Carbon 37 (1999) 493497

Transformation of carbon nanotubes to nanoparticles by ball

milling process
Y.B. Li*, B.Q. Wei, J. Liang, Q. Yu, D.H. Wu
Tsinghua University, Beijing 100084, China
Received 9 January 1998; accepted 16 July 1998

Abstract
Carbon nanotubes were treated by high-energy ball milling processing for different milling times, and the samples were
observed by HRTEM. The broken nanotubes and lots of carbon onion-like particles were obtained in the sample milled for
15 min. When the milling time was up to 60 min, carbon nanotubes turned into amorphous carbon. On the basis of HRTEM
observation of carbon nanotubes and carbon nanoparticles, we discuss the possible formation mechanism of nanoparticles
under the impact acting as driving force. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: A. Carbon nanotubes; Fullerene; D. Phase transitions

1. Introduction
Since carbon nanotubes were discovered by Iijima in
1991 [1], lots of research on the structures and properties
have been done. Carbon nanotubes, according to theoretical calculations and in-situ measurements, have exceptional electrical [2] and mechanical properties [3], which
predicates that carbon nanotubes may possess applications
in many fields. Carbon onion-like particles are one of the
accompanying products with carbon nanotubes in the
cathode deposits fabricated by the carbon-arc method [4].
Recently, carbon nanoparticles have been getting more and
more attention, and the proposed formation mechanism of
nanoparticles under different conditions have been reported
[57].
As mentioned above, structure changes of multi-shell
carbon nanostructures (carbon nanotubes and carbon onions) have been studied under different treatments, such as
laser irradiation [8], electron-bombardment [9] and hightemperature treatment [10], but the study on nanotube
structure changes under the action of drastic mechanical
force has not been reported up to now. In this paper, we
present the results of high-energy ball milling processing
of the mixtures of carbon nanotubes and iron powders. Ball
milling, also called mechanical alloying, is a favorable
technique for generation of equilibrium and non-equilibrium materials, like the amorphous or nanocrystalline
*Corresponding author.
0008-6223 / 99 / $ see front matter
PII: S0008-6223( 98 )00218-8

materials. As pointed out in ref. [11], the main event in the

alloying process is the collision between balls and free
powder particles. In the sample obtained by milling for 15
min, lots of carbon onion-like particles were found. Here,
the possible formation mechanism of carbon nanoparticles
under impact as the driving force is proposed.

2. Experimental
Carbon nanotubes were prepared by catalytic pyrolysis
of hydrocarbon gases, using a method like that in refs.
[12,13]. The fabrication of nanotubes was carried out in a
resistance-furnace. The catalyst was superfine Ni /Al powders with silica acting as catalyst carrier. The reactant
hydrocarbon gas was ethylene, and the decomposition
temperature was kept at 7008C. The raw materials, obtained after reacting for 15 min, were rinsed in the 10%
HNO 3 solution and in the 10% HF solution for 24 h,
respectively, so as to get rid of the catalyst in the mixtures.
After the remainder was rinsed by distilled water several
times, pure carbon nanotube powders were obtained. The
TEM image of carbon nanotubes obtained is shown in Fig.
1. The majority of fabricated carbon nanotubes consist of
several coaxial cylinders, the number of which varies from
15 to 25. The fabricated nanotube about 25 nm in average
diameter has a central hollow core about 10 nm in
diameter.
The materials for milling were mixtures of nanotubes

1999 Elsevier Science Ltd. All rights reserved.

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Y.B. Li et al. / Carbon 37 (1999) 493 497

Fig. 1. TEM images of carbon nanotubes fabricated by a catalytic

pyrolysis method.

and iron powder (purity .99.9%). It has been testified,

from the results of milling pure nanotubes and milling the
mixture of nanotubes and iron powder, respectively, under
the same milling conditions, that the addition of iron
powder can increase the carbon nanoparticle formation
rate, which resulted from the fact that iron particles
presumably can act as numerous tiny milling balls. In this
paper, the experiment results of milling the mixtures of
nanotubes and iron powder are reported. In experiments,
ball milling processing was done in a shaker mill. The vial
(dimension is f60360) and the balls were made of
stainless steel. The mixtures of 4 g iron powder, of average
particle size 1 mm, and 0.4 g carbon nanotubes were put
into the vial, and some balls (five balls of 17 g, five balls
of 7.5 g and 10 balls of 2 g each) were also put into the
container. Then air in the vial was pumped out and argon
gas was filled in. After these operations in turn were done
several times, the argon gas (1.2 atm pressure) was sealed
in the vial. In a group of experiments for observation on
evolution of carbon nanotube structure, milling times of 5
min, 10 min, 15 min and 60 min were selected. The vial
was cooled every 5 min from the external wall so that the
temperature was kept lower than 1008C during the experiments.
The mixtures obtained by milling were tested by SEM
and X-ray diffraction, and the results will be reported
elsewhere. After the mixtures were treated in the 10% HCl
solution and in the 10% HNO 3 solution for 24 h, the
remainder was rinsed with distilled water several times and
then filtrated and dispersed in ethyl alcohol with the aid of
an ultrasonic-wave cleaner. The suspensions were deposited on electron microscope copper grids and the samples
were analyzed on a H-9000 TEM with 300 keV accelerating voltage.

