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1968, 1970). p. p. 1105°C). The first involves a phase transition at 845°C. Actually, from the structural studies of Michelet et al. (1966, 1969a, 1970, 1975), Mazurier et al. (1973, 1974), Collin et al. , 1971). , 1973a, 1975), the R2GeS4 thiogermanites exist for R = La to Gd. They disproportionate at about 600°C. Their structure is unknown. sS14 and R6Ge3Sl4 compositions with the same hexagonal R6B2C2X~4 structure (section 9). A general view of the structural aspects of the preceding compounds has been presented by Michelet et al.
Coordination of the elements. In these compounds, the rare earths have their usual coordination from 8 to 6. The magnesium is six coordinated (MnY2S4 and Ho4FeST-types) or four-coordinated (spinel) as usual. In the solid solutions of the Th3P4-type Mg has an unusual 8-coordinated environment, which explains the small extent of the homogeneity range. The other divalent elements are 8-coordinated (Th3P4 and CaFe204 types), 7-coordinated (Yb3S4 and Er2MnS4 types) or 6-coordinated (NaC1 type solid solutions).
1968c, 1970, 1972), Dismukes et al. (1971), and Aliev et al. (1972, 1973) when X is S and by Julien-Pouzol (1968a,b,c, 1972) and Aliev et al, (1975) when X is Se. The distribution of the observed phases is shown in (fig. 12), as a function of the composition (n = Cu/(R + Cu)). Five structural types are identified. I. • 05 Cu7 5e R2Te3 05 Cu Fig. 12. Crystal types in the R2X3-Cu2X systems. A: Th~P4 type, B: monoclinic unknown structure, C: solid solutions of the hexagonal ErznCu2S• type, Ct: ScCuSz type, C2:Er2nCu2S2 type, C~: orthorhombic superstructure of the C-type, D: orthorhombic Cu~3La5Se~4, F: orthorhombic structure.