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1
Arts,Science and R.A. Patel Commerce College Bhadran, Gujarat, India.
2
Navjevan Science Collegxe, Dahod, Gujarat,India.
3
Arts, Commerce and Science College, Borsad, Gujarat,India.
4
Department of Physics, SPU, Vallabh Vidyanagar, Gujarat , India
Abstract: Polyanilines namely emeraldine, nigraniline Electronic doping is done rarely. Therefore, in the
and pernigraniline were prepared by chemical method present study electronically-doped polyanilines using
and were electronically-doped with organic acceptors organic electron-acceptors such as TCNE, TCNQ,
such as, TCNE, TCNQ, DDQ, Chloranil and KI-I2. DDQ, Chloranil and KI-I2 have been prepared and
The FTIR spectra of 20% and 50% doped polyanilines studied using FTIR spectroscopy.
were obtained and analyzed using small polaron model
which connected electrical conductivity with IR EXPERIMENTAL PROCEDURE
absorption. Emeraldine prepared by standard method
Emeraldine (SM) was prepared by standard method
and pure emeraldine as readily obtained wee used. The
using ammonium peroxy disulfate synthesis (27).
absorption profiles as experimentally obtained and as
Recently we standardized method of preparing other
calculated using small-polaron model were compared.
firms of polyanilines namely protoemeraldine,
This comparison leads to frequency dependence of
nigraniline and pernigraniline (28). Emeraldine (pure)
the real part of refractive index which shows
was obtained from standard chemical company of
dispersion shape as desired.
USA molecular structures of polyanilines are shown
Keywords: Infrared spectra, polaron (figure 1). Both forms of emeraldine (SM and Pure)
wewe doped with TCNE, (tetracyanoethylene),
PACS: 78-Optical properties, condensed-matter TCNQ(7,7,8,8 teracyano-p-quinodimethane), DDQ
spectroscopy, and other interactions of radiation (2,3-dichloro-5,6-dicyano-p-benzoquinone), Chloranil
and particles with condensed matter and KI-I2 in 20% and50%. It was found that
emeraldine prepared by standard method was less-
INTRODUCTION: oxidized than emeraldine (pure) obtained from
chemical company. Emeraldine (pure) was nearer to
Polyaniline polymers have been studied by many solid
nigraniline while emeraldine (sm) was nearer to
state physicists (1-6). Magnetic (7, 8) ,optical
protoemeraldine. This was concluded on the basis of
(7,9),photo-induced optical(10-12) and transport (13-
effect of doping increasing absorption in emeraldine
18) properties have been studied in details for
(sm) and decreasing absorption in emeraldine (pure)
polyaniline namely emeraldine. There are two types of
with any acceptor.
doping (1) protonic doping and (2) electronic doping.
Protonic doping is carried out by doping various acids Protoemeraldine(brown), emeraldine (green),
such as sulphonic acid (19), camphor-sulphonic acid nigraniline(blue) and pernigraniline (violet)were
(20), dibenzoyl tartaric acid (21), hetero-poly acid mixed with organic accrptors such as TCNE, TCNQ,
(22), H2SO4 (23), 2-acrylamido-2-methyl-1-propane DDQ ,Chloranil and KI-I2 and grinded in a morter
sulfonic acid (AMPSA), Lewic acids (25) and with a pastle till colour changed. Further these fine
sulphosalicylic,salicylic and citric acids (26). homogeneous powder were mixed with dry
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spectrograde KBr powder and again grinded. Palates in carriers and = / has dimension of mobility.
the form of circular discs were prepared from these W is the hopping probability. Under certain
mixtures with a manally operated compressing approximation, the d.c. conductivity takes the form
machine. These discs were placed in a dark chamber of (29).
GXFTIR single beam spectrophotometer fabricated by
Perkin Elmer Company, USA. = (1 ) exp( ) (2)
( )
( )= ( )+ (3)
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International Journal of Trend in Scientific Research and Development, Volume 1(2), ISSN: 2456-6470
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J is exchange integral and Ea is activation energy. Thus, the
80 Protoemeraldine +TCNE
dependence () he form of a weakly asymmetric gaussian Protoemeraldine +TCNQ
which has peak centered about = 4 and having half-width 60
Protoemeraldine + DDQ
Protoemeraldine + Chloranile
4 (32,33). Now the absorption coefficient is related AT() Protoemeraldine +KI-I2
with () according to 40
n c 20
= (6 )
4
1000 3000 5000
Wave Namber K Fig.2
4
= () (6 )
n c
30
These gaussians are plotted (Figure 2). Emeraldine(sm)+TCNE(20%)
Emeraldine(sm)+TCNQ(20%)
Emeraldine(sm)+DDQ(20%)
20
Emeraldine(sm)+Chloranile(20%)
AT() Emeraldine(sm)+KI-I2(20%)
( ) ( )
= (10) 10
( ) ( )
0
Since T() assumes n1 as a constant but actual E()
experimental curves contains n1 which depends on frequency. 1000 2000 3000 4000 5000 Fig.3
Wave Namber K
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100 Emeraldine(pure)+TCNE band since pernigraniline and its CTCS are purely
Emeraldine(pure)+TCNQ
Emeraldine(pure)+DDQ
semiconductors. The spin-orbit splitting of valence band and
Emeraldine(pure)+Chloranile consequent three transitions from valence sub bands to
Emeraldine(pure)+KI-I2
50
AT() conduction band are also evident in all of the CTCS of
pernigraniline.
0 80 Protoemeraldine +TCNE
Protoemeraldine +TCNQ
1000 2000 3000 4000 5000 Fig.4 Protoemeraldine + DDQ
Wave Namber K
60 Protoemeraldine + Chloranile
AT() Protoemeraldine +KI-I2
40
Emeraldine availed from a chemical method was more oxidized
than emeraldine prepared by standard method. Thus emeraldine 20
was more near nigraniline as obtained from a company while
1000 2000 3000 4000 Fig.6
emeraldine was more near protoemeraldine as prepared by Wave Namber K
30 4
Nigraniline + TCNE
Nigraniline + TCNQ
20 Nigraniline +DDQ
Nigraniline+Chloranile (Ah)1/2 2
Nigraniline +KI-I2
10
AT()
0
0
0.2 0.25 h 0.3 0.35 0.4
0 2000 4000 6000 Fig.5 Fig.7
Wave Namber K
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