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Carbon nanotube and polyaniline composite actuators*

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2003 Smart Mater. Struct. 12 626

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INSTITUTE OF PHYSICS PUBLISHING SMART MATERIALS AND STRUCTURES
Smart Mater. Struct. 12 (2003) 626–632 PII: S0964-1726(03)63530-5

Carbon nanotube and polyaniline

composite actuators*
May Tahhan1 , Van-Tan Truong2,3 , Geoffrey M Spinks1 and
Gordon G Wallace1
1
University of Wollongong, Intelligent Polymer Research Institute, Northfields Avenue,
Wollongong, NSW 2522, Australia
2
Defence Science and Technology Organisation, Platforms Sciences Laboratory,
Maritime Platforms Division, PO Box 4331, Melbourne, VIC 3001, Australia

E-mail: tan.truong@dsto.defence.gov.au

Received 3 March 2003, in final form 6 May 2003

Published 25 June 2003
Online at stacks.iop.org/SMS/12/626

Abstract
The actuation of a single-wall carbon nanotube (CNT) mat, an electrically
conducting polyaniline (PAn) film and a composite of these two materials
has been investigated in NaNO3 (1 M), NaCl (1 and 3 M) and HCl (1 M)
solutions. The expansion and contraction patterns of the PAn, CNT and
CNT/PAn samples are similar in these solutions. Fabrication of the
CNT/PAn samples by coating PAn (CNT:PAn = 3:1 by weight)
substantially enhanced the actuation strain (0.2–0.5%) of the CNT/PAn
composite compared to the low actuation strain (0.06%) of the pure CNT
mat. The actuation of PAn and CNT operates via different mechanisms.
Non-Faradaic electrochemical charging of the CNT bundles is the main
factor behind the expansion of CNT, while the expansion/contraction of PAn
is dependent on the redox reactions of the polymer. The displacement
pattern of the composite is dominated by the PAn component. However,
when a load is applied to the sample (up to 1.2 MPa) the CNT/PAn sample
behaves similarly to CNT samples, i.e. the actuation strain is almost
independent of the applied loads in contrast to pure conducting polymers.
This implies that the reinforcing effect of the CNT component is possibly
due to the inherent high Young’s modulus of the CNT bundles (∼640 GPa).

1. Introduction in these materials a high drive voltage is required. In some

Actuators directly convert electrical energy to mechanical
energy with a material response to applied electrical voltage.
Due to these characteristics that are similar to biological
muscles, actuators have been dubbed ‘artificial muscles’.
Applications of actuators have been found in robotics,
optical fibre switches, optical displays, prosthetic devices,
microscopic pumps and anti-vibration systems. Ferroelectric
and electrostrictive materials have been used as actuator
materials owing to their direct energy conversion. Of these
materials, shape memory alloys and electroactive ceramics
have been the most widely used. However, to realize actuations
* Presented at SPIE Smart Materials,Nano-, and Micro-Smart Systems (16–18
December 2002, Melbourne, Australia).
3 Author to whom any correspondence should be addressed.
cases, the applied voltages can reach a few hundred volts.
Electroactive conducting polymer (CP) actuators operat-
ing on electrochemical dopant intercalation were proposed a
decade ago [1, 2]. One of the attractive features of the CP ac-
tuators is a low drive voltage that does not exceed 5 V. Even at
low voltage, in suitable conditions CP actuators can reach an
actuation strain as high as 7% [3] generating stresses that are
comparable to or exceed those of biological muscles. Recently,
carbon nanotubes (CNT) have been demonstrated as an actu-
ator material [4]. CNT actuators have shown actuation strains
in the order of 0.2% with a drive voltage of a few volts [4].
Since the Young’s modulus of an individual CNT bundle has
been found to be approximately 640 GPa [5], a strain of 0.2%
gives an available stress of 1280 MPa from the bundles. Thus,
a CNT/CP composite may result in an actuator where the CP
component will contribute to a high actuation strain and the

