Current Applied Physics 4 (2004) 402–406

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Polymerisation and characterisation of conducting polyaniline

nanoparticle dispersions
S.E. Moulton *, P.C. Innis, L.A.P. Kane-Maguire, O. Ngamna, G.G. Wallace
Intelligent Polymer Research Institute, University of Wollongong, Wollongong, NSW 2522, Australia

Abstract

Micellar emulsion chemical polymerisation of polyaniline (PANI) using dodecylbenzenesulfonic acid (DBSA) as the micelle and
dopant was performed at 20 °C. It was necessary to use a ratio of 1:1:1 for aniline, oxidant (ammonium persulfate APS) and DBSA
to produce the PANI Æ DBSA in the emeraldine salt (ES) form in large quantities (40 g). The resulting polymer was a nanodispersion
with spherical particles 10 ± 2 nm in diameter and an electrical conductivity of 15 ± 3 S cm
1 as determined by transmission electron
microscopy (TEM) and the four-point probe method, respectively. UV–vis spectral characterisation showed the nanodispersion to
be highly doped. Complete deprotonation of the polymer to the emeraldine base form using 0.5 M NaOH was only possible upon
dilution to approximately 0.05% w/v polymer. Reduction of the polymer to leucoemeraldine using phenylhydrazine was relatively
slow; however, oxidation to pernigraniline in 0.25 M APS occurred instantaneously.
Ó 2003 Published by Elsevier B.V.

PACS: 81.07.)b; 82.35.)x; 82.35.Cd; 82.35.Lr; 82.35.Np

Keywords: Polyaniline; Nanodispersion; Dodecylbenzenesulfonic acid; UV–vis; Cyclic voltammetry

1. Introduction [10] showed that direct electronic communication of the

The poor processability of most inherently conduct-
ing polymers (ICPs) has limited their exploitation in
commercial applications. For this reason much effort
has been spent improving the processability of these
polymers, by developing new polymer dispersions [1],
water soluble polymers [2] and colloidal systems [3]. One
ICP in particular, polyaniline (PANI), has been at the
center of these studies due to the unique electrochemical
properties available [4,5] and its environmental stability
[1].
It is envisaged that the synthesis of ICP dispersions in
the nanodimension will lead to the development of
highly ordered [6] systems. Indeed it is these conducting
nanodomains embedded in a nonconducting dispersant
that ultimately determine the optical, electronic and
physical properties of the nanocomposite [7]. It has been
shown that as the nanoparticle size decreases, conduc-
tivity increases due to an increase in the degree of
doping and crystallinity [8]. Zhou et al. [9] and Gan et al.
*
Corresponding author. Tel.: +61-02-4221-5473; fax: +61-02-4221-
3114.
E-mail address: smoulton@uow.edu.au (S.E. Moulton).
surface electrons of a metallic nanoparticle with an
encapsulated polymer results in a red-shifting of the
optical plasmon adsorption band with respect to the
lone metal [6].
The aim of this work was to use the micelle poly-
merisation method developed by Han et al. [1] to syn-
thesise large quantities of PANI Æ DBSA nanodispersion.
To determine the suitability of this product for use in
the development of electronic textiles, the optical and
physical properties of the nanodispersion were charac-
terised using electrochemical and spectroscopic tech-
niques.
2. Experimental
2.1. Polymerisation procedure
A modified polymerisation procedure similar to Han
et al. [1] was used. The oxidant to monomer ratio was
increased to 1:1 in order to obtain PANI in the con-
ducting emeraldine salt (ES) form. Polymerisation was
carried out in a thermostated bath at 20 °C. Equimolar
quantities (1.3 M) of aniline (Aldrich) and DBSA (TCI)

1567-1739/$ - see front matter Ó 2003 Published by Elsevier B.V.

