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NANOCOMPOSITE MATERIALS
Synthesis, Properties and Applications
 NANOCOMPOSITE MATERIALS
Synthesis, Properties and Applications

EDITED BY
Jyotishkumar Parameswaranpillai | Nishar Hameed
Thomas Kurian | Yingfeng Yu
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742

© 2017 by Taylor & Francis Group, LLC

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Version Date: 20160627

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Contents
Acknowledgments
Editors
Contributors

Chapter 1 Introduction to Nanomaterials and Nanocomposites

Jyotishkumar Parameswaranpillai, Nishar Hameed, Thomas Kurian, and
Yingfeng Yu

Chapter 2 Classification of Nanomaterials and Nanocomposites

K. G. Gatos and Y. W. Leong

Chapter 3 Synthesis of Nanomaterials

A. Ramazani S.A., Y. Tamsilian, and M. Shaban

Chapter 4 Optical Properties of Nanomaterials

Veronica Marchante Rodriguez and Hrushikesh A. Abhyankar

Chapter 5 Microscopy of Nanomaterials

Mazeyar Parvinzadeh Gashti, Farbod Alimohammadi, Amir Kiumarsi,
Wojciech Nogala, Zhun Xu, William J. Eldridge, and Adam Wax

Chapter 6 Mechanical Properties of Nanomaterials

Shirin Shokoohi, Ghasem Naderi, and Aliasghar Davoodi

Chapter 7 Preparation of Nanocomposites

Linxiang He and Sie Chin Tjong

Chapter 8 Thermal Properties of Novel Polymer Nanocomposites

Jerzy J. Chru ciel

Chapter 9 Optical Properties of Nanocomposites

Enis S. Džunuzovi and Jasna V. Džunuzovi

Chapter 10 Rheological Behavior of Nanocomposites

Nicole R. Demarquette and Danilo J. Carastan
Chapter 11 Mechanical and Thermomechanical Properties of Nanocomposites
Nektaria-Marianthi Barkoula and Athanasios K. Ladavos

Index
Acknowledgments
We thank Dr. George Z. Kyzas, Dr. Anna Biedunkiewicz, Dr. Ningzhong Bao, Dr. Peng Tao,
Dr. Gheorghe Rusu, Dr. Cassagnau Philippe, Dr. Ke-Ke Yang, Dr. Francesco Ciardelli, Dr.
Andrea Pucci, Dr. Dimitris Achilias, and Dr. Seno Jose for their time and efforts in
evaluating the chapters.
Editors

Jyotishkumar Parameswaranpillai is an INSPIRE Faculty member in the Department of

Polymer Science and Rubber Technology of Cochin University of Science and Technology,
India. He earned his PhD in polymer science and technology (chemistry) from Mahatma
Gandhi University, Kerala, India. He has published approximately 40 papers in high-quality
international peer-reviewed journals on polymer nanocomposites, polymer blends and
alloys, and biopolymer, and has edited two books. Dr. Parameswaranpillai’s biographical
profile is listed in the Marquis Who’s Who in the World 2015 (32nd edition) in reference to
his outstanding achievement in the fields of polymer science and technology. In addition,
he received the Venus International Foundation award for the best young faculty
(science/chemistry) in the country for the year 2015.
Nishar Hameed earned his PhD from Deakin University in 2011. He received the Alfred
Deakin Best Doctoral thesis award and Vice Chancellors Award for outstanding academic
achievement from Deakin University. Dr. Hameed’s research has been mainly focused on
the preparation, processing, and characterization of nanostructured polymer materials. He
has extensive expertise in the development of self-assembled block copolymers and bio-
renewable plastics from natural resources. His current research is mainly focused on
processing and characterization of nanostructured precursors for high-performance carbon
fibers and thermoformable composite materials. As an early career researcher, Dr. Hameed
has an excellent track record in polymer processing and characterization with nearly 40
high-quality journal papers, more than 23 conference papers, and one patent. In recent
years, he has won a number of prestigious awards including the Victoria Fellowship and the
Endeavour Research Fellowship.
Thomas Kurian is a professor of polymer technology and former head of the Department of
Polymer Science and Rubber Technology, Cochin University of Science and Technology,
Kochi, Kerala, India. He has authored several journal articles and book chapters. Dr. Kurian
earned his PhD from the Indian Institute of Technology (IIT) Kharagpur; BSc in chemistry
from Kerala University; BTech, MTech, MBA, and PG Cert. (Germ.) from Cochin
University of Science and Technology; and PGDTRM (Post-Graduate Diploma in Teaching
and Research in Management) from IGNOU (Indira Gandhi National Open University),
India. He was JSPS (Japan Society for the Promotion of Science) postdoctoral fellow and
JSPS bridge fellow at Yamagata University, Japan.
Yingfeng Yu is a professor of polymer science and engineering and head of the laboratory
for polymer electronic packaging materials located at Fudan University, China. His
research interests include structure and property relationship study of polymer materials in
microelectronics and composites, thermosetting resins and high-performance polymers,
polymer blends, and nanocomposites. He has published 60 papers in international journals
devoted to polymers and materials.
Contributors
Hrushikesh A. Abhyankar
Centre of Automotive Technology
Cranfield University
Cranfield, Bedfordshire, United Kingdom

Farbod Alimohammadi
Department of Chemistry
Temple University
Philadelphia, Pennsylvania

and

Young Researchers and Elite Club

South Tehran Branch
Islamic Azad University
Tehran, Iran

Nektaria-Marianthi Barkoula
Department of Materials Engineering
University of Ioannina
Ioannina, Greece

Danilo J. Carastan
Center for Engineering, Modeling and Applied Social Sciences
Federal University of ABC (UFABC)
Santo André, Brazil

Jerzy J. Chru ciel

Textile Research Institute
Łód , Poland

Aliasghar Davoodi
Chemical, Polymeric and Petrochemical Technology Development Research Division
Research Institute of Petroleum Industry
Tehran, Iran

