Article

Copyright 2014 American Scientic Publishers

All rights reserved
Printed in the United States of America

Journal of
Nanoscience and Nanotechnology
Vol. 14, 87508755, 2014
www.aspbs.com/jnn

Preparation and Characterization of Copper-Graphite

Composites by Electrical Explosion of Wire in Liquid
T. N. Bien1 , W. H. Gu1 , L. H. Bac1
2 , and J. C. Kim1

1

School of Materials Science Engineering, University of Ulsan Daehak-Ro 93, Nam-Gu,

Ulsan, 680-749, South Korea
2
School of Engineering Physics, Hanoi University of Science and Technology, Hanoi, Vietnam
Copper-graphite nanocomposites containing 5 vol.% graphite were prepared by a powder metallurgy
route using an electrical wire explosion (EEW) in liquid method and spark plasma sintering (SPS)
process. Graphite rods with a 0.3 mm diameter and copper wire with a 0.2 mm diameter were used
as raw materials for EEWin liquid. To compare, a pure copper and copper-graphite mixture was
also prepared. The fabricated graphite was in the form of a nanosheet, onto which copper particles
were coated. Sintering was performed at 900  C at a heating rate of 30  C/min for 10 min and
under a pressure of 70 MPa. The density of the sintered composite samples was measured by the
Archimedes method. A wear test was performed by a ball-on-disc tribometer under dry conditions
at room temperature in air. The presence of graphite effectively reduced the wear of composites.
The copper-graphite
nanocomposites
prepared SCIENCE
by EEW had
lower wear rates than
pure copper
Delivered by Publishing
Technology to:
INST. FOR APPLIED
& ENGINEERING
RESEARCH/ACADEMIA
SINICA
material and simple mixed
copper-graphite.
IP: 140.109.57.11
On: Sat, 08 Nov 2014 10:13:56

Copyright:
American Scientific
Keywords: Copper-Graphite
Nanocomposites,
ElectricalPublishers
Explosion of Wire in Liquid, Spark
Plasma Sintering, Wear Resistant.

1. INTRODUCTION
Metal-graphite composites are attractive materials for
many applications such as engine brushes and generators or sliding contacts,1 self-lubrication parts for automotive pistons,2 and heat sink elements in multi-functional
electronic packaging systems.3 Copper-graphite composites are widely used in tribological engineering parts.4
Copper-graphite composites combine the positive characteristics of both components, i.e., high thermal and electrical conductivity of the copper with the low thermal
expansion coefcient and good lubricating properties of
the graphite.5
Copper-graphite composites are typically prepared by a
powder metallurgy (PM) process as the PM process offers
the possibility of obtaining uniform parts and reducing
production costs. However, PM has certain limitations primarily related to the poor afnity between copper and
graphite, which gives rise to weak interfaces with a negative effect on the structural, mechanical, and electrical
properties of the material.5
6 The lack of wetting between

Author to whom correspondence should be addressed.

8750

J. Nanosci. Nanotechnol. 2014, Vol. 14, No. 11

copper and graphite during composite processing can be

overcome by coating the graphite particles with copper
before consolidation. Moustafa et al.7
8 fabricated coppergraphite composites by a PM route using Cu-coated
graphite powders and a mixture of copper and graphite
powders. The copper-coated graphite powders possessed
lower wear rates and friction coefcients than those made
from pure copper and non-copper-coated graphite. Moreover, the copper-coated composites show a higher density
and yield strength.
In this work, the electrical explosion of wire (EEW)
in liquid was introduced to fabricate copper-graphite
nanocomposites. The EEW process has attracted attention
for fabrication of various nanosized powders due to the
simple and low-cost production.911 Homogenous coppercoated graphite nanocomposite powders were rst produced by EEW, and then the sintered composites were
produced by SPS.

2. EXPERIMENTAL DETAILS
The EEW in liquid was used to prepare graphite
nanosheets and copper powder. The experimental setup
1533-4880/2014/14/8750/006

doi:10.1166/jnn.2014.9995

Bien et al.

