Materials Science and Engineering A278 (2000) 66 76

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Effects of rare earths on the microstructure, properties and

fracture behavior of MgAl alloys
Yizhen Lu *, Qudong Wang, Xiaoqin Zeng, Wenjiang Ding, Chunquan Zhai,
Yanping Zhu
College of Materials Science and Engineering, Institute of Foundary Engineering, Shanghai Jiao Tong Uni6ersity,
Shanghai 200030, Peoples Republic of China
Received 20 May 1999; received in revised form 23 August 1999

Abstract
AZ91xRE and Mg6AlxRE magnesium alloys were studied, where x is 0, 1, 2 and 3% (in weight percent, wt.%),
respectively. Influence of rear earths (RE) on the microstructure was investigated. Fine morphology could be achieved by high
cooling rate. By casting fluidity spiral specimens, fluidities of the alloys were achieved. The hardness and microhardness of the
alloys was tested. RE improved fluidity and hardness. By casting specimens in permanent mold, tensile properties of the alloys
with different RE additions at ambient and elevated temperatures were studied. RE had little effect on ambient temperature tensile
strength of AZ91 alloy but greatly improved that of Mg 6Al alloy and high temperature tensile properties of both alloys. The
fracture behavior of the alloys, which was changed by RE and high temperature, was examined by scanning electron microscopy
(SEM) and optical microscopy. Fracture of the alloys is predominantly brittle cleavage or/and quasi-cleavage failure. 2000
Elsevier Science S.A. All rights reserved.
Keywords: Mg Al alloy; Rare earths (RE); Microstructure; Mechanical properties; Fracture

1. Introduction
As the lightest structural alloys, magnesium alloys
offer good combination of mechanical properties, corrosion resistance and castability [1]. In recent years,
research and development of magnesium alloys have
been greatly promoted by the lightweight requirement
in the automotive industry. However, commercial applications of magnesium alloys are limited because of
poor creep resistance and poor tensile properties at
elevated temperatures above 120C [2,3]. Rare earths
(REs) are important alloying elements to magnesium
alloys, which can improve casting characteristics, high
temperature properties and corrosion resistance [47]
without affecting the electrical conductivity of the base
alloys [2]. The Mg-rich side of most Mg-RE phase
diagrams is simple eutectic [8]. The commonly used
magnesium alloy systems containing rare earths are
* Corresponding author. Tel.: +86-21-6293-2549; fax: +86-216293-2548.
E-mail address: yzlv810@mail1.sjtu.edu.cn (Y. Lu)

MgZnREZr (ZE, EZ), MgAgREZr (QE),

MgYREZr (WE) and MgAlRE (AE) etc.
RE have been used in magnesium alloys for many
years, whereas the alloys of MgAlRE system have
been developed recently. Some investigations have been
done on the precipitation, morphology, structure, thermal stability and strengthening mechanisms of intermetallic phases when RE were added to MgAl alloys
[612]. RE were generally added to magnesium alloys
as misch metal (MM) because RE elements have the
similar behavior, but some studies were based on single
RE elements [9,13]. However, no systematic research
about the effects of RE on casting characteristics, ascast microstructure and mechanical properties has been
reported.
In the present work, AZ91 magnesium alloy, with its
aluminum content decreased or not, was adopted as the
master alloy and different RE additions were made.
Influences of RE on the microstructure, castability,
hardness, tensile properties at ambient and elevated
temperatures and fracture behavior were studied. The
mechanisms were analyzed.

