Polyaniline: Synthesis, Properties, and Application

Abstract

The methods of synthesis and the properties of polyaniline—a representative of the family of conducting polymers—are reviewed briefly. It is shown that variation in the conditions of aniline polymerization makes it possible to synthesize polymer materials with the desired structures and properties and, thus, to provide for the use of polyaniline in various fields of science and engineering. Special attention is given to the matrix synthesis of polyaniline as the main approach to obtain electroactive and conducting composite materials. The use of polyaniline and the related composite materials in polymer electronics is analyzed briefly.

Full text

ISSN 18112382, Polymer Science, Ser. C, 2014, Vol. 56, No. 1, pp. 144–153. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © Zh.A. Boeva, V.G. Sergeyev, 2014, published in Vysokomolekulyarnye Soedineniya, Ser. C, 2014, Vol. 56, No. 1, pp. 153–164.
144
INTRODUCTION
Conducting polymers belong to a peculiar family of
compounds composed of monomer units with conju
gated chemical bonds that, under certain conditions
(doping), ensure the electron conductivity of the poly
mer. From the commercial viewpoint, these polymers
show promise for the production of materials for vari
ous applications; they can replace metals and semicon
ductors, because they feature conductivity, low density,
and easy processability. Polyaniline (PANI)—a repre
sentatives from the family of conducting polymers—is
distinguished by easy synthesis and high environmental
stability.
Polyaniline consists of monomer units built from
reduced (
y
) and oxidized (
1
y
) blocks:
,
where
0
≤
y
≤
1
.
The redox state of the polymer is determined by the value of
y
, which may vary continuously from zero to unity.
At
y
= 0.5, polyaniline occurs in the form of emeraldine;
у
= 0 corresponds to the fully oxidized form, pernigra
niline, while
у
= 1 corresponds to the fully reduced form, leucoemeraldine [1]. Pernigraniline and emeraldine may
occur as either salts or bases [2, 3]:
*H
NH
NNN*
y1 − yx
*NNNN*
n
NNNN
HHHH
A
A
A
A
n
*H
NH
NNN*
n
*H
NH
NNN*
A
A
n
*H
NH
NH
NH
N*
n
Blue pernigraniline base Blue pernigraniline salt
Violet emeraldine base Green emeraldine salt
Colorless leucoemeraldine
–2e
–2HA
+2e
+2HA
–2e
–2HA
+2e
+2HA
–2e
–2HA
+2e
+2HA
–2e
–2HA +2e
+2HA
+4HA
–4HA
+2HA
–2HA
Polyaniline: Synthesis, Properties, and Application
Zh. A. Boeva* and V. G. Sergeyev
Faculty of Chemistry, Moscow State University, Moscow, 119991 Russia
*email: jboyeva@gmail.com
Received September 23, 2013
Abstract
—The methods of synthesis and the properties of polyaniline—a representative of the family of con
ducting polymers—are reviewed briefly. It is shown that variation in the conditions of aniline polymerization
makes it possible to synthesize polymer materials with the desired structures and properties and, thus, to pro
vide for the use of polyaniline in various fields of science and engineering. Special attention is given to the
matrix synthesis of polyaniline as the main approach to obtain electroactive and conducting composite mate
rials. The use of polyaniline and the related composite materials in polymer electronics is analyzed briefly.
DOI:
10.1134/S1811238214010032

POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 145
The forms of PANI have different colors, stabili
ties, and conductivities. Leucoemeraldine is a color
less substance characterized by an absorption band at
343 nm (in
N
methylpyrrolidone) [1]. Since this poly
mer contains only benzene and amino groups, leucoe
meraldine slowly oxidizes in air and is not electrically
conducting. Leucoemeraldine may be oxidized in an
acidic medium to the conducting emeraldine salt
(
p
doping). Pernigraniline is composed of alternating
aminobenzene and quinonediimine fragments.
Because the quinonediimine group is unstable in the
presence of nucleophiles, specifically water, pernigra
niline and its salts readily decompose in air. The emer
aldine salt of PANI is formed during protonation of
the emeraldine base with organic and inorganic acids.
As a rule, this process is referred to as doping. When
PANI in the form of the emeraldine base is treated
with acids, protons primarily interact with the imine
atoms of nitrogen; as a result, polycations appear [4].
Because positive charges localized on neighboring
nitrogen atoms increase the total energy of the poly
mer system, electron density tends to undergo redistri
bution; as a consequence, “unpairing” of the lone
electron pair of nitrogen atoms occurs without any
change in the amount of electrons in the system [5]. In
a chain, cation radicals appear; they are delocalized
over a certain conjugation length and provide the elec
tron conductivity of the polymer. The electron con
ductivity of polyaniline in the form of emeraldine
depends on its protonation and increases by ten orders
of magnitude as the degree of protonation is increased
from 0 to 20% [6]. Note that this behavior is typical for
polyaniline solely. The delocalization of PANI cation
radicals may occur not only via the intramolecular
mechanism but also via the intermolecular mecha
nism. In this case, chains of the conducting polymer
should be oriented in one direction so that the transfer
of
π
electrons from one polymer chain to another is
ensured [7]. This process occurs as a rule via van der
Waals interactions between benzene and quinoid rings
of PANI (
π
stacking) [8, 9]. The electron conductivity
of such a structured polyaniline may be as high as
(1.1–1.2)
×
10
3
S/cm [9].
