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 THIRD EDITION

CONDUCTIVE
ELECTROACTIVE
POLYMERS
Intelligent Polymer Systems
 THIRD EDITION

CONDUCTIVE
ELECTROACTIVE
POLYMERS
Intelligent Polymer Systems

Gordon G. Wallace
University of Wollongong, New South Wales, Australia

Geoffrey M. Spinks
University of Wollongong, New South Wales, Australia

Leon A. P. Kane-Maguire
University of Wollongong, New South Wales, Australia

Peter R. Teasdale
Griffith University, Queensland, Australia

Boca Raton London New York

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Taylor & Francis Group, an informa business
CRC Press
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Library of Congress Cataloging‑in‑Publication Data

Conductive electroactive polymers : intelligent polymer systems / Gordon G.

Wallace ... [et al.]. ‑‑ 3rd ed.
p. cm.
Includes bibliographical references and index.
ISBN 978‑1‑4200‑6709‑5 (alk. paper)
1. Smart materials. 2. Conducting polymers. I. Wallace, Gordon G. II. Title.

TA418.9.S62C648 2009
620.1’92‑‑dc22 2008023732

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Contents
Preface.......................................................................................................................xi
The Authors............................................................................................................ xiii

Chapter 1 Introduction........................................................................................... 1
What Are Intelligent Material Systems and Structures?............................................2
The Basis of the Revolution........................................................................................ 4
Identifying Macromolecular Building Blocks............................................................5
Academic Research in Conducting Polymers.............................................................5
Shorter-Term Opportunities: Other Applications of CEPs....................................... 10
Applications Utilizing the Polymers’ Inherent Conductivity................................... 11
Electrochemical Switching/Energy Storage/Conversion.......................................... 12
Polymer Photovoltaics (Light-Induced Charge Separation)..................................... 14
Display Technologies: Electrically Stimulated Light Emission............................... 15
Electrochromics........................................................................................................ 16
Electromechanical Actuators.................................................................................... 17
Separation Technologies........................................................................................... 18
Controlled-Release Devices...................................................................................... 21
Corrosion Protection................................................................................................. 22
Chemical Sensors...................................................................................................... 22
Biomedical Applications...........................................................................................24
Cellular Communications..............................................................................26
Sensors for Biomechanics.............................................................................. 27
Artificial Muscles: Manipulating Movement................................................. 27
Micro-Electromechanical Systems (MEMS) and other Microdevices.................... 31
Communication and Characterization Tools............................................................ 32
Electrochemical Methods......................................................................................... 32
Electrochemical Quartz Crystal Microbalance........................................................ 35
Resistometry............................................................................................................. 35
Electromechanical Analysis..................................................................................... 36
Chemical Analysis.................................................................................................... 37
Dynamic Contact Angle Analyses............................................................................40
Scanning Probe Microscopy..................................................................................... 42
In Situ Spectroscopy.................................................................................................46
UV-Visible Spectroscopy..........................................................................................46
Circular Dichroism (CD) Spectroscopy.................................................................... 47
Raman Spectroscopy................................................................................................ 48
Electron Spin Resonance (ESR) Spectroscopy......................................................... 49
Localized Electrochemical Mapping........................................................................ 51
Conclusions: Conducting Polymers as Intelligent Materials.................................... 51
References................................................................................................................. 53


vi Conductive Electroactive Polymers

Chapter 2 Assembly of Polypyrroles................................................................... 59

Electropolymerization—“A Complex Process Oversimplified”............................... 59
The Polymerization Environment/Cell Design......................................................... 63
Electrochemical Conditions......................................................................................66
Electrode Materials....................................................................................... 68
The Solvent.................................................................................................... 70
The Counterion/Cation Effect: Choice of Electrolyte................................... 71
The Monomer................................................................................................ 74
Chemical Polymerization.......................................................................................... 75
Mechanism of Chemical Polymerization...................................................... 75
Influence of Polymerization Conditions................................................................... 76
The Oxidant................................................................................................... 76
The Solvent.................................................................................................... 76
Polymerization Temperature......................................................................... 76
The Dopant Counterion (A–).......................................................................... 77
Achieving Regioselective Coupling with Pyrrole Monomers.................................. 77
In Situ Chemical Polymerization.............................................................................. 78
Routes to More Processable PPy’s............................................................................ 79
Counterion-Induced Solubilization................................................................ 79
Colloidal PPy Dispersions.............................................................................80
Side-Chain-Induced Solubilization............................................................... 81
Photochemically Initiated Polymerization............................................................... 83
Enzyme- and Acid-Catalyzed Polymerizations........................................................ 83
The Quest for Extra Functionality............................................................................84
Molecular Structure and Microstructure of PPy...................................................... 86
Molecular Weight, Branching, and Crosslinking.......................................... 86
Crystallinity and Molecular Order................................................................ 88
Surface Morphology and Film Density......................................................... 89
Nanostructured PPy’s................................................................................................ 91
References.................................................................................................................96

Chapter 3 Properties of Polypyrroles................................................................. 103

Electrical Properties: Conductivity......................................................................... 103
Switching Properties............................................................................................... 105
Chemical and Biochemical Properties................................................................... 114
Optical Properties of PPy’s..................................................................................... 119
Electronic Band Structure........................................................................... 119
UV-Visible-NIR Spectra: Dependence on Doping Level and Chain
Conformation.................................................................................... 120
Chiroptical Properties of Optically Active PPy’s................................................... 121
Electrochemical Asymmetric Synthesis, Chiral Separations, and Sensing........... 122
Mechanical Properties of PPy................................................................................ 123
Dry-State Mechanical Properties................................................................ 123
Environmental Effects on Mechanical Properties.................................................. 128
Contents vii

Conclusions............................................................................................................. 132
References............................................................................................................... 133

Chapter 4 Synthesis of Polyanilines.................................................................. 137

Electrochemical Polymerization............................................................................. 138
Mechanism of Electrochemical Polymerization.......................................... 138
Electrode Materials..................................................................................... 140
Concentration and Nature of the Dopant Acid (HA)................................... 140
Solvent......................................................................................................... 141
Temperature................................................................................................. 142
Monomer Type............................................................................................. 142
Colloidal PAn’s............................................................................................ 142
Chemical Polymerization........................................................................................ 143
Mechanism of Chemical Polymerization.................................................... 143
Polymerization Temperature....................................................................... 144
Nature and Concentration of the Dopant Acid (HA)................................... 144
Nature of the Oxidant.................................................................................. 145
Nature of the Solvent................................................................................... 146
Interfacial Polymerization........................................................................... 146
Self-Stabilized Dispersion Polymerization.................................................. 146
Achieving Regioselective Coupling with Aniline Monomers..................... 147
Template-Guided Synthesis......................................................................... 147
Comparison of Chemically and Electrochemically Prepared PAn.
Films................................................................................................. 147
Vapor-Phase Deposition.......................................................................................... 148
Photochemically Initiated Polymerization............................................................. 148
Enzyme-Catalyzed Polymerization........................................................................ 148
Polymerization Using Electron Acceptors.............................................................. 149
Miscellaneous Polymerization Methods................................................................. 150
Routes to More Processable PAn’s.......................................................................... 150
Emulsion Polymerization............................................................................. 150
Colloidal PAn Dispersions........................................................................... 151
Substituted PAn’s.................................................................................................... 152
Alkyl- and Alkoxy-Substituted PAn’s......................................................... 152
Covalently Bound Chiral Substituents........................................................ 153
Sulfonic Acid Substituted PAn’s.................................................................. 153
Postpolymerization Modification: Enhancing Functionality.................................. 154
Covalently Substituted PAn’s....................................................................... 154
Doping of EB with Brönsted Acids (HA).................................................... 155
Incorporation of Chiral Dopant Anions or Cations................................................ 156
Doping of EB with Lewis Acids.................................................................. 157
Doping of EB with Organic Electron Acceptors......................................... 158
Ion Implantation.......................................................................................... 158
Structure of PAn..................................................................................................... 158
Molecular Structure and Conformation.................................................................. 158
viii Conductive Electroactive Polymers

Molecular Weight.................................................................................................... 159

Chain Conformation............................................................................................... 160
Bulk Structure......................................................................................................... 160
Nanoscale Heterogeneity............................................................................. 160
Crystallinity, Molecular Order, and Conformation in Solid State.......................... 160
Solution-Cast Emeraldine Base.............................................................................. 161
Emeraldine Salt from Protonation of EB................................................................ 163
Solution-Cast Emeraldine Salt................................................................................ 163
Electropolymerized Emeraldine Salt...................................................................... 166
Influence of Water and “Secondary Dopants” on PAn Crystallinity..................... 166
Morphology and Density........................................................................................ 166
Nanostructured Polyanilines................................................................................... 168
Deposition in Nanoscale Matrices.......................................................................... 171
References............................................................................................................... 171

