CARBON 6 9 ( 2 0 1 4 ) 3 4 2 –3 5 4

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Dielectrophoretic modeling of the dynamic carbon

nanotube network formation in viscous media
under alternating current electric fields
a,*
A.I. Oliva-Avilés , F. Avilés b, V. Sosa a, G.D. Seidel c

a
Centro de Investigación y de Estudios Avanzados, Unidad Mérida, Departamento de Fı́sica Aplicada, A.P. 73-Cordemex, 97310 Mérida,
Yucatán, Mexico
b
Centro de Investigación Cientı́fica de Yucatán, Unidad de Materiales, Calle 43 No. 130 Col. Chuburná de Hidalgo, 97200 Mérida, Yucatán,
Mexico
c
Aerospace and Ocean Engineering Department, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA

A R T I C L E I N F O A B S T R A C T

Article history:
Received 17 August 2013
Accepted 11 December 2013
Available online 16 December 2013
The dynamic formation of carbon nanotube (CNT) networks in liquids under the applica-
tion of an alternating current electric field is investigated using the effective dipole model-
ing approach. Three mechanisms are investigated by a set of three independent nonlinear
differential equations derived from dielectrophoretic theory, viz. CNT rotation, CNT-to-CNT
Coulombic interactions, and CNT migration towards an electrode. The models consider the
effect of the electric field magnitude and frequency, the CNT’s concentration and aspect
ratio, and the viscosity of the surrounding medium. A layer at the CNT/liquid interface is
included and the effect of such a layer’s permittivity, electrical conductivity and thickness
is investigated. Modeling predictions allow the reconstruction of the dynamic sequence of
events leading to an aligned CNT network, which strongly depends on the CNT’s aspect
ratio and concentration. Experimental trends regarding the effect of frequency can only
be captured by considering an interface layer in the model.
 2013 Elsevier Ltd. All rights reserved.

1. Introduction desirable characteristics for the fabrication and optimization

Since early reports on carbon nanotube (CNT) manipulation
in liquids using electric fields [1,2], the electric field-guided
assembly of CNTs has attracted much attention due to its
non-invasive and potentially scalable characteristics, as well
as its relatively facile implementation. The CNT’s anisotropic
structure and its electrical properties render a rapid response
to applied electric fields, resulting in CNT orientation along
the field direction and the formation of an aligned network
with stable electrical connectivity between electrodes [1–3].
Alignment and precise control of CNT networks are highly
of high performance devices such as bio-, chemical and
piezoresistive sensors, field-effect transistors, AFM tips, force
transducers and nano-electromechanical switches, among
many others [3–5]. Although both direct current (DC) [6,7]
and alternating current (AC) [2,3,6,8,9] electric fields are able
to induce CNT alignment, AC fields have proven to be more
efficient to that aim. Theoretical [7,10–12] and experimental
[7,8,10,13–18] studies on CNT alignment and manipulation
by electric fields have been reported by several authors. When
an electric field is applied to a viscous medium containing
dispersed CNTs, an effective dipole is induced on the CNTs

* Corresponding author: Fax: +52 9999 812923.

E-mail address: andresivan19@hotmail.com (A.I. Oliva-Avilés).
0008-6223/$ - see front matter  2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.12.035
 CARBON 6 9 (2 0 1 4) 3 4 2–35 4
as a result of the different electrical properties between the
CNTs and their surrounding medium. The interaction be-
tween the dipoles induced on the CNTs and the applied elec-
tric field results in rotational and translational CNT motion
through a mechanism called dielectrophoresis (DEP) [19–21].
Although a complete understanding of the dynamics of CNT
networks formation under electric fields is still unclear, it is
generally accepted that the main governing mechanisms
are: (i) CNT rotation and alignment along the electric field
direction, (ii) CNT-to-CNT Coulombic interactions, and (iii)
CNT migration towards an electrode. When a dipole is in-
duced on a CNT, a torque will tend to orient the CNT along
the field direction [6,7,12–14,23]. Due to the induced dipoles,
contiguous CNTs will be mutually attracted promoting a
head-to-head contact and the formation of aligned structures
[7,9,11,21,24]. Furthermore, when a CNT reaches an electrode,
a remarkable change of the electric field distribution occurs at
the vicinity of the CNT apex, inducing a dielectrophoretic
force which tends to attract neighboring CNTs [1,9,11,14,23].
However, the sequence of these events and the time scale at
which they occur are yet unclear. Chen et al. [14] reported
on a controllable interconnection of singlewall carbon nano-
tubes (SWCNTs) under AC electric fields between microelec-
trodes, concluding that the DEP force and the electric field
redistribution at the CNT apex are responsible for the inter-
connection phenomenon. Farajian et al. [22] theoretically
investigated the polarization and aggregation of CNTs in sus-
pensions under electric fields based on two levels of organiza-
tion, viz. CNT alignment and CNT-to-CNT contact (chaining).
They modeled the CNTs as solid rods with hemispherical
ends and used an exact numerical approach based on self-
consistent Coulombic interactions with classical electrostat-
ics. Recently, Monti et al. [7] investigated the alignment of
SWCNTs by a DC electric field by considering three involved
phenomena, SWCNT rotation, translation and migration to-
wards the positive electrode. They proposed simplified differ-
ential equations for each mechanism and provided rough
estimates of the time required by each studied mechanism.
Other experimental reports have concluded that better CNT
alignment, dispersion and control can be achieved by increas-
ing the electric field frequency [2,8,16,23,25–28]. In a recent
experimental investigation, Oliva-Avilés et al. [13] reported
on the dynamic formation of a network of electric field-
aligned multiwall carbon nanotubes (MWCNTs) in liquids of
different viscosity, showing that AC frequencies at and above
the kHz range yield faster formation of aligned networks than
lower frequencies. These authors also observed that the mor-
phology of the final MWCNT network presents an important
dependence on the electric field frequency. Thus, among
other factors involved, the electric field frequency is expected
to play a key role on the different mechanisms involved on
the CNT behavior under the application of an AC electric field.
However, the dependence of the individual mechanisms gov-
erning the CNT network formation on the frequency remains
unclear, and the correlation with experiments is often contra-
dictory. Understanding the sequence of events and the role of
the electric field frequency, CNT’s concentration and aspect
ratio in the different phenomena occurring in a viscous
medium containing CNTs would represent an important step
towards tailoring such a CNT network.
343
Given this motivation, a modeling scheme consisting in a
set of three DEP-based nonlinear differential equations corre-
sponding to the major accepted mechanisms taking place in
the dynamics of the CNT network formation by the applica-
tion of an AC electric field is proposed herein. A layer at the
CNT/liquid interface is included in the DEP models and inves-
tigated in terms of its electrical conductivity, permittivity and
thickness. Only by considering such an interface layer, the
experimentally observed effect of the AC frequency on the
CNT network formation is adequately captured. Finally, a
description of the sequence of dynamic events occurring dur-
ing the formation of the CNT aligned network is proposed.
2. Modeling
A dielectrophoretic approach using electrodynamics is devel-
oped here to describe the dynamic motion of CNTs dispersed
in a liquid under the application of an AC electric field. The
set of governing equations corresponding to CNT rotation,
CNT-to-CNT Coulombic interactions and CNT migration to-
wards an electrode are presented in the following sections.
2.1. Model description
Fig. 1 shows a schematic of the three dynamic mechanisms
investigated herein, viz. CNT rotation (Fig. 1a), CNT-to-CNT
Coulombic interaction (Fig. 1b) and CNT migration towards
an electrode (Fig. 1c). Fig. 1a illustrates the mechanism of
CNT rotation towards the direction of the applied electric field
(E). The different electrical properties of the CNT and sur-
rounding medium induce an electric dipole on the CNT which
interacts with the electric field. As a result, a DEP torque is ex-
erted on the CNT which causes rotation along the field direc-
tion [6,7,12–14,22]. A schematic of the proposed CNT-to-CNT
Coulombic interaction mechanism is shown in Fig. 1b. Cou-
lombic interactions between (induced) opposite charges at
the ends of two contiguous CNTs cause mutual attraction, a
linking mechanism commonly known as ‘‘chaining’’
[7,9,11,21,24]. Finally, Fig. 1c illustrates the mechanism of
CNT migration towards an electrode. A pre-assumed condi-
tion for this scenario is that a CNT is attached to an electrode,
which can be envisioned as an extension of the electrode.
Thus, a substantial gradient on the (otherwise homogeneous)
electric field is generated at the vicinity of the CNT apex,
which tends to attract contiguous CNTs through a field gradi-
ent-dependent dielectrophoretic force [1,9,11,14,23]. The par-
allel electrodes configuration depicted in Fig. 1c aims to
simulate a simplified two-dimensional version of the cell uti-
lized for the electric field application in a previous experimen-
tal work of our research group [13].
Several types of forces can be present in a particle/liquid
system under electric fields, such as dielectrophoretic, gravi-
tational, Brownian, van der Waals, etc. For particles with
dimensions in the order of microns, it is generally accepted
that DEP forces dominate over the gravitational and Brownian
forces [21,27], at least during the time interval when the elec-
tric field is applied. Therefore, since the phenomenon of pos-
sible particle re-agglomeration after eliminating the electric
field is not included in this model, gravitational and Brownian
forces are not considered herein. Also, the fluid surrounding
344 CARBON 6 9 ( 2 0 1 4 ) 3 4 2 –3 5 4

