High strength Mg-Zn-Y alloys containing quasicrystalline particles

D. H. Bae and D. H. Kim

Center for Non-crystalline Materials, Department of Metallurgical Engineering, Yonsei University, 134 Shinchon-dong Seodaemun-gu, Seoul, 120-749, Korea example, AZ31, AZ61 and ZK60, normally exhibit the moderate Abstract High strength Mg-rich Mg-Zn-Y(-Zr) alloys, strengthened by quasicrystalline particles, have been developed by thermomechanical processes. The deformation behaviors of these alloys at room and high temperatures have been investigated and compared to those of commercial alloys AZ31, AZ61 and AZ91. Yield strengths of the Mg-Zn-Y alloys, which increase with an increase in the volume fraction of quasicrystalline phase, are relatively high due to the strengthening effect of quasicrystalline particles. At high temperatures (300 425oC), the flow stress levels of the Mg-Zn-Y alloys are lower than those of AZ31, AZ61 and AZ91, while their elongations to failure are larger. Quasicrystalline particles in the Mg-Zn-Y alloys resist coarsening during deformation at temperatures up to the eutectic temperature, leading to a stable distribution of quasicrystalline particles. Stability of both quasicrystalline particles and microstructure of the -Mg matrix in the Mg-Zn-Y alloys provides large elongation with no void opening at the interface between the quasicrystalline phase and the -Mg matrix. I. Introduction Significant interest currently exists in the development of wrought magnesium alloys with high strength, high corrosion resistance, and excellent formability at elevated temperatures for applications as structural parts. The typical wrought alloys, for strength at ambient temperature and poor creep resistance [1]. For the purpose of the practical usage of a wrought Mg alloy as structural parts, however, its mechanical properties of strength, fracture toughness, and creep resistance should be further improved in a low temperature regime, typically up to 200oC, and final products can be easily fabricated with low-cost using conventional forming technologies at elevated temperatures. Recently, it was reported that as-cast Mg-rich Mg-Zn-Y alloys (produced by permanent mould casting), which were consisted of a thermally stable icosahedral quasicrystalline phase (I-phase) in-situ formed as a second phase of the eutectic in the Mg matrix during solidification, exhibited yield stress from 180 to 480MPa at room temperature, depending on the volume fraction of I-phase [2]. Quasicrystals are isotropic and posses specially ordered lattice structure called the quasiperiodic lattice structure [3]. When an alloy possesses quasicrystals as a second phase, they are stable against coarsening at high temperatures due to the low interfacial energy of quasicrystals [4], providing the improved bonding properties in the I-phase/matrix interface. The disadvantage of the low eutectic temperature of a Mg-Zn binary alloy (~ 340oC) was also surmounted in the Mg-Zn-Y alloy since small amount of Yttrium could increase the eutectic temperature of the Mg-Zn-Y alloy significantly [5]. In this study, several Mg-rich Mg-Zn-Y alloys, each containing different amount of I-phase, were selected in the

Magnesium Technology 2002 Edited by H.I. Kaplan TMS (The Minerals, Metals & Materials Society), 2002

