Orthophosphates and Diphosphates Containing Zinc and Copper and Zinc and Cobalt.

Solid solutions of diphosphates of zinc and copper and of zinc and cobalt were synthesized from mixtures of pure diphosphates at temperatures up to 1000°C. Their X-ray diffractometry patterns varied continuously from one end member to the other. Solid solutions of orthophosphates of composition Zn3−xCox(PO4)2, with x= 0.4–1.6, were formed at temperatures up to 950°C; all exhibited the structure of γ-Zn3(PO4)2. Solid solutions of orthophosphates of composition Zn3−xCux(PO4)2 exhibited more-complex behavior. At 1000°C and copper contents of 20–80 mol%, a phase that is related to Cu3(PO4)2, termed here the “e-phase,” predominated. At 850°–950°C and in the region from 20 mol% to ∼33 mol% of copper, the solid solutions (the “η-phase”) adopted the structure of graftonite. At 800°–900°C and 10–15 mol% of copper, the solid solutions exhibited a new structure (the “δ-phase”), which we found to be related to the mineral sarcopside. At temperatures 950°C, the solutions that contained 5–15 mol% of copper (the “β-phase”) had the structure of β-Zn3(PO4)2, whereas at 800°–850°C, solutions with 5 mol% of copper (the “-phase”) exhibited the structure of γ-Zn3(PO4)2. Attempts to synthesize Cu+ZnPO4 and Cu+Cu2+Zn3(PO4)3 were unsuccessful.