Table of Contents Page No.

Certificates,Declaration & Acknowledgement………………………..1-4

Certificate by H.O.D……………………………………………………………..1

Certificate by project guide………………………………………………………..2

Declaration………………………………………………………………………..3

Acknowledgement……………………………………………………………..4

List of Tables & Figures………………………………………………………. 2

ABSTRACT………………………………………………………………… 3

1.Introduction ………………………………………………………………………………………..4

1.1 Background ………………………………………………………………………………………..5

1.2 Conductive polymer ……………………………………………………………………………6
1.3 Polyaniline …………………………………………………………………………………………..7
1.4 Application of conductive polymer ……………………………………………………….8
1.5 Smart textile connected to conductive polymer ……………………………………..8
2. Experimental
2.1 Materials …………………………………………………………………………………………..9
2.2 Intruments for characterization and measurement ………………………….9
2.3 Synthesis of polyaniline ………………………………………………………………..10
3. Results …………………………………………………………………………………………………………11
3.1 FTIR spectra analysis …………………………………………………………………………….12
3.2 UV-VIS spectra analysis ………………………………………………………………………..13
3.3 Optical Band gap analysis ………………………………………………………………………14,15
4. Conclusion and Discussion………………………………………………………………………………16
4.1 Future prospects ………………………………………………………………………………………16
5.References ……………………………………………………………………………………………17

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List of Figures &Tables
Fig.1. some the potential application of conductive polymer in microelectronics

Fig.2. Logarithmic conductivity ladder

Fig.3. Oxidation sates of PANI octamer

Fig.4. FTIR Spectra of PANI

Fig.5. UV-Vis Spectroscopy for PANI

Fig.6. Tauc plot of sample (1)

Fig.7. Tauc plot for sample (2)

Fig.8. Tauc plot for sample (3) electro deposited PANI

Table 1: FTIR Spectra Analysis and peak assignment of stretching frequency
Table 2: Degree of Oxidation of PANI formed by various methods.

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 Abstract

Electrochemical and spectroscopic analysis of PANI-ES for determining

the conductive properties and electronic structure of PANI samples.

Polyaniline in emeraldine salt (PANI-ES) form was successfully synthesiszed by oxidative

polymerization of aniline using potassium persulfate as oxidant in the presence of hydrochloric
acid acid as catalyst under room temperature.

The prepared powdered sample was characterized by Fourier Transform Infrared (FRIT)
spectroscopy. Using UV Spectroscopy the intensity of absorbance was recorded. Also FTIR
absorption Spectra showed all the characteristics bands of PANI-ES. The cyclic voltammetry
shows the electrochemical properties of polyaniline (PANI-ES)

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 .

Introduction
Conducting polymers belong to a peculiar family of compounds composed of monomer units
with conjugated chemical bonds that, under certain conditions , ensure the electron
conductivity of the polymer. From the commercial viewpoint, these polymers promise for
the production of materials for various applications; they can replace metals and
semiconductors, because they feature conductivity, low density ,and easy processability
.Polyaniline (PANI)—a representatives from the family of conducting polymers—is
distinguished by easy synthesis and high environmental stability.
PANI as a conducting organic material has attracted great attentions of researchers due to its
good environmental stability [1, 2],moderately high conductivity upon doping with simple
protonic acid [3], lower production cost, and easy synthesis compared with other conducting
polymers [4], such as polypyrrole and polythiophene. Polyaniline is considered as an air-
stable organic conducting polymer with interesting
electrochemical performance which makes it suitable for many practical applications [5–7],
especially in lithium ion batteries and electrochemical capacitor area [8–11].

, PANI is also very interesting for EC applications owing to its unique characteristics such as a
quick optical response and obvious color changes between light yellow, green, blue, and deep dark
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 colors. Furthermore, solution-processable PANI: polystyrene sulfonate (PANI:PSS) material
could be used in inkjet printing for large areas and precision patterns

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 1.1 Background

Among the major global problems (food crisis, crisis of drinking water, health issues etc. )
Again the global energy crisis is arising not only due to low abundance of conventional energy
sources but also due to enhanced contribution to the environmental issues by increasing
concentration of greenhouse gases in the atmosphere, resulting from gradual use of fossils
fuels as major energy sources . Therefore the way of getting rid of these two interrelated
global issues demands new sustainable energy resources.

Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic
polymers that conduct electricity.

Fig-1 overview of some the potential application of conductive polymer in

microelectronics.

