Characteristic of copper matrix simultaneously reinforced with

nano- and micro-sized Al

2
O
3
particles
Viseslava Rajkovic

, Dusan Bozic, Aleksandar Devecerski, Milan T. Jovanovic

Materials Science Laboratory, Institute of Nuclear Sciences Vinca, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia
A R T I C L E D A T A A B S T R A C T
Article history:
Received 25 June 2011
Received in revised form
23 February 2012
Accepted 27 February 2012
The effect of the simultaneous presence of nano- and micro-sized Al
2
O
3
particles on the mi-
crostructure and properties of copper matrix was the object of this study. The mixture of
inert gas-atomized prealloyed copper powder (with 1 wt.% Al) and 0.6 wt.% commercial
Al
2
O
3
powder (serving as micro-sized particles) was used as the starting materials.
Strengthening of the copper matrix was performed by treating the powders in the air for
up to 20 h in the planetary ball mill. During milling of the prealloyed powder, finely
dispersed nano-sized Al
2
O
3
particles were formed in situ by internal oxidation. The approx-
imate size of these particles was between 30 and 60 nm. The highest values of microhard-
ness were reached in compacts processed from 10 h-milled powders. The microhardness
of compact obtained from 10 h-milled powder was 3 times higher than the microhardness
of compact processed from as-received and non-milled prealloyed powder. At the maxi-
mum microhardness the grain size reaches the smallest value as a result of the synergetic
effect of nano- and micro-sized Al
2
O
3
particles. Recrystallization, which occurred during
prolonged milling, was the main factor influencing the decrease in microhardness. The in-
crease in electrical conductivity of compacts after 15 h of milling is the result of the de-
crease in microhardness and activated recrystallization processes.
2012 Elsevier Inc. All rights reserved.
Keywords:
Mechanical alloying
Internal oxidation
Nano- and micro-sized Al
2
O
3
particles
Strengthening
Microhardness
Electrical conductivity
1. Introduction
Strength and softening temperature of copper matrix may be
increased by finely dispersed oxide particles, whereas ade-
quate thermal and electrical conductivity are maintained at
room and elevated temperatures. These properties depend
on the amount, size, and uniformity of the dispersed particles.
Copper matrix, reinforced by mechanical alloying or internal
oxidation, has been extensively studied in recent years due
to its attained better properties compared to pure copper
and precipitation, or solid solution hardened copper. A unique
combination of high strength and conductivity at elevated
temperatures makes copper-based composites the best candi-
date for high temperature electric materials, such as spot
welding electrodes, lead wires, connectors, and other elec-
tronic devices. These materials are also ideal for the ITER
(International Thermonuclear Experimental Reactor) as high
heat flux components, like divertor and first wall [1].
High-energy milling is a very common and often applied
technique in powder metallurgy for the processing of copper
matrix strengthened with the fine dispersion of various
sized Al
2
O
3
particles. Nano-scaled grain structure may be
retained even during compaction. This fine-grained struc-
ture together with Al
2
O
3
particles contributes to copper ma-
trix strengthening. Depending on the method, nano-sized
Al
2
O
3
particles formed in situ by internal oxidation ranged
in size from 10 to 15 nm [2,3] to 50 nm [4,5]. It was reported
[6] that by internal oxidation in the air of prealloyed CuAl
powders, Al
2
O
3
particles ranging in size from 30 to 50 nm
were produced. On the other side, the size of Al
2
O
3
particles
produced by mechanical alloying was between 14 nm [7]
and 2 m [8,9].
M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
Corresponding author. Tel.: +381 11 3804 593; fax: +381 11 224.
E-mail address: visnja@vinca.rs (V. Rajkovic).
1044-5803/$ see front matter 2012 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2012.02.022
Avai l abl e onl i ne at www. sci encedi r ect . com
www. el sevi er . com/ l ocat e/ mat char
The influence of Al
2
O
3
particle size on the strengthening of
matrix is important since it affects the deformation and re-
crystallization of the copper matrix. Small and closely spaced
particles exert a pinning effect on the movement of grain
boundaries, resulting in retardation or even complete sup-
pression of recrystallization [7]. On the contrary, the matrix
with larger and widely spaced particles is prone to accelerated
recrystallization [10]. Thus, the presence of variously sized
particles and interparticle spacing can cause either retarda-
tion or acceleration of recrystallization of the matrix.
