Materials Science and Engineering A 380 (2004) 384393

Formation of Al2 Cu and AlCu intermetallics in Al(Cu) alloy

matrix composites by reaction sintering
M. Aravind, P. Yu, M.Y. Yau, Dickon H.L. Ng
Department of Physics, The Chinese University of Hong Kong, Shatin, Hong Kong, China

Received 9 January 2004; received in revised form 1 April 2004

Abstract

We report the fabrication and characterization of a series of Al(Cu) alloy-based matrix composites. The composites were produced by
sintering and rapid quenching three powder mixtures of Al and Cu with hypoeutectic, eutectic, and hypereutectic compositions. The morphology
of the reinforcements formed in the Al(Cu) matrices of these composites was found to be variable. A two-phase Al2 CuAl(Cu) nanoeutectic,
with lamellar spacing of 200300 nm, was found in the Al(Cu) matrix of the sample having hypoeutectic composition after it was oil-quenched
from 1000 C to room temperature. While oil quenching the sample with eutectic composition, produced single Al2 Cu crystals of 22.5 m
size, embedded in a lamellar nanoeutectic matrix. As for the hypereutectic alloy, the matrix of the oil-quenched sample consisted mainly of
Al2 Cu intermetallic, and a secondary phase of AlCu dendrites with dendrite arms spacing of 11.5 m.
2004 Elsevier B.V. All rights reserved.

Keywords: Aluminum; Copper; Intermetallic; Nanoeutectic; Dendrite

1. Introduction
Al-based and Alalloy-based metal matrix composites
(MMCs) have been widely used in automobile and aerospace
industries [1,2]. The reinforcements in many of these prod-
ucts are formed by in situ reaction techniques [35], and
the reinforcements obtained are usually thermodynamically
stable [6]. This method also improves interfacial contacts
between reinforcements and the matrices [79]. Ceramic
particle-reinforced Al matrix has been studied extensively,
and many of these MMC are fabricated according to the in
situ reaction mechanism between Al and selected metal ox-
ides like CuO, ZnO, SiO2 , MnO2 , and TiO2 [1014]. Despite
many of their advantages, the presence of the non-conductive
oxide reduces both the thermal and electrical conductivities
of these Al-based MMC products. In this work, we make
use of the in situ technique to reaction-sinter pure Al and Cu
powders. AlCu intermetallic compounds are formed dur-
ing the reactions, and these intermetallics act as secondary
phase reinforcements to the matrix. Copper is being used,
because it is one of the few elements that have relatively
Corressponding author. Tel.: +852 2609 6392; fax: +852 2603 5204.
E-mail address: dng@phy.cuhk.edu.hk (D.H.L. Ng).
high solubility in Al. Thus, the sintered AlCu product has
an Al(Cu) solid solution matrix that is mechanically tougher
than a pure Al matrix. Our objectives are to produce an
AlCu intermetallic-reinforced Al(Cu) alloy matrix compos-
ite by using the in situ technique, and to investigate the in
situ formed microstructure of the composite when different
compositions of Cu are being used. This work also studies
the effect of solidification conditions on the size of the re-
inforcements and the nature of the matrices. Microstructure
characteristics of the as-formed AlMMCs, as well as their
hardness are reported in this paper.
Nanometer-sized (nm-sized) materials have generated
great interest in the past decade, due to the specific prop-
erties exhibited by them, as compared to those of their
coarse-grained counterparts [1517]. A standard technique
for producing a composite that contains nm-sized rein-
forcements is by mixing and pressing the nm-sized pre-
cursors with the matrix material before sintering [1820].
However, the high cost of nm-sized particles and the dif-
ficulties of inhibiting grain growth during sintering have
limited the industrial application of this method. Thus, an-
other objective of this work is to illustrate the importance
of rapid cooling for obtaining nm-sized reinforcements
in the form of nanoeutectic in the Al(Cu) alloy-based
MMCs.

