Copyright © 2010 American Scientific Publishers Science of

All rights reserved Advanced Materials

Printed in the United States of America Vol. 2, 441–462, 2010

A Review on Synthesis Processing, Chemical and

Conduction Properties of Polyaniline and
Its Nanocomposites
Sadia Ameen1
∗ , M. Shaheer Akhtar2 , and M. Husain3
1
Energy Materials and Surface Science Laboratory, Solar Energy Research Center,
School of Chemical Engineering, Chonbuk National University, Jeonju, 561-756, Republic of Korea
2
New & Renewable Energy Material Development Center, Chonbuk National University, Jeonju, 561-756, Republic of Korea
3
Department of Physics, Jamia Millia Islamia, New Delhi 110025, India

REVIEW
Polyaniline (PANI) has been of great Delivered
interest toby
manyIngenta to: because of its reasonably good
researchers
University
conductivity, stability, easy preparation, of Auckland
affordability and redox properties compared to other con-
ducting polymers. This review reportsIP the synthesis, processing and the electronic applications of
: 130.216.12.217
PANI and its nanocomposites. The review presents
Thu, 30 Jun 2011 the08:48:22
complete survey of chemical and the elec-
trochemical synthesis of PANI. The mechanism of electrical conduction in PANI based on various
factors like oxidizing and reducing agents during the polymerization, use of different acid and base
dopants have been discussed. In the last part, this review focuses the recent developments of
semiconductor-conducting polymer hybrids or nanocomposite systems and their applications in p–n
heterostructured diodes and solar cells.
Keywords: Polyaniline, Electrical Conductivity, Dopants, Nanocomposites.

CONTENTS 8.8. Polyaniline–Polyvinyl Chloride Blends Doped with

Sulfamic Acid in Aqueous Tetrahydrofuran . . . . . . . . . . 450
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441 9. Concept of Polymerization of Aniline . . . . . . . . . . . . . . . . . . . 450
2. Methods for Synthesis of Polyaniline . . . . . . . . . . . . . . . . . . . 444 10. Physical Properties of Polyaniline . . . . . . . . . . . . . . . . . . . . . . 452
2.1. Chemical Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444 10.1. Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
2.2. Electrochemical Synthesis . . . . . . . . . . . . . . . . . . . . . . . 445 10.2. Conduction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 453
2.3. Synthesis by Other Conventional Methods . . . . . . . . . . . 445 10.3. Morphology and Structure . . . . . . . . . . . . . . . . . . . . . . . 453
3. Substituted Anilines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445 10.4. Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
4. Conditions Required for the Synthesis of Polyaniline . . . . . . . 445 11. Chemical Properties of Polyaniline . . . . . . . . . . . . . . . . . . . . . 453
5. Conduction in Polyaniline Through Doping Process . . . . . . . . 445 11.1. Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
6. The Concept of Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446 11.2. Acid Base Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
7. Oxidation States of Polyaniline . . . . . . . . . . . . . . . . . . . . . . . . 447 11.3. Oxidation and Reduction . . . . . . . . . . . . . . . . . . . . . . . . 454
8. Dopants for Polyaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447 11.4. Catalytic Ability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
8.1. Conduction Mechanism of Sodium Thiosulphate Doped 11.5. Electrochemical Properties . . . . . . . . . . . . . . . . . . . . . . . 455
Polyaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447 11.6. Redox Behavior and Conductivity . . . . . . . . . . . . . . . . . 455
8.2. Electrical Conductivity of Sulfamic Acid Doped 11.7. Doping/De-Dopoing and Capacitance . . . . . . . . . . . . . . . 455
Polyaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448 11.8. Redox Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
8.3. Polyaniline–Polyvinyl Chloride (PANI–PVC) Blends 11.9. Protonation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Doped with Sodium Thiosulphate . . . . . . . . . . . . . . . . . . 448 12. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
8.4. Electrical Characterization of Samarium (III) 13. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
Chloride-Doped Polyaniline . . . . . . . . . . . . . . . . . . . . . . 448 References and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
8.5. Spectroscopic (Optical) Properties of Praseodymium (III)
Chloride-Doped Polyaniline . . . . . . . . . . . . . . . . . . . . . . 449
8.6. Polyaniline Prepared with the Dopant Mixture 1. INTRODUCTION
of (ZrO2 /PbI2 ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
8.7. DC Conductivity of PANI Doped with Binary Dopant Until the early years of 20th century polymers were being
(ZrO2 /AgI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449 discarded and were known as electric insulators. Scien-
tist from many disciplines is now studying organic solids
∗
Author to whom correspondence should be addressed. that exhibit remarkable conducting properties. The basic

Sci. Adv. Mater. 2010, Vol. 2, No. 4 1947-2935/2010/2/441/022 doi:10.1166/sam.2010.1126 441

 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites Ameen et al.

requirement for polymers to become conducting is the
overlapping of molecular orbital to allow the formation of
delocalized molecular wave functions and secondly these
molecular orbital must be partially filled so that there is
a free movement of electrons through out the polymeric
structure. The unusual electronic properties such as elec-
trical conductivity, low ionization potential and high elec-
tron affinity are associated with the
-electron backbone
of the conjugated polymers. These extended
conjugated
systems of conducting polymers have alternating single
and double bonds along the polymeric chain.1 Conduct-
ing polymers are the latest edition to the organic conduct-
ing materials. For a long time, it was usual to consider
that the organic polymers are insulators. In addition to
the existing huge number of insulating polymers, there are
now some polymers that conduct electronically. Research
and developments in the field of polymers have brought
them very close to the metals in terms of their electrical-
REVIEW
conductivity of some metals and conducting polymers is
shown in Figure 1.
The interest in conducting polymers seems from the fact
that the polymers, being light in weight and readily mold-
able can replace the conventional electrically conduct-
ing materials in electrical and electronic applications. The
use of conducting polymers in various industries involves
lower fabrication and maintenance cost with higher dura-
bility and lightweight products.
The study has been made on the chemical structure
of the monomers and the polymers, which are noticeably
electronically conducting. It is found that all conducting
polymers have conjugated single and double bonds in their
structures. The word conjugated denotes an alteration in a
series of single and double (or rarely triple) bonds, along
which, under appropriate conditions, conduction can be
induced at the backbone of the polymer. Sasabe et al.2
observed the dielectric relation in certain polymers and

Delivered
properties. The combination of their usual properties with by Ingenta
attributedto:
it to a single relaxation process of the main
University
the ability to conduct electrically is very attractive. The of chains,
Aucklandcoupled with side chains. Butta et al.3 measured the
IP : 130.216.12.217
Thu, 30 Jun 2011 08:48:22
Sadia Ameen obtained Ph.D. in Chemistry, 2008 from Jamia Millia Islamia (Central Univer-
sity, India) and currently working as Post Doctoral fellow at Chonbuk National University,
South Korea. She has achieved Gold Medal in academics. Besides, she is holder of Merit
Scholarship and Merit Certificate for the best academic performances. She has obtained life
membership of various scientific societies like Society for Semiconductor Devices (SSD),
Indian Society for Analytical Chemist and IEEE Photovoltaic Specialists Society. She has
published 20 research articles in international SCI journals and conferences. Her research
interests consist of Synthesis of Conducting Polymers, Nanocomposites, Polymer blends,
Fabrication of Heterostructure Devices and Dye Sensitized Solar cells (DSSCs).

M. Shaheer Akhtar received Ph.D. in Chemical Engineering, 2008 from Chonbuk National
University, South Korea. Presently, he has been working as full time Professor at Chonbuk
National University, South Korea. He has published three patents (two Koreans and one
US patent) and has been awarded thrice for the best paper presentation award at KIChE
(Korean Institute of Chemical Engineers) biannual meeting, South Korea. After Ph.D., he
accepted a postdoctoral fellowship position in the Department of Semiconductor and Physics
Research at Chonbuk National University, South Korea. His research interest constitutes the
photoelectrochemical characterizations of thin film semiconductor nanomaterials, composite
materials, polymer based solid-state films, solid polymer electrolytes and electrode materials
for dye-sensitized solar cells (DSSCs).

M. Husain was born in Uttar Pradesh, India, in 1952. He is a Professor of Physics in

Jamia Millia Islamia (Central University, India) and has 26 years of experience in teach-
ing and research. He is author of more than 150 scientific publications in international
journals and has written 4 review articles in journals of repute. 30 candidates have been
awarded Ph.D under his guidance. He has organized various national and international con-
ferences and workshops. He has delivered 70 invited talks at national and international
levels. His field of specialization includes Materials Science (Amorphous Semiconductor,
X-ray Spectroscopy, ECR Plasma Etching, Nanostructures), CNTs, Conducting polymers,
and Dye-Laser Materials.

