Thermal Expansion and Response to Pressure of Double-ReO3 -Type Fluorides NaMVF6 (M = Nb, Ta)
Several II–IV double-ReO3-type (DROT) fluorides are known to exhibit strong negative thermal expansion (NTE) over a wide temperature range while retaining a cubic structure down to 120 K or lower. CaZrF6, CaNbF6, CaTiF6, and MgZrF6, embody these properties. In contrast to the behavior of these II–IV materials, the I–V DROT material, NaSbF6, has been reported to display a phase transition from rhombohedral to cubic above 300 K and positive thermal expansion both above and below the transition. In this work, NaNbF6 and NaTaF6 are shown to undergo first-order cubic-to-rhombohedral transitions on cooling to ~130 K. Above this transition, NaNbF6 shows modest NTE between 160 and 250 K, whereas NaTaF6 exhibits near-zero thermal expansion over the range 210–270 K. These I–V systems are elastically softer than their II–IV counterparts, with a zero pressure bulk modulus, K0, of 14.6(8) GPa and first derivative of the bulk modulus with respect to pressure, K0', of -18(3) for cubic NaNbF6, and K0 = 14.47(3) GPa and K0'= -21.56(7) for cubic NaTaF6. When subject to ~0.3 GPa at 300 K, both compounds exhibit a phase transition from F$$m\bar{3}m$$ to R$$\bar{3}$$. The R$$\bar{3}$$ phases exhibit negative linear compressibility over a limited pressure range. A further transition with phase coexistence occurs at ~2.5–3.0 GPa for NaNbF6 and ~4.5 GPa for NaTaF6. Compression of NaNbF6 in helium at room temperature and below provides no evidence for helium penetration into the structure to form a perovskite with helium on the A-site, as was previously reported for CaZrF6.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- AC05-00OR22725
- OSTI ID:
- 1828244
- Journal Information:
- Inorganic Chemistry, Vol. 59, Issue 19; ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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