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Acta Materialia 57 (2009) 13081317 www.elsevier.com/locate/actamat

The eect of Mg on the structure and properties of Type 319 aluminum casting alloys
J.Y. Hwang a, R. Banerjee a, H.W. Doty b, M.J. Kaufman c,*
Department of Materials Science and Engineering, University of North Texas, Denton, TX 76203, USA b General Motors Powertrain Group, Metal Casting Technology, Milford, NH 03055, USA c Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, CO 80401, USA Received 20 June 2008; received in revised form 8 November 2008; accepted 9 November 2008 Available online 26 December 2008
a

Abstract The precipitation hardening behavior of a Type 319 aluminum alloy (Al6.7 wt.% Si3.75 wt.% Cu) with and without 0.45 wt.% Mg has been investigated. It is shown that both h and Q phase exist in the as-cast samples and are dissolved during solution heat treatment. Subsequent articial aging results in the precipitation of both the metastable h0 phase typical of aged alloy 319 and, in the case of the Mgcontaining alloy, an additional and extremely small phase, which was identied as Q0 based on previous literature. Both types of precipitates have been characterized using transmission electron microscopy (TEM) and three-dimensional atom probe (3DAP) tomography. The Mg-containing alloy exhibits higher strength and lower ductility, presumably due to both solid solution strengthening and the presence of the ne Q0 phase. 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Aluminum alloys; Aging; Precipitation hardening; 3DAP; TEM

1. Introduction Type 319 aluminum casting alloys are widely used in the automotive industry due to their acceptable combination of mechanical properties, corrosion resistance, good castability and low cost [1]. Several attempts are being made to improve the mechanical properties including minor alloying additions. For example, it is shown that Mn additions result in ductility increases [2] while increases in strength have been observed in the case of Mg additions [3]. However, it remains unclear as to how such small additions of Mg inuence the microstructure and mechanical properties, i.e., whether it is primarily a solid solution hardening eect, a precipitation hardening eect or a combination of the two. For example, DasGupta et al. did not observe any signicant improvement in the mechanical properties of alloy 319 with the addition of 0.534 wt.%
*

Corresponding author. E-mail address: mkaufman@mines.edu (M.J. Kaufman).

Mg after a T5 heat treatment [4], whereas Zindel et al. reported that only 0.15 wt.% Mg resulted in a signicant increase in the hardness with no further increase up to 0.45 wt.% Mg [5]. These contrasting reports indicate that there is a relatively poor understanding of the articial aging response in these alloys. It is well established that metastable h0 -Al2Cu is the primary strengthening phase responsible for the precipitation hardening response of these alloys [6]. Small ($0.5%) Mg additions lead to increases in the T6 strength over Mg-free alloys [7]; while such increases have been reported in the literature, there have been considerable discrepancies in the identication of any additional ne-scale precipitates that form due primarily to the challenges in characterizing such nanoscale precipitates. For example, some authors reported the presence of additional small precipitates although the identication ranged from the binary b0 (Mg2Si type) phase [8], to the ternary S0 (Al2CuMg type) phase [9], to the quaternary Q0 (containing Al, Mg, Si and Cu) phase [10] in these AlSiCu based casting alloys containing Mg.

1359-6454/$34.00 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.actamat.2008.11.021