Nicole R. Demarquette
Metallurgical and Materials Engineering Department
University of São Paulo
São Paulo, Brazil

Enis S. Džunuzovi
Faculty of Technology and Metallurgy
University of Belgrade
Karnegijeva, Belgrade, Serbia

Jasna V. Džunuzovi
Institute of Chemistry, Technology and Metallurgy (ICTM)-Center of Chemistry
University of Belgrade
Karnegijeva, Belgrade, Serbia

William J. Eldridge
Department of Biomedical Engineering
Duke University
Durham, North Carolina

Mazeyar Parvinzadeh Gashti

Department of Textile, College of Engineering
Islamic Azad University
Tehran, Iran

K. G. Gatos
Megaplast S.A., Research and Development Center
Athens, Greece

Nishar Hameed
Carbon Nexus, Institute for Frontier Materials
Deakin University
Geelong, Victoria, Australia

Linxiang He
Department of Physics and Materials Science
City University of Hong Kong
Kowloon, Hong Kong

Amir Kiumarsi
Chang School of Continuing Education
Ryerson University
Toronto, Canada

Thomas Kurian
Department of Polymer Science and Rubber Technology
Cochin University of Science and Technology
Cochin, Kerala, India

Athanasios K. Ladavos
Department of Business Administration of Food and Agricultural Enterprises
University of Patras
Agrinio, Greece

Y. W. Leong
Institute of Materials Research and Engineering
Research Link
Singapore

Ghasem Naderi
Department of Rubber
Iran Polymer and Petrochemical Institute
Tehran, Iran

Wojciech Nogala
Institute of Physical Chemistry
Polish Academy of Sciences (PAS)
Warsaw, Poland

Jyotishkumar Parameswaranpillai
Department of Polymer Science and Rubber Technology
Cochin University of Science and Technology
Cochin, Kerala, India

A. Ramazani S.A.
Institute for Nanoscience and Nanotechnology
and
Department of Chemical and Petroleum Engineering
Sharif University of Technology
Tehran, Iran

Veronica Marchante Rodriguez

Centre of Automotive Technology
Cranfield University
Cranfield, Bedfordshire, United Kingdom

M. Shaban
Institute for Nanoscience and Nanotechnology
Sharif University of Technology
Tehran, Iran

Shirin Shokoohi
Chemical, Polymeric and Petrochemical Technology Development Research Division
Research Institute of Petroleum Industry
Tehran, Iran

Y. Tamsilian
Institute for Nanoscience and Nanotechnology
Sharif University of Technology
Tehran, Iran

Sie Chin Tjong

Department of Physics and Materials Science
City University of Hong Kong
Kowloon, Hong Kong

Adam Wax
Department of Biomedical Engineering
Duke University
Durham, North Carolina

Zhun Xu
MicroPhotoAcoustics (MPA) Inc
Ronkonkoma, New York

Yingfeng Yu
Department of Macromolecular Science
Fudan University
Shanghai, China
1 Introduction to Nanomaterials and
Nanocomposites
Jyotishkumar Parameswaranpillai, Nishar Hameed, Thomas Kurian, and
Yingfeng Yu

CONTENTS
1.1 Introduction to Nanomaterials
1.2 Advantages of Nanomaterials
1.3 Challenges and Opportunities
1.4 Nanocomposites
1.5 Topics Covered by the Book
References

1.1 INTRODUCTION TO NANOMATERIALS

Recently, scientists are more interested in nanomaterials and nanocomposites because they
form the foundation of nanotechnology. Nanomaterials and nanocomposites have a wide
range of applications from toys to aircraft. Nanomaterials are diminutive and their size is
measured in nanometers. By definition, they must have at least one dimension at the
nanoscale. Nanoscale materials are too small to be seen with the naked eye and even with
conventional optical microscopes. Therefore, we need highly sophisticated techniques for
the characterization of nanomaterials. Because of their high surface area, most of the
techniques are designed to analyze the surface. The techniques such as transmission
electron microscopy (TEM), cryogenic transmission electron microscopy (cryo-TEM), high
resolution scanning electron microscopy (HRSEM), atomic force microscopy (AFM),
scanning tunneling microscopy (STM), laser scanning confocal microscopy (LSCM),
scanning electrochemical microscopy (SECM), x-ray scattering, x-ray diffraction (XRD), x-
ray fluorescence spectroscopy (XRF), x-ray photoelectron spectroscopy (XPS) rheometry,
and electrical conductivity are used to identify size, composition, morphology, crystal
structure, and orientation of nanoparticles. Nanomaterials should be carefully analyzed.
Moreover, we should take care of the following: (1) specimen handling and (2)
environmental conditions. It is important to mention that a multitechnique approach is
required for the better characterization of nanomaterials.
 Nanomaterials can be either natural or synthetic (engineered nanomaterials). Examples
for naturally occurring nanomaterials are volcanic ash, soot from forest fires, etc.
Engineered nanomaterials are produced with specific shape, size, and surface properties.
Depending on the size and shape, nanomaterials are classified into 0-D (quantam dots,
nanoparticles), 1-D (carbon nanotubes, nanorods, and nanowires), 2-D (nanofilms), and 3-D
nanomaterials, where 0-D, 1-D, and 2-D nanomaterials are in close contact with each other
to form interfaces (powders, fibrous, multilayer, and polycrystalline materials). Usually the
performance of the nanomaterials depends more on the surface area than the material
composition. The recent advances in nanotechnology enable us to develop nanomaterials to
improve the quality of life. Examples for engineered nanomaterials are carbon nanotubes
(CNTs), carbon nanofibers (CNFs), graphene, fullerenes, silica, clay, metal, and metal
oxide nanomaterials.

