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M. Kochnev, DSc
PhD, Oleg V. Stoyanov, DSc, Gennady E. Zaikov, DSc,
and Renat M. Akhmetkhanov, DSc ISBN: 978-1-77188-038-1
90000
ISBN: 978-1-77188-038-1
ISBN: 978-1-77188-038-1 90000
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APPLIED RESEARCH ON
POLYMER COMPOSITES
 AAP Research Notes on
Polymer Engineering Science and Technology

APPLIED RESEARCH ON
POLYMER COMPOSITES

Edited by
Pooria Pasbakhsh, PhD, A. K. Haghi, PhD, and
Gennady E. Zaikov, DSc
CRC Press Apple Academic Press, Inc
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 v

ABOUT THE EDITORS

Pooria Pasbakhsh, PhD

Dr Pooria Pasbakhsh’s research has been centered on the development
and application of computational approaches and experimental tools on
modern polymers, halloysite nanotubes, and polymer clay nanocom-
spoites. He is currently Lecturer at School of Engineering, Monash Uni-
versity Sunway Campus, Malaysia.

Gennady E. Zaikov, DSc

Gennady E. Zaikov, DSc, is Head of the Polymer Division at the N. M.
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,
Moscow, Russia, and Professor at Moscow State Academy of Fine Chemi-
cal Technology, Russia, as well as Professor at Kazan National Research
Technological University, Kazan, Russia. He is also a prolific author, re-
searcher, and lecturer. He has received several awards for his work, includ-
ing the Russian Federation Scholarship for Outstanding Scientists. He has
been a member of many professional organizations and on the editorial
boards of many international science journals.

A. K. Haghi, PhD
A.K. Haghi, PhD, holds a BSc in urban and environmental engineer-
ing from the University of North Carolina (USA); an MSc in mechanical
engineering from North Carolina A&T State University (USA); a DEA
in applied mechanics, acoustics and materials from Université de Tech-
nologie de Compiègne (France); and a PhD in engineering sciences from
Université de Franche-Comté (France). He is the author and editor of 150
books and 1000 published papers in various journals and conference pro-
ceedings. Dr Haghi has received several grants, consulted for a number of
major corporations, and is a frequent speaker to national and international
audiences. Since 1983, he served as a professor at several universities. He
is currently Editor-in-Chief of the International Journal of Chemoinfor-
vi About the Editors

matics and Chemical Engineering and Polymers Research Journal and

on the editorial boards of many international journals. He is a member of
the Canadian Research and Development Center of Sciences and Cultures
(CRDCSC), Montreal, Quebec, Canada.
ABOUT AAP RESEARCH NOTES ON
POLYMER ENGINEERING SCIENCE
AND TECHNOLOGY

The AAP Research Notes on Polymer Engineering Science and Technology re-
ports on research development in different fields for academic institutes and indus-
trial sectors interested in polymer engineering science and technology. The main
objective of this series is to report research progress in this rapidly growing field.

Editor-in-Chief: Sabu Thomas, PhD

Director, School of Chemical Sciences, Professor of Polymer Science & Tech-
nology & Honorary Director of the International and Inter University Centre for
Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, India
email: [email protected]

Editorial Board

Alberto D’Amore, DSc

Department of Aerospace and Mechanical Engineering, The Second University
of Naples, Italy

Devrim Balköse, PhD

Professor, Izmir Polytechnic Institute, Turkey

Nekane Guarrotxena, PhD

Institute of Polymer Science and Technology (ICTP), Spanish National Research
Council (CSIC), Madrid, Spain

Abbas Hamrang, PhD

Professor and Senior Polymer Scientist, Manchester, UK; Independent Polymer
Consultant

Alfonso Jimenez, PhD

Professor of Analytical Chemistry and Materials Science, University of Alicante,
Spain

Gennady E. Zaikov, DSc

Head, Polymer Division, N. M. Emanuel Institute of Biochemical Physics,
Russian Academy of Sciences; Professor, Moscow State Academy of Fine Chem-
ical Technology, Russia; Professor, Kazan National Research Technological Uni-
versity, Kazan, Russia
BOOKS IN THE AAP RESEARCH
NOTES ON POLYMER ENGINEERING
SCIENCE AND TECHNOLOGY SERIES

• F
 unctional Polymer Blends and Nanocomposites: A Practical
Engineering Approach
Editors: Gennady E. Zaikov, DSc, Liliya I. Bazylak, PhD,
and A. K. Haghi, PhD

• P
 olymer Surfaces and Interfaces: Acid-Base Interactions and
Adhesion in Polymer-Metal Systems
Irina A. Starostina, DSc, Oleg V. Stoyanov, DSc,
and Rustam Ya. Deberdeev, DSc

• K
 ey Technologies in Polymer Chemistry
Editors: Nikolay D. Morozkin, DSc, Vadim P. Zakharov, DSc, and
Gennady E. Zaikov, DSc

• P
 olymers and Polymeric Composites: Properties, Optimization,
and Applications
Editors: Liliya I. Bazylak, PhD, Gennady E. Zaikov, DSc,
and A. K. Haghi, PhD

• A
 pplied Research on Polymer Composites
Editors: Pooria Pasbakhsh, PhD, A. K. Haghi, PhD, and
Gennady E. Zaikov, DSc

• H
 igh-Performance Polymers for Engineering-Based
Composites
Editors: Omari V. Mukbaniani, DSc, Marc J. M. Abadie, DSc, and
Tamara Tatrishvili, PhD
 Dedicated to
Professor Gennady E. Zaikov on the Occasion of
His Eightieth Birthday, 7 January 2015
CONTENTS

List of Contributors................................................................................... xiii

List of Abbreviations................................................................................ xvii
List of Symbols.......................................................................................... xix
Preface...................................................................................................... xxi
Foreword...................................................................................................xxv
1. Trends in New Generation of Biodegradable Polymers (Part 1)............. 1
A. L. Iordanskii, G. A. Bonartseva, Yu. N. Pankova, S. Z Rogovina,
K. Z. Gumargalieva, G. E. Zaikov, and A. A. Berlin

2. Trends in New Generation of Biodegradable Polymers (Part 2)........... 49

A. L. Iordanskii, S. V. Fomin, A. A. Burkov, Yu. N. Pankova, and G. E. Zaikov

3. Trends in New Generation of Biodegradable Polymers (Part 3)........... 63

A. P. Bonartsev, A. P. Boskhomodgiev, A. L. Iordanskii, G. A. Bonartseva,
A. V. Rebrov ,T. K. Makhina, V. L. Myshkina, S. A. Yakovlev, E. A. Filatova,
E. A. Ivanov, D. V. Bagrov, G. E. Zaikov, and M. I. Artsis

4. A Detailed Review on Physicochemical Properties, Synthesis,

and Application of Polyacetylene.............................................................. 81
O. A. Ponomarev, A. I. Rakhimov, N. A. Rakhimov, E. S. Titova, V. A. Babkin, and
G. E. Zaikov

5. Trends in Activated Carbon Fibers........................................................ 105

M. MehdiPour

6. Reinforcement of Polymer Nanocomposites: Variety of Structural

Forms and Applications........................................................................... 143
G. V. Kozlov, Yu. G. Yanovskii, and G. E. Zaikov

7. A Study on the Effects of the Modified Silica—Gelatin Hybrid

Systems on the Properties Paper Products............................................ 177
Przemysław Pietras, Zenon Foltynowicz, Hieronim Maciejewski, and
Ryszard Fiedorow

8. Development of Computational Techniques in Nanosystems.............. 191

V. I. Kodolov, N. V. Khokhriakov, V. V. Trineeva, M. A. Chashkin, L. F. Akhmetshina,
Yu. V. Pershin, and Ya. A. Polyotov
xii Contents

9. Calculating the Internal Structure and the Equilibrium Configuration

(Shape) of Separate Noninteracting Nanoparticles by the Molecular
Mechanics and Dynamics Interactions of Nanostructural
Elements.................................................................................................... 245
A. V. Vakhrushev and A. M. Lipanov

10. Trends in Ozonation of Polymer Compounds....................................... 279

M. P. Anachkov, S. K. Rakovsky, and G. E. Zaikov

Index........................................................................................................... 309
LIST OF CONTRIBUTORS

L. F. Akhmetshina
OJSC “Izhevsk Electromechanical Plant – Kupol”

M. P. Anachkov
S. K. Rakovsky, Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev bl.11,
1113 Sofia, Bulgaria, Email: [email protected]

M. I. Artsis
Institute of Biochemical Physics after N. M. Emanuel, Kosygina 4, Moscow 119991, Russia,
Email [email protected]
M. MehdiPour, University of Guilan, Rasht, Iran

V. A. Babkin
Volgograd State University Architecture and Civil Engineering Sebrykov Department,
Email: [email protected].

D. V. Bagrov
Faculty of Biology, Moscow State University, Leninskie gory, Moscow 119992, Russia

A. A. Berlin
N. N. Semenov’s Institute of Chemical Physics, RAS, Moscow, 119996 RF

A. P. Bonartsev
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, 119071
Moscow, Russia and Faculty of Biology, Moscow State University, Leninskie gory, 119992 Moscow,
Russia

G. A. Bonartseva
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, Moscow
119071, Russia

A. P. Boskhomodgiev
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, 119071
Moscow, Russia

A. A. Burkov
Vyatka State University, Kirov, 610000 RF, Email: [email protected]

M. A. Chashkin
OJSC “Izhevsk Electromechanical Plant – Kupol”

E. A. Filatova
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, 119071
Moscow, Russia
S. V. Fomin
Vyatka State University, Kirov, 610000 RF, Email: [email protected]
xiv List of Contributors

Zenon Foltynowicz
Faculty of Commodity Science, Poznan University of Economics, 61-875 Poznań, Poland

K. Z. Gumargalieva
N. N.Semenov’s Institute of Chemical Physics, RAS, Moscow, 119996 RF

A. L. Iordanskii
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, 119071
Moscow, Russia and N.N.Semenov Institute of Chemical Physics, Russian Academy of Sciences,
Moscow 119991, Russia

E. A. Ivanov
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, 119071
Moscow, Russia

N. V. Khokhriakov
Basic Research – High Educational Centre of Chemical Physics and Mesoscopy, Udmurt Scientific
Centre, Ural Division, Russian Academy of Sciences, Izhevsk and Izhevsk State Agricultural Acad-
emy

V. I. Kodolov
M. T. Kalashnikov Izhevsk State Technical University and Basic Research – High Educational Centre
of Chemical Physics and Mesoscopy, Udmurt Scientific Centre, Ural Division, Russian Academy of
Sciences, Izhevsk

G. V. Kozlov
Institute of Applied Mechanics of Russian Academy of Sciences, Leninskii pr, Moscow 119991,
Russian Federation, Email: [email protected]

Hieronim Maciejewski
Faculty of Chemistry, Adam Mickiewicz University, 61-614 Poznań, Poland and Poznań Science and
Technology Park of Adam Mickiewicz University Foundation, 61-612 Poznań, Poland

T. K. Makhina
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, 119071
Moscow, Russia
V. L. Myshkina
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, Moscow
119071, Russia

Yu. N. Pankova
N. N. Semenov’s Institute of Chemical Physics, RAS, Moscow, 119996 RF Email: aljordan08@gmail.
com

Przemysław Pietras
Faculty of Chemistry, Adam Mickiewicz University, Poznań, Poland
Ryszard Fiedorow, Faculty of Chemistry, Adam Mickiewicz University, 61-614 Poznań, Poland

Ya. A. Polyotov
M. T. Kalashnikov Izhevsk State Technical University and Basic Research – High Educational Centre
of Chemical Physics and Mesoscopy, Udmurt Scientific Centre, Ural Division, Russian Academy of
Sciences, Izhevsk
O. A. Ponomarev
Pushino, Institute of Mathematical Problem of Biology Russian Akademy of Science,
Email: [email protected]
List of Contributors xv

A. I. Rakhimov
Volgograd State University, Email: [email protected]

N. A. Rakhimov
Volgograd State University, Email: [email protected]

A. V. Rebrov
A. V. Topchiev Institute of Petroleum Chemistry. Leninskiy prosp, 119071 Moscow, Russia

S. Z. Rogovina
N. N. Semenov’s Institute of Chemical Physics, RAS, Moscow, 119996 RF

E. S. Titova
Volgograd State Technical University, Email: [email protected]
N. M. Emanuel Institute of Biochemical Physics of Russian Academy of Sciences, Moscow 119334,
Russian Federation, Email: [email protected]

V. V. Trineeva
Basic Research – High Educational Centre of Chemical Physics and Mesoscopy, Udmurt Scientific
Centre, Ural Division, Russian Academy of Sciences, Izhevsk and Institute of Mechanics, Ural Divi-
sion, Russian Academy of Sciences, Izhevsk

A. V. Vakhrushev
A. M. Lipanov, Institute of Mechanics, Ural Branch of the Russian Academy of Sciences, Izhevsk,
Russia Email: [email protected]

S. A. Yakovlev
A. N. Bach's Institute of Biochemistry, Russian Academy of Sciences, Leninskiy prosp, 119071
Moscow, Russia
Yu. G. Yanovskii
Institute of Applied Mechanics of Russian Academy of Sciences, Leninskii pra, Moscow 119991,
Russian Federation, Email: [email protected]
G. E. Zaikov
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow 119334
Russia, Email: [email protected]
LIST OF ABBREVIATIONS

AC activated carbon
ACFs activated carbons fibers
ACNF activated carbon nanofiber
AFM atomic force microscopy
AKDs ketene dimers
AMF advanced method of surface investigation
ASAs alkenyl succinic anhydrides
ASM atomicpower microscopy
BET Brunauer–Emmett–Teller
BJH Barrett–Joyner–Halenda
CNF carbon nanofiber
DFT density functional theory
DOM dissolved natural organic matter
EDLC electric double-layer capacitor
FGG food grade gelation
FTIR Fourier transform infrared spectroscopy
GCMC Grand Canonical Monte Carlo
HK Horvath–Kawazoe
LC liquid chromatography
LIBs lithium-ion batteries
MD molecular dynamics
MFC microbial fuel cell
MFCs microbial fuel cells
MSC molecular sieving carbon
MW molecular weight
MWCNTs multiwalled carbon nanotubes
PALS positron annihilation lifetime spectroscopy
PBI polybenzimidazol
PGAs polyglycolides
PHAs polyhydroxyalkanoates
PHB poly(R)-3-hydroxybutyrate
PIB polyisobutylene
xviii List of Abbreviations

PIs polyimides
PLAs polylactides
POs primary ozonides
PSA pressure swing adsorption
PSD pore size distribution
PVA poly (vinyl alcohol)
PVDF poly (vinylidene fluoride)
RGG research grade gelatin
RVC reticulated vitreous carbon
SANS small-angle neutron scattering
SEM scanning electron microscopy
SOCs synthetic organic chemicals
SPIP scanning probe image processor
STM scanning tunneling microscopy
SWCNTs single-walled CNT
T&O taste and odor
TEOS tetraethoxysilan
TSA temperature swing adsorption
WAXS wide angle X-ray scattering
XRD X-ray diffraction
LIST OF SYMBOLS

ϕif and ϕn relative volume fractions

νm polymer matrix Poisson’s ratio
ρn density
ρn nanocomposite density
ρn nanofiller particle
ϕn nanofiller volume fraction
νTC nanofiller (technical carbon)
a lower linear scale of fractal behavior
c nanoparticles concentration
C∞ characteristic ratio
k Boltzmann constant
kd effective rate constant of hydrolytic depolymerisation
kh effective hydrolysis constant
kn proportionality coefficient
KT isothermal modulus of dilatation
l0 main chain skeletal bond length
Mm constant molecular mass of monomer
Pn0 initial number-average degree of polymerization at time 0
Si quadrate area
Su nanoshungite particles specific surface
T testing temperature
Wn nanofiller mass content
PREFACE

Polymers play a significant part in humans’ existence. They have a role in

every aspect of modern life, such as health care, food, information tech-
nology, transportation, energy industries, and so on. The speed of develop-
ments within the polymer sector is phenomenal and, at same time, crucial
to meet the demands of today’s and future life. Specific applications for
polymers range from adhesives, coatings, painting, foams and packaging
to structural materials, composites, textiles, electronic and optical devices,
biomaterials, and many other uses in industries and daily life. Polymers
are the basis of natural and synthetic materials. They are macromolecules
and, in nature, are the raw material for proteins and nucleic acids, which
are essential for human bodies.
Cellulose, wool, natural and synthetic rubber, plastics are all well-
known examples of natural and synthetic types. Natural and synthetic
polymers play a massive role in everyday life, and a life without poly-
mers really does not exist. A correct understanding of polymers did not
exist until the 1920s. In 1922, Staudinger published his idea that polymers
were long chain molecules with normal chemical bonds holding them to-
gether. But for nearly 10 years, this idea did not attract much attention.
Around this period, other researchers such as Carothers who tended to-
ward Staudinger’s idea discovered a type of synthetic material that could
be produced by its constituent monomers. Later on, it was shown that as
well as addition reaction, polymers could be prepared through condensa-
tion mechanism.
The introduction of plastics is associated with the twentieth century,
but the first plastic material celluloid, was made in 1865. During the
1970s, clothes of polyester became fashionable, but by the 1980s, synthet-
ics lost the popularity in favor of natural materials. Although people were
less enthusiastic about synthetic fabrics for everyday wear, Gore-Tex and
other synthetics became popular for outdoor and workout clothing. At the
same time as the use of synthetic materials in clothing declined, alterna-
tive uses were found. One great example is the use of polyester for making
beverage bottles where it replaced glass with its shatterproof properties as
a significant property.
xxii Preface

In general, it can be said that plastics enhance and even preserve life—
for instance, Kevlar, when used in making canoes for recreation or when
used to make a bulletproof vest. Polyester enhances life, when this highly
nonreactive material is used to make replacement human blood vessels or
even replacement skin for burn victims. With all the benefits attributed to
plastics, they have their negative side. A genuine environmental problem
exists due to the fact that the synthetic polymers do not break down easily
compared with the natural polymers. Hence, there is a need not only to
develop biodegradable plastics but also to work on more effective means
of recycling. A lot of research is needed to study the methods of degrada-
tion and stabilization of polymers in order to design polymers according
to the end-use.
Among the most important and versatile of the hundreds of commer-
cial plastics is polyethylene. Polyethylene is used in a wide variety of ap-
plications because it can be produced in various forms. The first type to
be commercially exploited was called low-density polyethylene (LDPE).
This polymer is characterized by a large degree of branching, forcing the
molecules to pack together rather than loosely forming a low-density ma-
terial. LDPE is soft and pliable and has applications ranging from plastic
bags, containers, textiles, and electrical insulation, to coatings for packag-
ing materials.
Another form of polyethylene differing from LDPE in structure is high
density polyethylene (HDPE). HDPE demonstrates little or no branching,
resulting in the molecules to be tightly packed. HDPE is much more rigid
than LDPE and is used in applications where rigidity is important. Major
uses of HDPE are plastic tubing, bottles, and bottle caps. Other variations
of polyethylene include high and ultrahigh molecular mass ones. These
types are used in applications where extremely tough and resilient materi-
als are needed.
Rubber is the most important of all elastomers. Natural rubber
is obtained from the bark of the rubber tree and has been used by
humans for many centuries. It is a polymer with repeating units of
isoprene. In 1823, rubber was vulcanized with sulfur whilst heated
and this process made it to become the valuable material it is today.
In this process, sulfur chain fragments attack the rubber polymer
chains, which leads to cross-linking. Most of the rubber used in the
world is a synthetic variety called styrene-butadiene rubber.
Preface xxiii

Natural polymers unlike the synthetic ones do possess very complex

structure. Natural polymers such as cellulose, wool, and natural rubber are
used in many products in large proportions. Cellulose derivatives are one
of the most versatile groups of regenerated materials with various fields of
application. Cellulose is found in nature in all forms of plant life, particu-
larly in wood and cotton. The purest form of cellulose is obtained from the
seed hairs of the cotton plant that contains up to 95% cellulose. The first
cellulose derivatives came to the stage around 1845 when the nitration of
starch and paper led to discovery of cellulose nitrate. In 1865, for the first
time, a moldable thermoplastic made of cellulose nitrate and castor oil.
In 1865, the first acetylation of cellulose was carried out, but the first
acetylation process for use in industry was announced in 1894. In 1905, an
acetylation process was introduced which yielded a cellulose acetate solu-
ble in the cheap solvent acetone. It was during World War I when cellulose
acetate dope found importance for weather proofing and stiffening the fab-
ric of aircraft wings. There was a large surplus production capacity after
the war, which led to civilian end uses such as the production of cellulose
acetate fibers by 1920s. Cellulose acetate became the main thermoplastic
molding material when the first modern injection molding machines were
designed. Among the cellulose derivatives, cellulose acetates are produced
in the largest volume. Cellulose acetate can be made into fibers, trans-
parent films, and the less substituted derivatives are true thermoplastics.
Cellulose acetates are moldable and can be fabricated by the conventional
processes. They have toughness, good appearance, capable of many color
variations including white transparency.
New applications are being developed for polymers at a very fast rate
across the world at various research centers. Examples of these include
electroactive polymers, nanoproducts, robotics, etc. Electroactive poly-
mers are special types of materials that can be used for example as artificial
muscles and facial parts of robots or even in nanorobots. These polymers
change their shape when activated by electricity or even by chemicals.
They are light weight but can bear a large force which is very useful when
being utilized for artificial muscles. Electroactive polymers together with
nanotubes can produce very strong actuators. Currently, research works
are carried out to combine various types of electro active polymers with
carbon nanotubes to make the optimal actuator. Carbon nanotubes are very
strong, elastic, and conduct electricity. When they are used as an actua-
tor, in combination with an electroactive polymer, the contractions of the
xxiv Preface

artificial muscle can be controlled by electricity. Already works are under

way to use electroactive polymers in space. Various space agencies are
investigating the possibility of using these polymers in space. This tech-
nology has a lot to offer for the future, and with the ever increasing work
on nanotechnology, electro active materials will play very important part
in modern life.
This new volume presents leading-edge research in the rapidly chang-
ing and evolving field of polymer science as well as on chemical process-
ing. The topics in the book reflect the diversity of research advances in
the production and application of modern polymeric materials and related
areas, focusing on the preparation, characterization, and applications of
polymers. This volume also covers various manufacturing techniques. The
book will help fill the gap between theory and practice in industry.
This new book
• is a collection of articles that highlights some important areas of cur-
rent interest in polymer products and chemical processes.
• gives an up-to-date and thorough exposition of the present state of
the art of polymer analysis.
• familiarizes the reader with new aspects of the techniques used in the
examination of polymers, including chemical, physico-chemical and
purely physical methods of examination.
• describes the types of techniques now available to the polymer
chemist and technician, and discusses their capabilities, limitations,
and applications.
• provides a balance between materials science and mechanics as-
pects, basic and applied research, and high-technology, and high-
volume (low-cost) composite development.
The book introduces current state-of-the-art technology in mod-
ern materials with an emphasis on the rapidly growing technologies.
It takes a unique approach by presenting specific materials and then
progresses into a discussion of the ways in which these materials
and processes are integrated into today’s functioning manufactur-
ing industry. It follows a more quantitative and design-oriented ap-
proach than other texts in the market, helping readers gain a better
understanding of important concepts. Readers will also discover
how material properties relate to the process variables in a given
process as well as how to perform quantitative engineering analysis
of manufacturing processes.
FOREWORD

It is a pleasure to write the foreword to this “special AAP Research Notes”

on Applied Research on Polymer Composites dedicated to Professor Gen-
nady E. Zaikov. Gennady’s name is, of course, familiar to every scientist
and practising chemist from his pioneering works. From a personal per-
spective, Gennady has had a major impact on all of our lives, taking us
under his wing in one role or another during the formative stages of our
academic careers. Even though he formally retired many years ago, he
maintains a tireless enthusiasm for chemistry, writing books and original
papers, reviewing articles, attending chemistry meetings, and giving in-
vited lectures around the world. I am delighted to pay tribute to Gennady
for his friendship, his role as a teacher and mentor, and his important and
extensive contributions to polymer chemistry. This “AAP Research Note”
is a token of our appreciation of a truly outstanding scientist, Professor
Gennady E. Zaikov.
Gennady Efremovich Zaikov was born in Omsk, Siberia, where he also
graduated from their primary, middle, and high school. He also gradu-
ated from a musical school where he studied violin. However, his parents
Efrem and Matrena, decided that it might be better for their son to con-
tinue his education by following in the footsteps of his mother—a chem-
istry teacher in high school and Omsk’s medical institute. His father was
a mathematician and land-surveyor. Therefore, in 1952, Gennady moved
to Moscow where he entered the Moscow State University (MSU), and he
graduated with a chemistry degree in December 1957. His bachelor’s de-
gree dealt with the problem of separating Li6 and Li7 isotopes. After this,
he joined the Institute of Chemical Physics (ICP) in Moscow in February
1958.
Gennady was originally invited to ICP by Professor Nikolai Markov-
ich Emanuel. Under his guidance, G. E. Zaikov defended his PhD thesis
titled “Comparison of the Kinetics and Mechanism of Oxidation of the
Organic Compounds in Gaseous and Liquid Phases” in 1963. In 1968, he
defended a Doctor of Science thesis titled “The Role of Media in Radical-
Chain Oxidation Reactions”. In 1970, he became a full professor. In 1966,
Gennady became involved with polymer science. N. M. Emanuel asked
xxvi Foreword

Zaikov to work on problems associated with aging and stabilization of

polymers, and, later, with the combustion of polymeric materials. At that
time in the 1970s, there were about 1000 scientists in the USSR work-
ing on these problems including 200 scientists from ICP under Zaikov’s
leadership. The research was conducted on all aspects of these polymer
problems: thermal degradation, oxidation, ozonolysis, photodegradation
and radiation degradation, hydrolysis, biodegradation, mechanical degra-
dation, pyrolysis, and flammability.
After “perestroika and degradation” of the USSR in 1991, the new
Russian government reduced drastically the financial support of science.
Therefore, G. E. Zaikov has now with him in N. M. Emanuel Institute
only 20 coworkers (instead of 200 in 1970–1980s). Fortunately, he has
good scientific cooperation with 28 research centers of the former USSR
(Russia, Ukraine, Georgia, Belorussia, Armenia, Tadjikistan, etc.) and
with some research centers of Europe (Portugal, Spain, Belgium, Czech
Republic, Poland, Bulgaria, and Romania). G. E. Zaikov is an outstanding
scientist with expertise in wide areas of chemistry: chemical and biologi-
cal kinetics, chemistry and physics of polymers, history of chemistry, and
biochemistry.
In addition to his position at the N. M. Emanuel Institute, he is a Lec-
turer at the Moscow Institute of Fine Chemical Technology. He taught
his students from his own books: Degradation and Stabilization of Poly-
mers Physical Methods in Chemistry and Acid Rains and Environmen-
tal Problems G. E. Zaikov has written about 1800 original articles, 130
monographs (20 in Russian and 110 in English), and 250 chapters in 100
volumes. It is apparent from this work that he has made valuable contribu-
tions to the theory and practice of polymers—aging and development of
new stabilizers for polymers, organization of their industrial production,
life-time predictions for use and storage, and the mechanisms of oxidation,
ozonolysis, hydrolysis, biodegradation, and decreasing of polymer flam-
mability. New methods of polymer modification using the process of deg-
radation were introduced into practice by Zaikov. These methods allow
the production of new polymeric materials with improved properties. For
a last period, he is very active in the field of semiconductors and electro-
conductive polymers, polymer blends, and polymer composites including
nanocomposites.
G. E. Zaikov is a member of many editorial boards of journals pub-
lished in Russia, Poland, Bulgaria, the United States, and England. In the
Foreword xxvii

former Soviet Union (after academician N. M. Emanuel’s death), he head-

ed the team dealing with the problem of polymer aging in the USSR and
the Eastern European countries in the cooperation with the Soviet Acad-
emy of Sciences. His present position is Head of Laboratory, Member of
Directorium and Deputy of Department of the N. M. Emanuel Institute
of Biochemical Physics Russian Academy of Sciences, and Professor
of Polymer Chemistry at the Moscow State Academy of Fine Chemical
Technology. His fields of interest are chemical physics, chemical kinetics,
flammability, degradation and stabilization of polymers, diffusion, poly-
mer materials, kinetics in biology, and history of chemistry.
On his eightieth birthday, G. E. Zaikov is in the prime of his life. Al-
though support for scientists and research is now at a low point for many
in Russia, he is hopeful that for the sake of his country and its future that
this will improve. The practice of good science still exists in Russia, and
G. E. Zaikov has been and is a significant contributor. Many of Professor
Zaikov’s students are currently in leadership positions around the nation
and around the globe. Some of them are authors of the papers included in
this issue covering a wide range of topics related to polymer composites.
The topics are very broad ranging and cover industrial and practical issues.
This broad range of topics as well as the outstanding nature of the research
and publications is a direct measure of the impact that Professor Zaikov
has had and continues to have on research and development in the field
of polymer. I am truly delighted to dedicate this volume to Gennady on
behalf of the chemists and polymer science community as a thank you for
all of his current and future contributions to the community.
Professor A. K. Haghi, PhD
Member of Canadian Research and Development Center of
Sciences and Cultures, Montreal, Canada

This peer-reviewed volume is dedicated to Professor G. E. Zaikov in

celebration of his eightieth birthday and his distinguished career achieve-
ments. Professor Zaikov is a preeminent scientist of our times with numer-
ous groundbreaking and seminal works. He is a pioneer, leading researcher
and instigator of several important research directions that include theory
and practice of polymers—aging and development of new stabilizers for
polymers, organization of their industrial production, life-time predictions
for use and storage, and the mechanisms of oxidation, ozonolysis,
xxviii Foreword

hydrolysis, biodegradation, and decreasing of polymer flammability.,

among many others. Professor Zaikov’s research accomplishments are in-
credibly broad in both subjects and research methodologies. The topics of
his research span a wide spectrum of scientific areas including nanocom-
posites, polymers, elasticity and structures, and material science, just to
name a few. His research aspects involve modeling, hard and soft analysis,
the design of ingenious, efficient and effective computational schemes,
rigorous numerical analysis and error estimations, or whatever the prob-
lem at hand calls for. Professor Zaikov’s publications speak vividly of his
distinguished research career.
Ali Pourhashemi, PhD
Professor, Department of Chemical and Biochemical Engineering,
Christian Brothers University, Memphis, Tennessee, USA

It is our great privilege and pleasure to introduce this volume, which is

dedicated to Professor Gennady E. Zaikov on the occasion of his eighti-
eth birthday. Professor Gennady E. Zaikov has made many outstanding
contributions to the field of polymer science, particularly for the conser-
vation of biodiversity. His research has been based on various aspects of
modern materials, offering valuable contributions to modern chemistry,
food chemistry, and more recently, nanotechnology. During his distin-
guished and productive career, Gennady E. Zaikov has either authored or
coauthored over 200 peer-reviewed scientific books and a great number
of contributions in congress proceedings. This volume, on the occasion of
his eightieth birthday on January 7, 2015, represents a tribute to his out-
standing scientific contributions and an opportunity to express congratula-
tions and best wishes from all of us, colleagues, and friends. Our personal
thanks go also to all the authors and reviewers who have contributed to
the success of this special issue.
Abbas Hamrang, PhD
Professor and Senior Polymer Scientist,
Independent Polymer Consultant, Manchester, UK

This volume is dedicated to Professor G. E. Zaikov, Emeritus Professor

of Russian Academy of Sciences, on the occasion of his eightieth birth-
day. He is a distinguished Russian scientist and one of the most eminent
Foreword xxix

scientists of the last half-century. He has contributed much to the field

of semiconductors and electroconductive polymers, polymer blends, and
polymer composites including nanocomposites. He continues to contrib-
ute to this day. He is also an active member of many editorial board for
international journals. With the publication of this volume, we wish to
pay homage to his great scientific achievements and to thank him for his
friendship and kindness. We are honored to recognize Professor Zaikov’s
great contribution to the scientific world and wish him more fruitful ex-
periences in his further research. We also warmly thank all the authors for
their kind cooperation on the production of this volume.
Pooria Pasbakhsh, PhD
School of Engineering, Monash University
Sunway Campus, Malaysia

Professor Zaikov has been an enthusiastic promoter and practitioner

of global scientists, training and collaborating with students and research-
ers of different nationalities and of diverse cultural or educational back-
grounds. He has constantly and unselfishly contributed to the global dis-
semination of research in polymer materials, and his outstanding research
leadership and tireless service have positively impacted the worldwide
prospering of research in these areas.
The contributing authors of this special volume consist mostly of Pro-
fessor Zaikov’s former PhD students, postdoctoral fellows, and colleagues
who at one time or another had the opportunity to collaborate with Pro-
fessor Zaikov on various research projects. This collection of research
papers is a testimony of Professor Zaikov’s wide scope of research ac-
complishment and profound influence in the international research com-
munity on polymer composites and on scientific modeling. No doubt that
great thoughts and ideas will continue to stream out of Professor Zaikov’s
beautiful mind, bringing his already distinguished career to an even higher
plateau.
Sabu Thomas, PhD
Director, School of Chemical Sciences, Professor of Polymer Science &
Technology & Honorary Director of the International and Inter
University Centre for Nanoscience and Nanotechnology,
Mahatma Gandhi University, Kottayam, India
CHAPTER 1

TRENDS IN NEW GENERATION OF

BIODEGRADABLE POLYMERS
(PART 1)
A.L. IORDANSKII, G.A. BONARTSEVA, YU.N. PANKOVA,
S.Z. ROGOVINA, K.Z. GUMARGALIEVA, G.E. ZAIKOV, and
A.A. BERLIN

CONTENTS

1.1 Introduction....................................................................................... 2
1.2 Hydrolysis and Enzymatic Degradation of PHB.............................. 4
1.3 Biodegradation of PHB by Soil Microorganisms........................... 13
1.4 Biodegradation of PHB in Vivo in Animal Tissues........................ 16
1.5 Application of PHB........................................................................ 21
1.6 PHB as tissue engineering material and PHB in vitro
Biocompatibility............................................................................. 24
1.7 Novel Drug Dosage Forms on the Base of PHB............................ 30
1.8 Conclusions..................................................................................... 35
Acknowledgments.................................................................................... 35
Keywords................................................................................................. 35
References................................................................................................ 35
2 Applied Research on Polymer Composites

1.1â•…INTRODUCTION

Currently, the intensive development of biodegradable and biocompat-

ible materials for medical implication provokes comprehensive inter-
disciplinary studies on biopolymer structures and functions. The well-
known and applicable biodegradable polymers are polylactides (PLAs)
and polyglycolides (PGA), and their copolymers, poly-ε-caprolactone,
poly(orthoesters), poly-β-malic acid, poly(propylene fumarate), polyalkyl-
cyanoacrylates, polyorthoanhydrides, polyphosphazenes, poly(propylene
fumarate), some natural polysaccharides (starch, chitosan, alginates, aga-
rose, dextran, chondroitin sulfate, and hyaluronic acid), and proteins (col-
lagen, silk fibroin, spidroin, fibrin, gelatin, and albumin). As some of these
polymers should be synthesized through chemical stages (e.g. via lactic
and glycolic acids), it is not quite correct to define them as the biopoly-
mers.
Besides biomedicine applications, the biodegradable biopolymers at-
tract much attention as perspective materials in wide areas of industry,
nanotechnologies, farming, and packaging owing to the relevant combi-
nation of biomedical, transport, and physical-chemical properties. It is
worth to emphasize that only medical area of these biopolymers includes
implants and prosthesis, tissue engineering scaffolds, novel drug dosage
forms in pharmaceutics, novel materials for dentistry, and others.
Each potentially applicable biopolymer arranges a wide multidisci-
plinary network, which usually includes tasks of searching for efficacy
ways of biosynthesis reactions; economical problems associated with
large-scale production; academic studies of mechanical, physicochemical,
biochemical properties of the polymer and material of interest; technology
of preparation and using this biopolymer; preclinical and clinical trials of
these materials and products; a market analysis and perspectives of appli-
cation of the developed products and many other problems.
Poly(R)-3-hydroxybutyrate) (PHB) is an illustrative example for one
of centers for the formation of the above-mentioned scientific-techno-
logical network and a basis for the development of various biopolymer
systems [1, 2]. In recent decades, an intense development of biomedical
application of bacterial PHB in the production of biodegradable polymer
implants and controlled drug release systems [3–6] needs for compre-
hensive understanding of the PHB biodegradation process. Examination
of PHB degradation process is also necessary for development of novel
Trends in New Generation of Biodegradable Polymers (Part 1) 3

friendly environment polymer packaging [7–9]. It is generally accepted

that biodegradation of PHB both in living systems and in environment
occurs via enzymatic and nonenzymatic processes that take place simulta-
neously under natural conditions. It is, therefore, important to understand
both processes [6, 10]. Opposite to other biodegradable polymers (e.g.
PGA and PLGA), PHB is considered to be moderately resistant to degra-
dation in vitro as well as to biodegradation in biological media. The rates
of degradation are influenced by the characteristics of the polymer, such
as chemical composition, crystallinity, morphology and molecular weight
[11, 12]. Despite that PHB application in vitro and in vivo has been inten-
sively investigated, the most of the available data are often incomplete
and sometimes even contradictory. The presence of conflicting data can be
partially explained by the fact that biotechnologically produced PHB with
standardized properties is relatively rare and is not readily available due
to а wide variety of its biosynthesis sources and different manufacturing
processes.
Above-mentioned inconsistencies can be explained also by excess ap-
plied trend in PHB degradation research. At most of the papers observed in
this review, PHB degradation process has been investigated in the narrow
framework of development of specific medical devices. Depending on the
applied biomedical purposes, biodegradation of PHB was investigated un-
der different geometries: films and plates with various thickness [13–16],
cylinders [17–19], monofilament threads [20–22] and micro- and nano-
spheres [23, 24]. In these experiments, PHB was used from various sourc-
es, with different molecular weights and crystallinities. Besides, different
technologies of PHB manufacture of devices affect important character-
istics such as polymer porosity and surface structure ([14, 15]. Reports
related to the complex theoretical research of mechanisms of hydrolysis,
enzymatic degradation, and biodegradation in vivo of PHB processes are
relatively rare [13–15, 16, 25–27], which attaches great value and impor-
tance to these investigations. Nevertheless, the effect of thickness, size
and geometry of PHB device, molecular weight, and crystallinity of PHB
on the mechanism of PHB hydrolysis and biodegradation was not yet well
clarified.
4 Applied Research on Polymer Composites

1.2â•… HYDROLYSIS AND ENZYMATIC DEGRADATION OF PHB

1.2.1â•… NONENZYMATIC HYDROLYSIS OF PHB IN VITRO

Examination of hydrolytic degradation of natural poly((R)-3-hydroxybu-

tyrate) in vitro is a very important step for understanding of PHB bio-
degradation. There are several very profound and careful examinations of
PHB hydrolysis that was carried out for 10–15 years [25–28]. Hydrolytic
degradation of PHB was usually examined under standard experimental
conditions simulating internal body fluid: in buffered solutions with pH =
7.4 at 37°C but at seldom cases, the higher temperature (55°C, 70°C, and
more) and other values of pH (from 2 to 11) were selected.
The classical experiment for examination of PHB hydrolysis in com-
parison with hydrolysis of another widespread biopolymer, polylactic acid
(PLA), was carried out by Koyama N. and Doi Y. [25]. They compared
films (10 × 10 mm2 size, 50 µm thickness, 5 mg initial mass) from PHB
(Mn = 3,00,000, Mw = 6,50,000) with polylactic acid (Mn = 9,000, Mw =
21,000) prepared by solvent casting and aged for 3 weeks to reach equilib-
rium crystallinity. They have shown that hydrolytic degradation of natural
PHB is a slow process. The mass of PHB film remained unchanged at
37°C in 10 mM phosphate buffer (pH = 7.4) over a period of 150 days,
while the mass of the PLA film rapidly decreased with time and reached 17
per cent of the initial mass after 140 days. The rate of decrease in the Mn
of the PHB was also much slower that in the Mn of PLA.
The Mn of the PHB decreased approximately to 65 per cent of the ini-
tial value after 150 days, while the Mn of the PLA decreased to 20 per cent
(Mn = 2,000) at the same time. As PLA used at this research was with low
molecular weight, it is worth to compare these data with the data of hy-
drolysis investigation with the same initial Mn as for PHB. In other works,
the mass loss of two polymer films (PLA and PHB) with the same thick-
ness (40 µm) and molecular weight (Mw = 450,000) was studied in vitro.
It was shown that the mass of PLA film decreased to 87 per cent, whereas
the mass of PHB film remained unchanged at 37°C in 25 mM phosphate
buffer (pH = 7.4) over a period of 84 days, but after 360 days the mass of
PHB film was 64.9 per cent of initial one [29–31].
The cleavage of polyester chains is known to be catalyzed by the car-
boxyl end groups, and its rate is proportional to the concentrations of wa-
ter, and ester bonds those on the initial stage of hydrolysis are constant
Trends in New Generation of Biodegradable Polymers (Part 1) 5

owing to the presence of a large excess of water molecules and ester bonds
of polymer chains. Thus, the kinetics of nonenzymatic hydrolysis can be
expressed by a simplified equation [32-33]:

ln Mn=ln Mn0 – kht (1)

where Mn and Mn0 are the number-average molecular weights of a polymer

component at time t and 0, respectively and kh is the effective hydrolysis
constant.
The average number of bond cleavage per original polymer molecule,
N, is given by equation 2:

N = (Mn0/Mn) – 1 = kd MmPn0 t, (2)

where kd is the effective rate constant of hydrolytic depolymerization, and

Pn0 is the initial number-average degree of polymerization at time 0, Mm
is the constant molecular mass of monomer. Thus, if the chain scission is
completely random, the value of N is linearly dependent on time.
The molecular weight decrease with time is the distinguishing feature
of mechanism under nonenzymatic hydrolysis condition in contrast to en-
zymatic hydrolysis condition of PHB when Mn values remained almost un-
changed. It was supposed also that water-soluble oligomers of PHB with
molecular mass about 3 kDa may accelerate the hydrolysis rate of PHB
homopolymer [25]. In contrast, Freier et al. [14] showed that PHB hy-
drolysis was not accelerated by the addition of predegraded PHB: the rate
of mass and Mw loss of blends (70/30) from high-molecular PHB (Mw =
6,41,000) and low-molecular PHB (Mw = 3,000) was the same with degra-
dation rate of pure high-molecular PHB. Meanwhile, the addition of amor-
phous atactic PHB (at PHB) (Mw = 10,000) to blend with high-molecular
PHB caused significant acceleration of PHB hydrolysis: the relative mass
loss of PHB/atPHB blends was 7 per cent in comparison with 0 per cent
mass loss of pure PHB; the decrease of Mw was 88 per cent in comparison
with 48 per cent Mw decrease of pure PHB [14, 34]. We have showed that
the rate of hydrolysis of PHB films depends on Mw of PHB. The PHB films
of high molecular weight (Mw=450.000 and 1,000,000) degraded slowly
as it was described earlier, whereas films from PHB of low molecular
weight (Mw = 150,000 and 300,000 kDa) lost weight relatively gradually
and more rapidly [29–31].
6 Applied Research on Polymer Composites

To enhance the hydrolysis of PHB, a higher temperature was selected

for degradation experiments: 55°C, 70°C, and more [25]. It was showed
by the same research team that the weights of films (12 mm diameter, 65
µm thick) from PHB (Mn = 768 and 22 kDa, Mw = 1,460 and 75 kDa) were
unchanged at 55°C in 10 mM phosphate buffer (pH = 7.4) over a period
of 58 days. The Mn value decreased from 768 to 245 kDa for 48 days. The
film thickness increased from 65 to 75 µm for 48 days, suggesting that
water permeated the polymer matrix during the hydrolytic degradation.
Examination of the surface and cross section of PHB films before and after
hydrolysis showed that surface after 48 days of hydrolysis was apparently
unchanged, while the cross section of the film exhibited a more porous
structure (pore size < 0.5 µm). It was also shown that the rate of hydro-
lytic degradation is not dependent on the crystallinity of PHB film. The
observed data indicates that the nonenzymatic hydrolysis of PHB in the
aqueous media proceeds via a random bulk hydrolysis of ester bonds in the
polymer chain�����������������������������������尓�����������������������
films �����������������������������������尓����������������
and �����������������������������������尓������������
occurs throughout the whole film, as water per-
meates the polymer matrix [25–26]. Moreover, as ����������������������� over the whole degrada-
tion time the first-order kinetics was observed and the molecular weight
distribution was unimodal, a random chain scission mechanism is very
probable both on the crystalline surfaces and in the amorphous regions of
the biopolymer [14, 35]. For synthetic amorphous at PHB, it was shown
that its hydrolysis is a two-step process. First, the random chain scission
proceeds that accompanying with a molecular weight decrease. Then, at a
molecular weight of about 10,000, mass loss begins [28].
The analysis of literature data shows a great spread in values of rate of
PHB hydrolytic degradation in vitro. �����������������������������������尓����
It can be explained by different thick-
ness values of PHB films or geometry of PHB devices used for experiment
as well as by different sources, purity degree, and molecular weight of
PHB (Table 1.1). At 37°C and pH = 7.4, the weight loss of PHB (unknown
Mw) films (500 µm thick) was 3 per cent after 40 days incubation [38], 0
per cent after 52 weeks (364 days) and after 2 years (730 days) incubation
(640 kDa PHB, 100 µm films) [14–15], 0 per cent after 150 days incuba-
tion (650 kDa PHB, 50 µm film) [25�����������������������������������尓��
]�����������������������������������尓�
, 7.5 per cent after 50 days incuba-
tion (279 kDa PHB, unknown thickness of films) [37], 0 per cent after 3
months (84 days) incubation (450 kDa PHB, 40 µm films), 12 per cent
after 3 months (84 days) incubation (150 kDa PHB, 40 µm films) [29–30],
0 per cent after 180 days incubation of monofilament threads (30 µm in
diameter) from PHB (470 kDa) [22–23]. The molecular weight of PHB
Trends in New Generation of Biodegradable Polymers (Part 1) 7

dropped to 36 per cent of the initial values after 2 years (730 days) of stor-
age in buffer solution [15], to 87 per cent of the initial values after 98 days
[38], to 58 per cent of the initial values after 84 days [29–30] (Table 1.1).

TABLE 1.1â•… Nonenzymatic hydrolysis of PHB in Vitro

(Data for Comparison)

Type of Initial Size/thick- Condi-tions Relative Relative Time, Links

device Mw (kDa) ness (µm) mass loss loss of days
(%) Mw (%)

Film 650 50 37 C, pH = 0 35 150 25

7.4

Film 640 100 37°C, pH = 0 64 730 15

7.4

Film 640 100 37°C, pH = 0 45 364 14

7.4

Film 450 40 37 C, pH = 0 42 84 29-30

7.4

Film 150 40 37°C, pH = 12 63 84 29-30

7.4

Film 450 40 37°C, pH = 35,1 - 360 31

7.4

Film 279 - 37°C, pH = 7.5 - 50 36

7.4

Plate - 500 37°C, pH = 3 - 40 30

7.4

Plate 380 1,000 37°C, pH = 0 - 28 43

7.4

Plate 380 2,000 37°C, pH = 0 8 98 43

7.4

Thread 470 30 37°C, pH = 0 - 180 23

7.0

Thread - - 37°C, pH = 0 - 182 22

7.2
8 Applied Research on Polymer Composites

TABLE 1.1â•… (Continued)

Type of Initial Size/thick- Condi-tions Relative Relative Time, Links

device Mw ness mass loss loss of days
(kDa) (µm) (%) Mw
(%)

Micro- 50 250-850 37°C, pH = 0 0 150 42

spheres 7.4

Thread 470 30 37°C, pH = 0 - 180 22

5.2

Film 279 - 37°C, pH 100 - 28 36

= 10

Film 279 - 37°C, pH 100 - 19 36

= 13

Film 650 50 55°C, 0 68 150 25

pH = 7.4

Plate 380 2,000 55 C, pH = 0 61 98 43

7.4

Film 640 100 70°C, pH = - 55 28 14

7.4

Film 150 40 70°C, pH = 39 96 84 29–30

7.4

Film 450 40 70°C, pH = 12 92 84 29–30

7.4

Micro- 50 250-850 85°C, pH = 50 68 150 42

spheres 7.4

Micro- 600 250-850 85°C, pH = 25 - 150 42

spheres 7.4

In acidic or alkaline aqueous media, PHB degrades more rapidly: 0 per

cent degradation after 140 days incubation in 0.01 M NaOH (Ph = 11) (200
kDa, 100 µm film thickness) with visible surface changing [39], 0 per cent
degradation after 180 days incubation of PHB threads in phosphate buffer
(pH=5.2 and 5.9) [23], and complete PHB films biodegradation after 19
days (pH = 13) and 28 days (pH=10) [37]. It was demonstrated that after
20 weeks of exposure to NaOH solution, the surfaces of PHB samples
Trends in New Generation of Biodegradable Polymers (Part 1) 9

became rougher, along with an increased density in their surface layers.

From these results, one may surmise that the nonenzymatic degradation of
PHAs progresses on their surfaces before noticeable weight loss occurs as
illustrated in Figure 1.1 [39].

FIGURE 1.1â•… Scanning electron microscopic photographs of PHB films both before (0
wk, panels on the left) and after 20 weeks (panels on the right) of nonenzymatic hydrolysis
in 0.01 N NaOH solution (scale bars, 10 μm) [39].

It was also shown that treatment of PHB film with 1M NaOH caused
a decrease in pore size on film surface from 1–5 µm to around 1 µm,
which indicates a partially surface degradation of PHB in alkaline media
[40–41]. At higher temperature, no weight loss of PHB films and threads
was observed after incubation of 98 and 182 days in phosphate buffer
(pH=7.2) at 55°C and 70°C, respectively [22], 12 per cent and 39 per cent
of PHB (450 and 150 kDa, respectively) films after 84 days incubation at
70°C [35, 40], 50 per cent and 25 per cent after 150 days incubation of
microspheres (250–850 µm diameter) from PHB (50 kDa and 600 kDa,
respectively) [42].
During degradation of PHB monofilament threads, films, and plates,
the change of mechanical properties was observed under different condi-
tions in vitro [22, 43]. It was shown that a number of mechanical indices of
threads became worse: load at break lost 36 per cent, strain at break lost 33
per cent, Young’s modulus didn’t change, tensile strength lost 42 per cent
after 182 days incubation in phosphate buffer (pH=7.2) at 70°C. How-
ever, at 37°C the changes were more complicated: at first load at break
increased from 440 to 510 g (16 per cent) at 90th day and then decreased
to the initial value on 182nd day, strain at break increased rapidly from 60
to 70 per cent (in 17 per cent) at 20th day and then gradually increased to
10 Applied Research on Polymer Composites

75 per cent (in 25 per cent) at 182nd day, and Young’s modulus did not
change [22].
For PHB films, a gradual 32 per cent decrease in Young’s modulus and
77 per cent fall in tensile strength during 120-day incubation in phosphate
buffer (pH = 7.4) at 37°C [43] were demonstrated. For PHB plates, more
complicated changes were observed: at first, tensile strength dropped to
13 per cent at 1st day and then increased to the initial value at 28th day,
Young’s modulus dropped to 32 per cent �������������������������������
for 1st day �������������������
and then remain un-
changed up to 28th day, stiffness also decreased sharply to 40 per cent for
1st day and then remain unchanged up to 28th day [44].

1.2.2â•… ENZYMATIC DEGRADATION OF PHB IN VITRO

The examination of enzymatic degradation of PHB in vitro is the follow-

ing important step for understanding of PHB performance in animal tis-
sues and environment. The most papers observed degradation of PHB by
depolymerases of its own bacterial producers. The degradation of PHB in
vitro by depolymerase was thoroughly examined and mechanism of enzy-
matic PHB degradation was perfectly clarified by Doi [25–26]. At these
early works, it was shown that 68–85 per cent and 58 per cent mass loss
of PHB (Mw=650–768 and 22 kDa, respectively) films (50–65 µm thick)
occurred for 20 h under incubation at 37 °C in phosphate solution (pH =
7.4) with depolymerase (1.5–3 µg/ml) isolated from Alcaligenes faecalis.
The rate (ke) of enzymatic degradation of films from PHB (Mn=768 and 22
kDa) was 0.17 and 0.15 mg/h, respectively.
The thickness of polymer films dropped from 65 to 22 µm (32% of
initial thickness) during incubation. The scanning electron microscopic
examination showed that the surface of the PHB film after enzymatic deg-
radation was apparently blemished by the action of PHB depolymerase,
while no change was observed inside the film. Moreover, the molecular
weight of PHB remained almost unchanged after enzymatic hydrolysis:
the Mn of PHB decreased from 768 to 669 kDa or unchanged (22 kDa)
[25–26].
The extensive literature data on enzymatic degradation of PHB by
specific PHB depolymerases was collected in detail in review of Sudesh,
Abe, and Doi [45]. We would like to summarize some the most important
data. However, at first it is necessary to note that PHB depolymerase is
Trends in New Generation of Biodegradable Polymers (Part 1) 11

very specific enzyme and the hydrolysis of polymer by depolymerase is a

unique process. But in animal tissues and even in environment, the enzy-
matic degradation of PHB occurred mainly by nonspecific esterases [24,
46]. Thus, in the frameworks of this review, it is necessary to observe the
fundamental mechanisms of PHB enzymatic degradation.
The rate of enzymatic erosion of PHB by depolymerase is strongly de-
pendent on the concentration of the enzyme. The enzymatic degradation of
solid PHB polymer is heterogeneous reaction involving two steps, namely,
adsorption and hydrolysis. The first step is adsorption of the enzyme onto
the surface of the PHB material by the binding domain of the PHB depoly-
merase, and the second step is hydrolysis of polyester chains by the active
site of the enzyme. The rate of enzymatic erosion for chemosynthetic PHB
samples containing both monomeric units of (R)- and (S)-3-hydrohybutyr-
ate is strongly dependent on both the stereocomposition and tacticity of
the sample as well as on substrate specificity of PHB depolymerase.
The water-soluble products of random hydrolysis of PHB by enzyme
showed a mixture of monomers and oligomers of (R)-3-hydrohybutyrate.
The rate of enzymatic hydrolysis for melt-crystallized PHB films by PHB
depolymerase decreased with an increase in the crystallinity of the PHB
film, while the rate of enzymatic degradation for PHB chains in an amor-
phous state was approximately 20 times higher than the rate for PHB
chains in a crystalline state. It was suggested that the PHB depolymerase
predominantly hydrolyzes polymer chains in the amorphous phase and
then, subsequently, erodes the crystalline phase. The surface of the PHB
film after enzymatic degradation was apparently blemished by the action
of PHB depolymerase, while no change was observed inside the film.
Thus, depolymerase hydrolyses of the polyester chains in the surface
layer of the film and polymer erosion proceed in surface layers, while
dissolution and the enzymatic degradation of PHB are affected by many
factors such as monomer composition, molecular weight, and degree of
crystallinity [45]. The PHB polymer matrix ultrastructure [47] plays also
very important role in enzymatic polymer degradation [48].
In the next step, it is necessary to observe enzymatic degradation of
PHB under the conditions that modeled the animal tissues and body flu-
ids containing nonspecific esterases. In vitro degradation of PHB films in
the presence of various lipases as nonspecific esterases was carried out
in buffered solutions containing lipases [18, 49–50], in digestive juices
(for example, pancreatin) [14], simulated body fluid [51] biological media
12 Applied Research on Polymer Composites

(serum, blood, etc.) [23], and crude tissue extracts containing a mixture of
enzymes [24] to examine the mechanism of nonspecific enzymatic degra-
dation process. It was noted that a Ser..His..Asp triad constitutes the active
center of the catalytic domain of both PHB depolymerase [52] and lipases
[53]. The serine is a part of the pentapeptide Gly X1-Ser-X2-Gly, which
has been located in all known PHB depolymerases as well as in lipases,
esterases, and serine proteases [52].
On the one hand, it was shown that PHB was not degraded for 100
days with a quantity of lipases isolated from different bacteria and fungi
[49–50]. On the other hand, the progressive PHB degradation by lipases
was shown [18, 40–41]. PHB enzymatic biodegradation was also studied
in biological media: it was shown that with pancreatin addition no ad-
ditional mass loss of PHB was observed in comparison with simple hy-
drolysis [14], and the PHB degradation process in serum and blood was
demonstrated to be similar to hydrolysis process in buffered solution [31],
whereas progressive mass loss of PHB sutures was observed in serum and
blood: 16 per cent and 25 per cent, respectively, after 180 days incubation
[23], crude extracts from liver, muscle, kidney, heart, and brain showed
the activity to degrade the PHB: from 2 per cent to 18 per cent mass loss
of PHB microspheres after 17 h incubation at pH 7.5 and 9.5 [24]. The
weight loss of PHB (Mw = 2,85,000) films after 45 days incubation simu-
lated body fluid was about 5 per cent [51]. The degradation rate in solu-
tion with pancreatin addition, obtained from the decrease in Mw of pure
PHB, was accelerated about threefold: 34 per cent decrease in Mw after
incubation for 84 days in pancreatin (10 mg/ml in Sorensen buffer) ver-
sus 11 per cent decrease in Mw after incubation in phosphate buffer [14].
The same data was obtained for PHB biodegradation in buffered solutions
with porcine lipase addition: 72 per cent decrease in Mw of PHB (Mw =
4,50,000) after incubation for 84 days with lipase (20 U/mg, 10 mg/ml in
Tris-buffer) versus 39 per cent decrease in Mw after incubation in phos-
phate buffer [18]. This observation is in contrast with enzymatic degrada-
tion by PHB depolymerases which was reported to proceed on the surface
of the polymer film with an almost unchanged molecular weight [24–25].
It has been proposed that for depolymerases the relative size of the enzyme
compared with the void space in solvent cast films is the limiting factor for
diffusion into the polymer matrix [54], whereas lipases can penetrate into
the polymer matrix through pores in PHB film [40–41]. It was shown that
lipase (0.1 g/l in buffer) treatment for 24 h caused significant morphologi-
Trends in New Generation of Biodegradable Polymers (Part 1) 13

cal change in PHB film surface: transferring from native PHB film with
many pores ranging from 1 to 5 µm in size into a pore free surface without
producing a quantity of hydroxyl groups on the film surface. It was sup-
posed that the pores had a fairly large surface exposed to lipase, thus it
was degraded more easily (Figure 1.2) [40–41]. It also indicates that lipase
can partially penetrate into pores of PHB film but the enzymatic degrada-
tion proceeds mainly on the surface of the coarse polymer film achievable
for lipase. Two additional effects reported for depolymerases could be of
importance. It was concluded that segmental mobility in amorphous phase
and polymer hydrophobicity play an important role in enzymatic PHB
degradation by nonspecific esterases [14]. Significant impairment of the
tensile strength and other mechanical properties were observed during en-
zymatic biodegradation of PHB threads in serum and blood. It was shown
that load at break lost 29 per cent, Young’s modulus lost 20 per cent, and
tensile strength did not change after 180 days of incubation of threads, and
the mechanical properties changed gradually [23].

FIGURE 1.2â•… Scanning electron microscopy photographs documented the surface

structure of PHB polymer films: (a) PHB film; (b) PHB film treated with lipase (0.1 g/l at
30ºC and pH = 7.0 for 24 h) [41].

1.3â•… BIODEGRADATION OF PHB BY SOIL MICROORGANISMS

Polymers exposed to the environment are degraded by their hydrolysis,

mechanical, thermal, oxidative, and photochemical destruction, and bio-
degradation [7, 38, 55, 56]. One of the valuable properties of PHB is its
biodegradability, which can be evaluated using various field and labora-
tory tests. Requirements for the biodegradability of PHB may vary in ac-
cordance with its applications. The most attractive property of PHB with
14 Applied Research on Polymer Composites

respect to ecology is that it can be completely degraded by microorgan-

isms finally to CO2 and H2O. This property of PHB allows to manufacture
biodegradable polymer objects for various applications (Figure 1.3) [4].

FIGURE 1.3â•… Molded PHB objects for various applications. In soil burial or composting
experiments, such objects biodegrade in about 3 months [4].

