Structure of NaFeSiO4, NaFeSi2O6, and NaFeSi3O8 glasses and glass-ceramics

The crystallization of iron-containing sodium silicate phases holds particular importance, both in the management high-level nuclear wastes and in geosciences. Here, we study three asquenched glasses and their heat-treated chemical analogues, NaFeSiO4, NaFeSi2O6, and NaFeSi3O8 (with nominal stoichiometries from feldspathoid, pyroxene, and feldspar mineral groups – i.e., Si/Fe = 1, 2, and 3 respectively) – using a variety of techniques. Phase analyses revealed that as-quenched NaFeSiO4 cannot accommodate all Fe in the glass phase (some Fe crystallizes as Fe3O4), whereas as-quenched NaFeSi2O6 and NaFeSi3O8 form amorphous glasses upon quenching. NaFeSi2O6 glass is the only composition that crystallizes into its respective isochemical crystalline polymorph, i.e. aegirine, upon isothermal heat-treatment. As revealed by Mössbauer spectroscopy, iron is predominantly present as 4-coordinated Fe3+ in all glasses, though it is present as 6-coordinated Fe3+ in the aegirine crystals (NaFeSi2O6), as expected from crystallography. Thus, Fe can form the crystalline phases in which it is octahedrally coordinated, even though it is mostly tetrahedrally coordinated in the parent glasses. Thermal behavior, magnetic properties, iron redox state (including Fe K-edge X-ray absorption), and vibrational properties (Raman spectra) of the above compositions are discussed.