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Dynamics of carbon nanotube alignment by electric fields

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DOI: 10.1088/0957-4484/23/46/465710 · Source: PubMed

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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 23 (2012) 465710 (10pp) doi:10.1088/0957-4484/23/46/465710

Dynamics of carbon nanotube alignment

by electric fields
A I Oliva-Avilés1 , F Avilés2 , V Sosa1 , A I Oliva1 and F Gamboa1
1
Centro de Investigación y de Estudios Avanzados, Unidad Mérida, Departamento de Fı́sica Aplicada,
A.P. 73-Cordemex, 97310, Mérida, Yucatán, Mexico
2
Centro de Investigación Cientı́fica de Yucatán, Unidad de Materiales, Calle 43 No. 130 Colonia
Chuburná de Hidalgo, 97200, Mérida, Yucatán, Mexico

E-mail: andresivan19@hotmail.com

Received 26 June 2012, in final form 4 September 2012

Published 24 October 2012
Online at stacks.iop.org/Nano/23/465710
Abstract
The dynamics of multiwall carbon nanotube (MWCNT) alignment inside viscous media using
electric fields is investigated. Electrical current measurements were performed in situ during
the application of an electric field to liquid solutions of deionized water or dissolved polymer
containing MWCNTs. The variation of electrical current over time was associated to the
dynamics of the MWCNT network formation. The influence of the electric field magnitude
and frequency on the MWCNT network formation was studied. MWCNT migration towards
the negative electrode was observed when a direct current electric field was applied, whereas
formation of an aligned MWCNT network was achieved for an alternating current electric
field. The increase of the electric field frequency promotes a faster formation of an aligned
MWCNT network and thinner MWCNT bundles. A higher viscosity of the liquid medium
yields slower MWCNT alignment evidenced by a slower change of electrical current through
the viscous system. An analytical model based on the dielectrophoresis-induced torque, which
considers the viscosity of the medium, is also proposed to explain the dynamics of MWCNT
alignment. Furthermore, aligned MWCNT/polysulfone solid composites were fabricated and
electrically characterized. The solid composites presented anisotropic electrical conductivity,
which was more evident for low MWCNT concentrations (0.1–0.2 wt%).
S Online supplementary data available from stacks.iop.org/Nano/23/465710/mmedia
(Some figures may appear in colour only in the online journal)

1. Introduction et al [10] reported the orientation and purification of multiwall

Carbon nanotube (CNT) alignment inside liquid solutions
and polymers is a highly desirable feature for the
fabrication of CNT materials and nanostructured devices
with tailored properties. Mechanical, magnetic and electrical
techniques have been recently investigated for manipulating
CNTs in polymers and other viscous media. Although
mechanical [1–6] and magnetic [7–9] techniques have shown
promising results for CNT alignment, CNT structural damage
caused by mechanical processing and/or the need for high
magnetic fields (∼10–25 T) are often the concomitant
drawbacks of such techniques. Therefore, the application
of electric fields [10–16] emerges as a suitable option for
tailoring the CNT network within viscous media. Yamamoto
carbon nanotubes (MWCNTs) dispersed in isopropyl alcohol
using an alternating current (AC) electric field. Since
then, important research related to CNT manipulation by
electric fields has been conducted [11–16]. Several authors
have reported improved physical properties for electric
field-aligned CNT/polymer composites in the alignment
direction [14–16].
However, although CNT manipulation using electric
fields has proved to be a good option for the fabrication
of enhanced multifunctional materials, the dynamics of
such an alignment process is still unknown. The electrical
properties of the CNTs and the surrounding medium and the
characteristics of the applied electric field play important roles
in the CNTs response. These roles need to be investigated in

0957-4484/12/465710+10$33.00 1 c 2012 IOP Publishing Ltd Printed in the UK & the USA


Nanotechnology 23 (2012) 465710
Figure 1. Schematic of the experimental setup. (a) Cross-section of the cell used for the electric field application, (b) instrumentation.
order to shed light on the optimum experimental conditions
for tailoring the properties of nanostructured materials. From
the AC electrokinetics theory [17–20], it is known that
both the dielectrophoretic force and the orientation torque
exerted by a conductive particle surrounded by a dielectric
medium subjected to an electric field, are highly dependent
on the electric field magnitude, frequency and the electrical
properties of the particle and its surrounding medium.
Therefore, the main aim of this work is to investigate the
influence of the magnitude and frequency of the electric field
and the viscosity of the surrounding medium on the dynamics
of the CNT network formation inside liquid media.
