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Journal of
Nanoscience and Nanotechnology
Vol. 7, 16, 2007
1. INTRODUCTION
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
Cu-25 wt% W
- Cu
-W
Intensity (A.U.)
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
Intensity (A.U.)
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)
120
100
80
60
40
5
10
15
20
Crystallite Size of Cu
Crystallite Size of W
100
80
60
40
10
15
20
25
30
wt% Tungsten
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
% 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
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
140
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.
Hardness (MPa)
4.5
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.
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
RESEARCH ARTICLE
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.
(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.