Journal of Materials Science & Technology

Influence of zirconium content on the microstructure and mechanical properties of sand-cast Mg-10Gd-3Y alloys

Journal: Journal of Materials Science & Technology Manuscript ID: JMST-2014-0486 Manuscript Type: Research Article Date Submitted by the 25-Mar-2014 Author:

Complete List of Authors: Pang, Song Wu, guohua; , Zhang, Liang Liu, Wencai Zhang, Yang Conrad, Hans Ding, wenjiang; 800 , Keywords: Speciality: Magnesium alloy, Rare earth element, Grain refinement, Zirconium, Microstructure, Mechanical properities Grain Refinement, Magnesium Alloys, Mechanical Properties, Casting

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Influence of zirconium content on the microstructure and mechanical properties of sand-cast Mg-10Gd-3Y alloys Song Panga,b, Guohua Wua, Liang Zhanga, Wencai Liua, Yang Zhanga, Hans Conradb, Wenjiang Dinga
a

National Engineering Research Center of Light Alloy Net Forming and State Key Laboratory of Metal

Matrix Composite, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
b

Materials Science and Engineering Department, North Carolina State University, Raleigh, NC 27695-

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7907, USA

Abstract

The effect of Zr content on the microstructure and mechanical properties of sand-cast Mg10Gd-3Y alloys which occurred by adding 0 to 0.7 wt. % Zr at a cooling rate of 0.4 oCs-1 was determined. The morphology of the -Mg phase transformed from coarse equiaxeddendrites into relatively refined equiaxed-dendrites then into equiaxed grains with the eutectic compound transforming from a continuous network into a separated state. The average -Mg grain size decreased from 340 m to 47 m with two stages separated at 0.45 wt. % Zr content, and the volume fraction of the second phase decreased from 13.4 % to 8.1 %. There were two states of zirconium exist in the studied alloy, separated at 0.45 wt. % zirconium content. One was as the solution, and the other was as the cluster. The solute concentration could be improved by using Zr. The alloy with 0.61 wt. % Zr content has the optimum combination of YS of 152 MPa, UTS of 224 MPa and El of 7.3 %. The relationships between the microstructure and mechanical properties were discussed. The major cracking mode is transgranular (0001) cleavage of -Mg grains. Key words: Rare earth magnesium alloy; Zirconium; Sand-cast; Grain refinement; Microstructure; Mechanical properties

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Corresponding author: Guohua Wu Tel.: +86 21 54742630; fax: +86 21 34202794. E-mail addresses: ghwu@sjtu.edu.cn (G. Wu)
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1 Introduction With increasing global energy demand and high consciousness of environmental protection in recent years, magnesium alloys are very attractive structural parts for automotive and aerospace industries due to their low density and high strength per weight ratio [1-3]. Zirconium-refined magnesium alloys containing rare earth (Mg-RE-Zr) have recently been developed and studied, including the alloy-series of Mg-RE-Zn (ZE) [4], Mg-RE-Y (WE) [5], Mg-Nb-Zn (NZ) [6], Mg-Gd-Y (GW) [7]. Results in the literatures [8-10] gave that the Mg10Gd-3Y (GW103) alloy exhibited a better combination of strength and ductility than other Mg-Gd-Y alloys. Qians [4] notable work had established that the use of zirconium in these alloys not only ensures uniform and fine equiaxed grain structure [11-13], but also implied that there are two effective zirconium states in as-cast magnesium alloys. However, the main production method for the GW103 alloy is the sand-cast process, which can be used to manufacture extremely complex castings. There are still only a few research papers related to the microstructure and mechanical properties of sand-cast GW103 alloys. But most of these papers focus on the influence of the precipitate on the mechanical properties of the sand-cast alloys after heat treatment [14-16]. With the combination of higher strength and ductility than most magnesium alloys, Mg-10Gd-3Y [8-12] is of a considerable interest in both material science [13, 16-18] and the aerospace industry [7-10, 14-16]. The aim of this study is to investigate the influence of zirconium content on the microstructure and mechanical properties of sand-cast GW103alloys. 2 Experimental procedure

