Eutectic Nucleation and Growth in Hypoeutectic Al-Si Alloys

at Different Strontium Levels

A.K. DAHLE, K. NOGITA, J.W. ZINDEL, S.D. McDONALD, and L.M. HOGAN

The effects of different levels of strontium on nucleation and growth of the eutectic in a commercial
hypoeutectic Al-Si foundry alloy have been investigated by optical microscopy and electron backscat-
tering diffraction (EBSD) mapping by scanning electron microscopy (SEM). The microstructural
evolution of each specimen during solidification was studied by a quenching technique at different
temperatures and Sr contents. By comparing the orientation of the aluminum in the eutectic to that
of the surrounding primary aluminum dendrites by EBSD, the eutectic formation mechanism could
be determined. The results of these studies show that the eutectic nucleation mode, and subsequent
growth mode, is strongly dependent on Sr level. Three distinctly different eutectic growth modes
were found, in isolation or sometimes together, but different for each Sr content. At very low Sr
contents, the eutectic nucleated and grew from the primary phase. Increasing the Sr level to between
70 and 110 ppm resulted in nucleation of independent eutectic grains with no relation to the primary
dendrites. At a Sr level of 500 ppm, the eutectic again nucleated on and grew from the primary phase
while a well-modified eutectic structure was still present. A slight dependency of eutectic growth
radially from the mold wall opposite the thermal gradient was observed in all specimens in the early
stages of eutectic solidification.

I. INTRODUCTION normally accompany the refined eutectic structure, although

CONTROL of microstructure formation during solidifi-
cation is becoming increasingly important for manufacturers
of cast aluminum components. Not only does the microstruc-
ture determine the mechanical properties, but the evolution
of microstructure during the casting process also defines the
boundaries of the casting design, the castability, and the
susceptibility to formation of defects, and therefore, consis-
tency and quality of the products. Significant development
work has been performed to obtain means for monitoring,
assuring, and controlling microstructure development. Al-
Si alloys of hypoeutectic composition are the most widely
used aluminum foundry alloys today. Microstructure control
in these alloys is often obtained through further alloying
with, and/or in the presence of, other elements, notably Ti,
Mg, Cu, and Fe. Grain refinement can be obtained by the
use of commercial master alloy additions, although these
are not as effective as in the wrought alloys.[1]
Commercial Al-Si foundry alloys normally contain about
50 to 90 vol pct eutectic. Controlling the eutectic silicon
morphology by modification has been used extensively
industrially since about the 1970s to improve the mechanical
properties of the castings. Modification, obtained by addition
of Na or Sr, or by quench modification, changes the morphol-
ogy of silicon from a platelike or lamellar structure to a fine
fibrous structure, while modification by addition of Sb only
refines the silicon platelets. Improved mechanical properties
A.K. DAHLE, Senior Lecturer, K. NOGITA, Research Fellow, and S.D.
McDONALD, Postgraduate Student, are with the Department of Mining,
Minerals and Materials Engineering, The University of Queensland,
Brisbane, QLD 4072, Australia. J.W. ZINDEL, Senior Technical Specialist,
is with the Ford Research Laboratory, Ford Motor Company, Dearborn,
MI 48121. L.M. HOGAN, formerly Honorary Research Fellow, Department
of Mining, Minerals and Materials Engineering, The University of Queens-
land, is deceased.
Manuscript submitted June 20, 2000.
the benefits associated with modification can sometimes
be outweighed by altered porosity characteristics associated
with modification, particularly modification with stron-
tium.[2] Because the formation of eutectic often is the final
stage of solidification, it can be expected to have a significant
impact on the formation of casting defects, particularly
porosity, and castability. Recent work[3–6] has indicated that
our knowledge and understanding of this crucial stage in
the solidification process is very limited and that there are
three different possible eutectic nucleation and growth
modes depending on the solidification conditions. Figure 1 is
an illustration of the three proposed eutectic growth modes.[3]
These are nucleation at or adjacent to the wall and front
growth opposite the thermal gradient, (Figure 1(a)), nucle-
ation of eutectic on primary dendrites, (Figure 1(b)), and
heterogeneous nucleation of eutectic on nucleant particles
in the interdendritic liquid, (Figure 1(c). The black regions
in Figure 1 indicate the Al-Si eutectic during solidification
but do not show the coupled eutectic structure inside. If the
eutectic nucleates on the primary aluminum phase (mecha-
nism b), it can be expected that the crystallographic orienta-
tion of the aluminum in the eutectic is related to that of the
dendrites. On the other hand, if the eutectic is nucleated
separately in the interdendritic melt (mechanism c), it is
very likely that the aluminum and silicon still comprise a
common solidification front during growth, i.e., coupled
eutectic growth, as divorced eutectic growth has not been
reported for the Al-Si system. Therefore, the aluminum
phase forms a low-energy interface with the silicon that leads
the growth front, i.e., with a crystallographic orientation
relationship with the silicon and not with the surrounding
dendrites. If growth occurs from the wall (mechanism a), a
similar eutectic growth front can be expected. The orienta-
tion relationship between primary and eutectic aluminum
would depend on the operating nucleation and growth mech-
anism of the eutectic. It would be of great benefit to be able

