnetically guided to tumor cells before being internalized. Drug release is induced
at acidic pHs (present in intracellular endosomes and lysosomes) and could be
enhanced ~12-fold by AMF application [132]. The particles were cytotoxic against
tumor cells via drug release and hyperthermia individually, with further enhanced
efficacy in when they were used in combination. Another strategy utilized “smart”
microgel nanocomposites consisting of gold nanoparticles encapsulated with a
p(NIPAM-co-acrylic acid) hydrogel shell that could be internalized by specific
cancer cells and release drug due to the lower pH of local intracellular
environment [136].
There are several current nanocarrier systems in clinical trials designed to target
cancer regions, much more than any other disease or region of the body. The fact that
there are much more nanoparticles for chemotherapeutic delivery than any other
treatment speaks to the prevalence and threat of cancer to global healthcare and the
importance of finding better therapies to combat it. These clinical examples of
nanomedicines that target cancers are neatly summarized in an excellent review by
Xie et al. [88]. To be fair, most of these nanocarriers are liposomes, which can be
functionalized with similar moieties to polymeric nanoparticles, but are cheaper,
easier to manufacture, and simpler to get approved by regulatory bodies. They are
also less stable and prone to bursting upon injection, a significant issue that poly-
meric nanomedicines are not as liable to do [108]. Liposomes have been PEGylated
to avoid their rapid clearance by the MPS and prolong their circulation time [6, 94],
including Caelyx, which has been clinically approved to treat metastatic breast and
ovarian cancers as well as doxorubicin but with lesser side effects [137]. A poly-
meric micelle called Genexol-PM has been approved to deliver paclitaxel, a chemo-
therapeutic, to treat breast cancer [138]. Polymer-drug conjugates have also been
approved to treat leukemia and hepatocellular carcinoma, with asparaginase
functionalized with PEG [139] and neocarzinostatin functionalized with poly(sty-
rene-co-maleic acid) [140] respectively, to improve their circulation half-lives.
Advanced to preclinical trials are underway for several other drug-loaded polymeric
systems, including PLA microgels with a PEG coating, micelles, dendrimers, and
polymer-drug conjugates [88].
These delivery systems in preclinical trials and already in the clinic represent
significant strides for targeting with nanoparticles in the right direction. However
these materials are nowhere close to the “magic bullet” that this field is pursuing. The
1118 S. Campbell and N. Smeets

development of nanocarriers that can effectively target solid tumors represents the
major bottleneck in the advancement of cancer therapeutics and any gains that
have been made thus far in their targeting efficiency have been modest [88]. This
is because tumors are highly diverse and malleable entities that are extremely hard to
predict, with the variations in tumor type and conditions from patient to patient, so it
may be impossible to develop a particle to treat a given cancer type or even to predict
what a given particle will do and how effective it will be. In fact, even the way that
cancers are classified may be not be correct [141], which could inhibit the develop-
ment of clinical treatment methods. Incremental improvements in targeted delivery
will ultimately lead to substantially improved health outcomes, but the large focus on
drug delivery using targeting nanoparticles in this field at present may be not be the
best route for the field as a whole. As opposed to attempting to do everything at once
(nanoparticles are still relatively new, after all), an intensification of simpler, mac-
roscale cancer treatment systems might present as a more logical first step towards
using controlled release systems and getting polymeric release systems approved for
clinical use in the short term.

3.4 Alternative Cancer Therapies

Macroscale cancer therapies offer extended therapies over nanoparticles as they can
be implanted/injected adjacent to solid tumors, can be loaded with more drug, and
are not cleared nearly as rapidly. As noted in the section on brain delivery, biode-
gradable poly(carboxyphenoxypropane-co-sebacic acid) wafers that are implanted
after a tumor is removed and can release its payload as it degrades over 3 weeks in
this localized treatment regime have been in clinical use for years [57, 58]. Similar
implantable systems composed of biodegradable polymers have been explored and
clinically utilized post-surgery to help ensure that the cancerous tissues are fully
removed, deliver drug locally to decrease the impact of side-effects, and aid in the
infiltration of healthy tissues [142].
Similarly, macroscale hydrogel-based controlled release systems can improve
chemotherapy by delivering the chemotherapeutic directly to the tumor locally,
decreasing the degree of exposure of healthy tissues to the drug to avoid side effects,
increasing the half-life of the chemotherapeutic, prolonging the duration of action,
and protecting the activity of the drug of interest [121]. Hydrogels have been
explored for treating cancers with traditional chemotherapeutics, and combinations
of therapeutics, as well as for the delivery to siRNA to improve clinical outcomes
[121]. Prefabricated hydrogels made from “bottom-up” processes can be implanted
post-surgery or placed adjacent to tumorous regions to treat cancers. A clinical
example of this is the biodegradable VANTAS hydrogel that is implanted to deliver
controlled, sustained release of histrelin acetate to treat prostate cancer [143].
A significant drawback of “bottom-up” hydrogels is that they have to be synthesized
outside of the body and subsequently must be surgically implanted, which is
inconvenient for the patient and requires a significant amount of time from medical
professionals.
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1119

Hydrogels capable of controlled release that can make use in situ gelation via the
physical or chemical cross-linking of presynthesized polymer chains, using thermo-
gelation or the use of various biorthogonal (click) reactions, would be much more
convenient for all parties involved in cancer treatment [78, 144, 145]. As a result,
injectable hydrogels that can be administered to the body without invasive surgery
are being explored extensively in drug delivery research. For example, a hydrogel
comprised of dendrimers that thermoaggregate to form a gel after injection in the
body to locally deliver Dox and the radioisotope [131]. It was shown to exhibit
reduced side effects and improved tumor growth suppression and survival outcomes
in murine breast cancer models with this combination therapy [146]. This is an
example of the combination or concurrent therapies involving multiple chemother-
apeutics that have been used for years to combat the heterogeneity and diversity of
tumors, as well as the ability of cancer cells to develop resistance to drugs, to achieve
better patient outcomes [147].
Numerous strategies involving the delivery of a chemotherapeutic drug along with
radiotherapy and gene delivery are now being explored, within both nanomedicines
and macroscale hydrogel systems. For example, an in situ forming hydrogel com-
posed of Pluronic F27 (PEO99-PPO67-PEO99) was able to show significant breast
tumor suppression via the localized delivery of both paclitaxel, a common chemo-
therapeutic, and lapatinib, a HER2 kinase inhibitor, in an example of multiple
chemotherapeutic combination therapy [148]. Chemotherapeutics have also been
combined with microRNA in an implanted hydrogel scaffold for combined therapy
(cisplatin was the chemotherapeutic in this case) to show efficacy in shrinking the
tumor and prevent its metastasis for a specific form of breast cancer [149]. These
studies are examples of the clear benefits of treating tumors with a combination of
strategies to eliminate as much of the tumor as possible.
The same can be said for combining chemotherapy with hyperthermia treatments
[124, 126, 127]. Magnetic hyperthermia was discussed in the nanoparticle section,
but it is often difficult to accumulate sufficient quantities of magnetic nanoparticles
at the desired site to make the treatment effective [121]. Magnetic hydrogels with a
known concentration of magnetic nanoparticles (often SPIONs) can be placed or
injected into specific locations to obtain improved control over hyperthermia treat-
ments. Hydrogel-based materials can have other embedded nanoparticles to create
nanocomposite materials capable of facilitating hyperthermia as well, including gold
nanoparticles/nanoshells, graphene oxide, and carbon nanotubes, which generate
heat in response to near-IR irradiation [150]. Gold nanoparticles are generally used
more often than carbon nanotubes, due to their lesser toxicity, but neither can be
efficiently cleared from the body, unlike SPIONs [150]. “Smart” nanocomposite
hydrogels capable of externally-controlled release can be designed if the hydrogel
is made or thermosensitive polymers or if other thermosensitive components are
imbedded in the hydrogel along with the inorganic nanoparticles. A good example of
a “smart” nanocomposite hydrogels with the potential for concurrent chemotherapy/
hyperthermia is a thermosensitive injectable and PNIPAM-based hydrogel with
SPION cross-links was able to heat in response to an AMF and release a burst of
the model drug as the hydrogel heated and deswelled/compressed [151].
1120 S. Campbell and N. Smeets

