Sensors and Actuators B 120 (2007) 529–537

Characteristics and performance of ionic polymer–metal

composite actuators based on Nafion/layered silicate
and Nafion/silica nanocomposites
Vinh Khanh Nguyen a , Jang Woo Lee b , Youngtai Yoo a,b,∗
aArtificial Muscle Research Center, 1 Hwayang-dong, Gwangjin-gu, Seoul 143-701, Republic of Korea
b Department of Materials Chemistry and Engineering, Konkuk University, 1 Hwayang-dong, Gwangjin-gu, Seoul 143-701, Republic of Korea
Received 20 December 2005; received in revised form 8 March 2006; accepted 9 March 2006
Available online 27 April 2006

Abstract
Incorporation of a small amount (3–10 wt.%) of nanoparticulates such as layered silicate (montmorillonite) or fumed silica, forming a nanocom-
posite, may greatly alter the mechanical and electrical properties of the Nafion matrix. These nanocomposites were used as polyelectrolytes for
preparation of ionic polymer–metal composites (IPMCs) employing an electroless plating method. In the case of Nafion/silica nanocomposite-based
IPMCs, additional metal cations were incorporated via a silylation reaction of silica using an organosilane. Experimental results showed that the
water loss of the nanocomposite-based IPMCs was significantly reduced due to the barrier property of layered silicate and the hygroscopic nature of
fumed silica. In addition, finer and denser Pt grains were formed on the surface of the nanofiller-containing IPMCs as observed by SEM, resulting
in a higher current density when subjected to an electric field. As a consequence of these factors, compared to a pure Nafion-based IPMC, these
nanocomposite-based IPMCs exhibited larger blocking forces due to the increased water and cation content and better surface coverage of the Pt
electrode. IPMC containing 10 wt.% modified silica displayed nearly three times the blocking force with two times the displacement and a more
rapid response under an applied electric voltage than that of a Nafion-based IPMC.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Ionic polymer–metal composite; Actuators; Nanocomposites

1. Introduction
Ionic polymer–metal composites (IPMC) exhibiting large
bending deformations under a low electric field have recently
attracted a great deal of interest in the fields of dynamic sen-
sors, robotic actuators and artificial muscles due to advantages
including a large displacement, a low driving voltage, and their
biocompatibility, flexibility, and lighter weight. A typical IPMC
is composed of a neutralized ionic polymer membrane, Pt-
electrode layers, and an inner solution (usually water), which
serves as a dissociation medium for metal cations. When sub-
jected to an electric field, metal cations in the polymer membrane
move towards the negative electrode, carrying with them bound
water molecules. This ion-water flux causes a volume differ-
ence between two sides of the IPMC strip, producing a bending
∗ Corresponding author.
E-mail address: ytyoo@konkuk.ac.kr (Y. Yoo).
motion of the composite film towards the anode [1,2]. Therefore,
the capability and capacity of the migration of hydrated metal
cations are important aspects of the IPMC performance.
Nafion, a perflourinated polymer containing hydrogen (or
metal) sulfonate functional groups, is commonly used as a poly-
mer matrix in IPMC applications. Conventional Nafion-based
IPMCs have the major drawbacks of a short operation time and
a low generative blocking force. The short service life of IPMCs
in dry operations is due to the early loss of the inner solution
through natural evaporation, leakage resulting from the surface
expansion, and electrolysis at the operating voltage. Various
attempts have been made to improve the performance of IPMCs
in terms of durability as well as blocking force [3–9].
As documented in the relevant literature, two major
approaches have been employed that increase the operation
period of Nafion-based IPMCs. In the first approach, a more
durable inner solution was investigated for a replacement of
the aforementioned water. Bennett and Leo examined the use
of 1-ethyl-3-methylimidazolium trifloromethanesulfonate ionic

