From Quasicrystals to Crystals with Interpenetrating Icosahedra in Ca–Au–Al: In Situ Variable-Temperature Transformation

Pham, Joyce; Meng, Fanqiang; Lynn, Matthew J.; Ma, Tao; Kreyssig, Andreas; Kramer, Matthew J.; Goldman, Alan I.; Miller, Gordon J.

doi:10.1021/jacs.7b10358

Title: From Quasicrystals to Crystals with Interpenetrating Icosahedra in Ca–Au–Al: In Situ Variable-Temperature Transformation

Journal Article · Fri Dec 29 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b10358· OSTI ID:1425483

^[1];

^[2]; Lynn, Matthew J. ^[2]; Ma, Tao ^[2]; Kreyssig, Andreas ^[3]; Kramer, Matthew J. ^[2]; Goldman, Alan I. ^[3];

^[4]

Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Ames Lab., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States). Dept. of Physics and Astronomy; Ames Lab., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States). Dept. of Chemistry; Ames Lab., Ames, IA (United States)

The irreversible transformation from an icosahedral quasicrystal (i-QC) CaAu_4.39Al_1.61 to its cubic 2/1 crystalline approximant (CA) Ca₁₃Au_56.31(3)Al_21.69 (CaAu_4.33(1)Al1.67, Pa$$\bar{3}$$ (No. 205); Pearson symbol: cP728; a = 23.8934(4)), starting at ~570 °C and complete by ~650 °C, is discovered from in situ, high-energy, variable-temperature powder X-ray diffraction (PXRD), thereby providing direct experimental evidence for the relationship between QCs and their associated CAs. The new cubic phase crystallizes in a Tsai-type approximant structure under the broader classification of polar intermetallic compounds, in which atoms of different electronegativities, viz., electronegative Au + Al vs electropositive Ca, are arranged in concentric shells. From a structural chemical perspective, the outermost shell of this cubic approximant may be described as interpenetrating and edge-sharing icosahedra, a perspective that is obtained by splitting the traditional structural description of this shell as a 92-atom rhombic triacontahedron into an 80-vertex cage of primarily Au [Au_59.86(2)Al_17.14⟂_3.00] and an icosahedral shell of only Al [Al_10.5⟂_1.5]. Following the proposal that the cubic 2/1 CA approximates the structure of the i-QC and on the basis of the observed transformation, an atomic site analysis of the 2/1 CA, which shows a preference to maximize the number of heteroatomic Au–Al nearest neighbor contacts over homoatomic Al–Al contacts, implies a similar outcome for the i-QC structure. Analysis of the most intense reflections in the diffraction pattern of the cubic 2/1 CA that changed during the phase transformation shows correlations with icosahedral symmetry, and the stability of this cubic phase is assessed using valence electron counts. Finally, according to electronic structure calculations, a cubic 1/1 CA, “Ca₂₄Au₈₈Al₆₄” (CaAu_3.67Al_2.67) is proposed.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-07CH11358; AC02-06CH11357

OSTI ID:: 1425483

Report Number(s):: IS-J-9592; TRN: US1802115

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 4; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 5 works

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