Research & Development

129
May 2009
Microstructure variation and growth
mechanism of hypoeutectic Al-Si alloy
solidied under high pressure
Male, born in 1953, president of the Materials Forming Institute of
the Northeastern University (NEU). He graduated in 1977, majored
in foundry, and received his masters degree in 1980 from the NEU.
His research interests mainly focus on cast alloy, solidification
theory and technology. He has published more than 40 papers
in Acta Metallurgica Sinica, Journal of Materials Science, The
Chinese Journal of Nonferrous Metals, Foundry, etc.
E-mail: zhanggz@smm.neu.edu.cn
Received: 2008-09-08; Accepted: 2008-12-04
*Zhang Guozhi
*Zhang Guozhi, Yu Xifeng and Liu Xinggang
(School of Materials and Metallurgy, Northeastern University, Shenyang 110004, China)
Abstract: The microstructure of hypoeutectic Al-9.21wt.%Si alloy solidified under 5.5 GPa was studied. The
results show that the solidication microstructure is rened. The primary phase is the extended solid solution.
The solid solubility of Si in phase is up to 8.26wt.%. The growth mode of the phase is cellular, and this cellular
growth mechanism is interpreted in terms of the decrease of the diffusivity and the extended solid solution under
high pressure. By calculation, it can be known that the the diffusivity of solute in the liquid under normal pressure is
as high as two hundred times that under high pressure. The microhardness of the hypoeutectic Al-Si alloy solidied
under high pressure is higher than that of solidied under normal pressure. After annealing, Si precipitates from
the solid solution, the microhardness of the alloy decrease, but, still higher than that of solidied under normal
pressure.
Key words: Al-Si alloy; high pressure solidication; extended solid solution; cellular growth
CLC number: TG111.4 Document code: A Article ID: 1672-6421(2009)02-129-04
W
ith increasing development of the solidication technique,
high pressure has been applied to the solidification
process. As to the metals and alloys solidied under pressure,
not only the crystalline grains are rened, but also various non-
equilibrium microstructures can be obtained. For example,
amorphous solids can form by quenching melts under high
pressure
[1-4]
. The solid solubility of the alloying elements under
high pressure increases
[5]
. Boettinger, et al
[6]
studied the rapid
solidification microstructure of Ag-Cu alloy and found the
cellular microstructure along the growth direction. Similar
results were also observed by other investigators
[7-9]
. Li et al
[10]

investigated the interface morphologies and microstructure
of the directionally solidified Ni-5wt.%Cu alloy during the
dendrite-to-cellular transition at high growth rate. In this work,
hypoeutectic Al-9.21wt.%Si alloy was chosen for the study.
The microstructures of the hypoeutectic Al-Si alloys solidied
under high pressure were analyzed.
1 Experimental procedure
Pure Al (99.999%) and single crystal Si (99.999%) were used
to fabricate Al-9.21wt%Si alloy. The pouring temperature
was about 1,023 K. The casting for the test, i.e., the rod with
=25 mm was cast in a metal mould which was preheated to
about 473 K. The rod was machined into samples with 14 mm
in diameter and 12 mm in height. High pressure solidication
was performed on a DC-29C type of high pressure apparatus
with six-anvils. The assembly schematic for high pressure
solidication can be found from the ref. [5]. Indirect heating
of low voltage and large current was used to heat a graphite
sleeve and melt the alloy. High pressure was generated by
pressing the anvils by means of hydraulic rams. During the
whole experiment process, the six-anvils were cooled by water.
When the pre-pressure reading under fully sealed reached 2.0
GPa, the current through the graphite sleeve was switched
on to heat the sample. At the same time, the pressure was
increased continuously at a rate of 100 MPa per second. Then,
holding for 20 minutes when the temperature reached about
1,453 K and the pressure was up to about 5.5 GPa, the electric
current was shut off and the molten alloy began to cool down.
The samples were polished and etched. The structure scanning
and chemical composition analyses at micro-areas were
carried out on the electron probe microanalyzer, EPM -810Q,
and ZAF corrections. Phase structure analysis was performed
on a Rigaku DMAX/2400 X-ray diffractometer, with CuKa
radiation. The microhardness of the alloy was measured on a
PMT-3 type microhardness tester.
2 Experimental results and discussion
Figure 1 shows that the microstructure of the hypoeutectic
Al-9.21wt.%Si alloy, solidified under 2.0 GPa, consists of
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130
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primary a dendrites and (a+b) eutectic. And, the amount of
the (a+b) eutectic is more than that of the primary a dendrites.