0925-4005/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.03.015
530 V.K. Nguyen et al. / Sensors and Actuators B 120 (2007) 529–537

liquid as an inner solvent for Nafion-based IPMCs [3]. As

reported, the advantages of ionic liquids, compared to water,
have been identified as (i) superior stability and (ii) no risk of
electrolytic decomposition. However, these benefits come with
a loss of response speed, making the response speed much lower
than that of a conventional IPMC containing water. In another
study, Nasser investigated the use of ethylene glycol or glyc-
erol, having high electrolytic stability, as an inner solvent for
IPMCs [4,5]. They found that the rate of response of IPMCs is Fig. 1. Chemical formula of the organic modifier of Cloisite 30B.
low compared to water-containing IPMCs, due to the large size
and high viscosity of these solvents. In a second approach, an
2. Experimental
IPMC is given a protective surface coating in order to prevent
the loss of water. Cohen and Leary reported that an effective
2.1. Materials
barrier coating extended the operation period from a few min-
utes to many months [6], but they also found that the presence
A Nafion solution (DuPont DE-2021, 20 wt.% in a mixture
of the additional barrier layer on IPMCs could negatively affect
of aliphatic alcohol and water), with a total acid capacity of
the deformation because of the increased stiffness. Moreover,
0.95 meq/g (0.95 mmol H+ /1 g polymer), was purchased from
there is always a problem concerning the delamination of the
DuPont. The montmorillonite used in this study is a Cloisite
protective polymer layer.
product (Cloisite Na+ and Cloisite 30B) by Southern Clay Prod-
Shahinpoor and Kim demonstrated that the blocking force of
ucts. Cloisite Na+ is a natural MMT with a cation exchange
IPMCs was significantly enhanced by using a dispersing agent
capacity of 92.6 meq/100 g clay, while Cloisite 30B is a natural
in the reduction process, which enabled the formation of fine
MMT fully modified with an organic surfactant containing two
Pt polycrystals on the surface and increased the depth of Pt
hydroxyl groups, methyl tallow bis-2-hydroxyethyl quaternary
penetration [7]. Another method is to increase the thickness
ammonium chloride. Modification of the MMT is essential for
of the IPMC strip. It was reported that an IPMC with a 2 mm
good dispersion of the MMT in the polymer matrix. The chemi-
thickness exhibited a blocking force of 20 gf under an electric
cal formula of the organic modifier in the Cloisite 30B is given in
potential of 6 V [8]. Nam et al. prepared a Nafion/layered sil-
Fig. 1. The fumed silica (average particle size of 140 nm; surface
icate nanocomposite for IPMC applications where the layered
area of 200 m2 /g) was purchased from Sigma–Aldrich.
silicate (montmorillonite, MMT) was organically modified with
a cationic surfactant to lower the surface energy to be favorable
for a good dispersion. The blocking force of the IPMC is reported 2.2. Surface modification of fumed silica
to be larger than that of a conventional IPMC. Unfortunately, no
further detailed explanation was provided [9]. The surface modification of the fumed silica was car-
In this study, Nafion nanocomposites were prepared and used ried out through a silylation reaction with an organosi-
as starting materials for IPMCs. The incorporation of a nano- lane. Fumed silica was dispersed in a mixture of (3-
scale filler, typically ∼5 wt.%, into the polymer matrix results in mercaptopropyl)trimethoxysilane and toluene. The reaction
improved physical properties without sacrificing other important mixture was then heated and refluxed for 6 h at 115 ◦ C, result-
properties of the polymer [10]. The most commonly used filler ing in thiol groups grafted onto the surface of the silica. The
in the preparation of nanocomposites is MMT. A typical exam- thiol groups were then oxidized to sulfonic acid in an aqueous
ple of the utilization of MMT is the Nylon-6/layered silicate hydrogen peroxide solution (34.5 wt.%) at 40 ◦ C for 1 h. The
system [11]. Another filler of choice is nano-scale fumed silica. modified silica was then dried in a vacuum oven. Thermogravi-
It was expected that the nano-silica could be easily coupled with metric analysis (TGA 951; TA Instrument) and inductively cou-
an organic silane compound through the silanol groups on the pled plasma-atomic emission spectroscopy (ICP-AES; Spectro,
surface [12]. The advantages of using a Nafion nanocomposite Spectroflame Modula/EOP) were utilized for the determination
may be two-fold: (i) the stiffness of the polymer matrix can be of functionality. Scheme 1 illustrates the surface modification
increased, producing a larger blocking force of the IPMC and process of the fumed silica.
(ii) other important features of IPMC can be altered in a favor-
able manner. An example of this is that a well-dispersed layered 2.3. Preparation of Nafion/MMT and Nafion/silica
silicate can effectively lower the inner solution loss, due to the nanocomposites
barrier effect of the high aspect ratio, a disk-like silicate platelet
[13], allowing for a prolonged operation. Additionally, fumed A calculated amount of MMT (3, 5, and 7 wt.%) or silica (5
silica can be acidified and neutralized to introduce additional and 10 wt.%) was added to the Nafion solution. The mixture was
metal cations to the IPMC, which may exhibit an improved per- then placed in an ultra-sonicator for 2 h followed by mechanical
formance in terms of displacement and blocking force. stirring at 60 ◦ C. Following this, the mixture was poured into
The present paper discusses our recent results concerning a Teflon mold and dried in a vacuum oven at 60 ◦ C for 24 h in
the electrical properties and performance of Nafion/MMT and order to obtain a thin nanocomposite film with a desired thick-
Nafion/silica nanocomposite-based IPMCs. ness. Finally, an annealing step was performed by increasing the
 V.K. Nguyen et al. / Sensors and Actuators B 120 (2007) 529–537 531