Fig. 1 – Schematics of the three proposed mechanisms involved in the CNT network formation under application of an AC
electric field (E). (a) CNT rotation along the electric field direction, (b) CNT-to-CNT Coulombic interaction between contiguous
CNTs, and (c) CNT migration towards an electrode.

the CNTs is assumed to be of dielectric character and with a
low or negligible concentration of ions (such as deionized
water), so fluid flow-induced mechanisms such as electro-
osmosis and/or electro-thermal effects are deemed negligible
[21]. It has been found that in the case of DEP manipulation of
CNTs in low conductivity liquids, AC electro-osmotic flow,
buoyancy, and electro-thermal effects can also be neglected
[23,27,28]. On the other hand, for all three mechanisms inves-
tigated herein, the viscosity of the medium plays an impor-
tant damping role in the CNT motion, which opposes to the
DEP-induced force/torque. Thus, DEP and damping forces
and torques are the major effects considered in the proposed
models. It is important to point out here that neighboring
CNTs could experience both mutual interaction and attrac-
tion towards CNTs attached to an electrode even if they are
not aligned along the electric field direction. However, in or-
der to simplify the mathematical formulation keeping the
governing equations one-dimensional, the initial conditions
describing CNT-to-CNT Coulombic interaction and CNT
migration towards an electrode assume that the CNTs are
aligned along the field direction, or in other words, only the
x-component of the forces is considered. Such an assumption
seems to be reasonable as the main contribution to the trans-
lational CNT dynamics is expected to be given by the force
component corresponding to the electric field direction
(x-direction in Fig. 1).
Fig. 2 shows a schematic of the CNT/liquid dielectropho-
retic model. An individual CNT with a complex permittivity
eCNT is modeled as a rigid prollate ellipsoid immersed in a vis-
cous medium of complex permittivity em. An interface layer of
uniform thickness d and complex permittivity elay is included
in the model. This layer arises from the markedly dissimilar
electrical properties of the CNT and surrounding fluid and is
assumed to be composed mainly of surface charges at the
interface. Although the suspending medium considered in
this work is not an electrolyte but has very limited free ions,
the presence of bound ions (Stern layer) and/or a diffuse
double layer is not fully discarded. Regardless of the physical
nature of the interface layer, such a complex combination of
phenomena renders its own and distinctive electrical proper-
ties [21], as it will be further discussed. For dielectric materials
subjected to AC electric fields, the complex permittivity (e*) is
expressed by [20],
r
e ¼ e  j ð1Þ
2pf
where e is the electrical permittivity, r the electrical conduc-
tivity, f the frequency of the AC electric field and j2 = 1.
2.1.1. CNT rotation
In order to investigate the CNT rotational dynamics, a CNT
immersed in a viscous medium under the application of an
electric field is modeled, Fig. 1a. The CNT is considered as a
prollate ellipsoid with major and minor semi-axes of lengths
a and b, respectively, with the major axis forming an angle h
with the electric field direction. Hence, the CNT is considered
aligned along the field direction when h = 0. As initial condi-
tions, h and dh/dt at t = 0 were taken as h(t = 0) = 89 and dh/
dt(t = 0) = 0, with t as the elapsed time. The governing equa-
tion for the rotational motion of a CNT immersed in a viscous
medium under the application of an electric field is given by a
second-order nonlinear damped differential equation of h as a
function of time [7,13],
d h
2
dh 1
I þ 8pgr3e Kr þ Vem E2 Re½a  sin 2h ¼ 0 ð2Þ
dt2 dt 4
where,
m 2 2
I¼ ða þ b Þ ð3aÞ
5

4p2 ð1  p4 Þ
Kr ¼ h 2=3 2 Þ
i ð3bÞ
3 2p ð2p
Kt
2

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1  p2
Kt ¼  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  ð3cÞ
p2=3 ln pð1 þ 1  p2 Þ

ðe  e Þ2
a ¼ h  eq m i ð3dÞ
Fig. 2 – Schematic of the CNT/liquid system with an em þ eeq  em L ðeeq þ em Þ
interface layer of uniform thickness d.
 CARBON 6 9 (2 0 1 4) 3 4 2–35 4 345

