Chapter

Polyaniline: Synthesis Methods,

Doping and Conduction
Mechanism
Mohmmad Khalid, Ana Maria Borges Honorato and
Hamilton Varela

Abstract

Among all the conducting polymers, polyaniline holds a special position, due to
its unique properties such as low cost of monomers (aniline), distinguishable elec-
trical properties, excellent redox reversibility, high environmental stability and can
be easily polymerized in labs either by chemical or electrochemical methods. The
electrical properties of polyaniline pretty much depend upon the doping agents,
protonation of the constituent units in the chain backbone, and water content.
Conductive nature of polyaniline makes it a versatile conducting polymer for vari-
ety of applications such as gas sensors, supercapacitors, lithium ion batteries and
photovoltaic cells. The objective of this chapter is to provide basic concept of
polyaniline synthesis and its doping mechanism. We hope that this chapter will be
useful for academic as well as for research on polyaniline.

Keywords: polyaniline, synthesis, doping, dedoping, conduction mechanism

1. Introduction

The polymers to which we are more familiar are plastics—that do not con-
duct electricity, it means they behave as insulators. The commercial plastics
which are made up of saturated organic polymers are insulators, in contrast
those plastics are made up of conjugated polymers have the property of semi-
conductors. Scientists Alan J. Heeger, Alan G. MacDiarmid and Hideki Shira-
kawa have changed this concept with their pioneer invention—that a polymer
can behave as electricity conductor almost like a ‘metal’. Indeed, the polymers
that have conjugation in their repeating units combine the electrical properties
like traditional inorganic materials while providing mechanical flexibility and
low cost. In 1974 Shirakawa and his coworkers synthesized free standing
polyacetylene film with silvery appearance using Ziegler-Natta catalyst, but it
was electrically insulator. Somewhat later in 1977, Shirakawa, together with
MacDiarmid and Heeger discovered that the polyacetylene can be made con-
ductive after exposing it to the oxidizing agents like chlorine, bromine or iodine
which made polyacetylene 109 times more conductive than the pristine
polyacetylene [1]. For which they were awarded Nobel Prize in 2000. This
breakthrough gave the rise to the development of new kind of materials with
combine the properties of plastic and electrical conductivity.

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Polyaniline - From Synthesis to Practical Applications

“Unlike plastic, conducting polymers have alternating single and double bond with
sp2 hybridized structure in conjugated sequence along the chain backbone of the
polymer, which acquires delocalization of π-electron and consequently leads electri-
cal conduction”.

Since the discovery of conductive polyacetylene, the interest in conducting

polymers has emerged through in three stages: (a) the preliminary interest driven
by their unique properties and practical possibilities; (b) owing to the complications
in processing and poor mechanical properties; and (c) following the discovery of
solution and melt processability [2–4]. Though, a variety of conducting polymers
have been synthesized and investigated, polyaniline (PANI) is one of a class of
organic polymers that are intrinsically conducting. PANI and its derivatives are
being studied massively owing to their good combination of properties such as
stability, low price, ease of synthesis, and interesting redox properties associated
with its constituent’s units along the chain backbone of the polymer. Between each
repeating benzenoid and quinoid moieties there is nitrogen in the form of imino and
amino groups, which can be protonated and deprotonated. The conduction of
charge in conducting polymers has been of prime focus since the synthesis of
polyacetylene. The electrical conduction in polymer chain segments is depends
upon the several factors such as (a) method of synthesis, (b) method of processing
of polymer, (c) degree of crystallinity of polymer and (d) temperature. The unique
combination of properties of conducting polymers have led to considerable funda-
mental and technological interest in conducting polymers based materials over the
few decades, especially in organic electronics. However, the potential technological
applications of conducting polymers often require reasonable good conductive
materials. The electrical conductivity properties of the conducting polymers depend
upon the doping counter ions. Unlike other conjugated polymers, the electrical
conductivity of PANI is affected by doping and protonation of the polymer seg-
ments. Doping is a reversible to produce original polymer with little or no damage
of polymer backbone. In doped state, the polymer chain backbone consists of a
delocalized π-system. In undoped state the polymer chain backbone may have
conjugation like in polyacetylene but without conductivity, however, in case of
PANI (leucoemeraldine base form) gains conjugation only after doping or non-
conjugated form of PANI that is emeraldine base becomes conjugated only after
protonic acid doping. Conducting polymers containing π-conjugation system may
be doped without changing the number of electrons associated with polymer chain
backbone. However, the energy level is rather rearranged during doping process.
Therefore, the way to dope the polymer without involving redox chemistry is the
protonic acid doping. The acid doping level can be tuned by simply controlling the
pH of dopant solution. Among the conducting polymers PANI is the primary
example of doping to make highly conductive material. The emeraldine base form
of PANI is somewhat like an alternating block copolymer, during doping by acid
dopant emeraldine base converts into emeraldine salt form. The proton induced
spin unpaired mechanism leads to a structural change with one pair unpaired spin
per repeat unit without any alter in the number of the electrons. This remarkable
interconversion in PANI forms leads non-conductive behavior to highly conductive

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behavior. This phenomenon has very well described in the literature but it is still not
very well understood from the point of basic theory. Under this chapter we shall
shed some light upon doing and conduction mechanism of PANI with taking the
help of earlier reported research.

