Materials Chemistry and Physics 90 (2005) 367372

Comparative studies of solid-state synthesized polyaniline

doped with inorganic acids
Tursun Abdiryim, Zhang Xiao-Gang

, Ruxangul Jamal
School of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046,PR China
Received 19 April 2004; received in revised form 11 October 2004; accepted 19 October 2004
Abstract
Polyaniline (PANI) salts doped with inorganic acids (HCl, H
2
SO
4
and H
3
PO
4
) were directly synthesized by using solid-state polymerization
method. The FTIR spectra, UVvis absorption spectra and X-ray diffraction patterns were used to characterize the molecular structures of
the PANI salts. Voltammetric study was done to investigate the electrochemical behaviors of all these PANI salts. The PANI salts were
affected by varying the protonation media (HCl, H
2
SO
4
and H
3
PO
4
). The FTIR and UVvis absorption spectra revealed that all PANI
salts contained the conducting emeraldine salt phase at different oxidation state. The crystallinity of PANI doped with HCl was better
than those doped with H
2
SO
4
and H
3
PO
4
. The conductivity of the PANI doped with HCl is the highest among the inorganic acid doped
PANI.
2004 Elsevier B.V. All rights reserved.
Keywords: Polyaniline; Solid-state polymerization; Inorganic acids
1. Introduction
Polyaniline(PANI) is one of the most interesting con-
ducting polymers due to its environmental stability, ease in
preparation, exciting electrochemical, optical and electrical
properties and possible applications in rechargeable batter-
ies, microelectronics devices, biosensors, electrochromic
displays and chemical sensors[18]. PANI occurs in four
different oxidation states as shown in Fig. 1. It is insulating
with the conductivity of the order of 10
12
Scm
1
. Although
insulating in their neutral form, they can be rendered conduc-
tive through appropriate oxidation or reduction. Protonation
of emeraldine base gives rise to an increase of electronic
conductivity by several orders of magnitude [9]. Typically,
conducting PANI is synthesized by electrochemical or
chemical oxidation of aniline in acidic solutions [10,11].
Alternative methods have been designed to improve the
solubility and processibility of the synthesized PANI. Gong
et al. have reported solid-state synthesis of PANI doped with

Corresponding author. Tel.: +86 09918581940; fax: +86 09918581006.

E-mail address: azhangxg@163.com (Z. Xiao-Gang).
H
4
SiW
12
O
40
under 20

C by furbishing in mortar [12].

Kaner et al. have reported a solvent-free mechanochemical
route for the synthesis of PANI in which the reaction between
aniline salt and the oxidant, ammonium peroxydisulfate was
carried out by ball milling the reactants for one hour, in the
absence of solvent at ambient temperature [13].
Inthis paper, PANI dopedwithinorganic acids synthesized
by solid-state polymerization. The results were explained on
comparative basis. The effect of inorganic acids on the PANI
properties was discussed in detail.
2. Experimental
2.1. Synthesis
Aniline monomer was distilled under reduced pressure.
Other reagents, such as dopants (HCl, H
2
SO
4
and H
3
PO
4
),
oxidant (ammonium peroxydisulfate, APS) were used as re-
ceived (all the chemicals and aniline used were of ARgrade).
A typical solid-state polymerization procedure was as
following: precooled mortar was put in the ice bath, the
0254-0584/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2004.10.036
368 T. Abdiryim et al. / Materials Chemistry and Physics 90 (2005) 367372
Fig. 1. Four different redox forms of PANI: (a) leucoemeraldine base (fully
reduced form), (b) emeraldine base (half-oxidized form), (c) conducting
emeraldine salt (half-oxidized and protonated form) (d) pernigraniline base
(fully oxidized form).
temperature was kept at 0

C. 1 ml 37 wt.% HCl was put into

the mortar. Then freshly distilled aniline (1 ml) was added
dropwise. After grounding the reactant about 10 min, the
mixture became white paste, 2.2 g APS was added by fur-
ther grounding for 20 min until the color of solid changed to
black green. The greenish black precipitate of the polymer
was isolated by ltration, washed with ethylether, ethanol
and distilled water respectively until the solution is color-
less, and then dried under vacuum (0.075 MPa) at 50