2  3 2
eCNT þ 2a d
eCNT  elay d x dx em V2 E2 jb j2
m þ 6pgre K t þ ¼0 ð7Þ
eeq ¼ elay 4  5 ð3eÞ dt2 dt 16pa2 x2
elay þ 2a
d
eCNT  elay where the second and third terms on the left hand side are
the damping and Coulombic forces, respectively. Initial condi-
The coefficient I in Eq. (3a) is the CNT’s moment of inertia
tions for x and dx/dt in Eq. (7) were taken as x(t = 0) = x0 and
about an axis perpendicular to the CNT’s major axis, where m
dx/dt(t = 0) = 0 with CNT-to-CNT contact considered when
is the CNT’s mass. The second term in Eq. (2) represents the
x = 0. The initial separation distance (x0) depends on the
damping torque, with g being the viscosity of the surrounding
CNT dimensions and the weight fraction of CNTs in the liquid
medium and re the equivalent radius of a sphere of volume
(/CNT). To estimate x0, a representative volume element (RVE)
equal to that of the CNT (re = a1/3b2/3) [29–31]. Kr and Kt are,
needs to be assumed. To this aim, the CNTs were considered
respectively, the rotational and translational friction coeffi-
uniformly distributed in the total volume of the CNT/liquid
cients for prollate ellipsoids, where p = a/b is the CNT’s aspect
system and dispersed as individually aligned CNTs. The RVE
ratio [29–31]. The third term of Eq. (2) is the DEP-induced
was considered here as a rectangular prism of volume l2h,
aligning torque, where V is the CNT’s volume (V = 4pab2/3),
where l and h are the length and side-length of the square
em is the permittivity of the surrounding medium, E is the
prism, respectively, with a CNT located at the center, see
electric field magnitude and a* is the complex DEP polariza-
Appendix A. It is further assumed that the side-length is
tion factor for ellipsoidal particles under rotation, with
equal to the CNT diameter (h = 2b). The volume of the RVE
L = [ln (2p)  1]/p2 as the CNT’s major axis depolarization fac-
can be expressed as m/(qm/CNT), where qm is the density of
tor. A detailed derivation of the DEP-induced torque can be
the surrounding medium. With these assumptions, the initial
found in [13,20]. The expression for a* in Eqs. (3d) and (3e) ac-
CNT-to-CNT separation x0 is estimated by,
counts for an interface layer through the parameter eeq, which sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
depends on the layer dielectric properties (elay and rlay) and 2pabqCNT
x0 ¼  2a ð8Þ
thickness (d) [20]. For the limiting case of d = 0 or elay ¼ eCNT 3/CNT qm
(i.e. no interface layer), eeq ¼ eCNT and a* reduces to the polari-
zation factor of a model without interface layer [13,20]. A detailed description of the RVE and the derivation of Eq. (8)
are included in Appendix A.

2.1.2. Carbon nanotube-to-carbon nanotube Coulombic

2.1.3. Carbon nanotube migration towards an electrode
interaction
When a CNT contacts an electrode it can be considered as its
As a result of the electric field-induced polarization of the
extension, causing a redistribution of the electric field at the
CNTs, they tend to mutually attract due to the opposite
CNT’s free end and creating a local field of high intensity
charges present at their ends, see Fig. 1b. In order to calculate
and gradient [14]. Such a field gradient induces a dielectroph-
the force between neighboring charges of two aligned CNTs,
oretic force (FDEP) on other polarized CNTs which tends to at-
an effective induced charge qeff theoretically located at each
tract them towards the electrode [19–21]. The expression for
CNT end is estimated from the dipole moment definition

the DEP force (FDEP) of an ellipsoidal particle of volume V is gi-
d ¼ 2aqeff , where d* is the complex expression of such an
ven by [20,21],
effective dipole [7]. From DEP theory, the induced dipole mo-  
ment expression for a prollate ellipsoid under translational FDEP ¼ em VRe½b r jEj2
~ ð9Þ
motion is expressed in terms of the ellipsoid volume V, the
electric field magnitude E, the medium permittivity em and It is important to note that the expression for FDEP in Eq. (9)
the complex polarization factor b* as [20,21], depends on the real part of b*, while FCNT–CNT in Eq. (6) is pro-
 portional to |b*|2. By using Newton’s second law, the governing
d ¼ em VEb ð4aÞ
equation of motion for the CNT migration along the x-direc-
eeq  em tion towards an electrode (see Fig. 1c) is given by,
b ¼   ð4bÞ
2
em þ eeq  em L d x dx 4 2
m þ 6pgre Kt þ pab em Re½b ðrjE2 jÞx ¼ 0 ð10Þ
dt2 dt 3
Thus, the effective induced charge qeff at each CNT end can
The second and third terms on the left hand side of Eq. (10)
be expressed as,
are the damping and DEP-induced forces, respectively. It is
em VEb considered that both CNTs are initially at rest and separated
qeff ¼ ð5Þ
2a a distance of x0, given by Eq. (8) (see Fig. 1c). Due to the com-
The resulting expression for the Coulombic force (FCNT– plexity of the electrostatic problem, the distribution of the x-
CNT) between the induced charges of two neighboring CNTs is, component of the gradient of the squared electric field was
 2
numerically computed by finite element analysis and the de-
1 ðqeff Þ em V2 E2  2 tails can be found at Section S1 of the Supplementary mate-
FCNT–CNT ¼ 2
¼ jb j ð6Þ
4pem x 16pa2 x2
rial. Eqs. (2), (7), and (10) were numerically solved in
where x is the distance between two opposite-charged ends of MATLAB 7.12 using a Runge–Kutta algorithm.
two neighboring CNTs, as depicted in Fig. 1b.
By using Newton’s second law, the governing equation of 2.2. Material properties
the CNT translational motion along the x-direction towards
a contiguous CNT, both immersed in a viscous medium is gi- Specific medium and CNT electrical properties were chosen in
ven by, order to limit the number of parameters to be numerically
346 CARBON 6 9 ( 2 0 1 4 ) 3 4 2 –3 5 4