Another thermosensitive PNIPAM-based hydrogel nanocomposite containing

gold nanoshells that can generate heat in response to near-IR irradiation was
shown to release both Dox and DNA concurrently, and were shown to have an
enhanced burst release when near-IR was applied and induced deswelling of the
hydrogel (albeit only for a single cycle) [152]. These systems, particularly if they are
also injectable and biodegradable, are very promising as they could be capable of
achieving remotely-controlled, precise periodic delivery of therapeutics, also termed
chronopharmaceutical drug delivery, which would not only be useful for cancer,
but many other ailments as well [153].
Nanocomposites capable of chronopharmaceutical drug delivery that could deliver
externally-mediated bursts of release over multiple cycles would represent a signif-
icant step towards improved “on-demand” cancer therapy [153, 154]. In fact, periodic
bursts of chemotherapeutics have shown advantages over the sustained release
strategies [1]. The study that determined this was an interesting injectable and self-
healing alginate hydrogel that was able to have its calcium cross-links temporarily
disrupted by an external ultrasound source before rapidly self-healing. Ultrasound
applications were applied daily to delivered daily burst doses of mitoxantrone to
effectively shrink xenograft breast cancer tumors [1]. Another nanocomposite system
with chronopharmaceutical capability was an injectable hydrogel with embedded
SPIONs, thermosensitive microgels, and a model drug [2, 155]. This system could be
heated by short AMF applications, shrinking the thermosensitive microgels to
enhance the release of drug from the system, and this could be achieved for multiple
cycles for at least 5 days [2]. The field as a whole is edging closer and closer towards
injectable and degradable systems capable of improved chronopharmaceutical deliv-
ery over longer time frames that could benefit a wide range of therapies.
Responsive systems that respond to remote stimuli still have several challenges
ahead of them. Chiefly among these is that better chronopharmaceutical control is
required for nearly all systems before they can become clinically available, partic-
ularly for any of the injectable and biodegradable systems. Even if these advanced
“smart” systems were currently capable of well-defined spatiotemporal drug deliv-
ery, the trigger mechanisms for nearly all stimuli-responsive materials would have to
undergo numerous and complex enhancements and optimizations to scale these
actuators up from benchtop to clinical scales.
Another promising new avenue of cancer research is immunotherapy. Immuno-
therapy can successfully utilize the immune system to detect and treat cancers,
highlighted by recent clinical trials involving checkpoint blockade antibodies
[156–158]. Cancer vaccines are intended to initiate immune reactivity against
existing cancerous tissues through activating antigen presenting cells (APCs) to
provoke T lymphocyte cells to specifically lyse tumor cells [147]. Porous polymeric
biomaterials (made from gelatin, PLGA, and alginate hydrogels) can improve the
efficiency of these immunotherapies by controlling the environment that immune
cells come across antigens, cancerous cells, and stimulatory signals [147]. For exam-
ple, biomaterials can be used to control the rate at which antigens are exposed to
APCs, as a short, low-dose of antigen may lead to the failure of a T cell response, and
an overexposure to the antigen may lead to T cell exhaustion [147].
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1121

A biomaterial vaccine system made from a PLGA hydrogel was shown to be

capable of the sustained release of granulocyte macrophage-colony stimulating
factors (GM-CSFs) to promote APC accumulation in the scaffold [159, 160]. Within
this scaffold, nanoparticles of CpG oligonucleotides are presented to the APCs,
which become activated and then migrate to lymph nodes to initiate an anti-cancer
immune response. This response was sufficient to show complete the regression of
melanoma tumors in 47% of the mice studied [161]. This system is currently
undergoing clinical trials, and implantable scaffolds such as this are entirely modu-
lar, allowing for a wide range of immunostimulants to be incorporated in their
networks [147]. Adjuvants can also be incorporated to further promote immune
responses, such as aluminum salts, silica nanoparticles, or cage-like nanoparticles
called ISCOMATRIX [147, 162]. There are also several examples nanoscale sys-
tems designed to target lymph nodes or APC receptors, based on polystyrene (with
optimized sizes of 40 nm), pluronic, and PEGylated nanoparticles [147]. A signif-
icant portion of the macroscale hydrogel work has originated from David Mooney’s
lab, which recently developed porous, injectable, sponge-like cryogel that release
GM-CSFs ad CpG oligonucleotides to recruit APC to promote specific antitumor
immune responses [163]. Overall, using polymeric release systems to mediate the
delivery of cancer vaccines at controlled rates presents as a promising emerging
methodology to treat cancers from within the patient’s own body.
In summary, developing effective methods to treat the dynamic tumor microen-
vironment has proven challenging. Polymeric controlled release systems have made
great advances in cancer therapy, to the point where several advanced controlled
release systems have reached the clinic. These systems include both targeting
nanomedicines and macroscale biodegradable polymers and hydrogels. Research
towards more effective treatments involves the delivery of traditional chemothera-
peutic drugs, hyperthermia treatments, gene delivery, immunotherapy, and combi-
nations thereof. There are positive and negative qualities to each strategy and there is
no obvious single path to pursue. A single method or strategy to cancer or even a
specific subtype of cancer may be unrealistic, as the treatment strategy (along with its
regulatory approval process) would likely have to be as malleable as cancers are
known to be. Thus, a combination of these strategies is likely the best route, so
ensuring that there are minimal side effects for any given strategy/treatment will be
important. This is the direction that current cancer research is striving towards. As a
result, the successive small improvements in technology that are currently taking
place will likely lead to achieving minimizing side effects during treatment while
attaining consistently better outcomes in cancer therapy.

