This article was downloaded by: [Universidad Autnoma del Estado de Mxico]

On: 23 September 2014, At: 13:28

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Journal of Dispersion Science and Technology
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/ldis20
Influence of Electric Field on Dispersion of Carbon
Nanotubes in Liquids
Zhu YueFeng
a
, Zhang Chan
a
, Wang JingDong
a
, Shi Lei
a
& Liang Ji
a
a
Key Laboratory for Advanced Manufacturing by Materials Processing Technology,
Department of Mechanical Engineering , Tsinghua University , Beijing, P.R. China
Published online: 06 Feb 2007.
To cite this article: Zhu YueFeng , Zhang Chan , Wang JingDong , Shi Lei & Liang Ji (2006) Influence of Electric
Field on Dispersion of Carbon Nanotubes in Liquids, Journal of Dispersion Science and Technology, 27:3, 371-375, DOI:
10.1080/01932690500359582
To link to this article: http://dx.doi.org/10.1080/01932690500359582
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the Content) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
Inuence of Electric Field on Dispersion of Carbon Nanotubes
in Liquids
Zhu Yue-Feng, Zhang Chan, Wang Jing-Dong, Shi Lei, and Liang Ji
Key Laboratory for Advanced Manufacturing by Materials Processing Technology, Department of Mechanical Engineering,
Tsinghua University, Beijing, P.R. China
Production processes for carbon nanotubes commonly produce mixtures of solid morphologies
that are mechanically entangled or that self-associate into aggregates. The entangled or
aggregated carbon nanotubes often need to be dispersed in corresponding material matrices
in order to develop materials that have unique mechanical characteristics or transport
properties. The most effective method for dispersion of carbon nanotubes is to prepare uid
suspensions of them in liquid media with applications of surfactant or/and ultrasonication.
The authors propose an innovative dispersion method for carbon nanotubes by which an
electric eld is applied to suspensions of carbon nanotubes in liquids treated by surfactant
and ultrasonication. Compared to dispersion without the electric eld, the dispersion status
of carbon nanotubes in liquid media is evidently improved with the electric eld. The results
indicate that the electric eld conditions are effective for dispersion of carbon nanotubes in
liquids and that complex effects of electric eld, surfactant, and ultrasonication are benecial
for improvement of dispersion of carbon nanotubes.
Keywords Carbon nanotubes, dispersion, electric eld, ultrasonication, surfactant
INTRODUCTION
Carbon nanotubes (CNTs) have an interesting set of proper-
ties that position them for a wide variety of potential appli-
cations in composites. Their unusual properties include high
moduli of elasticity and strength, high aspect ratios, excellent
thermal and electrical conductivities, and magnetic properties
(Yu et al., 2000; Salvetat et al., 1999; Xie et al., 2000; Wong
et al., 1997; Yao et al., 2001; Hone et al., 1999, 2000; Kim
et al., 2001; Berber et al., 2000; Kaneto et al., 1999).
However, a number of current synthesis methods, especially
the methods yielding CNTs in mass production, produce
CNTs that are physically entangled. It is difcult for the
entangled CNTs to be applied in manufacturing or modication
of current practical materials. Important challenges to develop-
ing applications for these unique materials include: (1) puri-
cation and separation of CNTs by chemistry and
morphology, (2) uniform and reproducible dispersion, and
(3) orientation of these solids in liquid and melt phases.
One objective of dispersion science and technology is to
produce a suspension of independent, separated CNTs in
liquid media that then can be manipulated into preferred
orientations in one-dimensional (ber), two-dimensional (at
sheet), or three-dimensional (bulk solid) objects. Up to now,
there have been two different approaches to CNT dispersion:
mechanical (or physical) methods and chemical methods.
Mechanical dispersion methods, such as ultrasonication
(Koshio et al., 2001), high impact mixing (Kim et al., 2002;
Pierard et al., 2001), and high shear mixing (Hilding et al.,
2003), separate CNTs from each other, but, meanwhile, can
also fragment the nanotubes, decreasing their aspect ratio
during the processing. Chemical methods use surfactants or
functionalization to change the surface energy of the nano-
tubes, improving their wetting or adhesion characteristics and
reducing their tendency to agglomerate in the continuous
phase solvent. However, aggressive chemical functionaliza-
tion, such as using neat acids at high temperatures, can also
digest the nanotubes. Both mechanical and chemical methods
can alter the aspect ratio distribution of the nanotubes and
result in changes in the properties of their dispersions.
Recently, electric elds have been applied for orientation,
array, ltration, and purication of CNTs. Du et al. (2002)
prepared CNT lms by means of electrophoretic deposition
(EPD) with an external direct current (DC) electric eld and
investigated primarily the electric properties of the lms. Bae
et al. (2002) studied the eld-emission property of the EPD
CNT lms and found that the higher the graphitization
degree, the lower the resistivity of the lms, and then the
lower the critical exciting electric eld intensity for the
Received 23 July 2005; Accepted 8 August 2005.
Address correspondence to Zhu Yue-Feng, Key Laboratory for
Advanced Manufacturing by Materials Processing Technology,
Department of Mechanical Engineering, Tsinghua University,
Beijing 100084, P.R. China. E-mail: yfzhu@tsinghua.edu.cn
Journal of Dispersion Science and Technology, 27:371375, 2006
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print /1532-2351 online
DOI: 10.1080/01932690500359582
371
D
o
w
n
l
o
a
d
e
d

