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A reinvestigation of the Na 3 PO 4 -Mg 3 (PO 4 ) 2  binary at 1000 °C has identified two new ternary oxide phases and confirmed the existence of an orthorhombic solid solution phase in the vicinity of NaMg 4 (PO 4 ) 3 . Cubic  γ -Na 3 PO 4  shows a solid solution up to ~20 mol. % Mg 3 (PO 4 ) 2 . Between ~24 and ~29 mol. % a new  γ -Na 3 PO 4 -related rhombohedral superstructure phase is observed. At ~44 mol. % Mg 3 (PO 4 ) 2  a new phase with a cristobalite-related structure is observed, which on cooling rapidly to room-temperature transforms to KGaO 2 -type ( Pbca:  a  = 10.409(2) Å,  b  = 14.492(2) Å,  c  = 5.211(1) Å). The NaMg 4 (PO 4 ) 3  solid-solution phase extends between ~72 and 80 mol. % Mg 3 (PO 4 ) 2 . Surprisingly, and contrary to previous investigations, there is no phase at 50 mol. %, i.e. with stoichiometry NaMgPO 4 . All high-temperature annealing was performed in sealed Pt tubes to prevent loss of components to the atmosphere, which is suspected as the reason for the quite different results reported by some previous workers.

New phases in the Na 3 PO 4 -Mg 3 (PO 4 ) 2 binary quenched from 1000 °C