compositional range up to the eutectic Mg73.2Zn23Y3.8 (where the ratio of Zn to Y is around 6) since these alloys can be rolled at high temperatures. We utilized the conventional thermomechanical processes, i.e. hot-rolling and annealing, for the as-cast alloys. During the hot-rolling process, as-cast I-phase structure formed in the interdendritic region was broken to be changed to small particles distributed in the -Mg matrix. Uniaxal tension tests were performed on alloy sheets at room and high temperatures, and the effect of I-phase particles on flow behavior and correlated microstructural evolution during deformation was investigated. 2. Materials and Experimental Procedure For this study, test materials were Mg96Zn3.4Y0.6 and Mg95Zn4.3Y0.7 alloys in atomic percentage. A Mg94.8Zn4.3Y0.7Zr0.2 alloy was also prepared since an addition of small amount of Zr in the Mg-Zn-Y alloy may provide finer solidified microstructure [6]. For comparison, commercial alloys, AZ31 and AZ61, were provided by Korea Institute of Industrial Technology in the as-cast condition. Also an AZ91 alloy was provided in the hot-extruded condition. Each alloy was separately prepared by melting from high purity 99.9%Mg, 99.9%Zn, 99.95%Y and 99.9%Zr under a dynamic air/carbon dioxide/sulfur hexafluoride atmosphere. The as-cast Mg-Zn-Y(-Zr) alloys were consisted of two phases of Mg and I-phase of Mg3Zn6Y1 [7] as shown in Fig. 1 (a) of a SEM micrograph of a Mg94.8Zn4.3Y0.7Zr0.2 alloy, in which eutectic pockets were seen. All alloys except for an AZ91 alloy were hotrolled from 12 mm to 1 mm final thickness (reduction ~ 92%). An AZ91 alloy was hot-rolled 5 mm to 1 mm final thickness (reduction ~ 80%). The rolls were heated to around 100oC prior to rolling. The block samples were heated at 400oC for 10min and then rolled with a reduction of ~ 15% per one pass. The sheets were annealed at 400OC for 0.5 hour in an air circulating furnace. For Mg-Zn-Y(-Zr) alloys, the as-cast eutectic pocket structure was destroyed during rolling, providing the distribution of particles (0.5 2.0 m in size) in the -Mg matrix as shown in Fig. 1(b) of a SEM image of a hot-rolled Mg94.8Zn4.3Y0.7Zr0.2 alloy, in which the structure of I-phase remains [8]. The test materials were cut in three orthogonal sections, mechanically polished, and then etched with an etchant (1 ml HNO3, 24 ml water, and 75 ml ethylene glycol). The -Mg grains developed during hot-rolling via dynamic recrystallization (DRX) process were found to be equiaxied in all alloys, and the linear intercepted grain sizes of the alloys were listed in Table 1. Fine grained structure of an initial grain size (DO) of 7.7m was developed in Mg-Zn-Y and Mg-ZnY-Zr alloys due to the effect of large amount of particles in the DRX process. Grain size of an AZ91 alloy was found to be larger than that of an AZ61 alloy. This may be due to the lower reduction amount of the alloy in the hot- rolling process.

(a)

(b)

T L
Fig. 1. Secondary electron micrographs of a Mg94.8Zn4.3Y0.7Zr0.2 alloy: (a) as-cast; (b) hot-rolled on the L-T plane, where L and T refer to the longitudinal and transverse directions, respectively.

The volume fraction of I-phase, measured by an image analysis method, was around 8% for an Mg96Zn3.4Y0.6 alloy (see Table 1). During continuous heating at a heating rate of 0.67 K/s in differential thermal analysis (DTA), first endothermic peak appeared with onset temperature of around 440oC for Mg-Zn-Y and Mg-Zn-Y-Zr alloys as shown in Fig. 2. This peak was recognized as the melting of the eutectic pockets of the alloys. The finishing temperature of the second endotherm was around 640oC. Uniaxial tensile tests were carried out on dog-bone specimens of the hot-rolled sheets (specimen gauge length = 7mm) under a constant cross-head speed condition of an initial strain rate of 10-3s-1 at room temperature and under a constant strain rate condition at high temperatures up to 425 OC in the strain rate range of 10-4s-1 and 10-1s-1. Cross-head speed was controlled by computer through a digital interface board on an Instron-type machine. Before the test, the load train was preheated to the test temperature within a clamshell furnace having three heating zones independently controlled, and then the test was performed by

elongation observed in the large number of I-phase particles

2.0

As-cast

reinforced Mg-Zn-Y alloy is unusual. Generally, elongation is low for the alloy containing large amount of intermetallic particles since geometrically necessary dislocations are formed in the
Mg94.8Zn4.3Y0.7Zr0.2

1.5

1.0

region surrounding the hard particle, eventuating in decohesion from the matrix [9]. The Mg-Zn-Y alloys can be strengthened by large number of I-phase particles and solute atoms of Zn and Y in