0921-5093/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2004.04.013
 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393
2. Experiments
Al and Cu powders were used to prepare the AlCu
intermetallics-reinforced MMC samples. Weight percentage
of Cu added to Al was varied in order to produce different
types of intermetallics in the AlCu sample. The hypoeutec-
tic, eutectic, and hypereutectic compositions of AlCu alloy
were considered. According to the binary phase diagram
of AlCu, shown in Fig. 1 [21], Al powder with 17 wt.%
Cu was mixed for preparing the sample with hypoeutec-
tic composition, and the weight percentage of Cu were,
respectively 32.5 and 50 for the samples of eutectic and hy-
pereutectic compositions. High purity Al and Cu powders
(>99.7% purity) were mixed at the selected compositions
and cold pressed to form green compacts. The temperatures
at which reactions and phase transformations occurred in
the samples during sintering and cooling were measured by
differential thermal analysis (DTA). During DTA, the green
samples were heated in argon atmosphere in the furnace of
the analyzer, where the temperature was raised from ambi-
ent to 1000 C at a rate of 3 C/min. The phases formed in
the samples were identified by X-ray diffractometry (XRD),
using a Cu K radiation source. Green samples from each
composition were also heated in a tube furnace at 1000 C in
argon atmosphere for 1 h, before they were either cooled in a
power-off furnace, oil-quenched, or salt-solution-quenched
to room temperature. The microstructures of these sam-
ples were studied by scanning electron microscopy (SEM).
The chemical compositions of the in situ formed phases
were determined by energy dispersive X-ray spectrome-
try (EDS). The hardness of the samples was evaluated by
Vickers hardness tests. Each hardness value recorded was
an average of five distinct indented measurements made on
the sample surface. The topographic features of some of the
sintered samples were studied by atomic force microscopy
(AFM).
Fig. 1. An AlCu phase diagram showing the Al-rich region. [21].
385
3. Results
3.1. DTA analysis
The DTA curves obtained from the green compacts of the
alloys are shown in Fig. 2. The heating curves of all the three
alloys appeared similar, with a broad positive exothermic
region located between 550 C and about 606 C, whereas
the cooling curves were different. The cooling curve of the
hypoeutectic alloy exhibited three exothermic peaks located
at 601, 580, and 538 C, respectively, even though based
on the AlCu phase diagram, only a peak at 615 C corre-
sponding to the precipitation of proeutectic Al(Cu) and a
peak at 548 C corresponding to the eutectic reaction were
expected. In the cooling curve of the eutectic alloy, a sin-
gle peak was found at 534 C. It corresponded to the for-
mation of the two-phase Al2 CuAl(Cu) eutectic. Since this
alloy had a eutectic composition, no proeutectic Al(Cu) pre-
cipitation took place during solidification when the molten
sample was cooled from 1000 C to ambient. The cooling
curve of the hypereutectic alloy exhibited two peaks at 601
and 578 C. The first peak (at 601 C) was related to the pre-
cipitation of the proeutectic Al2 Cu phase. The hypereutec-
tic composition considered (50 wt.% Cu) was very close
to the peritectic composition of the AlCu alloy, hence the
first peak was related to the peritectic reactions, and the sec-
ond peak in the cooling curve was the result of peritectoid
reactions.
3.2. XRD analysis
Fig. 3 exhibits the XRD patterns of the three green
samples and the sintered samples that were brought to
room temperature by furnace-cooling, oil-quenching, or
salt-solution-quenching. During sintering, the reaction
Fig. 2. The DTA curves of the AlCu samples. The broad positive region
located between 550 and 606 C in the heating curves corresponds to the
exothermic reaction between Al and Cu.
386 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393
Fig. 3. The XRD patterns of the sintered AlCu samples (FC: furnace
cooled, OQ: oil quenched, SQ: solution quenched).
between Al and Cu can be described by the following
equation
heating
Al (s) + Cu (s) (Al, Cu) (l) (1)
where (s) and (l) indicate whether the reactant or the product
is in solid or liquid phase. In the diffraction patterns of the
hypoeutectic and eutectic alloys that were furnace-cooled,
Table 1
Summary of the XRD results: phases in the green and the sintered
AlCu samples (FC: furnace cooled, OQ: oil quenched, SQ: salt solution
quenched)
Samples Phases
Al Cu Al2 Cu AlCu
Hypoeutectic
Green
FC
OQ
SQ
Eutectic
Green
FC
OQ
SQ
Hypereutectic
Green
FC
OQ
SQ
peaks that corresponded to Al and intermetallic Al2 Cu were
found, with the intensity of the Al peaks being higher in the
hypoeutectic, and that of the Al2 Cu peaks being higher in
the eutectic alloy. As for the high Cu content hypereutectic
alloy, the only phases present in the sintered samples were
the two intermetallics: AlCu and Al2 Cu. The fractional vol-
ume of these intermetallics seemed to depend on the cooling
rate. It was observed that the hypereutectic alloy rapidly
cooled by quenching either in oil or in concentrated salt so-
lution had only a small fraction of AlCu phase, as reflected
by its low intensity peaks, with the intensity being slightly
higher in the oil-quenched sample. For the furnace-cooled
samples, where the cooling rate was slow, the amount of
Al(Cu) was the highest within the hypereutectic alloy. A
summary of the XRD results is listed in Table 1.
3.3. Microstructural analysis
The SEM image of the Al17 wt.% Cu green sample is
shown in Fig. 4. The SEM analysis of these green alloys
indicated that the Cu particles were distributed evenly in the
Al matrix after mixing. However, some Cu particles were
found aggregated to form larger lumps in the hypereutectic
samples where Cu concentration was high. Table 2 gives a
summary of the concentrations of Al and Cu in the sintered
hypoeutectic, eutectic and hypereutectic samples.
3.3.1. Hypoeutectic alloy
SEM micrographs in Fig. 5 are of the sintered hypoeu-
tectic alloy. The compositions of the different regions were
measured by the EDS attached to the SEM. Fig. 5a shows
the two-phase Al2 CuAl(Cu) eutectic formed in the Al(Cu)
matrix of the alloy which was furnace-cooled after sinter-
ing at 1000 C for an hour. The thickness of the lamellae
 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393 387