2. Synthesis of PANI

PANI can be synthesized by chemical or electrochemical method both methods

have own advantages. For example, through chemical process PANI can be synthe-
sized in powder form and in bulk amount, this is often difficult with electrochem-
ical process. However, by electrochemical technique PANI can be deposited on
various conductive substrates in the form of thin films, especially for the use in
electronic devices. In chemical synthesis, typically, aniline monomers are oxidized
by oxidizing agents such as ammonium persulfate, hydrogen peroxide, ferric chlo-
ride, and ceric nitrate/sulfate) in acidic medium (hydrochloric acid and sulfuric
acid) [5–8]. Generally, the chemical synthesis of PANI involves the use of acid
medium containing oxidizing agent and aniline monomers in water solution.
During reaction, the function of oxidizing agent is to remove a proton from aniline
unit without forming coordination complex, then the polymerization of aniline
monomers proceeds through redox process conjoining repeating monomer units
[9]. Which is most favorable for the production of PANI product in bulk amount. In
presence of oxidant (oxidizing agent) the polymer product undergoes oxidation at a
lower potential than the constituent reactant (aniline monomer) in acidic environ-
ment (below 3–4 pH). It is also interesting to note that the high molecular weight
PANI can be obtained during the polymerization by lowering the temperature of
the reaction near to
0°C. In general, for chemical synthesis procedures an aqueous
electrolyte medium is required to polymerize aniline monomers. Recently, Khalid
et al. [10] has developed a novel water-free synthesis of PANI, in which organic
phase-tetrahydrofuran was used instead of water, unlike traditional chemical
method. The oxidative polymerization of aniline in presence of aqueous acid solu-
tion has been shown below (Figure 1).
The first electrochemical synthesis of PANI was proposed by Letheby in 1962
[11] when he observed the growth of a blue-green powder pigment on platinum
anode electrolysis of a solution of aniline and sulfuric acid. The adherent thin films
of PANI can be electrodeposited through potentiostatic process by applying con-
stant potential between the range from 0.5 to 0.9 V with several seconds to
minutes, which involves placing three electrodes (working, counter and refer-
ence) into the solution containing monomers and electrolyte (HCl, and H2SO4)
[12]. Galvanostatic and potentiodynamic methods can also be used for the elec-
trodeposition of PANI. For electrodeposition, the three-electrode cell system is
employed using Pt counter, silver-silver chloride reference, and ITO or (Cu, Fe,
Au, graphite) working electrodes. The main advantage of electrochemically pre-
pared PANI is to obtain clean and ordered thin film in desirable shape and size. In

Figure 1.
Oxidative polymerization of aniline to polyaniline (X = Cl1, HSO4).

3
Polyaniline - From Synthesis to Practical Applications

Figure 2.
Mechanism of polymerization of aniline.

1962 Mohinler et al. [13] investigated the mechanism of the electrochemical oxi-
dation of aniline in sulfuric acid and deduced that the initial oxidation requires the
formation of an aniline radical as shown in Figure 2. Where these generated
radicals may combine in different ways to form PANI for example head-to-tail
coupling or tail-to-tail coupling.
Since 1984 the PANI is being used as an attractive conductive material for the
synthesis of conductive composites for variety of practical applications such as
electromagnetic shielding, microwave absorption [14–17], static electricity dissipa-
tion, heating elements, conducting glues, conducting membrane materials, and
paint coatings for anticorrosion property, and sensor materials [18–28]. Among the
conducting polymers, PANI is known for having probably the best combination of
stability, conductivity and low cost [3]. Despite having versatile use in large scale
industrial applications, many of the potential use of PANI yet need to be explored.
One of the major drawbacks of PANI is the lack of its processability. The most
promising approach to overcome this problem of PANI is the formation of com-
posite with using nonconducting polymers as matrix. Nevertheless, the synthesis
method to produce composites with specified characteristics remains number of
obstacles that need to be overcome. There are several known methods to synthesis
PANI-based composite materials are as follows:

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• Chemical in situ polymerization of aniline in a matrix or in a solution with a

matrix polymer;

• Dispersion polymerization of aniline in the presence of a matrix polymer in a

disperse or continuous phase of a dispersion;