investigated. Deionized water (DIW) was chosen as the sur-
rounding medium due to the availability of specific experi-
mental data on a MWCNT/DIW system [13]. The electrical
permittivity and conductivity for the CNT and DIW were set
as eCNT = 1 · 105 e0 [32], rCNT = 1 · 103 S/m [33], em = 80 e0 and
rm = 5.5 · 106 S/m [34], with e0 = 8.854 · 1012 F/m being the
free space permittivity. The CNT’s minor semi-axis was se-
lected as b = 5 nm, simulating MWCNTs used in a previous
experimental research [13]. The major semi-axis (a) was kept
as a free parameter in order to examine the influence of the
CNT’s aspect ratio. The electric field magnitude was fixed at
E = 3.33 kV/m (as in [13]) and the DIW viscosity was taken as
g = 0.001 Pa s [35].
3. Results
3.1. Determination of the interface layer parameters and
effect of frequency
The effect of the electric field frequency on the dynamics of
the three investigated mechanisms is captured by the com-
plex permittivity term, Eq. (1). The DEP terms describing the
mechanisms of CNT rotation, CNT-to-CNT Coulombic interac-
tion and CNT migration towards an electrode are proportional
to Re[a*], |b*|2 and Re[b*], respectively, see Eqs. (2), (6), and (9). It
was noted that the trends associated to variations in the
interface layer properties observed for Re[a*], |b*|2 and Re[b*]
as function of the electric field frequency are similar, and as
such, only the results for Re[a*] are presented here.
The results of Re[a*] vs. f for different properties of the
interface layer are presented in Fig. 3. Fig. 3a demonstrates
the behavior of Re[a*] for elay = 1 · 101 eCNT and rlay = 1 · 104
S/m (both values between those of the CNT and DIW) and dif-
ferent values of the interface layer thickness (d), which are ex-
pressed in terms of the CNT diameter (dCNT = 2b = 10 nm).
Except for d = 0, Re[a*] increases with increased frequency up
to a constant value. The value corresponding to such a con-
stant frequency is slightly shifted towards higher frequencies
as d increases. For the limiting case of d = 0 (no interface
layer), a constant value of Re[a*] = 2326 is observed for all
the frequency range examined, which according to Eq. (2)
would mean that the CNT rotational motion is frequency-
independent. However, such a behavior contradicts several
experimental observations, where it is shown that the electric
field frequency plays a key role on the alignment of CNTs,
with higher frequencies providing faster dynamics
[2,13,16,23,25,26]. On the other hand, all models that include
a finite interface layer reproduce the experimental trends
regarding the effect of frequency. Thus, the inclusion of an
interface layer in the model is necessary to capture such a fre-
quency effect. Fig. 3b presents the effect of varying the per-
mittivity of the interface layer. As can be observed, below
100 Hz Re[a*] is nearly constant (1000) regardless of the va-
lue of the interface layer permittivity. At low frequencies, the
DEP induced polarization in the CNTs (and therefore the mag-
nitude of Re[a*]) is governed by the electrical conductivity be-
cause the free charges at the CNT/liquid interface are still able
to follow the field direction [18–21]. This yields a constant
Re[a*] for f < 100 Hz since all the electrical conductivities were
fixed in Fig. 3b. Regardless of the value of elay, all curves pres-
ent two zones of nearly constant Re[a*], separated by a transi-
tion zone. For elay = 1 · 101 eCNT, the transition zone occurs
around 100–1000 Hz, increasing towards higher Re[a*] for
higher frequencies. For elay = 1 · 102 eCNT and elay = 1 · 103

(a) 2500
δ=0 (b) 2500
δ = dCNT -1
-4
εlay = 1 x 10 εCNT
2000 δ = 0.1 dCNT 2000 σlay = 1x10 S/m
Re[α*]

1500 -1 1500
εlay = 1 x 10 εCNT
Re[α*]

δ = dCNT -4
-2
εlay = 1 x 10 εCNT
1000 σlay = 1 x 10 S/m 1000

500 500
δ = 10 dCNT -3
εlay = 1 x 10 εCNT
0 0 1 2 3 4 5
0 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10 10 10
f (Hz) f (Hz)

(c) 2500
-7
σlay = 1 x 10 S/m
2000

-4
1500 σ = 1 x 10 S/m
Re[α*]

lay
-1
1000 σlay = 1 x 10 S/m

500 δ = dCNT
-1
εlay = 1 x 10 εCNT
0 0 1 2 3 4 5
10 10 10 10 10 10
f (Hz)

Fig. 3 – Re[a*] vs. f for various interface layer parameters for a CNT/DIW system. (a) Interface thickness variation, (b) dielectric
constant variation, and (c) electrical conductivity variation. (A colour version of this figure can be viewed online.)
 CARBON 6 9 (2 0 1 4) 3 4 2–35 4 347

eCNT, however, the transition zone is shifted towards higher 5

10
frequencies and towards lower values of Re[a*]. p = 1000
The effect of the electrical conductivity of the interface 4
10
layer is observed in Fig. 3c. For the cases rlay = 1 · 101 S/m

and rlay = 1 · 104 S/m, Re[a*] shows an increasing behavior
as the frequency increases, up to a plateau with identical
numerical value (1900). Such an increasing behavior occurs
within a frequency range of 10–1000 Hz, and the change in
Re[a*] are more pronounced for the highest value of electrical
conductivity (rlay = 1 · 101 S/m). On the other hand, a con-
stant value of Re[a*] of 2326 is observed for the case
rlay = 1 · 107 S/m for almost all the frequency range investi-
gated, except for frequencies near 100 kHz where a slight de-
crease in Re[a*] is appreciated.
From these results, it is clear that the inclusion of an inter-
face layer in the model is required to capture the effect of fre-
quency observed in the experiments. Such an interface layer
may arise from the combined characteristics of the charge
double layer surrounding the particle, the bound charge (being
these more related to electrolytic solutions) and/or the parti-
cle’s surface conductivity, as it has been previously reported
for systems consisting of microparticles and colloids im-
mersed in aqueous media [21,36–41]. From Fig. 3a, Re[a*] (as
well as |b*|2 and Re[b*], not shown) presents a marked increase
on a transition zone ranging approximately from 100 Hz to
1 kHz for d > 0. This behavior of Re[a*] agrees with our previous
experimental findings reported in [13], which led us to select
an interface thickness of d = dCNT (10 nm) for further analysis.
Regarding the permittivity of the interface layer, higher values
of Re[a*] (i.e. higher DEP torque) for higher frequencies (see
Fig. 3c) also matches the trends of our previous experimental
observations. Accordingly, elay = 1 · 101 eCNT (=1 · 104 e0) was
chosen as the layer permittivity for further analysis, being this
selected value numerically between the permittivities of DIW
and CNT. Following a similar rationale, the conductivity of the
interface layer was selected as rlay = 104 S/m, which is also
between that of the CNT and DIW. All the calculations pre-
sented hereafter will use such interface physical properties.
3.2. Dynamics of the carbon nanotube network formation
3.2.1. Rotation
In order to capture the influence of the frequency and CNT’s
aspect ratio on the dynamics of CNT rotation, Fig. 4 shows
Re[α*]
3 p = 100
10
2
10
p = 10
1
10 0 1 2 3 4 5
10 10 10 10 10 10
f (Hz)
Fig. 4 – Re[a*] vs. frequency for a CNT/DIW system with
different CNT’s aspect ratios. (A colour version of this figure
can be viewed online.)
the behavior of Re[a*] vs. f for CNTs with different aspect ra-
tios. For all cases examined, the behavior of Re[a*] resembles
that of a step function with a gradual transition zone around
100–5000 Hz (set by the interface layer). The magnitude of
Re[a*] increases with increased CNT’s aspect ratio, which is
explained by the behavior of the depolarization factor
L = [ln (2p)  1]/p2 in Eq. (3d), which decreases as p increases.
Based on the results of Fig. 4, an increase of the DEP torque
is expected with increased CNT’s aspect ratio.
Eq. (2) was used to estimate the time required for rota-
tional alignment as shown in Fig. 5 for E = 3.33 kV/m and
h0 = 89. Fig. 5a shows a representative set of curves of the dy-
namic evolution of the rotation angle corresponding to differ-
ent electric field frequencies for a fixed CNT aspect ratio of
p = 1000. The limiting case where no interface layer is consid-
ered (d = 0) is plotted as a thicker solid line. The time required
for CNT alignment (chosen at h = 0.1) is predicted on the or-
der of seconds, and decreases with increased frequency. The
dependence of the time required for CNT alignment with
the frequency can be explained by the behavior of Re[a*] dis-
cussed earlier. From Fig. 4 (p = 1000), it can be observed that
Re[a*] (and thus the DEP torque) increases with increased
frequency up to a plateau near f = 10 kHz. Such a plateau
explains the nearly constant time of alignment above such
a frequency. The model without interface (d = 0) is fre-
quency-independent for the range of frequencies examined
(1 Hz–100 kHz) and yields the lowest time of alignment

