Synthetic Metals 159 (2009) 1353–1358

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Polypyrrole microstructure deposited by chemical and electrochemical methods

on cotton fabrics
K. Firoz Babu, R. Senthilkumar, M. Noel, M. Anbu Kulandainathan ∗
Electro Organic, Central Electrochemical Research Institute, Karaikudi 630006, India

a r t i c l e i n f o a b s t r a c t

Article history: Electrochemically and chemically coated cotton fabrics with polypyrrole are comparatively evaluated
Received 1 January 2009 and characterized in order to produce the conducting fabrics/textiles. The polypyrrole coated fabric is
Received in revised form 4 March 2009 obtained electrochemically by constant current electrolysis (2 mA cm−2 ) at room temperature for 4 h. The
Accepted 6 March 2009
stability, electrical conductivity and electrochemical behaviour of such composite coating are evaluated by
Available online 21 April 2009
means of SEM, FTIR, TGA, DSC, four-probe conductivity, impedance spectroscopy and cyclic voltammetry.
When compared to chemical method thicker films of polypyrrole with globular microstructure could
Keywords:
be obtained by electrochemical technique and the conductivity of the polypyrrole film was also high
Conducting textiles
Polypyrrole
(1.9 × 10−2 to 3.3 × 10−1 S cm−1 ). The weight uptake and the electrical conductivity of the coated fabric
Electrochemical oxidation increase with concentration of pyrrole and time of electrolysis. Many other physico-chemical properties
Constant current electrolysis of the polypyrrole films obtained by the two methods were found to be qualitatively similar.
Cotton © 2009 Elsevier B.V. All rights reserved.
Electrical conductivity

1. Introduction
Modification of electrical properties on cotton fibres and fabric
employing conducting polymers to achieve specialized functional
properties is an active current research area. Conducting polyaniline
[1] and polypyrrole (Ppy) [2] were chemically coated on cotton fab-
ric using persulphate and ferric chloride respectively as oxidizing
agents. The polyaniline coated cotton fabric exhibits some antimi-
crobial activity [3]. The Ppy is an important conducting polymer
with high electrical conductivity and appreciable environmental
stability [4,5]. The Ppy coated fabrics also exhibit electrical heat-
ing behaviour [6]. A detailed report on the performance of the
Ppy coated cellulose fabric is available in literature [7]. Electro-
magnetic interference (EMI) shielding properties of the Ppy coated
nylon fabrics prepared via direct chemical polymerization tech-
niques have been evaluated [8]. The novel vapour phase two-stage
polymerization methods are introduced recently [9]. Methods for
improvement of the dielectric characterization techniques for the
measurement of such a conducting polymer coated fabrics are also
been developed [10]. Further functionalization of conducting poly-
mer coated fabrics using triethoxysilane is also possible [11].
A few reports on formation of conducting polymer coated tex-
tile fibres are noticed in recent literatures. The Ppy composites
have been chemically coated on cellulose as well as protein fibres
∗ Corresponding author. Tel.: +91 4565 227772; fax: +91 4565 227779.
E-mail address: manbu123@yahoo.com (M.A. Kulandainathan).
and their electrical properties were evaluated [12,13]. The continu-
ous vapour phase polymerization technique can also be employed
for coating cotton, nylon and wool yarns [14]. The conductivity of
polypyrrole coated fabric did not decrease significantly after sub-
jecting the fabric to the laundering test [15] as prescribed by textile
processing industry in Australia (AS 2001.4.15-1994).
Electrochemical polymerization of aniline as well as pyrrole on
cotton fibres was achieved by winding the fibre around the plat-
inum foil anode [16,17]. Modification of the Ppy covered nylon
and polyester fabrics through electrochemical method with the
Ppy/hybrid materials have been developed recently [18,19]. In the
present work, the electrochemical method is used to prepare the
Ppy coated cotton fabric by tightly fixing it on the graphite, which
serves as the anode material. The physico-chemical properties of
these conducting fabrics are evaluated and also compared with the
Ppy coated fabric prepared by chemical method.
2. Experimental
Cotton fabrics were scoured and bleached before coating with
the Ppy. Pyrrole (98%), ferric chloride (FeCl3 , AR Grade) and
sodium chloride (NaCl, AR grade) were purchased from SRL, India.
Deionised water was used for all the experiments. Pyrrole was dis-
tilled before use.
Chemical polymerization of pyrrole was carried out by keeping
the molar ratio 1:2:2 for monomer, NaCl and FeCl3 respectively in
all the experiments. The control cotton fabric sample (4 cm × 4 cm)
was impregnated in 0.1 mol L−1 pyrrole monomer solution con-

