Carbon 42 (2004) 1691–1697

www.elsevier.com/locate/carbon

Ball milling effect on the structure of single-wall carbon nanotubes

a,*
N. Pierard , A. Fonseca a, J.-F. Colomer b, C. Bossuot c, J.-M. Benoit d,e
,
G. Van Tendeloo b, J.-P. Pirard c, J.B. Nagy a
a
Laboratoire de R
esonance Magn
etique Nucl
eaire, FUNDP, 61 rue de Bruxelles, B-5000 Namur, Belgium
b
EMAT, University of Antwerp (RUCA), 171 Groenenborgerlaan, B-2020 Antwerp, Belgium
c
Laboratoire de G
enie Chimique, Universit
e de Liege, B6 Sart-Tilman, B-4000 Liege, Belgium
d
Max Planck Institut for Solid State Research, Heisenbergstr. 1, D-70569 Stuttgart, Germany
e
Institut des Mat
eriaux Jean Rouxel, LPC, 2 rue de la Houssinere, BP 32229, F-44322 Nantes Cedex 3, France
Received 16 June 2003; accepted 27 February 2004
Available online 8 April 2004

Abstract
The vibratory mill is used to decrease the single-wall carbon nanotubes (SWNTs) length and to increase their specific surface
area. Electron microscopy, Raman spectroscopy, X-ray diffraction and BET measurements indicated that the optimum time of
treatment seems to be 2 h. After that, the SWNTs quality decreases, with a complete disruption of the tubular structure leading to
multi-layered polyaromatic carbon materials observed after 50 h.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Carbon nanotubes; B. Grinding; D. Fracture, Mechanical properties, Surface areas

1. Introduction agate mortar. The ball milling effect on the morphology

Ball milling is regularly applied to carbon materials.
Applying graphite, it was used to produce highly curved
nanostructures [1,2], to insert lithium [3] or to improve
the hydrogen storage capacity of the material [4,5]. In
this paper, we propose to use this grinding method on
single-wall carbon nanotubes (SWNTs). Since their
discovery in 1993 [6,7], SWNTs are very promising
materials for various application fields: electric [8] and
thermal [9] conductivity, field emission [10], hydrogen
storage [11,12], molecular sieves [13], etc. Limitations to
last two applications are their great length (10 lm at
least) and the fact that the ends of the tubes are often
closed. In fact, to overpass the diffusion limits, short
nanotubes with open tips are required. In our previous
paper, the cleavage of multi-wall carbon nanotubes
(MWNTs) was described [14]. The average length of the
ball milled MWNTs, obtained in gram scale, is ca. 0.8
lm. The cleavage was caused by collision between one
agate ball and the nanotube powder contained in an
*
Corresponding author. Tel.: +32-817-24601; fax: +32-817-24600.
E-mail address: nathalie.pierard@fundp.ac.be (N. Pierard).
0008-6223/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.02.031
of cup-stacked carbon nanotubes have also been studied
[15]. The results are the shortening of the nanotubes and
the formation of nanobarrels exhibiting an increased
number of accessible active sites and anisotropic prop-
erties at both ends. Applying SWNTs, the possibility to
cleave them using diamond powder has been reported
[16] but the technique is limited by the contamination
by diamond particles.
The effect of ball milling on the structure and mor-
phology of SWNTs synthesized by laser ablation has
already been studied to promote the electrochemical
intercalation of lithium [17]. In this case, small times of
treatment are considered (10 min) to show that ball
milling induces disorder within the bundles and frac-
tures the nanotubes. In this paper, we report the use of
ball milling with longer time of treatment to reduce the
length of the single-walled carbon nanotubes (produced
in this case by a catalytic chemical vapor deposition
CCVD technique) and show that this process is effective
to produce short nanotubes. However, we show that
SWNTs, unlike MWNTs, do not resist indefinitely to
the ball-milling treatment because the formation of
multi-layered polyaromatic carbon materials occurs
for longer times of treatment.
1692 N. Pierard et al. / Carbon 42 (2004) 1691–1697
2. Experimental
2.1. Production of the long carbon nanotubes
SWNTs were synthesized by catalytic decomposition
of methane using Co supported on MgO as catalyst
[18]. The catalyst was prepared by the impregnation
method and contained 2.5 wt.% of cobalt. The pro-
duction of nanotubes was carried out at 1000 °C using
a methane flow of 80 and 300 ml/min of H2 as car-
rier gas. The cobalt catalyst and the support were
dissolved in concentrated HCl to obtain purified
SWNTs. The purified SWNTs contain some double-
wall nanotubes and encapsulated cobalt nanoparticles
(12 wt.% Co).
2.2. Ball milling process
Ball-milling apparatus (Vibration micro-Pulveriser
‘‘Pulverisette 0’’ Fritsch) is composed of an agate mortar
containing an agate ball (5 cm in diameter) where about
1 g of carbon nanotube powder was introduced. Ball-
milling amplitude (vertical vibration intensity) was
constant and 3000 vibrations/min were carried out.
Times between 1 and 50 h were experimented in air
atmosphere.
Fig. 1. TEM pictures of the carbon material: before ball milling (a), ball milled for 2 h (b), 8 h (c) and 50 h (d).
2.3. Characterization of the nanotubes
After each step, about 60 mg samples were taken for
characterization by different techniques. Structural
characteristics of purified and ball-milled SWNTs were
first observed using transmission electron microscopy
(TEM) (Tecnai, Philips and Jeol 200 CX microscopes).
The structural evolution of SWNTs is characterized by
X-ray diffraction (XRD) (PW3710 BASED, Philips, Cu
 and Raman spectroscopy (Jobin
Ka radiation: 1.5418 A)
Yvon T64000, green laser with an excitation wavelength
of 514.5 nm). Finally, BET measurements were also
performed to experiment the evolution of the specific
surface area during the treatment.
3. Results and discussion
3.1. SWNTs structural evolution during ball-milling
process
Low-resolution TEM observations revealed that first
the ball-milling treatment decreases the length of the
SWNTs (Fig. 1a and b). This point will be discussed in
Section 3.2. For the first three hours of ball milling there
is no significant destruction of nanotubes but longer
 N. Pierard et al. / Carbon 42 (2004) 1691–1697 1693