Fig. 4. The SEM micrograph of the Al17 wt.% Cu green sample.

in the eutectic was found to be about 23 m. When this
alloy was cooled rapidly by quenching, a nanoeutectic net-
work was observed within the Al(Cu) matrix. Fig. 5b and
c show the oil-quenched and the salt-solution-quenched
samples, respectively. The size of the Al(Cu) dendrite arm
(dark) in the oil-quenched sample was 510 m, and that in
the salt-solution-quenched one was 15 m. These Al(Cu)
dendrite arms were surrounded by the eutectic network
(in gray). The morphology of some of these samples was
further clarified by AFM. The sample for AFM was finely
polished on either side by a SiC paste of particle size
1 m. It was then etched for 30 s in a 1 M NaOH solu-
tion to remove the Al matrix and the Al component of the
eutectic, so that the width of the Al2 Cu lamellae of the eu-
tectic could be revealed. Fig. 6 shows an AFM micrograph
illustrating the topographic features of an oil-quenched
sample. The lamellar spacing of the eutectic in this sample
was determined to be about 200300 nm, and that of the
salt-solution-quenched sample was about the same, even
though its Al(Cu) dendrite arms appeared smaller than that
of the oil-quenched ones (Fig. 5b and c).
3.3.2. Eutectic alloy
Fig. 7a is a SEM micrograph of the eutectic alloy that
was furnace-cooled from 1000 C. This sample contained
a mixed microstructure comprising anomalous eutectic and
lamellar eutectic. It was reported in an earlier work that
anomalous eutectic was the result of independent nucleation

Table 2
Phases in the AlCu samples determined by EDS
Region Al (at.%) Cu (at.%) Formula of the phase

