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Comparison of effects of cerium, yttrium and gadolinium additions on as-cast microstructure and mechanical properties of Mg-3Sn-1Mn magnesium alloy
YANG Mingbo ()1,2,3, QIN Caiyuan ()1, PAN Fusheng ()3, ZHOU Tao ( )1
(1. Materials Science and Engineering College, Chongqing University of Technology, Chongqing 400054, China; 2. Key Laboratory of Automobile Components Manufacturing and Testing Technology of the Education Ministry, Chongqing University of Technology, Chongqing 400054, China; 3. National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing 400030, China) Received 28 December 2010; revised 18 February 2011

Abstract: The effects of Ce, Y and Gd additions on the as-cast microstructure and mechanical properties of Mg-3Sn-1Mn alloy were investigated and compared by using optical and electron microscopies, X-ray diffraction analysis, and tensile and creep tests. The results indicated that the microstructure of the Mg-3Sn-1Mn alloy with the addition of 0.87 wt.%Ce was refined while the microstructures of the alloys with the additions of 0.79 wt.%Y or 0.84 wt.%Gd were coarsened. Furthermore, adding 0.87 wt.%Ce to the Mg-3Sn-1Mn alloy could improve the tensile properties while adding 0.79 wt.%Y or 0.84 wt.%Gd gave a detrimental effects on the tensile properties. In addition, adding 0.87 wt.%Ce, 0.79 wt.%Y and 0.84 wt.%Gd to the Mg-3Sn-1Mn alloy could improve the creep properties. Among the three additions, the addition of 0.87 wt.%Ce was more suitable to further improve the strength and creep performance of the Mg-3Sn-1Mn alloy. Keywords: magnesium alloy; Mg-Sn-Mn alloy; Ce; Y; Gd; rare earths

Magnesium alloys are the lightest structural alloys commercially available and have great potential for applications in automotive, aerospace and other industries. However, the application of commercially available Mg-Al based alloys is limited at elevated temperatures by their poor creep behaviour[1]. Therefore, attempts have been made to develop new magnesium alloys having improved structural stability at high temperatures. Among many possibilities, Mg-Sn based alloys are of special interest[2]. Recently, great efforts have been made on searching suitable alloying elements in Mg-Sn system, and the obtained-results indicated that the mechanical properties of Mg-Sn based alloys may be further enhanced by adding RE, Ca, Zn and Mn as the ternary alloying elements[29]. According to the investigations of Bursik et al.[7], the creep resistance of the Mg-xSn-1Mn (x=3, 5 wt.%) ternary alloys is relatively higher than that of the Mg-3SnxCa and Mg-5Sn-xCa alloys (x=0.52.0 wt.%) which are thought to offer superior creep properties even compared to the creep resistant magnesium alloy AE42 (Mg-4Al2RE)[10,11]. Therefore, Mg-Sn-Mn system alloys are thought as a potential corrosion and creep resistant magnesium alloys. At present, though the above mentioned studies have been carried out to develop Mg-Sn-Mn alloys, these works mainly focused on the as-cast microstructural characterization and/or mechanical properties of a limited number of Mg-Sn-Mn alloys[7,8,12]. The investigations of the potential

for further improvement in strength and creep performance via further alloying/microalloying are very scarce in the literature. It is well known that the additions of rare earth (RE) elements such as Ce, Y and Gd in Mg-Sn based alloys can show a favorable effect on the mechanical properties. For example, the authors of this paper found that Ce or Y additions to Mg-3Sn-2Ca alloy could effectively improve the tensile and creep properties of the alloy[5,6]. At the same time, Grony et al.[13] reported that the Mg-Sn-Zn-Y quaternary alloys exhibited good comprehensive mechanical properties in wider temperature range due to the presence of several stable intermetallic compounds such as MgSnY. In addition, Shi et al.[14] found that Gd addition to the Mg-5Sn-1Ca alloy could form the GdMgSn phase with high thermal stability thus possibly resulted in a enhanced elevated temperature properties. Therefore, it is expected that Ce, Y and Gd additions to Mg-Sn-Mn alloys possibly give a beneficial effects on the mechanical properties. Due to the above mentioned-reasons, the present work investigated and compared the effects of Ce, Y and Gd additions on the as-cast microstructure and mechanical properties of Mg-3Sn-1Mn magnesium alloy.