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 32A, APRIL 2001—949

 Table I. Chemical Composition of 319 Alloys
(Weight Percent)
Alloy Si Cu Mg Fe Mn Ti Sr
Unmodified 7.06 3.37 0.18 0.61 0.34 0.11 ⬍0.002
70 ppm Sr 7.06 3.13 0.23 0.54 0.31 0.11 0.007
110 ppm Sr 7.06 3.13 0.20 0.60 0.30 0.11 0.011
500 ppm Sr 7.06 3.13 0.20 0.60 0.30 0.11 0.050

(a)

(b)

Fig. 2—Sketch of single-use cylindrical sample cup. All dimensions are

(c)
Fig. 1—Possible eutectic growth morphologies in the Al-Si system: (a)
front growth opposite the thermal gradient, (b) nucleation and growth
on the primary aluminum dendrites, and (c) independent heterogeneous
nucleation of eutectic grains in interdendritic spaces. The eutectic containing
Al and Si growing side-by-side is illustrated in black.
to control eutectic nucleation and growth and suitable means
of control need to be identified.
Furthermore, the effects of the different growth modes on
casting defect formation are of particular practical
importance.
The present work was conducted to gain further under-
standing about the effect of eutectic modification by different
levels of Sr on nucleation and growth of the eutectic in a
commercial hypoeutectic Al-Si alloy. The macrostructural
evolution of the eutectic during solidification was character-
ized by optical and scanning electron microscopy (SEM)
and crystallographic orientation mapping by electron back-
scattering diffraction (EBSD) of samples quenched at differ-
ent stages during the eutectic arrest.
II. EXPERIMENTAL
The composition of the base alloy, which is a variation
of Aluminum Association alloy 319, is given in Table I.
in millimeters.
Approximately 20 kg of the alloy was melted and held in
an electric resistance furnace at 720 ⬚C.
Samples were prepared from melts with four levels of Sr.
The as-received alloy contained approximately 0.007 wt pct
Sr (70 ppm Sr modification). A lance was used to inject a
commercial flux into the melt to lower the Sr level to below
0.002 wt pct (unmodified sample) using a nitrogen carrier
gas. Two additional Sr levels were produced by adding
AlSr10 master alloy to yield Sr levels of 110 and 500 ppm.
Custom made sample cups were designed to hold a ther-
mocouple in the center of the sample in order to monitor
the sample temperature during both the slow cooling and
quench segments of the experiments. Figure 2 shows a sketch
of the single-use sample cup. The cups consisted of a stain-
less steel tube with an outer diameter of 22 mm and wall
thickness of 0.9 mm, and with a 0.85-mm-thick cap welded
to the bottom of the tube to fully seal the bottom end. Cup
exteriors were coated with boron nitride to minimize the
amount of aluminum and dross adhering to the outside of
the cup. Samples were taken by submerging the cup into
the melt after allowing it to reach the melt temperature. The
sample was then placed in an insulating sleeve above a
quench tank and allowed to cool until the desired quench

950—VOLUME 32A, APRIL 2001 METALLURGICAL AND MATERIALS TRANSACTIONS A

temperature was reached, at which time the sample was
plunged into an ice-brine quench bath. The cooling rate of
the liquid at 610 ⬚C, just prior to nucleation of the solid,
was approximately 1.7 ⬚C/s, and the total solidification time
was approximately 300 seconds. The samples were then
sectioned perpendicular to the axis of the cylinder, 15 mm
from the bottom, and prepared for metallographic analysis.
Microstructures were studied in an optical microscope.
The samples were etched in a 10 g NaOH, 5 g K3Fe(CN)6,
and 60 mL H2O solution for 15 to 20 seconds after final
polishing to distinguish clearly between primary dendrites,
Al-Si eutectic, and quench liquid. The etchant preferentially
attacks the quenched liquid, which therefore appears black/
dark in the micrographs. Analysis of the microstructural
constituents and crystallographic orientation measurements
from primary dendrites and aluminum in the eutectic were
performed in a PHILIPS* XL30 SEM with an EBSD
*PHILIPS is a trademark of Philips Electronic Optics Ltd., Mahwah, NJ.

system attached. Sample preparation for EBSD mapping

was by an ion-milling procedure and further details on the
sample preparation and measurement technique have been
presented by Nogita and Dahle.[6] Several eutectic regions
were studied in each sample and representative results are
presented in this article.