442 Sci. Adv. Mater. 2, 441–462, 2010

Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
Fig. 1. Logarithmic conductivity ladder locating metals and conducting
polymers.
Delivered by Ingenta to:
dielectric properties of some polymers in theUniversity
microwave of Auckland
region and observed that there was an increase in IP : 130.216.12.217
dielectric
Thu, 30
constant with temperature. They also observed a maximum Jun 2011
Fig.08:48:22
2. Structures of conducting polymers.
value for dielectric loss in the amorphous zone i.e., tran-
sition between the glass temperature and melting point.
Some dielectric measurements of polymers regarding their
relaxation time were done by Mashimo.4 He developed a
theory describing the relaxation time of a polymer dilu-
ents system, using the Kramer’s rate constant theory at the
high friction limit5 together with the full volume theory.6
Mashimo7 described the temperature dependence of the
dielectric relaxation time of amorphous polymers satisfac-
tory by an expression derived from the theory of relax-
ation times for local conformational transitions in polymer
chain, which is also useful for the study of dielectric relax-
ation time in polymers.
Conducting polymers represent an important research
area with diverse scientific problems of fundamental signif-
icance and potential for commercial applications. Figure 2
shows the most extensively studied conducting poly-
mers such as polyacetylene, polyaniline, polythiophenes,
polypyrroles, poly(p-phenylene) and poly(p-phenylene sul-
phide) etc.
Considering the various potential applications, conduct-
ing polymers have attracted the attention of the scientific
community in various fields and are being considered as
a new generation material for wide ranging technological
applications.
After the successful synthesis of polyacetylene by
Shirakawa in 19748 and its subsequent doping in 1977,9
electronic conducting polymers have increased in demands
because of their many possible applications. These materi-
als have already been the subject of numerous reviews.10–13
Out of these polymers, polyaniline (PANI) in particu-
lar, is being studied more and more, and in recent years
has been the centre of considerable scientific interest
Sci. Adv. Mater. 2, 441–462, 2010
REVIEW
although polyaniline is not a new material and its exis-
tence has been known for the past 150 years. Fritzche14
undertook the first attempts to analyze ‘aniline blacks’.
This was followed by studies by Nietski15 who tried to
use the process for tinting cotton. Several authors such
as Lightfoot,16 Letheby,17 Yasin,18 Coquillon,19 Willstatter
and Dorogi,20 Green and Woodhead,21 Hofnan,22 Datta
Sen,23 Forpelstroeder,24 Gilchrist,25 Buchener,26 Joffe
and Petrinka,27 Lantz and Gascon,28 29 Goldschmidt,30–32
Khomutov and Gorbachev,33 Mohilner et al.,34 Lord and
Rogers35 and others had studied the products of chemical
and electrochemical oxidation of aniline. Jozefowicz
et al.36–42 led to a more precise understanding of PANI.
In the 1980s, Volkov et al.,43 Bard et al.,44 MacDiarmid
et al.,45–46 and Genis et al.47–49 had answered many of the
queries related to these conducting polymers. The interest
of researchers in polyaniline could possibly be linked to
the numerous applications that exist for electronic conduct-
ing polymers and, on the other hand, to the fact that aniline
is a cheap product and also a very stable material. Indus-
trialists are also getting infatuated and the leading world
chemical industries have research programmes based on
PANI.
The concern is related to the polymerization mecha-
nism, the structure of the material in its oxidation states,
the redox mechanisms, the electronic and ionic conduc-
tion mechanisms, the role of the doping ions, protons etc.
Related to the electrochemical behavior, the interpretation
of capacitative effects and electrostatic interactions is very
important. Still scientists have not completely understood
all the observed phenomena and the existing models need
to be elaborated to explain the experimental results.
443
 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
Much detailed information on the properties of PANI
has been obtained by recent investigations employing mod-
ern physicochemical, electrochemical and spectroscopic
methods. Using these results individually or in a coupled
mode, rapid phenomena and intermediate states can be
studied. This resulting information can thus be used in
proposing polymerization mechanisms for aniline and for
describing the structures of the products obtained. Now,
the world of polymer research is flourishing. Efforts are
being made to develop conducting polymers with optimal
properties. In order to accomplish this, a deeper under-
standing of the physics and chemistry of polymer com-
plexes must be attained. The aim of this article is not
to solve all the queries related to the subject but also to
present a bibliographic review on one of the most studied
polymers i.e., polyaniline.
2. METHODS FOR SYNTHESIS OF
REVIEW
POLYANILINE Delivered
University of in Auckland
General synthesis of PANI is done by direct IP : 130.216.12.217
oxidation
Thu, 30orJun
of aniline using an appropriate chemical oxidant by 2011
electrochemical oxidation on different electrode materi-
als. The first work related to the oxidation of aromatic
amines was described almost one and a half centuries
ago. The formation of blackish precipitates is observed
when aniline is oxidized in sulfuric or hydrochloric acid
medium at a platinum electrode. The first process prac-
ticed by Lightfoot had undergone numerous modifications.
Volkov believed that it was improbable that the products
obtained by electrolysis present similar analogous struc-
tures to those obtained by chemical oxidation in solution.
In the first case, the mechanism would be due to radi-
cals adsorbed at the surface of the electrode, whereas in
the second case it would be due to radicals distributed in
solution. However, no evident correlation between these
products can be deduced. Moreover, Bard et al. and Genis
et al. had observed that the first layers of PANI, deposited
on an electrode present different characteristics from the
subsequent layers. Most of the researchers admit that the
characteristics of the polymer depend on the mode of syn-
thesis. Chemical and electrochemical syntheses are the two
common modes of classical synthesis of polyaniline.
2.1. Chemical Synthesis
Molecular mass is always the governing criteria of the
quality of the material and some scientists believe that the
properties of the materials are not interesting, particularly
the stability, when the molecular mass is large. Lacaze
et al.50 had studied the polymerization of aniline in neu-
tral and basic media and researchers studied in acetonitrile
(with and without pyridine) and in aqueous solutions.51
The concentration of monomer employed lied between
0.01 and 1 M.
444
Ameen et al.
When aniline is mixed with the chemical oxidant in
a reaction vessel and left for a certain period of time
(the duration of which depends on the temperature and
the concentration of active species), the solution gradually
becomes colored and a black precipitate appears.52 Genis
et al. had observed that this phenomenon occurred in most
of the solvents.
Jozefowicz et al. had shown that the oxidations of ani-
line by a chemical oxidant could occur even at ambient
temperature. The same reaction took place with the rate
of reaction being dependent on the temperature in the
range 0–80  C. The enthalpy of reaction was high (H =
372 kJmo1−1 ) and did not vary with the initial temperature
between 0˚ and 77  C or with the concentration of aniline,
but varied linearly with the concentration of oxidant.
Thus, the oxidation reaction of aniline can be broken
down into two stages:
(1) A slow thermic stage which is dependent on pH, tem-
by Ingenta
perature andto: concentration of reactants. Dissolved oxygen
the solvent has no influence on the reaction in contrast
with other oxidizing species which decreases the induction
08:48:22
period.
(2) A fast exothermic stage which is temperature depen-
dent and varies slightly with the concentration of
oxidant.
Other chemical methods can also be employed. PANI
has also been synthesized as poly-p-phenylene amine by a
condensation/decarboxylation reaction involving polyani-
line carboxylate.53 In general, the polymer synthesized by
the above methods is isolated from the reaction medium
by filtration. The precipitate is then washed and con-
ditioned using an appropriate solvent depending on the
nature of the study being carried out by the relevant
authors.
Our research group has scrutinized that PANI is synthe-
sized by direct chemical oxidation method by using ammo-
nium persulphate as oxidant by the method suggested by
MacDiarmid. It is a low temperature oxidation reaction in
an acidic medium. About 100 ml of distilled aniline was
added in the 300 ml of 5 N HCl in a three-neck flask,
which was placed in an ice bath to maintain the tempera-
ture of reaction vessel about 10  C. 100 g of ammonium
persulphate (APS) was dissolved in 200 ml of distilled
water and this APS was added to aniline solution drop by
drop. Stirring of the reaction mixture was continued for
about 6 h to ensure the completion of the reaction, which
was indicated by the stabilization of temperature of the
reaction mixture. The reaction mixture was then filtered
and washed repeatedly with distilled water, until the filtrate
is free from acid. It was checked by pH of filtrate solution.
Dark greenish black colored PANI was obtained, which
was dried in oven at 110  C for 4 h and was grinded to
fine powder and sieved through 100 meshes to get homo-
geneous fine particles
Sci. Adv. Mater. 2, 441–462, 2010
Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
2.2. Electrochemical Synthesis
Anodic oxidation of aniline on an inert metallic elec-
trode is the most current method for the synthesis of
PANI. This method is more advantageous over classical
chemical methods. The resulting product is ‘clean’ and
does not necessarily need to be extracted from the ini-
tial monomer/oxidant/solvent mixture. This method offers
the possibility of coupling with physical spectroscopic
techniques such as visible, IR, Raman, and conductime-
try for in-situ characterizations. The anodic oxidation of
aniline is generally affected on an inert electrode material
which is usually platinum.54–62 Several other studies had
been carried out with other electrode materials: iron,63–65
copper,66 zinc, chrome-gold,67 lead, palladium68 and dif-
ferent types of carbon (vitreous, pyrolic or graphite69–71 or
on semiconductors).72–73 Depositions of PANI had finally
been effected on optically transparent electrodes (OTE),
generally formed from glass or from polymer films, which
Delivered
were rendered conducting by deposits of platinum, gold orby Ingenta to:
indium or tin oxides. 74–78
More recently, oxidative electro of 4.
University
IP :
polymerization of aniline intercalated in montmorillonite130.216.12.217
had been effected. 79 Thu, 30 Jun 2011
Theoretically, two electrons are necessary for the poly-
merization of aniline and a certain number of supplemen-
tary electrons are necessary to oxidize the polymer. Recent
investigations by some authors80–81 had led to the conclu-
sion that the rate of electrodeposition of PANI in aqueous
media is influenced by the anion concentration and not
by the acid concentration, although acidic conditions are
required for polymerization. These authors also concluded
that aniline oxidation is catalyzed by the fully oxidized
form of PANI, i.e., pernigraniline.
2.3. Synthesis by Other Conventional Methods
Millard and Shen had developed a gas-phase plasma
method for polymer synthesis.81–82 Diaz et al. had used
this process to synthesize various conducting polymers.83
This method had been mainly employed for the oxida-
tion of aniline and a few of its substituted derivatives. The
advantage of this process lied in the fact that the monomer
was polymerized in the absence of both the oxidant and
the solvent. The resulting product was extremely clean.
Furthermore, the supporting material did not need to be
conducting. On the other hand, the energy associated with
the plasma was often very high and led to degradation of
the polymer. Nayak and Bhakta84 and Nedungadi et al.85
had shown that it was possible to polymerize aniline in a
two-phase system. The polar phase was composed of an
aqueous solution of ferrous chloride and sulfuric acid and
the non-polar phase contained aniline and a mixture of
toluene and benzene. The PANI formed at the interface of
the two solutions. An electrochemical method could also
be coupled with a two-phase system. Salaneck et al. had
successfully vapour deposited PANI onto quartz by heating
Sci. Adv. Mater. 2, 441–462, 2010
the neutral emeraldine at 350  C.86 The resulting product
contained shorter chain lengths but was much less polluted
by oxygen.
3. SUBSTITUTED ANILINES
Other substituted anilines are also the subject of cur-
rent studies and may be prepared by various meth-
ods: it has been shown that N ,N -dimethylaniline,87–89
dimethylanilines90 and other N -alkylanilines,91 92
N -phenylaniline and N -benzenesulfaniline,93 o-, p- and
m-toluidine, o-chloroaniline,94 o-, m- and p-halogenated
anilines,95 phenylenediamines,96 aminophenol,97 m-
amino-benzenesulfonic acid,98 p-aminodiphenylamine,99
aminopyrene,100 diphenylamine,101 triphenylamine,102
1-amino-2-pyridine103 and mesotetrakis-(2-aminophenyl)
porphines104 can be used to form interesting semi-
conducting polymers.
REVIEW
Auckland
CONDITIONS REQUIRED FOR THE
SYNTHESIS OF POLYANILINE
08:48:22
(1) High purity of monomers, chemicals and solvents are
required for obtaining high quality polymer.
(2) The polymerization conditions should be strictly
controlled.
(3) Environment for polymerization should be inert and
dry because a slight variation in the polymerization con-
ditions may alter the nature of polyaniline obtained.
(4) Polyaniline should be kept in a dark, cool and dry
place as the chances are like PANI may undergo isomer-
ization reaction under light and heat.
5. CONDUCTION IN POLYANILINE
THROUGH DOPING PROCESS
Doping is a process to enhance the conductivity of a mate-
rial. Doping increases the number of charge carriers in
the materials, just as an impurity does in classical inor-
ganic semiconductors. But the process as applied in case
of inorganic semiconductors cannot be duplicated to poly-
mer field because the two processes are fundamentally
different. In polymers, dopant concentrations are excep-
tionally high as compared to those commonly encoun-
tered in doped inorganic semiconductors (typically in parts
per million ranges). In some cases, the dopant consti-
tutes about 50% of the final weight of the conducting
polymer composition. Thus, the system would be more
appropriately described as a conducting charge transfer
complex rather than a doped polymer. The doping of con-
jugated polymers generated high conductivities primarily
by increasing the carrier concentrations. This is accom-
plished by oxidation or reduction with electron acceptors
or donors respectively, thus resulting in positive or neg-
ative charges. For example, the polymer is oxidized by
445
 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
the acceptor dopant, which itself get reduced and thereby,
producing a radical cation (or hole) in the polymer chain.
If the hole can overcome the coulombic binding energy to
the acceptor anion with thermal energy or, at high dopant
concentrations, via screening of the coulomb charges of
the anion, it moves throughout the polymer and contributes
to the conductivity. Thus, we can say, p-type doping of the
polymer produces positive charges and n-type doping pro-
duces negative charges in the resulted polymer complex.
Dopant produces sites in the energy gap that lie close
to either the conduction or valance band. Conduction
is due to majority carriers i.e., either electrons forming
n-type conductors or holes forming p-type conductors with
conductivities of more than 10−7 Scm−1 . True metallic
behavior results, when the energy gap between filled and
empty state disappears. At low levels of loading, the con-
ductivity of the polymer dopant composite differs only
slightly from that of host polymer. It has been found that
the electronic structure of conducting polymers
can be by Ingenta
REVIEW
Delivered
manipulated by changing the pH of the solvent. For a of Auckland
University
particular polymer, its conductivity tends to be IPrelatively
: 130.216.12.217
insensitive to the identity of the doping agent.
Thu,The
30most
Jun 2011
important requirement for a dopant is sufficient oxidiz-
ing or reducing power to ionize the polymer. Conven-
tional polymers inherently have an insufficient number of
delocalized charge carriers. As a consequence, they must
be modified so that number of charge carriers or charge
carrier mobility is increased. Metals or metalloids have
been added to change the distribution of the occupied
states. Metal doping is viewed as an inhomogeneous pro-
cess, which creates local conductivity regions, separated
by isolative polymer regions.
Doping is basically quantitative and the carrier concen-
tration is directly proportional to the dopant concentration.
Doping in polymers is different from doping in inorganic
or traditional semiconductors. The conductivity of poly-
meric semiconductors depends upon many factors such as
(1) Nature and concentration of dopants
(2) Homogeneity of doping
(3) Carrier mobility
(4) Crystallinity
(5) Morphology of polymers.
Doping of conducting polymers involves random dis-
persion or aggregation of dopants in molar concentrations
in the disordered structure of entangled chains and fibrils.
In case of inorganic semiconductors, the doping gener-
ates either holes in the valence band or electrons in the
conduction band. On the hand, polymer doping leads to
the conjugational defect like solitons, polarons, bipolarons
in the polymer chain. As dopants are strong oxidizing or
reducing agents, so on doping positive or negative charge
carriers are developed in the polyaniline.
Polyaniline + Dopant
→ Oxidation (Doped polyaniline)+ + Dopant−
446
Ameen et al.
Polyaniline + Dopant
→ Reduction (Doped polyaniline)− + Dopant+
Doping is not merely an oxidation or reduction reac-
tion. It is found that doping results in rearrangement
of polymer chain and hence new ordered structures are
formed. Various oxidizing agents have been used by
various researchers: potassium dichromate,105 ammonium
persulfate or peroxydisulfate,106 hydrogen peroxide, ceric
nitrate and ceric sulfate. Recently, chromyl chloride and
trimethylsilylchloro chromate have been used to chemi-
cally oxidize 2-chloro- and 2-fluoroaniline.107 Hand and
Nelson used a quantity of the chemical oxidant which
was in excess of the corresponding stoichiometric quan-
tity. MacDiarmid et al. used a stoichiometric equivalent of
the oxidant, whereas Genis et al. preferred a quantity that
was inferior to the stoichiometric.
A degradation of the polymer can be observed if a
quantity to:
of oxidant is used. MacDiarmid et al. used
hydrochloric acid at pH 1, Genis et al. used a eutec-
tic mixture of hydrofluoric acid and ammonia.108 Some
08:48:22
researchers use alkaline or ammonium salts to the polymer
solution which act as a buffer, increasing the conductiv-
ity of the solution and the yield of the polymerization and
improving the quality of the polymers obtained. Recently,
Genis et al. had stipulated in the patent that the addition
of fluoride ions to any strong acid medium improved the
quality of the polymer.
6. THE CONCEPT OF DOPING
Conjugated organic polymers are either electrical insula-
tors or semiconductors. Polymers that can have their con-
ductivity increased by several orders of magnitude from
the semiconductor regime are generally referred to as elec-
tronic polymers and are of very great scientific and tech-
nological importance because of their use in light emitting
diodes.
The concept of doping is the unique, central, underly-
ing and unifying theme, which distinguishes conducting
polymers from all other types of polymers. During the
doping process, an organic polymer, either an insulator
or semiconductor having a small conductivity, typically
in the range from 10−10 to 10−5 S/cm, is converted to
a polymer, which is in the ‘metallic’ conducting regime
(≈1–104 S/cm). The controlled addition of known, usu-
ally small (<10%) non-stoichioetric quantities of chemical
species result in dramatic changes in the electronic, electri-
cal, magnetic, optical and structural properties of the poly-
mer. Doping is reversible to produce the original polymer
with little or no degradation of polymer backbone. Both
doping and undoping processes, involving dopant counter
ions, which stabilize the doped state, may be carried out
chemically or electrochemically.
Sci. Adv. Mater. 2, 441–462, 2010
Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites

By controllably adjusting the doping level, conductiv- 7. OXIDATION STATES OF POLYANILINE

ity anywhere between that of the non-doped (insulating
or semiconducting) and that of the fully doped (highly
conducting) form of the polymer can be easily obtained.
Conducting blends of a (doped) conducting polymer with
a conventional polymer (insulators), whose conductivity
can be adjusted by varying the relative proportions of each
polymer, can be made. This permits the optimization of
the best properties of each type of polymer.
In the doped state, the backbone of a conducting poly-
mer consists of a delocalized
-system. Whereas in the
undoped state, the polymer may have a conjugated back-
bone which retained in a modified form after doping, or
it may have a non-conjugated backbone, which becomes
truly conjugated only after p-doping, or a non-conjugated
structure which becomes conjugated only after protonic
acid doping.
Although, a lot of work has been done on synthesis
Figure 3 shows the various oxidation states of PANI.
The average oxidation state can be varied continuously
from the complete reduced PANI to the half oxidized
polyaniline and to completely oxidized PANI. The term
a leucoemeraldine, emeraldine and pernigraniline are the
different oxidation states of PANI respectively. In doped
PANI, the charged solitons are formed. These are charged
defects with no spin. A reducing i.e., donar type, dopant
introduces an electron to the PANI chain which couples
with a neutral defect resulting in a negative soliton with
zero spin. Likewise an oxidizing-acceptor type, dopant
abstract an electron from the polymer chain and apposi-
tive spinless soliton is formed. With increase in the doping
level more and more polarons interact to form bipolarons,
which is a di-cation.

Delivered
and substitution of PANI, but after reviewing the literature,by Ingenta
University
it is found that a hunger for new dopants is still in this
IP : 130.216.12.217
field. Therefore, our research group had done a work to
Thu, 30 Jun
search an effective doping agent for PANI and to study the
effect of this dopant on PANI conducting system. We have
synthesized PANI by famous MacDiarmid method and a
number of dopants have used like sulfamic acid, sodium
thiosulphate, samarium (III) chloride, praseodymium (III)
chloride, binary dopant (ZrO2 /AgI) and binary dopant
(ZrO2 /PbI2  have been used. The reason of selection
and DC conductivity of doped PANI are summarized in
Table I.
REVIEW
8. DOPANTSto: FOR POLYANILINE
of Auckland
8.1. Conduction Mechanism of Sodium Thiosulphate
2011 08:48:22
Doped Polyaniline
As shown in Figure 4, the conduction in PANI is explained
by assuming the validity of the band theory of solids for
PANI. When an electron is removed from the top of the
valence band (through oxidation) of conducting PANI, a
vacancy (a radical cation) equivalent a hole is created
that doesn’t delocalize completely but is delocalized only
over a few monomeric units deforming the PANI structure.
This partially delocalized radical cation is called a polaron

Table I. Dopants used in our research work.

DC conductivity of doped
Dopants used Reasons for selection PANI samples (−1 cm−1 )

(1) Sulfamic acid
(2) Sodium thiosulphate
(3) Samarium(III) Chloride
(4) Praseodymium(III) Chloride
(5) Binary dopant (ZrO2 /AgI)
(6) Binary dopant (ZrO2 /PbI2 )
Properties such as handling ease, solubility, and low corrosiveness are 11 × 10−4 –450 × 10−3
associated with this dopant. Sulfamic acid is a dry, non-volatile stable
solid acid, which is moderately soluble in water at room temperature.
It is an odorless translucent crystals or white crystalline powder. It is soluble 855 × 10−9 –367 × 10−7
in water and is stable in nature. It is incompatible with strong acid and is
not hazardous.
It is a strong Lewis acid of light yellow colored crystals. This dopant is 370 × 10−11 –130 × 10−9
stable in nature and has no hazardous effects.
It is a green colored powder having melting and boiling point (786  C and 187 × 10−11 –222 × 10−10
1710  C) respectively. It is stable in nature and does not show thermal
decomposition. PrCl3 is an excellent water-soluble crystalline powder and
doesn’t exhibit any dangerous chemical reaction. It is a moderately strong
Lewis acid.
ZrO2 , a luminescent material, is taken into an account as one of the dopant 928 × 10−10 –3763 × 10−6
material for PANI, which can open new directions for the research in the
field of optoelectronic devices. It makes no contribution in the
conductivity of PANI. In addition, on the other hand, AgI enhances the
conductivity of PANI but it is a nonluminescent material.
The increased ZrO2 concentration in the dopant mixture exhibits a high PL 270 × 10−13 –881 × 10−4
emission intensity, making it suitable for various optoelectronic
applications. However, DC-conductivity studies are carried out to study
the effect of doping on the electrical properties.

Sci. Adv. Mater. 2, 441–462, 2010 447

 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites Ameen et al.

that in all the samples, the plots of ln dc versus 1000/T

Fig. 3. Different oxidation states of polyaniline.
and has spin half. Now if another electron is removed
from the already oxidized polyaniline, it can create another
polaron or a bipolaron. Low level of doping gives rise to
REVIEW
are straight lines, indicating conduction in these samples
is through an activated process, having single activation
energy in the temperature range (300–400 K). The dc con-
ductivity (dc  can, therefore, be expressed by the usual
relation.
dc = o exp−E/KB T 
Where KB is the Boltzmann constant and o is the pre-
exponential factor.
From Figure 6 it is clear that the dc conductivity
increases with five orders of magnitude after doping. The
conductivity of highly doped sample does not show an
increase with the temperature. Though, the doped samples
do not behave like a good conductor, but they act like a
metal in the regime of semiconductor behavior.110
8.3. Polyaniline–Polyvinyl Chloride (PANI–PVC)
Blends
to: Doped with Sodium Thiosulphate

Delivered by Ingenta
polarons and high level of doping results in the formation
University of As
of bipolarons. These polarons and bipolarons are mobile
Auckland
shown in Figure 7, the conductivity of the blend
IP :
and under the influence of electric field, can move along
130.216.12.217
increases by four order of magnitude with the increased
Thu, 30 Jun 2011
the polymer chain exactly in the same manner as electrons
08:48:22
amount of doped PANI in the PANI–PVC blends. This
109 slight increase of the conductivity may not be only due to
and holes do in inorganic.
the carrier concentration but may also be due to the mobil-
8.2. Electrical Conductivity of Sulfamic Acid ity of the charge carriers at the Fermi level, which occurs
Doped Polyaniline at a high amount of doped PANI in the blends. Also, the
increase of conductivity is attributed to the increase of
The temperature dependence of dc conductivity for vari- localized states in the band gap.111
ous samples of PANI doped with different ratios of sul-
famic acid is shown in Figure 5. It is clear from the graph
8.4. Electrical Characterization of Samarium (III)
Chloride-Doped Polyaniline
H H
N N N N
The dc conductivity increases with the increase of dopant
concentration. Electrical conductivity results from the exis-
n
tence of charge carriers (through doping) and the ability of
Doping of Na2S2O3 these charge carriers to move along the
-bonded struc-
ture. Doping introduces carrier into the electronic struc-
ture. The attraction of an electron in one repeat unit to
S2O3- -

H .. .. H
N N N N
.. ..
n
Na+ Na+

Geometrical (bond length)

Relaxation (Quinoid to benzenoid)

S2O3- -

H H
N N N N
.. + . + . ..
n
Na Na
Fig. 5. Temperature dependence of dc conductivity for various PANI
Fig. 4. Doping of polyaniline with sodium thiosulphate. doped with sulfamic acid.

448 Sci. Adv. Mater. 2, 441–462, 2010

Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites

Fig. 6. Variation of dc conductivity versus different concentration of

sulfamic acid. Fig. 8. Photoluminescence spectra of PANI doped with different con-
centrations of praseodymium (III) chloride.

the nuclei in the neighboring unit leads to carrier delocal-by Ingenta to:

REVIEW
Delivered
ization along the polymer chain. Thus, doping of PANI of may
University Auckland
be due to the possibility of atoms/molecules of dopant
increases the conductivity by increasing the carrier concen- (PrCl3 , forming aggregation in the polymer chain.113
IP : 130.216.12.217
tration, which ultimately enhances the mobility
Thu,of30 charge
Jun 2011 08:48:22
carrier.112
8.6. Polyaniline Prepared with the Dopant
8.5. Spectroscopic (Optical) Properties of Mixture of (ZrO2 /PbI2 )
Praseodymium (III) Chloride-Doped Polyaniline
The optical properties, UV–visible absorption spectra have
As shown in Figure 8, the relative heights of the emission been taken on the solution of the doped PANI powders
peaks alter with different dopant concentrations and nature in THF and have been found that the absorption intensity
of solvents (due to polarity). It has been noticed that the decreases after doping. The absorption peak at around
intensities of peaks observed at 384 nm decrease with the 380 nm is attributed to the charge transfer
→
∗ tran-
increase of dopant concentration, which may be due to sition of aromatic rings and charge transfer groups. There
the role played by the interchain species. It is known that is a peak around 270 nm, which is attributed to inter band
the interchain species play an important role in the emis- transition n →
∗ transition of excitons in the aromatic
sion process of conjugated polymers. The observed reduc- ring.114
tion in the PL emission intensity peaks (noticed at 604 nm)

8.7. DC Conductivity of PANI Doped with

Binary Dopant (ZrO2 /AgI)

It has been reported that at low concentration of AgI in the

Fig. 7. Variation of dc conductivity versus different ratios of doped
PANI in a fixed ratio of PVC for the preparation of PANI–PVC blend.
binary dopant mixture, the DC conductivity of the doped
sample increases. This increase is most pronounced if sil-
ver iodide is not pure and contains impurities of metallic
Ag. This effect may be explained by the strong adhesion
of the small particles of metallic silver to ZrO2 . As a result
of which the extended defects in AgI strongly slows down.
The amount of AgI in the dopant mixture is responsible for
the introduction of large number of carriers into the elec-
tronic structure of polyaniline chain. Because of doping,
the attraction of an electron in one repeat unit to the nuclei
of the other neighboring unit leads to the carrier delo-
calization along the polymeric chain and hence increases
the charge carrier mobility, which ultimately increases the
conductivity of the doped PANI samples.115

Sci. Adv. Mater. 2, 441–462, 2010 449

 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
8.8. Polyaniline–Polyvinyl Chloride Blends Doped
with Sulfamic Acid in Aqueous Tetrahydrofuran
The crystallinity of PANI increases with the concentra-
tion of dopant. The increased crystallinity of PANI is
responsible for an increase in grain size. Ultimately, grain
boundaries increase and thus space charges are created
at the grain boundaries. At a lower temperature range,
the resistance of the grain boundaries is large and there-
fore, conduction is low. As temperature increases, the
grain boundary resistance decreases, and thus conductivity
increases.116
9. CONCEPT OF POLYMERIZATION OF
ANILINE
The wide variety of methods employed for the preparation
of PANI leads to the formation of products whose nature
and properties differ greatly. As a result of theDelivered
many stud- by Ingenta
REVIEW
ies carried out on PANI and its derivatives, University
a multitude of further
of polymerization mechanisms have been proposed by dif-
IP : 130.216.12.217
ferent authors. The polymerization reactionThu, is, in30
fact, a
Jun 2011 08:48:22
self-catalyzing reaction.117 The first step in the oxidation
of aniline is the formation of a radical cation, shown in
Figure 9 which is independent of the pH of the synthe-
sis medium (be it acidic or basic), and is the governing
criteria for the polymerization reaction.
Mohilner was the first to ascertain that in sulfuric acid
medium, between pH 2 and 5, the oxidation of aniline is an
ECE reaction, i.e., a succession of rapid electrochemical–
chemical–electrochemical reactions, mainly resulting in
para coupled chains, as depicted in Figure 10. He showed
that the polymerization is dependent on the square of the
concentration. This is supported by Zotti et al.118 who
agreed with the theory that the deposition is controlled
by slow charge transfer, switching from the conductive to
the insulating state at deposition potentials. However, para
coupling was not exclusive; radical cation coupling at the
ortho position, shown in Figure 11 might lead to low yields
of other products.
An intermediate product of the oxidation of aniline
had been identified by FTIR spectroscopy as being
p-aminodiphenylamine (PADPA). Its formation mecha-
nism is shown in Figure 12.
Mohilner et al. had also shown that PADPA is more eas-
ily electrochemically oxidized than aniline, as it was gen-
erally the case for dimerization reactions. Since PADPA
NH2 NH2
–
e
Fig. 9. Oxidation of aniline leading to the formation of a radical cation.
450
Ameen et al.
Fig. 10. Resonance stabilization of radical cation.
was an oxidation product of aniline, the intermediate steps
in the polymerization of aniline led to the oxidation of
PADPA to give the radical cation and subsequent forma-
tion of the quinone dication. Kitani et al. had more recently
verified this, showing that monomeric aniline is incorpo-
rated into the oxidized polymer at potentials lower than
its oxidation potential.119 The next steps in the polymer-
ization of PADPA are rapid and Mohilner et al. proposed
that the process occurs by the formation of the tetramer,
then formation
to: of the ocatamer, which polymerizes even
Auckland resulting in a polymer whose basic structure is that
of the
emeraldine. In sulfuric acid medium (2 to 6 M)
Hand and
Nelson and Bacon and Adams proposed the
same polymerization mechanism for aniline or its para
substituted derivatives, with elimination of the substituent
group. However, the results obtained by numerous work-
ers on the electro polymerization of ADPA have shown
that poly-ADPA (PADPA) chains are relatively short, hav-
ing molecular weights between 2800 and 30000, whereas
the molecular weights of PANI chains are around 80000.
Therefore, in the case of aniline, the process that occurs
after the oxidation of PADPA can follow several different
reaction pathways. The polymerization process can lead
to the formation of intermediate reaction products which
cannot be isolated, thus making it difficult to define the
limiting reaction of the process.
Recent studies, the electro polymerization of ani-
line can be reported as occurring by several different
attack mechanisms.120 These simplified attack mechanisms
clearly demonstrate the importance of the reactivity of the
aniline monomer and can be seen to occur by different
reaction sequences, involving successive addition of a neu-
tral or one of two oxidized forms of the monomer units
to the growing polymer chain. These mechanisms can be
Fig. 11. Reprentation of radical cation coupling.
Sci. Adv. Mater. 2, 441–462, 2010
Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites

Bacon and Adams and Wawzonek and MacIntyre122

Fig. 12. Formation mechanism of p-aminodiphenylamine (PADPA).
separated on the basis of the applied potential of electro
polymerization, shown in Figure 13.
(1) Nucleophilic addition of the aniline monomer (mech-
anisms 1 and 2)
(2) Radical addition (mechanism 3)
(3) Electrophilic addition of the two oxidized forms of the
aniline monomer (mechanisms 4 and 5)
showed that the oxidation of aniline or its para substituted
derivatives in acid or acetonitrile medium gives rise to the
formation of benzidines and PADPA, by a process which
is pH dependent. These reaction products result from tail-
to-tail and head-to-tail coupling respectively (which is in
accordance with some recent in situ Raman studies by
Holze123 with elimination of the group para to the amino
group (Fig. 3). These authors proposed the same process
for the oxidation reaction of ortho or meta substituted ani-
line in the same medium. According to these authors, a
large decrease in pH results in a 30–50% increase in the
production of benzidine with respect to PADPA. Waw-
zonek and Maclntyre had observed that the oxidation of
aniline and some of its substituted derivatives in basic or
acetonitrile medium in the presence of pyridine results in
the formation of azobenzene, shown in Figure 14.
They concluded that the ratio of PADPA/hydrobenzene
formed is controlled by the nature of the substituent on

REVIEW
Mechanisms 3, 4 and 5 are evident that the Delivered
electropoly-by Ingenta to: ring, but had not specified the precise influ-
the benzene
merization would be kinetically slower for University
the former of ence
Auckland
of the relevant substituents. Nevertheless, Breitenbach
group than for the latter. In fact, these mechanisms IP : 130.216.12.217
are and Hecker124–125 proposed that the oxidation mechanism
Thu, 30 Jun
certainly successive in the case of PANI. Effectively, the 2011 08:48:22
of aniline in acetonitrile/pyridine medium was similar to
thicker the film becomes the more the ohmic drop in the that in acid medium as described by Mohilner. The base
film increases, thus resulting in a subsequent decrease in removed a proton from the radical cation forming a neu-
the applied potential at the solution-polymer interface; this tral radical which oxidized to give the nitrenium cation.
favors mechanisms 1 and 2 as opposed to mechanisms 3 This nitrenium cation could attack the aniline to yield
and 5. Moreover, this would explain the eventual length of PADPA. More recently, Volkov et al. had confirmed these
the resulting PANI chains. Furthermore, Genis et al. have conclusions by carrying out studies on the oxidation prod-
shown that mechanism 5 mainly since the charge density ucts of aniline in acetonitrile/pyridine medium using clas-
is more delocalized in the polymer than in monomer. sical and multiple reflection IR spectroscopic and XPS
The mechanism 3 leads to coupling in the para posi- methods. The spectra of the anodic oxidative products of
tion, giving a polymer with greater structural regularity.121 aniline were identical to those of the chemically prepared

Fig. 13. The electropolymerization of aniline showed by several different attack mechanisms.

Sci. Adv. Mater. 2, 441–462, 2010 451

 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites Ameen et al.

10. PHYSICAL PROPERTIES OF

Fig. 14. Oxidation of aniline and some of its substituted derivatives in the observed results and was achieved by employing a well
basic or acetonitrile medium.
emeraldine. Volkov et al. had also identified PADPA as an
intermediate product, thus reinforcing Mohilner’s results.
Using the same method, they concluded that the poly-
mer films are free from impurities resulting from tail-to-
tail coupling. The polymerization mechanism of aniline is
REVIEW
POLYANILINE
10.1. Conductivity
The first conductivity studies on the oxidation products
of aniline indicated that these materials have interesting
electronic properties. Parini126 and Maleev127 quoted the
first values for the conductivity. Systematic studies on
the relationship between the conductivity of PANIs, their
mode of synthesis and their physicochemical properties
had enabled by Jozefowicz to reduce the discrepancies in
defined synthesis method which simply involved the oxi-
dation of aniline by ammonium persulfate in sulfuric acid
at pH 1, which yielded a material having a conductivity of
100 ohm−1 cm−1 . Jozefowicz et al. established simple rela-
tionships between the conductivity and the chemical poten-
tial for the species present in the solid matrix, as a function
of the degree
to: of protonation and hydration of the polymer.

Delivered by Ingenta
more complex in acid medium than in basic medium since The conductivity of PANI prepared electrochemically in
University of Auckland
the aniline monomer can act as a base and deprotonate its neutral phosphoric or basic (acetonitrile/pyridine) media is
IP : 130.216.12.217
own radical cation. Ohsaka et al. highlighted the difference much
Thu, 30 Jun 2011 08:48:22 weaker, being in the range 10–14 ohm−1 cm−1 .
in the behavior of the oxidation products of aniline pre- It has been shown that the polymer formed at 0  C is
pared in sulfuric acid medium (pH 1), neutral phosphoric more ordered and hence more conductive in the metallic
medium (pH 7), and in acetonitrile/pyridine (0.3 M) solu- region than that synthesized at 30  C.128 From conduc-
tion. The N–N liaison characteristic of the head-to-head tivity measurements, Travers et al. had observed that the
coupling was observed only in the spectra corresponding polymer exhibits a metal to insulator transition which is
to the products prepared under neutral or basic conditions. a function of the pH. The conductivity of the polymer
These authors had attributed the head-to-tail configura- is 5 ohm−1 cm−1 when the polymer is previously equili-
tion to the aniline oxidation products prepared in acidic brated at pH 6. MacDiarmid et al.129 had also described
medium, shown in Figure 15. a variation in the conductivity of both chemically and

Fig. 15. The head-to-tail configuration to the aniline oxidation products prepared in acidic medium.