Sand-cast Mg-10Gd-3Y-xZr (wt. %) alloy (GW103K) was employed in this study. The sand mold is shown in Figs. 1 (a) and (b). High purity Mg (99.95%) ingots, and Mg-25Gd (wt. %), Mg-25Y (wt. %) and Mg-30Zr (wt. %) master alloys were used. The melting process was carried out in an electric resistance furnace under the mixed atmosphere of CO2 and SF6 with the ratio of 100:1. After being refined at 750 oC the alloy melt was first held at 780 oC for 10 minutes, then cooled to 750 oC and poured into the sand cups. Specimens for microstructure observation and mechanical properties test were selected and cut at room temperature at the location shown in Fig. 1 (c). The chemical composition of the as-cast alloy
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was measured by an inductively coupled plasma analyzer (Perkin Elmer, Plasma-400), and the results are listed in Table 1. The cooling rate of selected sample was measured by K-type thermocouples placed in the c enter of the ingot. Time and temperature data was recorded by a self-assembly computer-aide d cooling curve analysis (CA-CCA) system. The cooling rate was determined using the formu la: CR = (Tliq -Tsol)/(tliq-tsol), where Tliq and Tsol are respective the solidification start temperat ure and the solidification end temperature (oC) respectively, and tliq and tsol are time taken fro m the cooling curve that correspond to Tliq and Tsol, respectively. These parameters were mar ked through the analysis of the cooling curve and its first differential curve which was introdu ced in literatures [7, 13].

The specimen for phase analysis and microstructure observation was successively ground u sing 400 and 800 grit SiC papers, and then polished using 6 m, 1 m diamond suspensions, f ollowed by 0.04 m OPS (MgO particles) solution. The phase analysis was then carried out b y X-ray diffraction (XRD) using Ni-filtered Cu-K radiation. After that, the same specimen was etched for microstructure characterization in a solution of HNO3 (4 Vol. %) and alcohol. The morphology and the microstructure observation were performed by optical microscopy (OM) and scanning electron microscopy (SEM, FEI SIRION 200/INCA OXFORD). The grai n size was measured using the linear intercept technique (ASTM 112-96). Five fields were co nsidered for each measurement with approximately 60 intercepts in each field depending on t he grain size. The volume fraction of second phase was determined by an image analyzer on optical metallographic sections [17]. The composition of phases was determined by the energ y dispersive spectrometer (EDS) attached to the SEM. The tensile properties were determined on the sheet-shaped specimens whose dimensions are also shown in Fig. 1(c) at the initial str ain rate of 5 10-4 s-1 using a Zwick/Roell Z020 tensile machine at room temperature. Each re ported value of the tensile properties (yield strength, ultimate tensile strength, and elongation) is the average value of five tests. The fracture surface was observed by SEM. 3 Results Thermal analysis

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3.1.

Figure 2 shows the cooling curve of the sand-cast GW103K alloy with 0.45 wt. %
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zirconium content. The solidification process includes two main reactions: (a) L () Mg; (b) L Mg + () Mg24RE5. The first derivative in Fig. 2 gives that the -phase solidification start temperature (Tliq) 642
o

C, the solidification end temperature (Tsol) 545 oC, and the corresponding time 236 s,

respectively. The cooling rate is thus approximately 0.4 oCs-1 in the present study. 3.2. Phase analysis

The X-Ray diffraction (XRD) patterns of the alloys are shown in Fig. 3. The XRD peaks are indexed as -Mg and -Mg24 RE5, based on the standard diffraction pattern. The identification of -Mg24 RE5 phase had been explained in literatures [6, 7]. Addition of zirconium made the diffraction peaks of the -Mg phase stronger but the diffraction peaks of the -Mg24Gd5 phase weaker. It was suggested that the addition of zirconium could probably aid the formation of the -Mg phase, and also decrease or weaken the formation of the Mg24Gd5 phase in this high solute content Mg alloy system. Furthermore, with increase in Zr content the diffraction peaks of -Mg phase shift slightly to smaller angles. To be noted is that the diffraction peaks of the -Mg phase shift forward more in the second group (Zr %: 0.45-0.70 wt. %) than the first group (Zr %: 0-0.45 wt. %). It implies that there may be two diverse factors involved in the formation of the -Mg crystal. 3.3. Metallographic characteristics