1.2 ADVANTAGES OF NANOMATERIALS

Nanomaterials exhibit unique optical, magnetic, electrical, chemical, and other properties.
These properties have great impact in electronics, sensors, energy devices, medicine,
cosmetics, catalysis, and many other fields [1–9]. For example, a wide range of electronic
products such as nanotransistors, organic light emitting diodes (OLED), and plasma
displays are due to the invention of nanomaterials. High performance portable batteries,
fuel cells, and solar cells are examples of the impact of nanomaterials in energy. Smart
drugs can target specific organs or cells in the body and are very effective in healing.
Nanomaterials can be added to polymers to make them stronger and lighter to develop
smart uniforms, nonwetting fabrics, fire-retardant fabrics, self-cleaning fabrics, self-
healing fabrics, decontaminating fabrics, lightweight high performance military aircrafts,
automobiles, etc. [10,11].
Because of their large surface area, metallic-based nanomaterials are highly reactive
with gases. This property of metallic-based nanomaterials can be used for applications such
as gas sensors and hydrogen storage devices [12,13]. Nanopesticides, nanofertilizers, and
nanoherbicides may have positive impact on crops [14]. The field of nanocatalysis is
rapidly growing. The large surface area and effective surface activity make nanomaterials
attractive candidates for use as catalysts. For example, for the production of biodiesel from
waste cooking oil aluminum dodeca-tungsto-phosphate (Al0.9H0.3 PW12O40) nanotubes are
used as solid catalyst [15]. In cosmetics, titanium dioxide and zinc oxide nanoparticles are
widely used [8].

1.3 CHALLENGES AND OPPORTUNITIES

Even though nanomaterials possess a wide range of applications, there are several issues to
be resolved. The effect of nanoparticles on the human/animal body is still a concern. Since
much about this regime is still unclear, careful analysis must be done to unravel the safety
problems of nanoparticles. For example, inhaling of nanoparticles may cause irritation in
the lungs and may lead to lung damage and cancer. The tendency of nanoparticles to
agglomerate because of weak van der Waals forces is a concern. Technology should be
developed to keep the nanoparticles apart so that their characteristic properties can be
retained. Nanomaterials and products made of them are very expensive compared to
traditional materials. It has been suggested that by increasing the use of nanomaterials in
various new applications, their production rate can be increased and thereby their cost can
be decreased. It is important to recognize that atomic weapons are possible to develop,
which may be very destructive. Therefore, nanomaterials should be used for constructive
applications. Another increasingly worrying fact is that widespread use of nanoparticles in
agriculture may spread nanoparticles into the environment and may adversely affect the soil
fertility, plant growth, and animals. Another prodigious task is to control the structure and
chemistry of metallic-based nanomaterials, before using them in gas sensors and for the
storage of hydrogen. The requirements of new materials, performance improvement,
extended product life, and cost of the product are still challenges. All of these facts point
toward the need for new improved technologies to enhance the performance of many
products with reduced cost.

1.4 NANOCOMPOSITES
Since nanomaterials possess exceptional properties, they are widely used to mix with the
bulk polymeric material to improve their properties. By definition, nanocomposites are
materials that are reinforced with nanoparticles. Based on the matrix material,
nanocomposites are classified into polymer matrix composites, metal matrix composites,
and ceramic matrix composites. In polymer matrix composites, the most important topic to
be considered is the dispersion of the nanofillers in bulk polymer matrix. Homogeneous
distribution of nanomaterials results in improved properties. But the tendency of particle
agglomeration due to the weak van der Waals forces between the nanomaterials results in
deterioration in properties. For example, homogeneous dispersion of CNTs, graphene,
CNFs, and clay in the polymer matrix improved mechanical, thermal, electrical, optical, gas
barrier, and flame retardancy properties of nanocomposites [16–21]. It is now well
established that for better dispersion of the nanomaterials in a polymer matrix, the
nanomaterials can be surface modified or functionalized [22–24]. Recently, it has been
shown that addition of compatibilizer also improved dispersion of the nanomaterials in the
polymer matrix [17]. Surface modification and functionalization of nanomaterials improve
the interfacial interaction or compatibility between the filler and matrix, which results in
better dispersion which in turn facilitates effective stress transfer of the matrix and filler to
develop high performance lightweight composites for advanced applications. A number of
techniques such as TEM, SEM, AFM, STM, XRD, and FTIR can be used to find the size and
distribution of filler in polymer matrix.

1.5 TOPICS COVERED BY THE BOOK

The book outlines a comprehensive overview on nanomaterials and nanocomposites and
their fundamental properties using a wide range of state-of-the-art techniques. Chapter 2
deals with the fundamentals of nanomaterials and their application in nanocomposites. An
overview of 0-D, 1-D, and 2-D nanomaterials is given in this chapter. Further applications
of 0-D, 1-D, and 2-D nanomaterials in thermoplastic, thermoset, and elastomeric
composites are discussed in detail. In the last part of the chapter, the current trends in
nanocomposites are described. Chapter 3 provides a comprehensive description on the
synthesis of 0-D, 1-D, 2-D, and 3-D nanomaterials. A number of routes including
microwave-assisted synthesis, sonochemical synthesis, chemical reduction method,
biological method, sol–gel method, aerosol method, emulsion method, microfluidic
method, laser ablation method, arc discharge method, and chemical bath technique for the
synthesis of different nanomaterials are presented. In Chapter 4, optical properties of
nanomaterials are discussed. Different techniques such as electronic absorption (UV–vis),
photoluminescence (PL), infrared (IR) absorption, Raman scattering, dynamic light
scattering, and x-ray-based techniques and their potential applications in the optical
properties of nanomaterials are discussed. Chapter 5 focuses on one of the most important
and powerful research techniques—“microscopy”—which provides valuable information
regarding size, shape, and morphology of nanomaterials. The purpose, advantages, and
limitations of different microscopic techniques such as SEM, TEM, scanning
electrochemical microscopy (SECM), photoacoustic microscopy, and hyperspectral
microscopy have been elaborated and pointed out the importance of using multimicroscopic
techniques to open new horizons in the characterization of nanomaterials. In Chapter 6, the
strength, hardness, toughness, fatigue, and creep of nanomaterials are presented. Chapter 7
discusses the various processing techniques such as solution mixing, melt compounding,
and in situ polymerization for the preparation of different polymer-based nanocomposites.
The preparation of CNTs and graphene sheets-based polymer nanocomposites are
considered. The advantages and disadvantages of different processing techniques are
discussed in detail. Chapter 8 focuses on the significance of thermal stability of polymer
composites in many demanding practical applications. The applications of techniques like
DSC, TGA, DTA, DMA, and TMA to analyze the thermal stability of polymers is presented
in this chapter. Chapter 9 provides a comprehensive overview of the recent findings and
advances on the investigation of linear and nonlinear optical properties of polymer
nanocomposites. Chapter 10 presents the role of rheology in identifying the structure and
processing characteristics of polymer nanocomposites. A comprehensive overview of the
progress in mechanical and thermomechanical performance of polymer nanocomposites is
given in Chapter 11.