III. RESULTS
A. Final Microstructures
Figure 3 shows samples that were allowed to solidify
completely without interruption by quenching. A fully equi-
axed dendritic microstructure was found in all samples, inde-
pendent of the level of Sr modification. A coarse lamellar
silicon structure is observed in the unmodified alloys,
whereas the alloys containing 70, 110, and 500 ppm Sr show
the typical fine fibrous eutectic structure. Although 500 ppm
Sr can be considered a very high level of strontium addition,
the sample did not show any signs of overmodification, such
as the presence of primary silicon particles or overmodifica-
tion bands. It is worthwhile emphasizing that eutectic bound-
aries often can be observed, and these are particularly
distinguishable at higher silicon levels. These boundaries
are characterized by a high degree of disorder and often
ternary eutectic precipitates. However, it is not possible to
identify the eutectic growth mode by visually inspecting the
microstructure solidified without interruption.
B. Optical Micrographs of Quenched Samples
Figure 4 shows cooling curves and derivative curves for
the four alloys. Three major phase diagram reactions can
be clearly observed in the cooling curves; primary phase
solidification, binary Al-Si eutectic, and ternary Al-Si-Cu
eutectic reaction. All samples were quenched during the
binary Al-Si eutectic reaction.
Optical micrographs of the unmodified alloy quenched at
different stages during the eutectic arrest are shown in Fig-
ures 5(a) to (c). Very little eutectic can be observed in the
sample quenched 19 seconds after the start of eutectic solidi-
fication (Figure 5(a)). Only quenched liquid, which appears
gray, and some large iron containing precipitates can be
found in addition to the primary dendrites. This sample did
Fig. 3—Microstructure at the end of solidification (unquenched): (a)
unmodified, (b) 70 ppm Sr, (c) 110 ppm Sr, and (d ) 500 ppm Sr.
contain growing eutectic, but at this early stage of eutectic
solidification, it was mostly located close to the walls, as
discussed later. Several small regions of eutectic growth can
be observed in the micrographs of the sample quenched 45
seconds after the start of the eutectic reaction (Figure 5(b)).
In most cases, the regions of eutectic growth are associated
with the tips of the dendrite arms, and rarely does the eutectic
seem to initiate and grow at their bases. The eutectic has
evolved further in the sample quenched 76 seconds after the
start of the eutectic arrest. It is clear that the eutectic has
formed close to the tips of the dendrite arms and that it tends
to grow into the liquid with a very irregular solid/liquid
interface. Branching of the silicon platelets can be observed.
Figure 6 shows optical micrographs of samples containing
70 ppm Sr, quenched at different stages during eutectic
growth. Only a small amount of eutectic is present 31 sec-
onds after the start of the eutectic arrest and most of the
sample consists of only quenched liquid in the interdendritic
areas (Figure 6(a)). Some small eutectic regions can be
discerned growing close to the tips of the dendrites. The
solid/liquid interface is quite compact, i.e., relatively smooth,
and the eutectic has a grainlike appearance. The connection
with the primary phase appears less than for the unmodified
alloy. Eutectic grain boundaries are clearly observed in the
sample quenched 95 seconds after the start of the eutectic
arrest (Figure 6(b)). What appears as several independent
eutectic grains can be observed, and the black regions are
the etched quenched liquid. The solid/liquid interface is very
smooth and the grains have a slight globular appearance.
The eutectic has developed further in the sample quenched

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 32A, APRIL 2001—951

 (a)
(c)
Fig. 4—Cooling curve and derivative curve of (a) unmodified alloy and alloys modified by (b) 70 ppm Sr, (c) 110 ppm Sr, and (d ) 500 ppm Sr. The
starting temperature and time for the eutectic reaction is indicated on each figure. Quench times quoted in this article are from the start time indicated as
teut for the eutectic arrest.
134 seconds after the eutectic arrest, and areas of impinge-
ment of eutectic grains can be observed, displaying a slightly
irregular appearance of the silicon particles compared to that
inside each eutectic grain. The eutectic grain boundaries can
be observed to pass through the central stem of some
dendrites.
Quenched samples of the alloy containing 110 ppm Sr are
shown in Figure 7. The evolution of eutectic solidification is
very similar to that observed in Figure 6. The eutectic appears
to solidify first in intergranular areas, and eutectic grain
boundaries can be observed to cut through primary dendrites
in the sample quenched 84 seconds after the start of the
eutectic arrest (Figure 7(c)).
Figure 8 shows optical micrographs of quenched samples
containing 500 ppm Sr. The eutectic appears to nucleate and
start growing at the tips of the dendrite arms in the sample
quenched 33 seconds after the start of the eutectic arrest
(Figure 8(a)). The eutectic grows into the intergranular areas
upon further solidification rather than solidifying the intra-
dendritic regions within the dendrite envelopes (Figure 8(b)
and (c)). It therefore, again, seems that the intergranular
regions are more preferred for eutectic growth.
Figure 9 shows optical micrographs from the wall region
of the unmodified alloy and alloys modified by 110 and 500
ppm Sr, respectively. Some dependency of eutectic volume
fraction with position from the wall can be observed in all
the samples, but open liquid channels penetrating to the
952—VOLUME 32A, APRIL 2001
(b)
(d )
surface of the sample are observed in all cases. The unmodi-
fied sample contains a thin layer of exuded eutectic liquid
on the surface that is not found in the modified samples.
C. Electron Backscattering Diffraction
Secondary electron images from the SEM with corres-
ponding EBSD orientation maps are shown for all alloys,
i.e., unmodified alloy and alloys containing 70, 110, and
500 ppm Sr, in Figures 10 through 13, respectively. The
color of the mapping pixels is identical when the difference
in crystallographic orientation of adjacent regions is less
than 5 deg, i.e., identical color indicates identical orientation.
The unmodified alloy contains relatively large silicon plate-
lets (Figure 10(a)), and the corresponding orientation map
(Figure 10(b)) shows that all the aluminum in the eutectic
has identical orientation and is, therefore, assigned the same
blue color. All primary phase in the pictured region has the
same color and, therefore, belongs to the same dendrite. The
mapping image also contains small lamellar-like regions
with different colors. These correspond to silicon particles
according to the secondary electron image and this was also
confirmed by simultaneous energy-dispersive X-ray (EDX)
measurements. Regions displayed in black are areas where
the system did not record sufficient crystallographic data
(diffraction data) to allow determination of crystallographic
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 5—Optical micrographs of unmodified samples quenched at various Fig. 6—Optical micrographs of the alloy modified by 70 ppm Sr and
times: (a) 19 s, (b) 45 s, and (c) 76 s, after the commencement of eutec- quenched at different times after the start of the eutectic arrest: (a) 31 s,
tic solidification. (b) 95 s, and (c) 134 s.