Scheme 1. Surface modification process of fumed silica.

temperature to 140 ◦ C for 2 h in order to improve the mechanical
properties of the solvent cast Nafion film and its intactness in
water.
2.4. Preparation of IPMC
IPMC was prepared from a nanocomposite film using a well-
known electroless plating method [14]. The process consisted
of two reduction steps. As is typical in this process, in the first
step the polymer film was allowed to ion-exchange with its
immersion in a Pt salt solution. Following this, a 3 wt.% NaBH4
solution was added to reduce the Pt cations, eight times every
30 min, while in the second step, a weaker reducing agent (5%
H2 NOH·HCl, 20% H2 NNH2 ) was employed to complete the
development of the electrode layer. The temperature was raised
from 40 to 60 ◦ C during the reduction. After the reduction steps,
Li+ -form IPMC was obtained by ion-exchange using a 1N LiOH
solution at room temperature for 24 h. The IPMC film was then
fully dried under vacuum, and allowed to uptake the inner sol-
vent (water) by immersion in deionized water.
2.5. Characterization
Morphology of Nafion nanocomposites was studied using X-
ray diffraction (XRD; Rigaku Denki Co., D/Max-2200). Scans
were performed under 40 kV and 30 mA of Cu K␣ radiation with
a characteristic wavelength of 0.154 nm, in a 2θ range of 1–10◦
with a scanning rate of 1◦ min−1 and a step of 0.025◦ . SEM
micrographs were obtained using an SEM instrument (JEOL,
JSM-6380) to examine the surface morphology and the deposi-
tion depth of the Pt-electrode layer. Cyclic voltammetry and
potentiostatic analysis experiments were used for an evalua-
tion of the electrical characteristics of the IPMC samples. CV
curves were obtained with a potentiostat–galvanostat (Wonat-
ech, WMPG 1000) in a water environment after 30 cycles of a
triangle voltage input of ±2 V with a step of 100 mV/s. Poten-
tiostatic analysis was carried out with a step voltage of ±2 V
and a frequency of 0.1 Hz. The blocking force of the IPMC was
measured with a load cell (Dacell, CB1-G150) and the tip dis-
placement was measured by a custom-made Pt clip with a laser
sensor equipped with a DAQ system. A Li+ -form IPMC sam-
ple was cut to specimens of 5 mm × 25 mm size. A sample was
supported vertically in air and fixed to 5 mm of length on both
sides, thus the actual effective length was 20 mm.
2.6. Sample identification
A number of IPMCs prepared from Nafion and its composite
films were abbreviated to sample codes for convenience. Table 1
gives detailed descriptions of each code and abbreviation.
3. Results and discussion
3.1. Dispersion of filler in the Nafion matrix
The XRD patterns of Nafion and nanocomposites prepared
in this study are shown in Fig. 2. The basal lattice spacing
(d0 0 1 spacing) of the MMT is calculated using Bragg’s equation