Chapter 5 Properties of Polyanilines................................................................. 179

Electrical Properties............................................................................................... 179
Conductivity................................................................................................ 179
Metallic Polyaniline.................................................................................... 182
Switching Properties............................................................................................... 183
Chemical Properties............................................................................................... 186
Mechanical Properties of Polyaniline..................................................................... 187
Electrochemically Prepared Films......................................................................... 187
Optical Properties of Polyanilines.......................................................................... 189
Base Forms of Polyaniline...................................................................................... 189
Circular Dichroism Spectra.................................................................................... 191
Chiral Discrimination and Asymmetric Induction with Chiral Polyanilines........ 193
Solvatochromism and Thermochromism............................................................... 193
References............................................................................................................... 194

Chapter 6 Synthesis and Properties of Polythiophenes..................................... 197

Synthesis of Polythiophene..................................................................................... 197
Electropolymerization................................................................................. 197
Chemical Polymerization............................................................................ 201
Vapor-Phase Polymerization........................................................................202
UV Polymerization of Oligothiophenes......................................................203
Substituted Polythiophenes.....................................................................................203
Poly(3-alkylthiophenes) and Poly(3-alkoxythiophenes)..............................203
Regioregular Substituted Polythiophenes...............................................................206
Regioregular Poly(3-alkylthiophenes) with Low Polydispersities and
Controlled Molecular Weights..........................................................207
Polythiophenes with Special Functional Groups....................................................208
Water-Soluble Polythiophenes.....................................................................208
Organic-Solvent-Soluble Chiral Polythiophenes.........................................208
Contents ix

Postpolymerization Modification: Enhancing Functionality.................................. 210

Structure of Polythiophenes.................................................................................... 211
Molecular Structure and Conformation.................................................................. 211
Molecular Weight........................................................................................ 211
Electropolymerized Polythiophenes....................................................................... 212
Crystallinity, Molecular Order, Conformation in Solid State..................... 212
Morphology and Density............................................................................. 213
Solution-Cast Polythiophenes................................................................................. 213
Properties of Polythiophenes.................................................................................. 216
Conductivity................................................................................................ 216
Mechanical Properties of Polythiophenes................................................... 217
Chemical Properties.................................................................................... 219
Switching Properties.................................................................................... 219
n-Doping of Polythiophenes........................................................................ 220
Optical Properties of Polythiophenes.......................................................... 221
Electronic Band Structure and UV-Visible Spectra.......................... 221
Thermochromism and Solvatochromism in Poly(3-
alkylthiophenes).................................................................. 221
Chiroptical Properties of Optically Active Polythiophenes........................ 222
Conclusions............................................................................................................. 225
References............................................................................................................... 226

Chapter 7 Processing and Device Fabrication................................................... 231

Integration/Fabrication after Polymerization......................................................... 231
Solution-Processable CEPs..................................................................................... 231
Melt-Processable CEPs........................................................................................... 233
Assembly of Conducting Polymers in Host Matrices............................................. 235
Chemical Polymerization........................................................................................ 235
Deposition on Glass/Plastics................................................................................... 235
Interfacial Polymerization...................................................................................... 238
Electrochemical Integration.................................................................................... 239
Device Fabrication.................................................................................................. 243
Fiber-Spinning Technologies.................................................................................. 243
Printing Technologies.............................................................................................246
References............................................................................................................... 249

Index....................................................................................................................... 253
Preface
Intelligent materials are being incorporated into many new applications/devices, and
the science develops at a breakneck pace. The new approach to material design,
synthesis, and system integration, as championed in this book with conducting elec-
troactive polymers, has many adherents. The desire to have built-in sensing, pro-
cessing, actuating, energy conversion, and storage functions continues to require
the identification of dynamic materials with chemical and physical properties that
are readily manipulated. The need to create these materials in different forms to
enable integration into or interfacing with other structures, including living bodies
and cells, is vital.
Natural polymers remain an inspiration and provide considerable stimulation for
researchers of artificial intelligent materials and systems. For example, antibodies
and enzymes provide the molecular recognition capabilities used so magnificently
by nature. Macromolecules are also the basis of that most useful of actuator systems:
muscles. Furthermore, it is the generation and transmission of electrical signals that
regulate the processes behind the formation and operation of these biosystems.
Rapid advances in synthetic polymer science and nanotechnology have now
placed us in a position to utilize the unique properties of this versatile class of mate-
rials. Our ability to design and assemble polymers from the molecular level, coupled
with a better understanding of structure–property relationships enables the design of
sophisticated structures. We believe that inherently conducting electroactive poly-
mers (CEPs) will continue to play a central role in the development of intelligent
material science over the following decades.
The parameters affecting the formation of important CEPs, such as polypyrroles,
polyanilines and polythiphenes are discussed. How these parameters can be used to
manipulate the chemical, physical, and energy parameters of these polymers is then
revealed. We attempt to clarify the chemical and energy parameters that determine
the structure and, hence, the chemical, electrical, and mechanical properties of these
fascinating structures. We present examples wherein the ability to manipulate the
structure and properties of conducting polymers is used to produce materials with
useful sensing, processing, and actuating capabilities.
We’ve tried to include all substantial developments and advances in this new
edition. Significant developments in biomedical applications, microelectromechani-
cal systems, and electronic textiles have been included, as has synthesis of nano-
structured CEPs. New methods for characterizing CEPs, such as electrochemical
Raman and electron spin resonance spectroscopy, have also been described. Signifi-
cant progress is also detailed in techniques for processing CEPs and the fabrication
of devices.

xi
The Authors
Gordon Wallace, Ph.D., D.Sc., FTSE, is cur-
rently executive research director of the ARC
Centre of Excellence for Electromaterials
Science, Intelligent Polymer Research Insti-
tute, University of Wollongong, New South
Wales, Australia. His research interests include
organic conductors, nanomaterials, and elec-
trochemical probe methods of analysis. A cur-
rent focus of his involves the use of these tools
and materials in developing biocommunica-
tions, from the molecular to skeletal domains,
in order to improve human performance via
medical bionics.
He completed his undergraduate (1979)
and Ph.D. (1983) degrees at Deakin Univer-
sity. He was awarded a D.Sc. from Deakin in
2000. In 1990 he was appointed as professor at
the University of Wollongong, and the follow-
ing year was awarded an Australian Research Council (ARC) QEII Fellowship in
1991. He was given an ARC Senior Research Fellowship in 1995. In 2002 he was
appointed to an ARC Professorial Fellowship, and in 2006 was awarded an ARC
Federation Fellowship.
He was elected as a fellow of the Australian Academy of Technological Sciences
and Engineering in 2003 and as a fellow of the Australian Academy of Science in
2007. He was elected as a fellow of the Institute of Physics (UK) in 2004 and is a
fellow of the Royal Australian Chemical Institute (RACI).
Dr. Wallace received the inaugural Polymer Science and Technology Award
from the Royal Australian Chemical Institute in 1992. He was awarded an ETS
Walton Fellowship by Science Foundation Ireland in 2003, and received the RACI
Stokes Medal for research in electrochemistry in 2004. Professor Wallace has pub-
lished more than 400 refereed publications and a monograph (two editions) on inher-
ently conducting polymers for intelligent material systems. He has supervised 50
Ph.D. students to completion.

xiii
xiv Conductive Electroactive Polymers

Geoffrey Spinks, Ph.D., is currently dis-

cipline advisor for materials engineering at
the University of Wollongong and a program
leader in the ARC Centre of Excellence for
Electromaterials Science. His research inter-
ests relate to the mechanical behavior of
organic conductors and polymeric nanoma-
terials. A particular focus of his involves the
development of actuator materials and sys-
tems, from the nano- to the macro-scale.
He completed his undergraduate (1986)
and Ph.D. (1990) degrees at the University of
Melbourne. He was appointed as a lecturer
at the University of Wollongong in 1989, and
subsequently was promoted to senior lecturer
(1995), associate professor (2001), and profes-
sor (2005). He became discipline advisor for
materials engineering in 2003.
He received the Australian Polymer Science and Technology Achievement
Award from the Royal Australian Chemical Institute (RACI) in 1998 and the Treloar
Prize from RACI in 1990. Professor Spinks has published more than 100 refereed
publications and a monograph (two editions) on inherently conducting polymers for
intelligent material systems. He has supervised 16 Ph.D. students to completion.