orientation. From this result, it is clear that the crystallo-

graphic orientations of the aluminum in the eutectic and orientation map for the alloy containing 70 ppm Sr is shown
the surrounding primary dendrite arms are identical in the in Figure 11. A modified eutectic with small fibrous silicon
unmodified alloy. particles can be observed. The EBSD result of the same area
A secondary electron image with corresponding EBSD indicates that the investigated eutectic region is surrounded

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 32A, APRIL 2001—953

Fig. 7—Optical micrographs of sample containing 110 ppm Sr and Fig. 8—Optical micrographs of alloy containing 500 ppm Sr quenched at
quenched at different times after the start of the eutectic arrest: (a) 33 s, different times after the start of the eutectic arrest: (a) 33 s, (b) 68 s, and
(b) 62 s, and (c) 84 s. (c) 76 s.

by dendrite arms that belong to two different equiaxed den- the eutectic has not nucleated on the primary aluminum
drites. A wide range of different orientations can be observed dendrites, as there is no systematic orientation relationship
within the eutectic region, representing a structure consisting between them. It is interesting to note that a different result
of very small grains. This indicates that the aluminum in is found within the small eutectic region between secondary

954—VOLUME 32A, APRIL 2001 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 9—Optical micrographs of near the wall region of quenched samples:
(a) unmodified (76 s after start of eutectic arrest), (b) 110 ppm Sr (33 s),
and (c) 500 ppm Sr (33 s).
dendrite arms on the bottom left-hand side of Figure 11(b)
and also in small regions adjacent to the dendrite arms in
the top part of the eutectic region. Here, the orientation of
eutectic aluminum is identical to the surrounding primary
dendrite arms.
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 10—Unmodified specimen: (a) SEM secondary electron image and
(b) EBSD orientation map of the same area. Crystallographic orientations
of aluminum in eutectic and surrounding primary dendrites are identical.
Figure 12 shows the secondary electron image and corres-
ponding EBSD orientation map from the specimen con-
taining 110 ppm Sr. A well-modified eutectic structure is
readily observed. The eutectic region is surrounded by sev-
eral dendrite arms. A range of different orientations of alumi-
num is observed within the eutectic, some replicating the
orientation of the adjacent dendrite arm. However, several
different orientations not similar to the dendrite arms are
also found. Black regions in Figure 12 are the result of
insufficient orientation information, usually correlating with
silicon particles, which often cause a shaded/deformed dif-
fraction pattern that the system cannot index, or no diffrac-
tion pattern at all.
Figure 13 shows the secondary electron image and corres-
ponding EBSD orientation map for the alloy containing 500
ppm Sr. The eutectic does not display any signs of overmodi-
fication, but rather a refined, well-modified silicon structure.
Figure 13(b) shows that two dendrites enclose the eutectic
region, and the orientation mapping data indicate that most
of the eutectic aluminum originated from the surrounding
dendrites, growing from each dendrite to form a grain bound-
ary in the center of the eutectic region. Some small areas
of different orientation are observed and also several black,
nonindexed silicon particles. A relatively large eutectic
region with a flake silicon structure and different aluminum
VOLUME 32A, APRIL 2001—955
Fig. 11—Sample modified by 70 ppm Sr: (a) SEM secondary electron
image and (b) EBSD orientation map of the same area. A wide variation
in orientations of the aluminum in the eutectic is observed.
orientation (shown in grey) is observed on the right-hand
side of the eutectic region.
It should be noted that the EBSD patterns from aluminum
and silicon are very similar since aluminum has a face-
centered cubic atomic structure and silicon has a diamond
cubic structure. In the case of the present measurements, the
EBSD program was set for indexing of diffraction patterns
from aluminum. Simultaneous analysis by EDX for compo-
sition measurements and indexing the EBSD map using
the silicon crystal structure, or further transmission electron
microscopy (TEM) observation, is therefore required to clar-
ify the orientation relationship between aluminum and sili-
con within the eutectic.
IV. DISCUSSION
The eutectic in Al-Si alloys is more complex than in
other aluminum alloys because silicon is a faceted phase.
Directional solidification studies have shown that the Al-Si
eutectic is a coupled eutectic, i.e., with eutectic aluminum
and silicon growing in a quasisteady-state condition, side-
by-side with a low-energy interface.[7,8,9] The growth front
of the unmodified Al-Si eutectic has been shown to be very
jagged and led by silicon, which has the smallest constitu-
tional undercooling and, therefore, projects ahead of the
956—VOLUME 32A, APRIL 2001
Fig. 12—Specimen modified by 110 ppm Sr: (a) SEM secondary electron
image and (b) EBSD orientation map of the same area. A wide distribution
of orientation of the aluminum in the eutectic is observed.
aluminum.[10] Silicon crystals grow strongly anisotropic
along certain crystallographic directions, and they, therefore,
become bounded by the more slowly growing facets, i.e.,
{111} habit planes.[8] The Al-Si eutectic is an irregular eutec-
tic. Due to a difficulty in changing the growth direction of
silicon, branching and termination of growth occurs so that
there is not a unique lamellar spacing in these alloys. Because
silicon can change its growth direction by twinning, there
may not necessarily always be a specific orientation relation-
ship between aluminum and silicon, since it has been sug-