Table 1
IPMC sample composition and characteristics
Samples Composition (wt.%) Code Thickness (mm)

Recasted Nafion – Nafion 0.32

Nafion/MMT nanocomposites Nafion/Cloisite Na = 97/3 Naf/MMT-3 0.29
Nafion/Cloisite Na = 95/5 Naf/MMT-5 0.30
Nafion/Cloisite Na = 93/7 Naf/MMT-7 0.28
Nafion/Cloisite 30B = 97/3 Naf/oMMT-3 0.30
Nafion/silica nanocomposites Nafion/unmodified silica = 95/5 Naf/uSil-5 0.31
Nafion/modified silica = 95/5 Naf/mSil-5 0.29
Nafion/modified silica = 90/10 Naf/mSil-10 0.28
532 V.K. Nguyen et al. / Sensors and Actuators B 120 (2007) 529–537
Fig. 2. XRD patterns of Nafion and nanocomposites prepared in this study: (a) () Naf/oMMT-3, (䊉) Naf/MMT-3, () Naf/MMT-5, and () Naf/MMT-7; (b) ()
Nafion, (䊉) Naf/uSil-5, and () Naf/MMT-5.
(2d sin θ = λ). The Cloisite Na+ and Cloisite 30B have d0 0 1
spacing of 1.13 and 1.82 nm at 2θ value of 7.84◦ and 4.84◦ ,
respectively. It can be observed from Fig. 2(a) that the XRD
patterns of nanocomposites containing the Cloisite Na+ have a
shifted intense peak to lower 2θ (ca. 6◦ ), which corresponds to
d0 0 1 spacing of 1.47 nm. The increase in d0 0 1 spacing usually
implies that a significant number of polymer chains have entered
the gallery of the MMT, resulting in the intercalation of pristine
MMT by the Nafion polymer chains. This may be attributable
to the limited compatibility between pristine MMT and Nafion.
On the other hand, a nanocomposite containing organically
modified MMT exhibited a featureless XRD pattern, indicat-
ing an exfoliated morphology. Generally, exfoliation of MMT is
observed when there is a strong attractive interaction between the
polymer matrix and the MMT [15]. In the case of the Naf/oMMT-
3 sample, hydroxyl groups of the organo-clay Cloisite 30B may
have strongly interacted with the sulfonic acid groups of the
polymer via hydrogen bonding, which is believed to be the pro-
moter of the exfoliation of MMT in a Nafion matrix.
Fig. 2(b) shows XRD patterns of Nafion, Naf/uSil-5 and
Naf/MMT-5. It is known that the ionic groups located on the
side chains of Nafion can form an ionic cluster network [16].
The intense peak appearing in the XRD pattern of Nafion at the
2θ angle of 2.7◦ indicates that the size of this ionic cluster is
approximately 3.27 nm. It appears that in Naf/uSil-5, the ionic
cluster network of Nafion remains intact, as the XRD pattern of
this nanocomposite has an intense peak at the same 2θ angle. In
the case of the Naf/MMT-5 sample, however, the corresponding
peak is shifted to a higher 2θ angle (3.58◦ ), implying a decrease
in the size of the ionic cluster (2.47 nm). This would have a
direct effect on the performance of the nanocomposite-based
IPMC actuator.
It was evidenced from the XRD experiments that both
Naf/MMT nanocomposites were successfully prepared. Gener-
ally, exfoliation is preferred to intercalation if the goal is simply
to improve the mechanical properties of the polymer mem-
brane. However, in an IPMC, exfoliated MMT platelets may
strongly hinder the migration of metal cations, which is crucial
for the bending mechanism. The restricted mobility of the metal
cations results in a much slower response, as will be discussed
in a later section. Conversely, in an intercalated nanocomposite-
based IPMC, the mobility of the metal cations is not greatly
reduced.
3.2. Introduction of metal cations
The bending mechanism of IPMCs under an applied voltage
is based on the movement of hydrated metal cations towards a
cathode. Therefore, an important factor in determining the per-
formance of an IPMC is the proportion of the metal cations
in the membrane. It is known that Nafion contains 0.95 mmol
H+ per 1 g polymer. Incorporation of modified silica into the
Nafion matrix increased the total metal cation content. TGA
and ICP-AES analyses were employed to access the content of
the sulfonic acid functional groups attached to the surface of
the silica filler by the modification process. In the TGA mea-
surement, a weight loss difference of approximately 8 wt.% was
recorded between the modified and unmodified silica samples
in a temperature range of 150–350 ◦ C, where the degradation of
sulphonic acid (Mw = 82) occurred. From these results, the acid
capacity of the modified silica can be estimated as 0.975 mmol/g
silica. The ICP-AES analysis, in which the H+ of sulfonic acid
was exchanged to Na+ , showed a relatively consistent result of
0.857 mmol/g. Considering the high density of inorganic fillers,
it was estimated that the metal cation content of Naf/mSil-5 and
Naf/mSil-10 increased by approximately 5 and 10%, respec-
tively, compared to the Nafion.
3.3. Performance of IPMCs
The performance of conventional IPMCs is directly related
to the metal cation migration and electro-osmosis of the inner
solution, the characteristics of the polymer film, and the elec-
trodes. Fig. 3 shows cross-sectional views of IPMCs prepared
from Nafion, Naf/MMT-5 and Naf/uSil-5 nanocomposites. The
thickness of the Pt-electrode layer was measured to be approx-
imately 7–8 ␮m. The surface SEM micrographs are also given
in Fig. 4, where a uniform deposition of Pt electrode can be
seen for all samples. It is important to note that the size of the
Pt grains is reduced in Naf/MMT- and Naf/Sil-based IPMCs,
 V.K. Nguyen et al. / Sensors and Actuators B 120 (2007) 529–537 533