Leon Kane-Maguire, Ph.D., is currently a

project leader in the ARC Centre of Excellence
for Electromaterials Science at the University
of Wollongong. His research interests are the
synthesis of conducting organic polymers and
characterizing their stereochemical and pho-
tophysical properties. A strong focus of his
recent work has been the synthesis of chiral
conducting polymers (especially polyanilines)
and their use as novel chiral electrodes for
electrochemical asymmetric synthesis.
Leon Kane-Maguire completed his under-
graduate (1964) and Ph.D. (1967) degrees
in chemistry at the University of Queensland, where he was awarded a University
Medal. After postdoctoral studies in the United States at Northwestern University,
in London at University College and at Cambridge University, he was appointed
as a lecturer in chemistry at University College Cardiff, Wales, in 1971. There, his
research focused on synthetic and mechanistic studies of organometallic reactions.
In 1983 he returned to Australia as professor and head of the department of
chemistry at the University of Wollongong. Since 1993 he has enjoyed a very fruitful
collaboration with Prof. Gordon Wallace in the area of electrically conducting poly-
mers, where his major contribution has been the development of chiral polyanilines.
The Authors xv

He has published 175 refereed papers and book chapters as well as a monograph on
conducting polymers. He has supervised 20 Ph.D. students to completion.

Peter Teasdale, Ph.D., is a senior lecturer in

environmental chemistry at Australian Rivers
Institute, Griffith University Gold Coast Cam-
pus. His current research interests include in
situ sensors for metals and nutrients, natural,
recycled and potable water quality, microbial
toxicology, and sediment biogeochemistry.
Peter is the current chair of the Royal Austra-
lian Chemical Institute Environment Division.
He has published over 40 refereed publications.
Coauthoring this book reflects his interest in
the field of conducting electroactive polymers,
the area in which he completed his Ph.D. in
1993 at the University of Wollongong.
 1 Introduction
Conducting electroactive polymers (CEPs) such as polypyrrole, polythiophene, poly-
aniline, and sulfonated polyaniline (1–4 shown subsequently) are complex, dynamic
structures that captivate the imagination of those of us involved in intelligent mate-
rial research.1,2,3,4,5

H H H
N N N
N + N + N
H H H x
A– A–
1

S S S
S + S + S
x
A– A–
2

(The number of monomer units per unit positive charge is usually 3–4 for polypyr-
role and polythiophene. A− is a counterion incorporated during synthesis.)

N N N N
H H y 1-y m
3

Polyaniline: leucoemeraldine (y = 1), emeraldine (y = 0.5), and pernigraniline (y =

0); m determines the molecular weight.
SO3– SO3–

H+
N N
H n
MeO MeO


 Conductive Electroactive Polymers

It is possible to create conducting polymers with a diverse range of properties. For

example, chemical properties can be manipulated to produce materials capable of
trapping simple anions, or to render them bioactive. Electrical properties can also
be manipulated to produce materials with different conductivities, capacitance, or
redox properties. After synthesis, the properties of these fascinating structures can
be manipulated further through electrochemical switching. The application of elec-
trical stimuli can result in drastic changes in the chemical, electrical, and mechan-
ical properties of CEPs. These complex properties can only be controlled if we
understand, first, the nature of the processes that regulate them during the synthesis
of the conducting polymers, and second, the extent to which these properties are
changed by the application of an electrical stimulus. It is these dynamic properties
of CEPs that are the focus of this text, because it is the ability to control them in
various operational environments that should lead to the development of Intelligent
Material Systems.
The state of the art is such that an understanding of these processes is now well
established, and an exciting fertile field lies before intelligent material research scien-
tists. We can, by design, control the chemical and electrical properties of conducting
polymers at the point of assembly. How these properties are likely to vary as a result of
application of external stimuli can also be manipulated by the synthesis process.
Of course, the molecular organization required to achieve the desired chemi-
cal and electrical properties will also determine the mechanical properties of any
practical structure we are to make. These three properties (chemical, electrical, and
mechanical) are inextricably linked.
The method of assembly is also important as it determines the physical form of
the materials. A wide variety of synthesis and processing methods now exist that
can be manipulated to produce materials in forms that can be integrated into truly
intelligent structures.
Before exploring these materials in detail, some general discussion of intelligent
material science is warranted.

What are Intelligent Material Systems and Structures?

This question has already been addressed by numerous authors,6,7,8,9,10 and many
definitions are employed. For the purpose of our work, we will use the following:
An intelligent material is capable of recognizing appropriate environmental stimuli,
processing the information arising from the stimuli, and responding to it in an appro-
priate manner and time frame. A further desirable feature is that the material should
ideally be self-powered, having energy conversion/storage functions (Figure 1.1).
What is particularly important is that the responses obtained be appropriate.
That is, they must result in desirable behavior that enhances the performance of the
material itself or the structure within which the material is operational. For exam-
ple, the first instance might involve the material responding to stress by increasing
strength. In the second instance, the material may become capable of initiating con-
trolled release of a drug as part of an environmentally stimulated (e.g., change in
temperature) biodegradation process. So, although the performance of the material
itself is not enhanced, that of the overall system is.
Introduction 

Information Processing

Sense

Actuate

Energy Conversion and Storage

Figure 1.1  An “intelligent material”: the surface of polypyrrole (as seen with an electron
microscope) in the shape of a human brain. The intelligent material, similar to our brain,
processes information from sensors to actuate an appropriate response, and is supported by
energy conversion/storage systems.

No matter what definition we employ, the underlying feature that differentiates

intelligent materials from more conventional ones is their dynamic character. With-
out such character, there can be no intelligence. However, this character must be
controllable, and the time frame within which it responds must be appropriate if
truly intelligent behavior is to be realized. If it is too slow, it may have no practical
application. If it is too fast, it may be useless, or even dangerous.
There is little doubt that intelligence is more demonstrable when physical pro-
cesses such as motion (mechanical activity) are apparent. However, we should
remember that in complex systems such as living entities, motion is a physical mani-
festation of activity at the molecular and electronic levels. Similarly, motion result-
ing from the application of an external force causes changes both at the molecular
and electronic levels within a material.
If the stimulus and response required are chemical or biochemical in nature,
involving activity only at the cellular, molecular, or even atomic level, then the use of
a single intelligent material may be possible. Also, a mechanical stress of a gradual
or slight nature may be recognized and responded to with a single material. How-
ever, in many applications, more that one material is required to perform the desired
functions. This is when we encounter intelligent material systems, which in turn may
be incorporated into much larger intelligent structures made up of a number of com-
ponent systems and materials of varying kinds and functions. In intelligent material
systems and structures, the individual functions of stimuli recognition, information
processing, and response generation are brought about by the combination of appro-
priate materials. The greater the severity and variety of the stimuli, and the more
demanding the requirements of the response, the more complex the intelligent mate-
rial structure must be.
However, again, there is the underlying fundamental requirement that the cre-
ation of intelligent material systems must involve the identification of molecular sys-
tems whose chemical and electrical properties can be manipulated and controlled.
To continue to operate effectively, the material may be required to learn, grow,
and even decay in a fashion determined by the operational environment. What is
 Conductive Electroactive Polymers

clear is that the properties of such materials must change with time; that is, they must
be dynamic. We must identify material systems in which chronological behavior
can be controlled, plotted, and predicted as a function of the environmental stimuli
that are likely to be encountered. Then, if the materials are to behave properly, we
must develop procedures to manipulate their molecular structure, and thereby their
dynamic character during the early stages of synthesis and processing.

The Basis of the Revolution

The diversity of approaches used to develop intelligent material systems and struc-
tures is a healthy symptom of the stage of development of this scientific endeavor.
At least two distinct approaches are currently obvious:

• Integration of functions at the bulk material level

• Integration of functions at the molecular level

The concept of intelligent material systems and structures emerged from the research
activities of the U.S. Army Research Office. Scientists here realized that integration
of appropriate materials at the bulk material level could produce a system capable of
monitoring and responding to environmental conditions. The concept of embedding
sensors and actuators within structures, coupled with localized processing, remains
the shortest-term approach to gaining benefits in the intelligent material area.
However, information is much easier to process and transmit in a material inte-
grated at the molecular level, and preferably integrated during processing or growth.
Nature and biological systems have refined this approach and provide many exam-
ples. There is indeed great potential for diversity at this level of organization.
Nature achieves intelligent behavior by assembling appropriate molecules in a
more sophisticated and timely fashion than we humans have been able to achieve
artificially to date. Macromolecular structures may be integrated into systems com-
posed of numerous other inorganic materials or, preferably as nature does, the active
(organic) components may create the required mechanical structure. The molecular
approach to the development of synthetic intelligent systems involves the design and
assembly of appropriate molecules to produce the properties required to sense, pro-
cess, and respond to information.
Progress in this approach may be accelerated by borrowing selected macromol-
ecules, such as proteins, from nature to become active components in our synthetic
structures. Nature has developed the appropriate stimuli recognition, information
processing and storage, and response mechanisms to allow life, as we know it, to
continue to exist. This is no mean feat, and to emulate it we must consider a macro-
molecular approach.
Many materials are, of course, composed of molecular building blocks. It is how
we put them together, and how we integrate and spatially distribute the components
required for intelligence that is important. This approach requires the identifica-
tion of suitable building blocks, that is, suitable molecular components. There is a
need for molecular conducting wires, molecular insulators, and molecular switches.
It will take some time to develop, understand, and integrate many of the molecular
Introduction 

components, but much work in the field of molecular engineering and molecular
electronics is already under way.
There is also a need for a more detailed chemical understanding of these mate-
rial systems. Inevitably, they involve chemical processes occurring at a dynamic
heterogeneous interface. The well-defined chemical rules that apply in homogeneous
solutions no longer apply. Instead, we must deal with chemical (molecular) interac-
tions in which spatial distribution of active sites occurs at the nanodimensional level,
and the fact that the nature of these sites varies as a function of time and environ-
mental stimuli is important.
Of course, not all molecular systems are suitable. It appears likely that only a
handful of systems will be produced to solve our intelligent material systems needs.
It is not so much that sophisticated molecules are required to produce materials
capable of sophisticated behavioral patterns; simple molecules, assembled creatively,
achieve this objective in nature, and this is something those of us involved in syn-
thetic materials aspire to.