doi:10.1016/j.cap.2003.11.059
 S.E. Moulton et al. / Current Applied Physics 4 (2004) 402–406
Table 1
Dispersion polymerisation conditions and characterisation data for the synthesis of PANI Æ DBSA
Reaction conditions
Aniline DBSA APS Temp.
(mol L
1 ) (mol L
1 ) (mol L
1 ) (°C)
0.65 0.65 0.65 20.0
were added to 100 mL of water in a round bottomed
flask mixed under mechanical stirring for 1 h. Hundred
milliliter of 1.3 M APS (Aldrich) (equimolar with aniline
and DBSA) was then added drop-wise to the milky
white aniline/DBSA solution. The polymerisation was
allowed to proceed for 2.5 h, at which time a dark green
dispersion was formed.
Purification of the polymerised dispersion was
achieved by dialysing against Milli-Q water using a
12,000 molecular weight cut off dialysis membrane
(Sigma) for 48 h. After dialysis, the dispersion was
centrifuged at 10,000 rpm for 10 min. The supernatant
was retained for residual aniline analysis by HPLC.
Approximately 100 mL of Milli-Q water was added to
the remaining solid. The water/solid mixture was shaken
to redisperse the solid, followed by centrifuging at
10,000 rpm for 10 min and repeated four times to re-
move DBSA.
2.2. Instrumentation
The UV–vis spectrum of the PANI Æ DBSA nanodi-
spersion was recorded using a Shimadzou UV-1601
UV–vis spectrophotometer. Morphological imaging was
obtained by transmission electron microscopy (TEM),
using a Hitachi H7000 TEM at 75 keV. Conductivity
measurements were performed on pressed pellets of
the dried nanodispersion using the four-point probe
method. Cyclic voltammetry (CV) characterisation was
carried out in a three electrode cell using a glassy carbon
working electrode with a platinum mesh and Ag/AgCl (3
M NaCl) auxiliary and reference electrodes, respectively.
Residual aniline determination was performed by re-
verse phase HPLC using a Waters Bondapak C18 col-
umn and a Linear UVIS 200 UV detector (kmax ¼ 258
nm).
3. Results and discussion
3.1. Polymerisation
Polymerisation of PANI Æ DBSA on a large scale
using the method outlined by Han et al. [1] (with a 1:0.5
monomer to oxidant ratio) was not possible. After 2.5 h
reaction time, the resulting product was yellow in col-
our, attributed to the formation of the reduced leuco-
403
Characterisation
Time Yield Particle size Conductivity
(min) (g L
1 ) (nm) (S cm
1 )
150 200 10 ± 2 15 ± 3
emeraldine form of PANI. When the ratio was increased
to 1:1 the formation of dark green emeraldine PA-
NI Æ DBSA occurred after 2.5 h, indicating the formation
of the conducting emeraldine salt form of PANI. Ex-
tended polymerisation times resulted in no improvement
in the PANI Æ DBSA conductivity. Therefore, the poly-
merisation time used for subsequent synthesis was lim-
ited to 2.5 h. To obtain the PANI Æ DBSA dispersion
with a high level of doping it was also necessary to use a
dopant (DBSA) ratio of 1. Dispersion polymerisation of
aniline using DBSA as the dopant and stabiliser was
performed at 20 °C using APS as the initiator-oxidant.
Reaction conditions and the characterisation data of the
PANI Æ DBSA nanodispersion are given in Table 1.
3.2. UV–vis spectroscopy characterisation of PANI 
DBSA
Characterisation using UV–vis spectroscopy (Fig. 1)
showed the PANI Æ DBSA dispersion (pH < 2) to be in
the conducting emeraldine salt (ES) form. It exhibited
localised polaron bands at 785 and approximately 420
nm and a p–p band at approximately 350 nm (Fig. 1).
The localised nature of the 785 nm polaron band indi-
cates the formation of doped PANI Æ DBSA in the
‘‘compact coil’’ conformation [11]. The p–p band at 350
nm and the 420 nm polaron band have overlapped to
form a flat or distorted single peak indicating a high
level of doping [1].
Fig. 1. UV–vis spectra of (i) PANI Æ DBSA in the ES form and (ii) after
dedoping to the EB form using 0.5 M NaOH.
404 S.E. Moulton et al. / Current Applied Physics 4 (2004) 402–406

