Journal of Materials Science and Engineering A 2 (2) (2012) 190-195

D DAVID PUBLISHING

Synthesis and Characteristics of Conducting Polymer-

Based Polypyrrole in Different Solvents

Nurhizwati Abd. Rahman, Tunku Ishak Tunku Kudin, Ab. Malik Marwan Ali and Muhd Zu Azhan Yahya
Ionic Materials & Devices (iMADE) Research Laboratory, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah
Alam, Malaysia

Received: April 06, 2011 / Accepted: April 23, 2011 / Published: February 10, 2012.

Abstract: Polypyrrole (PPy) was synthesized under dry nitrogen atmosphere by chemical polymerization. The oxidant agent, ferric
chloride, was mixed with several types of solvents, such as hydrochloric acid, deionized water, and acetonitrile, before the monomer
pyrrole was added. The resultant precipitate was filtered and rinsed with methanol and ethanol several times and dried in vacuum oven
at 40 C for over 12 h. Conductivity tests, x-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy
were carried out to investigate the structure and morphology of PPy. The conductivity of the prepared samples was studied in the
frequency range 100 Hz to 1 MHz over the temperature range 253-393 K. The degree of surface density of PPy powder was directly
related to its dependence on solvents, which can be represented via the following: H2O > ACN > HCl.

Key words: Polypyrrole, solvents effect, conducting polymer, chemical polymerization.