T ( C)
O

0.5

0.0

Mg96Zn3.4Y0.6

-0.5

the -Mg matrix. However, 18% drop in yield stress for the Mg94.8Zn4.3Y0.7Zr0.2 alloy, compared to that of the Mg95Zn4.3Y0.7 alloy having similar microstructure, indirectly infers that the
600 700

-1.0 300

400

500

strengthening effect of I-phase is only moderate. A Zr addition in the Mg-Zn-Y alloy may decrease the solubility of alloying elements in the -Mg matrix, softening the alloy. Further studies are necessary to clarify the compositional difference in the -Mg matrix between two different alloys. Thus, we believe that the improvement of mechanical properties by I-phase particles is somewhat different from those by intermetallic particles (i.e. Mg17Al12) in the Mg-Al-Zn alloys. The quasi-periodic lattice

Temperature, C

Fig. 2. DTA traces showing melting endotherms obtained during heating at a heating rate of 0.67 K/s for Mg96Zn3.4Y0.6 and Mg94.8Zn4.3Y0.7Zr0.2 alloys.

placing the specimen into the load train. Typically the heatingplus-holding time prior the test was around 10 min. The fluctuation of the temperature during the test was 1 C. Microstructures of the tested specimen were observed by optical microscope (OM) and scanning electron microscope (SEM). The -Mg grain size was determined by the linear intercept method. To understand the role of the I-phase during deformation, the interface between I-phase and the matrix was carefully examined using TEM. Thin foil specimens for TEM observation were prepared by an ion beam milling method and were observed in a JEOL 200CX microscope. 3. Results and Discussion 3.1 Mechanical behavior at room temperature The mechanical properties of 0.2 percent yield stress (0.2), ultimate tensile strength (UTS) and elongation to failure are listed in Table 1. The Mg96Zn3.4Y0.6 alloy shows the high level of yield stress around 210MPa and UTS 355MPa, similar to those of an AZ91 alloy, and large elongation around 23 percent. The large Table 1. Properties of tested Mg alloys at room temperature a. Alloy AZ31 AZ61 AZ91 Mg96Zn3.4Y0.6 Mg95Zn4.3Y0.7 Mg94.8Zn4.3Y0.7Zr0.2
a o

structure of I-phase provides the stable I-phase particle/matrix interface [4], which may be achieved by accommodating the lattice spacing between them, providing the lower lattice mismatching strain in the -Mg matrix. 3.2 Flow behavior and microstructural evolution during deformation at high temperatures Typically for magnesium alloys the extensive microstructural evolution by DRX or grain growth is occurred at high temperatures, depending on the deformation mechanism [10]. These processes influence the stress level during deformation and formability of the alloy. Stress vs strain curves at a strain rate of 10-3s-1 and a temperature of 300oC are shown in Fig. 3 for AZ31, AZ91, and Mg96Zn3.4Y0.6 alloys. The I-phase reinforced alloy exhibits the lower level of yield stress but higher elongation. The stress level is dependent on the strain. Typically the alloys containing second phase particles reach a peak at low strain and then decrease continuously with increasing strain. However, the AZ31 alloy exhibits strain hardening in the low strain range and

Grain Size (DO), m 17.6 9.9 13.4 7.8 7.7 7.8

Vol. Fraction of Second Phase

Yield Stress (0.2), MPa 152 175 225

UTS, MPa 275 320 395 355 370 325

Elongation to failure, % 22.0 19.8 18.2 23.4 19.7 23.5

0.08 0.09 0.09

210 220 180

Specimen dimension for tensile testing: gauge thickness, 1.0mm; gauge length, 7mm. Uniaxial tension test: initial strain rate, 10-3s-1.

be due to the particle pinning effect, decreasing the contribution of

100 90 80 70

Temp. = 300 C Strain Rate = 1x10 s AZ91 AZ31 Mg96Zn3.4Y0.6

-3 -1

grain boundary sliding to total elongation. For the AZ31 and AZ61 alloys, however, strain hardening is observed in the low strain range and then the flow stress decreases with increasing strain. This stress drop in the high stain range is found to be due to not recrystallization but necking. Both alloys exhibit an abnormal grain growth in this test condition as shown in
100 90