Preparation and Characterization of Copper-Graphite Composites by Electrical Explosion of Wire in Liquid

Table I. Conditions of the wire electrical explosion process.

Capacitance
Charging voltage
Cu wire diameter
Graphite rod diameter
Wire length of one explosion
Ambient liquid

Table II.
30 F
3 kV
0.2 mm
0.3 mm
25 mm
Ethanol

Parameters of ball-on-disc tribometer testing.

Ball diameter
Specimen diameter
Wear track diameter
Applied load
Speed
Distance

7 mm
15 mm
10 mm
10, 15, 20 N
50, 70, 90 rpm/min
15.7, 31.4, 62.8 m

room temperature to a sintering temperature at a heating

of the EEW process was described previously.12 Typirate of 30  C/min and then held for 10 min. The electric
cal experimental conditions are summarized in Table I.
power was turned off after the holding time, and the samGraphite rods with a diameter of 0.3 mm were used to
ple was cooled without control of the cooling rate. The
prepare the graphite nanosheets. Before explosion, the
density of the sintered composite samples was measured
graphite rods were treated with a mixture of concentrated
by the Archimedes method. A schematic illustration of the
sulfuric acid and nitric acid (4:1, v/v). The acid-treated
experimental procedure is shown in Figure 1.
graphite rods were washed several times with deionized
The wear properties of the sintered composites were
water and then dried at 60  C to remove any remaining
measured using a ball-on-disc tribometer. The tested samwater after they were immersed in a mixed acid solution
ples were in the shape of a disc shape 15-mm in diamfor 120 hrs. The dried graphite rods were exploded in
eter and 2-mm thick. The ball was tungsten carbide with
ethanol to produce the graphite suspension.
a 7-mm diameter. The wear tests were performed at varThe graphite suspension was used as a working liquid
ious loads, distances, and speeds, as shown in Table II.
for the preparation of copper powder for EEW. Copper
Each sample was weighed before and after each wear test.
wire (Nicola, 99.9%) with a diameter of 0.2 mm was used
For comparison, a pure copper and copper-graphite mixfor the explosion. Copper explosions were performed at a
ture was also prepared. The copper-graphite mixture was
number sufcient to result in 95 vol.% copper. The copprepared by a ball milling method. Milling was performed
per powder-coated graphite nanocomposite powders were
at room temperature for 30 min at 700 rpm using 5-mm
collected from the suspension by drying at 80  C under
diameter &chrome
steel balls, RESEARCH/ACADEMIA
and the ball-to-powder wt.SINICA
vacuum.
The
reduction
of
the
composite
powders
was
perDelivered by Publishing
Technology to: INST. FOR APPLIED SCIENCE
ENGINEERING
was 2014
maintained
at approximately 20:1. The sintering
formed at 700  C for 2 hrs in order
to remove the oxide
IP: 140.109.57.11
On: Sat,ratio
08 Nov
10:13:56
of pure copper
and copper-graphite mixture was the same
phase.
Copyright: American Scientific
Publishers
as that of the sample prepared by EEW.
The bulk samples were prepared by a spark plasma
sintering (SPS) machine (Sumitomo Coal Mining Co.,
Model 515S). The composite powder (4 g) was placed in a
3. RESULTS AND DISCUSSION
graphite die with an inner diameter of 15 mm. A pressure
Figure 2 shows the morphology of graphite prepared by
of 70 MPa was applied, and the sample was heated from
EEW in ethanol. The graphite after explosion was broken
into a sheet with a thickness of 20 nm. The graphite
sheets are of relatively uniform size with a range from 1
to 3 m.
After explosion of copper in the graphite suspension,
the copper-graphite suspension was dried and observed by
SEM. As shown in Figure 3, the copper particles had a
spherical shape. Copper particles size can be classied

Figure 1. Schematic illustration of the experimental procedure.

J. Nanosci. Nanotechnol. 14, 87508755, 2014

Figure 2.