REFERENCES
1. Z. Liu, J. Xu, D. Chen, and G. Shen, Flexible electronics based on inorganic nanowires, Chem. Soc. Rev., 2015,
44, 161–192.
2. W. Yang, P. Wan, H. Meng, J. Hu, and L. Feng, Supersaturation-controlled synthesis of diverse In 2 O3
 morphologies and their shape-dependent sensing performance, CrystEngComm, 2015, 17, 2989–2995.
3. V. Chabot, D. Higgins, A. Yu, X. Xiao, Z. Chen, and J. Zhang, A review of graphene and graphene oxide sponge:
Material synthesis and applications to energy and the environment, Energy Environ. Sci., 2014, 7, 1564–1596.
4. X. Lai, J. E. Halpert, and D. Wang, Recent advances in micro-/nano-structured hollow spheres for energy
applications: From simple to complex systems, Energy Environ. Sci., 2012, 5, 5604–5618.
5. R. K. Koninti, A. Sengupta, K. Gavvala, N. Ballav, and P. Hazra, Loading of an anti-cancer drug onto graphene
oxide and subsequent release to DNA/RNA: A direct optical detection, Nanoscale, 2014, 6, 2937–2944.
6. S. Xu, J. Shi, D. Feng, L. Yang, and S. Cao, Hollow hierarchical hydroxyapatite/Au/polyelectrolyte hybrid
microparticles for multi-responsive drug delivery, J. Mater. Chem. B, 2014, 2, 6500–6507.
7. Z. Zhao, D. Huang, Z. Yin, X. Chi, X. Wang, and J. Gao, Magnetite nanoparticles as smart carriers to manipulate
the cytotoxicity of anticancer drugs: Magnetic control and pH-responsive release, J. Mater. Chem., 2012, 22,
15717–15725.
8. K. Schilling, B. Bradford, D. Castelli, E. Dufour, J. F. Nash, W. Pape, S. Schulte, I. Tooley, J. Bosch, and F.
Schellauf, Human safety review of “nano” titanium dioxide and zinc oxide, Photochem. Photobiol. Sci., 2010, 9,
495–509.
9. V. Polshettiwar and R. S. Varma, Green chemistry by nano-catalysis, Green Chem., 2010, 12, 743–754.
10. G. Thilagavathi1, A.S.M. Raja1, and T. Kannaian, Nanotechnology and protective clothing for defence personnel,
Defence Sci. J., 2008, 58, 451–459.
11. R. Bogue, Nanocomposites: A review of technology and applications, Assembly Autom., 2011, 31, 106–112.
12. S. K. Gupta, A. Joshi, and M. Kaur. Development of gas sensors using ZnO nanostructures, J. Chem. Sci., 2010,
122, 57–62.
13. S. S. Mao, S. Shen, and L. Guo, Nanomaterials for renewable hydrogen production, storage and utilization, Prog. in
Nat. Sci.: Mater. Int., 2012, 22, 522–534.
14. C. R. Chinnamuthu and P. M. Boopathi, Nanotechnology and agroecosystem, Madras Agric. J., 2009, 96, 17–31.
15. J. Wang, Y. Chen, X. Wang, and F. Cao. Aluminium dodecatungstophosphate (Al0.9 H0.3 PW12 O40 ) nanotube as
soild acid catalyst one-pot production of biodiesel from waste cooking oil, BioResources, 2009, 4, 1477–1486.
16. N. Domun, H. Hadavinia, T. Zhang, T. Sainsbury, G. H. Liaghat, and S. Vahid, Improving the fracture toughness
and the strength of epoxy using nanomaterials—A review of the current status. Nanoscale, 2015, DOI:
10.1039/C5NR01354B.
17. J. Parameswaranpillai, G. Joseph, K. P. Shinu, S. Jose, N. V. Salim, and N. Hameed, Development of hybrid
composites for automotive applications: Effect of addition of SEBS on the morphology, mechanical, viscoelastic,
crystallization and thermal degradation properties of PP/PS–x GnP composites, RSC Adv., 2015, 5, 25634–25641.
18. P. Jyotishkumar, E. Logakis, S. M. George, J. Pionteck, L. Häussler, R. Haßler, P. Pissis, and S. Thomas,
Preparation and properties of multiwalled carbon nanotube/epoxy-amine composites, J. Appl. Polym. Sci., 2013,
127, 3063–3073.
19. L. Liu, M. Yu, J. Zhang, B. Wang, W. Liu, and Y. Tang, Facile fabrication of color-tunable and white light emitting
nano-composite films based on layered rare-earth hydroxides, J. Mater. Chem. C, 2015, 3, 2326–2333.
20. H. Liu, T. Kuila, N. H. Kim, B. Ku, and J. H. Lee, In situ synthesis of the reduced graphene oxide–
polyethyleneimine composite and its gas barrier properties, J. Mater. Chem. A, 2013, 1, 3739–3746.
21. K. Zhou, S. Jiang, C. Bao, L. Song, B. Wang, G. Tang, Y. Hu, and Z. Gui. Preparation of poly(vinyl alcohol)
nanocomposites with molybdenum disulfide (MoS2 ): Structural characteristics and markedly enhanced properties,
RSC Adv., 2012, 2, 11695–11703.
22. B. Faure, G. Salazar-Alvarez, A. Ahniyaz, I. Villaluenga, G. Berriozabal, Y. R. De Miguel, and L. Bergstrom,
Dispersion and surface functionalization of oxide nanoparticles for transparent photocatalytic and UV-protecting
coatings and sunscreens, Sci. Technol. Adv. Mater. 2013, 14, 023001.
23. E. Glogowski, R. Tangirala, T. P. Russell, and T. Emrick, Functionalization of nanoparticles for dispersion in
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389–414.
2 Classification of Nanomaterials and
Nanocomposites
K. G. Gatos and Y. W. Leong

