Research Summary High-Temperature Magnesium

Creep Resistant Mg-Al-Ca Alloys:

Computational Thermodynamics and
Experimental Investigation
Koray Ozturk, Yu Zhong, Alan A. Luo, and Zi-Kui Liu

The thermodynamic properties of the development. The emerging concept of by combining the data of the three binary
ternary Mg-Al-Ca system are investigated system materials design provides such systems assuming no ternary solubility
in this article, based on the Al-Ca, opportunities.6 In the system materials in the all binary compounds due to the
Al-Mg, and Ca-Mg binary systems. The design, the essential component is the lack of experimental data. No ternary
equilibrium phases in the Mg-Al-Ca computational thermodynamics, often interactions were introduced either.
alloys studied are the primary magnesium referred to as Calculation of Phase Figures 2–6 show five isothermal
matrix and C15-Al2Ca, as indicated by the Diagrams, or CALPHAD. sections of the magnesium-rich corner
calculated ternary phase diagrams. The Recently, research has been conducted of the ternary Mg-Al-Ca phase diagram
experimental results are in good agreement on Mg-Al-Ca-based alloys with or at room temperature (298 K), 563
with the thermodynamic calculations without additional alloying elements.7–14 K, 643 K, 673 K, and 773 K, based
using Thermo-Calc software. The addition of calcium to Mg-Al-based on the thermodynamic calculations
alloys improved the high-temperature using ThermoCalc software. The 298
INTRODUCTION
properties, such as creep resistance.15 K section (Figure 2) suggests that
Magnesium is the eighth most abundant However, few studies have been done both GM-B and GM-C alloys fall
element in the Earth’s crust and the on the thermodynamics and phase into the three-phase region (α-Mg +
third most plentiful element dissolved relationships in this alloy system.15–18 In C15-Al2Ca + γ-AlMg) for equilibrium
in seawater.1 It is the lightest structural the described work, the phase equilibria microstructure at room temperature. As
metal, with a density of 1.741 g/cm3, of two Mg-Al-Ca alloys were compared the temperature increases, the (α-Mg +
in comparison with the densities of with the thermodynamic calculations C15-Al2Ca) region widens significantly
aluminum (2.70 g/cm3) and iron (7.86 based on the CALPHAD approach19 and (Figures 3 and 4), and the face-centered
g/cm3). This makes magnesium alloys the Thermo-Calc software.20 cubic (fcc) C15-Al2Ca is supposed to
particularly attractive for weight reduction be the stable phase at both 563 K and
CALCULATED PHASE
and higher fuel efficiency transportation 643 K. However, note that the GM-C
DIAGRAMS
applications.2–4 The world consumption alloy is located near the border of the
of magnesium alloys in the automobile Figure 1 shows the calculated phase region where the hexagonal C14-Mg2Ca
industry has experienced a 15% annual diagrams of the three binary systems. becomes an equilibrium phase.
increase over the last decade.5 Thus, The thermodynamic description of the The calculated isothermals (Figures
there is an urgent need for efficient alloy Mg-Al-Ca ternary system was obtained 3, 4, and 6) were also compared to the

a b c
Figure 1. The calculated phase diagrams of the (a) Al-Ca, (b) Al-Mg, and (c) Ca-Mg binary systems.

40 JOM • November 2003

 Catterall et al. (1957)
HCP_A3 + Al2Ca
HCP_A3 + Mg2Ca
HCP_A3 + Al2Ca+Mg2Ca
HCP_A3 + Al2Ca+Mg17Al17
Present Study
HCP_A3 + Al2Ca
T=563K

Figure 2. A calculated isothermal section at 298 K Figure 3. A calculated isothermal section at 563 K and the
showing the alloy composition. experimental data by Catterall et al.16 and by this study.