• Emulsion polymerization

• Solution blending soluble matrix polymers

• Dry blending

• Melt processing

Above mentioned methods, each of these methods has its own advantages and
limitations. Specifically, the synthetic direction is preferred, as it produces inex-
pensive conducting composites, because of the use of inexpensive aniline instead
of more expensive PANI. The other reason of the use of this method is that it
produces composites which have conductivity only in a thin surface layer, have
good homogeneity and a low percolation threshold. On the other hand, blending
methods are sometimes seemed to be more technologically desirable from the
view point of large scale production, particularly in the case of melt procession
techniques. It can be concluded that the blending methods will probably become
very practicable when techniques to produce inexpensive, nanosized PANI will be
developed.

3. Doping and conduction mechanism

Polymers are insulators because of the intrinsic property of the C-C cova-
lent bonds. The primary requirement for a polymer to be conductive it must
have a conjugation in chain backbone for easy movement of the charge car-
riers. Since the single and double bonds are in conjugation with lone pair in
PANI backbone but it does not make PANI conductive, unless an intrinsic
charge-carriers is developed. Once the charge carriers are generated, the band
gap is reduced and system becomes conductive. The charge-carriers are pro-
vided extrinsically, typically by a charge transfer process (by partial oxidation
or partial reduction with appropriate doping agents), this term generally
known as ‘doping’. For example, the band gape in saturated polyethylene is
about 5 eV and decreases to about 1.5 eV in the fully conjugated system of
polyacetylene, hence, their respective conductivities increase from 1017 and
108 S cm1. The band theory model describes that the electrical conductivity
can be altered by either removal of the electrons from the valence band or by
oxidizing agent – creating positive charge, and donation of an electron to the
empty conduction band using reducing agent. Doping of the polymers may be
done with several techniques such as (a) gaseous doping, (b) solution doping,
(c) electrochemical doping, (d) self-doping, and (e) radiation induced doping.
Doping can also be achieved by irradiating the polymer by neutrons. However,
the conductivity in polymers is associated with charge carriers that do not have
free spins, unlike metals. During a donor or acceptor molecule to a conjugated
polymer, the reaction takes place is actually a redox reaction and quite differ-
ent from the doping of metals such as silicon and germanium, where

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Polyaniline - From Synthesis to Practical Applications

substitution of atoms take place in the lattice. The term ‘doping’ is common for
both conducting polymer and metals, but it should be noted that the doping of
conducting polymers is a result of the formation of a polymer salt and this
generally happened either by exposing the polymer to the dopant in solution or
by electrochemical process. The general reactions can be expressed as follows -
Eqs. (1) and (2):

ð1Þ

ð2Þ

where P represents a section of polymer chain. The first step is the creation of a
cation (or anion) radical, which is called a soliton or a polaron. This step may then
be followed by a second electron transfer with the formation of dication (or
dianion) known as bipolaron [29] as can be seen in Figure 3. P-type conducting
polymers are conventionally used in secondary batteries. These polymers are doped
by low molecular weight anions, such as perchlorate, chloride, and
tetrafluoroborate ions. Upon reduction, these polymers become neutral by releasing
the dopant anions and vice versa they capture the anion upon re-oxidation. It is

Figure 3.
A schematic diagram of evolution of charge-carriers in the form of polarons and bipolarons in polyphenylene [29].

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therefore, charging and discharging characteristics of secondary batteries depends