USE OF POLYANILINE IN ORGANIC
ELECTRONICS
The use of polyaniline in various areas of electron
ics and engineering is limited because its conductivity
is unstable at neutral pH and temperatures above
150
°
С
owing to dedoping of polymer chains. However,
in “closed” systems PANI may be used as an electrode
material.
Supramolecular structure of PANI:
Globules, nanotubes, fibrils
Properties
Use
Electron
conductivity
Semiconducting
properties
Electrical activity
Solar batteries
Transparent
antistatic
coatings
Flexible electrodes
Organic field transistors
Conducting fibers
Electromagnetic
screens
Actuators
Storage devices
Electrochromic glass
Anticorrosive coatings
Catalysts
Supercapacitors

146
POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
BOEVA, SERGEYEV
For example, fibrillar PANI was used to design a
rechargeable battery [10] with a specific energy of
280 (W h)/kg. On the basis of the composite material, the
secondary current source Zn–PANI–graphite with a
specific energy of 160 (W h)/kg was developed [11]. In
terms of specific energy, these current sources surpass
commercial analogs. However, their main drawback is
low stability during recharging; that is, on average, batter
ies lose 0.15% specific energy per cycle owing to degrada
tion of polyaniline and passivation of zinc. The advan
tages of PANIbased batteries are their reprocessability
and relative environmental compatibility during utiliza
tion in comparison to those of traditional current
sources.
Composite materials based on PANI are used more
frequently to manufacture supercapacitors, owing to
the high specific capacitance of the material, 450–
900 F/g [12–14], and the stability during recharging
(up to 1000 cycles). Graphene or carbon nanotubes,
which increase the capacitance characteristics of the
material, are used as the second component of these
composite materials [15, 16]. Note that electrodes
composed of PANI electrochemically deposited on
steel, as well as composite materials based on manga
nese oxide, likewise possess high capacitance and can
endure a large number of recharging cycles [17, 18].
Another application area of PANI in organic elec
tronics includes the design of photochromic devices
with modulated conductivity [19], organic field tran
sistors [20, 21], and polymer light diodes [22–24]. The
use of composite materials based on conducting poly
mers for the manufacture of transistors is often limited
by the low mobility of charge carriers and the grain
boundary effect. Nevertheless, the available tech
niques make it possible to prepare materials with a
high mobility of charge carriers (up to 3 cm
2
/(Vs))
and a high ratio of switchon/switchoff currents
(above
10
4
) [21, 25]. A technique of vacuum deposi
tion of oligomeric PANI and fullerenes to create
organic field transistors was developed. For this pur
pose, an insulator layer composed of oligomeric PANI
over which a fullerene layer functions as a semicon
ductor is evaporated on an aluminum gate electrode.
Aluminum evaporated over the fullerene layer serves as
a drain and a source of such transistor configuration.
The asprepared organic field transistors feature
highly reproducible characteristics; however, the ratio
of switchon/switchoff currents of the device is
~500
[26].
The efficiency of polymer lightemitting diodes con
taining PANI as conductive or emission layers depends
on the method of preparing the conducting polymer. For
example, lightemitting diodes based on PANI stabi
lized in organic solvents owing to the use of a low
molecularmass dopant possess relatively low efficiency
in comparison to that of organic semiconductors based
on poly(3,4ethylenedioxythiophene) [24].
In contrast, lightemitting diodes designed with the
use of the graft copolymer PANI–poly(4styrene
sulfonic acid) [22] surpass the known polymer analogs
in terms of performance characteristics and stability
because of the high chemical stability of the material.
Polyaniline doped with camphorsulfonic acid has
found use as an element of an electrically programma
ble permanent storage device [27] whose performance
mechanism is similar to that of a fuse.
Polyaniline deposited on tin fluoroxide is used
instead of platinum as an internal electrode in photo
electric cells (solar cells) [28, 29]. The replacement of
metal with the conducting polymer results in a gain in
the photoelectric conversion coefficient of a photo
electric cell to 7% (6% in the case of platinum) owing
to a more effective reduction of iodine on the elec
trode surface [30]. The employment of nanostructured
PANI in these systems makes it possible to increase
the efficiency of photoelectric cells to 11% [31], and
the manufacture of electrodes based on graphite and
PANI makes it possible to reduce the cost of solar bat
teries without any decrease in their performance [32].
When PANI is used as a component of an elec
tronic device, special conditions of synthesis or modi
fication of this conducting polymer are used to impart
the desired properties to it.
SYNTHESIS OF POLYANILINE
WITH THE DESIRED SUPRAMOLECULAR
STRUCTURE AND PROPERTIES
Polyaniline is, as a rule, prepared via the chemical
or electrochemical polymerization of aniline in the
presence of dopants. Depending on the synthesis pro
cedure; the temperature and time regimes; the types of
oxidant, dopant, and solvent; the voltage applied on
the electrode; etc., polyaniline featuring different
properties—namely, the structure, morphology, and
redox state—may be prepared.
Electrochemical Polymerization
It is commonly believed that the electrochemical
synthesis gives rise to the purest product, which is free
of admixtures and does not need special procedures
for the purification of polyaniline from the solvent and
unreacted monomer and initiator molecules. The
polymerization of aniline occurs on an electrode made
of inert conducting material. The electrochemical
polymerization of aniline is most often conducted in
aqueous solutions containing background electrolytes
and an acid [33].