0964-1726/03/040626+07$30.00 © 2003 IOP Publishing Ltd Printed in the UK 626

 Carbon nanotube and polyaniline composite actuators

CNT component to a high modulus. Some preliminary results

of CNT and polypyrrole (PPy) hybrid actuators have been re-
ported [6]. However, the PPy component did not exhibit any
effect on the composite and the actuation performance of the
hybrid was similar to that of CNT alone actuators. The effect
of Young’s modulus at the expansion and contraction states
has been experimentally revealed to be an important factor
influencing the actuation behaviour of materials [6, 7]. Re-
cently, several studies have reported chemical interactions oc-
curring between CNT and aniline [8] and CNT and polyaniline
(PAn) [9] leading to various types of new CNT/PAn compos-
ites [10–12].
The aim of this study is to explore the use of the CNT and
electrically conducting PAn composite as an actuator material.
The actuation synergism of PAn and CNT as actuator materials
and the ability of actuation in aqueous salt solutions and acid
solutions will be examined.

2. Materials and experimental details
2.1. Preparation of PAn (acid) film
Camphor sulfonic acid (1 M, Aldrich) was added to an aqueous
solution of distilled aniline (0.1 M, Aldrich). The solution
was placed in an ice bath. The PAn (salt) was obtained by
adding drop wise 41 ml of an aqueous solution of ammonium
potassium persulphate (8.35 g, 0.1 M) and leaving overnight for
the reaction to take place. The product was vacuum filtered and
then dispersed in distilled water. Excess NaOH pellets were
added to the solution to produce PAn (base). The mixture
was filtered and dried in an oven at 60 ◦ C overnight. The PAn
(base) was added to N -methyl pyrrolidine (NMP) to make up
a 4% (w/w) solution. This translated to 400 mg PAn (base) in
10 ml NMP. The mixture was cast on glass slides placed on a
hot plate and left to dry before peeling off.
The resulting film was soaked in HCl (1 M) to convert it
into the PAn (acid) form which was electrically conductive.
This sample is referred as PAn in the following sections.
2.2. Preparation of CNT mat
Single-walled CNT (80–90% purity manufactured by Hipco)
was used as received. CNT (25 mg) and 1 g of Triton X100 1%
(w/w) surfactant solution were added to 50 ml of distilled water.
This dispersion was sonicated for 0.5 h then filtered through a
previously wet PVDF membrane in an ethanol/distilled water
mixture (50:50) and washed with 600 ml distilled water and
600 ml of methanol to remove excess Triton X100.
2.3. Preparation of CNT/PAn composites
The composite was fabricated by first coating the above PAn
(base) (4% NMP solution) onto the CNT mat and dried on
a hot plate to remove NMP. This CNT/PAn (base) was then
soaked in a HCl (1 M) solution overnight to give CNT/PAn
(acid) composites (referred as CNT/PAn composites). The
CNT:PAn weight ratio was 3:1.
The sample size: (a) 6 mm long × 3 mm wide for the
NaNO3 (1 M) solution and (b) 9 mm long × 3 mm wide for
the NaCl (1 and 3 M) and HCl (1 M) solutions.
Figure 1. The uncoated CNT bundles are shown on the left and a
fully dense Pan/CNT composite on the right.
2.4. Conductivity
A four-point probe was used to measure the conductivity of
the sample: a constant current of 1 mA was passed across the
two outer electrodes and the voltage difference was measured
between the two inner electrodes after 10 s. This was repeated
four times for each sample.
2.5. Actuation tests
The actuation of the samples was tested using beam balance
apparatus (as described in [7]) where the sample was immersed
in electrolyte solution at a fixed tensile force and the length
changes measured using a linear variable distance transducer.
The test solutions were NaNO3 (1 M), HCl (1 M) and NaCl (1
and 3 M). The potential window varied between E = −1,
+1 V (versus Ag/AgCl) for PAn and E = −1, +0.7 V
(versus Ag/AgCl) for CNT and CNT/PAn composites with
a scan rate of 50 mV s−1 . The actuation strain, ε, due to
expansion/contraction of the sample is calculated using
ε = (l × 100)/lo (%)
where lo is the original length and l is the movement between
expansion and contraction.
A CNT/PAn sample was used to investigate the effect
of tensile load applied to the sample on the actuation strain.
The load was increased in the tensile mode from 2 to 30 g
(equivalent to stress of 0.08–1.23 MPa).
3. Results
3.1. Characterization of composite samples
The SEM micrograph (figure 1) clearly shows the effect of
dip coating the CNT mat in the PAn solution. The CNT
mat is completely impregnated by the PAn producing a rather
featureless surface morphology. The conductivities of the
various samples are reported in table 1. Curiously, the
conductivity of the CNT sample is only ∼10 S cm−1 which