In the present work, two types of particles having different
sizes, i.e. nano- and micro-sized Al
2
O
3
particles are employed
as strengtheners of copper matrix. The object of this paper
was to study the simultaneous effect of nano- and micro-sized
Al
2
O
3
particles on the microstructure, strengthening, and elec-
trical conductivity of the copper-based composites during the
processes of internal oxidation and mechanical alloying.
2. Experimental Procedure
The inert gas-atomized prealloyed copper powder (average
particle size 30 m) containing 1 wt.% Al (designation in
the further text: Cu1 wt.% Al) mixed with 0.6 wt.%Al
2
O
3
pow-
der (commercial grade: average particle size 0.75 m)
served as a starting material. This Cu1 wt.% Al +0.6 wt.%
Al
2
O
3
mixture (designation: Cu1Al +Al
2
O
3
) was milled in the
air for up to 20 h in the planetary ball mill. The weight ratio
of powder to steel balls was 1:35. Following milling, the mix-
ture was treated in hydrogen at 400 C for 1 h in order to elim-
inate the copper oxides that formed at the powder's surface
during milling. Compaction, executed by hot-pressing, was
carried out in an argon atmosphere at 800 C for 1 h under
the pressure of 35 MPa. Compacts from as-received and non-
milled Cu1 wt.% Al were also synthesized under the same
condition. The approximate dimensions of all compacts
were: 10 mm height and 10 mm diameter.
Milling in air of Cu1 wt.% Al promotes the formation of
finely dispersed Al
2
O
3
particles by internal oxidation [11]. It
was expected that during milling of Cu1Al +Al
2
O
3
the uniform
distribution of commercial Al
2
O
3
particles would be also
obtained without their fracturing or coarsening [12]. Conse-
quently, powders with uniformly dispersed Al
2
O
3
particles of
various sizes would be obtained in the refined copper matrix
after the process of milling.
The powder mixtures and corresponding compacts were
characterized by X-ray diffraction (XRD) analysis which was
performed using an X-ray powder diffractometer with CuK

Ni filtered radiation. The lattice parameter was determined

using the least square root method. The average lattice distor-
tion, i.e. the relative deviation of the lattice parameters from
their mean value (d/d) [13] and the grain size (D) were deter-
mined from the broadening () of the first four diffraction
lines (111, 200, 220 and 311) using the approach developed by
Williamson and Hall [14]:
cos
k
D

kd
d
sin 1
where the shape factor k=0.9 and the radiation wave length
=0.15405 nm.
The morphology and microstructure of the powder mix-
ture and compacts were characterized by light microscope,
Zeiss Axiovert 25. Two scanning electron microscopes (SEM)
were used: JEOL JSM 35 for microstructural investigations
and JEOL JSM-6610LV, equipped with an electron dispersive
X-ray spectroscope (EDS), for chemical analysis of particles
present in the copper matrix. Powder particle samples for
SEM microscope were mounted in acrylic resin. Polishing of
powders and compacts was performed using the standard
method, whereas a mixture of 5 g FeCl
3
and 50 ml HCl in
100 ml distilled water was used for etching.
Only a few compacts (processed from 10 to 20 h-milled
powders) corresponding to different levels of microhardness
were investigated with the transmission electron microscope
(TEM) JEOL JEM-7. For TEM characterization, thin slices (about
1 mm) of the material were cut from the central cross-section
of each compact. The slices were further thinned to 100 m
by conventional grinding. 3 mm disks were punched from the
central part of the slices and electropolished in a twin-jet elec-
tropolisher. The electropolishing was performed in the solu-
tion mixture CH
3
OHHNO
3
with the ratio 3:1 at 35 C, U=9 V
and I =20 mA.
The strengthening of the copper matrix was estimated by
microhardness measurement with applied load of 50 g and
time of indentation 20 s. The electrical conductivity (% IACS;
where IACS
20C
=0.5800 microhm
1
cm
1
) of the polished com-
pacts was measured using an apparatus Sigmatest operating
at 120 kHz withanelectrode diameter of 7 mm, whilst the den-
sity of the compacts () was determined by the Archimedes
method. The theoretical density of the compacts was calculat-
ed from the simple rule of mixtures, taking the fully dense
values for copper and Al
2
O
3
8.96 and 3.95 g cm
3
, respectively.
