Macromol. Symp. 2015, 357, 229–234 DOI: 10.1002/masy.

201500039 | 229

Optical and Structural Study of

Polyaniline/Polystyrene Composite Films
Anil Kumar,1 Lokesh Kumar Jangir,2 Yogita Kumari,2 Manoj Kumar,2
Vinod Kumar,1 Kamlendra Awasthi*2

Summary: Polyaniline (PANI) was synthesized by oxidative polymerization method

using potassium dichromate (K2Cr2O7) as an oxidising agent. X-ray diffraction (XRD)
and Fourier transform infrared spectroscopy (FT-IR) results confirm the emerlandine
salt formation of PANI. Polystyrene and PANI based composites were prepared by
solution cast method. Ultraviolet-visible spectrophotometry (UV-Vis) results of
polymer composite film in the range of 200–400 nm indicate the interaction
between neighbouring phenyl groups. Structural properties of the composite films
were determined by the Fourier transform infrared spectroscopy (FT-IR) and X-ray
diffraction (XRD). Morphological changes of PS-PANI film were investigated by
scanning electron microscopy (SEM) and optical micrographs.

Keywords: composite films; polyaniline; polystyrene

Introduction readily availability and fine processability

Polyaniline (PANI) is known for more than
100 years, and is the most useful conducting
polymer due to ease of synthesis and good
environmental stability. In addition, it has
high electrical conductivity and interesting
redox properties.[1] The casted films of
PANI are generally fragile and delicate due
to its poor mechanical and thermal proper-
ties with limited resistance to external
action. However, it is possible to enhance
its processability by preparing its compo-
sites in polymer matrix which enhance the
required mechanical properties.[2] In fact,
In the last three decades the conventional
polymeric materials such as PVA, PS, PSS
were used for the preparation of PANI
composites.[3,4] Excellent properties of
polystyrene (PS) polymeric material such
as its low cost, mechanical robustness,[5]
1
Department of Metallurgical and Materials Engin-
nering, Malaviya National Institute of Technology,
Jaipur, Rajasthan 302017, India
2
Department of Physics, Malaviya National Institute
of Technology, Jaipur, Rajasthan 302017, India
E-mail: kamlendra.awasthi@gmail.com,
rsanil.nit@gmail.com
makes it ideal candidate to be used for
composite film formation.[6,7] Modification
with PANI in the polystyrene (PS) mem-
brane is to distinguish the phases.[8,9] It was
observed that PANI gets accumulated at
particular sites in the matrix of the
polystyrene.
In solution mixing method, PANI and
polymer matrix are dissolved or disperse in
the same or in a different solvent. After the
evaporation of the solvent the PANI/
polymer composites were obtained.[10] Seg-
regation of two polymer phases takes place
more efficiently, in the lower viscosity
solvent as compared to the higher viscosity
molten polymer.[11] However, there is no
sufficient information on the optical and
structural property of the PANI/PS compo-
sites using K2Cr2O7 as an oxidising agent.
Agglomeration of PANI particles in PS
matrix is also not studied yet. In this paper,
PANI/PS composites were prepared via
solution cast method using dichloromethane
as solvent. The effect of different wt% of
PANI in polystyrene matrix for morphology
and optical properties of the composites are
studied. Structure of PANI/PS composite