1 Experimental
The Mg-3Sn-1Mn alloys with different compositions (Table 1) were prepared by adding pure Mg and Sn (>99.9 wt.%),

Foundation item: Project supported by the National Natural Science Foundation of China (50725413), the National Basic Research Program of China (973) (2007CB613704), the Chongqing Science and Technology Program of China (2010AC4085, 2009AB4134 and 2006AA4012-9-6), and the Program for Hundreds of Distinguished Leading Scientists of CQ CSTC (2010CSTC-HDLS) Corresponding author: YANG Mingbo (E-mail: yangmingbo@cqut.edu.cn; Tel.: +86-23-62563176) DOI: 10.1016/S1002-0721(10)60496-6

YANG Mingbo et al., Comparison of effects of cerium, yttrium and gadolinium additions on as-cast microstructure Table 1 Actual compositions of the experimental alloys (wt.%)
Nominal alloys 1 (Mg-3Sn-1Mn) 3# (Mg-3Sn-1Mn+1.0Y)
#

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2.1 Comparison of as-cast microstructure Fig. 1 shows the XRD results of as-cast alloys. It is found that the Mg-3Sn-1Mn ternary alloy is mainly composed of -Mg and Mg2Sn phases. Furthermore, it is found that the addition of 0.87 wt.%Ce, 0.79 wt.%Y and 0.84 wt.% Gd to the Mg-3Sn-1Mn alloy leads to the formation of the extra phases of the Mg12Ce, YMgSn and GdMgSn, respectively.

Sn 2.81

Mn 0.87 0.89 0.88 0.84

Ce 0.87

Y 0.79

Gd 0.84

Mg Bal. Bal. Bal. Bal.

2# (Mg-3Sn-1Mn+1.0Ce) 2.78 2.79 4# (Mg-3Sn-1Mn+1.0Gd) 2.80

Mg-4.38 wt.%Mn, Mg-29.24 wt.%Ce, Mg-17 wt.%Y and Mg-24.5 wt.%Gd master alloys made by Hunan Rare Earth Metal & Material Institute in China, which were melted in a resistance furnace and protected by 2 wt.% RJ-2 flux additions (45 wt.% MgCl+37 wt.% KCl+8 wt.% NaCl+ 4 wt.% CaF+6 wt.% BaCl). After Mg-Ce, Mg-Y or Mg-Gd master alloys were added to the melt at 740 C, the melt was homogenized by mechanical stirring. After complete mixing, the melt was held at 740 C for 20 min and then poured into a preheated permanent mould in order to obtain a casting. The specimens were fabricated from the castings for tensile and creep tests. Furthermore, the samples of the experimental alloy were subjected to a solution heat treatment (420 C/ 24 h+water cooled) in order to clearly reveal the grain boundaries and examine the microstructural stability at high temperatures. Table 1 lists the actual chemical compositions of the experimental alloys, which were inspected by inductively coupled plasma spectroscopy. The as-cast and solutionized samples of the experimental alloys were respectively etched in an 8% nitric acid solution in distilled water and a solution of 1.5 g picric, 25 ml ethanol, 5ml acetic acid and 10 ml distilled water, and then examined by using an Olympus optical microscope and JEOL/JSM- 6460LV type scanning electron microscope (SEM) equipped with Oxford energy dispersive spectrometer (EDS) with an operating voltage of 20 kV. The grain size was measured by the standard linear intercept method using an Olympus stereomicroscope. The phases in the experimental alloys were analyzed by D/Max-1200X type X-ray diffraction (XRD) operated at 40 kV and 30 mA. The tensile properties of the as-cast alloys at room temperature and 150 C were determined from a stress-strain curve. The tensile specimens tested at 150 C were heated in a bisected resistance furnace with the temperature controlled to be within 2 C and protected by CO2 atmosphere. The ultimate tensile strength (UTS), 0.2% yield strength (YS) and elongation to failure (Elong.) were obtained based on the average of three tests. The constant-load tensile creep tests of the as-cast alloys were performed at 150 C and 50 MPa for 100 h. Creep specimens were heated in a bisected resistance furnace with the temperature controlled to be within 2 C and protected by CO2 atmosphere. Creep strain was measured by extensometers which were attached directly to the surfaces of specimens. The total creep strain and minimum creep rates were respectively measured from each elongation versus time curve and averaged over three tests.