0379-6779/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2009.03.005
1354 K.F. Babu et al. / Synthetic Metals 159 (2009) 1353–1358
taining 0.2 mol L−1 NaCl and was mechanically stirred for 30 min.
Temperature was maintained at 4–6 ◦ C throughout the experi-
ments. After 30 min, 0.2 mol L−1 FeCl3 was added into the reaction
mixture and stirring continued for another 2 h. A black precipi-
tate was deposited on the cotton cloth. The excess polymer was
removed from the fabric by washing with water at 60 ◦ C for 15 min
and air dried. While studying the concentration effect of monomer
the molar concentrations of NaCl and FeCl3 were also increased to
keep their overall molar ratio of 1:2:2.
The electrochemical polymerization was performed under gal-
vanostatic condition. In a single compartment cell, cotton fabric
wounded on graphite electrode (all the edges and backside of
the electrode were completely masked using insulating tape and
the exposed area was 7 cm × 7 cm) and stainless steel were used
as anode and cathode respectively. A constant current of 100 mA
(2 mA cm−2 ) was subjected to the electrolyte containing 0.1 mol L−1
pyrrole and 0.2 mol L−1 NaCl. The pyrrole and NaCl ratio was kept
constant at 1:2 in all the experiments. The initial polymerization
of pyrrole occurred on the electrode surface (below the cotton fab-
ric) and after approximately 1 h, a black deposit was found on the
cotton surface. Observation of a uniform conducting polymer on
the cotton surface within 1 h was considered as the proper fixing of
the fabric on the electrode surface. The electrolysis was continued
for 4 h to complete the polymerization (charge passed was 5760 C).
After electrolysis, the fabric was taken out, washed with water at
60 ◦ C for 15 min and air dried.
Scanning Electron Microscopy images were obtained using
HITACHI Model S-3000H at various magnifications to study the
surface morphology of the control cotton and the Ppy coated
cotton fabrics. The control cotton was gold sputtered to get elec-
trical contact. The conductivity of the materials was measured
using a four-probe technique connected to a digital multimeter
(Keithley Model-2010) having a capacity of 2400 source meter and
2187 nano voltmeter. The thickness of the coated fabric before
and after coating with conducting polymer was determined using
Fig. 1. SEM images of the surface of (a) pure cotton fabric; Ppy coated cotton obtained using 0.1 mol L−1 pyrrole concentration by (b) chemical method and (c) electrochemical
method at a magnification of 1.0k.
PosiTector 6000 thickness meter. The difference between these
two measurements gave the thickness of the conducting poly-
mer. The control cotton fabric shows the thickness of 260 ␮m.
X-ray diffraction data sets were collected at room temperature on a
PANalytical X’PERT PRO system in Bragg–Brentano geometry using
Cu K␣1 (1.540 Å) radiation. The powder diffraction covered the
10◦ < 2 > 40◦ range with 0.0170◦ steps. FT-IR spectra were recorded
using PerkinElmer FTIR spectrophotometer, Model Paragon 500.
Gel permeation chromatograph was performed using the instru-
ment JASCO, Japan. Thermal stability of the Ppy coated fabrics was
determined by Thermogravimetric Analysis (TGA) and Differential
Scanning Calorimetry (DSC) using TA Instruments Model SDT Q600
(Software: Thermal Advantage) from 10 to 500 ◦ C at a heating rate
of 10 ◦ C/min under nitrogen atmosphere.
The cyclic voltammetry and impedance measurements were
performed using BAS IM6 Electrochemical Analyser, USA with
Thales 3.18-USB software. In a conventional three electrode sys-
tem, a graphite and the Ppy coated cotton covered graphite
(0.5 cm × 0.5 cm) were used the working electrode for cyclic