The degradation of PHB and its composites in natural ecosystems,

such as soil, compost, and bodies of water, was described in a number of
publications [4, 38, 55, 56]. Maergaert et al. isolated from soil more than
300 microbial strains capable of degrading PHB in vitro [55]. The bacteria
detected on the degraded PHB films were dominated by the genera Pseu-
domonas, Bacillus, Azospirillum, Mycobacterium, and Streptomyces, and
so on. The samples of PHB have been tested for fungicidity and resistance
to fungi by estimating the growth rate of test fungi from the genera As-
pergillus, Aureobasidium, Chaetomium, Paecilomyces, Penicillum, Trich-
oderma under optimal growth conditions. PHB film did exhibit neither
fungicide properties nor the resistance to fungal damage, and served as a
good substrate for fungal growth [57].
Biodegradability of PHB films under aerobic, microaerobic, and anaer-
obic conditions in the presence and absence of nitrate by microbial popu-
lations of soil, sludge from anaerobic and nitrifying/denitrifying reactors,
Trends in New Generation of Biodegradable Polymers (Part 1) 15

and sediment of a sludge deposit site, as well as to obtain active denitri-

fying enrichment culture degrading PHB (Figure 1.4) [58] were studied.
Changes in molecular mass, crystallinity, and mechanical properties of
PHB have been studied. A correlation between the PHB degradation de-
gree and the molecular weight of degraded PHB was demonstrated.
The most degraded PHB exhibited the highest values of the crystallin-
ity index. As it has been shown by Spyros et al., PHAs contain amorphous
and crystalline regions, of which the former are much more susceptible
to microbial attack [59]. If so, the microbial degradation of PHB must
be associated with a decrease in its molecular weight and an increase in
its crystallinity, which was really observed in the experiments. Moreover,
microbial degradation of the amorphous regions of PHB films made them
more rigid. However, further degradation of the amorphous regions made
the structure of the polymer much looser [58].

FIGURE 1.4â•… Undegraded PHB film (A) and PHB films with different degrees of
degradation after 2 months incubation in soil suspension: anaerobic conditions without
nitrate (B), microaerobic conditions without nitrate (C), and microaerobic conditions with
nitrate (D) [58].

PHB biodegradation in the enriched culture obtained from soil on the

medium used to cultivate denitrifying bacteria (Gil’tai medium) has also
been studied. The dominant bacterial species, Pseudomonas fluorescens
and Pseudomonas stutzeri, have been identified in this enrichment cul-
ture. Under denitrifying conditions, PHB films were completely degraded
for 7 days. Both the film weight and Mw of PHB decreased with time. In
contrast to the data of Doi et al. [26] who found that Mw of PHB remained
unchanged upon enzymatic biodegradation in an aquatic solution of PHB
depolymerase from Alcaligenes faecalis, in our experiments, the average
viscosity molecular weight of the higher and lower molecular polymers
decreased gradually from 1,540 to 580 kDa and from 890 to 612 kDa,
16 Applied Research on Polymer Composites

respectively. As it was shown at single PHB crystals [47], the “exo”-type

cleavage of the polymer chain, that is, a successive removal of the terminal
groups, is known to occur at a higher rate than the “endo”-type cleavage,
that is, a random breakage of the polymer chain at the enzyme-binding
sites. Thus, the former type of polymer degradation is primarily respon-
sible for changes in its average molecular weight. However, the “endo”-
type attack plays an important role during the initiation of biodegradation,
because at the beginning, a few polymer chains are oriented so that their
ends are accessible to the effect of the enzyme [60]. Biodegradation of
the lower molecular polymer, which contains a higher number of terminal
groups, is more active, probably, because the “exo”-type degradation is
more active in lower than in higher molecular polymer [58, 61].

1.4â•… BIODEGRADATION OF PHB IN VIVO IN ANIMAL TISSUES

The first scientific works on biodegradation of PHB in vivo in animal tis-

sues were carried out 15–20 years ago by Miller et al., and Saito et al [22,
24]. They are high-qualitative research studies that disclosed many impor-
tant characteristics of this process. As it was noted earlier, both enzymatic
and nonenzymatic processes of biodegradation of PHB in vivo can occur
simultaneously under normal conditions. However, it does not mean that
polymer biodegradation in vivo is a simple combination of nonenzymatic
hydrolysis and enzymatic degradation. Moreover, in vivo biodegradation
(decrease of molecular weight and mass loss) of PHB) is a controversial
subject in the literature. As it was noted above for in vitro PHB hydrolysis,
the main reason for the controversy is the use of samples made by various
processing technologies and the incomparability of different implantation
and animal models. Most of the research studies on PHB biodegradation
were carried out with the use of prototypes of various medical devices
on the base of PHB: solid films and plates [13, 16, 18, 31, 62], porous
patches [14, 15], porous scaffolds [63], electrospun microfiber mats [64],
nonwoven patches consisted of fibers [65–69], screws [31], cylinders as
nerve guidance channels and conduits [16, 20, 21], monofilament sutures
[22–23], cardiovascular stents [70], microspheres [24,71]. In vivo biodeg-
radation was studied on various laboratory animals: rats [14, 18, 20–24,
64], mice [16, 75], rabbits [13, 62, 70, 72], minipigs [15], cats [20], calves
[65], sheep [66–68], and even at clinical trials on patients [69]. It is
Trends in New Generation of Biodegradable Polymers (Part 1) 17

obviously that these animals differ in the level of metabolism very much:
for example, only weight of these animals differs from 10–20 g (mice) to
50 kg (calves). The implantation of devices from PHB was carried out in
different ways: subcutaneously [13, 16, 18, 22, 23, 72], intraperitoneally
on a bowel [14], subperiostally on the osseus skull [15–62], nerve wrap-
around [19–21], intramuscularly [71–72], into the pericardium [66–69],
into the atrium [65], and intravenously [24]. The terms of implantation
were also different: 2.5 h, 24 h, 13 days, 2 months [24]; 7, 14, 30 days
[21], 2, 7, 14, 21, 28, 55, 90, 182 days [22]; 1, 3, 6 months [13, 16, 19]; 3,
6, 12 months [65]; 6, 12 months [66]; 6, 24 months [69]; 3, 6, 9, 12, 18,
24 months [68].

FIGURE 1.5â•… Undegraded PHB film (A) and PHB films with different degrees of
degradation after 2 months incubation in soil suspension: anaerobic conditions without
nitrate (B), microaerobic conditions without nitrate (C), and microaerobic conditions with
nitrate (D) [58].

The entire study of PHB in vivo biodegradation was done by Go-

golewski et al. and Qu et al. [13, 16]. It was shown that PHB lost about
1.6 per cent (injection-molded film, 1.2 mm thick, Mw of PHB=130 kDa)
[16] and 6 per cent (solvent-casting film, 40 µm thick, Mw=534 kDa) [13]
of initial weight after 6 months of implantation. However, the observed
small weight loss was partially due to the leaching out of low molecular
weight fractions and impurities present initially in the implants. The Mw of
PHB decreased from 130,000 to 74,000 (57% of initial Mw) [16] and from
534,000 to 216,000 (40% of initial Mw) [13] after 6 months of implanta-
tion. The polydispersity of PHB polymers narrowed during implantation.
PHB showed a constant increase in crystallinity (from 60.7 to 64.8%) up
to 6 months [16] or an increase (from 65.0 to 67.9%) after 1 month and
a fall again (to 64.5%) after 6 months of implantation [13], which sug-
gests that the degradation process had not affected the crystalline regions.
These data are in accordance with those of PHB hydrolysis [25] and
18 Applied Research on Polymer Composites

enzymatic PHB degradation by lipases in vitro [14], where Mw decrease

was observed. The initial biodegradation of amorphous regions of PHB in
vivo is similar to PHB degradation by depolymerase [45].
Thus, the observed biodegradation of PHB showed coexistence of two
different degradation mechanisms in hydrolysis in the polymer: enzymati-
cally or nonenzymatically catalyzed degradation. Although nonenzymati-
cal catalysis occurred randomly in homopolymer, indicated by Mw loss
rate in PHB, at some point in a time, a critical molecular weight is reached
whereupon enzyme-catalyzed hydrolysis accelerated degradation at the
surface because easier enzyme/polymer interaction becomes possible.
However, considering the low weight loss of PHB, the critical molecu-
lar weight appropriate for enzymes predominantly does not reach, yet re-
sulting low molecular weight and crystallinity in PHB could provide some
sites for the hydrolysis of enzymes to accelerate the degradation of PHB
[13, 16]. Additional data revealing the mechanism of PHB biodegradation
in animal tissues was obtained by Kramp et al. in long-term implantation
experiments. A very slow, clinically not recordable degradation of films
and plates was observed during 20 months (much more than in experi-
ments mentioned earlier).
A drop in the PHB weight loss evidently took place between the 20th
and 25th months. Only initial signs of degradation were to be found on the
surface of the implant until 20 months after implantation, but no more test
body could be detected after 25 months [62]. The complete biodegrada-
tion in vivo in the wide range from 3 to 30 months of PHB was shown by
other research studies [65, 67–69, 73], whereas almost no weight loss and
surface changes of PHB during 6 months of biodegradation in vivo was
shown [16, 22]. Residual fragments of PHB implants were found after 30
months of the implantation of patches [66, 68]. A reduction of PHB patch
size in 27 per cent was shown in patients after 24 months after surgical
procedure on pericardial closure with the patch [69].
Significantly more rapid biodegradation in vivo was shown by other re-
search studies [13, 20, 23, 43, 65]. It was shown that 30 per cent mass loss
of PHB sutures occurred gradually during 180 days of in vivo biodegrada-
tion with minor changes in the microstructure on the surface and in vol-
ume of sutures [23]. It was shown that PHB nonwoven patches (made to
close atrial septal defect in calves) was slowly degraded by polynucleated
macrophages, and 12 months postoperatively no PHB device was identifi-
able but only small particles of polymer were still seen. The absorption
Trends in New Generation of Biodegradable Polymers (Part 1) 19

time of PHB patches was long enough to permit regeneration of a normal

tissue [65]. The progressive biodegradation of PHB sheets was demon-
strated qualitatively at 2, 6, and 12 months after implantation as weaken-
ing of the implant surface, tearing/cracking of the implant, fragmentation,
and a decrease in the volume of polymer material [21, 43, 72].
The complete biodegradation of PHB (Mw = 150 − 1,000 kDa) thin
films (10–50 µm) for 3–6 months was shown and degradation process was
described. The process of PHB biodegradation consists of several phases.
At initial phase, PHB films was covered by fibrous capsule. At second
phase, capsulated PHB films very slowly lost weight with simultaneous
increase of crystallinity and decrease of Mw and mechanical properties
of PHB. At third phase, PHB films were rapidly disintegrated and then
completely degraded. At fourth phase, empty fibrous capsule resolved
(Figure 1.5) [18, 31]. Interesting data were obtained for biodegradation in
vivo of PHB microspheres (0.5–0.8 µm in diameter). It was demonstrated
indirectly that PHB loss about 8 per cent of weight of microspheres ac-
cumulated in liver after 2 months of intravenous injection. A presence of
several types PHB degrading enzymes in the animal tissues extracts [24]
was demonstrated (Figure 1.6).

FIGURE 1.6â•… Biodegradation of PHB films in Vivo. Connective-tissue capsule with

PHB thin films (outlined with broken line) 2 weeks (98% residual weight of the film)
(left photograph) and 3 months (0% residual weight of the film) (left photograph) after
subcutaneous implantation [18].

Some research works studied a biodegradation of PHB threads with a

tendency of analysis of its mechanical properties in vivo [22, 23]. It was
shown that at first load at break, index decreased rapidly from 440 to 390
g (12%) at 15th day and then gradually increased to the initial value at 90th
and remain almost unchanged up to 182nd day [22] or gradually decreased
20 Applied Research on Polymer Composites

in 27 per cent during 180 days [23], strain at break decreased rapidly from
60 to 50 per cent (in 17% of initial value) at 10th day and then gradually
increased to 70 per cent (in 17% of initial value) at 182nd day [22] or did
not change significantly during 180 days [23].
It was demonstrated that the primary reason of PHB biodegradation
in vivo was a lysosomal and phagocytic activity of polynucleated mac-
rophages and giant cells of foreign body reaction. The activity of tissue
macrophages and nonspecific enzymes of body liquids made a main con-
tribution to significantly more rapid rate of PHB biodegradation in vivo in
comparison with rate of PHB hydrolysis in vitro. The PHB material was
encapsulated by degrading macrophages. Presence of PHB stimulated uni-
form macrophage infiltration, which is important for not only the degrada-
tion process but also the restoration of functional tissue.
The long absorption time produced a foreign body reaction, which was
restricted to macrophages forming a peripolymer layer [23, 65, 68, 72].
Very important data that clarifies the tissue response that contributes to
biodegradation of PHB was obtained by Lobler. A significant increase of
expression of two specific lipases after 7 and 14 days of PHB contact with
animal tissues was demonstrated. Moreover, liver-specific genes were in-
duced with similar results. It is striking that pancreatic enzymes are in-
duced in the gastric wall after contact with biomaterials [46]. Saito et al.
suggested the presence of at least two types of degradative enzymes in
rat tissues: liver serine esterases with the maximum of activity in alkaline
media (pH=9.5) and kidney esterases with the maximum of activity in
neutral media [24].
The mechanism of PHB biodegradation by macrophages was demon-
strated at cultured macrophages incubated with particles of low-molecular
weight PHB [74]. It was shown that macrophages and, to a lesser level,
fibroblasts have the ability to take up (phagocytize) PHB particles (1–10
µm). At high concentrations of PHB particles (>10 µg/mL), the phagocy-
tosis is accompanied by toxic effects and alteration of the functional status
of the macrophages but not the fibroblasts. This process is accompanied by
cell damage and cell death.
The elevated production of nitric oxide (NO) and tumor necrosis factor
alfa (TNF-α) by activated macrophages was observed. It was suggested
that the cell damage and cell death may be due to phagocytosis of large
amounts of PHB particles; after phagocytosis, polymer particles may fill
up the cells, and cause cell damage and cell death. It was also demonstrated
Trends in New Generation of Biodegradable Polymers (Part 1) 21

that phagocytized PHB particles disappeared in time because of an active

PHB biodegradation process (Figure 1.6) [74].

FIGURE 1.7â•… Phagocytosis of microparticles of PHB in macrophages. TEM analysis of

cultured macrophages in the presence (A) or absence (B) of 2 μg PHB microparticles/mL
for 24 h. Bar in B represents 1 μm, for A and B [74].

1.5â•… APPLICATION OF PHB

1.5.1â•… MEDICAL DEVICES ON THE BASE OF PHB AND PHB IN

VIVO BIOCOMPATIBILITY

The perspective area of PHB application is the development of implanted

medical devices for dental, cranio-maxillofacial, orthopedic, cardiovascu-
22 Applied Research on Polymer Composites

lar, hernioplastic, and skin surgery [3, 6]. A number of potential medical
devices on the base of PHB: bioresorbable surgical sutures [6, 22–23, 31,
75–76], biodegradable screws and plates for cartilage and bone fixation
[6, 24, 31, 62], biodegradable membranes for periodontal treatment [6, 31,
77, 78], surgical meshes with PHB coating for hernioplastic surgery [6,
31], wound coverings [79], patches for repair of a bowel, pericardial and
osseous defects [14–15, 65–69], nerve guidance channels and conduits
[20–21], cardiovascular stents [80], and so on was developed (Figure 1.7).

FIGURE 1.8â•… Medical devices on the base of PHB. (A) bioresorbable surgical suture;
(B) biodegradable screws and plate for cartilage and bone fixation; (C) biodegradable
membranes for periodontal treatment; (D) surgical meshes with PHB coating for
hernioplastic surgery, pure (left) and loaded with antiplatelet drug, dipyridamole (right)
[31].

The tissue reaction in vivo to implanted PHB films and medical devices
was studied. In most cases, a good biocompatibility of PHB was demon-
strated. In general, no acute inflammation, abscess formation, or tissue
necrosis were observed in tissue surrounding of the implanted PHB mate-
rials. In addition, no tissue reactivity or cellular mobilization occurred in
areas remote from the implantation site [13, 16, 31, 71]. On the one hand,
it was shown that PHB elicited similar mild tissue response as PLA did
[16], but on the other hand, the use of implants consisting of polylactic
acid, polyglicolic acid, and their copolymers is not without a number of
sequelae related with the chronic inflammatory reactions in tissue [81–85].
Subcutaneous implantation of PHB films for 1 month has shown that
the samples were surrounded by a well-developed, homogeneous fibrous
capsule of 80–100 µm in thickness. The vascularized capsule consists
primarily of connective tissue cells (mainly, round, immature fibroblasts)
aligned parallel to the implant surface. A mild inflammatory reaction was
manifested by the presence of mononuclear macrophages, foreign body
cells, and lymphocytes. Three months after implantation, the fibrous cap-
Trends in New Generation of Biodegradable Polymers (Part 1) 23

sule has thickened to 180–200 µm because of the increase in the amount

of connective tissue cells and a few collagen fiber deposits.
A substantial decrease in inflammatory cells was observed after 3
months, and tissues at the interface of the polymer were densely organized
to form bundles. After 6 months of implantation, the number of inflamma-
tory cells had decreased and the fibrous capsule, now thinned to about 80–
100 µm, consisted mainly of collagen fibers, and a significantly reduced
amount of connective tissue cells. A little inflammatory cells effusion was
observed in the tissue adherent to the implants after 3 and 6 months of im-
plantation [13, 16]. The biocompatibility of PHB has been demonstrated
in vivo under subcutaneous implantation of PHB films. Tissue reaction to
films from PHB of different molecular weights (300; 450; 1,000 kDa) im-
planted subcutaneously was relatively mild and did not change from tissue
reaction to control glass plate [18, 31].
At implantation of PHB with contact to bone, the overall tissue re-
sponse was favorable with a high rate of early healing and new bone for-
mation with some indication of an osteogenic characteristic for PHB com-
pared with other thermoplastics, such as polyethylene. Initially, there was
a mixture of soft tissue, containing active fibroblasts, and rather loosely
woven osteonal bone seen within 100 µm of the interface. There was no
evidence of a giant cell response within the soft tissue in the early stages of
implantation. With time this tissue became more orientated in the direction
parallel to the implant interface.
The dependence of the bone growth on the polymer interface is dem-
onstrated by the new bone growing away from the interface rather than
toward it after implantation of 3 months. By 6 months postimplantation,
the implant is closely encased in new bone of normal appearance with
no interposed fibrous tissue. Thus, PHB-based materials produce superior
bone healing [43].
Regeneration of a neointima and a neomedia, comparable to native
arterial tissue, was observed at 3–24 months after implantation of PHB
nonwoven patches as transannular patches into the right ventricular out-
flow tract and pulmonary artery. In the control group, a neointimal layer
was present but no neomedia comparable to native arterial tissue. Three
layers were identified in the regenerated tissue: neointima with a endo-
thelium-like lining, neomedia with smooth muscle cells, collagenous and
elastic tissue, and a layer with polynucleated macrophages surrounding
istets of PHB, capillaries and collagen tissue. Lymphocytes were rare. It
24 Applied Research on Polymer Composites

was concluded that PHB nonwoven patches can be used as a scaffold for
tissue regeneration in low-pressure systems. The regenerated vessel had
structural and biochemical qualities in common with the native pulmonary
artery [68]. Biodegradable PHB patches implanted in atrial septal defects
promoted formation of regenerated tissue that macroscopically and micro-
scopically resembled native atrial septal wall.
The regenerated tissue was found to be composed of three layers:
monolayer with endothelium-like cells, a layer with fibroblasts and some
smooth-muscle cells, collagenous tissue and capillaries, and a third layer
with phagocytizing cells isolating and degrading PHB. The neointima con-
tained a complete endothelium-like layer resembling the native endothe-
lial cells. The patch material was encapsulated by degrading macrophages.
There was a strict border between the collagenous and the phagocytizing
layer. Presence of PHB seems to stimulate uniform macrophage infiltra-
tion, which was found to be important for the degradation process and the
restoration of functional tissue.
Lymphocytic infiltration as foreign body reaction, which is common
after replacement of vessel wall with commercial woven Dacron patch,
was wholly absent when PHB. It was suggested that the absorption time
of PHB patches was long enough to permit regeneration of a tissue with
sufficient strength to prevent development of shunts in the atrial septal
position [65]. The prevention of postoperative pericardial adhesions by
closure of the pericardium with absorbable PHB patch was demonstrated.
The regeneration of mesothelial layer after implantation of PHB pericar-
dial patch was observed. The complete regeneration of mesothelium, with
morphology and biochemical activity similar to findings in native meso-
thelium, may explain the reduction of postoperative pericardial adhesions
after operations with insertion of absorbable PHB patches [67].
The regeneration of normal filament structure of restored tissues was
observed by immunohistochemical methods after PHB devices implan-
tation [66]. The immunohistochemical demonstration of cytokeratine, an
intermediate filament, which is a constituent of epithelial and mesodermal
cells, agreed with observations on intact mesothelium. Heparin sulfate
proteoglycan, a marker of basement membrane, was also identified [66].
However, in spite of good tissue reaction to implantation of cardiovascular
PHB patches, PHB endovascular stents in the rabbit iliac arteria caused
intensive inflammatory vascular reactions [80].
Trends in New Generation of Biodegradable Polymers (Part 1) 25

PHB patches for the gastrointestinal tract were tested using animal
model. Patches made from PHB sutured and PHB membranes were im-
planted to close experimental defects of stomach and bowel wall. The
complete regeneration of tissues of stomach and bowel wall was observed
at 6 months after patch implantation without strong inflammatory response
and fibrosis [14,86].
Recently, an application of biodegradable nerve guidance channels
(conduits) for nerve repair procedures and nerve regeneration after spinal
cord injury was demonstrated. Polymer tubular structures from PHB can
be modulated for this purpose. Successful nerve regeneration through a
guidance channel was observed as early as after 1 month. Virtually, all
implanted conduits contained regenerated tissue cables centrally located
within the channel lumen and composed of numerous myelinated axons
and Schwann cells. The inflammatory reaction had not interfered with the
nerve regeneration process. Progressive angiogenesis was present at the
nerve ends and through the walls of the conduit. The results demonstrate
good-quality nerve regeneration in PHB guidance channels [21, 87].
Biocompatibility of PHB was evaluated by implanting microspheres
from PHB (Mw=450 kDa) into the femoral muscle of rats. The spheres
were surrounded by one or two layers of spindle cells, and infiltration
of inflammatory cells and mononuclear cells into these layers was recog-
nized at 1 week after implantation. After 4 weeks, the number of inflam-
matory cells had decreased and the layers of spindle cells had thickened.
No inflammatory cells were seen at 8 weeks, and the spheres were encap-
sulated by spindle cells. The toxicity of PHB microspheres was evaluated
by weight change and survival times in L1210 tumor-bearing mice. No
differences were observed in the weight change or survival time compared
with those of control. These results suggest that inflammation accompany-
ing microsphere implantation is temporary as well as toxicity to normal
tissues is minimal [71].
The levels of tissue factors, inflammatory cytokines, and metabolites
of arachidonic acid were evaluated. Growth factors derived from endo-
thelium and from macrophages were found. These factors most probably
stimulate both growth and regeneration occurring when different biode-
gradable materials were used as grafts [46, 65, 67, 86]. The positive re-
action for thrombomodulin, a multifunctional protein with anticoagulant
properties, was found in both mesothelial and endothelial cells after peri-
cardial PHB patch implantation. Prostacycline production level, which
26 Applied Research on Polymer Composites

was found to have cytoprotective effect on the pericardium and prevent

adhesion formation, in the regenerated tissue was similar to that in na-
tive pericardium [65, 67]. The PHB patch seems to be highly biocompat-
ible, as no signs of inflammation were observed macroscopically and also
the level of inflammation associated cytokine mRNA did not change dra-
matically, although a transient increase of interleukin-1β and interleukin-6
mRNA through days 1-7 after PHB patch implantation was detected. In
contrast, tumor necrosis factor-α mRNA was hardly detectable throughout
the implantation period, which agrees well with a observed moderate fi-
brotic response [46, 86].

1.6â•… PHB AS TISSUE ENGINEERING MATERIAL AND PHB IN

VITRO BIOCOMPATIBILITY

Biopolymer PHB is a promising material in tissue engineering because of

its high biocompatibility in vitro. Cell cultures of various origins including
murine and human fibroblasts [15, 40, 78, 88–92], human mesenchymal
stem cells [93], rabbit bone marrow cells (osteoblasts) [36, 89, 94], hu-
man osteogenic sarcoma cells [95], human epithelial cells [90, 95], human
endothelial cells [96–97], rabbit articular cartilage chondrocytes [98–99]
and rabbit smooth muscle cells [100], and human neurons (Schwann cells)
[101] in direct contact with PHB when cultured on polymer films and
scaffolds exhibited satisfactory levels of cell adhesion, viability, and pro-
liferation. Moreover, it was shown that fibroblasts, endothelium cells, and
isolated hepatocytes cultured on PHB films exhibited high levels of cell
adhesion and growth (Figure 1.8) [102]. A series of 2D and 3D PHB scaf-
folds was developed by various methods: polymer surface modification
[97], blending [36, 78, 88, 90, 93, 99, 103], electrospinning [104–106],
salt leaching [36, 94, 107, 108], microspheres fusion [109], forming on
porous mold [110], and laser cutting [111].
Trends in New Generation of Biodegradable Polymers (Part 1) 27

FIGURE 1.9â•… Scanning electron microscopy image of 2 days growth of fibroblast cells on
films made of (a) PHB; (e) PLA; (500×). Cell density of fibroblasts grown on PHB film is
significantly higher vs. cell density of fibroblasts grown on PLA film [89].

It was also shown that cultured cells produced collagen II and glycos-
aminoglycan, which are the specific structural biopolymers formed in the
extracellular matrix [95, 98, 99]. A good viability and proliferation level of
macrophages and fibroblasts cell lines were obtained in the culturing in the
presence of particles from short-chain low-molecular PHB [74]. However,
it was shown that cell growth on the PHB films was relatively poor: the vi-
able cell number ranged from 1×103 to 2×105 [40, 89, 99]. An impaired in-
teraction between PHB matrix and cytoskeleton of cultured cells was also
demonstrated [95]. It was reported that a number of polymer properties
including chemical composition, surface morphology, surface chemistry,
surface energy, and hydrophobicity play important roles in regulating cell
viability and growth [112]. The investigation showed that this biomaterial
can be used to make scaffolds for in vitro proliferating cells [40, 89, 98].
The most widespread methods to manufacture the PHB scaffolds for
tissue engineering by means of improvement of cell adhesion and growth
on polymer surface are change of PHB surface properties and microstruc-
ture by salt-leaching methods and enzymatic/chemical/physical treatment
of polymer surface [40, 89, 98, 113]. Adhesion to polymer substrates is
one of the key issues in tissue engineering because adhesive interactions
control cell physiology. One of the most effective techniques to improve
adhesion and growth of cells on PHB films is the treatment of polymer
surface with enzymes, alkali, or low-pressure plasma [40, 113]. Lipase
treatment increases the viable cell number on the PHB film from 100 to
200 times compared to the untreated PHB film. NaOH treatment on PHB
28 Applied Research on Polymer Composites

film also indicated an increase of 25 times on the viable cell number com-
pared with the untreated PHB film [40].
It was shown that treatment of PHB film surface with low-pressure
ammonia plasma improved the growth of human fibroblasts and epithelial
cells of respiratory mucosa because of the increased hydrophylicity (but
with no change of microstructure) of polymer surface [90]. It was sug-
gested that the improved hydrophilicity of the films after PHB treatment
with lipases, alkali, and plasma allowed cells in its suspension to easily
attach on the polymer films compared to that on the untreated ones. The
influence of hydrophilicity of biomaterial surface on cell adhesion was
demonstrated earlier [114].
However, a microstructure of PHB film surface can also be responsible
for cell adhesion and cell growth [115–117]. Therefore, above-noticed
modification of polymer film surface after enzymatic and chemical treat-
ments (in particular, reduced pore size and a surface smoothing) is ex-
pected to play an important role for enhanced cell growth on the polymer
films [40]. Different cells prefer different surfaces. For example, osteo-
blasts preferred rougher surfaces with appropriate size of pores [115, 116]
while fibroblast prefer smoother surface, yet epithelial cells only attached
to the smoothest surface [117].
This appropriate roughness affects cell attachment as it provides the
right space for osteoblast growth, or supplies solid anchors for filapodia.
A scaffold with appropriate size of pores provided better surface proper-
ties for anchoring type II collagen filaments and for their penetration into
internal layers of the scaffolds implanted with chondrocytes. This could
be illuminated by the interaction of extracellular matrix proteins with the
material surface. Moreover, the semicrystalline surface PHB ultrastructure
can be connected with protein adsorption and cell adhesion [91, 92, 118].
The appropriate surface properties may also promote cell attachment and
proliferation by providing more spaces for better gas/nutrients exchange
or more serum protein adsorption [36, 94, 98]. Additionally Sevastianov
et al. found that PHB films in contact with blood did not activate the he-
mostasis system at the level of cell response, but they did activate the
coagulation system and the complement reaction [119].
The high biocompatibility of PHB may be due to several reasons. First
of all, PHB is a natural biopolymer involved in important physiological
functions in both prokaryotes and eukaryotes. PHB from bacterial origin
has property of stereospecificity that is inherent to biomolecules of all liv-
Trends in New Generation of Biodegradable Polymers (Part 1) 29

ing things and consists only from residues of D(-)-3-hydrohybutyric acid

[120–122]. Low-molecular weight PHB (up to 150 resides of 3-hydrohy-
butyric acid), complexed to other macromolecules (cPHB), was found to
be a ubiquitous constituent of both prokaryotic and eukaryotic organisms
of nearly all phyla [123–127]. Complexed cPHB was found in a wide va-
riety of tissues and organs of mammals (including human): blood, kidney,
vessels, nerves, vessels, eye, brain, as well as in organelles, membrane
proteins, lipoproteins, and plaques. cPHB concentration ranged from 3–4
µg/g wet tissue weight in nerves and brain to 12 µg/g in blood plasma
[128, 129]. In humans, total plasma cPHB ranged from 0.60 to 18.2 mg/l,
with a mean of 3.5 mg/l. [129]. It was shown that cPHB is a functional
part of ion channels of erythrocyte plasma membrane and hepatocyte mi-
tochondria membrane [130, 131].
The singular ability of cPHB to dissolve salts and facilitate their trans-
fer across hydrophobic barriers defines a potential physiological niche for
cPHB in cell metabolism [125]. However, a mechanism of PHB synthesis
in eukaryotic organisms is not well clarified that requires additional stud-
ies. Nevertheless, it could be suggested that cPHB is one of the prod-
ucts of symbiotic interaction between animals and gut microorganisms. It
was shown, for example, that E. coli is able to synthesize low-molecular
weight PHB and cPHB plays various physiological roles in bacteria cells
[127, 132].
Intermediate product of PHB biodegradation, D(-)-3-hydroxybutyric
acid is also a normal constituent of blood at concentrations between 0.3
and 1.3 mM and is present in all animal tissues [133, 134]. As it was noted
earlier PHB has a rather low degradation rate in the body in comparison
to, for example, poly(lactic-co-glycolic) acids, that prevent from increase
of 3-hydroxybutyric acid concentration in surrounding tissues [13, 16],
whereas polylactic acid release, following local pH decrease in implanta-
tion area and acidic chronic irritation of surrounding tissues is a serious
problem in application of medical devices on the base of poly(lactic-co-
glycolic) acids [135, 136]. Moreover, chronic inflammatory response to
polylactic and polyglycolic acids that was observed in a number of cases
may be induced by immune response to water-soluble oligomers that re-
leased during degradation of synthetic polymers [136–138].
30 Applied Research on Polymer Composites

1.7â•… NOVEL DRUG DOSAGE FORMS ON THE BASE OF PHB

An improvement of medical materials on the base of biopolymers by en-

capsulating different drugs opens up the wide prospects in applications
of new devices with pharmacological activity. The design of injection
systems for sustained drug delivery in the forms of microspheres or mi-
crocapsules prepared on the base of biodegradable polymers is extremely
challenging in the modern pharmacology.
The fixation of pharmacologically active component with the biopoly-
mer and following slow drug release from the microparticles provides an
optimal level of drug concentration in local target organ during long-term
period (up to several months). At curative dose, the prolonged delivery of
drugs from the systems into organism permits to eliminate the shortcom-
ings in peroral, injectable, aerosol, and the other traditional methods of
drug administration. Among those shortcomings hypertoxicity, instabil-
ity, pulsative character of rate delivery, ineffective expenditure of drugs
should be pointed out. Alternatively, applications of therapeutical polymer
systems provide orderly and purposefully the deliverance for an optimal
dose of agent that is very important at therapy of acute or chronic diseases
[1, 3, 6, 139].
An ideal biodegradable microsphere formulation would consist of a
free-flowing powder of uniform-sized microspheres less than 125 μm in
diameter and with a high drug loading. In addition, the drug must be re-
leased in its active form with an optimized profile. The manufacturing
method should produce the microspheres which are reproducible, scal-
able, and benign to some often delicate drugs, with a high encapsulation
efficiency [140, 141].
PHB as biodegradable and biocompatible is a promising material for
producing polymer systems for controlled drug release. A number of drugs
with various pharmacological activities were used for the development
of polymer-controlled release systems on the base of PHB and its copo-
lymers: model drugs (2,7-dichlorofluorescein [142], dextran-FITC [143],
methyl red [122, 144, 145], 7-hydroxethyltheophylline [146, 147]), anti-
biotics and antibacterial drugs (rifampicin [148, 149], tetracycline [150],
cefoperazone and gentamicin [151], sulperazone and duocid [152–155],
sulbactam and cefoperazone [156], fusidic acid [157], nitrofural [158]),
anticancer drugs (5-fluorouracil [159], 2′,3′-diacyl-5-fluoro-2’-deoxy-
uridine [71], paclitaxel [160, 161], rubomycin [162], chlorambucil and
Trends in New Generation of Biodegradable Polymers (Part 1) 31

etoposide [163]), antiinflammatory drug (indomethacin [164], flurbipro-

fen [165], ibuprofen [166]), analgesics (tramadol [167], vasodilator and
antithrombotic drugs (dipyridamole [168, 169], NO donor [170, 171],
nimodipine [174], felodipine [175]), proteins (hepatocyte growth factor
[176], mycobacterial protein for vaccine development [177], and bone
morphogenetic protein 7 [178]).
Various methods for manufacture of drug-loaded PHB matrices and
microspheres were used: solvent casting of films [144–147], emulsifica-
tion and solvent evaporation [148–164], spray drying [172], layer-by-layer
self-assembly [165], and supercritical antisolvent precipitation [173]. The
biocompatibility and pharmacological activity of some of these systems
were studied [71, 148, 154–156, 160, 161, 167, 171]. However, only a
few drugs were used for production of drug-controlled release systems on
the base of PHB homopolymer: 7-hydroxethyltheophylline, methyl red,
2′,3′-diacyl-5-fluoro-2′-deoxyuridine, rifampicin, tramadol, indomethacin,
dipyridamole, and paclitaxel [71, 154–156, 160–171]. The latest trend in
PHB drug delivery systems study is the development of PHB nanopar-
ticles loaded with different drugs [179–180].
The first drug-sustained delivery system on the base of PHB was de-
veloped by Korsatko et al., who observed a rapid release of encapsulated
drug, 7-hydroxethyltheophylline, from tablets of PHB (Mw = 2,000 kDa),
as well as weight losses of PHB tablets containing the drug after subcu-
taneous implantation. It was suggested that PHB with molecular weight
greater than 100 kDa was undesirable for long-term medication dosage
[146].
Pouton and Akhtar describing the release of low-molecular weight
drugs from PHB matrices reported that the latter have the tendencies to
enhance water penetration and pore formation [181]. The entrapment and
release of the model drug, methyl red (MR), from melt-crystallized PHB
was found to be a function of polymer crystallization kinetics and mor-
phology whereas overall degree of crystallinity was shown to cause no
effect on drug release kinetics. MR released from PHB films for 7 days
with initial phase of rapid release (“burst effect”) and second phase with
relatively uniform release. Release profiles of PHB films crystallized at
110˚C exhibited a greater burst effect when compared to those crystallized
at 60˚C. This was explained by better trapping of drug within polymeric
spherulites with the more rapid rates of PHB crystallization at 110˚C [144,
145].
32 Applied Research on Polymer Composites

Kawaguchi et al showed that chemical properties of drug and polymer

molecular weight had a great impact on drug delivery kinetics from PHB
matrix. Microspheres (100–300 µm in diameter) from PHB of different
molecular weight (65,000, 135,000, and 450,000) were loaded with pro-
drugs of 5-fluoro-2′-deoxyuridine (FdUR) synthesized by esterification
with aliphatic acids (propionate, butyrate, and pentanoate). Prodrugs have
different physicochemical properties, in particular, solubility in water
(from 70 mg/ml for FdUR to 0.1 mg/ml for butyryl-FdUR). The release
rates from the spheres depended on both the lipophilicity of the prodrug
and the molecular weight of the polymer. Regardless of the polymer, the
relative release rates were propionyle- FdUR > butyryl- FdUR > pentano-
yl- FdUR. The release of butyryl- FdUR and pentanoyl- FdUR from the
spheres consisting of low-molecular-weight polymer (Mw=65,000) was
faster than that from the spheres of higher molecular weight (Mw=135,000
or 450,000). The effect of drug content on the release rate was also stud-
ied. The higher the drug content in the PHB microspheres, the faster was
the drug release. The release of FdUR continued for more than 5 days [71].
Kassab developed a well-managed technique for manufacture of PHB
microspheres loaded with drugs. Microspheres were obtained within a size
of 5–100 µm using a solvent evaporation method by changing the initial
polymer/solvent ratio, emulsifier concentration, stirring rate, and initial
drug concentration. The drug overloading of up to 041 g rifampicin/g PHB
was achieved. Drug release was rapid: the maximal duration of rifampicin
delivery was 5 days. Both the size and drug content of PHB microspheres
were found to be effective in controlling the drug release from polymer
microspheres [149].
The sustained release of analgesic drug, tramadol, from PHB micro-
spheres was demonstrated by Salman et al. It was shown that 58 per cent
of the tramadol (the initial drug content in PHB matrix=18%) was released
from the microspheres (7.5 µm in diameter) in the first 24 h. Drug release
decreased with time. From 2 to 7 days, the drug release was with zero-
order rate. The entire amount of tramadol was released after 7 days [167].
The kinetics of different drug releases from PHB micro- and nanopar-
ticles loaded with dipyridamole, indomethacin, and paclitaxel was studied
[160,161,164,168,169]. It was found that the release occurs via two mech-
anisms, diffusion and degradation, operating simultaneously. Vasodilator
and antithrombotic drug, dipyridamole, and anti-inflammatory drug, in-
domethacin, diffusion processes determine the rate of the release at the
Trends in New Generation of Biodegradable Polymers (Part 1) 33

early stages of the contact of the system with the environment (the first
6–8 days). The coefficient of the release diffusion of a drug depends on its
nature, the thickness of the PHB films containing the drug, the weight ratio
of dipyridamole and indomethacin in polymer, and the molecular weight
of PHB. Thus, it is possible to regulate the rate of drug release by chang-
ing of molecular weight of PHB, for example [164]. The biodegradable
microspheres on the base of PHB designed for controlled release of di-
pyridamole and paclitaxel were kinetically studied. The profiles of release
from the microspheres with different diameters present the progression of
nonlinear and linear stages. Diffusion kinetic equation describing both lin-
ear (PHB hydrolysis) and nonlinear (diffusion) stages of the dipyridamole
and paclitaxel release profiles from the spherical subjects has been written
down as the sum of two terms: desorption from the homogeneous sphere
in accordance with diffusion mechanism and the zero-order release.
In contrast to the diffusivity dependence on microsphere size, the con-
stant characteristics of linearity are scarcely affected by the diameter of
PHB microparticles. The view of the kinetic profiles as well as the low rate
of dipyridamole and paclitaxel release are in satisfactory agreement with
kinetics of weight loss measured in vitro for the PHB films and observed
qualitatively for PHB microspheres. Taking into account kinetic results, it
was supposed that the degradation of PHB microspheres is responsible for
the linear stage of dipyridamole and paclitaxel release profiles (Figures 1.9
and 1.10) [24, 160, 161, 168, 169].
The biocompatibility and pharmacological activity of advanced drug
delivery systems on the base of PHB were studied [71, 148, 167–169].
It was shown that implanted PHB microspheres loaded with paclitaxel
caused the mild tissue reaction. The inflammation accompanying implan-
tation of PHB matrices is temporary and additionally toxicity relative to
normal tissues is minimal [169]. No signs of toxicity were observed af-
ter administration of PHB microspheres loaded with analgesic, tramadol
[167]. A single intraperitoneal injection of PHB microspheres containing
anticancer prodrugs, butyryl-FdUR, and pentanoyl-FdUR, resulted in high
antitumor effects against P388 leukemia in mice over a period of 5 days
[71]. Embolization with PHB microspheres in vivo at dogs as test animals
has been studied by Kasab et al. Renal angiograms obtained before and
after embolization and also the histopathological observations showed the
feasibility of using these microspheres as an alternative chemoemboliza-
tion agent [148]. Epidural analgesic effects of tramadol released from PHB
34 Applied Research on Polymer Composites

microspheres were observed for 21 h, whereas an equal dose of free trama-

dol was effective for less than 5 h. It was suggested that controlled release
of tramadol from PHB microspheres in vivo is possible, and pain relief
during epidural analgesia is prolonged by this drug formulation compared
with free tramadol [167].

FIGURE 1.10â•… Kinetics profiles of DPD release from PHB microspheres in vitro
(phosphate buffer, 37oC). A: general view of kinetic curves for the microspheres with
different diameters: 4(1), 19(2), 63(3), and 92(4) µm. The lines show the second stage of
release following the zero-order equation. B: Details of the curves for the microspheres
with the smaller diameters: 4(1), 19(2).

The observed data indicate the wide prospects in applications of drug-

loaded medical devices and microspheres on the base of PHB as implant-
able and injectable therapeutic systems in medicine for treatment of vari-
ous diseases: cancer, cardiovascular diseases, tuberculosis, osteomyelitis,
arthritis, and so on [6].
Trends in New Generation of Biodegradable Polymers (Part 1) 35

1.8â•…CONCLUSIONS

The natural PHB is unique biodegradable thermoplastics of considerable

commercial importance. With this review, we have attempted to systemati-
cally evaluate the impact of physicochemical factors on the hydrolysis and
the biodegradation of natural PHB both in vitro and in vivo. Clearly, the
degradation behavior observed is very much dependent on both physico-
chemical conditions, geometry, and structural and microbial properties. If
these conditions of (bio)degradation are known, the systems on the base
PHB can be designed in such biomedicine areas as medical devices (Sec-
tion 3.1), tissue scaffolds in bioengineering (Section 3.2), and develop-
ment of novel biodegradable therapeutic systems for drug delivery.

ACKNOWLEDGMENTS

The work was supported by the Russian Foundation for Basic Research
(grant no. 14-03-00405-a) and the Russian Academy of Sciences under the
program “Construction of New_Generation Macromolecular Structures”
(03/OC-14).

KEYWORDS

•â•¢ Biodegradable polymers

•â•¢ Enzymatic degradation
•â•¢ Hydrolysis
•â•¢ PHB

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CHAPTER 2

TRENDS IN NEW GENERATION OF

BIODEGRADABLE POLYMERS
(PART 2)
A. L. IORDANSKII, S. V. FOMIN, A. A. BURKOV,
YU. N. PANKOVA, and G. E. ZAIKOV

CONTENTS

2.1 Introduction..................................................................................... 50
2.2 Objects and Methods...................................................................... 50
2.3 Results and Discussion................................................................... 52
2.4 Conclusion...................................................................................... 60
Acknowledgements.................................................................................. 61
Keywords................................................................................................. 61
References................................................................................................ 62
50 Applied Research on Polymer Composites

2.1â•…INTRODUCTION

One of the most pressing problems facing humanity is increasing pollu-

tion. In this regard, question of recycling of synthetic polymeric materials
arises very sharply. Plastics production rates are growing exponentially
and the production volumes 100 millions of tons annually. One of the most
dynamic areas of the use of plastics is packaging industry (40–50% of
the total production of plastics). Thus, billions of tons of municipal solid
waste products constitute more than half of the short-term or one-time ap-
plication on the basis of large common polyolefins. A possible solution of
this problem is to create a biodegradable polymer composition. The fastest
growing trend in this area is the use of polyhydroxyalkanoates (PHAs).
Some physical and chemical characteristics of PHA are similar to these of
synthetic polymers (polypropylene, polyethylene).
However, in addition to their thermoplasticity, representatives of PHAs
have optical activity, increase induction period of oxidation, exhibit the
piezoelectric effect and, what is most important, they are characterized as
being biodegradable and biocompatible. At the same time, the PHAs have
disadvantages (high cost, brittleness), which can be partially or complete-
ly compensated by using composite materials based on blends with other
polymers, with dispersed fillers or plasticizers. Taking into account all the
above, we have suggested to create a mixed polymer composite based on
poly-3-hydroxybutyrate (PHB) and polyisobutylene (PIB).

2.2â•… OBJECTS AND METHODS

The objects of the study were high molecular weight PIB of mark “P-200”
and PHB Lot 16F. The poly-3-hydroxybutyrate was obtained by microbio-
logical synthesis in company “BIOMER®” (Germany). PHB is a white
fine powder; the density is 1.25 g/cm3, and the molecular weight is 325
kDa. Polyisobutylene of high molecular weight “P-200” is a white elastic
material, transparent in thin films, odorless, with density of 0.93 g/cm3,
and with molecular weight of about 175–225 kDa.
These materials have been chosen due to their economic expediency
and the valuable combination of physical and chemical, physical and me-
chanical, and other properties of individual polymers-PHB is a brittle ther-
moplastic; PIB an elastomer. Preparation of composite materials based on
Trends in New Generation of Biodegradable Polymers (Part 2) 51

combinations of plastics and elastomers is well known: plastics are used as

polymeric fillers in elastomers, improving their technological and working
characteristics; elastomers effectively improve strike viscosity and reduce
brittleness in compositions based on plastics.
The polymer compositions were prepared in the following proportions:
PHB:PIB=10:90, 20:80, 30:70, 40:60, 50:50, and 60:40 (by weight ratio
here and hereinafter). Then, the individual polymers were investigated.
The first stage of blending was carried out on laboratory mixing rolls with
the roll length of 320 mm and diameter of 160 mm. Temperature of the
back roll was 60°C, temperature of the front roll was 50°C. In these condi-
tions, the compositions were obtained, in which the micropowder of PHB
was distributed in the continuous matrix of PIB. Deeper joining, mutual
segmental solubility of polymers require an additional high temperature
treatment of compositions, so the second stage of the composition pro-
cessing was carried out in plunger extruder at the temperature of 185°C.
Average molecular weight of the elastomer was characterized by vis-
cometry method. Average molecular weight of PIB was calculated accord-
ing to the equation Mark-Houwink:

[h] = κ × Mma , (2.1)

[η]—the intrinsic viscosity, ml/g;

Mm—average molecular weight of the polymer;
К, α—constants for a given system “polymer-solvent”.
Heptane was used as solvent, the constants—К=1.58*10-4, α=0.69 [8].
For each sample, a series of solutions were prepared with different con-
centrations (0.2, 0.4, 0.6, 0.8, and 1.0 g/100 ml), and then determines the
relative, specific, and intrinsic viscosity. The calculated molecular weights
were presented in Table 2.1.
Investigation of the structure of the compositions by atomic force mi-
croscopy was performed on the tunnel atomic force microscope brands
Ntegra Prima �����������������������������������尓������������������
(�����������������������������������尓�����������������
company “NT–MDT”�����������������������������������尓�
)�����������������������������������尓
(cantilever NSG-01 with a frequen-
cy of 0.5–1 Hz). Investigations were carried out ������������������������
by ���������������������
semicontact mode. Mi-
crotome cuts were made on the brand Microm HM-525 (company “Ther-
moscientific,” Germany).
Investigation of the structure of the compositions was carried out by dif-
ferential scanning calorimetry on differential scanning calorimeter DSC-
60 (company “Shimadzu,” Japan). Samples of PHB–PIB blends weighing
52 Applied Research on Polymer Composites

several milligrams were placed in open aluminium crucibles with a diame-

ter of 5.8 mm, a height of 1.5 mm, and weighing 13 mg upper temperature
limit of 600°C. Temperature ranges from -100 to +250°C, heating rate of
10°/min. Liquid nitrogen is used to generate low temperature. Instrument
calibration was performed according to indium, tin, and lead.
The rheological curves of pure polymer melts and their mixtures were
obtained with the multifunction rheometer “StressTech” ��������������
(�������������
company “REO-
LOGICA Instruments AB,” Sweden). The measuring cell consisted of two
parallel planes (the lower plane was fixed, the upper plane being a rotating
rotor); the shear rate was 0.1 s-1, the temperature range was 443–513 K
(170–240°C). The lower limit of the temperature range was chosen by the
melting temperature of PHB (174.4°C—the data obtained for DSC), the
upper limit is the beginning of irreversible degradation in polymers.
Polymer samples were subjected to soil degradation in a laboratory at
a temperature 22–25°C. Samples in the form of a film thickness of 50 mm
was placed in the soil to a depth of 1.5–2 cm. Biodegradation rate was as-
sessed by evaluating the mass loss of the samples. Mass loss was fixed by
weighing the samples on an analytical balance.

2.3â•… RESULTS AND DISCUSSION

Properties of mixed polymer compositions are determined by many fac-

tors, among which in the first place should be allocated phase structure
(ratio and the size of the phase domains). Therefore, at the first stage of the
research attention has been paid to study the structure of formed composi-
tions. In the investigation of samples with a low content of PHB (10–30%
by weight) has been found that it forms a discontinuous phase, i.e., distrib-
uted in a continuous matrix PIB as separate inclusions of the order of 1–2
mm. The results of atomic force microscopy for the composition ratio of
PHB–PIB 20:80 were shown in Figure 2.1.
Trends in New Generation of Biodegradable Polymers (Part 2) 53

FIGURE 2.1â•… Photomicrographs of the relief of films with PHB–PIB ratio of 20:80 (scan
size 5 × 5 um) (a, b) and AFM phase contrast image of the film with a ratio of 20:80 PHB–
PIB (scan size 20 × 20 um) (c, d).

Atomic force microscopy is considered one of the most perspective

methods for studying polymer blends is because this method allows to
clearly define the phase boundary and its scale. Polymer identification was
performed by controlling the interaction of the probe with the sample sur-
face at different points. When approaching the surface of the cantilever is
deflected downward (to the sample) due to attractive forces until the probe
comes into contact with the sample. When the probe is withdrawn from
the studied surface, a hysteresis is observed, associated with the adhe-
sive forces. Adhesion forces between the probe and the sample are forcing
them to remain in contact, which causes the cantilever to bend. Phase of
54 Applied Research on Polymer Composites

the polymers were very clearly identified by mapping curves “approach-

removal” of the probe.
Probable range of the phase inversion is an important characteristic
for mixed biodegradable composites. This allows from a practical point of
view to establish the minimum concentration of PHB (at which a continu-
ous phase is formed) for intensive biodegradation as microorganisms must
be able to penetrate deep into the mixed composite. When compared with
the atomic force microscopy of samples with different proportions of the
components was found that in investigated materials continuous matrix
formation occurs when PHB content in the mixture of about 40–50 per
cent by weight.�����������������������������������尓���������������������
The results of atomic force microscopy for the composi-
tion ratio of PHB–PIB 50:50 shown in Figure 2.2.

FIGURE 2.2â•… Photomicrographs of the relief of films with PHB–PIB ratio of 50:50 (scan
size 10 × 10 mm) (a, b) and AFM phase contrast image of the film with a ratio of 50:50
PHB–PIB ((scan size 10 × 10 mm) (c) and 5 × 5 mm) (d).
Trends in New Generation of Biodegradable Polymers (Part 2) 55

Thus, by atomic force microscopy were determined scale structures

and distributions of polymers according to the ratio of the starting compo-
nents in the mixture, and the approximate range of probable phase inver-
sion (about 40–50% by weight of PHB).
Determination of the glass transition temperature is an informative
method of research, the phase structure of polymer blends. In the case of
mixed compositions, glass transition may occur in each phase separately,
if polymers do not interact with each other. In another case glass transition
in mixtures is fully cooperative process, involving macromolecules mixed
polymer segments. This composition would have single glass transition
temperature, which varies monotonically depending on the mixture com-
position [1]. The glass transition temperatures of polymer components of
the mixtures were determined by differential scanning calorimetry. The
results of DSC shown in Figure 2.3.

FIGURE 2.3â•… DSC curves of the samples (1-pure PIB, 2–20% PHB, 3-pure PHB).

In all cases, the specific heat jump was recorded, which corresponds
to the glass transition of phases polymers. It was noted that displacement
56 Applied Research on Polymer Composites

values of glass transition temperature of phase PIB to higher temperatures

with increasing content of PHB (from -68°C for pure PIB to -64°C for the
composition with 60 per cent by weight of the PHB). For PHB phase dis-
placement of values of glass transition temperature is shown in Figure 2.4.
As can be seen from the data presented, the displacement of values of
glass transition temperature of PHB occurs about 6–7°C. Most often in the
literature as reasons for this phenomenon is called a limited solubility of
the mixture components in each other (from a fraction of a few per cent)
[1–3]. However, for the polymers probability such variant is extremely
small because of the significant thermodynamic incompatibility. More
probable reasons of displacement of the glass transition temperature may
be changes of the supramolecular structure of polymers when mixing; as
well as differences in thermal expansion coefficients of polymers in the
region above and below the glass transition temperature.

FIGURE 2.4â•… Changes in the glass transition temperature of phase PHB.

The glass transition temperature change deserves attention because is

a sharp jump in the of PHB content of 50–60 per cent by weight. This
phenomenon may also be due to the probable phase inversion (previously
established by microscopy methods) at said ratio of the components. Con-
Trends in New Generation of Biodegradable Polymers (Part 2) 57

tinuous structure more rigid of PHB has a higher glass transition tempera-
ture than the individual inclusions of thermoplastic material, isolated from
each other by a continuous matrix of PIB. Thus, as a result of studies on
the structure of compositions of PHB–PIB was confirmed formation of
a heterogeneous two-phase system. For biodegradable polymer compo-
sitions, it may be advantage, because this system is more susceptible to
external influences destructive.
However, for practical use of PHB–PIB compositions is necessary to
evaluate the possibility of processing these materials into finished prod-
ucts.�����������������������������������尓������������������������������
As most polymer blends are processed by melting them, investiga-
tions of rheological properties of these compositions are of great scientific
and practical interest. Information about the structure of composition that
can be obtained on the basis of rheological investigation is the level of
intermolecular interactions, the degree of macromolecules ordering, the
phase structure of polymer blends. Dependence “melt viscosity—tempera-
ture” were investigated for all compositions. The viscosity values at vari-
ous temperatures for blends of polymers with different ratios are shown
in Figure 2.5.

FIGURE 2.5â•… The viscosity values at various temperatures for blends of polymers with
different ratios.
58 Applied Research on Polymer Composites

The viscosity values of the composition decreases considerably with

increasing temperature and increasing the content of PHB that gives the
chance regulation of technological properties of compositions in a wide
range. Based on the significant difference of the solubility parameters
calculated previously [5-6], it seems reasonable assumption on the for-
mation of a biphasic system melts of mixtures of these polymers. The
assumption of formation of two-phase mixtures of melts of these poly-
mers seems justified based on significant difference in the solubility pa-
rameters, which calculated previously [6]. Kerner–Takayanagi equation
applicable to describe the rheological properties of two-phase mixtures
of polymers [1]:

(7 - 5n m ) × hm + (8 -10n m ) × h f - (7 - 5n m ) × (hm - h f ) × f f
h = hm × , (2.2)
(7 - 5n m ) × hm + (8 -10n m ) × h f - (8 -10n m ) × (hm - h f ) × f f
η—viscosity of the mixture, Pa×s;
ηm—viscosity of the matrix, Pa×s;
ηf—viscosity of the dispersed phase, Pa×s;
φf—volume fraction of the dispersed phase;
νm—Poisson’s ratio of the matrix (assumed equal to 0.5).
This expression describes the dependence of the properties of the mix-
ture composition, excluding inevitable phase inversion in the mixture. Ac-
cording to Ref. (Paul, 2009a), the viscosity of the blend composition is
graphically expressed by the two curves corresponding to the two limiting
cases when one or the other phase is continuous throughout the range of
compositions of the polymer mixture. Theoretical values of the viscosity
of the compositions of various compositions were calculated based on the
viscosity base polymers. Calculations on model of Kerner-Takayanagi at
different temperatures are shown in Figure 2.6.
Trends in New Generation of Biodegradable Polymers (Part 2) 59

FIGURE 2.6â•… Viscosity of the composition at a temperature of 180°C (a) and 170°C (b)
(theoretical calculations on model of Kerner–Takayanagi; ▲ experimental data).

By analyzing data of Figure 2.6, it was found that PHB forms a contin-
uous matrix in the molten polymer at any ratio. The experimental values of
the viscosity are close to the bottom theoretical curve, which corresponds
to the calculation for the case of the formation of the matrix of PHB. Thus,
during the melting of PHB observed phase inversion phenomenon in ac-
cordance with the laws of Ref. [4, 6] more fluid melt PHB forms a continu-
ous phase in the entire range of concentrations.
Basic rheological parameters of polymer blends determined by the
properties of the polymer matrix, so the properties of melts are generally
defined by PHB. Lower viscosity of the melt blend composition (due to
the formation of a continuous matrix PHB) in this case will significantly
simplify the processing of the investigated materials. Also, the data in Fig-
ure 2.6 are consistent with the position that the greater the difference in
viscosity of mixed polymers, the earlier the formation of a continuous
matrix less viscous component.
Previous studies [7] revealed that the main physical and mechanical
characteristics (tensile strength, tensile modulus, and elongation at break),
PHB–PIB composition containing 30–50 per cent by weight of PHB, not
inferior to traditional polymers used in the production of packaging (poly-
ethylenes of different brands). But the undeniable advantage of the com-
positions PHB–PIB is the possibility of biodegradation.
60 Applied Research on Polymer Composites

It has been found that mixtures containing 40–60 per cent PHB step-
wise lose mass when exposed to soil. In the first stage (100 days), inten-
sive degradation of phase PHB occurs under the action of microorganisms.
The result of the first stage of this scenario is PIB samples with very high
surface area. In the second step (after 100 days), mass loss is stabilized and
is much slower.

TABLE 2.1â•… The average molecular weight of PIB samples

The intrinsic vis- The average molecu-

PIB samples
cosity lar weight

The original sample 0.68 185 000

The sample after 200 days of Exposure

0.65 175 000
in the soil (0% PHB)

The sample after 200 days of Exposure

0.49 115 000
in the soil (60% PHB)

As can be seen from Table 2.1, the average molecular weight PIB
sample (previously containing PHB) much less compared to the original
molecular weight PIB and PIB after exposure to soil. Significant impact
of PHB phase on the ability of PIB to degradation in soil was found by
research of the molecular weight of the elastomer. Destruction of the origi-
nal structure, PIB can occur due to physical factors (large specific surface
films), chemical factors (interaction of the products of biodegradation of
PHB with PIB phase, and initiation of the degradation of the elastomer)
and biological factors (accumulation of microorganisms biomass on the
surface of mixed films and therefore, some microorganisms can use the
matrix PIB as a carbonaceous substrate for growth.

