A combined CALPHAD/first-principles remodeling of the thermodynamics of Al-Sr: Unsuspected ground state energies by "rounding up the (un)usual suspects"

Yu Zhong, C. Wolverton, Y. Austin Chang, Zi-kui Liu

Research output: Contribution to journalArticle

68 Citations (Scopus)

Abstract

Despite numerous investigations, all previous efforts on thermodynamic modeling of Al-Sr have suffered from inaccurate energetics of either the solid-state compounds or of the liquid alloy. Here, we demonstrate a method yielding simultaneously, accurate solid-state and liquid energetics, as given by first-principles density functional calculations and experimental measurements, respectively. Via first-principles methods, we have investigated the T=0 K energetics of not only the reported ground state compounds in Al-Sr ("the usual suspects"), but also of a wealth of other possible crystal structures observed in isoelectronic alloy systems (somewhat more "unusual suspects"). We find: (i) LDA calculations surprisingly show that Al 2Sr in the C15 structure is slightly lower in energy than the observed CeCu2-type structure. However, GGA predicts the opposite order, consistent with the observed CeCu2-type/C15 stability. (ii) An as-yet-unreported Al5Sr4 compound (observed in Al-Ba) is found to be on the T=0 K ground state hull. (iii) An Al3Sr 8 phase, isostructural with the recently discovered Al 3Ca8 compound, is predicted to lie above the ground state hull and is not a T=0 K ground state. Using the first-principles formation enthalpies along with experimental thermodynamic and phase stability information, we have performed a new CALPHAD modeling of Al-Sr, including the three observed intermediate compounds as well as a hypothetical compound Al 3Sr8. Two different models of the liquid phase were considered: an associate and a random solution model. The descriptions resulting from the two liquid models are critically evaluated with respect to experimental data in the literature and the present first-principles results.

Original languageEnglish (US)
Pages (from-to)2739-2754
Number of pages16
JournalActa Materialia
Volume52
Issue number9
DOIs
StatePublished - May 17 2004

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Ground state
Thermodynamics
Liquids
Phase stability
Density functional theory
Enthalpy
Thermodynamic stability
Crystal structure

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Polymers and Plastics
  • Metals and Alloys

Cite this

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title = "A combined CALPHAD/first-principles remodeling of the thermodynamics of Al-Sr: Unsuspected ground state energies by {"}rounding up the (un)usual suspects{"}",
abstract = "Despite numerous investigations, all previous efforts on thermodynamic modeling of Al-Sr have suffered from inaccurate energetics of either the solid-state compounds or of the liquid alloy. Here, we demonstrate a method yielding simultaneously, accurate solid-state and liquid energetics, as given by first-principles density functional calculations and experimental measurements, respectively. Via first-principles methods, we have investigated the T=0 K energetics of not only the reported ground state compounds in Al-Sr ({"}the usual suspects{"}), but also of a wealth of other possible crystal structures observed in isoelectronic alloy systems (somewhat more {"}unusual suspects{"}). We find: (i) LDA calculations surprisingly show that Al 2Sr in the C15 structure is slightly lower in energy than the observed CeCu2-type structure. However, GGA predicts the opposite order, consistent with the observed CeCu2-type/C15 stability. (ii) An as-yet-unreported Al5Sr4 compound (observed in Al-Ba) is found to be on the T=0 K ground state hull. (iii) An Al3Sr 8 phase, isostructural with the recently discovered Al 3Ca8 compound, is predicted to lie above the ground state hull and is not a T=0 K ground state. Using the first-principles formation enthalpies along with experimental thermodynamic and phase stability information, we have performed a new CALPHAD modeling of Al-Sr, including the three observed intermediate compounds as well as a hypothetical compound Al 3Sr8. Two different models of the liquid phase were considered: an associate and a random solution model. The descriptions resulting from the two liquid models are critically evaluated with respect to experimental data in the literature and the present first-principles results.",
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A combined CALPHAD/first-principles remodeling of the thermodynamics of Al-Sr : Unsuspected ground state energies by "rounding up the (un)usual suspects". / Zhong, Yu; Wolverton, C.; Chang, Y. Austin; Liu, Zi-kui.

In: Acta Materialia, Vol. 52, No. 9, 17.05.2004, p. 2739-2754.

Research output: Contribution to journalArticle

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AB - Despite numerous investigations, all previous efforts on thermodynamic modeling of Al-Sr have suffered from inaccurate energetics of either the solid-state compounds or of the liquid alloy. Here, we demonstrate a method yielding simultaneously, accurate solid-state and liquid energetics, as given by first-principles density functional calculations and experimental measurements, respectively. Via first-principles methods, we have investigated the T=0 K energetics of not only the reported ground state compounds in Al-Sr ("the usual suspects"), but also of a wealth of other possible crystal structures observed in isoelectronic alloy systems (somewhat more "unusual suspects"). We find: (i) LDA calculations surprisingly show that Al 2Sr in the C15 structure is slightly lower in energy than the observed CeCu2-type structure. However, GGA predicts the opposite order, consistent with the observed CeCu2-type/C15 stability. (ii) An as-yet-unreported Al5Sr4 compound (observed in Al-Ba) is found to be on the T=0 K ground state hull. (iii) An Al3Sr 8 phase, isostructural with the recently discovered Al 3Ca8 compound, is predicted to lie above the ground state hull and is not a T=0 K ground state. Using the first-principles formation enthalpies along with experimental thermodynamic and phase stability information, we have performed a new CALPHAD modeling of Al-Sr, including the three observed intermediate compounds as well as a hypothetical compound Al 3Sr8. Two different models of the liquid phase were considered: an associate and a random solution model. The descriptions resulting from the two liquid models are critically evaluated with respect to experimental data in the literature and the present first-principles results.

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