Fig. 3. SEM images (cross-section) of (a) Nafion-IPMC, (b) Naf/MMT-5-IPMC, and (c) Naf/uSil-5-IPMC.

Fig. 4. SEM images (surface) of (a) Nafion-IPMC, (b) Naf/MMT-5-IPMC, and (c) Naf/uSil-5-IPMC.

possibly having to do with the nucleating effect of the filler due
to its favorable surface chemical structure and energy during
the reduction process. The smaller and denser aggregation of
Pt grains exhibit the so-called “granular damming effect”, mak-
ing it more difficult for water molecules to pass through, thus
providing a good protection against water leakage [7].
The higher performance of the Pt electrodes of Nafion/MMT-
and Nafion/Sil-based IPMCs was confirmed from the I–V curves
obtained by two-probe linear sweep voltammetry, measured on
the surface of the Pt-electrode layer of the IPMCs, as shown in
Fig. 5. It was observed that the I–V curves of Nafion/MMT- and
Nafion/Sil-based IPMCs have almost the same slope, which is
significantly higher than that of Nafion-IPMC. In Fig. 4(b and c),
though the morphologies of the Pt electrodes are different, the
dispersion of the Pt particles appears to be alike, which results
in nearly identical I–V curves. Considering that the thickness
of the Pt-electrode layer is almost identical for all these sam-
ples (∼7–8 ␮m), the higher current values for Naf/MMT- and
Naf/Sil-based IPMCs than that of Nafion-IPMC partially reflect
their denser Pt-electrode structures.
The water uptake and loss of various IPMCs are given in
Table 2. The water uptake was measured after soaking in water
at 80 ◦ C for 1 h. The water loss was determined by weighing the
IPMCs after applying an electric potential of 3 V dc for 5 min. A
rapid water loss from the IPMCs is the main reason for its short
life-time. There are three important mechanisms for water loss:
(i) water leakage from the surface electrode, (ii) natural evapora-
tion, and (iii) water loss due to electrolysis. It was observed that
Nafion-IPMC lost nearly 70 wt.% of its water after only 5 min.
Naf/MMT- and Naf/Sil-based IPMCs lost 25 and 45 wt.% during

Table 2
Summary of water uptake and loss of IPMC samples
Sample code Water uptake (wt.%) Water loss (wt.%)