Identifying Macromolecular Building Blocks

CEPs have emerged as one of the champions in intelligent material research. They
have all the desirable properties: they are readily engineered at the molecular level to
recognize specific stimuli; they facilitate transport of electrical information as they
are conductive; and they are capable of localized processing as well as actuation of
response mechanisms. A wide range of CEPs are available (Table 1.1).
CEPs have a further unique and practical advantage. The fact that they conduct
electricity means that we can communicate with them using electronic tools (com-
puters and interfaces) that have become part of our scientific lives. Information on
the behavior of these systems can be retrieved from real in situ environments using
existing and emerging characterization tools (described later). In addition, their
behavior can be manipulated in situ using appropriate electrical stimuli (Table 1.2).
In the Intelligent Polymer Research Institute (IPRI), the unique features of CEPs
were identified based on pyrrole, aniline, and thiophene. Stimuli-recognition sites
can be incorporated into these CEPs, for which information-processing capabilities
are inherent, and various response mechanisms can be integrated into them.
There is no doubt that conducting polymers are a class of materials destined
to play a major role in intelligent material science. As outlined in the remainder of
this text, the properties of these materials are versatile and possess the dynamism
required for intelligent behavior.

Academic Research in Conducting Polymers

Since their discovery in the mid-1970s, conducting polymers have been a hot
research area for many academic institutions. This research has supported the indus-
trial development of conducting polymer products and has provided the fundamental
understanding of the chemistry, physics, and materials science of these materials.
The impact of the field on science, in general, was recognized in 2000 by the award-
ing of the Nobel Prize for Chemistry to the three discoverers of conducting poly-
mers: Alan MacDiarmid, Alan Heeger, and Hideki Shirakawa (Figure 1.2).
 Conductive Electroactive Polymers

Table 1.1
Typical Conducting Polymer Structures
(in Undoped Form)
Name Structure
Polyacetylene (PAc)
C C
n

Polypyrrole (PPy)

N n
H

Polythiophene (PTh)

S n

Poly(ethylenedioxythiophene) (PEDOT)
O O

S
n

Polyseleneophene (X = Se)

Polyfuran (X = O)

X n

Poly(thienylene-vinylene) (PTV)

S
n

Poly(furylene-vinylene) (PFV)

O
n

Polyaniline (PAn) H
N
n

Poly(diphenylamine) H
N
n
Introduction 

Table 1.1 (Continued)
Typical Conducting Polymer Structures
(in Undoped Form)
Name Structure
Poly(para-phenylene) (PPP)

Poly(phenylene-vinylene) (PPV)

Poly(phenylenesulfide) (PPS)
S
n

Poly(phenylene ethynylene) (PPE)

Polycarbazole
n

N
H

Poly(indole)

N
H n

Poly(thieno[3,2-b]pyrrole) S

N
H n

Poly(thieno[3,2-b]thiophene) S

S
n

Continued
 Conductive Electroactive Polymers

Table 1.1 (Continued)
Typical Conducting Polymer Structures
(in Undoped Form)
Name Structure
Poly(fluorene)

H H

Polypyridine

N n

Table 1.2
Property Changes Typically Observed upon Electrical Stimulation
to Switch CEPs between Oxidized and Reduced States
Property Typical Change Potential Application
Conductivity From 10−7 to 103 S/cm Electronic components, sensors
Volume 10% Electromechanical actuators
Color 300 nm shift in absorbance band Displays, smart windows
Mechanical Ductile to brittle transition —
Ion permeability From 0 to 10−8 mol cm−2 s−1 in solution Membranes

Figure 1.2  The three discoverers of polyacetylene, the first inherently conducting poly-
mer: Alan Heeger, Alan MacDiarmid, and Hideki Shirakawa.
Introduction 

8000

6000

4000

2000

0
Journals
–1975 1976–
1981– Patents
1980 1986–
1985 1991–
1990 1996–
1995
(a) 2000

2500

2000

1500

1000

500

0
1995
1997
1999
2001 S1
(b) 2003
2005

Figure 1.3  Number of journal articles published annually relating to CEPs; (a) data
obtained from chemical abstracts (1975–2000); (b) data obtained from ISI Thomson Scien-
tific Web of Science (1995–2005).

A search of chemical abstracts over the period 1975–2000 shows the level of
publications increasing rapidly after 1980 (Figure 1.3a). The data suggest a peak in
patenting in the late 1980s, and the rate of scientific publications increased unabated
through the end of the 1990s. A similar trend is shown in journal articles tracked
by ISI Thomson Scientific Web of Science, with the steady increase in journals pub-
lished per year relating to CEPs continuing to the present time (Figure 1.3b).
Figure 1.4 shows the main areas of interest for papers published on CEPs, with
almost half of the publications relating to synthesis of new types of CEPs or modi-
fications to existing ones. The next largest area of research has been in the physics
of the conduction mechanisms, while applications of CEPs account for less than
20% of publications. A further breakdown of the areas of application of CEPs shows
a great deal of interest in batteries, followed by sensors, membranes, and polymer
light-emitting diodes (PLEDs). There has been a distinct move in recent years toward
biological/biomedical applications of CEPs.
10 Conductive Electroactive Polymers

Applications

Electrical
Conductivity

Synthesis

Actuators
Sensors

Batteries

Membranes

Photovoltaics

Corrosion LED

Figure 1.4  Scientific papers published on conducting polymers (1990–2000) categorized

into various topics.

Research in CEPs remains extremely fruitful, with fundamental studies under-

pinning the exciting commercial developments described in the following sections.

Shorter-Term Opportunities: Other Applications

of CEPs
In pursuing the development of intelligent materials, it is impossible to ignore the
shorter-term opportunities that are available for applications of CEPs. The science
is such that a better understanding of dynamic materials has been obtained, and this
has been used to advantage in the development of new and improved products.
The potential applications of conducting polymers have been discussed at
length in numerous reviews.11,12,13,14,15,16,17,18 From Figure 1.3 it is evident that the pat-
ent activity relating to conducting polymers peaked in the mid-to-late 1980s. The
rapid increase in patents in the early 1980s reflects the growing appreciation of the
versatility of conducting polymers in many application areas. The commercializa-
tion of conducting polymers has been particularly boosted since the mid-1990s by
breakthroughs in processing technologies that have given both soluble and melt-pro-
cessable forms of conducting polymers. The various spin-off application areas are
Introduction 11

described in the following sections, and processing and device fabrication technolo-
gies are described in Chapter 7.

Applications Utilizing the Polymers’

Inherent Conductivity
On realizing that polymers could be made electrically conductive, the possibility
of having lightweight conductors capable of replacing metals in many applications
was immediately grasped. However, this promise has not been realized to date. The
development of highly conducting polymers with adequate mechanical properties
and stability is yet to be achieved. However, materials with lower conductivities
(100–200 S/cm) that can be produced routinely are proving extremely useful in elec-
tromagnetic shielding applications.
Another area that utilizes the semiconducting nature of conducting polymers
is antistatic applications. Electrostatic discharge (ESD) is particularly damaging
for electronic components; a high-voltage surge can destroy componentry. Conse-
quently, all electronic components are shipped in antistatic packaging materials. It
is often desirable that the packaging material be transparent so that the contents can
be viewed. The challenge for antistatic coatings (metals and polymers) is to provide
both the desired levels of surface conductivity and transparency (coupled with adhe-
sion and scratch resistance).
A number of companies seek to overcome the limitations of existing materials
by using conducting polymers for ESD protection. The main materials currently in
use are ionic conductors, carbon-black-filled plastics, and vacuum metallized plas-
tics.19 Ionic conductors operate by absorbing moisture from the atmosphere to form
a conductive surface (1011–1012 Ω/square). They are highly transparent coatings, but
are also highly sensitive to moisture and become ineffective when humidity is low.
The ionic conductors are also easily removed by washing, so reuse of the container
is difficult. Carbon-black-loaded polymers give lower surface resistivities (103–105Ω/
square), which are suitable for electromagnetic interference shielding, but are too
low for ESD protection. Carbon-black-filled polymers are also intensely colored and
suffer from the loss of carbon particles from friction (a serious problem in clean-
room applications). Metallized plastics are only transparent for very thin coatings,
and adhesion to the polymer is difficult to achieve. Further development of conduct-
ing polymers to give acceptable surface resistivity (especially over time and after
repeated washing) and adhesion to the substrate will overcome many of the limita-
tions of existing methods for ESD protection. Similarly, highly conducting CEPs are
being investigated for shielding of electromagnetic interference (EMI). CEPs are
strong absorbers of electromagnetic radiation over a wide frequency range and CEP-
coated textile fabrics have been investigated for EMI shielding applications.20,21,22
Recently, conducting polymers have been considered for microelectronics appli-
cations. Electronics company Philips is involved in the development of “plastic chip”
technology using conducting polymers.23 In this application, a simple processor chip
is fabricated using polyaniline electrodes and a polythienylenevinylene semiconduc-
tor layer. The layers are spin-coated onto a polyimide substrate. Patterning of the
polyaniline electrodes is achieved by exposing the polymer to UV light through a
12 Conductive Electroactive Polymers