The optical microstructure of the GW103K alloy consists of equiaxed -Mg matrix and eutectic compounds at grain boundaries in Fig. 4. The -Mg phase appeared coarse equiaxeddendrites in the insert of Fig. 4 (a) in the zirconium-free alloy. The morphology of the -Mg phase transformed into relatively refined equiaxed-dendrites in inserts of Fig. 4 (b) and then into equiaxed grains in Figs. 4 (c)-(g), while the -Mg grain size was refined from 340 m to 249 m in Fig. 5 and progressively to 47 m in Fig. 5, with increase in zirconium content up to 0.19 wt. % and then to 0.70 wt. %. Adding zirconium not only refined the -Mg grain and changed its morphology, but also caused the eutectic compound transforming from a continuous network into a separated state
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and the volume fraction of the second phase (fV) decreasing from 13.4 % to 8.1 %. To be noted is that the second phase includes all of the phases except the -Mg phase in the present study. Figure 5 summarizes the influences of zirconium on the average -Mg grain size (d) and the volume fraction of second phase (fV) of sand-cast GW103 alloys. Additionally, the second phase is hardly distinguished by optical observation when the Zr content is more than 0.51 wt. % in Figs. 4 (f) and (g). Figure 6 shows the microstructure of sand-cast GW103 alloys with different zirconium content. The coarse eutectic compounds occurred along the grain boundary in the zirconiumfree GW103 alloy in Fig. 6 (a). With increase in zirconium the eutectic particles appeared more and more separated into the intercrystalline region in Figs. 6 (b) and (c). Besides the Mg phase and the eutectic compound, there also appeared some white precipitates with the cubic or rectangle shape along grain boundaries. Figure 7 shows the chemical composition of white particles and the eutectic zone with bright background identified by Energy Dispersive Spectrometer (EDS). It was found that white spots (points 1 and 3) are rich in the rare earth (Gd, Y) and solution content decreased in the eutectic zone (zone 2 and 4) with increased

zirconium content. 3.4. Mechanical properties

Figure 8 shows the effect of zirconium content on stress-strain curves of sand-cast GW103K alloys. During the tensile property test, the flow stress kept on increasing with Zr content up to 0.70 wt. %. Meanwhile, the total strain first increased with Zr content up to 0.61 wt. % but then decreased with further increase to 0.70 wt. %. Also to be noted is that some elongation occur obviously between the maximum stress and final fracture when zirconium content was lower than 0.19 wt. %. The effect of Zr content on the yield strength (YS), the ultimate tensile strength (UTS) and elongation (El) was presented in Fig. 9 (a). All these three parameters kept on increasing with increased zirconium content. Included in Fig. 9 (b) for comparison are the corresponding values of as-cast GW103 alloy formed through permanent mold [13]. The sand-cast GW103 alloy shows a little higher yield strength when zirconium content was higher than 0.51 wt. %. 4 Discussion
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4.1.

Phases

Addition of Zr made the diffraction peaks of -Mg phase stronger but the diffraction peaks of the -Mg24Gd5 phase reversely weaker (Fig. 3). Likely reasons could be described as the follow. (a) As is known that zirconium is a potent grain refiner for as-cast Mg alloys [4]. It can increase the constitutional undercooling of the alloy-melt system in the solidification process. This enhances the driving force for nucleation and growth of the -Mg grains, which in turn accelerates the solidification of the -Mg phase. The growth rate of the -Mg phase is thus higher than in the zirconium-free GW103 alloy. As a result, the rare earth atoms were inhibited from diffusing to the solid/liquid interface. It may probably decrease the solution content in the eutectic compounds. (b) It was reported that Mg-Gd alloys can absorb the Xray (Cu K), when the Gd content is more than 5wt. % [19]. Furthermore, it was proved that Mg5Gd phase existed in as-cast GW103K alloys [7, 19, and 20]. The absorption of X-ray and the noisy background could also influence the diffraction intensity of phases in the sand-cast alloy, which was probably supposed to be the reason why the diffraction peaks of Mg5Gd

phase was not clearly identified.