CONTENTS
2.1 Introduction to Nanomaterials and Nanocomposites
2.2 Nanomaterials
2.2.1 0-D Nanomaterials
2.2.2 1-D Nanomaterials
2.2.3 2-D Nanomaterials
2.2.4 Nanomaterials of Complex Structure
2.3 Thermoplastic Nanocomposites
2.3.1 Thermoplastics Filled with 0-D Nanomaterials
2.3.2 Thermoplastics Filled with 1-D Nanomaterials
2.3.3 Thermoplastics Filled with 2-D Nanomaterials
2.4 Thermoset Nanocomposites
2.4.1 Thermosets Filled with 0-D Nanomaterials
2.4.2 Thermosets Filled with 1-D Nanomaterials
2.4.3 Thermosets Filled with 2-D Nanomaterials
2.5 Elastomeric Nanocomposites
2.5.1 Elastomers Filled with 0-D Nanomaterials
2.5.2 Elastomers Filled with 1-D Nanomaterials
2.5.3 Elastomers Filled with 2-D Nanomaterials
2.6 Outlook
2.6.1 Trends in Thermoplastic Nanocomposites
2.6.2 Trends in Thermoset Nanocomposites
2.6.3 Trends in Elastomeric Nanocomposites
References
2.1 INTRODUCTION TO NANOMATERIALS AND NANOCOMPOSITES
During the last three decades, a significant interest in nanomaterials by both industry and
academia has emerged. The reason behind was the need for solutions in real-life
applications, where existing approaches were facing limitations (e.g., in electronics,
catalysis, medicine, etc.). The development of upgraded characterization and processing
techniques assisted the efforts of the scientists to evaluate the theoretical studies on
nanomaterials. This progress supplied more advanced tools for the investigation and
manipulation of the nanoscale world (Nabok 2005).
In general, nanomaterials are materials that are characterized by at least one dimension
in the nanometer (1 nm = 10−9m) range (Rao and Cheetham 2006). This length scale, which
lies within the atomic and the microscale, brings new physical and chemical properties to a
material (i.e., size effects). This becomes especially apparent when the nanomaterial has at
least one dimension between 1 and 100 nm (Murphy et al. 2004). Thus, it is now widely
accepted that this latter specific range covers the term of nanomaterial.
There are several types of nanomaterials classified according to their composition and
shape. A practical way for their classification is according to the structural features of their
elementary units and the number of dimensions, which are outside the nanoscale. Thus, they
can be zero-dimensional (0-D) like nanoparticles, one-dimensional (1-D) like nanorods, and
two-dimensional (2-D) like nanolayers (Vollath 2008). The various combinations of
nanomaterials may configure a broad spectrum of nanostructures characterized by their
discernible form and dimensionality. Accordingly, for example, a linear or a planar bonding
of nanoparticles, of a defined composition, creates a one- or a two-dimensional
nanostructured material, respectively. Prerequisite for the latter classification in addition is
to exhibit size effects (Pokropivny and Skorokhod 2006). Further, the construction of
ordered arrays of nanostructures can provide strategies for the manufacturing of
nanodevices (Rao and Cheetham 2001).
Besides, the combination of two or more components or phases with different physical
or chemical properties, wherein at least one of these components is in the nanometer scale,
and results to differentiated properties compared to the individual constituents, introduces
the class of nanocomposites. These present enhanced properties as compared to their
respective microcomposites mainly due to the size effects of the nanomaterials involved
(Pokropivny et al. 2007). The distinguished category of nanocomposites in which at least
one discontinuous nanosized phase is dispersed in a continuous polymeric medium (i.e.,
matrix) relates to polymeric nanocomposites and it is the subject of the present chapter. The
limited distance between the nanofillers, along with the huge surface area per mass, imparts
significant property enhancement (Manias 2007).