Values of density, microhardness, and electrical conduc-
tivity represent the mean value of five measurements per-
formed on the same compact.
3. Results and Discussion
3.1. Powders
The relationship between Cu1Al +Al
2
O
3
powder lattice param-
eter and milling time is shown in Fig. 1. During milling, lattice
parameter decreases with milling time. The decrease of lattice
parameter is the result of internal oxidation of aluminum,
which precipitates from the prealloyed copper, forming a fine
dispersion of Al
2
O
3
. The lattice parameter continuously de-
creases almost till the end of the milling process. This behavior
is due to facilitation of the oxidation process through the de-
formation progress of the copper matrix with the milling pro-
cess. The difference in the lattice parameters of prealloyed
Cu1 wt.% Al powders before (a
Cu1 wt.% Al
=0.36197 nm) and
after 20 h of milling (a
Cu1 wt.% Al
=0.36159 nm) is 0.10%. This
difference, similar to the difference (0.13%) in theoretical
lattice parameters of the prealloyed powder (a
Cu1 wt.% Al
=
0.36210 nm) and the copper powder (a
Cu
=0.36152 nm), indi-
cates that after 20 h of milling almost all the aluminumprecip-
itated from the copper matrix. Assuming that the complete
amount of aluminum was oxidized, it was calculated that
1.9 wt.% of Al
2
O
3
was produced in the copper matrix by
130 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
internal oxidation of 1 wt.% Al. This calculation was made
using the simple equation:
4Al 3O
2
2Al
2
O
3
: 2
Given that 427=108 g of aluminum oxide produces 204 g
of Al
2
O
3
, i.e. 2(227+316) =204 g, then oxidation of 1 g Al,
contained in the prealloyed copper, will generate 1.9 g of
Al
2
O
3
. Considering this result, it is supposed that the milled
powder mixtures with a total amount of 2.5 wt.% Al
2
O
3
parti-
cles have been obtained.
Full width at half maximum (FWHM) measured from XRD
patterns of Cu1Al +Al
2
O
3
powders shows a progress in line
broadening with milling time (Fig. 2), as a result of a severe
lattice distortion and grain size refinement [13].
The effect of milling time on the grain size and lattice dis-
tortion of Cu1Al +Al
2
O
3
powders is presented in Fig. 3. The
most intensive grain refinement occurs up to 10 h, when the
grain size decreases from 550 to 78 nm. With prolonged time
the grain size of milled powders decreases quite slowly,
being 78 and 76 nm after 10 and 20 h of milling, respectively.
Fig. 3 also illustrates a strong increase of Cu1Al +Al
2
O
3
powders crystal lattice distortion during the first 10 h of mill-
ing. When milled for a longer period of time, the lattice distor-
tion becomes less evident. The distortion appears as a result
of plastic deformation which is due to a decrease in the
grain size. It was shown that the contributions to the lattice
distortion may arise from internal stresses imposed by dislo-
cations and inhomogeneously distributed point defects [15].
The change of Cu1Al +Al
2
O
3
particles morphology with in-
creasing milling time is shown in Fig. 4. During high-energy
milling the powder particles change morphology and size as
a consequence of repeated deformation, fracturing and weld-
ing processes. According to these micrographs powder size
increases for up to 5 h of milling due to the welding predomi-
nance in the milling process (Fig. 4a). With longer milling time
the powder size decreases since the fracturing predominates
in the milling process. After 20 h of milling Cu1Al +Al
2
O
3
par-
ticles are rather small, but not equiaxed in shape (Fig. 4b). Dif-
ferent morphologies of these particles indicate that the
balance between fracturing and welding processes was not
achieved.
The composition of Cu1 wt.% Al powders changes during
milling. It was recently reported [6] that during high-energy
milling of prealloyed powders, the Al
2
O
3
particles formed
through the reaction of aluminum with oxygen from the air
are of nano-sized dimensions, i.e. most of the particles have
the approximate size of 50 nm or less. At higher magnification
SEM micrograph of 10 h-milled powder illustrates the presence
of particles with different morphologies (Fig. 5). Lamellae (L)
representing traces of previous individual powder particles
may be distinguished (Fig. 5a, b). A number of very small globu-
lar particles (N) are precipitated on these lamellae (Fig. 5b),
whereas coarse particles (M) of different morphologies with ap-
proximate size of 700 nmare also present inthe matrix (Fig. 5b).