4 Current Understanding/Trends and Future Prospective

The general theme underlying much of drug delivery research thus far is that while
there are extensive amounts of research taking place, few of these systems are in
clinical trials or have reached the market. This is due to the fact that the bulk of the
research is currently focused on the development of nanomedicines that are
1122 S. Campbell and N. Smeets

attempting to be “silver bullets” that solve all of the issues associated with conven-
tional delivery all at once. This is despite the fact that much of the nanomedicines
with targeting potential do not reach their intended site of action, with, at best, only
~5% of the best nanomedicines reaching their target [93, 118]. Thus far, nano-
medicines have only achieved marginal gains over much of the simple, conventional
drug delivery, which has stunted their commercialization potential. Indeed, in terms
of nanoparticles, mainly cancer-related treatments are clinically approved or are
undergoing clinical trials due to the toxicity of chemotherapeutics and the subse-
quent benefits of even minor improvement in targeting effectiveness [164, 165].
Achieving effective targeting will continue to be difficult to achieve, due to the
heterogeneity of the target tissues, especially between different individuals, and the
limited accessibility of many of the biological targets [118]. For example, cancer
nanomedicines mostly still rely on the EPR effect, which is unlikely to be clinically
relevant, as this is highly dependent on the specific tumor and individual [93]. The
rise of personalized medicine might shed light on how to detect some of these
differences to predict whether or not specific therapeutic strategies should be effec-
tive for specific individuals. In forthcoming decades, personalized medicine could
be coupled with more effective targeting therapeutics to achieve better outcomes to
a wide variety of therapies.
As the small but consistent improvements in the efficiency of these delivery
polymer-based delivery strategies continue, increasing numbers of improved deliv-
ery systems will ultimately be introduced into the clinic to improve the healthcare of
millions of people. Nanotechnology could revolutionize medicine, and, as indicated
by the rapidly increasing number of innovations in the field and the substantial
increase in nanotechnology-related patents, one thing is clear: it is here to stay.
That does not mean that the degree to which the drug delivery field as a whole is
focusing on targeting systems cannot be questioned. While targeting potential will
certainly improve much further as polymer technology and our understanding of the
underlying biology advance, the current emphasis on achieving better control over
drug release using nanotechnology may be neglecting alternative macroscale deliv-
ery strategies that have a good degree of potential. Such technologies are easier to be
characterized by regulatory agencies and could allow for novel, improved therapies
to help people all over the world in the next few years rather than decades. Indeed,
several of the more revolutionary breakthroughs in recent years regarding controlled
delivery are from macroscale system, namely the implantable MicroCHIPs device
that has unparalleled remote chronopharmaceutical control to treat osteoporosis
[166] and the injectable hydrogel scaffolds for immunotherapy [163]. While nano-
medicines have a bright future in the long term, the extent of the current shift
away from the development of macroscale therapeutic devices may inhibit the
commercialization of implantable or injectable polymer-based delivery systems
that could improve the healthcare system in the short term (and provide as a platform
for “smart” delivery strategies before more beneficial nanoscale examples arise).
There are, however, several scientific and regulatory challenges that must be
solved before much of this research leads to tangible commercial products. There are
significant challenges regarding the cost of commercializing these systems and the
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1123

regulatory concerns associated with new developments. For example, the cost of
developing novel hydrogel controlled release systems is estimated as $50 million
to $800 million USD, providing significant barriers to commericalization [167].
The systems discussed in this and the previous chapter involve drug release systems
have drug contained within a polymeric systems and are thus considered combina-
tion products by the regulatory agencies, which slows the regulatory process to
7–10 years [167]. In comparison, scaffolds without containing drug typically take
1–5 years to successfully advance through the regulatory process. This longer
timeframe can limit commercial viability with the finite timeframe for patent pro-
tection [167]. There is also a balance that must be met between complex “smart”
drug releasing systems that can improve therapy and simple systems that can more
easily traverse the FDA process.
Nanomedicines are generally trickier to achieve FDA approval from, as assessing
their safety is much more difficult. Most nanoparticles will end up in the lungs
(particularly if they are large, >150 nm), liver, kidney, and spleen [168]. Safety
concerns regarding the accumulation of materials in these organs are paramount, and
new methods of safely studying and analyzing the cumulative effects of nanoparticles
over time must be developed. This is why the development of new innovations in
materials and polymer systems that are biodegradable and can be efficiently cleared
from the body is of such importance. Furthermore, the toxicological effects of
functionalizing nanoparticles with specific targeting ligands must be further studied.
An important step towards realizing this will be the development of standardized
nanotoxicity assessments, along with innovations in tagging nanocarriers and observ-
ing their biodispersity over time, that will result in improved knowledge of what
properties and characteristics of nanoparticles cause toxicity and lead to safer, more
effective nanomedicines in the future [169]. A nanotoxicological classification sys-
tem (NCS) is currently being proposed in order to establish such a standardized
methodology for evaluating the safety of nanomedicines [170].
There are several other barriers that currently impede the process of getting a
controlled drug delivery system from the benchtop to the clinic. One major issue is
that there are often poor relations between 2D in vitro models and in vivo animal
studies, and incompatibilities between the animal models used in in vivo studies and
the humans that the drug systems are being developed for. These incompatibilities
have led to thousands of drug delivery systems failing as they go from in vitro to
in vivo studies or failing in preclinical and clinical studies as technologies that were
shown to be effective in animal models are ineffective or cause hazardous side
effects in humans. This unfortunately may be the case of several of the studies
showing success in mouse studies discussed in this chapter. The inverse is likely true
too, as several systems that may have been effective in humans and shown real
commercial promise may have been phased out earlier on when they exhibited
insufficient efficacies in 2D cell culture or in animal models.
Tissue engineering that focuses on the development of 3D models to test drugs and
polymeric drug releasing systems on are a potential solution to this issue. Hydrogels
can be used to engineer small scale 3D in vitro systems or can be incorporated into
emerging organ-on-a-chip technologies to better mimic conditions within the human
1124 S. Campbell and N. Smeets

body. This, along with improvements in tissue engineering of larger scale organoids
(often using hydrogels with specific functionalities to mirror human soft tissues),
could result in improved relations between preclinical and clinical studies
[121]. These systems could ultimately replace the use of 2D in vitro and animal
in vivo work in the future. If they are effective enough at mimicking human tissues,
they may ultimately be incorporated into and accelerate the regulatory process for
new drugs and drug delivery systems, and could be used to test how specific
individuals react to specific drugs or drug delivery systems [171].
There are several other emerging technologies that could significantly impact and
alter the direction of drug delivery research are on the horizon. Clustered regularly
interspaced short palindromic repeats (CRISPR)-Cas9 is a new disruptive gene
editing technology that is capable of site-specific modifications of DNA using
guide RNAs that recognizes the specific DNA target sequences in a surprisingly
simple process [172]. As a result, laboratories worldwide are utilizing this technol-
ogy throughout biology, but it will be crucial for many of these applications to
develop methods to safely and efficiently deliver Cas9 and its guide RNA via novel
nanoscale polymeric drug delivery systems. These early systems would likely
attempt to target specific cells by having certain surface functionalities to deliver
their payload within the cell.
The cells in your body constantly regulate the nutrients that they take in and
the waste products they excrete. Specialty cells can also regulate important proteins,
hormones, and growth factors in your body. This is how glucose levels are
maintained in the body to sustain normoglycemia. In this case, functioning beta
islet cells optimized to monitor glucose levels and deliver the appropriate amount of
insulin to regulate bodily glucose concentrations. Cellular therapies utilize regula-
tory cells like this to deliver appropriate levels of hormones and other materials to the
body. However, it is difficult to maintain healthy allogeneic or xenogeneic cells
without activating the immune system, which limits the duration of cellular therapies
[173]. As such, much research centers on prolonging the lifetime and efficacy of
these cellular therapies. The most successful example of this may be a system where
beta islet cells that produce and deliver insulin where encased in 1.5-mm tri-
azole–thiomorpholine dioxide-functionalized alginate hydrogel spheres [173]. The
size and functionality of the hydrogel spheres were carefully selected via combina-
torial library of materials as they were found to elicit minimal foreign body responses
over long time frames (>6 months) [174, 175]. The resulting hydrogel spheres were
able to keep the beta cells active and able to maintain normoglycemia in non-human
primates for an unprecedented 6 months, an extraordinary result [173]. This is a
perfect example of how effective cellular therapies can be in delivering drugs when
the integration of polymers and cells is designed correctly.
There are also several theories to counter the effects of aging that are currently
being explored. Senescent cells are cells that no longer grow and remain viable
[176]. These cells are thought to be a significant proponent of aging (and multiple
other chronic diseases) [176], as they build up over time, and a study that cleared just
30% of senescent cells showed significant improvements in age related phenotypes
in mice as a result [177]. These cells are believed to be dependent on antiapoptic
27 Drug Delivery: Localized and Systemic Therapeutic Strategies with Polymer. . . 1125