on the diffusion of ions into and out of the polymers. Alternatively, after the first
redox reaction, charge transfer complexes may form between charged and neutral
segments of the polymer. The reactions between conjugated polymers and oxidants
(p-type doping by an acceptor) or reductants (n-type doping by a donor) have been
observed to cause a dramatic increase in electrical conductivity. When doped with
protonic acids, the imine N in PANI gets protonated. This is because of the higher
basicity of the imine N as compared to the amine N. One of earlier surprises
associated with PANI was the fact that it can be doped by protons, which doesn’t
change the π-electron count of the system. However, this mystery is now resolved
by a very popular two-step model, for example, in case of polyphenylene and
polyaniline [30]. The emeraldine base of APNI consists two amine nitrogen atoms
followed by two imine nitrogen atoms and is a blue color insulating form of PANI.
This form can be transformed into a conducting form of PANI called as emeraldine
salt. Two different process are generally used to make emeraldine salt a green color
product (1) protonic acid doping and (2) oxidative doping. Protonic acid doping
corresponds to the protonation of the imine nitrogen atoms without electron
exchange. While in oxidative doping, emeraldine base goes through several stages
with electron exchanges.
Dopant concentration also does effect on number of spins and electrical con-
ductivity of the conducting polymer. The initial protonation of the two imine N
gives rise to a doubly charged bipolaron, the bipolaronic structure then spontane-
ously dissociates to give two polarons (radical cations). In later step, the polarons
separate to yield a polaron lattice. The polaron lattice resembles the fully reduced
leucoemeraldine form of polyaniline, but for the alternate amine N atoms that are
robbed of an electron. Similarly, the bipolaronic structure is formed by oxidative
doping of the adjacent N atoms, which is followed by coupling of lone electron on N
to form an extra bond (Figure 4). Thus, oxidative doping of the leucoemeraldine
base provides a viable route to the charge carriers in the PANI segments [31]. The
polarons and bipolarons are mobile under the influence of electric field and can
transport along the chain. The conduction mechanism is believed to involve
polaronic carriers i.e. the protonated emeraldine which consists of a delocalized
poly (semiquinone radical cation). By this way the most conductive form can be
approached through two different process—protonic acid and oxidative doping.
Protonic acid doping of emeraldine base segment with HCl results in protonation of
the imine nitrogen atom in the chain backbone and give emeraldine salt form
(Figure 5). According to magnetic theory, if the protonated emeraldine base has
dication (bipolaron), it should show diamagnetism property, however it shows a
paramagnetic characteristic, because of a poly-semiquinone radical cation – one
resonance form consisting of two separate polarons. Some common oxidizing
agents (p-type dopant) are HClO4, FeCl3, AsF5, I2, NH4BF4, SO3CF3, HCl, HNO3,
H2SO4, H3PO4, and some reductants are Li, K, Na, etc. By this way the highly
conductive doped form of.
As mentioned earlier, doping is a multi-steps process involving electron removal
from polymer chain segments leading to the generation of charge carriers. The
charge-carriers in the form of radical cations (p-type) or radical anions (n-type) are
thus produced on the polymer chains, which are called polarons (with spin) and
bipolarons/solitons (spinless). Doping allows electrons to flow due to the formation
of conduction bands, that makes PANI conductive. As doping occurs, the electrons
in conjugation are able to jump around the polymer chains. In general, “doping is
the act of adding a small amount of impurity (the dopant) to a material to alter its
properties” [32, 33]. The presence of a heteroatom (nitrogen) in the conjugated
path of PANI chain provides a way to dope PANI through non-redox routes and

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Polyaniline - From Synthesis to Practical Applications

Figure 4.
The two-step model that describes the disproportionation of a bipolaron to a pair of polarons in proton doped
PANI [31].

Figure 5.
Chemical structure of emeraldine salt [31].

have significant influence on the nature of the quasi-particles which are responsible
for charge transport. The doping can be carried out by reacting PANI with an acid
(HNO3, HCl, H2SO4) that pulls out the lone-pair of electrons from the double-
bonded imine N atoms and thereby creating vacancies in the π-electron cloud
[34–37]. This is fundamentally different from the analogues of polyacetylene,
where the doping cannot be associated with a particular atomic site. This converts
the imine (nitrogen with a double bond) sites to iminium (an imine with a positive
charge) sites. X (NO3, Cl1, HSO4) is the conjugate base of the acid used to dope
PANI. Similarly, PANI may also be doped by using organic dopant like para-toluene
sulfonic acid (p-TSA), camphor sulfonic acid (CSA) and dodecyl benzene sulfonic
acid DBSA [36], example is given in Figures 7 and 8. A general equation for doping
of a conjugated polymer may be given by the following chemical reactions – Eqs. (3)
and (4):

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P þ 2FeCl3 ! Pþ : FeCl4  þ FeCl2 (3)

P þ Na ! P : Naþ (4)

Another important aspect of doping is its reversal, called dedoping or compen-

sation or electrical neutralization of a doped polymer in which, for example, a
p-type doped polymer reacts with some reducing agents and regains its insulating
state. The dedoping agent, diffuses into polymer matrix and neutralizes the charge
of the system by a charge-transfer reaction. This process may involve chemical
reactions between the dedoping agent and carbonium ion or/and dopant leading to
the neutralization by charge-transfer. This process is fully reversible as doping and
dedoping can be repeatedly performed by exposing PANI to acid and base, respec-
tively, as shown in Figure 6. The change in resistance from the dedoped to the
doped form is easily measured electronically, making polyaniline an excellent sen-
sor for acids and bases. The generally used dedoping agents for p-type doped
conjugated polymers are ammonia, water, hydrazine, etc. and the chemical reaction
for the process may be given by the following Eqs. (5)–(7):