suitable mask. A photosensitizer molecule incorporated into the polyaniline absorbs

the UV light and induces a photochemical reaction that leads to an increase in con-
ductivity of 10 orders of magnitude. The end result is patterned tracks of conducting
polyaniline in a nonconducting matrix. The performance of the all-plastic circuits
is poor compared to silicon-based electronics. However, the devices are designed
for applications where low cost and mechanical flexibility are desired. One example
being pursued is the “smart label” to replace the ubiquitous barcode incorporated in
virtually all packaged products. As recently reviewed,24 prototype products based
on printed CEP circuits are showing promise. An example is the printed transistor
circuit produced by PolyIC in Germany.25
Conducting polymers also have other applications in microelectronics, as
reviewed by Angelopolous.26 Polyaniline layers have been shown to improve the
resolution of electron-beam patterning, where the conducting polymer prevents the
buildup of charge in the resist layer and so eliminates distortion. Polyaniline conduc-
tivities of 10 −4 S/cm were shown to be effective at eliminating resist layer charging.
Mitsubishi Rayon in Japan has been producing a water-soluble sulfonated methoxy-
aniline polymer for use in e-beam lithography. Similarly, IBM has introduced a fam-
ily of water-soluble polyanilines (PanAquas) that are effective at eliminating resist
layer charging when used as 200 nm-thick layers. The same polymers were also
shown to be effective in reducing charging of nonconducting specimens during scan-
ning electron microscopy. The advantage of using conducting polymers (compared
with more traditional sputtered metal coatings) is that the polymer can be easily dis-
solved so that specimens can be nondestructively analyzed.27 Other applications for
conducting polymers in microelectronics fabrication include the use of polyaniline
coatings for electroless deposition of copper connectors, and future applications may
include interconnects and even devices such as diodes and transistors.

Electrochemical Switching/Energy Storage/Conversion

The next most obvious applications of conducting polymers utilize their conductivity
and electroactivity. Conducting polymers such as polypyrrole are readily oxidized
and reduced, according to the reaction in Figure 1.5, in cases where the counterion
is able to freely leave the CEP matrix and is immobilized within the CEP matrix.
+
A– +e– + mA–
N N
n –e– n
H H
m m
AND/OR
+ 0
+e–, X+ A–
A– N X+
N
H n –e– H
m n m

[n, A–, m defined on page 1]

Figure 1.5  The electrodynamic character of polypyrroles.

Introduction 13

Table 1.3
Battery Performance Data
Open Circuit Voltage Charge Density
Anode Cathode (V) (Ah/kg)
Lithium Polyacetylene 3.5–3.9 100–300
Lithium Polyaniline 3.0–4.0 50–150
Lithium Polypyrrole 3.0–4.0 50–170

Source: From Angelopoulos, M. IBM I. Res. Dev. 2001, 45(1): 57.

The general changes in the properties of the polymer that accompany this reaction
are indicated in Table 1.2.
Anion movement predominates in cases where a small mobile dopant, e.g., Cl−,
is used. If large anion dopants such as polyelectrolytes are employed, then cation
movement will predominate.
The fact that conducting polymers can be charged and discharged has aroused
much interest among those involved in developing new rechargeable battery tech-
nologies.28 Conducting polymers are usually combined in a cell with lithium as the
other electrode, and a usable voltage of approximately 3 V is obtained. The achiev-
able energy densities are several times that of the nickel-cadmium and lead-acid
batteries. Typical performances of several CEP-based batteries are summarized in
Table 1.3.
These solid-state batteries were introduced commercially in the early 1990s
by Bridgestone (Japan), Allied Signal (USA), and Volta (Germany), but the prod-
ucts were discontinued because of low sales. The slow sales have been attributed
to the release of other competing battery technologies, such as lithium-ion batter-
ies. A breakthrough in battery design was announced by John Hopkins University
researchers in 1996.29 Whereas previous battery designs used a conducting polymer
as one electrode only (cathode), the new design incorporates a polymer cathode,
an anode, and electrolyte. The design gives good battery performance and has the
advantages of high flexibility and light weight. Such improvements may give a new
impetus to polymer battery commercialization. Alternatively, novel forms of CEPs
may facilitate their use as batteries in nonconventional applications. For example,
a recent report describes CEP fibers as battery materials, and conducting-polymer-
coated textiles have been shown to be highly effective battery electrodes.30 Fully
packaged CEP fiber batteries may be useful as a power source for wearable elec-
tronic systems.
Recent research has suggested that conducting polymers are also set to emerge in
devices used to store energy in the form of supercapacitors and photovoltaic systems.
The intense interest in these applications is driven by developments in electric-pow-
ered vehicles and alternative energy in general. Supercapacitors are those devices able
to store a charge of 50 F/g (or 30 F/cm3) or higher. This high storage capacity and abil-
ity to deliver high power density can be utilized in electronic equipment and electric
vehicles.31 The fast discharge rate obtainable from capacitors means that high power
14 Conductive Electroactive Polymers

ITO Coated Glass

Aluminium

Figure 1.6  Device design for polymer photovoltaic device (the thickness of the polymer
layer is greatly exaggerated).

can be delivered for short periods. Conducting polymers are being researched for
“redox supercapacitors.” In these devices, the redox chemistry of the polymer is used
in the same way as described earlier for batteries. However, the design of the device
is such that the conducting polymer is applied as a thin coating on a high-surface-area
substrate. This design allows for very rapid charging and discharging of the polymer
so that capacitor-like performance is obtained, with specific capacitances reported up
to 250 F/g (based on the weight of the polymer).28 All solid-state redox supercapaci-
tors using PTh and PPy with solid polymer electrolytes have been reported32 as having
storage capacities of 18 F/g, and more recent reports show that supercapacitors with
solid electrolytes can have capacities even higher than their liquid electrolyte counter-
parts.33 Ionic liquid electrolytes also provide significant advantages to supercapacitor
performance, such as greatly increased cycle life.34
The development of organic-inorganic hybrid materials as capacitors presents
additional opportunities,35 with the inherent capacity of metal oxides such as V2O5
being used to advantage.36

Polymer Photovoltaics (Light-Induced

Charge Separation)
Polymer photovoltaic devices using conducting polymers are also being developed.37
In a typical arrangement, the photosensitive polymer (such as PPV and its derivatives)
is sandwiched between two electrodes (Figure 1.6). One is a transparent material,
typically indium tin oxide (ITO)-coated glass, and the other electrode is a low-work-
function metal, such as aluminum or calcium. Light is absorbed by the polymer,
creating excitons (electron–hole pairs) that dissociate at an appropriate interface to
give charge separation and, hence, current flow. The advantages of using CEPs in
solar cells have been summarized recently:38

• Stable after absorption of visible light in an inert atmosphere

• Strong absorbers of visible light
• Tunable absorption spectrum
• High yield of charge generation when mixed with electron-accepting materials
Introduction 15

Efficiencies of polymer-based photovoltaic devices are currently low compared

with silicon semiconductor materials. However, polymer photovoltaics have the
potential to be manufactured very cheaply and can be applied to very large areas,
such as rooftops and exterior walls of buildings. The large surface areas can com-
pensate for the lower efficiencies to provide an adequate supply of electricity. Of
course, efficiencies are being improved by chemical modification of the polymer and
better design of the photovoltaic devices. One approach to polymer modification is to
attach “light-harvesting” groups to the polymer chains so as to increase the amount
of light absorbed. Once again, the fabrication of the device is critical in determining
device performance. It has been shown that formation of interpenetrating networks
of donor- and acceptor-type polymers results in marked improvements in photovol-
taic efficiency, as reviewed recently.39 The distance moved by the separated charge
is very small in CEPs due to low carrier mobilities,38 so efficient charges generation
requires a large interface between the electron donor (CEP) and the electron accep-
tor materials. Nanostructured metal oxides and Buckminster fullerenes have been
shown to be suitable acceptor materials.38
CEPs have also been used as the photoactive component in photoelectrochemi-
cal (Gratzel) cells40,41 as well as catalytic counter electrodes in place of platinum.42

