Arabian Journal of Chemistry (2017) 10, S2668–S2674

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Synthesis and characterization of polyaniline

and poly(aniline-co-o-nitroaniline) using
vibrational spectroscopy
Kuestan A. Ibrahim *

Department of Chemistry, College of Science, Salahaddin University, Kurdistan Region, Erbil, Iraq

Received 21 February 2013; accepted 21 October 2013

Available online 28 October 2013

KEYWORDS Abstract Due to the advantages of material abundance and synthetic simplicity, polyaniline can be
Poly aniline; used as a high capacity cathode material. However, its practical application in battery has been hin-
Copolymer; dered by poor electrochemical utilization and cycling instability. To solve these problems, we syn-
Industrial application; thesized the Polyaniline-co-o-nitroaniline aniline. The copolymers were synthesized for 1:1 and
Raman spectroscopy; 1:4 M ratios of aniline and o-nitroaniline in acidic medium using ammonium persulfate as oxidant
FTIR; and their properties were compared with that of polyaniline. The prepared samples have been char-
o-Nitroaniline acterized using number of techniques including Raman spectroscopy, FTIR, UV–vis, and conduc-
tivity. The polymers showed less electrical conductivity than polyaniline. Unlike polyaniline, the
presence of nitro group caused higher frequency dependence of electrical conductivity. The FTIR
bands at 1560, 1306 and 1148 cm 1 are corresponding to the polyaniline salt. The Raman band
observed in the range of 1100–1140 cm 1 is the characteristic of conductive polyaniline and is
due to the charge delocalization on the polymer backbone.
ª 2013 King Saud University. Production and hosting by Elsevier B.V. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

1. Introduction for commercially viable conducting polymers because of its un-

ique proton dopability, excellent redox recyclability, chemical
There is an explosive increase in the demand for composite stability, variable electrical conductivity (which can be varied
materials in the last two decades, which are now available as by changing the pH at which it is prepared), low cost and ease
materials with an unique combination of properties. Polyani- of synthesis (Khalid and Mohammad, 2007). Thus, the com-
line (PANI) has been in the forefront of the global search posites based on conducting polymers and insulating polymers
have been studied as materials for industrial products, such as
rechargeable batteries, conductive coatings, light emitting
* Tel.: +964 7504063415.
diodes, gas sensors and antistatic materials (Singh, 2007).
E-mail address: [email protected].
Intrinsically conductive polymers, including polyaniline
Peer review under responsibility of King Saud University.
PANI have the utilization potential in a large number of appli-
cations: rechargeable batteries (Sivakkumar and Saraswathi,
2004), sensors, electronic devices (Ogura et al., 1995; Borole
Production and hosting by Elsevier et al., 2004), light-emitting diodes (Falcoua et al., 2005),
http://dx.doi.org/10.1016/j.arabjc.2013.10.010
1878-5352 ª 2013 King Saud University. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
Synthesis and characterization of polyaniline and poly(aniline-co-o-nitroaniline) S2669

NH2

H H H
N N N NH2
n
(a)
O O O
NH2 O
NH2 N N

NO2 H H
NH N NH N
Cl
y n
(b)
Scheme 1 Electro-polymerization of (a) aniline and (b) aniline with o-nitroaniline (Upadhyay and Ahmad, 2010).

