Sensors and Actuators B 49 (1998) 240 247

Humidity sensors using polyvinyl alcohol mixed with electrolytes

Mu-Rong Yang *, Ko-Shao Chen
Department of Materials Engineering, Tatung Institute of Technology, Taipei, 104, Taiwan
Received 14 October 1996; received in revised form 6 March 1998; accepted 10 March 1998

Abstract
Resistive-type humidity sensors were fabricated by casting polyvinyl alcohol on comb-shaped electrodes. The impedance of the
PVA film decreased with increasing relative humidity (RH), the best sensing behavior being attained at a film thickness of 10 mm.
The addition of p-styrenesulfonate sodium (PSSD), sodium chloride or m-benzenedisulfonate disodium (MBSD) to the PVA film
was effective for improving the humidity sensitivity. The PSSD-added PVA film (1/15 in molar ratio) gave the best humidity
sensing performance among the films tested. With this film, the impedance measured at 1 kHz and 25C varied by more than four
orders of magnitude in the range of 1595% RH. A post-argon plasma treatment introduced to cross-link the PVA film was found
to improve not only the stability of the film at high humidity, but also the response rate and hysteresis problem without
deteriorating its sensitivity. 1998 Elsevier Science S.A. All rights reserved.
Keywords: Humidity sensors; Polyvinyl alcohol; Plasma treatment

1. Introduction
Various resistive-type humidity sensors using a
polyelectrolyte polymer have been developed so far.
Polyelectrolyte materials are, however, generally soluble
in water and therefore humidity sensors made from
them have a poor durability, particularly against water
or dew drops. When the polyelectrolyte is chemically
bonded on a hydrophobic film, the graft polymer film
will retain its humidity-sensing characteristic while being insoluble in water.
Sakai has proposed a series of graft copolymers
for humidity sensors, such as graft copolymerization
of polystyrenesulfonate [1] or quarterized poly(vinylpyridine) [2,3] onto polytetrafluoroethylene
(PTFE) and the grafting of 2-acrylamido-2-methylpropane sulfonate (AMPS) or 2-hydroxy-3-methacryloxypropyl trimethylammonium chloride (HMPTAC)
on microporous PE by g-ray post-polymerization
method [4,5], UV or catalytic initiation [6]. The disadvantage of the grafted film is that it takes a certain
amount of time for water vapor to penetrate into or out
of the grafted layer and, as a result, the response time
for the detection of humidity change is large.
* Corresponding author. Tel.: +886 2 5925252 (ext. 3414); fax:
+886 2 5936897; e-mail: mryang@mse.ttit.edu.tw
0925-4005/98/$19.00 1998 Elsevier Science S.A. All rights reserved.
PII S0925-4005(98)00134-8

Another method to solve the problem is to cross-link

the polymer film sensors. Both the poly(dimethyldiallylammonium chloride) film cross-linked by g-irradiation
on a four-electrode conductivity device [7] and the
poly(chloromethyl styrene) simultaneously cross-linked
and quaternized by the reaction with N,N,N%,N%-tetramethyl-1,6-hexanediamine on an alumina substrate
[8] exhibited excellent properties as humidity sensors.
Polyvinyl alcohol (PVA) is widely used in the fields
of papercoating, warpsizing, adhesives and biomaterials
recently [9]. In this study, PVA was adopted as a
humidity-sensing material, which has high affinity to
water owing to its many hydrophilic functional groups
[10]. It absorbs and desorbs moisture in the atmospheric air, changing the water content in the film [9]
and its polymeric network structure is similar to the
micropores in metal oxides. However, the intrinsic
impedance of PVA is so high [9] for the application of
sensor. In order to decrease the impedance of the film
at low relative humidity (RH) and thus to increase its
humidity sensitivity, an electrolyte, i.e. p-styrenesulfonate sodium (PSSD), sodium chloride (NaCl) or mbenzenedisulfonate disodium (MBSD), was added to
the film. It is known that polymer chains are crosslinked by exposure to a plasma [11]. Hence, a postplasma treatment was also attempted to improve the
stability of PVA-based films.

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2. Experimental

2.2. Plasma treatment

2.1. Sensor fabrication

The plasma treatment of the films was carried out

under 0.1 torr pressure for 20 min in a plasma deposition system (SAMCO, PD2S) at 100 watt power [14].
Plasma was generated with argon or hexa-methyldisilazane (HMDSZ), which was degassed by a freeze-andthaw cycle before use.

