Materials Science and Engineering B 176 (2011) 821–829

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Hazardous industrial gases identified using a novel polymer/MWNT composite

resistance sensor array
C.L. Yuana a,∗ , C.P. Chang b , Y. Song c
a
Deparment of Chemistry, R.O.C. Military Academy, No 1, Fengshon Kaohsiung, 830, Taiwan
b
Department of Chemical and Materials Engineering Chung Cheng Institute of Technology, National Defense University, Taiwan
c
Chung-shan Institute of Science and Technology, Armaments Bureau, M.N.D., Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: Hazardous industrial chemical gases pose a significant threat to the environment and human life. There-
Received 1 December 2010 fore, there is an urgent need to develop a reliable sensor for identifying these hazardous gases. In this
Received in revised form 15 February 2011 work, a silicon wafer microelectrode substrate for a resistance sensor was fabricated using the semi-
Accepted 22 March 2011
conductor manufacturing process. Conductive carbon nanotubes were then mixed with six different
polymers with different chemical adsorption properties to produce a composite thin film for the fabrica-
Keywords:
tion of a chemical sensor array. This array was then utilized to identify three hazardous gases at different
Hazardous gases
temperatures. Experimental results for six polymers for chemical gases, such as tetrahydrofuran (THF),
Multi-walled carbon nanotube
Resistance sensor array
chloroform (CHCl3 ) and methanol (MeOH) at different temperatures, indicate that the variation in sensi-
Principal component analysis tivity resistance increased when the sensing temperature increased. The poly(ethylene adipate)/MWNT
sensing film had high sensitivity, excellent selectivity, and good reproducibility in detecting all chemical
agent vapors. Additionally, this study utilized a bar chart and statistical methods in principal component
analysis to identify gases with the polymer/MWNT sensor.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction In 2008, Kim et al. used multi-wall carbon nanotubes (MWNTs)

Due to rapid industrial growth, chemical substances that
adversely affect human health and survival are common in urban
and rural environments. Accurate and fast detection of hazardous
industrial gases is essential to protect human health. Contempo-
rary chemical sensors using several different mechanisms include
gas chromatography–mass spectrometry [1], Raman surface spec-
troscopy [2], neutron activation analysis [3], nuclear magnetic
resonance spectroscopy [4], X-ray diffraction [5], cycle voltamme-
try [6], and ion mobility spectrometry [7]. However, these methods
are costly and require frequent calibration to maintain accuracy.
Therefore, a more reliable and inexpensive technique that uses
stable sensors, and can adjust pattern recognition according to vari-
ation in the chemical agent vapors absorptive matrix is needed
[8–13].
Carbon nanotubes were discovered in 1991 [3] and have since
garnered considerable interest for their potential use in the fabrica-
tion of novel materials. Carbon nanotubes have been investigated
for use in polymeric materials, wherein they improve the mechan-
ical properties of composites and devices that conduct electricity.
∗ Corresponding author. Tel.: +886 7 7429442; fax: +886 7 7429442.
E-mail address: junelong@mail2000.com.tw (C.L. Yuana).
and MWNT–PANI sensing films to recognize NH3 gas, respec-
tively. The MWNT–polymer sensing films had better sensitivity
than the MWNT sensing films [14]. The experimental studies of
MWNT–PANI sensing films focused on sensing film fabrication
and measuring the response of MWNT–PANI sensors to differ-
ent explosive vapors under various operating conditions, including
adsorption/desorption behavior and concentration [15]. In com-
parison with chemoresistive sensors, MWNT–polymer composite
sensors have many advantages, such as high sensitivity, rapid
response, good reproducibility, and long-term stability. To date,
only one study has investigated the interaction between polymers
and gases, but did not experimentally investigate multipoly-
mer/MWNT composite sensor arrays.
This work, analyzed the ability of novel polymer/MWNT sen-
sor arrays to identify certain gases. These sensors were designed
to swell reversibly and cause changes to the resistance for three
different temperature chemical vapors.
The reproducibility and stability of polymer/MWNT sens-
ing films in a microelectrode resistance system are shown
by a sensitivity chart of absorption/desorption, and informa-
tion patterns are established based on measurement results of
resistance. The bar chart and statistical methods in principal
component analysis are utilized to identify the three chemical
gases.

