Characterization investigations of a melt-spun ternary

Al8Si5.1Cu (in wt.%) alloy

M. Lutfi O

vec oglu
*
, Necip U

nlu, Niyazi Eruslu, Arda Genc

Department of Metallurgical and Materials Engineering, Faculty of ChemistryMetallurgy,
Istanbul Technical University, 34469 Maslak-Istanbul, Turkey
Received 7 February 2002; received in revised form 17 December 2002; accepted 7 January 2003
Abstract
A ternary Al 8Si 5.1Cu (in wt.%) alloy was rapidly quenched from the melt at cooling rates between 10
6
and 10
7
K/s
using the melt-spinning technique. The resulting ribbons were characterized using optical microscopy, scanning electron
microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and microhardness techniques. On the
basis of the Al peak shifts measured in the XRD scans, a solid solubility extension value of 3.83 at.% Si in Al was determined.
Whereas SEM investigations showed the presence of dendrites rich in Al, TEM investigations revealed nanosized spherically
shaped Si crystals 2025 nm in size. Both XRD and TEM investigations confirmed the absence of any intermetallic phase
formation. The microhardness value of the melt-spun alloy was measured as 201 kg/mm
2
.
D 2003 Elsevier Science B.V. All rights reserved.
Keywords: Melt-spinning; Characterisation methods; Metals; Alloys; Microstructure; Solidification; Ternary Al Si Cu alloy
1. Introduction
Rapid solidification processes (RSP) with cooling
rates higher than 10
3
K/s allow the preparation of
alloys with extraordinary properties; i.e. reduction in
grain sizes, extended solid solution ranges, reduced
levels of segregation and in some cases the formation
of metastable crystalline and amorphous phases [1
8]. Melt spinning of aluminum alloys at cooling rates
exceeding 10
6
K/s results in ribbons with superior
mechanical and thermal properties than their conven-
tionally processed counterparts. In the last 2 decades,
research investigations on the rapidly solidified Al
alloys have been focused mainly on their applications
in aerospace and automotive industries. The impor-
tance of Al Si and Al Si X alloys for automotive
applications with some engine parts like connecting
rod, cylinder sleeve, piston and valve retainer and
compressor parts like rotary compressor vane and
shoe disc has been well established [9]. The structural
and mechanical characterizations of rapidly solidified
hypoeutectic and hypereutectic binary Al Si, Al Fe
[1023] and Al Cu alloys [24] were investigated
previously.
Recently, research efforts have focused on the
effects of a third element addition to Al Si alloys
such as iron, copper, nickel and other transition
elements [2529]. These transition elements, when
alloyed in various combinations with aluminum, form
0167-577X/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0167-577X(03)00051-X
* Corresponding author. Tel.: +90-212-285-3355; fax: +90-212-
285-3427.
E-mail address: ovecoglu@itu.edu.tr (M.L. O

vec oglu).
www.elsevier.com/locate/matlet
Materials Letters 57 (2003) 32963301
fine dispersions of high-modulus second-phase par-
ticles, resulting in increased strength, wear resistance
and thermal stability [30]. Among the ternary Al Si
X alloys, the ternary Al Si Fe has been extensively
studied using rapid solidification techniques [28,29,
31], including melt-spinning [25]. However, there
exists no characterization work in the literature on
the melt-spun Al Si Cu ternary alloys in the hypo-
eutectic composition region of the Al Si binary. This
study aims to fill this vacuum.
The primary aim of this study is to characterize the
microstructure of a melt-spun alloy belonging to the
ternary Al Si Cu system. For this purpose, optical
microscopy, X-ray diffraction (XRD), scanning elec-
tron microscopy (SEM) and transmission electron
microscopy (TEM) investigations were carried out
on the Al 8Si 5.1Cu (in wt.%) alloy ribbons pro-
duced by melt-spinning. The microhardness values of
the ribbons were also measured.
2. Experimental procedure
Chemically pure metals of aluminum (ingot,
>99.95% purity), silicon (powder, >99.995% purity)
and copper (rod, >99.99% purity) were used as start-
ing materials. Technical specifications of the starting
materials including chemical purities are listed in
Table 1. Using these, two master alloys with the
compositions Al 25 wt.% Si and Al 10 wt.% Cu
were prepared by induction melting. This is followed
by stoichiometrically mixing and melting these alloys
to constitute the ternary Al 8.0 wt.% Si 5.1 wt.% Cu
alloy (now hereafter referred to as the Al8Si5Cu
alloy) composition. Remelting of the as-cast alloys
was performed in a graphite crucible using an H65-
type 350 kHz high-frequency furnace during melt-
spinning experiments. Rapidly solidified ribbons were
produced by free jet melt spinning in air by means of
impinging a jet of molten alloy onto the cylindrical
surface of a polished copper wheel with a diameter of
180 mm rotating at 3000 rpm. The temperature of the
melt before ejection was 100 jC above the liquidus
temperature. The dimensions of the as-produced rib-
bons were 610 mm in width, 701000 mm in length
and 6080 Am in thickness.
Melt-spun Al8Si5Cu ribbons were characterized
by using optical microscopy, scanning electron micro-
scopy (SEM) and X-ray diffractometry techniques.
Optical microscopy observations were conducted in
an Olympus MG model optical microscope. SEM
investigations were carried using a JEOL JSM-T330
scanning electron microscope operated at 25 kV and
linked with an energy dispersive spectrometry (EDS)
attachment. The XRD measurements were carried out
in a Philips PW3710 X-ray diffractometer using
CuKa radiation at 40 kV and 20-mA settings in the
2h range from 20j to 80j. Using standard metallo-
graphic techniques, optical mount specimens were
prepared for optical microscopy and SEM investiga-
tions followed by chemical etching in a 0.5% HF
solution for about 25 s. Transmission electron micro-
scopy (TEM) investigations were conducted on thin
foils prepared by dimpling and jet electropolishing 3-
mm discs drilled directly from the melt-spun ribbons
using the conditions of 30 V and 1520 mA in an
electrolyte consisting of 25 vol.% of HNO
3
and 75%
methanol cooled at 50 jC. The electropolished foils
were examined in a JEOL 2000EX operated at 200
kV. Microhardness measurements on melt-spun rib-
bons were made with a Vickers diamond indenter in a
Wolpert microhardness tester employing a load of 25
g. Ten indentations were taken from the longitudinal
section of the melt-spun ribbon and the mean value is
taken as the accepted value.
3. Results and discussion
Fig. 1a and b shows X-ray diffractometry (XRD)
patterns taken from the conventionally cast Al8Si5Cu
sample and from the wheel side of the melt-spun
Al8Si5Cu ribbon, respectively. Whereas diffraction
peaks belonging to the Al, Si and Al
2
Cu phases are
present in the conventionally cast Al8Si5Cu sample
(Fig. 1a), only diffraction peaks of the Al solid
solution are present in the melt-spun Al8Si5Cu ribbon
Table 1
Hardness values for melt-spun ribbon and conventionally cast
Al8Si5Cu samples
Alloy Hardness (kg/mm
2
)
Melt-spun ribbon Conventionally cast
Al 8Si 5.1Cu 201 F7.4 80 F5.2
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vec oglu et al. / Materials Letters 57 (2003) 32963301 3297

