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04-Graphene Nanosheet, Al2O3 Composite
04-Graphene Nanosheet, Al2O3 Composite
available at www.sciencedirect.com
A R T I C L E I N F O A B S T R A C T
Article history: Fully dense graphene nanosheet(GNS)/Al2O3 composites with homogeneously distributed
Received 15 October 2009 GNSs of thicknesses ranging from 2.5 to 20 nm have been fabricated from ball milled
Accepted 12 January 2010 expanded graphite and Al2O3 by spark plasma sintering. The percolation threshold of elec-
Available online 18 January 2010 trical conductivity of the as-prepared GNS/Al2O3 composites is around 3 vol.%, and this
new composite outperforms most of carbon nanotube/Al2O3 composites in electrical con-
ductivity. The temperature dependence of electrical conductivity indicated that the as-pre-
pared composites behaved as a semimetal in a temperature range from 2 to 300 K.
Ó 2010 Elsevier Ltd. All rights reserved.
* Corresponding authors: Address: School of Materials Science and Engineering, Shanghai University, 149 Yanchang Road, Shanghai
200044, China (J. Li), State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, Shanghai 200050, China (W. Jiang). Fax: +86 21 52413122.
E-mail addresses: jlli@shu.edu.cn (J. Li), wanjiang@mail.sic.ac.cn (W. Jiang).
0008-6223/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2010.01.017
1744 CARBON 4 8 ( 2 0 1 0 ) 1 7 4 3 –1 7 4 9
that of CNTs, nano-particles of the matrix have a good chance The morphology and microstructure of samples were char-
to attach to the large surfaces(lateral dimension above 1 lm acterized by field emission scanning electron microscopy
in average) and thus to prevent the agglomerates of graphene (FESEM) (JEOL JSM-6700F), transmission electron microscopy
and GNSs. (TEM) and high-resolution transmission electron microscopy
In terms of preparing graphene, the main problem is how (HRTEM) (JEOL 200CX).
to obtain a large amount of GNSs as thin as possible (for in-
stance, less than 10 layers). Typically there are three methods 3. Results and discussion
to prepare graphene sheets: micromechanical exfoliation,
epitaxial growth of graphene films and chemical processing 3.1. Microstructure of the as-prepared samples
including oxidation, exfoliation and reduction. Among them,
the last one seems to be the most promising as it has the po- The SEM image of expanded graphite presents a loose struc-
tential to enable massive production of GNSs. However, cer- ture containing multi-pores (Fig. 1a). Magnified image shows
tain sorts of functional groups are difficult to remove by the thickness of an individual flake is about 100 nm (Fig. 1b),
reduction, leaving a significant number of defects which im- which indicates expanded graphite is a good start for fabricat-
pair the electronic properties of GNSs severely. ing GNSs compared with natural flake graphite.
In this work, we used expanded graphite as a starting The SEM observations of the composites and monolithic
material to fabricate GNSs. To ensure the obtained GNSs have ceramic reveal no obvious defects in the specimens and the
a good electronic structure, we employed ball milling rather micrographs were featureless, as shown in Fig. 2, confirming
than re-intercalation by oxidation to further exfoliated ex- their fully dense structure. To evaluate the distribution of
panded graphite, and the as-prepared GNSs were dispersed GNSs in the ceramic matrix, fracture surface of the composite
homogeneously in powder mixtures at the same time. Then containing 1 vol.% GNSs was investigated (Fig. 2b). By compar-
dense bulk composites were prepared from the powder mix- ing with the pure Al2O3 ceramic (Fig. 2a), the growth of the
tures by SPS. The electrical conductivities of as-prepared grain are found to be restrained remarkably with the presence
composites are far higher than CNT/Al2O3 composites with of GNSs. Moreover, it is shown that the grain sizes of Al2O3 are
the same conductive phase content.
2. Experimental details
Fig. 2 – SEM images of fractured surfaces of (a) a pure Al2O3 ceramic and (b–d) a GNS/Al2O3 composite containing 1 vol.% GNSs;
(c) and (d) are magnified parts of (b).
homogeneous, which verify the good dispersion of GNSs in be seen that only very small fraction of overlap exist in the
the matrix (Fig. 2c). Compared with the pure Al2O3 ceramic, Al2O3 grain boundary (Fig. 3d), indicating the effectiveness
in GNS/Al2O3 composite the phenomena of transgranular and success of our strategy in preparing and dispersing of
fractures increase, suggesting the high strength of GNSs. GNSs.
The SEM images show no thin GNSs (below 20 nm) but a There are two key factors of preparing and dispersing
few pulled-out sheets dispersed in the matrix(marked by yel- GNSs well in our method. The first one is the usage of plane-
low rings in Fig. 2b), but most of these pulled-out sheets are as tary ball mill. The possibility of preparing tailored carbon
thick as 50 nm (Fig. 2d). This phenomenon can be explained nano-materials by mechanical deformation has been widely
as follows: when the sheets are thin (less than 20 nm) and investigated before [14–16], and the mostly used experimental
vertical to the fracture surface, they are easy to rupture under method is mechanical milling in a ball milling device. The two
the shearing stress. Besides, when the thin sheets are located most common types of ball milling equipments, planetary
on the fracture surface, they cannot be identified in a SEM im- and vibratory mills, have been both experimentally tested.
age due to the small thickness of GNSs. On the contrary, when In this study we exploit planetary ball mill as the main imple-
we get thick GNSs in the grain boundary, they are strong en- ment to exfoliate graphite into GNSs because the planetary
ough to bear the shearing stress and expose themselves when mill favors the cleavage of the particles [17]. One of the effec-
fractures occur. tive methods for preparing graphene is called laborious draw-
Further characterization of the microstructure of the com- ing or micromechanical exfoliation [18]. In a sense the
posites was carried out by TEM. Fig. 3 are representative TEM planetary ball mill method is another type of mechanical
and HRTEM images of a composite containing 5 vol.% GNSs. exfoliation because the shear component of the applied stress
The image reveals that the GNSs semi-wrap around the is dominant [16], as illustrated in Fig. 4.