experimental results of Catterall et al.16 Al2Ca, C14-Mg2Ca, Al3Ca8, Al14Ca13, alloy. No distinct peaks of the fcc C15-
on Mg-Al-Ca alloys. The agreement is Al 4Ca, AlMg-γ, and AlMg-β. The Al2Ca phase were detected. Instead, the
good except for the extent of the α-Mg liquidus surface is dominated by the XRD analysis showed some unknown
phase field at 643 K (Figure 4). The C15-Al2Ca phase extensively and by the peaks, of which two approximately
calculation predicted less calcium in C14-Mg2Ca phase to some extent. These matched the hexagonal C14-Mg2Ca
the α-Mg phase than the measured are the highest melting point compounds phase. A similar XRD pattern was also
values. This inconsistency may be due with relatively high stabilities in this obtained for the GM-B alloy. Replicas of
to experimental errors such as calcium ternary system. the as-cast GM-C sample were prepared
loss during the alloy preparation.16 A by overetching, which dissolves the
AS-CAST
comparison with the investigation of matrix phase and the eutectic magnesium
MICROSTRUCTURE
Ninomiya et al.17 is shown in Figure 5. but leaves the intermetallic phase on the
The calculated phase boundary between Both GM-B and GM-C have similar adhesive carbon tapes. Figure 10 shows
the two-phase (hcp + C15-Al2Ca) and microstructures; Figure 8 shows optical both the scanning-electron microscopy
three-phase (hcp + C15-Al2Ca + C14- micrographs of GM-C alloy samples (SEM) image of the hollow lamellae
Mg2Ca) regions is in agreement with the under different conditions. The primary and the energy-dispersive spectroscopy
experimental data points by Ninomiya α-Mg grains are surrounded by the (EDS) microanalysis results at differ-
et al.17 interconnected network of the grain ent spots. The EDS spectrum shows
The predicted liquidus projection of boundary phase in the as-cast condition. distinctive peaks from magnesium,
the Mg-Al-Ca system is presented in This phase, which forms during the aluminum, and calcium, indicating the
Figure 7 with respect to the composition eutectic solidification process, has a possible formation of a ternary Mg-
triangle. The liquidus surface is divided lamella-type morphology (Figure 8a). Al-Ca phase since the matrix effect is
into 11 primary crystallization fields: Figure 9 is the x-ray diffraction eliminated from the analysis.
Ca(fcc), Ca(bcc), Mg(hcp), Al(fcc), C15- (XRD) pattern for the as-cast GM-C A detailed XRD and transmission

Catterall et al. (1957)

HCP_A3
HCP_A3 + Al2Ca
HCP_A3 + Mg2Ca
HCP_A3 + Al2Ca+Mg2Ca
Present Study
HCP_A3 + Al2Ca
T=563K

Figure 4. A calculated isothermal section at 643 K and the Figure 5. A calculated isothermal section at 673 K showing
experimental data by Catterall et al.16 and by this study. the experimental data by Ninomiya et al.17

2003 November • JOM 41

 EXPERIMENTAL PROCEDURES cooling rates of die casting (on the order
of 100 K/s) can produce microstructures
Calculation of Phase Diagrams, which has been under development since the early 1970s, 21

