Solid solubility in the system NaLREETi₂O₆– ThTi₂O₆ (LREE, light rare-earth elements): experimental and analytical data

Abstract 

The existence of an incomplete solid solution series between loparite (NaLREETi₂O₆), a member of the perovskite mineral group, and thorutite (ThTi₂O₆) is established on the basis of experimental and mineralogical data. The products of low- and high-pressure synthesis in the system NaLaTi₂O₆– ThTi₂O₆ were studied by energy-dispersive spectrometry, X-ray diffractometry and Rietveld analysis. At atmospheric pressure, Th is incorporated in loparite as both ThTi₂O₆ and Na₂ThTi₃O₉. In synthetic systems, the maximum determined ThTi₂O₆ content of loparite is 18 mol%, with a corresponding A-site cation deficiency of 9%. The structure of such loparite is tetragonal and presumably derived from the cubic aristotype by octahedral rotation [I4/mcm, a=5.4652(1) Å, c=7.7476(2) Å]. At a pressure of 6 GPa, no solubility between loparite and ThTi₂O₆ is observed, and Th is accommodated in the loparite structure entirely as Na₂ThTi₃O₉ (up to 30 mol%). Naturally occurring loparite contains up to 29 mol% ThTi₂O₆, based on the conventional method of analysis recalculation, or 23.5 mol% ThTi₂O₆, assuming the presence of protons at the vacant A-sites. ThTi₂O₆ synthesized by the solid-state reaction, crystallizes with monoclinic symmetry [C2/m, a=9.8140(2) Å, b=3.8228(1) Å, c=7.0313(2) Å,β=118.82(1)°]. Atomic coordinates for ThTi₂O₆ obtained in this study from X-ray powder data, as well as structural parameters derived from the new data, are in a good agreement with those known from single-crystal refinement. ThTi₂O₆ does not crystallize at high pressure, and Th is accommodated in perovskite-type compounds and cubic ThO₂ that provide a twelve- and eight-fold coordination site for Th, respectively.