An in-situ XANES investigation of the interactions between iron, manganese and antimony in silicate melts

The analysis of iron, manganese and antimony in silicate glass is of great interest in chemistry, materials science, earth sciences and archaeological sciences. Yet, conclusions from different fields appear to be contradictory and many questions about redox reactions in glass remain. The purpose of this study is thus to discuss whether and how these multivalent elements interact in glass. Soda-lime silicate melts containing iron along with manganese and/or antimony have been analysed at different high temperatures under argon atmosphere. Using in-situ XANES at the Fe K-edge, redox thermodynamics, kinetics and diffusivities have been assessed for the different compositions. The data obtained show that antimony is more efficient at oxidising iron compared to manganese at all temperatures. The oxidising power trend would thus be Sb > Sb + Mn > Mn. Furthermore, hypotheses on the formation of Fe-Mn complexes are also reported in glasses with stoichiometric proportions of iron and manganese. Based on the determination of redox diffusivities, it appears that presence of other multivalent elements does not significantly affect the iron redox mechanisms and that diffusivity is essentially controlled by the mobility of calcium.