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Jahn et al. [10] reported that this quaternary phase forms such a small volume fraction of precipitates that it should be negligible for contributing to the hardening behavior. In addition, due to its very small dimensions, it has been dicult to characterize its structure and composition using conventional transmission electron microscopy techniques. As a result, there have been inconsistencies in the composition and structure reported by dierent investigators [1112]. The objectives of this study were to evaluate the role of Mg on the microstructure in both as-cast and aged samples, and to correlate the mechanical properties with the microstructural observations. Analytical transmission electron microscopy (TEM) was used to identify the structures and morphologies of the various precipitates in both the Mg-free and Mg-containing Type 319 aluminum alloys while three-dimensional atom probe tomography was used to measure the compositions of the various precipitates. The results from these combined techniques help to clarify the role of Mg on the precipitation hardening response of Type 319 aluminum alloys containing minor Mg additions. 2. Experimental procedures In order to investigate the eects of Mg on the precipitation hardening behavior of the 319 aluminum alloys, a Mg-free alloy and an alloy containing 0.45 wt.% Mg were used in these experiments. The overall compositions of these two alloys are presented in Table 1. The casting conditions and post-annealing treatments were described in another paper [2]. After casting, the samples were solution-treated at 488 C for 8 h and quenched in warm water. The subsequent T6 aging treatment was carried out at 193 C for 8 h. Microstructural characterization was performed using optical microscopy, scanning electron microscopy (Quanta 200 ESEM) and transmission electron microscopy. For the latter, both conventional and high-resolution TEM analyses were performed using both a FEI Tecnai F20 ST analytical HRSTEM and a Philips EM420 TEM on samples that were produced by conventional electropolishing and argon ion milling techniques. 3D atom probe tomography, using a local electrode atom probe (LEAP) from Imago, Inc., was used to determine the three-dimensional morphologies, and compositions of the various phases. For these studies, sharp, needle-like specimens (<100 nm tip radius) were prepared from the regions of interest using a NOVA 200 focused ion beam (FIB)-eld emission SEM system; these were then lifted out using an Omniprobe nanomanipulator and
Table 1 Compositions of the Type 319 aluminum alloys used in this study. Element (wt.%) Al Mg-free Mg-containing Bal Bal Si 6.7 6.7 Cu 3.75 3.75 Fe 0.6 0.5 Mg 0 0.45 Mn 0 0.02

attached to silicon microtips. The samples of interest were sharpened and then inserted into the LEAP 3DAP for analysis. All atom probe experiments were carried out in the electric-eld evaporation mode with the evaporation rate varying from 0.2% to 1.0% and the pulsing voltage at 20% of the steady-state applied voltage. The specimen temperature during atom probe analysis was held at 60 K. 3. Results 3.1. As-cast microstructures The as-cast microstructures of the two 319 aluminum alloys consist of a-Al dendrites, plate-shaped b-Al5FeSi intermetallics, eutectic Si, and equilibrium h-Al2Cu (Fig. 1). Fe is the most common impurity in aluminum alloys. Due to low solubility in aluminum, iron-containing intermetallic phases are formed during solidication. These iron-containing intermetallic phases have detrimental eects on the mechanical properties [2]. In the case of the

Fig. 1. SEM microstructures of the as-cast condition in Mg-free (a), and Mg-containing (b) Type 319 aluminum alloys.

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alloy containing Mg, an additional phase was observed near the h-Al2Cu or silicon phases (Fig. 1b). Energy dispersive X-ray spectroscopy (EDS) analysis revealed that this additional phase was probably the quaternary Q phase with a composition of approximately Al39 at.%Mg 29 at.% Si11 at.% Cu although there was some variation in the compositions measured from dierent quaternary particles; this is consistent with reports of this phase in the literature, namely that the Q phase has reported compositions in the following ranges: 1926 Al, 711 Cu, 36 42 Mg and 2129 Si, and has been reported as Al4Cu2 Mg8Si7, Al5Cu2Mg8Si6, Al4CuMg5Si4 and Al4Cu2Mg8Si5 [11]. Also, it was noted that the Q phase was always in contact with the h phase, which suggests that it probably forms

during the nal eutectic reaction during solidication, in agreement with the thermal analysis results reported by Samuel et al. [13]. Such variations are a bit surprising and appear to come from the dierent compositions and solidication conditions of the alloys being investigated as well as possible errors in the measurements. From the AlSiCuMg quaternary phase diagram at 775 K and 4 wt.% Cu [14], the quaternary Q phase is expected to form with the a-Al, Si, and h phases in agreement with our experimental results. However, there are still arguments as to whether the Q phase has a unique composition or whether it exists over a range of compositions [15]. Transmission electron microscopy was used to determine the crystal structure of the Q phase from the as-cast

Fig. 2. Bright eld TEM (BFTEM) image of the Q phase and corresponding selected area diraction patterns taken from the zone axes indicated in the schematic stereogram from the Mg-containing 319 as-cast sample.