b
y

[
U
n
i
v
e
r
s
i
d
a
d

A
u
t

n
o
m
a

d
e
l

E
s
t
a
d
o

d
e

M

x
i
c
o
]

a
t

1
3
:
2
8

2
3

S
e
p
t
e
m
b
e
r

2
0
1
4

electron emission taking place. This research successfully
realized directional transplantation of CNTs by means of
EPD processes. It should be mentioned that, in order to be
manipulated with EPD processes, it is necessary for CNTs to
be charged by proper functional treatments.
On the other hand, it is generally impossible to realize EPD
for CNTs without charges on their surfaces. Therefore, it is to
seek for other ways to manipulate CNTs. (Yamamoto et al.
1996, 1998) puried CNTs with and without charges in
liquid media by electrophoresis and dielectrophoresis, respect-
ively. Krupke et al. (2004) successfully separated the metallic
and semiconductive single-walled carbon nanotubes (SWNTs)
by the dielectrophoresis process with an alternating current
(AC) electric eld. The SWNTs were electrically dipolarized
under the electric eld and then arrayed under sufciently
high DC or AC voltage between the electrodes. Tang et al
(2005) controlled the lengths and exposures of CNTs in
liquid media and prepared atomic force microscopy probes
by dielectrophoresis under a 2 MHz AC electric eld.
The previously mentioned results demonstrated the effect of
electric elds on CNTs suspended in liquid media. Moreover,
an electric eld would not result in undesired digestion and
demolishing taking place during other mechanical or
chemical processes. In this study, DC electric eld together
with other treatments such as ultrasonication and surfactant
were applied to improve the dispersion of CNTs in liquid for
the potential application of CNTs in modication of practical
materials, and the dispersion mechanism of CNTs in liquids
under electric eld will be preliminarily analyzed.
EXPERIMENTAL SECTION
CNTs used in this study were prepared by the chemical vapor
deposition (CVD) method. Thereafter, the prepared CNTs were
treated with two different processes. One process is as follows:
the prepared CNTs were treated in HF for 24 hours to remove
catalyst particles and impurities, then the conglomerations of
the entangled CNTs were ball milled slightly, to obtain the
so-called original CNTs. The other process is as follows: 10 g
of the CNTs were added into 100 mL of a blend of dense
H
2
SO
4
and HNO
3
with a volume ratio 3 : 1 between H
2
SO
4
and HNO
3
, the blend was boiled for 30 min, rinsed continuously
to chemically neutralize with deionized water, and then dried to
obtain the so-called acid-treated CNTs.
Two kinds of suspensions of CNTs in liquid media were
prepared by adding 0.5 g of the original and acid-treated
CNTs, respectively, into 100 mL of deionized water and then
treating by ultrasonication for 30 min. Eight groups of suspen-
sion samples of the two kinds of CNTs in the liquid medium
were prepared from the suspensions as described in Table 1.
Here, specimens No. 14 were made from the suspension of
acid-treated CNTs in liquid, and specimens No. 58 were
made from the suspension of original CNTs in liquid.
Figure 1 shows the schematic drawing of CNT dispersion in
the suspension controlled by electric elds. The specimens
were taken from the suspensions with a pipette and dropped
onto a piece of ltering paper for observation.
The dispersion of CNTs in different specimens described in
Table 1 was observed by means of scanning electronic
microscopy (SEM).
RESULTS AND DISCUSSION
The dispersion of acid-treated CNTs in liquid media was
observed with SEM as shown in Figure 2. It is seen that
CNTs disperse well with few conglomerations in the suspen-
sion under DC electric eld for four hours (see Figure 2(a))
and under complex effect of both a 25 V DC electric eld
and ultrasonication for 30 min (see Figure 2(c)), and there
exist a number of conglomerations of CNTs in the suspension
without DC electric eld (see Figure 2(b), (d)).
In order to demonstrate the transplantation of CNTs in
liquids under an electric eld, an electrophoresis experiment
was carried out with the acid-treated CNTs in deionized
water under DC electric eld. During the electrophoresis
process, the CNTs transplanted to and deposited on the
anode and formed a layer of lm. This is in agreement with
FIG. 1. Schematic drawing of CNT dispersion in the suspension
controlled by electric elds.
TABLE 1
Preparation conditions of the suspension specimens
No. Preparation conditions
1 Acid-treated CNTs, 25 V DC electric eld for
4 hours
2 Acid-treated CNTs, placed statically for 4 hours
3 Acid-treated CNTs, 25 V DC electric eld and
ultrasonication for 0.5 hour
4 Acid-treated CNTs, ultrasonication for 0.5 hour
5 Original CNTs, 25 V DC electric eld for 4 hours
6 Original CNTs, placed statically for 4 hours
7 Original CNTs, 25 V DC electric eld and
ultrasonication for 0.5 hour
8 Original CNTs, ultrasonication for 0.5 hour
ZHU YUE-FENG ET AL. 372
D
o
w
n
l
o
a
d
e
d

