High-temperature mass spectrometric study of thermodynamic properties in the TiO2-Al2O3-SiO2 system and modeling

Rationale The TiO2-Al2O3-SiO2 system is the base for various glass-ceramic materials, which have great practical value for a large number of modern technologies. Many TiO2-Al2O3-SiO2 materials are synthesized or applied at high temperatures, which justifies the relevance of the present study. Methods The samples in the TiO2-Al2O3-SiO2 system were synthesized using the method of induction melting in a cold crucible. The thermodynamic properties of the TiO2-Al2O3-SiO2 system were studied using the Knudsen effusion mass spectrometric method. The derived thermodynamic functions were optimized within the generalized lattice theory of associated solutions (GLTAS) approach and compared with the results of calculation using the semiempirical Kohler, Muggianu, Toop, Redlich-Kister, and Wilson methods based on the corresponding data in the binary systems. Results The SiO2 selective vaporization from the samples under study was shown at temperatures above 1940 K. The thermodynamic properties in the TiO2-Al2O3-SiO2 system, including the TiO2-SiO2 system, were obtained in the temperature range 1965-2012 K and were optimized using GLTAS to obtain the consistent concentration dependences of the component activities and excess Gibbs energies. Conclusions Positive deviations from the ideal behavior were observed in the TiO2-Al2O3-SiO2 system at high temperatures. Comparison of these values with the results of the modeling based on the GLTAS approach allowed the recommendations regarding the optimal semiempirical methods for the excess Gibbs energy calculation in different concentration ranges to be made.