Fig. 1 XRD results of the as-cast alloys (1) 1# alloy; (2) 2# alloy; (3) 3# alloy; (4) 4# alloy

2 Results and discussion

Figs.2 and 3 show the SEM images of the low and high magnifications for the as-cast alloys, respectively. Combining the XRD and EDS results, the main intermetallic compounds in Fig. 3 are identified as Mg2Sn, Mg12Ce, YMgSn and GdMgSn phases. It is observed from Figs. 2 and 3 that the Mg2Sn and/or Mg12Ce phases in the ternary alloy and the Ce-containing alloy mainly distribute at the grain boundaries, and small amounts of Mg2Sn present within grains. Similarly, the YMgSn phases in the Y-containing alloy and the GdMgSn phases in Gd-containing alloy are also found to mainly distribute at the grain boundaries and within grains. Furthermore, it is observed from Fig. 3 that the YMgSn and GdMgSn phases mainly exhibit needle-like shape, and the particle-like YMgSn phases with small amounts are also observed. In addition, it is found from Fig. 3 that the Ce-containing alloy contains small amounts of CeMgSn phase with particle-like shape although the phase is not detected in the XRD results. Fig. 4 shows the optical images of the as-cast alloys. It is observed that the primary -Mg phases in all the alloys are dendritic in nature. Furthermore, it is found that, as compared with the ternary alloy, the Ce-containing alloy exhibits a relatively obvious trend towards a more equiaxed structure. However, the similar trend is not found in the Y- and Gdcontaining alloys. Fig. 5 shows the optical images of the solutionized alloys. It is observed that the grains of the Ce-containing alloy are finer than those of the ternary alloy. The average grain size is 275 m for the ternary alloy and after adding 0.87 wt.%Ce, its average size is 102 m, indicating that the addition of 0.87 wt.%Ce can refine the grains of the Mg-3Sn-1Mn alloy. Since it is very difficult to clearly reveal the grain boundaries of the Y- and Gd-containing alloys by the solution heat treatment (420 C/24 h+water

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Fig. 2 SEM images of low magnification for the as-cast alloys (a) 1# alloy; (b) 2# alloy; (c) 3# alloy; (d) 4# alloy

Fig. 3 SEM images of high magnification for the as-cast alloys and EDS results (a) 1# alloy; (b) 2# alloy; (c) 3# alloy; (d) 4# alloy; (e) EDS results of position A in (b); (f) EDS results of position A in (c)

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Fig. 4 Optical images of the as-cast alloys (a) 1# alloy; (b) 2# alloy; (c) 3# alloy; (d) 4# alloy

Fig. 5 Optical images of the solutionized alloys (a) 1# alloy; (b) 2# alloy; (c) 3# alloy; (d) 4# alloy

cooled), as shown in Figs. 5(c) and (d), the grain size of the two alloys can not be directly compared with that of the ternary alloy. However, it may be inferred from Fig. 4 that the grains of the Y- and Gd-containing alloys especially the Gd-containing alloy should be coarser than those of the ter-

nary alloy. Previous investigations[15] showed that Sn element in the Sn-containing magnesium alloys is commonly rich in the solid-liquid interface during solidification, which will induce a constitution undercooling at the solidification interface front, thus accelerating the growth of secondary