1. Introduction notable worldwide because they are economically

important and they satisfy electrical conductivity
Many researchers have recently paid attention to
requirements when doped, as they range from 10-5 to
conducting polymers, such as polyaniline [1],
102 Scm-1. The rapid progress of this conducting
polythiophene [2], and polypyrrole (PPy) [3].
polymer has inspired research interest in its technology
Compared with other conducting polymers, PPy has
applications in molecular electronics, gas sensors
relatively high conductivity [4] and environmental
[8-10], battery electrodes [11], light emitting diodes
stability. It has attracted specific interest due to its long
[12], and supercapacitors [13].
electrical and mechanical stability [5]. Most
Most prepared PPy exists as brittle powders that are
researchers have extensively studied electrochemically
insoluble and infusible, and have poor processability
polymerized electroactive PPy, rather than chemically
[14]. The poor processability of PPy has been clarified
polymerized PPy, because the former involves direct
by the existence of strong interchain interactions
formation of PPy with better control of polymer film
between structures [15, 16]. Few studies report the
thickness and morphology [6]. It is difficult to use a
advantages and disadvantages of the two techniques,
slurry method for coating on an aluminium foil current
and most work only report about PPy mass production,
collector in electrochemical synthesis. In contrast,
formation of yield, and the slurry coating method.
chemical synthesis offers mass production at
Conducting polymers prepared by chemical
reasonable costs, and the slurry coating method allows
polymerization exhibit high conductivity, good
the application of powders to aluminum current
stability, and negligible solubility in aqueous solutions.
collectors [7]. These conducting polymers (PPy) are
The detailed chemical synthesis of PPy is presented in
Corresponding author: Muhd Zu Azhan Yahya, professor, Ref. [17]. PPy prepared by oxidation of the monomer
research field: conducting polymer. E-mail: with chemical oxidants exists in the form of a black
mzay@salam.uitm.edu.my.
 Synthesis and Characteristics of Conducting Polymer-Based Polypyrrole in Different Solvents
powder. This is achieved by oxidation of
corresponding monomers using an oxidizing agent;
thus, it is preferred for mass-production in the industry
as it provides a low-cost and efficient route to achieve
polymerization [18]. In chemical polymerization, a
variety of oxidants are used, such as (NH4)2S2O8,
Na2S2O8, H2O2, I2, and salts of transition metals, such
as Fe3+, Cu2+, Cr6+, Ru3+, and Mn7+ [19]. The common
chemical oxidants used in the synthesis are FeCl3, other
salts of iron (III), and copper (II). Through chemical
polymerization, the oxidant reacts in a suitable solvent,
such as an acid, to form a mixture. When the monomer
is added, the mixture will again react with the
conjugated monomer. At this point, polymerization
takes place under constant stirring. The more oxidants
used, the higher the yield obtained [20]. However,
solubility is reduced if the oxidant ratio is too high [21].
According to previous studies, the type of oxidant
plays an important role in polymerization, but other
factors, including choice of solvents [22], techniques
[23], reaction time, and temperature, also influence the
properties of PPy. The range or variation can be quite
extensive, so in this work, only the solvent is
considered, while other factors are kept constant. In
some cases, the oxidant also plays the role of dopant.
For example, in the chemical polymerization of pyrrole
in a solution containing both an oxidant and a
functional anion, an anion of oxidant, such as Cl of
FeCl3, is easily incorporated as a dopant into the PPy
matrix, although doping by the functional anion is not
efficient [24].
When PPy is produced by oxidation in the presence
of FeCl3, the polymer is doped with Cl- anions. The
overall reactions can be represented by the following
stoichiometric equation [17]:
y microscope (FESEM). X-ray powder diffraction (XRD)
nC4H5N + (2+y)n FeCl3 [(C4H3N) n nyCl-]
+ (2 + y)n FeCl2 + 2nHCl
where y is the degree of PPy oxidation at the doping level.
2. Experiment
Hydrated ferric chloride (Sigma-Aldrich, 97%) as an
191
oxidant and various solvents, such as hydrochloric acid
(HCl), acetonitrile (ACN), and deionized water (H2O),
as dopants were used for PPy synthesis. Pyrrole
(Aldrich, 98%) was distilled before use. About 1.42 g
of FeCl3 was dissolved in 50 mL of 1 M HCl in a
round-bottom flask and stirred on a magnetic stirrer by
clamping it to the retort stand for 30 min. Two balloons,
one of which was filled with nitrogen gas, were placed
on top of the round-bottom flask. Crushed ice was put
around the round-bottom flask to ensure that the
temperature remained between 0-5 C. Approximately
1.22 mL of pyrrole was injected into the mixture for
another half an hour. At this stage, the solution turned
from green to black. The mixture was filtered and then
rinsed several times with methanol and ethanol. Finally,
the resultant precipitates were dried in the vacuum
oven at 40 C for over 12 h. For characterization, the
sample powders were pressed into a round pellet with a
diameter of 1.526 cm using a pressure of 200 kg/cm2.
The thickness was different for every sample but within
the range of 0.78-1.40 mm.
2.1 Material Characterization
The AC conductivity of the PPy pressed pellet was
measured using an HIOKI 3532-50 LCR-Hi-Tester in
the frequency range 100 Hz to 1 MHz over the
temperature range 253-393 K. The pellet was
sandwiched between the circular stainless steel-ion
blocking electrodes. Infrared spectra were taken with
Perkin-Elmer series at a resolution of 2 cm-1 and a scan
number of 16. The discs were prepared in the form of
KBr pellets, with a PPy to KBr ratio of 1:9 at room
temperature under atmospheric pressure. The surface
morphology of PPy was characterized by an FEI
Quanta FEG 200 F field emission scanning electron
patterns were collected using an Xpert Pro Pan
Analytical instrument using Cu K radiation at 45 kV
and 20 mA.
3. Results and Discussion
The amounts of PPy produced from different
192 Synthesis and Characteristics of Conducting Polymer-Based Polypyrrole in Different Solvents

Table 1 Amounts of PPy produced in different solvents.