With increase in zirconium content the diffraction peaks of -Mg phase shift slightly to smaller angles. It indicated that the solute (Gd, Y, and Zr) content increased in the Mg matrix. However, the movement of the diffraction peaks of -Mg phase was more in the second period (Zr %: 0.45~0.70 wt. %) than it in the first (Zr %: 0~0.45 wt. %). It indicated that there may be two factors which caused the different growth process of the -Mg grains. Considering the solubility of zirconium in magnesium alloys, it can be implied that some zirconium particles appear together with rare earth atoms at the white spot in Fig. 7 (e) and around the grain boundary zone in Fig. 7 (f). Additionally, some zirconium particles exist along the grain boundary and inside the -Mg grain. It was observed that fine white-bright particles contained pure zirconium particles with Zr-rich cores in the as-cast GW alloy [13], which was also supported by the SEM observation in the backscattered electron (BSE) mode [18] and by TEM [21]. Zr-rich cores are not always present inside the magnesium grains; they exist as well at grain edges, and each magnesium grain often contains more than one Zrrich core under normal cooling conditions [18]. Besides the zirconium particles, it could also be observed that some cubic&rectangle-shape
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precipitates appeared with high contrast ratio along the grain boundaries in Fig. 6. Based on the fact that the zirconium particles always appeared as the particle or the cluster, this kind of rectangle-shape precipitates might be some other phase which mainly consisting of the rare earth regarding to its chemical composition in Figs. 7 (b) and (e). It was reported that this kind of rectangle-shape precipitates were found the in rare earth magnesium alloy and proposed as a kind of rare earth hydride [22-24]. The affinity of H and Gd is higher than that of H and Mg, because the dissimilarity of Pauling electronegativity between Gd and H is larger than that between Mg and H. The Gibbs free energy (G298 K) for H2 and GdH2 is respectively -353.46 kJ/mol [23] and -460.46 kJ/mol [24]. As a result, GdH2 precipitate forms easily instead of H2 at room temperature. Furthermore, Pengs work proved that this rectangle-shape precipitate could only form in water condition, showed the electron diffraction pattern of GdH2 phase through TEM analysis and gave its formation mechanism, through comparing the sample prepared in by electropolishing method (without water) with the same sample prepared by mechanical polishing method (with water) [25, 26].

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4.2.

Microstructure refinement

The -Mg grain was refined step by step with increase in zirconium content in Fig. 4. Due to the influence of strong constitutional undercooling caused by the rare earth solutes, there was even no significant dendrites but coarse equiaxed-dendrites in the microstructure of the zirconium-free alloy in the insert of Fig. 4 (a). With increase in zirconium content firstly up to 0.19 wt. % and then to 0.70 wt. %, the corresponding morphology of the -Mg phase gradually transformed to relatively refined -Mg equiaxed-dendrites in Fig. 4 (b) and then to equiaxed grains in Figs 4 (c)-(g).

This phenomenon was directly caused by the fact that the original preferential growth of the -Mg phase was more and more restrained with increase in zirconium content. In the MgZr phase diagram [18], the solubility of zirconium is approximately 0.443 wt. %, which indicates that two states of zirconium exist in the studied alloy, when the addition of zirconium is approximately over 0.443 wt. % (included). The higher efficiency of zirconium in comparison with other elements regarding grain refinement is the grain growth restricting factor (GRF) [29-33] pertaining to the dissolved Zr. The GRF is formulated as mC0 (k-1), where m is the slope of the liquidus, C0 is the concentration of the solute in the melt, and k is
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the equilibrium partitioning coefficient (k = Cs/Cl, where Cs and Cl are respectively the solute concentrations of the solid and liquid at the interface). If this parameter was huge, the growth rate (and hence the latent heat evolved) would be small, thus allowing a huge number of segregates to act as nucleating sites. The growth restricting factor is nearly about 40 for zirconium in the magnesium melt [33], which clearly indicates that dissolved Zr is a most efficient grain refiner. Zirconium addition to magnesium is moreover a very successful grain refiner because a small amount of dissolved zirconium can activate the formation of undissolved zirconium particles for nucleating magnesium [34]. Undissolved zirconium particles were thought to be effective nucleons for magnesium due to the low mismatch between magnesium and zirconium [35]. In the general mechanism of grain refinement in magnesium alloys introduced by Ma [24] employing Emleys theory [30], it was reported that primary zirconium clusters segregated in the matrix at the temperature a little above the peritectic temperature. Due to the similarity of lattices and atomic sizes of magnesium and zirconium, zirconium clusters serve as nucleation sites. Recent evidence has shown that zirconium clusters, which exist in the melt well above the peritectic temperature, can effectively help magnesium grains nucleate [31]. The GRF is considered to represent the summation of each individual element, which means interactions between solutes are neglected [32]. It should be pointed out that Gd and Y may also serve as grain refiners. This is the reason why there were no obvious dendrites in the microstructure of the zirconium-free GW103 alloy. The effect of Gd and Y atoms on grain refinement is weaker than zirconium whether it is in solute state or

