Proceedings of the 12th SPVM National Physics Conference

c 2010 SPVM. All rights reserved. ISSN 1655-4620. http://physics.msuiit.edu.ph/spvm

1
Fabrication and Characterization of Polyaniline Films Doped
with Varying Concentrations of HCl for Ammonia Sensing
Application
Rowena S. Dulos∗ , Bianca Rae B. Sambo† and Filchito Renee G. Bagsican‡
Materials Science Laboratory, Physics Department, Mindanao State University - Iligan Institute of
Technology,
A. Bonifacio Avenue, Tibanga, 9200 Iligan City, Philippines

A lot of researches done for the ammonia sensitivity of the PAni but never consider the recovery of the
sample.In this paper, the ammonia sensitivity and the recovery of the doped PAni films are investigated.
The fabricated polyaniline films doped with varying concentrations of hydrochloric acid are electrically
characterized via two probe method. Polyaniline films shows an increase of conductivity upon increasing
the dopants concentraion. For the ammonia sensing capability of doped PAni films, samples are exposed to
ammonia gas for 30 minutes and the recovery of the samples are investigated. It is observed that the sample
with the highest dopant concentration exhibited the highest sensitivity for about 1395% and it exhibited the
fastest recovery when ammonia gas is removed. This active response of the doped PAni films to ammonia
gas indicated that they can be used as ammonia sensors.

1. Introduction researches are focused on PAni’s ammonia gas

Among the available intrinsically conducting
polymers (ICPs), polyaniline(PAni) has been
investigated extensively for over one hundred
years and attracted scientific interest as a con-
ducting material because of its inexpensive
monomer, its straightforward polymerazition
reaction and for its excellent stability[1]. Before
Pani can become a succesful conducting mate-
rial it undergo doping to enhance its conductiv-
ity level.
Doping process of PAni can be performed
in two different ways, the redox doping and
the protonic acid doping. In the case of pro-
tonic acid doping, the higher the acidity of the
dopant, the lower the resistivity of PAni thus
the higher is its conductivity. By changing the
doping level, the conductivity of polyaniline can
be modified to suit specific applications. The
changes in the doping level of PAni provide
a simple technique in detecting the analytes
present in the atmosphere. One of the analytes
that is abundant in the atmosphere is ammonia
gas, which is toxic and can be detected through
its pungent odor. The doping process of PAni
is reversible which is unique in a polymer thus
it plays the key role in the sensing mechanism
of a conducting polymer based sensor. A lot of
∗ Email address: rsdulos@gmail.com
† Email address:brsambo@yahoo.com
‡ Email address:tjbagsican@gmail.com
sensing capability but the recovery of PAni is
not investigated.
In this paper, the fabrication and the elec-
trical characteristics of PAni films doped with
various concentrations of HCl, during and after
exposure to ammonia gas are investigated. This
paper investigated the recovery of the sample
after exposure to ammonia gas.
2. Methodology
2.1. Sample Preparation
Aniline is polymerized using ammonium per-
sulfate (APS) as oxidizing agent and HCl as
dopant and the acidic environment in the poly-
merization resulting to a doped PAni solution.
To produce PAni film, doped PAni solution is
deposited on a glass slide through chemical bath
deposition.
2.2. Electrical Characterization
In determining the electrical characteristics
of the sample, two probe method is used. Two
thin wires are silver pasted on the sample and
current is supplied using low current source.
Low current source and the digital nanoameter
are connected in series while the voltmeter is
connected in parallel connection with the sam-
ple. The current is supplied by the low current
source and the corresponding voltage is mea-
sured by the voltmeter. The supplied current
is then incremented until the maximum cur-
 Fabrication and Characterization of Polyaniline .. — 2
rent that the sample can give is reached. This
process is done to determine the resistance of
the sample given the relationship shown in the
mathematical equation below.
V 0.8M
R= (1)
I 0.6M
where R is the resistance measured in ohms, V
is the potential difference measured in volts and
I is the current measured in amperes
2.3. Ammonia Sensing
For the ammonia sensitivity test, the sample
is placed inside the box enclosure fabricated by
M.K. Odarve to keep the majority of impuri-
ties present in the air from interacting with the
sample [2]. The sample is then characterized
via two probe method to investigate the elec-
trical behavior of the sample upon exposure to
ammonia gas. The equation in determining the
sensitivity of doped PAni films is defined below:
|Re − Rne |
S= × 100% (2)
Rne
where S is the sensitivity of the material,Rne
is the resistance before the exposure to analyte
and Re is the resistance per minute during ex-
posure to the analyte when the operating cur-
rent is supplied. To quantify the recovery of the
sample, same equation for sensitivity is used.
That is Re is the resistance of the sample after
the exposure to analyte.
3. Results and Discussion
3.1. Synthesized film
The polymerized PAni using APS as oxidant
and HCl as dopant has a dark green color.For
the PAni doped with 0.2M, 0.4M, 0.6M, 0.8M,
1.0M of HCl their color remains the same.
3.2. Electrical Characterization
PAni doped with 0.2M, 0.4M, 0.6M, 0.8M,
1.0M HCl are electrically characterized via two
probe method.Table 1 shows the corresponding
resistance of the samples doped with varying
concentrations of HCl. It is found that, when
the dopant concentration gets higher the sam-
ples decreases its resistance indicating an in-
crease on the conductivity of the sample. As
expected 1.M HCl has the lowest resistance op-
posite to 0.2M HCl which has the highest re-
sistance. Since 1.0M HCl has the highest resis-
tance thus it is the most conductive among the
fabricated PAni films.
Table 1
Resistivity of the PAni sample.
HCl Concentration Resistance MΩ
1.0M 6.19 + 3.24 × 10−2
7.45 + 6.46 × 10−3
8.85 + 1.31 × 10−1
0.4M 9.84 + 3.07 × 10−2
0.2M 10.00 + 2.41 × 10−16
3.3. Ammonia Sensing
The purpose of the fabrication of this doped
PAni film is for its sensing application. The
PAni films are tested for its ammonia sensitivity
by exposing the five samples doped with vary-
ing HCl concentrations to 1.0M N H4 OH. The
sensitivity and the behavior of the samples af-
ter the exposure are shown in Figures 1 to 5.
The green marker represents the percent differ-
ence of the PAni film’s resistance per minute be-
fore ammonia exposure when the operating cur-
rent was supplied and the resistance of the rod
from the I-V Curve before exposure, referred
to as the standard resistance. The blue marker
represents percent sensitivity of the film upon
exposure to ammonia gas and the red marker
represent the percent difference of the film’s re-
sistance per minute after the exposure and the
standard resistance. The red marker shows the
recovery of the doped Pani film.
Looking at the figures, the highest sensitiv-
ity is around 1,395% sensitivity which is exhib-
ited by PAni doped with 1.0M HCl. For the
0.2M HCl doped PAni film, its highest sensi-
tivity is around 22.69% while for the 0.4M HCl
doped PAni the highest is around 10.36%simi-
lar to 0.6M HCl which is around 10.71% sen-
sitivity. For the 0.8M HCl doped sample, its
sensitivity is around 32.48%.
. in
Figure 1. Sensitivity of 0.2M HCl doped PAni
PAni-HCl generally exhibited positive sensi-
tivities. This means that it increases its resis-
tance upon exposure to ammonia gas. Most of
the researches conducted on PAni as an ammo-
nia sensor showed that its ammonia mechanism
is governed by the protonation/deprotonation
principle wherein upon exposure, PAni goes
back to its base form or undoped state [4]. This
implies that during exposure, PAni is expected
to increase its resistance. As you can see in
R. Dulos, et al. • October 2010
3 — Fabrication and Characterization of Polyaniline ..