Hypoeutectic samples
Sintered at 1000 C and furnace cooled Eutectic 66 34 Al2 CuAl(Cu)
96 4
Matrix 96 4 Al(Cu)
Sintered at 1000 Coil-quenched and salt-solution-quenched Eutectic 73 27 Al2 CuAl(Cu)
94 6
Matrix 94 6 Al(Cu)
Eutectic samples
Sintered at 1000 C and furnace cooled Eutectic 61 39 Al2 CuAl(Cu)
97 3
Sintered at 1000 C oil-quenched Rosette 71 29 Al2 Cu
Eutectic background Al2 CuAl(Cu)
Hypereutectic samples
Sintered at 1000 C, and furnace cooled Light gray 54 46 AlCu
Dark gray 63 37 Al2 Cu
Sintered at 1000 Coil-quenched Dendrite 49 51 AlCu
Background 61 39 Al2 Cu
388 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393
Fig. 5. The SEM micrographs of the sintered hypoeutectic sample. (a)
Micrograph shows the micrometer-sized Al2 CuAl(Cu) eutectic in the
matrix of the furnace-cooled sample. (b) and (c) Micrographs of the
oil-quenched and salt-solution-quenched samples. The bright area is the
nanoeutectic network, and the dark background is the Al(Cu) matrix.
and growth of the two separate eutectic phases, whereas in
lamellar eutectic the two phases grew simultaneously [22].
In this furnace-cooled eutectic alloy, the anomalous region
(denoted by A in Fig. 7a) had well-defined Al(Cu) den-
drite cells of size 40 m. The Al(Cu) was surrounded by
Fig. 6. An AFM micrograph shows the Al2 Cu lamellae (200 nm) of the
Al2 CuAl(Cu) eutectic in an oil-quenched hypoeutectic sample.
a ribbon-like Al2 Cu intermetallic phase (gray). The lamel-
lar eutectic (region denoted by B in Fig. 7a) had lamel-
lae of Al(Cu) and Al2 Cu with average spacing of about
67 m. When the eutectic alloy was oil-quenched, its mi-
crostructure was entirely different. Its SEM micrographs, in
small and large scales, are shown in Fig. 7b and c, respec-
tively. It was found that many of the anomalous eutectics
in the matrix were converted to lamellar nanoeutectic net-
work. It was also observed that the sample contained some
flower-like colonies (rosettes), with an average grain size of
about 2.5 m, and they were uniformly distributed in the
matrix composed mostly of lamellar nanoeutectic with some
scattered anomalous nanoeutectic region. The EDS analysis
indicated that these rosettes contained Al2 Cu. The average
dendrite cell size of Al(Cu) in the minority anomalous eutec-
tic was less than 400 nm, whereas the lamellar width of the
majority lamellar nanoeutectic was less than 100200 nm.
3.3.3. Hypereutectic alloy
The SEM analysis on the hypereutectic alloy that was
furnace-cooled from 1000 C revealed two distinct phases
(not shown). The phases were found by EDS to be Al2 Cu and
AlCu. Fig. 8 shows an SEM micrograph of a hypereutectic
alloy sample after it was oil-quenched from 1000 C. Den-
drites (light-colored region) 11.5 m wide and 1015 m
long were found in this sample. These dendrites were de-
termined by EDS to be AlCu, and they were scattered uni-
formly in the Al2 Cu matrix (in dark).
3.4. Hardness
The Vickers hardness number (VHN) of the samples was
measured by using a Buehler 2100 microhardness tester with
 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393
Fig. 7. (a) SEM micrograph shows the anomalous (denoted by A) and the
lamellar (denoted by B) Al2 CuAl(Cu) eutectic regions in the eutectic
alloy furnace-cooled from 1000 C. (b and c) Micrographs show, in dif-
ferent scales, the Al2 Cu rosettes which are scattered in the Al2 CuAl(Cu)
eutectic matrix of the oil-quenched sample.
a 500 g load indenter. The results are listed in Table 3. It
was found that the VHN obtained from different regions
of the furnace-cooled samples had a relatively larger vari-
ation than those obtained from the rapidly cooled samples.
The average VHN of the furnace-cooled, oil-quenched and
389
salt-solution-quenched hypoeutectic alloys were 78, 130 and
126, respectively. For the eutectic alloy, the average VHN of
the furnace-cooled and oil-quenched samples were 148 and
270, respectively. The furnace-cooled hypereutectic sample
showed two distinct phases, Al2 Cu and AlCu. The VHN
obtained from these phases were 272 and 444, respectively.
As for the oil-quenched hypereutectic specimen which con-
tained AlCu dendrites, its overall VHN was determined to
be about 440. For comparison, a pure Al sample was also
prepared by a similar experimental procedure and its VHN
was found to be about 45.
4. Discussion
4.1. Phase transformations during cooling
Based on the results of XRD and those from microstruc-
tural analysis, it was possible to postulate the reactions that
occurred at the temperatures where the peaks were located
in the DTA cooling curves.
4.1.1. Hypoeutectic alloy
When molten hypoeutectic AlCu was cooled and solidi-
fied, Al(Cu) having a higher melting point was precipitated
initially as the proeutectic phase before the eutectic transfor-
mation. The transformation during cooling can be described
by the following equations
Al, Cu(l) Al(Cu)(s,proeutectic)
+ (Al, Cu) (l,eutecticcomposition) (2a)
(Al, Cu) (l, eutecticcomposition) Al2 Cu
+ Al(Cu)(s, eutectic) (2b)
According to the AlCu phase diagram (Fig. 1), a sin-
gle exothermic peak corresponding to the solidification of
proeutectic Al(Cu) was expected at 615 C. However, two
peaks were found at 601 and 580 C in the cooling curve of
the hypoeutectic sample (Fig. 2), and the explanation for the
occurrence of these peaks is as follows. The XRD pattern
of the hypoeutectic alloy (Fig. 3a) exhibited only the Al2 Cu
and the Al peaks. This implied that the two exothermic
peaks observed in the DTA cooling curve, at temperatures
above the eutectic temperature (548 C), could only be re-
lated to the formation of the Al(Cu) solid solution (Eq. (2a)).
Thus, these two peaks were probably parts of a split single
peak that corresponded to the solidification of proeutectic
Al(Cu) phase with different amounts of Cu in different re-
gions. Such a state was metastable, but this often happened
in sample with inhomogeneous composition where longer
time and higher temperature were required to achieve a
more uniform composition of its melt. Our EDS analysis
further confirmed that in some regions, the concentration of
Cu was about 2.9 wt.%, while in some others they were up
390 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393