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sample. As can be seen in Fig. 2, the Q phase was surrounded by the Al matrix, which contained some matrix dislocations. Selected area diraction patterns (SADPs) obtained from the Q phase indicated that it has a hexagonal (P space group) unit cell with a $ 1.04 nm and 6 c $ 0.4 nm, consistent with the structure reported by Arnberg [16] who reported that the composition of the Q phase was approximately Al4Cu2Mg8Si7. Although the composition measured in this study is slightly dierent, the structural similarity indicates that this is indeed the same phase reported previously. 3.2. Microstructure in the T6 condition The SEM microstructures of the Mg-free and Mg-containing 319 aluminum alloys after the T6 heat treatment are shown in Fig. 3. It is obvious that solution heat treatment and aging aected the microstructural features. For example, a signicant amount of the ne eutectic phases such as Al2Cu and Q phase were dissolved in the matrix. It is noteworthy that Mg additions did not change the microstructure even after the heat treatment except for the dissolution of the Mg-containing Q phase. TEM analysis of the Mg-free alloy reveals thin plate-like h0 precipitates lying parallel to the {0 0 1} planes (Fig. 4a). The streaking along the 0 0 2 systematic rows in the SAD pattern (inset in Fig. 4a) is consistent with the thin nature of these precipitates. The dark eld image (Fig. 4b) reveals that these thin plates are faceted and frequently are square or rectangular in shape with typical dimensions on the order of 100 nm on a side. These plates also exhibit what appear to be slots along {0 0 1} and both slots and facets parallel to {0 1 1}; the reasons for these features are unclear and further work is needed to resolve the associated energetics. The h0 -Al2Cu plate shaped precipitates have the typical orientation relationship with the aluminum matrix 0 0 1h0 ==0 0 1Al and < 1 0 0>h0 == < 1 0 0 > Al

Fig. 3. SEM microstructures of the T6 condition in the Mg-free (a) and Mg-containing (b) Type 319 aluminum alloys.

Fig. 4. (a) BFTEM image and [0 0 1] SAD pattern from the Mg-free alloy after the T6 heat treatment. The extra reections and streaking in the SADP are consistent with the presence of thin h0 precipitates. (b) Dark eld TEM (DFTEM) image taken using one of the h0 reections that cause the h0 plates that lie approximately normal to the beam to light up. Note their faceted nature where the major facets are parallel to {0 0 1}.

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Fig. 5. (a) BFTEM image and [0 0 1] SAD pattern from the Mg-containing alloy after the T6 heat treatment. The extra reections in the SADP result from the presence of small Q0 precipitates. (b) DFTEM image obtained using a reection from the Q0 phase.

In the case of the Mg-containing sample, other smaller precipitates were observed in addition to the h0 plates (see Fig. 5). These ne particles appeared either faceted or lath-like where the long dimension is $10 nm and the short dimensions are less than 5 nm. From quantitative TEM image analysis, the volume fractions of h0 and Q0 precipitates were measured to be approximately 3.5 and 0.038 vol.%, respectively. Based on the morphology, this

phase appears similar to that reported by both Jahn et al. [10] and Chakrabarti and Laughlin [11]. They suggested that this phase was either Q0 or Q where Q0 is similar in structure to the stable Q phase. However, it is hard to identify the crystal structure and chemistry of this phase using conventional TEM methods due to its very small dimensions in spite of the reasonably high number density. While there has been a large amount of research conducted on the

Fig. 6. STEM micrograph showing the Q0 and h0 precipitates (a). High-resolution TEM images of Q0 precipitates taken two white arrows (b and c) and EDS spectra of Q0 (d).

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h0 phase and the associated precipitation hardening behavior, there has been little work on the eects of Q0 precipitation, possibly due to the ne scale of this phase and the limitations in characterization techniques. In order to identify these smaller, lath-shaped precipitates, they were examined using both high-resolution phase contrast imaging and EDS experiments (Fig. 6). Because these precipitates are considerably smaller than typical TEM foil thicknesses, it is dicult to obtain easily interpretable phase contrast images, diraction patterns or composition analyses in the TEM given that the surrounding matrix material cannot be readily excluded. Even so, it is possible to note that these lath-shaped precipitates contain Al, Cu, Si, and Mg (see EDS spectrum in Fig. 6d). Further, it is clear that the precipitates are probably cylindrical in shape where the cylinder diameter is approximately 5 nm with lengths on the order of 1020 nm. In order to determine the composition of the h0 and Q0 precipitates, the Mg-free and Mg-containing samples were analyzed by three-dimensional atom probe tomography. The 3D reconstruction of a region containing two h0 precipitates in the Mg-free sample are shown in Fig. 7. The size of the reconstruction in this case is 80 nm 86 nm 25 nm. The elemental maps of the solute elements (Fig. 7a) reveal Cu (green) enrichment in the two plates with only slight segregation of the Si (red). Two 17 at.%

