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Copyright 2007 American Scientic Publishers

All rights reserved


Printed in the United States of America

Journal of
Nanoscience and Nanotechnology
Vol. 7, 16, 2007

Synthesis of CuW Nanocomposite by


High-Energy Ball Milling
T. Venugopal, K. Prasad Rao, and B. S. Murty
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036, India
The CuW bulk nanocomposites of different compositions were successfully synthesized by highenergy ball milling of elemental powders. The nanocrystalline nature of the CuW composite powder is conrmed by X-ray diffraction analysis, transmission electron microscopy, and atomic force
microscopy. The CuW nanocomposite powder could be sintered at 300400  C below the sintering
temperature of the un-milled CuW powders. The CuW nanocomposites showed superior densication and hardness than that of un-milled CuW composites. The nanocomposites also have three
times higher hardness to resistivity ratio in comparison to Oxygen free high conductivity copper.

Keywords: CuW Nanocomposite, Immiscible System, High-Energy Ball Milling, Electrical


Resistivity.

1. INTRODUCTION

Author to whom correspondence should be addressed.

J. Nanosci. Nanotechnol. 2007, Vol. 7, No. 5

2. EXPERIMENTAL DETAILS
The materials used in this study were 99.7% pure electrolytic Cu powder and 99.7% pure reduced W powder
with a particle size of <45 m (325 mesh). High-energy
ball milling experiments were carried out in a Fritsch
pulverisette-5 planetary ball mill with WC as milling
media. A ball to powder ratio of 10:1 was used with
toluene as a process control agent. The compositions studied were Cu-5, 10, 15, 20, 25, and 30 wt% W. Samples were taken out from the vial at regular intervals
during milling and were subjected to X-ray diffraction
(XRD) analysis using Shimadzu, XD-D1 diffractometer
with CuK radiation. Assuming that the distribution of
the grain size and the strain to the integrated intensities of peaks follow Cauchy and Gaussian distributions,
respectively, the grain size and the integral strain are then
estimated from the Cauchy and Gaussian integral breadth
components of the Voigt function.18 The nanocrystalline
nature of the ball-milled powders was established using

1533-4880/2007/7/001/006

doi:10.1166/jnn.2007.418

RESEARCH ARTICLE

Applications such as electronic packaging, manufacturing


of electrodes or contact terminals require materials with
high strength as well as high thermal and electrical conductivity. Cu is the most suitable material for such applications, but suffers from lower strength. Traditionally Cu
is strengthened by oxide and carbide dispersions but at
the expense of its electrical conductivity.13 In the recent
times metalmetal composites are gaining importance. In
this type of composites, both the matrix and dispersions
are metals and hence an insignicant reduction in electrical
conductivity is expected due to dispersion. The immiscible systems are ideal cases for the metalmetal composites. Cu and W are completely immiscible even in molten
state due to a high positive heat of mixing: +35 kJ/mol.4
As these elements are immiscible even in liquid state,
solid state synthesis process is more appropriate to synthesize CuW nanocomposites with Cu as matrix and
W as dispersoid. High-energy ball milling is one of the
widely used solid state processing technique to produce
nanocrystalline materials.511 A number of reports on highenergy ball milling of Cu and W deal with W rich side
of phase diagram.1215 Costa et al. gave a detailed account
on sintering behavior of WCu ball milled powders.15
They postulated that formation of composite particle during milling is a prerequisite to obtain good densication in WCu powders. Raghu et al. studied mechanical
milling of Cu-10.2 wt% W mixture and noted metastable
mutual solubility aided by oxygen impurity.16 Xiong et al.

studied the mechanical alloying (MA) of W70 Cu30 alloy


and reported the substitutional solid solution formation
in this composition.17 Gaffet et al. carried out a detailed
study on entire range of CuW system by high energy ball
milling.18 They reported amorphous phase formation in the
composition range from pure W to Cu70 W30 . It is evident
from the literature survey that the studies on the Cu rich
side of the CuW system are limited. The present study
throws light on the feasibility of Cu rich CuW nanocomposites as promising materials for electronic industry.

Synthesis of CuW Nanocomposite by High-Energy Ball Milling


(a)

Cu-25 wt% W

- Cu
-W

Intensity (A.U.)

Philips CM12 transmission electron microscope (TEM).


