Acta Materialia 52 (2004) 4273–4280

www.actamat-journals.com

Eutectic nucleation in Al–Si alloys

Stuart D. McDonald *, Kazuhiro Nogita, Arne K. Dahle
Division of Materials Engineering, The University of Queensland, St. Lucia Qld 4072, Brisbane, Australia
Received 5 March 2004; received in revised form 23 May 2004; accepted 26 May 2004
Available online 6 July 2004

Abstract

In addition to a change in silicon morphology, modification of aluminium–silicon alloys with strontium or sodium increases the
size of the eutectic grains. To determine the mechanism responsible, eutectic solidification in commercial purity and ultra-high purity
aluminium–silicon alloys, with and without strontium additions, was examined by a quenching technique. In the commercial un-
modified alloy, nucleation was prolific while in the high-purity unmodified alloy few eutectic grains nucleated. The addition of
strontium to the commercial alloy reduced the number of eutectic grains that nucleated. Addition of strontium to the high-purity
alloy did not significantly alter nucleation. It is concluded that commercial purity alloys contain a large number of potent nuclei that
are susceptible to poisoning by impurity modification. The flake-to-fibre transition that occurs with impurity modification is shown
to be independent of any change in eutectic nucleation mode and frequency.
Ó 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Casting; Eutectic solidification; Aluminium alloys; Modification

1. Introduction tium and sodium poison phosphorus-based nucleants

Recent research on eutectic solidification mechanisms
in hypoeutectic aluminium–silicon alloys has identified
large differences in the nucleation and growth modes of
unmodified and impurity modified alloys [1,2]. Eutectic
nucleation in unmodified alloys occurs by the nucleation
of a large number of eutectic grains, 1 at or near the
primary aluminium dendrite–liquid interface. Relatively
few eutectic grains nucleate in strontium modified alloys
and nucleation occurs independent of the surrounding
dendrites. The difference in the number and size of eu-
tectic grains is quite dramatic, as shown in the quenched
samples of Fig. 1. The reason for reduced nucleation
remains unclear, but it has been proposed that stron-
*
Corresponding author. Tel.: +61-7-3365-3669; fax: +61-7-3365-
3888.
E-mail address: s.mcdonald@minmet.uq.edu.au (S.D. McDonald).
1
For the purpose of this paper a eutectic grain refers to a connected
region of aluminium–silicon eutectic that has grown from a common
source. This definition implies nothing about crystallography and
either phase may be polycrystalline or monocrystalline depending on
the growth mechanisms that operate.
that are active in the unmodified alloy [1].
During eutectic growth, the eutectic interface growth
rate will vary inversely with the total eutectic solid–
liquid surface area of the system [3]. Because fewer
grains nucleate in modified alloys, the solid–liquid eu-
tectic interface is much smaller and consequently ad-
vances at a higher growth rate. This increase in growth
rate will contribute to refining the eutectic in modified
aluminium–silicon alloys [1,4] and it is difficult to sep-
arate the contributions of refinement occurring as a re-
sult of the increased growth rate and that resulting from
impurity modification. In fact, it has been suggested that
impurity modification occurs solely because of the in-
creased growth rate that arises due to altered nucleation
frequency and solid/liquid interfacial area [3].
The hypothesis that strontium additions cause mod-
ification by increasing the growth rate of the eutectic has
been tested by directionally solidifying unmodified and
strontium modified alloys [5]. It was found that alloys
modified with strontium have a smaller eutectic spacing
than unmodified alloys, even when both are grown at
identical velocities. The difference in spacing was not as