2. Electric field application to liquid solutions
containing MWCNTs
MWCNTs grown by chemical vapor deposition (‘Baytubes
C150P’) were supplied by Bayer MaterialScience3 . The
MWCNTs have inner and outer diameters of approximately
4 and 13 nm and a length in the range of 1–4 µm, yielding
a distribution of CNT aspect ratios (length/diameter) ranging
from 80 to 300 [21]. In order to study the influence of the
solution viscosity on the dynamics of the CNT alignment
and network formation, two liquid solutions, deionized
water (DIW) and dissolved polysulfone (DPSF), were used
as a medium to disperse and align the MWCNTs. The
room temperature viscosities of DIW and DPSF are 1 ×
10−3 Pa s [22] and 30 Pa s, respectively. DPSF viscosity was
measured with a rheometer (AR 2000, TA Instruments) using
the parallel plates technique. The MWCNT/DIW solution
consisted of 2.5 mg of MWCNTs dispersed into 4 ml of
DIW using an ultrasonic bath (8891-DTH Cole Palmer,
100 W, 42 kHz) for 2 h. The MWCNT/DIW suspension
was poured into a custom-made glass mold with aluminum
electrodes separated by 30 mm, figure 1(a), immediately
after taking the suspension out of the ultrasonic bath,
in order to prevent precipitation of the MWCNTs. For
the MWCNT/DPSF solution, 2.5 mg of MWCNTs were
dispersed into 4 ml of chloroform using an ultrasonic bath
for 2 h; at the same time, 500 mg of polysulfone (PSF,
3 Bayer MaterialScience, Leverkusen, Germany www.baytubes.com.
2
A I Oliva-Avilés et al
UDEL P1700)4 pellets were dissolved into 3 ml of chloroform
and mechanically stirred for 2 h. The chloroform solution
containing the dispersed MWCNTs and the dissolved PSF
were then mixed together and mechanically stirred for 15 min
to obtain the final MWCNT/DPSF solution. For the electric
field application, 4 ml of the MWCNT/DPSF liquid solution
were poured immediately after the 15 min stirring into the
glass mold shown in figure 1(a). The low concentration of
MWCNTs, the high viscosity of the DPSF and the subsequent
mechanical stirring of the MWCNT/DPSF solution yielded a
uniform MWCNT dispersion state before applying the electric
field, and this procedure was consistently followed for all
experiments. The initial state of dispersion is a concern which
was systematically controlled here, since this variable may
play an important role in the dynamic evolution of the CNT
network formation.
In different experiments, DC and AC voltages were
applied between the electrodes a few seconds (∼5 s) after
pouring the MWCNT solutions into the mold. The DC
voltage input was supplied by a data acquisition board
(National Instruments, USB-6216) while the AC voltage input
was supplied by an ultra-low distortion function generator
(Stanford Research System, DS360). Both DC and AC inputs
were amplified by a high-voltage power amplifier (Tegam,
2340), see figure 1(b). For the DC case, voltages of 50, 100
and 200 V were applied between the electrodes, yielding
electric fields of magnitude 1.6, 3.3 and 6.6 kV m−1 ,
respectively. For the AC case, the voltage was applied in
steps of 50 peak-to-peak volts (Vp–p ) from 50 to 400 Vp–p ,
corresponding to electric fields of magnitude (EAC ) ranging
from 1.6 to 13.3 kVp–p m−1 . The studied frequency (f )
ranged from f = 10 Hz to 100 kHz. The time of voltage
application was 3 min for all the experiments and the
solution was always liquid without appreciable change in
viscosity during the experiment. The electric current between
the electrodes was measured in situ during the entire field
application time and electric current versus time curves
were obtained for each experiment. For the electric current
measurements, a portable multimeter (Fluke 289) with data
logging capabilities was connected in series with the mold and
4 Solvay Advanced Polymers, Alpharetta, Georgia, USA www.
solvayadvancedpolymers.com.
Nanotechnology 23 (2012) 465710
Figure 2. Optical photographs of MWCNT/DIW solutions under application of an electric field. (a) V = 0 V,
(b) VDC = 200 V (EDC = 6.6 kV m−1 ) after 120 s, (c) VAC = 400 Vp–p (EAC = 13.3 kVp–p m−1 ) at 1 kHz after 5 s.
power amplifier, and plugged into a computer for real-time
data acquisition, see figure 1(b). In addition to the study
of CNT alignment in liquids, aligned MWCNT/PSF solid
composites were fabricated and the anisotropy in their DC
electrical conductivity (in solid state) was investigated. The
fabrication and characterization details of the solid composites
can be found in the supplementary data (available at stacks.
iop.org/Nano/23/465710/mmedia).