corrosion protection of metals (Karthikaiselvi et al., 2012; Elia Copolymers of aniline with m-nitroaniline (poly(aniline-co-
et al., 2001), conducting paints and glues, electromagnetic m-nitroaniline)) were readily synthesized in various molar ra-
shielding (Kuo et al., 1998; Upadhyay and Ahmad, 2010), anti- tios of co-monomers by chemical and electrochemical poly-
static formulations, gas-separation membranes coatings etc. merization. The copolymerization rate decreased with an
However, the major problem in applying these polymers is increasing ratio of m-nitroaniline in the monomer (Ding
their poor processibility by solvent or multitechniques. Most et al., 2012). Chemically oxidation copolymerization of aniline
of them are insoluble in common solvents and undergo degra- and o-chloroaniline with 4 M ratios has been performed using
dation before reaching the melting point. Also they have poor ammonium persulfate as an oxidant in HCl medium at 0–4 C
mechanical strength and are environmentally unstable. Many (Borkar, 2012) (showed structure of copolymers in Scheme 2).
researchers have succeeded in overcoming these problems The effect of different compositions of monomers on the
(MacDiarmid and Epstein, 1994; Waware and Umare, 2005; transport properties of poly(aniline-co-o-anisidine) by various
Ismail et al., 2008) and are generating polymer composites techniques such as optical, electrical and magnetic has been
and blends (Heegar, 2001; Pant et al., 2006; Mzenda et al., investigated and compared with the homopolymers (Umare
2002) which can show better stability and mechanical strength. et al., 2002). Electro chemical co-polymerization of o-anisidine
Several methods were used to overcome this problem including with o-toluidine was carried out in 1 M H2SO4 by cyclic vol-
N-substitutions or ring substitutions of aniline by aliphatic tammetry. The copolymer compositions were altered by vary-
large radicals, block copolymers and doping PANI base with ing the monomer feed ratios during electro synthesis (Borole
a functionalized protonic acid (Haba et al., 2000; Cao et al., et al., 2007, 2006) (structure of copolymers as shown in
1992; Yoon et al., 1994). Conducting polymers such as poly- Scheme 3).
acetylene, poly thiophene, and poly aniline (PANI) are semi- Copolymers of o-/m-toluidine with o-nitro aniline were
conductors in their pure form but become highly conducting chemically synthesized in various molar ratios of the comono-
upon doping (Salih, 2011). mers by emulsion polymerization. Although o-nitro aniline
Copolymerization offers a way of improving the process- does not homopolymerize, the copolymers of o-nitro aniline
ibility of PANI. The properties of the poly(substituted ani- with o-/m-toluidine could readily be synthesized. The copoly-
lines) like toluidine, anisidine, etc. depend on the type of mers show comparatively higher conductivity, better solubility
substitution like electron withdrawing, electron donating and higher thermal stability than the homopolymers, ortho-
groups (Scheme 1) or less affecting groups like alkyl groups. and meta-polytoluidines (Savitha and Sathyanarayana,
Electron withdrawing group decreases the electron density in 2004). The polyaniline family is challenging because of its con-
aniline, electron donating group increases the electron density ductivity and solubility in polar organic solvents that depend
in the phenyl ring, whereas alkyl group may not affect much to not only on the oxidation state but also on the degree of pro-
the electron density in aniline only some mild positive induc- tonation and nature of dopants. It is also observed that poly-
tive effect (+I) may increase the electron density (Upadhyay aniline-co-toluidine. Copolymer has better solubility than
and Ahmad, 2010). homo polymers in various organic solvents (Kumar, 2000; Bi-

O2N O2N

NH NH NH NH

(a) n

Cl Cl

NH NH NH NH

(b) n

Scheme 2 Structure of the: (a) poly(aniline-co-m-nitroaniline) and (b) poly(aniline-co-o-chloroaniline).

S2670 K.A. Ibrahim

OCH3 OCH3

NH NH NH NH

(a) n

CH3 OCH3 CH3 OCH3

NH NH NH NH

(b) n

Scheme 3 Structure of the: (a) poly(aniline-co-o-anisidine) and (b) poly(o-toluidine-co-o-anisidine).

lal, 2007). In this work, poly(aniline-co-o-nitro aniline) was washed with distilled water till washings were neutral to a
prepared and characterized using UV and FTIR spectroscopy pH indicator paper. The blue emeraldine base powder ob-
emphasizing to study the effect of incorporation of o-nitro ani- tained was then filtered and washed with a water and methanol
line on the resulting copolymers. mixture and finally dried under vacuum for 48 h.