Figure 2 shows the microstructure of the alloy solidied at 5.5
GPa, the cooling rate is as same as that of sample in Fig.1. The
microstructure solidied under the high pressure is composed
of a cells in majority, the amount of the (a+b) eutectic is very
minor. The morphology of the a phase has transited to cellular
under the high pressure. The X-ray diffraction analysis for the
alloy solidified under high pressure shows that the structure
consists of cubic a solid solution and diamond cubic b solid
solution, as shown in Fig.3. Figure 4 shows Al
ka
, Si
ka
X-ray
scanning for alloy solidied at 5.5 GPa. It can be noticed from
Fig.4 that the principal composition in the cellular crystals is
Al, and the amount of Al at the grain boundaries is relatively
lower compare to that of Si, the solid solubility of Si in a cell
is 8.26wt.%.
The experimental results indicate that the microstructure
of the alloy solidified under 5.5 GPa achieved significant
renement; the primary a phase has the nature of an extended
solid solution, and the solid solubility of Si in a phase has been
raised obviously, up to 8.26wt.%, compared with only 0.15wt.%
under normal pressure. The renement of the microstructure
and the increase of the solid solubility, solidied under high
pressure, are explained in the literature [5]. The melting
point of alloy increases with pressure increase, according to
the Clapeyron equation, thus the undercooling of the molten
alloy increases with increasing pressure, which promotes the
nucleation process, therefore the solidified microstructure
renes. In addition, with an increase of pressure, the atomic
diffusivity decreases, therefore the segregation degree of the
alloying elements reduce. There is no enough time for the
solute atoms to diffuse, and the solute atoms dissolve in the
solid-phase lattice during crystal growth, thus, an extended
solid solution forms.
The growth mode of the a phase solidified under high
pressure is cellular, as shown in Fig.2. It is difcult to obtain
cellular structure for Al-Si alloys solidified under normal
pressure. The growth mode of the crystal is affected by several
factors. The growth in pure metal is controlled by heat ux,
and the growth in alloy is primarily controlled by diffusion
of solute atoms. According to the kinetic theory for interface
stability
[11]
:
(1)
Where:
T
m
the melting point of pure metal whose solid-liquid
interface is plane;
C= c/L the constant of the surface tension; c is the solid-
liquid interface energy, L the crystalline latent heat of per unit
volume solvent;
the interfacial perturbation frequency;
g'=(K
s
/K)G;
g=(K
L
/K)G;
K
s
the thermal conductivity of the solid;
K
L
the thermal conductivity of the liquid;
Fig.1 Microstructure solidied at normal pressure
Fig.2 Microstructure solidied at 5.5 GPa
Fig.3 XRD spectrum for alloy solidied at 5.5 GPa
Fig.4 X-ray scanning for alloy solidied at 5.5 GPa
Research & Development
131
May 2009

K
= (K
s
+ K
L
);
G' the thermal gradient in the solid phase;
G the thermal gradient in the liquid phase
m the slope of the liquidus line in the phase diagram;
G
c
the concentration gradient of the solute when
perturbation does not happen;
v the growth rate of interface;
D the diffusivity of the solute in liquid phase;
=(v/2D)+[(v/2D)
2
+
2
]
1/2
the perturbation frequency
of the solute in liquid phase along solid-liquid interface;
k
0
the equilibrium distribution coefcient.
The stability of the solid-liquid interface is determined by
the positive or negative of the function S(). If the function
S() value is positive, the interface is in an unstable state.
Otherwise, if S() is negative, the interface becomes stable.
It can be seen from the equation (1) that the function S()
consists of three terms. The first term is determined by the
interface tension. The increase of the interface tension is
advantageous to the stability of the solid-liquid interface.
The second term is determined by the thermal gradient.
