Journal of Crystal Growth 218 (2000) 57}61

Generation of curved or closed-shell carbon nanostructures by

ball-milling of graphite
X.H. Chen 
*, H.S. Yang , G.T. Wu , M. Wang , F.M. Deng , X.B. Zhang,
J.C. Peng
, W.Z. Li
Department of Physics, Zhejiang University, Hangzhou 310027, People's Republic of China

Department of Applied Physics, Hunan University, Changsha 410082, People's Republic of China
Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, People's Republic of China
Received 14 February 2000; accepted 26 April 2000
Communicated by D.T.J. Hurle

Abstract
Curved or closed-shell carbon nanostructures were produced by ball-milling of graphite. A high resolution indicates
that the ball-milling not only produces bend of graphite sheets, forming carbon nanoarches, but also produces
closed-shell carbon nanostructures, nearly carbon &onions'. The possible formation mechanism is proposed.  2000
Elsevier Science B.V. All rights reserved.
Keywords: Graphite; Ball-milling; Nanoarches; Closed-shells nanostructures

1. Introduction
There has been an increasing interest in carbon
nanoclusters, which are typically in the range of
a few to a few tens of nanometers. The development
of a single arc-discharge method to synthesize macroscopic quantities of C and C [1,2] has stimu

lated researches for other fullerene-like molecules
and other novel forms of carbon. Higher fullerenes
such as C , C , C , C and C can be isolated
   

[3,4], and hollow carbon nanotubes have been discovered [5]. Furthermore, concentric shelled
graphitic spheres, e.g. carbon &onion', have been
produced by electron beam irradiation [6].

* Corresponding author.
E-mail address: cxhzju@263.net (X.H. Chen).

Among the methods to prepare nanostructured

materials, mechanical milling/alloying o!ers the
possibility of producing nanocrystalline structures
in di!erent alloy systems. The ball-milling technique has been used to prepare various kinds of
nanostructured materials, such as pure metallic elements [7,8], solid solutions and intermetallic compounds. In addition, for carbonaceous materials,
such as natural graphite, based on structural investigations by X-ray di!raction and Raman scattering,
it has been found that structural transformation
was obtained, and the defects were induced by
ball-milling [9,10]. For example, increase in
d
is in the step, which is similar to graphite

intercalation compound (GIC) [11]. Recently,
Huang et al. reported that nanoarches or curved
carbon nanostructures were formed during
high-milling of graphite [12]. In this report,
based on investigations by transmission electron

0022-0248/00/$ - see front matter  2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 0 ) 0 0 4 8 6 - 3

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X.H. Chen et al. / Journal of Crystal Growth 218 (2000) 57}61

microscopy, we have sought to study the structural

transformation in graphite produced by ball-milling. Apart from the nanoarches or highly curved
carbon nanostructures, we found closed-shell carbon nanostructures, nearly, carbon &onions'. Also,
the possible formation mechanism of carbon nanostructures is proposed.

2. Experimental procedure
The ball-milling is carried out in a conventional
planetary ball mill. A powder of pure graphite
(99.9%, 325 mesh) was placed in a hard-bearing
steel vial under a dry pure argon atmosphere. The
steel vial is sealed with an elastomer &O' ring seal.
The ball-milling is performed without interruption.
The weight ratio of steel balls to graphite powder is
40 : 1, and the rotation rate of the vial is 270 rpm.
Milling times of 150 and 250 h are selected. Highresolution images were taken in a side-entry JEOL
2010 transmission electron microscope with
a point-to-point resolution of 0.19 nm operated at
200 kV. The specimens were dispersed in acetone
by ultrasound, and then dropped on the holey
carbon grids.