2.4â•…CONCLUSION

There are some conclusions drawn in the course of studying structure and
properties of polymer system “PHB–PIB”:
1. Structure of mixed compositions of PHB–PIB investigated by
atomic force microscopy; confirmed the formation of a hetero-
geneous two-phase structure. PHB forms a continuous elongated
Trends in New Generation of Biodegradable Polymers (Part 2) 61

structure in the matrix of PIB when content of PHB in the mixture

is greater than 30 per cent.
2. Displacement of glass transition temperatures of individual phases
in a mixture of polymers determined by differential scanning calo-
rimetry. This may be indicative of their limited interaction, despite
the significant difference of the solubility parameters.
3. Comparison of experimental and theoretical values of viscosity
confirmed the formation of a continuous matrix less viscous PHB.
This greatly simplifies the processing of melts of compositions
PHB–PIB.
4. Microbial degradation of PHB phase occurs almost entirely within
100–125 days. The remaining friable matrix PIB are much more
susceptible to degradation by other destructive factors (oxygen of
the air, temperature, and mechanical stress).
5. Process of biodegradation of PHB phase influences on the structure
of PIB. This is reflected in a sharp decrease of average molecular
weight of PIB.

ACKNOWLEDGEMENTS

The work was supported by the Russian Foundation for Basic Research
(grant no. 13-03-00405-a) and the Russian Academy of Sciences under the
program “Construction of New Generation Macromolecular Structures”
(03/OC-14).

KEYWORDS

•â•¢ AFM
•â•¢ Blends
•â•¢ Degradation
•â•¢ DSC
•â•¢ Morphology
•â•¢ Poly(3-hydroxybutyrate)
•â•¢ Polyisobutylene
•â•¢ Rheology
•â•¢ Soil
•â•¢ Weight loss
62 Applied Research on Polymer Composites

REFERENCES

1. Kuleznev, V. N.; Mixtures of the Polymers. Moscow; 1980.

2. Paul, D.; and Bucknell, K.; Polyblend Compounds. Functional Properties. Saint Pe-
tersburg; 2009.
3. Paul, D.; and Bucknell, K.; Polyblend Compounds. Saint Petersburg: Systematics;
2009.
4. Malkin, A.; Rheology: Concepts, Methods, and Applications. St. Petersburg; 2007.
5. Iordanskii, A. L.; Fomin, S. V.; and Burkov, A. A.; Structure and melt rheology mixed
compositions of polyisobutylene and poly-3-hydroxybutyrate. Plastic Mater. 2012,
7(7), 13–16.
6. Schramm, G.; Basics Practical Rheology and Rheometry. Moscow; 2003.
7. Iordanskii, A. L.; Fomin, S. V.; and Burkov, A. A.; Investigation of the structure and
properties of biodegradable polymer composites based on poly-3-hydroxybutyrate and
polyisobutylene. Bull. Kazan University Technol. 2013, 16(9), 115–119.
8. Sangalov, Y. A.; Polymers and Copolymers of Isobutylene: Fundamental and Applied
Aspects of the Problem. Ufa; 2001.
CHAPTER 3

TRENDS IN NEW GENERATION OF

BIODEGRADABLE POLYMERS
(PART 3)
A. P. BONARTSEV, A. P. BOSKHOMODGIEV, A. L. IORDANSKII,
G. A. BONARTSEVA, A. V. REBROV T.K. MAKHINA,
V.L. MYSHKINA, S. A. YAKOVLEV, E. A. FILATOVA,
E. A. IVANOV, D. V. BAGROV, G. E. ZAIKOV, and M. I. ARTSIS

CONTENTS

3.1 Introduction..................................................................................... 64
3.2 Experimental................................................................................... 65
3.3 Results and Discussion................................................................... 68
3.4 Conclusion...................................................................................... 77
Keywords................................................................................................. 78
References................................................................................................ 78
64 Applied Research on Polymer Composites

3.1â•…INTRODUCTION

This work is designed to be an informative source for biodegradable

poly(3-hydroxybutyrate) and its derivatives’ research. We focus on hydro-
lytic degradation kinetics at 37 and 70oC in phosphate buffer to compare
PLA and PHB kinetic profiles. Besides, we reveal the kinetic behavior
for copolymer PHBV (20% of 3-hydroxyvalerate) and the blend PHB-
PLA. The intensity of biopolymer hydrolysis characterized by total weight
lost and the viscosity-averaged molecular weight (MW) decrement. The
degradation is enhanced in the series PHBV<PHB<PHB-PLA blend PLA.
Characterization of PHB and PHBV includes MW and crystallinity evolu-
tion (X-ray diffraction) and AFM analysis of PHB film surfaces before
and after aggressive medium exposition. The important impact of MW on
the biopolymer hydrolysis is shown.
The bacterial polyhydroxyalkanoates (PHAs) and their principal rep-
resentative poly(3-R-hydroxybutyrate) (PHB) create a competitive option
to conventional synthetic polymers such as polypropylene, polyethylene,
polyesters et al. These polymers are nontoxic and renewable. Their bio-
technology output does not depend on hydrocarbon production as well
as their biodegradation intermediates and resulting products (water and
carbon dioxide) do not provoke the adverse actions in environmental me-
dia or living systems [1–3]. Being environment friendly [4], the PHB and
its derivatives are used as the alternative packaging materials, which are
biodegradable in the soil or different humid media [5, 6].
The copolymerization of 3-hydroxybutyrate entities with 3-hydroxyoc-
tanoate (HO), 3-hydroxyheptanoate (HH), or 3-hydroxyvalerate (HV)
monomers modifies the physical and mechanical characteristics of the
parent PHB, such as ductility and toughness to depress its processing tem-
perature and embrittlement. Besides, copolymers PHB-HV [7], PHB-HH
[8], or PHB-HO [9] et al., have improved thermophysical and/or mechani-
cal properties, and hence they expand the spectrum of constructional and
medical materials/items. For predicting the behavior of PHB and its copo-
lymers in an aqueous media, e.g., in vitro, in a living body or in a wet soil,
it is essential to study kinetics and mechanism of hydrolytic destruction.
Despite the history of such-like investigations reckons about 25 years,
the problem of (bio)degradation in semicrystalline biopolymers is too far
from a final resolution. Moreover, in the literature the description of hy-
drolytic degradation kinetics during long-term period is comparatively
Trends in New Generation of Biodegradable Polymers (Part 3) 65

uncommon [10�����������������������������������尓�������������������������
–�����������������������������������尓������������������������
14]. Therefore, the main object of this chapter is the com-
parison of long-term degradation kinetics for the PLA, PHB, and its de-
rivatives, namely its copolymer with 3-oxyvalerate (PHBV) and the blend
PHB/PLA.
The contrast between degradation profiles for PHB and PLA makes
possible to compare the degradation behavior for two most prevalent bio-
degradable polymers. Besides, a significant attention is devoted to the im-
pact of molecular weight (MW) for above polymer systems upon hydro-
lytic degradation and morphology (crystallinity and surface roughness) at
physiological (37°C) and elevated (70°C) temperatures.

3.2â•…EXPERIMENTAL

3.2.1â•…MATERIALS

In this work, we have used poly-l-lactide (PLA) with different molecu-

lar weights: 67, 152, and 400 kDa (Fluka Germany); chloroform (ZAO
EKOS-1, RF); sodium valerate (Sigma-Aldrich, USA); and monosubsti-
tuted sodium phosphate (NaH2PO4, ChimMed, RF).

3.2.2â•… PHAS PRODUCTION

The samples of PHB and copolymer of hydroxybutyrate and hydroxyval-

erate (PHBV) have been produced in A.N. Bach’s Institute of Biochemis-
try. A highly efficient strain-producer (80 wt. % PHB in the dry weight of
cells), Azotobacter chroococcum 7Б, has been isolated from rhizosphere
of wheat (the sod-podzol soil). Details of PHB biosynthesis have been
published in Ref. [15]. Under conditions of PHBV synthesis, the sucrose
concentration was decreased till 30 g/L in medium; and after 10 h incuba-
tion, 20 mm sodium valerate was added. Isolation and purification of the
biopolymers were performed via centrifugation, washing, and drying at
60°C subsequently. Chloroform extraction of BPHB or BPHBV from the
dry biomass and precipitation, filtration, washing again, and drying has
been described in our previous work [15]. The monomer content (HB/
HV ratio) in PHBV has been determined by nuclear magnetic resonance
in accordance with procedure described earlier in Ref. [16]. The per cent
concentration of HV moiety in the copolymer was calculated as the ratio
66 Applied Research on Polymer Composites

between the integral intensity of methyl group of HV (0.89 ppm) and total
integral intensity the same group and HB group (1.27 ppm). This value is
21 mol per cent.

3.2.3â•… MOLECULAR WEIGHT DETERMINATION

The viscosity-averaged MW was determined by the viscosity (h) measure-

ment in chloroform solution at 30oC. The calculations of MW have been
made in accordance with Mark–Houwink equation [17]:

[h] = 7.7∙10−5∙М0,82

3.2.4â•… FILM PREPARATIONS OF PHAS, PLA, AND THEIR

BLENDS

The films of parent polymers (PHB, PHBV, and PLA) and their blends
with the thickness about 40μm were cast on a fat-free glass surface. We
obtained the set of films with different MW = 169 ± 9 (defined as PHB
170), 349 ± 12 (defined as PHB 350), 510 ± 15 kDa (defined as PHB 500),
and 950 ± 25 kDa (defined as PHB 1,000) as well as the copolymer PHBV
with MW = 1,056 ± 27 kDa (defined as PHBV).
In addition, we prepared the set of films on the base of PLA with same
thickness 40 μm and MW = 67 (defined as PLA 70), MW = 150 and 400
kDa. Along with them, we obtained the blend PHB/PLA with weight ratio
1:1 and MW = 950 kDa for PHB, and MW = 67 kDa for PLA (defined as
PHB + PLA blend). Both components mixed and dissolved in common
solvent, chloroform, and then cast conventionally on the glass plate. All
films were thoroughly vacuum processed for removing of solvent at 40°C.

3.2.5â•… HYDROLYTIC DEGRADATION IN VITRO EXPERIMENTS

Measurement of hydrolytic destruction of the PHB, PLA, PHBV films,

and the PHB-PLA composite was performed as follows. The films were
incubated in 15 ml 25 mm phosphate buffer, pH 7.4, at 37°C or 70°С in
a ES 1/80 thermostat (SPU, Russia) for 91 days; pH was controlled
Trends in New Generation of Biodegradable Polymers (Part 3) 67

using an Orion 420 + pH-meter (Thermo Electron Corporation, USA). For

polymer weight measurements films were taken from the buffer solution
every three day, dried, placed into a thermostat for 1 h at 40°С, and then
weighed with a balance. The film samples weighed 50–70 mg each. The
loss of polymer weight due to degradation was determined gravimetrically
using an AL-64 balance (Acculab, USA). Every three days, the buffer was
replaced by the fresh one.

3.2.6â•… WIDE ANGLE X-RAY DIFFRACTION

The PHB and PHBV chemical structure, the type of crystal lattice and
crystallinity was analyzed by wide angle X-ray scattering (WAXS) tech-
nique. X-ray scattering study was performed on device on the basis of 12
kW generator with rotating copper anode RU-200 Rotaflex (Rigaku, Ja-
pan) using CuK radiation (wavelength λ = 0.1542 nm) operated at 40 kV
and 140 mA. To obtain pictures of wide angle X-ray diffraction of poly-
mers two-dimensional position-sensitive X-ray detector GADDS (Bruker
AXS, Germany) with flat graphite monochromator installed on the pri-
mary beam was used. Collimator diameter was 0.5 mm [18]

3.2.7â•… ATOMIC FORCE MICROSCOPY OF PHB FILMS

Microphotographs of the surface of PHB films were obtained be means

of atomic force microscopy (AFM). The AFM imaging was performed
with Solver PRO-M (Zelenograd, Russia). For AFM imaging, a piece of
the PHB film (~2 × 2 mm2) was fixed on a sample holder by double-side
adhesive tape. Silicon cantilevers NSG11 (NT-MDT, Russia) with typical
spring constant of 5.1 N/m were used. The images were recorded in semi-
contact mode, scanning frequency of 1–3 Hz, scanning areas from 3 × 3
to 20 × 20 μm2, topography, and phase signals were captured during each
scan. The images were captured with 512 × 512 pixels. Image processing
was carried out using Image Analysis (NT-MDT, Russia) and FemtoScan
Online (Advanced technologies center) software.
68 Applied Research on Polymer Composites

3.3â•… RESULTS AND DISCUSSION

The in vitro degradation of PHB with different MW and its derivatives

(PHBV, blend PHB/PLA) prepared as films was observed by the changes
of total weight loss, MW, and morphologies (AFM, XRD) during the pe-
riod of 91 days.

3.3.1â•… THE HYDROLYSIS KINETICS OF PLA, PHB, AND ITS

DERIVATIVES

The hydrolytic degradation of the biopolymer and the derivatives (the

copolymer PHBV, and the blend PHB/PLA 1:1) has been monitored for
3 months under condition, which is realistically approximated to physi-
ological conditions, namely, in vitro: phosphate buffer, Ph = 7.4, tempera-
ture 37°C. The analysis of kinetic curves for all samples shows that the
highest rate of weight loss is observed for PLA with the smallest MW ≈
70 kDa and for PHB with relatively low MW ≈ 150 kDa (Figure 3.1). On
the base of the data in this figure, it is possible to compare the weight-loss
increment for the polymers with different initial MW. Here, we clearly see
that the samples with the higher MWs (300–1,000 kDa) are much stable
against hydrolytic degradation than the samples of the lowest MW. The
total weight of PHB films with MW = 150 kDa decreases faster compared
to the weight reduction of the other PHB samples with higher MWs=300
and 450 or 1,000 kDa. In addition, by the 91st day of buffer exposition the
residual weight of the low-MW sample reaches 10.5 per cent weight loss
that it is essentially higher than the weight loss for the other PHB samples
(see Figure 3.1 over again).
After establishing the impact of MW upon the hydrolysis, we have
compared the weight-loss kinetic curves for PLA and PHB films with the
relatively comparative MW = 400 and 350 kDa, respectively, and the same
film thickness. For the PLA films one can see the weight depletion with the
higher rate than the analogous samples of PHB. The results obtained here
are in line with the preceding literature data [8, 12, 19–21].
Having compared the destruction behavior of the homopolymer PHB
and the copolymer PHBV, we can see that the introduction of hydrophobic
entity (HV) into the PHB molecule via copolymerization reveals the hy-
drolytic stability of PHBV molecules. For PHBV, a hydrolysis induction
time is the longest among the other polymer systems and over a period of
Trends in New Generation of Biodegradable Polymers (Part 3) 69

70 days its weight loss is minimal (< 1% wt.) and possibly related with
desorption of low-molecular fraction of PHBV presented initially in the
samples after biosynthesis and isolation. The kinetic curves in Figure 3.1
show also that the conversion the parent polymers to their blend PHB-PLA
decreases the hydrolysis rate compared with PHB (MW = 1,000 kDa) even
if the second component is a readily hydrolysable polymer: PLA (MW =
70 kDa).
For the sake of hydrolysis amplification and its exploration simultane-
ously, a polymer exposition in aqueous media has usually been carried
out at elevated temperature [11, 19]. To find out a temperature impact on
degradation and intensify this process, we have elevated the temperature
in phosphate buffer to 70°C. This value of temperature is often used as the
standard in other publications (see e.g. Ref. [11]). As one should expect,
under such condition, the hydrolysis acceleration is fairly visible that is
presented in Figure 3.1(b). By the 45th day of PLA incubation, its films
turned into fine-grinding dust with the weight-loss equaled 50 per cent
(MW = 70 kDa) or 40 per cent (MW = 350 kDa). Simultaneously, the
PHB with the lowest MW = 170 kDa has the weight loss=38 wt per cent
and the film was markedly fragmented while the PHB samples with higher
MWs 350; 500; and 1,000 kDa have lost the less per cent of the initial
weight, namely 20, 15, and 10 per cent, respectively. In addition, for 83
days, the weight drop in the PHB-PLA blend films is about 51 wt. per cent
and, hence, hydrolytic stability of the blend polymer system is essentially
declined (see. Figures 3.1(a) and 3.1(b)).
At elevated temperature of polymer hydrolysis (70oC) as well as at
physiological temperature 37°C, we have demonstrated again that the
PHBV films are stable because by 95th day, they lost only 4 wt per cent.
The enhanced stability of PHBV relative to the PHB has been confirmed
by other literature data [21]. Here, it is worth remarking that during bio-
synthesis of the PHBV, two opposite effects of water sorption acting re-
versely each other occur. On the one hand, while the methyl groups are
replaced by ethyl groups, the total hydrophobicity of the copolymer is
enhanced, on the other hand; this replacement leads to decrease of crystal-
linity in the copolymer [22]. The interplay between two processes deter-
mines a total water concentration in the copolymer and hence the rate of
hydrolytic degradation. In general, in the case of PHBV copolymer (HB/
HV = 4:1 mol ratio), the hydrophobization of its chain predominates the
70 Applied Research on Polymer Composites

effect of crystallinity decrease from 75 per cent for PHB to ~60 per cent
for PHBV.

FIGURE 3.1â•… Weight loss in the phosphate buffer for PHB and its derivatives with
different MW (shown on the curves in kDa). 37oC, 70oC: ♦, ►, and◄ are PLA films with
MW = 70, 150, and 400 kDa respectively; ■, ▲, ●, and ▼ are PHB samples with 170; 350;
500; and 1,000 kDa, respectively; PHBV 1050 (); and PHB-PLA blend (Ã).

3.3.2â•… CHANGE OF MOLECULAR WEIGHT FOR PHB AND PHBV

On exposure of PHB and PHBV films to buffer medium at physiological

(37°C) or elevated (70°C) temperatures, we have measured both their to-
tal weight loss and the change of their MW simultaneously. In particular,
we have shown the temperature impact on the MW decrease that will be
Trends in New Generation of Biodegradable Polymers (Part 3) 71

much clear if we compare the MW decrements for the samples at 37° and
70°C. At 70°C, the above biopolymers have a more intensive reduction of
MW compared with the reduction at 37°C (see Figure 3.2). In particular,
at elevated temperature, the initial MW (= 350 kDa) has the decrement
by seven times more than the MW decrement at physiological condition.
In general, the final MW loss is nearly proportional to the initial MW of
sample that is correct especially at 70°C. As an example, after the 83-days
incubation of PHB films, the initial MW = 170 kDa dropped as much as 18
wt per cent and the initial MW = 350 kDa has the 9.1 wt per cent decrease.
Figure 3.2 shows that the sharp reduction of MW takes place for the
first 45 days of incubation; and after this time, the MW change becomes
slow. Combining the weight-loss (Section 3.1) and the MW depletion, it
is possible to present the biopolymer hydrolysis as the two-stage process.
On the initial stage, the random cleavage of macromolecules and the MW
decrease without a significant weight-loss occur. Within this time, the
mean length of PHB intermediates is fairly large and the molar ratio of the
terminal hydrophilic groups to the basic functional groups in a biodegrad-
able fragment is too small to provide the solubility in aqueous media. This
situation is true for the PHB samples with middle and high MW (350; 500;
and 1,000 kDa) when at 37°C their total weight remains stable during all
time of observation, but the MW values are decreased until 76, 61, and 51
wt per cent, respectively.
On the second stage of degradation, when the MW of the intermediate
molecules attains the some “critical” value and the products of hydrolysis
become hydrophilic to provide dissolution and diffusion into water medi-
um, the weight reduction is clearly observed at 70°C. This stage is accom-
panied by the changes of physical–chemical, mechanical, and structural
characteristics and a geometry alteration. A similar two-stage mechanism
of PHB degradation has been described in the other publications [23, 24].
Further, in the classical work of Reush [25], she showed that hydrophiliza-
tion of PHB intermediates occurs at relatively low MW namely, at several
decades of kDa. Our results provide evidences that the reduction of MW
till “critical” values to be equal about 30 kDa leads to the expansion of the
second stage, namely, to the intensive weight loss.
72 Applied Research on Polymer Composites

FIGURE 3.2â•… The molecular weight conversion of PHB and PHBV films during
hydrolysis in phosphate buffer (PBS), pH = 7.4°C, 37°C, and 70°C.

3.3.3â•… CRYSTALLINITY OF PHB AND PHBV

We have above revealed that during hydrolytic degradation, PHB and

PHBV show the MW reduction (Section 3.2) and the total weight decrease
(Section 3.1). In addition, by the X-ray diffraction (XRD) technique, we
have measured the crystallinity degree of PHB and PHBV that varied
depending on time in the interval of values 60–80 per cent (see Figure
3.3(a)). We have noted that on the initial stage of polymer exposition to
the aqueous buffer solution (at 37°C for 45 days), the crystallinity degree
has slightly increased and then, under following exposition to the buffer,
this characteristic is constant or even slightly decreased showing a weak
maximum.
When taking into account that at 37°C, the total weight for the PHB
films with MWs equal 350; 500; and 1,000 kDa, and the PHBV film with
MW equals 1,050 are invariable, a possible reason of the small increase in
crystallinity is recrystallization described earlier for PLA [26]. Recrystal-
lization (or additional crystallization) happens in semicrystalline polymers
where the crystallite portion can increase using polymer chains in adjoin-
ing amorphous phase [22].
Trends in New Generation of Biodegradable Polymers (Part 3) 73

At higher temperature of hydrolysis, 70°C, the crystallinity increment

is strongly marked and has a progressive trend. The plausible explana-
tion of this effect includes the hydrolysis progress in amorphous area of
biopolymers. It is well known that the matrices of PHB and PHBV are
formed by alternative crystalline and noncrystalline regions, which de-
termine both polymer morphologies and transport of aggressive medium.
In addition, we have revealed recently by H–D exchange FTIR technique
that the functional groups in the PHB crystallites are practically not acces-
sible to water attack.
Therefore, the hydrolytic destruction and the weight decrease are pre-
dominantly developed in the amorphous part of polymer [22, 27]. Hence,
the crystalline fraction becomes larger through polymer fragment desorp-
tion from amorphous phase. This effect takes place under the strong ag-
gressive conditions (70°C) and does not appear under the physiological
conditions (37°C) when the samples have invariable weight.
Owing to the longer lateral chains in PHBV, copolymerization modi-
fies essentially the parent characteristics of PHB such as decreasing
in crystallinity, the depression of melting and glass temperatures and,
hence, enhancing ductility and improvement of processing characteris-
tics [14, 28, 29]. In addition, we have founded out that the initial crystal-
linity of PHB films is a monotonically increased function of initial MW
(see Figure 3.3(b)). For samples with relatively low molecular weight, it
is difficult to compose the perfect crystalline entities because of a rela-
tively high concentration of terminal groups performing as crystalline
defects.
Thus, at physiological temperature the crystallinity, measured during
degradation by XRD technique, has an slightly extreme character. On the
initial stage of PHB degradation, the crystalline/amorphous ratio is in-
creased owing to additional crystallization through involvement of poly-
mer molecules situated in amorphous fields. By contrast, at 70°C after
reaching the critical MW values (see Section 3.2), the following desorp-
tion of water-soluble intermediates occurs. On the following stage, as the
degradation is developed till film disintegration, the crystallinity drop
must take place as result of crystallite disruption.
74 Applied Research on Polymer Composites

FIGURE 3.3â•… (a)—Crystallinity evolution during the hydrolysis for PHB and PHBV
films (denoted values of temperature and MW). (b)—crystallinity as function of initial
MW for PHB films prepared by cast method, (c) X-ray diffractograms for PHB films with
different molecular weight given under X-axis.
Trends in New Generation of Biodegradable Polymers (Part 3) 75

3.3.4â•… THE ANALYSIS OF FILM SURFACES FOR PHB BY AFM

TECHNIQUE

Morphology and surface roughness of PHB film exposed to corrosive me-

dium (phosphate buffer) have been studied by the AFM technique. This
experiment is important for surface characterization because the state of
implant surface determines not only mechanism of degradation but also
the protein adsorption and cell adhesion that are responsible for polymer
biocompatibility [30]. As the standard sample, we have used the PHB film
with relatively low MW = 170 kDa.
The film casting procedure may lead to distinction in morphology be-
tween two surfaces when the one plane of the polymer film was adjacent
with glass plate and the other one was exposed to air. In reality, as it is
shown in Figure 3.4, the surface exposed to air has a roughness formed
by a plenty of pores with the length of 500–700 nm. The opposite side
of the film contacted with glass (Figure 3.4(b)) is characterized by minor
texture and by the pores with the less length as small as 100 nm. At higher
magnification (here not presented) in certain localities, it can see the stacks
of polymer crystallites with width about 100 nm and length 500–800 nm.

FIGURE 3.4â•… AFM topographic images of PHB films (170 kDa) with a scan size of 18
× 18 μm: the rough surface of fresh-prepared sample (exposed to air)—(a) the smooth
surface of fresh-prepared sample (exposed to glass)—(b) the sample exposed to phosphate
buffer at 37oC for 83 days—(c) the sample exposed to phosphate buffer at 70oC for 83
days—(d) general magnificence is 300.
76 Applied Research on Polymer Composites

Inequality of morphology between two surfaces gets clearly evident

when quantitative parameters of roughness (rn) were compared. A rough-
ness analysis has shown that averaged value of this characteristic

1 N
Ra =
N
∑r
n =1
n

and a root-mean-square roughness

1 N

∑r
2
Rq = n
N n =1

for surfaces exposed to glass or air differ about ten times.

The variance of characteristics is related with solvent desorption con-
ditions during its evaporation for the cast film. During chloroform evapo-
ration from the surface faced to air, the flux forms additional channels
(namely the pores), which are fixed as far as the film is solidified and crys-
tallized. Simultaneously, during evaporation the morphology and texture
on the opposite side of film exposed to the glass support are not subjected
to the impact of solvent transport.
The morphology of the latter surface depends on energy interaction
conditions (interface glass-biopolymer tension) predominantly. The expo-
sition of PHB films to the buffer for long time (83 days) lead to a threefold
growth of roughness characteristics for glass-exposed surface and practi-
cally does not affects the air-exposed surface. It is interesting that temper-
ature of film degradation does not influence on the roughness change. The
surface characteristics of film surface have the same values after treatment
at 37°C and 70°C.
Summarizing the AMF data, we can conclude that during degrada-
tion the air-exposed, rough surface remained stable that probably related
with the volume mechanism of degradation (V-mechanism [31, 32]). The
pores on the surface provide the fast water diffusion into the bulk of PHB.
However, under the same environmental conditions, the change of surface
porosity (roughness) for glass-exposed surface is remarkable, showing the
engagement of surface into degradation process (S-mechanism [31, 32]).
Past findings show that along with the volume processes of polymer
degradation the surface hydrolysis can proceed. Several authors [20, 21]
Trends in New Generation of Biodegradable Polymers (Part 3) 77

have recently reported on surface mechanism of PHB destruction, but tra-

ditional viewpoint states a volume mechanism of degradation [12]. Here,
using an advanced method of surface investigation (AMF), we have shown
that for the same film under the same exterior conditions, the mechanism
of degradation could be changed depending on the prehistory of polymer
preparation.

3.4â•…CONCLUSION

Analyzing all results related with hydrolytic degradation of PHB and its
derivatives, the consecutive stages of such complicated process are pre-
sented as follows. During the initial stage, the total weight is invariable and
the cleavage of biomolecules resulting in the MW decrease is observed.
Within this time, the PHB intermediates are too large and hydrophobic to
provide solubility in aqueous media. Because the PHB crystallites stay
stable, the crystallinity degree is constant as well and even it may grow up
due to additional crystallization. On the second stage of hydrolysis, when
the MW of intermediates attain the “critical” value, which is equal about
30 kDa, these intermediates can dissolve and diffuse from the polymer
into buffer. Within this period, the weight loss is clearly observed. The
intensity of hydrolysis characterized by the weight loss and the MW decre-
ment is enhanced in the series PHBV<PHB<PHB-PLA blend<PLA.
The growth of initial MW (a terminal group reducing) impacts on
the hydrolysis stability probably due to the increase of crystallite perfec-
tion and crystallinity degree. The XRD data reflect this trend (see Figure
3.3(b)). Moreover, the surface state of PHB films explored by AFM tech-
nique depends on the condition of film preparation. After cast processing,
there is a great difference in morphologies of PHB film surfaces exposed
to air and to glass plate.
It is well known that the mechanism of hydrolysis could include two
consecutive processes: 1) volume degradation and 2) surface degradation.
Under essential pore formation (in the surface layer exposed to air), the
volume mechanism prevails. The smooth surface of PHB film contacted
during preparation with the glass plate is degraded much intensely than the
opposite rough surface (Figure 3.4).
78 Applied Research on Polymer Composites

In conclusion, we have revealed that the biopolymer MW determines

the form of a hydrolysis profile (see Figure 3.1). For acceleration of this
process, we have to use the small MW values of PHB. In this case, we
affect both the degradation rate and the crystalline degree (Figure 3.1b).
By contrast, for prolongation of service-time in a living system, it is pref-
erable to use the high-MW PHB that is the most stable polymer against
hydrolytic degradation.

KEYWORDS

•â•¢ atomic force microscopy

•â•¢ Biodegradable polymers
•â•¢ Crystallinity
•â•¢ X-ray diffraction

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CHAPTER 4

A DETAILED REVIEW ON
PHYSICOCHEMICAL PROPERTIES,
SYNTHESIS, AND APPLICATION OF
POLYACETYLENE
O. A. PONOMAREV, A. I. RAKHIMOV, N. A. RAKHIMOV,
E. S. TITOVA, V. A. BABKIN, and G. E. ZAIKOV

CONTENTS

4.1 Introduction..................................................................................... 82
4.2 Synthesis and Structure of Polyacetylene....................................... 82
4.3 Physicochemical Properties and Application of Polyacetylene......... 91
Keywords............................................................................................... 102
References.............................................................................................. 102
82 Applied Research on Polymer Composites

4.1â•…INTRODUCTION

Features of synthesis, structure, properties, and use of polyacetylenes are

considered in this chapter. Тhe catalytic polymerization of acetylene us-
ing different catalysts is shown. Plasmachemical synthesis of carbines is
considered. The results of studying the structure of polyacetylenes by elec-
tron spectroscopy are presented. The results of the research of the surface
morphology of polyacetylene are presented. Agency of receiving methods
of polyacetylene on its properties is shown.

4.2â•… SYNTHESIS AND STRUCTURE OF POLYACETYLENE

The chemical element in periodic system of D.I. Mendeleev—carbon pos-

sesses a variety of unique propertes. Scientists thought that two forms ex-
ists of crystal carbon only-diamond and graphite (opinion beginning of
60th years of XX century). These forms are widespread in the nature, and
they are known to mankind with the most ancient times.
The question on an opportunity of existence of forms of carbon with
sp-hybridization of atoms was repeatedly considered theoretically. In
1885, German chemist A. Bayer tried to synthesize chained carbon from
derivatives of acetylene by a step method. However, Bayer’s attempt to
receive polyin has appeared unsuccessful. He received the hydrocarbon
consisting from four molecules of acetylene, associated in a chain, and
appeared extremely unstable.
А. M. Sladkov, V. V. Korshak, V. I. Каsatochkin, and Yu. P. Кudryavcev
[1] observed loss of a black sediment of polyin compound of carbon hav-
ing the linear form at transmission acetylene in a water—ammonia solu-
tion of salt Cu (II) (oxidizing dehydropoly condensation of acetylene led
obviously to polyacetylenides of copper). This powder blew up at heating
in a dry condition, and in damp—at a detonation. Process of oxidative de-
hydropoly condensation of acetylene can be written down in a following
kind schematically [1] at x+y+z=n:
A Detailed Review on Physicochemical Properties, Synthesis 83

n H C C H
2+
Cu

H( C C ) Cu + H( C C ) H + Cu ( C C ) H
x y z

FeCl3

H( C C ) H
n
At surplus of ions Cu2+, the mix of various polyins and polyacetyl-
enides of copper various molecular weight is formed. Additional oxidation
of products received at this stage (with help FeCl3 or K3[Fe (CN)6]) leads
to formation polyins with the double molecular weight. The last do not
blow up any more at heating and impact, but contain a plenty of copper.
Possibly, trailer atoms of copper stabilize polyins by dint of to complex-
ation.
The content by carbon was 90 per cent of clean polyin (cleaning cleared
from copper and impurity of other components of the reactionary medi-
um). Only multihours’ heating of samples of polyin at 1,000°С in vacuum
has allowed to receive analytically pure samples of α-carbyne. Similar
processing results not only in purification but also in partial crystallization
of polyacetylene.
Under A.M. Sladkov’s offer such polyacetylene have named «carbyne»
* (from Latin carboneum (carbon) with the termination «in», accepted in
organic chemistry for a designation of acetylene bond).
By acknowledgement of polyin structures in chains is formation of
oxalic acid after ozonation hydrolysis of carbine [2, 3]:

New linear polymer with cumulene bonds was received [2, 3]. It is
named polycumulene. The proof of such structure became the fact that at
ozonation of polycumulene, only carbon dioxide is received:
84 Applied Research on Polymer Composites

Cumulene modification of carbyne (β-c arbyne) has been received on

specially developed by Sladkov two-stage method [3]. At the first stage,
spent polycondensation of suboxide of carbon (С3О2) with dimagnesium
dibromine acetylene as Grignard reaction with formation polymeric gly-
col:

At the second stage, this polymeric glycol reduced by stannous chlo-

ride hydrochloric acid:

High-molecular cumulene represents an insoluble dark-brown powder

with the developed specific surface (200–300 m2/g) and density 2.25 g/sm3.
At multihours heating at 1,000°С�����������������������������������尓���
and the depressed pressure, polycumu-
lene partially crystallizes. Two types of monocrystals have been found out
in received after annealing a product by means of transmission electronic
microscopy. Crystals corresponded to α- and β-modifications of carbyne.
One of the most convenient and accessible methods of reception car-
byne or its fragments is reaction of dehydrohalogenation of the some poly-
mers content of halogens (GP). Feature of this method is formation of the
carbon chain at polymerization corresponding monomers. The problem
at synthesis carbyne consists only in that at full eliminating of halogen
hydride with formation of linear carbon chain. Exhaustive dehydrohalo-
genation is possible, if the next atoms of carbon have equal quantities of
atoms of halogen and hydrogen. Therefore convenient GP for reception of
carbyne were various polyvinyliden halogenides (bromides, chlorides and
fluorides), poly(1,2-dibromoethylene), poly (1,1,2 or 1,2,3-trichlorobuta-
diene), for example:
A Detailed Review on Physicochemical Properties, Synthesis 85

The reaction of dehydrohalogenation typically carry out at presence

of solutions of alkalis (B−) in ethanol with addition of polar solvents. At
use of tetrahydrofuran synthesis goes at a room temperature. This method
allows avoiding course of collateral reactions. The amorphous phase only
cumulene modification of carbyne is received as a result. Then, crystal of
β-carbyne is synthesized from amorphous carbine by solid-phase crystal-
ization.
Next method is dehydrogenation of polyacetylene. At interaction of
polyacetylene with metallic potassium at 800°С and pressure 4 GPa led
to dehydrogenation and formation of potassium hydride, the carbon ma-
trix containing potassium. After removal of potassium from products (acid
processing) precipitate out brown plate crystals of β-carbyne in hexagonal
forms by diameter ~1 mm and thickness up to 1 mm. Carbyne also can be
received by various methods of chemical sedimentation from a gas phase.
Plasmochemical Synthesis of Carbyne. At thermal decomposition of
hydrocarbons (acetylene, propane, heptane, benzol), carbon tetrachloride,
carbon bisulfide, acetone in a stream nitrogen plasma is received the dis-
perse carbon powders containing carbyne. Monocrystals of white color
and (white or brown) polycrystals remain after selective oxidation of aro-
matic hydrocarbon. It is positioned, that formation of carbyne does not
depend by nature initial organic compound. The moderate temperature of
plasma (~3,200 K) and small concentration of reagents promote process.
Laser sublimations of carbon. Carbyne has been received at sedimen-
tation on a substrate of steams of negative ions of the carbon after laser
evaporation of graphite in 1971. The silvery-white layer was received on
a substrate. This layer, according to data X-ray and diffraction researches,
consists of amorphous and crystal particles of carbyne with the average
size of crystallites >10−5 sm.
Arc cracking of carbon. Evaporation in electric arc spectrally pure
coals with enough slow polymerization and crystallization of a carbon
steam on a surface of a cold substrate yields to product in which prevail
carbyne forms of carbon.
Ion-stimulated precipitation of carbyne. At ion-stimulated condensa-
tion of carbon on a lining simultaneously or alternately the stream of car-
bon and a stream of ions of an inert gas moves. The stream of carbon is
86 Applied Research on Polymer Composites

received by thermal or ionic evaporation of graphite. This method allows

to receive carbyne films with a different degree of orderliness (from amor-
phous up to monocrystalline layers), carbynes of the set updating, and also
a film of other forms of carbon. Annealing of films of amorphous carbon
with various near order leads to crystallization of various allotropic forms
carbon, including carbyne.
Sladkov has drawn the following conclusions on the basis of results of
experiments on synthesis carbyne by methods of chemical sedimentation
from gas phase:
• White sediments of carbyne are received, possibly, in the softest
conditions of condensation of carbon: high enough vacuum, small
intensity of a stream, and low energy of flying atoms or groups of
atoms, small speed of sedimentation.
• Chains, apparently, grow perpendicularly to a lining, not being
crosslinked among themselves.
• Probably, being an environment monovalent heteroatoms stabilise
chains, do not allow them to be crosslinked.
Reception of carbyne from carbon graphite materials leads by heating
of cores from pyrolytic graphite at temperature 2,700–3,200 K in argon
medium. This leads to occurrence on the ends of cores a silvery-white
strike (already through 15–20 s). This strike consists of crystals carbyne
that is confirmed by data of method electron diffraction.
In 1958 Natta with employees are polymerized acetylene on catalyst
system А1(С2Н5))3—Ti(OC3H7)4 [7, 8]. The subsequent researches [9–11]
led to reception of films stereoregular polyacetylene. The catalyst system
Al(Et)3—Ti(OBu)4 provides reception of films of polyacetylene predomi-
nantly (up to 98%).
Films of polyacetylene are formed on a surface of the catalyst or practi-
cally to any lining moistened by a solution of the catalyst (it is preferable
in toluene), in an atmosphere of the cleared acetylene [11]. The tempera-
ture and pressure of acetylene control growth of films [12, 13]. Homoge-
neous catalyst system before use typically maintain at a room temperature.
Thus, reactions of maturing of the catalyst occur [14]:

Ti(OBu)4+AlEt3→EtTi(OBu)3→AlEt2(OBu)

2EtTi(OBu)3→2Ti (OBu)3+CH4+C2H6
A Detailed Review on Physicochemical Properties, Synthesis 87

Ti(OBu)3+AlEt3→EtTi(OBu)2+Al(Et)2OBu

EtTi(OBu)2+AlEt3→EtTi(OBu)2+Al(Et)3

Aging of the catalyst in the beginning raises its activity. However,

eventually the yield of polyacetylene falls because of the further reduction
of the titan:

EtTi(OBu)3+Al(Et)3→Ti(OBu)4+Al(Et)2(OBu)+C2H4+C2H6

The jelly-like product of red color is formed if synthesis led at low

concentration of the catalyst. This product consists from confused fibrils
in the size up to 800 Å. Foam material with density from 0.4 to 0.4 g/sm3
is possible to receive from the dilute gels by sublimation of solvent at tem-
perature below temperature of its freezing [15].
Research of speed dependence for formation of films of polyacetylene
from catalyst concentration and pressure of acetylene has allowed to find
an optimum parity of components for catalyst Al/Ti = 4. Increase of this
parity up to 10 leads to increase in the sizes of fibrils [16]. Falling of speed
of reaction in the end of process speaks deterioration of diffusion a mono-
mer through a layer of the film formed on a surface of the catalyst [17].
During synthesis, the film is formed simultaneously on walls of a flask and
on a surface a catalytic solution. Gel collects in a cortex. The powder of
polyacetylene settles at the bottom of a reactor. The molecular weight (Мп)
a powder below, than gel, is also depressed with growth of concentration
of the catalyst up to 400–500 [18]. The molecular weight of jellous poly-
acetylene slightly decreases with growth of concentration of the catalyst
and grows from 2 × 104 up to 3, 6 × 104 at rise in temperature from –78 up
to −10°С. The molecular weight of polyacetylene in a film is twice less,
than in gel [19].
Greater sensitivity of the catalyst to impurity does not allow estimating
unequivocally influence of various factors on Mp of polyacetylene. Low-
molecular products with Mp~1,200 are formed at carrying out of synthe-
sis in the medium of hydrogen [20]. Concentration of acetylene renders
significant influence on Mp: at increase of its pressure up to 760 mm Hg
increases Mp up to 1,20,000 [14, 21]. Apparently, the heterogeneity of a
substratum arising because of imperfection of technics for synthesis, is the
reason for some irreproducibility properties of the received polymers. It
88 Applied Research on Polymer Composites

is supposed that synthesis is carried out on “surface” of catalytic clusters.

Research by EPR method has allowed to distinguish in the catalyst up
to four types of complexes [22]. Polyacetylene cis-transoid structures is
formed as a result.
Formation of trans-structure at heats speaks thermal isomerization. The
alternative opportunity trans-disclosing of triple bond in a catalytic com-
plex for a transitive condition is forbidden spatially [22, 23]. The structure
of a complex and a kinetics of polymerization are considered in works in
more detail [14, 24].
Parshakov A. S. with coauthors [25] have offered a new method of
synthesis organo-inorganic composites nanoclusters transitive metals in
an organic matrix by reactions of compounds of transitive metals of the
maximum degrees of oxidation with monomers that at the first stage repre-
sent itself as a reducer. Formed thus clusters metals of the lowest degrees
of oxidation are used for catalysis of polymerization a monomer with for-
mation of an organic matrix.
Thus it is positioned, that at interaction MoCl5 with acetylene in not
polar mediums there is allocation HCl, downturn of a degree of oxida-
tion of molybdenum and formation metallo-organic nanoclusters. Two
distances Mo–Mo are found out in these nanoclusters by method EXAFS
spectroscopy. In coordination sphere, Мо there are two nonequivalent
atom of chlorine and atom of carbon. On the basis of results MALDI-TOF
mass spectrometry, the conclusion is made that cluster of molybdenum has
12- or the 13-nuclear metal skeleton and its structure can be expressed by
formulas[Mo12Cl24(C20H21)]− or [Mo13Cl24(C13H8)]−.
Greater sensitivity of the catalyst impurity does not allow to estimate
unequivocally influence of various factors on Mn of polyacetylene. Low-
molecular products with M~1,200 are formed at carrying out of synthesis
in the environment of hydrogen [20]. Concentration of acetylene renders
significant influence on Мn:Мп increases up to 1,20,000 at increase of its
pressure up to 760 mm hg [14, 21]. Apparently, the heterogeneity of a
substratum arising because of imperfection of technics of synthesis, is the
reason for some non repeatability properties of the received polymers. It
is supposed that synthesis is carried out on “surface” of catalytic clusters.
Research by method EPR has allowed to distinguish in the catalyst up to 4
types of complexes [22].
А�����������������������������������尓���������������������������������
Polyacetylene cis-transoid structures is as a result formed. Forma-
tion a trans-structure at heats speaks thermal isomerization, previous crys-
A Detailed Review on Physicochemical Properties, Synthesis 89

tallization of circuits. The alternative opportunity a trans-disclosing of

triple bondin in a catalytic complex for a transitive condition is forbidden
spatially [22, 23]; in more detail, the structure of a complex and a kinetics
of polymerization are considered in works [14, 24].
Parshakov A.S. with coauthors [25] have offered a new method of syn-
thesis of organo-inorganic composites nanoclusters of transitive metals in
an organic matrix by reactions of connections of transition metals of the
maximum degrees of oxidation with monomers. Monomers represent it-
self as a reducer at the first stage. Formed thus clusters of metals of the
lowest degrees of oxidation are used for a catalysis of polymerization a
monomer with formation of an organic matrix.
Thus it is positioned, that at interaction MoCl5 with acetylene in not po-
lar mediums there is allocation HCl, downturn of a degree of oxidation of
molybdenum and formation metallo-organic nanoclusters. Two distances
Mo-Mo are found out in these clusters by a method of EXAFS-spectros-
copy. Two nonequivalent atoms of chlorine and atom of carbon are avail-
able in coordination sphere Мо. The conclusion is made on the basis of
results MALDI-TOF of mass-spectrometry, that cluster molybdenum has
12 or the 13-nuclear metal skeleton and its structure can be expressed by
formulas [Mo12Cl24(C20H21)]− or [Mo13Cl24(C13H8)]−.
Set of results of Infrared-, Raman-, MASS-, NMR –13С– and RFES has
led to a conclusion, that the organic part of a composite represents poly-
acetylene a trans-structure. Polymeric chains lace, and alongside with the
interfaced double bonds, are present linear fragments of twinned double
–HC=C=CH– and triple C≡C bonds.
Reactions of NbCl5 with acetylene also is applied to synthesis of the
organo-inorganic composites containing in an organic matrix clusters of
transitive elements not only VI, but other groups of periodic system.
Solutions of MoCl5 stated at a room temperature in benzene or tolu-
ene used for reception of organo-inorganic composites with enough high
concentration of metal. Acetylene passed through these solutions during
4–6 h. Acetylene preliminary refined and drained from water and possible
impurity. Color of a solution is varied from dark-yellow-green up to black
in process of transmission acetylene. The solution heated up, turned to gel
of black color and after a while the temperature dropped up to room. Re-
action was accompanied by formation HCl. Completeness of interaction
pentachloride with acetylene judged on the termination of its allocation.
90 Applied Research on Polymer Composites

The sediment, similar to gel, settled upon termination of transmission

acetylene. It filtered off in an atmosphere of argon, washed out dry solvent
and dried up under vacuum.
The received substances are fine-dispersed powders of black color, in-
soluble in water and in usual organic solvents. Solutions after branch of a
deposit represented pure solvent according to NMR. Formed compounds
of molybdenum and products of oligomerization acetylene precipitated
completely. The structure of products differed under the maintenance of
carbon depending on speed and time of transmission acetylene a little.
Thus relation C:H was conserved close to unit, and Cl:Mo—close to two.
The structure of products of reaction differed slightly in benzene and tolu-
ene (Table 4.1) and was close to MoCl1.9 ± 0.1(C30 ± 1H30 ± 1).

TABLE 4.1â•… Data of the element analysis of products for reaction MoCl5 with acetylene
in benzene and toluene

Per centage, weight

(%)
Solution C H Cl Mo

Calcu- F����
ind- Calcu- Calcu- F����
ind- Calcu-
Findings lated ings lated Findings lated ings lated

Benzene 65.94 5.38 11.70 16.98

64.67 5.38 12.73 17.22
Toluene 66.23 5.24 11.87 16.66

Presence on diffraction patterns the evolved products of a wide maxi-

mum at small corners allowed to assume X-ray�����������������������
amorphous or nanocrys-
����������������������
talline a structure of the received substances. By a method of scanning
electronic microscopy (SEM) it was revealed, that substances have low
crystallinity and nonfibrillary morphology (Figure 4.1(а)).
A Detailed Review on Physicochemical Properties, Synthesis 91

FIGURE 4.1â•… Photomicrographes MoCl1.9 ± 0.1(C30 ± 1H30 ± 1) according to (а) SEМ and (b)
АSМ.

4.3â•… PHYSICOCHEMICAL PROPERTIES AND APPLICATION OF

POLYACETYLENE

By results of atomicpower microscopy (ASM) particle size can be esti-

mated within the limits of 10 ������������������������������������尓�������
÷����������������������������������尓��������
15 nm (Figure 4.1(b)). By means of trans-
lucent electronic microscopy has been positioned, that the minimal size of
morphological element MoCl1.9 ± 0.1 (C30 ± 1H30 ± 1) makes 1 ÷ 2 nm.
Substances are steady and do not fly in high vacuum and an inert at-
mosphere up to 300°C. Formation of structures [Mo12Cl24(C20H21)]− and
[Mo13Cl24(C13H8)]�����������������������������������尓�������������������
is supposed also on the basis of mass-spectral of re-
searches.
Spectrum EPR of composite MoCl1.9 ± 0.1 (C30 ± 1H30 ± 1) at 300 К (Figure
4.2(а)) consists of two isotropic lines. The intensive line g = 1,935 is car-
ried to unpaired electrons of atoms of molybdenum. The observable size
of the g-factor is approximately equal to values for some compounds of
trivalent molybdenum. For example, in K3[InCl6]·2H2O, where the ion of
molybdenum Mo (+3) isomorphically substitutes In (+3), and value of the
g-factor makes 1.93 ± 0.061.
The line of insignificant intensity with g = 2,003, close to the g-factor-
free electron 20,023, has been carried to unpaired electrons atoms of car-
bon of a polyacethylene matrix. Intensity of electrons signals for atoms
molybdenum essentially above, than for electrons of carbon atoms of a
matrix. It is possible to conclude signal strength, that the basic contribu-
tion to paramagnetic properties of a composite bring unpaired electrons of
atoms of molybdenum.
92 Applied Research on Polymer Composites

FIGURE 4.2â•… Spectrum EPR of composite MoCl1.9 ± 0.1(C30 ± 1H30 ± 1) at 300 К, removed in
a continuous mode in (a)—X and (b)—W-range.

Spectrum EPR which has been removed in a continuous mode at 30

K, (Figure 4.2(b)) has a little changed at transition from X-to a high-fre-
quency W-range. Observable three wide lines unpaired electrons atoms
of molybdenum have been carried to three axial components with g1 =
1.9528, g2 = 1.9696 and g3 = 2.0156 accordingly. Unpaired electrons at-
oms of carbon of a polyacethylene matrix the narrow signal g = 2.0033
answers. In a pulse mode of shooting of spectra EPR at 30 K (Figure 4.3)
this line decomposes on two signals with g1 = 2,033 and g2 = 2.035. Pres-
ence of two signals EPR testifies to existence in a polyacethylene matrix
of two types of the paramagnetic centers of the various nature which can
be carried to distinction in their geometrical environment or to localized
and delocalized unpaired electrons atoms of carbon polyacethylene chain.
Measurement of temperature dependence of a magnetic susceptibility
Xg in the field of temperatures 77 ÷ 300 K has shown, that at decrease in
temperature from room up to 108 K the size of a magnetic susceptibility
of samples is within the limits of sensitivity of the device or practically is
absent. The sample started to display a magnetic susceptibility below this
temperature. The susceptibility sharply increased at the further decrease
in temperature.
The magnetic susceptibility a trans-polyacetylene submits to Curie law
and is very small on absolute size. Comparison of a temperature course Xχg
A Detailed Review on Physicochemical Properties, Synthesis 93

a composite and pure allows to conclude a trans-polyacetylene, that the

basic contribution to a magnetic susceptibility of the investigated samples
bring unpaired electrons atoms of molybdenum in cluster. Sharp increase
of a magnetic susceptibility below 108 K can be connected with reduction
of exchange interactions between atoms of metal.

FIGURE 4.3â•… Spectrum absorption EPR of composite MoCl1.9 ± 0.1(C30 ± 1H30 ± 1), removed
in a pulse mode in a W-range at (a)—30 K and (b)—its first derivative.

The size of electroconductivity compressed samples MoCl1.9 ± 0.1(C30 ±

H
1 30 ± 1
), measured at a direct current at a room temperature-(1.3 ÷ 3.3)·10−7
Ohm−1·cm−1 is in a range of values for a trans-polyacetylene and charac-
terizes a composite as weak dielectric or the semiconductor. The posi-
tioned size of conductivity of samples at an alternating current σ = (3.1 ÷
4.7)·10−3 Ohm−1·cm−1 can answer presence of ionic (proton) conductivity
that can be connected with presence of mobile atoms of hydrogen at struc-
ture of polymer.
Research of composition, structure and properties of products of inter-
action NbCl5 with acetylene in a benzene solution also are first-hand close
and differ a little with the maintenance of carbon (Table 4.2).
94 Applied Research on Polymer Composites

TABLE 4.2â•… Data of the element analysis of products of interaction NbCl5 with acetylene
in a solution and at direct interaction

The weights content (%)

С H Cl Nb

Findings Calculated Findings Calculated Findings Calculated Findings Calculated

In a solution

45.00 45.20 3.60 3.76 20.50 22.20 26.50 28.80

At direct interaction

41.60 45.20 4.02 3.76 22.81 22.20 27.78 28.80

To substances formula NbCl2±0,1(C12±1H12±1) can be attributed on the

basis of the received data. Interaction can be described by the following
equation:

NbCl5(solv/solid)+nC2H2→NbCl2±0,1(C12±1H12±1)↓+(n − 12)C6H6+3HCl↑+Q

The wide line was observed on diffraction pattern NbCl2±0,1(C12±1H12±1)

at 2θ = 23 − 24°C. It allowed to assume a nanocrystalline structure of the
received products.
Studying of morphology of surface NbCl2±0,1(C12±1H12±1), received by
direct interaction, method SEM has shown, that particles have predomi-
nantly the spherical form, and their sizes make less than 100 nm (Figure
4.4).
The globular form of particles and their small size testify to the big size
of their specific surface. It will be coordinated with high catalytic activity
NbCl2±0.1(C12±1H12±1).
Fibrils are formed in many cases as a result of synthesis [24]. The mor-
phology of polyacetylene films practically does not depend on conditions
of synthesis. Diameter of fibrils can change depending on these conditions
and typically makes 200–800 Å [14, 24]. At cultivation of films on sub-
strates, the size fibrils decreases. The same effect is observed at reception
of polyacetylene in the medium of other polymers. Time of endurance
(ageing) of the catalyst especially strongly influences of the size of fibrils.
The size of fibrils increases with increase in time of ageing. Detailed re-
search of growth fibrils on thin films a method of translucent electronic
A Detailed Review on Physicochemical Properties, Synthesis 95

microscopy has allowed to find out microfibrillar branchings on the basic

fibril (the size 30–50 Å) and thickenings in places of its gearing, and also
presence of rings on the ends of fibrils.

FIGURE 4.4â•… Microphoto of particles NbCl2 ± 0.1(C12 ± 1H12 ± 1), received by method SEM.

