Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF6

Hester, Brett R.; Wilkinson, Angus P.

doi:10.1021/acs.inorgchem.8b01912

Title: Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF₆

Journal Article · Thu Aug 23 00:00:00 EDT 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b01912· OSTI ID:1471617

Hester, Brett R. ^[1];

^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)

Strong volume negative thermal expansion over a wide temperature range typically only occurs in ReO₃-type fluorides that retain an ideal cubic structure to very low temperatures, such as ScF₃, CaZrF₆, CaHfF₆, and CaNbF₆. In this work, CaTiF₆ was examined in an effort to expand this small family of materials. However, it undergoes a cubic ($$Fm\overline{3}m$$) to rhombohedral ($$R\overline3$$) transition on cooling to ~120 K, with a minimum volume coefficient of thermal expansion (CTE) close to –42 ppm K^–1 at 180 K and a CTE of about –32 ppm K^–1 at room temperature. On compression at ambient temperature, the material remains cubic to ~0.25 GPa with K₀ = 29(1) GPa and K'₀ = –50(5). Cubic CaTiF₆ is elastically softer and shows more pronounced pressure induced softening, than both CaZrF₆ and CaNbF₆. In sharp contrast to both CaZrF₆ and CaNbF₆, CaTiF₆ undergoes a first-order pressure induced octahedral tilting transition to a rhombohedral phase ($$R\overline3$$) on compression above 0.25 GPa, which is closely related to that seen in ScF₃. Just above the transition pressure, this phase is elastically very soft with a bulk modulus of only ~4 GPa as octahedral tilting associated with a reduction in the Ca–F–Ti angles provides a low energy pathway for volume reduction. This volume reduction mechanism leads to highly anisotropic elastic properties, with the rhombohedral phase displaying both a low bulk modulus and negative linear compressibility parallel to the crystallographic c-axis for pressures below ~2.5 GPa. At ~3 GPa, a further phase transition to a poorly ordered phase occurs.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1471617

Journal Information:: Inorganic Chemistry, Vol. 57, Issue 17; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 21 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Thermal expansion
Anions
Compression
Phase transitions
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CSD 2000384: Experimental Crystal Structure Determination R., Hester, Brett; P., Wilkinson, Angus https://doi.org/10.25505/fiz.icsd.cc254kjf The current record is supplemented by this dataset	dataset	January 2018
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Title: Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF6

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Title: Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF₆