Cation Inversion in Slag Magnetite: Energy Loss Measurements of Fe-L₃ Edge Shift between Atom Columns

Abstract

Determination of cation disorder in inverse spinels like magnetite, Fe3O4, is of broad interest for applications in green technologies, storage devices, and nuclear waste management since cation distributions govern magnetic and electrical properties. Magnetite is a main component of slags produced by smelting of copper ores and contains potentially valuable trace elements. We address cation disorder as a factor controlling the behavior of these elements during atmospheric cooling from 1300 °C. To estimate cation disorder, we combine atomic-scale scanning transmission electron microscopy with electron energy loss spectroscopy. The inversion parameter (0.72) indicates minor partial ordering due to fast cooling from high temperature, resulting in skeletal textures. Trace element incorporation into magnetite, instead of exsolution of discrete nanoparticle phases is promoted. Our findings provide insights into the cooling behavior of spinels and facilitate robust thermodynamic modeling that addresses the stability of structures during cooling from melts. Findings carry implications for critical element recovery and prospects for transforming industrial waste into future resources.