gested that aluminum may not be able to change its growth
direction sufficiently fast to adapt to the rapid twinning of
silicon during eutectic growth.[8] Repeated epitaxial nucle-
ation of the aluminum on silicon during eutectic growth has
been reported by Kobayashi et al.,[11] Shamsuzzoha and
Hogan,[12] and Hogan and Song.[13]
Much work has been performed to understand the effect
of strontium and sodium in providing modification of the
silicon phase, and altered growth characteristics of eutectic
silicon, by the twin-plane re-entrant edge mechanism, are
now the generally accepted explanation. The effect of stron-
tium is to increase the twin density by so-called impurity
induced twinning, and it also yields a smoother eutectic
METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 13—Specimen modified by 500 ppm Sr: (a) SEM secondary electron
image and (b) EBSD orientation map of the same area. Crystallograhic
orientations of aluminum in eutectic and surrounding primary dendrites
are identical.
growth front during solidification.[11] Modification is also
accompanied by a depression in the eutectic temperature
and a shift of the eutectic point to higher silicon
concentrations.[11,14]
Despite the significant amount of research on solidifica-
tion of the Al-Si eutectic, the nucleation stage has not
received a similar amount of focus. It has been concluded
that the nucleation of silicon controls the solidification of
the eutectic,[8,11,15,16] i.e., the eutectic does not start to grow
until the first silicon has formed. However, it is worth empha-
sizing that the information available about nucleation is both
confusing and contradictory. It is generally believed that
silicon does not nucleate on aluminum.[16] However, the
pioneering work by Crosley and Mondolfo[17] showed that
aluminum can nucleate silicon at a few degrees undercooling
and silicon does not nucleate aluminum. To the contrary,
again, efficient nucleation of aluminum on silicon is evi-
denced by the formation of an aluminum halo around pri-
mary silicon crystals in hypereutectic alloys (while the
reverse does not readily occur), and also by the reported
epitaxial renucleation of aluminum on growing silicon
METALLURGICAL AND MATERIALS TRANSACTIONS A
lamellae in unmodified alloys. Silicon is the “leading phase”
during growth of the Al-Si eutectic, and according to the
theory proposed by Ohno,[18] this is strong evidence that
supports silicon being an efficient nucleant for aluminum,
whereas aluminum is a much less efficient nucleant for
silicon. The assertion is, therefore, that the formation of the
eutectic in hypoeutectic Al-Si alloys strongly depends on
the nucleant(s) for silicon, although direct evidence to sup-
port this statement seems to be lacking.
The observed evolution of the eutectic in the quenched
samples of the unmodified alloy in Figure 5, combined with
the EBSD orientation map in Figure 10, shows clearly and
unequivocally that the eutectic nucleates on or adjacent to
the primary aluminum dendrites and that eutectic aluminum
grows with the same orientation as that of the surrounding
primary dendrite. This corresponds to the mechanism illus-
trated in Figure 1(b). It is very interesting to note that the
results indicate that nucleation and growth of the eutectic
is concentrated on the tips of the dendrites in the early stages
of the eutectic arrest. Figure 14(a) presents a micrograph
from an unmodified sample quenched just after the eutectic
arrest, which lends further support to the theory that the
eutectic nucleates on the dendrite tips. This result, therefore,
clearly indicates that aluminum can act as a nucleant for the
eutectic, although it is not clear whether silicon is nucleated
directly on the aluminum or on particles just ahead of the
interface. In light of the results of Crosley and Mondolfo,[17]
who showed that aluminum is a relatively good nucleant for
silicon, the preceding result is not surprising and may indi-
cate that silicon nucleated on the aluminum dendrite. Eutec-
tic aluminum certainly did. Dahle et al.[3] have also shown,
by crystallographic studies, that the unmodified eutectic in
hypoeutectic Al-Si alloys nucleates on the dendrites. Inspec-
tion of the micrographs of quenched samples published by
Kim and Heine,[19] Flood and Hunt,[20] Denton and Spittle,[21]
and Hamed et al.[22] provides further indirect evidence of
eutectic nucleation on primary aluminum in unmodified
hypoeutectic Al-Si alloys.
The tendency for the eutectic to grow into the intergranular
liquid, rather than toward the center of the equiaxed dendrite
in the unmodified alloy, is also very interesting. One possible
explanation for this effect is that it can be related to a higher
degree of mixing and more unrestricted diffusion compared
to regions closer to the center of the equiaxed dendrites,
such as between secondary dendrite arms.
When the alloy contains strontium, the eutectic silicon
is transformed to a fibrous appearance, and the quenched
microstructures for 70 and 110 ppm Sr (Figures 6 and 7)
indicate that there has also been a transition in the nucleation
of the eutectic. Instead of being connected to the dendrites,
as for the unmodified alloy, the eutectic is now more distrib-
uted and fills the large intergranular areas. Eutectic grain
boundaries that intersect the dendrites are observed and there
seems to be no linkage between the evolution of the eutectic
and the presence of the equiaxed dendrites. The EBSD orien-
tation maps for these two Sr contents in Figures 11 and
12 show that there is no longer an orientation relationship
between the eutectic aluminum and the surrounding den-
drites. The eutectic growth mode at 70 and 110 ppm Sr is
according to the illustration in Figure 1(c). Figure 14(b)
shows a micrograph of a Sr-modified sample quenched just
after the start of the eutectic arrest, which nicely indicates
VOLUME 32A, APRIL 2001—957