b
y

[
U
n
i
v
e
r
s
i
d
a
d

A
u
t

n
o
m
a

d
e
l

E
s
t
a
d
o

d
e

M

x
i
c
o
]

a
t

1
3
:
2
8

2
3

S
e
p
t
e
m
b
e
r

2
0
1
4

the previous results of other researchers (Sun et al., 2002;
Esumi et al., 1996; Thomas et al., 2005) who reported that
the zeta potential of acid-treated CNTs was negative in
neutral solution. Figure 3(a), (b) show the CNT lms formed
on the surface of the anodes during electrophoresis carried
out by the authors and others. It indicates that surfaces of
the acid-treated CNTs were charged negatively in deionized
water.
Based on infrared ray spectrum analysis results (Jia et al.,
1999; Shaffer et al., 1998; Li et al., 2002), some functional
FIG. 2. Dispersion morphology of the acid-treated CNTs in liquid media under different conditions (SEM); note that the background is the bers of the
ltering paper.
FIG. 3. CNT lms deposited on the electric pole during the electrophoresis process (a) prepared by the authors; (b) prepared by Thomas et al. (2005).
INFLUENCE OF ELECTRIC FIELD ON DISPERSION OF CARBON NANOTUBES IN LIQUIDS 373
D
o
w
n
l
o
a
d
e
d

b
y

[
U
n
i
v
e
r
s
i
d
a
d

A
u
t

n
o
m
a

d
e
l

E
s
t
a
d
o

d
e

M

x
i
c
o
]