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dendrites and refining the grains. In addition, it is reported that the Mg2Sn compound which has high melting points and heat resistance, can restrain the growth of -Mg at high temperatures, consequently the grains are further refined[15]. It is well known that the solid solubility in -Mg matrix for Y, Gd and Sn elements is relatively high, and both Y and Gd atoms have relatively larger atomic radius than Sn atom (Y: 0.182 nm; Gd: 0.178 nm; Sn: 0.141 nm). Therefore, after Y or Gd additions to the Mg-3Sn-1Mn alloy, Y or Gd elements possibly hinder Sn atom diffusion from the -Mg matrix to the grain boundaries. Furthermore, Y or Gd additions to the Mg-3Sn-1Mn alloy respectively results in the formation of the YMgSn and GdMgSn phases distributed at grain boundaries and within grains. The two factors possibly cause an decrease in the amount of Sn distributed at grain boundaries. As a result, the Y- and Gd-containing alloys obtain relatively coarse microstructures although the YMgSn and GdMgSn phases in the two alloys possibly restrain the grain growth at high temperatures[6,14,15]. However, this needs to be further confirmed. As for the relatively finer grains of the Ce-containing alloy, it is possibly related to the following two aspects[15]: (1) It is well known that Ce atom has larger atomic radius than Sn atom (Ce: 0.183 nm; Sn:0.141 nm). After Ce addition to the Mg-3Sn-1Mn alloy, Ce element is rich in the solid-liquid interface during solidification due to their relatively low solid solubility in -Mg matrix, which hinders the Sn atom diffusion and induces the constitution undercooling at the solidification interface front; (2) The Mg12Ce phases possibly contribute to the grain refinement since it is reported that the Mg12Ce compound can restrain the grain growth at high temperatures. 2.2 Comparison of mechanical properties The tensile properties including ultimate tensile strength (UTS), 0.2% yield strength (YS), elongation (Elong.), and creep properties of the as-cast alloys are listed in Table 2. It is observed from Table 2 that the tensile properties at room temperature and 150 C for the Ce-containing alloy are higher than those of the ternary alloy, indicating that the addition of 0.87 wt.%Ce can improve the tensile properties of the Mg-3Sn-1Mn alloy. Furthermore, it is found that the Yand Gd-containing alloys exhibit relatively poorer tensile properties at room temperature and 150 C than the ternary alloy, indicating that the additions of 0.79 wt.%Y and 0.84 wt.%Gd are not beneficial to the tensile properties of the
Table 2 Tensile and creep properties of the as-cast alloys
Experimental alloys Tensile properties Room temperature UTS/MPa 1# alloy 2# alloy 3# alloy 4# alloy 129 (2.1) 165 (2.9) 118 (4.1) 102 (3.2) YS/MPa 108 (1.9) 134 (3.2) 93 (2.1) 87 (2.5) Elong./% 3.1 (0.20) 3.9 (0.15) 2.5 (0.17) 2.1 (0.23) 150 C UTS/MPa 118 (1.7) 148 (2.7) 107 (2.2) 94 (3.1) YS/MPa 99 (2.1) 122 (4.1) 85 (3.2) 80 (4.4)

Mg-3Sn-1Mn alloy. The relatively high tensile properties of the Ce-containing alloy is possibly related to the microstructural refinement of the alloy. In addition, since the Mg12Ce phase in the Ce-containing alloy is mainly precipitated at the grain boundary, it can suppress the movement of dislocations and play an important role in the improvement of the tensile properties. As for the poor tensile properties of the Y- and Gd-containing alloy as compared with the ternary alloy, the reason is possibly related to the following two aspects: (1) The microstructures of the Y- and Gd-containing alloys are relatively coarser than that of the ternary alloy; (2) It is well known that the presence of fine and uniform phases distributed along the grain boundaries is easier to act as an effective straddle to the dislocation motion thus improving the properties of engineering alloys[16]. Apparently, the coarse needle-like YMgSn and GdMgSn phases in the Y- and Gdcontaining alloys would give a detrimental effect on the mechanical properties. Actually, the difference in the tensile properties of the experimental alloys may be further confirmed from Fig. 6, which shows the SEM images of the tensile fractographs for the as-cast alloys tested at room temperature. As shown in Fig. 6, a number of cleavage planes and steps are present, and some minute lacerated ridges can also be observed in the localised areas of the tensile fracture surfaces, indicating that all the tensile fracture surfaces have mixed characteristics of cleavage and quasi-cleavage fractures. Obviously, the additions of 0.87 wt.%Ce, 0.79 wt.%Y or 0.84 wt.%Gd do not significantly change the fracture mode of the Mg-3Sn-1Mn alloy. However, the fracture surfaces of the ternary alloy and the alloys with the additions of 0.79 wt.%Y and 0.84 wt.%Gd exhibit relatively large cleavage-type facets (arrows A in Figs. 6(a), (c) and (d)). On the other hand, the cleavage-type facet in the fracture surface of Ce-containing alloy is relatively small. Therefore, the Cecontaining alloy exhibits relatively high tensile properties while the properties of other three alloys are relatively poor. In addition, it is observed from Table 2 that the creep properties at 150 C and 50 MPa for 100 h for the Ce-, Yand Gd-containing alloys are higher than those for the ternary alloy. Among the alloys with the additions of 0.87 wt.%Ce, 0.79 wt.%Y and 0.84 wt.%Gd, the creep properties of the Y-containing alloy is the highest, followed by those of the Gd- and Ce-containing alloys, respectively. Figs.7 and 8 show the SEM images of the low and high magnifications for the solutionized alloys, respectively. It is observed from