100 (a) MWCNT/DIW 50 (b) MWCNT/DIW

E = 3.33 kV/m; θ0 = 89° E = 3.33 kV/m
Time for alignment (s)

80 p = 1000 40 θ0 = 89°

60 10 Hz 30
p = 10
θ (°)

100 Hz p = 100
40 1 kHz 20 p = 1000
10 kHz
20 100 kHz 10
δ=0
0 0 1 2 3 4 5
0 10 20 30 40 10 10 10 10 10
t (s) f (Hz)

Fig. 5 – Predictions from the CNT rotation equation, Eq. (2). (a) Dynamic evolution of CNT rotation for different frequencies at
p = 1000, and (b) time required for alignment vs. frequency for three CNT’s aspect ratios. (A colour version of this figure can be
viewed online.)
348 CARBON 6 9 ( 2 0 1 4 ) 3 4 2 –3 5 4

(4 s), which is again consistent with the highest and con-
stant value of Re[a*] value observed in Fig. 3a for d = 0. Using
this method, times of alignment were obtained for all the
three aspect ratios examined herein. Fig. 5b shows the behav-
ior of the time required for CNT alignment as a function of
frequency for aspect ratios of p = 10, 100 and 1000. Faster
alignment is found for lower CNT aspect ratios. This result
indicates that, although p is present in both the viscous and
DEP torques, its relative contribution to the viscous torque be-
comes more relevant as p increases. Higher CNT’s aspect ra-
tios yield higher rotational friction. Regardless of the CNT’s
aspect ratio, the time required for rotational alignment de-
creases as the frequency increases up to a constant value,
which is between 4 and 10 s for all cases investigated. It is also
worth noticing that the initial condition h(t = 0) = 89 repre-
sents an extreme case, and in reality the CNTs are initially
randomly distributed. The effect of the magnitude of the
electric field on the time required for CNT alignment is fairly
obvious from an examination of Eq. (2). From this equation it
is observed that an increase in the electric field magnitude af-
fects solely the DEP torque by increasing its magnitude in a
quadratic fashion (third term in Eq. (2)) and therefore reduc-
ing the time required for CNT alignment. Similar arguments
apply to the term related to the DEP force in the CNT-to-
CNT Coulombic interaction mechanism (third term in Eq. (7)).
10
10
p = 1000
10
8 all CNT’s aspect ratios, the time for CNT-to-CNT contact de-
2
3.2.2. Carbon nanotube-to-carbon nanotube Coulombic
interaction
The influence of frequency on the CNT-to-CNT Coulombic
interaction is captured by the Coulombic force (FCNT–CNT)
through |b*|2. Fig. 6 shows the |b*|2 vs. f plots for CNTs with dif-
ferent aspect ratios (p).
In a similar fashion to that observed for Re[a*] in Fig. 4, the
behavior of |b*|2 resembles that of a step function with a tran-
sition zone around 100–1000 Hz and its magnitude increases
with increased p, which is also explained by the behavior of
the depolarization factor L. Based on results of Fig. 6, an in-
crease of FCNT–CNT is expected with increased CNT’s aspect
ratio.
Eq. (7) was numerically solved and the results are shown in
Fig. 7. The initial CNT-to-CNT separation x0, which depends
on the CNT’s aspect ratio, was estimated from Eq. (8)
considering qCNT = 2.16 g/cm3 [32], qm = 0.986 g/cm3 [34] and
/CNT = 6.25 · 104 [13].
Fig. 7a shows a representative set of curves of the dynamic
evolution of the normalized CNT-to-CNT separation distance
(x/x0) corresponding to different electric field frequencies for a
fixed CNT aspect ratio of p = 1000. The time required to obtain
CNT-to-CNT contact (x = 0) is predicted on the order of sec-
onds and decreases with increased frequency. The frequency
dependence of the time required for CNT-to-CNT contact can
be understood in terms of the behavior of |b*|2 discussed
earlier. Fig. 7b shows the behavior of the time required for
CNT-to-CNT contact as a function of the frequency for the
CNT aspect ratios investigated. Regardless of the frequency,
shorter times are predicted for larger CNT aspect ratios. For
creases as the frequency increases up to a constant value,
which is lower for larger aspect ratios.

p = 100
|β*|

6
10

3.2.3. Carbon nanotube migration towards an electrode

4
10 Fig. 8 shows the results obtained by solving the governing
p = 10 equation for CNT migration towards an electrode, Eq. (10).
2
10 0 1 2 3 4 5 Fig. 8a shows a representative set of plots of the dynamic evo-
10 10 10 10 10 10
lution of the normalized CNT-to-electrode separation (x/x0)
f (Hz)
with time for p = 1000. The time required for CNT-to-electrode
Fig. 6 –|b*|2
vs. f for a CNT/DIW system with different CNT’s contact (x = 0) decreases with increased frequency. As for the
aspect ratios. (A colour version of this figure can be viewed rotation case, the dependence of the time required for
online.) CNT-to-electrode contact can be understood in terms of the
Time for CNT-CNT contact (s)

