Orthophosphates and Diphosphates Containing Zinc and Copper and Zinc and Cobalt |
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Authors: | Carlos E Bamberger Eliot D Specht |
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Affiliation: | Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6118;Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6118 |
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Abstract: | 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 "ε-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. |
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