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Thermodynamic database of the phase diagrams in the Mg-Al-Zn-Y-Ce system

LIU Xingjun'), WANG Cuiping", WEN Mingzhong'), CHEN Xing", and PAN Fusheng"
1 ) Department of Materials Science and Engineering, Xiamen University, Xianien 361005, China

2) College of Materials Science and Engineering,Chongqing University, Chongqing 400045, China

(Received 2006-06-25)

Abstract: The Mg-Al-Zn-Y-Ce system is one of the key systems for designing high-strength Mg alloys. The purpose of the present article is to develop a thermodynamic database for the Mg-Al-Zn-Y-Ce multicomponent system to design Mg alloys using the calculation of phase diagrams (CALPHAD) method, where the Gibbs energies of solution phases such as liquid, fcc, bcc, and hcp phases were described by the subregular solution model, whereas those of all the compounds were described by the sublattice model. The thermodynamic parameters describing Gibbs energies of the different phases in this database were evaluated by fitting the experimental data for phase equilibria and thermodynamic properties. On the basis of this database, a lot of information concerning stable and metastable phase equilibria of isothermal and vertical sections, molar fractions of constituent phases, the liquidus projection, etc., can be predicted. This database is expected to play an important role in the design of Mg alloys.
Key words: thermodynamic database; CALPHAD method; phase diagram; Mg-Al-Zn-Y-Ce system; magnesium alloys

[This study was financially supported by the National Natural Science Foundation of China and Chongqing Science and Technology Commission.]

1. Introduction
Magnesium alloys are potential candidates for structural, automotive, and aerospace applications owing to their lowest density and remarkably high specific strength [l-31. Rare-earth elements Y and Ce are added to Mg alloys to improve the high temperature strength, creep resistance, and heat resistance by precipitation hardness [4]. The material design is necessary because the precipitation sequence is almost always complex in multicomponent magnesium alloys. The calculation of phase diagrams (CALPHAD) method is a powerful tool for designing materials because it helps not only to calculate the phase equilbria in multicomponent systems but also to simulate the phase consistency and solidification process of individual alloys [5]. The CALPHAD method provides a clear guideline for such selections
Correspondingauthor: LIU Xingjun

and helps to avoid long-term experiments. Thus, it could be a powerful tool that would help reduce cost and save time during the development of Mg alloys. The purpose of the present article is to construct a thermodynamic database of the phase equilibria of the Mg-Al-Zn-Y-Ce system on the basis of the CALPHAD method.

2. Thermodynamic models
The Gibbs energies of the liquid, fcc, bcc, hcp, and other solid-solution phases are described by the subregular solution model using the Redlich-Kister formula [6]. For instance, the Gibbs energy of a phase in an A-B-C ternary system is expressed as
G =

C
i=A,B C

O G ? X , + R T

C
c=A.B,C

x , I ~ x , + L ~ ~ x ~ x ~ +

(1) where "GI is the Gibbs energy of pure component i in the respective reference state, xiis the mole fracLtcxAxc

+ &xBxC + LkcxAxBxC

E-mail: lxj@xrnu,edu.cn

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tion of component i, and and the temperature and composition-dependent interaction energies in the binary and ternary systems, respectively. In the Mg-Al-Zn-Y-Ce system, there are many intermetallic compounds in the binary and ternary systems. Their Gibbs energies are described by the sublattice model [7]. The Gibbs energy of the pure component i, in its different phase states is obtained from the SGTE database [81. On the basis of the experimental information in some ternary systems, solubilities of the third elements in the intermetalliccompounds are considered in the present assessment.

3. Thermodynamic database
The present thermodynamic database contains the thermodynamic parameters for calculating the phase equilibria in binary and ternary alloys in the Mg-Al-Zn-Y-Ce system. The thermodynamic parameters for describing the Gibbs energy of each phase are evaluated by combining thermodynamic

models and the experimental data, including phase equilibria and thermodynamic properties. Regarding the present database, there are some important alloy systems for which there is little or no experimental data. Experimental studies to determine phase equilibria were carried out to obtain a better estimation of the thermodynamic parameters, with good agreement between the calculated and experimental data. The thermodynamic parameters were evaluated by Thermo-Calc software, which was originally developed by Sundman et al. [5].The information on the thermodynamic assessments and experiments in the binary and ternary systems is summarized in Tables 1 and2. The present thermodynamic database can provide a lot of information such as stable and metastable phase equilibria, phase fraction, and various thermodynamic quantities such as activity, mixing enthalpy, Gibbs energy of formation, driving forces for phase transformation, and simulation of solidification.