In the case of the electrochemical synthesis of
polyaniline, potentiostatic, galvanostatic, and poten
tiodynamic methods are applied [34]. In the first case,
the potential has a fixed value on the order of 0.7–
1.2 V (against a saturated calomel electrode) [35]; in
the last case, the potential varies in a cyclic mode from
–0.2 to 0.7–1.2 V (against a saturated calomel elec
trode). In the galvanostatic regime of aniline polymer

POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 147
ization, the fixed value of current density does not
exceed 10 mA/cm
2
[36].
The electrochemical polymerization of aniline,
whose most important aspects are considered in detail
in reviews [37, 38], makes it possible to synthesize
polyaniline with different properties and morpholo
gies. PANIbased composite materials prepared elec
trochemically have found use in organic field transis
tors [39, 40] and rechargeable batteries [10, 11].
Chemical Polymerization
The chemical polymerization of aniline is con
ducted with the use of various oxidants, among which
ammonium persulfate is most commonly used [41]. In
the presence of this oxidant, polyaniline is formed
with the highest yield (90%); it features high conduc
tivity (
~1.2
S/cm) and intrinsic viscosity in
N
meth
ylpyrrolidone (1.17 dL/g).
In order to prepare polyaniline in the form of the
emeraldine salt, polymerization is conducted in an
acidic medium (1 < pH
≤
3
) with the use of various
acids or buffer solutions.
The chemical synthesis of polyaniline is the simplest
way to prepare conducting polymers with various physic
ochemical properties and supermolecular structures.
Note that the conducting polymer may be applied on any
substrate (matrix). This circumstance gives chemical
synthesis an indisputable advantage over electrochemical
synthesis, in which a substrate must be a conductor.
pH < 3
Aniline
Hard template Monomer adsorption
on hard template
Oxidant
Oxidation of monomer—
polymerization
Hard template
with adsorbed monomer
PANI adsorbed on template—
final product
Partially negative charge
,
Anilinium cation,
Oxidized anilinium cation—reactive species
,
polyaniline
.
Scheme 1.

148
POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
BOEVA, SERGEYEV
Matrix (template) polymerization.
Matrix (tem
plate) polymerization [42] implies the chemical trans
formation of monomers or oligomers into macromole
cules in accordance with the structural–chemical infor
mation derived from the sequence of macromolecular
units of the template present in the reaction system.
During the template polyreaction, organization of the
monomer with the template occurs via various interac
tions (hydrogen bonds, Coulomb interactions, covalent
bonds, hydrophobic interactions); as a result, template
effects appear. Thus, template polymerization makes it
possible to control the composition and arrangement of
chemical units, the degree of polymerization, and the
isomeric composition of a daughter macromolecule and
to change the kinetics of the polyreaction [43]. In the
modern literature devoted to PANI,
template
implies
not only the polymer occurring in the common phase
with the monomer but also a solid substrate exhibiting
template effects. Therefore, templates are divided into
two kinds: hard and soft.
Hard templates
are inorganic
substrates than can interact with the monomer and
change both the parameters of the polymerization pro
cess and the morphology of the resulting polymer. Tem
plate polymerization occurs at the interface between the
hard template and the monomer and initiator solution.
Soft templates
imply surfactants and polymers [44].
Hard templates.
The general scheme of aniline poly
merization in the presence of a hard template (carbon
nanotubes, graphite, inorganic oxides) includes adsorp
tion of the monomer or aniline cation radical on the
matrix surface and polymerization (see Scheme 1).
pH < 3
Aniline
Oxidant
Soft template—
surfactant micelles
Growth of PANI chains into the
hydrophobic cores of the micelles
Partially negative charge
Anilinium cation
,
Oxidized anilinium cation—reactive species
Polyaniline
or p
artially negative
group
Entanglement
of micelles by PANI chains
Growth of PANI chains
near polar groups,
inversion of micelles
Sorption or solubilization of the
monomer by surfactant micelles
Scheme 2.

POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 149
The use of inorganic materials as templates makes
it possible to obtain composites in situ that combine
such properties of PANI as electron conductivity and
reactivity with respect to acid–base and redox interac
tions with mechanical characteristics of the template
[45, 46]. This approach is the most suitable when
PANI is used in the form of electrochromic glass [47],
supercapacitors and secondary cells [48], sensors [49],
and anticorrosive coatings [50].
The employment of anodized aluminum oxide or
vanadium oxide [51–52] as a hard template offers a
way to obtain composite materials with the fibrillar
morphology of PANI and to use these materials in
field emitters [51, 52] and lithiumion batteries [54].
If the chemical synthesis of polyaniline is per
formed in the presence of amorphous carbon, the
resulting composite material may be used as an indica
tor electrode suitable for determining various organic
compounds [49].
With the use of hard template, such as carbon nan
otubes [55] and graphene and their derivatives formed
as a result of oxidation and chemical modification [12,
13, 15, 16, 56] in the chemical polymerization of
aniline, composite materials with high capacitance
characteristics were produced [12, 13] and sensors
were manufactured on their basis [57].
Soft templates.
Polyaniline–surfactant polymer col
loid complexes
. In the presence of a soft template
(a surfactant), the polymerization of aniline occurs
around micelles of the surfactant once its first or sec
ond critical micelle concentration is attained [43].
The polymerization of aniline with the participation of
a surfactant as a soft template, which includes the
interaction of an aniline monomer or a cation radical
with surfactant micelles and the formation of PANI,
may be schematically presented as follows (see
Scheme 2).