pathways to persist in the body and are susceptible to be cleared by several drugs and
siRNAs known as synolytic agents [176]. “Smart” polymeric drug delivery devices
that are capable of delivering intermittent doses, potentially by periodic or
chronopharmaceutical delivery, of synolytic agents thus could have the potential to
treat the effects of aging and other chronic diseases [176].
There are also new mechanisms for targeting nanomedicines being developed.
For example, self-propelled nanocarriers are in the proof-of-concept stage, making
use of chemical reactions to aid the targeting of a nanomedicine to its desired target
[178]. This is a small step towards nanorobots that circulate in the blood stream and
search out diseases, what some people envision as the ultimate “silver bullet.”
Overall, the field of drug delivery still has a wide range of challenges that must
be overcome to translate some of the research involving polymeric systems into
commercial real-world products. Drug delivery is at the intersection of several other
complementary disciplines, including polymer chemistry, biology, nanotechnology,
medicine, toxicology, and more. It requires knowledge of each of these broad fields
in order to successfully design and produce novel drug carriers for specific purposes.
This is also still a young, cutting-edge field, and yet we may just be on the cusp of
many of these release systems reaching the market sooner rather than later.
The landscape of the field of drug delivery is constantly shifting and will change
significantly in the coming decades, with the recent disruptive technologies and
ideas spread within this field, including CRISPR technology, antiaging techniques,
the prospect of individualized medicine, organ-on-a-chip technologies, and many
more, as well as the introduction of new technologies that there is no way of
anticipating. The field is continuing to transition into improved solutions, there are
significant challenges up ahead. Issues associated with the regulatory system, quality
control, reproducibility, and toxicity are will be particularly important if clinical drug
delivery is to transition further towards nanoscale materials and systems [168]. How-
ever, these obstacles will be overcome, and, until then, the field of drug delivery
using polymer systems will continue to expand and become immensely beneficial to
health and well-being of people all over the world.

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Organic-Inorganic Hybrid Materials and
Their Applications 28
Rizwana Mobin, Tauseef Ahmad Rangreez, Hamida Tun Nisa Chisti,
Inamuddin, and Mashallah Rezakazemi

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136
1.1 Synthesis of Organic-Inorganic Hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1137
1.2 Classification of Organic-Inorganic Hybrid Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142
1.3 Applications of Organic-Inorganic Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1143
2 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1150
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1150

Abstract
The organic-inorganic composites in addition to providing new alternate mate-
rials represent a class that exhibit novel, astonishing features, and their properties
can be tailored to suit a particular application. These are developed by combina-
tions of two or more materials that differ in form or composition on a macroscale.
The matrix and the filler are two indispensable components of a composite. In this
chapter, synthetic routes, viz., sol-gel, blending, and emulsion polymerization,

R. Mobin
Government College for Women, Srinagar, India
e-mail: [email protected]
T. A. Rangreez (*) · H. T. N. Chisti
National Institute of Technology, Srinagar, India
e-mail: [email protected]; [email protected]
Inamuddin
Advanced Functional Materials Laboratory, Department of Applied Chemistry, Faculty of
Engineering and Technology, Aligarh Muslim University, Aligarh, India
e-mail: [email protected]
M. Rezakazemi
Faculty of Chemical and Materials Engineering, Shahrood University of Technology,
Shahrood, Iran
e-mail: [email protected]

© Springer Nature Switzerland AG 2019 1135

M. A. Jafar Mazumder et al. (eds.), Functional Polymers, Polymers and Polymeric
Composites: A Reference Series, https://doi.org/10.1007/978-3-319-95987-0_33
1136 R. Mobin et al.

classification, and application of organic-inorganic composites as ion-selective

membrane electrodes has been discussed. The ion-selective electrodes provide
simple, reliable, low cost, on-spot methods for the detection of heavy metal ions.
The field of hybrid materials is vast open and promising and newer possibilities to
improve their application are to be explored.

Keywords
Composite · Sol-gel synthesis · Selectivity · Ion-selective membrane electrode

1 Introduction

Since ages, nature has provided various materials that exhibit astonishing properties
and features (radiolarian and diatoms). It appears that nature has its own way
of combining/mixing materials at nanoscale, resulting in the formation of “smart
materials” that have characteristics which are a blend of the combining
components [1]. One of the greatest advantages of integration of components at
this level is miniaturization (maximum elementary functions) along with hybridiza-
tion between combining organic-inorganic components [2]. Bamboo, bone, wood,
feathers, etc are some examples of naturally occurring composites. Bamboo is
cellulose reinforced by silica, bone is an organic-inorganic composite of protein
(collagen) and minerals (calcium apatite), while as wood is a composite of cellulose
fiber in a matrix of lignin.
Man has long tried to replicate what nature has bestowed him with. It has always
had a quest for such materials which possess several distinct features simultaneously.
The mission to combine the properties of composite organic and inorganic compo-
nents seems to be too old as it dates back when Mesopotamians used a straw to
strengthen mud bricks, Egyptians used plywood with resistance to thermal expan-
sion and swelling. It is, however, important to note that these hybrid organic-
inorganic materials do not represent a simple mixture of components; rather these
have organic-inorganic components intimately mixed [3, 4]. In brief, the hybrids are
either homogeneous or heterogeneous systems. The homogeneous system is com-
posed of monomers and the miscible organic and inorganic component while as the
heterogeneous system has one component with dimensions from a few angstroms to
nanometers. It is also to be kept in mind that the properties of hybrids are not just
summed total of properties of individual components but the interface also plays a
major role [2]. On the basis of the nature of the interface, the hybrids have been
broadly grouped into two types. The organic and inorganic components are embed-
ded and only weak bonds (hydrogen, Van der Waals or ionic bonds) give the
cohesion to the whole structure in class I while in class II hybrids strong chemical
bonds (covalent or iono-covalent bonds) are present between the two phases.
The composite materials or composites may be considered to consist of two or
more constituent materials with different physical or chemical properties that are
designed in a manner which allows the components to remain separate and distinct at
macroscopic level [5]. The composites are electrically conducting when the organic
28 Organic-Inorganic Hybrid Materials and Their Applications 1137

conducting polymers are incorporated into the inorganic precipitates of polyvalent

metal acid salts. These materials have attained great significance owing to their
mechanical, chemical, and electrochemical properties. During the past decade,
researchers have shown great interest in the development of electrically conducting
organic-inorganic composite materials that exhibit higher conductivity at high and
subambient temperature. The composites can be expected to exhibit a wide range of
applications such as electronic, electrochromic, photoelectrochemical,
ion-exchange, photochromic, and electrodes, if the organic portion is composed
of intrinsically conducting polymers such as polyaniline, polypyrrole, poly
(3,4-ethylene dioxythiophene), and polystyrene sulfonate (PEDOT: PSS) [6].