Stresses imposed by larger particles are the main reason for the
appearance of microcracks (C) in the matrix (Fig. 5b).
3.2. Compacts
3.2.1. Microstructure
Fig. 6 illustrates the microstructure of compacts obtained
from milled Cu1Al +Al
2
O
3
powders. The compacts retained
Fig. 2 Effect of milling time on full width at half maximum
(FWHM) of Cu1 wt.% Al +0.6 wt.% Al
2
O
3
powders.
Fig. 3 Effect of milling time on grain size and lattice
distortion of Cu1 wt.% Al +0.6 wt.% Al
2
O
3
powders.
Fig. 1 Lattice parameter vs. milling time of Cu1Al +Al
2
O
3
powders. (In this and all following cases 0 on the X-axis
denotes as-received and non-milled condition regarding to
powders and corresponding compacts).
131 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
lamellar structure, a characteristic of high-energy milled pow-
der particles. Although lamellae are retained in compacts
processed from powders milled for 12 h, some changes in
the microstructure may be distinguished, i.e. the light areas
(denoted by arrows) indicate recrystallization which occurred
during hot-pressing (Fig. 6a). Note that recrystallization was
mostly initiated at the boundaries of the powder particles,
but in a lesser extent, is also visible at the corners of particles
where the concentration of stresses imposed during compac-
tion was highest. In compact processed from powder milled
for 20 h (Fig. 6b), the extent of recrystallization was extensive
and unrecrystallized particles were surrounded by recrystal-
lized areas.
A SEM micrograph of compact processed from 10 h-milled
powders is shown in Fig. 7. In the backscattered electron
image (BSE) small and large particles may be seen. The
inserted EDS spectrum shows the presence of aluminum and
oxygen in the small particle. Small amounts of iron probably
originated from the steel balls of the high-energy mill. Since
it was estimated that commercial Al
2
O
3
particles could not
be fractured during milling [12], then the structure of compact
processed from 10 h-milled Cu1Al +Al
2
O
3
powders consists of
nano- and micro-sized Al
2
O
3
particles embedded in the cop-
per matrix.
A SEM micrograph of the compact processed from 20 h-
milled powders is illustrated in Fig. 8. A wide recrystallized
area free of particles with annealing twins may be seen in
the BSE image, whereas the distinction between nano- and
micro-sized particles was difficult to establish.
Fig. 5 SEM micrographs of 10 h-milled Cu1Al +Al
2
O
3
particles. Arrows denote: (a) Lamellae (L); (b) nano-sized
particle (N); micro-sized particle (M); microcrack (C).
Fig. 6 Light micrographs. Microstructure of compacts
processed from Cu1Al +Al
2
O
3
powder after different milling
times. (a) 12 h; (b) 20 h. Arrows denote recrystallized regions.
Fig. 4 SEM micrographs. Morphology of Cu1Al +Al
2
O
3
particles after different milling times. (a) 1 h; (b) 20 h.
132 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
The effect of milling time on XRD pattern of Cu1Al +Al
2
O
3
powder and corresponding compacts is illustrated in Fig. 9.
The intensity of peaks decreases as milling time increases. Al-
though the difference in peak intensity of powder (Fig. 9a) and
compacts (Fig. 9b) is relatively small, it may be observed that
the peak intensity is somewhat higher in compacts, suggest-
ing increased grain size as a consequence of diffusion pro-
cesses during hot-pressing. Applying XRD analysis, it was
not possible to detect Al
2
O
3
due to very small particle size;
the same problem was also mentioned by other authors [16].
The change in the grain size of powder particles and corre-
sponding compacts as a function of milling time is shown in
Table 1. The grain size of compacts was calculated using Eq.
(1), based on the results of (FWHM) measured from XRD pat-
terns of compacts.
Results of Table 1 show that the grain size of both powders
and compacts decreases during shorter milling time, reaching
a minimum at 10 h, whereas with prolonged milling, an in-
crease in grain size occurs. In general, compacts are character-
ized by larger grains than powders; this may be ascribed to
diffusion processes during hot-pressing and their influence
on the grain growth.