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Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

67

Table 1
Chemical composition of misch metal (MM)
Element
Composition, wt.%

Ce
50.2

La
26.67

Nd
15.28

Pr
5.37

Fe
0.65

Si
0.01

Mg
0.38

Mn
0.11

Ca
0.01

P
0.003

Table 2
Chemical compositions of the studied alloys
Nominal alloy

AZ91
AZ911RE
AZ912RE
AZ913RE
Mg6Al
Mg6Al1RE
Mg6Al2RE
Mg6Al3RE

Composition, wt.%
Mg

Al

Zn

Mn

Ce

La

Nd*

Pr*

Total (RE)

Bulk
Bulk
Bulk
Bulk
Bulk
Bulk
Bulk
Bulk

8.12
7.41
7.28
7.42
5.52
5.59
5.07
5.28

0.923
0.828
0.823
0.872
0.509
0.634
0.496
0.584

0.142
0.174
0.150
0.168
0.113
0.115
0.132
0.120

0.483
0.944
1.45

0.469
1.01
1.77

0.258
0.505
0.802

0.245
0.558
0.901

0.146
0.288
0.447

0.142
0.318
0.530

0.0519
0.102
0.157

0.0499
0.112
0.186

0.939
1.84
2.86

0.907
2.03
3.39

* Contents of Nd and Pr were calculated according to the composition of misch metal (MM).

2. Experimental procedures

2.1. Experimental materials

AZ91 and Mg 6Al alloys were chosen as master
alloys. RE additions were made in the form of cerium
rich MM. Chemical compositions of MM and the
studied alloys are shown in Tables 1 and 2, respectively.
Mg6Al alloy was made from AZ91 and pure magnesium (99.95%). Only the contents of Ce and La were
measured.

formed in a SHIMADZU AG-100KNA material test

machine. The bars were fabricated to a gauge length of
50 mm and a gauge diameter of 10 mm for ambient
temperature tensile test and a gauge length of 25 mm
and a gauge diameter of 5 mm for elevated test. All the
tests were carried out at a strain rate of 1 mm min 1.
Three or four bars were tested for each alloy and
temperature and the average value was calculated. The
fracture surfaces were examined by scanning electron
microscope (PHLIIPS SEM515). Longitudinal sections
near the failure surfaces of the bars were examined by
optical microscopy. Samples for hardness (HBS2.5/

2.2. Experimental procedure

The master alloys were melted in a crucible electric
resistance furnace. RE of 1, 2 and 3wt.% were added
respectively when the temperature of the molten metal
was about 730C. Then the melt was held at 730C for
20 min to make sure that RE were completely dissolved. After that the melt was refined by JDMJ flux
(mainly chlorate) and was held at 730C for 30 min
before being adjusted to required temperature and cast.
The alloys were cast into resin-coated sand spiral
specimen moulds at pouring temperature of 750 9 3C
to study the fluidity, which was determined by the
length (mm) of spiral specimen. For each alloy average
value was achieved from two or three specimens. A step
specimen was cast for each alloy in a permanent mould
(Fig. 1) to investigate the microstructure and hardness
at different cooling rates. Test bars were cast in a
permanent mould (Fig. 2) at pouring and mould temperatures of 7309 3 and 200910C, respectively.
Tensile testing of the as-cast bars at ambient and
elevated (150C, short-time test) temperature was per-

Fig. 1. Step specimen mould (a) section for microstructure testing; (b)
section for hardness testing; (c) section for microhardness testing.

Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

68

Fig. 2. Test bar mould.

62.5/30) and microhardness (HV0.01) testing were cut

from step specimens (Fig. 1). Phases of the alloys were
analyzed by X-ray diffraction (XRD, RAX-10).

3. Results

3.1. Microstructure
Results of XRD analysis (Fig. 3) show the main

intermetallic in MgAlRE alloys were Mg17Al12 (bphase) and Al11RE3. The later may be Al4RE [11,14]
because Al4RE and Al11RE3 have similar peak values.
Only the peaks of AlCe and AlLa are clear. In
Mg6Al3RE alloy, one peak is different from
AZ913RE alloy. Through careful analysis, it was
determined that this may be an oxide CeAlO3
(Fig. 3).
Fig. 4 shows the microstructure of the AZ91xRE
alloys. As can be seen in the pictures, lower cooling
rate (thick section) leads to coarse grains and
precipitates. The morphology of AZ91 alloy is composed of a-Mg matrix and irregular b-precipitation
along grain boundaries (Fig. 4(a)), especially in thick
section with lower cooling rate. After REs were
added, a rod-like intermetallic phase Al11RE3
phase was observed and the volume of b-phase was
somewhat decreased (Fig. 4(cf)). More RE addition
caused further decreasing of the b-phase and coarsening of Al11RE3 because more aluminum atoms were
consumed by the formation of Al11RE3 phase. In
AZ912RE alloy, b-phase turned into fine particles
and the eutectic morphology was well developed (Fig.
4(e, f)).
Fig. 5 is the microstructure of Mg6AlxRE alloys. The reduction of aluminum was accompanied by
greatly decreasing of b-phase in all the alloys and no
coarse b-phase was observed any more, especially after REs were added. In Mg6Al3RE alloy where
REs were increased up to 3%, b-phase can hardly be
seen and clusters of Al11RE3 phase are distributed on
the matrix (Fig. 5). Again, higher cooling rate means
relatively finer morphology.