1.1 Synthesis of Organic-Inorganic Hybrids

Hybrid organic-inorganic materials played important role in the development of

numbers of advanced nanomaterials. These hybrid materials are not only used as an
alternative for the synthesis of new material for academic and research purpose but
also open new and innovative ways in developing a variety of smart materials with
promising applications used in the various field such as electronics, medicine,
biology, environment, optics, mechanics, etc. For the synthesis of organic-inorganic
hybrid materials, variety of methods have been developed. The commonly used
methods include sol-gel method, blending, and emulsion polymerization especially
the miniemulsion method is effective and promising in the preparation of polymer-
based hybrid materials.

1.1.1 Sol-Gel Method

For over two decades, the sol-gel method has been used for the synthesis of polymer-
based hybrid materials, and this method is still a promising method in developing
advanced hybrid materials enabling the configurational and structural control simul-
taneously because of newly developed sol-gel methods [7]. In this method, organic
polymers combine with inorganic solid materials at the nanoscale, form hybrid
materials with properties similar to both the materials used and also exhibiting
some new properties. These hybrid materials extensively used in biological, mechan-
ical, catalytic, optical, and other applications [8].

How Does the Sol-Gel Method Work?

In the sol-gel method, metal alkoxides are used which undergo hydrolysis reaction
followed by a condensation reaction (Fig. 1). These two stepwise reactions produce
inorganic networks. The organic molecules incorporate within the inorganic net-
works produced by the sol-gel method which generally include alumina, silica,
titania, vanadia, etc. is practicable when mild reaction condition is employed
[9–11]. By this sol-gel method, number of hybrid materials has been developed.
Due to easy availability, the well-known chemistry of silica and high stability of Si-O
bond, silica-based hybrids are extensively used.
1138 R. Mobin et al.

Fig. 1 Steps involved in sol-gel synthesis

The principal requirement for the sol-gel method to produce materials of high
homogeneity and transparency is the proper dispersion of organic part into the
inorganic matrix. The high reactivity of metal oxide other than silica causes aggre-
gation and nonhomogeneity in the sol-gel method. The interaction between organic
and inorganic material in sol-gel methods may be chemical or physical, depending
upon its interaction polymer-based hybrid materials are classified into two
categories.

1. Class I: It includes the hybrid materials in which physical interaction takes place
between organic and inorganic molecules.
2. Class II: It includes the hybrid materials in which chemical interaction takes place
between organic and inorganic molecules.

In Situ Hybrid Formation Via Sol-Gel Methods

In-situ hybrid materials prepared via the sol-gel method can be divided into three
types:

(i) Water catalyzed sol-gel method

(ii) Nonhydrolytic sol-gel method
(iii) The interpenetrating polymer network approach

Water Catalyzed Sol-Gel Method

In this method, monomeric unit combines with organic and metal alkoxide group,
which simultaneously forms an inorganic network and polymer chain in the presence
of a solvent (water). Depending on the type of organic group used, different methods
28 Organic-Inorganic Hybrid Materials and Their Applications 1139

Fig. 2 In-situ preparation of

polymer-metal oxide hybrid
materials by H2O-catalysed
sol-gel polymerization

have been used for the formation of in-situ hybrid materials which include a ring
opening process, the free radical process [8]. Figure 2 shows the general scheme for
the water catalyzed sol-gel method.

Nonhydrolytic Sol-Gel Method

In the nonhydrolytic sol-gel method, the reaction takes place in the absence of a
solvent. The first report in this regard appeared in 2001, which shows that the sol-gel
methods (polymerization of an organic monomer in bulk takes place simultaneously
with the formation of the inorganic network), are carried out in the absence of
solvent or water as a catalyst [12]. In this method, ligand exchange takes place in
the presence of metal halide or an organic molecule with oxygen donor moiety such
as alcohol, ether.
The silica-dimethylsiloxane hybrid material has been produced by nonhydrolytic
sol-gel (NHSG) method, in which NHSG synthesis occurs simultaneously along
silica ring-opening polymerization of hexamethylcyclotrisiloxane in the presence of
FeCl3 as a catalyst [13]. General reaction scheme for the nonhydrolytic sol-gel
method has been shown in Fig. 3.

The Interpenetrating Polymer Network

This process involves the simultaneous cross-linking process of organic and inor-
ganic groups, which results in the formation of the interpenetrated organic-inorganic
hybrid network. Figure 4 shows the general scheme of an interpenetrating network.
Example of interpenetrating polymer network is thermo-reversible interpenetrating
1140 R. Mobin et al.

Fig. 3 General reaction involved in NHSG method

Fig. 4 Representation of interpenetrated organic-inorganic composites

polymer network hybrids, prepared by an acid catalyzed sol-gel method in which

reaction of tetramethoxysilane takes place to produce silica network, as this hybrid
consists of the organic polymer chain and silica gel. This reaction took place via
Diels-Alder reaction, to produce an organic network in the presence of poly-
oxazoline polymers with maleimide and furan groups [14]. Bipyridyl which consists
of polystyrene and poly(ethylene oxide) is another example where a network is
formed in the presence of ruthenium salt.

1.1.2 Blending Method

There are three types of blending methods used in the synthesis of hybrid materials.

(i) Solution blending

(ii) Melt blending
(iii) Powder blending

Solution Blending
Solution blending method is one of the simplest methods for the synthesis of
organic-inorganic hybrid materials. This method first involves the preparation of
organic solution by dissolving the organic material in a suitable solvent and then the
inorganic material is introduced. Dispersion is carried out by ultrasonication or by
stirring. The resulting hybrid material can be easily processed to generate in the solid
state by solvent evaporation. This method is very simple and cost-effective but one
drawback is the aggregation of hybrid materials due to the agglomeration properties
of inorganic materials, which causes the inferior physical, chemical, and mechanical
properties of the hybrid material. To overcome this problem, good intermixing of
28 Organic-Inorganic Hybrid Materials and Their Applications 1141

Fig. 5 Organic-inorganic composites: (a) agglomeration (b) dispersion

organic and inorganic materials has been done so that the inorganic material is
properly dispersed in organic component (Fig. 5).

Melt Blending
Melt blending is similar to solution blending; the only difference is that in the case of
melt blending, organic solvent is not used, which make this method more environ-
mental friendly as compared to solution blending. In this method, organic material is
present in a melt state when the inorganic component is mixed. Polymer-based
hybrid materials are generally prepared by this method. In polymer-based hybrid
materials, polymers are combined with a variety of inorganic materials such as silica,
nanoclays, alumina, etc. [15–18].

