CARBON

5 0 ( 2 0 1 2 ) 6 3 3 6 3 6

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/carbon

Reduced damage to carbon nanotubes during

ultrasound-assisted dispersion as a result of
supercritical-fluid treatment
Woo Ram Jung a, Jin Hyuk Choi a, Naesung Lee a, Kwanwoo Shin b, Jun-Hyuk Moon c,
Young-Soo Seo a,*
a

Nano Science and Technology Department, Sejong University, Gunja-Dong, Gwangjin-Gu, Seoul 143-747, Republic of Korea
Department of Chemistry and Interdisciplinary Program of Integrated Biotechnology, Institute of Biological Interfaces, Sogang University,
Seoul 121-742, Republic of Korea
c
Department of Physics, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea
b

A R T I C L E I N F O

A B S T R A C T

Article history:

A pre-treatment method of carbon nanotubes for ultrasound-assisted dispersion in a solu-

Received 9 May 2011

tion is reported. Compared to untreated nanotubes, supercritical-fluid (SCF)-treated carbon

Accepted 29 August 2011

nanotubes were easily dispersed in an aqueous surfactant solution by using ultrasonica-

Available online 17 September 2011

tion. The nanotubes are found to be less damaged and less shortened, which was confirmed by Raman spectroscopy and dynamic light scattering, respectively. Supercritical
ethane was more effective than supercritical CO2 in treating the carbon nanotubes.
2011 Elsevier Ltd. All rights reserved.

1.

Introduction

Ultrasonication is one of the most effective, and common

methods for dispersing carbon nanotubes (CNTs) in a solution
because CNT aggregates that form mainly due to the van der
Waals interaction can be disrupted by the strong shear force
originating from cavitation effects [1]. However, ultrasonication can, often cause defects [2,3] on the CNTs as well as
break them apart [4,5], which degrade the electrical and the
physical properties of the CNTs. Therefore, efforts are being
made to minimize the defects that occur during ultrasoundassisted dispersion, for examples, by applying milder sonication combined with newly designed surfactants [6] and by
selecting appropriate dispersing solvents on the basis of the
physical parameters of the solvent-CNT interaction [7]. In this
study we report a pre-treatment method using supercritical
CO2 and ethane fluids to treat CNTs before ultrasound-as-

sisted dispersion. The supercritical-fluid (SCF)-treated CNTs

exhibit much improved dispersion and less damage during
ultrasonication than the untreated CNTs.
SCFs having both gas and liquid properties are known to
effectively extract targeted substances from a solid matrix. Recently, a polymer thin film was reported to be abnormally swollen in supercritical CO2, and the swelling ratio was strongly
related to the density fluctuation in supercritical CO2 [8] even
though the bulk polymers are almost immiscible with CO2.
Those effects were limited to polymer surfaces of less than
100 nm in depth, implying that supercritical fluids can affect
interfacial region of materials. Also, from the finding that once
the polymer thin film had been exposed to supercritical CO2,
the swollen film obtained after an abrupt release of pressure
had a lower reflective index [9,10], the density fluctuation in
supercritical CO2 was recognized to be affecting the film on a
molecular level. Here, we apply SCFs to CNTs.

* Corresponding author.
E-mail address: ysseo@sejong.ac.kr (Y.-S. Seo).
0008-6223/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2011.08.075

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5 0 ( 2 0 1 2 ) 6 3 3 6 3 6

Experimental

Highly purified CO2 and ethane gas were used as media for
supercritical fluids. Critical points for carbon dioxide and
ethane are 31.1 C and 72.8 atm and 32.2 C and 48.2 atm,
respectively. Multi-walled carbon nanotube (MWCNT,
NC7000) purchased from Nanocyl Inc. was used as received.
The carbon purity of the MWCNT was >90% and their outer
diameters were 10 nm. Other chemicals and solvents were
purchased from SigmaAldrich were used as received.
MWCNT was placed into a high pressure chamber and exposed to supercritical carbon dioxide (scCO2) or ethane (scEthane) under a fixed condition of 100 C and 120 atm for
23 h; then, the pressure was quickly released to atmospheric
condition. Four milligram of SCF treated MWCNT was then
dissolved in 40 ml of 0.5% sodium-dodecyl-sulfate (SDS) solution in a 100 ml bottle. The effect of ultrasonic power on the
CNT solution strongly depends on the sample size and concentration. Thus, we fixed the sample volume and concentration for all experiments at 40 ml of 0.1 mg/ml. Ultrasound
treatments were performed on the solution, by using a bath
sonicator (60 W, 28 kHz). The water bath temperature was
kept at room temperature during the sonication in order to
avoid undesirable aggregation. The solution was centrifuged
under 5000g for 10 min; then, the supernatant was collected.
The absorbance of the supernatant was measured by using an
UVvis spectrophotometer. Before the absorbance measurement of the supernatant solution, the solution was diluted
10 times with 0.5% SDS solution.