Fig. 3. X-ray diffraction (XRD) analysis result of Mg6Al 3RE (a) and AZ91 3RE (b),
, Mg; , Al11Ce3; ", Al11La3; , Mg17Al12; ,
CeAlO3.

Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

69

Fig. 4. Microstructure of AZ91xRE alloys: (a, c, e) thin section for AZ91, AZ91 1RE and AZ91 2RE; (b, d, f) thick section for AZ91,
AZ91 1RE and AZ912RE.

3.2. Effects of RE on properties

3.2.1. Fluidity
Fig. 6 shows the fluidity of the alloys. For AZ91
xRE alloys, with the increasing of RE additions, fluidity decreases at the beginning and then increases. With
RE addition of 3wt.%, the fluidity length is longer than

AZ91 alloy, which tends to go on increasing with

further RE additions. Fluidity of Mg6AlxRE alloys
is far less than that of AZ91xRE alloys all the time,
which is attributed to the decreasing of aluminum. For
Mg6AlxRE alloys, fluidity increased successively
with a rise in RE contents. From Mg6Al2RE alloy
to Mg6Al3RE alloy, the curve becomes flat.

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Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

3.2.2. Hardness
Hardness of the alloys is shown in Fig. 7. For
Mg6AlxRE alloys, decreasing of aluminum caused
the reduction of b-phase and solid solution of aluminum in the matrix. This leads to the greatly decreasing of the hardness, which is far less than that of
AZ91xRE alloys. For both AZ91 xRE and Mg
6AlxRE, alloys with more RE contents have higher
hardness. However, influences of REs on Mg6Al

xRE alloys are more effective. Hardness of all the

alloys increases with the increasing of cooling rate.
Fig. 8 shows the microhardness of the alloys matrix.
Again microhardness of Mg6AlxRE alloys is lower
due to the smaller amount of aluminum. With increasing RE additions, microhardness of the matrix increases
due to solid solution strengthening. The microhardnesses of AZ912RE alloy and AZ913RE alloy have
very little difference.

Fig. 5. Microstructure of the alloys: (a, c, e) thin section for Mg 6Al, Mg 6Al 1RE and Mg 6Al 2RE; (b, d, f) thick section for Mg6Al,
Mg 6Al 1RE and Mg6Al3RE.

Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

Fig. 6. The fluidity of the alloys.

Fig. 7. Hardness of the alloys.

Fig. 8. Microhardness of the matrix.

3.2.3. Tensile properties at ambient temperature

Fig. 9 shows the tensile properties of the alloys
tested at ambient temperature. Compared to AZ91
alloy, ultimate tensile strength (sb) of the alloys with

71

rare earth additions has little difference and the yield

strength (s0.2) somewhat increases (Fig. 9(a)). AZ91
2RE alloy has the highest elongation, which decreases
with an increase in RE content. Elongation of AZ91
3RE is lower than that of AZ91, which is ascribed to
the coarsening of Al11RE3 phase.
As can be seen in Fig. 9(b), Mg6AlxRE alloys
have better tensile properties than AZ91xRE alloys.
Ultimate strength of Mg6Al1RE is the highest,
which gradually decreased with further increasing of
RE contents. Ultimate strength of Mg6Al3RE is
approximate to that of AZ91. Because of the precipitation of Al11RE3 phase, yield strength is higher after
REs were added. Mg6Al1RE has the highest elongation, whereas elongations of Mg6Al 2RE and
Mg6Al3RE are lower than Mg6Al. Yield
strength and elongation have the same changing
rules as ultimate strength with the change of RE content.

