National Conference on VLSI and Communication (VCS-2012), 30-31, Oct 2012
Paper ID:VLSI/VCS-41
Methanol gas Sensing properties of PANi/HCl
nanocomposites
Mrudula K1, Sumanth Kumar D1, Jai Kumar B1, Ravi Prakash L1, H.M.Mahesh1*
1
Department of Electronic Science, Bangalore University, Jnanabharathi, Bangalore-560056, India
Abstract-In this paper we are reporting the methanol
sensing property of PAni/HCl. PAni/HCl is prepared
by chemical oxidation of Aniline in the presence of
Ammonium per sulphate in acidic medium, a simple
approach to gain good yield. The Morphology studies
shows the irregular-spherical shaped PANi/HCl
composites desired for the gas sensing property and
Spectroscopy results confirmed the presence of
PANi/HCl. The material exhibits good ohmic
behaviour which is best suitable for sensor
applications. Methanol being a volatile gas when
comes in contact with the surface of PAni/HCl pellet
undergoes surface adsorption redox process there by
change in resistance of the material. PAni/HCl is
subjected to different concentration of methanol gas
and sensing response is plotted as a result.
I. INTRODUCTION
Conducting polymer composites have been considered
as new class of materials due to their improved
properties compared with those inorganic materials [11].
These hybrid materials are most promising for the
fabrication of electronic devices that combine superior
electronic, magnetic and optical properties [12]-[15].
Recent research work on polyaniline, a conducting
polymer has been surveyed [16]. Conducting polymers
are conjugated organic material and have been
extensively studied for their promising applications in
energy storage batteries, LED s, electro chromic devices
(ECD s), gas sensors, etc.,[17]. According to the
literature reported elsewhere, most of the gas sensors
available in the market are conducting/ semiconducting
sensors, measuring the conductivity alteration under gas
adsorption having disadvantages like high operating
temperature, high manufacturing cost and bulky. The
methanol sensor proposed in this work use polyaniline as
a sensitive layer which can overcome above mentioned
disadvantages.
Methanol (CH3OH) is the simplest form of alcohol,
light, volatile, colorless, flammable liquid with a the solid form of aniline hydrochloride was separated.
distinctive odour very similar to, but slightly sweeter
than, ethanol (drinking alcohol) [1],[2]. Methanol
naturally produced in the anaerobic metabolism of many
varieties of bacteria and can be synthetically
manufactured from carbon oxides and hydrogen.
Methanol primarily used for the manufacture of other
chemicals and solvent such as paint remover, windshield
Department of Electronics & Communication, BIT, Bangalore
washing fluid, de-icing solution, duplicating fluids, solid
canned fuels, model airplane fuels, embalming fluids,
lacquers, and inks etc., it is also considered as better
choice for replacement of petroleum-based fossil fuels
[3]-[5]. Methanol is highly toxic gas with exposure limit
value of 30ml//Convert to ppm//for a period of 8-36 hrs
[6] can cause permanent damage to central nervous
system, metabolic acidosis, headache, nausea and ocular
toxicity photophobia, misty or blurred vision and
complete blindness [7],[8].
Methanol sensors are very important devices in
many industrial, food and beverage, agricultural and
biomedical applications. For instance, Daeil Kim et al.
[9] proposed ITO 50 nm/Au 5 nm/ITO 45 nm (IAI)
multilayer thin film gas sensor for the detection of
methanol at room temperature which had improved
performance than ITO sensors in lower operating
temperatures. Sotiropoulos et al.[10] fabricated a co-
planar electrode device with all electrodes (working,
counter and reference) on the same face of a Nafion
polymer electrolyte membrane for the amperometric
detection of gaseous methanol using Pt as the working
electrode.
II. EXPERIMENTAL
SYNTHESIS OF PANI/HCL
Polyaniline and its nanocomposites can be synthesized
by many methods. In the present work, PANi and its
nanocomposites were synthesized by oxidative chemical
polymerization method or simply chemical technique.
The main advantage of chemical synthesis is its ease and
capability to produce large volume of PANi good yield.
SYNTHESIS OF ANILINE HYDROCHLORIDE:
2ml of Aniline (S. D Fine Chemicals) with 3ml of conc.
Hydrochloric acid (Finar Chemicals) in a beaker at
30oC, on cooling the mixture at 2oC using an ice bath,
Then the solid polymer was washed with diethyl ether
(approx. 100ml) to remove excess aniline.
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 National Conference on VLSI and Communication (VCS-2012), 30-31, Oct 2012