The ball milled powders were compacted into pellets of
12 mm in a hydraulic press at a pressure of 700 MPa.
The pellets were sintered in a reducing atmosphere at 400,
500, 600, and 700  C. The densities of the pellets were
estimated precisely by using Archimedes principle. The
sintered pellets were also analyzed by XRD. A Dimension 3100 with Nanoscope IV, Digital Instruments, USA,
Atomic force microscope (AFM) was used in tapping mode
with a micro activated probe to assess the homogeneity and
grain size of nanocomposites. Hardness of nanocomposites
was measured by using Vickers micro-hardness tester at a
load of 200 g. The electrical resistivity of the nanocomposites was also measured by using Vander-pauw technique.
CuW composites were also made by compaction and sintering of un-milled Cu and W elemental powders in order
to compare its behavior with that of nanocomposites synthesized by high-energy ball milling.

Venugopal et al.

0h
5h
10 h
15 h
20 h

40

50

60

70

80

90

100

2 (degrees)
(b)

20 h of milling

- Cu
-W

RESEARCH ARTICLE

Figure 1(a) shows the XRD patterns of Cu-25 wt% W


powder mixture at different stages of ball milling. It is
clearly evident from the XRD patterns that with increasing
the time of milling, the X-ray peaks become broader. The
X-ray peak broadening can be attributed to the combined
effect of ne grain size and lattice strain. No peak shift is
observed in both Cu and W indicating that no solid solubility of either Cu in W or W in Cu could be achieved
during milling. There have been reports suggesting that
high-energy ball milling process results in extended solid
solubility in many systems.79 20 However, as Cu and W
are completely immiscible with very high positive heat of
mixing no solubility is observed in the present case. This
result is in conformity with the earlier reports by Aboud
et al.13 and Gaffet et al.17 who also found no solubility of
Cu and W in each other on mechanical alloying. The XRD
patterns of all other compositions showed a similar trend.
Figure 1(b) shows the XRD patterns of all the compositions
after ball milling for 20 h. It is evident from these XRD patterns that the XRD peaks of both Cu and W broaden with
increase in W content of the elemental powder mixtures.
The crystallite size of the Cu and W for Cu-25 wt% W
composite powder calculated from X-ray peak broadening
is presented in Figure 2(a) as a function of milling time.
With increase in milling time the crystallite size of both
Cu and W were decreased. After 20 h of high-energy ball
milling the crystallite size of Cu is 36 nm and that of W
is 38 nm. Figure 2(b) shows the crystallite size of Cu and
W for all the compositions after ball milling for 20 h. It
is interesting to note a signicant reduction in crystallite
size of W as a function of composition of the blend, while
that in case of Cu is less signicant. The crystallite size
of Cu and W reach more or less the same value of below
40 nm after 25 wt% W in the blend. The crystallite size
2

Intensity (A.U.)

3. RESULTS AND DISCUSSION


W - 30 wt%
W - 25 wt%
W - 20 wt%
W - 15 wt%
W - 10 wt%
W - 05 wt%

40

50

60

70

80

90

100

2 (degrees)
Fig. 1. XRD patterns of (a) Cu-25 wt% W nanocomposite powders
after different milling times. (b) CuW nanocomposite powders of various compositions after 20 h of ball milling.

of Cu is 29 nm and that of W is 33 nm for a composition of Cu-30 wt% W after 20 h of milling. The present
results conrm that the ner grain size can be obtained
in compositions with higher W content. Cu has an FCC
structure and is more ductile than W which has BCC structure. The inherent nature of the high-energy ball milling
is such that the ductile powder particles get attened by
the ball-powder-ball collisions, while the less ductile powder particles tend to fragment. The fragmented brittle powder particles get embedded in the ductile particles during
milling. This resulted in the reduced ductility of the composite particles. As the W content increases the ductility of
the composite particles also reduces which results in more
of fragmentation. Hence a ner grain size is obtained in
composite powders with higher W content.
Figure 3 shows the TEM dark eld image of Cu20 wt% W nanocomposite powder after 20 h of ball
milling. The inset of the Figure 3 represents the
J. Nanosci. Nanotechnol. 7, 16, 2007

Venugopal et al.
(a)

Synthesis of CuW Nanocomposite by High-Energy Ball Milling


Cu-25 wt.%W
Crystallite Size of Cu
Crystallite size of W

Crystallite size (nm)

120

100

80

60

40
5

10

15

20

Milling Time (h)


(b)
20 h of milling
120

Fig. 3. Microstructure of Cu-20 wt% W ball milled powders after 20 h


of ball milling. The inset shows the selected area diffraction pattern from
the sample.

