Sensors and Actuators B 72 (2001) 7579

Development of a polyaniline-based optical ammonia sensor

Zhe Jin, Yongxuan Su, Yixiang Duan*
Chemical Science and Technology Division, CST-9, MS K-484, Los Alamos National Laboratory, Los Alamos, NM 87545, USA
Received 2 May 2000; received in revised form 2 August 2000; accepted 8 August 2000

Abstract
A polyaniline lm was deposited on polyethylene surface by chemical oxidation of aniline monomer at room temperature. The ammonia
gas sensing capabilities of the polyaniline lm were studied using absorption spectroscopy method. A signicant change was observed in
the absorption spectra of the lm after it was exposed to ammonia gas. The optical ammonia gas sensors have a response time of less than
15 s and a fast regeneration time of less than 2 min at room temperature. The sensors have a detection limit of 1 ppm (v/v) for ammonia,
with a linear dynamic range from 180 to 18 000 ppm. # 2001 Elsevier Science B.V. All rights reserved.
Keywords: Optical sensor; Polyaniline; Ammonia

1. Introduction
Conducting polymers are a new class of sensing materials,
which can be prepared by a simple oxidative polymerization
method. They exhibit reversible pH-induced spectroscopic
and gas-induced conductivity changes. They also provide a
suitable structure for immobilization of ligands, enzymes
and antibodies. Therefore, their use in the development of
novel chemical and biological sensors has received considerable attention [13].
Conducting polymer gas sensors commonly rely on conductivity changes that occur when they are exposed to
certain gases. The dc conductivity of a polypyrrole lm
decreases with increasing ammonia gas concentration and
an ammonia gas sensor based on this property has been
developed [4]. At room temperature, the response time of
such a sensor was a few tens of minutes. By increasing the
temperature from 20 to 1008C, the response time was
shortened by a factor of 5. After treatment with NO2, the
response and sensitivity of the sensor deteriorated. The
major problems of this polypyrrole ammonia gas sensor
are slow response time, low sensitivity, irreversible response
and a controlled high temperature (1008C) requirement.
The dc conductivity of polyaniline lms also depends on
ammonia gas concentration. A polyaniline lm containing
nickel prepared by electrochemical oxidation could detect
ammonia gas in the range 110 000 ppm at room temperature [5]. The response time was reported to be around 2 min,
*
Corresponding author. Fax: 1-505-665-5982.
E-mail address: yduan@lanl.gov (Y. Duan).

much faster than that of a polypyrrole ammonia sensor,

however, the regeneration of the polyaniline sensor was slow
[6]. By heating the sensor layer up to 1041078C, it was
possible to regenerate the sensor completely within a short
period of time. In addition to ammonia gas, polyanilinebased sensors can also detect H2S, NOx and SO2. Detection
limits as low as 4 ppm can be achieved for H2S and NOx
gases with polyaniline gas sensors [7].
Recently, high- and multi-frequency ac conductivity measurement techniques have been used for conducting polymer
gas sensors [8,9]. The most important advantage of ac
conductivity measurement is that it is possible to distinguish
different chemical species with a single sensor. Organic
vapors, such as methanol, acetone and ethyl acetate, could
be detected by measuring ac conductivity changes of a
polyaniline gas sensor at different frequencies [9]. Another
technique, which can differentiate different chemical species, is the frequency counting interrogation technique [10].
In order to monitor characteristic resistance and capacitance
changes simultaneously, a conducting polymer sensor was
used as one of the arms of a four-channel Wien-bridge
oscillator system. From the combined patterns of frequency
changes in four channels, it was possible to detect the vapor
to which the system was exposed.
Gas sensors based on conducting polymers are operated
primarily by conductivity measurement techniques. There
are only very limited reports on conducting polymer optical
gas sensors [11]. A polyaniline optical sensor based on
the surface plasmon resonance has been developed. The
sensor was sensitive to NO2 and H2S. The detection limits
were about 50 ppm of vapor. However, the sensor response

0925-4005/01/$ see front matter # 2001 Elsevier Science B.V. All rights reserved.
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Z. Jin et al. / Sensors and Actuators B 72 (2001) 7579