Solvents Yield at room temperature (30 C) at 90 C
HCl 0.1264 g 7.40 10-5 Scm-1 5.83 10-3 Scm-1
ACN 0.0650 g 7.18 10-5 Scm-1 2.92 10-3 Scm-1
H2O 0.0990 g 2.06 10-6 Scm-1 1.81 10-4 Scm-1

solvents are listed in Table 1. The yield produced from

HCl (11%) is comparable with the results from a
previous study [15]. However, to the best of our
knowledge, there is no report available in the literature
on yields produced with ACN and H2O.
The conductivity of PPy pellets prepared using
different solvents is shown in Table 1. The highest
conductivity is found at 90 C. The highest
conductivities of PPy using HCl, ACN, and H2O as
solvents are 5.83 10-3, 2.92 10-3, and 1.81 10-4
Scm-1, respectively.
The scanning electron micrograph of PPy powders (a)
prepared from different solvents is shown in Fig. 1. The
degree of surface density of the PPy sample using H2O
as the solvent (Fig. 1c) has a much denser structure
compared with PPy obtained from HCl (Fig. 1a) and
ACN (Fig. 1b), where the surfaces are more spongy.
The surface density of PPy powders obtained from
different solvents used is in the order H2O > ACN >
HCl. A denser surface morphology shows decreased
amorphousity and conductivity compared with
sponge-like surface morphology. Regarding the denser
surface in PPy prepared from H2O (Fig. 1c), the lower (b)
conductivity could be due to the limited range over
which charge carriers must hop between agglomerates.
Long-range hopping is essential in amorphous surfaces
to increase conductivity. These results are synchronous
with the conductivity results. It can thus be concluded
that the surface density of PPy powders depends on the
solvents used during polymerization.
Analysis of XRD patterns in Fig. 2 shows a peak at
2 = 26.1o in PPy obtained from H2O at room
temperature. The peak is assigned to the interlayer
(c)
distance, dBragg, from the pyrrole to the pyrrole ring in
Fig. 1 Scanning electron micrograph of polypyrrole
the polymer. There is a small peak observed at 2 = surfaces prepared from different solvents: (a) hydrochloric
26.8o in the spectrum of PPy obtained from ACN and acid (b) acetonitrile, and (c) deionized water.
 Synthesis and Characteristics of Conducting Polymer-Based Polypyrrole in Different Solvents 193

intensity (a.u)
(a)

(b)

(c)

5 15 25 35 45 55 65 75 85
angle (2)
Fig. 2 X-ray diffraction pattern of polypyrrole in different solvents: (a) acetonitrile, (b) hydrochloric acid, and (c) deionized
water.

HCl, suggesting a less-amorphous structure of the
polymer. In contrast, a more-amorphous structure is
suggested by the high intensity peak observed in PPy
obtained from H2O. These findings are in agreement
with conductivity (Table 1) and surface morphology
(Fig. 1) results, which showed that the more amorphous
the characteristics of the materials are, the higher the
electrical conductivity values achieved.
The d-spacing or interlayer spacing is calculated
from Braggs equation. From Table 2, the highest
Table 2 Comparison of d-spacing of polypyrrole samples in different solvents.
Solvents 2 (o)
Hydrochloric acid 26.8
Acetonitrile 26.8
Deionized water 26.1
d-spacing is found in PPy obtained from H2O as a
solvent. Larger d-spacing between pyrrole rings and
lower conductivity, which makes it difficult for
electrons to hop from one layer to the next, are also
observed.
Fig. 3 shows the IR spectra of PPy powder prepared
from different solvents with their assignments in the
700 to 1,700 cm-1 spectral region. The spectra show a
very similar peak due to the same structure. The small
shifting of spectra may be caused by different thickness
d ()
3.32
3.32
3.42

1542 1453 108 962

1301
1183 1040 913 834
(a)
% Transmittance

(b)

(c)