2.2 NANOMATERIALS
There is a plethora of nanomaterials examined in the literature. Their significant role in
several applications makes their research a hot topic within materials science.
2.2.1 0-D NANOMATERIALS
Particulate nanomaterials constitute the most common category with a vast spectrum of
applications. It is well established that the confinement of the electron motion in three
dimensions induces new optical, electronic, magnetic, and chemical properties, which are
not observed in their bulk (Alivisatos 2004). This is related with the quantum effects and
the high surface to volume ratio of the nanoparticles. Figure 2.1 shows the effect of the
reduction of particle size on surface area and on melting temperature of gold (Buzea et al.
2007). Inert metals like gold and platinum become catalysts and opaque copper substances
become transparent under nanodimensions (Parab et al. 2009). Common metal
nanoparticles used in materials science involve silver, nickel, gold, and palladium, while
widely exploited metal oxides relate to titanium, copper, and iron (Basu and Pal 2011). For
example, nanosilver is famous for its antimicrobial properties (Sotiriou and Pratsinis 2010),
palladium nanoparticles have been extensively studied in relation to their catalytic action
(Cookson 2012), and titanium dioxide nanoparticles are well known for their high
photocatalytic activation (Pelaez et al. 2009) and use in cosmetics (Tyner et al. 2011).
Besides, nanoparticles such as silica (Rosso et al. 2006) or alumina (Siengshin et al.
2008) are well known for their prominent role as fillers in polymeric matrices. Depending
on the application, the nanoparticles are capped with functional groups, which provide
solubility and stability (Katz et al. 2003, Serrano-Ruiz et al. 2010). Grafting
macromolecules onto nanoparticles possess advantages over modification by low molecular
weight surfactants or coupling agents (Zhang et al. 2009). Especially for biomedical
applications dendritic structures have been proposed for the functionalization of the
nanoparticles (Nazemi and Gillies 2013). Bimetallic core–shell nanostructures have also
been proposed for their unique catalytic and biological sensing properties such as the gold–
platinum core–shell nanostructure (Mo and Du 2009).
A significant group within the 0-D nanomaterials relates to carbonic nanomaterials.
Fullerenes have been extensively examined, presenting interesting properties. Among this
group, the buckminsterfullerene (C60) with 60 carbon atoms is the most popular one. The
high degree of symmetry in its structure is mainly responsible for its characteristic
physicochemical, electronic, and magnetic properties (Mateo-Alonso et al. 2006). A rather
common particulate carbonic material which can be seen in nanodimensions is carbon
black, mainly exploited for its electrical, coloring, and reinforcing properties (Psarras and
Gatos 2011).
FIGURE 2.1 (a) Schematics illustrating a microparticle of 60 μm diameter about the size of a human hair shown in the
left at scale, and the number of nanoparticles with a diameter of 600 and 60 nm having the same mass as one
microparticle of 60 μm diameter. (b) Surface area normalized to mass versus particle diameter. (c) Gold melting
temperature as a function of particle diameter, according to Gibbs–Thomson equation, shown inset, the gold bulk
melting temperature is 1336 K. (With kind permission from Springer Science+Business Media: Biointerphases,
Nanomaterials and nanoparticles: Sources and toxicity, 2, 2007, 17–71, Buzea, C., Pacheco, I. I., Robbie, K.)

Biodegradability is desirable for several applications and nanofillers like starch have
been proposed for polymer reinforcement (Dufresne et al. 1996). Such types of fillers are
mainly extracted from maize, potatoes, corn, and rice and their hydrophilicity can be
resolved by suitable modification (Valodkar and Thakore 2011).
Polymeric materials have been used also for the fabrication of nanoparticles (Serrano et
al. 2006). In this case, controlling of the self-assembled block copolymer morphologies is a
facile way to create various nanoobjects like spheres and hollow spheres (Lazzari and
López-Quintela 2003).

2.2.2 1-D NANOMATERIALS

Highly emerging categories of nanomaterials relate to nanoscale-rods, -fibers, -wires, and -
tubes. Boron nitride nanotubes have been proposed for applications in electronic devices as
nanoscale insulators. For such applications, tubes of more than 1 mm in length have been
manufactured (Chen et al. 2008). In general, the template method has been extensively
exploited in the production of metal (e.g., Ni, Ag, and Fe), chalcogenide (e.g., MoS2 and
NdS2), and oxide (e.g., TiO2 and SiO2) nanotubes (Rao and Govindaraj 2011). The well-
known chemical vapor deposition (CVD) technique has been extensively used for the
production of zinc oxide nanomaterials (Schmidt-Mende and MacManus-Driscol 2007).
Semiconducting ZnO nanobelts, which were obtained by the CVD method, serve
applications in optoelectronics and piezoelectricity (Wang 2004).
Glass nanofibers fabricated by a high temperature taper-drawing process are promising
building blocks of nanoscale photonic devices due to their low-loss optical wave guiding
(Tong and Mazur 2008). Additionally, bioactive glass nanofibers, which were manufactured
by electrospinning using a glass sol–gel precursor with a bioactive composition, have been
shown to possess osteogenic potential in vitro (Kim et al. 2006).
Carbon nanotubes have attracted a great scientific interest within the 1-D nanomaterials.
Depending on their structure, they can be metallic or semiconducting, presenting properties
of ballistic transport, very high thermal conductivity, as well as optical polarizability
(Dresselhaus and Dai 2004). Apart from their use in nanodevices (Kinoshita et al. 2010), for
several other applications covalent (Bottari et al. 2013) or noncovalent functionalization
should take place (Tasis et al. 2009). The first functionalization method yields higher
stability while the latter route preserves the electronic structure of the nanotube (Bottari et
al. 2013). Carbon nanotubes have been very promising for their reinforcing efficiency in
polymeric matrices (Schadler et al. 1998, Moniruzzaman and Winey 2006).
Notwithstanding, within the carbonic 1-D nanomaterials, the carbon nanofiber appears as a
valuable candidate for the cost-effective manufacturing of polymer nanocomposites due to
its exceptional thermal, electrical, and reinforcing properties (Zhang et al. 2010).
The naturally occurring clay nanotube halloysite has been used for its capability to bear
chemically active agents for drug delivery (Abdullayev and Lvov 2013). Additionally, its
reinforcing action in polymers has been examined (Hedicke-Höchstötter et al. 2009). Bio-
nanomaterials are also an important group within the 1-D nanomaterials. For example,
cellulose is a linear polysaccharide macromolecule whose aggregates form fibrils of
nanodimensions. This material has been proposed for the manufacturing of polymer
nanocomposites with applications in the packaging sector mainly due to its biodegradability
(Siró and Plackett 2010).

