Integrated Experimental and Thermodynamic Modeling Investigation of Phase Equilibria in the PbO\u2013MgO\u2013SiO2 System in Air

Abstract

Magnesium oxide-based refractory materials are used industrially to contain the chemically aggressive slags present in lead smelting systems. In the present study an integrated experimental and thermodynamic modeling approach was taken to provide fundamental information on the chemical reactions taking place in these systems. New experimental phase equilibria and liquidus data were obtained for the PbO–MgO–SiO2 system in air in the temperature range 750 °C to 1740 °C. In the MgO–SiO2 binary, new experimental results were obtained at 1550 °C to 1740 °C and compared to the available thermodynamic data in the literature. The experiments were carried out using the high-temperature equilibration of oxide powder mixtures followed by rapid quenching of the samples. Electron probe X-ray microanalysis (EPMA) was used to determine the compositions of the solid and liquid phases present at equilibrium conditions. Phase equilibria and liquidus isotherms in the cristobalite and tridymite (SiO2), pyroxene (protoenstatite MgSiO3), olivine (forsterite Mg2SiO4), barysilite (Pb8MgSi6O21), massicot (PbO) and periclase (MgO) primary phase fields were measured, and the extent of the high-silica two-liquid immiscibility gap in equilibrium with cristobalite was determined. The experimental results were used to optimize the parameters in a thermodynamic database that was subsequently used to describe this multi-component, multi-phase system and predict the liquidus for the PbO–MgO–SiO2 system. The new data were used to characterize the chemical interactions of magnesia-based refractory with PbO–MgO–SiO2 slags.