was used to develop a thermodynamic description of the Mg-Al-Ca system. different from those expected in the
The thermodynamic descriptions of the pure magnesium, aluminum, and calcium elements equilibrium solidification conditions.26
are taken from the SGTE database.22 In the Mg-Al-Ca ternary systems, there are three Also, the GM-C alloy is closely located
binary systems: Al-Ca, Al-Mg, and Ca-Mg. The thermodynamic descriptions of Al-Mg23,24 near the borderline of the three-phase
are available in the literature, Ca-Mg is modified from the work of Agarwal et al,25 and the
Al-Ca system was studied in the present work. region where the hexagonal C14-Mg2Ca
Two alloys, Mg-4.5Al-1.9Ca (GM-B) and Mg-4.5Al-3.0Ca (GM-C) (all in weight percent is an equilibrium phase.
unless otherwise specified), were made by die casting at Lexington Die Casting, Lakewood,
NY. The melt temperature was controlled at around 950 K with the die surface temperature MICROSTRUCTURE OF
maintained at 623 K. The chemical analysis using inductively coupled plasma/atomic HEAT-TREATED SAMPLES
emission spectroscopy techniques was performed with the following results. For the
GM-B alloy, the chemical composition was (in weight percent) Mg-4.5Al-1.9Ca-0.27Mn- Figure 8 shows the network morphol-
0.003Fe-<0.002Ni-0.002Cu. For GM-C the composition was Mg-4.5Al-3.0Ca-0.27Mn- ogy of the ternary grain boundary phase
0.003Fe-<0.002Ni-0.003Cu. in the as-cast microstructure (Figure 8a)
Three types of samples were prepared for each alloy: as-cast, heat treated at 560 K, and during heat treatment. After exposure at
heat treated at 643 K. The alloys were sealed under an inert atmosphere during the heat
treatment for one week. At the end of the heat treatments, the samples were quenched 563 K for one week, the network is less
into water to retain the equilibrium structure. Microstructural observations were made complete and the lamellas decompose
using optical (Olympus BX60M) and scanning electron microscopes (Hitachi S-3500N and and become spherical (Figure 8b).
Philips XL20). Each sample was first cut from the as-cast and the quenched alloys using a This effect is more pronounced when
regular lab-scale diamond saw. The samples were then polished and etched using 4 vol.%
Nital solution (HNO3 in ethanol). For optical microscopy purposes, etching was performed
the temperature is increased to 643 K
only by applying the etchant on the surface for a short period of time (~10 s). This is because (Figure 8c). A similar phenomenon was
of the severe selective etching nature of these alloys. Primary magnesium grains dissolve very also observed by Liu et al.18
quickly on contact with the etchant as compared to the secondary phase. The XRD results for both GM-B and
The selective etching nature of the samples was utilized during the phase identifications GM-C alloys confirmed the formation
by x-ray diffraction (Scintag PadV) and qualitative chemical analysis by energy-dispersive
spectroscopy (EDS). The prolonged etching (~20 s) was performed by dipping the samples of the fcc C15-Al2Ca phase after the
in the etchant to increase the surface area of the intermetallic precipitates and its intensity one-week heat treatments at 563 K and
on the x-ray spectrum. Chemical mapping and spot analysis were also performed using 643 K, in agreement with the calculated
EDS. Both the bulk sample surfaces and their replicas were checked and compared with phase diagram shown in Figures 3 and 4.
each other. Replicas were prepared from the etched samples by placing an adhesive carbon
tape on their surface and detaching the tape from the samples. Figure 11 shows the EDS microanalysis
results of the small particles in the bulk
electron microscopy (TEM) investiga- the crystal structure of the (Mg, Al)2Ca alloys samples, where the magnesium
tion by Luo et al. on this lamellae-type phase is not verified in this study. peak is from the surrounding matrix
grain boundary phase15 suggested that The experimental results do not agree because of electron beam spreading.
the intermetallic phase was a ternary with the calculated equilibrium phase In the replica sample where the matrix
solid solution phase in the hexagonal diagram in Figure 2. Instead of the fcc interference is eliminated, the pre-
C14-Mg2Ca structure. It was represented C15-Al2Ca and γ-AlMg equilibrium cipitates in the heat-treated samples
by the chemical formula of (Mg, Al)2Ca, phases as suggested by the phase contained only aluminum and calcium
where some of the magnesium atoms diagram, a hexagonal ternary (Mg, (Figure 12). In addition, a quantitative
are replaced by aluminum atoms in the Al)2Ca lamellae structure is formed in analysis of the particles was performed
crystal lattice. This is in agreement the die-casting microstructure of the on the replica, showing the aluminum-
with the present EDS study although GM-C alloy. It is not unusual that the fast to-calcium ratio at about 2:1. This result
is a strong support of the XRD analysis
Catterall et al. (1957) for the existence of the fcc C15-Al2Ca
hcp (A3)
phase in the heat-treated samples.
hcp (A3) + Al2Ca
hcp (A3) + Mg2Ca IMPLICATIONS ON CREEP
hcp (A3) + Al2Ca+Mg2Ca RESISTANCE
The fact that the Mg-Al-Ca ternary
phase in the as-cast microstructure
decomposes into fcc C15-Al2Ca after
long-term exposures at 563 K or 643 K
does not necessarily suggest instability
of this ternary phase in the operating
temperatures of automotive powertrains
Figure 6. A calculated isothermal (< 523 K). In fact, the metallurgical
section at 723 K showing the
experimental data by Catterall stability of the ternary (Mg, Al)2Ca
et al.16 phase and its interfacial coherency with
the magnesium matrix were reported
to be responsible for the improved

