Materials Science & Engineering A 560 (2013) 365371

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Processing of coppercarbon nanotube composites by vacuum hot

pressing technique
A.K. Shukla a, Niraj Nayan a,n, S.V.S.N. Murty a, S.C. Sharma a, Prathap Chandran b,
Srinivasa R. Bakshi b, Koshy M. George a
a
b

Materials and Mechanical Entity, Vikram Sarabhai Space Centre, Trivandrum 695022, India
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036, India

a r t i c l e i n f o

abstract

Article history:
Received 26 May 2012
Received in revised form
23 August 2012
Accepted 21 September 2012
Available online 27 September 2012

Copper (Cu) matrix composites reinforced with 0.2, 5 and 10 vol% single wall carbon nanotubes
(SWCNT) and 5 and 10 vol% multi-wall carbon nanotubes (MWCNT) were processed by high energy
milling of pure copper powder with carbon nanotubes (CNTs) and subsequent consolidation by vacuum
hot pressing. Microstructural observations of the sintered composites revealed equiaxed twinned
microstructure for 0.2 vol% SWCNT composite and elongated grain structure, with CNT layers in
between, in composites having higher CNTs content. The porosity in the composites was associated
with CNT layers. The distribution of CNTs was found to be different in axial and transverse directions.
Signicant improvement in hardness of CuSWCNT composite was observed with increase in CNTs
content. Whereas, in case of MWCNT composite, hardness reduced for 10 vol% CNT composites.
Compression strength of the SWCNT samples was found to be higher than the MWCNT reinforced
samples.
& 2012 Elsevier B.V. All rights reserved.

Keywords:
Multiwall carbon nanotube
Single wall carbon nanotube
Vacuum hot pressing
Sintering
Copper
Composites

1. Introduction
Carbon nanotubes (CNTs) have been suggested as an excellent
reinforcement to improve the mechanical performance of metallic
materials due to their high elastic modulus, strength and aspect
ratio [1]. Novel composites have been developed by incorporating
CNTs into polymer, ceramic and metal matrices via various routes
to realize composites with outstanding properties over conventional composite materials [28]. Uniform dispersion of CNTs in
the matrix is the most important requirement to achieve uniform
properties in these composites. The ease of CNT dispersion in the
polymer matrix has resulted in considerably huge amount of
research in polymermatrix composites (PMCs) in order to
improve their electrical conductivity along with the enhancement
of mechanical properties [911]. However, work on metal matrix
composites has been relatively scarce primarily due to difculties
in achieving homogeneous dispersion of CNTs with in metal matrices
especially at high CNT loading [1215] and lack of suitable synthesis
techniques. Mechanical alloying and molecular level mixing [16]
have been the best dispersion techniques and have received the
maximum [1719]. In order to obtain excellent mechanical and
physical properties, several fabrication routes namely thermal

Corresponding author. Tel.: 91 471 256 3582; fax: 91 471 270 5048.
E-mail address: metnayan@gmail.com (N. Nayan).

0921-5093/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msea.2012.09.080

spraying [20], hot-pressing [21], hot extrusion [22], spark plasma

sintering [23] and electro-less deposition [24] have been used to
synthesize metalCNT composites.
Copper, due to its very high thermal and electrical conductivity, has always been a natural choice for the applications
where high thermal and electrical conductivity is required such
as welding electrode, high-voltage switches to more advanced
active-cooling applications, such as rst wall-and-diverter
interactive components in ssion, magnetic connement fusion
reactors, thrust chamber liners for reusable launch vehicle (RLV)
engines and rocket nozzle liners. However, pure copper has very
low strength and thus limits its usability. The effort to improve
the mechanical properties of the copper by alloying or dispersing with second phase leads to lower thermal and electrical
properties. The use of CNT as a reinforcement phase is expected
to improve the mechanical properties without harming the
thermal and electrical properties.
Several methods have been devised to synthesize CuCNT
composites. Cha et al. have devised new method called molecular
level mixing for synthesizing CuCNT powders from aqueous
solution of copper salts containing dispersed CNTs [16]. It was
shown that the presence of oxygen at the CuCNT interface resulted
in good load transfer affecting high degree of strengthening [25] in
compacts obtained by spark plasma sintering. Another technique
used for improving dispersion is by attaching CNTs to Cu akes
produced by ball milling by means of a binder [26]. Roll bonding

