Phase equilibria in the Fe–Zn–O system at conditions relevant to zinc sintering and smelting

Abstract

Zincite and spinel phases are present in the complex slag systems encountered in zinc/lead sintering and zinc smelting processes. These phases form extensive solid solutions and are stable over a wide range of compositions, temperatures and oxygen partial pressures. Accurate information on the stability of these phases is required in order to develop thermodynamic models of these slag systems. Phase equilibria in the Fe–Zn–O system have been experimentally studied for a range of conditions, between 900°C and 1580°C and oxygen partial pressures (pO₂) between air and metallic iron saturation, using equilibration and quenching techniques. The compositions of the phases were measured using Electron probe X-ray microanalysis (EPMA). The ferrous and ferric bulk iron concentrations were determined using a specially developed wet-chemical analysis procedure based on the use of ammonium metavanadate. XRD was used to confirm phase identification. A procedure was developed to overcome the problems associated with evaporation of zinc at low pO₂ values and to ensure the achievement of equilibria. An isothermal section of the system FeO–Fe₂O₃–ZnO at high ZnO concentrations at 1200°C was constructed. The maximum solubilities of iron and zinc in zincite and spinel phases in equilibrium were determined at pO₂ = 1 × 10⁻⁶ atm at 1200°C and 1300°C. The morphology of the zincite crystals sharply changes in air between 1200–1300°C from rounded to plate-like. This is shown to be associated with significant increase in total iron concentration, the additional iron being principally in the form of ferric iron. Calculations performed by FactSage with a thermodynamically optimised database have been compared with the experimental results.