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Influence of AC Electric Field on Macroscopic Network
of Carbon Nanotubes in Polystyrene
Xizhi Yang
a
, Yuefeng Zhu
b
, Lijun Ji
a
, Chan Zhang
a
& Ji Liang
a
a
Key Laboratory for Advanced Materials Processing Technology , Ministry of Education , P. R.
China
b
Department of Mechanical Engineering , Tsinghua University , Beijing, P. R. China
Published online: 23 Dec 2010.
To cite this article: Xizhi Yang , Yuefeng Zhu , Lijun Ji , Chan Zhang & Ji Liang (2007) Influence of AC Electric Field on
Macroscopic Network of Carbon Nanotubes in Polystyrene, Journal of Dispersion Science and Technology, 28:8, 1164-1168,
DOI: 10.1080/01932690701526740
To link to this article: http://dx.doi.org/10.1080/01932690701526740
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Inuence of AC Electric Field on Macroscopic Network of Carbon
Nanotubes in Polystyrene
Xizhi Yang, Yuefeng Zhu, Lijun Ji, Chan Zhang, and Ji Liang
Key Laboratory for Advanced Materials Processing Technology, Ministry of Education, P. R. China and Department of
Mechanical Engineering, Tsinghua University, Beijing, P. R. China
CVD-grown multiwall carbon nanotubes are dispersed in styrene monomer. During the
polymerization of styrene, an AC electric eld is applied to induce the CNTs to align along
the electric eld line to form a macroscopic nanotube network in polystyrene matrix. The die-
lectrophoresis force and the electric eld redistribution at the CNTs apexes are responsible for
alignment of the CNTs as well as bonding between the CNTs. Parameters such as eld strength
and nanotube weight fraction are varied. The results indicate that the macroscopic CNTs
alignment along electric eld direction can be observed only if the AC voltage reaches or is
higher than certain values, and the higher the electric eld frequency is, the more uniformly
the CNTs align along electric eld direction. In addition, nanotube concentration also affects
the alignment of CNTs. According to the results of this study, the CNTs will align into a devel-
oped network in polystyrene matrix under a proper combination of three parameters of the
electric eld voltage, frequency, and the CNTs concentration.
Keywords Carbon nanotubes, styrene, electric eld, composites
1 INTRODUCTION
Carbon nanotubes (CNTs) have remarkable properties that
have aroused much interest for a wide variety of potential
applications in composites. Their unusual properties include
high moduli of elasticity and strength, high aspect ratios, excel-
lent thermal and electrical conductivities, and magnetic proper-
ties.
[110]
One of the key requirements for composites is the
well dispersion of CNTs,
[1115]
and the controllable alignment
of CNTs also is an important requirement, especially for the
integration of nanotube-based devices.
Qin et al.
[16]
used grafting to and grafting from methods to
functionalize single-walled carbon nanotubes (SWNTs) with
polystyrene (PS). According to their tests, the nal functiona-
lized SWNTs dissolved well in organic solvents, and the
original SWNTs bundles were broken into very small ropes
or even individual tubes as revealed by AFM. Kimura
et al.
[17]
showed that multiwalled carbon nanotubes
(MWNTs) were aligned in a polyester matrix through
polymerizing a MWNTs-monomer dispersion inside a
magnet. The authors
[18,19]
reported that dispersion status of
carbon nanotubes in liquid media could be evidently
improved by effect of an electric eld.
Recently, electric eld was applied for orientation and array
of CNTs. Du et al.
[20]
prepared CNTs lms by electrophoretic
deposition (EPD) with an external direct current (DC) electric
eld and investigated primarily the electric properties of the
lms. Yamamoto et al.
[21,22]
and other researchers
[2325]
aligned CNTs between electrodes using DC and alternating
current (AC) electric elds due to the depolarization of
CNTs induced by electric elds. Chen et al.