452 Sci. Adv. Mater. 2, 441–462, 2010

Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
electrochemically prepared polymers with the pH of the
aqueous solution to which the polymer was exposed
before drying. The polymer exhibits a conductivity of
1 ohm−1 cm−1 when it is equilibrated at a pH between
−1 and +1, and 10 ohm−1 cm−1 when it is equilibrated at
a pH between 5 and 6. Elsewhere they indicate that the
conductivity of the polymer is a function of the level of
doping, with a value of 1 ohm−1 cm−1 for 15% doping, and
varying from 10 ohm−1 cm−1 for 0% to 10% doping. Mea-
surements carried out by Brahma130 revealed that PANI
doped with iodine exhibited a conductivity four orders of
magnitude greater than the undoped polymer. It had also
been observed by Kitani et al.131 that the resistance is
no longer measurable after the polymer had been treated
with a base such as sodium hydroxide. Wrighton et al.
and Glarum and Marshall132 had carried out in situ con-
ductivity measurements on PANI in aqueous sulfuric acid
solution as a function of the applied potential.
Delivered by Ingenta
10.2. Conduction Mechanism University of Auckland undergoes a thermal
IP : 130.216.12.217 crystalline polymer.
In a recent article, Wnek133 had proposed a conduction
Thu, 30 Jun 2011 08:48:22
mechanism for electrochemically prepared PANI. During
protonation of the polymer (which is in the basic emeral-
dine form) the cations become involved in disproportionate
reactions forming semiquinone radical cations, which are
subsequently responsible for the increase in the conductiv-
ity. Recent investigations by Salaneck et al.134 135 on the tal structures of perchlorate and tetrafluoroborate salts of
conduction mechanism of PANI had shown that the tem-
perature dependence of the electrical conductivity of the
polymer is indicative of one dimensional variable range
hopping Furthermore, De Surville et al. had observed that
PANI has a strong affinity for water; its absorption capac-
ity can be as large as 40% of the polymer’s weight,
depending on the preparation and equilibration conditions.
This is a possible explanation for the discrepancy in the
physical properties, such as conductivity, observed by dif-
ferent authors.136 Travers and Nechtschein had proposed
a reaction mechanism which takes the modes of transport
into account, by combining both the transfer of protons
and electrons.137 They had studied the proton exchange
process in solid PANI by NMR spectroscopy and have
shown that there is a permanent exchange between the
fixed protons of the nitrogen in the polymer (solid pro-
tons) and the water of hydration of the polymer (liquid
protons).138 This can be correlated with the polymer’s
transport and energy storage properties. Other sources have
demonstrated that an increase in the degree of hydration
of PANI has the same effect as a decrease in the level of
protonation of the polymer.139
10.3. Morphology and Structure
The adherence and the homogeneity of a PANI film on
an electrode varies according to the method of synthe-
sis employed. Diaz had observed weak adherence for a
Sci. Adv. Mater. 2, 441–462, 2010
polymer prepared by electrochemical oxidation at constant
potential, whereas good adherence results when poten-
tial cycling is employed. Kitani et al. had reported that,
using the same method, a thin homogenous film is initially
deposited on the electrode, followed by the formation of
an amorphous powder which eventually becomes detached
from the electrode surface. Electrochemical investigations
on the polymer growth by Thyssen et al. yielded evi-
dence for cross linking reactions leading to the formation
of hemispheres.140 Some authors have investigated con-
ducting films on various substrates using ellipsometry.141
The difficulties that arise in interpreting structural data
on PANI can be somewhat avoided by studying short
oligomers, the composition of which is less variable and
the geometric structures of which are more accessible. The
resulting model studies yield information that may not be
completely transferable to the longer polymers but can be
nevertheless, indicative. Recent studies involving scanning
electron to:
microscopic techniques reveal that doped amor-
REVIEW
phous PANI
142
transition to an oriented
partly
Furthermore, the results indi-
cate that during the thermal developing procedure a change
in the lattice structure occurs as a consequence of this abil-
ity of the polymer to ‘flow’. Spun fibers have been formed
which exhibit some crystallinity and the soluble parent
material can be recrystallized from solution.142 Baughman
et al. had used X-ray diffraction data to elucidate crys-
PANI.142
10.4. Thermal Stability
At the beginning of the century, Green and Woodhead
described PANI, which was prepared by chemical oxida-
tion in acid medium, as being a material which undergoes
irreversible transformations above 40  C. This theory was
soon disbanded and PANI prepared by both electrochemi-
cal and chemical methods is known to be a stable material.
In effect, Mohilner described electrochemically prepared
PANI as an amorphous powder which is stable between
0 and 300  C with a color which can vary from green to
blue-violet. Jozefowicz et al. and Langer confirmed this
by similar observations in the case of chemically prepared
PANI.143 Volkov noticed a similar stability for a material
prepared in an acetonitrile solution that was made basic
with pyridine.
11. CHEMICAL PROPERTIES OF
POLYANILINE
11.1. Solubility
It is generally accepted that PANI is insoluble in most
common organic and aqueous solvents, irrespective of the
method of synthesis. Nevertheless, Mohilner et al. had
shown that the polymer is easily dissolved in pyridine
453
 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
and DMF, strongly tinting the solutions blue. Furthermore,
De Surville et al. and Doriomedoff found that PANI is
slightly soluble in very acidic solutions, whereas the salts
of the polymer are completely insoluble in all commonly
employed solvents. Genis et al. had noticed that there is
always slight dissolution of the polymer in DMF. Thus,
this has made it possible to perform gel-permeation chro-
matography in order to evaluate the averaged molecular
mass of the soluble fraction.144 The synthesis of soluble
PANI is of great interest since the formation of a solu-
ble material is essential in order to facilitate post-synthesis
processing. There are two possible methods for preparing
soluble polymers:
(1) Formation of the polymer salt using an anionic dopant
which favors dissolution.
(2) Pre-functionalization of the starting monomer with a
suitable group prior to polymerization.
Chemical synthesis of soluble PANI by the former
REVIEW
method has been successfully accomplished byDelivered
Li et al. by Ingenta
145
University
and involves proton acid dopants of large molecular
size of Aucklandto exhibit redox exchange and ionic exchange prop-
such as toluene-p-sulfonic acid, sulfamilic acidIP 130.216.12.217 permi selectivity transport properties that depend
or : poly-
meric electrolyte-polystyrene sulfonic acid. Thu, 30 Jun 2011
The conduc-
tivity of these soluble materials is comparable to that of
the usual insoluble PANI. Genis et al. had formed a PANI
(poly-propylaniline) by the latter method to yield a mate-
rial which is highly soluble in various organic solvents in
146
the reduced state. Andreatta et al. has recently synthe-
sized a soluble PANI which is very processible and can be
spun in filament forms which are relatively crystalline.
11.2. Acid Base Functions
Determination of acidity constants by De Surviue, for
PANI prepared chemically by the oxidation of aniline
using ammonium persulfate in sulfuric acid, has revealed
two acid functions, a strong one and weak one. This author
observed that the two acid functions are independent of the
temperature of synthesis and the concentration of oxidant.
The presence of two acid functions has been confirmed by
the formation of sulfate and chloride complexes. In partic-
ular, the pKa of the weak function varies with the type of
anion, demonstrating the aptitude of PANI to form diverse
complexes, such as those proposed by Jozefowicz et al.
The correlation of the pH changes to complex is probably
not justified in this case. The variations in pK values are
more than likely due to electrostatic interaction phenom-
ena between the charges on the polymer and the doping
anions. From XPS experimental data, MacDiarmid et al.
had proposed that protonation of the polyemeraldine base
by protonic acids occurs at the nitrogen atoms. The result-
ing electronic charges are localized at the nitrogen atoms
with local geometrical changes occurring in the polymer
chains. The subsequent hypothesis of PANI involves the
proton-induced spin unpairing mechanism for protonated
quinoneimine moieties was supported by Wudl et al.
454
Ameen et al.
11.3. Oxidation and Reduction
The oxidation and the reduction of PANI can be affected
chemically or electrochemically, irrespective of the method
employed for the synthesis. Jozefowicz proposed the two
reaction sequences for the oxidation of the polymer
(1) The redox reaction occurs without modifying or
degrading the polymer chain, by a reversible amine-imine-
type transformation;
(2) The redox reaction modifies the polymer by ruptur-
ing the chain with subsequent hydrolysis which yields a
quinonic structure.
Hand and Nelson had studied the degradation of PANI
in aqueous media. Similar work was carried out by
Kobayashi et al., who consequently proposed a degrada-
tion mechanism that occurs via the imine form of PANI
which subsequently hydrolyses to form quinine hydro-
quinone structures (Fig. 11). These products are soluble in
aqueous to:solutions. Heterogenous PANI membranes were
shown
erties and
on the redox state of the polymer. De Surviue had observed
08:48:22
that the oxidation state of the polymer varies linearly with
temperature in the range 0 to 25  C and with the concen-
tration of oxidant. Nevertheless, the charge accumulated in
the polymer remains constant when the concentration of
oxidant reaches a certain value. These results have been
confirmed by Hand and Nelson. It had been observed by
Genis et al. and by MacDiarmid et al. that polyanilines
prepared both chemically and electrochemically undergo
reversible redox reactions in organic media without notable
degradation of the polymer.
11.4. Catalytic Ability
Since mineral semiconductors are sometimes useful as
catalysts147 their organic analogues have very quickly
become the subject of much investigation with regard to
their catalytic abilities. Galiard et al.148 had shown that
PANI shows important catalytic behavior in the decompo-
sition of nitrous oxide and in the isomerization of butadi-
ene. However, the correlation between the variation in the
number of paramagnetic centers and the catalytic power of
the polymer proposed by these authors is rather unconvinc-
ing. Moreover, they indicate that the catalytic properties
of PANI are sometimes better than those of mineral cata-
lysts; the authors maintain that the polymer has an active
surface which is greater than its geometric surface, is
quite heat resistant and possesses selective catalytic activ-
ity for certain reactions, which have, unfortunately, not
been specified. Noufi et al. had reported that certain reac-
tions involving electroactive species, such as Fe2+ /Fe3+ the
potential difference between the anodic and cathodic peaks
of the redox system of iron is decreased with respect to
that at the bare metallic electrode. Thus, the possible use
Sci. Adv. Mater. 2, 441–462, 2010
Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
of PANI-modified electrodes as electrocatalysts has been
studied.149
11.5. Electrochemical Properties
Many qualitative and quantitative studies have been car-
ried out on the electrochemical properties of PANI as a
function of the method of synthesis and the redox state
of the material. These types of investigations have been
concerned, in particular, with comparison of the electro-
chemical behavior of electroactive species in solution at
an inert electrode and at an electrode modified by a depo-
sition of PANI.
11.6. Redox Behavior and Conductivity
Diaz et al. initially showed that PANI is conducting in the
potential range 1.0 to 1.0 V (vs. SCE) irrespective of its
redox state. Some authors claim that by electrochemical
doping the conductivity of PANI can be switchedDelivered
on atby Ingenta
University
the initial stage of doping and switched off at high dop-
IP :
150
ing levels, as in a three, state switching process. The130.216.12.217
Thu, 30 Jun
potential range in which the polymer is conducting has 2011
been reduced to 0.1 to 0.71 V (vs. SCE) by Oyama et al.
They indicated that it can be used in this potential range
as an electrode material for selective oxidation or reduc-
tion of different electroactive species whose redox poten-
tials also lie in the same range. They have also discussed
the use of a polyaniline/graphite modified electrode as a
redox diode. Genis et al. had shown that PANI behaves
somewhat like polypyrrole; the polymer conducts in the
oxidized state between 0.2 V (vs. Ag/Ag+ in acetonitrile)
and 1.6 V, where degradation of the material begins to
occur. An in situ-conductivity study by Wrighton et al.
had shown that PANI is conducting in the potential range
0.2 to 0.65 V (vs. SCE) in sulfuric acid. The loss of con-
ductivity above 0.65 V is probably due to degradation
of the polymer in acid medium as opposed to being due
to some intrinsic property of the polymer. Genis et al.
had recently verified this and has attributed the modified
behavior of over-oxidized PANI to cross-linking reactions
which occur via the nitrenium aniline cation and the nitre-
nium polymer cation. Raman studies have indicated that
degradation occurs after the second oxidation at potentials
greater than 0.8 V versus SCE.151 Kobayashi et al. had
reported that the higher oxidized state of PANI is easily
oxidized by water to form p-benzoquinone. Hence, electro-
chemical studies carried out in dry non-aqueous solvents
permit the employment of a larger potential range than
when working in aqueous media. Studies on the acid–base
dissociation behavior indicate that approximately half of
the nitrogen atoms are involved in the redox reactions.152
XPS investigations indicate that the additional positive
charges of the oxidized polymer are delocalized over the
whole chains. Chrono coulometric experiments have shown
that 40% of the nitrogen takes part in the redox reactions
Sci. Adv. Mater. 2, 441–462, 2010
involving the first electrochemical system and 20% for the
second system. This corresponds to an overall doping level
of 60%. In other words, it is possible to remove 0.6 elec-
trons per aniline unit of the polymer chain.
11.7. Doping/De-Dopoing and Capacitance
Complex impedance measurement methods had been
used by Tanguy et al.153–155 to study the electrochemical
behavior of chemically synthesized PANI. The results were
analyzed by employing a model which is based on ionic
relaxation involving dopant ions. During electrochemical
oxidation (doping), anions in the solution become incorpo-
rated into the polymer to compensate the positive charges
in the chain; it is thought that there are two kinds of doping
sites in the polymer chain, which explains the significance
of the capacitive charge of such conducting polymers. The
investigations on emeraldine chloride yielded supporting
evidence for two different chloride counter: on sites, one of
REVIEW
to:
which is affected both by exposure to water vapour and by
of Auckland
thermal treatment.156 More recently, XPS investigations156
indicate the existence of three chlorine chemical environ-
08:48:22
ments for a PANI chloride salt. By coupling spectro elec-
trochemistry and cyclic voltammetry studies, Genis et al.
had demonstrated that the capacitive charge is propor-
tional to the doping level, as was previously proposed by
Feldberg.
11.8. Redox Mechanisms
A number of mechanisms have been proposed for the
redox behavior of PANI which takes into consideration the
effect of protonation and counter anion insertion. At what
stage this counter anion insertion actually occurs during
the oxidation of the polymer is a rather controversial
question.
11.9. Protonation Effects
All authors are in agreement with the fact that PANI syn-
thesized in acid solution is electroactive when the pH of
the medium is less than 3–4 and electro inactive when the
pH is neutral or basic. The polymer retains its electroactive
properties in non-buffered neutral acetonitrile and loses
them reversibly in basic media: In the case of methanol
or ethanol, the polymer must be preliminarily acidified in
order to render it electroactive. When PANI is synthesized
in a basic aqueous or organic medium, in particular in an
acetonitrile/pyridine mixture, it permanently loses its elec-
troactivity regardless of the medium in which it is subse-
quently studied.
12. APPLICATIONS
It is well appreciated that in view of its electrochemi-
cal properties, PANI can be used as material for modified
455
 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
electrodes157 as a corrosion inhibitor for semiconductors
in photo electrochemical assemblies, in microelectronics,
biosensors and as electrochromic material.158 As far as the
last application is concerned, some authors have even pro-
posed different polyaniline to obtain the three fundamental
colors of the chromatic circle.
Conducting polymer sensors and particularly polyani-
line based biosensors have been reported 159 160
for poten-
tiometric analysis,161 electrochemical studies162 163 and
some applications-pesticide determination with immobi-
lized cholinesterase.164 However, for the operation of elec-
trochemical biosensors a conjugation of the biochemical
and electrochemical reactions are required. For this aim,
the biological recognition element should be immobilized
at the electrode surface. There are two principal ways
of such immobilization: covalent linking and the entrap-
ment into gel or polymer matrixes. However, the former
method is not successful in certain cases because the elec-
REVIEW
trode surface becomes poisoned after treatment with the
Delivered by Ingenta
excess of bi-functional reagent required for the
enzyme of Aucklandconductivity and ESR measurements that have been
University
linking. The enzyme immobilization directly intoIP polymer
: 130.216.12.217
semiconductor films is seemed to be the Thu,
30 Jun 2011
most suitable
procedure.165 PANI is known to be a mediator of antibody
immobilization by entrapping the biological sensing ele-
ments in the polymer matrix.166 167 It has been shown that
these entrapped biological materials maintain their biolog-
ical activity.166 168 This entrapment feature is widely used
for direct measurement of antibody–antigen binding.169 170
As reported,171 172 a conductometric biosensor based on
a sandwich immunoassay format has also been designed
for microbial and viral detection. The biosensor consisted
of lateral-flow membranes as the platform, antibodies as
the bio-receptor and non-self doped PANI as the trans-
ducer. The presence of antigen is detected by measuring
the presence of PANI, which is manifested by an increase
in conductance (or a drop in resistance).173
Another application of PANI which has inspired most
interest is in the area of electrochemical batteries. The pos-
sible use of PANI as active anodic material in recharge-
able batteries was initially studied in 1969.174 Studies
were carried out on half-cells employing a product pre-
pared by the chemical oxidation of aniline in sulfuric
acid medium. Button-type electrodes prepared by com-
pression of a powder of the polymer possess good faradic
capacity both during charging (oxidation) and discharg-
ing (reduction). More recent systematic studies have been
undertaken by numerous groups175–184 the possible use of
PANI as an active electrode material. These investigations
deal with the behavior of PANI in aqueous and organic
media as a function of the mode of synthesis. Storage
cells which employ non-aqueous solvents have the advan-
tage of being compatible with lithium and so yield higher
voltages (3 to 4 V polymer-lithium), whereas the maxi-
mum is 2 V when zinc is employed in aqueous medium.
On the other hand, the weak conductivity of non-aqueous
456
Ameen et al.
solvents185–187 respect to aqueous solvents188–190 limits the
strength of the output current. Hence, rechargeable batter-
ies which employ non-aqueous media have a higher capac-
ity. For this reason much of the current work is centered on
two types of batteries: lithium/non-aqueous solvent/lithium
salt/polyaniline and metal/water/metal salt/polyaniline.
Tzamalis et al.191 worked on the infrared optical prop-
erties of polyaniline doped with 2-acrylamido-2-methyl-
1-propanesulfonic acid (AMPSA). They have reported
the results of dc conductivity measurements over a wide
temperature range (10–295 K) and at room tempera-
ture, absolute infrared reflectivity measurements of two
polyaniline-AMPSA films with different protonation levels.
Both samples display transport properties similar to other
doped conducting polymers on the metallic side of the
metal-insulator transitions. Lee et al.192 have reported the
dc conductivity of outstretched and stretched polyaniline
films prepared from it m-cresol using 0.60 HCSA per ring.
Kahol et al.193 reported the magnetic susceptibility, elec-
to:
trical
made on poly (o-methoxyaniline), poly (o-ethoxy aniline),
poly (2.5-dimethoxy aniline) and blends of polyaniline and
08:48:22
poly (o-methoxy aniline). These materials have doped with
many organic acids and they were also synthesized with
different monomer to oxidant ratio. A systematic study to
these materials reveals a constituent size effect, an aggre-
gation effect and usual electron localization properties.
Masnhara et al.194 had reported the dc conductivity mea-
surements in disordered system composed of a few per-
cent of either conducting polyaniline or polypyrole, mixed
with PMMA, striking periodical voltage which was similar
to those predicted to occur due to synchrony in network
of oscillators. The precise character of oscillations was
dependent strongly on temperature, magnetic field, applied
current and fabrication process. The oscillation was highly
nonlinear. The transition from periodic pulsing to chaos
was clearly seen and may be controlled in a given sample
by dc bias current, temperature and/or applied magnetic
field. Details of oscillating features will be reported and
comparison to models was presented. Sheats et al.195 had
been reported about conductive adhesives based on intrin-
sically conducting polymer (ICP’s). They could play an
important role in all polymer electronics by joining organic
field effect transistors (FET), organic light emitting diode
(OLED) e.g., ICP-based circuitry. Reaction with atmo-
spheric water vapor appeared to be an important factor
contributing to the degradation of conductivity, on the
exposure of the doped material to the air. Donar doped
polymers also have poor stability, presumably due to the
reaction with oxygen and water. In case of polypyrrole, air
stability is demonstrated as long as the polymer is held in
its doped, conductive state but polyaniline is found stable
in both neutral and oxidized form.
Metal nanoparticles dispersed within a conducting PANI
matrix has recently offered tremendous options for com-
bining the properties of the metal nanoparticles and
Sci. Adv. Mater. 2, 441–462, 2010
Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites

the electronic properties of conducting polymers.196–198
The conducting PANI/metal nanoparticles nanocomposites
have already found the potential applications such as light
emitting diodes and solar cells.199–202 Conducting PANI
and inorganic nanomaterials, particularly those of inor-
ganic oxides are of immense importance owing to their
unique properties and application aspects in technology.
Both of these materials act as model materials for carrying
out theoretical studies to gain insight into the relationship
between the structure and the properties of the materials.
However, the major limitation of these materials is their
individual functionalities. Amongst other inorganic mate-
rials, TiO2 and Zno have also been studied to prepare its
nanocomposite with conducting PANI and for the appli-
cation of photovoltaics. Our recent publication reports the
fabrication of a p–n heterojunction structure and solar cells
comprised of polyaniline (PANI) and metal nanoparticles.
Figure 16(a) demonstrates a porous TiO2 formed on
the FTO substrates. The film is composed Deliveredof the wellby Ingenta
the surface of TiO2 thin film. This assemblage confirms
the internalization of plasma deposited PANI into porous
TiO2 nanoparticles thin film substrates.
A schematic energy level diagram, shown in Figure 17,
indicates that the electrons from PANI, upon illumination,
jumps from the HOMO level to its LUMO level and thus,
as per step (2), these electrons are transferred from the C.B
to the V.B of TiO2 . The step (3) shows the transfer of elec-
trons from V.B to the HOMO of PANI and would move
ahead by following the same step (1), leading to the trans-
fer of electrons to the entire cell. During the entire cycle,
the recovery of the holes is accomplished at the counter
electrode.203 Therefore, the proposed mechanism presented
the may deliver the high transportation of charge carriers
during the operation of device under the illumination.
As shown in Figure 18, the proficient current in the
PANI/TiO2 heterojunction structure is attributed to the well
penetration of PANI molecules into the pores of the TiO2
to: thin film. The I–V characteristics ensured an
nanoparticle

REVIEW
crystalline TiO2 nanoparticles of size ∼25 nm, It is seen efficient
University of Auckland charge movement at the junction of PANI/TiO2
in Figure 9(b) that the PANI molecules are well pene- 204
IP : 130.216.12.217and thus, behaved as a typical ohmic system.
interface
trated into the porous TiO2 thin film upon the 30
Thu, plasma
Jun 2011The penetration of the PANI molecules into the crys-
08:48:22
enhanced polymerization. In addition, the particles size of talline ZnO nanoparticles thin film upon electrophoretic
TiO2 nanoparticles get altered and increased ∼10–15 nm deposition leads the accumulation of ZnO nanoparticles,
from its original particle size upon the deposition of shown in Figure 19. This assemblage confirms the sub-
plasma enhanced PANI. Moreover, the accumulation of stantive interaction and incorporation of electrophoretic
TiO2 nanoparticles occurs after the deposition of PANI on deposited PANI into the crystalline ZnO nanoparticles thin
film substrates. From the schematic diagram (Fig. 19(b)),
the uniform PANI (p-type) layer was deposited on the
ZnO (n-type) thin film by electrophoretic process and
finally make a top Pt thin layer contact to complete the
Pt/PANI/ZnO diode.
From the Figure 20, UV-Vis spectra clearly exhibits the
characteristic bands of PANI at 328 nm and 362 nm in

Fig. 17. An overview of the energy level diagram of the fabricated

Fig. 16. FESEM images of (a) pristine TiO2 (b) PANI/TiO2 thin film. devices FTO/TiO2 /PANI/Pt.

Sci. Adv. Mater. 2, 441–462, 2010 457

 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites Ameen et al.

Fig. 20. UV-Vis spectra of pristine PANI and PANI/ZnO thin film.

pair of the nitrogen atom in the PANI molecules. Con-

sequently, the extent of conjugation of PANI decreases,
REVIEW

Delivered by Ingenta to: in the increased intensity of the peak in

thus resulting
University of PANI/ZnO
Aucklandthin film substrate.205 Thus, the absorption of
IP : 130.216.12.217
PANI/ZnO thin film increases over the whole range of
Thu, 30 Jun 2011
Fig. 18. I–V characteristic curves of (a) plasma polymerized PANI and
08:48:22
visible light indicates that electrophoretically deposition is
(b) PANI/TiO2 thin film. effective to broaden the absorption of ZnO to visible light
range.
PANI/ZnO thin film and pristine PANI substrates respec- From Figure 21, I–V characteristics present the weak
∗
tively and are ascribed to
–
transitions. However, the rectifying with the non-linear nature for Pt/PANI/ZnO het-
bands at 604 and 618 nm are referred to n–
transi- ∗ erostructure diode. The non-linear nature of curve might
tions and represent the polarons formation into the con- resulted from the formation of Schottky contact between Pt
ducting PANI. The interaction between ZnO and PANI and PANI/ZnO layer. Moreover, the Pt layer on PANI/ZnO
contributes to the decrease in the degree of orbital overlap heterostructure might have originated a barrier between the
between the
electrons of the phenyl rings with the lone interfaces of PANI/ZnO layer and Pt layer, and is respon-
sible for the non-linear nature of I–V characteristics. The
obtained device exhibited a weak rectifying behavior with
low rectification ratio of ∼4.2. However, I–V characteris-
(a) tics of PANI/ZnO heterostructure shows the linear nature
of curve, which indicates that heterostructure device have
ohmic behavior without Pt layer. It is noteworthy that a
simple and the cost effective electrophoretic deposition

(b)

Fig. 21. I–V curve of fabricated Pt/PANI/ZnO heterostructure device

Fig. 19. (a) Surface view FESEM image of PANI/ZnO thin film and and inset shows the I–V curve of fabricated PANI/ZnO heterostructure
(b) schematic of heterostructure device. device.