The morphology of Al
2
O
3
particles is illustrated in TEM mi-
crographs (Fig. 10). In general, nano-sized particles are homo-
geneously distributed within the matrix and on the grain
boundaries. In compact processed from 10 h-milled powders
nano-sized particles (mainly globular and approximately be-
tween 30 and 60 nm in size) may be seen. Some of these
particles are formed on grain boundaries preventing grain
boundary migration and decreasing the rate of grain growth
(Fig. 10a). In addition to nano-sized particles, larger micro-
sized individual particles also appear in the matrix (Fig. 10a,
b). Dislocation network formed at large particle/matrix inter-
face may be seen (Fig. 10b). Although the grain boundaries in
TEM micrographs are poorly defined, it is obvious that grain
growth occurred at prolonged milling, i.e. from 100 to 150 nm
(after 10 h of milling) to approximately 300 nm (after 20 h of
milling) (Fig. 10c). The difference in calculated grain size
values (see Table 1) and those determined by TEM clearly ex-
ists. This difference may be fully attributed to the vaguely
defined grains in TEM micrographs. According to Fig. 10c a
Fig. 8 SEM micrograph. BSE image of compact processed
from 20 h-milled powders. Annealing twins in the
recrystallized area.
Fig. 9 XRD pattern of (a) Cu1Al +Al
2
O
3
powders and
(b) corresponding compacts after different milling times. All
peaks correspond to the copper matrix.
Table 1 The grain size of Cu1Al +Al
2
O
3
powders and
corresponding compacts as a function of milling time.
Cu1Al +
Al
2
O
3
Milling time (h)
0 3 5 10 12 15 20
Powder 550 287 136 78 82 90 98
Compact 630 295 142 90 104 138 200
Fig. 7 SEM micrograph. BSE image of compact processed
from 10 h-milled powders with inserted EDS spectrum of a
small particle.
133 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
coarsening of some Al
2
O
3
particles could be distinguished.
This increase of nano-sized Al
2
O
3
particles was reported sug-
gesting coarsening as a result of diffusion processes during
longer milling time [1].
3.2.2. Microhardness
Microhardness of compacts depends on the previous milling
time of Cu1Al +Al
2
O
3
powder (Fig. 11). Microhardness steeply
increases for up to 10 h of milling when the maximum micro-
hardness is reached. A rapid increase of the crystal lattice dis-
tortion reaching maximum value at approximately 10 h of
milling time (see Fig. 3) may be regarded as a result of lattice
deformation due to successive precipitation of nano-sized
Al
2
O
3
particles fromthe copper solid solution. Under the influ-
ence of diffusion processes during milling these particles are
precipitated within the matrix and at grain boundaries.
Nano-sized particles, finely distributed in the matrix and on
the grain boundaries, act as pinning points impeding further
movement of dislocations and their propagation. Thus, the
pinning force exerted by nano-sized particles on the grain
boundary prevents the grain growth.
The microhardness of compact obtained from 10 h-milled
powder (240 HV
0.05
) is much higher than the microhardness
processed from as-received and non-milled Cu1 wt.% Al
powder (74.5 HV
0.05
) compacted under the same conditions.
To explain this more than threefold increase in hardness,
two main influencing factors should be considered. The in-
crease in microhardness of compacts is a consequence of
the fine grain copper matrix structure and the presence of
the nano-sized Al
2
O
3
particles. These Al
2
O
3
nano-particles
are homogeneously located in the matrix grains having an av-
erage interparticle distance of less than 100 nm (see Fig. 10a).
It is known that a dislocation can bypass such particle by Oro-
wan bowing [17] leaving behind a dislocation loop around the
particle; the critical stress
Or
for bypassing depends on the
interparticle distance l according to
Or
l
1
. According to
the Orowan bowing mechanism and thermal mismatch be-
tween the matrix and reinforcement particles in metal matrix
composites [1821], by decreasing particulate size the strength
increases. Note that since the particles in this work are small
enough (less than 100 nm), the Orowan bowing mechanism
can be used to justify this behavior [19]. From the microhard-
ness and microscopic results it can be concluded that the flow
stress, necessary for plastic deformation of the composite in
contrast to the as-received material, is additionally increased
by dispersion-strengthening of the matrix grains.
Fig. 11 Effect of milling time on microhardness of
Cu1Al +Al
2
O
3
compacts.
Fig. 10 TEM micrographs. Compacts processed from
10 h-milled particles (a,b) and 20 h-milled powders (c).
Arrows, in Fig. 10a, c denote a part of large Al
2
O
3
particle.
