Redox stability and high-temperature electrical conductivity of magnesium- and aluminium-substituted magnetite

Spinel-type magnetite-based oxides, possessing relatively high electrical conductivity, are considered as promising consumable anode materials for high temperature pyroelectrolysis, a breakthrough low-CO2 steel technology to overcome the environmental impact of classical extractive metallurgy. The present work was focused on the analysis of phase stability, thermal expansion and high-temperature electrical conductivity in (Fe,Mg,Al)3O4 system under oxidizing and mildly reducing conditions. Metastable, nearly single-phase at room temperature (Fe,Mg,Al)3O4 ceramics was obtained by sintering at 1753–1773 K for 10 h in argon atmosphere. Thermal expansion and redox induced dimensional changes were studied on heating, using TG, XRD and dilatometry. The results revealed that magnesium improves the tolerance against oxidative decomposition and minimizes unfavorable dimensional changes in ceramic samples upon thermal cycling. Co-substitution of iron with aluminium and magnesium was proved to be a promising strategy for improvement of refractoriness and phase stability of Fe3O4-based spinels at elevated temperatures, without significant reduction in the electrical conductivity.