627
M Tahhan et al

CNT 2 PAn
1

Voltage (V)
Voltage (V)

0
0

-1 -1

-2
-2

4 4

Current (mA)
2 2
Current (mA)

0 0
-2
-2
-4
-4
-6
-8 -6
60
66
Displacement (µm)

64
Displacement (µm) 40

62 20
60 0
58
-20
56
-40
54
-60
0 200 400 600 800 1000 0 100 200 300 400 500
Time (s) Time (s)
Figure 2. The applied voltage, current and displacement of the CNT Figure 3. The applied voltage, current and displacement of the PAn
sample in NaNO3 (1 M) solution. sample in NaNO3 (1 M) solution.

is much lower than the value reported for similar SWNT
samples (>1000 S cm−1 [4]). The low value obtained for
the samples used in the present study may indicate that the
samples retain significant levels of contamination from the
preparation procedure (such as residual Triton X surfactant).
Interestingly, the CNT/PAn composite sample shows a four-
fold higher conductivity compared with either the pure PAn or
CNT samples. It is possible that the immersion of the CNT mat
in the PAn solution assists in the partial removal of impurities of
as-received CNT generated during the manufacturing process
and the added Triton X surfactant used to form the CNT
suspension. The purification of CNT systems using conjugated
polymer solutions has previously been reported by Curran and
co-workers [13].
3.2. Actuation in different electrolytes
The CNT (figure 2) and PAn (figure 3) samples showed a strain
of 0.05 and 0.83% in NaNO3 (1 M) solution, respectively. The
annealed CNT can reach a strain of 0.2% [4]. Spinks et al [6]
have reported strain values ranging from 0.05 to 0.08% for
annealed CNT mats. For the unannealed CNT presented in
this study, the actuation strain of 0.05% is reasonable given
that impurities embedded in the CNT mat could inhibit the
movement of the CNT strands. The actuation strain of 0.83%
in the PAn sample is comparable to the PAn sample in H2 SO4
(0.5 M) solution with a strain of about 1% [14]. The actuation
strain of the CNT/PAn composite was 0.23% (figure 4). The
coating of PAn on the CNT mat increased the actuation strain
of pure CNT from 0.05 to 0.23%.
The expansion/contraction patterns of the PAn and
CNT/PAn samples in HCl and NaCl solutions (figures 5–7)
are similar to those in the NaNO3 solution. The actuation
strains are shown in table 2 for each electrolyte.
3.3. The effect of applied stress on actuation
Figure 8 shows the effect of applied stress on the actuation
behaviour of a CNT/PAn composite sample in the NaNO3
(1 M) solution. The maximum applied stress was 1.23 MPa
and the actuation strain fluctuated between 0.07 and 0.11%
without showing any significant trend with increasing stress.
4. Discussion
A synergetic effect is found in the enhanced conductivity of the
CNT/PAn composite. As described above, the conductivity
of the composite is higher than its individual components
(table 1). As shown in figures 2–4 for the NaNO3 solution, the
higher conductivity leads to higher current (−10 to 14 mA) in
the composite than that in PAn (−2 to 3 mA) and CNT (−5
to 4 mA) in a similar applied voltage. Similar results were

628
 Carbon nanotube and polyaniline composite actuators

2 CNT+PAn CNT
1

1
Voltage (V)

Voltage (V)
0
0

-1 -1

-2 -2
16 4
12
2

Current (mA)
8
Current (mA)

4 0
0 -2
-4
-4
-8
-12 -6
-30
8 Displacement (µm)
Displacement (µm)

4
-35
0

-4 -40

-8

-12 -45
0 50 100 150 200 250 300 0 100 200 300 400 500 600 700
Time (s)
Time (s)
Figure 5. The applied voltage, current and displacement of the CNT
Figure 4. The applied voltage, current and displacement of the sample in NaCl (3 M) solution.
CNT/PAn composite sample in NaNO3 (1 M) solution.