Display Technologies: Electrically

Stimulated Light Emission
The process used for the photovoltaic device can be reversed to produce a light-emitting
diode. When an electric field is applied to two electrodes, as shown in Figure 1.7, elec-
trons are injected into the conduction band of the polymer layer from the cathode (usu-
ally a high-work-function metal, such as aluminum or calcium). At the ITO-glass anode,
electrons are removed from the valence band of the polymer, to produce vacancies, or
holes. The free electrons and holes move in opposite directions under the influence of
the electric field, and when they combine, a photon of light is emitted. The color of the
light emitted depends on the band gap between the valence and conduction bands in the
polymer. Appropriate derivitization of PPV polymers has produced polymer light-emit-
ting diodes (PLEDs) that emit the three primary colors: red, blue, and green.
The PLED was first demonstrated by Richard Friend and coworkers at Cambridge
University in 1990. The early PLED devices from Friend’s group in Cambridge had
an efficiency of only 0.01%, but this has now been improved to 4% or better, which

ITO Coated Glass +

CEP

–
Aluminium

Figure 1.7  Device design for a polymer light-emitting diode (PLED).

16 Conductive Electroactive Polymers

provides sufficient light to be seen in daylight. Early devices also suffered prob-
lems of stability, but improved lifetimes have been obtained by totally sealing the
devices from oxygen and moisture. Removal of excess heat also stabilizes the poly-
mer against degradation. A great many conjugated polymers and copolymer systems
have been investigated for use in PLEDs, with significant advances made in terms
of processability and color tuning. However, according to a recent review, a great
deal of work still remains to be done to fully understand the complex mechanisms
involved in device operation and to fully optimize device performance.43
PLEDs offer one of the most exciting prospects for conducting polymer com-
mercialization as they offer several advantages over existing technologies for flat
panel displays. Several breakthroughs in the synthesis and processing of electrolu-
minescent PPV by the Cambridge University group have spearheaded the commer-
cial development of flat screen displays. The first products were backlit displays for
automobile instrument panels and mobile phones. The displays were being manufac-
tured by electronics giant Philips in partnership with Cambridge Display Technolo-
gies, a company spun off from the original research at Cambridge University. Philips
released an electric razor in 2002 that used a PLED display. Uniax Corporation,
United States, has also entered into a partnership with Philips to commercialize con-
ducting polymer displays based on the research work of Nobel Laureate Prof. Alan
Heeger’s group at the University of California, Santa Barbara. PLED development
is also an interest for most major chemical companies, including DuPont, Hoechst,
and Dow Chemical.

Electrochromics
Another interesting application that uses the dynamic properties of conducting poly-
mers is electrochromic devices.44,45,46,47 An electrochromic device based on polypyr-
role is shown in Figure 1.8. The polypyrrole changes from colorless to black when
it is oxidized by the application of positive potentials. Similarly, polythiophene and
polyaniline undergo distinct color changes when an electrical potential is applied.

Figure 1.8  Example of electrochromic device based on polypyrrole-coated glass.

Introduction 17

Thin films of polythiophene can be switched from red (oxidized) to blue (reduced),
and polyaniline displays a spectrum of colors as different potentials are applied to it.
The polythiophenes are particularly interesting, given the diverse chemistries avail-
able to enable fine-tuning of the polymer band gap and, hence, the color changes
observed upon electrochemical switching.48,49,50,51,52 This has possible applications in
advertising displays and smart windows. This bistable material can also be used as
a memory storage device for information storage. All of the preceding applications
use conducting polymers in the solid state in environments in which the dynamic
character is readily characterized, controlled, and utilized. Recently, however, ionic
liquid electrolytes have proved to be very beneficial, especially in terms of enhanced
lifetime of CEP devices.53 One electrochromic device was cycled 106 times without
significant loss in performance.54

Electromechanical Actuators
More futuristic applications for conducting polymers that are receiving considerable
attention include electromechanical actuators (artificial muscles).55 Allied Signal
(now Honeywell International) is interested in the development of lower-power/
lower-voltage moving parts for micromachined optical devices. NASA has also been
involved in the development of low-power, lightweight actuators for the window
wiper on the Mars Explorer. Companies dedicated to the development of artificial
muscles based on conducting polymers have also emerged in recent years. Micro-
Muscle based in Sweden and EAMEX from Japan are both actively pursuing actua-
tors for biomedical and electronics applications. Academic laboratories have also
developed several demonstration products, including a variable camber hydrofoil,56
a gas valve,57 and a micropump.58
IPRI is also currently involved in the development of actuators for an electronic
Braille screen (Figure 1.9) in collaboration with Quantum Technology (Sydney, Aus-
Pin

Polymer Tube

Counter Electrode

Electrical Contact

Electrolyte

Figure 1.9  The electronic Braille screen based on conducting electroactive polymers.

18 Conductive Electroactive Polymers

tralia).59 Lack of a convenient user interface is the single biggest barrier to blind peo-
ple accessing information in the Internet age. The future of Braille lies in a low-cost
refreshable surface, or screen, where the individual Braille dots are raised and low-
ered electronically by low-voltage/low-power actuator systems, allowing changing
messages or decision options to be displayed.
We envisage the screen as a device consisting of multiple rows of a new type
of Braille cell. The pins making up each Braille cell of the screen are driven elec-
tronically by polymer actuators in place of the piezoelectric mechanisms of existing
technology. Because of its size and simple mechanical design, the proposed cell can
be used to make multiple lines of Braille. These can be manufactured in modular
building blocks suitable for use in a wide variety of product configurations, from a
full-page screen to electronic note takers, ATMs, etc. The target performance char-
acteristics for the actuating elements of the Braille cell are

• Axial movement of 0.5 mm in 0.2 s with a tensile load of 50 mN (1% strain;

5% s−1 strain rate; 0.2 MPa isotonic stress for a cell 50 mm high working
against a 0.1 N/m spring)
• Operating voltage < 20 V
• Operating lifetime > 106 cycles

Electromechanical actuators are materials that can change their physical dimensions
when stimulated by an electrical signal. In the case of conducting polymers, the vol-
ume change occurs as a result of ion movement into and out of the polymer during
redox cycling.60 The change in volume can be more than 10%; in length and thickness,
changes of more that 30% have recently been reported.61,62,63 When tested isometri-
cally (at constant length), the stress generated by volume changes is on the order of
10 MPa. The performance of conducting polymer actuators compares favorably with
natural muscle (10% stroke and 0.3 MPa stress) and piezoelectric polymers (0.1%
stroke and 6 MPa). Piezoelectric polymers are driven by high electric fields, usually
100–200 V, whereas conducting polymers require only 1–5 V to operate. Some of
the disadvantages of CEP actuators include slow response time and limited lifetime,
although recent studies have shown strain rates of >10%/s59,64 (natural muscle can
respond at 10%/s) so that bending-type actuators can operate at close to 100 Hz.65
An important development in conducting polymer actuators has been the use of
a solid polymer electrolyte (SPE),66 an important advance in terms of realizing prac-
tically useful devices. Figure 1.10 shows the bending operation of a solid-state actua-
tor consisting of five layers: gold, CEP, SPE, CEP, and gold. The SPE acts as both an
ion source and ion sink, and replaces the liquid electrolyte used in previous studies.
Ionic gels made by polymerizing a conventional polymer (such as polymethylmeth-
acrylate) in an ionic liquid have also been shown to be stable solid-state electrolytes
for CEP actuators.67 Such gels are inherently more stable, both environmentally and
electrochemically, than traditional SPEs.

Separation Technologies
The dynamic character of conducting polymers has been used to advantage in the
development of new smart membrane technologies.68,69,70,71,72 A membrane consist-
Introduction 19

T = 0.0s T = 0.50s

T = 1.0s T = 1.5s

T = 16.0s T = 20.0s

Figure 1.10 Time lapse photographs showing bending movement of bimorph-type actua-

tor (two active electrodes) made from polypyrrole and a porous membrane separator, and
activated by 1.5 V potential difference between the polymer electrodes.

ing of, or coated with, a CEP can be stimulated in situ using small electrical pulses
to trigger the transport of electroinactive ions such as K+ and Na+, transition metal
ions such as Cu2+ and Fe3+, small organic molecules such as sulfonated aromatics,
and even large macromolecular species such as proteins (see Figure 1.11). The flux
and selectivity attainable are dependent on several factors:

1. The composition of the membrane.

2. The porosity as determined by the CEP and/or a more porous substrate onto
which the polymer may be coated.
3. The electrochemical conditions used during operation (potential pulse
height and pulse width are critical).