Moreover, aniline may be solubilized by micelles
[58]. In both cases, the structure of the micelles deter
mines the morphology of the resulting conducting
polymer. For example, the use of cetyltrimethylam
monium bromide in the polymerization of aniline ini
tiated by ammonium persulfate leads to the formation
of PANI nanofibils with diameters of 60–90 nm and
lengths of ~1
μ
m [59]. Along with cationic surfactants,
compounds able to function as both dopants and
structuring agents are used in the chemical polymer
ization of aniline. For example, PANI nanotubes and
nanofibrils with controlled diameters may be prepared
with the use of
β
naphthalenesulfonic acid [60].
For the synthesis of polyaniline soluble in organic
solvents and/or aqueous media, it is possible to use 4
dodecylbenzenesulfonic acid [61–63]—which serves
simultaneously as a dopant and a counterion to pro
vide for solubility of PANI—as well as sodium dodecyl
sulfate [64–66], bis(ethylhexyl) sulfosuccinate, tet
radecyltrimethylammonium bromide [67], and dode
cyltrimethylammonium bromide [66] in combination
with hydrochloric acid, sulfuric acid,
p
toluene
NH
2
NH
2
H
N
NH2
H
NH
N
NH2
.
+
NH3
Cl
N
H
H
N
N
H
H
N
SO3
O3S
O3S
O3S
SO3
O3S
O3S
SO3
SO3
SO3
SO3
SO3
SO3
SO3
O3S
O3S
Oxidant
Oxidant
+
polyelectrolyte
template
Scheme 3.

150
POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
BOEVA, SERGEYEV
sulfonic acid, camphorsulfonic acid [68], or sulfosali
cylic acid [69] as dopants. In the case of 4dodecyl
benzenesulfonic acid, a product soluble in both water
[61] and chloroform [70] was isolated. The composite
materials based on polyaniline and surfactants have
been used in solar cells [71, 72].
Polymerization of aniline in the presence of poly
meric templates
:
Macromolecular templates.
PANI
with the desired morphology is synthesized via tem
plate polymerization in the presence of macromolec
ular templates—polyanions capable of undergoing
electrostatic interactions with PANI—and watersol
uble polymers that can form hydrogen bonds [73, 74].
The polyelectrolyte template (a polyacid) serves as a
highmolecularmass counterion that not only stabi
lizes polyaniline particles in a solution but also dopes
polyaniline, thereby providing for the formation of
the watersoluble conducting product [75] (see
Scheme 3).
When this template is used as a dopant, the thermal
stability of conductivity improves because the high
molecularmass dopant, as opposed to the low
molecularmass dopant, is removed at elevated tem
peratures only during decomposition [76]. If water
soluble polymers are used as templates, PANI is syn
thesized in the presence of lowmolecularmass acids
in order to obtain stable conducting dispersions.
Ammonium persulfate is usually used as an oxi
dizer of aniline in the template polymerization [74]. In
addition, in the polymerization of aniline, it is possible
to use hydrogen peroxide, whose oxidation is cata
lyzed by hemoglobin [77] or peroxidases [73, 78, 79],
as well as oxygen dissolved in the reaction mixture. In
the latter case, the oxidation of the substrate is cata
lyzed by laccases [80]. Polymerization is performed as
a rule in the presence of strong polyacids, such as
poly(4styrenesulfonic acid) and poly(2acrylamido
2methyl1propanesulfonic acid) [81–83], as well as
weak polyacids, such as poly(vinylphosphonic acid)
[84] and poly(acrylic acid) [85]. Along with polyelec
trolytes, polymers able to form hydrogen bonds with
polyaniline, poly(vinyl alcohol) [86], polyvinylpyri
dine, polyvinylpyrrolidone [87], polyacrylamide [88],
hydroxypropyl cellulose [74], etc., in combination
with dopants—lowmolecularmass acids—are used
as templates.
Template polymerization is conducted both under
homogeneous conditions and at the interface. During
the interfacial polymerization, aniline is dissolved in
the organic phase, while a polysalt (e.g., sodium
poly(4styrenesulfonate) (PSSNa)) and ammonium
persulfate are dissolved in the aqueous phase. Polya
niline formed at the interface is complexed with poly
aniline PSS
–
and gradually diffuses into the aqueous
phase. Depending on the [aniline]to[polysalt] ratio,
polymerization yields spherical particles of the
PANI–polyanion complex ([aniline] : [polysalt] < 1)
or extended structures composed of aggregated parti
cles of the complex ([aniline] : [polysalt] > 1) [89].
When template polymerization is performed under
homogeneous conditions, the sizes of particles of the
PANI–PSS complex depend on the molecular mass of
the used polyanion and the selected concentration
regime. For example, in the presence of PSSNa with
M
w
> 6800, the average diameter of particles of the inter
polymer complex is 2–3 nm at [aniline] = [PSSNa] <
4.5
×
10
–2
mol/L. If the concentration of the compo
nents is above this value, fibrillar aggregates with
diameters of 70–90 nm and lengths from 200 nm to
1
μ
m form. As the molecular mass of PSSNa is
decreased, polymerization yields particles with diam
eters of 100–130 nm that likewise consist of aggre
gated small particles [90].