Fig. 8. SEM micrograph of the oil-quenched hypereutectic. The dendrites (light) consist of AlCu intermetallic, and the dark background is the Al2 Cu
matrix.

to 5.7 wt.%. Thus, different melting points in this Al(Cu)
solid solution were expected, and this was reflected by the
multiple exothermic peaks at a temperature range from 615
to 575 C in the DTA cooling curve of our hypoeutectic
sample. As the alloy was further cooled, eutectic transfor-
mation occurred at temperature below 548 C (reaction 2b).
This was indicated by the occurrence of an exothermic peak
located between 542 and 530 C in the DTA cooling curve.
4.1.2. Eutectic alloy
In cooling the molten AlCu alloy with eutectic compo-
sition, eutectic were expected when the temperature of the
sample dropped below 548 C. This eutectic reaction can be
described by the previous Eq. (2b). In our DTA analysis, a
single exothermic peak was found between 541 and 530 C
in the cooling curve of the eutectic alloy (Fig. 2). This in-
dicated that the eutectic reaction given in Eq. (2b) was the
sole transformation process during cooling. In the SEM mi-
crostructural analysis of the sintered sample, the two-phase
Table 3
The Vickers hardness values of the AlCu samples and a sintered Al sample (FC: furnace cooled, OQ: oil quenched, SQ: salt solution quenched)
VHN alloys 1000 C, FC
Al2 CuAl(Cu) eutectics were observed: some in anomalous
form and some in lamellar form (Fig. 7).
4.1.3. Hypereutectic alloy
According to the AlCu phase diagram (Fig. 1), as the
molten AlCu alloy of the hypereutectic composition was
cooled from 1000 C, proeutectic Al2 Cu was expected to so-
lidify first. However, in an earlier work on an Al52 wt.%Cu
alloy [23], it was found that peritectic reaction had occurred
at 591 C, and peritectoid reaction had occurred at 563 C.
In this work, our hypereutectic sample contained 50 wt.% of
Cu and it was therefore possible to postulate the transfor-
mations of our molten hypereutectic alloy via the following
reactions
600 C
(Al, Cu)(l) + AlCu (s) Al2 Cu(s) peritectic reaction
(3)
578 C
AlCu (s) + Al2 Cu(s) AlCu(s) peritectoid reaction
1000 C, OQ 1000 C, SQ

Reinforcement Matrix Reinforcement Matrix Reinforcement Matrix

Hypoeutectic 78 10 130 2 126 3

Al2 CuAl(Cu) (micron size) Al(Cu) Al2 CuAl(Cu) Al(Cu) Al2 CuAl(Cu) Al(Cu)
(nanosize) (nanosize)
Eutectic 148 10 270 4 Brittle
Lamellar + anomalous eutectic Al2 Cu Lamellar nanoeutectic
Hypereutectic 444 8 272 8 440 3 Brittle
AlCu + Al2 Cu AlCu Al2 Cu
Al 45
Al
 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393
AlCu and AlCu had the same composition but different
crystal structures, the former was monoclinic and the other
was orthorhombic. These transformations were confirmed by
DTA, and indicated by the two exothermic peaks between the
range of 610570 C in the cooling curve of this alloy. The
peak located at 601 C was probably due to the formation of
Al2 Cu, a peritectic reaction and that at 578 C was due to the
formation of AlCu intermetallic, a peritectoid reaction. The
microstructural analyses by SEM and optical microscopy
revealed the presence of both Al2 Cu and AlCu phases in the
sintered product. During solidification of this hypereutectic
alloy, Al2 Cu was initially precipitated. By the peritectoid
reaction that followed, AlCu was formed at a lower melting
point.
4.2. Effects of cooling rate
4.2.1. On microstructures
The alloy samples were heated to 1000 C before they
were cooled by three different means. One of the samples
from each composition was slowly cooled in the power-off
furnace after sintering, while two others of the same type
were rapidly cooled by quenching in oil or in concentrated
salt solution. Quenching increased the rate of cooling, and
salt solution quenching provided an even higher cooling rate
to the sample than oil quenching. In this study, we found
that the microstructures of these samples depended strongly
on their compositions, as well as the rate of cooling with
which they were brought down to room temperature from
their molten states.
4.2.1.1. Hypoeutectic and eutectic alloys. During eutec-
tic formation, there is a diffusive mass transport. On rapid
solidification, as in the case of quenching, long range diffu-
sion is not possible resulting in the creation of fine eutectic
network. To the first approximation, the average lamellar
spacing of a eutectic structure can be determined by the
following expression [24],