Switching the polymer repeatedly between its available oxidation states facilitates
transport of ionic/molecular species through the polymer membrane. Changes in
20 Conductive Electroactive Polymers

250 E F
Concentration of MYO on

200
Receiving Solution

150 C D

100

50 A B

0
0 100 200 300 400
Time (min)
(a)

Membrane &
Connections

Gal/Pot
V C R
Ext. in
Feed Sol. Receiving Sol.
Electrochemical
Control Unit
(b)

Figure 1.11  (a) Controlled transport of myoglobin across a conducting polymer mem-

brane. Fast transport occurs when an electrical potential is applied to the polymer (0–A, B–C,
and D–E). Undetectable permeation occurs when no potential is applied (A–B, C–D, and
E–F). (b) Schematic diagram of the membrane transport cell. The membrane separates the
stirred feed and receiving solutions and is connected to a galvanostat/potentiostat for control
of the electrical potential and current.

permeability between these different states occur due to differences in their densi-
ties and charge. Consequently, different species will diffuse through the polymer
structure at different rates depending on the oxidation state of the membrane poly-
mer. Ionic species can also be “electrochemically pumped” through the membrane
by switching between oxidation states. If the polymer is synthesized using a large,
immobile counterion, then reduction of the polymer causes cations from the sur-
rounding electrolyte to be incorporated into the polymer. Subsequent reoxidation
of the polymer ejects these cations. In this manner, cations can be incorporated into
the polymer membrane from the feed solution and ejected into the receiving side of
the membrane. Selectivity to certain ions is based on size and charge. An exciting
prospect is in chiral separations, where chiral-conducting polymers can discriminate
between different hands of the target molecule.
Introduction 21

A B
5 mm

Stainless Eluent
Steel Flow
Module

Eluent
Flow Tantalum
Wire
Frit
Frit
Carbon Foil
Glass Wool Column
Filter Paper

Figure 1.12  Electrochemically controlled liquid chromatography column.

The full utilization of this fascinating new membrane technology is currently

limited by our ability to process and fabricate large-surface-area membrane struc-
tures at a reasonable cost. Such separation technologies should have a widespread
impact in chemical separations for processing and refining purposes and in con-
trolled-release technologies.73 The separation of neutral volatile organic species using
pervaporation has also been achieved using conducting polymer membranes,74,75 and
recently, the use of CEPs for gas separation has been explored.76,77
Electrochemically controlled chemical behavior can also be used to design sur-
faces capable of selective molecular recognition. This has potential for the develop-
ment of new chromatographic separation media.78 In fact, the chemical properties of
the chromatographic phase can be tuned in situ to effect the desired separation char-
acteristics. Using a specially designed chromatographic column (see Figure 1.12)
that allows electrical potentials to be applied during separation, the chemical affinity
of the polymer can be adjusted as required.

Controlled-Release Devices
Conducting polymer films and coatings are also ideal hosts for the controlled release
of chemical substances including therapeutic drugs, pesticides, fungicides, and
many others. Figure 1.5 shows that the oxidation/reduction of polymer involves the
movement of ionic species into and out of the polymer material. By incorporating the
target species as the dopant in the conducting polymer, the redox chemistry of the
polymer can be used to release the target species at the desired time.
Both anionic and cationic species can be incorporated into the polymer and
released at the desired time. Anionic species are the usual dopant ions incorporated
with PPy, PAn, and PTh polymers; however, it is also possible to trap cations. The
incorporation of cations involves synthesizing the polymer using a large, immobile
polyanion such as poly(vinyl sulfonate). When this polymer is reduced, the large
anion cannot leave the polymer, so cations from the surrounding electrolyte are incor-
porated into the polymer to balance the charge of the polyanion. Subsequent oxidation
of this polymer releases the cation species back into the surrounding electrolyte. The
possible ion flows during redox reactions of PPy are illustrated in Figure 1.5.
22 Conductive Electroactive Polymers

Initially, the ability to incorporate biomolecules during the growth of conduct-

ing polymers and to expel these molecules by electrical stimulation was seen as a
means to develop novel controlled-release systems79,80 for active ingredients such as
anticancer drugs (flouracil)81 or anti-inflammatories (dexamethasone).82
In other applications the release can also be automatically stimulated by a change
in the environment. For example, it is known that the galvanic coupling of conduct-
ing polymer coatings (such as polyaniline) to metals such as steel and aluminum
causes a reduction of the polymer from the emeraldine salt state to the leucoemeral-
dine base state, and this process involves the release of the dopant ion into the sur-
rounding electrolyte. It has been speculated83 that the dopant could be designed such
that it acts as a corrosion inhibitor for the metal so that the polymer can release the
inhibitor at the point when corrosive conditions first form. Indeed, a number of stud-
ies have shown that the dopant used with PAn has a large impact on the corrosion
protection provided by the polyaniline, suggesting that the inhibition process may be
involved in corrosion protection.

Corrosion Protection
Controlled release of corrosion inhibitors may be involved in new-generation corrosion
protection coatings based on conducting polymers.84,85 There is considerable evidence
indicating that conducting polymers provide beneficial protection to many metals in
a corrosive environment. Many studies since the mid-1980s have shown that a coat-
ing of PAn, PPy, or PTh can inhibit the corrosion rate of mild steel,86 stainless steel,87
aluminum,88 and copper.89 The conducting polymer can either be applied as a neat
coating or as a dispersion in another polymer binder. In most studies, a barrier topcoat
is also applied over the top of the conducting polymer “primer.” Figure 1.13 shows an
example from our laboratories illustrating the corrosion resistance of mild steel coated
with PAn primer/epoxy topcoat after a 3-yr immersion in saltwater. Although large
blisters have formed (after approximately 2 yr), there is little sign of steel rusting.
Elucidation of the corrosion mechanism is complicated by the many testing vari-
ables involved: type of polymer used; form in which the polymer is applied to the
metal; use, type, and thickness of the topcoat; preparation of the metal; and nature
of the corrosive environment. All of these factors will influence corrosion perfor-
mance. Elsenbaumer90 has proposed the concept that the conducting polymer pro-
motes the formation of a passive oxide at the polymer–metal interface. It is believed
that the dense nature of this oxide impedes electrochemical corrosion reactions.
Studies of the interface region have shown that oxide layers are present.91 However,
many other factors may also be involved in the overall process, such as the forma-
tion of metal ion–polymer complexes and the release of corrosion inhibitors by the
polymer; simple barrier protection has also been suggested as being involved in the
corrosion process. The use of conducting polymers as corrosion protection coatings
has recently been reviewed.92

Chemical Sensors
The combination of tunable chemical properties with the electronic properties
of conducting polymers has also had a tremendous impact on the development
Introduction 23

Figure 1.13  Steel sample coated with a polyaniline primer and an epoxy topcoat after a
3-yr immersion in saltwater—note the absence of corrosion products in the test solution.

of new sensors. The use of conducting polymers in sensors has been reviewed
recently.93,94,95,96,97,98,99,100 Sensing surfaces have been designed that are capable of
interacting with simple anions,101 metal ions,102,103 small organic molecules,104,105,106
or proteins.107,108 The electrical signals measured can be current flow, change in
capacitance, or change in resistance. The area of biosensors has proved particularly
interesting in this regard, as conducting polymer systems have been shown to be
capable of in situ control of antibody–antigen interactions, making them reversible
under selected conditions. The sensors are used in a flow-injection analysis mode
enabling rapid sample throughput.
Biosensors combine a specific biorecognition process with a signal transduction
process. In CEPs, biorecognition has been demonstrated through the incorporation
of oligonucleotides, enzymes, or antigens/antibodies into the polymer. The incor-
poration of these species has been achieved either by covalent attachment to the
polymer backbone or by use of the biological agent as a dopant. Once interaction
has occurred between the CEP and the target analyte, a signal must be detected
by the transduction system. Various means for detecting the interaction have been
developed including optical, electrical (e.g., by using a field-effect transistor), elec-
trochemical (including potentiometric, amperometric, or impedimetric approaches),
and mass changes (as detected by a quartz crystal microbalance, for example). The
extensive literature relating to CEP biosensors has recently been reviewed.109
Electronic nose systems that utilize conducting polymers as the sensor ele-
ments have also been developed.110,111,112,113,114 These systems utilize arrays of robust
CEPs, each with differing chemical selectivity, using changes in resistance as the
signal generation method. The change in resistivity (or conductivity) is brought
about either through a change in doping level or through a change in polymer
24 Conductive Electroactive Polymers