When the concentration of aniline is less than
4.5
×
10
⎯
2
mol/L, but polymers capable of hydrogen bond
ing are present, the resulting PANIs have different
morphologies that depend on the types of polymer and
dopant. For example, the template polymerization of
aniline performed at the presence of polyvinylpyrroli
done and hydrochloric acid gives rise to a complex of
the granular morphology composed of particles with
diameters of 50–150 nm [91]. If the polymerization of
aniline is conducted at the presence of poly(vinyl alco
hol) and hydrochloric acid, extended structures con
sisting of aggregated PANI particles with sizes of
~200–300
nm arise. If hydrochloric acid is replaced
with
p
toluenesulfonic acid, spherical particles of the
interpolymer complex with an average diameter of
300 nm form, while after addition of (
±
)camphor10
sulfonic acid, a PANI–PVA complex of a needle
shaped structure forms [79].
Depending on the polyelectrolytetemplateto
aniline ratio in the reaction medium, stoichiometric
PANI–polyelectrolyte complexes, which are isolated
as an individual phase [84, 92], or nonstoichiometric
watersoluble complexes, in which polyaniline occurs
in the conducting state, form [93]. At [aniline] : [PSS
Na] = 4 : 1, the formed complex is isolated as an indi
vidual phase in the form of flakes. In accordance with
the elementalanalysis data, N : S = 2.3 in this prod
uct; that is, charges of the template are fully neutral
ized by protonated quinonediimine nitrogen atoms of
PANI [92].
The conductivity of the complex formed during
template synthesis is practically independent of the
nature and strength of the polyacid. In most cases, this
parameter is
~10
–3
–10
–1
S/cm.
The composite materials synthesized with the use
of polymer soft templates may be modified in an
appropriate manner in order to solve practical prob
lems. For example, the precipitation of platinum and
ruthenium particles on a net composed of PANI–PSS
fibrils makes it possible to prepare a material with elec
trocatalytic properties useful for the oxidation of
methanol [94].
Solid polymer templates.
Polymer films and mem
branes—for example, polyethyleneterephthalate,
polyethylene, polypropylene, polystyrene, or polya

POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 151
mide6—are used as templates as well [95–97]. Note
that the majority of these composite materials are syn
thesized on the basis of amorphous or partially crystal
line polymers [98]. This circumstance is due to the fact
that the synthesis of polymer composites via in situ
polymerization involves swelling of a polymer matrix
in a monomer [99]. Highly crystalline polymers can
not absorb considerable amounts of organic com
pounds, because sorption predominantly occurs
toward amorphous regions; as a result, the use of these
polymers is confined. Composite materials based on
PANI and crystalline polymers are usually synthesized
with the use of membranes, while the polymerization
of aniline is performed in pores [98]. Note that the
morphology of PANI synthesized in polymer tem
plates differs from the morphology of polyaniline pre
pared without any template: In the former case, spher
ical particles with diameters of 60–100 nm form; in
the latter case, fibrils with diameters up to 300 nm
appear [99]. It is significant that, when polyaniline
occupies the whole volume of template pores, poly
merization continues on the template surface, where
polyaniline gives rise to fibrils.
In the case of composites based on PANI and PA
6, PA6.6, PA11, and PA10.10, the effect of the type
of template on the surface morphology of composite
materials was studied [100]. It was shown that the tem
plate does not exert the decisive effect on the surface
morphology; in all cases, PANI forms spherical parti
cles with diameters from 100 to 500 nm. The conduc
tivities of the composites are likewise comparable.
Poly(sulfonic acids) with perfluorinarted carbon
backbone (e.g.,
Nafion
®
) in the form of membranes
may be used as soft templates [101]. In this case, poly
merization is performed via the diffusion method: The
reaction vessel is divided into two compartments with
the aid of a membrane; aniline is loaded in one com
partment, and ammonium persulfate used as an oxi
dant is placed in the other. Polymerization yields the
composite material PANI–Nafion
®
, containing
intercalated polyaniline. It is assumed that such com
posite materials may serve as catalytic and gasdiffu
sion layers in the membrane–electrode block of a fuel
cell [102].
The use of polymeric templates in the form of films
and membranes in the synthesis of PANI makes it pos
sible to combine the mechanical properties of polymer
materials with such properties of PANI as conductiv
ity, pH sensitivity, and electrochemical activity [103,
104]. Therefore, these materials are used to design
sensors and actuators for various purposes [103, 105–
107].
CONCLUSIONS
During the past 10–15 years, a wide range of
diverse methods in the field of synthesis of polyaniline
that provide ways to control its structure and physico
chemical properties have been developed. The selec
tion of synthesis procedures is largely determined by
the tasks and application of polyaniline in a given area
of organic electronics. Owing to a wide spectrum of
properties, polyaniline is used as a material for sensors
and actuators, fuel cells, solar batteries, lithiumion
batteries, supercapacitors, fieldeffect transistors, and
many other purposes. With the use of the methods of
template synthesis of polyaniline, various composite
materials combining mechanical and physicochemi
cal properties of the template and PANI (pH sensitiv
ity, electron conductivity, various kinds of chromism,
and the ability to absorb electromagnetic radiation in
a wide wavelength range) may be synthesized.
REFERENCES
1. J. G. Masters, Y. Sun, A. G. MacDiarmid, and
A. J. Epstein, Synth. Met.
41
, 715 (1991).
2. A. G. MacDiarmid and A. J. Epstein, Faraday Discuss.
Chem. Soc.
88
, 317 (1989).
3. J. C. Chiang and A. G. MacDiarmid, Synth. Met.
13
,
193 (1986).
4. W. W. Focke, G. E. Wnek, and Y. J. Wei, Phys. Chem.
91
, 5813 (1987).