42 JOM • November 2003

 a

Figure 7. The liquidus projection of the Mg-Al-Ca ternary system with

isotherms (dotted lines).

creep resistance of Mg-Al-Ca alloys at K.14,27 Thermally stable phases present

c
temperatures up to 473 K.15 On the other at the grain boundary provide effective 20 µm
hand, Mg-Al-Ca alloys containing fcc pinning to resist grain boundary sliding, Figure 8. Optical micrographs of the
C15-Al2Ca in the die-cast microstructure hence, the improved creep resistance. GM-C alloy samples (a) as-cast, (b) heat
also demonstrated good creep resistance However, further research is needed treated at 563 K for one week, and (c) heat
treated at 643 K for one week.
and tensile strength up to 423 K,11 on the transformation kinetics of (Mg,
indicating that the fcc C15-Al2Ca can Al)2Ca to fcc C15-Al2Ca at the operating tion of the fcc C15-Al2Ca phase during
provide significant strengthening in the temperatures of automotive powertrains solidification. Because the formation of
grain boundaries. The thermal stability and their effects on creep. the γ phase is detrimental to the creep
of both (Mg, Al)2Ca and fcc C15-Al2Ca The liquidus projection of the Mg- strength at elevated temperatures, it
intermetallic phases can be inferred Al-Ca ternary system (Figure 7) is is important to completely remove the
from their high melting points and the presented as a starting point for future γ phase from the magnesium-based
eutectic temperatures. Mg2Ca has a experimental verification and refine- Mg-Al-Ca alloys for high-temperature
eutectic temperature of 718 K and a ment. It is noteworthy from the calcula- applications. It is calculated from the
melting temperature of 988 K, while tions that the addition of calcium to “L = hcp + Al2Ca” reaction that the
Al2Ca has a eutectic temperature of 973 liquid Mg-Al alloys in very small phase formation is avoided if the ratio
K and a melting temperature of 1,352 amounts (e.g., 1 mol.%) causes forma- of Al/Ca is less than ~2.1.

Figure 9. An X-ray
diffraction pattern of
the as-cast GM-C
alloy showing the (Mg,
Al)2Ca phase based
on the hexagonal C14-
Mg2Ca structure.

2003 November • JOM 43

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and General Motors Corporation for
ACKNOWLEDGEMENTS
permission to publish this paper.
This work is supported by the U.S. Koray Ozturk, Yu Zhong, and Zi-Kui Liu are
National Science Foundation CAREER References with the Department of Materials Science and
Award under the grant DMR-9983532. Engineering at Pennsylvania State University.
1. D. Kramer, U.S. Geological Survey—Minerals Alan A. Luo is a staff research engineer at General
The software program used for all Motors Research and Development Center.
Information (Washington, D.C.: USGS, 1997).
calculations is licensed from the Founda- 2. G. Craig, Use of WE-43A-T6 Magnesium in the MD600
tion for Computational Thermodynam- Helicopter Drive System (Coronado, CA: International For more information, contact A.A. Luo, General
ics, Stockholm, Sweden. The authors Magnesium Association, 1998), pp. 19–23. Motors Research and Development Center, Materials
3. H. Friedrich and S. Schumann, The Use of Magnesium and Processes Lab, 30500 Mound Road, Warren,
also acknowledge Anil Sachdev and Bob in Cars—Today and in the Future (Coronado, CA: Michigan 48090-9055; (586) 986-8303; fax (586)
Powell for reviewing the manuscript International Magnesium Association, 1998), pp. 986-9204; e-mail alan.luo@gm.com

44 JOM • November 2003