3. Results and discussion
3.1. Dynamics of MWCNT network formation in liquids
3.1.1. Macroscale observations of the MWCNT network
formation. The initial configuration of the MWCNT/DIW
solution before applying voltage (0 V) is shown in figure 2(a),
where MWCNT clusters are seen as small dark spots
randomly distributed in the deionized water. For DC
application, no appreciable changes in the network were
observed when a voltage of 50 V was applied (not shown).
However, when the voltage was increased to 100 V, MWCNT
migration towards the negatively charged electrode was
observed. This MWCNT migration towards the negative
electrode was faster when the DC voltage was increased
to 200 V. The state of the MWCNT/DIW solution after
2 min of 200 V DC is shown in figure 2(b) (see also
video in the supplementary data available at stacks.iop.org/
Nano/23/465710/mmedia). A markedly different behavior
was observed for AC voltages. For voltages below
150 Vp–p (EAC = 5 kVp–p m−1 ), no MWCNT migration
or macroscopic alignment was directly observed. However,
for AC voltages of 150 Vp–p and above, the formation of
an aligned MWCNT network was macroscopically observed
in the direction of the electric field (see figure 2(c) and
video in the supplementary data available at stacks.iop.org/
Nano/23/465710/mmedia). The formation of such an aligned
network was faster when the frequency of the applied field
was increased. Frequencies of 1 kHz and higher led to
an almost instantaneous MWCNT alignment between the
electrodes. The state of the MWCNT/DIW solution after
applying 400 Vp–p at 1 kHz for 5 s is shown in figure 2(c).
The migration of MWCNTs towards the negative
electrode when a DC electric field is applied can be explained
in terms of the theory of electrophoresis [18]. Electrophoresis
3
A I Oliva-Avilés et al
is a strong, polarity-dependent phenomenon related to a
double-layer formation at the surface of certain particles
suspended in aqueous media. This double-layer formation
consists on ions of one sign that collect at the particles’
surface while a surrounding counter-ion cloud shields this net
charge from the bulk of the fluid. When a DC electric field
is applied, the mobile counter-ion charge is set in motion,
creating a flow parallel to the surface, so that the particle
moves in response to the shear stresses exerted upon the
particle by this fluid convection [18]. On the other hand,
the aligned MWCNT network formed between electrodes
when an AC electric field was applied can be understood
in terms of dielectrophoresis and orientation phenomena
(both frequency dependent) experienced by the MWCNTs
due to their different electric properties with respect to the
surrounding medium. These phenomena will be discussed in
more detail in the next sub-sections.
3.1.2. In situ electrical current measurements. Due to
the much higher electric conductivity of the MWCNTs
(∼103 S m−1 [23]) compared to that of the DIW
(∼10−6 S m−1 [24]), chloroform (∼10−6 S m−1 [24])
and PSF (∼10−15 S m−1 [16]), measurable changes in the
electrical current that flows through the MWCNT/solvent
solution can exclusively be related to changes in the MWCNT
network. This fact was confirmed by initial experiments
that contained only the solvent (DIW, DPSF or chloroform,
without MWCNTs) within the cell and used the same setup
shown in figure 1, which did not yield any measurable
current. Also, additional experiments consisting of applying
the electric field to the MWCNT solutions in repetitive
sequential steps discarded the possibility of oxidation or
degradation effects on the MWCNTs due to the applied
voltages, which could potentially modify the current and/or
conductivity measured by the setup. Therefore, the MWCNT
network formation and its dependence on the magnitude and
frequency of the AC applied electric field is explained here
solely in terms of the electrical current that flows through
the cell depicted in figure 1. The AC voltage was varied
in steps of 50 Vp–p from 50 to 400 Vp–p and the current
flowing through the MWCNT/DPSF suspension was recorded
during 3 min. The frequency was varied from 10 Hz to
100 kHz for each applied voltage. The electric current (i) was
measured in situ during the AC electric field application with
Nanotechnology 23 (2012) 465710
Figure 3. Normalized electrical current versus elapsed time measured in situ during AC electric field application to MWCNT/DPSF
solutions for different frequencies of the electric field. (a) f = 10 Hz, (b) f = 100 Hz, (c) f = 1 kHz, (d) f = 10 kHz, (e) f = 100 kHz. imax
is the maximum current measured in each graph at t = 180 s and 400 Vp–p .
a multimeter connected in series with the power amplifier and
the cell containing the MWCNT suspension, see figure 1(b).
