Materials Science and Engineering A 393 (2005) 382386

Synthesis of copperalumina nanocomposite by reactive milling

T. Venugopal, K. Prasad Rao, B.S. Murty
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036, India
Received 16 August 2004; received in revised form 27 October 2004; accepted 27 October 2004

Abstract
Cu Al2 O3 nanocomposite is successfully synthesized by reactive milling of CuO/Cu2 O and Al. Wet milling in toluene transforms the
combustion reaction to a progressive reaction. The extent of reduction reaction increases with increase in excess reductant (Al). The crystallite
size of Cu obtained from reactive milling is much finer than that obtained from ball milling of Cu and Al2 O3 .
2004 Elsevier B.V. All rights reserved.
Keywords: Cu Al2 O3 nanocomposite; Reactive milling; Solid-state reaction; Atomic force microscopy

1. Introduction
Chemical reactions induced by high-energy ball milling
have been gaining importance because of their potential applications. Several mechanochemical reactions have been
studied so far to prepare microcrystalline and nanocrystalline
materials [1,2]. The chemical reactions induced by highenergy ball milling can be of either combustion reaction or
a progressive reaction. The self-propagating combustion reaction can be ignited during high-energy ball milling when
the reaction enthalpy is sufficiently high [3,4]. Such reactions
require a critical milling energy (milling time) for the combustion reaction to be ignited and the product particle size
fairly large in most of the cases, due to the possible grain
coarsening of the product phase.
The reaction between CuO/Cu2 O and Al is highly exothermic. A self-propagating combustion reaction can be easily
ignited resulting in high temperature and reaction rates. This
can result even in the melting of product Cu and separation of
Cu and Al2 O3 in some cases [5]. The enthalpies associated
with these reactions are:

3Cu2 O + 2Al 6Cu + Al2 O3

(H = 1172 kJ/mol Al2 O3 )
The self-propagating combustion reaction can be avoided
by reducing the activities of the reactant species. This
has been achieved by embedding the Al needed for
the reaction inside a carrier such as Cu(Al) solid solution or a Cu Al intermetallic compound [6,7]. The
Cu Al2 O3 nanocomposites were also synthesized by chemical routes [8,9] and thermo-chemical processes [10].
However, reactive milling is a simple and easy technique to achieve homogeneous nanocomposites on large
scale.
In the present study, attempts have been made to produce Cu Al2 O3 nanocomposites with 20 and 35 wt.% Al2 O3 .
In the present approach, the milling medium, toluene, has
been used as a tool to suppress the self-sustained combustion reaction and to aid in the progressive reaction in order
to obtain nanocomposites. The paper also discusses the influence of excess reductant (Al) on the completion of the
reaction.

3CuO + 2Al 3Cu + Al2 O3

(
H = 1209 kJ/mol Al2 O3 )

Corresponding author. Tel.: +91 44 2257 8589; fax: +91 44 2257 0509.
E-mail address: murty@iitm.ac.in (B.S. Murty).

0921-5093/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2004.10.035

2. Experimental details
The materials used in the experiments were Cu, Al2 O3 ,
CuO, Cu2 O and Al powders of <45 m (325 mesh). The sto-

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383

3. Results and discussion

Fig. 1(a) shows the XRD patterns of the CuO and Al powder mixture after different stages of milling with a stoichiometric amount of Al. The intensity of CuO XRD peaks reduced significantly within the first 10 h of ball milling. The
evolution of a broad Cu peak near 43 is also observed concurrently. In addition one can also see the second most intense
peak of Al2 O3 (1 0 4) peak with 98% intensity evolving as
a shoulder of CuO peak near 35 . The most intense peak of
Al2 O3 (1 1 3) falls very close to that of Cu near 43 . In order
to identify the Cu peak clearly the region between 40 and 46
has been enlarged in the Inset of Fig. 1(a). With the progress
of milling up to 40 h, the intensity of CuO peak further reduced marginally. This suggests that within the first 10 h of
ball milling most of the CuO reacted with Al to produce Cu
with a high reaction rate and that the reaction rate decreased
with further milling. The higher reaction rate in the initial
stages can be attributed to larger amount of reactant species
available in the initial stages of ball milling, which results
in a higher probability for the CuO and Al to be in contact
with each other. With the progress of milling and, hence, the
reaction, the product phases formed at the interface between
the reactants reduces the rate of reaction to some extent. The
XRD peak of the Cu evolved during reactive milling is very
broad suggesting its nanocrystalline nature. The completion
Fig. 1. XRD patterns of (a) reactive milled CuO + Al with stoichiometric
amount of reductant as a function of milling time and (b) Cu35 wt.% Al2 O3
powder mixture milled up to 20 h.