a
t

1
3
:
2
8

2
3

S
e
p
t
e
m
b
e
r

2
0
1
4

groups such as hydroxyl (OH), carboxyl (COOH), and car-
bonyl (.C55O) were loaded on surfaces of the acid-treated
CNTs. In the infrared absorption spectrum (Li et al., 2002),
there evidently existed peaks of carbonyl and hydroxyl func-
tional groups corresponding to wave lengths 1750 cm
21
and
3500 cm
21
, respectively. After a saponication reaction
boiling a blend of acid-treated CNTs and NaOH, the existence
of carboxyl functional group was also proved by a translation
of the carbonyl peak in the infrared spectrum (Jia, 1999).
Hydrogen ions were produced by ionization from the
carboxyl bonded on surfaces of the acid-treated CNTs, which
made them negatively charged. The charged CNTs in the sus-
pension were affected by the external DC electric eld and
other charged particles in the liquid beside the body forces
such as gravity and buoyancy. Their translation velocities
were different due to the different numbers of the charges on
individual CNTs and masses. So the entangled CNTs might
be detached. Therefore, the effect of DC electric eld on sus-
pensions of acid-treated CNTs in liquids could efciently
improve the dispersion of CNTs in liquids.
Specimen No. 3 was prepared under the complex effect
of both a 25 V DC electric eld and ultrasonication for
30 min. By comparison between Figure 2(a) and Figure 2(c),
it is found that, accompanied by ultrasonication, the effect of
DC electric eld for only 0.5 hour on the dispersion of acid-
treated CNTs in liquids was approximately similar to that
without sonication for 4 hours. In order to prove that the ne
dispersion effect of CNTs in specimen No. 3 was mainly attrib-
uted to the external electric eld, No. 4 specimen was prepared
under ultrasonication without electric eld. Comparing
Figure 2(d) with Figure 2(c), it is seen that the dispersion of
CNTs in liquids under effects of both external electric eld
and ultrasonication (see Figure 2(c)) is much better than that
with only ultrasonication (see Figure 2(d)). Therefore, it can
be concluded that the complex effect of both the external
electric eld and ultrasonication might be an efcient method
to disperse acid-treated CNTs in liquid media.
Dispersion status of the original CNTs in liquids shown in
Figure 4. By comparing Figure 4(a) with Figure 4(b), it is
found that the dispersion of the original CNTs in liquids
FIG. 4. Dispersion morphology of the original CNTs in liquid media under different conditions (SEM); note that the background is the bers of the ltering
paper.
ZHU YUE-FENG ET AL. 374
D
o
w
n
l
o
a
d
e
d

b
y

[
U
n
i
v
e
r
s
i
d
a
d

A
u
t

n
o
m
a

d
e
l

E
s
t
a
d
o

d
e

M

x
i
c
o
]