134 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
The results obtained in this work reveal that at the peak
values (at 10 h of milling time), the microhardness of Cu1Al +
Al
2
O
3
compact is higher than that of the Cu1 wt.% Al (without
addition of micro-sizedAl
2
O
3
particles), i.e. 240 vs. 220 HV
0.05
, re-
spectively, processed under the same conditions [11]. At this
stage, apart from the effect of nano-sized particles, the contri-
bution of micro-sized Al
2
O
3
particles to microhardness must
be taken into account. The extent of matrix hardening is addi-
tionally increased by the formation of the dislocation network
formed around these particles (see Fig. 10b). Thus, at the maxi-
mum microhardness the synergetic effect of nano- and micro-
sized Al
2
O
3
particles exhibits a marked effect on increased
microhardness of Cu1Al +Al
2
O
3
compacts with respect to Cu
1 wt.% Al.
Prolonged milling results in a slow drop in microhardness.
This is because the coarse particles, i.e. micro-sized Al
2
O
3
par-
ticles, under certain conditions may contribute to the increase
in grain size [10]. Namely, in the vicinity of micro-sized Al
2
O
3
particles, a cellular dislocation substructure may be created
with a markedly increased density of dislocations. The pro-
longed time of milling results in a significantly increased
subgrains number, which can be activated and become the
nucleation sites of newly created recrystallized grains. Light
(Fig. 6a, b), SEM (Fig. 8) and TEM(Fig. 10c) micrographs coupled
with the values of the grain growth with milling time (see
Table 1) indicate that the process of recrystallization, which
occurred during prolonged milling, was the main factor
influencing the microhardness decrease. On the other hand,
after reaching its maximum, microhardness of Cu1 wt.% Al
compacts remains practically unchanged [11], indirectly sug-
gesting that coarse Al
2
O
3
particles may be regarded as a signif-
icant parameter in decreasing microhardness of Cu1Al +Al
2
O
3
compacts during prolonged milling.
Unlike other papers reported in the literature, this paper
studies the effect of nano- and micro-sized particles simulta-
neously embedded in the copper matrix. These results indi-
cate that hardening of the copper matrix depends on several
different parameters, one of them being grain size. The influ-
ence of nano- and micro-sized particles is complex and diffi-
cult to be resolved. The influence of some parameters is
more pronounced during short milling time, whereas the in-
fluence of other parameters prevails with longer milling. The
twofold role of coarse Al
2
O
3
particles in matrix strengthening
must be emphasized. During shorter milling time these parti-
cles, together with nano-sized particles, contribute to the in-
crease of microhardness up to its maximum value. However,
the decrease in microhardness with longer milling time is re-
lated to the recrystallization for which development the
micro-sized Al
2
O
3
particles have a significant effect.
3.2.3. Density
Density of the Cu1Al +Al
2
O
3
compacts decreases with milling
time (Fig. 12). The significant drop in density occurred for up
to 15 h of milling time, when the fracturing of powder parti-
cles is the predominant process during milling. According to
Fig. 4 the morphology of powder particles influences the pack-
ing between particles during hot-pressing, indicating that the
better packing achieved during shorter milling time corre-
sponds to higher density. At the same pressures, coarser par-
ticles can be consolidated to a higher density than finer
particles of the same composition [22]. The results also sug-
gest that the densification by hot-pressing of milled powders
was not completed. The reason for such an inadequate
consolidation could also be related to insufficient applied
pressure of 35 MPa. It is quite disputable whether the precipi-
tation of nano-sized particles from the solid solution may
have any effect on the decrease of density. The measured
density of compacts processed from 10 h-milled powder
(7.75 g cm
3
) was 87% of the theoretical value (8.89 g cm
3
).
Since the measured density of the hot-extruded materials is
higher than 99.3% [23] hot-extruding seems to be a common
method of compacting. It should be noted that in this study
the theoretical density was calculated for the total amount
of Al
2
O
3
, i.e. 2.5 wt.%.
3.2.4. Electrical Conductivity
The results of electrical conductivity of compacts after differ-
ent times of milling are summarized in Table 2.
