Intermetallics 15 (2007) 1395e1400

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Short communication

Microstructure and microsegregation in directionally

solidified Mge4Al alloy
C. Zhang a, D. Ma a, K.-S. Wu a, H.-B. Cao a, G.-P. Cao a, S. Kou a,
Y.A. Chang a,*, X.-Y. Yan b
a
Department of Materials Science and Engineering, University of Wisconsin-Madison, 1509 University Avenue, Madison, WI 53706, USA
b
Alcoa Laboratories, Aluminum Company of America, Alcoa Center, PA 15069, USA

Received 23 August 2006; received in revised form 8 November 2006; accepted 25 January 2007
Available online 21 May 2007

Abstract

Directional solidification (DS) of a binary Mge4Al (wt.%) alloy was carried out to investigate the microstructures and microsegregation
under controlled solidification conditions. In directional solidification the microstructure depends on the growth rate V because the cooling
rate, which governs the solidification microstructure, is the product of the growth rate and the temperature gradient. The ability to produce simple
and uniform microstructures in directional solidification enables us to correlate the formation of the microstructure and its characteristic length
scales quantitatively with processing parameters. The morphology of the solideliquid interface and the microstructure of both the mushy zone
and the steady-state region were characterized at different levels of growth rates. With the help of an electron microprobe, microsegregation was
determined in a specimen directionally solidified with cooling rates ranging from 0.06 to 0.8 K/s. The calculated microsegregation results based
on the Scheil model deviated significantly from the experimental data, which is anticipated since back diffusion was not included due to the lack
of diffusivity data.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: A. Intermetallics, miscellaneous; C. Crystal growth; C. Casting; D. Microstructure

1. Introduction
In view of their low density when compared with other
structural metals, magnesium alloys have been considered as
materials of the future for the automobile industry in order
to decrease the weight to strength ratio and thus improve the
fuel efficiency. But their high temperature strength and creep
resistance pose a challenge for Mg alloys to be as automobile
powertrain components. A number of recently developed mag-
nesium alloys have shown promising high temperature
strength and creep resistance, such as AM50/60A (Mg-5/
6Ale0.4Mn), AJ62x (Mge6Ale2Sr, BMW), AX53x (Mge
4.5Ale3Cae0.27Mn) and AXJ530 (Mge4.5Ale3Cae
0.14Sre0.25Mn, GM) [1,2]. All commercial magnesium
alloys are developed from the MgeAl based alloys with Al
concentration varying within the range of 4e6 wt.%. Thus, un-
derstanding the solidification behavior of an Mg-rich alloy in
the MgeAl binary system is crucial.
The objective of the present study is to investigate the
microstructures and microsegregation of the binary Mge4Al
alloy under controlled directional solidification conditions.
The conditions enable us to correlate the formation of the
microstructure and its characteristic length scales quantita-
tively with processing parameters.
2. Experimental procedure
2.1. Sample preparation for directional solidification

* Corresponding author. Tel.: þ1 608 262 0389; fax: þ1 608 262 8353. A 316 stainless steel tube with a 3.25 mm I.D., 4.5 mm
E-mail address: chang@engr.wisc.edu (Y.A. Chang). O.D. and 457 mm length was used to load the alloy specimen