milling times progressively disrupt the SWNTs. Multi- d 002

layered polyaromatic carbon structures can be observed
after 8 h (Fig. 1c). For longer treatments, these struc-
tures disappear and seem to be transformed into
amorphous carbon (Fig. 1d). Without treatment
High-resolution transmission electron microscopy After 1 h
(HREM) observations (Fig. 2) confirm these results,
After 3 h
except the fact that after 50 h the material is not
amorphous but transformed into multi-layered polya- After 8 h
romatic carbon (Fig. 2d). Furthermore, high-resolution
After 24 h
observations give more information about the walls of
After 50 h
SWNTs. In fact, they get deteriorated after 8 h as seen
in Fig. 2c and, after 50 h the destruction of SWNTs 15 20 25 30 35 40
is complete (Fig. 2d). 2 Θ (°)
In order to complete the information about the evo-
Fig. 3. Evolution of d002 peak intensity on powder XRD spectra after
lution of the structure of SWNTs during the ball-milling different time of ball-milling process.
process, powder XRD spectra were measured before
and after 1, 3, 8, 24 and 50 h of ball milling and the
diffractograms are shown in Fig. 3. non-existent. It is only due to bundles of SWNTs and to
Before treatment, the d002 peak around 25° (2H), the small quantity of DWNTs. During the ball-milling
characteristic of the graphite interplanar space is almost process, the d002 peak intensity increases, confirming the