8 NH3 ! 6 NH4 þ þ 6 e þ N2 (5)

6 H2 O ! 4 H3 Oþ þ 4 e þ O2 (6)
þ 
P þe !P (7)

The overall doping and dedoping with acid halide can be expressed as follows:
Dedoping may also be effected by thermal treatment of doped-PANI with acid
halide and camphor sulfonic acid dopants (PANI-HCl and PANI-CSA) under ambi-
ent condition, as shown Figures 7 and 8 [36–38]. Kinetics of dedoping may be
studied by several methods, i.e. electrical conductivity measurements, X-ray dif-
fraction, optical spectroscopy etc. which may be interpreted into the depletion of
the extent of doping. Doping may also be processed by radiation in which the locally
oxidized chain is reduced by photo-absorption and in result an electron-hole pair
creates. High energy radiation such as γ-rays, electron beam, and neutron radiation
may be used.
Doping causes significant restructuring of the geometry of polymer. Apart from
the changes in bond lengths, the six membered rings also rotate to a more planar
configuration, thereby increasing the wave function overlap to make the electron
state more delocalized. Dedoped PANI is an insulator with a 3.8 eV band gap, on
doping, the conductivity changes by 10–12 orders of magnitude. There are several
debatable issues pertaining to the nature of the charge carriers, dimensionality of

Figure 6.
Doping and dedoping chemistry of PANI [34].

9
Polyaniline - From Synthesis to Practical Applications

Figure 7.
Dedoping process in PANI-HCl [36].

Figure 8.
Dedoping process in PANI-CSA [36].

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the conducting state and the effect of disorder on the charge transport in doped
PANI. Over the years, a great deal of experimental and theoretical endeavor has
been put to understand these fundamental issues. A lot of questions are still lying
unanswered. PANI can occur in a number of well-defined different oxidation states
as shown in Figure 9 [39]. There are several known oxidative states of PANI
ranging from fully reduced leucoemeraldine to partially reduced protoemeraldine,
and partially oxidized forms emeraldine and nigraniline to the fully oxidized form
pernigraniline. Unlike other polyaromatics, PANI’s oxidized states are insulating,
unless the charge carrier and proton is generated in particular partially oxidized
form (emeraldine) of PANI, this process, typically knows as ‘protonic acid doping’
[40]. The oxidation states of PANI can be induced through doping with oxidizing
agents such as iodine, cerium(IV) sulfate, and potassium dichromate, however the
obtained electrical conductivity is lower than that that of protonic acid doping
[41–45]. The conduction mechanism in PANI is due to the polaronic carrier that is
protonated emeraldine form of PANI, which involves the delocalization of poly-
semiquinone radical cation.
Furthermore, the electronic state of PANI can also be altered through electro-
chemical diffusion of dopant ions (also called as electrochemical doping) in the
polymer unites. This process can be done by applying a proper voltage between two
electrodes via a potential loading device to cause a reverse electrode reaction in
electrolyte solution. McManus et al. [46] reported the electrochemical doping of
polyaniline using phthalate buffer solution and suggested that polyaniline can be
reversibly doped into three forms: (i) closed valence-shell reduced form, (ii) a
radical cation intermediate form, and (iii) a closed valence-shell oxidized form. And
they found the conductivity highest for an intermediate range of oxidation during
electrochemical doping polyaniline also changes the absorption spectra. Recently,
the replacement of sulfate ion by Cl and ClO4 via electrochemical method [47].
Electrochemical doping is not limited to polyaniline but also can be observed other

Figure 9.
Different oxidation states of polyaniline [39, 44].

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Polyaniline - From Synthesis to Practical Applications

conducting polymers for example, Gennies and Pernaut [48] have demonstrated
that the diffusion coefficient of ClO4 into and out of the electrodeposited films of
polypyrrole (PPy). The electrochemical redox reaction follows the Nerstian relation
and the diffusion coefficient value of 6.0  1010 cm2 s1 was calculated at 298 K in
0.5 M LiClO4/acetonitrile electrolyte solution. The relationship with the variation in
LiClO4 concentration in the electrolyte and the value for doping is slightly lower
than that for undoping processes at 298 K. A model for time-dependence of con-
centration relaxation of holes S+, Li+ and ClO4 has been suggested for diffusion
during doping and undoping processes. Authors proposed that the diffusion
involves the concentration relaxation of all three species simultaneously to maintain
electroneutrality in the system. The diffusion coefficients for small dopants varies
from 105 to 1018 cm2 s1 [49–51]. Abalyaeva et al. [52] used a combination of
voltabsorbometry and chronoabsorbometry to estimate the coefficient of BF4
diffusion into 0.49 μm thick film of polyparaphenylene produced by vacuum evap-
oration and a value of 5.0  109 cm2 s1 was found. Stamm [53] estimated a value
of 3.0  106 cm2 s1 for AsF5 diffusion into oriented fibers of polyparaphenylene
produced by solid-state extrusion technique.
The water content is also does effect in the conductivity of the conducting
polymer. The conductivity is affected by the water content as completely dry
samples are five times less conductive than the samples containing some water [54].
The emeraldine base is soluble in N-methyl-pyrrolidone [55], but protonated
polyaniline is insoluble in organic solvents and only soluble in aqueous acids. Sub-
stitution of aniline monomer with alkyl or alkoxy groups improves the solubility in
organic solvents but has a negative influence on the conductivity [56–58]. The
position of the substituent also has an influence on the polymerization. The ortho-
and meta- isomers give the same polymer, but the reactivity of the meta- isomer is
considerably lower, resulting in a lower yield.