was slow and the total regeneration of the sensor was

impossible.
Conducting polymers are very promising gas sensing
materials; however, their potential in analytical chemistry
has not been fully utilized. Most gas sensors suffer from the
problems of slow response time and regeneration difculty.
In this paper, we report the use of absorption spectroscopy
method for ammonia sensing with a polyaniline lm. This
new optical sensor has a rapid response to ammonia gas and
regenerates easily, which is advantageous over the current
polymer gas sensors based on electrical conductivity measurements.
2. Experimental
2.1. Polyaniline film preparation
Polyaniline lms were prepared following the method
described in [12] with a slight modication. A piece of
polyethylene tube (i.d. 3.5 mm, o.d. 4.2 mm) was lled with
a 1 M hydrochloric acid solution containing 0.1 M of aniline
and ammonium persulfate, respectively. The polymerization
reaction was carried out for over 2 h at room temperature. A
uniform polyaniline lm was obtained in the inner wall of
the polyethylene tube. The tube was then rinsed repeatedly
with deionized water to get rid of loose polymer particles. A
Pyrex glass tube (i.d. 2 mm, o.d. 4 mm) was also tested for
preparation of polyaniline lms. The lm was usually
treated with 0.1 M hydrochloric acid before it was used
for ammonia detection. The lm thickness was determined
to be 100 nm with the method described in [13].
2.2. Absorption spectra measurements
An Ocean Optics Chem2000 spectrometer system (Dunedin, FL) was used to measure absorption spectra of the
polyaniline lms in the visible and near IR range. The
optical ammonia gas sensing system that was used with
this spectrometer is shown in Fig. 1. The system consists of a
light source, a polyaniline gas sensor, an optical beam
collection system, a spectrometer with a built-in CCD
detector and a computer for data collection and analysis.
The light source was a LS-1 tungsten halogen light source
powered with a 12 V dc power supply. A 74-VIS collimating
lens was used to convert divergent optical beams into a
parallel beam. A silica-core and silica-clad single-strand
optical ber, 2 m in length and 400 mm in diameter was
connected to the 74-VIS collimating lens and the spectrometer via SMA terminations. The spectrometer system was
optimized for the wavelength range of 360900 nm. A 2048element linear CCD-array detector was used for signal
detection. The detector was mounted on a 1 MHz ISAbus A/D card. The spectrometer was plugged in an ISA
slot of a Compaq Progsignia 320 desktop computer. Windows-based OOIChem software was used for data acquisi-

Fig. 1. Schematic diagram of the experimental set-up of ammonia gas

sensing based on absorption spectroscopic measurement.

tion and signal processing. A stream of nitrogen gas

containing ammonia was passed through the polyaniline
gas sensor and spectroscopic measurements were performed. Nitrogen gas (99.99%) was used as both carrier
and dilution gas to transfer ammonia to the sensor. All
spectroscopic experiments were performed at room temperature.
3. Results and discussion
3.1. Substrate effect on polyaniline film preparation
Stable lms of polyaniline and its derivatives were
obtained on the surface of polymer substrates such as
polystyrene [12]. We carried out polyaniline synthesis with
polyethylene and glass substrates. A uniform polyaniline
lm was obtained on the surface of polyethylene after 2 h
reaction at room temperature. However, it was difcult to
get uniform lms with a Pyrex glass tube. The treatment
of the glass with 0.1 M hydrochloric acid solution did
not improve the quality of the lm obtained. No
further effort was made to improve the quality of the
lm obtained on a glass substrate. A polyaniline lm
deposited on polyethylene surface was selected for ammonia
gas sensing.
3.2. Ammonia gas sensing
Polyaniline has many different oxidation states as shown
in Fig. 2. The basic form of polyaniline, commonly known as
emeraldine base (Fig. 2A), can be reduced to the leucoemeraldine base (Fig. 2B) or oxidized to the form of pernigraniline base (Fig. 2C).When ammonia gas is adsorbed on
an emeraldine base polyaniline lm, it can react with imine
nitrogen atoms to generate a protonated form of polyaniline,
resulting in signicant changes in electrical conductivity and
electronic absorption spectrum. This property of polyaniline
has been utilized for developing chemical sensors, especially gas sensors [57,11].
Fig. 3 shows the effect of ammonia gas on the absorption
spectra of polyaniline lms. The lm treated with hydrochloric acid showed distinct green color with a maximum

Z. Jin et al. / Sensors and Actuators B 72 (2001) 7579

77

Fig. 2. Chemical structures of polyaniline at different oxidation states.

absorbance at 800 nm (Fig. 3A), conrming that the lm was

totally protonated.
Ammonia gas has a strong effect on the spectrum of the
lm. When nitrogen gas containing 18 000 ppm ammonia
was passed through the sensor coated with a polyaniline lm
at a ow rate of 0.4 l/min, distinct color change from green
to blue was observed and the absorption maximum shifted to
620 nm (Fig. 3B). Fig. 4 shows the effect of different
concentrations of ammonia gas on the spectra of a polyaniline lm. The maximum absorption wavelength shifts gradually to a shorter wavelength with increasing ammonia
concentration. In order to obtain reproducible results, the
spectra were measured after 1 min equilibrium with the gas
samples. The spectrum change is reversible, indicating that
it is possible to use a polyaniline lm as an optical ammonia
gas sensing material.
The sensor response to ammonia was monitored at
600 nm. When ammonia concentration increased from 18
to 18 000 ppm, there was a fourfold increase in the absorbance. The detection limit is estimated to be 1 ppm from the
absorbance value obtained for 18 ppm ammonia, similar to
the limit reported for other ammonia gas sensors [6].