Stress (MPa)

60 50 40 30 20 10 0 0.0 0.1 0.2 0.3

(a)

Temp. = 425 C Strain Rate = 1x10 s

-1 -1

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

80 70

Strain

AZ61

AZ31 Mg96Zn3.4Y0.6 Mg94.8Zn4.3Y0.7Zr0.2

Stress (MPa)

60 50 40 30 20 10 0 0.0 0.2 0.4 0.6

Fig. 3. Stress vs strain curves for four different Mg alloys of AZ31, AZ91, and Mg96Zn3.4Y0.6 obtained from the uniaxial tension test conducted at a strain rate of 1x10-3s-1 and a temperature of 300OC.

0.8

1.0

1.2

1.4

then the flow stress decreases with increasing strain. This incubation strain may be necessary for dynamic recrystallization in the AZ31 alloy since the nucleation site of recrystallization is limited only to the grain boundaries. The AZ91 alloy shows the significant stress drop mainly due to the extensive DRX process (i.e. grain refinement from 13.4 to 7m). The intermetallic particles of Mg17Al12 in the AZ91 alloy can effectively provide the site for an initiation of recrystallization. However, the variation of flow stress for large amount of an I-phase particle reinforced alloy is much low. Since the particles are closely spaced in the Mg-Zn-Y alloy, particles can exert a significant pinning effect on both low and high angle grain boundaries, hindering recrystallization [11]. To further investigate the temperature and strain rate effect on the flow behavior and microstructural evolution, stress vs strain curves at a test temperature of 425 C and strain rates of (a) 10 s
o -1 -1

Strain

50 45 40 35

(b)

Temp. = 425 C Strain Rate = 1x10 s AZ31 AZ61

-3 -1

Stress (MPa)

30 25 20 15 10 5 0 0.0

Mg94.8Zn4.3Y0.7Zr0.2

Mg96Zn3.4Y0.6
0.2 0.4 0.6 0.8 1.0 1.2 1.4

Strain

and (b) 10-3s-1 are plotted in Fig. 4 for AZ31, AZ61, Mg96Zn3.4Y0.6 and Mg94.8Zn4.3Y0.7Zr0.2 alloys. The concurrent variation of average grain size (D) as a function of strain for largely strained samples can be related to the following form [12-13]. D = DO + (1) Fig. 5, providing only small uniform elongation. Fine grained MgZn-Y(-Zr) alloys showing large elongation under the high strain rate deformation condition is very attractive in industry for the fabrication of complex parts by the practically used forming technologies. At a strain rate of 10-3s-1, typically grains grow dynamically with increasing strain for all alloys as shown in Fig. 5. However, where is a constant and is a strain. Based on Eq. (1), Fig. 5 shows the values normalized initial grain size, (1/DO)(dD/d), are plotted as a function of strain rate for different alloys. At a high strain rate of 10 s , I-phase reinforced alloys also exhibit the lower level of yield stress but higher elongation. The Mg-Zn-Y alloy is found to be no grain elongation to loading direction but only a grain refinement as shown in Fig. 5. However, the flow stress slightly increases with increasing strain. This may
-1 -1

Fig. 4. Stress vs strain curves at two different strain rates of (a) 101 -1

s and (b) 10-3s-1 at a test temperature of 425OC for four different

Mg alloys of AZ31, AZ61, Mg96Zn3.4Y0.6 and Mg94.8Zn4.3Y0.7Zr0.2.

near the eutectic pocket before testing (see Fig. 1(b)) move away each other during deformation, being distributed more randomly in
1.5

the test specimen. Surprisingly, the particles do not coarsen, but

Abnormal grain growth

1.0

only the shape of the particle, initially faceted, evolves to be somewhat rounded as shown in Fig 6(b). The inset in Fig. 6(b) shows the diffraction pattern taken from the particle, in which a 5fold symmetry can be identified as an I-phase. The existence of Iphase in the deformed specimen clearly indicates that I-phase thermally equilibrates with -Mg phase. Furthermore, any debonding or nanoscale defect at the particle/matrix interface