as particles [13, 29-31].

The results in Fig. 5 suggest that there are two approximately linear relationships between zirconium content (CZr/wt. %) and average grain size (d/m) of the -Mg phase, which could be approximately divided at the zirconium content value of 0.45 wt. %. Being free of the grain refiner zirconium and cooled at a slow cooling rate (0.4 oCs-1), solute concentration probably occurred within both coarse -Mg dendrites and eutectic compounds regarding to the principles of solidification [27, 28] in Fig. 6. Figures 7 (c) and (f) showed that the chemical composition in the eutectic zone decreased with increase in zirconium content, which meant that the solution concentration was improved in the eutectic compounds. Before
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the eutectic reaction occurred in the equation (b) in section 3.1, the solid fraction of the liquid metal system increased with increase in zirconium content during the solidification due to the increased nuclei of the -Mg grains. Meanwhile, the rare earth atoms kept on transferred towards the liquid/solid interface regarding to the high mismatch between the structure of rare earth and magnesium atoms. However, the diffusion rate of the solute atoms is relatively slower in the liquid than it in the solid. As a result, the solution content decreased in the eutectic zone which formed at the end of the whole solidification process, and the solute distribution appeared more uniformly in the as-cast alloy.

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4.3.

Strengthening mechanism

Fig. 10 shows relationships between YS and the microstructure (d-1/2 and fV) of sand-cast GW103K alloys. Included in this relationship are the grain size, the volume fraction of the second phase (fV) and the presence of Zr in solution or as clusters and/or precipitates [18]. It was indicated that both the average grain size and the volume fraction of the second phase play significant roles in YS of sand-cast GW103K alloys within the grain size (d) range from 47 m to 340 m and the volume fraction of the second phase (fV) from 8.1% to 13.4%. Moreover, as indicated by the dashed lines in Figs. 4(a) and (b) it appears that there exist two regimes in each relationship, one for Zr contents below the solubility limit in Mg (0.443 wt. % [18]) and the other at higher contents where Zr clusters or precipitates can occur. It thus appeared that the Zr content per se could have a significant direct effect on YS, in addition to its indirect effect through its influence on grain size (d) and the volume fraction of the second phase (fV). The effect of each factor on the mechanical properties is thus hard to be separated out. Hence, in general, three factors contributed to the strengthening of sand-cast GW103K alloys: (a) grain boundary strengthening (b); (b) solid solution strengthening (s); and (c) second phase strengthening (Sec). In the present study, all these three factors were involved to given (sand-cast GW103K) = b + s + Sec. Furthermore, as mentioned before there are two states of zirconium in the studied alloy when the zirconium content was greater than 0.443 wt. % [18]. The contribution of the undissolved Zr to the strengthening of sand-cast alloys was involved in second phase strengthening (Sec). Besides strength, the ductility could be also influenced by the above factors. Figure 11
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presents SEM micrographs at two magnifications of the tensile fracture surface of specimens with 0, 0.45 and 0.70 wt. % Zr. Evident in Figs. 11 (a) and (b) (0 wt. % Zr) is (0001) cleavage of -Mg grains and cracks corresponding to the eutectic compound. In Figs. 11 (c) and (d) (0.45 wt. % Zr) there exist cleavage planes, cracks at the interface between the eutectic and the Mg grain and pores; the pores could be due to microporosity or the separation of Zr precipitates [4, 36]. In Figs. 11 (e) and (f) all three fracture modes (cleavage, eutectic cracks and interface separation) were visible but tented to be smaller in size due to the further refinement in microstructure by the Zr addition. Due to the low mismatch between the structure of zirconium and magnesium [35], it could be supposed that cracking may easily form and grow along the interface between these two different matrixes regarding to the principle for mechanical properties of cast metals [28]. Although the mount of cracking decreased as the refiner content increased, the amount of porosity would increase, because interdendritic feeding becomes more difficult in solidification. This is another possible factor for the formation of these cracks. In summary, the major cracking mode leading to separation appeared to be transgranular (0001) cleavage of the -Mg grains.