3.2.4. High temperature tensile properties at 150 C

Fig. 10 gives the high temperature tensile. Results
of the alloys with or without rare earth additions at
150C. As can be seen in Fig. 10, RE greatly improve
the high temperature tensile strength and elongation.
Ultimate tensile strengths of some alloys are even
close to the ultimate strength tested at ambient temperature. Yield strengths of the alloys are all lower
than those tested at ambient temperature.
For AZ91xRE alloys, the AZ912RE alloy has
the highest ultimate tensile strength and elongation
but relatively lower yield strength (Fig. 10(a)). AZ91
1RE has the highest yield strength. Elongations of the
alloys have the same rule as ultimate strengths.
High temperature tensile properties of Mg6Al
xRE alloys, which are a little lower than AZ91xRE
alloys, are relatively complicated (Fig. 10(b)). Mg
6Al2RE has the highest ultimate strength and Mg
6Al3RE has the highest yield strength. After REs
were added, elongation of the alloys decreased following the increasing of RE contents and elongation of
Mg6Al3RE is lower than that of Mg6Al.

Fig. 9. Tensile properties of the alloys at ambient temperature: (a) AZ91 xRE (b) Mg 6Al xRE.

Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

72

Fig. 10. Tensile properties of the alloys at 150C: (a) AZ91 xRE (b) Mg 6Al xRE.

3.3. Fractography of the alloys

3.3.1. SEM result
Fig. 11 shows SEM images of the tensile fracture
surface.
Fig. 11(a) is the image of AZ91 alloy at ambient
temperature, which has a secondary crack in the middle. The failure surface is composed of small cleavage
planes and steps formed by secondary cleavage and a
lot of secondary cracks could be observed. On some
planes, cleavage rivers consisting of steps can be seen.
The tensile fracture surface of AZ91 alloy tested at
ambient temperature assumes the characteristic of
cleavage fracture.
Fig. 11(b) shows the fractograph of the AZ911RE
alloy. Local areas of Fig. 11(b) assume the characteristic of quasi-cleavage and cleavage rivers can still be
found on some small planes.
Fig. 11(c) shows the morphologies of high temperature tensile fracture surface of AZ91 2RE alloy tested
at 150C. High temperature changed the fracture pattern. Compared with Fig. 11(b), Fig. 11(c) has more
characters of quasi-cleavage and less cleavage planes.
Steps were not formed through cleavage but tearing. It
is somewhat like gliding fracture but the failure is
brittle.
After aluminum was decreased, tensile fractures of
Mg6AlxRE alloys are a little random, which may be
the effect of the morphology change and volume reduction of b-phase. In the ambient temperature tensile
fracture of Mg6Al alloy, seldom regular plane can be
seen, but character of cleavage is still clear (Fig. 11(d)).
Additions of RE increased the cleavage steps in the
fracture surface (Fig. 11(e)). On testing at elevated
temperature (150C), more steps formed through tearing as can be seen in the fracture of Mg 6Al2RE
alloy and there are characters similar to quasi-cleavage
in local areas (Fig. 11(f)). However, the characters are
not as clear as the fracture of AZ91 2RE alloy tested
at 150C. Cleavage planes can still be seen.

3.3.2. Optical microscopy result

Compared with Fig. 11(a), Fig. 11(b) has less regular
cleavage planes and steps and less secondary cracks but
more micro-voids. This is consistent with the optical
microscopy result of the longitudinal section near the
failure surface (Fig. 12).
As shown in Fig. 12(a), in the failure of AZ91 alloy,
microcracks formed in the b/Mg interface and grain
boundaries and finally converged into long crack rivers. After REs were added (Fig. 12(b)), formation of
Al11RE3 effectively impeded the growth of microcracks
and the cracks tend to develop locally.
In the longitudinal section near the fracture surface
of Mg6Al alloy (Fig. 13), tiny cracks like fine hair can
be seen along the grain boundaries and b/Mg interface.
Then these fine-hair-line microcracks form larger voids
and finally lead to failure. This may explain the irregular morphologies of Mg6AlxRE alloys.