3.

Results and discussion

Absorbance of the supernatant solution at 580 nm is plotted

as a function of the sonication time in Fig. 1 As expected,
the absorbance of the supernatant solution increases with
increasing sonication time, indicating that the MWCNT becomes more dispersed with increasing sonication time. For
MWCNT without SCF treatment (pristine MWCNT) the

absorbance linearly increases with increasing sonication time

up to 150 min, after which the rate of increase is slower,
which means that the dispersion solution reaches a saturation level as previously reported [11]. On the other hand, for
MWCNTs after scCO2 or scEthane treatment, the absorbance
is higher compared to the pristine sample, and the difference
gradually increases with increasing sonication time. The saturation level of SCF-treated MWCNT solution seems to be
higher than that of the untreated MWCNT solution. After
200 min sonication, the absorbance of the supernatant solution prepared from pristine MWCNTs reaches 1.1 while, after
scCO2 and scEthane treatment, it becomes 1.4 and 1.7, respectively. In the inset of Fig. 1, supernatant solutions of pristine
and scEthane-treated MWCNTs dispersed in 0.5% SDS after
200 min sonication are displayed.
The better dispersion of the SCF-treated MWCNTs might
be attributed to penetration power induced by density fluctuation in the SCF, as previously mentioned. The SCF is assumed to penetrate through MWCNT aggregates and to
leave a structural footprint on them even after the pressure
is released, which provides easier access to the surfactants in
the aqueous solution during sonication. A similar effect was
also found for polymeric molecules; polymeric thin films treated with a supercritical fluid have a lower density, a reduced
glass transition temperature, an increased nanoscale-porosity, and a decreased dielectric constant, indicating that the
SCF provides the inter-molecular spacing in the matrix.
[9,10,12,13] Moreover, the enhanced dispersity of scEthanetreated MWCNT compared to scCO2 treated ones might be
due to the chemical compatibility of ethane to the MWCNT
being better than that of CO2.
Chemical defect formation on CNTs due to ultrasonication
can be analyzed by using Raman spectroscopy [14,15]. The
measurements were performed on the supernatant sample
dried on a glass substrate by using a Lanishaw inVia Raman
microscope with visible excitation at 633 nm. Fig. 2 presents
the Raman spectra of MWCNT samples treated by ultrasonication for various time intervals. Two distinctive peaks are observed; the disorder-induced mode (D band) centered at
1325 cm 1 and the graphite mode (G band) centered at

2.0
Pristine scEthane

1.2e+5

1.2
9.0e+4

0.8
Pristine
scCO2

0.4

scEthane

0.0

50

100

150

6.0e+4

Fig. 1 Absorbance at 580 nm of supernatant solution of

pristine (circles), supercritical CO2 (scCO2, squares) treated,
and supercritical ethane (scEthane, diamond) treated
MWCNTs for various sonication times. Inset: pristine and
scEthane-treated MWCNT supernatant solutions after
200 min sonication.

: 10 min
: 30 min
: 60 min
: 120 min
: 170 min
: 200 min

Pristine
scEthane

0.7

0.6

0.5
0

50

100

150

200

Sonication time (min)

3.0e+4
Solid line : Pristine
Dotted line : scEthane

200

Sonication time (min)

IG / ID

0.8

Intensity

Abs. at 580nm

1.6

0.0

500

1000

1500

2000

-1

Wavenumber (cm )
Fig. 2 Raman spectra of pristine (solid line) and scEthanetreated (dotted line) MWCNTs for various sonication times.
Inset: IG/ID is plotted as a function of the sonication time.

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Fig. 3 (a) SEM image of MWCNT aggregates before dispersion. (b) Cryo-electron microscopy image of MWCNT dispersed in
0.5% SDS solution.

the data previously reported [16] where the values ranged

from 350 nm after 2.5 min sonication to 140 nm after
30 min sonication with a 200 W horn-type sonicator. Even
though shorter sonication times were applied to the MWCNT
solution, similar results were obtained because a horn-type
sonicator that is dipped directly into the solution is harsher
than a bath-type sonicator. On the other hand, for supercritical-fluid-treated MWCNTs, the diameters were found to be
210 nm for scCO2 and 250 nm for scEthane-treated samples
after 200 min sonication.
The quick decrease in the particle diameter of the pristine
MWCNT at the early stage of sonication might be a consequence of the fast defect formation found in the Raman measurement. Likewise, scEthane-treated MWCNT having fewer
defects almost keeps their lengths in spite of sonication. Then,
for sonication times from 120 to 200 min, the diameters of
these samples are no longer shortened, which may be due to
the samples being well-dispersed. The change in the particle
diameter of scCO2-treated MWCNTwith increasing sonication
time lies between those for the pristine and the scEthane-treated MWCNTs, which is consistent with its middle dispersity, as
shown in Fig. 1. Thus, we have confirmed that well-dispersed
and less-damaged SCF-treated MWCNTs also resist well
against breakage caused by ultrasonication.
To further investigate the effect of SCF treatment, electrical
percolation threshold of MWCNT films was measured.