(b)
6

(a) 1.0 CNT/DIW; |E| = 3.33 kV/m

10
CNT/DIW
p = 1000 (x0 = 3.547 μm) 5
|E|=3.33 kV/m
10
0.8
4
10
0.6
10 Hz
x/x0

100 Hz 3
0.4 10
1 kHz p=10
10 kHz 2 p=100
0.2 100 kHz 10
p=1000
δ=0
0.0 1
10
0 100 200 300 400 1
10 10
2
10
3
10
4
10
5

t (s) f (Hz)

Fig. 7 – Predictions from the CNT-to-CNT Coulombic interaction equation, Eq. (7). (a) Dynamic evolution of the normalized
CNT-to-CNT separation distance (x/x0) for p = 1000, and (b) time required for CNT-to-CNT contact vs. frequency for three CNT’s
aspect ratios. (A colour version of this figure can be viewed online.)
 CARBON
(a) 1.0 CNT/DIW; |E| = 3.33 kV/m
p = 1000 (x0 = 3.547 μm)
0.8
0.6
10 Hz
x/x0
100 Hz
0.4
1 kHz
10 kHz
0.2 100 kHz
δ=0
0.0
0 20 40 60 80 100
t (s)
Fig. 8 – Predictions from the CNT migration equation, Eq. (10). (a) Evolution of the CNT-to-electrode distance for p = 1000, and
(b) time required for CNT-to-electrode contact vs. frequency for different CNT aspect ratios. (A colour version of this figure can
be viewed online.)
behavior of Re[b*] (not shown), which is very similar to that of
Re[a*]. As observed from Fig. 8b, the time required for CNT-to-
electrode contact follows a similar trend as that observed for
the other two mechanisms investigated, Figs. 5b and 7b.
From Eq. (10) it can be observed that the magnitude of the
DEP force (third term) depends on the gradient of the squared
electric field, which increases with increased electric field
magnitude. Thus, an increase in the electric field magnitude
(i.e. in the DEP force) will cause a reduction in the time re-
quired to achieve CNT-to-electrode contact.
3.3. Reconstruction of the sequence of events
Based on the previous examination of the mechanisms of
CNT rotation, CNT-to-CNT Coulombic interaction and CNT
migration towards an electrode, a sequence of the dynamic
events participating in the formation of an aligned CNT net-
work upon application of an AC electric field is proposed.
Such a sequence depends on the CNT’s aspect ratio, CNT con-
centration and electric field frequency, and the influence of
these major factors is examined. Fig. 9 shows the behavior
of these three mechanisms in terms of the electric field fre-
quency and CNT’s aspect ratio for a fixed value of CNT weight
fraction (/CNT = 6.25 · 104) and electric field magnitude
(E = 3.33 kV/m). The values of /CNT and E were chosen based
on a previous experimental investigation [13]. For short as-
pect ratios (p = 10, Fig. 9a) the model predicts that CNT align-
ment by rotation is by far the first event, followed by CNT-to
electrode contact and then CNT-to-CNT contact. For p = 100
(Fig. 9b), the same order in the sequence of events than that
for p = 10 is predicted, but the times required for CNT-to-elec-
trode contact and CNT-to-CNT contact are less apart. For
p = 1000 (Fig. 9c), the sequence of events depends on the
frequency. For f = 10 Hz and f = 100 Hz, CNT rotation occurs
first followed by CNT-to-electrode contact and CNT-to-CNT
contact. However, for frequencies of 1 kHz and above, the
sequence between CNT-to-CNT contact and CNT-to-electrode
contact is interchanged, with CNT rotation still occurring first.
For frequencies of above 1 kHz, all three events are predicted
to occur before t = 25 s. By comparing Fig. 9a–c it can be seen
that the time required for CNT rotation depends on the CNT’s
aspect ratio, but not strongly. However, the time required for
6 9 (2 0 1 4) 3 4 2–35 4 349
Time for CNT-to-electrode contact (s)
5
(b) 10
CNT/DIW
|E| = 3.33 kV/m
4
10
3
10
p=10
p=100
2
10 p=1000
1
10
120 1
10 10
2
10
3
10
4
10
5
f (Hz)
CNT-to-CNT contact and CNT-to-electrode contact decreases
up to 3 orders of magnitude as the aspect ratio (and the fre-
quency) increases. Thus, CNTs with low aspect ratios will
tend to first align along the electric field direction and then
to contact each other and/or the electrodes (chaining). As
the CNT aspect ratio increases (p  1000), CNT translational
and rotational mechanisms will occur at similar time scales
and the coupling effects and dynamics of such mechanisms
can be quite complex.
In order to investigate the effect of the CNT weight fraction
(/CNT) on the sequence of the dynamic events, elapsed times
for the three investigated mechanisms were obtained as a
function of /CNT and the results are presented in Fig 10. x0 de-
pends on /CNT through Eq. (8) and the values of x0 corre-
sponding to p = 10, 100 and 1000 (assuming b = 5 nm) are
shown in Table A1 of Appendix A.
For p = 10 (Fig. 10a), CNT rotation is by far the fastest event
for all CNT concentrations investigated, followed by CNT-to-
electrode contact and CNT-to-CNT contact. The behavior of
the time required for CNT rotation is independent of /CNT,
while the time required for the two translational mechanisms
decreases as /CNT increases. Similar trends are observed for
p = 100, but in this case the CNT-to-CNT contact and CNT-
to-electrode mechanisms are less apart, see Fig. 10b. For
p = 1000, however, the sequence of events depends strongly
on /CNT. For /CNT below 5 · 104, CNT rotation occurs first
followed by CNT-to-electrode contact and then CNT-to-CNT
contact. As /CNT increases up to 7 · 104, CNT rotation is still
the first event to occur, but the predicted times for CNT-to-
CNT contact and CNT-to-electrode contact become very sim-
ilar. Finally, for /CNT > 7 · 104 both translational mechanisms
are predicted to occur first (almost simultaneously), followed
by CNT rotation. The sequence of the predicted dynamic
events for different CNT’s aspect ratio and weight fractions
are summarized in Table 1.
Based on the observed results, it can be concluded that the
electric field-guided dynamic formation of CNT networks
within viscous media has a strong dependence on the
characteristics of the CNT/medium system and the parame-
ters of the applied AC electric field. Such a dynamics impacts
the final morphology of the resulting CNT-based materials
and, consequently, their effective physical properties.
350 CARBON 6 9 ( 2 0 1 4 ) 3 4 2 –3 5 4

(a) (b) 10
6 5
10 -4 -4
CNT/DIW; 6.25 x 10 wt% CNT/DIW; 6.25 x 10 wt%
5
10 |E| = 3.33 kV/m; p = 10 4 |E| = 3.33 kV/m; p = 100
10

Elapsed time (s)

Elapsed time (s)

4
10 3
10
3
10
2 CNT rotation
2 CNT rotation 10
10 CNT-to-CNT
CNT-to-CNT CNT-to-electrode
1
1 CNT-to-electrode 10
10
0 0
10 1 2 3 4 5
10 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10
f (Hz) f (Hz)

(c) 400 CNT/DIW; 6.25 x 10 wt%

-4

|E| = 3.33 kV/m; p = 1000

Elapsed time (s)

300 CNT rotation

CNT-to-CNT
CNT-to-electrode
200

100

0
1 2 3 4 5
10 10 10 10 10
f (Hz)

Fig. 9 – Time required for CNT rotation, CNT-to-CNT contact and CNT-to-electrode contact as a function of frequency for
different CNT’s aspect ratios (p). (a) p = 10, (b) p = 100, and (c) p = 1000. (A colour version of this figure can be viewed online.)

