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Solid solution of Ca9‐xMgxBi(VO4)7 in powder and ceramic forms are obtained by solid‐state reactions. Details of their crystal structures are determined for x = 0.25 and x = 0.5 by synchrotron radiation diffraction and the Rietveld method. The refinement has confirmed that Mg2+ is replacing Ca2+ in M5 position of a polar (S.G. R3c) β‐Ca3(PO4)2‐type structure. Thermal analysis, dielectric and second...
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