3.3. pH and redox switching

Deprotonation of a concentrated PANI Æ DBSA dis-

persion (20% w/v polymer) using NaOH (3 M) proved
difficult with the emeraldine salt (ES) undergoing only
partial deprotonation to the emeraldine base (EB), even
at the maximum pH of 12 attained during the alkaline
treatment. The UV–vis spectrum of this partially ded-
oped nanodispersion (not shown) exhibits a peak at
approximately 600 nm associated with the EB form as
well as a prominent shoulder at approximately 750 nm
associated with the ES form, confirming that the PA-
NI Æ DBSA at pH 12 is only partially deprotonated. The
difficulty in deprotonating this concentrated PA-
NI Æ DBSA may be due to the excess of DBSA present in
the nanodispersion.
When the PANI Æ DBSA nanodispersion was diluted
to approximately 0.05% w/v with Milli-Q water the
polymer was easily deprotonated using 0.5 M NaOH
(Fig. 1). Upon base treatment, the polaron bands of the
original p–p band at 350 nm shifted to 320 nm; and a
peak at 560 nm appeared which is assigned to the exci-
ton band of the EB form [12].
The reduction behaviour of 1 mL of the PA-
NI Æ DBSA nanodispersion treated with 100 lL of
aqueous (10 M) phenylhydrazine was followed using
UV–vis spectroscopy (Fig. 2a). After 10 min (solution
pH 11) reduction to the fully reduced leucoemeraldine
base (LB) form was almost complete, as evidenced by
the decreases in the 785 nm ES band and the appearance Fig. 2. (a) UV–vis spectra of (i) PANI Æ DBSA in the ES form and (ii)
after reduction using phenylhydrazine to the LB form. (b) UV–vis
of a strong characteristic p–p band at 330 nm. spectra of (i) PANI Æ DBSA in the ES form and (ii) after oxidation
The reduction of the PANI Æ DBSA nanodispersion using 0.25 M APS to the PS form.
using phenylhydrazine is obvious from the appearance
of a band at 330 nm which increases in intensity with
time, associated with the p–p band, characteristic of the
LB form of PANI [13]. As the reduction proceeds the
original ES polaron bands at 420 and 785 nm decrease
(Fig. 2a). An isobestic point is observed at approxi-
mately 375 nm, which agrees with Abd-Elwahed and
Holze [14] who investigated the ion size and memory
effects of electropolymerised polyaniline. The weak band
at 1052 nm is due to the presence of the reducing species,
phenylhydrazine.
Addition of 0.25 M APS to a dispersion of PA-
NI Æ DBSA in the ES form caused rapid (seconds) oxi-
dation to produce the aqua blue PANI Æ DBSA
pernigraniline salt (PS) (Fig. 2b). Upon oxidation, a
band at 680 nm appears, characteristic of the PS form of
polyaniline, while the peaks of the original ES disap-
Fig. 3. TEM of PANI Æ DBSA nanodispersion imaged at 200 k times
pear. magnification at 75 keV on copper/rhodium grids (ProSciTech––Aus-
tralia).
3.4. Transmission electron microscopy (TEM) and con-
ductivity
(ES) nanoparticles to be spherical with an average
The particle size and morphology was investigated diameter of 10 ± 2 nm. The shape of these nanoparticles
using TEM (Fig. 3). The image shows the PANI Æ DBSA is the same as that reported for other polyaniline
 S.E. Moulton et al. / Current Applied Physics 4 (2004) 402–406
dispersions [1,15,16] however the size is much smaller.
The size of these nanoparticles may be the reason for the
unusual reduction behaviour mentioned above. It has
been proposed that the electronic [17] and optical [18]
properties of nanostructures (< 100 nm) are unique be-
cause the majority of atoms are at the surface rather
than buried in the bulk of the material [6].
Conductivity measurements on three PANI Æ DBSA
(ES form) pellets showed the conductivity to be 15 ± 3
S cm
1 at room temperature. The particle size reported
here is much smaller than that presented by Han et al.
[1], who used small angle X-ray spectroscopy to deter-
mined particle size, while the conductivity of our sam-
ples is slightly less than what they reported (24 S cm
1 ).
3.5. Cyclic voltammetry (CV)
CV was performed on the as-synthesised PA-
NI Æ DBSA (ES form) nanodispersion using a glassy
carbon electrode as the working electrode (Fig. 4). The
CV is typical for PANI–ES [14,19] with the main peaks I
and II corresponding to the transformation of LB to ES
and ES to PS, respectively. On the reverse scan, peaks
II0 and I0 correspond to the conversion of PS to ES and
ES to LB, respectively. The E1=2 for the peaks I/I0 is
0.025 V, which is less positive than that recorded by
other researchers on dispersion/colloidal systems [20,21].
This lower E1=2 value implies that the PANI Æ DBSA
dispersion is harder to reduce. The presence of a small
redox peak around 0.5 V is associated with the forma-
tion of p-benzoquinone and hydroquinone as a side
product [19] upon cycling the potential to +0.9 V.
The increase in current density with successive scans
suggests film build up on the electrode surface. Aniline
determination of the first supernatant wash using re-
Fig. 4. Cyclic voltammogram of an as-polymerised PANI Æ DBSA dis-
persion in the ES form on a GC electrode after dialysis. 1st scan
originates at 0 mV with a scan rate of 100 mV s
1 (arrows show the
direction of the scan); 1 and 5 indicate the scan number. The potentials
are versus Ag/AgCl (3 M NaCl).
405
verse phase HPLC indicated that 0.13 mM of aniline
remained in the PANI Æ DBSA nanodispersion. The ob-
served current density increase may be due to poly-
merisation of this latter aniline on successive scans with
the excess DBSA acting as the dopant. However, when a
solution of 0.13 mM aniline containing DBSA was
polymerised potentiodynamically at a GC electrode, the
resulting CV showed no similarity to that shown in Fig.
4. It is therefore postulated that the increase in current
density may be due to coagulation of the PANI Æ DBSA
nanoparticles at the electrode on successive scans.
4. Conclusions
It is necessary to use a monomer to oxidant ratio of
1:1 to successfully chemically polymerise on a large scale
a PANI Æ DBSA nanodispersion. The nanodispersion
consists of conducting 10 ± 2 nm spherical nanoparticles
with a conductivity of 15 ± 3 S cm
1 , dispersed in non-
conducting DBSA. Electrochemical and spectroscopic
characterisation shows that the PANI Æ DBSA nanodi-
spersion is highly doped and electroactive with the three
oxidation states of PANI evident in the CV. The unu-
sual redox behaviour of the nanodispersion was con-
firmed by cyclic voltammetry and UV–vis spectroscopy.
The chemical and physical characteristics of this
PANI Æ DBSA nanodispersion make it a prime candidate
for use in the development of electronic textiles.
Acknowledgement
The authors wish to acknowledge the support of the
Australian Research Council.
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