3. Results and discussion

The HRTEM images of pristine graphite is
shown in Fig. 1. The original graphite is a crystalline material, and the layers are planar with a constant interlayer spacing and without noticeable
defects. After 150 h of ball-milling, the samples are
very heterogeneous as displayed in Figs. 2a and b.
Large stacks of graphite layers are not noticeably
broken and destroyed, only an exfoliation and
a crumpling of graphite sheets are generated. The
crumpled layers lead to various nanostructure.
Fig. 2 shows the bend or curvature of graphite
sheets at various angles in the samples after 150 h of
ball-milling. The bent angles of graphite sheets are
in the range of a few degrees to less than 1803.
Angles of about 90, 120 and 1503 are most frequently observed (arrows a, b and c in Fig. 2a).
Various nanoarches with one end closed were also
frequently observed in the samples after the ball-

Fig. 1. HRTEM image for pristine graphite.

milling of 150 h (arrow a in Fig. 2a and arrows

a and b in Fig. 2b). Some nanoarches, with bent
angle less than 453, are similar to the nanotube-like
morphology (arrows a and b in Fig. 2b). The formation of nanoarches or highly curved nanostructures
indicate that the graphite sheets have high #exibility and tenacity.
Apart from the morphology of the above nanostructures, the closed-shells graphite particles,
which are of polyhedral or spherical shapes, are
observed after 150 h of ball-milling. Fig. 2a shows
the polyhedral shapes of the particles or elongated
particles with a large hollow, which is similar to
that obtained by arc-discharge [13]. The inner
loops are not circular but consist of several segments of straight lines. The shapes of the capping
graphite sheets is quite similar to the structure of
ends of nanotubes reported by Iijima et al. [14].
From Fig. 2a, it can also be seen that the elongated
particles are not completely separated from the
graphitic stacks.
The image of closed-shell carbon particles obtained by 150 h milling is shown in Fig. 3. Fig. 3a
shows the image of a quasi-spherical graphitic particle, which is similar to that obtained by electron
irradiation except having a larger central hollow
core. The particles were made up of concentric
graphite sheets, which are related to the so-called
giant fullerenes, nearly carbon &onion'. Fig. 3b
shows another onion-like nanoparticle which consists of two components, an inner metal particle
and outer graphitic shells. The metal particle

X.H. Chen et al. / Journal of Crystal Growth 218 (2000) 57}61

59

Fig. 2. HRTEM image showing the high-curved graphite sheets or nanoarches produced by ball-milling for 150 h. (a) The di!erent
bending angles of the graphite sheets are showed in arrow a (903), arrow b (1203) and arrow c (1503), respectively. Two polyhedral shape
of carbon nanostructures are also showed in the image. (b) Various carbon nanoarches (arrow a, b, c and d), the &kink' in graphite sheet
(arrow e) and broken graphite sheets (arrow f) are seen.

Fig. 3. HRTEM images of the closed-shells nanostructures with (a) a hollow core, (b) an inner metal particle.

wrapped in graphitic shell may be introduced by

ball-milling as impurity [15]. The outer graphitic
layers tightly surround the metal particle without
any gap and bent to follow the curvature of the
surface of the metal particle. Although onion-like
carbon particles have been produced previously
under extreme conditions, such as very high-temperature (in the case of arc-discharge) [13] or highenergy electron irradiation [6], the formation of

onion-like nanoparticle by ball-milling of graphite,

to our knowledge, has not been reported before. It
is evident that these closed-shell carbon particles
are formed by bending of the sp sheets under the
heavy mechanical deformation.
Fig. 4 shows the images observed in the sample
obtained by milling for 250 h. We can see that the
sample is strongly disordered, and the crumpled
layers crisscross, leading to a microporous

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X.H. Chen et al. / Journal of Crystal Growth 218 (2000) 57}61

Fig. 4. HRTEM image for graphite ground 250 h of milling

time.

microtexture. From Fig. 4, it can also be seen that

the large unbroken aromatic layers are still remaining, despite strong exfoliation and crumpling of the
graphite sheets. Compared with the sample obtained by milling for 150 h, the sample obtained by
milling for 250 h do not possess distinguishable
carbon nanostructures. The strongly disorganized
structure of crumpling aromatic layers is similar to
the annealed carbon soot at 17003C prepared by
carbon arc method [16].
About the mechanism of formation, it is quite
noteworthy that nanoparticles are obtained here
without the help of intense electron or ionic beams,
as reported in Ref. [6]. It is claimed that the high
energy of the incident projectile creates many defects and provides enough structural #uidity to the
graphitic structure to allow a closure of the network. For the condition of arc-discharge, the
formation of the curvature of graphite sheets happened during the cooling of quasi-liquid carbon. In
the case of high-temperature-treated or electronirradiated samples, the curved or closed carbon
nanostructures is thought to minimize the energy of
the sp sheets by eliminating dangling bonds at the
end of the layer [6]. In the case of ball-milling, it is
obvious that the curved or closed carbon nanostructures are generated by bending of graphite
sheets. According to a report by Huang [12], the
nanoarches were formed by direct curling or bending of the #at sp sheets. However, based on the
investigation of high-resolution TEM image in
Fig. 2b, another possible formation mechanism of