2. Materials and methods 2.2.2. Copolymerization of aniline with o-nitro aniline (1:1, 1:4)
0.05 mol of each one of doubly distilled aniline and o-nitro ani-
2.1. Materials line were dissolved in HCl solution (1 M, 150 ml) to prepare
copolymer 1:1, and then placed in a flask was cooled to
Aniline (Fluka) was double distilled before use. o-nitro aniline 0 C. Based on the method of homopolymerization of aniline
(Aldrich) and all the reagents and solvents (ethanol, methanol) (2.2.1), (0.025 mol of aniline was mixed with 0.1 mol of o-nitro
were analytical grade and used after further purification. UV– aniline to prepare copolymer 1:4).
vis spectra were obtained on a Spectroscan80D, UV/visible
Spectro-photometer, with quartz cells of 1 cm optical path. 3. Results and discussion
Intrinsic conductivity measurements were recorded using a
Genard conductivity bridge (1659 RLC Digibridge, USA). The copolymers were synthesized using two different molar ra-
Infrared spectra were recorded at room temperature using tios of 1:1 and 1:4 of aniline: o-nitro aniline in the comonomers
BIORAD Excalibur (FTS 3000MX series) instrument. Raman feed. The general structure of the copolymer is shown in
spectroscopy measurements were done on an ISA lab-ram Scheme 1. The yield of the copolymers, decreases with increas-
model system using an Argon laser beam (50 mW ing o-nitro aniline content in the co-monomer feed. This could
632.28 nm laser diode for excitation). A confocal aperture of be due to the highly electron withdrawing nature of the nitro
200 lm and a spectral resolution of 5 cm 1 were used. group which reduces the electron density on the ring and also
the steric interferences hindering polymerization. The results
2.2. Methods agree with those obtained by Upadhyay et al. (2010). Strong
intermolecular interaction between nitro groups and the pola-
2.2.1. Homo polymerization of aniline ronic nitrogen atoms or hydrogen bonding can give rise to a
In a typical poly aniline experiment, doubly distilled aniline favorable six member chelate ring, forming localized structure
(10 ml, 0.1097 mol) dissolved in hydrochloric acid (HCl) solu- resulting in a lower conductivity.
tion (1 M, 100 ml) was placed in a flask equipped with a drop- The formation of hydrogen bonds between the oxygen of
ping funnel and cooled to 0 C. If monomers were not the –NO2 group and the –NH hydrogen localizes the electron
completely soluble in this medium, an additional HCl solution density on the ring leading to further decrease in the rate of
(1 M, 50 ml) was added. polymerization, (Scheme 4). It is of interest to note that o-nitro
The oxidizing agent was prepared by dissolving (1.25 g, aniline does not homopolymerize under conditions employed
0.0548 mol) ammonium persulfate in HCl solution (1 M, for the polymerization of aniline and its derivatives. This could
100 ml). The oxidant solution was added drop wise to aniline
solution with vigorous stirring at 0 C. A green precipitate
formed after 5–10 min. The reaction mixture was stirred for H H
N N NH NH
4 h at 0 C and for 20 h at room temperature. The reaction
n
mixture was poured into 200 ml water to complete the precip- (a)
itation and the polymer was collected on a glass frit, washed
O O
with distilled water and HCl solution (1 M) to remove un-re- O O
N N
H H
acted monomer. Collected green precipitates of emeraldine
N NH N
hydrochloride were washed with distilled water till these wash- NH
Cl
y n
ings were colorless. The filtered and washed precipitates were (b)
then treated with aqueous solution of ammonium hydroxide
(pH  9) under stirring for 6–8 h for effective un-doping to ob- Scheme 4 Structure of the (a) polyaniline and (b) copolymers
tain emeraldine base. This reaction mixture was filtered, (1:1 and 1:4).
Synthesis and characterization of polyaniline and poly(aniline-co-o-nitroaniline) S2671

PNAI POLY1:1 POLY 1:4 signed to an in plane deformation of the C–C bond of the
quinoid ring of the polyaniline (Cochet et al., 2000). The bands
at 1382 and 1595 cm 1 correspond to C–N+ stretching and C–
C stretching of the quinoid ring respectively (Wu et al., 2005).
A band at 1487 cm 1 was assigned to the formation of bipola-
rons (Barnard and Goff, 1999). The Raman shift at 1247 cm 1
Intensity (u/a)

corresponds to the C–N stretching in polaronic units (Jain and

poorni, 2010). The peak observed in the 1100–1140 cm 1 re-
gion is characteristic of conductive polyaniline and is due to
the charge delocalization on the polymer backbone (Kim
et al., 1988).