The electric current was normalized with the maximum
electric current measured (imax ) for each frequency, which
was reached after 3 min of applying the maximum voltage
(400 Vp–p ). The measured currents were on the order of µA.
Curves of normalized electrical current i/imax versus elapsed
time of voltage application (t) are shown in figure 3 for several
frequencies (f ) of the applied field.
Figure 3(a) shows i/imax versus t for the lowest frequency,
f = 10 Hz, and the MWCNT/DPSF solution. For 50 and
100 Vp–p , no electrical current flow was detected during
this experiment, suggesting that the current is either not
flowing through the experimental setup or its magnitude is
too small (<µA) to be registered by the instrumentation used.
Similarly, for all applied voltages at f = 10 Hz, no measurable
current was registered during the first seconds of voltage
application, which is observed by the fact that the curves are
shifted to the right with respect to t = 0 on the horizontal
4
A I Oliva-Avilés et al
axis. It can also be noted from figure 3(a) that the curves
corresponding to higher voltages are less shifted to the right on
the time axis, i.e. measurable currents were registered earlier
for higher voltages. The minimum voltage required to produce
‘instantaneous’ MWCNT alignment (and hence appreciable
current measurements) may be related to the electric field
screening effects among the MWCNTs within the bundles and
among the bundles themselves, see e.g. [25].
For figures 3(a)–(c), a continuous increase in the
measured electrical current with time is observed for
MWCNT/DPSF solutions. The flow of electrical current
through the MWCNT network is associated to the formation
of electrically percolative paths, which are known to form
at very low CNT concentrations (0.04 wt% in this case) for
the case of kinetic percolation in viscous liquids [26]. For a
frequency of 100 Hz, figure 3(b), the i/imax versus t curves
are only slightly shifted to the right with respect to t = 0
and the current flow was not detected only for 50 Vp–p .
When the frequency of the applied field increases to 1 kHz,
Nanotechnology 23 (2012) 465710
Figure 4. Normalized electrical current versus elapsed time measured in situ during AC electric field application to MWCNT/DIW
solutions at two frequencies. (a) f = 10 Hz, (b) f = 100 kHz. imax is the maximum current measured at t = 180 s and 400 Vp–p for each
graph.
figure 3(c), an electrical current is detected at the moment of
voltage application (no shifting observed) although the current
is still not measurable for 50 Vp–p . For the remaining applied
voltages at f = 1 kHz, the current sharply increases right at
the moment of voltage application, but it continues increasing,
taking more than 3 min to reach a steady state. This indicates
that, after 3 min at these conditions, there is still MWCNT
motion within the polymer solution and that the network
formation is still in a dynamic state. For applied frequencies
above 1 kHz, figures 3(d) and (e), all the applied voltages yield
a measurable electrical current which was instantaneously
detected after voltage application. A marked difference from
figures 3(a)–(c) is that for high frequencies the curves reach
their maximum right after voltage application and no changes
in electrical current are observed thereafter. This indicates
that, for frequencies above 1 kHz and voltages of 50 Vp–p and
above, the dynamic effects occur in significantly less than 1 s
and the aligned morphology of the network is defined almost
instantaneously.
As previously stated, changes in the electrical current
flowing through the MWCNT/DPSF system can be associated
to the formation of MWCNT conductive paths. According
to the results of figure 3, the magnitude of the applied
voltage determines the final magnitude of the electrical
current flowing through the system. The current increases
with increased voltage for all the frequencies studied, these
changes being nearly linear (Ohmic), especially for higher
frequencies. Increasing the frequency of the electric field
reduces the time required for the formation of aligned
conductive paths. The network formation is a dynamic
phenomenon which takes more than 3 min to reach a stable
(or quasi-stable) state for frequencies below 1 kHz. Above
1 kHz, the network formation is practically ‘instantaneous’
(1 s) and no further changes in the network dynamics
(electrical current) are observed thereafter, indicating a steady
state. These results are in qualitative agreement with the
macroscopic observations previously discussed, where higher
frequencies led to a more rapid formation of the MWCNT
network at the macroscale.
