Coupled experimental study and thermodynamic modeling of the MnO-Mn2O3-Ti2O3-TiO2 system

Abstract

A coupled experimental study and thermodynamic modeling of the MnO-Mn2O3-Ti2O3-TiO2 system at 1 bar total pressure is presented. Classical equilibration and quenching experiments followed by the phase analysis using electron probe microanalysis (EPMA) and X-ray diffraction (XRD) were employed to obtain equilibrium compositions of the liquid and solid solutions in air. The molten oxide phase was described by using the Modified Quasichemical Model which considers short-range ordering, and the Gibbs energies of the solid solutions (pseudobrookite, ilmenite and spinel) were described using the Compound Energy Formalism based on their crystal structures. A set of optimized model parameters of all phases was obtained, which reproduces all available and reliable thermodynamic data and phase diagrams within experimental error limits from 298 K (25 °C) to above the liquidus temperatures over the entire range of composition under oxygen partial pressures from metallic saturation to 1 bar. The complex phase relationships in the system have been elucidated and discrepancies among the experimental data have been resolved. The database of the model parameters can be accessed by FactSage software with the Gibbs energy minimization to calculate any phase diagrams and thermodynamic properties of the MnO-Mn2O3-Ti2O3-TiO2 system.