FESEM image of graphite nanosheets prepared by EEW.

8751

Preparation and Characterization of Copper-Graphite Composites by Electrical Explosion of Wire in Liquid

Bien et al.

Figure 3. FESEM micrographs of copper-graphite composite at (a) low and (b) high magnication.

into two groups: nanoparticles with a diameter smaller

reduction of the composite powder, the peak disappeared
because the copper oxide phase was reduced to pure
than 100 nm and ne particles with a diameter larger than
copper.
100 nm. The prepared graphite was in the form of a sheet,
Figures 6(a)(c) show optical microscopic images of
as described above. The copper particles were coated on
bulk samples sintered at different temperatures for a
the surface of the graphite sheets. The coating of copper
10 min holding time. The sintering temperature was
nanoparticles on graphite can overcome the limitations of
changed from 800 to 900  C. The microstructure of the
poor afnity between copper and graphite and produced
sintered sample depended on the sintering temperature.
better properties of graphite-copper composites, which are
The densication increased with increase in the sintershown below.
ing temperature. The white area on the images illustrates
Figure 4 shows the EDS results of copper-graphite
a good sintering area with few pores and good connecnanocomposite powders before and after reduction in
tivity between the particles. The sample from sintering
hydrogen at 700  C for 2 hrs. The nanocomposite powders
Delivered
by Publishing
to: INST.
FOR APPLIED
& ENGINEERING
RESEARCH/ACADEMIA
SINICA
at 800  C
had the largest black
area (pores). Therefore,
prepared
by EEW Technology
in ethanol contained
oxygen.
The oxy- SCIENCE
IP: 140.109.57.11 On: Sat, 08 Nov 2014 10:13:56
the porosity
was dominant at low sintering temperature.
gen in the sample may be due to the Copyright:
oxidation ofAmerican
copper Scientific
Publishers
When the sintering temperature increased, the porosity
during explosion by oxygen dilution in the liquid. Copgradually decreased. The density of these samples veried
per was in a vapor state when exploding and could have
the sintering results. The density of the sample sintered
reacted with the oxygen present in ethanol. Oxidation can
at 800  C was only 6.9 g/cm3 and the relative density
also occur during handling. The nanopowders are easily
was approximately 80%. The value reached 7.5 g/cm3 for
oxidized when they contact oxygen in air. The composite
the sample sintered at 870  C with a relative density of
powder with reduced hydrogen was pure, containing no
approximately 87%. The greatest density was 7.9 g/cm3 ,
oxygen.
for
the sample sintered at 900  C, and the relative density
Figure 5 presents XRD patterns of the copper-graphite
was
approximately 91%. The microstructure of the coppercomposite before and after reduction. The composite
graphite composite sample fabricated by milling contained
powder before reduction showed three main characterismany small black areas, and the black areas dominated
tic diffraction peaks for copper at 2 = 433, 50.4 and
74.0 degrees, corresponding to (111), (200) and (220)
crystal planes, respectively. This pattern conrms the formation of the FCC copper phase. The small peak at
2 = 265 was attributed to graphite. A very low peak
at 2 = 364 belonged to cuprous oxide (Cu2 O). After

Figure 4. EDS proles of a copper-graphite composite (a) before and

(b) after reduction.

8752

Figure 5. XRD patterns of copper-graphite composite powders

(a) before and (b) after reduction.

J. Nanosci. Nanotechnol. 14, 87508755, 2014

Bien et al.

Preparation and Characterization of Copper-Graphite Composites by Electrical Explosion of Wire in Liquid

Figure 8. The effect of speed on weight loss with a distance of 32 m

and load of 15 N.

manipulated and the weight loss was measured after each

variation. The specic wear rate was obtained by dividing the weight loss by the density, the total sliding distance, and the normal load of the test. Figure 7 illustrates
that the specic wear rate depended on the distance of the
Figure 6. Microstructures of copper-graphite composites prepared by
ball travel over the surface. When ball slid on the surface,
EEW after sintering by SPS at (a) 800  C, (b) 870  C, (c) 900  C,
wear occurred and the weight of the samples decreased.