3.2. Fourier transform infrared (FTIR)

FTIR spectra of both PANI and doped copolymer, are shown

1000 1200 1400 1600 1800 2000 in Fig. 2. The spectra of all the copolymers show the main
-1
Raman shift (cm ) bands in the region of 1590, 1508 and 1308 cm 1 correspond-
ing to the ring-stretching vibrations of the quinoid and benze-
Figure 1 Comparison between Raman spectra of PANI, copoly- noid rings of aniline and nitro aniline, respectively.
mer 1:1 and copolymer 1:4. Furthermore, the quinoid peak appears split, while the benze-
be due to the high electron withdrawing capacity of the nitro noid band is not split in the spectra. The quinoid band is sen-
group in nitro aniline reducing the electron density of the ring sitive to the structure, and hence, two bands at 1595 and
(Kumar, 2000). 1560 cm 1 arising from quinoid stretching of aniline and nitro
aniline ring segments are observed. A band near 1385 cm 1 is
3.1. Raman spectroscopy assigned to the C‚N+ stretching adjacent to the quinoid
structure while a medium intensity band at 1310 cm 1 is asso-
ciated with C–N stretching vibration in the alternate units of
Fig. 1 shows the Raman spectroscopy analysis of PANI and quinoid–benzenoid–quinoid rings as shown in Fig. 2. The
poly(aniline-co-o-nitroaniline). The band at 1485 cm 1 has peaks at 1304 and 1210 cm 1 correspond to N–H bending
been assigned to an in-plane deformation of the C–C bond and the symmetric component of the C–C (or C–N) stretching
of the quinoid ring of the doped PANI and band at modes. Most of the bands of the copolymers are asymmetric
1473 cm 1 corresponds to an in-plane deformation of the C– and symmetric stretching modes of the nitro group of o-nitro
C bond of the quinoid ring of the doped copolymer (1:1), aniline which occur at 1510 and 1346 cm 1, respectively
and (1:4) (Cochet et al., 2000). PANI spectra showed bands (Rao et al., 2000).
at 1471 and 1338 cm 1, which are due to the C‚N– and C– The band around 1170 cm 1 is attributed to B–(NH+)‚Q
N– stretching in quinoid and benzenoid rings, respectively. structure which is formed during the protonation process. A
While in case of copolymer (1:1), and (1:4), the same bands band at 1110 cm 1 is assigned to the C–H in plane bending.
were investigated at 1468 and 1320 cm 1, respectively (Pere- This confirms the presence of o-nitro aniline segments in the
pichka et al., 2004). A small band at 1174 cm 1 has been as- copolymer and also suggests an increase in the conjugation
of the nitro group with the ring. The significant lowering of
the frequencies can be related to the hydrogen bonds formed
between the oxygen of the nitro group and the hydrogen of
the amine group (Kumar, 2000).
The bands at 1145 and 831 cm 1 can be attributed to the in-
plane and out-of-plane C–H bending modes, respectively
(Ding et al., 2012) The strong band at 1145 cm 1 in the base
Absorbance (a/u)

COP 1:4
is much intense and broader in the salt spectrum. In addition
to the above peaks, the spectrum of the polyaniline exhibits
peaks at 3320 cm 1 that could be attributed to NH2 stretching
COP 1:1 mode and a band located at 1653 cm 1 related to the NH2
bending vibration, while the peak at 684 cm 1 is attributed
to NH2 wagging. In addition, the peak at 1580 cm 1 confirms
the presence of a protonated imine function, and the band
characteristic of conducting protonated form is observed at
PANI
1242 cm 1.

3.3. UV–visible spectroscopy

400 800 1200 1600 2800 3200 3600
-1
Wave number (cm )
The synthesized polymers were subjected to the physico-chem-
Figure 2 FTIR spectra of PANI, copolymer 1:1 and copolymer
ical characterization by using UV–vis spectroscopy as shown
1:4.
in Fig. 3.
S2672 K.A. Ibrahim

Figure 3 UV–vis spectra of the (a) polyaniline, (b) copolymer (1:1), and (c) copolymer (1:4).