Powder Blending
In the powder blending method, solid state powder is used in the synthesis of
organic-inorganic hybrid materials. This method is more advantageous as it does
not require any solvent (solvent blending) or heating to melt the organic substances
(melt blending). Organic materials with poor solubility in the organic solvent or high
melting materials cannot be processed with inorganic materials by solution and melt
blending methods; therefore, for such materials, powder blending is used. In the
powder blending method, high energy ball milling is used for the synthesis of hybrid
materials [19]. In case of high energy ball milling, organic and inorganic materials
have been mixed by a series of energy transfer. Agglomerates of inorganic materials
breakdown into smaller particles which results in homogeneous mixing of the
inorganic group into an organic matrix. The hybrid material formed by this method
exhibit the properties of the individual component as well as new properties
depending on the interaction of inorganic and organic matrix.
Some examples of hybrid materials prepared by this methods are polymers
combined with silica [20, 21], barium titanate [22, 23], titanium oxide [24], nickel
ferrite nanopowder [25], etc.
1142 R. Mobin et al.

1.1.3 Emulsion Polymerization

The process of emulsion polymerization is mainly used by industries to develop
adhesives, modifiers, paints, etc. The in-situ polymerization in the presence of
preformed inorganic particles which usually act as “seeds” and stabilizers results
in the development of composite colloids. The polymer latexes which are developed
by conventional emulsion polymerization can also be used for further growth of
inorganic domains either within or on the surface of these particles. Polymer silica
composites have been mostly developed by this method [26].

1.2 Classification of Organic-Inorganic Hybrid Materials

Hybrid materials are prepared by dispersing inorganic materials into the organic
matrix by various methods as described above. There are two types of interaction
between organic and inorganic materials. Depending upon these interactions, hybrid
materials are classified into two categories (Fig. 6).

1. Class I
2. Class II

Class I In this type of hybrid materials, the interaction between organic and
inorganic material is only physical interaction which includes hydrogen bonding,
π-π interaction (aromatic interaction), etc. In class I type hybrid material, both the
organic and inorganic material consists of some specific functional group which
develops physical interaction between these two materials. Polyamides, poly-
carbonates, polyurethanes, biopolymers possess H-bond functionality are widely
used in the synthesis of class I type hybrid materials [27–30]. Physical interaction
and homogenous mixture of organic and inorganic material forms occur only when
both the compounds have some specific functional groups if such groups are not
present then, in hybrid material incomplete homogeneity occurs which result in
phase separation between organic and inorganic materials. For example, silicate

Fig. 6 Classification of hybrid materials on the basis of the interaction between organic and
inorganic components
28 Organic-Inorganic Hybrid Materials and Their Applications 1143

(inorganic matrix) contain aromatic moiety easily generate the homogenous mixture
with an organic matrix which contains an aromatic group [31].

Class II In this type of hybrid materials, chemical bonding occurs between two
different phases. Different methods have been used for this purpose. Miscibility
between two different phases or the homogenous mixture of noncompatible organic
and inorganic materials can be obtained by adding compatibilizers. Compatibilizers
are macromolecules exhibiting good miscibility properties with both the organic and
inorganic parts which are incompatible with each other. For example, class II type of
hybrid material can be prepared by alkoxysilane (-Si(OR)3)-functionalized organic
compound and telechelic (with two identical reactive group) organic compounds
with functional moieties by co-condensation reaction [32–37].

1.3 Applications of Organic-Inorganic Composites

The commercial application of composites dates back to 1950. The organic-

inorganic composites represent materials with unusual properties often modified in
order to optimize their performance for a specific use. The use of composites has
gained momentum in the last 50 years as new analytical/spectroscopic techniques
and tools have become available which have led to the better understanding of
structure/properties relationship in these composites. The hybrid/composites have
revolutionized the field of biotechnology as biosensors and bioreactors. Active
biospecies have been immobilized on or in solid substrates to protect these from
denaturation [38]. The most widely used enzyme in sol-gel matrices is the glucose
oxidase (GOD) which catalyzes the oxidation of glucose by molecular oxygen and
finds application for diagnostic purpose (diabetes) and food industry. These hybrids
find wide application in paint industry leading to the development of all-weather
resistant coatings. In recent past, the hybrids have been used as barrier system/
protective coatings in solar cells, optics, electronics, and food packaging. In the field
of dentistry, organic-inorganic hybrids are used in fillings because it gives the same
color and texture to the tooth of a patient by adding different fillers [39]. These can
be used to change the shape, size, and color of the tooth and easily stick with tooth
and hence less tooth has to be removed.
Besides this, the organic-inorganic hybrids find a wide variety of application
particularly in the field of water processing, clinical diagnostics, safety, industrial
hygiene, process controls, quality controls, human comfort, critical care, emissions
monitoring, automotive, safety alarms, and more recently as ion-selective membrane
electrodes. The widespread application of hybrids as sensors in these fields has
economic, aesthetic, and social utility [40]. The ion-selective membrane electrodes
represent an important and widely used class of potentiometric sensors. The appli-
cations of organic-inorganic composites are so vast that it is beyond the scope of this
chapter, to sum up these all, thus the focus will be laid on only a few applications of
organic-inorganic composites.
1144 R. Mobin et al.

1.3.1 Water Softening

The hard water contains sparingly soluble magnesium (Mg2+) and calcium (Ca2+)
ions. The hardness is considered undesirable even leading to kidney stones due to
higher quantities of calcium ions and it influences the processing of water [41]. The
most commonly used technique for softening of water includes precipitation of Mg2+
and Ca2+ (ions) in the form of their carbonates. In chemical precipitation, bicarbon-
ates and alkaline chemicals are added which cause the formation of MgCO3 and
CaCO3 precipitates. The boiling of hard water is considered as a physical method but
the process consumes too much energy and is costly. Also being partially soluble
(carbonates) causes hindrance in the complete removal of these ions from the
drinking water [42].
The cation and anion exchangers can be used to selectively remove cations (Mg2+
and Ca2+) and anions (sulfate and dissolved organic matter (DOM)). The electrodi-
alysis, electrodeionization (EDI), and capacitive deionization (CDI) are better tech-
niques in water softening.
In comparison to calcium, magnesium is abundant in seawater and constitutes
about 83% of total hardness (TH) of seawater. Magnesium is necessary for several
life processes and is essential for normal cardiac electrophysiology, lipid metabo-
lism, and proper enzyme functions. Its deficiency causes hypomagnesemia and
cardiovascular diseases [43]. Mg2+ ions can be supplemented in the drinking water
in chloride/sulfate form but the process is not feasible cost-wise. Therefore, a new
approach of selective desalination of seawater to enrich for Mg2+ in the drinking
water has been adopted as an alternate method. A combination of ion exchange and
filtration-based approaches are used. Tang et al. [44] used a combination of ion
exchange and nanofiltration (NF) (filtration of water through a nanometer pore
size membrane), to selectively separate Mg2+ and SO42
from seawater. Cation
exchanger was used initially to remove salts and then NF to obtain MgSO4 rich
concentrate solution. Similarly, Enterazi et al. [45] showed that a combination of
ultrasound and ion exchange increased the efficiency of removal of Mg2+ and Ca2+.