C for
48 h.
To get other PANI salts, 1ml 37 wt.%HCl was replaced by
1 ml 96 wt.% H
2
SO
4
and 1 ml 87 wt.% H
3
PO
4
, respectively,
noted as PANI-H
2
SO
4
, PANI-H
3
PO
4
.
2.2. Characterization
FT-IR spectra of the polymers were obtained by using
a BRUKEREUINOX-55 Fourier transform infrared spec-
trometer (frequency range 3500400 cm
1
). UVvis spectra
of the polymer solution in m-cresol were recorded by us-
ing Shimadzu UV-2450 spectrophotometer in the range of
300900 nm. The X-ray diffraction studies were performed
on a D/Max 2400 X-ray diffractometer by using Cu K ra-
diation source ( =0.15418 nm). The scan range (2) was
10

70

. The room temperature conductivity was measured

on pressed pellets with a diameter of 1 cmby using two-probe
technique. Electrochemical measurements were carried out
with a classical three-electrode cell by using CHI660A elec-
trochemical workstation system. The working electrode was
a PANI lm electrode prepared by casting the DMF solution
of respective PANI salts on platinium electrode. The refer-
ence electrode was Ag/AgCl, and the counter electrode was
a 1 cm
2
area Pt ag.
Fig. 2. FT-IR spectra of PANI salts (a) PANI-HCl (b) PANI-H
2
SO
4
(c)
PANI-H
3
PO
4
.
3. Results and discussion
3.1. IR spectra
Fig. 2 shows the IR spectra of PANI salts synthesized
by solid-state polymerization method. The characteristic
bands at 15561565 cm
l
arises mainly from both C N
and C C stretching of the quinoid diimine unit, while the
T. Abdiryim et al. / Materials Chemistry and Physics 90 (2005) 367372 369
Table 1
Assignment of IR spectra of PANI salts
Sample C N C H
a
PANI-HCl 1559 cm
1
1483 cm
1
1298 cm
1
1108 cm
1
795 cm
1
PANI-H
2
SO
4
1558 cm
1
1475 cm
1
1296 cm
1
1109 cm
1
796 cm
1
PANI-H
3
PO
4
1558 cm
1
1475 cm
1
1296 cm
1
1124 cm
1
796 cm
1
a
Out-of-plane bending.
band near14751481 cm
l
is attributed to the C C aro-
matic ring stretching of the benzenoid diamine unit. The
12961298 cm
1
and 795797 cm
1
bands can be as-
signed to C N stretching of the secondary aromatic amine
and an aromatic C Hout-of-plane bending vibration, respec-
tively. These characteristic bands conrm that the PANI salts
contain the conducting emeraldine salt phase. The IR assign-
ments of PANI salts were listed in Table 1.
The results indicate that the backbone structures of PANI-
HCl, PANI-H
2
SO
4
, and PANI-H
3
PO
4
obtained in this solid-
state synthesis method are identical to each other and also to
those of PANI salts synthesized previously in conventional
chemical and electrochemical methods [10,14,15].
Based on the previous treatments of IR data in which the
quinoid and benzenoid units were identied [1618], the in-
tensity ratio of these two absorption bands at 1590 and
1500 cm
l
is indicative of the extent of oxidation state of the
polymer, whichreects the content of the quinoiddiimine and
benzene ring structute. The ratio is calculated as following:
R(intensity ratio) =
I
1590 cm
1
I
1500 cm
1
where I is absorption intensity.
The values calculated from the FT-IR data are listed in
Table 2 are R=0.870, 0.896 and 0.920 for PANI salts synthe-
sized by solid-state polymerization in the presence of HCl,
H
2
SO
4
, and H
3
PO
4
, respectively. An order in R (intensity
ratio) is PANI-H
3
PO
4
>PANI-H
2
SO
4
>PANI-HCl was ob-
served. In each case, the ratio of the two bands is less than 1.0
indicating that there are more benzene units within the poly-
mer. A value of 1.0 denes the emeraldine type structure and
the polymer can have higher conductivity [18]. From above
results, it can be concluded that the formation of fully reduced
phase are predominant in these PANI salts. A comparison of
the ratio of the relative intensity of quinoid to benzenoid ring
modes shows the highest ratio of 0.92 in PANI-H
3
PO
4
com-
pared to PANI-H
2
SO
4
and PANI-HCl. This may be due to
the pH value of each acid, because all acids are in the same
Table 2
The absorption intensity and R(intensity ratio) of quinoid and benzenoid
units in PANI salts
I
15561565 cm
1 I
14751481 cm
1 R (intensity ratio)
0.234 0.269 0.870
0.370 0.413 0.896
0.218 0.237 0.920
volume (1 ml), the pH value may be different with the [H
+
].
The small amount of water will determine the pH value of
them. For 1 ml 37 wt.% HCl, 96 wt.% H
2
SO
4
and 87 wt.%
H
3
PO
4
, an order of pH (HCl) <pH (H
2
SO
4
) <pH (H
3
PO
4
)
will be discovered. The pH value of the reaction medium ap-
pears to be one of the main parameters to affect the oxidation
state of the polyaniline, which determines its properties. The
higher the pH of the medium and the higher the oxidant con-
centration, the higher the oxidation state of PANI [19].This
is the reason for the ratio of the relative intensity of quinoid
to benzenoid ring modes shows the highest ratio in PANI-
H
3
PO
4
. To contrast with 37 wt.% HCl and 87 wt.% H
3
PO
4
,
96 wt.% H
2
SO
4
is more oxidative acid, which can also cause
further oxidation of polyaniline, but that pH (H
2
SO
4
) <pH
(H
3
PO
4
) will benet for reduction state of polyaniline dur-
ing the oxidative polymerization [19,20]. So the ratio of the
relative intensity of quinoid to benzenoid ring modes shows
between PANI-H
3
PO
4
and PANI-HCl.
3.2. UVvis spectra
Fig. 3 represents the UVvis absorption spectra of PANI
salts in m-cresol solution. These PANI salts show three
characteristic absorption peaks at 306324, 402412
and 828835 nm (Table 3). The absorption peak at
306324 nm can be ascribed to
*
transition of the ben-
zenoidrings, while the peaks at 402412and828835 nm
can be attributed to polaron
*
transition and polaron
transition, respectively,[2127], furthermore the peaks at
402412 and 828835 nm are related to doping level and
Fig. 3. UVvis spectra of PANI salt (a) PANI-HCl (b) PANI-H
2
SO
4
(c)
PANI-H
3
PO
4
.
370 T. Abdiryim et al. / Materials Chemistry and Physics 90 (2005) 367372
Table 3
The assignments of UVvis absorption peaks of PANI salts
Sample Wave length of absorption peak