(1/DO) dD / d

0.5

AZ31
Grain Growth Grain Refinement

AZ61

0.0

-0.5

Mg96Zn3.4Y0.6

-1.0 -4 10

10

-3

10

-2

10
-1

-1

10

cannot be seen in the test specimen. In general, particle/matrix debonding has been considered as an initial stage of the failure mechanism at high temperature deformation in the alloy consisting of intermetallic compound particles at grain boundaries, and the coalescence of many cavities at large strains can induce the

Strain Rate, s

Fig. 5. Grain size variation, (1/DO) dD/d, plotted as a function of strain rate at a test temperature of 425OC for three different Mg alloys of AZ31, AZ61 and Mg96Zn3.4Y0.6.

(a)
the variation of the stress level is relatively low for the AZ31 alloy having larger grains, compared to that for the AZ61 alloy exhibiting superplastic deformation (which is evinced by no diffuse necking in the deformed specimen and void formation at the grain boundaries), since the contribution of grain boundary sliding to total deformation is relatively low for the large grained alloy [14]. The Mg-Zn-Y alloy shows slight grain growth with no grain elongation to the load direction, providing a slight increase in the flow stress during deformation. The most interesting thing observed in the Mg-Zn-Y alloys is that elongation is quite large with no void formation, comparable to that in the superplastic AZ61 alloy containing large number of voids at the grain boundaries. Due to the pinning effect of large number of I-phase particles in the fine grained Mg-Zn-Y alloys, the contribution of grain boundary sliding to total elongation may be weak, providing no void formation, but the large elongation with the maintenance of the equiaxied grain shape can be achieved by grain boundary diffusion with the relatively lower grain growth processes. In addition, void formation at the particle/matrix interface may be difficult since the eutectic can be softened at this high temperature. 3.4 Role of quasicrystals in the improvement of mechanical properties To understand the role of I-phase particles in the alloy at high temperature, microstructures of a deformed specimen were examined. Figs. 6(a) and (b) show, respectively, a SEM image and a bright-field TEM image of the Mg95Zn4.3Y0.7 alloy deformed to a strain of around 1.0 with a strain rate of 10 s
o -4 -1

T L

(b)

Fig. 6. (a) SEM on the L-T plane and (b) bright-field TEM images of a I-phase particle in the Mg95Zn4.3Y0.7 alloy deformed to a strain of 1.0 at the test condition of a strain rate of 10-4s-1 and a test temperature of 400 OC. An electron diffraction pattern of a particle is inserted in (b).

at a test

temperature of 400 C. The flow stress of the alloy was constant (~ 10 MPa) over the strain range. The particles initially distributed

failure of such an alloy. For example, an intermetallic particle of Mg17Al12 in an AZ91 alloy [15]. Many defects have been reported to develop in the particle/matrix interface during the thermomechanical processing possibly due to the mismatched lattice structure of the particle to the matrix. Sometimes these defects can grow rapidly due to the constrained material flow near the particle at high temperature [16]. However, careful examination of the I-phase/matrix interface in the Mg95Zn4.3Y0.7 alloy does not reveal any defects. The structure of I-phase in MgZn-Y alloys is the face-centered I-phase [17], but the details on atomic structure are clearly unknown yet. However, the I-phase exhibits more isotropic characteristic than crystalline particles due to its high symmetric structure. This may provide the reasonably stable bonding with low strain energy at the matrix adjacent to the I-phase particle. In general, the matrix adjacent to the microscale intermetallic particle is highly stressed due to the mismatched lattice constants between the matrix and the particle. However, due to the quasiperiodic lattice structure of I-phase, the mismatched strain may be compromised by the I-phase particle, decreasing the stress concentration in the matrix near the I-phase particle. Within our knowledge, the diffusivity of Y in Mg is not available. However, low diffusivity is expected by considering large difference in atomic size between Mg and Y. Furthermore, the low interfacial energy of quasicrystals reduces the driving force for coarsening the particle, leading to the stable size of the particles [4]. These may be responsible for the negligible coarsening of Iphase during high temperature deformation as shown in Fig.6(a). 4. Conclusions In summary, fine grained magnesium alloys reinforced by quasicrystalline particles were easily developed by thermomechanical processes for as-cast Mg-rich Mg-Zn-Y and Mg-Zn-Y-Zr alloys. An addition of Zr in the Mg-Zn-Y alloy does not influence the hot-rolled microstructure but decreases the solubility of the alloying elements. The mechanical behaviors of the alloys at room and high temperatures was investigated and compared to those of commercial alloys AZ31, AZ61 and AZ91. Yield strengths of the Mg-Zn-Y alloys are relatively high due to the strengthening effect of quasicrystalline particles. But their strengthening effect is moderate. At high temperatures, the levels of flow stress of the Mg-Zn-Y alloys are lower than those of commercial magnesium alloys due to the softness of the eutectic region and finer grained structure. But the alloys exhibit much higher elongation at high strain rates and/or at low temperatures since large number of quasicrystalline particles in the Mg-Zn-Y alloys can effectively prohibit against microstructural evolution of the -Mg matrix during deformation. Furthermore, I-phase particles in the Mg-Zn-Y alloys are stable against coarsening