Crystallite size (nm)

Crystallite Size of Cu
Crystallite Size of W

100

80

60

40

10

15

20

25

30

wt% Tungsten

Fig. 2. (a) Crystallite size of Cu and W for Cu-25 wt% W as a function


of milling time. (b) Effect of composition on crystallite size of Cu and
W after 20 h of ball milling.

diffraction pattern with continuous rings, which conrms


the nanocrystalline nature of the composite powder. The
bright areas in the micrograph correspond to W crystallites.
The crystallite size calculated from X-ray peak broadening
is in close agreement to that of TEM observations.
Figure 4(a) represents the densication behavior of
CuW nanocomposite powders at various sintering
temperatures. The green densities of the CuW nanocomposite pellets vary from 80% to 85% of their respective
theoretical densities. With increase in sintering temperature, the density of the pellets increases. For compositions
Cu-5 to 20 wt% W, the peak density of about 95% was
reached at 500  C and for the compositions Cu-25 wt% W
and Cu-30 wt% W, the peak density was obtained at
600  C. The sintered density of the nanocomposites was
in the range of 93% to 95% of their respective theoretical
density, irrespective of their composition at 600  C without
any further change at higher temperatures. Figure 4(b)
shows the densication behavior of un-milled CuW powder mixture at various sintering temperatures. The density
of the green pellets was in the range of 77% to 81% of
their respective theoretical densities. During sintering these
J. Nanosci. Nanotechnol. 7, 16, 2007

RESEARCH ARTICLE

20

CuW composites reached their peak density over a temperature range of 900 and 1000  C. It has been observed
that the green density of the pellets decreased with increase
in W content. This may be due to the poor deformation
behavior of W. From these results one can also observe that
the amount of W in Cu plays a dominant role in obtaining
good density. With increase in W content the nal density
was lower and also the sintering temperature to achieve a
given density increased. This may be attributed to the high
melting point and low diffusion rates of W. One can also
observe that the ball milled powders attains a higher density than that of un-milled powders. During high-energy
ball milling, the harder W particles are embedded in the
Cu particles as Cu is more ductile than W. As milling
continues the Cu particles and the embedded W particles
become ner leading to nanocomposites. During sintering
of milled nanocomposite particles, the Cu phase in each
particle sinters together due to its lower melting point. In
addition, the nanocrystalline nature of the crystallites and
the milling induced defects also help in increasing the diffusivities leading to better sinterability of the milled composites in comparison to unmilled composites.
Figure 5 shows the crystallite size of as milled CuW
nanocomposites and after sintering at 500  C. In general,
the grain growth of the CuW composites during solid-state
sintering is negligible because Cu and W are completely
immiscible. In an immiscible system, the diffusion of one
species into other is restricted. As diffusion is one of the
essential requisites for grain growth, in such immiscible
systems not much of grain growth is expected on heating.
This is clearly evident from Figure 5, wherein the crystallite
size of both Cu and W do not signicantly increase by sintering at 500  C. It is also interesting to see that an increase
in the W content of the nanocomposite reduces the grain
growth of both Cu and W. Increase in W content reduces

Synthesis of CuW Nanocomposite by High-Energy Ball Milling


(a) 100

% Theoretical Density

milled for 20 h

90

80
Cu-5 wt% W
Cu-10 wt% W
Cu-15 wt% W
Cu-20 wt% W

70

Cu-25 wt% W
Cu-30 wt% W

Green

60
400

500

600

700

Temperature C

(b) 100

90

the probability of CuCu and WW contacts and increases


the probability of CuW interfaces and hence their tendency for grain growth due to the immiscible nature of the
two components.
Figures 6(a) and (b) are the AFM images of
Cu-10 wt% W and Cu-20 wt% W bulk nanocomposites
obtained in tapping mode technique. The nano-crystalline
nature of the composites is clearly evident from these
images. It is also important to note that the crystallite are
ner in case of 30 wt% W sample in comparison to 10 wt%
sample. Figures 7(a) and (b) represents the AFM phase
contrast images of Cu-10 wt% W and Cu-20 wt% W bulk
nanocomposites. AFM phase contrast image is obtained by
mapping the phase lag of the cantilever oscillation during
tapping mode scan. This phase lag is very sensitive to elastic properties of the materials and hence can distinguish the
micro constituents based on their elastic properties. As Cu
and W have quite different elastic modulii, one can easily
see the difference between the two in such an image and
thus this image is similar to back scattered electron image
in SEM, where the contrast arises from the difference in the
atomic number (number of electrons) of the constituents.