0921-5107/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2011.03.011
822 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829

Fig. 1. Six polymer structures.

2. Experimental 2.2. Fabrication of composite thin-film sensors

2.1. Materials
The multi-walled carbon nanotubes (MWNTs) were fabricated
by chemical vapor deposition (CVD) with a nominal outside diam-
eter (OD) of 30–40 nm. The six polymers, including ethyl cellulose
(EC), poly[methyl vinyl ether-alt-maleic acid] (PMVEMA), hydrox-
ypropyl methyl cellulose (HPMC), poly(alpha-methylstyrene)
(PMS), poly(vinyl benzyl chloride) (PVBC) and poly(ethylene adi-
pate) (PEA), were purchased from the Sigma–Aldrich Corporation
(Fig. 1). All chemical agents, such as chloroform (CHCl3 ), tetrahy-
drofuran (THF) and methanol (MeOH), were of analytical reagent
grade. Photolithography, a semiconductor manufacturing tech-
nique, was utilized for device fabrication.
The first MWNT (1 wt%) layer-modified electrode was prepared
by casting 1 mg/mL. The MWNTs were dissolved in methyl-ethyl-
ketone (MEK) and dispersed on the surface of an interdigitated
microelectrode (IME) device, which was air-dried at room tem-
perature. When MEK was volatilized, an MWNT conducting film
formed. The polymer layer was then constructed by drop-casting
1 wt% of different polymer solutions onto the MWNT-layer. After
vacuum drying for 24 h at 60 ◦ C, the multilayer film sensor device
was formed.
The functionalized polymer/MWNT samples were characterized
using several techniques. Observations of the double-layer mor-
phology were performed by scanning electron microscopy (SEM)
(JSM-6500F).
 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829 823

Fig. 2. Configuration of the interdigitated microelectrodes.

2.3. Fabrication and measurement of the gas sensing system

The sensor response was determined using a customized IME

device, which had 12 pairs of 1 mm wide gold electrodes, spaced
1 mm apart on an SiO2 wafer substrate (Fig. 2).
Fig. 3. Instrument for measuring resistance.
A computer multichannel in-house multimeter was used to
determine the lateral resistance of the nanostructured coating on
the IME. Resistance and frequency measurements were performed
simultaneously via computer control. All experiments were per-
formed at different temperatures (30, 40, 50 and 60 ◦ C) and 50–60%
humidity. The gas flow was controlled by a calibrated Aalborg mass-
flow controller (GFM-17). The flow rate of the vapor stream was
maintained at 100 mL/min. The vapor generating system was a Gas
Standard Generator (KIN-TEK 670 C, Laboratories, Inc., TX, USA).
The vapor stream was produced by drying vapor solvent and using
a controller to manipulate the vapor concentration. The IME devices
were built in-house, and connected via tubing to the vapor and air
pump in a Teflon chamber (inner diameter of 1/8 in.). The vapor
concentration (ppm) in the unit, calculated using weight loss and
analyte volume at different temperatures (Table 1), can be derived
by Eq. (1):
R×K
Conc. = (v/v in ppm) (1)
F
where K = {22.4(T + 273) × 760}/MW × 273 × P, R (mg/min) is the
analyte weight loss, and F (mL/min) is the flow rate.
Fig. 3 shows the apparatus for determining resistance. Air was
the gas carrier. Different vapor concentrations were generated by
an impingement system. At the start of the experiment, the test
chamber was purged with air for 30 min to ensure that no air
existed in the chamber and to establish a baseline. The chamber
was purged with air for 10 min and then the test vapor was at the
desired concentration for 5 min [15].
The sensitivity of the gas sensing thin film markedly influenced
the resistance of the gas sensor and its detection performance. Gen-
erally a sensor with higher sensitivity will have better detection
capability and a broader application range than a sensor with low
sensitivity. The sensitivity of the resistance gas sensor (S %) was
derived as
Rgas − Rair R
S %= × 100 = × 100 (2)
Rair Rair
where Rair is sensor resistance in air and Rgas is resistance after
absorbing gases at different temperatures.