The experimentally observed phenomena can be ex-
plained in terms of dielectrophoresis-induced force and
torque, which are phenomena highly dependent on the
5
A I Oliva-Avilés et al
electric field frequency. Both of them contribute to the
formation of CNT conductive paths within the solution. The
dielectrophoretic forces generate MWCNT motion which
leads to MWCNT chaining, whereas the induced torque
tends to align the MWCNTs in the direction of the electric
field [18, 19], creating aligned trajectories for electron
transport. Li et al [12] conducted simulations based on the
dielectrophoresis-induced torque and force on CNTs for a
CNT/isopropyl alcohol system and reported that the time
required for aligning CNTs in the direction of an AC electric
field (rotation) is much smaller (in the order of milliseconds)
than the time required for CNT translation (tens of seconds).
Therefore, it is expected that for high frequencies, MWCNT
orientation plays the main role in the network formation and
electron transport. On the other hand, for low frequencies,
both dielectrophoretic orientation and translation seem to
contribute to the dynamics of the formation of conductive
paths since low frequencies enable the competition of these
two factors.
The role of the fluid viscosity in the alignment of
MWCNTs was investigated by repeating the experiments
in figure 3 but using DIW. DIW has a considerably lower
viscosity (1 × 10−3 Pa s) than the DPSF (30 Pa s) examined
in figure 3. For the case of DIW, a similar electrical current
behavior was observed for all the examined frequency range,
so only the curves for the lowest (10 Hz) and highest
(100 kHz) frequencies are presented in figure 4. From
figure 4(a), it is seen that for all the applied voltages at
10 Hz, an electrical current is immediately registered as
soon as the voltage is applied and such a current remained
constant during all the time of voltage application. A similar
trend is also observed for voltages applied at f = 100 kHz,
figure 4(b). This fact suggests a very rapid formation of
conductive paths between the electrodes at any frequency for
a low viscosity liquid such as deionized water. However, for a
much more viscous solution such as DPSF, the time required
for the definition of conductive paths depends strongly on the
frequency, figure 3.
Based on the results for MWNCT/DPFS (figure 3) and
MWCNT/DIW (figure 4), it is clear that the viscosity plays
an important role in the dynamics of the MWCNT network
formation, acting as a drag force which acts in opposition
Nanotechnology 23 (2012) 465710
to the mechanisms that lead to such a network formation.
This role is more evident for low electric field frequencies.
Thus, both dielectrophoretic orientation and translation seem
to be affected by the viscosity of the medium, resulting in a
faster formation of conductive paths for systems with lower
viscosities.
3.1.3. Analytical modeling. To further investigate the
dynamics of MWCNT alignment in viscous media when
an AC electric field is applied, an analytical model which
considers the dielectrophoresis-induced torque [18, 19] and
the viscous effect of the surrounding medium is proposed.
By solving the rotational motion equation, the time required
for MWCNT alignment along the electric field direction was
predicted and correlated to the experimental observations. By
using Newton’s second law, the governing equation of the
rotational motion of a highly elongated ellipsoid immersed in
a viscous medium subjected to an AC external electric field is
given by, [27],
d2 θ
I + Tη + Talign = 0 (1)
dt2
where I is the moment of inertia of the CNT, θ is the angle
between the CNT longitudinal axis and the direction of the
electric field (see figure 5), d2 θ/dt2 is the second derivative of
θ with respect to time t, Tη is the damping torque and Talign
is the CNT dielectrophoretic-induced torque. The expressions
for Tη [19] and Talign (see supplementary data available at
stacks.iop.org/Nano/23/465710/mmedia) are given by
dθ
Tη = 8π η (2)
dt
Talign = 41 εm Re[α ∗ ]E2 sin2θ (3a)
(εp∗ − εm
∗ )2
α∗ = (3b)
∗ + (ε ∗ − ε ∗ )L ](ε ∗ + ε ∗ )
[εm p m x p m
σm,p
εm,p
∗
= εm,p − j (3c)
ω 10−6 S m−1 [24] and η = 30 Pa s (measured). The electric
where η is the viscosity of the medium,  is the volume
of the particle, εm is the permittivity of the surrounding
medium, E is the magnitude of the electric field, εm ∗ and
εp are complex numbers (j = −1) expressed in terms of
∗ 2
the electrical permittivities (ε) and conductivities (σ ) of the
medium (m) and particle (p), Lx is the depolarization factor,
ω is the angular frequency of the electric field (ω = 2π f )
and ‘Re’ means the real part of the complex expression within
brackets. A detailed derivation of these equations can be found
in the supplementary data (available at stacks.iop.org/Nano/
23/465710/mmedia).