*
transition Polaron
*
transition Polaron transition A
828835
/A
3023324
PANI-HCl 324 nm 403 nm 835 nm 0.92
PANI-H
2
SO
4
320 nm 402 nm 833 nm 0.77
PANI-H
3
PO
4
306 nm 412 nm 828 nm 0.63
formation of polaron [2325]. Based on the previous research
that the extent of doping can roughly be estimated from the
absorption spectra of the polyaniline, in which the ratio of
absorbances at 828835 nm (polaron) and 306324 nm
(
*
transition) indicated the doping level of polyaniline
[27], it was found that in the case of PANI salts the inten-
sity ratio (A
828835
/A
306312
) was smallest in PANI-H
3
PO
4,
which meant that the doping level of PANI-H
3
PO
4
was lower
than that of PANI-HCl and PANI-H
2
SO
4
.
3.3. XRD analysis
Crystallinity and orientation of conducting polymer have
been of much interest, because more highly ordered sys-
tems could display a metallic-like conductive state [28].
Pouget et al. made the detailed and systematical study
on the PANI prepared through conventional methods and
proposed a pseudoorthorhombic unit cell structure for
PANI [29]. In this study, the X-ray diffraction patterns
for the PANI powder doped with different inorganic acid
are shown in Fig. 4. The Bragg diffraction peaks of
2 =9.02

(d =9.804

A), 14.68

(d =6.034

A), 20.33

(d =4.368

A), 25.30

(d =3.520

A) can be found in the
X-ray diffraction patterns of the PANI-HCl. However, most
diffraction peaks disappeared in the PANI-H
2
SO
4
and PANI-
H
3
PO
4
. The diffraction peaks of PANI-HCl are relatively
sharp and strong. The detailed data are presented in Table 3.
Two peaks centered at 2 =20