Table 1
Concentration (ppm) of the six chemical vapors.

Temperature (◦ C) MeOH (ppm) CHCl3 (ppm) THF (ppm)

30 27,271 19,381 11,650

40 45,445 32,274 8,531
50 60,691 44,225 10,707 Fig. 4. Micrographs of (a) pure MWNTs and (b) PMS/MWNTs.
60 92,410 100,639 21,526
824 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829

3. Results and discussion
3.1. SEM of sensing films
Fig. 4 shows scanning electron micrographs of pure-MWNTs
and the PMS/MWNT double-layer film. Fig. 4a shows micrographs
of MWNTs, indicating that MWNTs with diameters of 30–80 nm
were well distributed on the surface of small bundles or single
tubes. These small bundles and single tubes, which were assembled
homogeneously on the substrate, should improve sensor perfor-
mance because most well-dispersed MWNTs are electrochemically
accessible. Conversely, the deposition of PMS on the MWNTs film
produced a multilayer morphology (Fig. 4b). The PMS particles
were spherical and rough (particles were about 100 nm), and
agglomeration was also observed. This uneven surface is beneficial
for gas adsorption. The anchoring of PMS covering the MWNT-
surface imparted compatibility and electron transfer which greatly
improved the material responsiveness and reversibility.
3.2. Gas-sensing resistivity response characteristics
This study used six different polymer/MWNT sensors to detect
three industrial chemical gases chloroform (CHCl3 ), tetrahydro-
furan (THF) and methanol (MeOH), at different temperatures.
The arrays of sensing films differed in terms of the chemical
and physical characteristics of the mediator molecules, which
include hydrogen-bonding properties, hydrophobicity, and chin
length or structure. Resistance variations were measured by
absorption/desorption tests under different vapor concentrations
at different temperatures. Fig. 5 shows that different absorp-
tion/desorption response may be produced by patterns of the six
polymer/MWNT composite sensing films. The sensitivity of the

Fig. 5. The tendency charts of polymer/MWNT thin film sensing three gases at different concentrations. (A) CHCl3 , (B) THF and (C) MeOH.
 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829 825

Fig. 5. (Continued )

PEA/MWNT sensing film increased dramatically by over 5, 15,
21, and 40% within 30 s after exposure to 19,381, 32,274, 44,225
and 100,639 ppm CHCl3 vapor at 30, 40, 50, and 60 ◦ C, respec-
tively. When the PEA/MWNT film was transferred from solvent
vapor into dry air, the sensitivity rapidly returned to the orig-
inal value after 33 s, which is a measure of the sensitivity and
the significant improvement in restoring performance at roughly
30 min after obvious stability (Fig. 5A-b). Otherwise exposure of the
PEA/MWNT film to THF and MeOH vapor results in excellent sensi-
tivity and reproducibility (Fig. 5B and C). In this study, the responses
of different films in the array to different vapors are reported,
including vapor molecules of chloride, cycle-oxide and hydroxide
groups. Fig. 5 shows a representative series of response character-
istics for sensing responses obtained for the three vapors of the
six-sensor array system EC/MWNTs, PMS/MWNTs, PVBC/MWNTs,
HPMC/MWNTs and PMVEMA/MWNTs sensing films. Fig. 5 shows
the response profiles for a selected exposure to vapor concen-
trations, and the corresponding response sensitivities against
concentration.
After sampling saturated absorption resistances for five times at
different temperatures, this work derived the standard deviation of
polymer/MWNT exposure to CHCl3 vapor as 4.7 × 10−1 –8.4 × 10−2
(Fig. 6a). The standard deviation of the polymer/MWNT exposure
to THF and MeOH was 1.2 × 10−1 –9.0 × 10−2 (Fig. 6b and c). These
low deviation rates show that the stability increased when using
polymer thin films to identify chemical gases at different tem-
peratures. The resistance variation can be further explored via
factors such as interaction forces among chemical gas molecules,
vapor pressure of chemical gas molecules, and polymer solubility
parameters.
826 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829