Compact processed from as-received and non-milled
Cu1Al +Al
2
O
3
powders shows the lowest electrical conductivi-
ty. During the following milling, precipitation of nano-sized
Al
2
O
3
particles contributes to the increase in electrical con-
ductivity, which is due to depletion of aluminum content in
solid solution. No significant change in electrical conductivity
was detected for up to 15 h of milling. The increase in electri-
cal conductivity after 15 h of milling is connected with the de-
crease in microhardness and recrystallization processes. It is
obvious that the electrical conductivity of compacts is much
lower than that of pure copper or some copper based, high
conductivity alloys. Nano-sized Al
2
O
3
particles form a great
number of interfaces considered as a possible source of addi-
tional electron scatter, which is a significant factor in reducing
conductivity [24].
Table 2 The effect of milling time on electrical
conductivity of Cu1Al +Al
2
O
3
compacts.
Compact Electrical conductivity (%IACS)
Milling time (h)
0

3 5 10 12 15 20
Cu1Al +Al
2
O
3
22 30.5 30.7 31.0 32.0 37.5 47.0
Fig. 12 Effect of milling time on density of Cu1Al +Al
2
O
3
compacts.
135 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
4. Conclusions
Simultaneously reinforced copper matrix with nano- and
micro-sizedAl
2
O
3
particles was obtainedbyhigh-energy milling
of the mixture containing inert gas-atomized prealloyed copper
powder with 1 wt.% Al and 0.6 wt.% commercial Al
2
O
3
powder.
- Milling of prealloyed powder promoted an amount of 1.9 wt.%
Al
2
O
3
by internal oxidation. Thus, the total amount of 2.5 wt.%
of nano- and micro-sized Al
2
O
3
particles have been obtained.
Lamellae, representing traces of previous individual powder
particles may be distinguished, whereas a number of very
small globular particles are precipitated on these lamellae.
Coarse particles of different morphologies with an approxi-
mate size of 700 nm are also present in the matrix
- Compacts processed from powders milled for 3 and 5 h
retained lamellar structure, a characteristic for high-energy
milledpowder particles. During longer milling time the lamel-
lar structure was somewhat changed as a result of recrystalli-
zation occurring during hot-pressing. In compact processed
from10 h-milledpowders nano-sizedparticles (mainlyglobu-
lar and approximately between 30 and 60 nmin size) prevent
grain boundary migration, decreasing the rate of the grain
growth. In addition to nano-sized particles, larger micro-
sized individual particles also appear in the matrix.
- The highest values of microhardness are reached in com-
pacts processed from10 h-milled powders. The microhard-
ness of compact obtained from 10 h-milled powder is 3
times higher (2400 MPa) than microhardness processed
from as-received and non-milled Cu1 wt.% Al powder
(745 MPa) compacted under the same conditions. At the
maximum microhardness the grain size reaches the smal-
lest value as a result of the synergetic effect of nano- and
micro-sized Al
2
O
3
particles.
- Prolonged milling results in a slow drop in microhardness.
This is because the micro-sized Al
2
O
3
particles under certain
conditions may contribute to an increase in the grain size.
The prolongedmilling time results ina significantly increased
subgrainnumber, whichcanbe activatedand become the nu-
cleationsites of newly formedrecrystallizedgrains. Recrystal-
lization, which occurred during prolonged milling, was the
main factor influencing the microhardness decrease.
- Density of the Cu1Al+Al
2
O
3
compacts decreases withmilling
time. The significant drop in density occurred for up to 15 h
of milling time, when the fracturing of powder particles is
the predominant process during milling. Morphologyof pow-
der particles influences the packing between particles during
hot-pressing, indicating that the better packing achieved
during shorter milling time corresponds to higher density.
- The increase in electrical conductivity of the Cu1Al +Al
2
O
3
compacts after 15 h of milling is connected with the de-
crease in microhardness and recrystallization processes.
Acknowledgment
This work was financially supported by the Ministry of Educa-
tion and Science of the Republic of Serbia through the Project
No 172005.
R E F E R E N C E S
[1] Kalinin MG, Fabritsiev AS, Singh NB, Tahtinen S, Zinkle JS.
Specification of properties and design allowables for copper
alloys used in HHF components of ITER. J Nucl Mater
2002;307311:66872.
[2] Upadhyaya A, Upadhyaya SG. Sintering of copper-alumina
composites through blending and mechanical alloying
powder metallurgy routes. Mater Des 1995;16:415.
[3] Guobin L, Jibing SL, Quanmei G, Ru W. Fabrication of the
nanometer Al
2
O
3
/Cu composite by internal oxidation. J Mater
Process Technol 2005;170:33640.