1359-6454/$30.00 Ó 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2004.05.043
4274 S.D. McDonald et al. / Acta Materialia 52 (2004) 4273–4280
Fig. 1. Comparison of the eutectic solidification modes in aluminium–
10 wt% silicon alloys quenched part way through eutectic solidifica-
tion: (a) a micrograph of an unmodified alloy (unetched), the fine
structure is quenched liquid; (b) macrograph of an alloy modified by
100 ppm strontium and etched, the dark circular regions show the
eutectic grains as they were at the time of quenching [1].
large as occurs in a typical sand casting and it could be
concluded that nucleation still must have a significant
effect on the refinement of the eutectic.
If the eutectic nucleation frequency can affect the
eutectic spacing, then a variety of techniques could be
used to control the microstructure. Techniques that in-
crease nucleation would be expected to coarsen the eu-
tectic, by decreasing the growth rate, and those that
decrease nucleation would be expected to refine the eu-
tectic, by increasing the growth rate. This may be why
vibration during solidification, which is expected to in-
crease nucleation, results in a coarsening of the eutectic
phases [6,7]. In contrast, superheating, which has been
proposed to dissolve potential nuclei, results in a re-
finement of the eutectic phases [8,9]. The addition of
phosphorus results in coarsening of the eutectic phases
[10,11], which supports the theory that phosphorus-
based compounds are effective as eutectic nucleation
sites.
From the above analysis, there is reason to suspect
changes in the nucleation and growth of eutectic grains
will occur with changes in alloy purity. This is certainly
the case in directional solidification, where increasing
the impurity level in the melt results in a columnar-to-
equiaxed transition in the eutectic growth mode [12].
Despite this, to the best of our knowledge, the effect of
alloy purity on the nucleation and growth of eutectic
grains in non-directionally solidified castings has not
been investigated. The current research was therefore
designed to compare eutectic solidification in hypoeu-
tectic aluminium–silicon alloys of commercial purity
and ultra-high purity. The objective was to examine the
influence of impurities on the nucleation of eutectic
grains in aluminium–silicon alloys and on the resulting
eutectic microstructure, particularly the size and mor-
phology of the eutectic silicon phase.
2. Experimental method
Alloys of commercial purity and ultra-high purity of
nominal composition aluminium–10 wt% silicon were
used for experimentation. The commercial purity alloys
were produced by placing the correct proportions of
commercial purity aluminium (major impurities 0.08
wt% Fe, 0.03 wt% Si) and silicon (major impurities 0.18
wt% Fe, 0.012 wt% Ti and 0.04wt% Ca) in a clay-
graphite crucible and melting in an electric resistance
furnace to a melt temperature of 760 °C. The phos-
phorus content of the commercially pure additions was
analysed by optical emission spectroscopy and induc-
tively coupled plasma atomic emission spectrophotom-
etry. If present, phosphorus was below the lower limits
of detection of both of these methods (<10 ppm). The
high-purity alloy was made by placing the correct pro-
portions of silicon and aluminium, each of 99.999 wt%
purity, in a covered sintered alumina crucible and
melting in an electric resistance furnace held at a tem-
perature of 760 °C. In the high-purity alloy experiments,
all additions and melt handling tools were thoroughly
cleaned with ethanol in an ultrasonic bath prior to use.
Strontium additions were made at a nominal level of 200
ppm using an aluminium–10 wt% strontium master al-
loy rod. The average commercial purity melt size was
approximately 1.5 kg while the average high-purity melt
size was 150 g.
Thermal analysis and quenching experiments were
performed in tapered stainless-steel cups as shown in
Fig. 2, which were coated with a thin layer of boron
nitride. Two samples were taken in parallel, one with
and one without a type-N thermocouple present. During
solidification the cooling curve from the thermocouple
was monitored on a real-time display and the sample
 S.D. McDonald et al. / Acta Materialia 52 (2004) 4273–4280