4. Discussion

4.1. Microstructure
Except for Al11RE3 precipitation, no other RE containing intermetallic was observed in the experiment.
According to Wei and Dunlop [9,12], because of the
high chemical stability of Al11RE3, RE are combined
with Al and form Al11RE3 until all the available RE
were used without any formation of pseudobinary Mg
RE phase or pseudoternary MgAlRE phase.
RE additions to MgAl alloys lead to the decrease of
volume and size of b(Mg17Al12) phase as a result of the
precipitation of Al11RE3. Formation temperature of
Al11RE3 is about 150C higher than Mg17Al12 phase
[12], which, along with the high stability of Al11RE3,
means the formation of Al11RE3 precedes that of bphase.
Higher cooling rate means finer grains and precipitates and morphology coarsens under lower cooling

Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

rate. It is because of this that Mg Al RE alloys are

just suitable for die-casting.

4.2. Fluidity
The fluidity of Mg Al RE alloys was greatly influenced by aluminum and RE. Aluminum can improve
the fluidity of magnesium alloys [15,16]. Influence of
RE on fluidity of magnesium alloys is more complicated, which was concluded as following:
(1) RE reduce the freezing range of magnesium alloys, which benefits fluidity.

73

(2) Al11RE3 has high latent heat [12]. Following the

formation of Al11RE3, much heat is given out, which
slows down temperature decreasing and prolongs the
fluidity time.
However, (3) RE have a high susceptibility to oxidation and reaction with fluxes [6,17,18], so inclusions in
the molten melt are increased and fluidity resistance
increases, which is disadvantageous to fluidity and
properties.
For AZ91xRE alloys, the negative facts play the
leading role until 3% RE content was achieved. In
AZ913RE alloy, the negative facts became negligible
and the positive facts took the place (Fig. 6).

Fig. 11. Fracture surface (scanning electron microscopy, SEM) of the alloys, (a) AZ91, tested at ambient temperature; (b) AZ91 1RE, tested at
ambient temperature; (c) AZ912RE, tested at 150C; (d) Mg 6Al, tested at ambient temperature; (e) Mg 6Al 1RE, tested at ambient
temperature; (f) Mg 6Al2RE, tested at 150C.

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Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

Fig. 12. Morphology of longitudinal section near the failure surface for (a) AZ91 and (b) AZ91 1RE. Right side is the fracture surface.

For Mg6Al xRE alloys, the improvement effects

were more important all the time, which may be related
to the reduction of aluminum.

4.3. Strengthening mechanism

Solid solubility of RE in magnesium is low (Table 3,
[19]), which is further reduced by the presence of Al [3].
In AZ91xRE alloys, when RE were increased to a
certain content in magnesium alloys, solid solution of
RE in matrix was saturated. Further additions would
only cause coarsening and volume increase of Al11RE3
phase without any further RE solution, which can also
be seen in the microstructure (Fig. 4). In Mg 6AlxRE
alloys, decreasing of aluminum offered more chances
for RE to dissolve into the matrix, which led to successively increasing of microhardness (Fig. 8). But even the
microhardness of Mg 6Al 3RE alloy is lower than
that of AZ91 alloy, which indicated that the solid
solution of aluminum is more important for
microhardness.
In AZ91 alloy, the main strengthening phase is
Mg17Al12, which has a low melting point of approximately 462C and poor thermal stability. Mg17Al12
phase can readily coarsen and soften at the temperatures exceeding 120 130C [5,6]. In addition, Mg17Al12
has a cubic crystal structure incoherent with the h.c.p.
magnesium matrix, which leads to the fragility of Mg/
Mg17Al12 interface. All of the above lead to the poor
high temperature tensile properties of AZ91 and Mg
6Al alloys at 150C (Fig. 10).
Additions of RE to AZ91 formed Al11RE3 precipitation in the alloy. Melting points of typical precipitates
in the alloys studied are shown in Table 4 [11].
Al11RE3 have much high melting points, which,
along with the low diffusion speed of RE elements in
magnesium at elevated temperatures, makes Al11RE3
have high thermal stability. Al11RE3 phase could re-