5. A. Heeger, Rev. Mod. Phys.
73
, 681 (2001).
6. J. Chiang and A. G. MacDiarmid, Synth. Met.
13
, 193
(1986).
7. A. J. Heeger, J. Phys. Chem. B
105
, 8475 (2001).
8. N. Gospodinova, D. A. Ivanov, D. V. Anokhin,
I. Mihai, L. Vidal, S. Brun, J. Romanova, and A. Tad
jer, Macromol. Rapid Commun.
30
, 29 (2009).
9. K. Lee, S. Cho, S. H. Park, A. J. Heeger, C.W. Lee,
and S.H. Lee, Nature (London)
441
, 65 (2006).
10. Kh. Ghanbari, M. F. Mousavi, and M. Shamsipur,
Electrochim. Acta
52
, 1514 (2006).
11. Kh. Ghanbari, M. F. Mousavi, M. Shamsipur, and
H. Karami, J. Power Sources
170
, 513 (2007).
12. K. Zhang, L. L. Zhang, X. S. Zhao, and J. Wu, Chem.
Mater.
22
, 1392 (2010).
13. H. Wang, Q. Hao, X. Yang, L. Lu, and X. Wang,
Nanoscale
2
, 2164 (2010).
14. P.J. Hung, K.H. Chang, Y.F. Lee, C.C. Hu, and
K.M. Lin, Electrochim. Acta
55
, 6015 (2010).
15. J. Yan, T. Wei, B. Shao, Z. Fan, W. Qian, M. Zhang,
and F. Wei, Carbon
48
, 487 (2010).
16. C. Peng, J. Jin, and G. Z. Chen, Electrochim. Acta
53
,
525 (2007).
17. T. C. Girija and M. V. Sangaranarayanan, Synth. Met.
156
, 244 (2006).
18. Z. Zhou, N. Cai, and Y. Zhou, Mater. Chem. Phys.
94
,
371 (2005).
19. Y. Bardavid, I. Goykhman, D. Nozaki, G. Cuniberti,
and S. J. Yitzchaik, Phys. Chem.
C
115
, 3123 (2011).
20. S. Jussila, M. Puustinen, T. Hassinen, J. Olkkonen,
H. G. O. Sandberg, and K. Solehmainen, Org. Elec
tron.
13
, 1308 (2012).
21. W. Wang, X. Lu, Z. Li, J. Lei, X. Liu, Z. Wang,
H. Zhang, and C. Wang, Adv. Mater. (Weinheim, Fed.
Repub. Ger.)
23
, 5109 (2011).

152
POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
BOEVA, SERGEYEV
22. M.R. Choi, T.H. Han, K.G. Lim, S.H. Woo,
D. H. Huh, and T.W. Lee, Angew. Chem., Int. Ed.
Engl.
50
, 6274 (2011).
23. D. H. Huh, M. Chae, W. J. Bae, W. H. Jo, and
T.W. Lee, Polymer
48
, 7236 (2007).
24.H. Bejbouj, L. Vignau, J. L. Miane, T. Olinga,
G. Wantz, A. Mouhsen, E. M. Oualim, and M. Har
mouchi, Mater. Sci. Eng. B
166
, 185 (2010).
25. W. Wang, Z. Li, X. Xu, B. Dong, H. Zhang, Z. Wang,
C. Wang, R. H. Baughman, and S. Fang, Small
7
, 597
(2011).
26. M. IrimiaVladu, N. Marjanovic, A. Vlad, A. M. Ramil,
G. HernandezSosa, R. Schwoodiauer, S. Bauer, and N.
S. Sariciftci, Adv. Mater. (Weinheim, Fed. Repub. Ger.)
20
, 3887 (2008).
27. A. W. Marsman, C. M. Hart, G. H. Gelinck,
T. C. T. Geuns, and D. M. De Leeuw, J. Mater. Res.
19
, 2057 (2004).
28. Q. Li, J. Wu, Q. Tang, Z. Lan, P. Li, J. Lin, and L. Fan,
Electrochem. Commun.
10
, 1299 (2008).
29. Z. Li, B. Ye, X. Hu, X. Ma, X. Zhang, and Y. Deng,
Electrochem. Commun.
11
, 1768 (2009).
30. L. Bay, K. West, B. Winterjensen, and T. Jacobsen, Sol.
Energy Mater. Sol. Cells
90
(3), 341 (2006).
31. J. Zhang, T. Hreid, X. Li, W. Guo, L. Wang, X. Shi,
H. Su, Z. Yuan, Electrochim. Acta
55
(11), 3664
(2010).
32.H. Sun, Y. Luo, Y. Zhang, D. Li, Z. Yu, K. Li, and
Q. Meng, J. Phys. Chem.
114
, 11673 (2010).
33. T. Lindfors and L. Harju, Synth. Met.
158
, 233 (2008).
34. S. K. Mondal, K. R. Prasad, and N. Munichandraiah,
Synth. Met.
148
, 275 (2005).
35. O. L. Gribkova, A. A. Nekrasov, A. A. Isakova,
V. F. Ivanov, A. V. Vannikov, Elektrokhimiya
42
, 1208
(2006).
36. T. Kobayashi, H. Yoneyama, and H. Tamura, J. Elec
troanal. Chem.
177
, 293 (1984).
37. C. Li, H. Bai, and G. Shi, Chem. Soc. Rev.
38
, 2397
(2009).
38. J. Heinze, B. A. FrontanaUribe, and S. Ludwigs,
Chem. Rev.