458 Sci. Adv. Mater. 2, 441–462, 2010

Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
technique provides the improved performance of the p–n
heterostructure devices.
13. CONCLUSION
The investigations of PANI and nanocomposite materi-
als are an active exploration of the research because of
its low cost, easy synthesis, and unique properties. This
review accounts several important factors for achieving
the high purity and high yield PANI; (i) high purity
of monomers, chemicals and solvents are required for
obtaining high quality polymer, (ii) environment for poly-
merization should be inert and dry because a slight vari-
ation in the polymerization conditions as it may alter the
nature of the obtained polyaniline and (iii) PANI should
be kept in a dark, cool and dry place since the chances
are PANI may undergo isomerization reaction under light
and heat. The choice of solvents, electrolytes, reactant
References and Notes
Deliveredtoby Ingenta to:
concentrations and synthesis conditions are important
University
obtain a regular PANI structure with high possible molec- of Auckland
IP : 130.216.12.217
ular mass. The reviewed data confirms that the electronic
Thu, 30
and optical properties could be easily controlled by Jun
the 2011 08:48:22
oxidizing/reducing agents and acid/base doping during
the polymerization procedures. Various organic/inorganic
acids, metal chlorides and metal oxides are used as dopant
materials for improving the conduction properties in the
PANI molecules. The review analyzes the effect of vari-
ous dopants on the conductivity properties of PANI. The
chemical and electrochemical procedures for PANI are
reviewed in terms of its chemical stability, solubility,
oxidation-reduction, electrochemical reactions and cat-
alytic properties. Importantly, it has been proposed that the
two reaction sequences are required for the oxidation of
the polymer; (i) the redox reaction which occurs without
modifying or degrading the polymer chain, by a reversible
amine-imine-type transformation and (ii) the redox reac-
tion due to the modification of the polymer by ruptur-
ing the polymeric chain with subsequent hydrolysis and
yields a quinoid structure. The reviewed data manifests
the diversity of PANI nanocomposites and their poten-
tial applications. Particularly, the nanocomposites of PANI
and metal oxide nanomaterials (TiO2 , ZnO) display the
immense importance owing to their advanced and unique
properties in the application of nanotechnology. It has been
proved that nanocomposites act as model materials for car-
rying out the theoretical studies to gain insight into the
relationship between the structure and the properties of
the materials, even though, the major limitation of these
materials are their individual functionalities. Here, TiO2
and ZnO have been studied to prepare PANI nanocom-
posite by PECVD and electrophoretic techniques for the
application of electrical devices such as diodes and solar
cells. Our progressive work has indicated that the mor-
phological, crystalline, optical and electrical conductive
properties have advanced characteristics as compared to
Sci. Adv. Mater. 2, 441–462, 2010
PANI alone. These advanced properties have significantly
enhanced the performance of the fabricated of p–n het-
erojunction structure devices and solar cells comprised of
polyaniline (PANI) and metal nanoparticles. Despite of the
availability of vast amount of research on the synthesis of
PANI and its nanocomposites, still much research work are
needed to improve the quality and processing of the mate-
rials in order to make commercial products for the prac-
tical use. There are certain issues to modify the research
work in this field; (i) Synthesis of highly conducting PANI
salt in organic carrier solvent form or in the powdered form
with high molecular weight and crystallinity, (ii) prepara-
tion of freestanding films with excellent electrical, spectral,
thermal, and mechanical properties and (iii) preparation of
highly conducting polymer blends or composite films with
less amount of PANI by industrially acceptable methods.
REVIEW
1. M. Gerard, A. Chaubey, and B. D. Malhotra, Biosens. Bioelectron.
17, 345 (2002).
2. H. Sasabe and S. Saito, J. Poly. Sci. 6, 1401 (1968).
3. E. Butta, M. Colamia, Corsi-Semin. Chim. 8, 211 (1968).
4. S. Mashimo, J. Chem. Phys. 67, 2651 (1977).
5. H. A. Kraners, Physica 7, 284 (1940).
6. H. Cohen and D. J. Turnbell, Chem. Phys. 31, 1164 (1959).
7. S. Mashimo, J. Polym. Sci. Polym. Phys. 19, 213 (1981).
8. T. Ito, H. Shirakawa, and S. Ikeda, J. Polym. Sci. Polym. Chem.
12, 11 (1974).
9. C. K. Chiang, C. R. Fincher, Y. W. Park, A. J. Heeger,
H. Shirakawa, E. J. Luis, S. C. Gau, and A. J. MacDiarmid, Phys.
Rev. Lett. 39, 1098 (1977).
10. (a) E. M. Genis, M. Lapkowski, and C. Tsintavis, New J. Chem.
12, 181 (1988); (b) T. A. Skotheim, Handbook of Conducting Poly-
mers, Marcel Dekker, New York (1986).
11. J. E. Frommer and R. R. Chance, Electrically Conductive Poly-
mers, Encyclopedia of Polymers Sciences and Engineering, Wiley,
New York (1986).
12. R. J. Waltman and J. Bargon, Can. J. Chem. 64, 76 (1986).
13. (a) G. K. Chandler and D. Pletcher, Electrochem. 10, 117 (1985);
(b) R. L. Greene and G. B. Street, Science 226, 651 (1984);
(c) W. Hayes, Contemp. Phys. 26, 421 (1985).
14. J. Fritzsche, J. Prakt. Chem. 20, 453 (1940).
15. R. Nietski, Ber. 11, 1093 (1878).
16. Lightfoot, Br. Patent, 151 (1863).
17. H. Letheby, J. Am. Chem. Soc. 15, 161 (1962).
18. T. Yasin, Bull. Chem. Soc. Jpn. 10, 306 (1935).
19. J. J. Coquillon, Compt. Rend. 81, 408 (1875).
20. R. WiUstatter and S. Dorogi, Ber. 42, 4118 (1909).
21. A. G. Green and A. E. Woodhead, J. Chem. Soc. 97, 2388 (1910).
22. K. A. Hofnan, Ber. 45, 3329 (1912).
23. D. Sen, J. Am. Chem. Soc. 39, 747 (1917).
24. F. Forpelstroeder, Compt. Rend. 82, 331 (1876).
25. L. Gilchrist, J. Phys. Chem. 8, 539 (1904).
26. H. T. Buchener, Ber. 40, 3412 (1907).
27. I. S. Joffe and R. M. Petrikina, J. Russ. Phys. Chem. Soc. 62, 1101
(1930).
28. R. Lantz and J. Gascon, Bull. Soc. Chim. Fr. 55 (1960).
29. R. Lantz and J. Gascon, Bull. Soc. Chim. Fr. 727 (1961).
30. S. Goldschmidt, Bet. 53, 28 (1920).
31. S. Goldschrnidt, Bet. 55, 3216 (1922).
32. S. Goldschmidt, Bet. 55, 3220 (1922).
459
 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites
33. N. E. Khomutov and S. V. Gorbachev, Z F. Khim. 24, 1101 (1950).
34. D. M. Mohilner, R. N. Adams, and W. J. Argersinger, J. Am. Chem.
Soc. 84, 3618 (1962).
35. S. S. Lord and L. B. Rogers, Anal. Chem. 26, 284 (1954).
36. M. Doriomedoff, F. H. Cristofini, R. De Surville, M. Josefowicz,
L. T. Yu, and R. Buvet, J. Chim. Phys. 68, 1055 (1971).
37. M. Josefowicz, L. T. Yu, J. Perichon, and R. Buret, J. Polym. Sci.
22, 1187 (1969).
38. L. T. Yu, J. Petit, M. Josefowicz, G. Belorgey, and R. Buyer, C. R.
Acad. Sci., Set. 260, 5026 (1965).
39. M. F. Combarel, G. Balorgey, M. Josefowicz, L. T. Yu, and
R. Buyer, C. R. Acad. Sci., Set. C 262, 459 (1966).
40. L. T. Yu, S. Borreton, M. Josefowicz, and R. Buvet, Comm. Syrup.
Int. Chim. Macromol., IUPAC, Prague (1965).
41. P. Constantini, G. Belorgey, M. Josefowicz, and R. Buyer, C. R.
Acad. Sci., Set. C 258, 6421 (1964).
42. M. Josefowicz, Thesis, University of Paris (1963).
43. A. Volkov, Thesis, University of Paris VI (1983).
44. C. M. Carlin, L. J. Kepley, and A. J. Bard, J. Electrochem. Soc.
132, 353 (1985).
45. A. G. MacDiarmid, J. C. Chiang, M. Halpern, W. S. Huang, S. L.
Mu, N. L. D. Somasiri, W. Wu, and S. I. Yaniger, Mol. Cryst., Liq.
REVIEW
Cryst. 121, 173 (1985). Delivered by Ingenta
46. A. G. MacDiarmid, N. L. D. Somasiri, W. University
R. Salaneck, of Auckland Millard, J. R. Hollahan, and T. Bell, Techniques and Applica-
I. Lundstrsrn, B. Liedberg, M. A. Hasan, R. Erlandsson, IP : 130.216.12.217
and
P. Konrasson, Springer Series in Solid State Sciences 63, 178
(1985).
Thu, 30 Jun 2011 08:48:22
47. E. M. Genis and C. Tsintavis, J. Electroanal. Chem. 195, 109
(1985).
48. E. M. Genis, C. Tsintavis, and A. A. Syed, Mol. Cryst., Liq. Cryst.
121, 181 (1985).
49. J. P. Travers, J. Chroboczek, F. Devreux, F. Genoud,
M. Nechtschein, A. A. Syed, E. M. Genis, and C. Tsintavis, Mol.
Cryst. Liq. Cryst. 121, 195 (1985).
50. A. Volkov, G. Tourillon, P. C. Lacaze, and J. E. Dubols, J. Elec-
troanal. Chem. 115, 279 (1980).
51. G. Ramya, C. Renugadevi, C. R. K. Rao, and D. C. Trivedi, React.
Funct. Polym. 68, 701 (2008).
52. L. T. Yu, M. S. Borredon, M. Jozefowicz, G. Belorgey, and
R. Buvet, J. Polym. Sci. 10, 2931 (1987).
53. D. Vachon, R. O. Angus, F. L. Lu, M. Nowak, Z. X. Liu,
H. Schaffer, F. Wudl, and A. J. Heeger, Synth. Met. 18, 297 (1987).
54. J. Bacon and R. N. Adams, J. Am. Chem. Soc. 90, 6596 (1968).
55. E. M. Genis and C. Tsintavis, J. Electroanal. Chem. 200, 127
(1986).
56. A. F. Diaz and J. A. Logan, J. Electroanal. Chem. 111, 111 (1980).
57. R. Noufi, A. J. Nozik, J. White, and L. F. Warren, J. Electrochem.
Soc. 129, 226 (1982).
58. T. Kobayashi, H. Yoneyama, and H. Tamura, J. Electroanal. Chem.
161, 419 (1984).
59. A. Kitani, J. Yano, and K. Sasaki, Chem. Lett. 13, 1565 (1984).
60. E. M. Genis and M. Lapkowski, J. Electroanal. Chem. 220, 67
(1987).
61. T. Ohsaka, Y. Ohnuki, N. Oyama, G. Katagiri, and K. Kamlsako,
J. Electroanal. Chem. 161, 399 (1984).
62. B. Wang, J. Tang, and F. Wang, Synth. Met. 13, 329 (1986).
63. G. Mengoli, M. T. Munari, P. Bianco, and M. M. Musiani, J. Appl.
Polym. Sci. 26, 4247 (1981).
64. (a) M. Musiani, G. Mengoli, and F. Furlaneto, J. Appl. Polym. Sci.
29, 4433 (1984); (b) G. Mengoli, M. M. Musiani, B. Pelli, and
E. Vecchi, J. Appl. Polym. Sci. 28, 1125 (1983).
65. D. W. DeBerry, J. Electrochem. Sac. 132, 1022 (1985).
66. G. Mengoli, M. T. Munari, and C. Folonari, J. Electroanal. Chem.
124, 237 (1981).
67. E. W. Paul, A. J. Ricco, and M. S. Wrighton, J. Phys. Chem.
89, 1441 (1981).
460
Ameen et al.
68. B. Pfeiffer, A. Thyssen, M. Wolff, and J. W. Schultze, Int.
Workshop-Electrochemistry of Polymer Layers, Duisburg, F.R.G.,
17 (1986).
69. R. L. Hand and R. F. Nelson, J. Electrochem. Sac. 125, 1059
(1978).
70. R. L. Hand and R. F. Nelson, J. Am. Chem. Sac. 96, 850 (1974).
71. N. Oyama, Y. Ohnuki, K. Chiba, and T. Ohsaka, Chem. Lett.
12, 1759 (1983).
72. R. Noufi, A. J. Nozik, J. White, and L. F. Warren, J. Electrochem.
Soc. 129, 226 (1982).
73. B. A. Blajeni, I. Taniguchi, and J. O’M. Boekris, J. Electroanal.
Chem. 149, 291 (1983).
74. T. Kobayashi, H. Yoneyama, and H. Tamura, J. Electroanal. Chem.
161, 419 (1984).
75. E. M. Genis and M. Lapkowski, J. Electroanal. Chem. 220, 67
(1987).
76. E. M. Geniès and P. Noël, Synth. Met. 46, 285 (1992).
77. E. M. Genis and M. Lapkowski, Synth. Met. 21, 117 (1987).
78. E. M. Genis, M. Lapkowski, C. Santier, and E. Vieil, Synth. Met.
18, 631 (1987).
79. H. Inoue and H. Yoneyama, J. Electroanal. Chem. 233, 291 (1987).
80. G. Zotti, S. Cattarin, and N. Comlsso, J. Electroanal. Chem.
to: (1988).
239, 387
81. M.
tions of Plasma Chemistry, Wiley, New York (1974).
82. M. Shen, Plasma Chemistry of Polymers, Marcel Dekker,
New York (1976).
83. R. Hernandez, A. F. Diaz, R. Waltman, and J. Bargon, J. Phys.
Chem. 88, 3333 (1984).
84. B. Nayak and R. C. Bhakta, J. Appl. Electrochem. 13, 105 (1983).
85. (a) P. A. K. Nedungati, A. Gupta, S. K. Mukherji, and K. Zutshi,
J. Electrochem. Soc. 35, 302 (1986); (b) P. A. K. Nedungati,
A. Gupta, S. K. Mukherji, and K. Zutshi, Int. Workshop- Electro-
chemistry of Polymer Layers, Duisburg, F.R.G., Sept., 1.4 (1986).
86. K. Uvdal, M. Loglund, P. Danneton, L. Bertilsson, S. Strafstrom,
and W. R. Salaneck, Synth. Met. 29, 451 (1989).
87. N. Oyama, T. Ohsaka, and T. Shimizu, Anal. Chem. 57, 1526
(1985).
88. G. Hambitzer and J. Heitbaum, Int. Workshop-Electrochemistry of
Polymer Layers, Duisburg, F.R.G., 2.4 (1986).
89. T. Ohsaka, T. Okajima, and N. Oyama, J. Electroanal. Chem.
200, 159 (1986).
90. P. Snauwaert, R. Lazzaroni, J. Riga, and J. J. Verbist, Synth. Met.
21, 181 (1987).
91. W. Shenglong, W. Fosong, and G. Xiaohui, Synth. Met. 16, 99
(1988).
92. S. K. Manohar, A. G. MacDiarmid, K. Kromack, J. M. Ginder, and
A. J. Epstein, Synth. Met. 29, 349 (1989).
93. E. M. Genis, J. F, Penneau, and M. Lapkowski, New J. Chem.
12, 765 (1988).
94. T. Hahiwara, T. Demura, and K. Iwata, Synth. Met. 18, 317 (1987).
95. P. Snauwaert, R. Lazzaroni, J. Riga, and J. J. Verbist, Synth. Met.
18, 335 (1987).
96. (a) W. R. Heineman, H. J. Wieck, and A. M. Yacynych, Anal.
Chem. 52, 345 (1980); (b) N. Oyama, K. Chiba, Y. Ohnuki, and
T. Ohsaka, Nippon Kagaku Kaishi 6, 1172 (1985); (c) J. Yano,
A. Kitani, R. Vasquez, and K. Sasaki, Nippon Kagaku Kaishi
6, 1124 (1985); (d) K. Chiba, T. Ohsaka, Y. Ohnuki, and N. Oyama,
J. Electroanal. Chem. 219, 117 (1987).
97. C. Barbero, J. Zerbino, L. Sereno, and D. Posadas, Electrochim.
Acta 32, 693 (1987).
98. A. Kitani, J. Yano, and K. Sasaki, J. Electroanal. Chem. 209, 227
(1986).
99. K. Sasaki, M. Kaya, J. Yano, A. Kitani, and A. Kunai, J. Elec-
troanal. Chem. 215, 401 (1986).
100. (a) N. Oyama, K. Kirabayashi, and T. Ohsaka, Bull. Chem. Soc.
Jpn. 59, 2071 (1986); (b) N. Oyama and T. Ohsaka, Synth. Met.
Sci. Adv. Mater. 2, 441–462, 2010
Ameen et al. A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites

18, 375 (1987); (c) T. Ohsaka, K. Hirabayashi, and N. Oyama,
Bull. Chem. Soc. Jpn. 59, 3423 (1986); (d) N. Oyama, T. Hirokawa,
S. Yamamura, N. Ushizawa, and T. Shimomura, Anal. Chem.
59, 258 (1987); (e) A. Kitani, J. Yano, A. Kunai, and K. Sasaki,
J. Electroanal. Chem. 221, 69 (1987); (f) N. Oyarna, T. Ohsaka,
and M. Nakanishi, J. Macromol. Sci. 24, 375 (1987).
101. U. Hayat, P. N. Bartlett, G. H. Dodd, and J. Barker, J. Electroanal.
Chem. 18, 371 (1987).
102. Y. Ohsawa, M. Ishikawa, T. Miyamato, Y. Murofushi, and
M. Kawai, Synth. Met. 18, 371 (1987).
103. U. Hayat, P. N. Bartlett, and G. H. Dodd, Polym. Commun. 27, 362
(1986).
104. K. A. Maeor, Y. O. Su, L. A. Miller, and T. G. Spiro, Inorg. Chem.
26, 2594 (1987).
105. (a) H. Kuzmany, E. M. Geniès, and A. A. Syed, Springer Series
in Solid State Sciences 63, 223 (1985); (b) H. Kumany and N. S.
Sariciftci, Synth. Met. 18, 353 (1987).
106. H. A. Pohl and E. H. Engelhardt, J. Phys. Chem. 66, 2085 (1962).
107. M. S. Yun and D. P. Kang, Synth. Met. 29, 343 (1989).
108. E. M. Geneis and M. Lapkowski, J. Electroanal. Chem. 236, 199
(1987).
109. S. Ameen, V. Ali, M. Zulfequar, M. M. Haq, and M. Husain, Cur-
134. B. Lundberg, W. R. Salaneck, and I. Lundstrsm, Synth. Met. 21, 143
(1987).
135. W. R. Salaneck, I. Lundstrsm, T. Hjertberg, C. B. Duke, A. Paton,
E. M. Conwell, W. S. Huang, N. L. D. Somasiri, A. F. Richter, and
A. G. MacDiarmid, Synth. Met. 18, 291 (1987).
136. F. Wudl. R. O. Angus, F. L. Lu, P. M. Allemand, D. J. Vachon,
M. Nowak, Z. X. Liu, and A. J. Heeger, J. Am. Chem. Soc.
109, 3677 (1987).
137. J. P. Travers and M. Nechtachein, Synth. Met. 21, 135 (1987).
138. M. Nechtschein and C. Santier, J. Phys. 47, 935 (1986).
139. M. Nechtschein, C. Santier, J. P. Travers, A. Alix, and M. Ripert,
Synth. Met. 18, 311 (1987).
140. (a) A. Thyssen, A. Hochfeld, R. Kessel, A. Meyer, and J. W.
Schulzte, Synth. Met. 29, 357 (1989); (b) A. Thyssen, A. Borgerd-
ing, and J. W. Schulzte, Macromol. Chem. 8, 143 (1987).
141. A. Redondo, E. TicianeUi, and S. Gottcsfeld, Synth. Met. 29, 265
(1989).
142. (a) B. Wessling and H. Volk, Synth. Met. 16, 127 (1986);
(b) A. Andreatta, Y. Cao, J. C. Chiang, A. J. Heeger, and P. Smith,
Synth. Met. 26, 383 (1988); (c) R. H. Baughman, J. F. Wolf,
E. Eckardt, and L. W. Shacklette, Synth. Met. 25, 121 (1988);
(d) J. Langer, Solid State Commun. 26, 839 (1978).