1.6 Conducvity(× 10−3 S cm−1)

The first absorption band of p–p* bond has appeared at (PANI)
280–295 nm, is assigned to the p–p* transition of the benzenoid 1.4 Conducvity(× 10−3 S cm−1) (co-
polymer 1:1)
ring on the basis of the earlier studies on polyaniline and it is Conducvity(× 10−3 S cm−1) (co-
related to the extent of conjugation between the adjacent phe- 1.2
conductivity S cm-1

polymer 1:4)
nyl rings in the copolymer chain. The second absorption band
1
located at 605–635 nm is attributed to the quinoid ring transi-
tion (charge transfer from HOMO of the benzenoid ring to
0.8
LUMO of the quinoid ring) (Tzou and Gregory, 1993). This
band is dependent on the overall oxidation state of the poly- 0.6
mer. The absorption spectrum of the polyaniline salt doped
with HCl shows bands at 326, 433 and 630 nm, with higher 0.4
conductivity (Yang and Shaolin, 2008).
A characteristic band for polaron-p* transition appeared at 0.2
450 nm, indicating that the resulting PANI emeraldine salt was
in the doped state (Abd Razak et al., 2009). At low concentra- 0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
tions of o-nitro aniline in the comonomers feed, delocalization weight (gm)
due to the presence of alternating electron donating and with-
drawing groups may not be very effective, resulting in a Figure 4 Effect of dopant aminophenole sulfate salt on conduc-
copolymer with lower conductivity. tance of polyaniline, copolymer (1:1) and (1:4).
At high or low concentrations of o-nitro aniline in the
copolymer, steric effects of the substituent may predominate density of the ring (Kumar, 2000). The lower conductivity of
over the electronic effects and lead to a lowering in conductiv- the copolymer with a higher feed content of o-nitro aniline
ity. This seems understandable since conductivity is dependent can be rationalized on the basis of the effects of the nitro
on the orientation of the phenyl rings as well as on the electron groups on the copolymer structure.
Synthesis and characterization of polyaniline and poly(aniline-co-o-nitroaniline) S2673

1.6
Conducvity(× 10−3 S cm−1) Figs. 4 and 5 and the details of results presented in Tables 1
(PANI)
and 2. It is apparent that the conductance of the polymers in-
Conducvity(× 10−3 S cm−1)
1.4 (co-polymer 1:1)
creases as the weights of the dopant material increases. This
is caused by both increased separation of the copolymer chain
Conducvity(× 10−3S cm−1)
1.2 (co-polymer 1:4) due to the presence of side groups and the presence of electron-
withdrawing NO2 group in the copolymer chain (Upadhyay
conductivity S cm-1

1 and Ahmad, 2010; Yang and Shaolin, 2008). Synthesized

copolymers are depending on their synthesis, the dopants,
0.8
and the concentration of the reactants used. The higher conduc-
0.6
tivity of polyaniline obtained by the present method could be
attributed due to a more homogeneous protonation of the
0.4 imine nitrogen and better ordered chain conformation of the
polymer (Rao et al., 2002). It has been observed that, copoly-
0.2 mers possess a lower conductivity as compared with homo
polyaniline. This could be related to the presence of nitro group
0 NO in the components. As well, the conductivity decreases with
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
increasing nitro aniline content in copolymers. On the other
weight (gm)
hand, the conductivity increases with increasing dopant con-
Figure 5 Effect of dopant bromophenole sulfate salt on centration given in Table 1. But also Higher electrical conduc-
conductance of polyaniline, copolymer (1:1) and (1:4). tivity poly anilineCQ than copolymer (1:1, 1:4), copolymer
(1:1) has higher conductivity from copolymer (1:4) by the high-
3.4. Conductivity of poly aniline and copolymers er nitro group decrease the conductivity of copolymer. The re-
sults are similar to those achieved by Rao et al., 2002.
It is obvious that the conductivity of the copolymer decreases
with increasing concentration ratio of aniline to nitro aniline 4. Conclusion
in the mixture and is lower than that of polyaniline, the influ-
ence of weight of dopant material on the conductance of the The o-nitro aniline was copolymerized with aniline by chemi-
polyaniline and polyaniline-co-o-nitro aniline is shown in cal oxidative polymerization with ammonium persulfate as