3. Results and discussion

The sample obtained by milling for 5 min was composed of carbon nanotubes. Most of them were integrated
nanotubes similar to the original structures, but some were

broken and nanotubes with one end opened were obtained.

When the milling time was up to 10 min, the proportion of
broken nanotubes increased and some carbon nanoparticles
were found in the sample. In the sample obtained by
milling for 15 min, lots of carbon onion-like particles were
observed, and some amorphous carbon was also produced.
When the mixture was milled for 60 min, the sample was
mainly composed of amorphous carbon, which was confirmed by SAD pattern.
The images of some carbon nanoparticles are shown in
Fig. 2. Fig. 2a shows the image of a spherical carbon
onion-like particle, which is similar to that obtained by
electron irradiation on polyhedral nanoparticles [7] except
having a larger central hollow core (4 nm in diameter).
Fig. 2b shows the image of an ellipsoidal carbon particle
with a large inner hollow space and irregularly closed at
some sites of shells (indicated with arrows). In Fig. 2c, a
poorly crystallized carbon nanoparticle can be seen.
Fig. 3 shows the images of some carbon nanotubes
observed in the sample obtained by milling for 15 min. In
Fig. 3a, one end of a carbon nanotube is connected with an
incompletely closed ellipsoid. The fissure of layers at the
site A and the carbon sheets for closing the ellipsoid at the
site B can be seen. In Fig. 3b, the image of a completely
closed ellipsoidal carbon nanoparticle and connecting
carbon nanotube can be observed. From Fig. 3b, it can be
seen that at the site C some layers of nanotube and
nanoparticle are identical, which implies that the carbon
nanoparticle is not completely separated from the
nanotube, but at the site D the nanoparticle is completely
separated from the nanotube.
The ball milling process is very complicated and its
result may relate to several factors, such as ball to powders
weight ratio, container temperature and medium in the vial.
Compared with carbon nanotubes fabricated by carbon-arc
method, which are straight [1], carbon nanotubes fabricated by catalytic pyrolysis of hydrocarbon gases often
possess more defects and demonstrate localized kinks and
bends (as shown in Fig. 1). Under the conditions of
experiments, high-frequent collisions and high velocity of
steel balls make the impact on nanotubes very high. In the
milling process, the iron powder acts as a great number of
tiny milling balls, which results in very frequent impacts
on nanotubes. In the following discussion, the impacts on
nanotubes caused by steel balls are mainly discussed for
the convenience of discussion. Calculations of the elastic
properties of nanotubes confirm that they are extremely
rigid in the axial direction and are most likely to distort
perpendicular to the axis [14]. On the basis of the structure
changes of nanotube observed by TEM, we propose the
carbon nanoparticle formation mechanism as shown in Fig.
4.
If the point of impact is situated near the low stiffness
parts of the nanotube such as the bends in nanotubes (as
shown in Fig. 4a), and the impact on the nanotube is high
enough to damage the nanotube cylinder structure of the
segment at the point of impact, that segment may fully

Y.B. Li et al. / Carbon 37 (1999) 493 497

495

Fig. 2. TEM images of some carbon nanoparticles.