Table 1. The thickness and conductivity of the prepared samples.

Sample Thickness (mm) Conductivity (S cm−1 )
CNT 0.049 11.7
PAn 0.04 10
CNT/PAn 0.169 53
also observed in other test solutions (figures 5–7). Therefore,
it is shown that the electrochemical efficiency is higher in the
composite as compared with pure PAn and CNT due to the
higher conductivity reducing resistive losses.
In comparison to the pure PAn samples, the composite
system shows similar actuation strains (table 2). In some
electrolytes (NaCl solutions) the composite actuation is
actually higher than the pure PAn, which may be due to the
improved conductivity of the composite sample. In other
electrolytes the composite system shows slightly reduced
actuation in comparison to the pure PAn. In these samples, the
reinforcing effect of the nanotubes may restrict the movement
of the polymer matrix.
In all cases tested, the CNT/PAn composite showed
significantly higher actuation strain compared with the pure
CNT. As shown in figures 2–7, the direction of actuation
of the composite systems indicates that the PAn component
dominates in the composites system. This result differs
significantly from that reported earlier for PPy/CNT composite
systems. In the previous study [6], the composite system
showed no effect of the polymer addition with the composite
showing equivalent actuation behaviour to the CNT mat. This
is due to the fact that only a very thin coating of PPy was applied
to the CNT bundles and it was argued that the expansion and
contraction of the PPy layer on the CNTs was insufficient to
induce movement of the nanotubes themselves. In this study, a
much higher proportion of polymer (25 wt%) was incorporated
into the composite such that actuation of the PAn within the
pores of the CNT network was sufficient to induce macroscopic
strain of the nanotube networks. This also reflects the intimate
interactions between CNT and PAn in the composite [8, 9] at
the molecular level.
The actuation of PAn and CNT operates under different
mechanisms. Baughman and co-workers [4] indicated that
non-Faradaic electrochemical charging of the CNT is the main
factor behind the expansion of CNT bundles. The charged
species can be positive or negative depending on the sign
of the applied voltage. Therefore, the CNT mat expands at
the maximum and minimum voltage values and shrinks to
the original length at a voltage close to 0 (figure 2). On the
other hand, the expansion/contraction of CPs is dependent on
the redox reactions of the polymers. At maximum V , the
PAn component is oxidized and the volume simultaneously

629
M Tahhan et al

2
PAn CNT+PAn
1

1
Voltage (V)

Voltage (V)
0

-1 -1

-2
-2
1
8
6

Current (mA)
Current (mA)

4
0
2
0

-2
-1
-4
0
16
Displacement (µm)

Displacement (µm)
-10
12

-20 8

4
-30
0

-40 -4
0 100 200 300 400 500 600 700 0 50 100 150 200 250 300
Time (s) Time (s)
Figure 6. The applied voltage, current and displacement of the PAn Figure 7. The applied voltage, current and displacement of the
sample in NaCl (3 M) solution. CNT/PAn composite sample in NaCl (3 M) solution.

Table 2. Actuation strain in various electrolytes. 0.12

Strain (%) 0.10

Actuation Strain (%)