Fig. 2. A schematic (cut-away and exploded for clarity) of the exper-
imental set-up for thermal analysis. Two samples were taken simul-
taneously, one with and one without a thermocouple, the cup without
a thermocouple was quenched approximately half-way through eu-
tectic solidification.
without a thermocouple was quenched when the eutectic
reaction was approximately 50% complete. Although it
is acknowledged that solidification will not proceed
identically in both cups, this method prevents the ther-
mocouple from interfering with solidification or from
damaging the microstructure during quenching. The
commercial purity alloys were sampled by submerging
the stainless-steel cups into the clay-graphite crucible.
However due to limitations in the melt size, the high-
purity melt was sampled by pouring from the alumina
crucible. In both cases melt transfer was performed
gently and with a minimum of turbulence. The average
cooling rate of the liquid prior to solidification was
1.5 °C/s.
Three characteristic temperatures were measured for
each reaction detected on the cooling curves according
to the method of Tamminen [13]. These temperatures
were the nucleation temperature, TN , defined as the first
noticeable change on the derivative of the cooling curve,
the minimum temperature prior to recalescence, TM , and
the growth temperature, TG , defined as the maximum
reaction temperature reached after recalescence. Solidi-
fication of the quench samples was interrupted approx-
imately halfway through the eutectic reaction by
plunging the sample into a water bath at room tem-
perature. The calibration of thermocouples was checked
Table 1
Compositions of the four Al-10 wt% Si alloys (wt%)
Alloy Si Sr
Unmodified commercial purity 9.84 <0.01
Unmodified high purity 9.57 <0.01
Strontium modified commercial purity 9.70 0.019
Strontium modified high purity 10.20 0.015
4275
before and after use, using the high-purity aluminium.
From numerous calibration experiments, errors in rel-
ative temperature measurements are estimated at less
than 0.5 °C.
Samples were prepared for microscopy using stan-
dard techniques with the final polishing stage being
produced by 0.05 lm colloidal silica. Macrostructures
were captured using a high resolution flatbed scanner
after etching for 60 s at room temperature in a mixture
of 60 ml water, 10 g sodium hydroxide and 5 g of po-
tassium ferricyanide (modified Murakami reagent).
Optical microscopy was performed on both unetched
and etched samples as indicated in the micrographs.
3. Results
The chemical analysis of the four alloys used in ex-
perimentation is shown in Table 1. The level of phos-
phorus was below the lower limit of detections for the
analysis techniques used. Assuming that no phosphorus
contamination occurred during melting and pouring, the
level should be less than 10 ppm for the commercial
purity alloy and less than 1 ppm for the high-purity
alloy.
The cooling curves obtained during solidification of
the commercial purity and high-purity alloy are shown
in Fig. 3 and 4. The characteristic temperatures for the
primary and eutectic reactions obtained from these
curves are shown in Table 2. Strontium additions to the
unmodified commercial alloy caused an increase in rec-
alescence at the eutectic temperature and a depression of
the eutectic growth temperature, as commonly observed
in the literature. Relative to the commercial purity un-
modified alloy, the high-purity unmodified alloy had a
significantly increased amount of recalescence and a
marginally decreased growth temperature. The addition
of strontium to the high-purity alloy resulted in an in-
crease in the amount of recalescence, but did not depress
the growth temperature.
The eutectic microstructure of the unmodified com-
mercial alloy was a typical mixture of coarse silicon
flakes, often radiating from polyhedral silicon crystals as
shown in Fig. 5(a). In comparison, the eutectic in the
high-purity alloy (Fig. 5(b)) was extremely refined, con-
taining short, closely spaced silicon flakes. The addi-
tion of strontium to both the commercial (Fig. 5(c)) and
Fe Cu Mg Mn Ti
0.09 <0.01 <0.01 <0.01 0.01
<0.01 <0.01 <0.01 <0.01 <0.005
0.11 <0.01 <0.01 <0.01 0.01
<0.01 <0.01 <0.01 <0.01 <0.005
4276 S.D. McDonald et al. / Acta Materialia 52 (2004) 4273–4280