conformation. Vapors such as NO2 (A), H2S (D), and NH3 (D) that are either elec-
tron donors (D) or electron acceptors (A) have a dramatic effect on conductivity.
Changes in polymer chain conformation can also affect conductivity by increas-
ing or decreasing the localization length over which electrons can move freely.
Importantly, both mechanisms appear to be fully reversible in most cases, because
the conductivity can be reset to the original values by exposing the polymer to a
“neutral” vapor, such as dry nitrogen (Figure 1.14).
Such an approach has been used to develop customized noses (specific arrays of
polymers) for classification of beers, detection and identification of microorganisms,
olive oil characterization, and detection/classification of BTEX compounds (volatile
organic carbons).
Conducting polymer sensors can be operated either to quantitatively measure
the concentration of a target vapor species or to qualitatively analyze a complex
mixture of vapors. For single vapors, the detection limits can be in the low-ppm
region. Exposure to a mixture of vapors results in a unique pattern of responses,
which is usually deciphered using standard chemometric techniques. The pattern
can be used like a fingerprint to identify certain products, or to establish the qual-
ity of foodstuffs, wines, perfumes, etc. The electronic nose has similar compo-
nents as the natural nose; this is illustrated in Figure 1.15.
The electronic nose has found the most widespread application in the food
industry. Ongoing research is aimed at improving the selectivity and sensitivity
both in the vapor and solution phases using resistometric and other detection
systems. Particular emphasis has been placed on chemical functionalization of
the polymer to increase the selectivity of the sensor to the desired species in a
complex mixture. The sensitivity at present is limited primarily by the method
of sensor fabrication: the detection limit is lowered by producing ultrathin and
coherent layers of the conducting polymer. Screen-printing and ink-jet printing
techniques provide some interesting opportunities in this regard. Improvements
in device fabrication should expand applications to environmental and biomedi-
cal areas.

Biomedical Applications
The most striking advances in research areas concerned with the application of
CEPs has in recent years been in the area of biomedical applications. The wet
and soft nature of conducting polymers combined with their multifunctionality
makes them immediately interesting. The separate functions of controlled surface
energy, controlled release, and actuation are being exploited for many applica-
tions, both internal (implants) and external to the body. For implants, biocom-
patibility is a required attribute that is met by a number of CEP formulations. A
number of biomedical and bioengineering applications are described in the fol-
lowing sections to illustrate the enormous potential of conducting polymers in the
area of bionics—requiring effective interfacing of the biological and electronic
worlds to improve human performance. The following examples cover bionic
applications at the cellular (relevant to implantable devices) and skeletal (relevant
to wearable) levels.
Introduction 25

(Delta R)/R

–0.02

–0.01

00.0

0.01

0.02

0.03

0.04

0.05

0.06
1.0
56.0
111.0
166.0
221.0
276.0
331.0

EtoH 50%
386.0
441.0

Tol 10%
496.0
551.0

PPy/HBSA Responses to Toluene

606.0
661.0
716.0
771.0

Tol 30%
Time (secs)

826.0
881.0
936.0
991.0
1046.0
1101.0
Tol 50%

1156.0
1211.0
1266.0
1321.0
1376.0
EtoH 50%

1431.0
1486.0
1541.0
1596.0
1651.0

(a)

(b)

Figure 1.14  The electronic nose. (a) Response of conducting polymer sensor to different
concentrations of toluene (Tol) and ethanol (EtOH). (b) Photograph of portable electronic
nose with an array of conducting polymer sensors (bottom left).
26 Conductive Electroactive Polymers

Natural Artificial
Smell Smell

Receptors of the Transduction from

Chemical to Array of Sensors
Olfactory
Electrical Signal

First Signal
Olfactory Bulb Signal Preconditioning
Processing

Olfactory Cortical Area Mapping Statistical Processing

Higher Centres Recognition Pattern Recognition

Perception Classification

Figure 1.15  Similarities between natural and artificial noses.

Cellular Communications
The versatility in the synthesis of some CEPs (especially polypyrrole) now enables
a range of bioactive surfaces to be created. For example, the incorporation of pro-
teins115 such as enzymes or antibodies is readily achieved. Combined with the chemi-
cal tuning available, this can be used in the development of biocompatible and/or
new surfaces for biotechnology processing applications. Studies116,117,118 involving the
growth and control of biological cell cultures on conducting polymers were initiated
in the early 1990s (Figure 1.16). Using this approach, it is envisaged that electrical
and chemical stimuli can be used to address living cells in culture and thereby stimu-
late and regulate growth.
The ability to support mammalian cell growth on CEP surfaces is enhanced by
the application of electrical stimuli. The majority of studies to date have focused on
Reservoir
Supply of
Nutrients

Membrane

Cell Culture Medium

Cells Cells
Membrane

Removal of Receiving
Products Solution Activation
of Growth
Hormone
Factors

Figure 1.16  Schematic illustration of the use of intelligent membranes for cell culturing.
Introduction 27

nerve cells. Given the enormous benefits to be gained from effectively interfacing
nerves and conducting materials for implants such as the cochlear implant or artificial
retina, this is not surprising. The possibility of using such materials for nerve repair
either in the peripheral nervous system or even for spinal chord regeneration under-
scores the need for this ongoing research. It was shown in 1994117 that the growth
and differentiation of PC12 cells can be assisted by electrically controlled release of
a nerve growth factor protein. Langer’s group118 has subsequently shown that neurite
outgrowth on polypyrrole is facilitated by passage of current through the structure. It
has also shown that the electrochemical effects on cell growth are fibronectin depen-
dent,119 a finding recently substantiated by Schmidt.120 It has been demonstrated that
neural glial cells can be attracted to and grown on PPy-coated electrodes containing
the nonapeptide CDPGYIGSR.121 Improved adhesion of osteoblast cells to titanium-
coated PPy containing a synthetic peptide has been observed.122
Even without the release of chemical species, CEPs have also been demonstrated
to be potentially very useful materials for tissue-engineering scaffolds.123 Electrical
stimulation of CEPs was found to promote favorable cell growth, including nerve
cells, leading to the development of CEPs for a range of implant applications.
In a recent work, it was shown that a neurotrophin (NT3) can be incorporated
into polypyrrole124 and released using mild electrical stimulation. These materials
were found to promote a significant increase in neurite extension from a cochlear
explant (Figure 1.17).125 At the skeletal level, materials capable of both monitoring
and manipulating human movement are important.

Sensors for Biomechanics

Conducting polymers can also be used as sensors for the physical environment,
particularly for strain or stress. Polypyrrole strain gauges have been constructed
from both neat films and from coated stretch fabrics, such as Lycra®. Strain gauge
materials are characterized by their gauge factor (change in resistance per change in
length), dynamic range, linearity, and hysteresis. These parameters are illustrated in
Figure 1.18. The use of polypyrrole to stretch fabrics to give strain gauge materials
having a dynamic range up to 100% has opened up several new exciting applications.
Figure 1.18 shows that an almost linear strain gauge response with low hysteresis
can be obtained from polypyrrole-coated Lycra from 20 to 60% strain. These results
compare with existing capacitive-based strain gauges that show a gauge factor of
2–4 and dynamic range to only 4%.
CEP materials have particular application in the field of biomechanics, where the
strain gauge fabrics can be incorporated into regular sports clothing. Figure 1.19 shows
an example of a patented knee sleeve using PPy and Lycra combined with a feedback
device that emits an audible signal when the knee angle reaches a preset degree.

Artificial Muscles: Manipulating Movement

Numerous examples of developing conducting polymer actuators to operate as artifi-
cial muscles have been described in the literature. For example, a steerable cochlear
implant with the CRC Cochlear Implant. (Melbourne, Australia), is under develop-
ment.126 The microactuator will assist surgeons during implantation of the “Bionic
28 Conductive Electroactive Polymers

(a) (b)

50
*

40
Neurites per Explant

30

20

10

0
PPy PPy PPy/NT3 PPy/NT3
Stim Stim
(c)

Figure 1.17  Electrical stimulation of PPy for release of NT3. Explants were grown for 24
h on CAM-coated PPy/pTS or PPy/pTS/NT3 and subjected to a biphasic current pulse stimu-
lus for 1 h. Neurite outgrowth was examined after a further 3 d in culture. A greater number
of neurites per explant were observed on explants grown on (a) the stimulated PPy/pTS/NT3
compared to explants grown on (b) stimulated PPy/pTS. (c) Stimulation of PPy/pTS did not
significantly alter the number of neurites per explant compared to unstimulated PPy/pTS (p
= 1.0). On the other hand, explants grown on PPy/pTS/NT3 with applied stimulation had
enhanced outgrowth of neurites compared to explants grown on unstimulated PPy/pTS/NT3
and stimulated or unstimulated PPy/pTS (p < 0.001). (R.T. Richardson et al. 2007. Biomateri-
als, 28, 513. With permission from Elsevier.)
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LEXANDRINE herdsmen

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