Baxter Samuel J, Loske Katharina V, Lloyd Ii Anthony J, Wilkinson Angus P
Inorg Chem. 2020 May 18;59(10):7188-7194. doi: 10.1021/acs.inorgchem.0c00629. Epub 2020 May 6.
Density measurements suggest that the incorporation of ZrF into the cubic ReO-type structure of ScZrF is associated with the creation of anion interstitials. X-ray total scattering measurements are consistent with the conversion of corner-sharing octahedra to edge-sharing polyhedra as the solid solutions become richer in ZrF. The cubic (3̅) to rhombohedral (3) cooperative octahedral tilting transition seen for ScF moves to a higher pressure as increasing amounts of zirconium are added, and it is eventually suppressed completely ( = 0.4 and 0.5) so that the cubic phase persists to high pressure until an amorphization occurs. All the samples studied ( = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) display pressure-induced softening, and increasing the zirconium content leads to a higher zero-pressure bulk modulus. The incorporation of "excess fluoride" into ReO-type fluorides is a powerful tool for suppressing the generally unwanted phase transitions seen when subjecting these materials to stress.
密度测量表明，将ZrF掺入ScZrF的立方ReO型结构中与阴离子间隙的产生有关。X射线全散射测量结果表明，随着固溶体中ZrF含量的增加，角共享八面体向边共享多面体转变。ScF中观察到的立方（3̅）到菱面体（3）的协同八面体倾斜转变随着锆含量的增加向更高压力移动，最终被完全抑制（ = 0.4和0.5），使得立方相在高压下持续存在直至发生非晶化。所有研究的样品（ = 0.0、0.1、0.2、0.3、0.4和0.5）都表现出压力诱导的软化，并且增加锆含量会导致更高的零压力体积模量。将“过量氟化物”掺入ReO型氟化物中是一种强大的工具，可用于抑制这些材料在受力时通常不需要的相变。