ichiometric amount of powders was decided based on the reactions given in the previous section. Reactive milling has
also been carried out with 10, 20 and 30 wt.% of excess
reductant (Al) than stoichiometric amount. Ball milling of
Cu with 20 and 35% Al2 O3 was also done for comparison.
The milling was carried out in a high-energy planetary ball
mill (Fritsch pulverisette-5) in toluene medium at a milling
speed of 300 rpm. WC milling media with a ball to powder
weight ratio of 10:1 were used for milling. 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 Cu K 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 component of the Voigt function [11]. The
nanocrystalline nature of the ball-milled powders was established using Philips CM12 transmission electron microscope
(TEM). The powders were also analyzed for crystallite size
with scanning probe microscope (Nanoscope IV, Digital Instruments, USA) in the tapping mode with a microactivated
probe.

Fig. 2. XRD patterns of reactive milled CuO + Al with different amounts of

excess reductant after (a) 20 h and (b) 40 h of milling.

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in Fig. 2(a and b), respectively. With increasing the amount

of Al, the intensity of the CuO peak decreased suggesting an
increase in the reaction kinetics. The fraction of CuO or Cu2 O
reacted during milling has been calculated by considering the
intensity of CuO or Cu2 O XRD peaks from the following
expression.
AB
A
where A is the intensity of CuO or Cu2 O peak before milling,
B the intensity of CuO or Cu2 O peak after milling for certain
time, and C is the fraction of CuO or Cu2 O reacted.
It should be noted that the XRD intensities depends on
many other factors such as amount of nanocrystalline and/or
amorphous phase and, hence, the above equation will give
only an approximate value of the extent of reaction. Fig. 3
shows the fraction of CuO reacted with Al as a function
of milling time for various excess amounts of Al. The figure clearly indicates that about 7080% of the reaction
is complete within 10 h of milling. Further milling up to
40 h brings in only a marginal reaction. It is important to
note that Fig. 3 gives only a trend for easy comparison
of different samples and that the values shown cannot be
strongly relied on due the above-mentioned reason. With inC=

Fig. 3. Fraction of CuO reacted as a function of milling time for various

amounts of excess reductant.

of the reaction in this case is expected to result in a composite of Cu35% Al2 O3 . Fig. 1(b) shows the XRD patterns
Cu35% Al2 O3 powder mixture milled for different periods.
A comparison of the peak broadening of Cu in Fig. 1(a and
b) makes it clear that the crystallite size of Cu formed by
reactive milling is much finer than that obtained by milling
of Cu Al2 O3 mixture.
The XRD patterns of CuO + Al powder mixtures milled for
20 and 40 h with different amount of excess Al are presented

Fig. 4. XRD patterns of (a) reactive milled Cu2 O + Al with stoichiometric

amount of reductant as a function of milling time and (b) Cu20 wt.% Al2 O3
powder mixture milled up to 20 h.

Fig. 5. XRD patterns of reactive milled Cu2 O + Al with different amounts

of excess reductant after (a) 20 h and (b) 40 h of milling.

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385

Fig. 6. Fraction of Cu2 O reacted as a function of milling time for various

amounts of excess reductant.

creasing the amount of excess aluminum the reaction proceeds towards completion. However, even with 30% excess Al, about 10% of unreacted CuO remains after 40 h of
milling.
Fig. 4(a) shows the XRD patterns of the Cu2 O and Al powder mixture after different duration of reactive milling with
stoichiometric amount of Al. Though the peak intensity of
Cu2 O is significantly reduced with increase in milling time,
the Cu2 O peaks do not disappear even after 40 h of milling,
suggesting that the reaction does not go for completion up
Fig. 8. (a) Crystallite size and (b) lattice strain of Cu in reactively milled
Cu2 O + Al.

