The phase relationships of the quasibinary systems CUC1-M U C1 2 (M" = Mn, Cd) were studied by high-temperature X-ray methods and difference thermal analyses (DTA). Four phases have been established: CdCl 2 -type M"_ x Cu 2x Cl 2 and α-CuI-type Cu\_ y M". Sy Cl solid solutions (above 361 and 321 °C, respectively), and β-and y-CuCl with negligible solubility for M u . The phase widths of the Cd containing compounds are 0 < χ < 0.35 at 25°C, 0 < χ < 0.6at315°C, and 0 < y < 0.4at420°C; those of the manganese compounds are similar. The crystal structures of α-CuI-type Cu 2 MnCl 4 at 400° C and of Mn 0 .84Cu 0 . 32 Cl 2 and y-CuCl both at 60° C were determined by means of neutron powder diffraction. The structures were refined by Rietveld's method to final R, = 1.7, 6.0, and 2.5%, respectively. The hitherto unknown high-temperature α-polymorph of CuCl can be stabilized by Mn" and Cd". The α-CuI-type solid solutions are fast Cu + ion conductors with conductivities of σ > 10 _I Ω~ι cm -1 above 350° C.
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