Since Tη depends on dθ/dt and Talign on sin2θ,
equation (1) is a second-order nonlinear damped differential
equation. Equation (1) is also dependent on the frequency of
the electric field (f = ω/2π ), permittivities and conductivities
(through εm ∗ and ε ∗ included in the term T
p align ), see (3). The
solution of (1), θ (t), describes the dynamic evolution of the
angle θ between the major axis of the CNT (x-axis) and the
electric field direction, see figure 5. An initial value θ (t =
6
A I Oliva-Avilés et al
Figure 5. Schematic of an elongated body aligned in the x-direction
and the components of the applied electric field E.
0) = θ0 is given to the particle and is considered aligned
when θ = 0◦ , so the time required for such an alignment
condition can be estimated. By considering a MWCNT as a
highly elongated ellipsoid, the time for MWCNT alignment
was calculated using DIW and DPSF as surrounding media.
The volume () and the moment of inertia (I) of the MWCNT
were taken as  = π(ro2 − ri2 )l and I = (1/12)ml2 , where
ro , ri , l and m are the outer radius, inner radius, length and
mass of the MWCNT, respectively. In our case, the numerical
values employed were ro = 6.5 nm, ri = 2 nm and l =
1 µm, according to the dimensions of the MWCNTs used
in the experiments; the mass (m = 1.2 × 10−16 g) was
estimated from the density of graphite (2.16 g cm−3 ) [12].
For a highly elongated particle Lx ≈ (4ro2 /l2 ) [ln(l/ro ) −
1] [18], which in our case is in the order of 10−6 . The
MWCNT electrical permittivity and conductivity values used
were εp = 2000ε0 [12] and σp = 1 × 103 S m−1 [23],
respectively, ε0 being the permittivity of the free space (ε0 =
8.85 × 10−12 F m−1 ). The values of permittivity, conductivity
and viscosity used for DIW are εm = 80ε0, σm = 5.5 ×
10−6 S m−1 [24] and η = 1 × 10−3 Pa s [22], while the
corresponding values for DPSF were εm = 4.7ε0, σm = 1 ×
field magnitude was E = 6.6 kV m−1 , which corresponds to
400 Vp–p in the experimental setup.
In order to investigate the influence of the electric
field frequency (f = ω/2π ) on the magnitude of the
dielectrophoresis-induced torque from the proposed model,
Re[α ∗ ] was computed for DIW and DPSF as surrounding
media and the results are presented in figure 6. For DIW,
a nondimensional value of 1466 is obtained for frequencies
below f ∼ 10 MHz, which suddenly drops to a value of
22 in the window of 107 –109 Hz and stays constant at 22
thereafter. A similar trend is observed for DPSF, with the
same initial value (1466) for frequencies below f ∼ 1 GHz
and a sudden decrease to a value of 328 for frequencies
above 10 GHz. As seen from figure 6, Re[α ∗ ] presents
a similar behavior to the well-known Clausius–Mossotti
factor [18, 19], which is dominated by the particle (σp ) and
medium (σm ) electrical conductivities at low frequencies,
and by the particle (εp ) and medium (εm ) permittivities
at high frequencies [18, 19]. The difference of several
Nanotechnology 23 (2012) 465710
Figure 6. Real part of α ∗ as a function of the electric field
frequency for a MWCNT immersed in deionized water (solid line)
and dissolved polysulfone (dashed line).
orders of magnitude between the MWCNT conductivity
and the medium (DIW or DPSF) conductivity results in a
similar value of Re[α ∗ ] (1466) at low frequencies for both
solutions. However, the mismatch between the MWCNT
and medium permittivities is significantly lower than that
between conductivities, which yields different values of
Re[α ∗ ] for DIW (22) and DPSF (328) for high frequencies.
The constant value of Re[α ∗ ] = 1466 corresponds to the range
of frequencies experimentally investigated herein (f = 10 Hz
to 100 kHz) and such a value will be used in (3a) for the
solution of (1). The proposed model and expression of the
Clausius–Mossotti factor are obviously a simplification of
the actual experimental conditions, in an attempt to capture
the foundations of the dynamic phenomenon. The model
considers only a single CNT and does not take into account
CNT-to-CNT interactions, as well as the presence of ion layers
in the CNT–medium interphase [18, 19], which would render
a more complex expressions of the Clausius–Mossotti factor
and the governing differential equation (1).
Figure 7 shows θ (t) from the numerical solution of (1) for
two liquid media, DIW (figure 7(a)) and DPSF (figure 7(b)).