REVIEW
rent Applied Physics 9, 478 (2009). Delivered by Ingenta to:
143. M. Doriomedoff, Thesis, University of Paris VI (1974).
110. S. Ameen, V. Ali, M. Zulfequar, M. M. Haq, and M.University 144. A.
Husain, Cur- of Auckland Watanabe, K. Mori, Y. Iwasaki, and Y. Nakamura, J. Chem.
Soc., Chem. Commun. 3 (1987).
rent Applied Physics 7, 215 (2007). IP : 130.216.12.217
145. S. Li, Y. Cao, and Z. Xue, Synth. Met. 20, 141 (1987).
111. S. Ameen, V. Ali, M. Zulfequar, M. M. Haq, and M. Husain, Phys-
ica B 403, 2861 (2008).
Thu, 30 Jun 2011 146.08:48:22
G. Bidan, E. M. Genies, and J. F. Penneau, J. Electroanal. Chem.
271, 59 (1989).
112. S. Ameen, V. Ali, M. Zulfequar, M. M. Haq, and M. Husain,
147. F. Dawans, J. Galard, P. Texssif, and R. Traynard, J. Polym. Sci.
J. Appl. Polym. Sci. 112, 2315 (2009).
4, 1385 (1963).
113. S. Ameen, V. Ali, M. Zulfequar, M. M. Haq, and M. Husain, Phys-
148. J. Gallard, M. Nechtschein, M. Soutif, and R. Traynard, Bull. Soc.
ica E 40, 2805 (2008).
Chim. Fr. 2209 (1963).
114. S. Ameen, G. B. V. S. Lakshmi, and M. Husain, J. Phys. D: Appl.
149. G. Mengoli, M. M. Nusiani, G. Zotti, and S. Valcher, J. Electroanal.
Phys. 42, 105104 (2009).
Chem. 202, 217 (1986).
115. S. Ameen, V. Ali, M. Zulfequar, M. M. Haq, and M. Husain,
150. (a) P. M. McManus, S. C. Yang, and R. J. Cushman, J. Chem. Soc.
J. Polym. Sci., Part B: Polym. Phys. 45, 2682 (2007).
Chem. Commun. 1556 (1985); (b) R. J. Cushman, P. McManus,
116. S. Ameen, V. Ali, M. Zulfequar, M. M. Haq, and M. Husain, Cen-
and S. C. Yang, Macromol. Chem., Rapid Commun. 8, 69 (1987);
tral. Europ. J. Chem. 4, 565 (2006).
(c) R. J. Cushman, P. McManus, and S. C. Yang, J. Electroanal.
117. Y. B. Shim and S. M. Park, Synth. Met. 29, 169 (1989).
Chem. 291, 335 (1986); (d) A. Watanabe, K. Mori, Y. Iwasaki,
118. G. Zotti, S. Cattarin, and N. Comisso, J. Electroanal. Chem.
Y. Nakamura, and S. Niizuma, Macromolecules 20, 1793 (1987).
235, 259 (1987). 151. N. S. Sariciftci and H. Kuzmany, Synth. Met. 21, 157 (1987).
119. A. Kitani and K. Sasaki, Stud. Org. Chem. 30, 377 (1987). 152. V. A. Krylov, Y. I. Kurys, and V. D. Pokhodenko, Theore. Expert.
120. E. M. Genis, J. F. Penneau, M. Lapkowski, and A. Boyle, J. Elec- Chem. 29, 154 (1993).
troanal. Chem. 269, 63 (1989). 153. E. M. Genis and E. Vieil, Synth. Met. 20, 97 (1987).
121. E. M. Genis, M. Lapkowski, and J. F. Penneau, J. Electroanal. 154. W. R. Salaneck, I. Lundstrm, W. S. Huang, and A. G. MacDiarmid,
Chem. 249, 97 (1988). Synth. Met. 13, 291 (1986).
122. S. Wawzonek and T. W. MacIntyre, J. Electrochem. Soc. 114, 1025 155. (a) J. Tanguy, N. Mermillod, and M. Hoclet, Synth. Met. 18, 7
(1967). (1986); (b) N. Mermillod, J. Tanguy, M. Hoclet, and A. A. Syed,
123. R. Holze, J. Electroanal. Chem. 224, 253 (1971). Synth. Met. 18, 359 (1986).
124. M. Breitenbach and K. H. Hecker, J. Electroanal. Chem. 29, 309 156. J. Yue and A. J. Epstein, Macromolecules 24, 4441 (1991).
(1971). 157. J. Zak and J. W. Strojek, Acta Polytech. Stand. 178, 35 (1987).
125. M. Breitenbach and K. H. Hecker, J. Electroanal. Chem. 33, 45 158. A. Akhtar, H. A. Weakliem, R. M. Paiste, and K. Gaughan, Synth.
(1971). Met. 26, 203 (1988).
126. V. P. Parini, Vysokomol. Soedin. 3, 1870 (1961). 159. M. Trojanowicz, T. Krawczynski, and P. W. Alexander, Chem. Anal.
127. V. I. Maleev, Vysokomol. Soedin. 4, 848 (1962). 42, 199 (1997).
128. (a) M. Gohlamian and A. Q. Contractor, J. Electroanal. Chem. 160. D. T. Hoa, T. N. Suresh Kumar, N. S. Punekar, R. S. Srinivasa,
252, 126 (1988); (b) J. C. Chiang and A. G. MacDiarmid, Synth. R. Lal, and A. Q. Contractor, Anal. Chem. 64, 2645 (1992).
Met. 13, 193 (1988). 161. A. A. Karyakin, O. A. Bobrova, L. V. Lukachova, and E. E.
129. W. S. Huang. B. D. Humphrey, and A. G. MacDiarmid, J. Chem. Karyakina, Sens. Actuators B 33, 34 (1996).
Soc. 82, 2385 (1986); (b) A. G. MacDiarmid, J. C. Chiang, A. F. 162. G. Erdogdu and A. E. Karagozler, Talanta 44, 2011 (1997).
Richter, and A. J. Epstein, Synth. Met. 18, 285 (1987). 163. E. I. Iwuoha, D. S. Villaverde, N. P. Garcia, M. R. Smyth, and
130. A. Brahma, Solid State Commun. 57, 673 (1986). J. M. Pingarron, Biosens. Bioelectron. 12, 749 (1997).
131. A. Kitani, I. Izumi, J. Yano, Y. Hiromoto, and K. Sasaki, Bull. 164. A. N. Ivanov, L. V. Lukachova, G. A. Evtugyn, E. E. Karayakina,
Chem. Soc. Jpn. 57, 2254 (1984). S. G. Kiseleva, H. C. Budnikov, A. V. Orlov, G. P. Karpacheva, and
132. S. H. Glarum and J. H. Marshall, J. Electrochem. Soc. 134, 142 A. A. Karyakin, Bioelectrochemistry 55, 75 (2002).
(1987). 165. L. V. Lukachova, A. A. Karyakin, E. E. Karyakina, and L. Gorton,
133. G. E. Wnek, Synth. Met. 15, 213 (1986). Sens. Actuators B 44, 356 (1997).

Sci. Adv. Mater. 2, 441–462, 2010 461

 A Review on Synthesis Processing, Chemical and Conduction Properties of PANI and Its Nanocomposites Ameen et al.

166. O. A. Sadik and J. M. V. Emon, Biosens. Bioelectron. 11, i (1996). 186. J. Barthel, H. J. Gores, and G. Schmeer, Ber. Bunsenges. Phys.
167. S. B. Adeloju and G. G. Wallace, The Analyst 121, 699 (1996). Chem. 83, 911 (1979).
168. S. Cosnier, Biosens. Bioelectron. 14, 443 (1999). 187. M. Salomon and E. J. Plichta, Electrochim. Acta 29, 911 (1979).
169. T. A. Sergeyeva, N. V. Lavrik, and A. E. Rachkov, Sens. Actua- 188. G. Jones and M. Dole, J. Am. Chem. Soc. 52, 2245 (1930).
tors, B 34, 283 (1996). 189. C. Masson and J. B. Culvern, J. Am. Chem. Soc. 71, 2387 (1945).
170. M. Gerard, A. Chaubey, and B. D. Malhotra, Biosens. Bioelectron. 190. J. F. Roughton, J. Appl. Chem. 1, 2141 (1951).
17, 345 (2002). 191. G. Tzamalis, N. A Zaidi, C. C. Z. Homes, and A. P. Monkman,
171. Z. M. Tahir and E. C. Alocilja, Biosens. Bioelectron. 18, 813 Phys. Condens. Matter 13, 6306 (2001).
(2003). 192. W. P. Lee, K. R. Brenneman, A. D. Gudmundsdottir, M. S. Platz,
172. Z. M. Tahir, E. C. Alocilja, and D. L. Grooms, Sensors Journal P. K. Kahol, A. P. Monkman, and A. J. Epstein, Synth. Met.
IEEE 5, 757 (2005). 101, 819 (1999).
173. Z. M. Tahir, E. C. Alocilja, and D. L. Grooms, Sensors 7, 1123 193. P. K. Kohol, Solid State Commun. 124, 93 (2002).
(2007). 194. N. Masnhara, E. Boetcher, J. P. Mc, G. G. Farland, S. David, and
174. F. Cristofini, R. De Surville, M. Josefowicz, L. T. Yu, and R. Buvet, K. Nancy, Physica D 89, 169 (1995).
C. R. Acad. Sci., Set. C 268, 1346 (1969). 195. C. Sheats and J. R Roitman, Account of Chemical Research
175. A. Kitani, M. Kaya, and K. Kitani, Denki Kagaku 52, 847 (1984). 32, 2000 (1999).
176. A. Kitani, M. Kaya, and K. Kitani, J. Electrochem. Soc. 133, 1069 196. A. B. R. Mayer, Poly. Adv. Technol. 12, 96 (2001).
(1986). 197. R. Gangopadhyay and A. De, Chem. Mater. 12, 608 (2000).
177. A. G. MacDiarmid, J. C. Chiang, M. Halpern, W. S. Huang, J. R. 198. J. Ditiger, S. Klein, and T. W. Ebbesen, Adv. Mater. 18, 1267
Krawczyk, R. J. Mammone, S. L. Mu, N. L. D. Somasiri, and (2006).
W. Wu, Polym. Prepr. 25, 248 (1984). 199. V. Bliznyuk, B. Ruhstaller, P. J. Brock, U. Scherf, and S. A. Carter,
178. A. G. MacDiarmid, S. L. Mu, N. L. D. Somasiri, and W. Wu, Mol. Adv. Mater. 11, 1257 (1999).
REVIEW

Cryst. Liq. Cryst. 121, 187 (1985). Delivered by Ingenta to: D. Corr, D. Lupo, F. Pichot, and M. Ryan, Adv. Mater.
200. U. Bach,
179. M. Gholamian, J. Sundaram, and A. Q. Contractor, University
Langmuir of Auckland
14, 845 (2002).
3, 741 (1987). 201. T. He, Y. Ma, Y. Cao,W. Yang, and J. Yao, J. Electro. Anal. Chem.
IP : 130.216.12.217
180. E. M. Genis, P. Hany, and C. Santier, J. Appl. Electrochem. 18, 751 514, 129 (2001).
(1988).
Thu, 30 Jun 2011 08:48:22
202. Y. R. Leroux, J. C. Lacroix, K. I. Chane-Ching, C. Fave, N. Felidj,
181. T. Nakajima and T. Kawogoe, Synth. Met. 28, 629 (1989). G. Levi, J. Aubard, J. R. Krenn, and A. Hohenau, J. Am. Chem.
182. M. Mitzumoto, M. Namba, S. Nishimura, H. Miyadera, M. Koseki, Soc. 127, 16022 (2005).
and Y. Kobayashi, Synth. Met. 28, 639 (1989). 203. S. Ameen, M. S. Akhtar, G. S. Kim, Y. S. Kim, O. B. Yang, and
183. E. M. Genis, P. Hany, and C. Santier, Synth. Met. 28, 647 (1989). H. S. Shin, J. Alloys Comp. 487, 382 (2009).
184. L. W. Shacldette, R. Hatami, T. R. Jow, and M. Maxfield, Synth. 204. S. Ameen, S. G. Ansari, M. Song, Y. S. Kim, and H. S. Shin,
Met. 28, 655 (1989). Superlattices Microstruct. 46, 745 (2009).
185. H. Ikeda, R. Hatami, T. Saito, and H. Tamura, Denki Kagaku 205. S. Ameen, M. S. Akhtar, S. G. Ansari, O. B. Yang, and H. S. Shin,
45, 314 (1977). Superlattices Microstruct. 46, 872 (2009).

Received: 5 February 2010. Accepted: 8 May 2010.

462 Sci. Adv. Mater. 2, 441–462, 2010