[26]
demonstrated
the controllable inter connection of SWNTs under AC
electric eld. It was reported that the interconnected carbon
nanotubes were found to be parallel with the electric ux.
Martin et al.
[27]
exerted both AC and DC electric elds
during nanocomposite curing and aligned conductive
nanotube networks in epoxy matrix were observed.
The results mentioned above demonstrate an obvious effect
of electric elds on dispersion and distribution morphology of
CNTs in different matrix. In this paper, we exert an external
AC electric eld on the suspension of CNTs during the
polymerization of styrene to prepare composites with a macro-
scopic CNTs network in PS matrix, and demonstrate the
relationship between the formation of the CNTs network and
the AC electric eld conditions. Moreover, the effect of the
CNTs concentration is preliminarily studied.
The project was sponsored by the Foundation of National Natural
Science, P. R. China (Grant No. 10332020) and the Innovation Fund
for Outstanding Scholar of Henan Province, P. R. China (Grant
No. 0521001000).
Received 1 October 2006; Accepted 15 October 2006.
Address correspondence to Yuefeng Zhu, Department of Mechan-
ical Engineering, Tsinghua University, Beijing 100084, P. R. China.
E-mail: yfzhu@tsinghua.edu.cn
Journal of Dispersion Science and Technology, 28:11641168, 2007
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print /1532-2351 online
DOI: 10.1080/01932690701526740
1164
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2 EXPERIMENTAL
The CNTs used in this article were prepared by chemical
vapor depositing (CVD) method. The prepared CNTs were
treated in HF for 24 hours to remove catalyst particles and
other impurities, then, the conglomerations of the entangled
CNTs were ball milled slightly. Thereafter, the so-called
original CNTs were obtained. Morphology of the so-called
original CNTs was carried out with LEO 1530 eld emission
scanning electron microscope (FE-SEM) operating with an
accelerating voltage of 10 kV. The morphology is shown in
Figure 1. The styrene monomer used was produced by Guang-
dong Shantou Xilong Chemical Factory (Shantou, Guangdong
Province, China).
The suspension was prepared by dispersing the original
CNTs in styrene monomer for various CNTs concentrations,
and 2,2-azoisobytyronitrile (AIBN) also was added into the sus-
pension as a reaction initiator. A rough-dispersed CNT suspen-
sion was achieved by sonicating the solution for 8 10
minutes. Then, the rough-dispersed CNT suspension was
dropped into a Bunsen beaker in which electrodes were set for
introducing electric eld as shown in Figure 2. The wall of
the Bunsen beaker was accessorized with a piece of aluminum
foil as one electrode, and a copper rod with a diameter of
1 mm was set in the center of the beaker as another electrode.
The beaker was put into water bath with a temperature of
758C during the polymerization of the styrene monomer. At
the same time, an AC electric eld was exerted on the suspen-
sion. The applied AC voltage was varied from 100 V to 300 V
(virtual value) while the AC frequency was tuned from 45 Hz
to 500 Hz. The concentration of CNTs in the styrene was
changed from 0.05 wt% (called No. 1) to 0.1 wt% (called No.
2). After two hours polymerization process of the styrene
monomer, layers of CNTs-styrene composites were prepared.
An AC electric eld was supplied by an AC power supply
(Instek APS 9301, Taiwan Guwei Electric Com Taiwan,
China). Morphologies of the samples were recorded by
means of a scanner (Microtek Artixscan 1010plus). A visc-
ometer (NDJ-1, Shanghai Precision & Scientic Instrument
Co. Ltd., Shanghai, China) was used to test the viscosity of
the suspensions.