Nafion 10.6 67.1

Naf/MMT-3 13.5 29.2
Naf/MMT-5 15.6 25.0
Naf/MMT-7 17.3 23.1
Naf/oMMT-3 14.0 21.9
Naf/uSil-5 16.5 48.0
Naf/mSil-5 16.0 41.2
Fig. 5. I–V curves measured by a two-probe method for () Nafion-IPMC, (䊉) Naf/mSil-10 16.0 40.0
Naf/MMT-5-IPMC, and () Naf/uSil-5-IPMC.
534 V.K. Nguyen et al. / Sensors and Actuators B 120 (2007) 529–537

Fig. 6. Cyclic I–V curves of (a) Naf/MMT-IPMCs and (b) Naf/Sil-IPMCs.

that period of time, respectively. This significant decrease in
water loss of Naf/MMT-IPMCs may be explained by the barrier
effect of the well-dispersed layered silicate platelets (tortuous
path effect [13]), which efficiently prevents from a leakage of
water. In addition, the better packing of fine Pt grains on the sur-
face of the electrode of IPMCs based on Nafion nanocomposites
(shown in Fig. 4) provides better protection for IPMCs in terms
of water leakage to some extent as well. Moreover, IPMCs con-
taining fillers showed higher incidences of water uptake than
Nafion-IPMCs. In pristine MMT, sodium cations may adsorb
and trap extra water molecules into the galleries between MMT
layers, resulting in a higher water uptake, while the hygroscopic
nature of silica seems to be responsible for the increase of water
uptake in the Nafion/Sil nanocomposite.
The electrical properties of IPMCs were investigated employ-
ing cyclic voltammetry and potentiostatic analysis. Fig. 6 shows
current–voltage hysteresis curves of IPMCs made from (a)
Naf/MMT and (b) Naf/Sil, recorded under ±2 V triangle voltage
input with a scan rate of 100 mV/s. From Fig. 6, the following
observations are noteworthy: (i) the shape of the I–V hysteresis
curves implies simply a motion of metal cations induced by the
applied voltage with decomposition behavior due to the elec-
trolysis of water was detected at approximately ±1.5 V, which
is consistent with other results [7,17], and (ii) the current den-
sity of an IPMC increases with the filler content. It should be
kept in mind that MMT contains free Na+ cations in the gal-
leries between clay platelets, which contribute to the increase
of current density observed in Naf/MMT-IPMCs. On the other
hand, additional metal cations, introduced to modified silica, are
believed to be responsible for the large increase of current den-
sity in Naf/mSil-IPMCs. This conclusion is supported by the
significant difference of cyclic voltammetric behavior between
Naf/mSil-5-IPMC and Naf/uSil-5-IPMC shown in Fig. 6(b). The
higher current density observed for IPMCs based on Naf/MMT
and Naf/Sil nanocomposites implies the higher capacitance of
a double layer formed along the interface of the surface elec-
trode/electrolyte, meaning a higher energy storage ability of
IPMCs that usually leads to a larger deformation under an elec-
tric field.
In Fig. 7, the results of the potentiostatic analysis are pre-
sented for (a) Naf/MMT-IPMCs and (b) Naf/Sil-IPMCs. The
potential was initially kept at 2 V for 10 s, during which the
current decreased exponentially. The following important obser-
vations are extracted from Fig. 7. First, the current density is
significantly higher for Naf/MMT- and Naf/Sil-based IPMCs,
which may be attributable to (i) the extra metal cations in the
nanocomposites and (ii) the presence of a larger double-layer
charging area, which is confirmed after interpreting the curve
for Naf/uSil-5-IPMC, as the current is proportional to the area.
Secondly, the charge transfer under time t, reflected by the area

Fig. 7. Potentiostatic analysis for (a) Naf/MMT-IPMCs and (b) Naf/Sil-IPMCs.