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Summary and Conclusions

The influence of zirconium content ranging from 0 to 0.70 wt. % on the microstructure and mechanical properties of sand-cast Mg-10Gd-3Y alloys was investigated. The following is a summary and the related conclusions:

(1) The morphology of the -Mg phase transformed from coarse equiaxed-dendrites into relatively refined equiaxed-dendrites and then into equiaxed grains with the eutectic compound transforming from a continuous network into a separated state. (2) The average -Mg grain size decreased from 340 m to 47 m with two stages separated at zirconium content of 0.45 wt. %, and the volume fraction of the second phase decreased from 13.4 % to 8.1 %. The addition of zirconium could reduce the solute concentration. (3) There were two states of zirconium exist in the studied alloy, separated at 0.45 wt. % zirconium content. One was as the solution, and the other was as the cluster. (4) YS, UTS and El increased by 65 %, 72 % and 1026 %, respectively. The alloy with 0.61 wt. % zirconium had the optimum combination of YS of 152 MPa, UTS of 224 MPa and El
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of 7.3 %. Both grain size and the volume fraction of the second phase play roles in strength of alloys with transgranular (0001) cleavage of -Mg grains as the major cracking mode. Acknowledgments This project is sponsored by National Natural Science Foundation of China (No. 51275295), Funded Projects of SAST-SJTU Joint Research Centre of Advanced Aerospace Technology (No. USCAST2012-15), Research Fund for the Doctoral Program of Higher Education of China (No. 20120073120011) and Science Research Fund for the doctoral of Higher Education of China (No. 20130073110052). The authors also would like to thank Laboratories Management Center for the use of their SEM and the Zwick T1-FR020TN.A50 electronic universal material testing machine system. References

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[19] N. Hort, Y. Huang, D. Fechner, M. Strmer. C. Blawert, F. Witte, C. Vogt, H. Drcker, R. Willumeit,
K. Kainer, F. Feyerabend, Acta Biomaterialia 6 (2010) 1714-1725. [20] S. He, X. Zeng, L. Peng, X. Gao, J. Nie, W. Ding, J. Alloys Comp. 427 (2007) 316-323. [21] H. Cao, M. Wessen, Metall. Mater. Trans. A. Phys. Metall. Mater. Sci. 35 A (2004) 309-319. [22] K. Zheng, J. Dong, X. Zeng, W. Ding, Mater. Sci. Tech. 24 (2008) 320-326. [23] Y. Yang, L. Peng, P. Fu, B. Hu, W. Ding, J Alloy. Compd. 485 (2009) 245-248. [24] M. Vece, S. Zevenhuizen, J. Kelly, Appl. Phys. Lett. 81 (2002) 12-13. [25] Q. Peng, Y. Huang, J. Meng, Y. Li, K. Kainer, Intermetallics, 19 (2011) 382-389. [26] W. Gan, Y. Huang, L. Yang, K. Kainer, M. Jiang, H. Brokmeiera, N. Horta, J. Appl. Cryst. 45 (2012)

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17-21.

[27] K. Wilfried, D.J. Fisher. Fundamentals of solidification. Trans Tech Publications, Aedermannsdorf,

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Switzerland, 1986, p.193.

[28] J. Campbell. Castings, 2nd Ed. Butterworth Heinemann, Oxford, UK, 2003, p.151. [29] M. Qian, A. Das, Scripta Mater. 54 (2006) 881-886.