Fig. 5. (Continued )

Based on these response data, this study further compared
the response sensitivities (Fig. 7). From the bar chart and radar
chart (Fig. 7), the PEA/MWNTs, EC/MWNTs, PMVEMA/MWNTs and
PVBC/MWNTs had highly resistant absorption variation rates for
the three gases at different concentrations. Additionally, the resis-
tance variation rate of HPMC/MWNTs and PMS/MWNTs for MeOH
had an increasing tendency to sensitivity. However, exposure to
CHCl3 and THF caused a sensitivity response that decreased than
the responses of the polymer/MWNT composite thin film sen-
sors to EC, PEA, PVBC and PMVEMA (Fig. 7). Thus, experimental
results indicate that all sensing materials had higher sensitivity
for the hydroxide compounds than for chloride and cycle-oxide
vapor analytes. Additionally, for hydroxide vapor, the response
sensitivity increase with high specificity constitutes an unprece-
dented example resulting from a unique combination of the
hydrogen-bending donor/acceptor and hydrophobicity of the poly-
mer/MWNT structure [16]. These experimental results show that
these polymer/MWNT composite thin-film sensors were selective
for the three industrial gases at different temperatures.
3.3. Adsorption/desorption mechanism of gas-sensing film
behavior
According to the data on adsorption/desorption, the response
mechanism of gas-sensing film behavior may be associated with
differences in the physical adsorption properties of MWNTs and
polymers for different organic chemical vapors. A highly polar
surface energy component was observed for MWNTs, which was
 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829
Fig. 6. Standard deviations of polymer/MWNT thin film sensing three gases with 5
cycles. (a) CHCl3 , (b) THF and (c) MeOH.
significantly different than that of a carbon-black particle [17],
leading to different interactions between MWNTs and polymers.
Moreover, the layered polymer/MWNT composites had central
hollow core structures, permitting analytes to permeate the poly-
mer/MWNT film through both the inner and outer layers, thereby
allowing polymers to swell rapidly. Furthermore, when inter-
layer interactions between carbon nanotubes were introduced,
the polymer/MWNTs changed from metal-like to semiconductor-
like, resulting in increased resistance. Whether MeOH can induce
827
Fig. 7. Resistance bar chart of six polymer/MWNTs for three gases at different con-
centrations.
a change in the conductive performance by adsorption on the
polymer/MWNT surface requires further study. This structure facil-
itates the formation of intramolecular and intermolecular hydrogen
bonds [18], wherein electronic transitions from the valance band
to mid-band gap states occur when the polaron state contains one
electron and the bipolaron state is completely empty (i.e. con-
tains two holes). In this case, polymeric “swelling” and “shrinking”
destroy the original film structure or configuration. At the same
828 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829