 V.K. Nguyen et al. / Sensors and Actuators B 120 (2007) 529–537 535

Fig. 8. Blocking force of (a) Naf/MMT-IPMCs and (b) Naf/Sil-IPMCs.

under the curves, is also much larger for nanocomposite-based
IPMCs, especially in the case of Nafion/mSil-10-IPMC. Here,
the integrated area is more than three times that of Nafion-
IPMC (0.029 W/cm2 versus 0.090 W/cm2 ). This indicates that
Naf/mSil-10-IPMC consumes three times more charges, which
most likely displays much larger blocking force and displace-
ment under an electric field, as the charge consumption in an
IPMC is partially consumed in performing mechanical work.
The performance of IPMC was evaluated by measuring the
blocking force and the tip displacement under an electric poten-
tial of 3 V. The results are presented in Figs. 8–10. All of the
samples have a dimension of 5 mm × 20 mm with a thickness in
the region of 300 ␮m. Fig. 8 shows that Nafion-IPMC exhibits a
maximum blocking force of 0.6 gf after 10 s, followed by a fast
relaxation that causes an abrupt decay in the blocking force. The
fast relaxation of Nafion-IPMC is mainly attributed to residual
stress induced by the difference in the stiffness between the poly-
mer matrix and the Pt-electrode layer as well as to the loss of
water [18–20]. In contrast, IPMCs made from nanocomposites
showed a larger blocking force with a limited (Naf/Sil-IPMCs)
or complete (Naf/MMT-IPMCs) lack of relaxation during the
testing period. The effect of the filler on the blocking force can
be discussed as follows: (i) by incorporation of the filler into the
polymer, the water loss of the IPMC was significantly reduced
(due to the barrier effect of the clay platelet discussed earlier),
(ii) extra metal cations introduced with the filler enhanced the
blocking force, as a larger hydraulic force was induced, and
(iii) the incorporation of the filler also increased the stiffness of
the polymer, which may have also contributed to the improve-
ment of the blocking force. The effect of the dispersion of the
MMT can also be evaluated from Fig. 8(a). It is important to
note that although the blocking force increases the response
rate of Naf/MMT-IPMCs decreases with filler content. This is
because a higher MMT concentration in the IPMC in all proba-
bility exhibits a larger barrier effect, resulting in more restriction
of movement of bound metal cations. Moreover, as observed in
Fig. 2(b), the incorporation of MMT resulted in a reduced ion
channel size of Nafion, which was also partially responsible for
the delayed response of Naf/MMT-IPMCs. The IPMC based
on exfoliated Nafion/MMT nanocomposite (Naf/oMMT-3) has

Fig. 9. Displacement of various IPMCs at different times under 3 V dc.

536 V.K. Nguyen et al. / Sensors and Actuators B 120 (2007) 529–537
Fig. 10. Displacement of () Nafion, (䊉) Naf/MMT-3, () Naf/MMT-5, ()
Naf/mSil-5, and () Naf/mSil-10 IPMC samples under 3 V, 1 Hz.
essentially reached the maximum blocking force in roughly
1000 s, which is clear evidence of the strong barrier effect of
the MMT. Ironically, “well-dispersed” MMT-exfoliated disper-
sion appears to have had an adverse effect. Conversely, it was
found that the incorporation of modified silica into the Nafion
matrix greatly increased the blocking force, which appeared to
be a logical consequence of the improved electrical properties
of these Naf/mSil-IPMCs, as shown in Figs. 6 and 7. The block-
ing force of Naf/mSil-10-IPMC was found to be approximately
three times of that of Nafion-IPMC.
The results of the tip displacement measurements are shown
in Figs. 9 and 10. The displacement was recorded by subjecting
the IPMC sample to a 3 V dc (Fig. 9) and 3 V ac with a frequency
of 1 Hz (Fig. 10). It is observed from Fig. 9 that Nafion-IPMC
reached the maximum tip displacement after approximately 20 s,
and then a fast relaxation occurred. In the case of Naf/MMT-5-
IPMC, no relaxation was observed during the experiment, while
Naf/mSil-5-IPMC showed a limited relaxation after approxi-
mately 30 s. The speed of response appeared to be lower for Naf/
MMT-5-IPMC and higher for Naf/mSil-5-IPMC. These obser-
vations are in agreement with the blocking force experiments.
Under an ac voltage, a faster response rate and a larger
displacement were observed for Naf/mSil-IPMCs. In contrast,
Naf/MMT-IPMCs exhibited a slower response and a smaller
displacement under the same experimental conditions. The rea-
sons lying behind these observations are that the silica filler has
no barrier effect due to its low aspect ratio, while more time is
required for Naf/MMT-IPMCs to reach the same displacement.
3.4. Evaluation of thermodynamic efficiency
The total inputted electrical energy of IPMCs is consumed
in the following categories; (i) mechanical bending, (ii) Joule
heating, (iii) electrolysis of water, and (iv) I–V hysteresis due to
the water transport inside the IPMC. According to Shahinpoor
and Kim [7], the thermodynamic efficiency (Eff ) is the ratio
of the power induced by the mechanical work to the inputted
electrical power:
 