Fig. 2. HREM pictures of the carbon material: before ball-milling (a), ball milled for 1 h (b), 8 h (c) and 50 h (d).
1694 N. Pierard et al. / Carbon 42 (2004) 1691–1697
progressive destruction of the SWNTs. The increasing of
the d002 peak is characteristic of increasing multi-layered
polyaromatic carbon content of the sample. The multi-
layered polyaromatic carbon material originates from
the collapsing of SWNTs into graphene planes. After 50
h of ball-milling treatment, some multi-layered poly-
aromatic carbon materials becoming prevalent can be
observed by HREM (Fig. 2d).
Furthermore, the tangential and breathing modes of
SWNTs in Raman spectroscopy [19] brought comple-
mentary information on the evolution of the carbon
species during the process. In the range 1300–1700 cm
1 ,
the spectra clearly show two peaks (Fig. 4). The peak
around 1580 cm
1 corresponds to the tangential C–C
stretching modes (G band) that are characteristic of
graphitic structure in SWNTs. The other one around
1350 cm
1 (asymmetric mode: D band) is assigned to
the residual ill-organized graphite (impurities and de-
fects on nanotubes).
The increase in intensity of the D band confirms the
progressive SWNTs disruption and the production of
disordered carbon during the process. The quality factor
(ratio between the area of G band and the sum of areas
of G and D bands: G/(G+D)) [20] can be used to
characterize the SWNTs content of the samples. The
quality factor decreases progressively with increasing
time of the process (Table 1). As we corroborated the
G band
D band
Without treatment
After 3 h
After 8 h
After 24 h
After 50 h
1200 1400 1600 1800 2000
Wavenumber (cm-1)
Fig. 4. Raman spectra (excitation wavelength k ¼ 514:5 nm) after
different times of ball-milling process: tangential modes of SWNTs.
Table 1
Evolution of quality factors of SWNTs after different times of ball-
milling process
Ball-milling time (h) Quality factor (%)
0 90
3 75
8 61
24 52
result with the TEM analysis, for the first 3 h, the de-
crease of the quality factor is essentially due to the
SWNT cutting. Further milling causes the cutting but
also the destruction of nanotubes. As a result, the
intensity of the G band and the quality factor decrease
as a function of time of treatment. Note that multi-
layered polyaromatic carbon structures are also repre-
sented by a G band at 1580 cm
1 [21]. It is the reason
why there is no disappearing but only broadening of
this band.
On the other hand, in the range 130–275 cm
1 , the
A1g modes (breathing modes) give an idea of the resis-
tance of the SWNTs to the ball-milling treatment, as a
function of their diameter (Fig. 5). Applying the equa-
tion which relates the nanotube diameter (d) to the
wavenumber (k) d ðnmÞ ¼ 223:75 (cm
1 nm)/k (cm
1 )
[22], eight different SWNT diameters (ranging from 0.9
to 1.5 nm) were found in the original sample. After 4 h
of ball milling, all peaks nearly disappear, indicating the
SWNT destruction. If we focus on the first four hours of
treatment, it seems that larger tubes, having their Ra-
man peaks at lower wavelength require less mechanical
energy to be destroyed. Hence, small tubes are more
resistant to compression in the vibratory ball milling.
Note that the intensity of the radial mode decreases
more rapidly than the tangential mode due to the fact
that the former mode is characteristic of SWNTs while
the G mode arises from the contribution of all carbon
structures present in the sample.
3.2. Cut SWNTs
The length of individual SWNTs is difficult to mea-
sure by TEM. In fact, before ball-milling treatment, the
small diameter of SWNTs requires the use of high
magnifications to visualize them, but this makes it
impossible to visualise the entire nanotube. Also tubes
180 (12.4 Å)
175 (12.8 Å)
165 (13.6 Å)
145 (15.4 Å) 200 (11.2 Å)
225 (9.9 Å) 257 (8.7 Å)
243 (9.2 Å)
Without treatment
After 0.5 h
After 1 h
After 2 h
After 3 h
After 4 h
After 8 h
After 24 h
After 50 h
120 140 160 180 200 220 240 260 280 300
Wavenumber (cm-1)
Fig. 5. Raman spectra (excitation wavelength k ¼ 514:5 nm) after
different times of ball-milling process: radial modes of SWNTs.
 N. Pierard et al. / Carbon 42 (2004) 1691–1697 1695

often get entangled, which also makes it difficult to 10

estimate their length. After the ball-milling process, 9 experimental agregate diameter
SWNTs tend to be compacted by the ball and form even 8 calculated aggregates diameter
7

Size (m)
larger aggregates of entangled SWNTs that cannot be 6 aggregation function
observed individually. To solve the problem, we make 5 SWNTs length
the hypothesis that the aggregate surface observed by 4
3
TEM (Fig. 1b) is proportional to the SWNT length. 2
Following this hypothesis, we calculate the evolution of 1
0
the SWNT aggregates surface during the ball-milling 0 1 2 3 4 5 6 7 8
process. For this determination, each aggregate was Ball-milling time (h)
assimilated to a parallelogram and the length and the
width of each aggregate were estimated. To obtain an Fig. 7. Evolution of SWNTs length, experimental and calculated
average size of the aggregate, this surface was then aggregates diameter and aggregation function as a function of time
during the ball-milling process.
assimilated to a circle for the aggregates diameter
determination. The results are presented in Fig. 6. The
average aggregates diameter decreases with the ball- tubes in the aggregates. As the process goes on, the
milling time, meaning that the process decreases the aggregation of SWNTs progressively increases. This is
length of the tubes. This decrease seems to stabilise the reason why the aggregate diameter never goes to
around 1.6 lm, after 2 h of treatment. The aggregates zero as the SWNTs disrupt. To estimate the length of
diameter stabilisation could be due to the competition SWNTs, a hypothesis was made that the experimental
between the cutting and the aggregation of the na- aggregates diameter is the sum of the SWNTs length and
notubes. Nevertheless, the quality of the tubes decreases an aggregation function:
after 4 h of ball milling. This is the reason why 2 or 3 h
of treatment are the optimum time to obtain cut na- Exp: aggregates diameter ðlmÞ
  