time, the polymer volume increased when it swelled, and the inter-
layer distance between MWNTs increased, breaking the conducting
network and leading to a significant increase in film electrical resis-
tance. Notably, the swelling of polymer chains wrapped around
MWNTs differs from that of a pure polymer matrix. The for-
mer involves the influence of interactions on the surface of the
polymer/MWNTs and gases [19], while the interaction among poly-
mer chains differs in the latter case because aggregation occurs
easily. Thus, the ability of the polymer alone to shrink is not
sufficient to explain the aforementioned phenomenon. To date,
no study has investigated the absorption kinetics for the inter-
action between polymers and MWNT. One researcher suggested
that the polymer molecular structure and atomic interactions at
MWNT interfaces significantly influence sensor system properties
[20]. Another researcher suggested that weak electrostatic or non-
covalent interactions between highly delocalized electron systems
of polymer and MWNTs may affect the molecular recognition abil-
ity of solvent molecules by PEA [21]. For covalently functionalized
MWNTs, polymer chains are individually anchored onto the tube
surface, forming a nanoscale layer of coverage (where the thickness
depends on polymer amount), especially for the case of high con-
ducting polymer amounts between MWNTs. A hopping mechanism
was responsible for intertube charge transfer between MWNTs and
intertube modulation of the MWNTs network in lieu of a conduc-
tivity change [21].

3.4. Pattern recognition by PCA

The PCA statistical method was applied to the signal of the opti-
mized sensor array, and input data from the primary matrix were
normalized responses, which were chosen to represent the rela-
tive resistance change (R/R0 ) of the polymer/MWNT sensors. The
PCA data were obtained from the correlation matrix (centered and
standardized data) [22]. The responses of the three polymer/MWNT
sensors were normalized by the sum of all sensor response val-
ues for a given analyte. This normalization process reduced array
response dependence on vapor concentration and slightly reduced
sensor drift effects. Fig. 8 shows 3D plots for the three groups at four
concentrations of CHCl3 , THF and MeOH vapors obtained by apply-
ing PCA to the normalized responses of the six polymer/MWNT
sensing films. As shown by the data points for the high concen-
trations, analytical results demonstrate that all vapors were easily
separated. Between the four dots of 19,381, 32,274, 44,225 and
100,639 ppm (Fig. 8a), another evolved region of organic agents
can be fixed in the feature plane analyzed (PC1 –PC2 ) with a high
cumulative variance exceeding 96.54%. As previously noted, the
largest portion of variance was from the first principal component
(PC1 ), which was also the most important in dot discrimination. The
second principal component (PC2 ) contained relatively less infor-
mation (3.43%), whereas the third principal component included
the smallest variation (0.025%). Fig. 8b and c shows the four dots for
11,650, 8531, 10,707, and 21,526 and 27,271, 45,445, 60,691, and
92,410 ppm. With the high cumulative variance exceeding 99.56
and 91.7%, the second principal component (PC2 ) contained less
information (0.31 and 7.35%), and the third principal component
(PC3 ) had the smallest variation (0.13 and 0.94%). Thus, no redun-
dant sensors existed in the studied array.

4. Conclusions
Fig. 8. PCA score plots of three groups in the 3D PCA space (a) CHCl3 , (b) THF and
(c) MeOH. This study demonstrated that coating six polymers on the
surface of MWNTs can produce standardization of gas sensing prop-
erties for the detection of CHCl3 , THF, and MeOH vapors. The sen-
sitivities of polymer/MWNT films for the three solvents in decreas-
ing order were PEA/MWNTs > EC/MWNTs > PMVEMA/MWNTs >
 C.L. Yuana et al. / Materials Science and Engineering B 176 (2011) 821–829
PVBC/MWNTs > HPMC/MWNTs > PMS/MWNTs, which corresponds
to the order of decreasing conductivity. Experimental results
demonstrate that the PEA/MWNT sensor had high sensitivity,
excellent selectivity, good reproducibility, and long stability for
all investigated concentrations of vapors. Modification of the elec-
tronic structure of MWNTs by chemical functionalization proved
valuable to the development of an advanced sensor material. Thus,
the adsorption and desorption behavior of polymer chains cov-
ering MWNTs and the interaction between the polymer chains
and analytes play important roles in gas sensing. In summary,
this work developed polymer-functionalized MWNT sensor plat-
forms for the detection of vapors from chemical agents at different
temperatures. This study applied PCA to determine the perfor-
mance of as-fabricated films for exposure to three chemical agents.
The devices developed can be extended to PEA/MWNT sensors for
highly sensitive and specific molecular detection.
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