Synthesis and characterization of polyaniline as emeraldine salt

Isha Gawri, Swati Khatta, K. P. Singh, and S. K. Tripathi

Citation: AIP Conference Proceedings 1728, 020287 (2016); doi: 10.1063/1.4946338

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Published by the American Institute of Physics
 Synthesis and Characterization of Polyaniline as
Emeraldine Salt
Isha Gawri, Swati Khatta, K.P. Singh, S.K. Tripathi*

Department of Physics, Center of Advanced Study in Physics,

Panjab University, Chandigarh-160 014 (INDIA)
*
Corresponding author: [email protected]; [email protected];
Tel.:+91-172-253622; Fax: +91-172-2783336

Abstract. Polyaniline in emeraldine salt (PANI-ES) form was successfully synthesized by oxidative polymerization of
aniline using ammonium peroxidisulphate as oxidant in the presence of hydrochloric acid as catalyst under ice bath
condition. The as prepared powdered sample was characterized using X-Ray Diffraction (XRD) and Fourier Transform
Infrared (FTIR) spectroscopy. Using XRD, the average crystalline size was found to be 5.63 nm and d-spacing
corresponding to crystalline peak 2θ = 25.08° had come out to be 4.2 Å. Also FTIR absorption spectra showed all the
characteristics bands of PANI –ES. The ohmic contact between the PANI-ES film and the substrate was confirmed by
Current-Voltage (I-V) characterization.

INTRODUCTION
The interest in conducting polymers is growing rapidly due to their wide range of applications. Conducting
polymers are actually organic polymers which can conduct electricity. Intrinsically conducting polymers such as
polypyrrole, polythiophene, polyaniline, polyacetylene , etc exhibit unique properties namely reversible
doping/dedoping process, easily processable and controllable chemical and electrochemical properties. A very
important fact is that organic polymers posses the optical, electrical and magnetic properties of a metal and at the
same time also retain the fundamental properties of polymers like mechanical properties, processability etc and can
be given another name as synthetic metal [1]. Conducting polymers have wide range of applications in the field of
electronic device e.g. displays, sensors, energy-storage devices, transistors etc. An interesting fact about conducting
polymers is that they can have different oxidation states and also exhibits semiconductor properties ,therefore can
respond by changing characteristics like conductivity, density, color, magnetic properties under external influence.
Out of all conducting polymers PANI possess controlled conductivity combined with ionic and proton conductivity,
non-linear optical properties, redox activity and paramagnetism. Also in aggressive chemical environment the
polymer is highly stable and in addition to it, it is also non-toxic in nature. The other significant feature of PANI is
high thermal stability and low manufacturing cost. Due to unique properties of PANI, it has a wide range of
applications as optoelectronics, biosensors, gas sensors, microelectronics [2-3] indicators, erasable information
storage, shielding of electromagnetic interference, energy storage and transformation, catalyst, solar cells, LED’s,
coating for metallic surfaces etc. [4].The conducting polymer PANI has highly ordered structure consisting of
benzoid and oxidized quinoid units as shown in figure. The polymer chain forms a zigzag lying in one plane and π –
electron clouds overlap above and below the plane. However in PANI chains para-substituted aniline fragments are
linked in “head-to-tail” configuration and constituted 95% of polymer chain.

FIGURE 1: Structure of PANI Emeraldine Salt (PANI-ES).

International Conference on Condensed Matter and Applied Physics (ICC 2015)

AIP Conf. Proc. 1728, 020287-1–020287-4; doi: 10.1063/1.4946338
Published by AIP Publishing. 978-0-7354-1375-7/$30.00

020287-1
 Polyaniline shows various oxidation states out of them, three major oxidation states are (i) Leucoemeraldine
(LE) (white /clear and colourless) (ii) Emeraldine (green for emeraldine salt (ES) and blue for emeraldine base (EB))
and (iii) Pernigraniline (PE) (blue/violet). LE is in fully reduced state, PE is in fully oxidized state while EB form is
completely neutral. It changes from EB to ES by doping in which the imine nitrogen’s are protonated by an acid.
Due to high stability, Out of all the three forms of PANI, emeraldine form is considered to be most stable form.
Emeraldine salt form is obtained when emeraldine base is doped with acids preferably non-oxidizing such as HCl,
H2SO4 or organic acids i.e. by oxidative doping. The emeraldine salt form has very high conductivity of the order of
10-1S/cm as compared to emeraldine base form which has conductivity value of 10-10 S/cm [5]. The crystallinity is
greatly influenced by doping because as the doping level increase, crystallinity also increases [6]. The aim of this
paper is to study and analyze the structure and morphology of the chemically synthesized PANI in Emeraldine salt
(ES) form using XRD and FTIR for the determination of cell parameters and crystallinity.

EXPERIMENTAL DETAILS
Polyaniline was synthesized by in-situ polymerization of aniline with ammonium peroxidisulphate as an oxidant
and hydrochloric acid (HCl) as a catalyst [7-9]. In this process 10 ml of 0.3 M aniline was dissolved in 80 ml of 1M
HCl solution and the whole solution were added in 250 ml beaker with Teflon coated magnetic stirrer. The synthesis
was carried under ice bath condition at 0o- 5oC. Then a solution of 0.3M ammonium peroxidisulphate and 80 ml of
1 M HCl was prepared in a separate beaker. This prepared solution was then added to the above prepared aniline
solution drop wise over a period of 1h with continuous stirring. The polymerization process was maintained at 0 oC
throughout the reaction. After the addition of ammonium peroxidisulphate, the stirring was continued for further 5h
for the completion of reaction. The dark green solution obtained after stirring was kept overnight. The precipitates
produced in the reaction were washed with 1 M HCl and distilled water repeatedly around 7-8 times until the wash
solution become colorless. Then obtained product was dried under vacuum at 70°C to obtain PANI-ES in powder
form.