Table 1 The values of conductivity for the PANI and co-polymers (1:1 and 1:4) doped with sample dopants aminophenol sulfonic
acid.
3
Weight (gm) Conductivity Conductivity (·10 S cm 1) Conductivity (·10 3
S cm 1)
(·10 3 S cm 1) (PANI) (co-polymer 1:1) (co-polymer 1:4)
0.00 0.1225 0.130 0.035.8
0.01 0.148 0.187 0.118
0.02 0.163 0.334 0.168
0.03 0.372 0.461 0.197
0.04 0.570 0.537 0.374
0.05 0.668 0.656 0.482
0.06 0.735 0.748 0.630
0.07 0.856 0.874 0.764
0.08 0.955 0.979 0.916
0.09 1.184 1.097 1.060
0.10 1.378 1.207 1.428

Table 2 The values of conductivity for the PANI and co-polymers (1:1 and 1:4) doped with sample dopants bromophenole sulfonic
acid.
3
Weight (gm) Conductivity Conductivity (·10 S cm 1) Conductivity (·10 3
S cm 1)
(·10 3 S cm 1) (PANI) (co-polymer 1:1) (co-polymer 1:4)
0.00 0.424 0.083.3 0.025
0.01 0.506 0.127 0.060.2
0.02 0.549 0.176 0.194
0.03 0.656 0.318 0.258
0.04 0.754 0.403 0.491
0.05 0.943 0.512 0.612
0.06 1.015 0.672 0.670
0.07 1.070 0.738 0.749
0.08 1.146 0.890 0.909
0.09 1.249 0.999 1.079
0.10 1.416 1.060 1.218
S2674 K.A. Ibrahim