notubes of 0.4 or 0.1 lm, respectively (Fig. 7). Longer t
ball-milling treatment is not interesting because of the ¼ 10 1
e
ðln 2=p1 Þt þ 1:6ð1
e
ðln 2=p2 Þt Þ
p1 þ t
competition with the SWNT destruction.
As the aggregate diameter is not the length of where 10 lm is the initial length of SWNTs before
SWNTs, we establish hereafter a model based on the treatment, t is the grinding time (h), p1 is the period of
one used for MWNTs [14] to estimate the length of the the SWNT length exponential decrease function, 1.6 lm
is the ultimate aggregates diameter and p2 is the period
of the exponential in the aggregation function.
4h
The best correlation is obtained for p1 and p2 equal to
16
12 Average diameter: 1.6 ± 0.2 µm 0.75 and 1.5 h, respectively (Fig. 7). The period of the
8 SWNTs length evolution (0.75 h) is shorter than those of
4
0 MWNTs (2 or 3 h); this is in agreement with a lower
3h resistance of the SWNTs to the ball-milling treatment.
20
16 Average diameter: 1.2 ± 0.2 µm For some applications such as gas storage, a
12
Number of aggregates

8 parameter that is more important than the decrease of

4
0 the length of the nanotubes is the accessibility of the
2h
12
Average diameter: 1.8 ± 0.2 µm
8
4 1800
0 1600
1h
12 1400
Average diameter: 2.2 ± 0.2 µm
8 1200
SBET (m /g)

4 1000
2

0 800
8 0.5 h 600
Average diameter: 4.0 ± 0.2 µm 400
4 200
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 0 5 10 15 20 25 30 35 40 45 50 55
Aggregates diameter (µm) Ball-milling time (h)
Fig. 6. Diameter distribution histograms of SWNT aggregates after Fig. 8. Evolution of the specific surface area as a function of time of
0.5, 1, 2, 3, 4 h of ball-milling process. ball-milling process for 1 g of SWNTs (relative error 10 %).
1696 N. Pierard et al. / Carbon 42 (2004) 1691–1697
tube cavities to gases. This is the reason why the specific
surface areas of the sample are measured after different
ball-milling times. The surface area evolution of a
sample during the ball-milling process is represented in
Fig. 8. First of all, the main observation is the great
increase of the specific surface area for the first 2 h of
process. The increase of the specific surface area can be
explained by the opening of the nanotube tips during the
milling. After that, the specific surface area decreases
due to the compaction, decreasing the outer surface of
the tubes accessible to the gas. As already reported [23],
the reversible hydrogen adsorption capacity of carbon
samples is correlated with their specific surface area. In
the present study, 2 h of ball-milling treatment seems to
be the best time of treatment for maximum reversible
hydrogen storage capacity. Recently, results concerning
the hydrogen storage capacity of ball-milled MWNTs
have been published [24]. In this study, the increase of
the hydrogen capacity was related to the increase of the
ball-milling time during the first 10 h. After that the
capacity drops due to the insertion of impurities coming
from the balls but also due to the disruption of the
MWNTs. On the other hand, ball-milled graphite [4]
and activated carbon [25] were also studied for their
hydrogen storage. Ball-milled graphite during 80 h leads
to crystallites formation (less than 4 nm) and the surface
area is only of the order of 10 m2 /g while ball-milled
activated carbon during 10 h affects the particles size (<1
lm after 10 h) and decreases the specific surface area of
40% (600 m2 /g). In our case, the specific surface area is
only 3 m2 /g after 50 h of ball milling, confirming the
total disruption of SWNTs to form multi-layered
polyaromatic carbon.
4. Conclusion
Like MWNTs, SWNTs produced by CCVD can also
be cut at gram scale by ball-milling treatment. The
vibratory mill can be used to decrease the nanotubes
length, but SWNTs do not resist very long milling times.
The optimum time of treatment to cut SWNTs, to keep
the tubular structure and to maximise their specific
surface area is 2 h. After that a progressive destruction
of SWNTs arises. After 50 h, a complete disruption of
the tubular structure and the formation of multi-layered
polyaromatic material are observed. In the future, many
parameters such as ball amplitude, process time, ball
material, . . . that can also modulate the final SWNTs
length and surface area, should be investigated.
Acknowledgements
N. Pierard acknowledges support from FRIA. The
authors thank the Belgian Programme on Inter Uni-
versity Poles of Attraction (OSTC-PAI-IUAP no. 5/1),
NANOCOMP contract (HPRN-CT-2000-00037) and
Wallonia Region contracts (SYNATEC no. 0014622,
no. 0014526 and BINANOCO no. 115008).
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