K Salt-solution quenching the eutectic sample had made it too
= porous and brittle for microstructural analysis.
V
where V is the growth rate of the eutectic and K the solid-
ification constant related to a particular system. Quenching
the sample was in effect increasing the velocity of solidifi-
cation (i.e. growth rate of the solid phase), thus it decreased
the value of l in the eutectic. In the hypoeutectic alloy
when molten AlCu alloy was rapidly oil-quenched or
solution-quenched, V was extremely high and l was therefore
small, and a two-phase Al2 CuAl(Cu) nanoeutectic network
in the Al(Cu) matrix was produced, shown in Fig. 5b and
c. The salt-solution-quenched sample (Fig. 5c) had a much
finer nanoeutectic network than that of the oil-quenched one
(Fig. 5b). On the other hand, a nanostructured eutectic ma-
trix was created when the eutectic alloy was quenched in oil
(Fig. 7b and c). In the furnace-cooled hypoeutectic and eu-
391
tectic alloys, l was relatively large (in micron-size). Fig. 5a
shows the micron-sized eutectics that were embedded in
the Al(Cu) matrix of the hypoeutectic alloy and Fig. 7a
shows that for the furnace cooled eutectic alloy the matrix
was formed of micron sized eutectics. The furnace-cooled
alloy with eutectic composition contained two types of
Al2 CuAl(Cu) eutectic, the anomalous one and the lamellar
one (Fig. 7a). Since a fine lamellar eutectic structure has a
relatively higher interfacial energy, the reduction of this en-
ergy will act as a driving force for the transformation of fine
lamellar eutectic to a coarser microstructure of anomalous
eutectics that is thermodynamically more stable. In the cool-
ing of the eutectic alloy, the Al(Cu) dendrite phase solidified
first and released heat to the interdendritic molten phase.
This remnant melt, which was now slightly undercooled, so-
lidified with a smaller growth velocity (V). Thus, the nucle-
ation and growth rates of the two phases in the eutectic were
different, and this led to a large interlamellar distance () re-
sulting in an anomalous structure. However, when the alloy
was rapidly cooled by quenching, V was high, and the two
phases of the eutectic grew simultaneously. Hence, large and
extensive formation of structure in the sample was unlikely,
instead the sample contained mostly a lamellar pattern. Evi-
dence of this claim was shown in Fig. 7b and c. In the SEM
of the oil-quenched eutectic alloy only a small percent-
age of the anomalous eutectic was present with the matrix
being mainly lamellar nanoeutectic. The formation of the
single-crystal Al2 Cu rosettes in the quenched eutectic alloy
can be explained as follows. In the fcc structures, dendrite
arms are normally oriented along the (1 0 0) directions. How-
ever, under particular growth conditions, these directions
are not followed, and rosettes result. An earlier work [25]
also reported that above some critical value of V, the lamel-
lar front would undergo a large-scale destabilization leading
to single-crystal colonies at near-eutectic concentrations or
to dendrites at off-eutectic concentration. In our case, when
alloy sample with eutectic composition was oil-quenched,
Al2 Cu rosettes were formed, and they were found scattered
in the lamellar Al2 CuAl(Cu) nanoeutectic matrix (Fig. 7b).
4.2.1.2. Hypereutectic alloys. It is known that peritectic
reaction involves one solid phase reacting with a liquid
phase to produce a second solid phase upon cooling [26].
The usual product of peritectic solidification is the primary
phase, surrounded by the peritectic phase and the remaining
liquid. On slow furnace cooling the hypereutectic alloy, the
primary AlCu phase was formed surrounded by the peritec-
tic Al2 Cu phase. When the alloy was oil-quenched, dendritic
AlCu was found dispersed in the Al2 Cu matrix (Fig. 8). It
was also shown earlier [27] that at a high cooling rate the
peritectic phase could grow directly from the melt instead
of via the peritectic reaction. The cooling rate in our hyper-
eutectic alloy was very high, as it was sintered at 1000 C
and then quenched in either oil or concentrated salt solution.
392 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393
Thus, the probable rapid precipitation of the peritectic