Sample 1 M NaNO3 1 M HCl 1 M NaCl 3 M NaCl

0.08
CNT 0.05 — — 0.06
PAn 0.83 and 0.79a 0.33 0.10 0.10
0.06
CNT/PAn 0.23 and 0.54a 0.31 0.35 0.42

0.04

increases (due to the incorporation of dopant anions) with the

0.02
CNT component. However, the increase in volume of the
two composite components is not additive. This implies that
the transport of ions to the composite may not be sufficient 0.00
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
to meet the ion requirements of both composite components. Applied Stress (MPa)
At a negative (minimum) V value, the CNT sample expands
at negative voltage, whereas the PAn component is reduced Figure 8. The effect of applied stress on the actuation strain of the
and thus contracts (due to the expulsion of dopant anions). CNT/PAn composite sample in NaNO3 (1 M) solution.
Overall, the composite sample is seen to contract at negative
voltage, due to the domination of the PAn component. Close The combination of high modulus nanotubes with the
examination of the actuation strain presented in figure 4 active PAn matrix should lead to improved stress generation of
illustrates the opposing effects of the two components in the composite systems. It has previously been shown [7] that
the composite system. At negative V a kink is observed the actuation of CPs is greatly reduced at high applied stresses
in the displacement response illustrating the simultaneous due to the effects of changes in the polymer Young’s modulus
contraction of the PAn component with the expansion of the during the redox cycling. The effect of applied stress on the
CNT component. actuation strain can be expressed using the following equation

630

(see the appendix, equation (A.7)):
l f ≈ lo + ( f lo / A)(1/E d − 1/E o ).
Large changes in elastic modulus (E o and E d ) at the contraction
and expansion states have been reported for CPs [7] leading to
much reduced strains at high loads (i.e. E o < E d ). In contrast,
the change in the Young’s modulus for CNT is negligible over
the potential range used during the actuation tests, so that
the CNT actuation remains largely unchanged with increasing
applied load [6]. In this study, the composite system showed
only a small decrease in strain with a 15-fold increase in
applied stress (figure 8). This result highlights the reinforcing
effect of the CNT and illustrates the superior performance of
the composite systems at high loads as compared with pure
CPs [6, 7].
5. Conclusion
Addition of PAn by simply coating a CNT mat substantially
enhanced the actuation strain of the original CNT mat. The
observed actuation for the composite systems was similar (and
sometimes higher) to that measured for pure PAn samples.
The actuation was found to be dominated by the PAn redox
processes although the CNT provided a reinforcing effect that
allowed high strains to be maintained at high applied stresses.
In addition, the nanotubes increased the conductivity of the
composite leading to improved electrochemical efficiencies.
Optimization of the CNT/PAn composites using different
fabrication methods to achieve a high actuation strain
contributed by the PAn component and high Young’s modulus
(40–100 GPa) by the CNT component would lead to a high
actuation work-per-cycle. In addition, selecting a suitable
input voltage pattern to reduce the opposite movement of
the CNT and PAn components at negative voltages may help
achieve the highest actuation strain. These aspects merit
further study.
Appendix
The effect of an applied load on the actuation strain can be
derived as follows. As shown in figure A.1, we have
l f = lo + yd − yo (A.1)
where lo is the displacement between contraction and
expansion states without a load f ; l f is the displacement
between contraction and expansion states with a load f ; yo is
the displacement by the load f at the contraction state and yd
is the displacement by the load f at the expansion state.
It should be noted that the contraction state is a reduced
state in CPs or a neutral state (no charge) in CNT and that the
expansion state is an oxidized state in CPs or a charged state
(positive or negative charge) in CNT.
Hook’s law gives
f / A = E d (yd /l f ) (A.2)
f / A = E o (yo /lo ) (A.3)
where A is the cross sectional area of the sample, E o the
Young’s modulus at the contraction state, E d the Young’s
Carbon nanotube and polyaniline composite actuators
lo
lf
yo
lo
lf
f
yd
f
Figure A.1. Schematic diagram showing the effect of a load and an
applied voltage on the contraction and expansion states of a sample.
modulus at the expansion state, lo the sample length at the
contraction state in the absence of f and l f is the sample length
at the expansion state in the absence of f .
From equations (A.1), (A.2) and (A.3), we have
l f = lo + (l f f /E d A) − (lo f /E o A) (A.4)
l f = lo + lo . (A.5)
Equations (A.4) and (A.5) give
l f = lo (1 + f /E d A) + ( f lo / A)(1/E d − 1/E o ). (A.6)
Since f / A  E d
l f ≈ lo + ( f lo / A)(1/E d − 1/E o ). (A.7)
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