during deformation near the melting temperature of the eutectic, forming the stable quasicrystalline particle/matrix interface. Those stabilities provide large elongation with no void opening at the interface between the quasicrystalline particle and the -Mg matrix. The observed mechanical properties of high strength at room temperature and large elongation at high temperatures can open interesting perspectives for the applications of such quasicrystalline paticle reinforced composite materials as sheet components. Acknowledgements This work was funded by Creative Research Initiatives of the Korea Ministry of Science and technology. References 1. M. M. Avedesian and H. Baker, eds., Magnesium and Magnesium alloys, (ASM Inter., Metal Park, OH 44073, 1999). 2. E. S. Park, S. Yi, J. B. Ok, D. H. Bae, W. T. Kim, and D. H. Kim, submitted to Proc. MRS Fall Meeting, Boston, MA, (2001). 3. C. Janot, Quasicrystals, (Oxford, Clarenson Press, 1994). 4. J. M. Dubois, P. Plaindoux, E. Belin-Ferre, N. Tamura and D. J. Sordelet, Proceedings of the 6th international Conference on Quasicrystals, ed. Fujiwara and Takeuchi, World Scientific, Singapore, (1997). 5. E. M. Padezhnova, E. M. Melnik, and T. V. Dovatkina, Akademiia Nauk SSSR, Izvestiia, Metally, (1982), 179. 6. W. F. Smith, Structure and Properties of Engineering Alloys, (McGraw-Hill, Inc., New York, 1993), 542. 7. A. P. Tsai, A. Niikura, A. Inoue and T. J. Masumoto, Mater. Res., 12 (1997), 1468. 8. D. H. Bae, S. H. Kim, W. T. Kim and D. H. Kim, submitted Mater. Trans., JIM (2001). 9. T. H. Courtney, Mechanical behavior of Materials, (McGrawHill, Inc., 1990), 426. 10. A. Galiyev, R. Kaibyshev and G. Gottstein, Acta Mater, 49 (2001), 1199. 11. F. J. Humphreys and M. Hatherly, Recrystallization and Related Annealing Phenomena, (Pergamon, Oxford, 1995). 12. D. S. Wilkinson and C. H. Caceres, Acta metall., 32 (1984), 1335. 13. F. Li, D. H. Bae and A. K. Ghosh, Acta Mater., 45 (1997), 3887. 14. D. H. Bae and A. K. Ghosh, Acta Mater., 48 (2000), 1207. 15. Y. Z. Lu, Q. D. Wang, W. J. Ding, X. Q. Zeng and Y. P. Zhu, Mat. Lett., 44 (2000), 265. 16. A. K. Ghosh, D. H. Bae and S. L. Semiatin, Mat. Sci. Forum. 304-306 (1999), 609. 17. E. Abe, H. Takakura, A. Singh and A. P. Tsai, J. Alloys and Compounds, 283 (1999), 169.