Essential changes in morphology of a film at isomerization of poly-

acetylene are not observed. The film consists from any way located fi-
brils. Fibrils sometimes are going in larger formations [23]. Formation
of a film is consequence of interaction fibrils among themselves due to
adhesive forces. The big practical interest is represented catalytic system
AlR3–Ti(oBu)4 [48]. Polyacetylene is received on it at −60°С, possesses
fibrous structure and can be manufactured usual, accepted in technology
of polymers by methods.
Particle size increases from 100 up to 500 Å at use of the mixed catalyst
and the increase in density of films is observed. A filtration of suspension
it is possible to receive films of any sizes. On the various substrates pos-
sessing good adhesive properties, it is possible to receive films dispersion
of gel. Polymer easily doping AsF5, FeCl3,I2, and other electron acceptors.
Preliminary tests have shown some advantages of such materials at their
use in accumulators [48]. Gels polyacetylene with the similar properties,
96 Applied Research on Polymer Composites

received on others catalytic systems, represent the big practical interest

[49]. Data on technological receptions of manufacturing of polyacetylene
films from gels with diameter of particles 0.01–1.00 mm are in the patent
literature [50].
Films are received at presence of the mixed catalyst at an interval of
temperatures from—100 up to –48°C. These results testify to an opportu-
nity of transition to enough simple and cheap technology of continuous
process of reception of polyacetylene films. Rather accessible catalysts
are WC16 and МоС16. Acetylene polymerizes at 20°С and pressure up to
14 atm at their presence. However the received polymers contain carbonyl
groups because of presence of oxygen and possess low molecular weight
[51]. The complex systems including in addition to WC16 or МоС16 tet-
raphenyltin are more perspective for reception of film materials. The film
of doped predominantly (90%) a trans-structure with fibrous morphology
is formed on a surface of a concentrated solution of the vanadic catalyst.
Diameter of fibrils of the polymer received on catalyst MoC15-Ph4Sn, can
vary within the limits of 300–10,000 Å; in case of catalyst WC16-Ph4Sn, it
reaches 1,2 105 Å [30].
Research of a kinetics of polymerization of acetylene on catalysts
Ti(OBu)5–Al(Et)3, WCl6–PhtSn, MoCl5–Ph4Sn, Ti(CH2CeH5), has shown,
that speed of process falls in the specified number [31]. Films, doped by
various acceptors [CH (SbF5) 0.7]n, [CH (CF3S03H) 0.8]m– had conductivity
10–20 Ohm–1·cm–1 at 20°C. New original method of reception of films
doped in a trans-form is polymerization of a 7,8-bis (trifluoromethyl) tri-
cycle [4,2,2,0] deca-3,7,9-trien (BTFM) with disclosing a cycle.
Polymerization occurs on catalytic system WC16-Sn(CH3)4, precipi-
tated on surfaces of a reactor. The film prepolymer as a result of heat-
ing in vacuum at 100–150° detaches trifluoromethyl-benzene. The silvery
film polyacetylene is formed. The density of polymer reaches 1, 1 g/cm3
and comes nearer to flotation density polyacetylene, received in other
ways. Received this method of amorphous polyacetylene has completely
a trans-configuration and does not possess fibrous structure. The rests of
1,2-bis(trifluoromethyl-benzene) are present at polymer according to in-
frared-spectroscopy. Crystal films of polyacetylene with monoclinic sys-
tem and β = 91,5° are received at long heating of prepolymer on networks
of an electronic microscope at 100° in vacuum. Improvement of a method
has allowed to receive films and completely oriented crystal polyacety-
A Detailed Review on Physicochemical Properties, Synthesis 97

lene. In the further ways of synthesis of polymers from others monomers

have been developed.
Naphthalene evolves at heat treatment of prepolymer in the first case.
Anthracene evolves in the second case. Purification polymer from residual
impurities occurs when the temperature of heat treatment rise���������
. Accord-
ing to spectral researches, the absorption caused by presence of sp-hybrid
carbon is not observed in films. Absorption in the field of 1,480 сm–1
caused by presence of C=C bonds in Spectra КР of considered polymers,
is shifted compared to the absorption observed in polyacetylene, received
by other methods (1,460 cm–1).
It is believed that it is connected with decrease of size of interface
blocks. The obtained films are difficult doping in a gas phase due to its
high density. Conductivity of initial films reaches 10–200 (Ohm·cm–1)
when doped with bromine or iodine in a solution [51].
Solutions of complex compound cyclopentadienyl-dititana in hexane
and sodium cyclopentadienyl complex have high catalytic activity. Films
with a metallic luster can be obtained by slowly removing the solvent
from the formed gel polyacetylene in vacuum. It is assumed that the active
complex has a tetrahedral structure. Polymerization mechanism is similar
to the mechanism of olefin polymerization on catalyst Ziegler–Natta.
Obtained at –80°C cis-polyacetylene films after doping had a conductivity
of 240 (Ohm·cm–1).
Classical methods of ionic and radical polymerization do not allow
to receive high-molecular polymers with system of the conjugated bonds
because of isomerization the active centers [2] connected with a polyene
chain. Affinity to electron and potential of ionization considerably varies
with increase in effective conjugated. One of the methods, allowing to
lead a cation process of polymerization, formation of a complex with the
growing polyconjugated chains during synthesis. Practical realization of
such process probably at presence of the big surplus of a strong acceptor
of electrons in the reaction medium. In this case, the electronic density of
polyene chain falls. The probability of electron transfer from a chain on
the active center decreases accordingly.
Polyacetylene films were able to synthesize on an internal surface of a
reactor in an interval of temperatures from –78 up to –198°С at addition of
acetylene to arsenic pentafluoride. Strips of absorption cis-polyacetylene
are identified in the field of 740 cm–1 and doped complexes in the field of
900 and 1,370 cm–1.
98 Applied Research on Polymer Composites

Similar in composition films were prepared by polymerization vinyl-

acetylene in the gas phase in the presence SbF5. However, to achieve a
metallic state has failed. Soluble polyenes were obtained in solution AsF3
in the by cationic polymerization, including soluble agents. Polymeriza-
tion was carried out at the freezing temperature of acetylene. From the
resulting solution were cast films with low conductivity, characteristic of
weakly doped polyacetylene with 103 molecular weight. Spectral studies
confirmed the presence of the polymer obtained in the cis-structure. Practi-
cal interest are insoluble polymers with a conductivity of 10–3 (Ohm-cm−1),
obtained at –78°С polymerization of acetylene in the presence AsF5, Na-
AsF, SiF, AsF3, BF3, SbF5, and PF6.
Effective cocatalyst of cationic polymerization of acetylene and its de-
rivatives are compounds of bivalent mercury and its organic derivatives.
As a result, the reactions of oxide or mercury salts with proton and aprotic
acids into saturated hydrocarbon formed heterogeneous complexes. They
are effectively polymerized acetylene vinylacetylene, phenylacetylene,
propargyl alcohol. Polyacetylene predominantly trans-structure with a
crystallinity of 70 per cent was obtained in the form of films during the
polymerization of acetylene on the catalyst surface. According to X-ray
studies, the main reflection corresponds to the interplanar distance d=3.22
Å. Homogeneous catalyst obtained in the presence of aromatic ligands.
Active complex of the catalyst with acetylene is stable at low tempera-
tures. The alkylation of solvent and its interpolymerization with acetylene
is in the presence of aromatic solvents (toluene, benzene). In the infra-
red spectrum of the films revealed absorption strias corresponding to the
aromatic cycle. Patterns of polymerization of acetylene monomers, the
effect of temperature and composition of the catalyst on the structure and
properties of the resulting polymers were studied. Morphology of the films
showed the absence of fibrils.
Almost all of the above methods of synthesis polyacetylene with
high molecular weight lead to the formation of insoluble polymers. Their
insolubility due to the high intermolecular interaction and form a network
structures. For the polymers obtained by Ziegler catalyst systems, the
cross-link density of the NMR data of 3–5 per cent. This is confirmed by
ozonolysis. Quantum chemical calculations confirm that the isomerization
process intermolecular bonds are formed.
The most accessible and promising method for synthesis of the
polyacetylene of linear structure is the polymerization of acetylene in
A Detailed Review on Physicochemical Properties, Synthesis 99

the presence of metals VIII group, in the presence with reducing agents
(catalyst Luttlnger). Polyacetylene with high crystallinity was obtained
by polymerization of acetylene on the catalyst system Co(NO3)2–
NaBH4 with component ratio 1:2. Both components are injected into
the substrate containing monomer, to prevent the death of a catalyst.
Raising the temperature and the concentration of sodium borane leads
to partial reduction of the polymer. The activity of nickel complex can
be significantly improved if the polymerization leads in the presence of
NaBH2. Crystalline polymers, obtained at low temperatures, do not contain
fibrils. Crystallites have dimensions of 70 Å.
A typical reflex observed at 23.75°С (d=3.74 Å) confirms the trans-
structure of the polymer. Palladium complexes are ineffective in obtaining
high molecular weight polymers. Catalyst Luttlnger enables one to obtain
linear polymers of cis-structure, characterized by high crystallinity. The
yield of polyacetylene is 25–30 g/g catalyst.
Chlorination of the freshly prepared polymers at low temperatures
allows to obtain soluble chlorpolymers about 104 molecular weight [27].
Although the authors argue that the low-temperature chlorination, in
contrast to hydrogenation, there is no polymer degradation, data suggest
that an appropriate choice of temperature and solvent derived chlorinated
polymers have a molecular weight up to 2,5·105. Destruction more visible
at chlorination on light and on elevated temperatures. The proof of the
linear structure of polyacetylene is the fact that soluble iodinated polymers
are obtained by iodination polyacetylene suspension in ethanol.
Systematic studies of methods for the synthesis of polyacetylene allowed
to develop a simple and convenient method of obtaining the films on various
substrates wetted by an ethereal solution of the catalyst. The disadvantages
of these films, as well as films produced by Shirakava [24, 25] are difficult
to clean them of residual catalyst and the dependence of properties on the
film thickness. Much more manufacturable methods for obtaining films of
polyacetylene spray pre-cleaned from residues of the catalyst in a stream
of polyacetylene gels inert gas or a splash of homogenized gels [49]. The
properties of such films depend on the conditions of their formation. Free
film thickness of 2–3 mm are filtered under pressure in an inert atmosphere
containing a homogenized suspension of polyacetylene 5–10 g/liter. The
suspension formed in organic media at low temperatures in the presence of
the catalyst Co(NO3)2-NaBH4. The films obtained by spraying a stream of
100 Applied Research on Polymer Composites

inert gas, homogeneous, have good adhesion to substrates made of metal,

polyurethane, polyester polyethylenetereftalate, polyimide, etc.
Suspension of polyacetylene changes its properties with time
significantly. Сross-linking and aggregation of fibrils observed in an inert
atmosphere at temperatures above −20°С. This leads to a decrease in the
rate of oxidation and chlorination. The morphology of the films changes
particularly striking during the aging of the suspension in the presence of
moisture and oxygen: increasing the diameter of the fibrils, decreasing
their length, breaks and knots are formed. The suspension does not change
its properties in 2 weeks.
Preparation of soluble polymers with a system of conjugated double
bonds, and high molecular weight is practically difficult because of
strong intermolecular interactions. Sufficiently high molecular weight
polyacetylene were obtained in the form of fine-dispersed particles during
the synthesis on a Luttinger catalyst in the presence surfactants: copolymer
of styrene and polyethylene with polyethylene oxide. Acetylene was added
to the catalyst and the copolymer solution in a mixture of cyclohexane-
tetrahydrofuran at –60°С and heated to –30°С. Stable colloidal solutions
with spherical particles in size from 40 to 2,000 Å, formed. The density of
selected films is 1.15 g/cm3. Colloidal solutions of polyacetylene can be
obtained in the presence of other polymers that prevent aggregation of the
forming molecules of polyacetylene.
Polyacetylene obtained in the presence of Group VIII metals, in
combination with NaBH4, has almost the same morphology, as a polymer
synthesized by Shirakawa [25]. The dimensions of fibrils lay in the range
300–800 Å, and depend on the concentration of the catalyst, the synthesis
temperature and medium [27].
Thermogravimetric curves for the polyacetylene, there are two
exothermic peaks at 145 and 325°С [16]. The first of these corresponds
to an irreversible cis-trans isomerization. Migration of hydrogen
occurs at 325°С, open chain and cross-linking without the formation of
polyacetylene volatile products. The color of the polymer becomes brown.
A large number of defects appears. In the infrared spectrum there are
absorption bands characteristic of the CH2, CH3, -C=C- and -C2H5- groups
[16].
Structuring polymer occurs in the temperature range 280–380°. But
72 per cent of initial weight of polyacetylene losses at 720°С. The main
products of the decomposition of polyacetylene are benzene, hydrogen and
A Detailed Review on Physicochemical Properties, Synthesis 101

lower hydrocarbons [15]. The crystallinity of polyacetylene reduced when

heated in air to 90° after several hours. The brown amorphous substance,
similar cuprene, obtained after 70 hours.
Catalytic hydrogenation of polyacetylene leads to the formation of
cross-linked product [29]. Non-crosslinked and soluble products are
obtained in the case of hydrogenation of polyacetylene doped with alkali
metals [30, 31]. Polyacetylenes are involved in redox reactions that occur
in processing strong oxidizing and reducing agents (iodine, bromine,
AsF5, Na-naphthalene in order to significantly increase the electrical
conductivity [32].
Practical use of polyacetylene is complicated by its easy oxidation by
air oxygen [33]. Oxidation is easily exposed to the polymer obtained by
polymerization of acetylene [34, 35]. The cis-or trans –(CH)x in air or oxygen
for about an hour exposed to the irreversible oxidative degradation [36,
37]. The limiting value of weight gain due to absorption of polyacetylene
(absorption) of oxygen from air oxidation at room temperature is 35 per
cent [33]. The resulting product is characterized by the formula [(C2H2)
O0,9]n. The ease of oxidation depends on the morphology of the polymer
and changes in the series of crystal amorphous component the surface of
the fibrils [35]. The absorption of oxygen begins at the surface of fibrils,
and then penetrates. Polyacetylene globular morphology is more stable to
the effects of O2 than polymer fibrillar structures [38].
Polyacetylene obtained by polymerization of acetylene in Ziegler–
Natta catalysts, after doping Cl2, Br2, I2, AsF5 becomes a semiconductor
in the form of flexible, silvery films “organic metals” [39]. Doping with
iodine increases the amorphous samples d 6·10–5, and crystal to 7·102
Ohm–1·cm–1 [40]. The highest electrical conductivity of the polyacetylene
compared with those obtained by other methods, the authors [41] explain
the presence of catalyst residues. In their view, the concentration of the
structure of sp3-hybridized carbon atoms is relatively little effect on the
conductivity as compared with the influence of catalyst residues. Doping
with iodine films of polyacetylene obtained by metathesis polymerizing
cyclooctatetraene leads to an increase in their electrical conductivity 10–8 to
50–350 Ohm–1·cm–1 [42], and have received polymerization of benzvalene
with ring opening from 10–8–10–5 to 10–4–10–1 Ohm–1·cm–1 [43].
Conductivity increases when pressure is applied to polyacetylene,
obtained by polymerization of acetylene [44] and interphase
dehydrochlorination of PVC [45]. Anomalously large (up to ten orders of
102 Applied Research on Polymer Composites

magnitude) an abrupt increase in conductivity when the load is found for

iodine-doped crystalline polivinilena—conversion product of PVC [46].
Magnetic properties of polyacetylene significantly depend on the
configuration of chains [47]. In the EPR spectrum of the polymerization
of polyacetylene singlet line with g-factor of 2.003 [48] and a line width
(ΔH) of 7 to 9.5 Oe for the cis-isomer [49] and from 0.28 to 5 Oe for
the trans-isomer [50] observed. According to other reports [47], the cis-
isomer, syn-synthesized by polymerization of acetylene at 195 K, the
EPR signal with g-factor = 2.0025 is not observed. This signal appears
when the temperature of polymerization increases, when the trans-isomer
in the form of short chains mainly at the ends of the molecules is 5–10
wt per cent [51]. The morphology of polyacetylene also has an effect on
the paramagnetic properties. The concentration of PMC in the amorphous
polyacetylene is ~1,018 spin/g, and in the crystal −1,019 spin/g [51].

KEYWORDS

•â•¢ Carboneum
•â•¢ Carbyne
•â•¢ Physicochemical properties
•â•¢ Polyacetylene

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Drobot, D. V.; Nefedov Dаn, V. I.; 2009, 427(5), 641–645 p.
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Am. Phys. Soc. 1979, 24, 480–483
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molec. 1980, 13(2), 457–459.
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Rapid Commun. 1985, 6(10), 685–692.
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J.; Chem. Phys. 1979, 70(3), 1132–1136.
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CHAPTER 5

TRENDS IN ACTIVATED CARBON

FIBERS
M. MEHDIPOUR

CONTENTS

5.1 Introduction................................................................................... 106

5.2 Activated Carbon Fibers: Properties and Application.................. 109
5.3 Molecular sieving carbons: Properties and Application................110
5.4 Importance of controlling of pore size in porous carbon materials
and supercapacitors........................................................................111
5.5 Carbon Nanotube: Properties and Application..............................113
5.6 Carbon Nanfiber: Properties and Application................................118
5.7 Activated Carbon Nanotube: Properties and Application............. 121
5.8 Pore Formation in Carbon Materials, Pore Characterization and
Analysis of Pores.......................................................................... 125
5.9 Recently Study Works about Controlling Pore Size..................... 130
Keywords............................................................................................... 134
References.............................................................................................. 134
106 Applied Research on Polymer Composites

5.1â•…INTRODUCTION

In this chapter, we focus on the pore size controlling in carbon-based

nanoadsorbent to apply simulation and modeling methods and describe
the recent activities about it. Significant progress has been made in this
process throughout recent years. Essential emphasis is put on the control-
ling of both micro and mesoporosity and its applications. For the con-
trol of mesopores, many novel methods are proposed such as catalytic
activation, polymer blend, organic gel, and template carbonization, for
analyzing micropore distribution in activated carbons assumes an array of
semi-infinite, rigid slits of distributed width whose walls are modeled as
energetically uniform graphite. Various kinds of pores in solid materials
are classified into intraparticle pores and interparticle pores according to
the origin of the pores and the structural factors of the pores are discussed
as well as the methods for evaluation of the pore-size distribution with mo-
lecular adsorption (molecular resolution porosimetry), small angle X-ray
scattering, mercury porosimetry, nuclear magnetic resonance, and thermo-
porosirmetry [1–46]. The main aim in the controlling of micropores is to
produce molecular sieving carbon (MSC) with uniform micropore struc-
ture, that applied in special membranes or produce some carbon compos-
ites that remove special contaminate from aqueous environments as adsor-
bent [47–53]. Despite difference in particle size, the adsorption properties
of activated carbon and carbon based nanoadsorbents(ACF–ACNF–CNF
and CNT), are basically the same because the characteristics of activated
carbon (pore size distribution, internal surface area,and surface chemis-
try) controlling the equilibrium aspects of adsorption are independent of
particle [54–120]. The excellently regular structures of CNTs and other
carbon nanostructures and its composites facilitate accurate simulation of
CNTs’ behavior by applying a variety of mathematical, classical, and nu-
merical methods and simulation, Such as Grand Canonical Monte Carlo
(GCMC) simulation, Car—Parrinello molecular dynamics (CPMD), the
ab initio density functional theory (DFT), atomistic and molecular dynam-
ics simulation (MDS), LJ potential, HK Method, BJH Method, DR, etc.
Adsorption isotherms can be simulated and modeled for this system using
GCMC or DFT and other methods, pore-size distributions and PSD curves
are determined from experimental isotherms and using such models and
finally experimental and model results of carbon material samples is com-
pared, adapted and model is verified [121–145].
Trends in Activated Carbon Fibers 107

5.1.1â•… ACTIVATED CARBON: PROPERTIES AND APPLICATION

TABLE 5.1â•… Technical advantages and disadvantages of existing modification techniques

Modification Treatment Advantages Disadvantages

Chemical char- Acidic Increases acidic func- May decrease bet surface
acteristics tional groups on ac sur- area and pore volume,
face. Enhances chela- may give off undesired
tion ability with metal so2 (treatment with h2so4)
species or no2 (treatment with
hno3) gases, Has adverse
effect on uptake of or-
ganics

Basic Enhances uptake of or- May, in some cases, de-

ganics crease the uptake of met-
al ions

Impregnation Enhances in-built cata- May decrease BET sur-

of foreign ma- lytic oxidation capabil- face area and pore vol-
terial ity ume

Physical charac- Heat Increases BET surface Decreases oxygen sur-

teristics area and pore volume face functional groups

Biological char- Bioadsorption Prolongs ac bed life Thick biofilm encapsu-

acteristics by rapid oxidation of lating ac may impede
organics by bacteria diffusion of adsorbate
before the material can species
occupy adsorption sites

Activated carbon (AC) has been most effective adsorbent for the re-
moval of a wide range of contaminants from aqueous or gaseous environ-
ment. It is a widely used adsorbent in the treatment of wastewaters due to
its exceptionally high surface areas which range from 500 to 1,500 m2g–1,
well-developed internal microporosity structure [1]. While the effective-
ness of ACs to act as adsorbents for a wide range of pollutant materials is
well noted and more research on AC modification are presented due to the
need to enable ACs to develop affinity for special contaminants removal
from wastewater [2]. It is, therefore, essential to understand the various
important factors that influence the adsorption capacity of AC due to their
108 Applied Research on Polymer Composites

modification so that it can be tailored to their specific physical and chemi-

cal attributes to enhance their affinities pollutant materials. These factors
include specific surface area, pore-size distribution, pore volume, and
presence of surface functional groups. In general, the adsorption capacity
increases with specific surface area due to the availability of adsorption
site, whereas pore size and micropore distribution are closely related to
the composition of the AC, the type of raw material used, and the degree
of activation during production stage [3]. Here, we summarize the various
AC modification techniques and their effects on adsorption of chemical
species from aqueous solutions, modification of AC in granular or pow-
dered form were reviewed. Based on extensive literature reviews, the au-
thors have categorized the techniques into three broad groups, namely,
modification of chemical, physical, and biological characteristics that are
further subdivided into their pertinent treatment techniques (Table 5.1 lists
and compares the advantages and disadvantages of existing modification
techniques with regards to technical aspects that are further elucidated in
the following sections [1–4].
While these characteristics are reviewed separately as reflected by
numerous AC modification research, it should be noted that there were
also research with the direct intention of significantly modifying two or
more characteristic and that the techniques reviewed are not intended to
be exhaustive. The adsorption capacity depends on the accessibility of the
organic molecules to the microporosity that is dependent on their size [5].
AC can be used for removing taste and odor (T&O) compounds, synthetic
organic chemicals (SOCs), and dissolved natural organic matter (DOM)
from water.
PAC typically has a diameter less than 0.15 mm, and can be applied
at various locations in a treatment system. GAC, with diameters ranging
from 0.5 to 2.5 mm, is employed in fixed-bed adsorbents such as granular
media filters or post filters. Each of these factors must be properly evalu-
ated in determining the use of activated carbon in a practical application.
The primary treatment objective of activated carbon adsorption in a par-
ticular water treatment plant determines the process design and operation;
multiple objectives can not, in most cases, be simultaneously optimized
[5–40].
It is critical in either case to understand and evaluate the adsorption
interactions in the context of drinking water treatment systems. Activated
carbons are prepared from different precursors and used in a wide range of
industries. Their preparation, structure, and applications were reviewed in
Trends in Activated Carbon Fibers 109

different books and reviews. High BET surface area and light weight are
the main advantages of activated carbons. Usually activated carbons have
a wide range of pore sizes from micropores to macropores, which shows a
marked contrast to the definite pore size of zeolites [41–46].

5.2â•… ACTIVATED CARBON FIBERS: PROPERTIES AND

APPLICATION

Activated carbons fibers (ACFs) have been prepared recently and devel-
oped a new field of applications. They have a number of advantages over
granular activated carbons. The principal merit to prepare activated carbon
in fibrous morphology is its particular pore structure and a large physi-
cal surface area. Granular activated carbons have different sizes of pores
(macropores, mesopores, and micropores), whereas ACFs have mostly
micropores on their surfaces. In granular activated carbons, adsorbates al-
ways have to reach micropores by passing through macropores and meso-
pores; whereas in ACFs, they can directly reach most micropores because
micropores are open to the outer surface and hence, exposed directly to
adsorbates. Therefore, the adsorption rate, as well as the amount of ad-
sorption, of gases into ACFs is much higher than those into granular acti-
vated carbons [1–3]. In recent work, the amount of adsorption of toluene
molecules is much higher, and desorption proceeds faster in ACFs than
granular activated carbons, effective elimination of SO from exhausted
gases by using ACFs was too. A very high specific surface area up to 2,500
m2g–1 and a high micropore volume up to 1.6 cm3g–1 can be obtained in
isotropic-pitch-based carbon fibers. For the preparation of these carbon
fibers with a very high surface area such as 2,500 m2g—1, precursors that
give a carbon with poor crystallinity are recommended; thus, mesophase-
pitch-based carbon fibers did not give a high surface area, whereas isotro-
pic pitch-based carbon fibers did.
Other advantage of ACFs is the possibility to prepare woven clothes
and nonwoven mats, which developed new applications in small purifica-
tion systems for water treatment and also as a deodorant in refrigerators
in houses, recently reported. In order to give the fibers an antibacterial
function and to increase their deodorant function, some trials on support-
ing minute particles of different metals, such as Ag, Cu and Mn, were per-
formed. Table 5.2 presented comparison between properties of activated
carbon fibers and granular activated carbons [13–46].
110 Applied Research on Polymer Composites

TABLE 5.2â•… Comparison between properties of activated carbon fibers and granular
activated carbons

Activated carbon fibers Granular activated carbons

700–2,500 900–1,200

Surface area 0.2–2.0 ~0.001

mean diameter of pores (nm) <40 from micro- to macropores

5.3â•… MOLECULAR SIEVING CARBONS: PROPERTIES AND

APPLICATION

Molecular sieving carbons (MSCs) have a smaller pore size with a

sharper distribution in the range of micropores in comparison with other
activated carbons for gas and liquid-phase adsorbates. They have been
used for adsorbing and eliminating pollutant samples with a very low con-
centration (ethylene gas adsorption to keep fruits and vegetables fresh,
filtering of hazardous gases in power plants, etc.) An important application
of these MSCs was developed in gas separation systems [1–2].
The adsorption rate of gas molecules, such as nitrogen, oxygen, hy-
drogen, and ethylene, depends strongly on the pore size of the MSC; the
adsorption rate of a gas becomes slower for the MSC with the smaller pore
size. The temperature also governs the rate of adsorption of a gas because
of activated diffusion of adsorbate molecules in micropores: the higher the
temperature, the faster the adsorption [47–49].
By controlling (swinging) these parameters, temperature and pressure
of adsorbate gas, gas separation can be performed. Depending on which
parameter is controlled, swing adsorption method is classified into two
modes: temperature swing adsorption (TSA) and pressure swing adsorp-
tion (PSA). Adsorption of oxygen into the MSC completes within 5 min,
but nitrogen is adsorbed very slowly, less than 10 per cent of equilibrium
adsorption even after 15 min. From the column of MSC, therefore, nitro-
gen rich gas comes out on the adsorption process, and oxygen-rich gas is
obtained on the desorption process. By using more than two columns of
MSC and repeating these adsorption/desorption processes, nitrogen gas is
isolated from oxygen. This swing adsorption method for gas separation
has advantages such as low-energy cost, room temperature operation, and
compact equipment [50–53].
Trends in Activated Carbon Fibers 111

5.4â•… IMPORTANCE OF CONTROLLING OF PORE SIZE IN

POROUS CARBON MATERIALS AND SUPERCAPACITORS

The main objective of this chapter is to provide a brief review of the pore-
size control that is an important factor, influencing application of activated
carbon or carbon nanostructures adsorption in drinking water treatment
or other adsorbent application. Different pore sizes in carbon materials
are required for their applications. Therefore, the PSD in carbon materials
has to be controlled during their preparation, by selecting the precursor,
process, and condition of carbonization, and also those of activation. A
wide-range broad distribution in pore size and shape is usually obtained in
carbon materials. The control of pore size in carbons is essential to com-
pete in adsorption performance with porous inorganic materials such as
silica gels and zeolites, and to use the advantages of carbon materials such
as high chemical stability, high temperature resistance, and low weight.
For applications in modern technology fields, not only high surface
area and large pore volume, but also a sharp pore-size distribution at a def-
inite size and control of surface nature of pore walls are strongly required.
In order to control the pore structure in carbon materials, studies on the
selection of precursors and preparation conditions have been extensively
carried out and certain successes have been achieved [1–3]. Pore sizes and
their distributions in adsorbents have to comply with requirements from
different applications. Thus, relatively small pores are needed for gas ad-
sorption and relatively large pores for liquid adsorption, and a very narrow
PSD is required for molecular sieving applications. Macropores in carbon
materials were found to be effective for sorption of viscous heavy oils.
Recent novel techniques to control pore structure in carbon materials can
be expected to contribute to overcome this limitation [41–46].
One of newest applications that shows importance of pore structure
control in carbon materials is an electric double-layer capacitor (EDLC)
or supercapacitor that is an energy storage device that utilizes the EDL
formed at the interface between an electrode and the electrolyte. EDLCs
are well documented to exhibit significantly higher specific powers and
longer cycle lifetimes compared with those of most of rechargeable bat-
teries, including lead acid, Ni-MH, and Li-ion batteries. Hence, EDLCs
have attracted considerable interest, given the ever increasing demands
of electric vehicles, portable electronic devices, and power sources for
memory backup.
112 Applied Research on Polymer Composites

The capacitance of an EDLC depends on the surface area of the elec-

trode materials. Therefore, activated carbons are necessary materials for
EDLC electrodes because of their large surface area, highly porous struc-
ture, good adsorption properties, and high electrical conductivity. The
electrochemical performance of EDLCs is related to the surface area, the
pore structure, and the surface chemistry of the porous carbon. Various
types of porous carbon have been widely studied for use as electrode ma-
terials for EDLCs.
Their unusual structural and electronic properties make the carbon
nanostructures applicable in, inter alia, the electrode materials of EDLCs
and batteries. Activated carbon nanofibers are expected to be more useful
than spherical activated carbon in allowing the relationship between pore
structure and electrochemical properties to be investigated to prepare the
polarizable electrodes for experimental EDLCs, EDLCs are well docu-
mented to exhibit significantly higher specific powers and longer cycle
lifetimes compared with those of most of rechargeable batteries, including
lead acid, Ni-MH, and Li-ion batteries [20–34–45].
Hence, EDLCs have attracted considerable interest, given the ever
increasing demands of electric vehicles, portable electronic devices, and
power sources for memory backup. The capacitance of an EDLC depends
on the surface area of the electrode materials. Therefore, activated carbons
are necessary materials for EDLC electrodes because of their large surface
area, highly porous structure, good adsorption properties, and high electri-
cal conductivity. The electrochemical performance of EDLCs is related to
the surface area, the pore structure, and the surface chemistry of the porous
carbon.
Various types of porous carbon have been widely studied for use as
electrode materials for EDLCs. Their unusual structural and electronic
properties make the carbon nanostructures applicable in the electrode ma-
terials of EDLCs and batteries. The principle of electrochemical capaci-
tors, physical adsorption/desorption of electrolyte ions in solution, was ap-
plied for water purification by using different carbon materials [108–113].
This work is concerned with such pore control methods proposed by
researchers that their ultimate goal is to establish a method with tailoring
carbon material pore structures to reach any kind of application. Research-
ers would like to much effort that have made to control micro and meso-
pores in carbon materials, and prepare them in achieving the stnal goal.
The presence of mesopores in electrodes based on CNTs, due to the central
Trends in Activated Carbon Fibers 113

canal and entanglement enables easy access of ions from electrolyte. For
electrodes built from multiwalled carbon nanotubes (MWCNTs), specific
capacitance in a range of 4–135 F/g was found. For single-walled carbon
nanotubes (SWCNTs), a maximum specific capacitance of 180 F/g is re-
ported. A comparative investigation of the specific capacitance achieved
with CNTs and activated carbon material reveals the fact activated carbon
material exhibited significantly higher capacitance. Supercapacitor CNTs-
based electrodes were fabricated by direct synthesis of nanotubes on the
bulk Ni substrates, by means of plasma enhanced chemical vapor deposi-
tion of methane and hydrogen. The specific capacitance of electrodes with
such nanotubes was of 49 F/g. MWCNTs were electrochemically oxidized
and their performance in EDLCs was studied [45–64–68].

5.5â•… CARBON NANOTUBE: PROPERTIES AND APPLICATION

An article by Iijima that showed that carbon nanotubes are formed during
arc-discharge synthesis of C60, and other fullerenes also triggered an out-
burst of the interest in carbon nanofibers and nanotubes. These nanotubes
may be even single-walled, whereas low-temperature, catalytically grown
tubes are multiwalled. It has been realized that the fullerene-type mate-
rials and the carbon nanofibers known from catalysis are relatives, and
this broadens the scope of knowledge and of applications. This chapter
describes the issues around application and production of carbon nano-
structures. Electrospinning is a simple and versatile method for generat-
ing ultrathin fibers from a rich variety of materials that include polymers,
nanocomposites, and ceramics. In a typical process, an electrical potential
is applied between a droplet of a polymer solution, or melt, held at the end
of a capillary tube and a grounded target. When the applied electric field
overcomes the surface tension of the droplet, a charged jet of polymer
solution is ejected.
The following parameters and processing variables affect the electros-
pinning process: (i) system parameters such as molecular weight, molecu-
lar weight distribution and architecture (branched, linear, etc.) of the poly-
mer, and polymer solution properties (viscosity, conductivity, dielectric
constant, and surface tension, charge carried by the spinning jet) and (ii)
process parameters such as electric potential, flow rate and concentration,
distance between the capillary and collection screen, ambient parameters
114 Applied Research on Polymer Composites

(temperature, humidity and air velocity in the chamber) and finally mo-
tion of the target screen. Morphological changes can occur upon decreas-
ing the distance between the syringe needle and the substrate. Increasing
the distance or decreasing the electrical field decreases the bead density,
regardless of the concentration of the polymer in the solution. Elemental
carbon in the sp2 hybridization can form a variety of amazing structures.
The nanotubes consisted of up to several tens of graphitic shells (so-
alled multi-walled carbon nanotubes (MWNTs)) with adjacent shell sepa-
ration of ∼0.34 nm, diameters of ∼1 nm and high length/diameter ratio.
Two years later, Iijima and Ichihashi synthesized single-walled carbon
nanotubes (SWNTs). There are two main types of carbon nanotubes that
can have high structural perfection. SWNT consist of a single graphite
sheet seamlessly wrapped into a cylindrical tube. WNTs comprise an array
of such nanotubes that are concentrically nested like rings of a tree trunk
[54–57].
Recent discoveries of fullerene, a zero-dimensional form of carbon
and carbon nanotube, which is a one-dimensional form, have stimulated
great interest in carbon materials overall. Fullerenes are geometric cage-
like structures of carbon atoms that are composed of hexagonal and pen-
tagonal faces. When a bucky ball is elongated to form a long and narrow
tube of few nanometers diameter approximately, which is the basic form
of carbon nanotube. This stimulated a frenzy of activities in properties
measurements of doped fullerenes. The discovery of fullerenes led to the
discovery of carbon nanotubes by Iijima in 1991. The discovery of carbon
nanotubes created much excitement and stimulated extensive research into
the properties of nanometer scale cylindrical carbon networks.
Many researchers have reported mechanical properties of carbon nano-
tubes that exceed those of any previously existing materials. Although
there are varying reports in the literature on the exact properties of car-
bon nanotubes, theoretical and experimental results have shown extremely
high modulus, greater than 1 TPa (the elastic modulus of diamond is 1.2
TPa) and reported strengths 10–100 times higher than the strongest steel at
a fraction of the weight. Indeed, if the reported mechanical properties are
accurate, carbon nanotubes may result in an entire new class of advanced
materials [58–62].
In addition to the exceptional mechanical properties associated with
carbon nanotubes, they also possess superior thermal and electric proper-
ties such as thermally stable up to 2,800°C in vacuum, thermal conduc-
Trends in Activated Carbon Fibers 115

tivity about twice as high as diamond, electric current carrying capacity

1,000 times higher than copper wires. These exceptional properties of car-
bon nanotubes have been investigated for devices such as field emission
displays, scanning probe microscopy tips, and microelectronic devices.
Carbon nanotubes present significant opportunities to basic science and
nanotechnology, and pose significant challenge for future work in this
field. The approach of direct growth of nanowires into ordered structures
on surfaces is a promising route to approach nanoscale problem and create
novel molecular scale devices with advanced electrical, electromechanical
and chemical functions [54].

5.5.1â•… CNT COMPOSITE-BASED ADSORBENTS

Potential practical applications of CNTs such as chemical sensors, field

emission, electronic devices, high sensitivity nanobalance for nanoscopic
particles, nanotweezers, reinforcements in high-performance composites,
biomedical and chemical investigations, anode for lithium-ion batteries,
supercapacitors, and hydrogen storage have been reported. Even though
the challenges in fabrication may prohibit realization of many of these
practical device applications, the fact that the properties of CNTs can be
altered by suitable surface modifications can be exploited for more im-
minent realization of practical devices. In this respect, a combination of
CNTs and other nanomaterials, such as nanocrystalline metal oxide/CNTs,
polymer/CNTs and metal filled CNTs may have unique properties and re-
search have therefore been focused on the processing of these CNT-based
nanocomposites and their different applications [54–57].
Adsorption of single metal ions, dyes and organic pollutants on CNT-
based adsorbent composites is one of the most important applications of
these materials. MWCNT/iron oxide magnetic composites were prepared
and used for adsorptions of several metal ions. The CNTs were purified by
using nitric acid which results in modification of the surface of the nano-
tubes with oxygen containing groups like carbonyl and hydroxyl groups.
The adsorption capability of the composite is higher than that of nanotubes
and activated carbon. The sorption of ions such as Pb(II) and Cu(II) ions
on the composite were spontaneous and endothermic processes based on
the thermodynamic parameters (ΔH, ΔS, and ΔG) calculated from tem-
perature dependent sorption isotherms. Alumina-coated MWCNTs were
116 Applied Research on Polymer Composites

synthesized and reported for its utilization as adsorbent for the removal
of lead ions from aqueous solutions in two modes. With an increase in
influent pH between 3 and 7, the percentage of lead removed increases.
The adsorption capacity increases by increasing agitation speed, contact
time and adsorbent dosage. The reported composite can be regenerated as
it was confirmed by SEM and EDX analysis [58–60].
CNTs can be combined with various metal oxides for the degradation
of some organic pollutants too. Carbon nanotubes/metal oxide (CNT/MO)
composites can be prepared by various methods such as wet chemical, sol
gel, physical and mechanical methods. To form nanocomposite, CNTs can
be combined with various metal oxides like Ti2O3, ZnO, WO3, Fe2O3, and
Al2O3. The produced nanocomposite can be used for the removal of various
pollutants. Nanoscale Pd/Fe particles were combined with MWNTs and the
resulted composite was used to remove 2,4-dichlorophenol (2,4-DCP). It was
reported that the MB adsorption was pH-dependent and adsorption kinetics
was best described by the pseudo-second-order model. Iron oxide/CNT com-
posite was reported to be efficient adsorbent for remediation of chlorinated
hydrocarbons. The efficiency of some other nanocomposites such as CNT/
alumina, CNT/titania and CNT/ZnO has also been reported [60–62].
Most important CNT-based as adsorbent composites include: CNT–
chitosan composites, CNT–ACF, CNTs–Fe3O4, CNTs–dolomite, CNTs–
cellulose, and CNTs–graphene. Chitosan (CS) is one of the best adsorbents
for the removal of dyes due to its multiple functional groups, biocompat-
ibility and biodegradability, but its low mechanical strength limits its com-
mercial applications. Impregnation of CS hydrogel beads with CNTs (CS/
CNT beads) resulted in significant improved mechanical strength. In CS/
CNT composite, CNTs and CS are like a symbiosis, CNTs help to improve
the mechanical strength of CS, whereas CS helps reduce the cost of CNTs
for adsorption, while the resulted composite solves the problem of separat-
ing CNTs from aqueous medium. To resolve the aggregation and disper-
sion problem of CNTs, prepared the CNTs/activated carbon fabric (CNTs/
ACF) composite and its application was investigated for the removal of
phenol and basic violet 10 (BV10). CNTs/ACF was prepared via directly
growing nanoscaled CNTs on microscaled carbon matrix. Polyacryloni-
trile was used as a source of carbon. From the results, it was observed that
dye adsorption equilibrium time for CNTs/ACF is shorter as compared to
ACF and monolayer adsorption capacity does not display a linear increase
with increasing the BET surface area.
Trends in Activated Carbon Fibers 117

The decoration of CNTs tends to lower the porosity of the ACF from
1,065 to 565 m2/g. The adsorption of BV10 onto ACF and CNTs/ACF was
162.4 and 220 mg/g, respectively. This finding indicates that the total mi-
croporosity of ACF cannot be fully accessed by the dye molecules. There-
fore, the appearance of CNTs plays a positive role in (i) facilitating the
pore accessibility to adsorbates and (ii) providing more adsorptive sites for
the liquid-phase adsorption. This reflects that CNTs/ACF contains a large
number of mesopore channels, thus preventing the pore blockage from the
diffusion path of micropores for adsorbates to penetrate [72–73].
Incorporation of magnetic property in CNTs is another good technique
to separate CNTs from solution. The magnetic adsorbent can be well dis-
persed in the water and easily separated magnetically. Magnetic-modified
MWCNTs were used for removal of cationic dye crystal violet (CV), thio-
nine (Th), janus green B (JG), and methylene blue (MB). To find the op-
timum adsorption, effect of various parameters including initial pH, dos-
ages of adsorbent and contact time have been investigated. The optimum
adsorption was found to be at pH 7.0 for all dyes. The removal efficiency
of cationic dyes using GG/ MWCNT/Fe3O4 is higher as compared with
other adsorbents such as MWCNTs and MWCNT/Fe3O4.
The magnetic GG/MWCNT/Fe3O4 possesses the high adsorption prop-
erties and magnetic separation and can therefore be used as magnetic
adsorbents to remove the contaminants from aqueous solutions. A novel
magnetic composite bioadsorbent composed of chitosan wrapping mag-
netic nanosized γ-Fe2O3 and MWCNTs (m-CS/γ-Fe2O3/MWCNTs) was
prepared for the removal of methyl orange. The adsorption capacity of
MO onto m-CS/γ-Fe2O3/ MWCNTs was 2.2 times higher than m-CS/γ-
Fe2O3. The adsorption capacity of MO onto m-CS/γ-Fe2O3/MWCNTs was
also higher than MWCNTs. Kinetics data and adsorption isotherm data
were better fitted by pseudo-second-order kinetic model and by Lang-
muir isotherm, respectively. The researchers think CS is responsible for
the exothermic adsorption process because with the increase in the tem-
perature, polymeric network of CS changed/deshaped, which reduced the
porosity of the biosorbent and hindered the diffusion of dye molecules at
high temperature [58–62–72–73].
Recently, a novel adsorbent was developed by inserting MWCNTs
into the cavities of dolomite for scavenging of ethidium the foam line
CNTs/dolomite adsorbent. Foam-like ternary composite PUF/diatomite/
dispersed-MWCNTs, gave the highest capacities for adsorption of these
118 Applied Research on Polymer Composites

dyes, followed by PUF/agglomerated-MWCNTs, and then PUF/dispersed-

MWCNTs. Adsorption isotherm study revealed the monolayer adsorption
at higher concentration and multilayer adsorption at lower concentration.
Pseudo first-order kinetics gives the best fitted results compared to the
pseudo second order.
From the results, it is evident that carboxylic group on the adsorbent
plays the important role for the removal of MB as ionized to COO− at
higher pH and bind with MB through electrostatic force. Self-assembled
cylindrical graphene–MCNT (G–MCNT) hybrid, synthesized by the one
pot hydrothermal process was used as adsorbent for the removal of methy-
lene blue in batch process. G–MCNT hybrid showed good performance
for the removal of MB from aqueous solution. The adsorption capacity
of G–MCNTs is much higher than MCNTs. Therefore, G–CNTs hybrid
could be utilized as an efficient adsorbent for environmental remediation
[72–73].

5.6â•… CARBON NANFIBER: PROPERTIES AND APPLICATION

Carbon nanofibers (diameter range, 3–100 nm) have been known for a
long time as a nuisance that often emerges during catalytic conversion of
carbon-containing gases. The recent outburst of interest in these graphitic
materials originates from their potential for unique applications as well as
their chemical similarity to fullerenes and carbon nanotubes. This chapter
focused on the growth of nanofibers using metallic particles as a catalyst
to precipitate the graphitic carbon. First, it summarized some of the ear-
lier literature that has contributed greatly to understand the nucleation and
growth of carbon nanofibers and nanotubes. Thereafter, it described in
detail recent progress to control the fiber surface structure, texture, and
growth into mechanically strong agglomerates. It is argued that carbon
nanofibers are unique high surface area materials (200 m1/g) that can ex-
pose exclusively either basal graphite planes or edge planes. It is shown
that the graphite surface structure and the lyophilicity play a crucial role
during metal emplacement and catalytic use in liquid phase catalysis.
An article by Iijima showed that carbon nanotubes are formed during
arc-discharge synthesis of C60, and other fullerenes also triggered an out-
burst of the interest in carbon nanofibers and nanotubes. These nanotubes
may be even single walled; whereas, low-temperature, catalytically grown
Trends in Activated Carbon Fibers 119

tubes are multiwalled. It has been realized that the fullerene type materi-
als and the carbon nanofibers known from catalysis are relatives and this
broadens the scope of knowledge and of applications. It has been realized;
however, that arc-discharge and laser-ablation methods lead to mixtures of
carbon materials and thus to a cumbersome purification to obtain nanofi-
bers or nanotubes [88].
From an application viewpoint, some of best application of carbon
nanofibers include carbon nanofibers as catalyst support materials, carbon
nanofiber-based electrochemical biosensors, CNF-based oxidase biosen-
sors, CNF-based immunosensor and cell sensor and hydrogen storage. The
overall economics are affected by the fiber yield, the feedstock used, the
rate of growth, and the reactor technology [88–92].The growth of paral-
lel fibers using iron as the catalyst has been studied in detail by high-
resolution transmission electron microscopy (HR-TEM). It is noted that
the graphite layers grow at an angle iron surface, thus leading to parallel
fibers. The diameter of the fibers can be varied by variation of the met-
al particle size. If we want to vary the fiber diameter for a macroscopic
sample, however, we need a narrow metaI particle-size distribution. In
general, one can say that the fibers do not contain micropores and that
the surface area can range from 10 to 200 m2/g and the mesopore volume
ranges between 0.50 and 2.0 mL/g. Note that these pore-volume data are
obtained within fibers as grown, specific treatments in the liquid phase can
be applied to largely reduce the pore volume and to obtain much denser
and compact fiber structures.
Compared to the large volume of literature on the mechanism of growth,
the studies on the macroscopic, mechanical properties of bodies consisting
of agglomerates of carbon nanofibers have been limited in number give a
useful description of the tertiary structures that can be obtained; that is,
“bird nests,” nepo “net,” and “combedyarn.” In general, porous bodies of
carbon nanofibers are grown from porous supported metal catalyst bodies.
Some others in the size range of micrometer to millimeter. As carbon pre-
cursors, PAN and pitches were frequently used, probably because both of
them are also used in the production of commercial carbon fibers.
In addition, poly (vinyl alcohol) (PVA), polyimides (PIs), polybenz-
imidazol (PBI) poly (vinylidene fluoride) (PVDF), phenolic resin and
lignin were used. In order to convert electrospun polymer nanofibers to
carbon nanofibers, carbonization process at around 1,000°C has to be ap-
plied. In principle, any polymer with a carbon backbone can potentially be
120 Applied Research on Polymer Composites

used as a precursor. For the carbon precursors, such as PAN and pitches,
so-called stabilization process before carbonization is essential to keep
fibrous morphology, of which the fundamental reaction is oxidation to
change resultant carbons difficult to be graphitized at high temperatures
as 2,500°C [89–90].
Carbon is an important support material in heterogeneous catalysis, in
particular for liquid-phase catalysis. A metal support interaction between
Ru and C was suggested as a possible explanation for these very interest-
ing observations. More recent work focuses on the use of platelet type
fibers exposing exclusively graphite edge sites. Using a phosphorus-based
treatment, preferential blocking of so-called armchair faces occurs. Depo-
sition of nickel onto the thus modified CNF enabled one to conclude that
the nickel particles active for hydrogenation of light alkenes reside on the
zigzag faces. More characterization work is needed to substantiate these
interesting claims. Others have carried out, by far, the most extensive
work on CNF as carbon support material. A driving force for exploring
CNF supports was related to the replacement of active carbon as support
for liquid phase catalysis. For the CNF support, no shift of the PSD is ap-
parent, whereas with an activated carbon (AC) support, severe attrition is
apparent.
They compare the PSD after ultrasonic treatment of the CNF and of
the AC support. Clearly, AC displays a much broader PSD with, moreover,
a significant number of fines. Nanocomposite electrodes made of carbon
nanofibers and paraffin wax were characterized and investigated as novel
substrates for metal deposition and stripping processes. Since CNFs have
a much larger functionalized surface area compared to that of CNTs, the
surface active groups to volume ratio of these materials is much larger
than that of the glassy-like surface of CNTs. This property, combined with
the fact that the number and type of functional groups on the outer surface
of CNFs can be well controlled, is expected to allow for the selective im-
mobilization and stabilization of biomolecules such as proteins, enzymes,
and DNA. Also, the high conductivity of CNFs seems to be ideal for the
electrochemical transduction. Therefore, these nanomaterials can be used
as scaffolds for the construction of electrochemical biosensors [64–68].
Compared with conventional ELISA-based immunoassays, immuno-
sensors are of great interest because of their potential utility as specific,
simple, label-free and direct detection techniques and the reduction in size,
cost, and time of analysis. Due to its large functionalized surface area and
Trends in Activated Carbon Fibers 121

high surface active groups-to-volume ratio. Hydrogen storage is an essen-

tial prerequisite for the widespread deployment of fuel cells, particularly
in transport. Huge hydrogen storage capacities, up to 67 percent, were re-
ported. Unfortunately such astonishing values could not confirmed by oth-
er research teams worldwide.. Some reviews provides basics of hydrogen
storage on carbon materials, the types of carbon materials with potential
for hydrogen storage, the measured hydrogen storage capacities of these
materials, and based on calculations, an approximation of the theoretical
achievable hydrogen storage capacity of carbon materials [91–92].

5.7â•… ACTIVATED CARBON NANOTUBE: PROPERTIES AND

APPLICATION

Electrospinning, a simple approach to make very fine fibers ranging from

nano-to-micro scales, is attracting more attention due to the high porosity
and high surface area to volume ratio of electrospun membranes. These
properties contribute to potential applications of electrospun membranes
in carbon and graphitic nanofiber manufacturing, tissue scaffolding, drug
delivery systems, filtration and reinforced nanocomposites. The research-
ers also tried poly (amic acid) as a precursor to make activated carbon
nanofibers. These studies employed physical activation to produce pores
in precursor fibers. Compared with physical activation, the chemical ac-
tivation process has important advantages, including low heat treatment
temperature, short period of processing time, large surface area and high
carbon yield; however, there has been no work reported for chemically
activated carbon nanofibers from electrospun PAN. The effects of elec-
trospinning variables, such as applied voltage, pump flow rate, and dis-
tance between the needle tip and collector, on the resulting nanofiber
diameters were studied. Mechanical properties, such as tensile, tear and
burst strength, of electrospun PAN nonwoven membranes were measured
and the quantitative relationships between membrane thickness and these
properties were established [93–94–95].
Other physical properties, such as air permeability, interfiber pore size
and porosity, were also studied. Activated carbon nanofibers were produced
from electrospun PAN by chemical activation with potassium hydroxide
(KOH) as the activating agent. They were characterized by morphology,
Fourier transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller
122 Applied Research on Polymer Composites

(BET) surface area, total pore volume and pore size distribution. There are
two processes for manufacturing the carbon nanofiber (CNF), namely, the
vapor-grown approach and the polymer spinning approach. The activated
carbon nanofiber (ACNF) is the physically or chemically activated CNF,
which have been, in many investigations, practically applied in electric
double layer capacitors, organic vapor recovery, catalyst support, hydro-
gen storage, and so on. In practice, the physical activation method involves
carbonizing the carbon precursors at high temperatures and then activating
CNF in an oxidizing atmosphere such as carbon dioxide or steam [96–97].
The chemical activation method involves chemically activating agents
such as alkali, alkaline earth metals, some bases such as potassium hy-
droxide (KOH) and sodium hydroxide, zinc chloride, and phosphoric acid
(H3PO4). In essence, most chemical activation on CNF used KOH to get
highly porous structure and higher specific surface area. Unfortunately,
large amount of solvent were needed to prepare the polymer solution
for electrospinning and polymer blend, causing serious environmental
problem thereafter. A series of porous amorphous ACNF were studied.
Utilizing the core/shell microspheres that were made of various polymer
blends with solvent. In their approach, the phenol formaldehyde-derived
CNF were chemically activated by the alkaline hydroxides, and the thus-
prepared ACNF were applied as super-capacitor electrodes and hydrogen
storage materials [98–99–100].
In a continuous effort, some researchers proceed to investigate and
compare the various chemical activation treatments on the CNF thus pre-
pared, with particular emphasis on the qualitative description and quan-
titative estimation on the surface topology by AFM, and their relation to
the microstructure of ACNF. PAN fiber following the spinning process
by several ways such as modification through coating, impregnation with
chemicals (catalytic modification) and drawing/stretching with plasticizer.
The post spinning modifications indirectly affect and ease the stabiliza-
tion in several ways such as reducing the activation energy of cyclization,
decreasing the stabilization exotherm, increasing the speed of cyclization
reaction, and also improving the orientation of molecular chains in the
fibers.
One of the well-known posts spinning treatment for PAN fiber pre-
cursor is modification through coatings. The PAN fibers are coated with
oxidation resistant resins such as lubricant (finishing oil), antistatic agents,
and emulsifiers which are basically used as spin finish on the precursor
Trends in Activated Carbon Fibers 123

fiber. Coating with certain resins also acts in the same manner as the co-
monomer in reducing the cyclization exotherm thus improving the me-
chanical properties of the resulting carbon fibers. Due to their excellent
lubricating properties, silicone based compounds are mostly used as the
coating material for PAN precursor fibers. Tensile load and tear strength
of electrospun PAN membranes increased with thickness, accompanied
with a decrease in air permeability; however, burst strength was not sig-
nificantly influenced by the thickness [101–102–103].
Electrospun PAN nanofiber membranes were stabilized in air and then
activated at 800°C with KOH as the activating agent to make activated
carbon nanofibers. Stabilized PAN membranes showed different breaking
behaviors from those before stabilization. The activation process gener-
ated micropores which contributed to a large surface area of 936.2 m2/g
and a micropore volume of 0.59 cc/g. Pore size distributions of electros-
pun PAN and activated carbon nanofibers were analyzed based on the Du-
binin–Astakhov equation and the generalized Halsey equation. The results
showed that activated carbon nanofibers had many more micropores than
electrospun PAN, increasing their potential applications in adsorption.
Based on a novel solvent-free co-extrusion and melt-spinning of polypro-
pylene/(phenol formaldehyde polyethylene) based core/sheath polymer
blends, a series of activated carbon nanofibers (ACNFs) have been pre-
pared and their morphological and microstructure characteristics analyzed
by scanning electron microscopy, atomic force microscopy (AFM), Ra-
man spectroscopy, and X-ray diffractometry with particular emphasis on
the qualitative and quantitative AFM analysis. Post spinning treatment of
the current commercial PAN fiber based on the author’s knowledge, re-
ports on the post spinning modification process of the current commer-
cial fiber are still lacking in the carbon fiber manufacturers’ product data
sheet, which allows us to assume that the current commercial carbon fibers
still do not take full advantage of any of these treatments yet. During sta-
bilization and carbonization of polymer nanofibers, they showed signifi-
cant weight loss and shrinkage, resulting in the decrease of fiber diameter
[104–107].
From an application viewpoint, Some of best application of carbon
nanofibers include: ACNF as anodes in lithium-ion battery, Organic re-
moval from waste water using, ACNF as cathode catalyst or as anodes for
microbial fuel cells (MFCs), Electrochemical properties of ACNF as an
electrode for supercapacitors, Adsorption of some toxic industrial solu-
tions and air pollutants on ACNF [108–120].
124 Applied Research on Polymer Composites

Activated carbon nanofibers (ACNFs) with large surface areas and

small pores were prepared by electrospinning and subsequent thermal and
chemical treatments. These activated CNFs were examined as anodes for
lithium-ion batteries(UBs) without adding any non-active material. Their
electrochemical behaviors show improved lithium-ion storage capability
and better cyclic stability compared with unactivated counterparts. The de-
velopment of high-performance rechargeable lithium-ion batteries (LIBs)
for efficient energy storage has become one of the components in today’s
information rich mobile society [114].
Microbial fuel cell (MFC) technologies are an emerging approach to
wastewater treatment. MFCs are capable of recovering the potential en-
ergy present in wastewater and converting it directly into electricity. Us-
ing MFCs may help offset wastewater treatment plant operating costs and
make advanced wastewater treatment more affordable for both developing
and industrialized nations. In spite of the promise of MFCs, their use is
limited by low power generation efficiency and high cost. Some research-
ers conclude that the biggest challenge for MFC power output lies in reac-
tor design combining high surface area anodes with low ohmic resistances
and low cathode potential losses. Power density limitations are typically
addressed by the use of better suited anodes, use of mediators, modifica-
tion to solution chemistry or changes to the overall system design. Em-
ploying a suitable anode, however, is critical since it is the site of electron
generation.
An appropriately designed anode is characterized by good conductiv-
ity, high specific surface area, biocompatibility and chemical stability.
Anodes currently in use are often made of carbon and/or graphite. Some
of these anodes include but are not limited to: graphite plates/rods/felt,
carbon fiber/cloth/foam/paper and reticulated vitreous carbon (RVC). Car-
bon paper, cloth and foams are among the most commonly used anodes
and their use in MFCs has been widely reported employ activated carbon
nanofibers (ACNF) as the novel anode material in MFC systems. Com-
pared with other activated carbon materials, the unique features of ACNF
are its mesoporous structure, excellent porous interconnectivity, and high
bioavailable surface area for biofilm growth and electron transfer [115].
Among the diverse carbonaceous adsorbents, activated carbon fiber
(ACF) is considered to be the most promising due to their abundant mi-
cropores, large surface area, and excellent adsorption capacity. Therefore,
the investigation of formaldehyde adsorption has been steadily conducted
Trends in Activated Carbon Fibers 125

using ACFs. However, most of precedent works have generally concerned

about removal of concentrated formaldehyde in aqueous solution (forma-
lin, and thus there was limited information whether these materials could
be used in the practical application, because the concentration of formal-
dehyde in indoor environment was generally very low (below 1 ppm). The
nitrogen containing functional groups in ACF played an important role in
increasing formaldehyde adsorption ability, as also described elsewhere.
However, the PAN-based ACFs still have problems in a practical applica-
tion, because the adsorption capability is drastically reduced under humid
condition [116–120].

5.8â•… PORE FORMATION IN CARBON MATERIALS, PORE

CHARACTERIZATION AND ANALYSIS OF PORES

About pore formation in carbon materials, this is accepted that all carbon
materials, except highly oriented graphite, contain pores, because they are
polycrystalline and result from thermal decomposition of organic precur-
sors. During their pyrolysis and carbonization, a large amount of decom-
position gases is formed over a wide range of temperatures, the profile of
which depends strongly on the precursors. Since the gas evolution behav-
ior from organic precursors is strongly dependent on the heating condi-
tions, such as heating rate, pressure, etc., the pores in carbon materials
are scattered over a wide range of sizes and shapes. These pores may be
classified as shown in Table 5.3 [1–2–3].

TABLE 5.3â•… Classification of pore formation in carbon materials

(1) Based (2) Based on (3) Based on

on their their size their state
origin

Intrapar- Intrinsic intrapar-

ticle pores ticle pores
Extrinsic intra- Micropores < 2 nm Open
particle pores pores
126 Applied Research on Polymer Composites

TABLE 5.3â•… (Continued)

Interpar- Rigid interpar-

ticle pores ticle pores Mesopores 2~50 nm Ultramicro- Closed
Flexible interpar- pores <0.7 pores
ticle pores nm (latent
pores)

Macropores > 50 nm Supermi-

cropores
0.7–2 nm

Table 5.3 shows that based on their origin, the pores can be categorized
into two classes, intraparticle and interparticle pores. The intraparticle
pores are further classified into two, intrinsic and extrinsic intraparticle
pores. The former class owes its origin to the crystal structure, that in most
activated carbons, large amounts of pores of various sizes in the nano-
meter range are formed because of the random orientation of crystallites;
these are rigid interparticle pores.
A classification of pores based on pore sizes was proposed by the Inter-
national Union for Pure and Applied Chemistry (IUPAC). As illustrated in
Table 5.3, pores are usually classified into three classes: macropores (>50
nm), mesopores (2–50 nm) and micropores (<2 nm). Micropores can be
further divided into supermicropores (with a size of 0.7–2 nm) and ultra-
micropores (<0.7 nm in size). Since nanotechnology attracted the attention
of many scientists recently, the pore structure has been required to be con-
trolled closely. When scientists wanted to express that they are controlling
pores in the nanometer scale, some of them preferred to call the smallest
pores nanosized pores, instead of micro/mesopores [1–2].
Pores can also be classified on the basis of their state, either open or
closed. In order to identify the pores by gas adsorption (a method which
has frequently been used for activated carbons), they must be exposed to
the adsorbate gas. If some pores are too small to accept gas molecules
they cannot be recognized as pores by the adsorbate gas molecules. These
pores are called latent pores and include closed pores. Closed pores are not
necessarily in small size. Pores in carbon materials have been identified by
different techniques depending mostly on their sizes. Pores with nanome-
ter sizes, that is, micropores and mesopores, are identified by the analysis
of gas adsorption isotherms, mostly of nitrogen gas at 77 K [41–46].
Trends in Activated Carbon Fibers 127

The basical theories, equipments, measurement practices, analysis pro-

cedures and many results obtained by gas adsorption have been reviewed
in different publications. For macropores, mercury porosimetry has been
frequently applied. Identification of intrinsic pores, the interlayer space
between hexagonal carbon layers in the case of carbon materials, can be
carried out by X-ray diffraction (XRD). Recently, direct observation of
extrinsic pores on the surface of carbon materials has been reported using
microscopy techniques coupled with image processing techniques, name-
ly scanning tunneling microscopy (STM) and atomic force microscopy
(AFM) and transmission electron microscopy (TEM) for micropores and
mesopores, and scanning electron microscopy (SEM) and optical micros-
copy for macropores [1–3].
The most important pore characterization methods include scanning
tunneling microscopy (STM), atomic force microscopy (AFM), transmis-
sion electron microscopy (TEM), gas adsorption, calorimetric methods,
small-angle X-ray scattering (SAXS), small-angle neutron scattering
(SANS), positron annihilation lifetime spectroscopy (PALS), scanning
electron microscopy (SEM), optical microscopy, mercury porosimetry,
and molecular resolution porosimetry. Adsorption from solution using
macromolecules has been applied to macropore analysis, but we still need
more examinations. It is difficult to compare one adsorption isotherm with
another, but determination of the deviation from the linearity using a stan-
dard adsorption isotherm is accurate. The plot constructed with the aid of
standard data is called a comparison plot. The representative comparison
plots are the t and alpha plots [41–42].
The molecular adsorption isotherm on nonporous solids can be well
described by the BET theory. The deviation from the linearity of the t plot
gives information on the sort of pores, the average pore size, the surface
area, and the pore volume. However, the t plot analysis has the limited
applicability to the microporous system due to the absence of explicit
monolayer adsorption. The construction of the alpha plot does not need
the monolayer capacity, so that it is applicable to microporous solids.
The straight line passing the origin guarantees multilayer adsorption,
that is, absence of meso and/or micropores; the deviation leads to valu-
able information on the pore structures. A nonporous solid has a single
line passing the origin, while the line from the origin for the alpha plot of
the mesoporous system bends. The slopes of the straight line through the
origin and the line at the high as region gives the total and mesoporous sur-
128 Applied Research on Polymer Composites

face areas, respectively. The type of the alpha plot suggests the presence of
ultramicropores and/or supermicropores. Detailed analysis results will be
shown for the micropore analysis [43–46].
In the discussion of the mesopore shape, the contact angle, is assumed
to be zero (uniform adsorbed film formation). The lower hysteresis loop
of the same adsorbate encloses at a common relative pressure depending
to the stability of the adsorbed layer regardless of the different adsorbents
due to the so called tensile strength effect. This tensile strength effect is
not sufficiently considered for analysis of mesopore structures. The Kel-
vin equation provides the relationship between the pore radius and the
amount of adsorption at a relative pressure. Many researchers developed a
method for the calculation of the pore size distribution on the basis of the
Kelvin equation with a correction term for the thickness of the multilayer
adsorbed film.
They so called BJH (Barret–Joyer–Halenda) and DH (Dollimore–
Heal) methods have been widely used for such calculations. However, in
other articles, only a simple Fortran program for the DH method is shown.
(This program can be easily used for the analysis of the mesopore size dis-
tribution). The thickness correction is done by the Dollimore–Heal equa-
tion. One can calculate the mesopore size distribution for cylindrical or
slit-shaped mesopores with this program. Therefore, the adsorption branch
provides more reliable results. However, the adsorption branch gives a
wide distribution compared to the desorption branch due to gradual up-
take. Theoretical studies on these points are still done [133].
The pore size distribution from the Kelvin equation should be limited
to mesopores due to the ambiguity of the meniscus in the microporous
region. It is well known that the presence of micropores is essential for the
adsorption of small gas molecules on activated carbons. However, when
the adsorbate is polymer, dye or vitamin, only mesopores allow the ad-
sorption of such giant molecules and can keep even bacteria. The impor-
tance of mesopores has been pointed out not only for the giant molecule
adsorption, but also for the performance of new applications such as elec-
tric double layer capacitors. Thus, the design and control of mesoporosity
is very desirable both for the improvement of performance of activated
carbon and for the development of its new application stelds [1–3].
Important parameters that greatly affect the adsorption performance
of a porous carbonaceous adsorbent are porosity and pore structure. Con-
sequently, the determination of pore size distribution (PSD) of carbon
Trends in Activated Carbon Fibers 129

nanostructures adsorbents is of particular interest. For this purpose, various

methods have been proposed to study the structure of porous adsorbents.
A direct but cumbersome experimental technique for the determination
of PSD is to measure the saturated amount of adsorbed probe molecules
which have different dimensions.
However, there is uncertainty about this method because of network-
ing effects of some adsorbents including activated carbons and carbon
nanostructures. Other experimental techniques that usually implement for
characterizing the pore structure of porous materials are mercury porosim-
etry, X-ray diffraction (XRD) or small angle X-ray scattering (SAXS), and
immersion calorimetry.
A large number of simple and sophisticated models have been pre-
sented to obtain a realistic estimation of PSD of porous adsorbents. Rela-
tively simple but restricted applicable methods such as Barret, Joyner, and
Halenda (BJH), Dollimore and Heal (DH), Mikhail et al., (MP), Horvath
and Kawazoe (HK), Jaroniec and Choma (JC), Wojsz and Rozwadowski
(WR), Kruk–Jaroniec–Sayari (KJS), and Nguyen and Do (ND) were pre-
sented from 1951 to 1999 by various researchers for the prediction of PSD
from the adsorption isotherms [133–139].
For example, the BJH method which is usually recommended for mes-
oporous materials is in error even in large pores with dimension of 20
nm. The main criticism of the MP method, in addition to the uncertainty
regarding the multilayer adsorption mechanism in micropores, is that we
should have a judicious choice of the reference isotherm. HK model was
developed for calculating micropore-size distribution of slit-shaped pore;
however, the HK method suffers from the idealization of the micropore
filling process. Extension of this theory for cylindrical and spherical pores
was made by Saito and Foley and Cheng and Ralph. By applying some
modifications on the HK theory, some improved models for calculating
PSD of porous adsorbents have been presented. Gauden et al. extended the
Nguyen and Do method for the determination of the bimodal PSD of vari-
ous carbonaceous materials from a variety of synthetic and experimental
data. The pore range of applicability of this model besides other limita-
tions of ND method is its main constraint.
In 1985, Bunke and Gelbin determined the PSD of activated carbons
based on liquid chromatography (LC) [133]. Choice of suitable solvent
and pore range of applicability of this method are two main problems
that restrict its general applicability. More sophisticated methods such
130 Applied Research on Polymer Composites

as molecular dynamics (MD), Monte Carlo simulation, grand canonical

Monte Carlo simulations (GCMS), and density functional theory (DFT)
are theoretically capable of describing adsorption in the pore system.
The advantages of these methods are that they can apply on wide range
of pores width. But, they are relatively complicated and provide accu-
rate PSD estimation based on just some adsorbates with specified shapes
[140–145].