collapse. The stress caused by deformation of collapsed

segment may make the layers near the point of impact
ruptured (as shown in Fig. 4b). If all the shells of the
cylinder structure rupture, broken nanotubes with one end
opened are obtained. If only some layers rupture, the small
curved graphene sheets likely containing pentagons produced by ball milling processing may deposit on the
fractures to eliminate the dangling bonds, resulting in the
closure of the carbon nanoparticle (as shown in Fig. 4c).
With the rupture and closure keeping on, the nearly closed
ellipsoidal nanoparticle is formed at the end of the carbon
nanotube acting as the parent of the nanoparticle (see Fig.
4d). Then the formed carbon nanoparticle may completely
separate from the nanotube.
The carbon shells of the newly formed ellipsoidal
nanoparticles (as shown in Fig. 4e) are imperfect at some
sites, and the nanoparticle has a large inner hollow space.
According to Ugarte [7], the quasi-spherical carbon onions
are the most stable form of carbon particles. The ellipsoid
shape particles with a large number of defects are in a

metastable state in the light of the theory of minimization

of surface area, so we propose here that they tend to turn
into spherical onion-like particles under the action of the
impact of milling balls. The carbon atoms in imperfect
shells may vibrate drastically enough to be knocked into
the hollow center, resulting in the spherical carbon shells
and the high concentration of carbon atoms in the hollow
space (see Fig. 4f). These carbon atoms deposit on the
inner layer, and thus the newly formed inner shell make
the hollow space diminished. The nearly perfect spherical
onion-like particle shown in Fig. 4g was formed. Because
the spherical carbon onions are in the most stable state, and
the energy obtained by the impact of steel balls is limited
under the conditions used in these experiments, the spherical carbon onions with a hollow inner core cannot be
turned into the more compact structure [7] that is obtained
by electron irradiation.
With steel balls colliding continuously on the spherical
carbon onions, when the energy accumulated in the shells
is high enough to break the perfect structure, the regular

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Y.B. Li et al. / Carbon 37 (1999) 493 497

shells may be destroyed and turned into the imperfect

shells of nanoparticles shown in Fig. 4h. The low stiffness
of the nanoparticles owing to the amorphous shells make
them destroyed easily and turned into amorphous carbon,
which is in accord with the result observed in the sample
obtained by milling for 60 min.

4. Conclusion
Carbon nanoparticles can form at the broken end of
nanotubes under the action of the impact of steel balls by
ball milling processing, and we propose that ellipsoidal
nanoparticles with a large inner space tend to turn into
spherical nanoparticles with a small inner space. It has
been suggested by Dravid et al. [15] that carbon nanotubes
sometimes can be fractured and the broken nanotubes may
be the precursors to closed-shell fullerenes. The fact that
carbon nanoparticles are obtained by ball milling processing of carbon nanotubes confirms their hypothesis. Moreover, the results of ball milling supply a new way to
fabricate carbon onion-like particles and help to understand
the relations between two kinds of carbon nanostructures.

Acknowledgements
This research was carried out under the financial support
of the National Nature Science Foundation of China
(Project 59501012).

Fig. 3. TEM images of some nanotubes in the sample obtained by

milling for 15 min.

References
[1] Iijima S. Nature 1991;354:56.
[2] Ebbesen TW, Lezec HJ, Hiura H, Bennett JW, Ghaemi HF,
Thio T. Nature 1996;382:54.

Fig. 4. Schematic illustration of the carbon nanoparticle formation process. (a) Nanotube; (bd) nanotube collapse at the low-stiffness
segment and carbon nanoparticle form at the broken end; (eg) ellipsoidal nanoparticle turns into spherical onion-like nanoparticle; (h) the
damaged nanoparticle with amorphous shells.

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[3] Treacy MMJ, Ebbesen TW, Gibson JM. Nature
1996;381:678.
[4] Miki-Yoshida M, Castillo R, Ramos S, Rendon L, Tehuacanero S, Zou BS, Jose-Yacaman M. Carbon 1994;32:231.
[5] Banhart F, Fuller T, Redlich Ph, Ajayan PM. Chem Phys
Lett 1997;269:349.
[6] Lozovik YuE, Popov AM. Phys Lett A 1994;189:127.
[7] Ugarte D. Carbon 1995;33:989.
[8] Wei BQ, Zhang JH, Liang J, Wu DH. Carbon, in press.
[9] Ugarte D. Nature 1992;359:707.

497

[10] de Heer WA, Ugarte D. Chem Phys Lett 1993;207:480.

[11] Herr U. Key Eng Mater 1995;103:113.
[12] Endo M, Takeuchi K, Igarashi S, Kobori K, Shiraishi M,
Kroto HW. Carbon 1995;33:873.
[13] Hernadi K, Fonseca A, Nagy JB, Bernaerts D, Lucas AA.
Carbon 1996;34:1249.
[14] Tersoff J, Ruoff RS. Phys Lett 1994;73:676.
[15] Dravid VP, Lin X, Wang Y, Wang XK, Yee A, Ketterson JB,
Chang RPH. Science 1993;259:1601.