80
Cu-5 wt% W
Cu-10 wt% W
Cu-15 wt% W

70

Cu-20 wt% W
Cu-25 wt% W
Cu-30 wt% W

Green

60
600

700

800

900

1000

Temperature C

Fig. 4. Densication behavior of CuW (a) 20 h ball milled and


(b) un-milled powders at various temperatures.
160
Crystallite size of Cu after sintering
Crystallite size of W after sintering
Crystallite size of Cu before sintering
Crystallite size of W before sintering

140

Crystallite size (nm)

RESEARCH ARTICLE

% Theoretical Density

unmilled

Venugopal et al.

120
100
80
60
40
20
5

10

15

20

25

30

wt% Tungsten
Fig. 5. Crystallite size of Cu and W as measured from X-ray peak
broadening after sintering at 500  C for all the compositions.

Fig. 6. AFM images of pallets sintered at 500  C clearly reveals the


nano grains of Cu and W in (a) Cu-10 wt% W, (b) Cu-20 wt% W.

J. Nanosci. Nanotechnol. 7, 16, 2007

Synthesis of CuW Nanocomposite by High-Energy Ball Milling


2800
2400

Hardness (MPa)

4.5

Hardness of composite (unmilled)


Hardness of Nanocomposite
Resistivity of composite (unmilled)
Resistivity of Nanocomposite

4.0

2000

3.5

1600

3.0

1200
2.5

Resistivity (-cm)

Venugopal et al.

800
2.0
400
5

10

15

20

25

30

Wt% Tungsten
Fig. 8. Effect of composition on the hardness and electrical resistivity of CuW bulk nanocomposites and CuW composites made from
un-milled powders.

Table I.

Hardness and resistivity of CuW composites.

Composition
OFHC Cu
Cu-5% W
Cu-10% W
Cu-15% W
Cu-20% W
Cu-25% W
Cu-30% W
a

Milling
condition

unmilled
milled
unmilled
milled
unmilled
milled
unmilled
milled
unmilled
milled
unmilled
milled

Hardness (MPa)

Electrical
resistivity
(-cm)

Hardness/resistivity
Ratio (HR ratio)
MPa/-cm

HR ratio
normalized
with OFHC Cu

369a
491
1286
526
1385
601
1649
707
2001
837
2395
908
2529

1.72a
1.97
2.04
2.26
2.69
2.45
2.99
2.72
3.71
3.03
3.84
3.35
3.94

214.5
249.0
629.6
232.5
514.7
245.3
550.3
259.6
538.4
276.1
624.3
270.4
641.4

1
1.16
2.93
1.08
2.40
1.14
2.57
1.21
2.51
1.28
2.91
1.26
2.99

From Ref. [22].

J. Nanosci. Nanotechnol. 7, 16, 2007

RESEARCH ARTICLE

Fig. 7. AFM phase contrast images of pallets sintered at 500  C


shows the distribution of Cu and W in (a) Cu-10 wt% W, (b) Cu20 wt% W.

In the above images, the light color corresponds to Cu


and dark color corresponds to W. A homogeneous distribution of Cu and W is evident from these images. These
images also indicate that the microstructure is ner in case
of 30 wt% W sample in comparison to 10 wt% W sample.
The Vickers micro-hardness was measured on sintered
bulk CuW nanocomposites and also on sintered CuW
composites synthesized from un-milled powders. These
results are presented as a function of composition in
Figure 8. The nanocomposites showed a superior hardness
values than that of un-milled composites. This is due to the
ner grain size of nanocomposites, in agreement with HallPetch relation. From this gure one can also observe that
the hardness of composites synthesized from ball milled
powders and un-milled powders increases signicantly
with an increase in W content. This increase in hardness is
due to the dispersion strengthening of W in Cu matrix.
Figure 8 also shows a plot of electrical resistivity
measured on the sintered nanocomposites and also on
sintered CuW composites synthesized from un-milled

Synthesis of CuW Nanocomposite by High-Energy Ball Milling

CuW nanocomposites have good promise as high strength


conductors.