5.9â•… RECENTLY STUDY WORKS ABOUT CONTROLLING PORE

SIZE

Summary of some recently reported papers about confirmal modeling of

controlling of pore size in carbon-based nanoadsorbent are presented in
Table 5.4 [8–40–121–145].

TABLE 5.4â•… Summary of recently confirmal models for controlling of pore size in carbon
based nano adsorbents

Applied model and simulation

Carbon material type References
methods

AC, ACF, MSC _ T.k et al., (2000) [8]

Carbon structures _ K.k et al., (1994) [9]

G CMC and DFT (Monte Carlo

Ac j.p.o et al., (1998) [10]
simulations)

N2 and SIMULATION NONE LO-

Carbon structures Ch.L et al., (1993) [11]
CAL THEORY model

Ac G CMC D.C et al., (2005) [12]

ACF H2S adsorption W.F et al., (2005) [13]

C-ZIFs _ T.R.B et al., (2009) [14]

Carbon structures ND and DFT P.k et al., (2003) [15]

Trends in Activated Carbon Fibers 131

TABLE 5.4â•… (Continued)

Applied model and simulation

Carbon material type References
methods

Ru. L.T et al., (2005)

Ac N2 and T-plot
[16]

Ac Montecarlo simulations P.K et al., (2008) [17]

p-carbon NLDFT-BjH method A.p et al., (2007) [18]

C.L.M et al., (1998)

ACF and AAPFs DR equation
[19]

AAC _ M.E. et al., (2001) [20]

ACH structure _ K.g et al., (2000) [21]

ACF _ C.P et al., (2000) [22]

W.M.D et al., (2000)

Ac _
[23]

ACF _ C.P et al., (2001) [24]

AC IAST–freundlich model K.E et al., (2001) [25]

ACF _ Y.L.M et al., (2001) [26]

R.F.P.M et al., (2001)

MSC, AC _
[27]

P-ACS _ J.B-Y et al., (2002) [28]

GCMS and SIE equation—meth-

AC D.C et al., (2002) [29]
ane adsorption

AC _ X.P et al., (2005) [30]

Carbon structures _ O.T et al., (2003) [31]

Carbon structures _ J.Z et al., (2007) [32]

132 Applied Research on Polymer Composites

TABLE 5.4â•… (Continued)

Applied model and simulation

Carbon material type References
methods

Carbide-derived car-
_ J.Ch et al., (2006) [33]
bons

C-xerogels _ C.L et al., (99) [34]

Carbide-derived car-
_ Y.G et al., (2003) [35]
bons CDCs

Carbon black NLDFT E.A.U et al., (2006) [36]

Carbon Structures _ S.H et al., (2003) [37]

Monte carlo simulation nadsorp- M P.M et al., (2006)

Glassy Carbon
tion [38]

Carbon Structures DFT–Ar adsorption at 77 K R.J.D et al., (2000) [39]

N2 adsorption-and DR equation– N. R K et al., (2000)

AC
BjH [40]

N2 adsorption at 77 K J.B.Y et al., (2002)

P-Asc
–BjH method [121]

DRS equation- C.L.M et al., (2000)

Acf
N2 adsorption at 150 C [122]

G.G-Z et al., (2009)

AC DFT–N2 adsorption at 77 K [123]

AC DS-HK-IHK A.O et al., (2012) [124]

CNT composite Molecular dynamics simulation Zhijun et al., [125]

(MDS)–PMF (2009)

CNT/SIO2 MDS-AIREBO Ong et al., [126] (2010)

CNT MDS–PEOE algorithm-PME Liu et al., [127] (2009)

Trends in Activated Carbon Fibers 133

TABLE 5.4â•… (Continued)

Applied model and simulation

Carbon material type References
methods

CNT/PE composite MDS–Brenner–Newtonian equation Zhang et al., [128] (2011)

SW/CNT MDS–quantum potential–GCMC Irle et al., [129] (2009)

SW/CNT MDS–CPMD–DFT Zang et al., [130] (2009)

CNT/Polymer MDS–SHAKE algorithm–DL– Frankland et al., [131]

Poly (2002)

SW/CNT M D S – G C M C – L J – L O R E N T S Frankland et al., [132]

BERTHELOT (2002)

CNT/polymer compos- MDS–NPT Han et al., [133] (2007)

ite

2D graphene ADS–DFT–APMD–PAW Lehtinen et al., [134]

(2010)

SW/CNT MDS–Brenner Shigeo.M., [135] (2003)

CNT ropes GCMC Williams et al., [136]

(2000)

CNT/sodium MDS Diao et al., [137] (2008)

CNT Abintio, K. Sh-Hamil Noel.[138] (2010)

CNT MDS–USHER algorithm–LJ po- D.Nicholls et al., [139]

tential (2012)

Nanotube MDS–PES–Verlet algorithm A.Ribos et al., [140]

(2009)

CNF MDS–GRASP–RFF F.Sanz.N et al., [141]

(2010)

SW/CNT MDS–DFT–B3LYP Shibuta et al., [142]

(2003)

CNT MDS–LJ potential Mao et al., [143] (1999)

Metal membranes EMD–GCMC–LJ potential Mao et al., [144] (2010)

CNT MDS-LJ–TIP5P A.T et al. [145] (2009)

134 Applied Research on Polymer Composites

The recently research works about controlling of pore structure in car-

bon materials that categorized as fallowing include: First, using the grand
canonical Monte Carlo (GCMC) method, or other simulation methods to
determine adsorption isotherms in Ar (87 K) or N2 (77k) that are simu-
lated for all the carbon sample structures to reach optimum condition in
experimental works. Second, experimental works to obtained PSD curves
that show samples structures maybe micro or mesoporous (with different
ratio of micro/mesopores). Finally PSD curves are calculated using the
Horvath–Kawazoe (HK), density functional theory (DFT), D-R method,
Barrett–Joyner–Halenda (BJH) approaches and other mathematical meth-
ods and this model results with those predicted by the experimental work
results compared and adapted, to prove selected mathematical model is
significant and simulation that applied is verified [121–145].

KEYWORDS

•â•¢ Activated carbon fibers

•â•¢ Activated carbon tailoring
•â•¢ Carbon nanostructure-based adsorbent
•â•¢ Controlling of pore size
•â•¢ Modeling methods
•â•¢ Pore-size distribution

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CHAPTER 6

REINFORCEMENT OF POLYMER
NANOCOMPOSITES: VARIETY
OF STRUCTURAL FORMS AND
APPLICATIONS
G. V. KOZLOV, YU. G. YANOVSKII, and G. E. ZAIKOV

CONTENTS

6.1â•…Introduction................................................................................... 144
6.2â•…Experimental................................................................................. 146
6.3â•… Results and Discussion................................................................. 147
6.4â•…Conclusions................................................................................... 172
Keywords............................................................................................... 172
References.............................................................................................. 173
144 Applied Research on Polymer Composites

6.1â•…INTRODUCTION

The experimental analysis of particulate-filled nanocomposites butadi-

ene—styrene rubber/fullerene-containing mineral (nanoshungite) was ful-
filled with the aid of force-atomic microscopy, nanoindentation methods,
and computer treatment. The theoretical analysis was carried out within the
frameworks of fractal analysis. It has been shown that interfacial regions
in the aforementioned nanocomposites are the same reinforcing element
as nanofiller. The conditions of the transition from nano to microsystems
were discussed. The fractal analysis of nanoshungite particles aggregation
in polymer matrix was performed. It has been shown that reinforcement of
the studied nanocomposites is a true nanoeffect.
The modern methods of experimental and theoretical analysis of poly-
mer materials structure and properties allow not only to confirm earlier
propounded hypotheses, but also to obtain principally new results. Let us
consider some important problems of particulate-filled polymer nanocom-
posites, the solution of which allows to advance substantially in these ma-
terials’ properties understanding and prediction.
Polymer nanocomposites multicomponentness (multiphaseness) re-
quires their structural components to be quantitative characteristics deter-
mination. In this aspect, interfacial regions play a particular role, as it has
been shown earlier, that they are the same reinforcing element in elasto-
meric nanocomposites as nanofiller actually [1]. Therefore, the knowledge
of interfacial layer dimensional characteristics is necessary for quantita-
tive determination of one of the most important parameters of polymer
composites, in general,—their reinforcement degree [2, 3].
The aggregation of the initial nanofiller powder particles in small or
large particle aggregates always occurs in the course of technological pro-
cess of making particulate-filled polymer composites in general [4] and
elastomeric nanocomposites in particular [5]. The aggregation process
explains composites (nanocomposites) macroscopic properties [2–4]. For
nanocomposites, nanofiller aggregation process gains special significance,
as its intensity can be the one, that nanofiller particle aggregates size
exceed 100 nm of—the value, which is assumed (though conditionally
enough [6]) as an upper dimensional limit for nanoparticle.
In other words, the aggregation process can result to the situation when
primordially supposed nanocomposite ceases to be one. Therefore, at pres-
ent several methods exist, which allow to suppress nanoparticles aggrega-
Reinforcement of Polymer Nanocomposites 145

tion process [5, 7]. This also assumes the necessity of the nanoparticles
aggregation process as quantitative analysis. It is well-known [1, 2], that
in particulate-filled elastomeric nanocomposites (rubbers) nanofiller parti-
cles form linear spatial structures (“chains”). At the same time in polymer
composites, filled with disperse microparticles (microcomposites), parti-
cles (aggregates of particles) of filler form a fractal network, which defines
polymer matrix structure (analog of fractal lattice in computer simulation)
[4]. This results to different mechanisms of polymer matrix structure for-
mation in micro- and nanocomposites. If, in the first filler particles (aggre-
gates of particles), fractal network availability results to “disturbance” of
polymer matrix structure, which is expressed in the increase of its fractal
dimension df [4], then in case of polymer nanocomposites at nanofiller
contents change, the value df is not changed and equal to matrix polymer
structure fractal dimension [3]. As it has been expected, the change of the
composites of the indicated classes structure formation mechanism defines
their properties, in particular, reinforcement degree [9, 11, 12]. Therefore
nanofiller structure fractality strict proof and its dimension determination
are necessary.
As it is known [13, 14], the scale effects are often found at the study
of different materials mechanical properties. The dependence of failure
stress on grain size for metals (Holl-Petsch formula) [15] or of effective
filling degree on filler particles size in case of polymer composites [16] are
examples of such effect. The strong dependence of elasticity modulus on
nanofiller particles diameter is observed for particulate-filled elastomeric
nanocomposites [5]. Therefore, it is necessary to elucidate the physical
grounds of nano- and micromechanical behavior scale effect for polymer
nanocomposites.
At present a disperse material wide list is known, which is able to
strengthen elastomeric polymer materials [5]. These materials are very di-
verse on their surface chemical constitution, but the small size of particles
is a common feature for them. Based on the observation the hypothesis
was offered that any solid material would strengthen the rubber at the con-
dition, which it was in a very-dispersed state and could be dispersed in
polymer matrix. Edwards [5] points out that filler particles small size is
necessary and, probably, the main requirement for reinforcement effect
realization in rubbers. Using modern terminology, the nanofiller particles,
for which their aggregation process is suppressed as far as possible, would
be the most effective ones for rubbers reinforcement [3, 12]. Therefore,
146 Applied Research on Polymer Composites

the theoretical analysis of a nanofiller particles’ size influence on polymer

nanocomposites reinforcement is necessary.
Based on the aforementioned discussion, the purpose of this work is to
provide the solution of the aforementioned paramount problems with the
help of modern experimental and theoretical techniques on the example of
particulate-filled butadiene—styrene rubber.

6.2â•…EXPERIMENTAL

The industrially made butadiene—styrene rubber of mark SKS-30, which

contains 7.0–12.3 per cent cis and 71.8–72.0 per cent trans-bonds, with
density of 920–930 kg/m3 was used as matrix polymer. This rubber is fully
amorphous one. Fullerene-containing mineral shungite of Zazhoginsk’s
deposit consists of ~30 per cent globular amorphous metastable carbon
and ~70 per cent high-disperse silicate particles. Besides, industrially
made technical carbon of mark no 220 was used as nanofiller.
The average size of technical carbon, nano, and microshugite particles
makes up 20, 40, and 200 nm, respectively. The indicated filler content is
equal to 37 mass per cent. Nano and microdimensional disperse shungite
particles were prepared from industrially output material by the original
technology processing. The size and polydispersity analysis of the re-
ceived in milling process shungite particles was monitored with the aid
of analytical disk centrifuge (CPS Instruments, Inc., USA), allowing to
determine with high precision size and distribution by the sizes within the
range from 2 nm to 50€mcm.
Nanostructure was studied on atomic-forced microscopes Nano-DST
(Pacific Nanotechnology, USA) and Easy Scan DFM (Nanosurf, Swit-
zerland) by semi-contact method in the force modulation regime. Atom-
ic-force microscopy results were processed with the help of specialized
software package scanning probe image processor (SPIP). The SPIP is
a powerful program package for processing images, obtained on SPM,
AFM, STM, scanning electron microscopes, transmission electron mi-
croscopes, interferometers, confocal microscopes, profilometers, optical
microscopes, and so on. The given package possesses the whole function
number, which is necessary at images precise analysis, in a number of
which the following ones are included:
Reinforcement of Polymer Nanocomposites 147

- the possibility of three-dimensional reflecting objects obtaining,

distortions automatized leveling, including Z-error mistakes re-
moval for examination of separate elements, and so on;
- quantitative analysis of particles or grains, >40 parameters can be
calculated for each found particle or pore: area, perimeter, mean
diameter, the ratio of linear sizes of grain width to its height dis-
tance between grains, coordinates of grain center of mass can be
presented in a diagram form or in a histogram form.
The tests on elastomeric nanocomposites nanomechanical properties
were carried out by a nanointentation method [17] on apparatus Nano Test
600 (Micro Materials, Great Britain) in loades wide range from 0.01 mN
to 2.0 mN. Sample indentation was conducted in 10 points with interval of
30 mcm. The load was increased with constant rate up to the greatest given
load reaching (for the rate 0.05 mN/s−1 mN). The indentation rate was
changed in conformity with the greatest load value counting, that loading
cycle should take 20 s.
The unloading was conducted with the same rate as loading. In the
given experiment the “Berkovich indentor” was used with the angle at
the top of 65.3° and rounding radius of 200 nm. Indentations were carried
out in the checked load regime with preload of 0.001 mN. For elasticity
modulus calculation the obtained result in the experiment by nanoindenta-
tion course dependences of load on indentation depth (strain) in 10 points
for each sample at loads of 0.01, 0.02, 0.03, 0.05, 0.10, 0.50, 1.0, and 2.0
mN were processed according to Oliver-Pharr method [18].

6.3â•… RESULTS AND DISCUSSION

In Figure 6.1, the obtained data according to the original methodics results
of elasticity moduli calculation for nanocomposite butadiene—styrene
rubber/nanoshungite components (matrix, nanofiller particle, and inter-
facial layers), received in interpolation process of nanoindentation data,
are presented. The processed in SPIP polymer nanocomposite image with
shungite nanoparticles allows experimental determination of interfacial
layer thickness lif, which is presented in Figure 6.1 as steps on elastomeric
matrix-nanofiller boundary.
The measurements of 34 such steps’ (interfacial layers) width on the
processed SPIP images of interfacial layer’s various section gave the mean
148 Applied Research on Polymer Composites

experimental value lif = 8.7 nm. Besides, nanoindentation results (Figure

6.1, figures on the right) showed that interfacial layers elasticity modu-
lus was only 23–45 per cent lower than nanofiller elasticity modulus, but
higher than the corresponding parameter of polymer matrix in 6.0–8.5
times. These experimental data confirm that for the studied nanocompos-
ite interfacial layer is a reinforcing element to the same extent as nanofiller
actually [1, 3, 12].

(Strain 150 nm).

FIGURE 6.1â•… The processed SPIP image of nanocomposite butadiene—styrene rubber/
nanoshungite, obtained by force modulation method, and mechanical characteristics of
structural components.
Source: According to the Data of Nanoindentation (Strain 150 nm).

Let us fulfill the value lif theoretical estimation according to the two
methods and compare these results with the ones obtained experimentally.
The first method simulates interfacial layer in polymer composites as a
result of interaction of two fractals—polymer matrix and nanofiller sur-
face [19, 20]. In this case, there is a sole linear scale l, which defines these
fractals interpenetration distance [21]. As nanofiller elasticity modulus is
essentially higher than the corresponding parameter for rubber (in the con-
sidered case—in 11 times, see Figure 6.1), then the indicated interaction
Reinforcement of Polymer Nanocomposites 149

reduces to nanofiller indentation in polymer matrix and then l = lif. In this

case, it can be written as in what follows [21]:
2 ( d - dsurf ) / d
 Rp 
l if ≈ a   , (6.1)
 a 
where a is a lower linear scale of fractal behavior, which is accepted for
polymers as equal to statistical segment length lst [22], Rp is a nanofiller
particle (more precisely, particle aggregates) radius, which for nanoshun-
gite is equal to ~84 nm [23], d is dimension of Euclidean space, in which
fractal is considered (here d = 3), dsurf is fractal dimension of nanofiller
particle aggregate surface.
The value lst is determined as follows [24]:

lst = l0C∞ , (6.2)

where l0 is the main chain skeletal bond length, which is equal to 0.154
nm for both blocks of butadiene—styrene rubber [25], C¥ is characteristic
ratio, which is a polymer chain statistical flexibility indicator [26], and is
determined with the help of Eq. (6.3) [22]:
1/ 2
 S  , (6.3)
Tg = 129 
 C∞ 
where Tg is glass transition temperature, equal to 217 K for butadiene—
styrene rubber [3], S is macromolecule cross-sectional area, determined
for the mentioned rubber according to the additivity rule from the fol-
lowing considerations. As it is known [27], the macromolecule diameter
quadrate values are equal for polybutadiene −20.7 Å2 and for polystyrene
−69.8 Å2. Having calculated cross-sectional area of macromolecule, simu-
lated as a cylinder, for the indicated polymers according to the known
geometrical formulas, let us obtain 16.2 and 54.8 Å2, respectively. Further,
accepting S as the average value of the adduced above areas, let us obtain
for butadiene—styrene rubber S = 35.5 Å2. Then, according to Eq. (6.3) at
the indicated values Tg and S let us obtain C¥ = 12.5 and according to Eq.
(6.2)—lst = 1.932 nm.
The fractal dimension of nanofiller surface dsurf was determined with
the help of the equation [3]:

Su = 410 R pdsurf - d , (6.4)

150 Applied Research on Polymer Composites

where Su is nanoshungite particles specific surface, calculated as in what

follows [28]:

3
Su =
rn R p , (6.5)

where rn is the nanofiller particle aggregate density, determined according

to the formula [3]:

rn = 0.188 R p ( ) 1/3 . (6.6)

The calculation according to Eqs. (6.4)–( 6.6) gives dsurf = 2.44. Further,
based on the calculation by the indicated mode parameters, let us obtain

the theoretical value of interfacial layer thickness lifT = 7.8 nm, from Eq.
(6.1). This value is close enough to the obtained one experimentally (their
discrepancy makes up ~10%).
The second method of value l ifT estimation consists of the two follow-
ing equations [3, 29]:

fif = f n ( d surf - 2)
(6.7)

and

 R + l T  3 
fif = fn  p if
- 1
 R p   , (6.8)
 
where jif and jn are relative volume fractions of interfacial regions and
nanofiller, accordingly.
The combination of the indicated equations allows to receive the fol-
lowing formula for lifT calculation:

liTf = R p ( d surf - 1)
1/3
- 1
. (6.9)
 

The calculation according to Eq. (6.9) gives lifT = 10.8 nm for the consid-
ered nanocomposite, which also corresponds well enough to the experi-
ment (in this case discrepancy between lif and lifT makes up ~19%).
Reinforcement of Polymer Nanocomposites 151

In conclusion, let us note the important experimental observation,

which follows from the processed data by program SPIP results of the
studied nanocomposite surface scan (Figure 6.1). As one can see, at one
nanoshungite particle surface from one to three (in average—two) steps
can be observed, structurally identified as interfacial layers. It is signifi-
cant that these steps width (or lif) is approximately equal to the first (the
closest to nanoparticle surface) step width. Therefore, the indicated obser-
vation supposes that in elastomeric nanocomposites an average of two in-
terfacial layers are formed: the first is at the expense of nanofiller particle
surface with elastomeric matrix interaction, as a result of which molecular
mobility in this layer is frozen and its state is glassy-like one, and the sec-
ond—at the expense of glassy interfacial layer with elastomeric polymer
matrix interaction. The most important question from the practical point of
view is whether one interfacial layer or both serve as nanocomposite rein-
forcing element. Let us fulfill the following quantitative estimation for this
question. The reinforcement degree (En/Em) of polymer nanocomposites is
given by the equation in what follows [3]:

En
= 1 + 11(f n + fif ) ,
1.7
(6.10)
Em

where En and Em are elasticity moduli of nanocomposite and matrix poly-

mer, respectively (Em = 1.82 MPa [3]).
According to Eq. (6.7) the sum (jn + jif) is equal to:

fn + fif = fn ( dsurf - 1) , (6.11)

if one interfacial layer (the closest to nanoshungite surface) is a reinforc-

ing element and

fn + 2f if = fn ( 2dsurf - 3) , (6.12)

if both interfacial layers are reinforcing elements.

The value jn is determined according to the equation in what follows
[30]:

Wn
fn =
rn , (6.13)

where Wn is nanofiller mass content, rn is its density, determined accord-

ing to Eq. (6.6).
152 Applied Research on Polymer Composites

The calculation according to Eqs. (6.11) and (6.12) gave the following
En/Em values: 4.60 and 6.65, respectively. Since the experimental value
En/Em = 6.10 is closer to the value, calculated according to Eq. (6.12),
then both interfacial layers are the reinforcing elements for the studied
nanocomposites. Therefore, the coefficient 2 should be introduced in the
equations for value lif determination (e.g. in Eq. (6.1)) in case of nanocom-
posites with elastomeric matrix. Let us consider that Eq. (6.1) in its initial
form was obtained as a relationship with proportionality sign, i.e., without
fixed proportionality coefficient [21].
Thus, the aforementioned used nanoscopic methodics allow estimating
both interfacial layer and structural special features in polymer nanocom-
posites and its sizes and properties. For the first time it has been shown that
two consecutive interfacial layers are formed in elastomeric particulate-
filled nanocomposites, which are reinforcing elements for the indicated
nanocomposites. The proposed theoretical methodics of interfacial layer
thickness estimation, elaborated within the frameworks of fractal analysis,
give well enough correspondence to the experiment.
For theoretical treatment of nanofiller particle aggregate growth pro-
cesses, and final sizes, traditional irreversible aggregation models are in-
applicable, because it is obvious that in nanocomposite aggregates a large
number of simultaneous growth takes place. Therefore, the model of mul-
tiple growth, offered in Ref. [6], was used for nanofiller aggregation de-
scription.
In Figure 6.2, the images of the studied nanocomposites, obtained in
the force modulation regime, and corresponding nanoparticle aggregates
fractal dimension df distributions are adduced. As it follows from the ad-
duced values d fag (d fag = 2.40–2.48), nanofiller particle aggregates in the
studied nanocomposites are formed by a mechanism particle-cluster (P–
Cl), i.e., they are Witten—Sander clusters [32]. The variant A, was chosen
which according to mobile particles are added to the lattice, consisting of
a large number of “seeds” with density of c0 at beginning of simulation
. Such model generates the structures, which have fractal geometry on
short length scales with value df ≈ 2.5 (see Figure 6.2) and homogeneous
structure on large length scales. A relatively high particle concentration c
is required in the model for uninterrupted network formation [31].
Reinforcement of Polymer Nanocomposites 153

FIGURE 6.2â•… The images, obtained in the force modulation regime, for nanocomposites,
filled with technical carbon (a) nanoshungite, (b) microshungite, and (c) corresponding to
them fractal dimensions d fag .
154 Applied Research on Polymer Composites

In case of “seeds” high concentration c0 for the variant A, the following

relationship was obtained [31]:

= N = c / c0 , (6.14)
ag
df
Rmax

where Rmax is nanoparticles’ cluster (aggregate) greatest radius, N is

nanoparticles’ number per one aggregate, c is nanoparticles’ concentra-
tion, c0 is “seeds” number, which is equal to nanoparticles’ clusters (ag-
gregates) number.
The value N can be estimated according to the equation in what follows
[8]:
1/ 2
S N , (6.15)
2 Rmax =  n 
 πh 
where Sn is cross-sectional area of nanoparticles, of which an aggregate
consists, h is a packing coefficient, which is equal to 0.74 [28].
The experimentally obtained nanoparticle aggregate diameter 2Rag was
accepted as 2Rmax (Table 6.1) and the value Sn was also calculated accord-
ing to the experimental values of nanoparticle radius rn (Table 6.1). In
Table 6.1, the values N for the studied nanofillers, obtained according to
the indicated method, were adduced. It is significant that the value N is
maximum for nanoshungite despite larger values rn in comparison with
technical carbon.
T
Furthermore, Eq. (6.14) allows to estimate the greatest radius Rmax of
nanoparticle aggregate within the frameworks of the aggregation model
[31]. These values Rmax
T
are adduced in Table 6.1, from which their reduc-
tion in a sequence of technical carbon—nanoshungite—microshungite,
that fully contradicts to the experimental data, i.e., to Rag change (Table
6.1). However, we must not neglect the fact that Eq. (6.14) was obtained
within the frameworks of computer simulation, where the initial aggregat-
ing particle sizes are the same in all cases [31]. For real nanocomposites
the values rn can be distinguished essentially (Table 6.1). It is expected that
the value Rag or Rmax
T will be the higher, the larger is the radius of nanopar-
ticles, forming aggregate, i.e., rn. Then, the theoretical value of nanofiller
particle cluster (aggregate) radius RagT can be determined as follows:
Reinforcement of Polymer Nanocomposites 155

RTag = kn rn N 1/ df
ag
, (6.16)

where kn is the proportionality coefficient, in the present work accepted

empirically equal to 0.9.

TABLE 6.1â•… The parameters of irreversible aggregation model of nanofiller particles

aggregates growth

Nanofiller Rag rn N Rc
T
(nm) (nm) Rmax R T
ag (nm)
(nm) (nm)

Technical carbon 34.6 10 35.4 34.7 34.7 33.9

Nanoshungite 83.6 20 51.8 45.0 90.0 71.0

Microshungite 117.1 100 4.1 15.8 158.0 255.0

The comparison of experimental Rag and calculated, according to the

Eq. (6.16), RagT values of the studied nanofiller particle aggregates radius

shows their good correspondence (the average discrepancy of Rag and RagT
makes up to 11.4%). Therefore, the theoretical model [31] gives a good
correspondence to the experiment only in case of consideration of aggre-
gating particles real characteristics and, in the first place, their size.
Let us consider two more important aspects of nanofiller particles ag-
gregation within the frameworks of the model [31]. Some features of the
indicated process are defined by nanoparticle diffusion at nanocomposite
processing. Specifically, length scale, connected with diffusible nanopar-
ticle, is correlation length x of diffusion. By definition, the growth phe-
nomena in sites, remote more than x, are statistically independent. Such
definition allows to connect the value x with the mean distance between
nanofiller particle aggregates Ln. The value x can be calculated according
to the equation as in what follows [31]:

, (6.17)
ag
x 2 ≈ ñ-1Ragd f -d +2

where c is nanoparticles concentration, which should be accepted equal to

nanofiller volume contents jn, which is calculated according to Eqs. (6.6)
and (6.13).
156 Applied Research on Polymer Composites

The values rn and Rag were obtained experimentally (see histogram of

Figure 6.3). In Figure 6.4 the relation between Ln and x is adduced, which,
as it is expected, proves to be linear and passing through coordinates ori-
gin. This means that the distance between nanofiller particle aggregates is
limited by

FIGURE 6.3â•… The initial particles diameter (a) their aggregates size in nanocomposite,
(b) and distance between nanoparticles aggregates, (c) for nanocomposites, filled with
technical carbon, nano, and microshungite.

Mean displacement of statistical walks, by which nanoparticles are

simulated. The relationship between Ln and x can be expressed analyti-
cally as follows:

Ln ≈ 9.6x nm (6.18)

The second important aspect of the model [31] in reference to nano-

filler particle aggregation simulation is a finite nonzero initial particle con-
centration c or jn effect, which takes place in any real systems. This effect
is realized at the condition x ≈ Rag, which occurs at the critical value Rag
(Rc), determined according to the relationship [31]:
ag
c ~ Rcdf -d . (6.19)
Reinforcement of Polymer Nanocomposites 157

The right-hand side of Eq. (6.19) represents cluster (particles aggre-

gate) mean density. This equation establishes that fractal growth contin-
ues only, until cluster density reduces up to medium density, in which it
grows. The calculated values Rc, according to Eq. (6.19), for the consid-
ered nanoparticles are adduced in Table 6.1, from which it follows that
they give reasonable correspondence with this parameter experimental
values Rag (the average discrepancy of Rc and Rag makes up 24%).

FIGURE 6.4â•… The relation between diffusion correlation length x and distance between
nanoparticles aggregates Ln for considered nanocomposites.

As the treatment [31] was obtained within the frameworks of a more

general model of diffusion-limited aggregation, its correspondence to the
experimental data indicated unequivocally, such that aggregation process-
es in these systems were controlled by diffusion. Therefore, let us consider
briefly the nanofiller particle diffusion. Statistical walkers diffusion con-
stant z can be determined with the aid of the equation as in what follows
[31]:

x ≈ (z t ) , (6.20)
1/ 2

where t is walk duration.

Equation (6.20) supposes (at t = const) z increases in a number tech-
nical carbon—nanoshungite—microshungite as 196–1069–3434 relative
158 Applied Research on Polymer Composites

units, i.e., diffusion intensification at diffusible particles size growth. At

the same time, diffusivity D for these particles can be described by the
well-known Einstein’s relationship as in what follows [33]:

kT
D= , (6.21)
6πhrna

where k is Boltzmann constant, T is temperature, h is medium viscosity, a

is numerical coefficient, which further is accepted equal to 1.
In its turn, the value h can be estimated according to equation as in
what follows [34]:

h 2.5f n , (6.22)
= 1+
h0 1 - fn
where h0 and h are initial polymer and its mixture with nanofiller viscos-
ity, respectively.
The calculation according to Eqs. (6.21) and (6.22) shows that within
the aforementioned nanofiller number the value D changes as 1.32–1.14–
0.44 relative units, i.e., reduces in three times, which was expected. This
apparent contradiction is due to the choice of the condition t = const (where
t is nanocomposite production duration) in Eq. (6.20). In real conditions
the value t is restricted by nanoparticle contact with growing aggregate
and then instead of t the value t/c0 should be used, where c0 is the seeds
concentration, determined according to Eq. (6.14). In this case, the value z
for the indicated nanofillers changes as 0.288–0.118–0.086, i.e., it reduces
in 3.3 times, which corresponds fully to the calculation according to the
Einstein’s relationship (Eq. (6.21)). This means that nanoparticle diffusion
in polymer matrix obeys classical laws of Newtonian rheology [33].
Thus, the disperse nanofiller particle aggregation in elastomeric matrix
can be described theoretically within the frameworks of a modified model
of irreversible aggregation particle-cluster. The obligatory consideration
of nanofiller initial particle size is a feature of the indicated model applica-
tion to real system description. The indicated particles’ diffusion in poly-
mer matrix obeys classical laws of Newtonian liquids hydrodynamics. The
offered approach allows to predict nanoparticle aggregate final parameters
as a function of the initial particles’ size, their contents, and other factors.
At present there are several methods of filler structure (distribution)
determination in polymer matrix, both experimental [10, 35] and theo-
retical [4]. All the indicated methods describe this distribution by fractal
Reinforcement of Polymer Nanocomposites 159

dimension Dn of filler particle network. However, correct determination of

any object fractal (Hausdorff) dimension includes three obligatory condi-
tions. The first is the aforementioned determination of fractal dimension
numerical magnitude, which should not be equal to object topological di-
mension. It is well known [36], that any real (physical) fractal possesses
fractal properties within a certain scales range. Therefore, the second con-
dition is the evidence of object self-similarity in this scale range [37]. Fi-
nally, the third condition is the correct choice of measurement scale range
itself. As it has been shown in Refs. [38, 39], the minimum range should
exceed at any rate one self-similarity iteration.
The first method of dimension Dn experimental determination uses the
following fractal relationship [40, 41]:

ln N , (6.23)
Dn =
ln r
where N is a number of particles with size r.
Particle sizes were established on the basis of atomic-power microsco-
py data (see Figure 6.2). For each from the three-studied nanocomposites
no less than 200 particles were measured, the sizes of which were united
into 10 groups and mean values N and r were obtained. The dependences
N(r) in double logarithmic coordinates were plotted, which proved to be
linear and the values Dn were calculated according to their slope (see Fig-
ure 6.5).

FIGURE 6.5â•… The dependences of nanofiller particles number N on their size r for
nanocomposites BSR/TC (1) BSR/nanoshungite and (2) BSR/microshungite.
160 Applied Research on Polymer Composites

It is obvious that at such approach fractal dimension Dn is determined

in two-dimensional Euclidean space, whereas real nanocomposite should
be considered in three-dimensional Euclidean space. The following rela-
tionship can be used for Dn re-calculation for the case of three-dimensional
space [42]:
1/ 2
d + D2 ± ( d - D2 ) - 2
2

  , (6.24)
D3 =
2
where D3 and D2 are corresponding fractal dimensions in three- and two-
dimensional Euclidean spaces, respectively, and d = 3.
The calculated dimensions Dn, based on the aforementioned method,
are adduced in Table 6.2. The values Dn for the studied nanocomposites
are varied within the range of 1.10–1.36, i.e., they characterize more or
less branched linear formations (“chains”) of nanofiller particles (aggre-
gates of particles) in elastomeric nanocomposite structure. Let us remind
that for particulate-filled composites polyhydroxyether/graphite, the value
Dn changes within the range of ~2.30–2.80 [4, 10], i.e., for these materials
filler particles network is a bulk object, but not a linear one [36].

TABLE 6.2â•… The dimensions of nanofiller particles (aggregates of particles) structure in

elastomeric nanocomposites

Nanocomposite Dn, Eq. (6.23) Dn, the Eq. d0 dsurf jn Dn, Eq.
(6.25) (6.29)

BSR/TC 1.19 1.17 2.86 2.64 0.48 1.11

BSR/nanoshungite 1.10 1.10 2.81 2.56 0.36 0.78

BSR/microshungite 1.36 1.39 2.41 2.39 0.32 1.47

Another method of Dn experimental determination uses the so-called

“quadrates method” [43], which consists of the following parameters. On
the enlarged nanocomposite microphotograph (see Figure 6.2), a net of
quadrates with quadrate side size ai, changing from 4.5 to 24 mm with
constant ratio ai+1/aI = 1.5, is applied and then quadrates number Ni, in to
which nanofiller particles hit (fully or partly), is counted up. Five arbitrary
net positions concerning microphotograph were chosen for each measure-
Reinforcement of Polymer Nanocomposites 161

ment. If nanofiller particles’ network is a fractal, then the following rela-

tionship should be fulfilled [43]:

N i ~ Si- Dn / 2 , (6.25)

where Si is quadrate area, which is equal to a . 2

i

In Figure 6.6 the dependences of Ni on Si in double logarithmic co-

ordinates for the three-studied nanocomposites, corresponding to the re-
lationship Eq. (6.25), is adduced. As one can see, these dependences are
linear, which allows to determine the value Dn from their slope. The deter-
mined values Dn, according to Eq. (6.25), are also adduced in Table 6.2,
from which a good correspondence of dimensions Dn, obtained by the two
aforementioned methods, follows (their average discrepancy makes up to
2.1 per cent after these dimensions re-calculation for three-dimensional
space according to Eq. (6.24)).

FIGURE 6.6â•… The dependences of covering quadrates number Ni on their area Si,
corresponding to the relationship Eq. (6.25), in double logarithmic coordinates for
nanocomposites on the basis of BSR. The designations are the same, that in Figure 6.5.

As it has been shown in Ref. [44], the usage for self-similar fractal
objects at Eq. (6.25) is based on the equation as in what follows:
162 Applied Research on Polymer Composites

N i - N i -1 ~ Si- Dn (6.26)

In Figure 6.7, the dependence, corresponding to Eq. (6.26), for the

three-studied elastomeric nanocomposites is adduced. As one can see, this
dependence is linear, passes through origin of coordinates, which accord-
ing to Eq. (6.26) is confirmed by nanofiller particle (aggregates of parti-
cles) “chains” self-similarity within the selected ai range. It is obvious that
this self-similarity will be a statistical one [44]. Let us note that the points,
corresponding to ai=16 mm for nanocomposites butadiene—styrene rub-
ber/technical carbon (BSR/TC) and butadiene—styrene rubber/micro-
shungite (BSR/microshungite), do not correspond to a common straight
line. Accounting for electron microphotographs of Figure 6.2 enlargement
gives the self-similarity range for nanofiller “chains” of 464–1472 nm.
For nanocomposite butadiene—styrene rubber/nanoshungite (BSR/nanos-
hungite), which has no points deviating from a straight line of Figure 6.7,
ai range makes up 311–1,510 nm, which corresponds well enough to the
aforementioned self-similarity range.

FIGURE 6.7â•… The dependences of (Ni − Ni + 1) on the value S i- D / 2 , corresponding to the

n

relationship Eq. (6.26), for nanocomposites on the basis of BSR. The designations are the
same, that in Figure 6.5.
Reinforcement of Polymer Nanocomposites 163

Measurement scales Si minimum range should contain at least one self-

similarity iteration as shown in Refs. . In this case the condition for ratio
of maximum, Smax, and minimum, Smin, areas of covering quadrates should
be fulfilled [39]:

Smax
> 22/ Dn . (6.27)
Smin

Hence, accounting for the aforementioned restriction let us obtain

Smax/Smin=121/20.25 = 5.975that is larger than values 22 / Dn for the studied
nanocomposites, which are equal to 2.71–3.52. This means that measure-
ment scales range is chosen correctly.
The self-similarity iterations number m can be estimated from the in-
equality [39]:
Dn / 2
 Smax 
 S  > 2m . (6.28)
min

Using the aforementioned values of Eq. (6.28) parameters, m = 1.42

− 1.75 is obtained for the studied nanocomposites, i.e., in our experiment
conditions self-similarity iterationnumber is larger than unity, which again
confirms correctness of the value Dn estimation [35].
In addition, let us consider the physical grounds of smaller values
Dn for elastomeric nanocomposites in comparison with polymer micro-
composites, i.e., the causes of nanofiller particle (aggregates of particles)
“chains” formation in the first ones. The value Dn can be determined theo-
retically according to the equation as in what follows [4]:

Dn + 2.55d 0 - 7.10 ,
fif =
(6.29)4.18

where jif is the relative fraction of interfacial regions, and d0 is nanofiller

initial particle surface dimension.
The dimension d0 estimation can be carried out with the help of Eq.
(6.4) and the value jif can be calculated according to Eq. (6.7). The results
of dimension Dn theoretical calculation according to Eq. (6.29) are ad-
duced in Table 6.2, from which a theory and experiment good correspon-
dence follows. Eq. (6.29) indicates unequivocally to the cause of a filler
in nano and microcomposites different behavior. The high (close to 3, see
164 Applied Research on Polymer Composites

Table 6.2) values d0 for nanoparticles and relatively small (d0 = 2.17 for
graphite [4]) values d0 for microparticles at comparable values jif are such
cause for composites of the indicated classes [3, 4].
Hence, the aforementioned results have shown that nanofiller parti-
cle (aggregates of particles) “chains” in elastomeric nanocomposites are
physical fractal within self-similarity (and, hence, fractality [41]) range of
~500–1,450 nm. In this range, their dimension Dn can be estimated accord-
ing to Eqs. (6.23), (6.25), and (6.29). The cited examples demonstrate the
necessity of the measurement scales range with correct choice.
As it has been noted earlier [45], the linearity of the plots, correspond-
ing to Eqs. (6.23) and (6.25), and Dn nonintegral value do not guarantee
object self-similarity (and, hence, fractality). The nanofiller particle (ag-
gregates of particles) structure low dimensions are due to the initial nano-
filler particles surface high fractal dimension.
In Figure 6.8, the histogram is adduced, which shows elasticity modu-
lus E change, obtained in nanoindentation tests, as a function of load on
indenter P or nanoindentation depth h. If the dependences E(P) or E(h) are
identical qualitatively for all the three considered nanocomposites, then
the dependence E(h) for nanocomposite BSR/TC was chosen, which re-
flects the indicated scale effect quantitative aspect in the most clearest
way.

FIGURE 6.8â•… The dependences of reduced elasticity modulus on load on indentor for
nanocomposites on the basis of butadiene—styrene rubber, (a) filled with technical carbon,
(b) micro, and (c) nanoshungite.
Reinforcement of Polymer Nanocomposites 165

In Figure 6.9, the dependence of E on hpl (see Figure 6.10) is adduced,

which breaks down into two linear parts. Such dependences on elasticity
modulus—strain are typical for polymer materials in general and are due
to intermolecular bonds anharmonicity [46].

FIGURE 6.9â•… The dependence of reduced elasticity modulus E, obtained in nanoindentation

experiment, on plastic strain hpl for nanocomposites BSR/TC.

it has been shown in Ref. that the dependence E(hpl) first part at hpl ≤
500 nm is not connected with relaxation processes and has a purely elastic
origin. The elasticity modulus E on this part changes in proportion to hpl
as:

E = E0 + B0 hpl , (6.30)

where E0 is “initial” modulus, i.e., modulus, extrapolated to hpl = 0, and

the coefficient B0 is a combination of the first and second kind elastic con-
stants. In the considered case, B0 < 0. Furthermore, Grüneisen parameter
gL, characterizing intermolecular bonds anharmonicity level, can be deter-
mined as in what follows [47]:
166 Applied Research on Polymer Composites

1 1 B0 1 , (6.31)
gL ≈ - -
6 2 E0 (1 - 2n )
where n is Poisson ratio, accepted for elastomeric materials equal to
~0.475 [36].
According to Eq. (6.31), the following values has been calculated: gL:
13.6 for the first part and 1.50—for the second. Let us note the first from
gL adduced values is typical for intermolecular bonds, whereas the second
value gL is much closer to the corresponding value of Grüneisen parameter
G for intrachain modes [46].
Poisson’s ratio n can be estimated by gL (or G) known values according
to the equation as in what follows [46]:

 1+ n  . (6.32)
g L = 0.7 
 1 - 2n 
The estimated values according to Eq. (6.32) are n = 0.462 for the de-
pendence E(hpl) first part and n = 0.216 for the second one. If for the first
part the value n is close to Poisson’s ratio magnitude for nonfilled rubber
[36], then in the second part, the additional estimation is required. As it is
known [48], a polymer composites (nanocomposites) Poisson’s ratio value
nn can be estimated according to the equation as in what follows:

1 fn 1 - fn
nn
=
n TC
+
nm
, (6.33)

where jn is nanofiller volume fraction, nTC and nm are nanofiller (tech-

nical carbon) and polymer matrix Poisson’s ratio, respectively.
The value nm is equal to 0.475 [36] and the magnitude nTC is estimated
as follows [49]. As it is known [50], the nanoparticles TC aggregates frac-
ag
tal dimension d f value which is equal to 2.40 and then the value nTC can
be determined according to equation [50]:

d fag = ( d - 1) (1 + n TC ) . (6.34)

wherenTC = 0.20 and nn according to Eq. (6.33) gives the value 0.283,
which is close enough to the value n = 0.216 according to Eq. (6.32) esti-
mation. The obtained values n and nn comparison demonstrates that in the
dependence E(hpl) (hpl < 0.5 mcm), the first part in nanoindentation tests
rubber-like polymer matrix (n = nm≈ 0.475) is included and the second
Reinforcement of Polymer Nanocomposites 167

part—the entire nanocomposite as homogeneous system n = nn ≈ 0.22 is

included [51].
Let us consider reduction E at hpl growth (Figure 6.9) within the frame-
works of density fluctuation theory, which value y can be estimated as
follows [22]:

rn kT
y= , (6.35)
KT

where rn is nanocomposite density, k is Boltzmann constant, T is testing

temperature, and KT is isothermal modulus of dilatation, connected with
Young’s modulus E by the relationship [46]:

E . (6.36)
KT =
3(1 - n )
The scheme of volume of the deformed at nanoindentation material Vdef
calculation in case of using Berkovich indentor is adduced in Figure 6.10
and the dependence y(Vdef) in logarithmic coordinates was shown in Fig-
ure 6.11. As it follows from the data of Figure 6.11, the density fluctuation
growth is observed at the increased deformed material volume. The plot
y(ln€Vdef) extrapolation to y = 0 gives ln Vdef ≈ 13 or Vdef( Vdefcr ) = 4.42≈ 105
nm3. Having determined the linear scale lcr of transition to y = 0 as ( Vdefcr
)1/3, let us obtain lcr = 75.9 nm, which is close to nanosystems dimensional
range upper boundary [6], which is equal to 100 nm. Thus, the aforemen-
tioned results stated that nanosystems are such systems in which density
fluctuations are absent, and always taking place in microsystems.
As it follows from the data of Figure 6.9, the transition from nano to
microsystems occurs within the range hpl = 408–726 nm. Both the afore-
mentioned values hpl and (Vdef)1/3 ≈ 814–1,440 nm can be chosen as the
linear length scale ln, corresponding to this transition. Based on the com-
parison of these values ln with the distance between nanofiller particle ag-
gregates Ln (Ln = 219.2 − 788.3 nm for the considered nanocomposites,
see Figure 6.3) it follows that for transition from nano to microsystems,
ln should include at least two nanofiller particle aggregates and surround
them with layers of polymer matrix, which is the lowest linear scale of
nanocomposite simulation as a homogeneous system. It is easy to see that
nanocomposite structure homogeneity condition is harder than the afore-
mentioned system obtained from the criterion y = 0. Let us note that such
168 Applied Research on Polymer Composites

method, namely, a nanofiller particle and surrounding it polymer matrix

layers separation, is widespread at a relationship derivation in microcom-
posite models.

FIGURE 6.10â•… The schematic image of berkovich indentor and nanoindentation process.

It is obvious that Eq. (6.35) is inapplicable to nanosystems, since y →

0 assumes KT → ∞, which is physically incorrect. Therefore the value E0,
obtained by the dependence E(hpl) extrapolation (see Figure 6.9) to hpl = 0,
should be accepted as E for nanosystems [49].
Reinforcement of Polymer Nanocomposites 169

FIGURE 6.11â•… The dependence of density fluctuation y on volume of deformed in

nanoindentation process material Vdef in logarithmic coordinates for nanocomposites BSR/
TC.

Hence, the aforementioned results have shown that elasticity modu-

lus change at nanoindentation for particulate-filled elastomeric nanocom-
posites is due to a number of causes, which can be elucidated within the
frameworks of anharmonicity conception and density fluctuation theory.
Application of the first from the indicated conceptions assumes that in
nanocomposites during nanoindentation process local strain is realized,
affecting polymer matrix only, and the transition to macrosystems means
nanocomposite deformation as homogeneous system.
The second from the mentioned conceptions has shown that nano- and
microsystems differ by density fluctuation which does not exists in the
first but in the second. The last circumstance assumes that for the consid-
ered nanocomposites, density fluctuations take into account nanofiller and
polymer matrix density difference. The transition from nano- to microsys-
tems is realized in the case when the deformed material volume exceeds
nanofiller particle aggregate and surrounds it layers of polymer matrix
combined volume [49].
170 Applied Research on Polymer Composites

The elastomeric nanocomposites reinforcement degree En/Em descrip-

tion was derived as in what follows [3]:
En
= 15.2 1 - ( d - dsurf )  ,
1/ t

 
(6.37)
Em

where t is index percolation, equal to 1.7 [28].

From Eq. (6.37) it follows that nanofiller particle (aggregates of par-
ticles) surface dimension dsurf is the parameter, controlling nanocomposites
reinforcement degree [53]. This postulate corresponds to the known prin-
ciple about the decisive role of numerous division surfaces in nanomateri-
als as the basis of their properties change [54]. From Eqs. (6.4) to (6.6) it
follows unequivocally that the value dsurf is defined by nanofiller particles
(aggregates of particles) size Rp only. In its turn, from Eq. (6.37) it follows
that elastomeric nanocomposites reinforcement degree En/Em is defined by
the dimension dsurf, the size Rp. This means that the reinforcement effect
is controlled by nanofiller particles’ (aggregates of particles) sizes and in
virtue of this is the true nanoeffect.
In Figure 6.12, the dependence of En/Em on (d − dsurf)1/1.7 is adduced,
corresponding to Eq. (6.37), for nanocomposites with different elasto-
meric matrices (natural and butadiene—styrene rubbers, NR, and BSR)
and different nanofillers (technical carbon of different marks, nano- and
microshungite). Despite the indicated distinctions in composition, all ad-
duced data are described well by Eq. (6.37).

FIGURE 6.12â•… The dependence of reinforcement degree En/Em on parameter (d-dsurf)1/1.7

value for nanocomposites (1) NR/TC, (2) BSR/TC, and (3) BSR/Shungite.
Reinforcement of Polymer Nanocomposites 171

In Figure 6.13, two theoretical dependences of En/Em on nanofiller

particle size (diameter Dp), calculated according to Eqs. (6.4), (6.6), and
(6.37), are adduced. However, at the curve 1, the calculated value Dp for
the initial nanofiller particles was used, and at the curve 2 the value Dpag
for—nanofiller particle aggregates size was used (see Figure 6.3). As it
was expected [5], the growth En/Em at Dp or Dpag reduction, along with the
calculation of Dp (nonaggregated nanofiller), gives higher En/Em values
in comparison with the aggregated one ( Dpag using). At Dp ≤ 50 nm faster
growth En/Em at Dp reduction is observed than at Dp > 50 nm, which was
cr
also expected. In Figure 6.13, the critical theoretical value D p for this
transition, calculated according to the aforementioned general principles
[52-–54], is pointed out by a vertical shaded line. In conformity with these
principles the nanoparticles size in nanocomposite is determined accord-
ing to the condition, when division surface fraction in the entire nanomate-
rial volume makes up about ≥ 50 per cent.
This fraction is estimated approximately by the ratio 3lif/Dp, where lif
is interfacial layer thickness. As mentioned earlier, the data of Figure 6.1
gave the average experimental value lif ≈ 8.7 nm. Furthermore, from the
condition 3lif/Dp ≈ 0.5 let us obtain Dp ≈ 52 nm, which is shown in Figure
6.13 by a vertical shaded line. As it was expected, the value Dp ≈ 52 nm
acts as a boundary between regions of slow (Dp > 52 nm) and fast (Dp ≤
52 nm) En/Em growth at Dp reduction. In other words, the materials with
nanofiller particle size Dp ≤ 52 nm (“super-reinforcing” filler according to
the terminology of Ref. [5]) should be considered as true nanocomposites.
Let us note in conclusion that although the curves 1 and 2 of Figure
6.13 are similar, nanofiller particle aggregation, which the curve 2 accounts
for, reduces essentially enough nanocomposite reinforcement degree. At
the same time. the experimental data correspond exactly to the curve 2
that was to be expected in virtue of aggregation processes, which always
took place in real composites [4] (nanocomposites [52-–55]). The values
dsurf, obtained according to Eqs. (6.4)–(6.6), correspond well to the experi-
mentally determined ones. Therefore, for nanoshungite and two marks of
technical carbon, the calculation by the aforementioned method gives the
following dsurf values: 2.81, 2.78, and 2.73, whereas experimental values
of this parameter are equal to: 2.81, 2.77, and 2.73; i.e., practically a full
correspondence of theory and experiment was obtained.
172 Applied Research on Polymer Composites

FIGURE 6.13â•… The theoretical dependences of reinforcement degree En/Em on nanofiller

particles size Dp, calculated according to Eqs. (6.4), (6.6), and (6.37), at initial nanoparticles
(1) and nanoparticles aggregate (2) size using. The boundary value Dp (3), corresponding to
true nanocomposite. Experimental data for nanocomposites NR/TC (4), BSR/TC (5), and
BSR/shungite (6).

6.4â•…CONCLUSIONS

Hence, the stated aforementioned results have shown that the elastomeric
reinforcement effect is the true nanoeffect, which is defined by the initial
nanofiller particle size only. The indicated particle aggregation, always
taking place in real materials, changes and reduces reinforcement degree
quantitatively. This effect theoretical treatment can be received within the
frameworks of fractal analysis. For the considered nanocomposites the
nanoparticle size upper limiting value makes up ~ 52 nm.

KEYWORDS

•â•¢ Nanocomposites
•â•¢ Nanofillers
•â•¢ Polymer reinforcement
Reinforcement of Polymer Nanocomposites 173

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CHAPTER 7

A STUDY ON THE EFFECTS OF THE

MODIFIED SILICA–GELATIN HYBRID
SYSTEMS ON THE PROPERTIES OF
PAPER PRODUCTS
PRZEMYSŁAW PIETRAS, ZENON FOLTYNOWICZ, HIERONIM
MACIEJEWSKI, and RYSZARD FIEDOROW

CONTENTS

7.1 Introduction................................................................................... 178

7.2 Materials and Methods.................................................................. 179
7.3 Results and Discussion................................................................. 181
7.4 Conclusions................................................................................... 189
Keywords............................................................................................... 189
References.............................................................................................. 189
178 Applied Research on Polymer Composites

7.1â•… INTRODUCTION

Since the beginning of papermaking in Western Europe, gelatin was used

to reduce the sorption of water (paper sizing) by papers to improve the
buffer effect and feathering of the inks [1]. Nowadays, papers are sized
with synthetic sizes such as alkyl ketene dimers (AKDs) and alkenyl suc-
cinic anhydrides (ASAs), which were developed for the paper industry in
1953 and 1974, respectively [2], but gelatin sizing continues to be used for
artist quality papers.
Hybrid materials consisting of biopolymer and silica raise hopes for
obtaining materials of high compatibility to tissues and interesting prop-
erties. Such hybrids find application as biocompatible materials, bone
substituents, as well as immobilizers of enzymes, catalysts and sensors,
pre-ceramic materials, and many others [3, 5, 6]. A very convenient and ef-
fective method for preparing such systems is sol–gel technique. Biocom-
posites obtained by the aforementioned method have exceptional proper-
ties such as high plasticity, low modulus of elasticity, and high strength
[3–7].
Gelatin is a product of thermal denaturation of collagen presents in
bones and animal skins. It is formed as a result of temperature action on
three-chain polypeptide helix of collagen which undergoes unwinding to
give gelatin balls. It is not a homogeneous product and its composition
depends on collagen origin. Molecular weight of gelatin ranges between
80,000 and 2,00,000. Gelatin is a fully biodegradable material [8, 11]. It
dissolves in water after heating to about 40°C. Gelatin has its greatest ap-
plication in food, pharmaceutical, and photographic industries. Its poten-
tial applications include bone reconstructions, biocatalysis, drug distribu-
tion control in living organisms, and others [3, 12].
In the case of hybrid materials, the formation of durable bonds between
biopolymer and inorganic gel is of great importance. The fundamental role
in the formation of such bonds is played by silane coupling agents such
as aminosilanes, glycidoxysilanes, and others [13]. For gelatin-containing
systems the most frequently selected coupling agent is glycidoxypropyltri-
methoxysilane. Ren et al. [14, 15] described synthesis of porous siloxane
derivatives of gelatin and 3-glycidoxypropyltrimethoxysilane (GPTMS),
prepared by sol–gel technique in the presence of HCl. Furthermore, Ren et
al. [16] described synthesis of gelatin-siloxane hybrids with gelatin bound
terminally to siloxane chains, using GPTMS as a coupling agent. Smitha
A Study on the Effects of the Modified Silica–Gelatin 179

et al. [17] presented a method for immobilization of gelatin molecules in

mesoporous silica by carrying out tetraethoxysilane (TEOS) hydrolysis
under conditions of controlled pH. Pietras et al. [18] described preparation
of silica–gelatin hybrid materials by sol–gel method using ethyl silicate
(U740) as a silica precursor and GPTMS as a coupling agent.
In this chapter we present syntheses of silica–gelatin hybrid materi-
als aimed at obtaining possibly the highest degree of compatibility of the
systems prepared by the integration of two types of polymers–organic bio-
polymer (gelatin) and inorganic polymer (silica gel) using GPTMS as a
coupling agent. The obtained hybrid materials were applied as modifiers
of paper products. The modified paper products were characterized from
the point of view of the influence of employed impregnants on functional
parameters such as basis weight change, durability on elongation, durabil-
ity on rupture, absorptiveness of water, and burning time.

