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Materials Letters 136 (2014) 251253

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

UVVIS spectroscopic studies of one pot chemically synthesized


polyindole/poly(vinyl acetate) composite lms
D.J. Bhagat n, G.R. Dhokane
Arts, Science and Commerce College, Chikhaldara, 444807 Maharashtra, India

art ic l e i nf o

a b s t r a c t

Article history:
Received 5 June 2014
Accepted 2 August 2014
Available online 11 August 2014

This letter reports the UVVIS spectroscopic studies of novel one pot synthesized polyindole/poly(vinyl
acetate) (PIN/PVAc) composite lms chemically using an oxidant nickel nitrate. The surface morphology
of the prepared sample was analyzed through eld emission scanning electron microscope (FE-SEM),
which shows irregular, non-porous structure and spongy amorphous morphology. The UVVIS spectroscopy was performed to study optical parameters of PIN/PVAc composite lms. These polymeric
composite lms exhibited strong absorption below 250 nm with a well-dened absorption peak at
around 225 nm. The optical band gap energy values of the prepared samples range over 3.9245.146 eV.
However, the maximum optical conductivity of PIN/PVAc composite lm was found to be 2.92  108 s  1
at 350 nm.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
UVVIS spectroscopic
Polymers
Polyindole/poly(vinyl acetate)
Composite lms
Spectroscopy
Polymeric composites

1. Introduction

2. Experimental

Conducting polymer composites are signicant materials, rising


with a lot of potential applications in various modern areas. In
recent decades, the scientists have focused toward the synthesis
and development of new efcient composite materials derived
from conducting polymers like polypyrrole, polythiopene and
polyaniline. Several improvements in physical and chemical properties like mechanical and thermal durability, solvent resistivity,
dielectric properties and process ability rather than development
of new polymers are also observed [15]. These conducting
polymer materials are mostly being used in electronic devices
such as nonlinear optics, electrochemical display devices, polymer
light emitting diode, and optical devices [611]. Polyindole has
received excellent research interest because of its close structural
similarities with both polyaniline and polypyrrole [1214]. Therefore, it is necessary to study the optical properties of polyindole
and its composites.
This letter is aimed at presenting a more systematic report on
the novel UVVIS spectroscopic study of polyindole/poly(vinyl
acetate) (PIN/PVAc) composites lms. The one pot chemically
synthesized composite lms were characterized by using eld
emission scanning electron microscope (FE-SEM) analysis, UVVIS
spectroscopy.

All chemicals, such as monomer indole, oxidant nickel nitrate,


methanol used as organic media, were of analytical grade and
procured from SD Fine Chemicals, India. The poly(vinyl acetate) (PVAc)
was procured from Himedia Chemicals, India, with molecular weight
30,00050,000. PIN/PVAc composite lms were synthesized chemically using an oxidant nickel nitrate. Solutions of PVAc were prepared
by dissolving 1 g PVAc in 9 ml methanol. Then 0.5 g indole was added
into PVAc solution and stirred for 1 h. The indole was polymerized by
adding nickel nitrate with varying weight percentage (25, 30, 35, 40,
45, 50 wt%), respectively. The reaction mixture was stirred for 2 h to
complete polymerization reaction. Finally, synthesized composite
solutions were kept for 1 h to get settled down. Then, the reaction
solutions were cast on the chemically cleaned and optically plane glass
substrate to developed lms. To drying lms, through an isothermal
evaporation of organic media, the whole assembly was placed for 24 h
in a dust-free chamber at constant temperature. Finally, lms were
washed with hot distilled water and removed from the glass plate.
Then, lms were again dried for 6 h at room temperature. By adopting
same route, successful synthesis of six samples of different wt % was
carried out.

3. Results and discussion


n

Corresponding author.
E-mail address: bhagatd@rediffmail.com (D.J. Bhagat).

http://dx.doi.org/10.1016/j.matlet.2014.08.003
0167-577X/& 2014 Elsevier B.V. All rights reserved.

The PIN/PVAc composite lm was analyzed through eld emission


scanning electron microscope (FE-SEM) (JEOL JSM-6360) to study

252

D.J. Bhagat, G.R. Dhokane / Materials Letters 136 (2014) 251253

1.6

9
25 wt%
30 wt%

1.4

35 wt%
40 wt%

1.2

Absorption

45 wt%

25 wt%
30 wt%
35 wt%
40 wt%
45 wt%
50 wt%

1.0

0.8
200

250
300
Wavelength (nm)

50 wt%

350

4.0

4.5

5.0

5.5

6.0

Photon energy (eV)

Fig. 1. (A) FE-SEM micrograph. (B) UVVIS spectrum. (C) Plot of h versus photon energy (eV).