110
, 4724 (2010).
39. M. M. Alam, J. Wang, Y. Guo, S. P. Lee, and
H.R. Tseng, J. Phys. Chem. B
109
, 12777 (2005).
40. A. K. Wanekaya, M. A. Bangar, M. Yun, W. Chen,
N. V. Myung, and A. Mulchandani, J. Phys. Chem.
111
, 5218 (2007).
41. J. Stejskal and R. G. Gilbert, Pure Appl. Chem.
74
,
857 (2002).
42. S. Polowinski, Prog. Polym. Sci.
27
, 537 (2002).
43.
Encyclopedia of Polymers
, Ed. by V. A. Kabanov
(Sovetskaya entsiklopediya, Moscow, 1974), Vol. 2 [in
Russian].
44. H. D. Tran, D. Li, and R. Kaner, Adv. Mater. (Wein
heim, Fed. Repub. Ger.)
21
, 1487 (2009).
45. M. Gonzalez, B. G. Soares, M. Magioli, J. A. Marins,
and J. Rieumont, J. SolGel Sci. Technol.
63
, 373
(2012).
46. S. Zuo, W. Liu, C. Yao, X. Li, Y. Kong, X. Liu, H.
Mao, and Y. Li, Chem. Eng. J.
228
, 1092 (2013).
47. T. Hwang, M. Quilitz, and H. J. Schmidt, New Mat.
Electrochem. Syst.
10
, 237 (2007).
48. L. Pan, H. Qiu, C. Dou, Y. Li, L. Pu, J. Xu, and Y. Shi,
Int. J. Mol. Sci.
11
, 2636 (2010).
49. K. A. Milakin, A. N. Korovin, E. V. Moroz, K. Levon,
A. GuiseppiElie, and V. G. Sergeyev, Electroanalysis
25
, 1323 ().
50. S. Sathiyanarayanan, S. Devi, and G. Venkatachari,
Prog. Org. Coat.
56
, 114 (2006).
51. S. M. Yang, K. H. Chen, and Y. F. Yang, Synth. Met.
152
, 65 (2005).
52. C. W. Wang, Z. Wang, M. K. Li, and H. L. Li, Chem.
Phys. Lett.
341
, 431 (2001).
53. M. Malta, G. Louarn, N. Errien, and R. M. Torresi,
Electrochem. Commun.
5
, 1011 (2003).
54. F. Cheng, W. Tang, C. Li, J. Chen, H. Liu, P. Shen, and
S. Dou, Chem.Eur. J.
12
, 3082 (2006).
55. P. Gajendran and R. Saraswathi, Pure Appl. Chem.
80
,
2377 (2008).
56. J. Shen, C. Yang, X. Li, and G. Wang, Am. Chem.
Soc., Appl. Mater. Interfaces
5
, 8467 (2013).
57. M. Ding, Y. Tang, P. Gou, M. J. Reber, and A. Star,
Adv. Mater. (Weinheim, Fed. Repub. Ger.)
23
, 536
(2010).
58. W. Liu, A. L. Cholli, R. Nagarajan, J. Kumar,
S. K. Tripathy, and K. J. Senecal, J. Am. Chem. Soc.
121
, 11345 (1999).
59. G. C. Li and Z. K. Zhang, Macromolecules
37
, 2683
(2004).
60. Z. X. Wei, Z. M. Zhang, and M. X. Wan, Langmuir
18
,
917 (2002).
61. N. Kuramoto and A. Tomita, Polymer
38
, 3055
(1997).
62. J. E. Osterholm, Y. Cao, F. Klavetter, and P. Smith,
Synth. Met.
55
, 1034 (1993).
63. J. E. Osterholm, Y. Cao, F. Klavetter, and P. Smith,
Polymer
35
, 2902 (1994).
64. J. Du, J. Zhang, B. Han, Z. Liu, and M. Wan, Synth.
Met.
155
, 523 (2005).
65. N. Kuramoto and E. M. Genies, Synth. Met.
68
, 191
(1995).
66. P. Dallas, D. Stamopoulos, N. Boukos, V. Tzitzios,
D. Niarchos, and D. Petridis, Polymer
48
, 3162
(2007).
67. J. Stejskal, M. Omastova, S. Fedorova, J. Prokes, and
M. Trchova, Polymer
44
, 1353 (2003).
68. Rao P. Swapna, S. Subrahmanya, and D. N. Sathya
narayana, Synth. Met.
128
, 311 (2002).
69. RaoP. Swapna, D. N. Sathyanarayana, and S. Pala
niappan, Macromolecules
35
, 4988 (2002).
70. N. Kuramoto and A. Tomita, Synth. Met.
88
, 147
(1997).
71. M.Y. Chang, C.S. Wu, Y.F. Chen, B.Z. Hsieh, W.
Y. Huang, K.S. Ho, T.H. Hsieh, and Y.K. Han, Org.
Electron.
9
, 1136 (2008).
72. Y.K. Han, Y.J. Lee, and P.C. Huang, J. Electro
chem. Soc.
156
, K37 (2009).
73. L. Samuelson, A. Anagnostopulos, K. S. Alva,
J. Kumar, and S. Tripathy, Macromolecules
31
, 4376
(1998).

POLYMER SCIENCE Series C
Vol . 56
No. 1
2014
POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 153
74. J. Stejskal, M. Spirkova, A. Riede, M. Helmstedt,
P. Mokreva, and J. Prokes, Polymer
40
, 2487 (1999).