(a)
(b)
Fig. 14—Samples quenched at the beginning of eutectic solidification
showing (a) nucleation on the tips of the dendrites in an unmodified speci-
men and (b) independent nucleation in the interdendritic liquid in a Sr-
modified specimen.
the growth of a eutectic grain in the center of an interdendritic
channel, totally independent of the primary phase. Indepen-
dent nucleation of eutectic grains has also been reported in
the work by Laslaz,[16] Dahle et al.,[3] and Wang et al.[5]
Further support can be found in reinterpreting the quenched
microstructures published by Denton and Spittle[21] and
Hamed et al.[22]
Further inspection of the EBSD orientation maps for the
samples containing 70 and 100 ppm Sr in Figures 11(b) and
12(b), respectively, indicate that the sizes of the isoorienta-
tion areas for eutectic aluminum are very different, and much
larger at 110 ppm Sr. The significance of these isoorientation
areas is not quite clear. The eutectic interface is normally
quite smooth upon Sr modification, as also confirmed by
the quenched microstructures in Figures 6 and 7. However,
it is possible that silicon is still the leading phase during
growth of the Al-Si eutectic and that renucleation of alumi-
num occurs. Larger isoorientation areas at the higher level
of Sr modification may therefore be the result of a smoother
958—VOLUME 32A, APRIL 2001
growth front and, therefore, less renucleation of eutectic
aluminum, but the result clearly indicates a stronger tendency
for some eutectic nucleation on the dendrite arms with 110
ppm Sr.
A closer inspection of the micrographs presented in Fig-
ures 6 and 7, particularly for the longer quench times, indi-
cates that small aluminum “particles” can be observed in
locations close to the center of a large fraction of all eutectic
grains. These centrally located aluminum particles are quite
round in shape and are significantly smaller than the second-
ary dendrite arms, which may indicate that they are separate
and formed separately. They are likely to be rodlike rather
than spherical. The presence of these particles raises the
question as to whether they acted as nucleation sites for the
eutectic grains, or were perhaps the first stage of eutectic
solidification before the coupled eutectic started growing.
Further studies are required to investigate and confirm
this effect.
When the alloy is modified by 500 ppm Sr, the quenched
microstructures indicate that the eutectic is again associated
with the equiaxed dendrites, and again nucleating close to
their tips, i.e., different from the samples containing 70 and
110 ppm Sr. The EBSD orientation data (Figure 13(b)) shows
clearly that the eutectic has grown from the dendrites,
according to the illustration in Figure 1(b), and identical to
what has been found in the unmodified alloy. Although a
fully modified structure is observed, the nucleation mecha-
nism and macroscopic growth mode has changed. This is
very interesting, as it shows that the nucleation and macro-
scopic evolution of the eutectic is independent of the appear-
ance of eutectic silicon, i.e., flake or fibrous. A strontium
level of 500 ppm is much larger than that used in commercial
operations (50 to 300 ppm), although overmodification (with
the presence of primary silicon particles and overmodifica-
tion bands) is generally not associated with Sr. Large stron-
tium-containing phases can often be found at high Sr
concentrations.
It is clear from the previous discussion that strontium
exerts a significant influence on the nucleation and growth
of the Al-Si eutectic. The effect of strontium on the growth
of silicon is well documented and will not be discussed
further in the present article. However, the nucleation behav-
ior of the eutectic grains requires further discussion. The
nucleation behavior and the resulting macroscopic distribu-
tion of eutectic within the mushy zone can be expected to
have a significant influence on interdendritic permeability
and, therefore, to significantly affect and control the amount
and distribution of porosity. The significance of eutectic
growth mode on porosity formation has been studied and
discussed further by McDonald et al.[2] and Dahle et al.[23]
The modification effect, i.e., altering the silicon morphol-
ogy from flakes to fibers, of elements such as Na and Sr
was initially related to altered nucleation characteristics. The
AIP particles were found to be very efficient nucleants for
silicon, and Crosley and Mondolfo[17] suggested that the
modification effect of Na, which is similar to Sr, was that
it neutralized active nucleants for silicon, such as the AIP
particles. Phosphorus is well known to be a good nucleant
for primary silicon in hypereutectic Al-Si alloys and is used
