Predicting the Benefits of Adding Ternary Elements to Al-Sc Alloys Darko Simonovic1,2 and Marcel H. F.

Sluiter1,2 1 Materials Science and Engineering, Delft University of Technology, Mekelweg 2, Delft, 2628 CD, Netherlands 2 Netherlands Institute for Metals Research, Mekelweg 2, Delft, 2628 CD, Netherlands

ABSTRACT We seek to explain 1) the effectiveness of substituting Sc with Dy, Er, Y and 2) the loss of properties when Sc is replaced with Yb, Gd and Sm [1]. For a preliminary insight into the stability of structures we utilize the concept of Atomic Environment Type (AET) as pertaining to trialuminides. Electronic density functional total energy calculations at zero temperature are performed to obtain the enthalpy of mixing of quasi-binary Al-Sc-X structures. Estimates of the entropy are used to compute the stability regions of Al3Sc1-X L12 phase. We show that Sc is completely miscible with X=Dy, Er, Y and that there is a miscibility gap for X=Yb, Gd and Sm at temperatures near the aging temperature of Al-Sc alloys.

INTRODUCTION Scandium in Al alloys may be used in various ways, e.g. as precipitation-strengthener, as grain refiner, as recrystallization inhibitor and for enhancing superplastic properties. Among alloying elements it gives the highest increase of strength per atomic percent. The extraordinary beneficial effects of Sc are due to it forming a very fine dispersion of coherent Al3Sc precipitates with L12 structure [2,3]. The high price of Sc has limited its practical application. Less expensive alloying elements that might partially substitute for Sc in Al3Sc precipitates are therefore of considerable interest [1,4]. Ti and especially Zr are the most widely used elements in ternary Al-Sc-X alloys. Zr forms a stable Al3Zr phase with D023 structure, but it can precipitate metastably with L12 structure, e.g. when nucleated and grown on primary L12 Al3Sc precipitates. The small diffusivity of Zr prevents Al3Sc encapsulated in Al3Zr from coarsening. Al3Ti is known to exist in two stable forms: Al3Ti (tI32) stable below 950C, and Al3Ti (tI8) D022 stable between 950 and 1387C [5]. Ti also precipitates metastably with the L12 structure in Al-Sc-Ti alloys. Both Al3Ti and Al3Zr can be stabilized into L12 structure with addition of third alloying element [6]. Recently, the substitution with rare earths elements has been claimed to be beneficial [1]. Karnesky et al. showed that substituting 0.02 at.% of Sc with Dy, Er and Y in 0.08 at.% Al-Sc retains hardness, whereas for Yb, Gd and Sm hardness is reduced. For Yb the loss of hardness is attributed to shorter aging time (larger diffusion in Al) whereas for Gd and Sm the hardness loss is attributed to reduced solubility in Al3Sc phase (at an aging temperature of 300C).

It is known that Al- late rare earth element (RE) trialuminides exhibit progressively more cubic character [7]. Er forms a stable L12 structure in Al-Er alloys. Al3Ho and Al3Dy take rhombohedral and hexagonal structures and Al3Y has a hexagonal D019 structure. All three of them can form metastable trialuminides with L12 structure. Mid-series RE Gd and Sm form trialuminides with the hexagonal D019 structure and the cubic L12 structure has not been observed, not even as a metastable phase. This study examines the ab initio predictions concerning phase stability of quasi-binary Al3Sc - Al3RE alloys and compares with the available experimental data, mainly given in [1]. Moreover, we consider several other third alloying elements.

THEORY A general requirement for alloying elements X to partially replace Sc in Al3Sc is that X strongly favors the Sc sublattice over the Al sublattice, and that X strongly prefers the atomic environment that Sc has in Al3Sc. Furthermore X should not promote occurrence of other phases and X should have a small diffusivity. When X interacts strongly with Sc, other intermetallics may form leaving less Sc for the beneficial Al3Sc dispersion. Therefore we require that X takes the same Atomic Environment Type (AET) and a similar lattice parameter in Al3X as Al3Sc, as well as a similar low solubility in the Al solid solution. The Atomic Environment Type of Sc in Al3Sc, 122,2 (c,c), is shown in figure 1. Since trialuminides are ordered structures and we assumed that Sc and X take the same AET, ternary stable structures should be ordered with respect to Al while Sc and X could interchange on the Sc sublattice (later on we check this assumption). This limits us, at least initially, in considering quasi-binaries only when searching for X with high solubility in Al3Sc. It turns out that most of the structures with Sc AET are L12, D022 and D023. The L12, D022 and D023 structures can be represented with a common cell composed of 4 fcc cubes (see figure 1). This allows us to perform electronic density functional total energy calculations with minimal systematic errors. We considered all possible arrangements of Al, Sc and X elements using this Al12(Sc1-X)4 supercell with as constraints that the AET of Al, Sc and X are preserved. Using these constraints, a fourth type of structure (tetragonal type) appears in the 4fcc supercell that does not seem to appear in Nature. All possible arrangements of elements with = 0, 0.25 and 0.5 are shown in figure 1. They are classified into 4 categories (based on underlying binary structures): L12, D022, D023 and tetragonal.