Cu iso-concentration surfaces (isosurface) are shown in Fig. 7b; the two dierent perspective views of the isosurfaces provide a better view of the h0 morphology in the aluminum matrix and are consistent with the TEM images in Fig. 4. The one-dimensional compositional prole through the h0 phase (Fig. 7c) suggests a Cu concentration of 33%, consistent with Al2Cu and negligible concentrations of the other elements. Furthermore, the thickness of the plates is approximately 3 nm with widths (lengths) around 60 nm. 3DAP data from the Mg-containing sample (Fig. 8) indicates two dierent types of precipitates, consistent with the morphologies of the precipitates observed in the TEM (Figs. 5 and 6). The size of the reconstruction in this case was 62 nm 65 nm 55 nm. The Al ions were distributed throughout the matrix, while the Cu, Mg, and Si ions were primarily concentrated in the precipitates (Fig. 8a) with Cu enrichment in the larger h0 phase and Cu, Mg and Si enrichment in the smaller, presumably Q0 phase. Two different perspective views of the isosurfaces for Cu (20 at.%), Mg (25 at.%), and Si (10 at.%) are shown in Fig. 8b. The composition of the large phase was $66 at.% Al and 33 at.% Cu and, therefore, must correspond to the h0 phase, whereas the composition of the smaller phase appears to be approximately 21 at.% Al, 13 at.% Cu, 42 at.% Mg, and 24 at.% Si. A composition prole through one of the small precipitates (Fig. 8c) indicates

Fig. 7. Three-dimensional iso-concentration surface of the h0 precipitates in the Mg-free alloy at T6 condition (a) and (b); Cu (green), Si (red) and Mg (blue). The compositional proles through the h0 phase along the cylindrical line are shown in (c). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

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Fig. 8. Three-dimensional iso-concentration surface of the h0 precipitates in the Mg-containing sample at T6 condition (a) and (b); Cu (green), Si (red), Mg (blue). The compositional proles through the Q0 phase along the cylindrical line is shown in (c). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

that these precipitates have almost the same composition as the equilibrium Q phase described in the as-cast sample in Fig. 2. In addition, this phase is dierent from the ternary S (Al2CuMg) and binary b (Mg2Si) type precip-

itates reported in some alloys and, therefore, appears to be similar to the Q phase that was present in the as-cast material but went into solution during the solution heat treatment.

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Fig. 9. Ultimate tensile strength and % elongation of Mg-free and Mgcontaining samples in the as-cast (blue) and the T6 (red) conditions. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

3.3. Mechanical property studies The ultimate tensile strengths and percentage elongations of the as-cast and T6 alloys with and without Mg (Fig. 9) indicate that there is slightly higher UTS in the as-cast alloy containing Mg. Such small increases in UTS with Mg additions have been reported previously [3]. A considerably greater enhancement in UTS was observed after heat treating the alloys to their T6 condition. Specifically, there is an approximately 67% increase in the UTS of the Mg-containing alloy from 196 to 328 MPa upon aging, while in the case of the Mg-free alloy, only a 30% increase in UTS was observed after the same heat treatment. Unfortunately, the Mg-containing material displays a signicant decrease in ductility after aging; this strengthening eect and loss in ductility is believed to be due to Q0 precipitation as will be discussed in the following section. The lower elongations of the Mg-containing alloy in the T6 condition precluded a comparison of the yield strengths possibly due, in part, to the presence of the iron-containing b phase [2]. In spite of the limited ductility, the results indicate that it is possible to obtain a desirable strength enhancement in the 319 type aluminum alloys with proper additions of Mg and after appropriate heat treatments. 4. Discussion Even though there are considerable compositional differences between 319 casting alloys when compared with 2xxx and 6xxx series wrought alloys, which also contain Al, Si, Cu with Mg as primary alloying elements, they do rely on similar types of strengthening precipitates [19]. Chakrabarti and Laughlin summarized the phase elds of the quaternary AlMgSiCu system and the precipitation