(a) 6
CNT/DIW; p = 10 (b) 10 CNT/DIW; p = 100
10 |E| = 3.33 kV/m; f = 100 kHz |E| = 3.33 kV/m; f = 100 kHz
Elapsed time (s)
Elapsed time (s)

4
10
4
10

CNT rotation 2 CNT rotation

2 10
10 CNT-to-CNT CNT-to-CNT
CNT-to-electrode CNT-to-electrode

0 0
10 10
0 2 4 6 8 10 0 2 4 6 8 10
-4 -4
φCNT (10 ) φCNT (10 )

(c) 10
5

CNT/DIW; p = 1000
|E| = 3.33 kV/m; f = 100 kHz
Elapsed time (s)

CNT rotation
3
10 CNT-to-CNT
CNT-to-electrode

1
10

-1
10
0 2 4 6 8 10
-4
φCNT (10 )

Fig. 10 – Time required for CNT rotation, CNT-to-CNT contact, and CNT-to-electrode contact as a function of CNT weight
fraction (/CNT) for different CNT’s aspect ratios. (a) p = 10, (b) p = 100, and (c) p = 1000. (A colour version of this figure can be
viewed online.)
 CARBON 6 9 (2 0 1 4) 3 4 2–35 4
Table 1 – Predicted sequence of dynamic events for different CNT’s aspect ratio (p) and weight fraction (/CNT).The results are a
summary of Fig. 10.
p /CNT (104)
10 1–10
100 1–10
1000 1–5
1000 5–7
1000 7–10
4. Discussion
According to the models proposed here, the consideration of
an interface layer in a CNT/liquid system allows to capture
the trends observed in several experiments regarding the role
of the electric field frequency on the formation of CNT net-
works. The presence of an interface layer in a particle/liquid
system under the application of electric field has been pro-
posed by several authors [17,18,21,36–41]. Although the nat-
ure and composition of such a layer are quite complex and
different from that of the CNT and surrounding dielectric
medium, it is generally accepted that its electrical conductiv-
ity and permittivity should be a gradient of the large mis-
match between the electrical properties of the conducting
particles and the suspending dielectric medium [21,36,40].
In aqueous suspensions, the interface layer may include free
surface charges, bound ions (Stern layer) and/or a diffuse dou-
ble layer, among others [17,18,21,36,40,41]. All these effects
enhance the mobility of electrical charges, contributing to
the formation of a sizable surface conductivity [40,41].
According to Morgan and Green [21,36], for low conductive
solutions the Debye length (associated to the interface layer’s
thickness) is of the order of a few nanometers. The electrical
properties of the interface layer are expected to be highly sen-
sitive to the particle’s and suspending medium’s properties
such as electrical conductivity, pH and valence of the
solution, and the possible presence of reagents that can be
adsorbed on the particle surface, among others [40]. Although
the precise composition of the interface layer in the existent
experimental reports on CNTs suspending in liquids is still
unknown, it is clearly shown here that the presence and prop-
erties of such a layer are fundamental to determine the polar-
ization of CNTs in an electric field. The thickness (10 nm) and
electrical properties (in between those of the particle and sus-
pending medium) selected for modeling the interface layer in
this work are those that better fit the experimental trends
presented in [13] and such a selection yields results that are
in very reasonable agreement with several other experimen-
tal works and the aforementioned discussion.
An additional feature of the model predictions is the effect
of the frequency of the applied electric field. According to
Figs. 7–9, the results predict that increasing the electric field
magnitude and frequency yields a faster dynamics of the
mechanisms involved in the formation of CNT networks.
Sequential photographs of the dynamic evolution of a CNT
network suspended in a solution under electric fields of low
(10 Hz) and high (100 kHz) frequencies are shown in Section S2
of the Supplementary material. Hilding et al. [42] studied the
351
Sequence of events
CNT rotation ! CNT-electrode ! CNT–CNT
CNT rotation ! CNT-electrode ! CNT–CNT
CNT rotation ! CNT-electrode ! CNT–CNT
CNT rotation ! CNT-electrode  CNT–CNT
CNT-electrode  CNT–CNT ! CNT rotation
electric field-induced alignment of MWCNTs dispersed in
water with assistance of a non-ionic surfactant and reported
that the alignment rate increased with increased field
strength and increased frequency. Also, they observed that
MWCNT alignment was achieved for t < 1 s and MWCNT
translation an chaining was observed after few minutes for
electric field magnitudes and frequencies above 7 kV/m and
20 Hz. Kumar et al. [8] experimentally studied the influence
of AC electric fields on the assembly of SWCNTs, reporting
that individual SWCNTs align along the AC electric field direc-
tion and move towards the electrodes, being this process
more efficient with increased frequency. These authors also
reported that, for AC fields, CNT-to-CNT contact (chaining)
was mainly observed in isolated SWCNTs (far from the elec-
trode). In different experimental works, Wei et al. [15] and
Riahifar et al. [43] reported a transient AC frequency range be-
tween 100 Hz and 10 kHz for a MWCNT/DIW and ZnO nano-
rods/acetone solutions, respectively, which is very similar to
the frequency transient range predicted here (see Figs. 4 and
6). This is also consistent with our previous experimental
findings for MWCNT/DIW solutions [13]. Zhao et al. [44] exper-
imentally studied the alignment of SWCNTs dispersed within
DIW and reported that higher degree of alignment and assem-
bly is achieved with increased frequencies while higher volt-
ages increases the number of SWCNTs spanning the
electrodes. Chen et al. [14] experimentally observed that the
assembly of a SWCNT network formed between a pair of par-
allel electrodes separated by a gap of 5 lm under an electric
field occurred by a sequence of migration of SWCNTs to the
electrode, chaining and bridging, in that sequential order. A
similar sequence of assembly was observed by Yang et al.
[45], reporting that the MWCNT network formation within a
liquid polymer starts from the electrode, where MWCNTs
are first attached and then a chaining process is promoted
due to tip-to-tip interactions. On the other hand, Li et al.
[32] conducted simulations based on the DEP-induced torque
and force on CNTs for a CNT/isopropyl alcohol system and re-
ported that the time required for aligning CNTs in the direc-
tion of an AC electric field (rotation) is much smaller (in the
order of milliseconds) than the time required for CNT transla-
tion (tens of seconds). As noticed from the discussion above,
different trends regarding the sequence of events related to
the formation of CNT networks have been reported by several
authors, thus indicating that there is not a unique trend for
such a sequence but it rather depends on several physical fac-
tors, as reported herein.
From the experimental evidence and the literature survey
discussed in this section it is seen that the models presented
352 CARBON 6 9 ( 2 0 1 4 ) 3 4 2 –3 5 4
here are able to reproduce the observed experimental trends
regarding the formation of CNT networks. The models are
also able to highlight the role of the most relevant mecha-
nisms and parameters involved in the dielectrophoretic phe-
nomenon, and to propose a reasonable dynamic sequence of
events which is a convoluted effect of several physical param-
eters of the system under consideration.
5. Conclusions
The formation of an aligned CNT network in a viscous med-
ium under the application of an AC electric field was mod-
eled by a classic dielectrophoretic approach considering
three mechanisms: CNT rotation towards the electric field
direction, CNT-to-CNT Coulombic interaction and CNT
migration towards an electrode. A CNT/liquid system includ-
ing an interfacial layer of electrical conductivity and permit-
tivity intermediate between those of the CNT and liquid and
thickness equal to the CNT diameter (10 nm) was modeled.
The experimental trends regarding the effect of the field’s
frequency on the dynamic formation and alignment of the
CNT network can only be captured by the model by includ-
ing such an interfacial layer. Higher AC frequency promotes
a faster CNT network formation, yielding lower elapsed
times for CNT alignment, CNT-to-CNT contact and CNT-to-
electrode contact. According to the models, the sequence
of the dynamic events involved in the CNT alignment and
network formation is strongly dependent on the CNT’s as-
pect ratio and on the CNT’s weight fraction in the viscous
solution. For CNTs of relatively low aspect ratios (p < 100),
CNT rotation occurs before CNT attraction towards another
CNT or an electrode. However, as the CNT aspect ratio in-
creases all three phenomena occur at similar time scales.
The influence of the CNT concentration on the nominal
CNT-to-CNT separation distance also has a strong impact
on the CNT’s network dynamics. For low CNT weight concen-
trations (/CNT < 7 · 104), CNT rotation is the first event,
while for higher concentrations CNT-to-CNT contact and
CNT-to-electrode contact occur first and nearly simulta-
neously. Despite the simplicity of the proposed models and
their assumptions, the predicted times for CNT alignment
are in reasonable agreement with those experimentally
determined in the literature. The fact that the trends ob-
served in the experiments can only be reproduced by the
inclusion of an interface layer between the CNT and the li-
quid represents an important step towards understanding
the electric field-based manipulation of CNTs for technolog-
ical applications. Understanding the dynamic formation of
such CNT networks is expected to lead to more reliable mul-
tifunctional materials that can be tailored by electric fields.
Acknowledgments
This work was supported by CONACYT-CIAM project No.
188089 of Dr. Avilés. A.I.O. acknowledges CONACYT for his
PhD scholarship and the additional financial support for his
visiting position at Virginia Tech through the ‘‘Becas Mixtas’’
program. A.I.O. would also like to thank Adarsh Chaurasia
at Virginia Tech for many fruitful discussions.
Appendix A. Initial separation between two
contiguous CNTs
By assuming that the CNTs are homogeneously dispersed
within a surrounding medium (liquid), a representative vol-
ume element (RVE) of the CNT/liquid system can be consid-
ered as an individual CNT and its corresponding medium,
whose volume (VRVE) can be expressed as,
Vm þ NV
VRVE ¼ ðA1Þ
N
where Vm is the total volume of the liquid, V is the volume of
an individual CNT and N is the total number of CNTs.
N = MCNT/m, with MCNT as the total mass of the CNTs and m
the mass of an individual CNT. The value of m can be esti-
mated from m = VqCNT, with qCNT as the density of the CNT.
The CNT is considered as a prollate ellipsoid of volume
V = 4pab2/3, with a and b as the CNT’s major and minor
semi-axis, respectively. Vm in Eq. (A1) can be expressed in
terms of the density of the liquid (qm) and the mass of the to-
tal liquid (Mm) as Vm = Mm/qm. Thus, for a CNT/liquid system
with a CNT weight fraction /CNT = MCNT/(Mm + MCNT), VRVE in
Eq. (A1) can be written as,
 