(Fig. 1b). As expected, there is no intermetallic phase
formation between Al, Si and Cu in the melt-spun
Al8Si5Cu ribbon. This conforms with those of U

nlu
et al. [25] who also reported the absence of any
intermetallic phase formation. Furthermore, Si peaks
are absent in the as-quenched Al8Si5Cu ribbon,
suggesting complete dissolution of Si in Al to form
the solid solution. However, within the limits of
detection by X-ray diffraction (typically about 5
vol.%), the absence of Si and Cu peaks alone cannot
be considered sufficient evidence of complete disso-
lution. First of all, due to the fact that Cu has a low
solubility in Al, Cu dissolution in Al can be neglected.
Secondly, considering the equilibrium solid solubility
of Si, the present results indicate that the Si solubility
in a-Al has been extended by melt spinning. Solid
solubility extension of Si in a-Al matrix as a conse-
quence of rapid solidification has been reported
extensively [9,3235]. To determine the solid solu-
bility extension of Si in Al for the melt-spun hypo-
eutectic Al8Si5Cu alloy of the present study, the line
shift values of the measured Al(111) and (200) dif-
fraction lines in Fig. 1b were used, which yielded an
Al lattice parameter value of 0.404243 nm. Using the
linear relationship between the lattice parameter and
the atomic fraction of Si given by Bendijk et al. [16], a
solid solubility extension of 3.83 at.% Si in a-Al for
the hypoeutectic melt-spun Al8Si5Cu alloy can be
determined. This value is in agreement with those
given by Van Rooyen et al. [32], Van Mourik et al.
[10] and Timmermans and Froyen [35] for the binary
Al Si alloy and U

nlu et al. [25] for the ternary Al

Si Fe alloy who achieved quenching rates similar to
the present study.
Optical microscopy, SEM and TEM techniques
were used to characterize the resultant cross-sectional
microstructure of the melt-spun Al8Si5Cu ribbon
which exhibited typical structural refinement due to
high cooling rates and the morphology, distribution
and nature of the phases in the as-quenched micro-
structure. Fig. 2a displays the respective cross-sec-
tional optical micrograph showing three distinct
adjacent zones: (i) a featureless zone on the wheel
side (chill side), (ii) a transition zone with a columnar
structure and (iii) a zone containing Al-rich dendrites.
The featureless zone, often referred to as zone A, is
unique to rapidly quenched alloys [20,30], and it
indicates good contact between the ribbon and the
wheel. It appears featureless after etching as a result of
grain refinement due to high cooling rates [16,30,36].
The average thickness of the featureless zone varies
between 2 and 3 Am, which is about four times
smaller than that for the melt-spun ternary Al Si
Fe alloy; a rather small depth attributed to the higher
thermal conductivity of Cu. On the other hand, the
transition zone between the featureless zone and the
dendritic zone is more evident and has a uniform
depth of about 20 Am and contains columnar grains
oriented almost perpendicular to the wheel contact
surface. The thickness of the dendritic zone is about
40 Am. Fig. 2b displays a representative SEM micro-
graph taken from the cross-section of the melt-spun
Fig. 1. XRD patterns of the Al8Si5Cu alloy taken from: (a) the
conventionally cast sample and (b) the wheel side surface of the
melt-spun ribbon.
M.L. O