voltammetry. A platinum foil and saturated calomel electrode were
the counter and reference electrodes respectively. The test solutions
were deaerated at least 15 min with N2 to eliminate interfering oxy-
gen. All the experiments were performed at 300 ± 2 K. Impedance
measurements were made in the frequency range of 10 mHz to
100 KHz and the amplitude was 10 mV, by sandwiching the Ppy
coated cotton fabric (1 cm diameter) between two stainless steel
(SS304) blocking electrodes contacts, without any electrolyte.
3. Results and discussion
Cotton fabric is a non-conducting material. Providing electrical
contact to such fabric to enable electrochemical polymerization is
indeed a difficult task. In the present work, it is possible to tightly fix
the cotton fabric on graphite substrate and form a uniform polymer
film on the cotton surface under galvanostatic condition at a current
 K.F. Babu et al. / Synthetic Metals 159 (2009) 1353–1358
Fig. 2. SEM images of the surface of (a) pure cotton fabric; Ppy coated cotton obtained using 0.1 mol L−1 pyrrole concentration by (b) chemical method and (c) electrochemical
method at a magnification of 5.0k.
density of 2 mA cm−2 . The electrochemically formed conducting
polymer film is found to possess some specific advantageous when
compared to their chemically formed counter parts. Some of these
properties are highlighted here.
Scanning Electron Microscopy (SEM) was used to examine the
morphology and structural characterization of modified cotton sur-
faces. The SEM micrographs obtained for pure cotton, chemically
and electrochemically coated cotton fibres (magnification 1k) are
shown in Fig. 1(a–c) respectively. Some patchy and rough deposits
are noticed in chemically (Fig. 1b) coated fibres. The electrochem-
ically coated fibre surfaces show significant smoothness (Fig. 1c)
at fibre level, which is comparable to the surface of pure cotton
fibre (Fig. 1a). The same result is further confirmed by comparing
the surface structure of single fibre as shown in Fig. 2 (magnifica-
tion 5k). Rough deposits on the chemically (Fig. 2b) coated fibre is
clearly noticed when compared to pure cotton fibre (Fig. 2a) and
electrochemically coated fibre (Fig. 2c).
The electrochemical approach becomes more favourable when
thicker Ppy films are formed using high initial concentrations of
pyrrole monomer. SEM images of the Ppy coated cotton fibres using
0.3 mol L−1 monomer are presented in Fig. 3. The Ppy deposited by
chemical method (Fig. 3a) is rough whereas the morphology of the
electrodeposited polymer (Fig. 3b) presented a better organization
and a globular appearance. The electrochemical polymerization
produced fairly thick Ppy film, exhibiting almost complete coverage
of the fibre surface.
The weight uptake and the electrical conductivity of polymer-
coated cotton fabrics are presented in Fig. 4. When compared to
the chemically coated fabric, electrochemical method shows sig-
nificantly higher weight uptake. This is also confirmed by the SEM
results presented above. In the electrochemical method, polymer-
ization proceeds through anodic oxidation of pyrrole. Hence the
probability of formation of positively charged Ppy backbone with
Cl− counter-ions ensuring the higher conductivity, continuous film
1355
formation and growth. The conductivity measured using four-probe
method found a monotonically increase with increase in concentra-
tion in both cases (Fig. 4b). Electrochemically coated Ppy exhibits
the conductivity in the range of 1.9 × 10−2 to 3.5 × 10−1 S cm−1 ,
which is higher than that of chemically coated fabric (3.9 × 10−3
to 9.4 × 10−2 S cm−1 ).
The increase in thickness of the coated fabric was found to