7.2â•… MATERIALS AND METHODS

7.2.1â•…MATERIALS

Gelatin employed in the study originated from porcine skin (type A, iso-
electric point (pI)=8, 300 Bloom, dry matter 90%) was purchased from
Aldrich (research grade gelatin (RGG)) and edible porcine gelatin (food
grade gelation (FGG)) was purchased from Kandex, Ltd.. Ethyl silicate-
U740 (40% SiO2), TEOS, and GPTMS were obtained from Unisil Ltd.,
(Tarnów, Poland) and glacial acetic acid from Aldrich.
The modification was performed on white paper Lux 80 g/m2 for black
and white printing and copying, manufactured by International Paper ,
Poland, as well as cardboard for painting and building purposes, manu-
factured by Blue Dolphin Tapes, Poland. To compare properties of the
impregnated paper materials with those commercially available, we have
also subjected to impregnation of a packing paper manufactured by Hoo-
mark, Ltd., Jędrzychowice, Poland (PP) and a cardboard A1 170 g/m2
manufactured by Kreska, Bydgoszcz, Poland (TZ).
180 Applied Research on Polymer Composites

7.2.2â•… SILICA–GELATIN HYBRID MATERIALS

The starting sol was obtained by hydrolysis and condensation of an appro-

priate amount of ethyl silicate (U740, d = 1.05 g/cm3, 40% SiO2) or TEOS
(d = 0.933 g/cm3, 28.85% SiO2) and GPTMS in water in the presence of
acetic acid as pH control agent. In the typical experiment 166 g of TEOS
or 120 g of U740, 61 g of GPTMS, and 60 g of acetic acid were used.
The amount of silica formed as a result of hydrolysis and condensation of
both precursors was constant and taken into account each time when pro-
portions of ethyl silicate or TEOS to GPTMS were chosen. The mixture
was vigorously stirred and heated at 85°C for 6 h to yield functionalized
silica gel. At the next stage, gelatin was added to the obtained sol and the
mixture was heated at 60°C for 2 h with vigorous stirring. Codes and com-
positions of samples obtained are shown in Table 7.1. Then this gel was
applied as the impregnant for paper products.

TABLE 7.1â•… Percentage of gelatin* and codes of silica–gelatin hybrid materials based on
TEOS and U740

Gelatin added [%] TEOS-based sample coding U740-based sample coding

0 T0 U0

50 T1 U1

100 T2 U2

150 T3 U3
*Calculated with reference to theoretical amount of silica formed from TEOS or U740.

7.2.3â•… MODIFICATION OF PAPER PRODUCTS

A 350 ml of the impregnant gel (ca. ¼ of obtained silica–gelatin hybrid

system) was placed into a photographic tray. Six sheets of paper of A4
size or cardboard were modified in a given portion of the impregnant. The
impregnation was carried out by deep coating method for 5 min (FGG5
and RGG5) or for 15 min (FGGS15 and RGG15). Then, the impregnated
sample was hung over the tray to enable the excess impregnant to flow
away. This was followed by drying of the sample in an air recirculation
oven at 60°C for 30 min. The preparations obtained were designated as
FGG5, FGG15, RGG5, and RGG15, respectively.
A Study on the Effects of the Modified Silica–Gelatin 181

7.2.4â•… CHARACTERIZATION OF THE SYSTEMS

The obtained materials were characterized from the point of view of

changes in functional parameters such as basis weight change, durability
on elongation, durability on rupture, absorptiveness of water, and burning
time.
Changes in grammage were measured as follows: samples of 1,000
mm2 area were cut out of modified paper with the accuracy of 0.5 mm2.
Each sample was weighed on a balance with the accuracy of three sig-
nificant digits. Measurements were performed for 10 samples of each
modified paper and results were averaged. Durability on elongation was
determined using tensile testing machine VEB TIW Rauenetein ZT; work-
ing length was 100 mm, sample width 15 mm, elongation speed 20 mm/
min. Durability on rupture of cardboards weighing over 250 g/cm2 was
measured with the use of an apparatus made by Lorentzen & Wettre Co. at
initial pressure of 0.5 MPa. Absorptiveness of water was measured by the
Cobb method in compliance with the standard ASTM D3285-93 (2005) by
determining the Cobb60 index; sample surface area was 100 cm2. Burn-
ing time was measured under controlled conditions in a closed chamber
equipped with a burner for combustion of samples; height of the burner
flame was 1.5–2 cm.

7.3â•… RESULTS AND DISCUSSION

7.3.1â•… CHARACTERIZATION OF MODIFIED PAPER PRODUCTS

Within the study two series were synthesized of silica–gelatin hybrid sys-
tems based on TEOS and U740 with increasing gelatin (FGG or RGG)
content. The prepared silica–gelatin hybrid systems were used for the im-
pregnation of paper products PB, TM, PP, and TZ to evaluate the effect of
silica precursors applied in the study, as well as that of origin and concen-
tration of gelatin on selected qualitative and functional parameters of the
paper products studied.
All samples of paper products maintained their initial shape and size
after impregnation and drying and no curling up occurred. However, an in-
crease in the rigidity of samples was observed. The use of the impregnant
had no influence whatsoever on the possibility of writing with a ball pen,
182 Applied Research on Polymer Composites

pencil, or felt-tip pen on the samples. Organoleptic evaluation with naked

eye did not show color changes in the investigated paper samples, except
for TM in the case of which color darkening was observed. No separation
of impregnant from paper was noticed during cutting of modified paper
samples into smaller pieces required for different analyses. The samples
have retained their shape after cutting they did not curl up.

7.3.2â•… BASIS WEIGHT CHANGE

Changes in the weightage of PB samples modified with hybrid systems

based on TEOS as well as FGG and RGG were shown in Figure 7.1. One
can notice that weightage of a given modified paper increases when com-
pared with that of non-modified (NM) paper. Analogous situation was ob-
served for all paper samples impregnated with all hybrid systems studied.
Initial weightages of investigated papers were 80 g/m2 for PB, 289 g/m2
for TM, 51 g/m2 for PP and 170 g/m2 for TZ. The highest values of impreg-
nated paper weightage were observed for the last samples of a given series
modified with systems based on TEOS and U740 with the greatest FGG
or RGG gelatin content. The weightage of PB increased to reach the high-
est value of 110 g/m2 for the sample T3 FGG5. In the case of TM, analo-
gously to the aforementioned paper samples, the weightage raises with
increasing gelatin content to the maximum value of 363 g/m2 in the case
of the last sample of FGG15 series based on TEOS. The raise in weight-
age with increasing gelatin content in impregnants was also observed for
all control paper samples. In the case of PP, the weightage increases to 71
g/m2, whereas for TZ it increases to 194 g/m2. The increase in weightage
of all samples of all series of papers modified with hybrid materials when
compared with starting papers testifies for the penetration of impregnants
used in the papers investigated. This fact is additionally proved by the ap-
pearance and behavior of samples during their preparation and analyses
(impregnant was not coming off paper during cutting out and no splinters
were formed while testing strength of samples).
A Study on the Effects of the Modified Silica–Gelatin 183

FIGURE 7.1â•… Weightage of non-modified (NM) PB and TEOS-modified (T0-T3) PB.

7.3.3â•… DURABILITY ON ELONGATION

Durability on elongation is the maximum tensile force acting on width unit

of a sample at which the sample remains unbroken. The measurement of
the aforementioned parameter consists of placing a sample in holders of
tensile testing machine and stretching the sample with a constant speed un-
til the latter underwent breaking. The value of tensile force at the moment
of breaking was recorded. Averaged results of measurements of breaking
resistance of PB impregnated with hybrid materials based on TEOS and
FGG as well as RGG were shown in Figure 7.2. In the case of PB and TM,
an improvement in this parameter was observed, whereas in that of PP and
TZ a slight reduction in durability on elongation was noticed. Values of the
aforementioned parameter were 3.8, 5.4, 6.2, and 9.4 kN/m for unmodi-
fied PB, TM, PP, and TZ, respectively.
The durability on elongation of impregnated PB increased with a rise
in gelatin content for all series of both hybrid systems. The highest values
184 Applied Research on Polymer Composites

were observed for the last samples of a given series and were 6.0, 6.2, 5.3,
and 5.1 kN/m for FGG5 and RGG5 series for hybrid systems based on
TEOS and U740, respectively. Similarly as it was in the case of PB, also
in that of TM an increase was observed in the durability on elongation.
The aforementioned parameter has the highest value for T3 sample of
FGG5 series and equals to 9.1 kN/m for hybrid systems based on TEOS
and for U3 sample of FGG5 series being equal to 9.4 kN/m for hybrid
systems based on U740. In contrast to previous paper products, in the
case of PP and TZ, a small decrease was observed in the durability on
elongation. In the case of PP, the highest reduction in this parameter oc-
curs for T1 sample of RGG15 series and equals to 4.5 kN/m, whereas for
other samples of all series it ranges between 5.2 and 6.0 kN/m. Results
obtained for TZ show that the highest decrease in the durability on elon-
gation takes place for T2 sample from FGG5 series and is equal to 7.8
kN/m, whereas for most of samples from other series it is in the range
of 8–9 kN/m.

FIGURE 7.2â•… Durability on elongation of NM PB and PB modified with TEOS (T0–T3).

A Study on the Effects of the Modified Silica–Gelatin 185

7.3.4â•… DURABILITY ON RUPTURE

Burst is the strength of a single sheet of paper to withstand homoge-

neous pressure acting perpendicularly to the surface of the sheet. It is
the basic parameter for evaluation of strength of packing paper and
corrugations of corrugate board. The measurement consists in tight-
ening a paper sample between two rings of flexible membrane which
undergoes bulging under the effect of pressure of air delivered until the
sample breaks. Bursting strength of a sample corresponds to maximum
value of pressure that resulted in the sample breakage. The measure-
ment was carried out for 10 TM-modified samples and results were
averaged. Figure 7.3 shows averaged results for TM modified with hy-
brid systems based on U740 and FGG as well as RGG. It is clearly seen
in the figure that bursting strength of impregnated TM is considerably
greater than that of non-impregnated TM for which the burst was 252
kPA. In the case of cardboard modified with hybrid systems based on
U740 an increase in bursting strength is noticeable for both FGG series
with the rise in gelatin content.
The values change from 350 to 531 kPa and 359 to 482 kPa for FGG5
and FGG15 series, respectively. For both RGG series, a decrease in
bursting pressure was observed in the case of gelatin-containing samples
when compared with samples impregnated with pure silica sol; however,
the decrease was small (from 539.0 to 514.5 kPa and from 414.5 kPa do
393.0 kPa for RGG 5 and RGG15 series, respectively). In the case of
samples modified with TEOS-based hybrid systems the bursting strength
increased as much as to 555.5 kPa for samples from FGG5 and RGG5
series and to 548.0 kPa for those from RGG15 series. Finally, one can
conclude that the impregnation of TM with the studied hybrid systems
resulted in the increase of bursting strength which in some cases was
over 100 per cent.
186 Applied Research on Polymer Composites

FIGURE 7.3â•… Durability on rupture of NM TM and TM modified with U740 (U0–U3).

7.3.5â•… ABSORPTIVENESS OF WATER

Absorptiveness of water is the mass of water absorbed by 1 m2 of paper

at a specified time and specified conditions. The measurement consists in
determining the mass of water absorbed by a paper sample of 100 cm2 area
in a specified time under the water level of 1 cm. Measurements were per-
formed for 10 samples of each modified paper and results were averaged.
The change in absorptiveness of water for PB samples modified with
hybrid systems based on TEOS and FGG as well as RGG was presented
in Figure 7.4. In the case of PB and TM an improvement in this parameter
was observed, whereas in that of PP and TZ a considerable increase oc-
curred in water absorptiveness. The relevant values were 95 g/m2, 554 g/
m2, 30 g/m2, and 58.5 g/m2 for NM PB, TM, PP, and TZ, respectively. Re-
duction in the absorptiveness of water was observed for impregnated PB
with increase in gelatin content for all series of both hybrid systems. The
smallest value was found for T3 sample of TEOS-based RGG5 systems
(64 g/m2). In the case of TM, the water absorptiveness decreased for all
samples modified with all hybrid systems studied with increased gelatin
content, similarly as it was in the case of PB.
A Study on the Effects of the Modified Silica–Gelatin 187

The lowest water absorptiveness (169 g/m2) was found for the last
sample of FGG5 series based on U740. In contrast to previously tested
paper samples, all samples of modified PP and TZ were characterized by
increased absorptiveness of water. In the case of PP, the greatest increase
in this parameter occurred for all T0 samples of all series based on TEOS
(the relevant values: 44, 47, 44, and 47 g/m2) and for all U0 samples of all
series of systems based on U740 (the relevant values: 37, 48, 37, and 48
g/m2). For all TZ samples, the absorptiveness of water increased with the
rise in gelatin content. The highest values of this parameter were found
for last samples of all series for both hybrid systems. They were 195, 200,
182, and 182 g/m2 for FGG5, FGG15, RGG5, and RGG15 series of TEOS-
based systems and 167, 181, 190, and 198 g/m2 for FGG5, FGG15, RGG5,
and RGG15 series of U740-based systems.

FIGURE 7.4â•… Absorptiveness of water of NM PB and TEOS-modified (T0-T3) PB.

7.3.6â•… BURNING TIME

The measurement of this parameter consists in placing a paper sheet

sample in the flame of a burner and determining the burning time. (The
188 Applied Research on Polymer Composites

burner was removed after the sample caught fire.) Ten samples of each
modified paper were subjected to the measurement and results were
averaged. The averaged results of burning time measurements for PB
modified with hybrid systems based on U740 and FGG as well as RGG
are given in Figure 7.5. Burning time for all series of modified paper
samples was longer when compared with non-impregnated (NM) pa-
per samples for which it was 9, 44, 9, and 21 s for PB, TM, PP, and
TZ, respectively. In the case of PB the longest burning time (21 s) was
observed for a sample from FGG5 series of TEOS-based system. In ad-
dition, in the case of TM an extension of burning time occurred with
increasing gelatin content in all series of hybrid systems based on TEOS
and U740. The longest burning time was 54 s for last samples from FG15
and RGG5 series of TEOS-based systems. An increase in burning time
was also observed in the case of PP for which it was 17 s (for T3 sample
from FGG5 series of TEOS-based systems) and in the case of TZ for
which it was 35 s (for samples of TEOS-based systems).

FIGURE 7.5â•… Burning time of NM PB and PB modified with U740 (U0-U3).

A Study on the Effects of the Modified Silica–Gelatin 189

7.4â•…CONCLUSIONS

Results of the study conclude that the kind of silica precursor (TEOS or
ethyl silicate) has no significant effect on upgrading selected function-
al properties of paper products. More important parameters appeared to
be the kind and amount of gelatin added. Such parameters as weightage,
absorptiveness of water as determined by the Cobb method, bursting
strength, and burning time depend on gelatin content. A greater change
in the studied parameters was observed in the case of RGG gelatin when
compared with food grade gelatin. It was also established that the hybrid
materials applied as impregnants for paper products either considerably
(TM) or slightly (PB) improve functional parameters of materials NM by
manufacturers during the production process. In the case of paper products
(PP, TZ) pre-modified in their production process, no changes or a slight
deterioration of the studied parameters were observed.

KEYWORDS

•â•¢ Ethyl silicate

•â•¢ Gelatin
•â•¢ Paper
•â•¢ Paper product modification
•â•¢ Sol–-gel
•â•¢ Tetraethoxysilane

REFERENCES

1. Dupont, A. L.; J. Chromatogr. A. 2002, 950, 113–124.

2. Roberts, J. C.; Paper Chemistry. 2nd Ed. Blackie: Glasgow; 1996.
3. Smitha, S.; Shajesh, P.; Mukundan, P.; Nair, T. D. R.; Warrier, K. G. K.; Colloids and
Surfaces B: Biointerfaces 55. 2007, 38–43.
4. Watzke, H. J.; Dieschbourg, C.; Adv. Colloid Interface Sci. 1994, 50, 1.
5. Schuleit, M.; Luisi, P. L.; Biotechnol. Bioeng. 2001, 72, 249.
6. Liu, D. M.; Chen, I. W.; Acta Mater. 1999, 47, 4535.
7. Yuan, G. L.; et al. Chem. 2000, 159, 45.
8. Boanini, E.; Rubini, K.; Panzavolta, S.; Bigi, A.; Acta Biomater. 2010, 6, 383–388.
190 Applied Research on Polymer Composites

9. Bigi, A.; Cojazzi, G.; Panzavolta, S.; Roveri, N.; and Rubini, K.; Biomater. 2002, 23,
4827–4832.
10. Karim, A. A.; and Bhat, R.; Food Hydrocolloids. 2009, 23, 563–576.
11. Bigi, A.; Cojazzi, G.; Panzavolta, S.; Rubini, K.; and Roveri, N.; Biomater. 2001, 22,
763–768.
12. Ren, L.; Tsuru, K.; Hayakawa, S.; Osaka, A.; Biomater. 2002, 23, 4765–4773.
13. Advincula, M.; Fan, X.; Lemons, J.; Advincula, R.; Colloids Surf.: B, 2005, 42, 29.
14. Ren, L.; Tsuru, K.; Hayakawa, S.; and Osaka, A.; Biomater. 2002, 23, 4765.
15. Ren, L.; Tsuru, K.; Hayakawa, S.; Osaka, A.; J. Non-Cryst. Solids. 2001a, 285, 116.
16. Ren, L.; Tsuru, K.; Hayakawa, S.; and Osaka, A.; J. Sol-Gel Sci.Tech. 2001b, 21, 115.
17. Smitha, S.; Mukundan, P.; Pillai, P. K.; and Warrier, K. G. K.; Mater. Chem. Phys.
2007, 103, 318.
18. Pietras, P.; Przekop, R.; and Maciejewski, H.; Ceramics–Silikáty. 2013, 57, 58–65.
CHAPTER 8

DEVELOPMENT OF
COMPUTATIONAL TECHNIQUES IN
NANOSYSTEMS
V. I. KODOLOV, N. V. KHOKHRIAKOV, V. V. TRINEEVA,
M. A. CHASHKIN, L. F. AKHMETSHINA, YU. V. PERSHIN, and
YA. A. POLYOTOV

CONTENTS

8.1 The Quantum Chemical Investigation of Metal/Carbon Nanocom-

posites Interaction with Different Media and Polymeric
Compositions................................................................................ 192
8.2 The Metal/Carbon Nanocomposites Influence Mechanisms
on Media and on Compositions.................................................... 221
8.3 The Compositions Modification Processes by Metal/Carbon
Nanocomposites............................................................................ 228
Keywords............................................................................................... 243
References.............................................................................................. 243
192 Applied Research on Polymer Composites

8.1â•… THE QUANTUM CHEMICAL INVESTIGATION OF METAL/

CARBON NANOCOMPOSITES INTERACTION WITH DIFFERENT
MEDIA AND POLYMERIC COMPOSITIONS

8.1.1â•… THE QUANTUM CHEMICAL INVESTIGATION OF

HYDROXYL FULLERENE INTERACTION WITH WATER

Currently various sources contain experimental data that prove radical

changes in the structure of water and other polar liquids when super small
quantities of surface active nanoparticles (according to a number of pa-
pers—about thousandth of percent by weight) are introduced. When the
water modified with nanoparticles is further applied in technological pro-
cesses, this frequently results in qualitative changes in the properties of
products, including the improvement of various mechanical characteris-
tics.
The investigation demonstrates the results of quantum-chemical mod-
eling of similar systems that allow making the conclusion on the degree of
nanoparticle influence on the structure of water solutions. The calculations
were carried out in the frameworks of ab initio Hartree–Fock method in
different basis sets and semi-empirical method PM3. The program com-
plex GAMESS was applied in the calculations [1]. The equilibrium atomic
geometries of fragments were defined and the interaction energy of mo-
lecular structures Eint was evaluated in the frameworks of aforementioned
energy models. The interaction energy was calculated by the following
formula:

Eint = E - Ea - Eb , (1)

where E is the energy of the molecular complex with an optimized struc-

ture, Ea and Eb are the bond energies of isolated molecules forming the
complex. Whencalculating Ea and Eb the molecule energy was not addi-
tionally optimized.
At the first stage quantum-chemical investigation of ethyl alcohol mol-
ecule interaction with one and a few water molecules was carried out. The
calculations were carried out in the frameworks of different semi-empiri-
cal and ab initio models. Thus based on the data obtained we can make a
conclusion on the error value that can occur due to the use of simplified
models with small basis sets. The calculation results are given in Table 8.1.
Development of Computational Techniques in Nanosystems 193

TABLE 8.1â•… Equilibrium parameters of the complex formed by the molecules of ethyl
alcohol and water

Calculation Method Eint , kcal/mol R9-10 R3-9 Q3 Q9 Q10

PM3 1.88 2.38 0.95 –0.33 0.20 –0.37

3–21G 11.29 1.80 0.97 –0.74 0.41 –0.72

6–31G 7.52 1.89 0.96 –0.81 0.48 –0.83

TZV 6.90 1.91 0.96 –0.64 0.42 –0.83

3–21G MP2 13.17 1.78 1.00 –0.64 0.35 –0.63

TZV**++ MP2 6.27 1.90 0.97 –0.49 0.33 –0.65

TZV MP2 7.52 1.84 0.99 –0.58 0.39 –0.79

TZV+ MP2 for the

Geometry Obtained
by the Method 6–31G 6.27 1.89 0.96

The geometrical structure of the complex formed by the ethyl alcohol

and water molecules are given in Figure 8.1.

FIGURE 8.1â•… Equilibrium geometric structure of the complex formed by the molecules of
ethyl alcohol and water. optimization by energy is carried out in the basis 6–31G.

The energy minimization of the structure demonstrated was carried out

on the basis 6–31G. The atom numbers in Figure 8.1 correspond to the
designations given in the Table 8.1.
The calculations demonstrate that equilibrium geometrical parameters
of the complex change insignificantly in the calculations by different
methods. It should be noted that in the structures obtained without electron
correlation the atoms 3, 9, 10, and hydrogen of water molecule are in one
plane. The structure planarity is distorted when considering electron corre-
lation by the perturbation theory MP2. Even more considerable deviations
194 Applied Research on Polymer Composites

from the planarity are observed when calculating by the semi-empirical

method PM3. In this case, the straight line connecting the atoms 3 and 9
become practically perpendicular to the water molecule plane. At the same
time, the semi-empirical method gives the hydrogen bond length exceed-
ing ab initio results by over 20 percent.
The analysis of energy parameters indicates that the energy of interac-
tion of molecules inside the complex calculated by the Eq. (1) is adequately
predicted in the frameworks of Hartree–Fock method in the basis 6–31G.
If for the geometrical structure obtained by this method the calculations of
energy are made in the frameworks of more accurate models, the calcula-
tion results practically coincide with the successive accurate calculations.
The atom charges obtained by different methods vary in a broad range,
in this case no regularity is observed. This can be connected with the im-
perfection of the methodology of charge evaluation by Mulliken.
The investigation of water interaction with the cluster of hydroxyfuller-
ene C60 [OH ]10 was carried out in the frameworks of ab initio Hartree–Fock
method in the basis 6–31G. To simplify the calculation model the cluster
with the rotation axis of fifth order of fullerene molecule C60 was applied.
Figure 8.2(а) demonstrates the fullerene molecule structure optimized by
energy, and Figure 8.2(b) demonstrates the optimized structure of the clus-
ter C60 [OH ]10 .

FIGURE 8.2â•… Equilibrium geometric structure of the molecule C60 (Figure 8.2(а)) and
cluster C60 [OH ]10 (Figure 8.2(b)). Optimization by energy is carried out in the basis 6–31G.
Development of Computational Techniques in Nanosystems 195

All the calculations were carried out preserving the symmetry of mo-
lecular systems.
The pentagon side length calculated in the fullerene molecule is 1.452
Ǻ, and bond length connecting neighboring pentagons—1.375 Ǻ. These
results fit the experimental data available and results of other calculations
[2].
To evaluate the energy of interaction of the cluster with water, the com-
plex C60 [OH ]10 ⋅10 H 2O with the symmetry C5 was studied. The complex
geometry obtained in the basis 6–31G is given in Figure 8.3.

FIGURE 8.3â•… Molecular system formed by the cluster C60 [OH ]10 and 10 water molecules.
Optimization by energy is carried out in the basis 6–31G.

The complex geometrical parameters and atom charges are shown in

Table 8.2.
196 Applied Research on Polymer Composites

TABLE 8.2â•… Equilibrium parameters of the complex C60 [OH ]10 ⋅10 H 2O (calculations by
ab initio method in the basis 6–31G)

Charges

Q1 Q2 Q3 Q4 Q5 Q6

0.17 –0.78 0.50 –0.86 0.46 0.42

Bond Lengths

R1–2 R2–3 R3–4 R4–5 R4–6

1.42 0.97 1.86 0.95 0.95

The atom numeration in Table 8.2 corresponds to the numeration given

in Figure 8.3.

TABLE 8.3â•… Characteristics of the complexes formed by the molecules C60 [OH ]10 ,
C2 H 5OH with water. Ab initio calculations in the basis 6–31G

€ Eint, kcal/mol L,A QH QO (OH) QO (H2O)

C60(OH)10+10H2O 12.69 1.86 0.5 –0.78 –0.86

C2H5OH+H2O 7.52 1.89 0.47 –0.81 –0.83

H2O+H2O 8.37 1.89 0.42 –0.82 –0.76

Table 8.3 contains the comparison of the breaking off energy of wa-
ter molecule from the complexes C60 [OH ]10 ⋅10 H 2O , C2 H 5OH ⋅ H 2O ,
H 2O ⋅ H 2O . Besides, the table gives the lengths of hydrogen bonds in these
complexes L and charges of Q atoms of oxygen and hydrogen of OH group
and oxygen atom of water molecule. All the calculations are carried out by
ab initio Hartree–Fock method in the basis 6–31G. The calculations dem-
onstrate that the energy of interaction of ethyl alcohol molecule with water
is somewhat less than the energy of interaction between water molecules.
At the same time, nanoparticle C60 [OH ]10 interacts with water molecule
about two times more intensively. When comparing the atom charges of
the complexes it can be seen that the molecule π—fullerene electrons in
the nanoparticle act as a reservoir for electrons. Thus, the molecule OH
group is practically electrically neutral. This intensifies the attraction of
Development of Computational Techniques in Nanosystems 197

water molecule oxygen. Therefore, the strength of hydrogen bond in the

complex C60 [OH ]10 ⋅10 H 2O increases.
To evaluate the cluster sizes with the center in nanoparticle C60 [OH ]10
that can be formed in water, semi-empirical calculations of energies of at-
tachment of water molecules to the nanoparticle C60 [OH ]2 with the chain
formation are carried out (Figure 8.4). Semi-empirical method PM3 was
applied in the calculations. Water molecules are attached to the chain suc-
cessively; after each molecule is attached, the energy is minimized.

FIGURE 8.4â•… Model system formed by the cluster C60 [OH ]10 and chain from five water
molecules. Optimization by energy is carried out by semi-empirical method PM3.

Table 8.4 contains the results obtained for the chain growth from the
nanoparticle, alcohol molecule, and water molecule. Bond energies of
water molecules with the chain growing from C60 [OH ]2 over two times
exceed similar energies for the chain growing from OH- group of alcohol
molecule and water molecule.
198 Applied Research on Polymer Composites

TABLE 8.4â•… Energies of attachment of water molecule to the chain connected with the
molecules C60 [OH ]10 , C2 H 5OH . Semi-empirical calculations by the method PM3.

n (H2O)n C2H5OH+n H2O C60(OH)2+nH2O

1 –1.40 –4.06

2 –1.99 –2.19 –4.83

3 –2.38 –2.51 –5.02

4 –2.54 –2.58 –4.88

5 –2.56 –2.68 –4.71

6 –2.66 –3.04

At the same time, the energy of hydrogen bond first increases till the
attachment of the third molecule, and then gradually decreases. When the
sixth molecule is attached, the energy decreases in discrete steps.
Thus, the investigations demonstrate that hydroxyfullerene molecule
forms a stable complex in water, being surrounded by six layers of water
molecules. Obviously, the water structure is reconstructed at considerably
larger distances. The introduction of insignificant number of nanoparticles
results in complete reconstruction of water medium, and, therefore, in
considerable change in the properties of substances obtained on its basis.
Thus, the results are reported on the considerable change in the properties
of constructional materials obtained on the water basis after the insignifi-
cant additions of active graphite-like nanoparticles with chemical proper-
ties similar to the ones of hydroxyfullerene.

8.1.2â•… INFLUENCE COMPARISON OF HYDROXYL

FULLERENES AND METAL/CARBON NANOPARTICLES WITH
HYDROXYL GROUPS ON WATER STRUCTURE

Quantum-chemical investigations of the interactions between hydroxyl-

ated graphite-like carbon nanoparticles, including metal containing ones,
and water molecules are given. Hydroxyfullerene molecules, as well as
carbon envelopes consisting of hexangular aromatic rings, and envelope
containing a defective carbon ring (pentagon or heptagon) are considered
as the models of carbon hydroxylated nanoparticles. The calculations dem-
Development of Computational Techniques in Nanosystems 199

onstrate that hydroxyfullerene molecule C60 ( OH )10 ⋅ ( H 2O )10 forms a stron-

ger hydrogen bond with water molecule than the bond between water mol-
ecules. Among the unclosed hydroxylated carbon envelopes, the envelope
with a pentagon forms the strongest hydrogen bond with water molecule.
The presence of metal nanocluster increases the hydrogen bond energy in
1.5–2.5 times for envelopes consisting of pentagons and hexagons.
At present we can find in the literature experimental data confirming
radical changes in the structure of water and other polar liquids when small
quantities (about thousandth percent by mass) of surfacants are introduced
[3–5]. When further used in technological processes, the water modified
by nanoparticles frequently results in qualitative changes of product prop-
erties including the improvement of different mechanical characteristics.
The chapter is dedicated to the investigation of water molecule inter-
actions with different systems modeling carbon-enveloped nanoparticles,
including those containing clusters of transition metals. All the calcula-
tions were carried out following the same scheme. At the first stage, the
geometry of complete molecular complex was optimized. At the second
stage, the interaction energy of the constituent molecular structures Eint
was assessed for all optimized molecular complexes. The interaction en-
ergy was calculated by the formula Eint = E - Ea - Eb ,
where E is the bond energy of the optimized structure molecular
complex, Ea and Eb - are bond energies of isolated molecules forming
the complex. When calculating Ea and Eb , the molecule energy was not
additionally optimized. The energy of chemical bonds was assessed by
the same scheme. All the calculations were carried out with the help of
software PC-GAMESS [6]. Both semi-empirical and ab initio methods
of quantum chemistry with different basis sets were applied in the cal-
culations. Besides, the method of density functional was used. The more
detailed descriptions of calculation techniques are given when describing
the corresponding calculation experiments.
At the first stage, the quantum-chemical investigation of the interaction
of α-naphthol and β-naphthol molecules with water was carried out within
various quantum-chemical models. Thus, based on the data obtained the
conclusion on the error value can be made, which can be resulted from the
application of simplified methods with insufficient basis sets. There are
three isomers of naphthol molecule named α-naphthol (complex with wa-
ter is shown on Figure 8.1(a)), trans-rotamer and cis-rotamer of β-naphthol
(Figures 8.5(b) and 8.5(c)).
200 Applied Research on Polymer Composites

FIGURE 8.5â•… Equilibrium geometric structure of the complex formed by the molecules
of α-naphthol (Figure 8.5(a)), Trans-β-naphthol (Figure 8.5(b)) and Cis-β-naphthol (Figure
8.5(c)) with water. The optimization by energy was carried out at HF/6–31G Level.

We denote them as α-naphthol, trans-β-naphthol, and cis-β-naphthol

as in what follows. The calculations within all methods applied, except
for the semi-empirical one, showed that cis-β-naphthol is the most stable
isomer, α-naphthol has almost equal stability, and trans-β-naphthol is the
least stable structure. This conclusion is in accordance with available ex-
perimental data [7, 8].
The results for the complexes with α-naphthol are given in Table 8.5.

TABLE 8.5â•… Equilibrium parameters of the complex formed by α-naphthol molecules and
water. In the column Eint The interaction energy between water molecules in dimer is given
in brackets for comparison

Calcu-
lation
Eint , kJ/mol r1- 2 , nm r2- 3 , nm r3- 4 , nm q1 q2 q3
Method
PM3 16.27 (8.32) 0.1364 0.0963 0.1819
HF 3–21G 68.66 (46.11) 0.1361 0.098 0.1701 0.45 –0.82 0.44
HF 6–31G 43.91 (33.13) 0.1365 0.0961 0.1805 0.39 –0.85 0.50
HF 31.91 (23.61) 0.1345 0.0954 0.194 0.42 –0.81 0.52
6–31G*
HF 42.65 (30.75) 0.1367 0.0984 0.1855 0.31 –0.72 0.48
6–31G*
MP2
DFT 42.58 (32.33) 0.136 0.0983 0.1821 0.28 –0.69 0.44
6–31G*
B3LYP
Development of Computational Techniques in Nanosystems 201

The geometry structure of the complex formed by naphthols and wa-

ter molecules is shown in Figure 8.5. The structures given in Figure 8.5
were obtained by minimizing the energy using Hartree–Fock method in
the basis 6–31G. The numbers of atoms in Figure 8.5 correspond to those
given in Table 8.5. The calculations demonstrate that equilibrium geomet-
ric parameters of the complex vary insignificantly when applying different
calculation methods. It should be pointed out that in the structures ob-
tained at HF/6–31G level of theory without taking into account of electron
correlation, atoms 2, 3, 4, and hydrogens of water molecule are almost in
one plane.
The structure planarity is broken with the inclusion of polarization
functions into the basis set and electron correlation consideration. The
semi-empirical calculation forecasts the planarity disturbance of the atom
group considered. The hydrogen bond for β-naphthol complexes is longer
than one for α-naphthol. These values are 0.1812 nm for cis-β-naphthol
and 0.1819 nm for trans-β-naphthol calculated at HF/6–31G level. The
values obtained at MP2/6–31G* level of theory are 0.1861 nm and 0.1862
nm. They are in accordance with the results of more accurate calculations
0.1849 nm and 0.1850 nm [9].
The second column in Table 8.1 demonstrates the energy of interac-
tion between α-naphthol and water molecule calculated using Eq. (1). The
interaction energies between water molecules in water dimer are given in
brackets for comparison. Although all energy characteristics for different
methods vary in a broad range, the ratio of energies Eint for the complex
of water with α-naphthol and water dimer is between 1.3–1.4. Thus, we
can assume that Hartree–Fock method in the basis 6–31G provides quali-
tatively correct conclusions for the energies of intermolecular interaction.
It should be pointed out that energy Eint calculated in the basis 6–31G
agrees numerically with the results of more accurate calculations. Nev-
ertheless, the interaction energies between water and α-naphthol exceed
experimental value 24.2 ± 0.8 kJ/mol [5]. The energies of interaction be-
tween water molecules in dimer are overestimated as well. The errors are
known to be caused by the superposition of basis sets of complex mol-
ecules (basis superpositional error (BSSE)) and zero-point vibration en-
ergy (ZPVE). Calculations completed have shown that BSSE decreases
the interaction energy by 10–20 percent depending on the basis, but does
not lead to qualitative changes. The ZPVE results in additional decrease in
the energies of intermolecular interaction.
202 Applied Research on Polymer Composites

Thus taking into account ZPVE and BSSE considerably improves the
accordance with the available data. Interaction energy between water and
α-naphthol is 30 kJ/mol in the basis 6–31G after correction. In general,
analysis of energy parameters shows that all the models considered give
the correct correlation for energies and demonstrate that the energy of in-
teraction between water and α-naphthol molecules exceeds the energy of
interaction between water molecules. Numerical accordance with experi-
mental value is achieved only after taking into account electronic correla-
tion at the MP2 level.
In this model, the interaction energy after all the corrections men-
tioned becomes 23.7 kj/mol. Cis-β-naphthol is known to be more stable
than trans-isomer. The energy difference calculated in 6–31G basis set is
3.74 kJ/mol that is equal to experimental value [8]. HF/6–31G binding en-
ergy for water dimer is 18.9 kJ/mol after corrections (experimental value
is 15±2 kJ/mol [10]). As in the case of α-naphthol complex MP2 calcula-
tion is necessary to obtain value that is equal to experimental value.
The vibrational frequencies of naphthols and their complexes with wa-
ter molecule were calculated and multiplied by a scaling factor of 0.9034
[8]. IR-active frequencies corresponding to naphthol OH-group stretching
are 3660 cm-1 for trans-β-naphthol and 3654 cm-1 for cis-β-naphthol. They
are in accordance with experimental frequencies 3661 cm-1 and 3654 cm-1
[8]. The influence of hydrogen bond on naphthol OH-group stretching cal-
culated in this chapter is overestimated. Calculated frequencies at HF/6–
31G level of theory in the presence of water molecule are 3479 cm-1 for
trans-β-naphthol and 3466 cm-1 for cis-β-naphthol (for comparing experi-
mental values are 3523 cm-1 and 3512 cm-1, respectively). The same result
was observed in research [8]. The atom charges obtained within different
methods vary in a broad range without any regularity. It can be connected
with the imperfectness of Mulliken’s charge evaluation technique.
Thus, comparison of calculation results with experimental data dem-
onstrates ab initio Hartree–Fock method in the 6–31G basis set provides
qualitatively correct conclusion on hydrogen bond energies for systems
considered. This model was applied to investigate the interaction between
water and hydroxyfullerene cluster C60 [OH ]10 . Hydroxyfullerene is a prop-
er object for quantum-chemical modeling of interaction between activated
carbon nanoparticle and water. At the same time hydroxyfullerene is of
great interest because of its possible applications in medicine, for water
disinfection, and for polishing nanosurfaces.
Development of Computational Techniques in Nanosystems 203

The cluster with the rotation axis C5 was used in our research of hy-
droxyfullerene to simplify the calculation model. Figure 8.6(а) demon-
strates the structure of C60 molecule optimized by energy, and Figure
8.6(b) demonstrates the optimized structure of cluster C60 [OH ]10 . All the
calculations were carried out conserving the symmetry C5 of molecular
systems.

FIGURE 8.6â•… Equilibrium geometric structure of C60 molecule (а) and cluster C60 [OH ]10
(b).

The optimization by energy is carried out at HF/6–31G level.

TABLE 8.6â•… Equilibrium parameters of the complex C60 [OH ]10 ⋅ 10 H 2O (HF/6–31G
calculation)

Charges

q1 q2 q3 q4 q5 q6

0.17 –0.78 0.50 –0.86 0.46 0.42

Bond lengths, nm

r1- 2 r2-3 r3- 4 r4-5 r4-6

0.142 0.097 0.186 0.095 0.095

204 Applied Research on Polymer Composites

TABLE 8.7â•… Characteristics of the complexes formed by C60 [OH ]10 and α-naphthol
molecules and water HF/ 6–31G calculation.

Complex
Eint , kJ/mol L, nm qH qo (OH ) qo ( H 2 O)

C60 [OH ]10 ⋅ 10H 2O 53.09 0.186 0.5 –0.78 –0.86

C10 H 7 OH ⋅ H 2O 43.91 0.181 0.5 –0.85 –0.84

H 2O ⋅ H 2O 33.13 0.189 0.47 –0.88 –0.83

The length of pentagon side in the fullerene molecule was 0.1452 nm,
and the length of bond connecting the neighboring pentagons −0.1375 nm.
These results agree with the experimental data available and results of
other calculations [11, 12].

FIGURE 8.7â•… Molecular system formed by the cluster C60 [OH ]10 and 10 water molecules.
The optimization by energy is carried out at HF/ 6–31G Level.
Development of Computational Techniques in Nanosystems 205

Complex C60 [OH]10 ⋅ 10H 2O with symmetry C 5 was considered to obtain

the interaction energy of cluster C60 [OH ]10 and water. The geometric struc-
ture of the complex optimized by energy is given in Figure 8.7. The com-
plex geometric parameters and atom charges are given in Table 8.6. The
atoms are enumerated in the same way as in Figure 8.7. Table 8.7 contains
the water molecule isolation energies from complexes C60 [OH ]10 ⋅ 10H 2O ,
C10 H 7 OH ⋅ H 2O , H 2O ⋅ H 2O . Besides, the table contains the lengths of hydro-
gen bonds in these complexes L and charges Q of oxygen and hydrogen
atoms of fullerene OH group and oxygen atom of water molecule. The
calculations demonstrate that the energy of interaction between nanopar-
ticle C60 [OH ]10 and water molecule is nearly twice as big as the interaction
energy of water molecules in dimer. Basis set superposition error was also
analyzed. The calculation indicates that the account of this effect decreases
the energies of intermolecular interaction by 15 per cent. The qualitative
conclusions from the calculations do not change, and the gain in the inter-
action energy for the complex C60 [OH ]10 ⋅ 10H 2O increases insignificantly in
comparison with other complexes. When comparing the atom charges of
the complexes, it can be concluded that fullerene π-orbitals in nanoparticle
act as a reservoir for electrons. Thus, the charge of hydroxyfullerene ОН
group decreases. This increases the attraction of water molecule oxygen
and the strength of hydrogen bond in complex C60 [OH ]10 ⋅ 10H 2O .
To estimate the size of the cluster with the center in nanoparticle
C60 [OH ]10 that can be formed in water, the semi-empirical calculations of
energies of water molecules adding to nanoparticle C60 [OH]2 with chain
formation were made (Figure 8.8). The semi-empirical method PM3 was
used in calculations. Water molecules were bonded to the chain conse-
quently; the energy was minimized after each molecule was added. Table
8.8 demonstrates the comparative results obtained for the chain growth
from both nanoparticle and water molecule. The binding energy of water
molecule with the chain growing from C60 [OH ]2 over twice as big as similar
energies for the chain growing from the water molecule.
At the same time, the energy of hydrogen bond first increases before
the addition of the third molecule and then slowly decreases. When the
sixth molecule is added, the energy decreases step-wise. Thus, the research
demonstrates that hydroxyfullerene molecule forms a stable complex in
water, being surrounded with six layers of water molecules. It is clear that
206 Applied Research on Polymer Composites

the water structure changes at much longer distances. The introduction of

insignificant number of nanoparticles results in complete reconstruction of
aqueous medium, and, consequently, to sufficient changes in the proper-
ties of substances obtained on its base.

FIGURE 8.8â•… Model system formed by cluster C60 [OH ]2 and five water molecule chain.
The optimization by energy was carried out with semi-empirical method PM3.

TABLE 8.8â•… Energies of binding water molecules to the chain connected with molecules
C60 [OH ]2 and water chain (in kJ/mol). Semi-empirical calculations with PM3 method

N
[H 2 O]n C60 [OH ]2 + n ⋅ H 2O

1 16.99

2 8.33 20.21

3 9.96 21.00

4 10.63 20.42

5 10.71 19.71

6 11.13 12.72

In some experimental works carbon nanoparticles are obtained in gels

of carbon polymers in the presence of salts of transition metals [13]. At
the same time, nanocomposites containing metal nanoparticles in carbon
Development of Computational Techniques in Nanosystems 207

envelopes are formed. The envelope structure contains many defects but it
mainly has an aromatic character. The nanoparticles considered are widely
used for the modification of different substances; therefore, it is interesting
to investigate the influence of metal nuclei on the interaction of carbon-
enveloped nanoparticles with polar fluids.
The systems demonstrated in Figures 8.9–8.11 were considered as the
nanoparticle model containing a metal nucleus and hydroxylated carbon
envelope. In all the figure of the paper, carbon and hydrogen atoms are not
signed. At the same time, carbon atoms are marked with dark spheres and
hydrogen atoms-with light ones. Clusters comprising two metal atoms are
introduced into the system to model a metal nucleus. Carbon envelopes
are imitated with 8-nucleus polyaromatic carbon clusters. The carbon en-
velope indicated in Figure 8.9 contains one pentagonal aromatic ring, and
the envelope in Figure 8.11 contains one heptagon. The envelope in Figure
8.10 contains only hexagonal aromatic rings.
The corresponding number of hydrogen atoms is located on the bound-
aries of carbon clusters. Besides, one OH - group is present in each of
the carbon envelopes. Thus, the chemical formula of hydroxylated carbon
envelope with pentagonal defect C23 H11OH hydroxylated with defectless
carbon envelope- C27 H13OH , and for the hydroxylated carbon envelope
with heptagonal defect- C31 H15OH . Copper and nickel are taken as metals.
The interaction of the considered model systems with water molecules is
investigated in this chapter.

FIGURE 8.9â•… Complex Cu2C23 H11OH ⋅ H 2O with hexagonal defect in carbon envelope.
208 Applied Research on Polymer Composites

FIGURE 8.10â•… Complex Cu2 C27 H13OH ⋅ H 2 O .

FIGURE 8.11â•… Complex Cu2C31 H15OH ⋅ H 2O with heptagonal defect in carbon

envelope.

The calculations are made in the frameworks of density functional with

exchange-correlative functional B3LYP. For all the atoms of the model
system, apart from oxygen, the basis set 6–31G was applied. Polariza-
tion and diffusion functions were added to the basis set for more accurate
calculations of hydrogen bond energy and interaction of hydroxyl group
with carbon envelope. Thus, the basis set 6−31+G* was used for oxygen
atoms. The basis sets from Ref. [14] were used for atoms of transition
metals, and the bases from software PC-Games were applied for the rest
of the elements.
Development of Computational Techniques in Nanosystems 209

Hydrogen bond energy in water dimers calculated in this model ex-

ceeded 22 kJ/mol being a little more than the value obtained in the frame-
works of the more accurate method—19.65 kJ/mol [15]. The experimental
value is 14.9 ± 2 kJ/mol [15]. If we consider the energy of zero oscillations
of dimer and water molecules in the frameworks of the calculation model,
hydrogen bond energy decreases to 12.57 kJ/mol and becomes similar to
the experimental value. When the basis extends due to polarization func-
tions on hydrogen atoms, hydrogen bond energy goes down by 2 per cent.

TABLE 8.9â•… Bond lengths (in angstrems)

Compound C -O O-H O H

C23 H11OH
1.492 0.973 –

Cu2C23 H11OH 1.450 0.973 –

Ni2C23 H11OH 1.454 0.973 –

C27 H13OH 1.545 0.974 –

Cu2C27 H13OH 1.469 0.973 –

Ni2C27 H13OH
1.464 0.972 –

C31 H15OH
1.506 0.973 –

Cu2C31 H15OH 1.470 0.973 –

Ni2C31 H15OH 1.455 0.972 –

H 2O – 0.969 –

C23 H11OH ⋅ H 2O 1.470 0.981 1.967

Cu2C23 H11OH ⋅ H 2O
1.439 0.984 1.869

Ni2C23 H11OH ⋅ H 2O
1.440 0.985 1.893

C27 H13OH ⋅ H 2O 1.524 0.979 2.119

210 Applied Research on Polymer Composites

TABLE 8.9â•… (Continued)

Compound C -O O-H O H

Cu2C27 H13OH ⋅ H 2O 1.451 0.984 1.911

Ni2C27 H13OH ⋅ H 2O 1.449 0.981 1.964

C31 H15OH ⋅ H 2O 1.490 0.979 2.024

Cu2C31 H15OH ⋅ H 2O 1,453 0.981 1.964

Ni2C31 H15OH ⋅ H 2O 1.446 0.979 1.997

H 2O ⋅ H 2O
– 0.978 1.906

At the first stage of the investigation we minimized the energy of all

the considered structures in the presence of water molecule and without
it. In Figures 8.9–8.11, you can see the optimized geometric structures for
complexes containing copper cluster. In the second column of Table 8.5,
we can find the lengths of C - O bond formed by OH - group with carbon
envelope atom for the calculated complexes, the bond length in hydroxyl
group in the third column, and the lengths of hydrogen bond for com-
plexes with a water molecule in the fourth column.
The analysis of geometric parameters demonstrates that in all cases
a metal presence results in the decrease of C - O bond length formed by
OH - group with the carbon envelope atom. The especially strong effect is
observed in the defectless carbon envelope which is explained by a high
stability of defectless graphite-like systems. The metal availability results
in the increased activity of the carbon envelope due to the additional elec-
tron density and destabilization of aromatic rings. The defects of carbon
grid have a similar effect.
At the same time, the pentagonal defect is usually characterized by the
electron density excess, and the heptagonal one by its lack. If we compare
the two metals clusters considered, we see that for the system with pen-
tagonal defect copper influence is stronger than nickel one, and for the
rest of the systems we observe the opposite effect. A metal has only an
insignificant influence on O - H bond length.
Development of Computational Techniques in Nanosystems 211

The interaction with water molecule results in the increase of O - H

bond length in the hydroxyl group of carbon envelope and decrease of
C - O bond length. In the presence of metal the length of hydrogen bond
decreases in all the cases, and copper clusters cause the formation of short-
er hydrogen bonds. In our calculations, we took into account the BSSE. In
Table 8.6 we see the interaction energies of the considered model systems
with water molecule. In Table 8.6, the energy of intermolecular interaction
in water dimer calculated using the basis 6−31+G* is given for compari-
son.
From Table 8.6, we observe that the interaction of hydroxylated car-
bon envelopes with water molecule is significantly weaker than the in-
termolecular interaction in water dimer. The strongest hydrogen bond is
formed in case of the envelope with pentagonal defect C23 H11OH . This
result correlates with the minimal length of C - O bond in the envelope
C23 H11OH (Table 8.9). Thus, hydrogen bond is getting weaker in the hy-
droxyl group and it provides the formation of a stronger hydrogen bond.
The main conclusion from Table 8.6 is a considerable strengthening of hy-
drogen bond in metal systems. For complex Cu2C27 H13OH ⋅ H 2O with de-
fectless carbon envelope the energy of hydrogen bond increases in 2.5× in
comparison with a similar complex without metal. The greatest energy of
hydrogen bond is obtained for complex Ni2C27 H13OH ⋅ H 2O . This energy
exceeds the energy of hydrogen bond in water dimer by over 40 per cent.

TABLE 8.10â•… Interaction energy of model clusters with water molecule (kJ/mol)

Compound
Eint

C23 H11OH ⋅ H 2O 18.12

Cu2C23 H11OH ⋅ H 2O
26.06

Ni2C23 H11OH ⋅ H 2O 31.56

C27 H13OH ⋅ H 2O 11.01

Cu2C27 H13OH ⋅ H 2O 27.04

212 Applied Research on Polymer Composites

TABLE 8.10â•… (Continued)

Compound
Eint

Ni2C27 H13OH ⋅ H 2O 19.65

C31 H15OH ⋅ H 2O
15.08

Cu2C31 H15OH ⋅ H 2O 13.75

Ni2C31 H15OH ⋅ H 2O 16.88

C60 ( OH )2 ⋅ H 2O
21.98

H 2O ⋅ H 2O 22.37

It should be noted that in the frameworks of model HF/6–31G the en-

ergy of hydrogen bond for hydroxyfullerene C60 ( OH )10 ⋅ ( H 2O )10 is higher
than the energy of hydrogen bond in water dimer by 60 percent (Table 8.7).
The semi-empirical calculations for complex C60 ( OH )2 ⋅ H 2O predict that
the energy of hydrogen bond two times exceeds the one in water dimer.
When calculating by the method described in the final part of this chapter,
the energy of hydrogen bond for hydroxyfullerene C60 ( OH )10 ⋅ ( H 2O )10 is
higher by 37 per cent than the bond energy in water dimer. Thus, taking
into account diffusion and polarization functions we considerably change
the results. The additional reason for the difference in the calculation of
complex C60 ( OH )10 ⋅ ( H 2O )10 is the use of the method of hydrogen bond
energy evaluation with breaking off all water molecules while preserving
the system symmetry.
The main conclusion from the calculation results presented is a consid-
erable increase in hydrogen bond energy with water molecule for carbon
graphite-like nanoparticles containing the nucleus from transition metal
atoms. Besides, the energy of C - O bond between carbon envelope and
hydroxyl group increases in the presence of metal. Thus, the probability of
the formation of hydroxylated nanoparticles increases. The nanoparticles
considered have a strong orientating effect on water medium and become
the embryos while forming materials with improved characteristics. A
similar effect is observed when water molecule interacts with hydroxy-
Development of Computational Techniques in Nanosystems 213

fullerene. In this case, the interaction energy depends considerably on the

number of OH– groups in the molecule. Thus, the interaction energy of
water molecules with hydroxyfullerene in cluster C60 ( OH )10 ⋅ ( H 2O )10 ex-
ceeds the interaction energy in water dimer by 40–60 percent depending
on the calculation model by 40–60 per cent. At the same time, for complex
C60 ( OH )2 ⋅ H 2O hydrogen bond is a little weaker than in water dimer.

8.1.3â•… QUANTUM-CHEMICAL INVESTIGATION OF

INTERACTION BETWEEN FRAGMENTS OF METAL–CARBON
NANOCOMPOSITES AND POLYMERIC MATERIALS FILLED BY
METAL CONTAINING PHASE

There is a strong necessity to define formulations components processes

conditions for nanostructured materials filled by metallic additives. An-
other task is optimization of components, nanocomposites and diluents
combination and, in what follows, curing processes with determined tem-
perature mode. The result of these arrangements will be materials with
layerwise homogeneous metal particles/nanocomposites distribution for-
mulation in ligand shell.
The result of these arrangements will be homogeneous metal particles/
nanocomposites distribution in acetylacetone ligand shell. In the capac-
ity of conductive filler silver nanoclusters/nanocrystals and copper-nickel/
carbon nanocomposites can be used. It should be lead to decrease volume
resistance from 10−4 to 10−6 Ω·cm and increase of adhesive/paste adhesion.
Silver filler is more preferable due to excellent corrosion resistance and
conductivity, but its high cost is serious disadvantage. Hence alternative
conductive filler, notably nickel-carbon nanocomposite was chosen to fur-
ther computational simulation. In developed adhesive/paste formulations
metal containing phase distribution is determined by competitive coordi-
nation and cross-linking reactions.
There are two parallel technological paths that consist of preparing
blend based on epoxy resin (ER) and preparing another one based on poly-
ethylene polyamine (PEPA). Then prepared blends are mixed and cured
with diluent gradual removing. Curing process can be tuned by complex
diluent contains of acetiylacetone (AсAс), diacetonealcohol (DAсA) (in
ratio AсAс:DAсA=1:1) and silver particles being treated with this com-
plex diluent. The ER with silver powder mixing can lead to homogeneous
214 Applied Research on Polymer Composites

formulation formation. Blend based on PEPA formation comprises AA

and copper-/nickel-carbon nanocomposites introducing. Complex diluent
removing tunes by temperature increasing to 150–160ºC. Initial results
formulation with 0.01 percent nanocomposite (by introduced metal total
weight) curing formation showed that silver particles were self-organized
and assembled into layer-chained structures.
Acetylacetone (AcAc) infrared spectra were calculated with Hyper-
Chem software. Calculations were carried out by the use of semi-empirical
methods PM3 and ZINDO/1 and ab initio method with 6–31G** basis set
[16]. Results of calculation have been compared with instrumental mea-
surement performed IR-Fourier spectrometer FSM-1201. Liquid adhesive
components were preliminary stirred in ratio 1:1 and 1:2 for the purpose
of interaction investigation. Stirring was carried out with magnetic mixer.
Silver powder was preliminary crumbled up in agate mortar. Then acety-
lacetone was added. Obtained mixture was taken for sample after silver
powder precipitation.
Sample was placed between two KBr glass plates with identical clamps.
In the capacity of comparative sample were used empty glass plates. Every
sample spectrum was performed for five times and the final one was cal-
culated by striking an average. Procedure was carried out in transmission
mode and then data were recomputed to obtain absorption spectra.
There are four possible states of AA: ketone, ketone-enol, enol A, enol
B (Figure 8.12). Vibrational analysis is carried out with one of semi-em-
pirical of ab initio methods and can allow to recognize different states of
reagents by spectra comparison.

FIGURE 8.12â•… Different states of acetylacetone.

Development of Computational Techniques in Nanosystems 215

The vibrational frequencies are derived from the harmonic approxima-

tion, which assumes that the potential surface has a quadratic form. The
association between transition energy ∆E and frequency ν is performed by
Einstein’s formula

DE=h · ν (2)

where h is the Planck constant. IR frequencies (~1012 Hz) accord with gaps
between vibrational energy levels. Thus, each line in an IR spectrum rep-
resents an excitation of nuclei from one vibrational state to another [17].
Comparison between MNDO, AM1 and PM3 methods were performed
in [18]. Semi-empirical method PM3 demonstrated the closest correspon-
dence to experimental values.
In the Figure 8.13 showed experimental data of IR-Fourier spectrom-
eter AA measurement and data achieved from the National Institute of
Advanced Industrial Science and Technology open database. Peaks com-
parison is clearly shown both spectra generally identical. IR spectra for
comparison with calculated ones were received from open AIST database
[1]. As it can be concluded from AIST data, experimental IR spectrum was
measured for AA ketone state.
As we can see, most intensive peak 1622 cm−1 belongs to C=O bond
vibrations. Oxygen relating to this bond can participate in different coor-
dination reactions. Peaks 915 cm−1 and 956cm−1 belong to O-H bond vibra-
tions. This bond can also take part in many reactions.
Computational part is comprised several steps. There were several
steps in computational part. Firstly, geometry of AA was optimized to
achieve molecule stable state. Then vibrational analysis was carried out.
Parameters of the same computational method were used for subsequent
IR spectrum calculation. Obtained IR spectra are shown in Figure 8.14.
216 Applied Research on Polymer Composites

FIGURE 8.13â•… Experimental IR spectrum of acetylacetone obtained from IR-Fourier

FSM-1201 spectrometer (a) and IR spectrum of acetylacetone received from open AIST
database (b).
Development of Computational Techniques in Nanosystems 217

FIGURE 8.14â•… (Continued)

218 Applied Research on Polymer Composites

FIGURE 8.14â•… IR spectra of acetylacetone calculated with hyperChem software: semi-

empirical method ZINDO/1 (a); semi-empirical method PM3 (b); ab initio method with
6–31G** basis set (c); ab initio method with 6–21G basis set (d).

Vibrational analysis performed by HyperChem was showed that PM3

demonstrates more close correspondence with experimental and ab ini-
tio calculated spectra than ZINDO/1. As expected, ab initio spectra were
demonstrated closest result in general. As we can see at Figure 8.14(c) and
8.14(d), peaks of IR spectrum calculated with 6–21G small basis set are
staying closer with respect to experimental values than ones calculated
Development of Computational Techniques in Nanosystems 219

with large basis set 6–31G**. Thus it will be reasonable to use both PM3
and ab initio with 6–21G basis set methods in further calculations.

FIGURE 8.15â•… IR spectra obtained with ab initio method with 6–21G basis set:
acetylacetone (a); acetylacetone with silver powder (b); experimental data obtained from
IR-Fourier FSM-1201 spectrometer: acetylacetone with silver powder in comparison with
pure acetylacetone (c).
220 Applied Research on Polymer Composites

As shown on Figures 8.15(a) and 8.15(b), peaks are situated almost

identical due to each other with the exception of peak 1,573 cm−1 (Fig-
ure 8.15(b)) which was appeared after silver powder addition. Peak 1,919
cm−1 (Figure 8.15(b)) has been more intensive as compared with similar
one on Figure 8.15(a).
Peaks are found in range 600–700 cm−1 should usually relate to metal
complexes with acetylacetone [19, 20]. IR spectra AA and AA with Ag+
ion calculations were carried out by ab initio method with 6–21G basis set.
PM3 wasn’t used due this method hasn’t necessary parametrization for sil-
ver. In the case of IR spectra ab initio computation unavoidable calculating
error is occurred hence all peaks have some displacement. Peak 549 cm−1
(Figure 8.15(b)) is equivalent to peak 638 cm−1 (Figure 8.15(c)) obtained
experimentally and it is more intensive than similar one on Figure 8.4.
Peak 1974 cm−1 was displaced to mark 1919 cm-1 and became far inten-
sive. It can be explained Ag+ influence and coordination bonds between
metal and AA formation.

FIGURE 8.16â•… Different ways of complex between metal and AA formation: kentone
with metal (a); enol with metal (b).

Complexes between silver and AA depending on enol or ketone state

can form with two different ways (Figure 8.16).
IR spectra of pure acetylacetone and acetylacetone with silver were
calculated with different methods of computational chemistry. PM3 meth-
od was shown closest results with respect to experimental data among
semi-empirical methods. It was established that there is no strong depen-
dence between size of ab initio method basis set and data accuracy. It was
found that IR spectrum carried out with ab initio method with small basis
set 6–21G has more accurate data than analogous one with large basis
set 6–31G**. Experimental and calculated spectra were shown identical
picture of spectral changes with except of unavoidable calculating error.
Development of Computational Techniques in Nanosystems 221

Hence PM3 and ab initio methods can be used in metal-carbon complexes

formations investigations.