clearly visible in the unmodified high-purity alloy sam-

ple, Fig. 6(b), both as a layer at the wall and as inde-
pendent grains in the interior of the sample. Eutectic
grains are not visible in the unmodified commercial
purity sample because they are too small to be resolved,
as seen in the optical micrograph in Fig. 7(a). An optical
micrograph of a eutectic grain in the high-purity sample
is shown in Fig. 7(b). Typically, the eutectic grains vis-
ible in the unmodified commercial alloy sample were
asymmetrical and at most, a few hundred micrometers
in their longest dimension at the time of quenching. A
Fig. 3. Typical cooling curves for the commercial purity alloy in the
unmodified and Sr modified conditions. The broken line shows the large number of these grains were present, most being
equilibrium eutectic temperature of 577 °C. The second cooling curve located at the dendrite–liquid interface. Few eutectic
has been displaced along the time-axis for clarity. grains nucleated in the unmodified high-purity sample
and they were roughly circular in cross section. The final
eutectic grain size cannot be determined but at the time
of quenching the grains were up to 4 mm in diameter.
There were very few eutectic grains observed in the
quenched strontium modified commercial purity sample
as seen in the macrograph of Fig. 6(c). It appears that
the addition of strontium to this commercial alloy has
reduced the number of eutectic grains that nucleate.
A micrograph of a typical eutectic grain in the strontium
modified commercial purity sample is shown in Fig. 7(c).
These grains were orders of magnitude larger than those
in the equivalent unmodified alloy (Fig. 7(a)). The ad-
Fig. 4. Typical cooling curves for the high-purity alloy in the un- dition of strontium did not significantly alter the num-
modified and Sr modified conditions. The broken line shows the ber of eutectic grains that nucleated in the high-purity
equilibrium eutectic temperature of 577 °C. The second cooling curve alloy as seen by comparing the macrographs of Fig. 6 (b)
has been displaced along the time-axis for clarity. and (d). The eutectic grain density, already quite low in
the unmodified high-purity alloy (in comparison to the
Table 2 commercial alloy), did not decrease further with the
Reaction temperatures (nucleation, minimum and growth) for the addition of strontium. The appearance of the eutectic
primary and eutectic reactions in each of the four experimental alloys grains in the unmodified and strontium modified high-
Reaction TN (°C) TM (°C) TG (°C) purity alloys was also very similar as can be seen by
Unmodified Primary Al 593.4 592.5 593.8
comparing the micrographs of Fig. 7(b) and (d).
commercial Al–Si eutectic 577.7 576.7 577.8
purity
Unmodified Primary Al 593.8 590.0 591.4 4. Discussion
high purity Al–Si eutectic 573.1 572.4 576.3
Sr modified Primary Al 592.2 590.3 592.0
commercial Al–Si eutectic 571.5 569.3 573.4
Microstructure evolution during solidification of
purity commercial hypoeutectic aluminium–silicon alloys can
Sr modified Primary Al 589.9 588.8 591.2 be considered as being comprised of two main stages.
high purity Al–Si eutectic 571.1 570.2 576.8 The first stage involves the nucleation and growth of
aluminium dendrites and the second stage is the nucle-
ation and growth of the aluminium–silicon eutectic. At
high-purity alloys (Fig. 5(d)) refined the eutectic structure the time when eutectic nucleation occurs, the conditions
and resulted in a flake-fibrous transition in the mor- in the melt will in part be imposed by the characteristics
phology of the silicon phase. The eutectic spacing of the of the previous reaction. In particular, the dendritic
modified high-purity alloy was much finer than that of growth could affect both the distribution of heteroge-
the modified commercial alloy. neous nuclei and the concentration in the liquid near the
Typical macrographs of the commercial purity and dendrite–liquid interface and thereby influence the nu-
high-purity quenched samples, with and without stron- cleation of silicon, which is required prior to cooperative
tium additions are shown in Fig. 6. Eutectic grains growth of the aluminium–silicon eutectic.
are not visible in the macrograph of the unmodified It is evident from the results that eutectic nucleation
commercial purity alloy sample in Fig. 6(a), but are in the commercial unmodified alloy is much more pro-
 S.D. McDonald et al. / Acta Materialia 52 (2004) 4273–4280 4277

Fig. 5. Typical eutectic microstructures of fully solidified alloys in the unetched state: (a) unmodified commercial purity; (b) unmodified high purity;
(c) strontium modified commercial purity;(d) strontium modified high purity.

