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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
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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
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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).
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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