Crystallization of high temperature self-flux of system Na 2 O-K 2 O-TiO 2 -P 2 O 5 was investigated at different molar ratios (Na+K)/P = 0.9; 1.0 or 1.2 and Na/K = 1.0 or 2.0 over the temperature range 1000-650°C. The conditions of formation of complex phosphates K 0.10 Na 0.90 Ti 2 (PO 4 ) 3 (NASICONrelated) and K 0.877 Na 0.48 Ti ІІІ 0.357 Ti ІV 1.643 (PO 4 ) 3 (langbeiniterelated) have been established. The new obtained compounds were investigated using FTIR-spectroscopy, powder and single crystal X-ray diffraction and optical microscopy methods. The influence of alkaline metal nature on the structure formation of complex phosphates in the high temperature self-fluxes is discussed.
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