HR ratio normalized with OFHC Cu

Cu-W composite (unmilled)


Cu-W Nanocomposite

4. CONCLUSIONS

0
5

10

15

20

25

30

wt.% Tungsten
Fig. 9. Effect of composition on the normalized hardness to electrical
resistivity (HR) ratio of CuW composites made from milled and unmilled powders.

RESEARCH ARTICLE

Venugopal et al.

powders as a function of composition. The resistivity of


the nanocomposite increases with increase in W content.
Two reasons may be cited for this increase in resistivity. Firstly, with increase in W content the grain size is
reduced. A ner grain size material will have higher volume of grain boundary area which acts as obstacles for
current conduction path. Secondly, with increase in W content the less conductive material in the composite increases
and hence the resistivity of the composite increases. This
fact is also evident from the resistivity plot of composite
from un-milled powders. The resistivity of CuW composite from un-milled powders also increases with increase
in W content. The resistivity of Cu-30 wt% W nanocomposite is about 3.94 -cm. Cheng et al. reported the
resistivity of 5 h ball milled copper as 3.36 -cm.21
The resistivity of oxygen free high conductivity (OFHC)
Cu is 1.71 -cm,22 which indicates that the resistivity
reduces to about 51% of that of OFHC Cu in case of
nanocrystalline Cu and with the addition of 30% W in the
nanocomposite it further decreases only by 7% reaching
about 44% of that of OFHC Cu. The hardness and electrical resistivity values of all the composites are given in
Table I. The hardness to resistivity ratio (HR ratio) was
calculated and normalized with that for OFHC Cu and the
results are shown in Table I. Figure 9 shows the variation
of normalized HR ratio of CuW composites as a function of composition. Interestingly, CuW nanocomposites
showed a higher normalized HR ratio than unmilled CuW
composites. This indicates that the increase in hardness is
much higher than the increase in the resistivity in case of
nanocomposites. The results indicate that an increase in
HR ratio of about three times is possible with the CuW
nanocomposites in comparison to the OFHC Cu, which
is a signicant increase. These results suggest that the

(1) CuW bulk nanocomposites were successfully synthesized by high energy ball milling process followed by cold
compaction and sintering.
(2) The sintering temperature of the nanocomposite powders is 300400  C lower than that for un-milled CuW
composite powders.
(3) Nanocrystallinity of the milled CuW nanocomposites
is retained even after sintering to near theoretical density
(95%), which is evident by AFM and XRD crystallite
size analysis.
(4) W delayed the grain coarsening of Cu by pinning the
grain boundaries.
(5) The bulk nanocomposites showed superior hardness
than that of un-milled composites.
(6) The hardness to electrical resistivity ratio of
Cu-30% W nanocomposite is three times higher than that
of OFHC Cu.

References and Notes


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5. A. Gleiter, Prog. Mater. Sci. 33, 223 (1989).
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12. T. Aboud, B. Z. Weiss, and R. Chaim, Nanostruc. Mater. 6, 405
(1995).
13. J. C. Kim, S. S. Ryu, Y. D. Kim, and I. H. Moon, Scripta Mater.
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420 (2001).
15. F. A. da Costa, A. G. P. da Silva, and U. U. Gomes, Powder Tech.
134, 123 (2003).
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Mater. Sci. Eng. A304, 438 (2001).
17. C. S. Xiong, Y. H. Xiong, H. Zhu, T. F. Sun, E. Dong, and G. X.
Liu, Nanostruc. Mater. 5, 425 (1995).
18. E. Gaffet, C. Louison, M. Harmelin, and F. Faudot, Mater. Sci. Eng.
A134, 1380 (1991).
19. T. H. Keijser, J. I. Langford, E. J. Mittemeijer, and A. B. P. Vogels,
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20. O. Drbohalav and A. R. Yavari, Acta Metall. Mater. 43, 1799 (1995).
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Received: 26 February 2006. Revised/Accepted: 13 September 2006.


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J. Nanosci. Nanotechnol. 7, 16, 2007