sequences of both the metastable and equilibrium phases [11]. According to them, the Q0 phase is a metastable version of the Q phase (similar composition and hexagonal crystal structure) and forms with a lath-like morphology. In addition, they showed that the Q0 phase is likely to maintain the crystal structure and morphology from the peak aged through the overaged conditions. Thus, it appears that the metastable phase in our study is the Q0 phase even though there are some slight dierences between the reported compositions and morphologies. Ravi and Wolverton suggested that the composition variation of the Q0 precipitates should be temperature dependent, which could explain the various compositions reported for the Q0 phase and the confusion arising from the use of dierent nomenclatures for the same phase [20]. The present results indicate good agreement with Q0 type precipitates and provide both composition, as measured by 3DAP, and morphology, as determined by TEM. Signicantly however, even though the morphology and composition of this phase were identied, it was dicult to ascertain the structure and orientation relationship with the matrix due to the very small size. These characterization challenges appear to be the reason for some of the confusion in the literature surrounding the identication of these precipitates in both wrought and cast aluminum alloys. Indeed, the metastable phases in the quaternary AlMgSiCu system have been variously reported as different phases with dierent stoichiometries [11,1719]. Given these challenges, attempts were made to coarsen the precipitates by subjecting a T6 sample to an overaging treatment of 300 C for 48 h. TEM analysis (Fig. 10) revealed both h0 -Al2Cu precipitates, still having plate-like morphologies along {0 0 1} matrix planes, and coarsened Q precipitates (circled area); the latter were examined at higher magnication (Fig. 10a) and using microdiraction. The microdiraction pattern was indexed as being consistent with the same hexagonal P  structure as observed in 6 the as-cast material described above. Thus, coarsened Q precipitates can apparently be formed by coarsening the Q0 precipitates during aging. Given that both of these are quaternary phases with similar compositions that are consistent with the Al4Cu2Mg8Si7 phase reported by Mondolfo [14], it is not surprising that they are also structurally similar. Furthermore, Gao et al. [21] reported the orientation relationship (OR) between Q phase and the face-centered 3 cubic (fcc) matrix as <0 0 0 1>Q//<0 0 1>Al and {2 1  0}Q// {1 0 0}Al. Given that the c-axis of the Q phase is similar in magnitude to the lattice parameter of Al, it has been suggested that the c-axis should align along a cube axis of the matrix in order to minimize strain energy [15]. These precipitates have also been reported to have {5 1 0} habit planes, which have been related to the similar repeat distances along these planes in the two structures [11]. In the case that Q precipitates lie along {5 1 0} matrix habit planes which, in turn, are parallel to [2 11 0]Q for perfect plane matching, the orientation relationship can also be written as <2 11 0>Q//<5 1 0>Al, (0 0 0 1)Q//{0 0 1}Al

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Fig. 10. BFTEM image (a) and microdiraction pattern from the Mg-containing alloy after the overaging treatment (b). The orientation relationship between aluminum matrix and two dierent h0 and Q precipitates are illustrated in (c) and (d).

[11,2223]. In the present study, the orientation relationship observed between aluminum and the Q phase was determined in the overaged samples and is presented in

Fig. 10c and d. Schematics of the SADPs from these overaged Q particles (Fig. 10d) indicate that the OR can be written as:

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< 5 14 0>Q == < 0 0 1>Al ; 0 0 0 1Q ==1 0 0Al Weatherly et al. suggested that when TEM foils are oriented along the [001] zone axis of the matrix, the Q precipitates should be elongated along either the [0001], [5 14 0] or  3  0 orthog1 2 onal zone axes of the Q phase based on this OR [15]. The present results are consistent with these suggestions. They also reported that Q precipitates found in the AA6111 alloys appear similar to those observed in the 319 alloys. Closer examination of the iso-concentration surfaces in Fig. 8b indicates that there may have been heterogeneous nucleation of the h0 plates on the edge of lath type-Q0 precipitates. Given that the SADP in Fig. 10c still indicates that the OR does not change from that reported above, it appears that the lath-shaped Q0 precipitates may play a signicant role not only as a hardening phase but also as heterogeneous nucleation sites for the h0 phase. This is consistent with the results of Gao et al., who suggested a signicant increase in the number density of h0 plates in the Al4Cu0.3Mg0.5Si alloy compared to a silicon-free alloy [21]. They suggested that the lath-like Q precipitates, only observed in the presence of Si, may provide heterogeneous nucleation sites for the h0 phase. The eect of the Q0 precipitates on the heterogeneous nucleation of h0 will be discussed in a separate paper. This study suggests that the precipitation sequence in the Mg-containing 319 aluminum alloy is as follows: AlSS ! GP zones ! h0 Q0 ! h Q The plate-shaped h0 and cylindrical-shaped Q0 precipitates form with specic orientation relationships with the matrix. As a result, both precipitates appear to strengthen this alloy based on well-established particle hardening models that relate the crystal structure and morphological features. A more quantitative treatment of the precipitation hardening eects from these two dierent precipitates needs to be performed in future studies. 5. Conclusions The compositions and morphologies of nanoscale h0 and Q precipitates in a Mg-containing Type 319 aluminum alloy have been characterized using both three-dimensional atom probe tomography and high-resolution transmission electron microscopy. It is shown that the Q0 precipitates are lath-shaped and enriched in Mg, Cu and Si with a composition almost identical to that of the stable Q (Al4Cu2Mg8Si5) phase that is present in the as-cast condition. Further, the h0 phase appears as thin plates with a
0