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 1.2Conductive polymer
Electro active biomaterials are a part of a new generation of ‘‘smart’’ biomaterials
that allow the direct delivery of electrical, electrochemical and electromechanical
stimulation to cells. Furthermore, a great advantage of conductive polymers is that
their chemical, electrical and physical properties can be tailored to the specific
needs of their application by incorporating antibodies, enzymes and other
biological moieties. [1,4,7,8] Additionally, these properties can be altered and
controlled through stimulation (e.g. electricity, light, pH) even after synthesis.
[3,9–11] It can provide electromagnetic shielding of electronic circuits. It can be
used as antistatic coating material to prevent electrical discharge exposure on
photographic emulsions. Usage in electroluminescent displays (mobile telephones)

FIG-2 Logarithmicconductivity ladder locating some

metal and conductive polymer

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 1.3 Polyaniline

The second most studied conductive polymer after PPy is polyaniline (PANI), also known as
aniline black [2,14,45]. It exists in various forms based on its oxidation level: the fully
oxidized pernigraniline base, half-oxidized emeraldine base and fully reduced
leucoemeraldine base [2,14] . Of these, PANI emaraldine, is the most stable and conductive
[2,14]. PANI has many advantages, such as ease of synthesis, low cost, good environmental
stability, and the ability to be electrically switched between its conductive and resistive states
[46–50]

FIG-3 Oxidation sates of PANI octamer

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 1.4. APPLICATIONS USING POLYANILINE BASED CONDUCTIVE POLYMER

Innovation of conductive polymers provided various fields of research in applied science and
research development in academic centers and industrial sectors as well.
The interest in electrically conductive fibres and fabrics is growing rapidly in areas such as
sensing, electrostatic discharge, corrosion protection, dust and germ free clothing, monitoring,
data transfer in clothing and in military applications . The basic element to achieve all
these purposes is the modification of the mechanical and electrical properties of fibres and
fabrics to obtain the new functionality in the textile applications. [1, 21] Electrically
conductive,
colored and transparent thin films and coatings, which would otherwise be difficult to
achieve with conventional filled materials, can be made using polyaniline based compositions.
The stability and solubility of polyaniline can be controlled by the selection of an appropriate
method of polymerization. Polyaniline is soluble in several common organic solvents,
and can be deposited by different coating methods on the surface of fabrics and yarn as
well as many other materials. [21-22].

1.5 SMART TEXTILE CONNECTED TO CONDUCTIVE POLYMERS

Mass production of fibres and their weaving into textiles dates back to the early stages of the
industrial revolution. The assembly of fibres through weaving and other processes are the
basis of the mass production of textiles. Both conductivity and mechanical properties of
conducting polymers could be improved by producing fibres. Textile production technologies
for
the making of conducting polymer fibres are an extremely attractive prospect. [1-2]

PANI was used to design a rechargeable battery [10] with a specific energy of 280 (Wh)/kg.
On the basis of the composite material, the secondary current source Zn–PANI–graphite with
a specific energy of 160 (W h)/kg was developed [11]

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 2. EXPERIMENTAL

2.1 MATERIALS

All the reagents purchased from commercial suppliers and were used as received. conc.
hydrochloric acid (HCl) was purchased from Mereck life science pvt. Ltd.N-methyl-2
pyrolidone (NMP) were purchased from Aldrich, ethanol was purchased from Mereck
Millipore. Acetone was purchased from Mereck Life Science Pvt.Ltd., Aniline was purchased
from Aldrich. potassium per sulfate was purchased from Mereck Life Science Pvt.Ltd.

2.2 Intruments for characterization and measurement

 Fourier Transform Infrared (FTIR) Spectroscopy :

The infrared spectra in the range of 400-4000 cm were recorded on a Perkin-Elmer
(Model-Frontier MIR FIR) FTIR Spectrometer. The spectra of the neat products were
recorded as KBr pellets by mixing the samples well with KBr.
 UV-Vis Spectroscopy:
The electronic absorption spectra were recorded using Shimadzu UV-2550
Spectrophotometer. The sample dissolved in a suitable solvent was placed in a quartz
cuvette.
 Raman Spectroscopy:
Raman spectra were recorded on RENISHAW (Model: RENISHAW BASIS SERIES
WITH 514 LASERS)
 Cyclic Voltammetry (CV):
CV voltammogram were recorded on biologic SAS analyzer (Model-SP-150)

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 2.3 Synthesis

Synthesis of polyaniline (Method1)

Synthesis of PANI has been carried out by chemical method.A solution of 1ooml 0.1m
aniline solution was prepared ,also a solution of 40ml 1m HCl is prepared and both the
solution are mixed.0.1m Kps solution is prepared .
The kps solution is mixed with the aniline-HCl solution dropwise and kept overnight .
The resulting product is filtred and washed with water. Then the product obtained is dried
in oven and vessicator.

Synthesis of polyaniline (Method 2)

A 0.1M 100ml aniline solution is prepared and a 1M 100ml HCl solution is prepared. Both the
solutions are mixed. A paper is dipped in the resulting solution. To it added 0.1M kps solution
dropwise and kept overnight. The obtained solution is filtred and wash with water, then the
product is dried in oven or vessicator.