depend on the initial concentration of the monomer. The thick-
ness increased by 30 ␮m when the monomer concentration was
0.1 mol L−1 and 120 ␮m when the concentration was 0.3 mol L−1 .
Similar thickness values were obtained for chemically and electro-
chemically coated fabric with same concentration of monomer.
Cyclic voltammetric experiments were carried out to compare
the electrochemical behaviour of Ppy coated cloth and Ppy film
directly deposited on graphite electrodes. Fig. 5a and b show the
voltammetric responses of plain graphite and Ppy coated graphite
in 0.1 mol L−1 NaCl solution. A broad oxidation and reduction
regions correspond to the oxidized and reduced state of Ppy film
were observed (Fig. 5b). Plain graphite covered with a cotton cloth
exhibited similar background current response observed for plain
graphite surface without the cotton cloth (compare Fig. 5c and b).
The plain graphite electrode covered with a Ppy coated cloth also
exhibited the voltammetric behaviour, which is similar to Ppy film
covered graphite electrode (compare Fig. 5d and b). The Ppy film
was coated on graphite as well as cotton cloth under identical
galvanostatic experimental conditions with (0.1 mol L−1 ) pyrrole
monomer for recording the voltammogram presented in Fig. 5b and
d. These responses clearly indicate that the qualitative similarity in
the electrochemical behaviour of Ppy film formed on graphite as
well as cotton fabric.
Impedance spectra for the Ppy coated fabric prepared by electro-
chemical method using different concentrations of monomer are
shown in Fig. 6. The Ppy coated fabric exhibits only a single bulk
arc. When the pyrrole concentration increases, the shape of the
1356 K.F. Babu et al. / Synthetic Metals 159 (2009) 1353–1358
Fig. 3. SEM images of the surface of Ppy coated cotton obtained using 0.3 mol L−1 pyrrole concentration by (a) chemical method and (b) electrochemical method at a
magnification of 5.0k.
impedance spectrum remains the same. But, the surface resistiv-
ity of the coated fabric reduced from 132.86  for 0.1 mol L−1 to
17.06  for 0.5 mol L−1 , as expected. These results can be correlated
with the conductivity data measured using four-probe method.
The conducting polymer deposits obtained on the fabrics were
dissolved in THF and their average molecular weight was deter-
mined using gel permeation chromatograph. The average molecular
weight of the electrochemically deposited polymer (6062) is
slightly lower than the chemically (7541) deposited polymer.
Fig. 4. Plots of the (a) weight uptake and (b) conductivity vs concentration of the
pyrrole of coated fabrics.
Apparently the average monomer units are also slightly lesser in
electrochemically formed polymer (93 units) than the chemically
formed polymer (116 units). These calculations presume that in all
these cases, simple condensation of pyrrole units occur throughout
the reaction time. However the difference in the average molecu-
lar weight is nearly 20% suggesting that polymers of more uniform
structure with less number of monomer units are formed during
electrochemical method.
XRD measurements also confirmed the formation of poly crys-
talline conducting polymer. Pure Ppy film was found to give a
broad XRD peak around 2 values of 26◦ [4,20]. As shown in Fig. 7,
pure cotton fabric does not exhibit any XRD signal in this region.
However distinct intensity signal in this region is noticed for chem-
ically (2 = 25.72◦ ) and electrochemically (2 = 25.60◦ ) deposited
Fig. 5. Cyclic voltammetry of (a) pure graphite, (b) polypyrrole coated graphite, (c)
pure cotton wounded graphite and (d) polypyrrole coated cotton wounded graphite
in 0.1 mol L−1 NaCl at 20 mV s−1 .