In the actual experimental conditions, CNTs are initially
distributed over a wide range of orientations with respect to
Figure 7. Predicted MWCNT orientation angle according to (1) for two surrounding media. (a) Deionized water, (b) dissolved polysulfone.
7
A I Oliva-Avilés et al
the electric field direction (0◦ < θo < 90◦ ). Therefore, (1) was
numerically solved considering three values of θo , 89◦ , 45◦
and 10◦ , and assuming a MWCNT initial angular velocity
dθ/dt (t = 0) = 0 for all cases. According to the predictions
of figure 7(a), when the MWCNTs are immersed in DIW
the time for MWCNT alignment (θ = 0) when θo = 89◦ is
∼10 ms, which is about twice the time required for alignment
when θo = 45◦ and about four times the time required for
θo = 10◦ . Thus, the time required for MWCNT alignment
in DIW predicted by the dielectrophoretic model is of the
order of the milliseconds. On the other hand, for a medium
with higher viscosity such as DPSF, figure 7(b), the time
required for aligning the MWCNTs is in the order of minutes,
and a distribution of times is predicted depending on the
MWCNT initial conditions. The higher viscosity and the
lower permittivity of DPSF yield a higher damping term and
lower dielectrophoresis-induced torque in (1), which makes
MWCNT alignment slower in the DPSF system than in the
DIW one. The numerical results obtained with the presented
model are in agreement with the experimental observations
previously discussed, where the electrical current reached a
steady state as soon as the electric field is applied for DIW,
whereas 3 min were not enough to reach a steady state for the
DPSF system, see figures 3 and 4.
3.2. Characterization of solid MWCNT/PSF composites
3.2.1. Morphology. The surface morphology of MWCNT/
PSF solid composites aligned by an electric field of
magnitude EAC = 13.3 kVp–p m−1 (V = 400 Vp–p ) and
frequencies ranging from 10 Hz to 100 kHz was examined.
Macroscopically aligned MWCNT networks were achieved
for all the studied frequencies. However, the MWCNT
aligned network was more uniform for high frequencies
(1 kHz and above). Figure 8 presents optical photographs
of 0.5 wt% composites fabricated under the application
of f = 10 Hz, figure 8(a), and f = 1 kHz, figure 8(b).
An aligned MWCNT/PSF specimen at f = 1 kHz was
chosen as representative for the composites fabricated at high
frequencies (1, 10 and 100 kHz) since all of the specimens
look similar at the macroscale. The electric field was applied
Nanotechnology 23 (2012) 465710
Figure 8. Optical photographs of solid MWCNT/PSF composite films at 0.5 wt% fabricated at EAC = 13.3 kVp–p m−1 (V = 400 Vp–p ) and
two frequencies. (a) 10 Hz, (b) 1 kHz. The direction of the electric field is vertical.
Figure 9. SEM micrograph of a MWCNT bundle within a
MWCNT/PSF film aligned with the electric field direction.
along the vertical direction of figure 8. From figure 8(a), it
can be observed that for low frequencies, MWCNT chains
(bundles) are aligned along the field direction (vertical),
although some chains seem to be slightly curved and
nonuniformly spaced. For high frequencies, figure 8(b), the
MWCNT chains are also aligned in the direction of the
applied field, but the MWCNT chains are thinner, straighter
and more uniformly dispersed and aligned along the electric
field direction compared to figure 8(a). Thus, high frequencies
promote the formation of more uniform, better dispersed and
aligned MWCNT networks, at least at the macroscale.
Figure 9 shows an SEM image of an aligned
MWCNT/PSF (solid) film fabricated at 0.5 wt% under an
electric field of EAC = 13.3 kVp–p m−1 (V = 400 Vp–p )
and f = 1 kHz. Thermal evaporation of a thin layer of
gold (∼15 nm) was used in an attempt to melt the polymer
covering the MWCNTs and to better image the film surface.
A MWCNT bundle (covered by polymer) is seen at the
center of the image aligned with the direction of the applied
electric field (vertical), confirming the orientation of bundles
of MWCNTs.