3 RESULTS AND DISCUSSIONS
3.1 Inuence of AC Voltage on the CNTs Network
The morphologies of the sample No. 2 prepared under
different electric eld conditions are shown in Figure 3. In
the samples prepared under the AC frequency of 500 Hz and
different voltages, there are few CNTs aligning along the direc-
tion of the electric eld with the AC voltage of 100 V and most
of the CNTs are entangled and aggregated near the aluminum
foil (see Figure 3a). Powering up the voltage to 250 V, most of
the CNTs are obviously aligned along the electric eld direc-
tion and the alignment is actinoid starting from the copper
rod (see Figure 3b). Although some CNTs are entangled and
aggregated, they are dispersed more uniformly than that
shown in Figure 3a. As the AC voltage reaches 300 V, the
alignment of CNTs becomes ne and dense especially in the
central region near the copper rod, although there exist some
heterogeneous aggregations of CNTs in the fringe region
near the aluminum foil (see Figure 3c). When the voltage
rises to 300 V, the alignment of CNTs under frequency of
500 Hz is not as good as that under 450 Hz. So the samples
are prepared under voltage of 300 V and frequency of
450 Hz in this experiment.
Martin et al.
[27]
proposed that dielectrophoresis effect could
induce nanotube movement towards the electrode for those
nanotubes in close proximity to the electrodes under effect of
an AC eld. In case of CNTs bundles, dielectrophoresis also
can make them to array along the electric eld direction.
When an electric eld is applied across two electrodes, depo-
sition of CNTs on the surface of one electrode occurs, which
lead to a remarkable change of the electric eld distribution,
and the nanotube apex demonstrates extremely high strength
and gradient of electric eld.
[26]
This results in the directional
movement of CNTs in liquid and axially or breadthwise con-
nection to the surface-xed nanotube apexes along the
electric eld gradient. As a result, CNTs bundles will bridge
FIG. 2. Schematic drawing of the experimental devices.
FIG. 1. Morphology of so-called original CNTs (FE-SEM).
AC ELECTRIC FIELD ON MACROSCOPIC NETWORK OF CARBON NANOTUBES 1165
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the two electrodes. In addition, the AC voltage must be high
enough to overcome thermal energy of Brownian motion and
resistance against rotation of the CNTs bundles in the
viscous suspension environment. Due to the limitation of the
AC power supply, the highest voltage is 300 V in this exper-
iment. According to the experimental results, the higher the
AC voltage is, the more CNTs align along the electric eld
line. However, the strength and gradient of electric eld at
the CNTs apexes will be enhanced as the voltage increases,
and transverse movement of CNTs to the surface-xed
nanotube will augment. This will result in that the CNTs
bundles align along the electric eld line and meanwhile
connect each other breadthwise. This will form rather a dendri-
tic network than electric-eld-lined network of the CNTs.
3.2 Inuence of AC Frequency
The alignment morphologies of the CNTs in the composites
are shown in Figure 4. It can be seen that even though the AC
voltage is 300 V, alignment of the CNTs along the electric eld
direction cannot be obtained under low frequencies of the AC
electric eld (see Figures 4a and 4b). Only when the frequency
is up to 250 Hz, there will be CNTs alignment along electric
eld direction (see Figures 4c4e).
FIG. 3. Morphologies of the CNTs network under different AC voltages and frequencies.
FIG. 4. Morphologies of the CNTs under an AC voltage of 300 V with various frequencies.
X. YANG ET AL. 1166
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It is observed that CNTs alignment started from live wire.
Aluminum foil is made to be live wire. The distinction of the
CNTs network structure under different AC frequency is
clear. As the frequency increases (see Figure 4), the CNTs
network structure is more regular and more CNTs align
along the electric eld line.
As shown in Figure 4a, there is no alignment of CNTs with
the AC frequency of 45 Hz. Some CNTs are entangled and
aggregated in the central region. As the AC frequency
reaches 100 Hz, a few of CNTs align along the electric eld
direction, especially in the fringe region near the aluminum
foil (see Figure 4b). Under the AC frequency of 250 Hz, the
CNTs near the fringe region are obviously aligned along the
electric eld direction, and in the central region, some CNTs
are free of alignment (see Figure 4c). With the AC frequency
increasing further, the alignment of CNTs is denser (see
Figures 4d and 4e). In Figure 4d, the threads composed of
CNTs are curved, and this phenomenon is attributed to the
occasional change of the electric eld distribution. Once a
piece of the thread becomes curved after the alignment of
CNTs completes, the electric eld distribution around it will
be changed and the other threads nearby will be inuenced in
turn.