main stability in heat treatments at 500C [9]. So sliding

of grain boundaries and growth of cracks were effectively prevented at elevated temperatures and high temperature properties were improved. This may have
more effective influence on high temperature creep
properties of the alloys, which is undergoing in the
laboratory.
According to Nair et al., cerium rich MM had little
effects on the ambient temperature tensile properties of
magnesium alloys in as-cast condition [2], which is
agreement with Fig. 9. The precipitation of Al11RE3

Fig. 13. Morphology of longitudinal section near the failure surface

for Mg 6Al. Right side is fracture surface.
Table 3
Solid solubility of alloying elements in magnesium
Alloying element

Matrix solubility, at.%

Al
Zn
Nd
Pr

11.8
3.3
0.1
0.09

Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

75

Table 4
Melting points of the main precipitates in the alloys
Precipitates

Mg17Al12

Al11La3

Al11Nd3

Al11Ce3

Al11Pr3

Melting point, C

462

1240

1235

1235

1240

Fig. 14. Formation of steps through (a) secondary cleavage and (b) tearing.

Fig. 15. Schematic of quasi-cleavage fracture.

phase impeded the formation and incipient growth of

the cracks, which improved the yield strength (Fig.
9(a)). The changing of elongation with RE content
always has the same rule with the change of ultimate
tensile strength.

4.4. Fracture
With a h.c.p. structure, failure of magnesium alloys is
usually brittle through cleavage or quasi-cleavage fracture. In cleavage fracture, micro-cracks develop along
certain crystal planes, which is (0001) for magnesium.
Two parallel cracks with relatively high differential
altitude can form steps through the pattern of secondary cleavage or tearing (Fig. 14). During the growth
of cracks, the two patterns are interchangeable. RE
additions changed the formation of the steps from
secondary cleavage to tearing.
In quasi-cleavage fracture, cracks came into being in
local areas, grew locally and finally formed morphologies of pits. The fracture procedure is shown in Fig. 15
schematically [20]. It is also a kind of brittle fracture
but different from cleavage. It is a rather complicated
fracture pattern. The planes on the fracture surface
were not coherent with certain crystal orientation but

formed through combination of locally formed microcracks. During the combination, tearing ridges were
formed. The bottoms of the pits are not strict cleavage
planes but consist of several somewhat sunken planes
with secondary cracks (Fig. 16). Both RE additions and
elevated temperature make the failures of the alloys
tend to be quasi-cleavage, especially for AZ91xRE
alloys.

Fig. 16. Quasi-cleavage: local magnification of Fig. 11(c) (AZ91

2RE, 150C).

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Y. Lu et al. / Materials Science and Engineering A278 (2000) 6676

5. Conclusions

References

(1) With additions of RE, rod-like Al11RE3 precipitate phase was observed with gradually reduced and
refined Mg17Al12. Higher cooling rate leads to finer
morphology.
(2) Generally speaking, RE increases fluidity of Mg
Al alloys. But for AZ91 alloy, increasing of RE is
accompanied by firstly decreasing and subsequently
increasing of fluidity.
(3) RE improved hardness and microhardness.
Higher cooling rate means higher hardness.
(4) RE had little effect on the ultimate tensile
strength of AZ91 alloy tested at ambient temperature,
but greatly increased that of Mg 6Al alloy. RE greatly
improved high temperature tensile strength and elongation of AZ91 and Mg 6Al alloys tested at 150C. Yield
strength increased after RE was added. Too much RE
additions can cause the coarsening of Al11RE3 and have
little benefit for mechanical properties. Content of RE
of 1 or 2% is acceptable for reasonable mechanical
properties.
(5) The tensile failures of AZ91 and Mg 6Al alloys
tested at ambient temperature are cleavage fracture.
Elevated temperature and RE additions both made the
failure of the alloys to be quasi-cleavage fracture.

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