The phase equilibria of the ternary system CaCl2 – NaCl – CaO in the area which enriched of calcium and sodium chloride were investigated by the methods of differential-thermal analysis and powder X-ray phase analysis. In the systems were determined the equilibrium concentration of calcium oxide and the composition of the phases, which at the same time exist in an equilibrium state at different temperatures. The surfaces of liquidus and solidus were established, the compositions of the sections of the ternary system CaCl2–NaCl–CaO were defined, which recommended for electrochemical reduction of refractory metal oxides (titanium, zirconium and other), which allow electrolysis in the temperature range from 550 to 1000 °С. Five polythermal sections of the NaCl – CaCl2 – CaO ternary system were studied. For each polythermal section the regions of existence of the liquid and solid phases were established. For each polythermal section state diagrams were constructed. Used X-Ray phase analyses it was established the compositions of liquid and solid phases for each polythermal sections. The phases of which the system consists were determined. At a constant ratio of components [NaCl]:[CaCl2] = 1.06 (mol.) in the melts of the ternary system CaCl2 – NaCl – CaO, the equilibrium content of calcium oxide reaches 12.0 mol.%, while their crystallization temperature does not exceed 550 °C. This allows us to recommend mixtures of this composition for electrochemical reduction of refractory metal oxides in a wide range of temperatures (from 550 to 1000 °C) with a high content of both calcium and sodium chlorides (not less than 40 mol.%) and oxide. calcium (up to 12.0 mol.%). The eutectic of this ternary system has a melting point of 480 ° C and corresponds to he composition (mol.%): CaCl2 (45.8) – NaCl (47.0) – CaO (7.2).
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