8.2â•… THE METAL/CARBON NANOCOMPOSITES INFLUENCE

MECHANISMS ON MEDIA AND ON COMPOSITIONS

The modification of materials by nanostructures (NS) including metal/car-

bon nanocomposites consists in the conducting of the following stages:
1. The choice of liquid phase for the making of finely dispersed sus-
pensions intended for the definite material or composition.
2. The making of finely dispersed suspension with sufficient stability
for the definite composition.
3. The development of conditions of the finely dispersed suspension
introduction into composition.
At the choice of liquid phase for the making of finely dispersed suspen-
sion it should be taken the properties of NS (nanocomposites) as well as
liquid phase (polarity, dielectric penetration, viscosity).
It is perspective if the liquid phase completely enter into the structure
of material formed during the composition hardening process. When the
correspondent solvent, on the base of which the suspension is obtained, is
evaporated, the re-coordination of nanocomposite on other components
takes place and the effectiveness of action of NS on composition is de-
creased.
The stability of finely dispersed suspension is determined on the opti-
cal density. The time of the suspension optical density conservation de-
fines the stability of suspension. The activity of suspension is found on the
bands intensity changes by means of IR and Raman spectra. The intensity
increasing testify to transfer of NS surface energy vibration part on the
molecules of medium or composition. The line speading in spectra testify
to the growth of electron action of nanocomposites with medium mol-
ecules. Last fact is confirmed by x-ray photoelectron investigations.
The changes of character of distribution on nanoparticles sizes take
place depending on the nature of nanocomposites, dielectric penetration
and polarity of liquid phase. Below characteristics of finely dispersed sus-
pensions of metal/carbon nanocomposites are given. The distribution of
nanoparticles in water, alcohol and water-alcohol suspensions prepared
based on the above technique are determined with the help of laser ana-
222 Applied Research on Polymer Composites

lyzer. In Figures 8.17, 8.18 you can see distributions of copper/carbon

nanocomposite in the media different polarity and dielectric penetration.

FIGURE 8.17â•… Distribution of copper/carbon nanocomposites in alcohol.

FIGURE 8.18â•… Distribution of copper/carbon nanocomposites in water.

FIGURE 8.19â•… Distribution of nickel/carbon nanocomposites in water.

Development of Computational Techniques in Nanosystems 223

FIGURE 8.20â•… Distribution of iron/carbon nanocomposites.

When comparing the figure we can see that ultrasound dispergation

of one and the same nanocomposite in media different by polarity results
in the changes of distribution of its particles. In water solution the aver-
age size of Cu/C nanocomposite equals 20 nm, and in alcohol medium—
greater by 5 nm.
Assuming that the nanocomposites obtained can be considered as os-
cillators transferring their oscillations onto the medium molecules, we can
determine to what extent the IR spectrum of liquid medium will change,
e.g. polyethylene polyamine applied as a hardener in some polymeric
compositions, when we introduce small and supersmall quantities of nano-
composite into it.
IR spectra demonstrate the change in the intensity at the introduction
of metal/carbon nanocomposite in comparison with the pure medium (IR
spectra are given in Figure 8.21). The intensities of IR absorption bands
are directly connected with the polarization of chemical bonds at the
change in their length, valence angles at the deformation oscillations, i.e.
at the change in molecule normal coordinates.
When NS are introduced into media, we observe the changes in the
area and intensity of bands, that indicates the coordination interactions and
influence of NS onto the medium (Figures 8.21–8.23).
224 Applied Research on Polymer Composites

FIGURE 8.21â•… IR spectrum of polyethylene polyamine.

Special attention in PEPA spectrum should be paid to the peak at 1598

сm−1 attributed to deformation oscillations of N-H bond, where hydrogen
can participate in different coordination and exchange reactions.

FIGURE 8.22â•… IR spectrum of copper/carbon nanocomposite finely dispersed suspension

in polyethylene polyamine medium (ω (NC) = 1%).
Development of Computational Techniques in Nanosystems 225

FIGURE 8.23â•… IR spectrum of nickel/carbon nanocomposite fine suspension (FS) in

polyethylene polyamine.

(ω (NC) = 1%)

In the spectra wave numbers characteristic for symmetric νs(NH2) 3352

сm−1 and asymmetric νas(NH2) 3280 сm−1 oscillations of amine groups
are present. There is a number of wave numbers attributed to symmetric
νs(СH2) 2933 сm−1 and asymmetric valence νas(СH2) 2803 сm-1, deforma-
tion wagging oscillations νD(СH2) 1349 сm−1 of methylene groups, de-
formation oscillations of NH νD (NH) 1596 сm-1 and NH2 νD(NH2) 1456
сm−1 amine groups. The oscillations of skeleton bonds at ν(CN) 1,059–
1,273 сm-1 and ν(CС) 837 сm−1 are the most vivid. The analysis of inten-
sities of IR spectra of PEPA and fine suspensions (FS) of metal/carbon
nanocomposites based on it revealed a significant change in the intensities
of amine groups of dispersion medium (for νs(NH2) in 1.26 times, and for
νas(NH2) in approximately 50 times).
Such demonstrations are presumably connected with the distribu-
tion of the influence of nanoparticle oscillations onto the medium with
further structuring and stabilizing of the system. Under the influence of
nanoparticle the medium changes which is confirmed by the results of IR
226 Applied Research on Polymer Composites

spectroscopy (change in the intensity of absorption bands in IR region).

Density, dielectric penetration, viscosity of the medium are the determin-
ing parameters for obtaining FS with uniform distribution of particles in
the volume. At the same time, the structuring rate and consequently the
stabilization of the system directly depend on the distribution by particle
sizes in suspension.
At the wide range of particle distribution by sizes, the oscillation fre-
quency of particles different by size can significantly differ, in this connec-
tion, the distortion in the influence transfer of nanoparticle system onto the
medium is possible (change in the medium from the part of some particles
can be balanced by the other). At the narrow range of nanoparticle distri-
bution by sizes the system structuring and stabilization are possible. With
further adjustment of the components such processes will positively influ-
ence the processes of structuring and self-organization of final composite
system determining physical-mechanical characteristics of hardened or
hard composite system.
The effects of the influence of NS at their interaction into liquid me-
dium depend on the type of NS, their content in the medium and medium
nature. Depending on the material modified, FS of NS based on different
media are used. Water and water solutions of surface-active substances,
plasticizers, foaming agents (when modifying foam concretes) are applied
as such media to modify silicate, gypsum, cement and concrete composi-
tions. To modify epoxy compounds and glues based on ERs the media
based on polyethylene polyamine, isomethyltetrahydrophthalic anhydride,
toluene and alcohol—acetone solutions are applied.
To modify polycarbonates and derivatives of polymethyl methacrylate
dichloroethane and dichloromethane media are used. To modify polyvinyl
chloride compositions and compositions based on phenolformaldehyde
and phenolrubber polymers alcohol or acetone-based media are applied.
The FS of metal/carbon nanocomposites are produced using the above
media for specific compositions. In IR spectra of all studied suspensions
the significant change in the absorption intensity, especially in the regions
of wave numbers close to the corresponding nanocomposite oscillations,
is observed. At the same time, it is found that the effects of nanocomposite
influence on liquid media (FS) decreases with time and the activity of the
corresponding suspensions drops.
The time period in which the appropriate activity of nanocomposites
is kept changes in the interval 24 hours – 1 month depending on the nano-
Development of Computational Techniques in Nanosystems 227

composite type and nature of the basic medium (liquid phase in which
nanocomposites dispergate). For instance, IR spectroscopic investigation
of FS based on isomethyltetrahydrophthalic anhydride containing 0.001%
of Cu/C nanocomposite indicates the decrease in the peak intensity, which
sharply increased on the third day when nanocomposite was introduced
(Figure 8.24). Similar changes in IR spectra take place in water suspen-
sions of metal/carbon nanocomposites based on water solutions of sur-
face-active nanocomposites.

FIGURE 8.24â•… Changes in IR spectrum of copper/carbon nanocomposite FS based on

isomethyltetrahydrophthalic anhydride with time.

(а – IR Spectrum on the First Day After the Nanocomposite was Intro-

duced, b – IR Spectrum on the Second Day, c – IR Spectrum on the Third
Day)
In Figure 8.25 you can see IR spectrum of iron/carbon nanocomposite
based on water solution of sodium lignosulfonate in comparison with IR
spectrum of water solution of surface-active substance.
228 Applied Research on Polymer Composites

FIGURE 8.25â•… Comparison of IR spectra of water solution of sodium lignosulfonate (1)

and FS of iron/carbon nanocomposite (0.001%) based on this solution on the first day after
nanocomposite introduction (2), on the third day (3), on the seventh day (4), 14th day (5)
and 28th day. (6)

As it is seen, when nanocomposite is introduced and undergoes ultra-

sound dispergation, the band intensity in the spectrum increases signifi-
cantly. Also the shift of the bands in the regions 1100 – 1,300 сm−1, 2,100 –
2,200 сm−1 is observed, which can indicate the interaction between sodium
lignosulfonate and nanocomposite. However after 2 weeks the decrease in
band intensity is seen. As the suspension stability evaluated by the optic
density is 30 days, the nanocomposite activity is quite high in the period
when IR spectra are taken. It can be expected that the effect of foam con-
crete modification with such suspension will be revealed if only 0.001%
of nanocomposite is introduced.

8.3â•… THE COMPOSITIONS MODIFICATION PROCESSES BY

METAL/CARBON NANOCOMPOSITES

8.3.1â•… GENERAL FUNDAMENTALS OF POLYMERIC MATERIALS

MODIFICATION BY METAL/CARBON NANOCOMPOSITES

The material modification with the using of Metal/Carbon Nanocompos-

ites is usually carried out by finely dispersed suspensions containing sol-
Development of Computational Techniques in Nanosystems 229

vents or components of polymeric compositions. We realize the modifi-

cation of the following materials: concrete foam, dense concrete, water
glass, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polymethyl
methacrylate, polycarbonate, ERs, phenol-formaldehyde resins, reinforced
plastics, glues, pastes, including current conducting polymeric materials
and filled polymeric materials.
Therefore it is necessary to use the different finely dispersed suspen-
sion for the modification of enumerated materials. The series of suspen-
sions consist the suspensions on the basis of following liquids: water, etha-
nol, acetone, benzene, toluene, dichlorethane, methylene chloride, oleic
acid, polyethylene polyamine, isomethyl tetra hydrophtalic anhydrite,
water solutions surface-active substances or plasticizers. In some cases
the solutions of correspondent polymers are applied for the making of the
stable finely dispersed suspensions. The estimation of suspensions stabil-
ity is given as the change of optical density during the definite time (Figure
8.26)

FIGURE 8.26â•… The change of optical density of typical suspension depending on time.

Relative change of free energy of coagulation process also may be as

the estimation of suspension stability –
230 Applied Research on Polymer Composites

ΔΔF = lg kNC/kNT (3),

where kNC – exp( -ΔFNC/RT) – the constant of coagulation rate of nano-

composite, kNT - exp( -ΔFNT/RT) – the constant of coagulation rate of car-
bon nanotube, ΔFNC, ΔFNT – the changes of free energies of corresponding
systems (Figure 8.27).

FIGURE 8.27â•… The comparison of finely dispersed suspensions stability.

The stabilityof metal/carbon nanocomposites suspension depend on the

interactions of solvents with nanocomposites participation (Figure 8.28).

FIGURE 8.28â•… Microphotographs of Co/C nanocomposite suspension on the basis of

mixture “dichlorethane—oleic acid” (a) and Oleic Acid (b).

The introduction of metal/carbon nanocomposites leads to the changes

of kinematic and dynamic viscosity (Figure 8.29).
Development of Computational Techniques in Nanosystems 231

FIGURE 8.29â•… The dependence of dynamic and kinematic viscosity on the Cu/C
nanocomposite quantity.

For the description of polymeric composition self organization the crit-

ical parameters (critical content of NS critical time of process realization,
critical energetic action) may be used. The equation of NS influence on
medium is proposed –

W = n/N exp{antb/T} (4)

where n – number of active NS, N – number of NS interaction, a – activity

of NS, t - duration of self organization process, T – temperature, b - degree
of freedom (number of process direction).

8.3.2â•… ABOUT THE MODIFICATION OF FOAM CONCRETE

BY METAL/CARBON NANOCOMPOSITES SUSPENSION

The ultimate breaking stresses were compared in the process of compres-

sion of foam concretes modified with copper/carbon nanocomposites ob-
tained in different nanoreactors of polyvinyl alcohol [21, 22]. The sizes
of nanoreactors change depending on the crystallinity and correlation of
acetate and hydroxyl groups in PVA which results in the change of sizes
and activity of nanocomposites obtained in nanoreactors. It is observed
that the sizes of nanocomposites obtained in nanoreactors of PVA matrixes
16/1 (ros) (NC2), PVA 16/1 (imp) (NC1), PVA 98/10 (NC3), correlate as
NC3 > NC2 > NC1. The smaller the nanoparticle size the greater its activ-
ity, and the less amount of NS is required for self-organization effect.
232 Applied Research on Polymer Composites

FIGURE 8.30â•… The dependence of breaking stresses on quantity (%) of metal/carbon

nanocomposites.

At the same time, the oscillatory nature of the influence of these nano-
composites on the compositions of foam concretes is seen in the fact that if
the amount of nanocomposite is 0.0018% from the cement mass, the signifi-
cant decrease in the strength of NC1 and NC2 is observed. The increase in
foam concrete strength after the modification with iron/carbon nanocompos-
ite is a little smaller in comparison with the effects after the application of
NC1 and NC2 as modifiers. The corresponding effects after the modification
of cement, silicate, gypsum, and concrete compositions with NS is defined
by the features of components and technologies applied.
Development of Computational Techniques in Nanosystems 233

These features often explain the instability of the results after the modi-
fication of the foregoing compositions with NS. Besides during the modi-
fication the changes in the activity of FS of NS depending on the duration
and storage conditions should be taken into account. In this regard, it is
advisable to use metal/carbon nanocomposites when modifying polymeric
materials whose technology was checked on strictly controlled compo-
nents.
In this chapter the possibilities of developing new ideas about self-
organization processes and about NS and nanosystems are discussed on
the example of metal/carbon nanocomposites. The obtaining of metal/car-
bon nanocomposites in nanoreactors of polymeric matrixes is proposed to
consider as self-organization process similar to the formation of ordered
phases which can be described with Avrami equation. The application of
Avrami equations during the synthesis of nanofilm structures containing
copper clusters has been tested. The influence of NS on active media is
given as the transfer of oscillation energy of the corresponding NS onto
the medium molecules.
The IR spectra of metal/carbon and their finely dispersed suspensions
in different media (water and organic substances) have been studied for
the first time. It has been found that the introduction of super small quanti-
ties of prepared nanocomposites leads to the significant change in band
intensity in IR spectra of the media. The attenuation of oscillations gener-
ated by the introduction of nanocomposites after the time interval specific
for the pair “nanocomposite—medium” has been registered.
Thus, to modify compositions with finely dispersed suspensions it is
necessary for the latter to be active enough that should be controlled with
IR spectroscopy. A number of results of material modification with finely
dispersed suspensions of metal/carbon nanocomposites are given, as well
as the examples of changes in the properties of modified materials based
on concrete compositions, epoxy and phenol resins, polyvinyl chloride,
polycarbonate, and current-conducting polymeric materials.

8.3.3â•… THE MODIFICATION OF EPOXY RESINS BY METAL/

CARBON NANOCOMPOSITES SUSPENSIONS

The IR spectra of polyethylene polyamine and metal/carbon nanocompos-

ite FS based on it with concentrations 0.001%–0.03% from polyethylene
234 Applied Research on Polymer Composites

polyamine mass are analyzed and their comparative analysis is presented.

The possible processes flowing in FS during the interaction of copper/
carbon nanocomposite and polyethylene polyamine are described, as well
as the processes influencing the increase in adhesive strength and thermal
stability of metal/carbon nanocomposite/epoxy compositions.
This decade has been heralded by a large-scale replacement of conven-
tional metal structures with structures from polymeric composite materi-
als (PCM). Currently, we are facing the tendency of production growth of
PCM with improved operational characteristics. In practice, PCM charac-
teristics can be improved when applying modern manufacturing technolo-
gies, e.g., the application of “binary” technologies of prepreg production
[23], as well as the synthesis of new polymeric PCM matrixes or modifica-
tion of the existing polymeric matrixes with different fillers.
The most cost-efficient way to improve operational characteristics is
to modify the existing polymeric matrixes; therefore, currently the group
of polymeric materials modified with NS is of special interest. The NS
are able to influence the supermolecular structure, stimulate self-organi-
zation processes in polymeric matrixes in supersmall quantities, and thus
contributing to the efficient formation of a new phase “medium modified
– nanocomposite” and qualitative improvement of the characteristics of
final product – PCM. This effect is especially visible when NS activity
increases which directly depends on the size of specific surface, shape of
the particle, and its ultimate composition [22]. Metal ions in the NS used
in this work also contribute to the activity increase as they stimulate the
formation of new bonds.
The increase in the attraction force of two particles is directly propor-
tional to the growth of their elongated surfaces; therefore, the possibility
of NS coagulation and decrease in their efficiency as modifiers increases
together with their activity growth. This condition and the fact that the
effective concentrations to modify polymeric matrixes are usually in the
range <0.01 mass percent impose specific methods for introducing NS into
the material modified. The most justified and widely applicable are the
methods for introducing NS with the help of FS.
Quantum-chemical modeling methods allow quite precisely defining
the typical reaction of interaction between the system components, predict
the properties of molecular systems, and decrease the number of experi-
ments due to the imitation of technological processes. The computational
results are completely comparable with the experimental modeling results.
Development of Computational Techniques in Nanosystems 235

The optimal composition of nanocomposite was found with the help

of software HyperChem v. 6.03. Cu/C nanocomposite is the most effec-
tive for modifying the ER. Nanosystems formed with this NC have higher
interaction energy in comparison with nanosystems produced with Ni/C
and Co/C nanocomposites. The effective charges and geometries of nano-
systems were found with semi-empirical methods.
The fact of producing stable FS of nanocomposite on PEPA basis and
increasing the operational characteristics of epoxy polymer was ascer-
tained. It was demonstrated that the introduction of Cu/C nanocomposite
into PEPA facilitates the formation of coordination bonds with nitrogen
of amine groups, thus resulting in PEPA activity increase in ER harden-
ing reactions. It was found out that the optimal time period of ultrasound
processing of copper/carbon nanocomposite FS is 20 min.
The dependence of Cu/C nanocomposite influence on PEPA viscosity
in the concentration range 0.001–0.03% was found. The growth of specific
surface of NC particles contributes to partial decrease in PEPA kinematic
viscosity at concentrations 0.001% and 0.01% with its further elevation
at the concentration 0.03%. The IR investigation of Cu/C nanocomposite
FS confirms the quantum-chemical computational experiment regarding
the availability of NC interactions with PEPA amine groups. The intensity
of these groups increased several times when Cu/C nanocomposite was
introduced.
The test for defining the adhesive strength and thermal stability cor-
relate with the data of quantum-chemical calculations and indicate the
formation of a new phase facilitating the growth of cross-links number
in polymer grid when the concentration of Cu/C nanocomposite goes up.
The optimal concentration for elevating the modified ER adhesion equals
0.003% from ER weight.
At this concentration the strength growth is 26.8%. From the concen-
tration range studied, the concentration 0.05% from ER weight is optimal
to reach a high thermal stability. At this concentration the temperature of
thermal destruction beginning increases up to 195°С. Thus, in this work
the stable FS of Cu/C nanocomposite were obtained. The modified poly-
mers with increased adhesive strength (by 26.8%) and thermal stability
(by 110°С) were produced based on epoxy resins and FS.
236 Applied Research on Polymer Composites

8.3.4â•… THE MODIFICATION OF GLUES BASED ON

PHENOL–FORMALDEHYDE RESINS BY METAL/CARBON
NANOCOMPOSITES FINELY DISPERSED SUSPENSION

In modern civil and industrial engineering, mechanical engineering, and

so on, extra strong, rather light, durable metal structures, wooden struc-
tures, and light assembly structures are widely used. However, they de-
form lose stability and load-carrying capacity under the action of high
temperatures; therefore, fire protection of such structures is important is-
sue for investigation.
To decrease the flammability of polymeric coatings it is advisable
to create and forecast the properties of materials with external intumes-
cent coating containing active structure-forming agents —regulators of
foam cokes structure. At present, metal/carbon nanocomposites are such
perspective modifiers. The introduction of nanocomposites into the coat-
ing can improve the material behavior during the combustion, retarding
the combustion process [24, 25]. In this regard, it is advisable to modify
metal/carbon nanocomposites with ammonium phosphates to increase the
compatibility with the corresponding compositions.
The grafting of additional functional groups is appropriate in strength-
ening the additive interaction with the matrix and, thus, in improving the
material properties. The grafting can contribute to improving the homoge-
neity of NS distribution in the matrix and suspension stability. Owing to
partial ionization additional groups produce a small surface charge with
the result of NS repulsion from each other and stabilization of their disper-
sion. Phosphorylation leads to the increase in the influence of NS on the
medium and material being modified, as well as to the improvement of the
quality of NS due to metal reduction [26–28].
The glue BF-19 (based on phenol–formaldehyde resins) is intended
for gluing metals, ceramics, glass, wood, and fabric in hot condition, as
well as for assembly gluing of cardboard, plastics, leather, and fabrics in
cold condition. The glue compositions are organic solvent, synthetic resin
(phenol–formaldehyde resins of new lacquer type), and synthetic rubber.
When modifying the glue composition, at the first stage the mixture of
alcohol suspension (ethyl alcohol + Me/C NC modified) and ammonium
polyphosphate (APPh) was prepared. At the same time, the mixtures con-
taining ethyl alcohol, Me/C NC, and APPh, were prepared. At the second
Development of Computational Techniques in Nanosystems 237

stage the glue composition was modified by the introduction of phospho-

rus containing compositions prepared into the glue BF-19.
The interaction of nanocomposites with APPh results in grating phos-
phoryl groups to them that allowed using these nanocomposites to mod-
ify intumescent fireproof coatings. The sorption ability of functionalized
nanocomposites was studied. It was found out that phospholyrated NS
have higher sorption ability than nanocomposites not containing phospho-
rus. Since the sorption ability indicates the nanoproduct activity degree,
it can be concluded that nanocomposite activity increases in the presence
of active medium and modifier (APPh). The IR spectra of suspensions
of nanocomposites on alcohol basis were investigated. It was found that
changes in IR spectrum by absorption intensity indicate the presence of
excitation source in the suspension. It was assumed that NS are such
source of band intensity increase in suspension IR spectra.
The glue coatings were modified with metal/carbon nanocomposite.
It was determined that nanocomposite introduction into the glue signifi-
cantly decreases the material flammability. The samples with phospholy-
rated nanocomposites have better test results. When phosphorus contain-
ing nanocomposite is introduced into the glue, foam coke is formed on the
sample surface during the fire exposure. The coating flaking off after flame
exposure was not observed as the coating preserved good adhesive proper-
ties even after the flammability test.
The nanocomposite surface phospholyration allows improving the
nanocomposite structure, increases their activity in different liquid media
thus increasing their influence on the material modified. The modifica-
tion of coatings with nanocomposites obtained finally results in improving
their fire-resistance and physical and chemical characteristics.

8.3.5â•… THE MODIFICATION OF POLYCARBONATE BY

METAL/CARBON NANOCOMPOSITES

Recently, the materials based on polycarbonate have been modified to im-

prove their thermal-physical and optical characteristics and to apply new
properties to use them for special purposes. The introduction of NS into
materials facilitates self-organizing processes in them. These processes
depend on surface energy of NS which is connected with energy of their
238 Applied Research on Polymer Composites

interaction with the surroundings. It is known [21] that the surface energy
and activity of nanoparticles increase when their sizes decrease.
For nanoparticles the surface and volume are defined by the defective-
ness and form of conformation changes of film NS depending on their
crystallinity degree. However, the possibilities of changes in nanofilm
shapes with the changes in medium activity are greater in comparison with
NS already formed. At the same time, sizes of nanofilms formed and their
defectiveness, i.e. tears and cracks on the surface of nanofilms play an
important role [22]
When studying the influence of supersmall quantities of substances in-
troduced into polymers and considerably changing their properties, appar-
ently we should consider the role which these substances play in polymers
possessing highly organized supermolecular regularity both in crystalline
and in amorphous states. It can be assumed that the mechanism of this
phenomenon is in the NS energy transfer to polymer structural formations
through the interface resulting in the changes in their surface energy and
mobility of structural elements of the polymeric body. Such mechanism
is quite realistic as polymers are structural-heterogenic (highly dispersed)
systems.
Polycarbonate modification with supersmall quantities of Cu/C nano-
composite is possible using FS of this nanocomposite which contributes
to uniform distribution of nanoparticles in polycarbonate solution. Poly-
carbonate “Actual” was used as the modified polycarbonate. The FS of
copper/carbon nanocomposite was prepared combining 1.0, 0.1, 0.01, and
0.001% of nanocomposite in polycarbonate solution in ethylene dichlo-
ride. The suspensions underwent ultrasonic processing.
To compare the optical density of nanocomposite suspension in poly-
carbonate solution in ethylene dichloride, as well as polycarbonate and
polycarbonate samples modified with nanocomposites, spectrophotometer
KFK-3-01а was used. Samples in the form of modified and non-modified
films for studying IR spectra were prepared precipitating them from sus-
pension or solution under vacuum. The obtained films about 100 mcm
thick were examined on Fourier-spectrometer FSM 1201.To investigate
the crystallization and structures formed the high-resolution microscope
(up to 10 mcm) was used.
To examine thermal–physical characteristics the lamellar material on
polycarbonate and polymethyl methacrylate basis about 10 mm high was
prepared. Three layers of polymethyl methacrylate and two layers of poly-
Development of Computational Techniques in Nanosystems 239

carbonate were used. Thermal–physical characteristics (specific thermal

capacity and thermal conductivity) were investigated on calorimeters IT-c-
400 and IT-λ-400.During the investigation the nanocomposite FS in poly-
carbonate solution in ethylene dichloride was studied, polycarbonate films
modified with different concentrations of nanocomposite were compared
with the help of optical spectroscopy, microscopy, IR spectroscopy, and
thermal–physical methods of investigation.
The results of investigation of optical density of Cu/C nanocomposite
FS (0.001%) based on polycarbonate solution in ethylene dichloride are
given in Figure 8.31. As seen in Figure 8.31, the introduction of nanocom-
posite and polycarbonate into ethylene dichloride resulted in transmission
increase in the range 640–690 nm (approximately in three times). At the
same time, the significant increase in optical density was observed at 790
and 890 nm. The comparison of optical densities of films of polycarbon-
ate and modified materials after the introduction of different quantities of
nanocomposite (1.0, 0.1, 0.01%) into polycarbonate is interesting (Figure
8.32).

FIGURE 8.31â•… Curves of optical density of suspension based on ethylene dichloride

diluted with polycarbonate and Cu/C nanocomposite in the concentration to polycarbonate
0.001% (1) and ethylene dichloride (2).
240 Applied Research on Polymer Composites

Comparison of optical density of suspension containing 0.001% of

nanocomposite and optical density polycarbonate sample modified with
0.01% of nanocomposite indicates the proximity of curves character. Thus,
the correlation of optical properties of suspensions of nanocomposites and
film materials modified with the same nanocomposites is quite possible.

FIGURE 8.32â•… Curves of optical density of reference sample modified with Cu/C
nanocomposites in concentration 1%, 0.1%, 0.01%.

Examination of curves of sample optical density demonstrated that

when the NS concentration was 1% from polycarbonate mass, the visible-
light spectrum was absorbed by about 4.2 per cent more when compared
with the reference sample. When the nanocomposite concentration was
0.1 percent, the absorption decreased by 0.7 per cent. When the concentra-
tion was 0.01 per cent, the absorption decreased in the region 540–600 nm
by 2.3 per cent, and in the region 640–960 nm – by 0.5 per cent.
During the microscopic investigation of the samples the schematic
picture of the structures formed was obtained at 20-mcm magnification.
The results are given in Figure 8.33. From the schematic pictures it is
seen that volumetric structures of regular shape surrounded by micellae
were formed in polycarbonate modified with 0.01% Cu/C nanocompos-
ite. When 0.1% of nanocomposite was introduced, the linear structures
distorted in space and surrounded by micellae were formed. When Cu/C
Development of Computational Techniques in Nanosystems 241

nanocomposite concentration was 1%, large aggregates were not observed

in polycarbonate.

FIGURE 8.33â•… schematic picture of structure formation in polycarbonate modified with

Cu/C nanocomposites in concentrations 1%, 0.1%, 0.01% (From left to the right), 20-mcm
magnification.

Apparently, the decrease in nanocomposite concentration in polycar-

bonate can result in the formation of self-organizing structures of bigger
size. In Ref. [3], there is an hypothesis on the transfer of nanocomposite
oscillations onto the molecules of polymeric composition, and the inten-
sity of bands in IR spectra which sharply increases even after the introduc-
tion of supersmall quantities of nanocomposites. In our case, this hypoth-
esis was checked on modified and non-modified samples of polycarbonate
films.
In Figure 8.34, the IR spectra of polycarbonate and polycarbonate
modified with 0.001% of Cu/C nanocomposite can be observed.

FIGURE 8.34â•… ir spectra of reference sample (upper) and polycarbonate modified with
Cu/C nanocomposites in concentration 0.001% (Lower).
242 Applied Research on Polymer Composites

As seen in IR spectra, the intensity increases in practically all regions,

indicating the influence of oscillations of Cu/С nanocomposite on all
the systems. The most vivid changes in the band intensity are observed
at 557€сm−1, in the region 760–930€сm−1, at 1,400€сm-1, 1,600€сm-1, and
2,970€сm−1. Thus, polycarbonate self-organization under the influence of
Cu/C nanocomposite takes place with the participation of certain bonds,
for which the intensity of absorption bands goes up. At the same time,
the formation of new phases is possible which usually results in thermal
capacity increase. However, thermal conductivity can decrease due to the
formation of defective regions between the aggregates formed. Table 8.11
contains the results of thermal–physical characteristics studied.

TABLE 8.11â•… Thermal–physical characteristics of polycarbonate and its modified analogs

Nanocomposite content in polycarbonate (%)

Parameters
0%, ref. 1% 0.1% 0.01%

m ´ 10–3, kg 1.9 1.955 1.982 1.913

h ´10 , m
–3
9.285 9.563 9.76 9.432
Сsp, J/kg
1440 1028 1400 1510
К
Λ 0.517 0.503 0.487 0.448

It is demonstrated that when the NS concentration in the material de-

creases, thermal capacity goes up which is confirmed by the results of pre-
vious investigations. Thermal conductivity decline, when the NS concen-
tration decreases, is apparently caused by the material defectiveness When
Cu/C nanocomposites are introduced into the modified material, the NS
can be considered as the generator of molecules excitation, which results
in wave process in the material. It is found that polycarbonate modifica-
tion with metal/carbon containing nanocomposites results in the changes
in polycarbonate structure influencing its optical and thermal–physical
properties.
Development of Computational Techniques in Nanosystems 243

KEYWORDS

•â•¢ Hydroxyfullerene molecules

•â•¢ quantum-chemical investigation
•â•¢ Semiempirical method

REFERENCES

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1347–1363.
2. Copley, J. R. D.; Neumann, D. A.; Cappelletti, R. L.; Kamitakahara, W. A.; J. Phys.
Chem. Solids. 1992. V. 53. N 11. Р. 1353–1371.
3. Sh. Lo, V. Li, Russian chemical journal, 5, 40–48 (1999)
4. А.N. Ponomarev, Constructional materials, 6, 69–71 (2007).
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power engineering and ecology, 4, 36–41 (2005)
6. A.A. Granovsky, PC GAMESS version 7.1.5 (http://classic.chem.msu.su/gran/
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14, 1347–1363 (1993)
7. Bürgi, T.; Droz, T.; Leutwyler, S.; Chemical Physics Letters 1995, 246, 291–299.
8. Matsumoto, Y.; Ebata, T.; Mikami, N. J.; Chem. Phys. 1998, 109, 6303–6311.
9. Schemmel, D.; Schütz, M. J.; Chem. Phys. 2008, 129, 034301.
10. Famulari, A.; Raimondi, M.; Sironi, M.; Gianinetti, E.; Chemical Physics 1998, 232,
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11. Hedberg, K.; Hedberg, L.; Bethune, D.S.; et al., Science 1991, 254, 410–412.
12. Copley, J. R. D.; Neumann, D. A.; Cappelletti, R. L.; Kamitakahara, W. A.; J Phys
Chem Solids 1992, 53, 1353–1371.
13. Lipanov, A. М.; Kodolov, V. I.; Khokhriakov, N. V.; Didik, A. А.; Kodolova, V.V.;
Semakina, N. V.; Alternative power engineering and ecology, 2005, № 2. P. 58–63
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Wang, J. Nieplocha, E. Apra, T.L. Windus, W.A. de Jong, Comput. Phys. Commun.,
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A. Famulari, M. Raimondi, M. Sironi, E. Gianinetti Chemical Physics, 232, 289–298
(1998)
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cgi-bin/cre_index.cgi?lang=eng
16. HyperChem 8 manual. Computational Chemistry, 2002. p. 149, p. 369.
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in organic chemistry.–M.: Chemistry, 1971–264p.
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nanostructures and its expression in nanoreactors of polymeric matrixes and active
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meric materials, 2010.-Iss. 2–3. Pp. 40–43.
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CHAPTER 9

CALCULATING THE INTERNAL

STRUCTURE AND THE EQUILIBRIUM
CONFIGURATION (SHAPE) OF
SEPARATE NONINTERACTING
NANOPARTICLES BY THE
MOLECULAR MECHANICS AND
DYNAMICS INTERACTIONS OF
NANOSTRUCTURAL ELEMENTS
A. V. VAKHRUSHEV and A. M. LIPANOV

CONTENTS

9.1 Introduction................................................................................... 246

9.2 Problem Statement........................................................................ 249
9.3 The Calculation of the Pairwise Interaction of the
Two Nanostructure Elements........................................................ 251
9.4 Problem Formulation for Interaction of Several Nanoelements... 254
9.5 Numerical Procedures and Simulation Techniques...................... 256
9.6 Results and Discussions ............................................................... 258
9.7 Nanoparticles Interaction.............................................................. 262
9.8 Conclusions................................................................................... 275
Acknowledgments.................................................................................. 276
Keywords............................................................................................... 277
References.............................................................................................. 277
246 Applied Research on Polymer Composites

9.1â•…INTRODUCTION

The properties of a nanocomposite are determined by the structure and

properties of the nanoelements, which form it. One of the main tasks in
making nanocomposites is building the dependence of the structure and
shape of the nanoelements forming the basis of the composite on their
sizes. This is because with an increase or a decrease in the specific size
of nanoelements (nanofibers, nanotubes, nanoparticles, and so on), their
physical—mechanical properties such as coefficient of elasticity, strength,
deformation parameter, and so on, are varying over one order [1–5].
The calculations and experiments show that this is primarily due to a
significant rearrangement (which is not necessarily monotonous) of the
atomic structure and the shape of the nanoelement. The experimental in-
vestigation of the aforementioned parameters of the nanoelements is tech-
nically complicated and laborious because of their small sizes. In addition,
the experimental results are often inconsistent. In particular, some authors
have pointed to an increase in the distance between the atoms adjacent to
the surface in contrast to the atoms inside the nanoelement, whereas others
observe a decrease in the aforementioned distance [6].
Thus, further detailed systematic investigations of the problem with
the use of theoretical methods, i.e., mathematical modeling, are required.
The atomic structure and the shape of nanoelements depend both on their
sizes and on the methods of obtaining which can be divided into two main
groups:
1. Obtaining nanoelements in the atomic coalescence process by
“assembling” the atoms and by stopping the process when the
nanoparticles grow to a desired size (the so-called “bottom—up”
processes). The process of the particle growth is stopped by the
change of physical or chemical conditions of the particle forma-
tion, by cutting off supplies of the substances that are necessary
to form particles, or because of the limitations of the space where
nanoelements form.
2. Obtaining nanoelements by breaking or destructing more massive
(coarse) formations to the fragments of the desired size (the so-
called “up—down” processes).
In fact, there are many publications describing the modeling of the
“bottom-up” processes [7–8], whereas the “up-down” processes have been
studied very little. Therefore, the objective of this work is the investigation
Calculating the Internal Structure and the Equilibrium 247

of the regularities of the changes in the structure and shape of nanopar-

ticles formed in the destruction (“up-down”) processes depending on the
nanoparticle sizes, and building up theoretical dependences describing the
aforementioned parameters of nanoparticles.
When the characteristics of powder nanocomposites are calculated it
is also very important to take into account the interaction of the nanoele-
ments since the changes in their original shapes and sizes in the interaction
process during the formation (or usage) of the nanocomposite can lead to
a significant change in its properties and a cardinal structural rearrange-
ment. In addition, the experimental investigations show the appearance of
the processes of ordering and self-assembling leading to a more organized
form of a nanosystem [9–15].
In general, three main processes can be distinguished: the first pro-
cess is because of the regular structure formation at the interaction of the
nanostructural elements with the surface where they are situated; the sec-
ond one arises from the interaction of the nanostructural elements with
one another; the third process takes place because of the influence of the
ambient medium surrounding the nanostructural elements. The ambient
medium influence can have “isotropic distribution” in the space or it can
be presented by the action of separate active molecules connecting na-
noelements to one another in a certain order. The external action signifi-
cantly changes the original shape of the structures formed by the nanoele-
ments. For example, the application of the external tensile stress leads to
the “stretch” of the nanoelement system in the direction of the maximal
tensile stress action; the rise in temperature, vice versa, promotes a de-
crease in the spatial anisotropy of the nanostructures [10]. Note that in the
self-organizing process, parallel with the linear moving, the nanoelements
are in rotary movement. The latter can be explained by the action of mo-
ment of forces caused by the asymmetry of the interaction force fields of
the nanoelements, by the presence of the “attraction” and “repulsion” local
regions on the nanoelement surface, and by the “non-isotropic” action of
the ambient as well.
The aforementioned phenomena play an important role in nanotechno-
logical processes. They allow developing nanotechnologies for the forma-
tion of nanostructures by the self-assembling method (which is based on
self-organizing processes) and building up complex spatial nanostructures
consisting of different nanoelements (nanoparticles, nanotubes, fullerenes,
super-molecules, and so on) [15]. However, in a number of cases, the ten-
dency towards self-organization interferes with the formation of a desired
248 Applied Research on Polymer Composites

nanostructure. Thus, the nanostructure arising from the self-organizing

process is, as a rule, “rigid” and stable against external actions. For ex-
ample, the “adhesion” of nanoparticles interferes with the use of separate
nanoparticles in various nanotechnological processes, the uniform mixing
of the nanoparticles from different materials and the formation of nano-
composite with desired properties. In connection with this, it is important
to model the processes of static and dynamic interaction of the nanostruc-
ture elements. In this case, it is essential to take into consideration the
interaction force moments of the nanostructure elements, which causes the
mutual rotation of the nanoelements.
The investigation of the aforementioned dependences based on the
mathematical modeling methods requires the solution of the aforemen-
tioned problem on the atomic level. This requires large computational aids
and computational time, which makes the development of economical cal-
culation methods urgent. The objective of this work was the development
of such a technique. This chapter gives results of the studies of problems of
numeric modeling within the framework of molecular mechanics and dy-
namics for investigating the regularities of the amorphous phase formation
and the nucleation and spread of the crystalline or hypocrystalline phases
over the entire nanoparticle volume depending on the process parameters,
nanoparticles sizes, and thermodynamic conditions of the ambient. In ad-
dition, the method for calculating the interactions of nanostructural ele-
ments is offered, which is based on the potential built up with the help of
the approximation of the numerical calculation results using the method
of molecular dynamics of the pairwise static interaction of nanoparticles.
Based on the potential of the pairwise interaction of the nanostructure ele-
ments, which takes into account forces and moments of forces, the method
for calculating the ordering and self-organizing processes has been devel-
oped.
The investigation results on the self-organization of the system con-
sisting of the presence of two or more particles and the analysis of the
equilibrium stability of various types of nanostructures has been car-
ried out. These results are a generalization of the authors’ research in
[16–24]. A more detailed description of the problem can be obtained in
these works.
Calculating the Internal Structure and the Equilibrium 249

9.2â•… PROBLEM STATEMENT

The problem on calculating the internal structure and the equilibrium con-
figuration (shape) of separate non-interacting nanoparticles by the mo-
lecular mechanics and dynamics methods has two main stages:
1. The “initiation” of the task, i.e., the determination of the conditions
under which the process of the nanoparticle shape and structure
formation begins.
2. The process of the nanoparticle formation.
Note that the original coordinates and initial velocities of the nanopar-
ticle atoms should be determined from the calculation of the macroscopic
parameters of the destructive processes at static and dynamic loadings
taking place on both the nanoscale and the macroscale. Therefore, in the
general case, the coordinates and velocities are the result of solving the
problem of modeling physical—mechanical destruction processes at dif-
ferent structural levels. This problem due to its enormity and complexity is
not considered in this chapter. The detailed description of its statement and
the numerical results of its solution are given in the works of the authors
[16–19].
The problem of calculating the interaction of ordering and self-organi-
zation of the nanostructure elements includes three main stages: the first
stage is building the internal structure and the equilibrium configuration
(shape) of each separate non-interacting nanostructure element; the second
stage is calculating the pairwise interaction of two nanostructure elements;
and the third stage is establishing the regularities of the spatial structure
and evolution with time of the nanostructure as a whole. Let us consider
the aforementioned problems in sequence.

9.2.1â•… THE CALCULATION OF THE INTERNAL STRUCTURE

AND THE SHAPE OF THE NON-INTERACTING
NANOELEMENT

The initialization of the problem is in giving the initial coordinates and

velocities of the nanoparticle atoms.
     , (9.1)
xi = xi 0 ,Vi = Vi 0 , t = 0, xi ⊂ Ω k
250 Applied Research on Polymer Composites

   
where x i 0 ,x i are original and current coordinates of the i th atom; Vi 0 , Vi
are initial and current velocities of the i th atom, respectively; Ω k is an
area occupied by the nanoelement.
The problem of calculating the structure and the equilibrium configura-
tion of the nanoelement will be carried out with the use of the molecular
dynamics method taking into consideration the interaction of all the atoms
forming the nanoelement. Since, at the first stage of the solution, the na-
noelement is not exposed to the action of external forces, it is taking the
equilibrium configuration with time, which is further used for the next
stage of calculations.
At the first stage, the movement of the atoms forming the nanoparticle
is determined by the set of Langevin differential equations at the boundary
conditions Eq. (9.1) [25]
 Nk
d Vi   
mi ⋅ = ∑ Fij + Fi (t ) - a i mi Vi , i = 1,2,. ..,N k ,
dt j =1 (9.2)
 
dx i
= Vi ,
dt

where N k is the number of atoms forming each nanoparticle, mi is the

mass of the i th atom, a i is the “friction” coefficient in the atomic struc-

ture, and Fi (t ) is a random set of forces at a given temperature which is
given by Gaussian distribution.
Usually, the interatomic interaction forces are potential and determined
by the relation

 n
∂Φ (rij )
Fij = - ∑  , i = 1, 2,...,N k , j = 1, 2,...,N k , (9.3)
1 ∂rij

where rij is a radius-vector determining the position of the i th atom rela-
tive to the j th atom; Φ(rij ) is a potential depending on the mutual posi-
tions of all the atoms; n is the number of interatomic interaction types.

In the general case, the potential Φ(rij ) is given in the form of the sum
of several components corresponding to different interaction types:

Φ ( rij ) = Φ cb + Φ va + Φ ta + Φ pg + Φ vv + Φ es + Φ hb . (9.4)
Calculating the Internal Structure and the Equilibrium 251

Here the following potentials are implied: Φ cb —of chemical bonds, Φ va

—of valence angles, Φ ta —of torsion angles; Φ pg —of flat groups; Φ vv —
of Van der Waals contacts; Φ es —of electrostatics; and Φ hb —of hydrogen
bonds.
The aforementioned addends have different functional forms. The pa-
rameter values for the interaction potentials are determined based on the
experiments (crystallography, spectral, calorimetric, and so on) and quan-
tum calculations [25].
Giving original coordinates (and forces of atomic interactions) and ve-
locities of all the atoms of each nanoparticle in accordance with Eq. (9.2),
at the start time, we find the change of the coordinates and the velocities of
each nanoparticle atoms with time from the equation of motion Eq. (9.1).
Since the nanoparticles are not exposed to the action of external forces,
they take some atomic equilibrium configuration with time that we will
use for the next calculation stage.

9.3â•… THE CALCULATION OF THE PAIRWISE INTERACTION OF

THE TWO NANOSTRUCTURE ELEMENTS

At this stage of solving the problem, we consider two interacting nanoele-

ments. First, let us consider the problem statement for symmetric nanoele-
ments, and then for arbitrary shaped nanoelements.
First of all, let us consider two symmetric nanoelements situated at the
distance S from one another (Figure 9.1) at the initial conditions
   
xi = xi 0 ,Vi = 0, t = 0, xi ⊂ Ω1  Ω 2 , (9.5)

where Ω1, Ω 2 are the areas occupied by the first and the second nanopar-
ticle, respectively.

We obtain the coordinates x i 0 from Eq. (9.2) solution at initial condi-
tions (9.1). It allows calculating the combined interaction forces of the
nanoelements
N1 N2
  
Fb1 = -Fb 2 = ∑ ∑F , ij (9.6)
i =1 j =1
252 Applied Research on Polymer Composites

where i, j are the atoms and N1 , N 2 are the numbers of atoms in the first
and the second nanoparticles, respectively.

Forces Fij are defined from Eq. (9.3).
In the general case, the force magnitude of the nanoparticle interaction

Fbi can be written as product of functions depending on the sizes of the
nanoelements and the distance between them:

Fbi = Φ11 ( Sc ) × Φ12 ( D) (9.7)

FIGURE 9.1â•… Scheme of the nanoparticle interaction; A—an enlarged view of the
nanoparticle fragment.
Calculating the Internal Structure and the Equilibrium 253


The Fbi vector direction is determined by the direction cosines of a vector
connecting the centers of the nanoelements.
Now, let us consider two interacting asymmetric nanoelements situated
at the distance Sc between their centers of mass (Figure 9.2) and oriented
at certain specified angles relative to each other.
In contrast to the earlier problem, the interatomic interaction of the
nanoelements leads not only to the relative displacement of the nanoele-
ments but also to their rotation as well. Consequently, in the general case,
the sum of all the forces of the interatomic interactions of the nanoele-

ments is brought to the principal vector of forces Fc and the principal mo-

ment M ñ
N1 N2
   
Fc = Fb1 = -Fb 2 = ∑
i =1
∑F ,
j =1
ij
(9.8)

N1 N2
    
M c = M c1 = - M c 2 = ∑ ∑r cj × Fij , (9.9)
i =1 j =1


where rcj is a vector connecting points c and j .
The main objective of this calculation stage is building the dependenc-
es of the forces and moments of the nanostructure—nanoelement interac-
tions on the distance Sc between the centers of mass of the nanostructure
nanoelements, on the angles of mutual orientation of the nanoelements
Θ1 , Θ 2 , Θ3 (shapes of the nanoelements) and on the characteristic size D
of the nanoelement. In the general case, these dependences can be given
in the form

 
Fbi = Φ F ( Sc , Θ1 , Θ 2 , Θ 3 , D) , (9.10)

 
M bi = Φ M ( Sc , Θ1 , Θ 2 , Θ 3 , D) , (9.11)
254 Applied Research on Polymer Composites

 
FIGURE 9.2â•… Two interacting nanoelements; M , F are the principal moment and the
principal vector of the forces, respectively.

For spherical nanoelements, the angles of the mutual orientation do

not influence the force of their interaction; therefore, in Eq. (9.12), the
moment is zero.
In the general case, functions in Eqs. (9.11) and (9.12) can be ap-
proximated by analogy with Eq. (9.8) as the product of functions
S0 , Θ1 , Θ 2 , Θ 3 , D , respectively. For the further numerical solution of the
problem of the self-organization of nanoelements, it is sufficient to give
the aforementioned functions in their tabular form and to use the linear (or
non-linear) interpolation of them in space.

9.4â•… PROBLEM FORMULATION FOR INTERACTION OF SEVERAL

NANOELEMENTS

When the evolution of the nanosystem as whole (including the processes

of ordering and self-organization of the nanostructure nanoelements) is in-
vestigated, the movement of each system nanoelement is considered as the
movement of a single whole. In this case, the translational motion of the
Calculating the Internal Structure and the Equilibrium 255

center of mass of each nanoelement is given in the coordinate system X1,

X2, X3, and the nanoelement rotation is described in the coordinate system
Z1, Z2, Z3, which is related to the center of mass of the nanoelement (Figure
9.2). The system of equations describing the aforementioned processes has
the form.

 d 2 X 1k
N e
 Mk 2
= ∑ FXkj + FXke ,
 dt j =1
1 1

 N
 d 2 X 2k e
Mk = ∑ FXkj + FXke ,
 dt 2
j =1
2 2

N
 d 2 X 3k e
 Mk 2
= ∑ FXkj + FXke ,
 dt j =1
3 3

 N (9.12)
 k d 2Θ1k d Θ k2 d Θ3k k e

 J Z1 2
+ ⋅ ( J Z - J Zk ) = ∑ M Zkj + M Zke ,
dt dt dt 3 2 1 1
 j =1

 d 2Θ 2k d Θ1k d Θ3k k e N

 J Zk2 2
+ ⋅ ( J Z - J Zk ) = ∑ M Zkj + M Zke ,
 dt dt dt 1 3
j =1
2 2

 N
 k d 2Θ 3k d Θ k2 d Θ1k k e

 J Z3 2
+ ⋅ ( J Z - J Zk ) = ∑ M Zkj + M Zke ,
 dt dt dt 2 1
j =1
3 3

where X i , Θi
k
are coordinates of the centres of mass and angles of the spatial
k

kj kj kj
orientation of the principal axes Z , Z , Z of nanoelements; FX , FX , FX
1 2 3 1 2 3
ke ke ke
are the interaction forces of nanoelements; FX1 , FX 2 , FX 3 are external forc-
es acting on nanoelements; N e is the number of nanoelements; M k is
ke ke ke
a mass of a nanoelement; M Z1 , M Z2 , M Z3 are the moment of forces of the
nanoelement interaction; M Z1 , M Z2 , M Z3 are the external moments acting
ke ke ke

k k k
on nanoelements; and J Z1 , J Z 2 , J Z3 are moments of inertia of a nanoelement.
The initial conditions for the system of Eqs. (9.13) and (9.14) have the
form

    dΘk d Θ 0k
X k = X0k ; Θ k = Θ 0k ; V k = V0k ; = ; t = 0, (9.13)
dt dt
256 Applied Research on Polymer Composites

9.5â•… NUMERICAL PROCEDURES AND SIMULATION

TECHNIQUES

In the general case, the problem formulated in the previous sections has
no analytical solution at each stage; therefore, numerical methods for solv-
ing are used, as a rule. In this chapter, for the first stages, the numerical
integration of the equation of motion of the nanoparticle atoms in the re-
laxation process are used in accordance with Verlet scheme [26]:
n
    Nk     , (9.14)
( )
xin +1 = xin + Dt Vin + ( Dt ) 2 / 2mi  ∑ Fij + Fi - a i mi Vin 
 j =1 

  Nk   Nk  
Vin +1 = (1 - Dta i ) Vin + ( Dt / 2mi )((∑ Fij + Fi )n + (∑ Fij + Fi )n +1 ) ,(9.15)
j =1 j =1

n  n
where x i , Vi are a coordinate and a velocity of the i th atom at the n
th step with respect to the time, and Dt is a step with respect to the time.
The solution of Eq. (9.13) also requires the application of numerical
methods of integration. In the present work, Runge–Kutta method [27] is
used for solving Eq. (9.13).

1 k
( X ik ) n +1 = ( X ik ) n + (Vi k ) n Dt + ( m1i + m2ki + m3ki ) Dt , (9.16)
6

1 k
(Vi k ) n +1 = (Vi k ) n + ( m1i + 2 m 2ki + 2 m3ki + m 4ki ) . (9.17)
6

( ( ) ( ) )
mlik = Φ ik tn ; X ik ,...; Vi k ... Dt ,
n n

Dt Dt mk
m 2ki = Φ ik (tn + ;( X ik + Vi k ) n ,...;(Vi k ) n + 1i ,...) Dt ,
2 2 2
Dt Dt Dt mk
m3ki = Φ ik (tn + ;( X ik + Vi k + m1ki )n ,...;(Vi k )n + 2i ,...) Dt ,
2 2 4 2
Calculating the Internal Structure and the Equilibrium 257

k k k k k Dt k k
m 4i = Φ i (t n + Dt; ( X i + Vi Dt + m 2i ) n ,...; (Vi ) n + m 2i ,...)Dt .
2
Dt
(9.18) m 4ki = Φ ik (tn + Dt;( X ik + Vi k Dt + m 2ki )n ,...;(Vi k )n + m 2ki ,...) Dt
2


N
1 e
Φ ik = (∑ FXkj + FXke ) (9.19)
M k j =1 3 3

dΘk 1

(Θik )n +1 = (Θik )n + ( i )n Dt + (λ1ki + λ 2ki + λ3ki ) Dt
(9.20) dt 6

d Θ ik dΘk 1 (9.21)
( ) n +1 = ( i ) n + (λ1ki + 2λ 2ki + 2λ3ki + λ 4ki )
dt dt 6

d Θ ik ,
λ1ki = Ψik (tn ;(Θ ik ) n ,...;( ) n ...) Dt
dt

Dt d Θ ik Dt dΘk λk
λ 2ki = Ψik (tn + ;(Θ ik + ) n ,...;( i ) n + 1i ,...) Dt ,
2 dt 2 dt 2

λ3ki = Ψik (tn +

Dt
;(Θik +
d Θik Dt Dt dΘk λk
+ λ1ki )n ,...;( i )n + 2i ,...) Dt
, (9.22)
2 dt 2 4 dt 2

d Θ ik Dt dΘk
λ 4ki = Ψik (tn + Dt ;(Θ ik + Dt + λ 2ki ) n ,...;( i ) n + λ 2ki ,...) Dt .
dt 2 dt

N
1 d Θ k2 d Θ 3k k e
Ψ1k = k
(- ⋅ ( J Z - J Zk ) + ∑ M Zkj + M Zke ) ,
JZ dt dt 3 2
j =1
1 1
1

N
1 d Θ1k d Θ 3k k e
Ψk2 = k
(- ⋅ ( J Z - J Zk ) + ∑ M Zkj + M Zke ) , (9.23a)
JZ dt dt 1 3
j =1
2 2
2

N
1 d Θ1k d Θ 2k k e
Ψ3k = k
(- ⋅ ( J Z - J Zk ) + ∑ M Zkj + M Zke ) ,
JZ dt dt 1 2
j =1
3 3
3
258 Applied Research on Polymer Composites

where i =1, 2, 3; k =1, 2, N e

9.6â•… RESULTS AND DISCUSSIONS

Let us consider the realization of the aforementioned procedure taking the

calculation of the metal nanoparticle as an example.
The potentials of the atomic interaction of Morse (Eq. (9.23b)) and
Lennard-Johns (Eq. (9.24)) were used in the following calculations
  
Φ (rij ) m = Dm (exp(-2λ m ( rij - r0 )) - 2exp(- λ m ( rij - r0 ))) , (9.23b)

 
12
 σ  
6
σ
Φ ( rij ) LD = 4ε    -     , (9.24)
 r   rij  
  ij 

where Dm , λm , r 0 , ε , σ are the constants of the materials studied.
For sequential and parallel solving the molecular dynamics equations,
the program package developed at Applied Mechanics Institute, the Ural
Branch of the Russian Academy of Sciences, and the advanced program
package NAMD developed at the University of Illinois, and Beckman In-
stitute (USA) by the Theoretical Biophysics Group were used. The graphic
imaging of the nanoparticle calculation results was carried out with the use
of the program package VMD.

9.6.1â•… STRUCTURE AND FORMS OF NANOPARTICLES

At the first stage of the problem, the coordinates of the atoms positioned
at the ordinary material lattice points (Figure 9.3, (1)) were taken as the
original coordinates. During the relaxation process, the initial atomic sys-
tem is rearranged into a new “equilibrium” configuration (Figure 9.3, (2))
in accordance with the calculations based on Eq. (9.6)–( 9.9), which sat-
isfies the condition when the system potential energy is approaching the
minimum (Figure 9.3, the plot).
Calculating the Internal Structure and the Equilibrium 259

FIGURE 9.3â•… The initial crystalline (1) and cluster (2) structures of the nanoparticle
consisting of 1331 atoms after relaxation; the plot of the potential energy U [J] variations
for this atomic system in the relaxation process ( n number of iterations with respect to
the time).

After the relaxation, the nanoparticles can have quite diverse shapes:
globe-like, spherical centered, spherical eccentric, spherical icosahedral
nanoparticles, and asymmetric nanoparticles (Figure 9.4).

FIGURE 9.4â•… nanoparticles of diverse shapes, depending on the number of atoms they
consist of.
260 Applied Research on Polymer Composites

In this case, the number of atoms N significantly determines the shape

of a nanoparticle. Note, that symmetric nanoparticles are formed only at
a certain number of atoms. As a rule, in the general case, the nanoparticle
deviates from the symmetric shape in the form of irregular raised portions
on the surface. Besides, there are several different equilibrium shapes for
the same number of atoms. The plot of the nanoparticle potential energy
change in the relaxation process (Figure 9.5) illustrates it.
As it follows from this figure, the curve has two areas: the area of the
decrease of the potential energy and the area of its stabilization promot-
ing the formation of the first nanoparticle equilibrium shape (1). Then, a
repeated decrease in the nanoparticle potential energy and the stabilization
area corresponding to the formation of the second nanoparticle equilib-
rium shape are observed (2). Between them, there is a region of the tran-
sition from the first shape to the second one (P). The second equilibrium
shape is more stable due to the lesser nanoparticle potential energy. How-
ever, the first equilibrium shape also “exists” rather long in the calculation
process. The change of the equilibrium shapes is especially characteristic
of the nanoparticles with an “irregular” shape. The internal structure of the
nanoparticles is of importance since their atomic structure significantly
differs from the crystalline structure of the bulk materials: the distance
between the atoms and the angles change, and the surface formations of
different types appear. In Figure 9.6, the change of the structure of a two-
dimensional nanoparticle in the relaxation process is shown.

FIGURE 9.5â•… The plot of the potential energy change of the nanoparticle in the relaxation
process.
Calculating the Internal Structure and the Equilibrium 261

1—a region of the stabilization of the first nanoparticle equilibrium

shape; 2—a region of the stabilization of the second nanoparticle equi-
librium shape; and P—a region of the transition of the first nanoparticle
equilibrium shape into the second one.

FIGURE 9.6â•… The change of the structure of a two-dimensional nanoparticle in the

relaxation process:1—the initial crystalline structure; 2, 3, 4—the nanoparticles structures
which change in the relaxation process; p—pores; and c—the region of compression.

Figure 9.6 shows how the initial nanoparticle crystalline structure (po-
sition 1) is successively rearranging with time in the relaxation process
(positions 2, 3, 4). Note that the resultant shape of the nanoparticle is not
round, i.e., it has “remembered” the initial atomic structure. It is also of
interest that in the relaxation process, in the nanoparticle, the defects in the
form of pores (designation “p” in the figure) and the density fluctuation
regions (designation “c” in the figure) have been formed, which are absent
in the final structure.
262 Applied Research on Polymer Composites

9.7â•… NANOPARTICLES INTERACTION

Let us consider some examples of nanoparticles interaction. Figure 9.7

shows the calculation results demonstrating the influence of the sizes of
the nanoparticles on their interaction force. One can see from the plot that
the larger nanoparticles are attracted stronger, i.e., the maximal interaction
force increases with the size growth of the particle. Let us divide the inter-
action force of the nanoparticles by its maximal value for each nanopar-
ticle size, respectively. The obtained plot of the “relative” (dimensionless)
force (Figure 9.8) shows that the value does not practically depend on the
nanoparticle size as all the curves come close and can be approximated to
one line.
Figure 9.9 displays the dependence of the maximal attraction force
between the nanoparticles on their diameter that is characterized by non-
linearity and a general tendency towards the growth of the maximal force
with the nanoparticle size growth.
The total force of the interaction between the nanoparticles is deter-
mined by multiplying of the two plots (Figures 9.8 and 9.9).