SYNTHESIS OF POLYNILINE:
2.59g Aniline hydrochloride dissolved in 50ml distilled
water. 5.71g Ammonium per sulphate (S D Fine
Chemicals) was dissolved in 50ml distilled water. Then
both the solutions were mixed. Because the
polymerization of aniline is an exothermic reaction,
temperature rises with the progress of polymerization.
After stirring for one hour, the solution was left to rest samples are as shown in Figure 2. The most important
over night. The precipitate was filtered and washed with vibrational bands which allows the identification of
1mol HCL followed by further washing with deionised Polyaniline in the reference spectrum are: 830 cm-1 out of
water and methanol to get polyaniline emeraldine salt. plane C-H bond, 1330 cm-1aromatic C-N-C bond, 1490 cm-1
aromatic C=C double bond, 1590 cm-1 nitrogen bond
between benzoid and quinoid rings. The weak and the broad
III. RESULTS AND DISCUSSIONS band near 3400cm-1 in the spectra assigned to the N-H
The systematic studies on the Morphology, Spectroscopy, stretching mode. Different peaks and their characteristics
Conducting and Methanol gas sensing properties of these obtained in the present work for PAni are given in Table 1.
polymers are sparse. The PAni/HCl nanocomposite sensor The spectra clearly exhibit the presence of quinoid and
was synthesized employing the techniques as outlined in the benziod ring vibrations at 1591cm-1, thereby indicating the
above section and the sensor was studied for its FTIR, SEM, oxidation state of Emeraldine Salt (ES) PAni. The strong
Electrical conductivity and Methanol gas sensing band at 1190cm-1 was described by MacDiarmid et al[20].
characteristics of PAni/HCl. The results of this study have As the electronic like band (-N=quinoid=N-) and is
been presented and discussed here. considered to be measure of the degree of delocalization of
MORPHOLOGY OF PANI/HCL electrons and thus it is characteristic peak of PAni
The figure 1 shows the typical SEM images of PANi/HCl conductivity [21],[22].
sample. The analysis of SEM shows large numbers of
honeycomb clews with an average diameter of about 1µm Table 1: IR absorption of PAni/HCl sample.
that are composed of interconnected agglomers [18]. These Standard Vibrational Resultant
honeycomb structures are loosely arranged, smooth, uniform Reference assignments absorption band
and highly porous. Such a uniform and porous morphology absorption
is desirable because it enables a material with high ionic bands (cm-1)
conductivity to achieve fast charge/discharge rates [19]. 1590 Benzenic - 1569.23
quinonics nitrogen
1490 Aromatic C=C bond 1500.00
1330 Aromatic amine 1315.38
1190 C-N-C 1130.77
920 Poly-conjugated 900.00
system
830 C-H out-of-plane 807.69

(a) Low resolution (2µm)

(b) High Resolution (1µm)

Figure 1: SEM images of PANi/Hcl

The main criterion for any sensing material is to have large

surface area compared to volume of the material and the
sensitivity of the material. The presence of irregular-
spherical shaped particle structures of PANi/HCl was very
promising for the sensing application.
FTIR SPECTRA
IR response of PAni/HCl samples was measured and
spectrums (Transmittance Vs Wave number) of PAni/HCl
Figure 2: FTIR Spectrum of PANi/HCl
CURRENT-VOLTAGE CHARACTERISTICS
The current-voltage characteristics of the Polyaniline was
evaluated by measuring the voltage with varying current at
room temperature in order to see whether the Polyaniline
sample possess the ohmic contact or rectifying contacts.

Department of Electronics & Communication, BIT, Bangalore 30

 National Conference on VLSI and Communication (VCS-2012), 30-31, Oct 2012
Figure 3: I-V characteristics.
A linear relationship of the I-V characteristics is shown in
the figure 3 (i.e. the potential difference across its ends is
directly proportional to current flowing through it). As
depicted in figure 5.5, the I-V characteristic is almost linear.
The linear fit yields a regression value of 0.96 confirming a
best linear fit. This indicates that, the PANi/HCl exhibits
good ohmic behaviour and best suitable for sensor
applications.
Gas Sensing Response
The PAni/HCl pellets of size <2mm thick and 12mm
diameter were prepared using pelletizer and was studied for
methanol gas sensor applications. The two probe technique
of resistance measurement is employed in turn to measure
voltage. The two electrical contacts were made on the
polyaniline pellets by copper wire and silver paste. The
electrically wired polyaniline pellets was enclosed in a glass
chamber and a known quantity of methanol was passed into
chamber and results are reported in term of change in
voltage (resistance) of the PANi/HCl Vs time of the gas
exposed. Now constant current in mA range (here 8.1mA) is
applied to its contacts and output voltage is measured with
respect to ground terminal. For various concentrations of
methanol vapours, change in output voltage is recorded and
plotted considering concentrations along x-axis, voltage
along y-axis. Output voltage linearly decreases as it interacts
with gas molecules. The Concentration V/s Voltage shown
in figure 4, which depicts that for every raise in 1 PPM of
gas there is a decrease in 0.375mV across the sensor.
Figure 4: Concentration V/s Voltage Characteristics
Department of Electronics & Communication, BIT, Bangalore
IV. CONCLUSIONS
PAni/HCl nanocomposite appears to be a good
candidate to realize gas sensors because of its sensitivity
at room temperature, ease of synthesis by various
methods and low cost. At present, the trend seems to be
the use of composites of Polyaniline as the sensitive
layer. The morphological investigation reveals the
presence of irregular-spherical shaped PAni/HCl nano-
composites which is desirable for gas sensing
applications. The presence of PAni/HCl in the prepared
composites is confirmed by FTIR spectroscopy results.
The sensor output is linear, thus ohmic behaviour depicts
that for every raise in 1 PPM of gas concentration there
is a decrease in 0.375mV across the sensor.
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