Al2 Cu from the melt resulted in the higher volume fraction
of Al2 Cu in the quenched samples. Such a phenomenon of
an increase in one phase and a decrease in the other during
rapid solidification had also been reported by Li et al. [28]
in NiAl alloy system. The rate of cooling when quenched
in salt solution was higher, and hence the volume fraction
of Al2 Cu in the salt solution-quenched sample was larger
than that in the oil quenched one. This claim was confirmed
by the XRD patterns of the hypereutectic (Fig. 3c) which
showed an increased intensity in the Al2 Cu peaks as the
rate of cooling increased, and by SEM of the oil quenched
alloy which had a matrix of Al2 Cu. This result also showed
that cooling rate played an important role in the phase
selection during phase transformations. The competitive
growth phase selection theory [29] which explains phase
transitions, states that the dominant phase is the one which
possesses higher growth velocity at a given undercooling.
Thus, in the solidification of our hypereutectic alloy we
found that the intermetallic Al2 Cu was the dominant phase.
4.2.2. On microhardness
Table 3 illustrates that the hardness of the samples in-
creased with increasing Cu content. Thus, under any partic-
ular cooling condition, the hypereutectic alloy was harder
than the hypoeutectic and eutectic alloys. For example, the
hardness value of the oil-quenched hypereutectic was 440
while that of the hypoeutectic and the eutectic alloys were
respectively, 130, and 270. The increase in hardness was also
due to the formation of hard intermetallics in the matrix of
the sintered alloys with larger amount of Cu. Furnace-cooled
hypereutectic alloy had AlCu and Al2 Cu intermetallic re-
gions, with the VHN of AlCu region (444) being double
that of Al2 Cu region (272). The copper content in AlCu
was more than that in the Al2 Cu intermetallic, this could be
the reason for its high VHN. The table also shows the rein-
forcements and the matrices formed in the sintered alloys at
different cooling rates. As evident from the table the VHN
from different regions on the surface of the furnace cooled
alloys showed a large variation (612%), as compared to
the quenched alloys (0.62%). On quenching, uniform mi-
crostructures were formed with the matrix reinforced by
smaller reinforcements, as compared to the furnace-cooled
alloys, hence the variation in microhardness obtained from
the surface of the alloys were much less. The hardness of
these alloys was governed by the relative volume fractions of
eutectic and dendritic phase. The hardness was also found to
increase when the eutectic and dendritic spacings decreased.
For instance the hardness of the furnace-cooled eutectic alloy
was 148 while that of the oil-quenched alloy was 270. The
eutectic and hypereutectic alloys became very brittle when
they were quenched in concentrated salt solution, whereas
the microhardness of the solution quenched hypoeutectic
sample was more or less the same as that of the oil-quenched
sample. Fig. 5b and c, show that the inter-dendritic spac-
ing in the oil-quenched hypoeutectic was larger than that
in the solution-quenched sample. However, the relative vol-
ume fraction of the eutectic and dendritic structures in both
quenched samples was more or less equivalent, and this
could explain the comparable microhardness values obtained
from the two quenched hypoeutectic samples.
In general, when the alloys were rapidly cooled by
quenching, the overall microhardness of the samples in-
creased as compared to those cooled in the power-off
furnace. In the hypoeutectic alloy, the increased hardness
of 130 for the oil-quenched sample as compared to 78 for
the furnace-cooled sample was attributed to the decrease in
lamellar spacing in the two-phase nanoeutectic network re-
inforcing the Al(Cu) matrix. Cavities with irregular shapes
formed by salt-solution-quenching the hypoeutectic alloy
had made AFM examination difficult and unreliable, hence
no conclusions could be formulated on finer lamellar spac-
ing in the solution-quenched sample. In the eutectic alloy,
the increase in hardness from 148 for the furnace-cooled to
270 for the oil-quenched sample was attributed to the trans-
formation of the coarser anomalous nanoeutectic matrix to
