Phase equilibria and crystal chemistry of the R-Cu-Ti-O systems (R=lanthanides and Y)

As part of the study of interaction of the Ba₂RCu₃O_6+z (R=lanthanides and Y) superconductor with SrTiO₃ buffer, phase equilibria of the subsystem, R₂O₃-TiO₂-CuO (R=Nd, Y, and Yb), have been investigated in air at 960 °C. While the phase relationships of the two phase diagrams with smaller R (Y and Yb) are similar, substantial differences were found in the Nd₂O₃-TiO₂-CuO system, partly due to different phase formation in the binary R₂O₃-TiO₂ and R₂O₃-CuO systems. R₂CuTiO₆ and R₂Cu₉Ti₁₂O₃₆ were the only ternary phases established in all the three diagrams. R₂Cu₉Ti₁₂O₃₆ belongs to the perovskite-related [AC₃](B₄)O₁₂ family which is cubic Im3. Depending on the size of R³⁺, R₂CuTiO₆ crystallizes in two crystal systems: Pnma (R=La-Gd), and P6₃cm (R=Dy-Lu). The structure and crystal chemistry of the Pnma series of R₂CuTiO₆ (R=La, Nd, Sm, Eu, and Gd) are discussed in detail in this paper. Patterns for selected members of R₂CuTiO₆ have also been prepared and submitted for inclusion in the Powder Diffraction File (PDF).