(d) composites prepared by milling and sintering at 900 C and (e) pure
For some initial slides of the ball on the surface, the wear
copper.
surface was relatively rough. Wear occurred easily, and
the wear &rate
increased quickly,
showing a steep slope ofSINICA
Delivered
by
Publishing
Technology
to:
INST.
FOR
APPLIED
SCIENCE
ENGINEERING
RESEARCH/ACADEMIA
the total surface area (Fig. 6(d)). In comparison with samIP: 140.109.57.11 On: Sat,the
08 curve.
Nov 2014
10:13:56
The
surface
was
gradually
glazed; therefore, the
ples fabricated by EEW, the microstructure
exhibited
weak Scientific Publishers
Copyright:
American
wear
rate
declined.
The
pure
copper
had a much higher
contact between the copper, graphite, and copper matrix,
wear
rate
than
copper-graphite
composites.
The low spe3
which resulted in a smaller density (7.6 g/cm ) than that
cic
wear
rate
of
the
copper-graphite
composite
was due
3
of the copper-graphite prepared by EEW (7.9 g/cm ). The
to
a
smeared
graphite
layer
at
the
sliding
surface,
which
microstructure of the copper samples was dense with no
acted
as
a
solid
lubricant.
Alternatively,
in
the
case
of the
pores, as observed in the optical image (Fig. 6(e)). The
copper-graphite
composites,
the
wear
rate
of
the
copperdensity of these samples was very high, with a value of
graphite composite prepared by EEW was lower than that
8.8 g/cm3 .
of the mixed composite. The low wear of this sample was
The effects of load, speed, and distance on the specic
most likely due to its hardness. The hardness of the EEW
wear rate are shown in Figures 79. These variables were
composite was 97 HV, whereas that obtained by mixing

Figure 7. The effect of distance on weight loss with a load of 10 N

and speed of 50 rpm.

J. Nanosci. Nanotechnol. 14, 87508755, 2014

Figure 9. The effect of load on weight loss with a distance of 32 m

and speed of 50 rpm.

8753

Preparation and Characterization of Copper-Graphite Composites by Electrical Explosion of Wire in Liquid

Bien et al.

Figure 10. Photographs of the wear tracks and corresponding worn surfaces of (a), (d) copper and copper-graphite composites prepared by (b), (e)
milling and (c), (f) EEW.

Delivered
Technology
to: INST.
FOR
& ENGINEERING
RESEARCH/ACADEMIA
much smoother
than that of
pure copper and copper-SINICA
wasby
85Publishing
HV. The relationship
between
wear
andAPPLIED
hardness SCIENCE
IP:
7
13