4. Conclusion

The doping concept in conducting polymers is a unique and play central role to
enhance the conductivity which distinguish them from other ordinary polymers.
The doping mechanism in polyaniline holds especial representation among all
conducting polymers due its unique oxidation states. In the light of aforementioned
observation, the basic concept of polyaniline synthesis, doping and conduction
mechanism permits in-depth exploration not only for fundamental scientific inter-
est but also further technological applications.

Acknowledgements

The authors would like to place on record thanks to the São Paulo Research
Foundation (FAPESP) for financial support under ongoing projects of Grant Nos.
2017/00433-5 and 2013/16930-7.

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DOI: http://dx.doi.org/10.5772/intechopen.79089

Author details

Mohmmad Khalid1*, Ana Maria Borges Honorato2 and Hamilton Varela1

1 Institute of Chemistry of São Carlos, University of São Paulo, São Carlos, SP,
Brazil

2 Center of Advanced Science and Engineering for Carbon (Case4carbon),

Department of Macromolecular Science and Engineering, Case Western Reserve
University, Cleveland, OH, USA

*Address all correspondence to: mkansarister@gmail.com

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

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Polyaniline - From Synthesis to Practical Applications

References

[1] Shirakawa H, Louis EJ, MacDiarmid [9] Gospondinova N, Terlemezyan L.

AG, Chiang CK, Heeger AJ. Synthesis Conducting polymers prepared by
of electrically conducting organic oxidative polymerization: Polyaniline.
polymers: Halogen derivatives of Progress in Polymer Science. 1998;23:
polyacetylene (CH)x. Journal of the 1443-1484
Chemical Society, Chemical
Communications. 1977:578-580 [10] Mohd K, Tumelero MA, Brandt IS,
Pla Cid CC, Pasa AA. Large slabs and
[2] Salaneck WR, Lundström I, Rånby allihn condenser type structures of
B. Nobel Symposium in Chemistry: polyaniline by an innovative one-pot
Conjugated Polymers and Related approach. RSC Advances. 2014;4:31689-
Materials: The Interconnection of 31691
Chemical and Electronic Structure.
Oxford: Oxford Science; 1993 [11] Letheby H. On the production of a
blue substance by the electrolysis of
[3] Cao Y, Smith P, Heeger AJ. sulfate of aniline. Journal of the
Counterion induced processibility of Chemical Society. 1862;15:161
conducting polyaniline and of
conducting polyblends of polyaniline in [12] Mohd K, Tumelero MA, Zoldan VC,
bulk polymers. Synthetic Metals. 1992; Pla Cid CC, Franceschini DF, Timm RA,
48:91-97 Kubota LT, Moshkalev SA, Pasa AA.
Polyaniline nanofibers–graphene oxide
[4] Heeger AJ. Polyaniline with nanoplatelets composite thin film
surfactant counterions-conducting electrodes for electrochemical
polymer materials which are processible capacitors. RSC Advances. 2014;4:
in the conducting form. Synthetic 34168-34178
Metals. 1993;57:3471-3482
[13] Mohilner DM, Adams RN,
[5] MacDiarmid AG. A novel role for Argersinger WJ. Investigation of the
organic polymers (Nobel lecture). kinetics and mechanism of the anodic
Angewandte Chemie, International oxidation of aniline in aqueous
Edition. 2001;40:2581-2590 sulfuric acid solution at a platinum
electrode. Journal of the American
[6] Willstatter R, Dorogi S, Chemical Society. 1962;84:3618-3622
Anilinschwarz U. III Eur. Journal of
Inorganic Chemistry. 1909;42: [14] Pud A, Ogurtsov N, Korzhenko A,
4118e413542 Shapovala G. Some aspects of
preparation methods and properties of
[7] Austerweil GV. Application du polyaniline blends and composites with
pouvoir sélectif des échangeurs d’ions organic polymers. Progress in Polymer
dans le traitement de certains liquides Science. 2003;28:1701-1753
alimentaires. Comptes Rendus de
l'Académie des Sciences. 1951;233:1190- [15] Taka T. EMI-shielding
1191 measurements on poly(3-octyl
thiophene) blends. Synthetic Metals.
[8] Yasuda A, Shimidzu T. Chemical and 1991;41:1177-1180
electrochemical analyses of polyaniline
prepared with FeCl3. Synthetic Metals. [16] Cottevieille D, Le-Mehauté A,
1993;61:239-245 Challioui C, Mirebeau P, Demay JN.