as a grain refiner in these alloys. However, if the observed
effect of Sr on eutectic nucleation was a result of interaction
with dispersed particles in the melt, it is very difficult to
METALLURGICAL AND MATERIALS TRANSACTIONS A
understand the reversion of the nucleation mechanism at
500 ppm Sr. The quenched microstructures of the unmodified
alloy indicate that nucleation occurs at the tips of the den-
drites. This effect could be the result of the phenomenon of
particle pushing where nonwetted particles are pushed ahead
of the evolving dendrites, as well as nucleation directly on
the interface. If heterogeneous nucleant particles pushed
ahead of the interface are activated, their point of activation
can be expected when the constitutional undercooling for
the nucleating phase is sufficient to cause nucleation of the
eutectic and when the melt composition is sufficiently close
to the eutectic.
It seems probable that the formation of the eutectic in
hypoeutectic Al-Si alloys is also governed by a columnar-
equiaxed transition (CET), where nucleation on the dendrites
(Figure 1(b)) can be considered “columnar” and independent
eutectic grains (Figure 1(c)) “equiaxed.” The change from
radial growth from the wall (Figure 1(a)) to evenly distrib-
uted over the cross section is also likely to be the result of
a CET. Hunt[24] has proposed a mathematical model describ-
ing the CET. At low thermal gradients and high growth
rates, equiaxed grains are expected. The driving force for
the transition is constitutional undercooling and the potency
of the nucleants present. The effect of strontium can be
twofold. It is likely to be segregated into the liquid ahead
of the primary dendrites, therefore potentially increasing the
constitutional undercooling. More likely, however, is that it
affects the nucleants present in the melt according to the
theory proposed by Crosley and Mondolfo.[17] The reversion
of eutectic nucleation for 500 ppm Sr is very surprising and
may be an indication that the effect of Sr is related to the
presence of some strontium containing particles, or other
inclusions introduced with the strontium addition, that act
as nucleants for the eutectic. Although active at 70 and 110
ppm Sr, these particles may have become too large to be
efficient nucleants at higher Sr contents, or they may be of
different composition and/or crystal structure. More detailed
studies of the effect of Sr on nucleant population is required
to clarify the mechanism by which strontium affects the
macroscopic distribution of solidifying eutectic in hypoeu-
tectic Al-Si alloys. The observed difference in eutectic nucle-
ation and growth at 500 ppm, compared to 70 and 110
ppm Sr, correlates very well with the observations made
by DasGupta et al.[25] who found that the eutectic arrest
temperature increased with Sr additions above 100 ppm.
They also found that the normal connected network of silicon
fibers in a seaweed structure vanished at Sr levels exceeding
100 ppm, although the eutectic was still well modified, as
in the present work. DasGupta et al.[25] also found that there
was a change in fracture mode, from ductile to more brittle,
when the level of strontium exceeded 100 ppm.
Figure 9 shows that the eutectic does show a tendency to
radiate inward from the mold wall, similar to the mode
illustrated in Figure 1, in the initial stages of the eutectic
arrest for all samples. However, open channels penetrating
to the surface of the samples were observed in all samples
and these remained open for a significant part of the eutectic
arrest. Eutectic growth was observed with a relatively uni-
form distribution in samples quenched further into the eutec-
tic arrest. This result, therefore, indicates that the eutectic
did not solely grow radially from the wall, but this growth
METALLURGICAL AND MATERIALS TRANSACTIONS A
mechanism dominates in the early part of the eutectic solidi-
fication. The initial growth from the wall may be a result
of a CET, and the local isotherms and thermal gradients in
the sample in the initial stages of the eutectic arrest would
therefore be important. Further studies of the effect of ther-
mal gradient (during eutectic solidification) and growth rate
are warranted to determine their effect in controlling the
nucleation behavior of the eutectic in hypoeutectic Al-Si
alloys.
The nucleation behavior of the eutectic between dendrite
arms in hypoeutectic Al-Si alloys raises an interesting point.
Our crystallographic orientation measurements often show
identical orientation of the eutectic aluminum and the sur-
rounding secondary dendrite arms. These areas often contain
a single relatively large silicon flake that is visible between