14 140.109.57.11 On: Sat, 08 Nov 2014 10:13:56
graphite Publishers
mixed samples. Major deformation appeared on
has been widely investigated,
showing
thatAmerican
sample Scientific
Copyright:
the pure copper milled composite. The copper surface
wear decreases with increasing hardness. A harder sample
without graphite experienced high friction; therefore, the
is able to better resist wear than a softer sample. This study
sliding surface was highly deformed. However, the coppershowed that the hardness of the copper-graphite obtained
graphite milling sample also exhibited high deformation
by EEW was greater than that of copper-graphite obtained
as it is weaker bonding between graphite and the copby milling. Therefore, the lower wear rate of samples fabper matrix. The weak bonding leads to rapid removal of
ricated by EEW may be affected by their hardness.
graphite and copper from the surface, which could not
Figure 8 illustrates that the wear rate did not depend on
withstand the friction force and high deformation formed
the speed as none of the curves demonstrate a change in
on the sliding surface.
speed. The EEW sample showed the optimal wear, similar
to the wear distance case in Figure 7. Figure 9 presented
the effects of load on the wear properties. The load dra4. CONCLUSIONS
matically affected the specic wear rate. The specic wear
Copper-graphite nanocomposites were prepared by EEW
rate in all samples was greatest at 10 N, decreased at 15 N,
in liquid. Graphite was in the form of a nanosheet, and a
and then increased at a load of 20 N. The copper-coated
small amount of copper oxide was detected in the comgraphite composites prepared by EEW had the smallest
posite powder. Pure copper-graphite nanocomposites were
specic wear rate for all ranges of the applied normal
obtained after reduction of the composite in hydrogen at
load.
700  C for 2 hrs. The composite powder sintered by SPS at
Figure 10 showed the photographs of the worn sur900  C for 10 min had good sintering ability and high denface of the copper, mixed copper-graphite, and coppersity. The copper-graphite nanocomposites exhibited a siggraphite prepared by EEW. The wear track illustrates that
nicant decrease of wear. Additionally, the specic wear
the copper sample had the largest track. The mixed copperrate of copper-graphite prepared by EEW was less than
graphite had a narrower track than the pure copper samthat of pure copper and mixed copper-graphite composple but a larger track than the copper-graphite prepared
ites. This work demonstrated a novel method to fabricate
by EEW. Furthermore, the surface damage of the coppercopper-graphite composites.
graphite prepared by EEW was much less than that of
pure copper and mixed copper-graphite. The worn surAcknowledgment: This work was supported by
face of the copper-graphite sample obtained by EEW was
the 2013 Research Fund of University of Ulsan.
8754

J. Nanosci. Nanotechnol. 14, 87508755, 2014

Bien et al.

Preparation and Characterization of Copper-Graphite Composites by Electrical Explosion of Wire in Liquid

References and Notes

1. J. W. Kaczmar, K. Pietrzak, and W. Wosinski, J. Mater. Process
Tech. 106, 58 (2000).
2. A. Rodrguez-Guerrero, S. A. Snchez, J. Narciso, E. Louis, and
F. Rodrguez-Reinoso, Acta Mater. 54, 1821 (2006).
3. T. Oku, A. Kurumada, T. Sogabe, T. Oku, T. Hiraoka, and K. Kuroda,
J. Nucl. Mater. 257, 59 (1998).
4. P. K. Rohatgi, S. Ray, and Y. Liu, Int. Mater. Rev. 37, 129 (1992).
5. J. M. Casstevens, H. G. Rylander, and Z. Eliezer, Wear 48, 121
(1978).
6. K. C. Owen, M. J. Wang, C. Persad, and Z. Eliezer, Wear 120, 117
(1987).
7. S. F. Moustafa, S. A. El-Badry, A. M. Sanad, and B. Kieback, Wear
253, 699 (2002).

8. S. F. Moustafa, S. A. El-Badry, and A. M. Sanad, Powder Metall.

40, 201 (1997).
9. Y. A. Kotov and O. M. Samatov, Nanostruct. Mater. 12, 119
(1999).
10. G. S. Yun, L. H. Bac, J. S. Kim, Y. S. Kwon, H. S. Choi, and J. C.
Kim, J. Alloys and Compounds 509S, S348 (2011).
11. L. H. Bac, Y. S. Kwon, J. S. Kim, Y. I. Lee, D. W. Lee, and J. C.
Kim, Mater. Res. Bull. 45, 352 (2010).
12. L. H. Bac, J. S. Kim, and J. C. Kim, Res. Chem. Intermediat. 36, 795
(2010).
13. M. Ghorbani, M. Mazaheri, and A. Afshar, Surf. Coat. Tech. 190, 32
(2005).
14. I. Ahmad, A. Kennedy, and Y. Q. Zhu, Wear 269, 71 (2010).

Received: 17 April 2013. Accepted: 10 December 2013.

Delivered by Publishing Technology to: INST. FOR APPLIED SCIENCE & ENGINEERING RESEARCH/ACADEMIA SINICA
IP: 140.109.57.11 On: Sat, 08 Nov 2014 10:13:56
Copyright: American Scientific Publishers

J. Nanosci. Nanotechnol. 14, 87508755, 2014

8755