PVA was mixed with re-distilled water to 1:10 in

mass ratio and maintained for 24 h at room temperature to swell. The mixture was then warmed up and
kept at 343 K in a thermostat bath for 12 h to dissolve
PVA completely before the solution was allowed to
cool down [12]. An electrolyte, i.e. PSSD (Tokyo Kasei
Company), NaCl (Fentons Chemical Company) or
MBSD (Tokyo Kasei), was added to the solution at
various molar ratios. Vigorous stirring was necessary
for the salt to dissolve completely and mix homogeneously with PVA. The respective ions in this state are
reported to exist as molecular complexes [13]. The
solution was cast on an alumina substrate (1 1 cm)
with a pair of comb-shaped electrodes and dried in
vacuum for 12 h at room temperature. Each electrode
comb had seven teeth, 0.3 mm wide and 7.5 mm long,
arranged parallel at an interval of 1 mm. The distance
between the interdigited electrodes was 0.2 mm. The
electrodes (AgPd) were screen-printed and connected
to lead wires with silver paste.

2.3. Characterization of humidity sensor

The sensor device was fixed in a vessel in which RH
and temperature was controlled. The impedance of
each polymer film was measured with a LCZ meter
(Hewlett Packard, 7274A) at an applied voltage of 1
volt and a frequency of 1 kHz. The water content of the
film at a given value of RH was measured gravimetrically as follow:
Water content (%)=

Wx W0
100%
W0

Wx and W0 are the mass of the film at given RH and at

water-free state, respectively. W0 was obtained by placing the film in a vacuum chamber at 40C for 2 days.

Fig. 1. The effects of electrolyte addition to PVA film (molar ratio 1:15) on water-absorptive properties at 25C.

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Fig. 2. Humidity sensing properties of electrolyte-added PVA films at 25C (molar ratio 1:15).

Fig. 3. Response transients for electrolyte-added PVA films at 25C (molar ratio 1:15).

3. Results and discussion

3.1. Film thickness effect

The selection of a proper PVA film thickness is of
great importance for a humidity sensor, because it
affects the diffusion of water molecules inside the film
and the absorption capacity of the PVA film. The

impedance versus RH correlations were measured for

three PVA films with different thicknesses (2.5, 10 and
30 mm). As RH increased, more water was absorbed by
the films causing the impedances to decrease. However,
the behavior was somewhat different depending on
thickness. The impedances tended to decrease with a
decrease in thickness over the measured RH range from
15 to 95%. The thinnest film (2.5 mm) exhibited the

M.-R. Yang, K.-S. Chen / Sensors and Actuators B 49 (1998) 240247

Fig. 4. Hysteresis curves for electrolyte-added PVA films at 25C (molar ratio 1:15).

Fig. 5. Activation energy for conduction as a function of RH.

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M.-R. Yang, K.-S. Chen / Sensors and Actuators B 49 (1998) 240247

Fig. 6. Stability test for PSSD-added PVA film (molar ratio 1:15) after the post argon plasma treatment (solid lines for the as-prepared and dotted
lines for the argon-plasma treated).

lowest impedance, while the thickest (30 mm) exhibited

the highest. The dependence of impedance on RH
(humidity sensitivity), on the other hand, was the steepest with the film of an intermediate thickness (10 mm).
These results suggest that the change of film thickness is
accompanied by changes in film microstructure or water-absorptive property. On the basis of these results,
the film thickness was set to be 10 mm in the following
studies.

3.2. Electrolyte effect

Beside the hydrophilicity of PVA, the water absorption capacity of the PVA film will also depend on the
electrical field of coexistent ions if an electrolyte is
added to the film. In fact the addition of the electrolytes
to the PVA film (1:15 in molar ratio) increased the
water vapor absorption, as shown in Fig. 1. MBSD
provides twice as many sodium ions as PSSD can per
molecule. That is the reason why the MBSD-added
PVA film absorbs more water than the PSSD-added
PVA film at each RH. The coexistence of small chloride
ions may be the reason why the addition of NaCl led to
the greatest water content at each RH. In each case, the
water content increased sharply in the RH range above
80%.

The effects of the addition of PSSD, NaCl and

MBSD to the PVA film on the humidity-sensing characteristics are shown in Fig. 2. The impedance of the
pure PVA film decreased with increasing RH only in
the high RH range above about 50%. For the electrolyte-added films, however, the impedances tended to
begin to decrease at lower RH values, giving rise to
larger changes in magnitude. Obviously the sensitivity
of PVA film was much improved with the addition of
these electrolytes. Especially, PSSD was the most attractive additive which improved RH sensitivity in the
low RH range down to 10%. The impedance versus RH
correlations are seen to be considerably different from
the water content versus RH correlations (Fig. 1). This
seems to imply that, in the electrolyte-added films, the
protonic conduction (Grotthus conduction) is less important than the other ionic conductions. Of the ions
dissociated from PSSD and MBSD, Na + is far more
mobile than the counter-ions, so that the conduction by
Na + ions is assumed to be predominant in the resultant films. The absorption of water vapor results in
swelling of the film and greater mobility of Na + ions,
making the impedance of the film decreasing as RH
increases. An increase in the number of dissociated
Na + ions will also contribute to the increases of electrical conductance with increasing RH. Among the three

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245

Fig. 7. Response transients for PSSD-added PVA film (molar ratio 1:15) after the post argon plasma treatment.

electrolytes, NaCl was the most effective for increasing

the amount of water absorption, as previously described, whereas MBSD was the most effective for
decreasing the impedance of PVA film. It is concluded
that the humidity sensing properties can be remarkably
improved by the addition of the electrolytes, though the
resulting sensing behavior is not so simple.
The content of the electrolytes was varied to be to be
1:50, 1:15 and 1:5 in molar ratio to PVA. For each
electrolyte, its increase tended to increase the RH sensitivity more or less. From the stability point of view,
however, too much an increase in electrolyte content
seemed to be unfavorable. The electrolyte content was
therefore fixed to 1:15 to PVA in the present study.