Al2O3 grains and connect with each other to form a network The other important factor is the selection of dispersal
structure (Fig. 3a). It is observed that more than half of the media. It is well-known that the presence of a liquid in the
GNSs are below 10 nm in thickness and sheets with the thick- milling process leads to lubrication, moderates the violent
ness of more than 20 nm have rarely been observed. Some of shocks and avoids large agglomerates of the particles. For in-
the GNSs are as thin as 2.5 nm, which means it comprises of stance, Inam et al. have reported dimethylformamide as an
only seven layers of graphene, as shown in Fig. 3c. It can also effective dispersant for making CNT/ceramic composites
1746 CARBON 4 8 ( 2 0 1 0 ) 1 7 4 3 –1 7 4 9
Fig. 3 – TEM and HRTEM images of a GNS/Al2O3 composite containing 5 vol.% GNSs: (a) GNSs surrounding Al2O3 nano-
particles; (b) a magnified image of GNSs with a thickness of about 10 nm in (a); (c) GNSs with a thickness of 2.5 nm; (d) overlap
of GNSs between Al2O3 nano-particles.
called the percolation threshold, the dc conductivity of the 50 K, respectively, which suggests that the conductivity is not
composites exhibits a dramatic rise of eight to ten orders in mainly controlled by fluctuation induced tunneling mecha-
magnitude. The experimental results have shown that pure nism in the GNS/Al2O3 composite.
Al2O3 is an insulator with extremely low electrical conductiv- We presume that the low value of t arises from the unique
ity (1013 S/m), but the electrical conductivity increased structure of the GNS network. The paper-like GNSs unques-
sharply as the content of GNSs was close to percolation tionably form a three dimensional network, the shape of
threshold around 3 vol.% (Fig. 5). GNS, however, is far from spherical. Furthermore, during
This behavior can be described by the percolation theory. SPS, the applied pressure leads to some preferable in-plane
According to the theory [21–23], as the conducting loading is arrangements of GNSs. As a result of such a combination of
above the percolation threshold, the dc conductivity of the two dimensional and three dimensional configurations, the
composites follows the power law as described by composite does not present as a random three dimensional
system. The t = 1.54 reveals the complicate GNS network of
rdc ¼ rc ðPGNSs Pc Þt ; for PGNSs > Pc ð1Þ
a fractal dimensions.
where rdc and rc are the dc conductivities of the composite As shown Fig. 5, the samples’ conductivities increase with
and conducting component, respectively. PGNSs is the volume the growth of volume fraction of GNSs. The increase in the
fraction of the GNSs, Pc is the critical volume fraction or perco- GNS content results in the increase of internanosheet con-
lation threshold, and the exponent t reflects the dimensional- nections, and consequently numerous conductive paths be-
ity of the system and has been calculated to be 1.3 and 2.0 come available. The conductivity increases due to
corresponding to two and three dimensions, respectively [24]. availability of a large number of charge carriers traveling
The fitting curve to Eq. (1) is shown in Fig. 5, and we got through the entire network. It is worthy to mention that
Pc = 3 ± 0.405 vol.% and t = 1.54 ± 0.22. The percolation thresh- the electrical conductivity still increases quickly when GNS
old value confirms the experimental result and is much lower content is above percolation threshold, the highest value
than that of the graphene/silica composite film fabricated by we obtained is 5709 S/m in 15 vol.% GNSs/Al2O3 composite,
spin-coating graphene on glass and SiOx/silicon substrates which is 170% higher than the best result of SWCNT/Al2O3
[25], while higher than the value of CNT-reinforced compos- composite with the same conductive phase content [29]. This
ites reported by Rul et al. [6] (0.64 vol.%, SWCNT/MgAl2O4 phenomenon is very important and different from most
composites) and Ahmad et al. [26] (0.79 vol.%, MWCNT/ CNT-reinforced ceramic composites, in which electrical con-
Al2O3 composites). ductivity levels off when the conductive phase content is
The low value of t = 1.54 indicates that charge seems not to above percolation threshold [10,11,26], mainly because of
transport through a random three dimensional network of intrinsic property of CNTs. Firstly, the CNTs tend to agglom-
GNSs. Previous works [6,26,27] show that a low value of t in erate with the content increasing in the matrix. When the
a bulk material is inductive to thermally induced hopping content of the CNTs exceeds the percolation threshold, most
transport between disconnecting or weakly connecting parts of the added CNTs form ‘‘bundles’’ and ‘‘ropes’’ which have
of the network, also known as fluctuation induced tunneling little contribution to the electrical conductivity. Besides, gen-
mechanism, which is accompanied by a relatively high value erally the connection between CNTs is of a point–point touch
of t (2) at low temperatures [27,28]. However, in our research, form that leads to a high resistance. In contrast with CNTs,
the fitting values of t were found to be 1.38 and 1.44 at 2 and GNSs are connected by an area–area touch form, which re-
Fig. 5 – Electrical conductivities of GNS/Al2O3 composites as a function of filler volume fraction. Inset: log rdc plotted against
log (PGNSs Pc), where Pc is percolation threshold (see text).
1748 CARBON 4 8 ( 2 0 1 0 ) 1 7 4 3 –1 7 4 9
R E F E R E N C E S
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