the oxidizing agent in acidic medium using different feed ratios Ding, L., Qin, Li, Zhou, D., Cui, H., Tang, R., Zhai, J., 2012.
of the comonomers. Although o-nitro aniline does not homo- Electrochimica Acta 77, 302.
polymerize, these copolymers exhibited higher conductivities Elia, L.F.D., Ortiz, R.L., Marquez, O.P., Marquez, J., Martinez, Y.,
and good solubility in solvent DMSO than the homo-polyan- 2001. The Electrochemical Society 148, C297.
Falcoua, A., Ducĥenea, A., Hourquebieb, P., Marsacqb, D., 2005.
iline and this may be attributed to greater electron delocaliza-
Synthetic Metals 149, 115.
tion and the presence of hydrogen bonding and inter chain Heegar, A.J., 2001. Synthetic Metals 125 (1), 23.
linking due to the nitro group of o-nitro aniline. Raman spec- Haba, Y., Segal, E., Narkis, M., Titelman, G.I., Siegmann, A., 2000.
tra indicate the presence of the quinoid ring in polyaniline Synthetic Metals 110, 189.
structure. UV visible spectra show the presence of different Ismail, Y.A., Ahmad, A., Mohammed, F., 2008. Journal of Macro-
rings, higher conductivity of polyaniline than copolyaniline- molecule Science Part A 45, 650.
o-nitroaniline after doping with aminophenol sulfonic salt Jain, M., Poorni, S.A., 2010. Synthetic Metals 160, 1727.
and bromophenole sulfonic salt, and that the conductivity of Kim, Y.H., Foster, C., Chiang, J., Heeger, A.J., 1988. Synthetic Metals
polyaniline doped with bromophenole sulfonic salt is slightly 26, 49.
higher than that with aminophenol sulfonic salt. Kuo, C.T., Chen, S.A., Hwang, G.W., Kuo, H.H., 1998. Synthetic
Metals 93, 155.
Kumar, D., 2000. Synthetic Metals 114, 369.
Khalid, M., Mohammad, F., 2007. Polymer Letters 1 (11), 711.
Acknowledgements Karthikaiselvi, R., Subhashini, S., Rajalakshmi, R., 2012. Arabian
Journal of Chemistry 5, 517.
Mzenda, V.M., Goodman, S.A., Auret, F.D., 2002. Synthetic Metals
I would like to gratefully acknowledge Dr. Mukhtar H. 127, 285.
Ahmed (Department of Chemistry, College of Science, Sala- MacDiarmid, A.G., Epstein, A.J., 1994. Synthetic Metals 65, 103.
haddin University, Kurdistan region, Erbil, Iraq. Nanotech- Ogura, K., Koura, M., Nakayama, M., 1995. The Electrochemical
nology Integrated Biomedical Engineering Center (NIBEC), Society 142 (9), L152.
University of Ulster, jordanstown, BT37 0QB, Belfast, UK.) Perepichka, D.F., Wudl, F., Wilson, R.S., Sun, Y., Schuster, I.D.,
for recording the FTIR, Raman spectra and helpful discus- 2004. Journal of Materials Chemistry 14, 2749.
sions. Also I thank Dr. Sheeren and Miss Bayan from the Pant, H.C., Patra, M.K., Negi, S.C., Bhatia, A., Vadera, S.R., Kumar,
chemistry department for recording the UV–vis and conductiv- N., 2006. Journal of Bulletin Material Science 29, 379.
ity measurements. Rao, P.S., Sathyanarayana, D.N., Palaniappan, S., 2002. Macromol-
ecules 35, 4988.
Rao, P.S., Anand, J., Palaniappan, S., Sathyanarayana, D.N., 2000.
References European Polymer Journal 36, 915.
Singh, T.V., 2007. Polymer Letters 1 (5), 308.
Abd Razak, S.I., Ahmad, A.L., Sharif Zein, S.H., 2009. Journal of Sivakkumar, S.R., Saraswathi, R., 2004. Journal Applied Electro-
Physical Science 20 (1), 27. chemistry 34, 1147.
Barnard, M.C., Goff, A.H., 1999. Synthetic Metals 102, 1342. Salih, R.A., 2011. Iraqi National Journal of Chemistry 43, 319.
Borole, D.D., Kapadi, U.R., Mahulikar, P.P., Hundiwale, D.G., 2004. Umare, S.S., Borkar, A.D., Gupta, M.C., 2002. Bulletin Material
Polymer Advanced Technology 15, 306. Science 25 (3), 235.
Bilal, S., 2007. Unpublished PhD thesis, Technischen Universität Savitha, P., Sathyanarayana, D.N., 2004. Synthetic Metals 145, 113.
Chemnitz, Germany. Tzou, K., Gregory, R.V., 1993. Synthetic Metals 53, 365.
Borkar, A.D., 2012. Journal of Chemical and Pharmaceutical Upadhyay, P.K., Ahmad, A., 2010. Analytical & Bioanalytical
Research 4 (7), 3526. Electrochemistry 2 (3), 139.
Borole, D.D., Kapadi, U.R., Mahulikar, P.P., Hundiwale, D.G., 2006. Waware, U.S., Umare, S.S., 2005. Reactive & Functional Polymers 65,
Materials Letters 60 (20), 2447. 343.
Borole, D.D., Kapadi, U.R., Mahulikar, P.P., Hundiwale, D.G., 2007. Wu, T.M., Lin, Y.W., Liao, C.S., 2005. Carbon 43, 734.
Designed Monomers & Polymers 10 (5), 449. Yoon, C.O., Moses, D., Heeger, A.J., Cao, Y., 1994. Synthetic Metals
Cochet, M., Louarn, G., Quillard, S., Buisson, J.P., Lefrant, S., 2000. 63, 47.
Journal of Raman Spectroscopy 31, 1041. Yang, Y., Shaolin, Mu., 2008. Electrochimica Acta 54, 506.
Cao, Y., Smith, P., Heeger, A.J., 1992. Synthetic Metals 48 (1), 91.