(d =4.3684.461

A)
and 25

(d =3.5203.560

A) were observed in X-ray scat-
Fig. 4. The X-ray diffraction patterns for PANI salts (a) PANI-HCl (b) PANI-
H
2
SO
4
(c) PANI-H
3
PO
4
.
tering patterns of all PANI salts. The peak centered at
2 =20

may be ascribed to periodicity parallel to the poly-

mer chain, while the peaks at 2 =25

may be caused by
the periodicity perpendicular to the polymer chain [30]. The
peak at 2 =20

also represents the characteristic distance

between the ring planes of benzene rings in adjacent chains
or the close-contact interchain distance [31]. For PANI-HCl,
the peak of 2 =25

(110 face) is stronger than that of

2 =20

(100 face), which is similar to that of highly doped

emeradine salt [29]. However, for PANI-H
2
SO
4
and PANI-
H
3
PO
4
, the peak of 2 =25

(110 face) is weaker than

that of 2 =20

(100 face), which is similar to that of

less doped emeradine salt. The d-space corresponding to the
peak at 2 =20

is in the order of PANI-H

3
PO
4
>PANI-
HCl >PANI-H
2
SO
4
. The PANI chains produced under more
acidic conditions have less structrural defects (e.g., non-para
linkages in PANI chains), which will cause the fractions of
crystalline phase increasing in PANI [32]. For 1 ml 37 wt.%
HCl, 96 wt.% H
2
SO
4
and 87 wt.% H
3
PO
4
, an order of pH
(HCl) <pH(H
2
SO
4
) <pH(H
3
PO
4
) will be discovered, which
will lead to the different crystallinity.
3.4. Cyclic voltammograms
The redox properties of the PANI salts were investigated
with cyclic voltammetry. Fig. 5 shows the cyclic voltammo-
grams (CVs) of the polymer lms on Pt in 1 mol/L H
2
SO
4
.
The redox peaks of PANI salts are similar to the PANI salts
such as PANI-H
3
PO
4
, PANI-H
2
SO
4
and PANI-HCl prepared
electrochemically that previously reported [33]. The anodic
and cathodic potentials are listed in Table 4. Three redox cou-
ples are observed in the CVs of PANI-H
2
SO
4
and PANI-HCl,
while the two redox couples are in the CV of PANI-H
3
PO
4
.
In the positive sweep the rst redox peak (at ca.
0.260.35 V) is well-known as the formation of radical
cations (polaronic emeraldine) [34] and the second redox
couple at ca. 0.70.8 V is the formation of diradical dications
(represented by the resonance structures: bipolaronic pern-
igraniline and protonated quinonediimine) [35] through the
oxidation of PANI salts. The intermediate peaks of relatively
low intensity absorbed between 0.40.6 V, these peaks have
been associated to the degradation of PANI salts [36]. The
redox peaks are relatively are sharp in CVs of PANI-H
2
SO
4
,
PANI-HCl, however, broad peaks and most positive poten-
tial shift in the rst redox potential are observed in the CV
of PANI-H
3
PO
4
, these were due to the high pH of H
3
PO
4
,
which will lead to more oxidation state of PANI, on the con-
trary, the quinoid unit is more elctron-withdrawing unit than
T. Abdiryim et al. / Materials Chemistry and Physics 90 (2005) 367372 371
Table 4
The2 values, intensity and pseudoorthorhombic indexation(hkl) [28] of PANI salts
2 (intensity) (hkl)
PANI-HCl d (