qCNT 1  /CNT
VRVE ¼ V þ1 ðA2Þ
qm /CNT
For /CNT  1 (as for the investigated values in this work),
VRVE in Eq. (A2) can be simplified as,
VqCNT
VRVE ¼ ðA3Þ
/CNT qm
The RVE considered here is a rectangular prism of vol-
ume l2h, where l and h are the RVE’s length and side-length,
respectively, and the CNT is located at the center, see
Fig. A1a. Since a planar architecture is modeled, the value
of the through-thickness dimension (h) is assumed to be
equal to the CNT diameter (2b). Fig. A1b illustrates a sche-
matic of two adjacent RVEs with initial separation between
the CNT ends as x0.
The RVE’s length (l) can thus be obtained by equating the
RVE volume (l2h) to the right-hand side term of Eq. (A3) and
solving for l, i.e.,
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
VqCNT
l¼ ðA4Þ
h/CNT qm
According to Fig. A1b, the initial separation between two
contiguous CNTs is x0 = l  2a, which leads to Eq. (8).
Table A1 shows x0 (initial condition for Eqs. (7) and (10)) for
the investigated values of CNT’s aspect ratio (p = a/b) and
CNT’s weight fraction (/CNT) from 1 · 104 to 1 · 103. In
Table A1 x0 was calculated from Eq. (8) by setting b = 5 nm,
qCNT = 2.16 g/cm3 and qm = 0.986 g/cm3, while a and /CNT were
varied. According to the selected RVE, the maximum values of
/CNT (for the limiting case l = 2a) are estimated as /CNT = 1.15
· 103 and 1.15 · 101 for p = 10 and p = 1000, respectively. The
values of x0 listed in Table A1 were used to solve the corre-
sponding differential equations and to construct the curves
of elapsed time vs. /CNT presented in Fig. 10.
 CARBON 6 9 (2 0 1 4) 3 4 2–35 4 353

(a) (b)

Fig. A1 – Schematic of the RVE. (a) Three-dimensional sketch of the selected RVE, and (b) initial separation (x0) between the
ends of neighboring CNTs.

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