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230 | Macromol. Symp. 2015, 357, 229–234
was characterized by XRD and FT-IR
spectra while the Morphology was studied
through SEM and optical imaging. More-
over, optical properties of the composites
were also examined by the UV visible
spectra.
Experimental Section
Materials
Polystyrene polymer matrixes used in
current study were purchased from
HIMEDIA. Aniline (99.0%), dichloro-
methane (99.0 %), K2Cr2O7 (AR grade)
and HCl (AR grade) were purchased from
MERCK.
Synthesis of Polyaniline
The polyaniline was synthesized using
chemical oxidative polymerization from
aniline (5 ml) in 1M HCl (100 ml) aqueous
solution. The solution was stirred until
the complete dissolution of aniline. Then
the solution was placed in ice bath at
0
C temperature. 1M K2Cr2O7 solution
was added dropwise until the suspension
of aniline changes its colour to green
(scheme 1a). The pH of the reaction mixture
was maintained in acidic medium and
Scheme 1.
Schematic presentation for synthesis of PANI(a) and PANI doped PS.
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temperature of the reaction mixture was
also controlled during reaction. Then the
solution was placed at 2
C for 24 hour.
Afterward, reaction solution was filtered
using wattman paper followed by washing
with 1M HCl solution.[12] Finally the mate-
rial was dried at 60
C in the oven in air. The
obtained material was appeared in green
colored powder form.
Preparation of Polystyrene/PANI
Composite Film
The composites were prepared through
solution cast method.[13] PS was doped
with 0.5 wt%, 1.0 wt%, and 5.0 wt% of
PANI. For this purpose, at first dichloro-
methane was added to 0.0803 g of polystyr-
ene followed by stirring at room
temperature till the PS is completely dis-
solved. Then 0.5 wt%, 1.0 wt%, and 5.0 wt%
of PANI was added to the solution
(Scheme 1b).
The reaction solution was then kept
under constant stirring for 5 h. This solution
was then casted in the petridish floating on
the mercury.
Material Characterization
PANI was studied using XRD (X’pert pro
panalytical) and FT-IR (Perkin Elmer) by
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Macromol. Symp. 2015, 357, 229–234
making PANIþKBr pellet. The structural
characterization of 0.5 wt%, 1.0 wt%, and
5.0 wt% of PANI in PS was done using
XRD and FT-IR spectroscopy. UV-Vis
(Perkin Elmer) measurements were per-
formed for optical study of the composite
film. The morphology and optical micro-
graph of the composite film were analysed
using SEM (Nova nanoSEM FEI) and
optical microscopy (ZEISS).
Results and Discussion
The XRD pattern of polyaniline is shown in
Figure 1(a). The diffractogram of PANI
exhibit the typical reflection peaks at 2u
equal to 20.4
and 25.1
which can be
ascribed to the periodicity parallel and
perpendicular to the polymer chain,[14,15]
Figure 1(b) presents the diffraction pat-
terns of PS and PANI doped PS composite
films. The broad reflection peak in the 2u
range of 15–25
is due to PS while the
predominant peak around 20.1
could be
attributed to the ordered PS chain.[16] As
depict in Figure 1(b) the peak at angle 10.2