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has also been used for dispersing CNTs between thin Cu foils [27].
Ball milling has been used by several authors for CuCNT composites [2831]. Consolidation of the ball milled powders has been
reported by high pressure torsion [31] and SPS [32].
There are only a few reports on synthesis of CuCNT composites by hot pressing which is a very versatile technique. Bulk
composites for real life applications can be produced by hot
pressing. Therefore, the purpose of the present investigation
was (a) to synthesize CuCNT composites by mechanical alloying
and consolidate them through hot pressing; (b) to study the effect
of type of CNT on the microstructure and properties and (c) to
study effect of CNT content on the mechanical properties. In order
to achieve the above objectives, CuCNT composite powders were
processed by high energy milling of pure copper with 0.2, 5 and
10 vol% SWCNTs and 5 and 10 vol% MWCNTs. The composite
powders were sintered by vacuum hot pressing technique. The
hot pressed composites have been characterized using optical
microscopy, SEM, XRD and bulk hardness testing. The results
obtained are discussed in the paper.

2. Experimental procedures
Copper (99.9% pure,  140 mesh) and CVD grown multi walled
carbon nanotubes (MWCNT) (approximately 1575 nm in diameter
and 520 mm in length, having purity more than 90% supplied by
Nanolab Inc, USA) and CVD grown single walled carbon nanotubes
(SWCNT) (approximately less than 2 nm in dia., supplied by
Thomas Swan & Co. LTD., UK), were used in the present experimental study. No functionalization of the nanotubes was carried
out prior to mixing. Fig. 1 shows the SEM images of the starting
feed stock. Measured amounts of CNTs to achieve a volume percent
(vol%) of 0.2, 5 and 10 in case of CuSWCNT and 5 and 10 in case of
CuMWCNT were mixed with copper powder in stainless steel
mixing jar containing stainless steel balls of 10 mm diameter
(giving initial ball to powder ratio (BPR)5:1).The density of
MWCNT used in this study as quoted by the manufacturer was
1.8 g/cm3 and that of SWCNT was 1.2 g/cm3. While calculating the
relative density of the composite powders, the density of the pure
copper was considered as 8.9 g/cm3; for the MWCNT reinforced
Cu composites, the weight percentage of CNT is 1.06 for 5 vol% of
CuCNT composite while it is 2.25 for 10 vol% CuCNT composite.
On the other hand, for the SWCNT reinforced Cu composites, the
weight percentage of CNTs is 0.71 for 5 vol% of CuCNT composite
while it is 1.5 for 10 vol% CuCNT composite. The jar was lled with
argon and agitated in an Attritor mill (Szegvari make) at 200 rpm
for milling time of 20 h. Changes in the size and shape of the

particles on milling was studied using SEM. The composite powder

was hot mounted and polished and observed with SEM to reveal
the cross section of a milled powder particle and elucidate the
dispersion of CNTs.
The composite powders were hot pressed in a graphite die using
30 MPa uniaxial stress under high vacuum (10  5 mbar) in a 250 T
capacity/2000 1C rated Industrial Vacuum Hot Press. Sintering
temperature of 700 1C and soaking time of 30 min was used for
hot pressing CuCNT composite. The compacts produced underwent delamination in the center on cooling and were repressed at a
temperature of 725 1C under identical conditions. This leads to a
defect free bulk composite. Fig. 2 shows the prole of temperature
versus time of vacuum hot pressing operation. A constant stress of
30 MPa was applied for the entire hot pressing cycle until the
initiation of the cooling cycle. For repressed samples this stress was
maintained until cooling up to 500 1C.
The microstructure of the sintered samples of 65 mm diameter
and 5 mm height were characterized using optical microscopy, SEM
and Raman spectroscopy. Density of the compacts was measured
using the water immersion technique. The metallographic samples
were etched with (FeCl3 HClH2O) solution for revealing microstructure of the hot pressed composites. SEM was used to evaluate
the distribution of the nanotubes in the powder as well as the
matrix. Elemental analysis of the composite materials was carried
using EDAX attached to ESEM. Raman spectroscopy was carried out
to study the changes undergone by CNTs during the fabrication
process.
Brinell hardness of the composite was measured using 2.54 mm
dia. steel ball as indenter with 31.25 kgf load. The compression tests
were performed using an Instron 3367 table top tester with a 30 kN

Fig. 2. Temperature cycle used during the processing of the samples.