Table 1. Information on thermodynamic assessment i binary systems n

Table 2. Information on experimental data and thermodynamic assessment in ternary systems

Liu X.J. ef al., Thermodynamic database of the phase diagrams in the Mg-Al-Zn-Y-Cesystem
Continued Table 2

443

4. Examples of calculation
4.1. The Mg-Al-Zn-Ysystem
In this quaternary system, the phase equilibria in the Mg-Al-Zn and Mg-Zn-Y ternary systems have been assessed by Liang et al. [2S] and Shao et al. [35],respectively. The thermodynamic assessments of the A1-Zn-Y and Mg-Al-Y systems were carried out by our group [22, 301. Figs. 1 and 2 show the assessed phase diagram and Gibbs energy of formation of the compounds in the Zn-Y binary system, where the calculated results are in good agreement

with the experimental data [42-431. The thermodynamic parameters in the AI-Zn-Y system have been evaluated on the basis of the experimental data [40]. The isothermal section at SOOOC with a comparison of the experimental data are calculated and shown in Fig. 3, where no ternary compounds are found, and A1 is soluble in the YZn compound. On the basis of the assessed thermodynamic parameters, the liquid projection of the A1-Zn-Y system is predicated (Fig. 4), where there are three eutectic reactions and twelve peritectic reactions.

\ A

~ 3 .Chi&

e l ul.[42]

Mason et a/.[43

20

40 60 Zn J at.%

80

20

40 60 Zn i at.%

80

Zn

Fig. 1. Calculated phase diagram of the Zn-Y system compared with experimental data.

Fig. 2. Calculated Gibbs energy of formation at 773 K compared with experimental data.

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Y
A Three phase region 3 Two phase region

Three phase region

o Two phase region

80

a 7 phase

A1 J at.(?

Fig. 3. The calculated isothermal-sectionof the Al-Zn-Y ternary system at 500OC with experimental data [271.
Al I at.%

Fig. 5. Calculated isothermal-section of the Mg-AI-Y ternary system at 4 O C with experimental data [27]. OO

Znhcp

20

40 60 Al I at.%

80

fcc

A1

g
2 3 E

900

Fig. 4. Calculated liquidus-surface of the AI-Zn-Y ternary system.

600

In the Mg-Al-Y ternary system, the isothermal section at 400C and the Mg2A13-A12Yand T-YA~, vertical sections were determined by differential thermal analysis, X-ray diffraction, and metallography [29]. Fig. 5 shows the calculated isothermal section at 400C with the experimental data. It is seen that A1 has a higher solubility in the MgY and Mg2Y compounds, and Mg in the A12Y compound, but no solubility of Mg in the AlY compound, and there is a ternary compound (T phase, A4MgY) in the Al-rich region. The calculated vertical section at Mg&-Al2Y section is shown in Fig. 6, where the detailed phase equilibria are given at lower temperatures.
4.2. The Mg-Al-Zn-Cesystem

300 Y 0.00 5 Mg 40.0 Al60.0

10

15 20 Y I at.%

25

30 Y 33.3 Mg 0.00 A1 66.7

Fig. 6. Calculated vertical section at the Mg&-AI2Y region with experimental data [29].

In the Mg-Al-Zn-Ce quaternary system, the thermodynamic assessments of the Al-Zn-Ce and

Mg-Zn-Ce systems were carried out by this study group [23, 381. Figs. 7 and 8 show the assessed phase diagram and Gibbs energy of formation of the compounds in the Zn-Ce binary system, where the calculated results are in good agreement with the experimental data [44]. Fig. 9 shows the calculated isothermal section at 320C in the Al-Zn-Ce ternary system compared with the experimental data [41]. In this system, the complete thermodynamic assessment cannot be carried out because only a part of the experimental data of the isothermal section at 320C

Liu X.J. et al., Thermodynamic database of the phase diagrams in the Mg-Al-Zn-Y-Cesystem

445

is available. Further experiments should be carried out in the future.

1100

Ce
o Single phase regon
Two phase region

r-----l

Ce,

Three phase region

A I at.% 1
Fig. 9. Calculated isothermal-section of the Al-Zn-Ce system at 3 O C with experimental data [41]. 2O

Ce

20

40 60 Zn I at.%

SO

Zn

Fig. 7. Calculated phase-diagram in the Zn-Ce system with experimental data [44].

5. Summary
A thermodynamic database of the Mg-AIZn-Y-Ce system was basically developed on the basis of the CALPHAD method. Necessary experiments should be carried out for the thermodynamic assessments of the A1-Y-Ce and Zn-Y-Ce systems. This database should prove to be a powerful tool for developing new Mg alloys.

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