3.3. Rates and hysteresis of response

The response transients of the electrolyte-added PVA
(1:15 in molar ratio) on an abrupt change in humidity
between 40 and 80% RH are shown in Fig. 3. The
values of ordinate axis have been converted from
impedance to RH according to Fig. 2 for the convenience of comparison. The quickest response was observed with the PSSD-added film, with which the 90%
response time was about 3 or 2 min for increasing or
decreasing RH, respectively. The other films, particularly the NaCl-added one, showed the most sluggish
response and recovery. These films having slower response showed larger hysteresis, as shown in Fig. 4.
From the fastest response, the least conspicuous hysteresis and the steep dependence of impedance on RH
in the wide RH range (10 95%), the PSSD-added PVA
film (1:15) was judged to deserve further investigations.
From the Arrhenius plots of the impedances at various
temperatures, the activation energy of conduction was
determined for this film as a function of RH. As shown

in Fig. 5, the activation energy decreased monotonously

with increasing RH, in contrast to the case of the
microporous film of polyethylene-graft-poly (HMPTAC) which reportedly shows a maximum in activation
energy around 40% RH [6]. This behavior seems to
reflect that the conductivity of the PSSD-added PVA
film is contributed mainly by Na + ions, not by
protons.

3.4. Effects of plasma post-treatments

The electrolyte-added PVA films as prepared were
found to lack the stability of impedance with an elapse
of time, as exemplified for the PSSD-added film shown
in Fig. 6. The impedance of the as-prepared film
showed significant drifts during 2060 min after exposure to each RH. It was found that an argon plasma
treatment was fairly effective for increasing the stability, as shown in Fig. 6. The cross-linking of PVA
molecules in the film by the argon plasma seems to be
responsible for the increased stability. At the same time,
the argon plasma treatment was effective for improving
the rates of response, as shown in Fig. 7. The argon
plasma-treated film took about 1.5 min to respond to
an abrupt change in RH upward or downward, about 1
s of the time needed by the untreated film for the
corresponding change. It was also somewhat effective
for decreasing hysteresis as shown in Fig. 8. Probably
the treatment introduces a porous hydrophilic layer on
the surface of the film. In contrast, a plasma treatment
in HMDSZ vapor deteriorated sensing properties with
regards to response rate and hysteresis, as shown in
Figs. 7 and 8. In this case, silicone-containing deposits
appear to introduce hydrophobic sites on the film [13]
and to impede the diffusion of water vapor inside and
outside.

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Fig. 8. Hysteresis curves for PSSD-added PVA film (molar ratio 1:15) after the post argon plasma treatment.

4. Conclusions
A PVA-based film mixed with PSSD showed rather
good humidity sensing properties, i.e. steep dependence
of impedance on RH, wide humidity range covered,
quick response and small hysteresis. A plasma posttreatment in argon improved the stability of the film
during storage in dry atmosphere.

Acknowledgements
The authors are indebted to Mr. Hsien-Lung Pan for
the experimental work. The authors are also grateful
for the financial support provided by Tatung Institute
of Technology, Taipei, Taiwan, under the grant B841702-01.

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Biographies
M.R. Yang studied material science at the National
Taiwan University and received his M.S. degree from
the Department of Materials Science and Engineering
in June 1989. Since 1991 he has been employed at the
Tatung Institute of Technology. His research interests
are centered on the sensor device development and
plasma technology.
Ko-Shao Chen was born in Pingtung, Taiwan in
April 1951. He received B.Sc. Chemical Engineering
from Chung Yuan Christian University Taiwan 1973,

247

M.Sc. in Applied Chemistry 1979 and Dr. Eng. in

Electronic Materials Science from Shizuoka University
(Japan) 1983. After he finished his Ph.D. degree, he
joined the Department of Materials Engineering,
Tatung Institute of Technology, Taipei, Taiwan as an
Associate professor in August 1983. Since 1987 he has
been a professor in Tatung Institute of Technology. He
was visiting scholar at the Research Center for Biomedical Engineering, Kyoto University (Japan) during the
period September 1990 to August 1991. His fields of
interest include surface modification by plasma polymerization and surface graft copolymerization and also
research in the field of humidity and biosensors.