lific than it is in the high-purity unmodified sample. It is
concluded that the higher levels of impurities in the
commercial alloy encourages nucleation. There are two
main ways in which this can occur, firstly through the
creation of a constitutionally undercooled zone and
secondly through the presence of nuclei. It is of interest
to examine which of these is more likely to be respon-
sible for the comparatively large number of eutectic
grains observed in the commercial purity alloy.
Recent research has proposed that the primary alu-
minium grain structure develops due to a wave of nu-
cleation events triggered by the formation of
constitutionally undercooled zones [14]. The effective-
ness of a solute element at creating a constitutionally
undercooled zone can be described by the growth re-
striction factor, Q, defined as follows
X silicon alloys and the following discussion applies to the additional
Q¼ ml;i C0;i ðki
1Þ; ð1Þ
where ml is the gradient of the liquidus line, C0 is the
concentration of the solute and k is the partition coef-
ficient for each element, i. The physical significance of Q,
is that it corresponds to the initial rate of development
of this undercooled zone. The rate of development of the
undercooled zone, Q, is of importance as it determines
how far the interface can travel before a new grain is
nucleated. A high growth restriction factor will corre-
spond to a small grain size.
The principle of a growth restriction factor has not
been applied to the nucleation of eutectic grains, al-
though this can be done provided the appropriate con-
stants can be determined. 2 During solidification of a
2
It is acknowledged that the silicon segregation at the dendrite–
liquid interface may also affect eutectic nucleation in aluminium–
effect of a ternary impurity.
4278 S.D. McDonald et al. / Acta Materialia 52 (2004) 4273–4280
Fig. 6. Macrographs of the quenched and etched samples: (a) unmodified commercial purity; (b) unmodified ultra-high purity.
binary eutectic (containing a and b phases) each phase
will reject a ternary element i according to the value of
the individual solid–liquid distribution coefficients, kai
and kbi . The average solid–liquid distribution coefficient
can be expressed as a weighted arithmetic mean of kai
and kbi and the volume fractions of the phases, fa and fb
[15]
kðabÞi ¼ kai fa þ kbi fb : ð2Þ
If the slope of the binary eutectic valley, mðabÞi is as-
sumed to be linear it can be calculated easily from the
following equation
CTi
mðabiÞi ¼ ; ð3Þ
TT
577
where CTi is the concentration of element i in the li-
quid of ternary eutectic composition, TT is the ternary
eutectic temperature and 577 is the eutectic tempera-
ture of the binary aluminium–silicon alloy. The aver-
age distribution coefficient, kðabÞi together with the
slope of the binary eutectic in the ternary system,
mðabÞi can be used to calculate the growth restriction
factor, Q using Eq. (1).
With reference to Table 1, the major impurity in the
commercial alloy is iron at a concentration of 0.09 wt%.
At this level, iron remains in solution until a ternary
reaction at CTFe ¼ 0:7 wt% and TT ¼ 576 °C. Using the
values fAl ¼ 0:87 and fSi ¼ 0:13, kab ¼ 0:017 [16] and the
assumption that the solubility of iron in solid silicon is
negligible (the distribution coefficient kSi;Fe being equal
to zero) a value of Q ¼ 0:00117 can be calculated.
Ordinarily, growth restriction factors are calculated
for a nominal solute content of 1 wt% so that effects of
different elements can be readily compared against each
other. For 1 wt% iron, the growth restriction factor for
the binary aluminium–silicon eutectic reaction would be
equal to 0.013. Solutes that are effective at refining pri-
mary aluminium grains have growth restriction factors
orders of magnitude larger than this (for example tita-
nium in aluminium has Q  220). This indicates that
constitutional undercooling is not likely to be respon-
sible for the large-scale nucleation of eutectic alumin-
ium–silicon grains that occurs in commercial alloys. The
reason that iron impurities are not effective at refining
the size of eutectic aluminium–silicon grains by in-
creasing constitutional undercooling is that the slope of
the binary eutectic valley in the ternary system is ex-
tremely shallow.
Theoretically, strontium additions to the commercial
alloy would increase the level of solute and the growth
 S.D. McDonald et al. / Acta Materialia 52 (2004) 4273–4280 4279

Fig. 7. A comparison of typical eutectic grains in samples quenched during eutectic solidification (samples are in etched condition): (a) unmodified
commercial purity; (b) unmodified high purity; (c) strontium modified commercial purity; (d) strontium modified high purity. Note the difference in
scale of the micrograph of (a).