FIGURE 9.7â•… The dependence of the interaction force F [N] of the nanoparticles on the
distance s [nm] between them and on the nanoparticle size: 1—d = 2.04; 2—d = 2.40; 3—d
= 3.05; 4—d = 3.69; 5—d = 4.09 [nm].
Calculating the Internal Structure and the Equilibrium 263

FIGURE 9.8â•… The dependence of the “relative” force F of the interaction of the
nanoparticles on the distance S [nm] between them.

FIGURE 9.9â•… The dependence of the maximal attraction force Fmax [N] the nanoparticles
on the nanoparticle diameter d [nm].

Using the polynomial approximation of the curve in Figure 9.5 and the
power mode approximation of the curve in Figure 9.6, we obtain
264 Applied Research on Polymer Composites

F = ( -1.13S 6 + 3.08S 5 - 3.41S 4 - 0.58S 3 + 0.82 S - 0.00335)103 , (9.25)

Fmax ⋅ = 0.5 ⋅ 10 -9 ⋅ d 1.499 , (9.26)

F = Fmax ⋅ F , (9.27)

where d and S are the diameter of the nanoparticles and the distance be-
tween them [nm], respectively; Fmax is the maximal force of the interaction
of the nanoparticles [N].
Dependences Eqs. (9.25)–(9.27) were used for the calculation
of the nanocomposite ultimate strength for different patterns of
nanoparticles’ “packing” in the composite (Figure 9.10).

FIGURE 9.10â•… Different types of the nanoparticles’ “packing” in the composite.

FIGURE 9.11â•… The dependence of the ultimate strength σ [MPa] of the nanocomposite
formed by monodisperse nanoparticles on the nanoparticle sizes d [nm].
Calculating the Internal Structure and the Equilibrium 265

Figure 9.11 shows the dependence of the ultimate strength of the nano-
composite formed by monodisperse nanoparticles on the nanoparticle
sizes. One can see that with the decrease of the nanoparticle sizes, the
ultimate strength of the nanomaterial increases, and vice versa. The cal-
culations have shown that the nanocomposite strength properties are sig-
nificantly influenced by the nanoparticles’ “packing” type in the material.
The material strength grows when the packing density of nanoparticles
increases. It should be specially noted that the material strength changes
in inverse proportion to the nanoparticle diameter in the degree of 0.5,
which agrees with the experimentally established law of strength change
of nanomaterials (the law by Hall-Petch) [18].

σ = C ⋅ d -0.5 , (9.28)

where C = C max =2.17 × 104 is for the maximal packing density; C = Cmin
=6.4 × 103 is for the minimal packing density.
The electrostatic forces can strongly change force of interaction of
nanoparticles. For example, numerical simulation of charged sodium
(NaCl) nanoparticles system (Figure 9.12) has been carried out. Consid-
ered ensemble consists of eight separate nanoparticles. The nanoparticles
interact due to Van-der-Waals and electrostatic forces.
Results of particles center of masses motion are introduced in Figure
9.13 representing trajectories of all nanoparticles included into system. It

shows the dependence of the modulus of displacement vector R on time.

One can see that nanoparticle moves intensively at first stage of calcula-
tion process. At the end of numerical calculation, all particles have got

new stable locations, and the graphs of the radius vector R become sta-
tionary. However, the nanoparticles continue to “vibrate” even at the final
stage of numerical calculations. Nevertheless, despite of “vibration”, the
system of nanoparticles occupies steady position.
266 Applied Research on Polymer Composites

FIGURE 9.12â•… Nanoparticles system consists of eight nanoparticles NaCl.

FIGURE 9.13â•… The dependence of nanoparticle centers of masses motion R on the time
t; a, b --the nanoparticle positions at time 0 and t, accordingly; 1–8–are the numbers of the
nanoparticles.

However, one can observe a number of other situations. Let us consid-

er, for example, the self-organization calculation for the system consisting
of 125 cubic nanoparticles, the atomic interaction of which is determined
by Morse potential (Figure 9.14).
Calculating the Internal Structure and the Equilibrium 267

FIGURE 9.14â•… The positions of the 125 cubic nanoparticles: (a)–initial configuration;
(b)—final configuration of nanoparticles.

As you see, the nanoparticles are moving and rotating in the self-or-
ganization process forming the structure with minimal potential energy.
Let us consider, for example, the calculation of the self-organization of
the system consisting of two cubic nanoparticles, the atomic interaction
of which is determined by Morse potential [12]. Figure 9.15 displays pos-
sible mutual positions of these nanoparticles. The positions, where the
principal moment of forces is zero, corresponds to pairs of the nanopar-
ticles 2–3; 3–4; 2–5 (Figure 9.15) and defines the possible positions of
their equilibrium.

FIGURE 9.15â•… Characteristic positions of the cubic nanoparticles.

268 Applied Research on Polymer Composites

FIGURE 9.16â•… The dependence of the moment M [Nm] of the interaction force between
cubic nanoparticles 1–3 (see in Figure 9.9) on the angle of their relative rotation θ [rad].

Figure 9.16 presents the dependence of the moment of the interaction

force between the cubic nanoparticles 1–3 (Figure 9.15) on the angle of
their relative rotation. From the plot follows that when the rotation angle
of particle 1 relative to particle 3 is π / 4 , the force moment of their inter-
action is zero. At an increase or a decrease in the angle the force moment
appears. In the range of π / 8 < θ < 3π / 4 the moment is small. The force
moment rapidly grows outside of this range. The distance S between the
nanoparticles plays a significant role in establishing their equilibrium.
If S > S0 (where S0 is the distance, where the interaction forces of the
nanoparticles are zero), then the particles are attracted to one another. In
this case, the sign of the moment corresponds to the sign of the angle θ
deviation from π / 4 . At S < S0 (the repulsion of the nanoparticles), the
sign of the moment is opposite to the sign of the angle deviation. In other
words, in the first case, the increase of the angle deviation causes the in-
crease of the moment promoting the movement of the nanoelement in the
given direction, and in the second case, the angle deviation causes the
increase of the moment hindering the movement of the nanoelement in
the given direction. Thus, the first case corresponds to the unstable equi-
librium of nanoparticles, and the second case–to their stable equilibrium.
The potential energy change plots for the system of the interaction of two
cubic nanoparticles (Figure 9.17) illustrate the influence of the parameter
S . Here, curve 1 corresponds to the condition S < S0 and it has a well-
Calculating the Internal Structure and the Equilibrium 269

expressed minimum in the 0.3< θ <1.3 region. At θ <0.3and θ >1.3, the

interaction potential energy sharply increases, which leads to the return of
the system into the initial equilibrium position. At S > S0 (curves 2–5), the
potential energy plot has a maximum at the θ =0 point, which corresponds
to the unstable position.

FIGURE 9.17â•… The plots of the change of the potential energy E [Nm] for the Interaction
of two cubic nanoparticles depending on the angle of their relative rotation θ [rad] and the
distance between them (positions of the nanoparticles 1–3, Figure 9.9).

The carried-out theoretical analysis is confirmed by the works of the

scientists from New Jersey University and California University in Berke-
ley who experimentally found the self-organization of the cubic micro-
particles of plumbum zirconate–titanate (PZT) [28]: the ordered groups
of cubic micro-crystals from PZT obtained by hydrothermal synthesis
formed a flat layer of particles on the air–water interface, where the par-
ticle occupied the more stable position corresponding to position 2–3 in
Figure 9.15.
Thus, the analysis of the interaction of two cubic nanoparticles has
shown that different variants of their final stationary state of equilibrium
270 Applied Research on Polymer Composites

are possible, in which the principal vectors of forces and moments are
zero. However, there are both stable and unstable stationary states of this
system: nanoparticle positions 2–3 are stable, and positions 3–4 and 2–5
have limited stability or they are unstable depending on the distance be-
tween the nanoparticles.
Note that for the structures consisting of a large number of nanopar-
ticles, there can be a quantity of stable stationary and unstable forms of
equilibrium. Accordingly, the stable and unstable nanostructures of com-
posite materials can appear. The search and analysis of the parameters
determining the formation of stable nanosystems is an urgent task.
It is necessary to note that the method offered has restrictions. This is
explained by change of the nanoparticles form and accordingly variation
of interaction pair potential during nanoparticles coming together at cer-
tain conditions.

FIGURE 9.18â•… Different type of nanoparticles connection (merging and coupling).

The merge (accretion [4]) of two or several nanoparticles into a single

whole is possible (Figure 9.18). Change of a kind of connection cooperat-
ing nanoparticles (merging or coupling in larger particles) depending onits
sizes, it is possible to explain on the basis of the analysis of the energy
Calculating the Internal Structure and the Equilibrium 271

change graph of connection nanoparticles (Figure 9.19). From Figure 9.19

it follows that although with the size increasing of a particle, energy of
nanoparticles connection Enp grows, its size in comparison with superfi-
cial energy Es of a particle sharply increases at reduction of the sizes of
nanoparticles. Hence, for finer particles, energy of connection can appear
sufficient for destruction of their configuration under action of a mutual
attraction and merging in larger particle.

FIGURE 9.19â•… Change of energy of nanoparticles connection Enp [Nm] and Enp ratio to
superficial energy Es depending on nanoparticles diameter d [nm]. Points designate the
calculated values. ontinuous lines are approximations.

Spatial distribution of particles influences on rate of the forces hold-

ing nanostructures formed from several nanoparticles. On Figure 9.20 the
chain nanoparticles, formed by coupling of three nanoparticles (from 512
atoms everyone), located in the initial moment on one line. Calculations
have shown that, in this case, nanoparticles form a stable chain. Thus, par-
ticles practically do not change the form and cooperate on small platforms.
In the same figure (Figure 9.20) the result of connection of three
nanoparticles located in the initial moment on a circle and consisting of
256 atoms everyone is submitted. In this case particles incorporate among
272 Applied Research on Polymer Composites

themselves “densely,” contacting on a significant part of the external sur-

face.
Distance between particles at which they are in balance is much less
for the particles collected in group ( L3np < L2 np ). It also confirms the graph
0 0

of forces from which it is visible that the maximal force of an attraction

between particles in this case (is designated by a continuous line) is some
times more than at an arrangement of particles in a chain (dashed line)
F3np > F2 np .

FIGURE 9.20â•… Change of force F [N] of three nanoparticles interaction, consisting of

512 atoms everyone, and connected among themselves on a line and on the beams missing
under a corner of 120 degrees, accordingly, depending on distance between them L [nm].

Experimental investigation of the spatial structures formed by nanopar-

ticles [4] confirms that nanoparticles gather to compact objects. Thus, the
internal nuclear structure of the connections area of nanoparticles consid-
erably differs from structure of a free nanoparticle.
Nanoelements’ kind of interaction depends strongly on the tempera-
ture. Figure 9.21 shows the picture of the interaction of nanoparticles at
different temperatures It is seen that with increasing temperature the in-
teraction of changes in sequence occurs (Figure 9.22): coupling (1,2) and
merging (3,4). With further increase in temperature the nanoparticles dis-
persed.
Calculating the Internal Structure and the Equilibrium 273

FIGURE 9.21â•… Change of nanoparticles connection at increase in temperature.

FIGURE 9.22â•… Curve of temperature change.

274 Applied Research on Polymer Composites

Finally, we will consider problems of dynamics of nanoparticles. The

analysis of interaction of nanoparticles among themselves also allows to
draw a conclusion on an essential role in this process of energy of initial
movement of particles. Various processes at interaction of the nanoparti-
cles, moving with different speed, are observed: the processes of agglom-
erate formation, formation of larger particles at merge of the smaller size
particles, absorption by large particles of the smaller ones, and dispersion
of particles on separate smaller ones or atoms.
For example, in Figure 9.23, the interactions of two particles are mov-
ing towards each other with different speed are shown. At small speed of
moving is formed steady agglomerate (Figure 9.23).
In Figure 9.23 (left), interaction of two particles moving towards each
other with the large speed is shown. It is visible that steady formation in
this case is not appearing and the particles collapse.

FIGURE 9.23â•… Pictures of dynamic interaction of two nanoparticles: (a) an initial

configuration nanoparticles; (b) nanoparticles at dynamic interaction, (c) the “cloud” of
atoms formed because of dynamic destruction two nanoparticles.

Nature of interaction of nanoparticles, along with speed of their move-

ment, essentially depends on a ratio of their sizes. In Figure 9.24, pictures
of interaction of two nanoparticles of zinc of the different size are pre-
sented, as well as in the earlier case of a nanoparticle move from initial
situation (1) towards each other. At small initial speed, nanoparticles in-
corporate at contact and form a steady conglomerate (2).
Calculating the Internal Structure and the Equilibrium 275

FIGURE 9.24â•… Pictures of interaction of two nanoparticles of zinc: 1 – initial configuration

of nanoparticles; 2 – connection of nanoparticles, 3,4 – absorption by a large nanoparticle
of a particle of the smaller size, 5 –destruction of nanoparticles at blow.

At increase in speed of movement larger nanoparticle absorbs smaller,

and the uniform nanoparticle (3, 4) is formed. At further increase in speed
of movement of nanoparticles, owing to blow, the smaller particle inten-
sively takes root in big and destroys it.
The given examples show that use of dynamic processes of pressing
for formation of nanocomposites demands a right choice of a mode of the
loading providing integrity of nanoparticles. At big energy of dynamic
loading, instead of a nanocomposite with dispersion corresponding to the
initial size of nanoparticles, the nanocomposite with much larger grain that
will essentially change properties of a composite can be obtained.

9.8â•…CONCLUSIONS

In conclusion, the following basic regularities of the nanoparticle forma-

tion and self-organization should be noted.
276 Applied Research on Polymer Composites

1. The existence of several types of the forms and structures of

nanoparticles is possible depending on the thermodynamic condi-
tions.
2. The absence of the crystal nucleus in small nanoparticles.
3. The formation of a single (ideal) crystal nucleus defects on the
nucleus surface connected to the amorphous shell.
4. The formation of the polycrystal nucleus with defects distributed
among the crystal grains with low atomic density and change inter-
atomic distances. In addition, the grain boundaries are non-equilib-
rium and contain a great number of grain-boundary defects.
5. When there is an increase in sizes, the structure of nanoparticles
is changing from amorphous to roentgen-amorphous and then into
the crystalline structure.
6. The formation of the defect structures of different types on the
boundaries and the surface of a nanoparticle.
7. The nanoparticle transition from the globe-shaped to the crystal-
like shape.
8. The formation of the “regular” and “irregular” shapes of nanopar-
ticles depending on the number of atoms forming the nanoparticle
and the relaxation conditions (the rate of cooling).
9. The structure of a nanoparticle is strained because of the different
distances between the atoms inside the nanoparticle and in its sur-
face layers.
10. The systems of nanoparticles can form stable and unstable nano-
structures.

ACKNOWLEDGMENTS

This work was carried out with financial support from the Research Program
of the Ural Branch of the Russian Academy of Sciences: the projects 12-P-
12-2010, 12-C-1-1004, 12-Т-1-1009, and was supported by the grants of
Russian Foundation for Basic Research (RFFI) 04-01-96017-r2004ural_а,
05-08-50090-а, 07-01-96015-r_ural_а, 08-08-12082-ofi, and 11-03-
00571-а. The author is grateful to his young colleagues Dr. A.A. Vakhru-
shev and Dr. A.Yu. Fedotov for active participation in the development of
the software complex, calculations, and analyzing of numerous calcula-
Calculating the Internal Structure and the Equilibrium 277

tion results. The calculations were performed at the Joint Supercomputer

Center of the Russian Academy of Sciences.

KEYWORDS

•â•¢ Hypocrystalline phases

•â•¢ Nanocomposites
•â•¢ Nanostructural elements

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24. Alikin, V. N.; Vakhrouchev, A. V.; Golubchikov, V. B.; Lipanov, A. M.; Serebrennikov,
S. Y.; Development and Investigation of the Aerosol Nanotechnology. Moscow: Mash-
inostroenie, 2010.196 p. (in Russian)
25. Heerman, W. D.; Computer Simulation Methods in Theoretical Physics. Berlin:
Springer-Verlag; 1986.
Verlet, L.; “Computer “experiments” on classical fluids I. Thermo dynamical properties of
Lennard-Jones molecules”, Phys. Rev., 159, 98–103, 1967.
26. Korn, G. A.; and Korn, M. T.; Mathematical Handbook. New York: McGraw-Hill
Book Company; 1968.
27. Self-organizing of microparticles piezoelectric materials, News of chemistry, date-
news.php.htm.
CHAPTER 10

TRENDS IN OZONATION OF
POLYMER COMPOUNDS
M. P. ANACHKOV, S. K. RAKOVSKY, and G. E. ZAIKOV

CONTENTS

10.1 Introduction................................................................................... 280

10.2 Experimental................................................................................. 281
10.3 Results and Discussion................................................................. 282
10.4 Polychloroprene............................................................................ 300
10.5 DSC Study of Thermal Decomposition of Partially Ozonized
Diene Rubbers............................................................................... 302
10.6 Conclusions................................................................................... 304
Keywords............................................................................................... 305
References.............................................................................................. 305
280 Applied Research on Polymer Composites

10.1â•…INTRODUCTION

The interest in the reaction of ozone with polydienes is mainly due to the
problems of ozone degradation of rubber materials [1–4] and the applica-
tion of this reaction to the elucidation of the structures of elastomers [5–8].
It is also associated with the possibilities of preparing bifunctional oligo-
mers by partial ozonolysis of some unsaturated polymers [9–12]. Usually,
the interpretation of experimental results are based on a simplified scheme
of Criegee’s mechanism of C=C-double bond ozonolysis, explaining only
the formation of the basic product, ozonides [13, 14].
The reactions of ozone with 1,4-cis-polybutadiene Diene 35 NFA hav-
ing the linking of the butadiene units in the rubber macromolecules as
in what follows: 1,4-cis (47%), 1,4-trans (42%), 1,2-cis (11%), 1,4-cis-
polyisoprene (Carom IR 2200), 1,4-trans-polychloroprene (Denka M 40),
and 1,4-trans-polyisoprene have been investigated in CCl4 solutions. The
changes of the viscosity of the polymer solutions during the ozonolysis
have been characterized by the number of chain scissions per molecule of
reacted ozone (j). The influence of the conditions of mass-transfer of the
reagents in a bubble reactor on the respective j values has been discussed.
The basic functional groups—products from the rubbers ozonolysis have
been identified and quantitatively characterized by means of IR-spectros-
copy and 1H-NMR spectroscopy. A reaction mechanism, which explains
the formation of all identified functional groups, has been proposed. It has
been shown that the basic route of the reaction of ozone with elastomer
double bonds, the formation of normal ozonides, does not lead directly to a
decrease in the molecular mass of the elastomer macromolecules because
the respective 1,2,4-trioxolanes are relatively stable at ambient tempera-
ture. The most favorable conditions for ozone degradation emerge when
the cage interaction between Cri�����������������������������������尓������
е�����������������������������������尓�����
gee intermediates and respective carbon-
yl groups does not proceed. The amounts of measured different carbonyl
groups have been used as an alternative way for evaluation of the inten-
sity and efficiency of the ozone degradation. The thermal decomposition
of partially ozonized diene rubbers has been investigated by Differential
Scanning Calorimetry DSC. The respective values of the enthalpy, the ac-
tivation energy, and the reaction order of the 1,2,4-trioxolanes have been
determined.
In most cases, quantitative data on the functional groups formed dur-
ing the reaction are missing [15–18]. At the same time alternative con-
Trends in Ozonation of Polymer Compounds 281

version routes of Criegee’s intermediates, which lead to the formation of

carbonyl compounds and some other so-called “anomalous products” of
the ozonolysis, are of great importance for clarifying the overall reaction
mechanism [19–21]. The mechanism of ozone degradation of rubbers is
also connected with the non-ozonide routes of the reaction, because the
formation of the basic product of ozonolysis, normal ozonide, does not
cause any chain scission and/or macromolecule cross-linking [22].
In this article, the changes in the molecular mass of different types of
diene rubbers during their partial ozonolysis in solution have been investi-
gated. By means of IR and 1H-NMR spectroscopy ozonolysis products of
the elastomers have been studied. The effects of the nature of the double
bond substituents and its configuration on the degradation mechanism
have been considered. By using differential scanning calorimetry the ther-
mal decomposition of the functional groups of peroxide type has also been
investigated.

10.2â•…EXPERIMENTAL

10.2.1â•…MATERIALS

Commercial samples of 1,4-cis-polybutadiene (SKD, E-BR); polybutadi-

ene (Diene 35 NFA, BR); 1,4-cis-polyisoprene (Carom IR 2200, E-IR),
and polychloroprene (Denka M 40, PCh) were used in the experiments
(Table 10.1). The 1,4-trans-polyisoprene samples were supplied by Prof.
A. A. Popov, Institute of Chemical Physics, Russian Academy of Sciences.
All rubbers were purified by three-fold precipitation from CCl4 solutions
in excess of methanol. The aforementioned elastomer structures were con-
firmed by means of 1H-NMR spectroscopy. Ozone was prepared by pass-
ing oxygen flow through a 4–9 kV electric discharge.

10.2.2â•… OZONATION OF THE ELASTOMER SOLUTIONS

The ozonolysis of elastomers was performed by passing an ozone—oxy-

gen gaseous mixture at a flow rate of v = 1.6 ´ 10−3 ± 0.1 l/s through a
bubbling reactor, containing 10–15 ml of polymer solution (0.5–1 g in
CCl4) at 293 K. Ozone concentrations in the gas phase at the reactor inlet
([O3]i) and outlet ([O3]u) were measured spectrophotometrically at 254 nm
282 Applied Research on Polymer Composites

[23]. The amount of consumed ozone (G, mole) was calculated by the Eq.
(10.1):

G = v([O3]I – [O3]u)t (10.1),

where t is the ozonation time (s). The degree of conversion of the double
C=C bonds was determined on the basis of the amount of reacted ozone
and the reaction stoichiometry [23].

TABLE 10.1â•… Some characteristics of polydiene samples

Elastomer Monomeric Unsatura- 1,4-cis 1,4-trans 1,2- 3,4- Mv × n

unit tion degree (%) (%) (%) (%) 10−3
(%)

SKD –CH=CH- 95–98 87–93 3–8 3–5 – 454 2.1

Diene 35 –CH=CH- 97 47 42 11 298 2.63

NFA

Carom IR –C(CH3)=CH- 94–98 94–97 2–4 – 1–2 380 2.0

2200

1,4-Trans PI –C(CH3)=CH- 95–97 95–97 310 2.3

Denka M40 –C(Cl)=C- 94–98 5 94 – – 180 1.8

Note: Mv is the average molecular weight, determined viscosimetrically from equation [h]
= k × Mva', where [h] = (h1/C)(1+0.333h1), h1 = hrel – 1, hrel is the intrinsic viscosity; C is the
solution concentration; k = 1.4×10−4 —Staudinger’s constant, and a' = 0.5 − 1.5—constant
depending on the rubber type, being one for natural rubber; Mv » Mw; n = Mw/Mn, where
Mw and Mn are the average weight and number average molecular mass, respectively [22].

10.3â•… RESULTS AND DISCUSSION

Florry [24] has shown that the reactivity of the functional groups in the
polymer molecule does not depend on its length. It is also known that some
reactions of the polymers proceed more slowly when compared with their
low molecular analogs (catalytic hydrogenation). The folded or unfolded
forms of the macromolecules provide various conditions for contact of
the reagents with the reacting parts [4, 25]. By using the modified version
Trends in Ozonation of Polymer Compounds 283

of this principle [26], it is possible to explain the proceeding of reactions

without any specific interactions between the adjacent C=C bonds and the
absence of diffusion limitations. The study of the mass-molecular distri-
bution (MMD) is a very sensitive method for establishing the correlation
between molecular weight (Mw) and the reactivity.
The theory predicts that the properties of the system, polymer—solvent
can be described by the parameter of so-called globe swelling (g), which
defines the free energy (F) of the system and thus the rate constant of the
reaction. For a reversible reaction, i.e., polymerization—depolymeriza-
tion, the dependence of the rate constant of the chain length growing on
the molecular weight is expressed by the following equation:

ln kpj/kp∞ = –const. (5g − 3/g).(dg/dM).M0 (10.2)

where Mo is the molecular weight of the studied sample and kp is the rate
constant for infinitely long macromolecules. A good correlation between
the theoretical and experimental data for polystyrene solutions in benzene
has been found in Ref. [27].
The study of the polymer degradation is complicated by their structural
peculiarities on molecular and supramolecular level and diffusion effects.
It is difficult to find simple model reactions for clarification of particular
properties and for the express examination of the proposed assumptions.
An exception, in this respect, is the ozone reaction with C=C bonds, whose
mechanism has been intensively studied and could be successfully applied
upon ozonolysis of polymeric materials [28].
Table 10.2 summarizes the rate constants of the ozone reactions with
some conventional elastomers and polymers and their low molecular ana-
logs, synthesized by us. It is seen that the reactivities of elastomers and
polymers and their corresponding low molecular analogs, as it is demon-
strated by their rate constants, are quite similar, thus suggesting similar
mechanisms of their reaction with ozone. This statement is also confirmed
by: (1) the dependence of k on the inductive properties of substituents:
for example k of polychloroprene is higher than that of vinylchloride due
to the presence of two donor substituents and (2) the dependence of k on
the configuration of the C=C bond in trans-isomer (gutta-percha) and cis-
isomer (natural rubber).
284 Applied Research on Polymer Composites

TABLE 10.2â•… Rate constants of ozone reactions with polymers and low molecular analogs
in CCl4, 20°C

Compound M.W. k × 10−4, M−1 s−1

Polychloroprene 8 ´ 105 0.42 ± 0.1

Vinylchloride 62.45 0.18

2-Bromopropene 121 0.28 ± 0.05

Polybutadiene 3.3 × 105 6.0 ± 1

Cyclododecatriene-1,5,9 162 35 ± 10

Poly(Butadiene-Co-Styrene) 8 × 104 6±1

Gutta-percha 3 × 104 27 ± 5

Natural Rubber 1 × 106 44 ± 10

2-Me-Pentene-2 85 35 ± 10

Squalene 410 74±15

Polystyrene 5 × 105 0.3 × 10−4

Cumene 120 0.6 × 10−4

Polyisobutylene 1.7 × 105 0.02 × 10−4

Cyclohexane 84 0.01 × 10−4

It has been found out that the effects, related either to the change in
the macromolecule length or to the folding degree, do not affect the ozon-
olysis in solution. Probably this is due to the fact that the reaction is car-
ried out in elastomeric solutions, in which the macromolecules are able
to do free intramolecular movements and they do not react with adjacent
macromolecules. Moreover, the rate of macromolecules reorganization is
probably higher than the rate of their reaction with ozone as the experi-
ment does not provide any evidence for the effects of the change in the
parameters mentioned above [29].
However, it should be noted that k values of the elastomers are about
2–6 times lower than those of the low molecular analogs.
The accuracy of activation energy (Ea) determination does not allow
to estimate the contribution of the two parameters: pre-exponential factor
(A) or Ea for the decrease in k. If we assume that the mechanism of ozone
Trends in Ozonation of Polymer Compounds 285

reaction with monomers and elasomers is similar, i.e., the reactions are
isokinetic, then Amon = Apol. At kmon/kpol = 2 ÷ 6 the difference in Ea at 20°C
will be 0.5–1.0 kcal/mol. At the low experimental values of Ea, these dif-
ferences will become commensurable and thus the determination of Ea
is not sufficiently accurate. In this case two assumptions could be made
which can give a reasonable explanation for the lower values of kpol: (1)
the reorientation of the macromolecules is a slower process than that of
olefins, which would results in Apol < Amon and (2) the addition of ozone
to C=C bonds is accompanied by the rehybridization of the C-atoms from
sp2 to sp3 and the movements of the polymer susbstituents during the for-
mation of activated complex will be more restricted than those in olefins,
mainly because of their greater molecular mass and sizes.
This will ultimately result in decrease of the rate constant. Table 10.2
shows some examples of ozonolysis of saturated polymers—polystyrene
and polyisobutylene. These reactions take place not through the mecha-
nism of ozone reaction with the double bonds but through a hidden radical
mechanism with rate constants of four to five orders of magnitude lower.

10.3.1â•…POLYBUTADIENES

Because of the high viscosity and high value of rate constants, the reaction
takes place either in the diffusion or in the mixed region. To obtain correct
kinetic data we have used the theory of boundary surface [30]:

[O3] = a[O3]0 × exp[–d(kcD)1/2], (10.3)

where [O3] is the ozone concentration at a distance d, a the Henry’s coef-

ficient, [O3]0 the equilibrium ozone concentration in the gas phase at the
reactor inlet, d the penetration depth of ozone from the interphase surface
[22], k the rate constant of the ozone reaction with double bonds, c the
concentration of the monomeric units, and D is the diffusion coefficient of
ozone in the liquid phase.
It was found out that the relative viscosity decreases exponentially
upon ozonation of SKD solutions (Figure 10.1). As the viscosity is propor-
tional to the molecular weight it follows that the polydiene consumption
should be described by first or pseudo-first order kinetics.
286 Applied Research on Polymer Composites

FIGURE 10.1â•… Dependence of the relative viscosity (hrel) of SKD solutions (0.6 g in 100
ml CCl4) on reaction time at ozone concentrations of (1)—1 × 10−5 M; (2)—4.5 × 10−5 M,
and (3)—8.25 × 10−5 M.

The value of f, corresponding to the number of degraded polymeric

molecules per one absorbed ozone molecule can be used to calculate the
degradation efficiency. The value of this parameter (f) may be estimated
using the following equation:

f = 0.5 [(Mvt)−1 − (Mv0)−1] P/G, (10.4)

where Mvt is the molecular weight at time moment T, Mvo the initial mo-
lecular weight, P the polymer amount, and G is the -amount of consumed
ozone.
The dependence of f on G is a straight line for a given reactor and it
depends on the hydrodynamic conditions in the reactor. It is seen from
Figure 10.2 that the f values are increasing linearly with the reaction time
and decreasing with increase in ozone concentration. The corresponding
dependences for Carom IR 2200 and Denka M40 ozonolysis are similar.
The f values for G ® 0 were used to avoid the effect of hydrodynamic
factors on them.
Trends in Ozonation of Polymer Compounds 287

FIGURE 10.2â•… Dependence of f on G for SKD (0.6/100) at various ozone concentrations:

(1)—1 × 10−5 M, (2)—4.5 × 10−5 M, and (3)—8.25 × 10−5 M.

FIGURE 10.3â•… Dependence of f on ozone concentration for elastomer solutions: —(1)

SKD (0.6/100), (2) Carom IR 2200 (0.6/100), and (3) Denka M40 (1/100).
288 Applied Research on Polymer Composites

The values of f found for SKD, Carom IR 2200, and Denka M40 at
[O3]=1 × 10−5 M amount to 0.7 × 10−2, 0.78 × 10−2, and 0.14, respectively,
and the slopes are −40, −70, and 200 M−1, respectively. Substituting with
the known values for the parameters in Equation (3) we have obtained d
within the range of 1 × 10−3 − 2 × 10−4 cm, which indicates that the reac-
tion is taking place in the volume around the bubbles, and hence in the
diffusion region.
The ozonolysis of polydienes in solutions is described by the Crie-
gee’s mechanism. The C=C bonds in the macromolecules are isolated as
they are separated by three simple C–C bonds. According to the classical
concepts, the C=C bonds configuration and the electronic properties of the
groups bound to them, also affect the polymer reactivity; similarly they do
this in case of the low molecular olefins. The only difference is that the
polymer substituents at the C=C bonds are less mobile, which influences
the sp2–sp3 transition and the ozonides formation. In the first stage, when
primary ozonides (POs) (Scheme 1, reaction 1) are formed, the lower mo-
bility of the polymer substituents requires higher transition energy, the
rate being respectively lower, compared to that with low molecular olefins
and the existing strain accelerates the PO decomposition to zwitterion and
carbonyl compound.
The lower mobility of the polymer parts impedes the further ozonide
formation and causes the zwitterion to leave the cage and pass into the
volume, which in turn accelerates the degradation process. The latter is
associated with either its monomolecular decomposition or its interaction
with low molecular components in the reaction mixture. The efficiency of
degradation is determined by the C=C bonds location in the macromol-
ecule, for example, at C=C bond location from the macromolecule center
to its end, is in the range from 2 to 1.

M1 = (1/g)M0, (10.5)

where M2 = M0 − M1; 1 ≤ g ≤ 2 is the coefficient pointing the C=C-bond lo-

cation; M0, M1, and M2 are the molecular weights of the initial macromol-
ecule and of the two degradated polymer parts, respectively. At g = 2, i.e.,
when the broken C=C bond is located in the macromolecule center, the
values of M1 and M2 will be exactly equal to M0/2, at g ® 1, i.e., at terminal
C=C bond in the polymer chain, the value of M1 will be approximated to
M0 and thus the value of M2 will be practically insignificant. For example,
Trends in Ozonation of Polymer Compounds 289

M2 may be 50–1,000, which is three to four orders of magnitude less than

that of the macromolecule and in fact degradation process will not occur.
The viscosimetric determination of the molecular weight, which we
have applied in our experiments, has accuracy of ±5 per cent and does
not allow the differentiation of molecular weights of 22,700, 19,000, and
9,000 for the corresponding types of rubbers. This suggests that the cleav-
age of C=C bonds, located at distances of 420, 280, and 100 units from
the macromolecule end, would not affect the measured molecular weight.
Since the reaction of elastomers ozonolysis proceeds either in the dif-
fusion or in diffusion-kinetic region, at low conversions each new gas
bubble in the reactor would react with a new volume of the solution. On
the other hand, the reaction volume is a sum of the liquid layers surround-
ing each bubble. It is known that the depth of the penetration from the gas
phase into the liquid phase is not proportional to the gas concentration and
thus the rise of ozone concentration would increase the reaction volume to
a considerably smaller extent than the ozone concentration.
This leads to the occurrence of the following process: intensive degra-
dation processes take place in the micro-volume around the bubble and one
macromolecule can be degraded to many fragments, whereas the macro-
molecules out of this volume, which is much greater, may not be changed
at all. Consequently with increase in ozone concentration, one may expect
a reduction of coefficient MMD and increase in the oligomeric phase con-
tent. This will result in apparent decrease of f in case of the viscosimetric
measurements. The discussion above enables the correct interpretation of
the data in Figure 10.3.
In the spectra of the ozonized polybutadienes the appearance of bands
at 1,111 and 1,735 cm−1, which are characteristic for ozonide and aldehyde
groups, respectively, is observed [22, 31]. It was found that the integral
intensity of ozonide peak in the 1,4-cis-polybutadiene Emulsion Bu-
tadiene Rubber (E-BR) spectrum is greater and that of the aldehyde is
considerabl�����������������������������������尓�������������������������
y�����������������������������������尓������������������������
smaller in comparison with �������������������������������
the ���������������������������
respective peaks in the ��� Di-
ene 35 NFA (BR) spectrum at one and the same ozone conversion degree
of the double bonds. The differences in the aldehyde yields indicate that,
according to IR-analysis, the degradation efficiency of the BR solutions is
greater.
The 1H-NMR spectroscopy provides much more opportunities for
identification and quantitative determination of functional groups, formed
during ozonolysis of polybutadienes [32]. Figure 10.4 shows spectra of
290 Applied Research on Polymer Composites

ozonized E-BR. The signals of the ozonolysis products are decoded in

Table 10.3 on the basis of Figure 10.5. The ozonide—aldehyde ratio,
determined from NMR spectra, was 89:11 and 73:27 for E-BR and
BR, respectively. The peak at 2.81 ppm is present only in the spectra of
ozonized Diene 35 NFA. It is usually associated with the occurrence of
epoxide groups [33]. The integrated intensity of that signal as compared
to the signal of aldehyde protons at 9.70–9.79 ppm was about 10 per cent.
Similar signal at 2.75 ppm has been registered in the spectra of ozonized
butadiene-nitrile rubbers, where the 1,4-trans double bonds are dominant
[31].

FIGURE 10.4â•… (a,b,c) 1H-250 MHz NMR spectra of E-BR solutions (0.89 g/100 ml
CCl4) ozonized to 18 per cent conversion of the double bonds (external standard TMS;
digital resolution 0.4 Hz, 20°C).
Trends in Ozonation of Polymer Compounds 291

According to Refs. [2, 10]�����������������������������������尓���������

two isomeric forms of ���������������������
1,2,4-trioxolanes ex-
ist.�����������������������������������尓���������������������������������
The ratio�����������������������������������尓�����������������������
�����������������������������������尓��������������������������������
between them is a function of the double bond stereochem-
�����������������������������������尓����������������������
istry, steric effect of the substituents, and the conditions of ozonolysis. It
was found out only on the low molecular weight alkenes [19, 21]. The
1
H-NMR spectroscopy is the most powerful method for determination of
the cis/trans ratio of ozonides (in the case of polymers it is practically the
only one method that can be applied). The measuring is based on the dif-
ferences in the chemical shifts of the methine protons of the two isomers:
the respective signal of the cis form appears in lower field as compared to
the trans one [19, 21].
The multiplet on Figure 10.3 in the area of 5.1–5.18 ppm could be
interpreted as a result of partial overlapping of triplets of trans- and cis-
ozonides: 5.12 ppm (t, J » 5 Hz, 2H) and 5.16 ppm (t, J » 5 Hz, 2H), respec-
tively. It is interesting to note that the cis/trans ratio of the E-BR 1,2,4-tri-
oxolanes is practically equal to that obtained from cis-3-hexene [19, 34].
The resolution of the respective BR spectrum does not allow consideration
in detail of the multiplicity of the signals at 5.10 and 5.15 ppm. In this
case, the area of the signals is widened, most probably due to the presence
of ozonide signals of the 1,2-monomer units [20].
The basic route of the reaction, the formation of normal ozonides, does
not lead directly to a decrease in the molecular mass of the elastomer mac-
romolecules, because the respective 1,2,4-trioxolanes are relatively stable
at ambient temperature (by analogy with Scheme 1 of polyisoprenes, see
as in what follows) [31, 32]. The most favorable conditions for ozone deg-
radation emerge when the cage interaction (Scheme 1, reaction 3) does not
proceed. Therefore, the higher the ozonide yield the lower the intensity of
ozone degradation of the polybutadienes and vice versa. As it was already
determined the ozonide yields for the 1,4-cis- and 1,2- monomer units are
close to 83–90 per cent, whereas that for the 1,4-trans units is about 50
per cent.
The amount of aldehyde groups is usually used for evaluation of the
intensity and efficiency (number of chain scissions per molecule of reacted
ozone) of ozone degradation of elastomers. In this case, it should be taken
into account that the dominant route of degradation leads to the formation
of 1 mole of aldehyde from 1 mole of ozone [32].
292 Applied Research on Polymer Composites

FIGURE 10.5â•… Selection of protons with characteristic signals in the 1H-250 MHz NMR
spectra of partially ozonized polybutadiene macromolecules.

10.3.2â•…POLYISOPRENES

The positive inductive effect of the methyl group in polyisoprene enhanc-

es the rate of ozone addition to the double bonds from 6 ´ 104 for SKD to 4 ´
105 M−1s−1 for Carom IR 2200. The infrared spectra of ozonized 1,4-trans-
polyisoprene (Z-IR) show two intense bands at 1,100 and 1,725 cm-1, char-
acteristic of ozonide and keto groups, respectively [19, 35]. These spectra
are identical with the well-known spectra of 1,4-cis-polyisoprenes (E-IR),
as far as ozonide and carbonyl bands are concerned [22, 36]. It was found
that the integrated intensity of the peak at 1,100 cm−1 in the E-IR and Z-IR
spectra is equal for one and the same amount of reacted ozone. By analogy
with the peak at 1110 cm−1, the integral intensity of the peak at 1,725 cm−1
is also one and the same. The latter show that, according to the infrared
spectra, the degradation efficiencies of E-IR and Z-IR with respect to the
amount of consumed ozone do not practically differ.
Trends in Ozonation of Polymer Compounds 293

TABLE 10.3â•… Assignment of the signals in the 1H-NMR spectra of partially ozonized
E-BR and BR rubbers
Assignment of the signals Chemical shifts (ppm) Literature

(according Figure 10.4) E-BR BRA

a 5.10–5.20 5.05–5.18 [19, 34]

max 5.12, 5.16 max 5.10, 5.15

b 1.67–1.79 1.66–1.80 [7, 19]

max 1.72, 1.76 max 1.73

c 9.75 9.74 [33]

d 2.42–2.54 2.42–2.54 [33]

max 2.47 max 2.50

e 2.27–2.42 2.27–2.42 [33]

max 2.35 max 2.35

f max 2.81 [33]

The 1H-NMR spectroscopy affords much more opportunities for iden-

tification and quantitative determination of functional groups formed on
ozonolysis of polyisoprenes. Figure 10.6 shows spectra of non-ozonized
and ozonized E-IR. Changes in the spectra of ozonized elastomers are
decoded in Table 10.4 on the basis of Figure 10.7. It is seen that besides
ketones, aldehydes are also formed as a result of ozonolysis. A comparison
between methylene and methine proton signals of the non-ozonized poly-
isoprenes and the corresponding ozonide signals indicates a considerable
overlap in the ranges 1.60–1.90 and 4.5–5.5 ppm. A signal overlap is also
registered in the 2.00–2.20 ppm region, characteristic of methyl protons
of keto groups. Because of the reasons mentioned above, the ozonides and
aldehydes were quantified by using the integrated intensity of the signals
at 1.40 (a) and 9.70–9.79 (g) ppm, respectively.
Ketone amounts were determined as a difference between the total in-
tensity of the methylene signals from aldehydes and ketones, 2.40–2.60
and 2.35–2.60 ppm, respectively, and the doubled intensity of the aldehyde
signal at 9.70–9.79 ppm. Thus, the obtained ozonide—ketone—aldehyde
ratio was 40:37:23 and 42:39:19 for 1,4-cis-polyisoprene and 1,4-trans-
polyisoprene, respectively. The peak at 2.73 ppm, present in the spectra
294 Applied Research on Polymer Composites

of both ozonized elastomers, is associated with the occurrence of epoxide

groups [33, 37]. The integrated intensity of that signal as compared to
the signal at 9.70–9.79 ppm was 21 and 15 per cent for E-IR and Z-IR,
respectively.
Current ideas about the mechanism of C=C double bond ozonolysis in
solution are summarized in Schemes 1 and 2 [19, 21, 34]. As a result of
the decomposition of the initial reaction product, PO, zwitterionic species
is formed, termed as Criegee’s intermediates or carbonyl oxides (hereafter
referred to as CI) (Scheme 1, reactions 2 and 2’). Two intermediates are
formed from asymmetric olefins: monosubstituted CI (MCI) and disub-
stituted CI (DCI), if their syn and anti stereoisomers are not taken into
account.
It is known that carbonyl oxides are predominantly formed at carbon
atoms with electron-donating substituents [19]. Excellent correlations
of the regioselectivities of MO fragmentation with electron donation by
substituents (as measured by Hammett and Taft parameters) have been
obtained, consistent with the effects expected for stabilization of a zwite-
rionic carbonyl oxide [20]. According to Ref. [23], for polyisoprenes the
ratio between the two intermediates, DCI and MCI, is 64:36.
Ozonides are the basic product of polyisoprene ozonolysis in non-
participating solvents. It is known that the dominant part of ozonides is
formed through the interaction between CI and the corresponding carbon-
yl group, which originate from the decomposition of one and the same PO,
i.e., a solvent cage effect is operating (Scheme 1, reactions 3 and 3’) [19,
34]. With simple olefins the so-called normal ozonides are over 70 per cent
[26]. Cross-ozonide formation is also observed (Scheme 1, reactions 5 and
5’). The amount of cross-ozonides is dependent upon the structure of the
double bonds, their concentration in the solution, temperature, and solvent
nature. Reference data indicate that the cross-ozonide yield is strongly re-
duced at C=C bond concentrations of the order of 0.1 M, with non-polar
solvents, and at temperatures over 0°C [19]. It is reasonable to expect that
the polymeric nature of the double bonds in the polyisoprenes would ad-
ditionally impede the formation of cross-ozonides. Our estimates showed
that the amount of cross-ozonides, formed on ozonolysis of both elasto-
mers, is < 10 per cent of their total quantity. A very small percentage in the
overall balance of reacted ozone is the share of the reaction of polymeric
ozonides formation (Scheme 1, reactions 4 and 4’) [22].
Trends in Ozonation of Polymer Compounds 295

TABLE 10.4â•… Assignment of the signals in the 1H-NMR spectra of partially ozonized 1,4-
cis-, and 1,4-trans-polyisoprenes

Assignment of the signals Chemical shifts Literature

(ppm)

(according Figure 10.4) E-IR Z-IR

a Max 1.41 Max 1.40 37, 38

b 1.70–1.78 1.68–1.82 37
Max 1.71

c 2.10–2.20 2.10–2.20 33

d 2.22–2.40 2.22–2.35 33
Max 2.33, 2.36 Max 2.29, 2.33

e 2.40–2.60 2.35–2.55 33
Max 2.47 Max 2.48, 2.46

f Max 2.73 Max 2.73 33

g Max 9.76 Max 9.77 33

In the presence of two types of intermediates, DCI and MCI, it is inter-

esting to follow their further conversion with a view to the reaction prod-
ucts determined by 1H-NMR spectroscopy. The reaction between CI and
carbonyl groups is usually considered to be 1,3-cycloaddition [20, 34]. In
this connection the CI—aldehyde interaction is the most effective one: it
readily precedes with high ozonide yields. Ketones are considerably less
dipolarophilic and good yields of ozonides are limited to special condi-
tions involving particularly reactive ketones, intramolecular reactions, or
where ketone is used as the reaction solvent and is therefore present in
large concentration [19–21]. To evaluate the contribution of reactions 3
and 3’ (Scheme 1), it is useful to discuss two hypotheses: (1) no reaction
proceeds between MCI and ketone, the registered amount of ozonides be-
ing formed in reaction 3; (2) because of the solvent cage effect already
mentioned, both the reactions can be considered with practically equal
rate constants. Then, the ozonide yields would be proportional to the ratio
between the two zwitterions (64:36). In this case, the corresponding yields
of the reactions DCI + aldehyde and MCI + ketone can be calculated from
the following system of equations:
296 Applied Research on Polymer Composites

Y=x+y (10.6)

x/y = 64/36 (10.7)

where Y is the total ozonide yield, x and y are the corresponding ozonide
yields with the former and the latter reactions, respectively. Results are
given in Table 10.5. A comparison between the aldehyde amounts from
both hypotheses and NMR data shows that the former hypothesis leads to
results that are much closer to the experimental data.
More complicated is the question of the other conversion routes with
carbonyl oxides outside the solvent cage. It is generally accepted that
the deactivation of DCI from low molecular olefins normally takes place
through a bimolecular reaction mechanism. At low temperatures (below
−70oC) dimeric peroxides are formed (Scheme 2, reaction 1), whereas
higher temperatures give rise to the formation of carbonyl compounds and
evolution of oxygen (Scheme 2, reaction 2) [20]. However, on compar-
ing the yields of keto groups, determined from 1H-NMR spectra, with the
amounts of ketones and DCI, presented in table

FIGURE 10.6â•… (Continued)

Trends in Ozonation of Polymer Compounds 297

FIGURE 10.6â•… 1H-250 MHz NMR spectra of 1,4-cis-polyisoprene solutions (1 g/100

ml CCl4): (a) non-ozonized; (b) ozonized to 23 per cent conversion of the double bonds
(external standard TMS; digital resolution 0.4 Hz, 20oC).

5, it is seen that reaction 2, if occurring at all, is not dominating during

DCI conversion. From kinetic evaluations of CI concentrations in solu-
tion it follows that under comparable experimental conditions these con-
centrations are four to six orders of magnitude lower than those of the
C=C bonds [23]. Very likely, interactions between two or more DCI are
hindered by extremely low values of CI concentration and mostly by the
polymeric nature of substituent.
R1. Under these conditions, DCI tautomerization followed by decom-
position of hydroperoxides, formed in the excited state (Scheme 2, reac-
tions 3 and 4), seems most probable.
298 Applied Research on Polymer Composites

FIGURE 10.7â•… Selection of protons with characteristic signals in the 1H-250 MHz NMR
spectra of partially ozonized polyisoprene macromolecules.

SCHEME 1â•… Criegee’s Mechanism of Formation of Ozonides.

Trends in Ozonation of Polymer Compounds 299

TABLE 10.5â•… Intermediates and products of the ozonolysis of 1,4-cis-, and 1,4-trans-
polyisoprenes

DCI + Aldehydes (64%) MCI + Ketones (36%)

Ozonides Aldehydes DCI Ozonides Ketones MCI

(%) (%) (%) (%) (%) (%)

Hypothese (i)

E–IR 40 24 24 0 36 36

Z–IR 42 22 22 0 36 36

Hypothese (ii)

E–IR 26 38 38 14 22 22

Z–IR 27 37 37 15 21 21

On going into MCI conversion routes it appears that MCI has the
lower stability and lifetime of these intermediates when compared with
DCI. Reference data on the proceeding of reactions 1 and 2 (Scheme 2)
during ozonolysis of low-molecular olefins in solution are missing [34].
On ozonolysis of 1,4-trans-polychloroprene the share of CI of the MCI
type is over 80 per cent, in agreement with the induction effect of the
chlorine atom [23]. However, no aldehyde groups in the ozonized poly-
mer solution were found [39]. It follows that the interaction between
MCI entities, if any, is not the dominating deactivation reaction with
these intermediates. The most probable MCI monomolecular deactiva-
tion route is assumed to be the isomerization of the MCI intermediates
through hot acid to radicals (Scheme 2, reactions 5, 6, 7), because no
acid groups were detected (Scheme 2, reaction 8). According to the lit-
erature, reaction 5 (Scheme 2) does not occur with DCI intermediates
[21].
300 Applied Research on Polymer Composites

SCHEME 2â•… Non-Ozonide Routes of Deactivation of Criegee’s Intermediates.

Another route of carbonyl oxide deactivation is double-bond epoxi-

dation. Various schemes of olefin epoxidation during ozonolysis have
been suggested but the epoxidation through CI (Scheme 2, reaction 9) is
presumed to be the most probable with the C=C bonds in polyisoprenes
[20, 21]. Since a peak at 2.73 ppm has also been observed under similar
conditions on ozonolysis of acrylonitrile—butadiene copolymers [31], as
well as during ozonolysis of polybutadienes, it can be assumed that the
epoxidation reaction takes place with the participation of both types of CI.

10.4â•… POLYCHLOROPRENE

The electron-accepting properties of the chlorine atom at the polychloro-

prene double bond reduces the reactivity of Denka M40 as demonstrated
by its relatively low rate constant, i.e., k = 4 ´ 103 M−1s−1. In this reaction
the ratio between the zwitterions A and B, according to theoretical cal-
culations, is in favor of A, the ratio being A/B = 4.55. The A formation
is accompanied by choroanhydryde group formation and that of B with
aldehyde one. In both cases the ozonides formation is insignificant and the
Trends in Ozonation of Polymer Compounds 301

zwitterions react predominantly in the volume resulting in enhancement of

the degradation process. The intensive band detected at 1795 cm−1 in the
IR spectrum of ozonized Denka M40 solutions (Figure 10.8) is character-
istic of chloroanhydride group [39]. This fact correlated well with the con-
clusion about the direction of the PO decomposition. The band at 955 cm−1
is also typical of chloroanhydrides. Two other bands—at 1,044 and 905
cm−1 may be attributed to the C–O vibrations. The valent vibrations char-
acteristics of HO-groups are observed in the region of 3,050–3,500 cm−1.
The iodometrical analysis of active oxygen in the ozonized Denka M40
solutions shows that the amount of O–O groups is ~43 per cent. It is of in-
terest to note that the HI reaction with ozonized polychloroprene solutions
occurs quantitatively for 3–4 h, while in SKD the same proceeds only to
20 per cent after 24 h. The aforementioned data, however, provide insuf-
ficient information for the preferable route of the zwitterions deactivation
(via dimerization, polymerization of zwitterions, or secondary processes).
The DSC analysis of the products of Denka M40 ozonolyis reveals that
the chloroprene rubber ozonolyis yields polyperoxide as the enthalpy of
its decomposition is found to be very close to that of dicumeneperoxide
(DCP), The higher value of Ea (approximately two times of that of DCP)
testifies the possible formation of polymer peroxides [4].

FIGURE 10.8â•… Infra-red spectra of denka M40 solutions: (1)—non-ozonized; (2)—

ozonized to 40 per cent conversion.
302 Applied Research on Polymer Composites

10.5â•… DSC STUDY OF THERMAL DECOMPOSITION OF

PARTIALLY OZONIZED DIENE RUBBERS

The thermal decomposition of the ozonized diene rubbers can exercise

influence on the ageing processes as an initiator of the oxidation reactions
[40]. On the other hand, it is of interest for the elastomers modification
and oligomerization [6]. The importance of the DSC method to the inves-
tigation of 1,2,4-trioxolanes is based on high values of the enthalpy of the
reaction of ozonide thermal decomposition and on the temperature range
in which it takes place [41–43]. An intense and relatively broad exother-
mic peak is characteristic for the thermograms of the partially ozonated
1,4-cis-polybutadiene (E-BR), Diene 35 NFA (BR), 1,4-cis-polyisoprene
(E-IR), 1,4-trans-polyisoprene (Z-IR), and 1,4-trans-polychloroprene
(PCh), recorded in the range of 60–200oC (Figure 10.9). In practical, no
thermal effects are detected in the respective thermograms of the nonozon-
ized samples.
For an objective consideration on the enthalpy changes it is necessary
to normalize DH values with respect to the amount of consumed ozone
(G). It is distributed on the whole mass of the ozonated sample. The whole
mass is a sum of the mass of nonozonated rubber and mass of the incorpo-
rated in diene macromolecules oxygen atoms, grouped as a moles ozone.
Determination of the amounts of the incorporated ozone (Ginc) in rubber
samples is performed in [43]. The corresponding values of the coefficient
of incorporation of ozone (cinc), defined as a ratio of the amounts of in-
corporated (Ginc) and consumed (G) ozone is Presented in Table 10.6. ���
Us-
ing DH1 values and ratio of the functional group, deduced from the NMR
spectra, the enthalpy of the ozonide thermal decomposition (DH2) has been
evaluated. The data of Table 10.6 clearly show tendency of increasing of
DH2 values with the number of alkyl substituents of the ozonides.
There are no considerable differences between the values of the activa-
tion energy (E) and reaction order (n) of the ozonide thermal decomposi-
tion with E-IR and Z-IR (Table 10.7). The smaller E values of the polyiso-
prene ozonides in comparison with those of E-BR ozonides and 1-decene
ozonide are, most probably, due to the lower thermal stability of small
amounts of oligomeric peroxides, which are present among the reaction
products of E-IR and Z-IR ozonolysis [36].
Trends in Ozonation of Polymer Compounds 303

FIGURE 10.9â•… DSC curve of partially ozonated diene 35 NFA rubber (BR).

TABLE 10.6â•… Enthalpy changes on the thermolysis of partially ozonated diene rubbers

Sample DH cinc DH1, Ozonide (mole)/ DH2 (kJ/

incorp. Ozone mole ozon-
(J/g) (kJ/mole O3)
(mole) ide)

E-BR 954.07 0.93 332 0.96 373

BR 854.83 0.87 271 0.89 350

E-IR 576.19 0.62 182 0.65 453

Z-IR 576.62 0.62 178 0.67 426

PCh 704.57 0.81 254

1-Decene 349 [Ref. 7]

Ozonide
304 Applied Research on Polymer Composites

TABLE 10.7â•… DSC analysis of the ozonized rubbers decomposition [43]

*Tm as E N
( C)
o
(kJ/mole)

E-BR 147 0.67 125 1.0

BR 145 0.68 117 0.96

E-IR 160 0.68 111 1.04

Z-IR 149 0.68 113 1.08

PCh 96 0.55 70 1.25

1-Decene ozonide 117 0.63 132 1.0

*T m and as Values at Heating rate of 5oC/min; Tm and as are Temperature and Degree of
Conversion at the DSC peak Maximum, respectively.

10.6â•…CONCLUSIONS

The ozone reaction with a number of polyidienes with different configu-

rations of the double bonds and various substituents was investigated in
CCl4 solution. �����������������������������������尓�����������������������
The changes of the viscosity of the polymer solutions dur-
ing the ozonolysis were characterized by the determination of the number
of chain scissions per molecule of reacted ozone (j). The influence of the
conditions of mass-transfer of the reagents in a bubble reactor on the re-
spective j values was discussed.
The basic functional groups—products from the rubbers ozonolysis
were identified and quantitatively characterized by means of IR-spectros-
copy and 1H-NMR spectroscopy. The aldehyde—ozonide ratio was 11:89
and 27:73 for E-BR and BR, respectively. In addition, epoxide groups
were detected, only in the case of BR, their yield was about 10 per cent of
that of the aldehydes. On polyisoprenes the ozonide—ketone—aldehyde
ratio was 40:37:23 and 42:39:19 for E-IR and Z-IR, respectively. Besides
the already-specified functional groups, epoxide groups were also detect-
ed, their yields being 8 and 7 per cent for E-IR and Z-IR, respectively,
with respect to reacted ozone. In the case of 1,4-trans-polychloroprene,
the chloroanhydride group was found to be the basic carbonyl product.
Trends in Ozonation of Polymer Compounds 305

A reaction mechanism that explains the formation of all identified

functional groups was proposed. It has been shown that the basic route
of the reaction of ozone with elastomer double bonds—the formation of
normal ozonides does not lead directly to a decrease in the molecular mass
of the elastomer macromolecules, because the respective 1,2,4-trioxolanes
are relatively stable at ambient temperature. The most favorable condi-
tions for ozone degradation emerge when the cage interaction between
Crigee’s intermediates and respective carbonyl groups does not proceed.
The amounts of measured different carbonyl groups have been used as an
alternative way for evaluation of the intensity and efficiency of the ozone
degradation.
The thermal decomposition of partially ozonated diene rubbers was
investigated by DSC. The respective values of the enthalpy, the activation
energy, and the reaction order of the 1,2,4-trioxolanes were determined.

KEYWORDS

•â•¢ 1
H-NMR spectroscopy
•â•¢ Monomers
•â•¢ Ozonation
•â•¢ Ozonolysis
•â•¢ Polyisobutylene

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 Applied Research on Polymer Composites Pasbakhsh
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Editors:
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Pooria V. Mukbaniani,
Pasbakhsh,
High-Performance A. DSc,
PhD,Polymers Marc
K. Haghi, J. M.and
PhD, Abadie,
Gennady
for Engineering-Based DSc,
E. and Tamara
Zaikov,
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Gennady
A. K. Haghi, PhD Zaikov,PhDDSc
Editors:Polymers
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High-Performance Omari V.of
Analysis Mukbaniani,
forPolymers DSc, Marc
Engineering-Based J. M. Abadie, DSc, and Tamara Tatrishvili, PhD
Composites
Gennady E. Zaikov, DSc
Editors:
Editors: Aleksandr
Omari M. Kochnev,
V. Mukbaniani,
Compositional
and Renat
Compositional
Analysis
M. Akhmetkhanov,
Editors: Aleksandr
Analysis
PhD,
DSc, of
Marc
DSc
M. Kochnev,
of Polymers
J.Oleg V. Stoyanov,
M. Abadie,
Polymers DSc, DSc, Gennady
and Tamara E. Zaikov,
Tatrishvili, DSc,
PhD
PhD, Oleg V. Stoyanov, DSc, Gennady E. Zaikov, DSc,
Gennady E. Zaikov, DSc
and Renat
Editors: Aleksandr M. Akhmetkhanov,
M. Kochnev, DSc
PhD, Oleg V. Stoyanov, DSc, Gennady E. Zaikov, DSc,
and Renat M. Akhmetkhanov, DSc ISBN: 978-1-77188-038-1
90000
ISBN: 978-1-77188-038-1
ISBN: 978-1-77188-038-1 90000
90000

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9 781 771 88 038 1
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