0966-9795/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2007.01.009
1396 C. Zhang et al. / Intermetallics 15 (2007) 1395e1400
for directional solidification. The molten magnesium alloy was
sucked into the tube under vacuum. As shown in Fig. 1, a mild
steel crucible holding an Mge4Al alloy ingot (w50 g) was
placed inside a quartz tube that was closed at one end and
sealed at the other end with an O-ring in a water-cooled copper
cover. A thin stainless steel tube was inserted through an O-
ring at the center of the copper cover. One end of the stainless
steel tube was placed near the top of the crucible inside the
quartz tube, and the other end was connected to a three-way
valve. The quartz tube assembly was then put in a vertical re-
sistance furnace, pumped down to 30 mTorr, back filled and
purged with carbon dioxide gas through the three-way valve
before the furnace was turned on. After the ingot was com-
pletely melted, the stainless steel tube was pushed down into
the liquid metal to suck it up by vacuum. This sample prepa-
ration procedure was found reliable in our previous studies on
Al alloys [3e6].
2.2. Directional solidification
Directional solidification was used in the present study be-
cause in directional solidification the microstructure is unidi-
rectional, well-defined and easy to control. The directional
solidification apparatus consisted of a vertical resistance fur-
nace (Fig. 2) and a high precision position table. The resis-
tance furnace was equipped with three heating zones. This
three-zoned furnace provided the capability of maintaining
the desired temperature gradient for directional solidification,
since each zone could be controlled separately. A water-cool-
ing jacket was placed at the bottom of this vertical furnace in
order to promote unidirectional solidification of the melt. The
stainless steel tube containing the alloy was inserted through
the cooling jacket. The position of the tube was fixed by
a sample holder with about 25 cm of the tube length exposed
to the hot zone and the remaining 10 cm positioned in the cold
zone. The sample holder was firmly attached to the position
table. Since the position table was coupled with a micro-step
motor and a computer controlled indexer, the movement of
Vacuum
Water Out
Water In
Copper Cover
Quartz Tube
Stainless Steel
Tube
Steel Crucible
Molten Alloy
Heat Insulator
Resistant Furnace
Fig. 1. A schematic diagram of sample preparation in the vertical furnace.
Temperature Controller II Temperature Recorder
Temperature Controller I
Temperature Controller III
Thermocouple Furnace Housing
Fixture
Heating Coils
Thermocouples
Thermocouples
Stainless Steel
Fiberfrax Tube
Insulation
Melt
Cooling Jacket
Water Out Water In
Sample Holder
Fig. 2. A schematic diagram of directional solidification system.
the specimen was accurately and smoothly controlled at
speeds varying between 0.2 mm/s and 40 mm/s within the sta-
tionary furnace. Each of the alloy specimen was superheated
to about 100  C above the alloy liquidus temperature for 1 h
prior to carrying out directional solidification. The samples
were solidified for about 10 cm with a preset pulling speed.
After the solidified alloy reached the desired length, the spec-
imen was immediately quenched into a water bucket. A typ-
ical cooling curve was measured and the average cooling rate
derived from this cooling curve is w0.2 K/s. By dividing the
cooling rate by the growth rate, the temperature gradient in
the furnace was 4 K/mm. In the following text, the growth
rate V will be used as the processing parameter instead of
cooling rate. However, the two can be easily related to
each other through the temperature gradient.
2.3. Sample characterization
For subsequent characterization, the solidified sample was
cut in both longitudinal and transverse sections to investi-
gate the quenched interface morphology and the microstruc-
ture of the mushy zone and the steady-state region. The
solidification microstructures were examined by using the
optical microscopy and the Scanning Electron Microscopy
(SEM) (JEOL JSM-6100 and FEG LEO-1530). Transverse
sections of the completely solidified samples without etching
were subjected to a CAMECA SX-50 electron microprobe
to examine the microsegregation caused by the solute redis-
tribution during dendritic solidification. An area-scan
method was adopted to determine microsegregation, in
which 400 points within an area of 600  600 mm2 were
measured automatically. After collecting the data, a mathe-
matical treatment similar to that available in the literature
 C. Zhang et al. / Intermetallics 15 (2007) 1395e1400 1397

700 700
(a) (b)
600 650
Liquid
500
L + α(Mg)
600
α(Mg)
400 β

T [°C]
T [°C]

550
300
α(Mg) + β
500
200

450
100
L + α(Mg) + β
0 400
0 10 20 30 40 50 60 70 80 90 100 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mg Al Fraction of solid

Fig. 3. (a) Equilibrium phase diagram of MgeAl binary system; (b) calculated solidification path of Mge4Al alloy using Scheil model.