1700 1500 1300 1100 900 700

-1
wavenumbers (cm )
Fig. 3 Fourier transform infrared (FTIR) spectra of polypyrrole in different solvents: (a) hydrochloric acid, (b) deionized
water, and (c) acetonitrile.
194 Synthesis and Characteristics of Conducting Polymer-Based Polypyrrole in Different Solvents
while preparing the disc. Each spectrum shows the
broadband at 1,500 cm-1 to 1,600 cm-1 which maximum
at about 1,542 cm-1. According to Cui et al. [25], this
band can be assigned to the antisymmetric pyrrole ring
[2,5-subtituted pyrrole] while a small peak at 1,453
cm-1 can be assigned to the symmetric pyrrole ring
vibrations. A broad peak at 1,301 cm-1 indicates the
stretching vibration of C-H [ C-H] bonding. The small
peak at 1,089 cm-1 and 834 cm-1 indicates the hydroxyl
group [-OH], whereas the sharp peak at 1,040 cm-1 is
attributed to in-plane N-H deformation in the pyrrole
ring. The peak at 962 cm-1 [25] and 913 cm-1 [26] is due
to the =C-H out-of-plane vibrations. The very tiny
peak at 1,183 cm-1 describes the stretching vibration of
N-C [ N-C] bond.
4. Conclusions
The maximum conductivity value obtained was 5.83
10-3 Scm-1; this was found in PPy obtained from HCl
as the solvent. IR spectra revealed that the peaks at
-1 -1
1,542 cm and 1,453 cm represent to the symmetric
pyrrole rings, thus proving that the yield produced was
PPy. Less-amorphous structures were found in PPy
obtained from H2O as the solvent, whereas
more-amorphous structures were observed in PPy from
HCl and ACN. The surface density of PPy in different
solvents was found to be in the order of H2O > ACN >
HCl. Denser surface morphology showed
decreased amorphousity and conductivity of the
samples. The PPy sample obtained from H2O as a
solvent showed the largest d-spacing between pyrrole
rings and yielded the lowest conductivity, indicating
that electrons faced difficulties in hopping from one
layer to the next. It can be concluded that the yield
surface density and conductivity of PPy could be
controlled by the solvents used during polymerization.
Acknowledgments
Nurhizwati Abd Rahman would like to thank the
Ministry of Science, Technology, and Innovation of
Malaysia for the PGD scholarship awarded to her.
References
[1] S. Bhadra, D. Khastgir, N.K. Singha, J.H. Lee, Progress
in preparation, processing and applications of polyaniline,
Progress in Polymer Science 34 (2009) 783-810.
[2] G.Y. Han, G.Q. Shi, Conducting polymer electrochemical
actuator made of high-strength three-layered composite
films of polythiophene and polypyrrole, Sens. Actuators B
99 (2004) 525-531.
[3] S. Marcos, R. Hortiguela, J. Galban, J.R. Castillo, O.S.
Wolfbeis, Characterization of a urea optical sensor based
on polypyrrole, Mikrochim. Acta. 130 (1999) 267-272.
[4] H.C. Kang, K.E. Geckeler, Enhanced electrical
conductivity of polypyrrole prepared by chemical
oxidative polymerization: effect of the preparation
technique and polymer additive, Polymer 41 (2000)
6931-6934.
[5] O. Yavuz, M.K. Ram, M. Aldissi, P. Poddar, H. Srikanth,
Polypyrrole composites for shielding applications, Synth.
Met. 151 (2005) 211-217.
[6] A. Kassim, Z. Basar, H.N.M.E. Mahmud, Effects of
preparation temperature on the conductivity of polypyrrole
conducting polymer, Proc. Indian Acad. Sci. (Chem. Sci.)
114 (2) (2002) 155-162.
[7] K.A. Noh, D.W. Kim, C.S. Jin, K.H. Shin, J.H. Kim, J.M.
Ko., Synthesis and pseudo-capacitance of