Creep properties 150 C and 50 MPa for 100 h Total creep Minimum creep strain/% rate/108 s1 1.95 (0.05) 1.20 (0.06) 1.00 (0.04) 1.09 (0.07) 5.41 (0.31) 3.34 (0.53) 2.79 (0.16) 3.02 (0.31)

Elong./% 10.3 (0.88) 15.4 (0.92) 9.1 (0.92) 8.4 (1.2)

Note: the data in the bracket is the standard error

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Fig. 6 SEM images of the tensile fractographs for the as-cast alloys tested at room temperature (a) 1# alloy; (b) 2# alloy; (c) 3# alloy; (d); 4# alloy

Fig. 7 SEM images of the low magnification for the solutionized alloys (a) 1# alloy; (b) 2# alloy; (c) 3# alloy; (d) 4# alloy

Figs.7 and 8 that a majority of the Mg2Sn phases in the ternary alloy have dissolved into the matrix after the solid solution heat treatment. However, it is further found from Figs.7 and 8 that the solutionized microstructures of the Ce-, Y- and Gd-containing alloys seem to be similar to their as-cast microstructures, indicating that the thermal stability of the secondary phases in the three alloys is relatively high. Since the creep properties of magnesium alloys are mainly related to the structure stability at high temperatures, the improvement

of the creep properties for the Ce-, Y- and Gd-containing alloys is possibly related to the precipitation of the Mg12Ce, YMgSn and GdMgSn with relatively high thermal stability. As for the relatively higher creep properties of the Y- and Gd-containing alloys as compared with the Ce-containing alloy, the relatively coarse microstructures of the Y- and Gd-containing alloys are one of the possible reasons. However, this needs to be further investigated.

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Fig. 8 SEM images of the high magnification for the solutionized alloys (a) 1# alloy; (b) 2# alloy; (c) 3# alloy; (d) 4# alloy

3 Conclusions
(1) The additions of 0.87 wt.%Ce, 0.79 wt.%Y and 0.84 wt.%Gd to the Mg-3Sn-1Mn alloy resulted in the formation of the Mg12Ce, YMgSn and GdMgSn phases, respectively. In addition, the microstructure of the alloy with the addition of 0.87 wt.%Ce was refined while the microstructures of the alloys with the additions of 0.79 wt.%Y or 0.84 wt.%Gd were coarsened. (2) The difference in the tensile and creep properties of the Mg-3Sn-1Mn alloys with the additions of 0.87 wt.%Ce, 0.79 wt.%Y and 0.84 wt.%Gd was relatively obvious. The addition of 0.87 wt.%Ce could improve the tensile and creep properties. However, the additions of 0.79 wt.%Y and 0.84 wt.%Gd gave a detrimental effect on the tensile properties although they were beneficial to the creep properties. Among the three additions of 0.87 wt.%Ce, 0.79 wt.%Y and 0.84 wt.%Gd, the addition of 0.87 wt.%Ce was more suitable to further improve the strength and creep performance of the Mg-3Sn-1Mn alloy.

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