grows with the increase of PANI. This
could be ascribed to the periodicity of PS
chain which is perpendicular to the PANI.
Moreover, the most prominent peak of
PANI emerges at 23.4
and its intensity
increases with the dopant concentration.
However, it is most interesting to note that
Figure 1.
X-ray diffraction patterns of PANI (a) and different wt% of PANI doped PS (b).
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| 231
for 1.0 wt% of PANI this peak is rather
weak.
Figure 2 shows the FT-IR spectra of
PANI and PANI doped PS composite
films. Figure 2(a), represents the FT-IR
spectra of pure PANI. The peaks at 3400–
3200 cm1 are related to N-H stretching
vibration[17] while the aromatic C–H
stretching is represented by the peak at
2930 cm1. Characteristic peaks at 1550 and
1464 cm1 represent the C═C stretching
vibration of quinoid and benzenoid rings,
respectively.[18] The C-N stretching vibra-
tions are attributed to the peak at
1293 cm1.[19]
FT-IR spectra of pure PS and PANI
doped PS are presented in Figure 2(b).
Characteristic peak at 3100–3000 cm1 can
be attributed to C–H aromatic stretching
vibration. Asymmetrical and symmetrical
stretching vibrations of CH2 are repre-
sented by the peak at 2847 cm1. Peaks at
1595 and 1487 cm1 represent the stretch-
ing vibration of benzene ring while peaks at
698 and 757 cm1 are due to C-H out of
plane bending vibration of benzene ring.[20]
Overall intensity of the peaks in composite
films is lowered as compared to the pure PS
as seen in Figure 2(b), with increasing the
PANI content. However, there is no
significant change on in the intensities of
the peaks in 0.1 wt% PANI doped PS.
Figure 3 shows the absorption spectra of
PANI and PANI doped PS. The shoulder
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232 | Macromol. Symp. 2015, 357, 229–234
Figure 2.
FT-IR spectra of PANI (a) and different wt% of PANI doped PS(b).
in the range of 200–400 nm is due to the
association interaction between the neigh-
bouring phenyl groups in PS. The flexibility
of the PS chains allows free rotation of
two phenyl group about carbon-carbon
bond. The UV exposed sample exhibits an
increase of absorbance over the 280-320nm
range, which indicates the absorbing photo-
product i.e conjugated double bond are
present in PS. Due to UV absorption of
PANI the absorption of PS/PANI compo-
site film is increased. This may be due to the
fact that, minute dispersion of PANI in the
PS film may produce some photogenerated
electrons and holes under UV light
illumination.[21]
Figure 3.
UV of 0.0 wt%, 0.5 wt%, 1.0 wt% and 5.0 wt% of PANI doped PS.
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Optical micrograph of 0.0 wt%, 0.5 wt%,
1.0 wt% and 5.0 wt% of PANI doped in
polystyrene are also shown in Figure 4. It
is evident that pure PS (Figure 4a) has
non-uniformity in the structure. It is
evident from Figure 4 that, with increasing
the amount of PANI, fragility of PS and
agglomeration of PANI is increased
simultaneously.
Specifically, Figure 4(d) indicates more
agglomeration of PANI particles as com-
pared to the Figure 4(b,c).
In order to quantify this further we have
recorded high resolution FESEM images of
the PS film prepared with the different wt%
of the PANI as shown in Figure 5. The PS
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Macromol. Symp. 2015, 357, 229–234 | 233

Figure 4.
Optical micrograph of 0.0 wt%(a), 0.5 wt%(b), 1.0 wt%(c) and 5.0 wt%(d) of PANI doped PS.

Figure 5.
SEM images of 0.0 wt%, 0.5 wt%, 1.0 wt% and 5.0 wt% of PANI doped PS.

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234 | Macromol. Symp. 2015, 357, 229–234
presents a uniform structure with the pore
which may be due to the fast rate of
evaporation of DCM solvent and the low
polymer concentration.Agglomeration of
the PANI particle is increased with the
higher doping in PS.[22]
It is also interesting to note that with the
doping of PANI, DCM solvent evaporates
with the slow rate because there are no
pores seen in the micrograph. The higher
rate of PANI shows the non-uniformity of
PS and it may be the reason for increased
fragility of the composite films.
Conclusion
The PANI and different wt% of PANI
doped PS film were successfully synthesized
using HCl dopant and DCM as solvent.
Fourier transform infrared (FT-IR) spectro-
scopy and X-ray diffraction (XRD) revealed
the interaction between the PS host matrix
with PANI particles and amorphous nature
of the PANI and its composite film.
Absoption spectra of PS film is increased
proportionaly with PANI content. Optical
and Scanning electron microscopies (SEM)
images of composite film shows heteroge-
neous distribution of conducting PANI in
continuous PS host matrix.
Acknowledgements: Authors are thankful to
Material Research Center, MNIT Jaipur for
using characterization facilities. Authors are also
thankful to Ms. Deepa, Ms. Suchi (Department
of Physics, Banasthali Vidyapeeth) and Prabhat
K. Sharma (Department of Physics, MNIT
Jaipur) for assisting in experimental part of this
work. Authors KA and MK acknowledges the
financial support from DST under INSPIRE
faculty award.
ß 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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