2.2.3 2-D NANOMATERIALS

The nanoconfinement in one dimension of a material creates a 2-D structure, which relates
to nanoscale layers, disks, platelets, and flakes. Iron oxide nanoflakes have been proposed
as anode material for lithium batteries with better performance in capacity fading on
cycling compared to their nanoparticle or nanotube counterparts (Reddy et al. 2007).
Patterned gold nanodisk arrays have been used to enhance the efficiency of organic
photovoltaic devices (Diukman et al. 2011), while silver nanoplates were found to improve
the bacterial killing capacity compared to silver nanoparticles or nanorods (Pal et al. 2007).
Regarding the carbonic 2-D nanomaterials, graphene is the most heavily investigated
one during the last decade. Its 1-atom thick planar honeycomb structure imparts high
mechanical, thermal, electrical, and gas barrier properties (Seppälä and Luong 2014). It can
find application in chemical and biological sensors (Jiang 2011), photovoltaics (Jariwala et
al. 2013), and the interest in the electron-device community is tremendously growing
(Schwierz 2010). For example, palladium– graphene junctions have been proposed for the
development of high performance transistors due to their low contact resistance (Xia et al.
2011). Besides, graphene appears to be a potential candidate for solar energy applications as
transparent conductors and photoactive components in solar cells (Jariwala et al. 2013).
Additionally, the superior tribological properties of graphene make it suitable to serve as an
additive in lubricant oils or as a self-lubricating material (Berman et al. 2014). For
dispersing graphene in polymeric matrices, functionalization is usually required (Kuilla et
al. 2010). Apart from single graphite layers (i.e., graphene), exfoliated graphitic
nanoplatelets can find various applications as a rather inexpensive 2-D nanofiller
(Stankovich et al. 2006b).
Silicate platelets have been extensively investigated for manufacturing of polymer
nanocomposites. In nature, these platelets are abundantly found in phyllosilicate minerals
in the form of aggregated stacks (Theng 1979). The forms of clay (of natural origin) or
layered silicates (of synthetic origin), which are able to expand their interlayer spacing and
disperse their single silicate platelets in a medium are potential candidates for mixing with
polymers. It is very common to attach organic cations on the silicate layers in order to
render the latter organophilic and assist their exfoliation in the polymer matrix
(Bhattacharya et al. 2008). The dispersion of a small amount of such platy nanofillers in a
polymer yields significant improvement in mechanical, gas barrier, and flame retardant
properties (Gatos and Karger-Kocsis 2011). In contrast to layered silicates, layered double
hydroxides (LDH) have positively charged layers stacked one on another with small anions
and water molecules sandwiched in the interlayer region (Pradhan et al. 2008).

2.2.4 NANOMATERIALS OF COMPLEX STRUCTURE

In practice, various combinations of the above-described nanomaterials may create
complicated structures with special form and dimensionality. For example, zinc oxide can
be formed in a plethora of structures and symmetries such as tripods, tetrapods, and
nanocombs (Banerjee et al. 2006). Nanoporous materials, which are assigned as 3-D
nanostructures (Foa Torres et al. 2014), have potential applications in separation, catalytic,
biomedical, and heat transfer applications (Plawsky et al. 2009). Besides, researchers have
created numerous complex structures like flower-like or urchin-like, which actually belong
to the group of 3-D nanostructured materials. Nanomaterials or nanostructured materials,
which are not found dispersed in the polymer matrix, for example, polymer confined in a
nanoporous inorganic matrix (Duran et al. 2011), will not be a subject of the present
chapter.

2.3 THERMOPLASTIC NANOCOMPOSITES

The development of multifunctional thermoplastic materials for a particular application
often requires the incorporation of one or more types of nanofillers. Some of the functions
that can be attained with the presence of nanofillers in polymer matrices include (but are
not limited to) enhancements in mechanical performance, chemical resistance, barrier to
oxygen or moisture, compatibility between different phases in polymer blends, and
electrical or thermal conductivity. The dimensionality (size, shape, and morphology) of the
nanofiller is one of the main considerations when choosing suitable nanofillers to be
incorporated into a thermoplastic resin. Types of nanofillers with different dimensionalities
but of the same chemical composition may result in nanocomposites with significant
differences in properties such as viscosity, mechanical performance, crystallinity, thermal
stability, and conductivity. This is especially apparent for systems containing 1-D and 2-D
nanofillers whereby the aspect ratio and orientation of the fillers are important in
determining the final properties of the composite.