Figure 1. 122,2 (c,c) Atomic Environment Type of Sc in Al3Sc (left) and designed Al12(Sc1-X)4 structures with = 0, 0.25 and 0.5 (right).

Having limited ourselves to appropriate elements X, the enthalpy of mixing of quasibinaries then gives insight in the solubility of X into Al3Sc (L12) precipitates. It will be necessary to verify the solubility of X if X has metastable 122,2 (c,c) AET (such as for X=Dy and Ho) or if X have AET that differ from Sc (X=Sm and Gd) in their respective binary trialuminides. Mixing enthalpies of quasi-binaries As L12, D022, and D023, as well as the newly found tetragonal structures differ from each other with regard to the distribution and number of (100) anti phase boundaries (APBs), the computed enthalpies do not only provide insight in the mixing behavior but also give information about APBs and the deformations which can cause these APBs as a function of composition. The primary interest is the Al3Sc1-X L12 phase. The quasi-binary enthalpy of mixing (per supercell) can be defined as:
STR H mix = H STR [ Al12 ( Sc1 X )4 ]

(1 ) H L12 [ Al3Sc ] H L12 [ Al3 X ]

(1)

When the mixing enthalpy vanishes for compositions and all structures (STR) of the L12 type the quasi-binary solution is ideal. Then, there are no interactions between the Sc and X species and configurational entropies can be computed trivially by considering the Sc-X sublattice only, see equation 2. The Al sublattice would remain occupied purely by Al, so that it does not contribute to the configurational entropy. Other, temperature dependent, contributions to the enthalpy and entropy we will neglect for the present purposes. If the enthalpy of mixing is small, this picture would still be of use as it would give a slight overestimate of the configurational entropy only. The configurational entropy per supercell can thus be expressed as a function of the fractions Sc (cSc) and X (cX) on the Sc-X sublattice, where we used cSc + cX = 1,

Sconf = 4 k (cSc ln cSc (1 cSc ) ln(1 cSc ) ) .

(2)

The configurational entropy represents the true excess entropy only when there are no alternate metastable structures close to the ground state structure and when the phonon contribution to the entropy is a proper average of that of the Al3Sc and Al3RE terminal compositions.

DISCUSSION
The enthalpy of mixing of quasi-binaries Al12(ScRE1-)4 , where RE represent Sm, Gd, Dy, Er, Yb and Y has been computed. Enthalpies for Sm and Er are presented in figure 2 (figures for other RE are similar). Three bands are observed, the lowest band corresponds to L12 based structures; the middle band pertains to structures with two APBs, whereas the structures in the highest band have four APBs per supercell. Variations in the enthalpy are small in comparison to the difference in enthalpy between bands, with the data for Yb varying the most. The large enthalpy difference makes L12 like particles immune to structural transformations involving APBs.

Figure 2. Enthalpy of mixing for Al3Sc-Al3Sm (left) and Al3Sc-Al3Er (right). Phase diagrams and solubility range
A rough understanding of the quasi-binary phase diagram can be obtained from ground state enthalpies only. Here, we will be concerned with order-disorder on the minority sublattice (Sc) of the L12 like phases only using a regular solution model. Other phases in the full ternary phase diagram are not taken into account in this segment of the phase-diagram, because we look at systems where the ordered binary Al3RE L12 phases are highly stable and we neglect the liquid phase. We obtain ternary L12 solid solutions and low temperature miscibility gaps that can have validity well below the melting temperatures of Al3Sc and Al3RE only. This is not a serious restriction because trialuminides have high melting temperatures (above 1600K) and the region of interest is below the melting temperature of Al (930K). For calculating a quasi-binary phase diagram, the enthalpy for the whole composition range is needed. As our computations are limited to 5 compositions (including the two terminal compositions) per quasi-binary some kind of interpolation is needed. We used a cubic polynomial to represent the compositional dependence of the mixing enthalpy, but a spline fit gave transition temperatures and solubility limits within 1%. Alloys investigated by Karnesky et al. [1] had 0.06 at.% Sc and 0.02% RE aged at 300C. Since Sc and especially RE elements have small solid solubility limits in Al at 300C, we can assume that practically all Sc and RE is in the ordered structures. Based on the overall composition, Karnesky et al. [1] assumed that 25% of Sc could be replaced by RE in Al3(Sc-RE) quasi-binaries. Of course, for efficient substitution of Sc we would like to dissolve higher RE fractions in Al3Sc. Low solubility of RE in Al3Sc might cause formation of Al3RE phases, which are undesirable (higher lattice parameter, small solubility at eutectic temperature [4]), and which might moreover dissolve some Sc, making less Sc available for precipitating Al3Sc. Maximum solubility of RE at 300C (cX@ 300C) and the temperature of complete miscibility (Tmix) that our model gives are presented in the table I.

