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The structural state of iron in oxidized vs. reduced glasses at 1 atm: A57Fe Mössbauer study

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Abstract

A general model for the structural state of iron in a variety of silicate and aluminosilicate glass compositions in the systems Na2O-Al2O3-SiO2-Fe-O, CaO-Al2O3-SiO2-Fe-O, and MgO-Al2O3-SiO2-Fe-O is proposed. Quenched melts with variable Al/Si and NBO/T (average number of nonbridging oxygens per tetrahedrally coordinated cation), synthesized over a range of temperatures and values of oxygen fugacity, are analyzed with57Fe Mössbauer spectroscopy.

For oxidized glasses with Fe3+/∑Fe>0.50, the isomer shift for Fe3+ is in the range ∼0.22–0.33 mm/s and ∼0.36 mm/s at 298 K and 77 K, respectively. These values are indicative of tetrahedrally coordinated Fe3−. This assignment is in agreement with the interpretation of Raman, luminescence, and X-ray,K-edge absorption spectra. The values of the quadrupole splitting are ∼0.90 mm/s (298 K and 77 K) in the Na-aluminosilicate glasses and compare with the values of 1.3 mm/s and 1.5 mm/s for the analogous Ca- and Mg-aluminosilicate compositions. The variations in quadrupole splittings for Fe3+ are due to differences in the degree of distortion of the tetrahedrally coordinated site in each of the systems.

The values of the isomer shifts for Fe2+ ions in glasses irrespective of Fe3+/∑Fe are in the range 0.90–1.06 mm/s at 298 K and 1.0–1.15 mm/s at 77 K. The corresponding range of values of the quadrupole splitting is 1.75–2.10 mm/s at 298 K and 2.00–2.35 mm/s at 77 K. The temperature dependence of the hyperfine parameters for Fe2+ is indicative of noninteracting ions, but the values of the isomer shift are intermediate between those values normally attributable to tetrahedrally and octahedrally coordinated Fe2+. The assignment of the isomer-shift values of Fe2+ to octahedral coordination is in agreement with the results of other spectral studies.

For reduced glasses (Fe3+/∑Fe≈<0.50), the value of the isomer shift for Fe3+ at both 298 K and 77 K increases and is linearly correlated with decreasing Fe3+/∑Fe in the range of\(f_{O_2 } \) between 10−3 and 10−6 atm when a single quadrupole-split doublet is assumed to represent the absorption due to ferric iron. The increase in value of the isomer shift with decreasing\(f_{O_2 } \) is consistent with an increase in the proportion of Fe3+ ions that are octahedrally coordinated. The concentration of octahedral Fe3+ is dependent on the\(T - f_{O_2 } \) conditions, and in the range of log\(f_{O_2 } \) between 10−2.0 and 10−5 a significant proportion of the iron may occur as iron-rich structural units with stoichiometry similar to that of inverse spinels such as Fe3O4, in addition to isolated Fe2+ and Fe3+ ions.

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  1. Geophysical Laboratory, Carnegie Institution of Washington, 20008, Washington, DC, USA

    David Virgo & Bjørn O. Mysen

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  1. David Virgo
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Virgo, D., Mysen, B.O. The structural state of iron in oxidized vs. reduced glasses at 1 atm: A57Fe Mössbauer study. Phys Chem Minerals 12, 65–76 (1985). https://doi.org/10.1007/BF01046829

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