75. W. Liu, A. Anagnostopulos, F. F. Bruno, K. Senecal,
J. Kumar, S. Tripathy, and L. Samuelson, Synth. Met.
101
, 738 (1999).
76. H. S. Moon and J. K. Park, Synth. Met.
92
, 223
(1998).
77. X. Hu, Synth. Met.
150
, 1 (2005).
78. A. V. Caramyshev, E. G. Evtushenko, V. F. Ivanov,
A. R. Barcelo, M. G. Roig, V. L. Shnyrov, R. B. Van
Huystee, I. N. Kurochkin, A. K. Vorobiev, and
I. Y. Sakharov, Biomacromolecules
6
, 1360 (2005).
79. R. CruzSilva, J. RomeroGarcia, J. L. Angulo
Sanchez, A. LedezmaPerez, E. AriasMarin, I. Mog
gio, and E. FloresLoyola, Eur. Polym. J.
41
, 1129
(2005).
80. A. V. Karamyshev, S. V. Shleev, O. V. Koroleva,
A. I. Yaropolov, and I. Yu. Sakharov, Enzyme Microb.
Tec h nol .
33
, 556 (2003).
81. W. Li, M. Zhu, Q. Zhang, and D. Chen, Appl. Phys.
Lett.
89
, 103 (2006).
82.J. E. Yoo, J. L. Cross, T. L. Bucholz, K. S. Lee,
M. P. Espe, and Y.L. Loo, J. Mater. Chem.
17
, 1268
(2007).
83. V. F. Ivanov, O. L. Gribkova, K. V. Cheberyako,
A. A. Nekrasov, V. A. Tverskoi, and A. V. Vannikov,
Russ. J. Electrochem.
40
(3), 339 (2004).
84. R. Nagarajan, S. Tripathy, J. Kumar, F. F. Bruno, and
L. Samuelson, Macromolecules
33
, 9542 (2000).
85. H. Hu, J. M. Saniger, and J. G. Banuelos, Thin Solid
Films
347
, 241 (1999).
86. R. CruzSilva, C. RuizFlores, L. Arizmendi,
J. RomeroGarcia, E. AriasMarin, I. Moggio,
F. F. Castillon, and M. H. Farias, Polymer
47
, 1563
(2006).
87. T. Sulimenko, J. Stejskal, I. Krivka, and J. Prokes, Eur.
Polym. J.
37
, 219 (2001).
88. P. Ghosh, A. Chakrabarti, and S. K. Siddhanta, Eur.
Polym. J.
35
, 803 (1999).
89. C.W. Kuo and T.C. Wen, Eur. Polym. J.
44
, 3393
(2008).
90. S. Dorey, C. Vasilev, L. Vidal, C. Labbe, and N. Gos
podinova, Polymer
46
, 1309 (2005).
91. P. Ghosh, S. K. Siddhanta, and A. A. Chakrabarti, Eur.
Polym. J.
35
, 699 (1999).
92.W. Liu, J. Kumar, S. Tripathy, K. J. Senecal, and
L. Samuelson, J. Am. Chem. Soc.
121
, 71 (1999).
93.S. Roy, J. M. Fortier, R. Nagarajan, S. Tripathy,
J. Kumar, L. A. Samuelson, and F. F. Bruno, Biomac
romolecules
3
, 937 (2002).
94. F.J. Liu, L.M. Huang, T.C. Wen, C.F. Li,
S.L. Huang, and A. Gopalan, Synth. Met.
158
, 603
(2008).
95. A. A. Pud and M. Tabellout, J. Mater. Sci.
36
, 3355
(2001).
96. M. Chipara and D. Hui, Composites B
34
, 637 (2004).
97. K. G. Neoh and B. K. Tay, Polymer
41
, 9 (2000).
98. A. L. Volynskii, E. G. Rukhlya, L. M. Yarysheva, and
N. F. Bakeev, Nanotechnol. Russ.
2
(5–6), 44 (2007).
99. S. A. Saifullina, L. M. Yarysheva, A. V. Volkov,
A. L. Volynskii, and N. F. Bakeev, Polym. Sci., Ser. A
38
(7), 1172 (1996).
100. Q. Zhang, X. Wang, Y. Geng, D. Chen, and X. Jing,
J. Polym. Sci. B
40
, 2531 (2002).
101. N. P. Berezina, A. A. Kubaisy, S. V. Timofeev, and
L. V. Karpenko, J. Solid State Electrochem.
4
, 1
(2006).
102. H. Gharibi, M. Zhiani, R. Mirzaie, M. Kheirmand,
A. Entezami, K. Kakaei, and M. Javaheri, J. Power
Sources
157
, 703 (2006).
103. I. P. Men’shikova, O. A. Pyshkina, E. A. Men’shikov,
E. N. Nasybulin, K. A. Milakin, K. Levon, and
V. G. Sergeev, Polym. Sci., Ser. A
51
(6), 1008 (2009).
104. I. P. Men’shikova, O. A. Pyshkina, K. Levon, and
V. G. Sergeev, Colloid J.
71
(2), 243 (2009).
105. Z. Jin and Y. Su, Sens. Actuators B
71
, 118 (2000).
106. S. K. Dhawan and D. Kumar, Sens. Actuators B
40
, 99
(1997).
107. Y. A. Ismail, M. K. Shin, and S. J. Kim, Sens. Actua
tors
B
136
, 438 (2009).
Translated by T. Soboleva