From Quasicrystals to Crystals with Interpenetrating Icosahedra in Ca–Au–Al: In Situ Variable-Temperature Transformation
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Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.
For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.
The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).
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The Department of Chemistry was founded in 1880.
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1880-present
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- College of Liberal Arts and Sciences (parent college)
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Abstract
The irreversible transformation from an icosahedral quasicrystal (i-QC) CaAu4.39Al1.61 to its cubic 2/1 crystalline approximant (CA) Ca13Au56.31(3)Al21.69 (CaAu4.33(1)Al1.67, Pa3̅ (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 [Au59.86(2)Al17.14□3.00] and an icosahedral shell of only Al [Al10.5□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. According to electronic structure calculations, a cubic 1/1 CA, “Ca24Au88Al64” (CaAu3.67Al2.67) is proposed.
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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see DOI: 10.1021/jacs.7b10358. Posted with permission.