14
Polyaniline: Synthesis Methods, Doping and Conduction Mechanism
DOI: http://dx.doi.org/10.5772/intechopen.79089

Industrial applications of polyaniline. [25] Wessling B, Posdorfer J. Corrosion

Synthetic Metals. 1999;101:703-704 prevention with an organic metal
(polyaniline): Corrosion test results.
[17] Makela T, Sten J, Hujanen A, Isotalo Electrochimica Acta. 1999;44:2139-2147
H. High-frequency polyaniline shields.
Synthetic Metals. 1999;101:707-707 [26] Gangopadhyay R, De A. Conducting
polymer composites: Novel materials for
[18] Jonas F, Heywang G. Technical gas sensing. Sensors and Actuators B.
applications for conductive polymers. 2001;77:326-329
Electrochimica Acta. 1994;39:1345-1347
[27] Singh V, Mohan S, Singh G, Pandey
PC, Prakash R. Synthesis and
[19] Stenger-Smith JD. Intrinsically
characterization of polyaniline-
electrically conducting polymers.
carboxylated PVC composites:
Synthesis, characterization and their
applications. Progress in Polymer Application in development of ammonia
sensor. Sensors and Actuators B. 2008;
Science. 1998;23:57-79
132:99-106
[20] Malyshev VV, Pislyakov AV.
[28] Koul S, Chandra R, Dhawan SK.
Investigated of gas-sensitivity of sensor
Conducting polyaniline composite: A
structures to carbon monoxide in a wide
reusable sensor material for aqueous
range of temperature, concentration
ammonia. Sensors and Actuators B.
and humidity of gas medium. Sensors
2001;75:151-159
and Actuators B. 2007;23:71-81
[29] Mohammad F. Comparative studies
[21] Bakhshi AK. Electrically conducting on diffusion behaviour of
polymers-from fundamental to applied- electrochemically prepared
research. Bulletin of Materials Science. polythiophene and polypyrrole: Effect
1995;18:469-495 of ionic size of dopant. Synthetic Metals.
1999;99:149-154
[22] Hanhi K, Lonnberg V, Pyorala K,
Loennberg V, Pyoeraelae K. [30] Stafstrom S, Bredas JL, Epstein AJ,
Electroconductive thermoplastic Woo HS, Tanner DB, MacDiarmid AG.
elastomer blend-comprising doped Polaron lattice in highly conducting
polyaniline blended with ABA styrene polyaniline: Theoretical and optical
block copolymer or olefin polymer studies. Physical Review Letters. 1987;
blended with crosslinked elastomer. 59:1464-1467
WO Patent 9. 1997;706:213
[31] Wang L, Jing X, Wang F. On the
[23] Misoska V, Ding J, Davey JM, Price iodine-doping of polyaniline and poly-
WE, Ralph SF, Wallace GG. Polypyrrole ortho methylaniline. Synthetic Metals.
membranes containing chelating 1991;41:739-744
ligands: Synthesis, characterisation and
transport studies. Polymer. 2001;42: [32] Scherr EM, MacDiarmid AG,
8571-8579 Manohar SK, Masters JG, Sun Y, Tang
X, Druy MA, Glatkowski PJ, Cajipe VB,
[24] Davey JM, Ralph SF, Too CO, Fischer JE, Cromack KR, Jozefowitcz
Wallace GG, Partridge AC. ME, Ginder JM, McCall RP, Epstein AJ.
Electrochemically controlled transport Polyaniline: Oriented films and fibers.
of metal ions across polypyrrole Synthetic Metals. 1991;41:735-738
membranes using a flow-through cell.
Reactive and Functional Polymers. [33] Epstein AJ, Ginder JM, Zuo F,
2001;49:87-98 Bigelow RW, Tanner DB, Richter AF,