A) PANI-H
2
SO
4
d (

A) PANI-H
3
PO
4
d (

A)
9.02

(w) 9.804 10.14

(w) 8.723 001

14.68

(m) 6.034 011

20.33

(w) 4.368 20.70

(s) 4.291 19.90

(s) 4.461 100

25.30

(s) 3.520 24.98

(w) 3.565 25.01

(s) 3.560 110

w, weak; m, medium; s, strong.
Fig. 5. The Cyclic voltammograms of PANI salts in 1 mol/LH
2
SO
4
solution
scan rate: 50 mV/s (a) PANI-HCl (b) PANI-H
2
SO
4
(c) PANI-H
3
PO
4
.
the benzenoid unit in polymer chain, this cause to the rst
redox potential shifts to higher potential [37].
3.5. Conductivity
The conductivity of PANI depends on the degree of dop-
ing, oxidation state, particle morphology, crystallinity, inter-
or intrachain interactions, molecular weight, etc. [25]. The
conductivity of PANI salts is listed in Table 5. From the re-
sults of IR spectra, UVvis spectra and cyclic voltammo-
gram studies, the conductivity differences of PANI salts can
be concluded for the characteristics of inorganic acids (e.g.,
HCl, H
2
SO
4
and H
3
PO
4
). The PANI produced under more
acidic conditions has a higher electrical conductivity [31],
Polyaniline has proved particularly interesting for its good
conductivity upon doping with nonoxidizing acids [10,11].
From Table 6, one can see that the conductivity of polyani-
line synthesized in HCl is the largest and that in H
3
PO
4
is the
smallest in the three acids.
All these acids were used without further dilution. 96 wt.%
H
2
SO
4
is more oxidative, polyprotic and strong acid while
87 wt.%H
3
PO
4
is polyprotic, nonoxidizing and not as strong
as other acids and 37 wt.% HCl is nonoxidizing strong acid.
Wheninsame volume (inthis case 1 mL), the amount of water
in the acids will determine the pHvalue and oxidative ability.
The amount of water is in the order of HCl >H
3
PO
4
>H
2
SO
4
.
In the same experimental condition, strong acid is benet
for the yield of PANI and conductivity, while the weak acid
has an opposite behavior [19]. Zhang et al. reported an order
of PANI-HCl >PANI-H
2
SO
4
>PANI-H
3
PO
4
in conductivity
Table 5
The redox potentials of PANI salts
Sample I (rst
redox peak)
II (intermediate
peaks)
III(second redox
peak)
E
pa
/V E
pc
/V E
pa
/V E
pc
/V E
pa
/V E
pc
/V
PANI-HCl 0.26 0.08 0.56 0.49 0.79 0.67
PANI-H
2
SO
4
0.26 0.07 0.54 0.48 0.79 0.69
PANI-H
3
PO
4
0.35 0.15 0.58 0.42
Table 6
The Conductivity values and yields of PANI salts
Sample Conductivity (S/cm) Yield (%)
PANI-HCl 12 82
PANI-H
2
SO
4
3.8 78
PANI-H
3
PO
4
0.8 75
372 T. Abdiryim et al. / Materials Chemistry and Physics 90 (2005) 367372
absorved, in which the PANI salts are chemically prepared
[15]. The conductivities of the solid-state synthesized PANI
salts were in the order of PANI-HCl >PANI-H
2
SO
4
>PANI-
H
3
PO
4
, this is well matched with the report above. But the
ratio of the relative intensity of quinoid to benzenoid ring
modes is related to the conductivity of polyaniline, i.e., the
higher the relative intensity of the absorption peaks of quinoid
to benzenoid ring modes to that of doped anions, the greater
is the conductivity of polyaniline [38]. However, the con-
ductivity of polyaniline is affected by its doping level and
crystalline structure. Above all, The lowest conductivity of
the PANI-H
3
PO
4
has may be due to a possible reason that
the molecular size of H
3
PO
4
, which is larger than that of
HCl [15], except highest pH value of H
3
PO
4
, lowest doping
level and crystallinity of PANI salt which also leads to lower
conductivity [32].
4. Conclusion
Polyaniline(PANI) doped with inorganic acids (e.g., HCl,
H
2
SO
4
and H
3
PO
4
) were synthesized by solid-state poly-
merization. Spectroscopic studies showed here is the highest
ratio of the relative intensities of the quinoid to benzenoid unit
in H
3
PO
4
doped PANI and leucoemeraldine phase is formed
predominantly in PANI salts.These results were further sup-
ported by conductivity measurements and cyclic voltamme-
try. More crystalline PANI salt was obtained by doping with
HCl comparing with other inorganic acids in this method.
Among these inorganic acids, HCl was found to be more suit-
able as a protonic acid media in order to attain a PANI with
high conductivity in this solid-state polymerization. These
differences mainly depended on the characteristics of inor-
ganic acids (e.g., HCl, H
2
SO
4
and H
3
PO
4
): small amount of
water in the acids; strong and weak oxidizability of the acids.
All these lead to PANI salts in different oxidation state, yield
and structure.
Acknowledgements
This work was supported by The National Foundation of
Science of China (No. 20403014), it was also supported by
XiBu ZhiGuang Science Foundation of China.
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