350

Particle diameter (nm)

1595 cm 1. The intensities of the D and G bands were taken

after baseline corrections. Each spectrum was normalized
such that the D-band intensity was the base line.
Apparently, for both pristine and scEthane-treated
MWCNTs, the G-band intensity gradually decreases with
increasing sonication time, meaning that more defects are
generated on the CNTs. More quantitatively, the intensity ratio of the G band and the D band, IG/ID was analyzed, and is
plotted as a function of the sonication time in the inset of
Fig. 2. A smaller value of the ratio means that more defects
can be found. The ratio for the pristine MWCNT sample decreases and becomes 0.60 after 50 min sonication whereas
for the scEthane-treated sample, the ratio decreases to 0.65.
And for sonication time up to 200 min, the ratio difference
between the two samples keeps maintained. Thus, the
scEthane-treated MWCNT might be less affected by the sonication. After MWCNTs that are aggregated and entangled in
dry state as shown in Fig. 3(a) are dispersed in the surfactant
solution, they are found as disentangled and individually separated tubes in the supernatant solution, measured by cryoelectron microscopy as shown in Fig. 3(b). We believe that
the dispersed tubes which should be more flexible than the
aggregated ones might be less affected by the sonic power.
Therefore, scEthane-treated MWCNT that is easily dispersed
could be less damaged by sonication than the pristine
MWCNT.
Defect formation on CNTs can also lead to CNT breakage, as
previously mentioned. The average diameters of the MWCNTs
dispersed in supernatant solutions were determined using dynamic light scattering (DLS). A Brookhaven Instruments BI-200
system, equipped with a 35 mW He-Ne laser (k = 632.8 nm),
was used for the light scattering measurements. The DLS measurements were performed at a fixed angle of 90 to the incident beam at 25 C. We used an autocorrelator to measure
the intensity autocorrelation function of the scattered light.
The autocorrelation function was analyzed with a CONTIN
algorithm which is useful for polydisperse systems. From the
algorithm, the hydrodynamic diameter was calculated from
the diffusion constant based on a sphere model.
In Fig. 4, hydrodynamic particle diameter of MWCNT is
plotted as a function of sonication time. For pristine MWCNT,
it is measured to be 275 nm after 10 min sonication, after
which it drastically decreases with increasing sonication
time. After 200 min sonication, the diameter becomes almost
half its original size, i.e. 150 nm. This result is consistent with

Pristine
scCO2

300

scEthane

250
200
150
100

50

100

150

200

Sonication time (min)

Fig. 4 Hydrodynamic diameters of MWCNT measured by
dynamic light scattering. Dotted lines are guide lines for the
eye.

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by Ministry of Education, Science and Technology (MEST,

2010-0027810).

R E F E R E N C E S

Fig. 5 Surface resistance of MWCNT films prepared from

MWCNT with and without scEthane treatments. The lines
are guide lines for the eye. In inset MWCNT films on the PET
films are displayed.

MWCNT solution after 200 min sonication was filtered

through anodized aluminum oxide (AAO) disc with pore size
of 0.2 lm and then MWCNT film on the disc was transferred
onto optically transparent polyethyleneterephthalate (PET)
film after AAO disc was dissolved in NaOH solution. Detailed
experimental procedures can be found in elsewhere [16]. Surface resistance of the MWCNT film was measured using 4point probe. In Fig. 5, surface resistance is plotted as a function
of optical transmittance measured at 580 nm. Images of
MWCNT films on the PET films are presented in inset. Electrical threshold of two sets of the films with and without scEthane treatment was roughly indicated by arrow. Electrical
threshold of the film prepared from the pristine MWCNT is
62% while the one from scEthane-treated MWCNT is 72%.
Because CNTwith shorter length has higher electrical percolation threshold than the longer one [17], it is again confirmed
that scEthane-treated MWCNT has longer length than the untreated one after ultrasonication.

4.

Conclusion

We found that once MWCNTs have been treated by supercritical fluids, they are easily dispersed by ultrasonication in an
aqueous surfactant solution. These easily dispersed MWCNTs
are then less damaged and less shortened by ultrasonication
because they are flexible and less entangled. Moreover scEthane treatment was found to be more effective than the
scCO2 treatment due to the formers chemical similarity to
the CNTs.

Acknowledgments
This work was partly supported by a Korea Research Foundation Grant funded by the Korean Government (MOEHRD, KRF2007-313-D00365) and by the Mid-career Researcher Program
through a National Research Foundation (NRF) grant funded

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