Phase Equilibria Laws in the SrS-Ln₂S₃ (Ln = Yb-Lu, Y, or Sc) Systems

Abstract

Complex sulfides with the SrS: Ln₂S₃ ratio equal to 3: 1, 1: 3, or 1: 4 for Ln = Y or Lu have been predicted on the basis of thermodynamic analysis of previously designed SrS-Ln₂S₃ (Ln = Tb, Dy, or Er) phase diagrams. Phase diagrams for the SrS-Ln₂S₃ (Ln = Tm, Lu, or Sc) systems have been designed for the first time. These systems form congruently melting compounds SrLn₂S₄ (CaFe₂O₄ type structure, orthorhombic crystal system). Unit cell parameters, heats of melting, and microhardnesses have been determined. For SrTm₂S₄, the respective values are as follows: a = 1.181 nm, b = 1.421 nm, c = 0.396 nm, 2040 K, ΔH _m = 188 kJ/mol, 3500 MPa; for SrLu₂S₄: a = 1.187 nm, b = 1.416 nm, c = 0.392 nm, 2070 K, ΔH _m = 190 kJ/mol, 3540 MPa; and for SrSc₂S₄: a = 1.180 nm, b = 1.410 nm, c = 0.390 nm, 2100 K, ΔH _m = 206 kJ/mol, 3650 MPa. The increase in the melting temperatures and the heats of melting calculated for the SrLn₂S₄ compounds correlate with their classification as thio salts.