[7e9] was applied to obtain the concentration profiles with
respect to each component. In this method, the aluminum
content was firstly arranged in an ascending order. Ordered
integer numbers were then assigned to the sorted points and
the integer numbers were normalized linearly to a scale
from 0 to 1. These normalized fractions were used for plot-
ting the profiles of solute distribution. The fraction of each
phase in the microstructure was measured using image anal-
ysis software.
3. Results and discussion
3.1. Phase diagram and solidification path of
Mge4Al alloy
Fig. 3(a) shows the equilibrium phase diagram of the MgeAl
binary system calculated from the thermodynamic description
obtained by Zuo et al. [10] using Pandat [11,12]. Using the
Scheil model, which is based on the assumptions of complete

Fig. 4. Optical micrographs showing the solidification microstructures of an Mge4Al alloy quenched during directional growth at 5 mm/s (a, b) and 30 mm/s (c, d),
respectively; (b) and (d) were obtained from transverse cross-sections in the mushy zones but close to the quenched interfaces. The arrows indicate the dendritic
growth direction.
1398 C. Zhang et al. / Intermetallics 15 (2007) 1395e1400

(a) (b)

500 m 500 m

(c) (d)

500 m 500 m

(e)
Primary dendrite arm spacing (λ1), μm

(f) Experimental data

Hunt-Lu model λ1 = 2750*V-0.59

Cellular Dendritic

500 m
1 10 100
Growth rate V (μm/s)

Fig. 5. Optical micrographs obtained from the transverse cross-sections near the quenched interfaces, showing five types of a(Mg) dendritic morphology in the
Mge4Al alloy directionally grown at 15 mm/s (a), 30 mm/s (b), 50 mm/s (c), 100 mm/s (d) and 200 mm/s (e). The average primary arm spacing (l1) of the a(Mg)
dendrites is also plotted against a function of the applied growth rate (V) in (f).

mixing in the liquid but no diffusion in the solid, we calculated
the solidification path of Mge4Al alloy. The sequence of phase
formation is: Liquid / Liquid þ a(Mg) / Liquid þ a(Mg)
þ b(Mg17Al12) / a(Mg) þ b, as shown in Fig. 3(b). The pri-
mary solidified phase is a(Mg), and the eutectic structure of
a(Mg) þ b forms at the end of solidification. This information
will help us understand the solidification of this binary system
and the resultant microstructure, which governs its properties
and ultimately its performance in service.
3.2. Directional solidification microstructures
Optical microstructures for the Mge4Al alloy are presented
in Figs. 4 and 5. In the present communication, we studied the
variations in the solidified interface morphology of Mge4Al
alloy with the growth rate by quenching each specimen after
10 cm directional growth. As shown in Fig. 4(a) and (c), the
quenched liquid is ahead of the solideliquid interface. Behind
the interface is the mushy zone, where the solid and the liquid
coexist. Two types of phases are shown in this region, the
white phase being a(Mg) and the dark one the quenched inter-
dendritic liquid. The latter contains fine eutectic of a(Mg) þ b
as revealed by SEM at higher magnifications. Two types of in-
terface morphology have been identified based on the growth
form (or pattern) of the primary a(Mg) phase, as shown in
Fig. 4. When the growth rate V < 15 mm/s, a(Mg) exhibits
a cellular-dendritic structure (Fig. 4(a, b) with coarse trunks
and side-branches. On the other hand, when V  30 mm/s,
a(Mg) shows a morphology with thinner primary trunks and
finer secondary and tertiary arms (Fig. 4(c, d)), typical of
 C. Zhang et al. / Intermetallics 15 (2007) 1395e1400
Fig. 6. Optical and BSE micrographs showing the complete solidified microstructures of an Mge4Al alloy during directional growth at 5 mm/s (a, b) and 30 mm/s
(c, d), respectively. The arrows indicate the dendritic growth direction.
well-developed dendrites. The primary arm spacing (l1, as il-
lustrated in Fig. 5(a)) is a characteristic length that is known to
have a marked effect on the mechanical properties and the
subsequent homogenization treatment [13,14]. It is also likely
that l1 may play an important role in determining the creep be-
havior of magnesium alloys. As shown in Fig. 5(f), l1 de-
creases with increasing growth rate. Furthermore, the
variation of l1 with the growth rate can be well rationalized
by the HunteLu model [15], where l1 is a power law function
of the growth rate V with an index of 0.59, i.e. l1 fV 0:59 .
Apart from the quenched interface morphology, the solidi-
fication microstructure after complete directional growth has
also been characterized. Fig. 6(a) and (c) show the optical mi-
crographs of the longitudinal sections. Due to the dendrite arm
coarsening and impingement, primary trunks and secondary
arms are no longer as well-defined as those in the mushy
zone (Fig. 4(a) and (c)). In the optical micrographs in
Fig. 6(a) and (c), which are different from those in the mushy
zone, the white phase is still a(Mg) but the dark phase is b and
no liquid is left. Fig. 6(b) and (d) shows the SEM Backscat-
tered Electron (BSE) images taken from the transverse section
in the steady-state region. Since the contrast of BSE image is
mainly from the mean atomic number, the phase with a higher
mean atomic number shows up brighter in the BSE image. The
1399
dark phase is primary a(Mg) and the bright one is the b phase
due to its relatively high Al concentration. The b phase ap-
pears as a divorced eutectic and is distributed uniformly but
discontinuously in the interdendritic regions (shown later in
Fig. 7(a)). Studies have shown that the poor elevated temper-
ature creep properties of MgeAl binary alloys are due to the
thermal instability of the discontinuous of b phase in the grain
boundary at elevated temperatures [2]. In the current study, the
volume fraction of b phase in the completely solidified struc-
ture was measured by image analysis under different growth
rates, as given in Table 1. It is found that the volume fraction
of secondary b decreases with increasing growth rate. The
fractions of the b phase at various growth rates was calculated
using the Scheil model, which are about 0.6e1.2% higher than
the experimentally measured values in the present work.
3.3. Microsegregation
Microsegregation phenomena are of technical importance
because they can have significant implications on the proper-
ties of the alloys, such as the inhomogeneous precipitation,
fatigue behavior and corrosion resistance, etc. Fig. 7(a) is
a typical SEM BSE image of the Mge4Al specimen subject
to the microsegregation measurement. Fig. 7(b) shows the
1400 C. Zhang et al. / Intermetallics 15 (2007) 1395e1400