Synthesis of polyaniline PANI (Method 3)

A 40ml chloroform in 0.25M aniline solution is prepared. A solution of 80ml 1M HCl and
1.46gm kps is prepared. Henceforth the two solution is mixed dropwise and kept overnight,
The product is centrifuged and washed with distilled water.The solution obtained is filtred
and dried in oven.

Synthesis of polyaniline PANI (Method 4)

The electrochemical synthesis of polyaniline was carried out using 0.1 M aniline solution and
1 M HCl solution . The potential varies in a cyclic mode from –0.2 to 0.7–1.2 V (against a
saturated calomel electrode).

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 3. Result

3.1 FTIR Spectra Analysis

Table no.1

Wavenumber of peaks Characteristics Band of

(cm-1) Wave number
C=C skeletal vibration of
non oxidized moiety
Description of
3413-3452 Stretching vibration of IR spectrum
N-H bond Of quinoid
2929 Stretching of rings
unsaturated system
1629-1618 N-H (Broad scissoring)

811 N-H (broad oop

bending)
Description of IR
1484-1488 C=C stretching-benzoid Spectrum of
rings Benzoid
1113-1130 C-H in plane bending
aromatic

808-815 C-H out of plane Description of

bending of 1,4 ring
IR spectrum of
1305-1385 C-N stretching in Quinoid-
quinoid unit-benzenoid
unit-quinoid unit benzenoid units

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 Fig-4 FTIR Spectra of PANI

Table no.2 Degree of Oxidation of PANI formed by various methods

Sample Degree of Oxidation

Sample(1) 1.007
Sample(2) 0.990
Sample(3) 0.987
Sample(4) 0.971

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3.2 UV –VIS Spectra analysis

FIG-5 UV-Vis Spectroscopy for PANI

UV-visible spectra of aqueous PANI contain absorption peaks in the (1) 300-340 nm region and
in the (2 ) 550-800 nm region. The doped PANI show the characteristic absorption bands at
330-340 nm wave lengths in region (1) shifted to red perhaps due to micro-environment effect,
and wavelengths in region (2) which is due to the π-π* transition of benzoid rings and the
formation of polaron.
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3.3 Optical Band gap analysis

Fig-6 Tauc plot of sample (1)

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 Fig-7 Tauc plot for sample (2)

Fig-8 Tauc plot for sample (3) electro deposited PANI

The band gap was estimated using the transition rate equation for direct band gap
semiconductor. The absorption coefficient for direct transition is given by the alpha
(hv)=A(hv - Eg) n
where hv= photon energy ,a= absorption coefficient ( k is the absorption index or absorbance),
Eg is the band gap energy. A= constant, n= ½ for the allowed direct band. The exponent ‘n’
depends on the type of transition and it may have values 1/2, 2, 3/2 and 3 corresponding to the
allowed direct, allowed indirect, forbidden direct and forbidden indirect transitions, respectively
Here the optical band gap decreases as the degree of oxidation decreases. The corresponding
optical Band gap are 4.72 nm, 4.332 nm. 4.69 nm respectively.

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4. Conclusion and Discussion

From Characterization data and results, it can be concluded that we have synthesized
successfully all the desired product ( PANI-EB,PANI-ES) .A simple route for synthesizing
polyaniline by using potassium per sulfate (KPS) as the oxidant. The spectroscopic features of
the synthesized polyaniline powder are in good agreement with those of literature values.The
degree of oxidation is found to be decrease with the change in methods of preparation of
PANI.The optical band gap is calculated indirectly from Tauc plot.

UV-visible spectra of aqueous PANI contain absorption peaks in the (1) 300-340 nm region and
in the (2 ) 550-800 nm region. The doped PANI show the characteristic absorption bands at
330-340 nm wave lengths in region (1) shifted to red perhaps due to micro-environment effect,
and wavelengths in region (2) which is due to the π-π* transition of benzoid rings and the
formation of polaron.

FTIR spectra of PANI and ES-PANI powder were performed with a tensor 37 in the
transmittance mode. Fig 4 shows FTIR spectra of EB-PANI and ES-PANI. The peaks
assignments table 1 are in good agreement with the published values [20,21]

4.1 Future prospects

Polyaniline, after its rediscovery in the 1980’s has travelled the arduous route from laboratory
benches to commercial markets in less than a decade’s time. The possibilities disclosed by its
unique characteristics are challenging, fascinating and farsighted. The time may not be that far,
before the versatile and vast potential of this unique polymer is genuinely established and
effectively utilized in the designing of smart and functional devices to reign the future consumer
markets with authenticity”.

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