[4] Palma HR, Sepulveda OA. Contamination effects on
precipitation hardening of Cu-alumina alloys
prepared by mechanical alloying. Mater Sci Forum
2003;416418:1627.
[5] Tiang B, Liu P, Song K, Li Y, Ren F. Microstructure and
properties at elevated temperature of nano-Al
2
O
3
particles
dispersion-strengthened copper base composite. Mater Sci
Eng A 2006;435436:70510.
[6] Rajkovic V, Bozic D, Stasic J, Devecerski A, Bojanic S,
Jovanovic TM. Strength and thermal stability of Cu-Al
2
O
3
composite obtained by internal oxidation. Rev Metal 2010;46:
5209.
[7] Naser J, Riehemann WJ, Ferkel H. Dispersion hardening of
metals by nanoscaled ceramic powders. Mater Sci Eng A
1997;234236:4679.
[8] Ahn HJ, Song HI, Hahn DY. Cu-based cermets prepared by
mechanical alloying. Mater Trans, JIM 1996;37:7337.
[9] Mukhtar A, Zhang LD, Kong C, Munroe P. Microstructure and
thermal stability of nanostructured Cu7.5vol.%Al
2
O
3
composite powders produced by high energy mechanical
milling. 2009 IOP Conf Ser: Mater Sci Eng 2009;4:012005 (5pp),
doi:10.1088/1757-899X/4/1/012005.
[10] Humphreys JF. Recrystallization mechanisms in two-phase
alloys. Metal Sci 1979:13645 [MarchApril].
[11] Rajkovic V, Boi D, Deveerski A. The properties of high
energy milled prealloyed copper powders containing
1 wt.%Al. J Serb Chem Soc 2007;72:4553.
[12] Rajkovic V, Eric O, Bozic D, Mitkov M, Romhanji E.
Characterization of dispersion strengthened copper with
3 wt%Al
2
O
3
by mechanical alloying. Sci Sintering 2004;36:
20511.
[13] Lonnberg B. Characterization of milled Si
3
N
4
powder using
X-ray peak broadening and surface area analysis. J Mater Sci
1994;29:322430.
[14] Williamson GK, Hall WH. X-ray broadening from filed
aluminium and wolfram. Acta Metall 1953;1:2231.
[15] Indenbom LV, Kaganer MV. X-ray analysis of internal
stresses in crystals II. Phys Status Solidi A
1999;122:97109.
[16] Jena KP, Brocchi EA, Solorzano GI, Motta SM. Identification of
a third phase in Cu-Al
2
O
3
nanocomposites prepared by
chemical routes. Mater Sci Eng A 2004;371:728.
[17] Ferkel H. Properties of copper reinforced by laser-generated
Al
2
O
3
-nanoparticles. Nanostruct Mater 1999;11:595602.
[18] Khorshid TM, Jahromi JAS, Moshksar MM. Mechanical
properties of trimodal Al matrix composites reinforced by
nano- and submicron-sized Al
2
O
3
particulates developed by
wet attrition milling and hot extrusion. Mat Des 2010;31:
38804.
[19] Miller WS, Humphreys FJ. Strengthening mechanisms in
particulate metal matrix composites. Scripta Metall Mater
1991;25:338.
[20] Zhang Z, Chen DL. Contribution of Orowan strengthening
effect in particulate reinforced metal matrix
nanocomposites. Mater Sci Eng A 2008;483484:14852.
136 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7
[21] Szraz Z, Trojanov Z, Cabbibo M, Evangelista E.
Strengthening in a WE54 magnesium alloy containing
SiC particles. Mater Sci Eng A 2007;462:2259.
[22] Gutmanas YE. Consolidation of powders under high
pressures-cold sintering. In: Arzt E, Shultz L, editors.
New Materials by Mechanical Alloying Techniques.
Germany: Deutche Gesellschaft fur Metallkunde e.V; 1989.
p. 12942.
[23] Preston O, Grant JN. Dispersion strengthening of copper by
internal oxidation. Trans Metall Soc AIME 1961;221:16473.
[24] Shi Z, Yan M. The preparation of Al
2
O
3
-Cu composite by
internal oxidation. Appl Surf Sci 1998;134:1036.
137 M A T E R I A L S C H A R A C T E R I Z A T I O N 6 7 ( 2 0 1 2 ) 1 2 9 1 3 7