Table I. Solubility limit at 300C and temperature of complete miscibility for Al3Sc-Al3RE quasi-binary systems computed using regular solution model. Sm Gd Dy Er Yb Y Tmix[C] 823 467 257 109 363 245 cX@ 300C 1.6 at.% 9.0 at.% 20.8 at.% -

Dy, Er and Y are completely miscible with Sc in Al3Sc like structure at the usual aging temperature of Al-Sc alloys. Naturally, there are changes in precipitate properties such as the lattice parameter and the maximal supersaturation that can be achieved in Al-Sc-RE alloys which place restrictions to the amount of RE available for substituting Sc. Sm, Gd and Yb are not completely miscible at the aging temperature of Sc. Concentrations used in [1] (25 at.% of Al3RE in Al3Sc) are larger than the solubility limit at the aging temperature which is most significant for Sm and least significant for Yb. As one might expect, this is also the order in which the hardness increases. Furthermore it suggests that lowering of hardness for the case of addition of Yb (compared with equivalent pure Al-Sc alloy) may be due to the limited solubility of Yb in Al3Sc alone. By measuring the hardness as function of the RE concentration relative to the Sc concentration experimentally, our predictions for the RE solubility limit in Al3Sc can be checked more rigorously. Zr and Ti do not have terminal L12 structures and thus our previously used L12 minority sublattice model will not give the correct solubility in Al3Sc. However, it is readily apparent that Zr is more soluble in Al3Sc than Ti (see figure 4) because Zr gives only a very small mixing enthalpy. The bands observed for RE elements can be identified here also, but variation with composition is much larger. When the concentration of Zr and Ti is increased, the precipitates become more prone to transform to APB variants of L12.

Figure 3. Miscibility gaps in quasi-binary phase diagrams for Al3Sc-Al3Sm (left) and Al3ScAl3Er (right).

Figure 4. Enthalpy of mixing for Al3Sc-Al3Ti (left) and Al3Sc-Al3Zr (right).

It is tempting to use the above enthalpies for the prediction of quasi-binary phase diagrams Al3Sc - Al3Zr and Al3Sc - Al3Ti. In spite of the crudeness of the model agreement with experiment appears fair: solubility limit for Al3Zr in Al3Sc at 600C is reported around 55 % and solubility of Al3Sc in Al3Zr is reported around 16 %. Calculated solubility limits, when a regular solution model is used, are 28 % of Al3Zr in Al3Sc and 13 % vice versa, thus a slight underestimation of the solubility at the Sc-rich side and a probably fortuitous agreement at the Zr-rich side.

CONCLUSIONS
In this study we presented a simple analysis for the efficacy of Sc replacement by alloying elements in Al3Sc through calculations on selected quasi-binaries of Al3Sc - Al3X type, where X was carefully selected. The analysis suggests that late RE and Zr and to a much lesser extend Ti can serve for the purpose of replacing Sc. Using density functional calculations for the enthalpy of mixing and rough approximations for the entropy we derived solubility limits in the quasi-binary fcc-based phase diagram between ordered Al3Sc and Al3X phases. Our simple regular solution model is not so good when the enthalpy of mixing strongly deviates from ideal and when the terminal Al3X ordered structure does not have the L12 structure. Calculations for Al-Sc-RE (where RE = Sm, Gd, Dy, Er, Yb and Y), Al-Sc-Zr and Al-Sc-Ti are in reasonable agreement with experimental results.

ACKNOWLEDGMENTS
This research was carried out under projectnumber MC4.05212 in the framework of the Strategic Research program of the Netherlands Institute for Metals Research (www.nimr.nl).

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