nanoarch is presented. Fig. 2b shows the various

nanoarches marked by arrowheads a, b, c and d,
respectively. Nanoarches a and b consist of multilayers of curved graphitic sheets, which can be
thought to be formed by direct bending of the #at
sp sheets, while the nanoarches c and d may be
formed by another way. By careful observation of
nanoarches c or d, we can see that it is the smallest
nanoarch generated by only two neighboring
graphite sheets linked together. We may conclude
that they could not be produced by direct bending
of #at graphite sheets. In fact, in the milling process,
high-frequent collisions and the high velocity of
steel balls make the local pressure very high
(2}6 GPa), and long duration ball-milling produced
a su$ciently high temperature. On the other hand,
the characteristic structure of the graphite, which
consists of hexagonal linked layers bonded through
localized in-plane p(sp) hybrids and delocalized
out-of-plane p orbits, gives it a high in-plane
strength while there is a relatively weak out-ofplane interaction. Therefore the ball-milling process induces a high defect density. Arrow e in Fig.
2b indicates a typical &kink', which may be introduced with weak deformation of graphite sheets by
ball-milling. When the energy generated by ballmilling is high enough to break the covalent bonds
within the graphite layers, vacancies including
dangling bonds are formed (arrow f in Fig. 2b). It is
likely that the dangling bonds are eliminated by the
high temperature produced by ball-milling. So,
when two ruptured graphite sheets are adjacent,
they tend to quench by producing C}C bonds to
eliminate the dangling bonds, and two adjacent
sheets linked together, result in the formation of
nanoarch (arrows c and d in Fig. 2b). Therefore, we
believe that these nanoarches are produced not
only by direct bending of graphite sheets, but also
by regraphization of local broken graphite sheets.
As for the formation of onion-like nanoparticles
by ball-milling, a two-stage model is proposed.
First, the #at graphite sheets are bent or curved by
ball-milling, and the graphite sheets are imperfect
and include many defects and dangling bonds. Second, when the ends of the two curved graphite
sheets are very close to each other, the high-energy
ball-milling provides enough energy to graphitize
for imperfect graphitic structure and to allow

X.H. Chen et al. / Journal of Crystal Growth 218 (2000) 57}61

a closure of the network. From an energetic point

of view, the quasi-spherical carbon &onions' are the
most stable form of carbon particles [17]. When
the highly curved graphitic stacks with one end
opened are obtained, they are in a metastable state
in the light of the theory of minimization of surface
area, so the need to minimize the energy drives this
curling up to spherical forms like onions.
Upon increasing milling, the cumulated mechanical energy produces a high density of defects into
the graphene planes, provoking an intense stripping and folding of the aromatic layers, and the
lamellar microtexture is progressively destroyed.
The typical carbon nanostructures obtained by
milling for 150 h have been lost in the sample obtained by milling for 250 h (Fig. 4). So, the results of
the ball-milling not only relate to ball to power
ratio, the rotation rate of the vial and medium in
the vial, but also relate to the milling time. With
increasing ball-milling time, di!erent carbon structure and microtexture are obtained. The curved or
closed-shells carbon nanostructures are produced
only in the intermediate stage of milling.

4. Conclusion
Highly curved carbon nanostructures or closedshell graphite particles are formed by ball-milling of
graphite. Their formation is explained by bending
of the #at sp graphite layers directly, as well as by
linking of broken graphite sheets under mechanical
deformation. The results of ball-milling processing
of graphite supply a new method to produce carbon nanostructures, especially onion-like carbon
nanoparticles.

61

Acknowledgements
The authors acknowledge the "nancial support
from the Natural Science Foundation of China
(Grant no. 59972031).

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