Figure 2. Sensitivity of 0.4M HCl doped PAni Figure 5. Sensitivity of 1.0M HCl doped PAni

of the sample before exposure to ammonia gas.

4. Conclusion and Recommendation

Highly conductive polyaniline is obtained by
increasing the dopant concentration. Regard-
less of the dopant concentration of the sample,
samples are capable of sensing ammonia gas and
is able to recover after exposure which is a good
characteristic of a sensor since it implies that
the films are reusable. For a deeper explaina-
tion on the behavior of the doped PAni films,
it is recommended to investigate morphological
characteristics of the samples using SEM.
Figure 3. Sensitivity of 0.6M HCl doped PAni
5. References
1. A.J. Heeger,”Semiconducting and Metallic Poly-
mers: The Forth Generation of Polymeric
Materials”,N obelLecture,December 8,2000. ”‘:
Progress in Polymer Science, (2009),34,783810
2. A.Z.Sadek, W.Wlodarski , K.Kalantar-Zadeh, C.
Baker, R.B. Kaner,”Doped and dedoped polyani-
line nanofiber based conductometric hydrogen gas
sensors:”‘Sensors and Actuators A, (2007),139,5357
3. M.K.Odarve,”HCL Doped Polyaniline for Ammonia
Gas Sensing”, An Undergraduate Thesis. Mindanao
State University - Iligan Institute of Technology, Ili-
gan City.2009.
4. H. Bai, and G. Shi,”Gas Sensor Based Conducting
Polymer:”Sensor 7,(2007),267-307.

Figure 4. Sensitivity of 0.8M HCl doped PAni

the Figures 1, 3, 4, 5, when the samples are

exposed to ammonia gas its sensitivity percent-
age increases thus the samples are sensitive to
ammonia gas. It is also noticed that after the
samples are exposed to ammonia gas, it was
able to recover to its original state as shown in
Figures 2, 4 and 5 since the percent difference
drops approaching to the sensitivity percentage

R. Dulos, et al. • October 2010