1.3.2 Enzyme Immobilization Agents

The immobilization by ionic/electrostatic interactions is an adsorption approach that
works on the same principle as ion exchange chromatography [46]. The charged
groups present on the protein surface interact with oppositely charged ions on the ion
exchange resin. The pH plays a significant role in the loading of proteins (operational
pH). If the operational pH is higher than the isoelectric point of the protein, it
exhibits a net negative charge and interacts with positively charged exchange
media. On the other hand, if the operational pH is lower than the isoelectric point
of protein; it shows a positive net charge and therefore interacts with negative
exchange agents [47]. Hence, it is possible to use cationic and anionic media for
enzyme separation and immobilization based on their net surface charge. Ion
exchange is one of the oldest approaches for enzymatic immobilization and is
simple, fast, and cost-effective. However, the enzyme immobilization by ion
exchange is a multistep process, wherein the enzyme is attached to the carrier only
if the number of charge interactions is high enough to compensate for the medium’s
28 Organic-Inorganic Hybrid Materials and Their Applications 1145

ionic strength [48]. Since the adsorption involves weak interactions, therefore, the
effects of immobilization on enzyme conformational structure tend to be less drastic,
promoting high catalytic activities [49, 50]. However, the possible solution to
increase the adsorption strength is the use of polymer-coated carriers. Polymers
tend to increase the load bearing capacity using a flexible and adaptable bed for the
enzyme. This allows adsorption of the larger part of the protein surface, increasing
the contact surface [51]. Several instances using ion exchange resins as immobili-
zation carriers in the food industry have already been reported [49]. These carriers
are inexpensive, abundant, mechanically strong, chemically stable, nontoxic, non-
polluting, and easily regenerated after use [52].

1.3.3 Decolourization
The traditional sugar processing is a broad area that can benefit from technologies
based on ion-exchangers as most of the coloring matter present in sugar liquors show
an anionic character and can be removed by ion-exchange resins. These processes
have been an important part of sugar processes since the 1980s and significantly
improve the profitability of the sugar processing; however, they are still not a
standard in sugar production facilities [53]. Till recently, the ion-exchangers have
been used either as processing aids (decalcification) in sugar-recovering technolo-
gies and in decolorizing of sugar solutions.

1.3.4 Ion-Selective Membrane Electrode

The International Union of Pure and Applied Chemistry (IUPAC) described [54] an
ion-selective membrane electrode (ISME) as: an electrochemical sensor, based on
thin films or selective membranes as recognition elements, and is an electrochemical
half-cell equivalent to other half-cells of the zeroth (inert metal in a redox electro-
lyte), 1st, 2nd, and 3rd kinds. These devices are distinct from systems that involve
redox reactions (electrodes of zeroth, 1st, 2nd, and 3rd kinds), although they often
contain a 2nd kind electrode as the “inner” or “internal” reference electrode. The
potential difference response has, as its principal component, the Gibbs energy
change associated with permselective mass transfer (by ion-exchange, solvent
extraction or some other mechanism) across a phase boundary. The ISME has to
be used in conjunction with a reference electrode (i.e., “outer” or “external” refer-
ence electrode) in order to form a complete electrochemical cell. The measured
potential differences (ISME versus outer reference electrode potentials) are linearly
dependent on the logarithm of the activity of a given ion in solution.
The foundation of work on the ion-selective membrane was laid by Oswald (1890)
with the discovery that for an electrolyte a membrane can be impermeable [55]. The
membrane potential at the boundary is a result of the difference in concentration at
the membrane. Latter Donan confirmed the same in 1911 [56]. The basic work
related to ISME is still considered that of Michaelis and Fujita [57].
The use of ion-exchange membranes for industrial use got impetus from the work of
Juda and MC Rae [58] and Winger et al. [59] who developed stable, highly selective
ion-exchange membranes exhibiting low resistance. The ion-selective membrane elec-
trode selectively determines the activity of a particular ionic species. The main
1146 R. Mobin et al.

Fig. 7 Schematic representation of the ion-selective membrane electrode cell

constituent of these electrodes is membrane composed of permselective ion-conducting

materials separating the sample from the inside of the electrode (Fig. 7).
The surrounding environment determines the potential of the working electrode
while the reference electrode potential is kept constant by a solution containing the
ion of interest at a constant activity. The potential difference (cell potential) is related
to the concentration of the dissolved ion as the potential of reference electrode
remains constant. The development of an ion-selective membrane electrode specific
to a given ion is very typical and different strategies to produce a specific electrode,
selective to particular species depend primarily on the nature and composition of the
membrane material. Hence the research in this area is wide open and has applications
to an almost unlimited number of analytes; with the preparation of particular analyte
selective membrane electrode based on dopant and ionophore matrix of the mem-
brane being the only limitation. These find potential application in several diverse
fields of food, drug, biological, waste material treatment, and environmental mon-
itoring owing to their better selectivity, low electrical resistance, improved thermal
and mechanical properties. The ion-selective membrane electrodes offer low cost,
nondestructive, robust, portable, higher sensitive, and selective procedure for the
determination of heavy toxic metal ions. The harmful/hazardous effects of heavy
toxic metals have necessitated the rapid, on-spot, selective determination of these
ions in portable and groundwater. The ion-selective electrodes can be used for the
detection of both the cationic and anionic ions.

Physicochemical Properties of Ion-Selective Membrane Electrodes

Several parameters, viz., electrode response or membrane potential, detection limit,
response time, working pH range, selectivity, and interference, are to be evaluated to
study the characteristics of the membrane electrode.
28 Organic-Inorganic Hybrid Materials and Their Applications 1147

Electrode Response or Membrane Potential

The potential determination is one of the main characteristics involved in the
working of ion-selective membrane electrode. Since the potential of an individual
electrode cannot be determined, it is required to measure emf of the half-cell of an
electrochemical cell. The two half-cells are separated by the ion-selective membrane
with their respective reference electrodes. A membrane potential (emf) is developed
across the membrane separating the two solutions 1 and 2 with both having the same
ions. This potential developed across the membrane is given by the Eq. (1)
2 3
ð2
RT 4 ½aA 1

Em ¼ ln
Z y
Z A t y d ln a 5 (1)
ZAF ½aA 2
1

where A = counter ion, Y = co-ion, Z = charge on ions, ty = transference number of

co-ions in the membrane phase, [aA]1 and [aA]2 = activities of the counter ions in the
solution 1 and 2, a = mean ionic activity of the electrolyte.

Detection Limit
The working concentration range of an ISME is evaluated from the analyte concen-
tration range within which it follows Nernstian equation. It is also defined as the
activity range of an ion between the upper and lower detection limits of an
ion-selective membrane electrode. The ISMEs exhibit a point where the electrode
response starts to deviate from the theoretical value and the ISME loses its specificity
towards the primary ion. The presence of various interfering ions in the form of
impurities also plays a significant role in governing the detection limit of ISME. The
extrapolation of the linear part of the calibration curve of ISME gives the limit of
detection of the membrane electrode (Fig. 8).

Response Time
According to the IUPAC recommendations, the time which elapses between the
instant when an ion-selective membrane electrode and a reference electrode (ISME
cell) are brought into contact with a sample solution (or at which the activity of the
ion of interest in a solution is changed) and the first instant at which the emf/time
slope (ΔE
Δt ) becomes equal to a limiting value selected on the basis of the experimental
conditions and/or requirements concerning the accuracy (e.g., 0.6 mV/min.) is
defined as response time.
It has also been described as the time necessary to attain an equilibrium value
(steady potential) within 1 mV after a tenfold increase or decrease in the concen-
tration of the test solution.