surface morphology as displayed in Fig. 1(A). The FE-SEM micrograph


depicts the non-porous and non-uniform structure. The nature of
particles is irregular in structure and the surface is of spongy
amorphous nature. The FE-SEM micrograph reects the aggregation
as well as an agglomeration of particles. The thickness of lms
was recorded through DIGIMATIC micrometer with least count
0.001 mm. The thickness of lms was measured in the range of
175368 m. The optimum value of thickness was found to be
0.0368 cm for 40 wt% oxidant concentration. The UVVIS spectroscopy was done through Agilent Technologies, Cary 60 UV-VIS, to
study various optical properties of PIN/PVAc composite lms. The
Fig. 1(B) shows UVVIS spectrum of PIN/PVAc composite lms. The
analysis of the spectrum was carried out with a view to explore their
optical parameters. The % absorption was higher on the lower wavelength side represented in Fig. 1(B). It was clearly observed from the
gure that strongest peak of absorption appears at wavelength 225
nm. The optical band gap of PIN/PVAc composite lms was calculated
by the plot of h versus photon energy (eV) as the displayed in
Fig. 1(C). The material has many applications depending upon its
optical band gap. The relation between absorption coefcient () and
incident photon energy (h) can be expressed by the following relation
[15]:

Ah  Egn
h

where A is constant and Eg is optical band gap of material. The values


of the optical band gap of PIN/PVAc composite lms have been
determined in the energy range of 3.92465.1465 eV. The optical
band gap energy values obviously represent that this material has

potential application in photocatalytic activities and optical devices.


The gure clearly shows that PIN/PVAc composite lm of 40 wt%
oxidant has least optical band gap energy, which was found to be
3.9246 eV. It can be seen clearly from the gure that the optical band
gap energy decreases with increase in wt% concentration of oxidant
up to 40 wt% of oxidant. Optical band gap energy starts to increase
with further increase in wt% concentration of oxidant.
Fig. 2(A) represents a dependence of extinction coefcient on
photon energy. The extinction coefcient is a measure of fraction
of light lost owing to scattering and absorption per unit distance of
penetration medium. Extinction coefcient has been determined
by the following relation [16]:
k =4

where k is extinction coefcient, is % absorption coefcient and is


wavelength. As shown in Fig. 2(A), the decrease in extinction coefcient with an increase in photon energy represents that the fraction of
light lost owing to scattering and absorbance increases. Also, the loss
factor decreases with increase in photon energy. Moreover, the optical
absorption edge can be observed clearly in all samples. The curve of
extinction coefcient clearly displays that scattering decreases gradually from 3.5 eV to 6.5 eV for constant distance of penetration medium.
Fig. 2(B) shows the plot of refractive index (n) as a function of
wavelength () for composite lms. The refractive index (n) has been
determined using the following relation [17]:
n


1=2
1
1

1
Ts
Ts

D.J. Bhagat, G.R. Dhokane / Materials Letters 136 (2014) 251253

253

Fig. 2. (A) Plot of extinction coefcient versus photon energy. (B) Plot of refractive index versus wavelength.

with gradual increase in absorption coefcient for all samples. The


maximum value of optical conductivity for PIN/PVAc composite lms
is 2.92  108 s  1 at 350 nm.
4. Conclusion
The absorption spectrum of PIN/PVAc composite lms analyzed
range over 200350 nm for the determination of optical parameters.
The optical conductivity increases with increase in wavelength and
this can be attributed to increase in absorption. The PIN/PVAc composite lm of 40 wt% oxidant has highest optical conductivity value
and was found to be 2.92  108 s  1 at 350 nm. The estimated optical
band gap energy has accepted values for photovoltaic activities and
has potential for application in solar cells and optical devices. The
optical band gap indicates that PIN/PVAc composite lms have
semiconducting properties.
Fig. 3. Plot of optical conductivity () versus wavelength.

where n is refractive index and Ts is % transmission coefcient. It can


be observed that the refractive index of all samples decreases with
increase in wavelength; it reects that the PIN/PVAc composite lms
represent normal dispersion behavior. The extinction coefcient and
refractive index decrease with increase in wavelength that may be
correlated with an increase in absorption coefcient and decrease in
the transmittance.
The optical response of material is generally calculated in terms
of optical conductivity () through the following relation [18]:

nc
4

where is the absorption coefcient, c is the velocity of light and n is


the refractive index. Fig. 3 represents the plot of optical conductivity
versus wavelength. From the gure, it can be observed that optical
conductivity directly depends upon an absorption coefcient and
refractive index of PIN/PVAc composite lms. It can be noticed that
optical conductivity increases rapidly over the range of 225350 nm.
From Fig. 3, it is clearly observed that optical conductivity increases
with increase in wt% of oxidant up to 40 wt% of oxidant. Further,
increase in wt% of oxidant results in decrease of the optical conductivity. The values of optical conductivity for all samples are
calculated in the range of 1.342.92  108 s  1 at 350 nm. The optical
conductivity was found to increase gradually after 225 nm, correlated

Acknowledgment
Authors are very much thankful to the Principal, Arts, Science and
Commerce College, Chikhaldara, for providing the necessary facilities.
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