The increase of the thermal gradient is also benecial to the
stability of solid-liquid interface. When the thermal gradient
is negative, the solid-liquid interface becomes unstable. mG
c

in the third term is affected by the concentration of the solute
in the solid-liquid interface front. The less the concentration
of the solute is, the smaller the value of mG
c
is, which can
be favorable to alternate the interface morphology towards
stable. The fraction in the third term shows the effect of the
fluctuation and solute diffusion on the solid-liquid interface
stability. With a decrease in the diffusivity D, the value of the
fraction reduces, which does not change the algebraic symbol
for the third term, but contributes to the transformation of S()
value into negative direction, therefore makes the solid-liquid
interface tend towards stable. The change of the pressure has
little effect on the rst two terms, but has great effect on the
diffusivity D. The principal reason is that high pressure makes
the diffusivity of the solute in liquid phase very small. The
relationship between the diffusivity of the solute in liquid
phase and the pressure is given by:
(2)
Where R is the gas constant, T the temperature of the liquid
alloy, d the distance of the atomic free travel, h
0
the viscosity
of the liquid alloy at atmospheric pressure and normal
temperature, P the applied pressure, V
0
the original volume of
the liquid alloy. According to the equation (2), the ratio of the
diffusivity D
1
at high pressure to the diffusivity D
0
at normal
pressure can be given by:
(3)
For t he hypoeut ect i c Al - 9. 21wt . %Si al l oy, under
experimental conditions, T=1,453 K, V
0
=1.1410
-5
m
3
/mol, the
effect of pressure on diffusivity ratio D
1
/D
0
can be obtained by
equation (3), as shown in Fig.5. With an increase in pressure,
Fig.5 Effect of the pressure on D
1
/ D
0
the diffusivity ratio decreases rapidly. After the pressure
increase up to 4.0 GPa, the changing rate of the diffusivity
ratio decreases. When the alloy solidies under 5.5 GPa, the
diffusivity of solute in the liquid is sharply reduced to be only
about 0.0052 times as much as that under normal pressure.
Therefore the value of the fraction in the third term reduces,
which results in the value of the third term in the equation
(1) decreased greatly. In addition, under high pressure and
rapid growth conditions, because of the formation of the
supersaturated solid solution, the concentration of the solute
in the front of the solid-liquid interface drops, which causes
the value of mG
c
lower, thus the value of the third term in the
equation (1) decreases. Therefore the function S() tends to
negative, which potentially alternate the crystal growth of Al-
Si alloy towards the stable interface, and the growth mode of
the a phase is cellular and not dendritic. So, the pressure can
make the solid-liquid interface morphology changeable.
Figure 6 shows the microstructures of the alloy solidified
under 5.5 GPa after annealing, from which it can be observed
that Si has precipitated from a solid solution as shown
in Fig.6(a). With prolonging of the annealing time, the
precipitated Si increases in quantity and enlarges in size,
as Fig.6(b). Table 1 shows the microhardness of the alloys
solidified at different conditions, the microhardness of the
alloy solidied at 5.5 GPa is 2.5 times as high as that of the
alloy solidied under normal pressure. The microhardness of
the alloy solidied under 5.5 GPa decreases with increasing
annealing time, but is still higher than that of the alloy
solidied under normal pressure. The reason is that, under high
pressure solidication conditions, the solid solubility of Si in a
phase can be as high as 8.26wt.% and reaches a supersaturated
state. This extended solid solution acts a strong solution-
strengthening function, which makes the microhardness of
the alloy solidied under high pressure higher than that of the
alloy solidified under normal pressure. This extended solid
solution is metastable, when the alloy is in annealing, the
supersaturated Si in a solid solution precipitates, as shown
in Fig.6, thus the solution-strengthening effect weakens. The
precipitated Si has a precipitation-strengthening action. With
prolonged annealing, the precipitated Si increase in quantity
and enlarges in size, which makes the microhardness further
reduced. The alloy after annealed still has some of the solution-
strengthening and precipitation-strengthening function.
Therefore, after annealed at 583 K for 8 h, the microhardness
of the alloy solidied under high pressure is still 1.7 times as
high as that of the alloy solidied under normal pressure.
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This project is supported by the National Natural Science Foundation of China (grant No. 59571040).
3 Conclusions
(1) Under the condition of high pressure applied, the
solidication microstructure of the hypoeutectic Al-9.21wt.%Si
alloy achieves signicantly renement. The primary a phase is
an extended solid solution. The extended solid solubility of Si
in a phase can be up to 8.26wt.%.
(2) During the solidication under high pressure, the growth
of the primary a phase is cellular rather than dendritic that
usually obtained under normal pressure. The cellular growth
mechanism of the a phase has been explained in terms of the
decrease of the diffusivity of solute in the liquid phase.
(3) The microhardness of the hypoeutectic Al-9.21wt.%Si
alloy solidied under 5.5 GPa is 2.5 times of that of the alloy
solidified under normal pressure. With prolonged annealing
time, the precipitated Si from a solid solution increases in
its quantity and enlarges in its size, and the microhardness of
the alloy is still higher than that of the alloy solidied under
normal pressure.
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Sample A B C D
Microhardness (Hm) 33.5 84.7 61.6 55.2
Note: A: solidied at normal pressure; B: solidied at 5.5 GPa; C: solidied
at 5.5 GPa with annealing at 583 K for 6 h; D: solidified at 5.5 GPa with
annealing at 583 K for 8 h.
Table 1 Microhardness of the alloy solidied at
different conditions
Fig.6 SEM image after annealing at 583 K for 6 h (a) and 8 h (b), respectively
(a) (b)