2.3.1 THERMOPLASTICS FILLED WITH 0-D NANOMATERIALS

The incorporation of nanoparticles into commodity thermoplastics such as polyolefins, as
well as engineering thermoplastics such as polyamide, poly(ethylene terephthalate), and
polycarbonate were mainly targeted at influencing impact response, structural rigidity,
thermal stability, thermal and electrical conductivity, and wear resistance.
The initial intention of incorporating low cost minerals such as CaCO3 in polyolefin
was merely to reduce the overall material’s cost. Later, it was discovered that CaCO3 was
able to enhance both the stiffness and the impact performance of the polyolefin especially
when the particles were homogeneously dispersed. Zhu et al. have emphasized the
importance of CaCO3 nanofiller dispersion on the crystallization, morphology, and
mechanical performance of PP (Zhu et al. 2014). These authors recommended an effective
method to obtain quantitative particle size distribution curves from microscopy images,
which can be correlated to the mechanical performance of the composites. More recently,
CaCO3 nanoparticles have been used to impart further functionalities with the creation of
different polymorphic crystalline forms of CaCO3, that is, calcite, aragonite, and vaterite.
However, not all polymorphs can be easily produced since calcite is thermodynamically
more stable than all other forms. Aragonite can be found naturally in shells of cockles and
snails. It has been reported that using diethylenetriaminepentaacetic acid (DTPA), the
polymorphism of CaCO3, with the application of various temperatures can be controlled
(Gopi et al. 2013).
The physical properties of CaCO3 depend on the type of polymorphic composition and
this in turn influences the properties of the composites (Karamipour et al. 2011, Thumsorn
et al. 2011, Yao et al. 2014). Thumsorn et al. reported that the incorporation of aragonite-
CaCO3 derived from cockle shells into PP was able to impart higher stiffness to the
composites as compared with those filled with conventional calcite-CaCO3 (Thumsorn et
al. 2011). Yao et al. have used aragonite clam shell-derived CaCO3 (CS) and compared its
function with commercially available calcite nano-CaCO3 (Yao et al. 2014). CS was treated
with furfural (FCS) and hydrochloric acid (ACS) in order to improve its hydrophobicity,
enhancing the impact performance of the system. It was reported that the FCS treatment
was particularly effective for the dispersion of FCS in PP even at high filler contents.
CaCO3 acted as an effective nucleating agent for PP decreasing the crystallization rate and
size of the spherulites. Karamipour et al. (2011) have found that the presence of nano-
CaCO3 enabled the PP matrix to sustain high modulus at elevated temperatures especially
when the nanofiller contents increased above 5 wt%. Many of these reports, however, have
not indicated remarkable increments in the composite strength. The reason behind is the
bonding between CaCO3 particles and the matrix resin, which consist of weak van der
Waals forces insufficient to cause “bridging interactions” between the polymer chains
mediated by the filler particles (Jancar et al. 2010). Therefore, CaCO3 is not reported to
cause notable shifts in glass transition temperature (Tg) of polymers although it affects
their crystallization kinetics.
The usage of fullerene-like nanoparticles such as tungsten disulfide (WS2) and
molybdenum disulfide (MoS2) as reinforcements for polymers is an emerging strategy that
can provide similar or enhanced performance (e.g., wear) when compared to
nanocomposites reinforced with 1-D or 2-D nanofillers. Further to that, this strategy is
expected to be cost-effective and environmentally friendly (Naffakh et al. 2013). These
fullerene-like nanoparticles (FNP) are inherently unstable in the sheet form due to their
abundant ring atomic structure and tend to curl into hollow nanoparticles.
Due to their higher surface to volume ratio, nanoparticles have significantly higher
surface energy than micron-sized particles. Therefore, they are prone to agglomeration
during melt blending with thermoplastics. Various approaches are used to disperse 0-D
nanoparticles including vigorous mechanical shearing, solution blending, surface treatment,
polymer grafting onto nanofiller, in situ polymerization, and in situ growth of
nanoparticles. Nanosilica, for example, possesses surface hydroxyl groups and tends to
agglomerate via hydrogen bonding. In this case, use of organic surfactants or grafting of
polymers to the surface of the nanoparticle is a common approach to increase affinity
between the nanoparticles and the thermoplastic matrix.
Aso et al. (2007) successfully improved the dispersion of nanosilica in thermoplastic
elastomer copolyetherester through surface modification with dimethyl dichlorosilane
(DDS). They reported that the interaction between the methylene groups in the silane and
the methylenic chains in the elastomer was much stronger as compared to the hydrogen
bonds created between the hydroxyl groups in untreated nanosilica and the ester groups in
the elastomer. Through this interaction, the elongation at break as well as the creep
resistance of the nanocomposite was significantly improved. In this system, it was found a
good state of dispersion even at filler loadings up to 6 wt%. On the contrary, agglomeration
was detected for 3 wt% of untreated nanosilica.
In the case of nano-CaCO3, surface treatment with stearic acid or a certain type of
silanes (aluminate or titanate) has been proposed to promote dispersion in PP (Wan et al.
2006; Liu et al. 2007; Meng and Dou 2009). Use of compatibilizers such as PP-g-MAH
combined with silane treated filler is another approach for a fine dispersion of nanoparticles
in this matrix (Palza et al. 2011). In another case, PP-methyl-POSS has been exploited to
disperse the untreated nanosilica (Lin et al. 2009). For TiO2 nanoparticles, trisilanol
isobutyl polyhedral oligomeric silsesquioxane (TSIB-POSS) has been reported to act as a
compatibilizer for promoting dispersion in PP. The polar silanol groups in TSIB-POSS were
able to interact with the TiO2 particles while the nonpolar groups interacted with PP
(Wheeler et al. 2008).
Leong et al. synthesized toughening agents based on a block copolymer of polyhedral
oligomeric silsesquioxane (MA-POSS) and enantiopure poly(D-lactic acid) (PDLA) or
poly(L-lactic acid) (PLLA) [PDLA-b-P(MA-POSS) or PLLA-b-P(MA-POSS)], and
incorporated them as filler in a PLA matrix via melt compounding (Leong et al. 2014). This
approach exploited the formation of a stereocomplex to enhance the filler-matrix interfacial
adhesion and subsequently to promote filler dispersion. The resulting PLA nanocomposite
exhibited synergistic enhancement in stiffness and toughness even at very low nanofiller
concentrations.

2.3.2 THERMOPLASTICS FILLED WITH 1-D NANOMATERIALS

Due to their considerable length in one dimension, nanofibers, nanotubes, or nanowhiskers
tend to entangle each other. Unlike 0-D nanoparticles where agglomeration can often be
overcome by mechanical agitation or surface treatment, entanglements between 1-D
nanofillers require significantly more energy to separate and disperse in thermoplastic
matrices. Therefore, it is more important to prevent 1-D nanofillers from entangling in the
first place in order to promote dispersion during the mixing process with the
thermoplastics.
Carbon nanotube (CNT) is one of the most promising 1-D nanofillers since its inception
in 1991 (Ijima 1991). It has been incorporated into thermoplastics to achieve properties
such as electrical and thermal conductivity, stiffness, strength, and fracture toughness.
Various strategies have been used to enhance the dispersion of CNTs in thermoplastics, for
example, electropolymerization, electrodeposition, esterification, ring-opening metathesis
polymerization (ROMP), atomic transfer radical polymerization (ATRP), radical-addition
fragmentation chain transfer polymerization (RAFT), and amidation (Chen et al. 1998;
Gómez et al. 2003; Cui et al. 2004, Kong et al. 2004; Qin et al. 2004). Wu et al. (2010)
dispersed multiwalled CNT (MWCNT) in polyamide by creating a MWCNT–polyamic acid
colloidal suspension, which under an electric field deposited coherent MWCNT–polyimide
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