restriction factor and result in enhanced nucleation of
eutectic grains. The fact that strontium additions actu-
ally decrease nucleation, supports the theory that the
major role of impurities in the eutectic solidification of
unmodified commercial aluminium–silicon alloys is as
active nucleants for eutectic grains. The reason that
eutectic nucleation is so prolific in the commercial alloys
is likely to be because of a large population of potent
nuclei. The location of eutectic grains along the den-
drite–liquid interface indicates that the nuclei are pushed
during dendrite growth. It is unlikely that the dendrites
themselves nucleate the eutectic grains as they are
present in both the commercial purity and high-purity
alloy. It is possible that the nuclei are AlP particles,
which are found as a primary phase in most commercial
aluminium–silicon alloys [17]. This is not in conflict with
the phosphorus analysis being less than 10 ppm, as
phosphorus-rich particles which nucleate silicon at low
undercoolings have been identified even in alloys of
99.995% purity [18].
Although the eutectic structure of the unmodified
high-purity alloy is considerably refined, it is still plate-
like and no fibrous silicon was found in the sample. This
is despite the eutectic growth mode being almost iden-
tical to that of the strontium-modified commercial and
strontium modified high-purity alloys.
Currently the most accepted mechanism for modifi-
cation is that the impurity atoms are adsorbed at the
growth interface forcing the silicon crystals to twin [19].
It has been suggested that increased twin boundary en-
ergy associated with the growth of silicon in the presence
of strontium atoms is the cause of the extra undercool-
ing that typically accompanies strontium modifica-
tion [5]. In the current research modification of the
4280 S.D. McDonald et al. / Acta Materialia 52 (2004) 4273–4280
high-purity alloy resulted in a fibrous eutectic silicon
phase but the eutectic growth undercooling did not in-
crease (Fig. 4). This indicates that eutectic growth
undercooling may not be directly linked to the modifi-
cation process and may only occur in the presence of
additional impurity elements. The mechanism for the
increased undercooling may relate to a build-up of sol-
ute at the eutectic growth interface that does not occur
in the commercial unmodified alloys due to differences
in the shape and distribution of eutectic grains. Clarifi-
cation of this issue is important for two reasons, firstly it
may reveal the true mechanism of modification and
secondly because the eutectic growth temperature is
the most commonly used non-destructive method of
assessing the level of modification.
5. Conclusions
Eutectic solidification was examined using a
quenching technique in both high-purity and com-
mercial purity hypoeutectic aluminium–silicon alloys
with and without strontium additions. A large number
of eutectic grains nucleated in the commercial purity
unmodified alloy, each growing with an asymmetrical
grain shape and coarse interphase spacing. In the
unmodified high-purity alloy, on the other hand, very
few grains nucleated and each grain grew with a
flatter, spherical interface. The eutectic in the un-
modified high-purity alloy was well refined although
the silicon maintained a flake-like rather than fibrous
morphology.
Eutectic nucleation in the unmodified high-purity
sample was similar to that of the strontium modified
commercial purity alloy. Both unmodified high-purity
and strontium-modified commercial purity alloys have a
reduced eutectic grain density compared to unmodified
commercial alloys. A rudimentary analysis suggests that
constitutional undercooling in the commercial unmodi-
fied alloy would be insufficient to account for the large
number of eutectic grains compared to the high-purity
alloy. Instead, a high number of potent nuclei must be
present. The composition of these nuclei is unknown.
However, it appears they can be removed or poisoned
by impurity modification treatments. The addition of
strontium to the high-purity alloy did not significantly
alter eutectic nucleation, most likely because there were
few nuclei to remove or poison.
The refinement of the eutectic in the high-purity
sample supports the hypothesis that a reduction in the
number of eutectic grains results in a higher eutectic
growth rate. The increased interface velocity caused by
reduced nucleation is not sufficient to cause a flake-fi-
brous transition. The flake-fibrous transition that occurs
due to strontium additions is independent of any chan-
ges in the nucleation mode.
An analysis of cooling curves revealed a lack of eu-
tectic growth undercooling during solidification of the
strontium modified high-purity alloy, despite a flake-fi-
brous transition in the silicon morphology. This indi-
cates that eutectic growth undercooling is not a
fundamental characteristic of strontium modification
but is caused indirectly due to the presence of additional
impurities in commercial alloys.
Acknowledgements
The authors like to thank Dr. Karl Forwald and
Mr. Torfinn Buseth of Elkem Solar for the generous
supply of the high-purity silicon used in these experi-
ments and Dr. Gustav Heiberg of Det Norske Veritas
for the supply of the high-purity aluminium and sintered
alumina crucibles.
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