10
(a) (b)

Concentration of Al (wt. )
Scheil calculation result
8
Experimental result 15μm/s
Experimental result 50μm/s
6 Experimental result 200μm/s
(Mg)
4

10 m 0
0.0 0.2 0.4 0.6 0.8 1.0
Fraction of solid

Fig. 7. (a) Transverse section of the Mge4Al alloy directionally grown at V ¼ 200 mm/s showing a completely solidified microstructure; (b) the measured Al con-
centration profile as a function of the fraction of solid, as compared to the Scheil model of microsegregation.

measured concentration profile of Al as a function of the frac- with increasing growth velocity (V) such that lV 0:59 is
tion of solid at the growth rates of 15, 50 and 200 mm/s. The Al a constant, which is consistent with the prediction of the
content increases gradually as solidification proceeds but HunteLu model.
abruptly upon the formation of the secondary b phase. As 4. Microsegregation was investigated experimentally and
shown in the same figure, the concentration profiles were was calculated using the Scheil model. Significant discrep-
also calculated by the Scheil model. It is noted that the con- ancies between the calculated and experimental results
centration profile of Al at high growth rate is closer to the were observed as anticipated since back diffusion was
Scheil model. Fig. 7(b) shows appreciable discrepancies be- not taken into consideration in the Scheil model. With in-
tween calculated and experimental results, which indicates creasing growth rate, the experimental data approached the
that the Scheil model is not adequate to describe the microse- Scheil model as also anticipated.
gregation in the Mge4Al binary alloy. This is not surprising
since the Scheil model does not consider back diffusion of
Al in the solid a(Mg) phase. A satisfactory thermodyna-
Acknowledgements
micekinetic model is not yet available for predicting microse-
gregation of Al in a(Mg) due to the lack of diffusivity data.
The authors acknowledge the support of NSF FRG Grant
No. DMR-0309468 and Wisconsin Distinguished Professor-
4. Conclusions ship for financial support and Profs. T.M. Pollock and J.W.
Jones of the University of Michigan for their helpful
1. The solidification microstructure of the Mge4Al binary comments.
alloy was characterized using directional solidification.
At the solideliquid interface and in the mushy zone, the
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