Selectivity Coefficients
The selectivity coefficient is one of the important factors of ion-selective membrane
electrodes, which determines the potential applicability of an electrode. The ISME
yield a potential that is primarily due to the ion of interest usually called the primary
1148 R. Mobin et al.

Fig. 8 Ion-selective
membrane electrode
calibration curve

ion while other interfering ions are called secondary ions. However, the ISME
cannot be exclusively specific to a single ion. The actual response of a binary
mixture of primary (A) and secondary (B) ions is given by Nikoloskii-Eisenman
Eq. (2) [60]. A detailed theory of the processes at the interference of these mem-
branes, which generate the potential, is available elsewhere [61–63].

2:303 RT h X pot ZA i
E ¼ E0 þ log aA þ K A ð aA Þ Z B (2)
ZAF
The lower the value of K pot
A,B, the more selective is the electrode. For ideally selective
pot
electrodes, the K A,B would be zero. Thus, the selectivity coefficient plays a great role
while determining the selectivity of a particular ion-selective membrane electrode.
Figure 8 shows the effect on selectivity of ISME due to the presence of the various
the interfering ions. As such the inconsistent nature of the selectivity coefficient is
not considered a desirable trait of ISME [64–66]. Two main methods, separate
solution method and mixed solution method, are generally used for determining
the selectivity coefficient of ISME [67].

Life Time
The period of time during which the slope and detection limit of an ISME do not
undergo any significant change represents its lifetime. Several factors which include
the deterioration of the plasticizer, polymer, and the electroactive material are the
main reasons for the deviation in the response of the membrane electrode. Thus, the
period during which the electrode response remains reasonably constant represents
the lifetime of ISME.

Effect of pH
These ISMEs work only within a specific pH range, and thus it is essential to find out
the effect of pH on the electrode response. In order to determine the working pH
28 Organic-Inorganic Hybrid Materials and Their Applications 1149

Table 1 Some important heavy metal ion-selective composite ion-exchangers

S. No. Composite material Application Ref.
1 Polypyrrole Th(IV) phosphate Pb(II) selective [72]
2 Poly-o-toluidine Ce(IV) phosphate Cd(II) selective [73]
3 Polyaniline Sn(IV) phosphate Pb(II) selective [74]
4 Poly(methylmethacrylate) Zr(IV) phosphate Pb(II) selective [75]
5 Polyacrylamide Th(IV) phosphate Pb(II) selective [76]
6 Acrylamide aluminum tungstate Pb(II) selective [77]
7 Poly-o-anisidine Sn(IV) arsenophosphate Pb(II) selective [78]
8 Acrylonitrile Sn(IV) tungstate Pb(II) selective [79]
9 Polyacrylamide apatite Pb(II) selective [80]
10 Macrocyclic diamide sulfur Cd(II) selective [81]
11 B2O3/TiO2 nanocomposite Cd(II) selective [82]
12 Ethylenediamine tetra acetic acid Sn(IV) iodate Pb(II) selective [83]
13 Acrylamide Zr(IV) arsenate Pb(II) selective [84]
14 Acrylamide stannic silicomolybdate Pb(II) selective [85]
15 Poly(methylmethacrylate) Ce(IV) molybdate Pb(II) selective [86]
16 Polyaniline Ce(IV) molybdate Cd(II) selective [87]
17 Poly-o-methoxyaniline Zr(IV) molybdate Cd(II) selective [88]
18 Poly-o-toluidine stannic molybdate Pb(II) selective [89]
19 Poly-o-anisidine Sn(IV) phosphate Cd(II) selective [90]
20 Polyaniline Sn(IV) molybdate Pb(II) selective [91]
21 Polyaniline zirconium titanium phosphate Hg(II) selective [92]
22 Nylon-6,6 Sn(IV) phosphate Hg(II) selective [93]
23 Poly-o-toluidine Zr(IV) phosphate Hg(II) selective [94]
24 Poly-o-toluidine Th(IV) phosphate Hg(II) selective [95]
25 Polyaniline Sn(IV) phosphate Hg(II) selective [96]
26 Poly-o-anisidine Sn(IV) phosphate Sb(II) selective [97]
27 Cellulose acetate-Zr(IV) molybdophosphate Cr(III) selective [98]
28 Polyaniline-Sn(IV)tungstophosphate Pb(II) selective [99]
29 Polyaniline Sn(IV) silicomolybdate Pb(II) selective [100]
30 Polyaniline Zr(IV) arsenate Pb(II) selective [101]
31 Poly-o-toluidine Zr(IV) tungstate Pb(II) selective [102]
32 Polyaniline Ti(IV) arsenate Pb(II) selective [103]
33 Polyaniline Ti(IV) phosphate Pb(II) selective [104]
34 Polyaniline Sn(IV) tungstoarsenate Cd(II) selective [105]
35 Polyaniline Sn(IV) silicate Cd(II) selective [106]
36 Poly-o-toluidine Sn(IV) tungstate Pb(II) selective [107]
37 Polyaniline Sn(IV) tungstomolybdate Pb(II) selective [108]
38 Polyaniline Ti(IV) arsenophosphate Cd(II) selective [109]
39 Polyaniline Sn(IV) silicophosphate Pb(II) selective [110]
40 Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Cd(II) selective [111]
Zr(IV) phosphate
41 Polyaniline tungstophosphate Pb(II) selective [112]
(continued)
1150 R. Mobin et al.

Table 1 (continued)
S. No. Composite material Application Ref.
42 Carboxymethyl cellulose Sn(IV) phosphate Pb(II) selective [113]
43 Polyaniline Zr(IV) sulfosalicylate Pb(II) selective [114]
44 Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Pb(II) selective [115]
Zr(IV) monothiophosphate
45 Cellulose acetate Zr(IV) molybdophosphate Cd(II) & Pb [116]
(II) selective
46 Single-walled carbon nanotubes Ce(IV) phosphate Cd(II) selective [117]

range of the ion-selective membrane electrode, different solutions of varying pH

with constant ion concentration are prepared and the electrode potential is recorded
at each pH. The electrode potential is plotted against pH value and the pH over which
the potential of ion-selective membrane electrode remains constant is taken as the
working pH range of the electrode.
Thus these ion-selective membrane electrodes have several attractive features as a
simple instrument, high sensitivity and selectivity, low cost, and fast response
[68–71].
Table 1 represents various composites that are specifically selective for various
heavy metal ions.

2 Conclusion

The organic-inorganic composites have already made in-roads in various industries.

The advance research in the field is moving at a very fast rate owing to usefulness in
various sciences, physical, chemical, material, biological, etc. The composites pro-
vide both integration and miniaturization, thus opening the vast field for their
application. The simple methods of development of these composites provide
ample opportunities to alter, modify, and club various distinguishing characteristics
in a single entity. The composites as ion-selective membrane electrodes provide fast,
on-spot, reliable, cost-effective means for the detection, determination, and removal
of various heavy metal ions.

Acknowledgments Tauseef Ahmad Rangreez is thankful to SERB, New Delhi for grant under
SERB N-PDF (File No. PDF/2017/001724).

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