 K.F. Babu et al. / Synthetic Metals 159 (2009) 1353–1358
Fig. 6. Impedance plot of electrochemically prepared Ppy coated cotton fabric using
different monomer concentrations (a) 0.1, (b) 0.2, (c) 0.3 and (d) 0.5 mol L−1 .
conducting polymers. This XRD signal can arise due to the scat-
tering from Ppy chains at the interplanar spacing [21]. These data
suggests that a conducting polymer prepared by the above methods
possess good structural similarities.
Molecular structures of the resulting Ppy obtained using chem-
ical and electrochemical methods were characterized by FT-IR
spectra in the range from 4000 to 400 cm−1 , with 50 scansions and
4 cm−1 of resolution. Typical responses obtained for the powdered
pure cotton and Ppy coated cotton powder pelleted with potas-
sium bromide are presented in Fig. 8. It is clearly seen that the
characteristic Ppy peaks are located around 1540 and 1460 cm−1
due to symmetric and asymmetric ring stretching modes respec-
tively [22,23]. A distinct absorption peak at 1540 cm−1 was also
observed by earlier workers attributed to the presence of C C ring
stretching band of Ppy. The spectrum showed other characteristic
peaks of Ppy at 1170 and 1036 cm−1 for coated fabrics has been
assigned to the bipolaronic due to over oxidation and N–H defor-
mation respectively [24,25]. This observation is the conformity for
the Ppy formation on cotton fabric.
Thermal gravimetric analysis of pure cotton fabric exhibits sub-
stantial weight loss in three stages in the temperature range up to
289 ◦ C (I stage), between 289 and 370 ◦ C (II stage) and above 370 ◦ C
Fig. 7. X-ray diffraction patterns of (a) pure cotton fabric; Ppy coated cotton obtained
using 0.1 mol L−1 pyrrole concentration by (b) chemical method and (c) electrochem-
ical method.
1357
Fig. 8. FT-IR analysis of (a) pure cotton fabric; Ppy coated cotton obtained using
0.1 mol L−1 pyrrole concentration by (b) chemical method and (c) electrochemical
method.
(III stage) is shown in Fig. 9. In the first stage, a weight loss up to 9%
is noticed, which may correspond to a loss due to the moisture and
adsorbed molecules. The weight loss in the second stage is indeed
substantial which has been contributed to the degradation of cel-
lulose. The decomposition of Ppy coated cotton fabrics followed a
similar tendency as that of pure cotton fabrics. At 500 ◦ C, the residue
obtained for electrochemically and chemically coated cotton fabrics
are about 25% and 20% respectively, whereas the pure cotton shows
only 9%. The excess residue available in the coated fabrics is due to
the presence of Ppy.
The DSC spectrum (Fig. 10) shows that the pure cotton fabric
exhibits two broad exothermic peaks of decomposition (Tdec ) at
366.71 and 406.91 ◦ C and the enthalpies of decomposition (Hdec )
determined by peak integration, correspond to these tempera-
tures are 50.30 and 134.6 J g−1 respectively. The Ppy influences on
the cotton fabric and shows only a narrow peak of Tdec by shift-
ing the temperature to 373.84 ◦ C for chemically and 361.49 ◦ C for
electrochemically coated cotton fabrics. Simultaneously the Hdec
Fig. 9. TGA analysis of analysis of (a) pure cotton fabric; Ppy coated cotton obtained
using 0.1 mol L−1 pyrrole concentration by (b) chemical method and (c) electrochem-
ical method.
1358 K.F. Babu et al. / Synthetic Metals 159 (2009) 1353–1358

erties that are quite similar to electrochemically formed counter

parts.

Acknowledgments

The authors thank Department of Science and Technology, India

for the financial support to carry out this work. The authors also
thank Prof. A.K. Shukla, Director, CECRI, for his support and encour-
agement.

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