The inuence of the frequency on the CNTs alignment is
due to the perfection of the CNTs orientation at right angle
to the electrode increased with increase of applied AC fre-
quency. Kumar et al.
[25]
reported that an improved CNT orien-
tation could be achieved with AC electric eld of high
frequency, this was due to alternating force exerted rapidly
on eld-induced dipoles of the nanotubes and the nanotubes
oriented nearly at right angle to the metal electrodes. Accord-
ing to the experiment results of this paper, it is believed that a
congruent voltage and frequency can induce CNTs aligned har-
moniously along the electric eld direction. As discussed
above, low voltages cannot provide enough power for CNTs
to conquer thermal energy of Brownian motion and resistance
against rotation of the CNTs bundles in the viscous suspension
environment, and low frequencies cannot lead right angle of
the CNTs orientation to the electrode. In our tests, an AC
electric eld of 300 V and 450 Hz is proper for alignment of
the CNTs in PS matrix.
3.3 Inuence of CNTs Concentration
Effects of CNTs concentration on their network structure
are shown in Figure 5. It is seen that, as the CNTs concentration
is 0.05 wt% (No. 1), under the same conditions, the alignment
of CNTs is more uniform than that of sample No. 2. With the
AC voltage of 250 V and frequency of 500 Hz, there are less
CNTs entangled in sample No. 1 than that in sample No. 2
(see Figures 5a and 5b). Under the AC voltage of 300 V and
frequency of 450 Hz, the network structure of CNTs in
sample No. 1 is more homogeneous than that in sample No.
2 (see Figures 5c and 5d).
FIG. 5. Morphologies of CNTs network formed under different AC elec-
tric eld conditions.
AC ELECTRIC FIELD ON MACROSCOPIC NETWORK OF CARBON NANOTUBES 1167
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Viscosities of the suspension with different CNTs concen-
tration are measured. The viscosities of samples No. 1 and No.
2 are 8.67 mPas and 11.34 mPas, respectively. The lower the
viscosity of the suspension is, the lower the resistance against
the rotating CNTs is, and the more freely the CNTs move in
the suspension. As a result, alignment of CNTs is more likely
along the electric eld direction. According to the viscosity
test, the viscosity of sample No. 1 is lower than that of sample
No. 2. So the CNTs alignment in sample No. 1 is more
uniform than that in sample No. 2 under the same conditions.
4 CONCLUSIONS
CNTs are dispersed in styrene monomer and then an AC
electric eld is applied to induce the CNTs to align along the
electric eld line to form a macroscopic network in PS
matrix after polymerization. Dielectrophoresis force and the
electric eld redistribution at the CNTs apexes are considered
to be responsible for alignment of the CNTs as well as bonding
between pieces of the CNTs. Under different electric eld con-
ditions, various morphologies of the CNTs network structures
can be obtained. The results indicate that only when the AC
voltage reaches certain intensity, which is high enough to
overcome thermal energy of Brownian motion and resistance
against rotation of the CNTs bundles in the viscous suspension
environment, a macroscopic CNTs alignment along the electric
eld direction can be observed. And high electric eld fre-
quency is good for CNTs alignment, for the perfection of the
CNT orientation at right angle to the electrode increased with
increase of the applied electric eld frequency. In addition,
CNTs concentration also affects the alignment of CNTs
because the viscosity of the suspension is different with
various CNTs concentrations and there is less resistance
against rotation of the CNTs bundles in the low viscous suspen-
sion environment. The CNTs will align into a developed
network in PS matrix under a proper combination of three par-
ameters of the electric eld voltage, frequency, and the CNTs
concentration.
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