Fig. 1. SEM images of (a) Cu powder and (b) MWCNT used in the study.

A.K. Shukla et al. / Materials Science & Engineering A 560 (2013) 365371

load cell. Two tests were performed on cylindrical samples of

diameter 4 mm and length 5 mm with a cross head speed of
1 mm/min.

3. Results and discussion

3.1. Microstructural observations
It is well known that the mixing process and its duration
determine the effective dispersion of CNTs in the metal powder.
This has been studied a lot in AlCNT composites. During the
early stages of milling, copper powders get gradually deformed
into aky shaped particles as seen in Fig. 3. Simultaneously,
disintegration of agglomerated CNT ropes or lumps into the
individual CNT takes place which subsequently gets embedded
into the deformed copper particles. As this process continues, due
to continuous impact, welding, fracturing and re-welding of
Cu particles takes place and the CNTs get dispersed in between
the copper layers. Fig. 3 shows the change in the morphology of
the different composite powders after milling for 20 h. After
milling for 20 h, the CNTs are located inside the copper composite
powders rather than on the surface. The evolution of the morphological changes during the milling of CuCNT composite
powders is explained in detail elsewhere [33]. It is observed that
the ake size is smaller in CuSWCNT composite than the
CuMWCNT composite. This could be due to the larger surface
area/volume ratio of SWCNT which will lead to more coating of the
akes and prevent cold welding during milling. A reason for the
large size and the aky nature of the MWCNT containing powders
could be that the presence of CNTs between the layers helps in easy
ow/deformation of the Cu particles under the impact action during
ball milling. The ake shape of the powder suggest that the CNTs
are not distributed like particles throughout the copper matrix
but rather like layers between copper layers thus giving a lamellar
structure to milled powders. In order to study the microstructure
of individual ake, they were mounted and polished and observed
in SEM. Fig. 4 shows the polished cross section of the milled
powders showing the lamellar morphology of the CuCNT akes
with CNTs embedded between the layers. The schematic of the
process leading to formation of such layered structures is shown
in Fig. 5.
In order to study effect of the milling process on the CNTs,
Raman spectroscopy was carried out on the 20 h milled samples.

367

Fig. 6 shows the presence of the D and G peaks in the Raman

spectra of the milled powders which are characteristic of the
carbon nanotubes. It is observed that the SWCNTs seem to be
highly damaged in the 0.2 wt% composite as shown by the broad
D and G peaks which seem to merge together. Raman spectra of
amorphous carbon results in a single broad peak between 1000
and 1800 cm  1 [34]. The more damage of SWCNT in case of 0.2%
composite could be due to the shearing between copper particles
due to milling. Since only a small amount of SWCNTs are there,
there is a chance that maximum number of them are damaged
during milling. When the amount is increased to 510%, saturation is achieved in terms of occupying the space between the
akes and hence several CNTs are possibly retained. It is observed
from 5% and 10% SWCNT composites, the intensity of the D-peak
to G-peak reduces with increase in CNT content indicating that
more and more CNTs are retained as % increases. The MWCNT
composites indicate that for both 5% and 10% composites, the
CNTs are identically affected. The different behavior of the SWCNT
composite powder is due to the large surface area/volume (about
10 times) compared to MWCNT.
The CuCNT composite powders were sintered by vacuum hot
pressing method with optimized sintering parameters. During
sintering of CuMWCNT, it was noticed that sintered compact
was getting delaminated from the middle of the cross section. It
was also observed that the degree of delamination increased with
increase in vol% of MWCNT. The same phenomena were observed
during hot pressing of Cu5 vol% SWCNT but not in Cu0.2 vol%
SWCNT composite. This delamination can be attributed to elastic
nature of carbon nanotube and large mismatch of coefcient of
thermal expansion (CTE) of CNT and copper matrix. The coefcient of thermal expansion (CTE) of CNTs is negative and close to
zero [35] while copper is known to have high thermal expansion
coefcient. Also it is to be noted that since reaction between
copper and CNTs does not occur, they may act as obstacle towards
sintering.
The relative density of compacted CuCNT composites was
calculated by the ratio of the measured Archimedes density relative
to calculated theoretical density of the composite by the rule of
mixtures. The relative densities of the processed composites are
presented in Fig. 7. It can be clearly seen from Fig. 7 that the relative
densities are similar for the 5% and 10% CNT composites and is
more than 95%. The 0.2% composite showed a slightly smaller
relative density of around 90% which could be due the fact that CNT
retard the sintering behavior. In case of higher CNT loading, the

Fig. 3. SEM micrographs showing the morphology of the as-milled (20 h) powders (a) Cu0.2 vol% SWCNT composite (b) Cu5 vol% SWCNT composite (c) Cu10 vol%
SWCNT composite (d) Cu5 vol% MWCNT composite and (e) Cu10 vol% MWCNT composite.