15
Polyaniline - From Synthesis to Practical Applications

Huang WS, MacDiarmid AG. Insulator- [43] MacDiarmid AG. Conjugated

to-metal transition in polyaniline. Polymers and Related Materials (Proc.
Synthetic Metals. 1987;18:303-309 81st Nobel Symposium). Oxford
University Press; 1993. p. 73. Chap. 6
[34] MacDiarmid AG, Epstein AJ. The
concept of secondary doping as applied [44] Feast WJ, Tsibouklis J, Pouwer KL,
to polyaniline. Synthetic Metals. 1994; Groenendaal L, Meijer EW. Synthesis,
65:103-116 processing and material properties of
conjugated polymers. Polymer. 1996;37:
[35] Kuzmany H, Sariciftci NS, 5017-5047
Neugebauer H, Neckel A. Evidence for
two separate doping mechanisms in the [45] Louboutin JP, Barniere F. Doping
polyaniline system. Physical Review mechanism of a conducting polymer:
Letters. 1988;60:212-215 Iodine-doped polyacetylene. Journal of
Physics and Chemistry of Solids. 1982;
43:233-241
[36] Neoh KG, Pun MY, Kang ET, Tan
KL. Polyaniline treated with organic
[46] McManus PM, Yang SC, Cushman
acids: Doping characteristics and stability.
RJ. Electrochemical doping of
Synthetic Metals. 1995;73:209-215
polyaniline: Effects on conductivity and
optical spectra. Journal of the Chemical
[37] Rannou P, Nechtschein M, Travers
Society, Chemical Communications.
JP, Berner D, Wolter A, Djurado D.
1985:1556-1557
Aging of PANI: Chemical, structural and
transport consequences. Synthetic
[47] Abalyaeva VV, Dremova NN.
Metals. 1999;101:734-737
Electrochemical doping of polyaniline
with the tetracyanoquinodimethane
[38] Pandey SS, Annapoorni S, Malhotra anion. Russian Journal of
BD. Synthesis and characterization of Electrochemistry. 2016;52:746-753
poly(aniline-co-o-anisidine): A
processable conducting copolymer. [48] Gennies EM, Pernaut JM.
Macromolecules. 1993;26:3190-3193 Spectroelectrochemical studies of the
redox and kinetic behaviour of
[39] Kang ET, Neoh KG, Tan KL. polypyrrole film. Synthetic Metals.
Polyaniline: A polymer with many 1984;10:117-129
interesting intrinsic redox states.
Progress in Polymer Science. 1998;23: [49] Kaufman JH, Mele EJ, Heeger AJ,
277-324 Kaner R, MacDiarmid AG. Electric field
enhanced diffusion in trans-(CH)x.
[40] Chiang JC, MacDiarmid AG. Journal of the Electrochemical Society.
‘Polyaniline’: Protonic acid doping of the 1985;132:1131-1133
emeraldine form to the metallic regime.
Synthetic Metals. 1986;13:193-205 [50] Chien JCW. Polyacetylene. New
York: Academic Press; 1984
[41] MacDiarmid AG, Chiang JC, Richter
AE, Somasiri NLD, Epstein AJ. In: [51] Foot PJS, Mohammad F, Calvert PD,
Alcacer L, editor. Conducting Polymers. Billingham NC. Diffusion in conducting
Dordrecht, Holland: Reidel; 1987. p. 105 polymers. Journal of Physics D: Applied
Physics. 1987;20:1354-1360
[42] MacDiarmid AG, Chiang JC, Richter
AF, Epstein AJ. Polyaniline: A new [52] Abalyaeva VV, Zakhidor AA, Li SB,
concept in conducting polymers. Khidekel ML, Kogan YL.
Synthetic Metals. 1987;18:285-290 Optoelectrochemical effect in thin

16
Polyaniline: Synthesis Methods, Doping and Conduction Mechanism
DOI: http://dx.doi.org/10.5772/intechopen.79089

polyphenylene films. Bulletin of the

Academy of Sciences of the USSR,
Series D (Chemical Sciences). 1984;33:
2150-2151

[53] Stamm M. Synthesis and

characterisation of conducting oriented
fibres of polyparaphenylene. Molecular
Crystals and Liquid Crystals. 1984;105:
259-265

[54] Boara G, Sparpaglione M. Synthesis

of polyanilines with high electrical
conductivity. Synthetic Metals. 1995;72:
135-140

[55] Angelopoulos M, Ray A,

MacDiarmid AG, Epstein AJ.
Polyaniline: Processability from aqueous
solutions and effect of water vapor on
conductivity. Synthetic Metals. 1987;21:
21-30

[56] Yue J, Epstein AJ. Synthesis of self-

doped conducting polyaniline. Journal
of the American Chemical Society. 1990;
112:2800-2801

[57] Rahman AKM, Samuelson L,

Minehan D, Clough S, Tripathy S, Inagaki
T, Yang XQ, Skotheim TA, Okamoto Y.
Ordered LangmuirBlodgett films of
polypyrrole and analogs. Synthetic
Metals. 1989;28:237-244

[58] Han C, Hong S, Yang K, Bai M, Lu

C, Huang C. Highly conductive new
aniline copolymers containing
butylthio substituent. Macromolecules.
2001;34:587-591

17