a pair of arms, the remainder being aluminum. It seems
probable that in such cases the silicon nucleated first from
the melt (necessarily Si-rich because of Si rejection from
the dendrite). Growth of the silicon flake would consume
the excess silicon, leaving growth of the dendrite to resume
to solidify the remaining melt and initiate two-phase eutectic
growth, somewhat similar to a divorced eutectic growth
mechanism. Further studies to support this theory should
be considered.
V. CONCLUSIONS
The macrostructural evolution and solidification of eutec-
tic in hypoeutectic Al-7Si-3Cu-0.2Mg (319) alloys with dif-
ferent levels of strontium was characterized by optical
microscopy, SEM, and EBSD mapping analysis of samples
quenched during solidification.
The results show that the eutectic nucleates on the primary
phase in the unmodified alloy. Nucleation seems to occur
at the tips of the dendrites and the eutectic has a tendency
to evolve into intergranular regions rather than filling the
dendrite envelopes.
With 70 and 110 ppm Sr, eutectic grains are nucleated
in the intergranular regions independently of the equiaxed
aluminum dendrites. A well-modified eutectic silicon struc-
ture is also observed.
At 500 ppm Sr, the eutectic is still well modified, but is
found to nucleate on the dendrites as in the unmodified alloy.
This shows that nucleation of eutectic grains is independent
of the modification of the silicon phase promoted by stron-
tium additions.
Some tendency for the eutectic to evolve radially inward
from the mold wall in the early stages of the eutectic arrest
was observed. However, a relatively uniform distribution of
growing eutectic was found later during eutectic solidi-
fication.
It seems likely that strontium affects the number and
potency of the nucleants for silicon available in the interden-
dritic liquid. Because a reversion in nucleation mode is
observed at 500 ppm Sr, it is possible that Sr containing
particles promote independent nucleation at low Sr levels,
while these particles have become too large or have changed
potency at higher Sr levels.
ACKNOWLEDGMENTS
This project is funded by a large grant from the Australian
Research Council (ARC) and is also supported by an award
from the Kazato Research Foundation, Japan.
VOLUME 32A, APRIL 2001—959
 REFERENCES
1. Y.C. Lee, A.K. Dahle, D.H. StJohn, and J.E.C. Hutt: Mater. Sci. Eng.
A, 1999, vol. A259, pp. 43-52.
2. S.D. McDonald, K. Nogita, A.K. Dahle, J.A. Taylor, and D.H. StJohn:
AFS Trans., 2000, vol. 108, pp. 463-70.
3. A.K. Dahle, J. Hjelen, and L. Arnberg: Proc. 4th Decennial Int. Conf.
on Solidification Processing (SP97), J. Beech and H. Jones, eds.,
Sheffield, United Kingdom, 1997, pp. 527-30.
4. A.K. Dahle, J. Hjelen, and L. Arnberg: Electron Microscopy 1998,
Proc. ICEM 14, Institute of Physics Publishing. Materials Science 1,
Bristol, United Kingdom, 1998, vol. 2, pp. 135-36.
5. Q.G. Wang, D. Apelian, L. Arnberg, S. Gulbrandsen-Dahl, and J.
Hjelen: AFS Trans., 1999, vol. 107, pp. 249-56.
6. K. Nogita and A.K. Dahle: Materials Characterization, in press.
7. D.C. Jenkinson and L.M. Hogan: J. Cryst. Growth, 1975, vol. 28, pp.
171-87.
8. S.-Z. Lu and A. Hellawell: Metall. Trans. A, 1987, vol. 18A, pp.
1721-33.
9. M. Shamuzzoha, L.M. Hogan, and J.T. Berry: AFS Trans., 1992, vol.
100, pp. 619-29.
10. S.-Z. Lu and A. Hellawell: JOM, 1995, Feb., pp. 38-40.
11. K. Kobayashi, P.H. Shingu, and R. Ozaki: Proc. Int. Conf. Solidification
and Casting, Metals Society, London, 1979, pp. 101-05.
960—VOLUME 32A, APRIL 2001
12. M. Shamuzzoha and L.M. Hogan: J. Cryst. Growth, 1986, vol. 76,
pp. 429-39.
13. L.M. Hogan and H. Song: Acta Metall., 1987, vol. 35, pp. 677-80.
14. M.D. Hanna, S.-Z. Lu, and A. Hellawell: Metall. Trans. A, 1984, vol.
15A, pp. 459-69.
15. M.G. Day: J. Inst. Met., 1970, vol. 98, p. 57.
16. G. Laslaz: Proc. 4th Int. Conf. on Molten Aluminum Processing, Ameri-
can Foundrymen’s Society, Des Plaines, IL, 1995, pp. 459-80.
17. P.B. Crosley and L.F. Mondolfo: AFS Trans., 1966, vol. 74, pp.
53-64.
18. A. Ohno: The Solidification of Metals, Chijin Shokan Co. Ltd.,
Tokyo, 1976.
19. C.B. Kim and R.W. Heine: J. Inst. Met., 1963–64, vol. 92, pp. 367-76.
20. S.C. Flood and J.D. Hunt: Met. Sci., 1981, vol. 15, pp. 287-94.
21. J.R. Denton and J.A. Spittle: Mater. Sci. Technol., 1985, vol. 1, pp.
305-11.
22. Q.S. Hamed, R. Elliott, and P.S. Cooper: in Light Metals 1992, E.R.
Cutshall, ed., TMS, Warrendale, PA, 1991, pp. 1391-97.
23. A.K. Dahle, J.A. Taylor, and D.A. Graham: Aluminum Trans., 2000,
vol. 3 (1), pp. 17-30.
24. J.D. Hunt: Mater. Sci. Eng., 1984, vol. 65, pp. 75-83.
25. R. Dasgupta, C.G. Brown, and S. Marek: AFS Trans., 1988, vol. 96,
pp. 297-310.
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