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Fig. 4. SEM micrographs of polished cross section of the 20 h milled powders of (a) Cu0.2 vol% SWCNT composite (b) Cu5 vol% SWCNT composite (c) Cu10 vol% SWCNT
composite (d) Cu5 vol% MWCNT composite and (e) Cu10 vol% MWCNT composite.

Fig. 5. Schematic of morphological changes occurring during milling of CopperCNT powders.

Fig. 7. Relative density of the different vacuum hot pressed CuCNT composites.

Fig. 6. Raman spectra showing the presence of D and G peaks corresponding to

CNTs in the 20 h milled samples.

CNTs can go into the pores and ll them achieving near theoretical
densities. In order to analyze the pores and CNT distribution, the
cross sectional microstructure of the samples was studied using SEM.
Fig. 8(af) show the optical micrographs of the sintered
CuSWCNT composites. It can be clearly seen from Fig. 8 that
the compacts are dense and there are no major macro porosities.
The Cu0.2 vol% SWCNT seems to have some porosity and has an
equiaxed microstructure which is different than the rest of the
samples. Presence of annealing twins is also seen which is typical
of copper. The samples with higher CNT content seem to have a
layered morphology with CNTs between the grains. It seems that
the grains have deformed during the hot pressing with CNTs in
between having a lubricating effect. This is supported by the fact

that with the increase in CNT content, the grains become more
and more deformed. The porosities are mainly in the regions
containing the CNTs. EDS spectra (not shown here) taken from the
porosities revealed the presence of Carbon peaks, while at other
locations revealed only copper peaks. It is seen that the microstructure of the Cu10 vol% SWCNT is very ne indicating the
CNTs and their clusters inhibit sintering and grain growth by
obstructing the motion of interfaces. Fig. 9 shows the microstructures of the polished cross sections of the CuMWCNT
samples. It is observed that the same layered type morphology
is observed with CNTs at the grain boundaries. The grains are
elongated perpendicular to the pressing direction. It is seen that
there is considerable elongation. There is a possibility that the
CNTs aid the ow of the Cu perpendicular to the applied stress by
reducing the friction between the particle interfaces. This clearly

A.K. Shukla et al. / Materials Science & Engineering A 560 (2013) 365371

369

Fig. 8. Optical micrographs of the polished top surface and cross section respectively of (a) and (b) Cu0.2 vol% SWCNT, (c) and (d) Cu5 vol% SWCNT and (e) and (f) Cu
10 vol% SWCNT.

Fig. 9. Optical micrographs of the polished top surface and cross section respectively of (a) and (b) Cu5 vol% MWCNT, and (c) and (d) Cu10 vol% MWCNT.

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explains why the Cu0.2 vol% SWCNT is equiaxed while the other
high CNT containing phases are elongated.
The higher volume fraction CNT composites reveal network of
CNT along the grain boundaries. Some grain boundaries devoid of
CNT network are also evident. It can be marked that the micrographs of the cross section of sintered composite reveals more
predominant layered structure as compared to the micrographs of
the axial direction. The quantity as well as the continuity of the
dark phase layer (CNTs and porosities) is increasing with increase
in CNT volume fraction in the composite. The starting powder,
comprising of embedded CNT layers, being ake shape will stack
over each other during hot pressing. An increase in darker phase

Fig. 10. Raman spectra of hot pressed compacts showing the presence of D- and
G-peak characteristic of carbon nanotubes.

Fig. 11. Brinell hardness of the CuCNT composites.