[30] E. Emley Principles of magnesium technology. Pergamon Press,Oxford, UK, 1966, p.126. [31] M. Qian, D. StJohn, Int. J. Cast Met. Res. 22 (2009) 256-259.

[32] I. Nagli, A. Smolej, M. Doberek, Metalurgija 48 (2009) 147-150. [33] M. Easton, D. Stjohn, Acta Mater. 49 (2001) 1867-1878.

[34] Y. Lee, A. Dahle and D. StJohn, Metal, Mater. Trans A 31 (2000) 2895-2906.

[35] Y. Tamura, N. Kono, T. Motegi, E. Sato, J. Jpn. Inst. Light Metals 47 (1997) 679-684.

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List of figures
Fig. 1. Photographs of the sand mold (a, b), and schematic of the casting (c) with location and dimensions of the specimen for microstructure observation and mechanical properties test (mm); the fracture usually occurs at the shaded section. Fig. 2. The cooling curve of the sand-cast GW103 alloy with 0.45 wt. % Zr. Define: TLiq-Solidification starts, and TS-Solidification ends. Fig. 3. X-ray diffraction patterns of the sand-cast GW103 alloys (wt. % Zr): (a) 0; (b) 0.19; (c) 0.45; (d)

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Fig. 4. Optical microstructures of sand-cast GW103 alloys with different Zr contents (wt.%): (a) 0; (b) 0.19; (c) 0.39; (d) 0.45; (e) 0.51; (f) 0.61; and (g) 0.70. Numbers on micrographs: (1)-Mg matrix, (2) Mg24RE5 eutectic compound, (3) inclusion.

Fig. 5. Influence of Zr content on the average grain size (d) and the volume fraction of the second phase (fV) of sand-cast GW103 alloys.

Fig. 6. SEM micrographs of the alloys with different Zr contents (wt. %): (a) 0; (b) 0.45; (c) 0.70. Fig. 7. EDS results of the present sand-cast alloys with different Zr contents: (a) 0 wt. % with (b) for spot 1, and (c) for zone 2, (d) 0.51 wt. % with (e) for spot 3, and (f) for zone 4. Fig. 8. The effect of Zr content on the engineering strain-stress curves of the sand-cast GW103 alloys. Fig. 9. (a) The tensile properties of sand-cast alloys and (b) the permanent mold cast alloys [13]. Fig. 10. (a) The empirical relationship between YS and d-1/2 and (b) the empirical relationship between YS and the volume fraction of the second phase fV. Fig. 11. Typical SEM images at two magnifications showing the fracture surfaces of sand-cast GW103 alloys with different Zr contents: (a) and (b) 0, (c) and (d) 0.45 wt. %, (e) and (f) 0.71 wt. %.

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(a)

(b)

(c)

Fig. 1. Photographs of the sand mold (a, b), and schematic of the casting (c) with location and dimensions of the specimen for microstructure observation and mechanical properties test (mm); the fracture usually occurs at the shaded section.

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750 Cooling curve First derivative 700

5 4 3 2

Temperature [ C]

0 600

-1 -2

550

Ts

-3 -4

500

50

100

150

200 250 Time [s]

300

350

-5 400

Fig. 2 The cooling curve of the sand-cast GW103 alloy with 0.45 wt. % Zr. Define: TLiq-Solidification starts, and TS-Solidification ends.

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dT/dt [ C/s]

650

Tliq

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a -Mg Mg24Gd5

Intensity

Fig. 3. X-ray diffraction patterns of the sand-cast GW103 alloys (wt. % Zr): (a) 0; (b) 0.19; (c) 0.45; (d)

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(a)

(b)

(c) 2 1

(d) 1 2

(e) 2

Fig. 4. Optical microstructures of sand-cast GW103 alloys with different Zr contents (wt.%): (a) 0; (b) 0.19; (c) 0.39; (d) 0.45; (e) 0.51; (f) 0.61; and (g) 0.70 Numbers on micrographs: (1) -Mg matrix, (2) Mg24RE5 eutectic compound, (3) inclusion.

