Phase diagrams of systems SrF 2(Y, Ln)F 3. II. Fusibility of systems and thermal behavior of phases

Abstract

The phase diagrams of 14 SrF 2(Y, Ln)F 3 systems are given, where Ln are all the lanthanides except Pm and Eu. The diagrams have been constructed for temperature intervals from 850°C to the melting points according to the thermal and X-ray analysis. The fusibility diagrams for 12 systems have been obtained for the first time. The oxygen content in the specimens before and after thermal treatment was checked. The thermal behavior of the three types of solid solutions has been studied: (1) with the fluorite-type defective structure and its derivatives; (2) with the defective structure of the lanthanum fluoride, and (3) α-YF 3(α-UO 3) types. Maxima reflecting a noticeable effect of thermal stabilization on the fluorite-type structure by the heterovalent isomorphous substitution have been found for the majority of systems (with Ln = LaHo). The Sr 1− x Ln x F 2+ x nonstoichiometric fluorite phases are formed in all the systems. Similar maxima corresponding generally to irrational compositions are present on the fusibility curves of the Ln 1− y Sr y F 3− y nonstoichiometric phases with the LaF 3-type structure (tysonite). Tysonite solid solutions are in all the systems, too. Nonstoichiometric phases with the α-YF 3-type structure are formed in the systems with Ln = ErLu. They are decomposed in the process of cooling and are the most unstable. The structure of the phase diagrams in the regions adjacent to lanthanide trifluorides are determined by polymorphism and morphotropy of the above-named compounds. Changes in the thermal stability of the nonstoichiometric phases and double chemical compounds in the series of lanthanides have been observed. The SrF 2(Y, Ln)F 3 systems studied give examples of the formation of phases with the highest concentrations of point defects among all the known binary fluoride systems (up to 50 at.%). The thermal stabilization effect of the nonstoichiometric phases with the fluorite structure results in the fact that the series of the two-component compositions is melted at considerably higher temperatures as compared with scandium fluoride, the most refractory single-component fluoride compound. This effect leads to formation of tysonite-type solid solutions with melting points exceeding 1500°C (mp of LaF 3—the most refractory fluoride material with tysonite-type structure).