Fig. 3. Spectroscopic changes of a polyaniline film upon protonation/

deprotonation reaction: (A) 0.1 M hydrochloric acid; (B) 18 000 ppm
ammonia.

Fig. 4. Effect of different concentrations of ammonia gas on the spectra of

a polyaniline film. Ammonia concentration (ppm): (1) 225; (2) 450; (3)
900; (4) 1800; (5) 9000; (6) 18 000.

The resistance change of a polyaniline lm is controlled

by ammonia diffusion into the lm, which can be expressed
by the following equation [6]:
R R0 expaNg

(1)

Here, R0 is the initial resistance, N the ammonia concentration and where a and g are constants. Since the absorbance
change is also controlled by the same diffusion process, the
relationship between absorbance and ammonia concentration can be expressed by rearranging Eq. (1):
A A0 expaNg

(2)

Here, A0 is the initial absorbance and A is the absorbance at a

concentration of N. From Eq. (2), log lnA=A0 is proportional to log N.
The typical calibration curve obtained with Eq. (2) is
shown in Fig. 5. The linear range is 18018 000 ppm with a
linear regression coefcient of 0.998. There is a deviation at
a lower ammonia concentration (<180 ppm) (not shown in

Fig. 5. Calibration curve of the ammonia sensor obtained with Eq. (2).

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Z. Jin et al. / Sensors and Actuators B 72 (2001) 7579

hydrochloric acid solution at room temperature. Such a

treatment results in the formation of a green lm immediately and a complete regeneration of the sensor. As an
alternative method, a nitrogen gas containing hydrochloric
acid can also be used to regenerate the sensor. The method is
rapid, simple and reproducible. Therefore, polyaniline
ammonia gas sensors based on absorption spectroscopy
method have signicant advantages over the conventional
sensors based on conductivity measurements not only in
response and regeneration time but also in ease of sensor
regeneration. The optical ammonia gas sensors developed
are more suitable for practical applications.
4. Conclusions
Fig. 6. The spectroscopic response of a polyaniline film to ammonia
admissionremoval cycles. The absorbance was monitored at 620 nm. Gas
on: a stream of nitrogen gas containing 200 ppm ammonia was passed
through the sensor; gas off: a stream of pure nitrogen gas was passed
through the sensor; gas flow rate: 800 ml/min.

the gure). The sensor was usually treated with 0.1 M

hydrochloric acid before experiments. This treatment may
contribute to the loss of ammonia gas and results in deviation
from the straight line at lower ammonia concentrations.
3.3. Sensor response and regeneration
Fig. 6 shows one cycle curve, which represents spectroscopic change of a polyaniline lm to ammonia intake
followed by its regeneration in nitrogen stream at room
temperature. The absorbance at 600 nm in 200 ppm ammonia ambient reaches close to 90% of the maximum within
15 s, then it drifts slowly upwards. When the ammonia is
turned off, the absorbance immediately decreases to less
than 10% of its peak height within 10 s. The absorbance is
only 2.5% higher than the baseline after 2 min regeneration,
which is accomplished by passing nitrogen gas over the
polyaniline lm and the lm is almost totally regenerated at
room temperature. In comparison, it is impossible to regenerate a polypyrrole ammonia gas sensor after exposing it to
10 ppm ammonia [4]. Polyaniline ammonia gas sensors
based on conductivity measurements have a response time
of around 2 min [5,6]. Polyaniline ammonia gas sensors
based on surface plasmon resonance have a response time of
over 10 min and the sensor response is irreversible [11].
The polyaniline gas sensors based on conductivity measurement can only be partly regenerated by passing air
through the sensor to remove the ammonia adsorbed on
the surface. The polyaniline lm does not fully regain its
initial detection value after ammonia desorption. In order to
fully regenerate the sensor, a thermal method, in which the
sensor was heated for up to 1041078C, was proposed [6].
The method is complicated and has signicant restrictions in
practical use. The new optical ammonia gas sensor developed can be fully regenerated by treating it with a dilute

We have presented an optical ammonia gas sensor based

on a polyaniline lm prepared by chemical oxidation. The
lm shows signicant spectroscopic changes upon exposure
to ammonia gas at room temperature. By employing absorption spectroscopy as a detection method, we have successfully developed an optical ammonia gas sensor which is
sensitive, stable, fast in response and easy to regenerate. The
new sensor effectively eliminates the limitations associated
with the current conducting polymer gas sensors, which are
based on conductivity measurements.
Acknowledgements
The authors would like to thank Joshua Smith for technical editing of the manuscript.
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