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400 Average -Mg grain size (d) 350 300 10 Valume of the second phase (fV ) 12 14

d / m

8 200 150 4 100

I
6

II
50

2 0 0.8

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Zr /wt.%

Fig. 5. Influence of Zr content on the average grain size (d) and the volume fraction of the second phase (fV)

of sand-cast GW103 alloys.

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fV / %

250

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(a)

(b)

Fig. 6. SEM micrographs of the alloys with different Zr contents (wt. %): (a) 0; (b) 0.45; (c) 0.70.

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(c)

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(a)

(b)

Element MgK GdL YK

Wt% 51.33 29.42 19.25

At% 83.95 07.44 08.61 ZAF

(c)

Element MgK GdL YK Matrix

Wt% 07.20 47.52 45.28 Correction

At% 26.73 27.29 45.99 ZAF

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Correction

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Element MgK GdL YK ZrK Matrix

Wt% 30.40 18.25 19.32 32.03 Correction

At% 64.63 06.00 11.23 18.15 ZAF

(f)

Element MgK GdL YK ZrK Matrix

Wt% 56.85 08.31 09.23 25.60 Correction

At% 84.24 01.90 03.74 10.11 ZAF

Fig. 7. EDS results of the present sand-cast alloys with different Zr contents: (a) 0 wt. % with (b) for spot 1, and (c) for zone 2, (d) 0.51 wt. % with (e) for spot 3, and (f) for zone 4.

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240 220 200 180 Stress /MPa 160 140 120 100 80 60 40 20 Zr content 0 0.19% 0.51% 0.61% 0.70% 0 1 2 3 4 5 6 7 Strain /% 8 9 10 11

Fig. 8. The effect of Zr content on the engineering strain-stress curves of the sand-cast GW103 alloys.

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240 220 200 180 160 140 120 100 8

Strengthen /MPa

(a)

Elongation /%

6 4 2 0 0.0 0.1 0.2 0.3 0.4 Zr / wt. % 0.5 0.6

UTS YS El

Strengthen /MPa

Elongation /%

Fig. 9. (a) The tensile properties of sand-cast alloys and (b) the permanent mold cast alloys [13].

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YS UTS El

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0.3

0.4 0.5 0.6 Zr / wt. %

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160 (a) 150 140

8.1, 0.70 8.3, 0.61 9.7, 0.51 10.2, 0.45 10.8 0.39

YS / MPa

130 120 110 100 90 12.8, 0.19 13.4, 0 fv (%), Zr(%) 0.06 0.08

Equation

y = a + b*x

Instrumental Weight 5.47886 Residual Sum of Squares -Pearson's r Adj. R-Square G G 0.98728 Value Intercept Slope 60.10133 653.74052 Standard Error 3.71896 30.2628

YS / MPa

Fig. 10. (a) The empirical relationship between YS and d-1/2 and (b) the empirical relationship between YS and the volume fraction of the second phase fV.

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160 (b) 150 140 130 120 110
Equation Weight Residual Sum of Squares Pearson's r Adj. R-Square

0.10 -1/2 -1/2 d / m

0.12

0.14

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47,0.70 51,0.61
y = a + b*x Instrumental 17.63225 -0.95906 V alue Intercept Slope 248.61794 -1113.38019

54,0.51 60,0.45

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Standard Error 9.49938 93.57919 G G

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0.08

0.09

0.10

0.11 fV / %

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Fig. 11. Typical SEM images at two magnifications showing the fracture surfaces of sand-cast GW103 alloys with different Zr contents: (a) and (b) 0, (c) and (d) 0.45 wt. %, (e) and (f) 0.71 wt. %.

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List of Tables Table 1 Chemical composition (wt. %) of GW103K alloys at different pouring temperatures.

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Table 1 Chemical composition (wt. %) of studied Mg10Gd3Yx Zr alloys.

Alloy 1# 2# 3# 4# 5# 6# 7# Gd 10.07 10.11 10.04 10.09 10.08 10.12 10.10 Y 2.68 2.62 2.71 2.70 2.67 2.74 2.75 Zr 0.0022 0.19 0.39 0.45 0.51 0.61 0.70 Mg Bal. Bal. Bal. Bal. Bal. Bal. Bal.

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