(CNTs and porosities) intensity with increase in CNT volume

fraction is observed.
Fig. 10 shows the Raman spectra of the hot pressed CuCNT
compacts. It is observed that the characteristic D- and G-peaks
corresponding to CNTs are present in the compacts. When
compared to Fig. 6, it is observed that the intensity ratio of D-peak
to G-peak is higher in the compacts indicating that there are more
defects in the CNTs present in the hot pressed compacts which are
introduced as a result of the hot pressing process.
3.2. Mechanical properties of CuCNT composites
Fig. 11 presents the Brinnel hardness of hot pressed composites
for various Cu/CNT composites. Brinnel hardness gives the average
value of the indentation hardness for the composite due to the large
indent it creates. It can be seen that, for Cu/SWCNT composite,
hardness increases with increase in CNT content. This can be
attributed to the strengthening effect of the CNTs in the composite.
As the strength of CNTs is higher than Cu, the increase in content of
CNTs lead to increase in strength (reected as hardness) of sintered
composite. The strengthening effect of CNTs to metal matrix has
been studied and explained by many researchers. In case of the
multiwall carbon nanotube reinforced composite, Kim et al. [32]
have observed hardness increases almost linearly with increasing
the CNTs volume fraction. The Cu/MWCNT composites behaved in a
different manner. It is observed that SWCNT are more effective
than MWCNT in improving the properties. This could be attributed
to the fact that SWCNTs are stronger than MWCNTs. In-situ tensile
tests on CNTs have shown higher strength of CNTs with smaller
diameter [36]. It is seen that the hardness of the 5% MWCNT
composite is higher than that of the 10% MWCNT composite. This
can be explained based on the microstructure. The distinctly layered
structure observed in MWCNT composite is responsible for this kind
of behavior. It is seen that the network structure around the grains
increases with increase in CNT content and might be the weaker
regions where sliding of grains might take place during the Brinell
test leading to lower hardness.
Fig. 12 shows the compressive stress strain curves of the
samples. It is seen that in accordance with the hardness values,
the compressive strength of the Cu10 vol% SWCNT is the highest.
The deviation from linear behavior occurs at a load of 210 MPa
for Cu0.2% SWCNT, 330 MPa for Cu5% SWCNT, 310 MPa for
Cu10% SWCNT, 170 MPa for Cu5% MWCNT and 180 MPa for
Cu10% MWCNT sample. These values (except for Cu0.2%
SWCNT) are lower than the compressive yield strengths reported
by Kim et al. for Cu (150 MPa), Cu5% MWCNT (360 MPa) and Cu
10% MWCNT (455 MPa) [25]. This again illustrates the effect of
having good dispersion produced by molecular level mixing and

Fig. 12. Representative stressstrain curve of the samples in compression.

A.K. Shukla et al. / Materials Science & Engineering A 560 (2013) 365371

the presence good load transfer on the strengthening attainable in

these composites. The Cu0.2 vol% SWCNT sample behaves like
ductile copper and gets deformed to a button without failing.
The 5 and 10 vol% SWCNT samples are however moderately
ductile and fracture after some strain. They are reasonably strong
compared to composites prepared by Kim et al. which had good
CNT dispersion. On the other hand the CuMWCNT samples seem
to deform at lower load under compression than the CuSWCNT
samples. The network of MWCNTs present in between the Cu
grains in the samples probably are weaker regions and fail
prematurely and aid the deformation by promoting grain sliding.
The network type CNT structures could be useful in improving the
wear resistance of the composites.

4. Conclusions
Following conclusions can be drawn from this study.
1. High energy milling up to 20 h resulted in entrapment of CNTs
in a layered fashion between the Cu akes.
2. Bulk (65 mm dia.  5 mm thick) CuMWCNT and CuSWCNT
composites were successfully sintered by conventional hot
pressing operation. Repressing operation was carried out to
eliminate delamination that occurred in the central region of
the composites.
3. The microstructure showed distinct CNT layers present at the
particle interfaces which have strong effect on the properties.
The intensity ratio of D-peak to G-peak in Raman spectra was
found to be higher for the compacts compared to respective
milled powder indicating increased defect generation during
hot pressing.
4. The hardness of the composites increased with increase in the
vol% of SWCNT whereas it decreased in case if MWCNT which
was explained based on the strong presence of CNT layers
between the grains.
5. The compressive strength of the SWCNT containing composites is higher compared to MWCNT composites. The network
structure of CNTs at the grain boundaries might be reducing
the strength by failing prematurely and aiding grain sliding.
6. This study also shows that SWCNTs are better reinforcements
compared to MWCNTs.

Acknowledgments
The authors are also grateful to Director, (VSSC) for encouragement and kind permission to publish this work. SR Bakshi
would like to thank ISRO-IITM Cell for funding.

371

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