vec oglu et al. / Materials Letters 57 (2003) 32963301 3298

hypoeutectic Al8Si5Cu ribbon showing a fine and
homogeneous dendritic structure. A series of EDS
analyses carried out on the dendrites revealed that
they are rich in aluminum, indicating that the primary
Al-rich phase in Al Si Cu system of this study grew
dendritically. It is possible to estimate the cooling rate
of the melt-spinning process by measuring the den-
drite arm spacing which depends on the degree of
supercooling and thus on the rate of cooling. The
average dendrite arm spacing on the dendrites shown
in Fig. 2b is measured approximately as 0.36 Am,
which is about 30 times smaller than that measured for
the conventionally cast counterpart (f11.42 Am) of
the same alloy. Using the relationship introduced by
Matyja et al. [37], the dendrite arm spacing of 0.36
Am corresponds to a cooling rate of 1.14 10
7
K/s for
the melt-spun hypoeutectic Al8Si5Cu alloy. Fig. 2c is
a bright-field (BF) TEM micrograph taken from the
featureless zone of the hypoeutectic Al8Si5Cu alloy
ribbon. Fine distribution of nanosized particles spher-
ical in shape and ranging from 20 to 25 nm in size is
revealed in the microstructure. Selected area diffrac-
tion pattern (SADP) taken from this region (Fig. 2d) is
indexed as arising from two phases. Whereas the spot
pattern is indexed as the a-Al matrix phase, the ring
pattern corresponds to the Si phase which has a
Fig. 2. (a) Representative optical micrograph taken from the cross-section of the melt-spun Al8Si5Cu ribbon. (b) SEM micrograph of the cross-
section of the melt-spun Al8SiCu ribbon. (c) Bright-field TEM micrograph taken from the featureless zone of the melt-spun Al8Si5Cu ribbon
revealing nanosized silicon particles in the a-Al matrix, (d) corresponding selected area diffraction pattern. Zone axis is from Refs. [112].
M.L. O

vec oglu et al. / Materials Letters 57 (2003) 32963301 3299

diamond cubic structure with the lattice parameter
a = 0.5431 nm. From the double diffraction informa-
tion shown in Fig. 2d, it can be inferred that nanosized
discrete Si particles are crowded inside a-Al grains in
the featureless zone. The average size of these discrete
Si particles is close to those detected by Birol [20] in
the featureless zone and smaller than those detected
by Apaydin [23] of the binary melt-spun Al Si alloys
at the eutectic composition.
Table 1 lists the Vickers microhardness value of the
melt-spun Al8Si5Cu ribbon and its conventionally
cast alloy having the same composition. It is evident
from Table 1 that the microhardness of the as-
quenched hypoeutectic alloy is approximately 2.5
times more than its conventionally cast counterpart.
Furthermore, these values are significantly higher than
those for the binary melt-spun Al Si alloys having
similar chemical composition to the alloys of the
present investigation, i.e. 201 vs. 195 kg/mm
2
for
the melt-spun Al 12 wt.% Si [20]. Although quench-
ing rates similar to those reported were employed in
the present investigation, we believe that the hardness
improvement for the hypoeutectic Al8Si5Cu alloy is
due to the solid solution strengthening effect of Cu in
the a-Al matrix.
4. Conclusions
On the basis of the results reported in this study,
the following conclusions can be drawn:
(1) XRD patterns revealed only the a-Al solid
solution peaks for the hypoeutectic Al 8Si
5.1Cu alloy ribbon. There are no intermetallic
phase formations between Al, Si and Cu. Based
on the peak shift measurements on the XRD
scans, a solid solubility extension value of 3.83
at.% Si in Al was determined for the hypoeutectic
Al 8Si 5.1Cu alloy ribbon.
(2) The cross-sections of the melt-spun Al8Si5Cu
ribbon exhibited featureless, transition and den-
dritic zones. Based on the measurements of the
dendrite arm spacings, an average cooling rate of
1.14 10
7
K/s was predicted.
(3) TEM investigations taken from the featureless
zone of the melt-spun Al8Si5Fe alloy revealed
the presence of nanosized (2025 nm) spheri-
cally shaped Si particles inside the grains of the
a-Al matrix.
(4) Microhardness value of the melt-spun hypoeu-
tectic Al Si Cu alloy is 201 kg/mm
2
, which
corresponds to a hardness improvement of about
2.5 times than that of the conventionally cast
alloy having the same composition.
Acknowledgements
The authors wish to thank Ms. Nurten Dinc er for
her help and contributions during the SEM inves-
tigations of this study. The initial phase of this
investigation was funded by the State Planning
Organization (DPT) under the project title Develop-
ment of Al alloys by Osprey Process and this is
gratefully acknowledged.
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