RESULTS AND DISCUSSION

The structural, spectroscopic and electrical properties are vital parameters to understand the behaviour of the
sample under the respective optimized conditions and hence for its practical applications. Therefore we conducted
XRD to study its crystal structure and to determine average crystalline size. The data for material was collected by a
Philips PW-1729 diffractometer using Cu– Kα radiation with wavelength λ=1.541Å, voltage 50 kV and current 100
mA. Powder diffraction patterns were obtained in step scanning mode with scattering angle 2θ = 10°-80° in a step of
0.02°. FTIR was conducted to analyze the chemical composition. The Perkin-Elmer-RX1 FTIR spectrometer was
used for recording the spectra of sample in the frequency region 400-4000 cm-1. I-V was taken to check the ohmic
behaviour of the prepared sample by using two probe method with the help of picoammeter and Keithley 6517-A
programmable current and voltage source.

XRD Characterization

The X-ray diffraction pattern of PANI-ES shows two characteristics peaks at 2θ = 20.87° and 2θ = 25.08°
corresponds to (020) and (110) crystal planes of PANI. The average crystalline size is calculated as 5.631 nm by
using Debye – Scherer equation [10-11]
kλ
D
(1)
βCosθ

where k is shape factor for average crystallite, β is full width at half maxima (FWHM) of crystalline planes in
radians. The d-spacing corresponding to highest crystalline peak was calculated using Bragg’s relation:

2d sin θ
nλ (2)

where n is an integer, θ is the angle between incident and reflected rays and λ is the wavelength of the X-ray which
is 1.54Å for Cu target. The d-spacing corresponding to crystalline peak 2θ = 25.08° is 4.2Å.

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 Due to fiber nature and planar nature of benzoid and quinoid functional groups, PANI (ES) exhibits low degree
of crystallinity. In this salt, form the presence of polarons or charge defects enhances the crystallinity. In a particular
crystal plane, the degree of orientation of polymer chains is determined by the sharpness of peak. Also in a particular
plane the population of crystallites is represented by intensity of peak. The crystallinity of a polymer depends upon
the degree of regularity in arrangement of polymer chains. Hence the crystallinity increases as the arrangement of
polymer chains become highly ordered and regular. The arrangement of chains further depends upon the interactions
between the adjacent polymer chains which may be electrostatic interaction or interchain hydrogen bonding. In the
present case, PANI has the capability of forming H-bonds through amine groups present on its backbone. The better
orientation of polymer chains is due to strong interchain H-bonding and dipole-dipole interaction between the amine
groups of each chain of polymer [12].

FIGURE 2: XRD pattern of PANI-ES. FIGURE 3: FTIR pattern of PANI-ES.

FTIR Spectral Analysis

Figure 3 shows the FTIR spectrum of PANI (ES) form synthesized by in-situ polymerization of aniline. The spectra
show all the major bands of PANI (ES). In the spectra the bands observed at 3350 cm-1 and 3288 cm-1 were due to
asymmetric N-H stretching. The polymer also shows the absorption band at 1680 cm-1 was attributed to C-C
stretching mode vibrations. The peak at 1557 cm-1 was due to aromatic C-C stretching. There is another peak present

FIGURE 4: I-V characteristics of PANI-ES

at 1460 cm-1 which is attributed to C=N stretching in aromatic compounds. The characteristic peak at 1282 cm-1 was
due to C-N stretching of secondary aromatic amines. The presence of quinonoid unit in PANI (ES) was confirmed
by the presence of band at 1158 cm-1. The absorption peaks lies below 1000 cm-1 are the characteristics of mono

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substituted benzene. The absorption band at 855 cm-1 is attributed to out of plane C-H bending 1, 4-disubstituted
benzene ring. The two bands at 688 cm-1 and 507 cm-1are attributed to aromatic ring and C=N amino quinine
respectively [13-14].

I-V characterization

I-V characteristics were taken by using two probe method on the prepared film of PANI (ES). The solution was
prepared by using m-cresol as a solvent to enhance the solubility and then deposited on cleaned glass substrate by
using dip coating technique and dried at 70°C under vacuum. Figure 4 shows the I-V characteristics of PANI (ES)
which clearly indicates that ohmic contact has been established between the Polyaniline film and glass substrate.
These measurements were taken in vacuum at room temperature.

CONCLUSION
This work presents the successful synthesis of PANI in emeraldine salt form by using in-situ oxidative
polymerization method. The characterization of the prepared sample was done using XRD and FTIR spectroscopy.
The XRD pattern of PANI-ES shows a sharp peak at 2θ = 25.08° with d-spacing value 4.2 Å. The formation of
emeraldine salt form was confirmed by FTIR absorption bands. The establishment of ohmic contacts was confirmed
by I-V characteristics.

ACKNOWLEDGMENTS
Ms. Isha Gawri is thankful to University Grant Commission (UGC), N. Delhi for providing the fellowship.

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