Fig. 7. (a) Crystallite size and (b) lattice strain of Cu in mechanically milled
Cu Al2 O3 mixtures.

to 40 h. The completion of the reaction in this case is expected to result in a composite of Cu20% Al2 O3 . Fig. 4(b)
shows the XRD patterns of the Cu20% Al2 O3 powder mixture after different stages of milling. A comparison of the
above two figures shows significant peak broadening in case
of reactive milling, suggesting finer crystallite size in comparison to that milled with Al2 O3 . The XRD patterns of the
Cu2 O and Al powder mixtures milled with different excess
amount of Al for 20 and 40 h are presented in Fig. 5(a and
b), respectively. A marginal decrease in Cu2 O peaks is observed with increase in the amount of excess Al. Complete
disappearance of Cu2 O peaks is not evident even with 30%
of excess Al up to 40 h of milling. Fig. 6 shows the influence
of excess Al on the fraction of Cu2 O reacted as a function
of milling time. The reaction of Cu2 O shows a similar phenomenon as that of CuO. However, excess Al appears does
not seem to have a significant role in improving the reaction kinetics in case of Cu2 O. Similar to Fig. 3, Fig. 6 also
should be used for getting an idea of the trend of the reaction.
The crystallite size and lattice strain of the Cu calculated
from X-ray peak broadening is presented in Figs. 7 and 8,
respectively, for the mechanically milled and reactive milled
(Cu2 O) cases, respectively. The crystallite size of Cu after
20 h of ball milling of Cu20 wt.% Al2 O3 and Cu35 wt.%
Al2 O3 is 50 nm and 40 nm, respectively (Fig. 7(a)). In com-

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20 nm as shown in Fig. 9(a). The atomic force microscopy

has also shown particles in the size range of 2050 nm as
shown in Fig. 9(b).
From the present results it is evident that the reaction is
incomplete. In addition, no signature of a combustion reaction was observed suggesting that the presence of toluene
has suppressed the combustion reaction and has promoted the
progressive reaction. The earlier studies [5] have shown that
the ball milling of CuO and Al ignites a combustion reaction
and the reaction product consists of microcrystalline Cu with
fine Al2 O3 particles of size 0.11 m. In the present study,
the adhesion of toluene on the surface of the powder particles
reduced the activities of the reactant species and, hence, the
rate of reaction. The suppression of the combustion reaction
has helped in reducing the temperature generated during the
reactive milling and thus restricting the grain coarsening of
the nanocrystalline Cu formed by the reactive milling. This
transformation of a combustion reaction to a progressive reaction has yielded nanocomposite of Cu and Al2 O3 with both
the components with a crystallite size in the range of about
20 nm.

4. Conclusions
The Cu Al2 O3 nanocomposite with both the components
having a crystallite size of about 20 nm has been successfully synthesized by reactive milling of CuO/Cu2 O and Al.
The self-propagating combustion reaction was inhibited and
transformed to progressive reaction by the use of toluene
as milling medium, which resulted in formation of nanostructured Cu and Al2 O3 . The crystallite size of Cu obtained by reactive milling is much finer than that obtained
by milling of Cu and Al2 O3 . Excess Al up to 30% does
not significantly increase the reaction kinetics during reactive milling.

Fig. 9. (a) TEM dark field image of reactively milled CuO + Al after 40 h of
milling and (b) atomic force microscopy image of CuO + Al ball milled for
40 h.

parison the crystallite size of Cu reaches to as low as 10 nm

within 20 h of reactive milling of Cu2 O with Al, as shown in
Fig. 8(a). Similar results have been observed during the reactive milling of CuO with Al. Excess Al does not significantly
alter the crystallite size of Cu obtained by reactive milling.
Fig. 7(b) and Fig. 8(b) clearly show that the reactively milled
sample has higher strain (maximum of 1.4%) in comparison
to the ball milled Cu + Al2 O3 mixture (maximum of 0.4%)
after 20 h of milling. The TEM studies have confirmed the
formation of nanocomposites with a crystallite size of about

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