a
t

1
3
:
2
8

2
3

S
e
p
t
e
m
b
e
r

2
0
1
4

under a 25 V DC electric eld for four hours is not impro-
ved, and evident conglomerations still exist in specimen
No. 5. An electrophoresis experiment was carried out with
the original CNTs in deionized water, and it was found
that there was a layer of CNT lm deposited on neither the
anode nor the cathode during the electrophoresis process.
The electrophoresis results indicated no charge on surfaces
of the original CNTs in deionized water. In a static electric
eld, there is no surplus electric charge inside the
entangled CNT conglomerations as conductors in balance in
charge. All of the induced charges distribute on the external
surfaces of the conductor conglomerations. It is difcult for
an external electric eld to act on the individual nanotubes in
CNT conglomerations. Therefore, the effect of the external
static electric eld on the suspension could have little
improvement on the dispersion of the original CNTs in
water.
Because the external static electric eld demonstrates
little effect on the entangled original CNTs without surplus
electric charges, the complex effects of the static electric
eld and ultrasonication could not be brought into play as
they are on the acid-treated CNTs but demonstrate only the
effect of simple ultrasonication. Seriously entangled CNT
conglomerations exist in Figure 4(c), (d), which agrees, with
that described above.
CONCLUSIONS
The suspensions of CNTs in deionized water were prepared
with different CNTs, that is, the original and acid-treated
CNTs, respectively. An external DC electric eld was
exerted on the suspensions to improve the dispersion of
CNTs in liquids. The results indicated that the electric eld
noticeably improved the dispersion of the acid-treated CNTs
in deionized water. Moreover, the companion effect of an
electric eld with ultrasonication was effective in improving
the dispersion of acid-treated CNTs in liquids. The improve-
ment of dispersion of acid-treated CNTs resulted from the
functional groups loaded on the surfaces of the CNTs
after being treated with acids. On the other hand, the electric
eld improved little the dispersion of the original CNTs in
deionized water, so did as electric eld companied by the
ultrasonication because of no charge on surfaces of the
original CNTs.
ACKNOWLEDGMENTS
The project was sponsored by the Foundation of National
Natural Science, China (Grant No.10332020) and the Inno-
vation Fund for Outstanding Scholar of Henan Province,
China.
REFERENCES
Bae, J.C. and Yoon, Y.J., and Lee, S.-J., et al. (2002) Physica B, 323:
16870.
Berber, S., Kwon, Y.K., and Tomanek, D. (2000) Phys. Rev. Lett.,
84 (20): 461316.
Du, C., Heldbrant, D., and Pan, N. (2002) Mater. Lett., 57: 43438.
Esumi, K., Ishigami, M., Nakajima, A., Sawada, K., and Honda, H.
(1996) Carbon, 34: 27981.
Hilding, J., Grulke, E. A., Zhang, Z.G., and Lockwood, F. (2003)
J. Dispers. Sci. Technol., 24 (1): 141.
Hone, J., Whitney, M., Piskoti, C., and Zettl, A. (1999) Phys. Rev. B,
59 (4): R2514R2516.
Hone, J., Llaguno, M.C., Nemes, N.M., Johnson, A.T., Fischer, J.E.,
Walters, D.A., Casavant, M.J., Schmidt, J., and Smalley, R.E.
(2000) Appl. Phys. Lett., 77 (5): 66668.
Jia, Z.J. A study on CNTs/polymer composites. (1999) Ph. D. diss.
Tsinghua University: Beijing.
Jia, Z., Wang, Z., Liang, J., Wei, B., and Wu, D. (1999) Carbon, 37:
90306.
Kaneto, K., Tsuruta, M., Sakai, G., Cho, W.Y., and Ando, Y. (1999)
Synth. Met., 103 (13): 254346.
Kim, P., Shi, L., Majumdar, A., and McEuen, P.L. (2001) Phys. Rev.
Lett., 87 (21): 215502/1215502/4.
Kim, Y.A., Hayashi, T., Fukai, Y., Endo, M., Yanagisawa, T., and
Dresselhaus, M.S. (2002) Chem. Phys. Lett., 355 (34): 27984.
Koshio, A., Yudasaka, M., and Iijima, S. (2001) Chem. Phys. Lett.,
341 (56): 46166.
Krupke, R., Hennrich, F., Kappes, M.M., and Lohneysen, H.v. (2004)
Nano Lett., 4: 139599.
Li, Y. and Ding, J., and Chen, J., et al. (2002) Mater. Res. Bull., 37:
31318.
Pierard, N., Fonseca, A., Konya, Z., Willems, I., Van Tendeloo, G.,
and Nagy, J.B. (2001) Chem. Phys. Lett., 335 (12): 18.
Salvetat, J.P., Bonard, J.M., Thomson, N.H., Kulik, A.J., Forro, L.,
Benoit, W., and Zuppiroli, L. (1999) Appl. Phys. A-Mater.,
69 (3): 25560.
Shaffer, M.S.P., Fan, X., and Windle, A.H. (1998) Carbon, 36:
160312.
Sun, J., Gao, L., and Li, W. (2002) Chem. Mater., 14 (12): 516972.
Tang, J. and Yang, G., and Zhang, Q., et al. (2005) Nano Lett., 5:
1114.
Thomas, B.J.C., Boccacciniw, A.R., and Shaffer, M.S.P. (2005) J. Am.
Ceram. Soc., 88 (4): 98082.
Wong, E.W., Sheehan, P.E., and Lieber, C.M. (1997) Science,
277 (5334): 197175.
Xie, S., Li, W., Pan, Z., Chang, B., and Sun, L. (2000) J. Phys. Chem.
Solids, 61 (7): 115358.
Yamamoto, K., Akita, S., and Nakayama, Y. (1996) Jpn. Appl. J.
Phys., 35: L917.
Yamamoto, K., Akita, S., and Nakayama, Y. (1998) J. Phys. D Appl.
Phys., 31: L34L36.
Yao, Z., Zhu, C.C., Cheng, M., and Liu, J. (2001) Comp. Mater. Sci.,
22 (34): 18084.
Yu, M.F., Lourie, O., Dyer, M.J., Moloni, K., Kelly, T.F., and
Ruoff, R.S. (2000) Science, 287 (5453): 63740.
INFLUENCE OF ELECTRIC FIELD ON DISPERSION OF CARBON NANOTUBES IN LIQUIDS 375
D
o
w
n
l
o
a
d
e
d

b
y

[
U
n
i
v
e
r
s
i
d
a
d

A
u
t

n
o
m
a

d
e
l

E
s
t
a
d
o

d
e

M

x
i
c
o
]

a
t

1
3
:
2
8

2
3

S
e
p
t
e
m
b
e
r

2
0
1
4