the finer lamellar nanoeutectic matrix. In the oil-quenched
hypereutectic alloy, the increase in overall hardness of the
sample to 440 could be attributed to the increase of the
Al2 Cu intermetallic in the matrix.
5. Conclusions
Rate of solidification was found to have a great im-
pact on the microstructures of the reinforcements and
matrices formed in the AlCu alloys. When samples
were quenched in either oil or salt solution after sin-
tering at 1000 C: (a) the hypoeutectic alloy exhibited
nanometer-sized eutectic-reinforced Al(Cu) matrix (b) the
eutectic alloy contained single crystal rosettes of Al2 Cu
embedded in the lamellar nanoeutectic matrix, and (c) the
AlCu dendrite-reinforced Al2 Cu matrix was formed in the
hypereutectic alloy. It was also found that the fractional
volume of the AlCu phases: Al2 Cu and AlCu formed dur-
ing fabrication depended on the starting composition of the
alloy and the cooling condition. In the hypereutectic alloy
with near peritectic composition, the volume fraction of the
Al2 Cu phase increased and that of AlCu decreased with
increasing cooling rate. In all samples, the microhardness
of the oil-quenched ones were higher than those measured
from the furnace-cooled samples due to the formation of
(a) lamellar nanoeutectic network in the hypoeutectic (b)
lamellar nanoeutectic matrix reinforced by Al2 Cu in the eu-
tectic, and (c) Al2 Cu matrix reinforced by the hard AlCu in
the hypereutectic. The microhardness of the hypereutectic
was found to be higher than that of either the hypoeutectic
or the eutectic alloy, and was attributed to the presence of
the AlCu intermetallics with higher content of Cu. As ex-
pected, the microhardness of these AlCu alloys exceeded
that of a pure Al sample that had undergone similar heat
treatments.
 M. Aravind et al. / Materials Science and Engineering A 380 (2004) 384393
Acknowledgements
The work is supported by a RGC 2001 Earmarked Re-
search Grant (Project code: 2150303).
References
[1] J.C. Williams, E.A. Starke Jr., Acta Mater. 51 (2003) 5775.
[2] M.E. Smagorinski, P.G. Tsantrizos, S. Grenier, A. Cavasin, T.
Brzezinski, G. Kim, Mater. Sci. Eng. A 244 (1998) 86.
[3] R. Subramanian, C.G. McKamey, J.H. Schneibel, L.R. Buck, P.A.
Menchhofer, Mater. Sci. Eng. A 254 (1998) 119.
[4] S. Gorsse, J.P. Chaminade, Y.L. Petitcorps, Comp. A: Appl. Sci.
Manuf. 29 (1998) 1229.
[5] S.C. Tjong, Z.Y. Ma, Mater. Sci. Eng. R 29 (2000) 49.
[6] G.J. Zhang, Y. Beppu, T. Ohji, S. Kanzaki, Acta Mater. 49 (2001) 77.
[7] J. Subrahmanyam, M. Vijayakumar, J. Mater. Sci. 27 (1992) 6249.
[8] A.W. Urquhart, Mater. Sci. Eng. A 144 (1991) 75.
[9] R.M. Aikin Jr., J. Organomet. 49 (1997) 35.
[10] P. Yu, C.J. Deng, N.G. Ma, M.Y. Yau, D.H.L. Ng, Acta Mater. 51
(2003) 3445.
[11] G. Chen, G.X. Sun, Mater. Sci. Eng. A 244 (1998) 291.
[12] W. Liu, U. Koster, Mater. Sci. Eng. A 210 (1996) 1.
[13] R.A. Andrievski, A.M. Glezer, Scripta Mater. 44 (2001) 1621.
393
[14] E.H. Jordan, M. Gell, Y.H. Sohn, D. Goberman, L. Shaw, S. Jiang,
M. Wang, T.D. Xiao, Y. Wang, P. Strutt, Mater. Sci. Eng. A 301
(2001) 80.
[15] A.S. Edelstein, R.C. Cammarata (Eds.), Nanomaterials: Synthesis,
Properties and Applications, IOP, Bristol, UK, 1996.
[16] G.B. Sergeev, A.V. Nemukhin, B.M. Sergeev, T.I. Shabatina, V.V.
Zagorskii, Nano. Mater. 12 (1999) 1113.
[17] M.D. Frogley, D. Ravich, H.D. Wagner, Comp. Sci. Techol. 63 (2003)
1647.
[18] L. Gao, H.Z. Wang, H. Kawaoka, T. Sekino, K. Niihara, J. Eur.
Ceram. Soc. 22 (2002) 785.
[19] P.C. Maity, P.N. Chakraborty, S.C. Panigrahi, Mat. Lett. 20 (1994)
93.
[20] I.C. Barlow, H. Jones, W.M. Rainforth, Acta Mater. 49 (2001) 1209.
[21] Metallography, Structures and Phase Diagrams, Metal Handbook,
OH, 1973, p. 259.
[22] X.R. Liu, C.D. Cao, B. Wei, Scripta Mater. 46 (2002) 13.
[23] J.L. Murray, Int. Met. Rev. 30 (1985) 211.
[24] W. Kurz, D.J. Fisher (Eds.), Fundamentals of Solidification, Third
Trans. Tech. Pub., 1989, p.104.
[25] R.M. Jordan, J.D. Hunt, J. Cryst. Growth 11 (1971) 141.
[26] W.F. Smith, Foundations of Materials Science and Engineering,
McGraw-Hill, New York, 1993.
[27] K. Nagashio, K. Kuribayashi, Acta Mater. 50 (2002) 1973.
[28] J. Li, Y.L. Tang, N. Shen, W. Pan, J. Alloys. Comp. 329 (2001) 157.
[29] R. Trivedi, W. Kurz, Int. Mater. Rev. 39 (1994) 49.