INTERACTION IN CROSS SECTIONS Cu(Ag)7PS6 – Cu(Ag)8Ge(Sn)S6
DOI:
https://doi.org/10.32782/pcsd-2022-4-1Keywords:
X-ray phase analysis, differential thermal analysis, boundary solid solution, eutectic pointAbstract
The interactionalong the Cu(Ag)8Ge(Sn)S6 – Cu(Ag)7PS6 polythermal sectionsin the Cu2S – GeS2 – P2S5 and Ag2S – Ge(Sn)S2 – P2S5 systems were investigated by X‑ray diffraction, microstructural method and differential thermal analysis. The Cu8GeS6 – Cu7PS6 section is quasi-binary at 300 K and characterized by significant solid solutionsranges, up to 30 mol. % Cu8GeS6 based on HT modification of Cu7PS6 and from 9 to 32 mol. % Cu7PS6 between LT of both compounds. Solid solubility based on HT-Cu8GeS6 does not exceed ∼5 mol. %. However, the section is not a quasibinary system in the entire studied temperature range due to the peritectic melting of both starting compounds. First and 0-70 mol. % Cu7PS6, solid solutions of LT-Cu2S crystallize from the melt; then the crystallization process continues in a certain temperature range by the reaction of the formation of a single-phase region of solid solutions Cu8–xGe1–xPxS6 of cubic structure (S.G. F43m) of LT of both copper-containing argyrodites. Two-phase regions at room temperature are 5‑9 mol. % Cu7PS6 (S.G. Pna21 + S.G. F43m) and 32-69 mol. % Cu7PS6 (S.G. P213 + S.G. F43m). The Ag8Ge(Sn)S6 – Ag7PS6 systems are quasi-binary sections of the corresponding quasi-ternary systems Ag2S – Ge(Sn)S2 – P2S5 and are characterized by the complete mutual solubility of the components both in the liquid and in the solid state between the high-temperature modifications of these compounds (Ag8‑xGe(Sn)1‑xPxS6). Germanium-containing system is Type I of Rosebohm classification, while tin-containing system is Type III of Rosebohm classification with a minimum at 65 mol. % Ag7PS6. In the subsolidus region at 300 K, single-phase regions are separated by two-phase regions of 25-65 mol. % Ag7PS6 (S.G. Pna21 + S.G. F43m) and 75-85 mol. % Ag7PS6 (S.G. P213 + S.G. F43m) in the Ag8GeS6 – Ag7PS6 system, and ∼25-42 mol. % Ag7PS6 (S.G. Pna21 + S.G. F43m) and ∼65-73 mol. % Ag7PS6 (S.G. P213 + S.G. F43m) in the Ag8SnS6 – Ag7PS6 system. The formation of substitution solid solutions of Cu8–xGe1–xPxS6 and Ag8‑xGe(Sn)1–xPxS6 compositions with increasing temperature expands the area of t he high-temperature cubic phase (S.G. F43m). The formation of HM solid solutions at each of the three sections significantly lowers the temperature of the polymorphous transitions of all starting compounds.
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