Pmech
Eff (%) = × 100 (1)
Pelect
Pmech is calculated from the blocking force Ft , assuming an
uniformly distributed load over the length of IPMC [7].
Pmech = Ft × ν (2)
where ν is the velocity of the IPMC strip under the applied
voltage.
The thermodynamic efficiency for the IPMC sample pre-
pared in this study is briefly estimated by an interpretation of
the experimental results given in Figs. 7–9, as follows. For
Naf/MMT-IPMCs, Pelect is nearly identical (as the charge trans-
fer is nearly identical for all samples, cf. Fig. 9), while the block-
ing force and displacement decrease (Figs. 8 and 9), leading
to an overall decrease in Eff . Conversely, compared to Nafion-
IPMC, Naf/mSil-IPMCs have a higher Eff , as the increase in
Pmech exceeds the increase in Pelect . Naf/mSil-10-IPMC exhibits
nearly three times larger blocking force and two times larger dis-
placement, which gives approximately six times larger Pmech .
As the charge transfer increases three times (Fig. 7), the Eff pro-
duced by this IPMC is approximately two times higher than that
of Nafion-IPMC.
4. Conclusions
IPMCs based on Nafion/MMT and Nafion/silica nanocom-
posites were prepared and examined for their actuation behavior.
Nano-scale fumed silica was sulfonic acid functionalized and
neutralized prior to mixing in a Nafion solution in order to
increase the metal cation content. The blocking force of IPMCs
was improved by incorporating these fillers into the polymer
matrix, due to the additional cations in the MMT or in the mod-
ified silica. The charge transfer of Naf/mSil-10-based IPMCs
measured up to three times that of conventional IPMCs. A higher
water uptake and a slower water loss were observed in both types
of nanocomposite IPMCs. These improvements may be resulted
from a large increase in the blocking force and a displacement
of IPMCs based on the nanocomposites. Naf/mSil-10-IPMC
has three times larger blocking force, with a 200% increase in
deformation. In the case of Naf/MMT nanocomposites, a strong
barrier effect and a slow response were exhibited, especially in
the exfoliation morphology.
Acknowledgements
This work was supported by the Korea Research Foundation
Grant (KRF–2004-005–D00046). The authors would also like
to acknowledge the financial support of Konkuk University.
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Biographies
Vinh Khanh Nguyen received his PhD in chemical engineering (polymers) for
his work on the polypropylene ionomer nanocomposite at Chonbuk National
University. He is curently working as a research fellow at the Artificial Muscle
Research Center of Konkuk University. His research interests include the tailor-
ing and design of polymer nanocomposites, ionomers, electroactive polymers
and MEMS.
Jang Woo Lee graduated with a bachelor’s degree in industrial chemistry from
Konkuk University, in South Korea in 2000. He joined Pharmacia & Upjohn and
worked in sales from 2000 to 2002, and joined Hanmi Fine Chemical (under
Hanmi Phamaceutical Company) as an antibiotic synthesizer from 2002 to 2004.
He entered the graduate school at Konkuk University in the fall of 2004 and is
currently in a master’s course in the Department of Materials Chemistry and
Engineering at Konkuk University. He is involved with the Artificial Muscle
Research Center at the university as an assistant researcher.
Young Tai Yoo graduated from the Virginia Polytechnic Institute and State
University in 1988, and received his PhD in chemical engineering. He joined
Eastman Kodak and worked as a research scientist from 1988 to 1991. Then
he joined the Department of Materials Chemistry and Science at KonKuk Uni-
versity. His research interests include bioactive polymers, drug delivery system,
and actuators.