3.2.2. Anisotropic electrical conductivity. In order to
investigate the electrical anisotropy of the aligned composites,
8
A I Oliva-Avilés et al
the DC electrical conductivity of MWCNT/PSF solid
composites with different MWCNT weight concentrations
was measured in the parallel (σpar ) and perpendicular
(σperp ) directions with respect to the direction of the
electric field. Figure 10(a) presents the average DC electrical
conductivity (σ ) of these samples measured for composites
fabricated under an electric field of magnitude EAC =
13.3 kVp–p m−1 (V = 400 Vp–p ) and f = 1 kHz. For both
curves, an abrupt increase in conductivity with respect to that
of the neat polymer (∼10−15 S m−1 [16]) is observed at
0.1 wt%. This sharp increase in conductivity can be explained
in terms of the formation of an electrically percolated network
within the composite, as has been extensively discussed in
the literature [16, 28–30]. For the lowest MWCNT content
(0.1 wt%), σpar increased by 11 orders of magnitude and
σperp by 7 orders of magnitude with respect to the electrical
conductivity of the neat polymer (0 wt%). For all MWCNT
concentrations σpar is higher than σperp , revealing anisotropy
in the electrical behavior of the composite. As revealed by
figure 10(b), the σpar /σperp ratio increases with increased
MWCNT concentration for concentrations up to 0.2 wt%,
but decreases for higher MWCNT concentrations being
σpar /σperp ≈ 1 for 0.5 wt%.
The electrical anisotropy of the aligned composites can
be explained in terms of the MWCNT network anisotropy
and density. The formation of aligned MWCNT conductive
paths along the composite promotes electron transfer in
such an alignment direction, since the electrons have
more straight paths (less scattering) available for traveling
between the electrodes. For this reason, the composite
electrical conductivity measured in the parallel direction
is higher than the one measured perpendicular to the
alignment direction. For the transverse direction, electrons
have more discontinuous and separated conductive paths to
travel between the electrodes, but transverse CNT-to-CNT
contact (or tunneling) is still possible. For low MWCNT
concentrations, electrons flow more easily along the aligned
MWCNT conductive paths than across them, because of the
relative large separation between the transverse paths and
discontinuity among them. However, once a critical network
density is reached (about 0.5 wt% in our case), electrons
can easily travel in both directions so the anisotropy is lost.
Nanotechnology 23 (2012) 465710
Figure 10. Average DC electrical conductivity (σ ) as a function of MWCNT weight concentration for aligned MWCNT/PSF composites
oriented parallel (σpar ) and perpendicular (σperp ) to the direction of the electric field. (a) σ versus MWCNT weight concentration for both
directions, (b) σpar /σperp versus MWCNT weight concentration.
Thus, according to these results, MWCNT solid composites
with anisotropic electrical conductivity can be achieved at low
MWCNT concentrations (≤0.3 wt%) by using AC electric
fields of ∼13 kVp−p m−1 at frequencies on the order of kHz.
4. Conclusions
The dynamics of electric field-induced MWCNT alignment
in liquid solutions was investigated. Changes in the electrical
current flowing through the MWCNT solution during the
electric field application were measured and related to the
MWCNT network formation dynamics. The influence of
the electric field magnitude, frequency and viscosity of the
solution on the formation of the MWCNT aligned network
was investigated. MWCNT migration towards the negative
electrode was observed when a 6.6 kV m−1 DC electric field
was applied, while an aligned MWCNT network was achieved
upon application of AC electric fields as low as 5 kVp–p m−1 .
Faster formation of the aligned MWCNT network was
achieved by increasing the electric field frequency (in the
order of kHz), and higher degree of alignment, dispersion
and uniformity of the MWCNT network were observed
for such high frequencies. A dielectrophoretic model for
the dynamics of MWCNT alignment in viscous media was
proposed and the predicted times for MWCNT alignment
were in agreement with the experimental measurements.
SEM micrographs confirmed the alignment of MWCNT
bundles within the MWCNT/PSF composite films. Aligned
composites at different MWCNT concentrations presented an
anisotropic electrical conductivity, with significantly higher
conductivity along the alignment direction than across it.
Such an anisotropic electrical conductivity is more evident
for composites with low MWCNT concentration (0.1 and
0.2 wt%) and disappears for composites with 0.5 wt%.
The results of this research indicate that once a minimum
magnitude of AC electric field is achieved (∼5 kVp–p m−1 ),
the critical factor governing MWCNT alignment in viscous
media is the frequency of the applied field.
9
A I Oliva-Avilés et al
Acknowledgments
This work was supported by CONACYT (Mexico). The
authors wish to thank Jorge Aguilar (UQRoo), Alejandro
May (CICY), Oscar Ceh and Wilian Cauich (both from
CINVESTAV) for their valuable support. Assistance of Rene
Maas with photography and video is also strongly appreciated.
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