composition near Al2Cu and no other components. Likewise, the ner precipitates appear to be quaternary in nature and have been designated Q0 to be consistent with previous investigators. The orientation relationship of the Q0 precipitate is <5 14 0>Q0 //<0 0 1>Al, (0 0 0 1)Q0 //{1 0 0}Al with the aluminum matrix. Acknowledgements The authors would like to acknowledge the General Motors Powertrain Division for providing nancial support for this study. The authors also acknowledge the Center for Advanced Research and Technology at the University of North Texas supported by the Army Research Laboratory for access to the experimental facilities used for this study. References
[1] Li Z, Samuel AM, Samuel FH, Ravindran C, Valtierra S, Doty HW. Mater Sci Eng A 2004;367:96. [2] Hwang JY, Doty HW, Kaufman MJ. Mater Sci Eng A 2008;488:496. [3] Tavitas-Medrano FJ, Gruzleski JE, Samuel FH, Valtierra S, Doty HW. Mater Sci Eng A 2008;480:356. [4] DasGupta R, Brown CC, Marek S. AFS Trans 1989;97:245. [5] Zindel JW, Kofeldt KA, Godlewski LA, Vijayaraghavan R, Donlon WT. SAE world congress & exhibition, Detroit, MI, April 2006. [6] Weakley-Bollin SC, Donlon WT, Wolverton C, Jones JW, Allison JE. Metall Mater Trans A 2004;35:2407. [7] Hatch JE. Aluminum: properties and physical metallurgy. ASM; 1984. [8] Ouellet P, Samuel FH. J Mater Sci 1999;34:4671. [9] Mishra RK, Smith GW, Baxter WJ, Sachdev AK, Franetovic V. J Mater Sci 2001;36:461. [10] Jahn R, Donlon WT, Allison JE. Automotive alloys. TMS; 1999. p. 247. [11] Chakrabarti DJ, Laughlin DE. Prog Mater Sci 2004;49:389. [12] Eskin DG. J Mater Sci 2003;38:279. [13] Samuel FH, Ouellet P, Samuel AM, Doty HW. Metall Mater Trans A 2004;29:2871. [14] Mondolfo LF. Aluminum alloys: structure and properties. London: Butterworths; 1976. p. 648. [15] Weatherly GC, Perovic A, Mukhopadhyay NK, Lloyd DJ, Perovic DD. Metall Mater Trans A 2001;32:213. [16] Arnberg L, Aurivillius B. Acta Chem Scand A 1980;34:1. [17] Cayron C, Sagalowicz L, Beort O, Buat PA. Phil Mag A 1999;79:2833. [18] Matsuda K, Uetani Y, Sato T, Ikeno S. Metall Mater Trans A 2001;32:1293. [19] Wolverton C. Acta Mater 2001;49:3129. [20] Ravi C, Wolverton C. Acta Mater 2004;52:4213. [21] Gao X, Nie JF, Muddle BC. Mater Sci Forum 1996;217222:1251. [22] Sagalowicz L, Lapasset G, Hug G. Phil Mag Lett 1996;74:57. [23] Wang X, Esmaeili S, Lloyd DJ. Metall Mater Trans A 2006;37:2691.