chemically-prepared polypyrrole powder, J. Power
Sources 124 (2003) 593-595.
[8] F. Selampinar, L. Toppare, U. Akbulut, T. Yalcin, S.
Suzer, A conducting composite of polypyrrole II as a gas
sensor, Synthetic Metals 68 (1995) 109.
[9] L. Geng, S. Wang, Y.Q. Zhao, P. Li, S.M. Zhang, W.P.
Huang, et al., Study of the primary sensitivity of
polypyrrole/r-Fe2O3 to toxic gases, Mater. Chem. Phys. 99
(2006) 15-19.
the
[10] L. Geng, Y.Q. Zhao, X.L. Huang, S.R. Wang, S.M. Zhang,
W.P. Huang, et al., The preparation and gas sensitivity
study of polypyrrole/zinc oxide, Synth. Met. 156 (2006)
1078-1082.
[11] J.R. Ellis, Handbook of conductivity polymers, New York,
1986, p. 501.
[12] J. Gao, A.J. Heeger, J.Y. Lee, C.Y. Kim, Soluble
polypyrrole as the transparent anode in polymer
light-emitting diodes, Synth. Met. 82 (1996) 221-223.
[13] R.K. Sharma, A.C. Rastogi, S.B. Desu, Pulse polymerized
polypyrrole electrodes for high energy density
electrochemical supercapacitor, Electrochem. Com. 10
(200) 268-272.
[14] N. Arsalani, K.E. Geckeler, Novel electrically conducting
polymer hybrids with polypyrrole, Reactive & Functional
Polymers 33 (1997) 167-172.
[15] M.V. Zeller, S.J. Hanh, High molecular weight soluble
 Synthesis and Characteristics of Conducting Polymer-Based Polypyrrole in Different Solvents
polypyrrole, Surf. Interf. Anal. (SIC) 1988, 11: 327
[16] S.A. Chen, C.S. Liao, Conductivity relaxation and chain
motions inconjugated conducting polymers: neutral
poly(3-alkylthiophenes), Macromolecules 26 (11) (1993)
2810.
[17] A. Pron, Z. Kucharski, C. Budrowski, M. Zagorska, S.
Krichene, J. Suwalski, et al., Spectroscopy studies of
selected conducting polypyrroles, Journal of Chemical
Physics 83 (1985) 5923
[18] A. Laforgue, P. Simon, J.F. Fauvarque, J.F. Sarrau, P.
Lailler, Hybrid Supercapacitors Based on Activated
Carbons and Conducting Polymers, J. Electrochem. Soc.
148 (10) (2001) A1130-4.
[19] W. Chen, X.B. Wan, N. Xu, G. Xue, Ordered conducting
polypyrrole doped with sulfopropyl ether of
beta-cyclodextrin, Macromolecules 36 (2003) 276-278.
[20] J.Y. Lee, D.Y. Kim, C.Y. Kim, Synthesis of soluble
polypyrrole of the doped state in organic solvents,
Synthetic Metals 74 (1995) 103-106.
[21] K.T. Song, J.Y. Lee, H.D. Kim, D.Y. Kim, S.Y. Kim, C.Y.
Kim, Solvent effects on the characteristics of soluble
polypyrrole, Synthetic Metals 110 (2000) 57-63.
195
[22] K.A. Noh, D.W. Kim, C.S. Jin, K.H. Shin, J.H. Kim, J.M.
Ko, Synthesis and pseudo-capacitance of
chemically-prepared polypyrrole powder, Journal of
Power Sources 124 (2003) 593-595.
[23] H.C. Kang, K.E. Geckeler, Enhanced electrical
conductivity of polypyrrole prepared by chemical
oxidative polymerization: effect of the preparation
technique and polymer additive, Polymer 41 (2000)
6931-6934.
[24] T. Shimidzu, A. Ohtani, T. Iyoda, K. Honda,
Charge-controllable polypyrrole/polyelectrolyte
composite membranes: Part 2. Effect of incorporated
anion size on the electrochemical oxidation-reduction
process, Journal of Electroanalytical Chemistry and
Interfacial Electrochemistry 224 (1987) 123-135.
[25] L. Cui, J. Li, X.G. Zhang, Synthesis and characterization
of core-shell nanostructured PPy/V2O5 composite,
Materials Letters 63 (2009) 683-686.
[26] T.K. Vishnuvardhan, V.R. Kulkarni, C. Basavaraja, S.C.
Raghavendra, Synthesis, characterization and a.c.
conductivity of polypyrrole/Y2O3 composites, Bull. Mater.
Sci. 29 (1) (2006) 77-83.