The Environment of Fe3+/Fe2+ Cations in a Sodium Borosilicate Glass
2017
The neutron diffraction isotopic substitution technique is employed to investigate the environment of Fe3+/Fe2+ cations in a sodium borosilicate glass matrix of composition 0.210Na2O0.18511B2O30.605SiO2. The neutron diffraction data were obtained using the D4c diffractometer at the Institut Laue-Langevin (ILL; Grenoble, France), and were recorded for three samples; the base glass, the base glass incorporating natural Fe2O3 (12 mol.%) and a similar glass containing Fe2O3 enriched in 57Fe. The data are Fourier transformed to yield the real-space total correlation function, T(r), and the first co-ordination shells of the Fe3+/Fe2+ cations are investigated via a peak fit to the isotopic difference correlation function TFe(r).
It is concluded that the iron is mainly present as Fe3+ cations, both tetrahedrally and octahedrally co-ordinated by oxygen atoms, plus a small fraction (0.07 ± 0.01) of Fe2+ cations in octahedral co-ordination. The Fe3+ tetrahedral fraction is 0.45 ± 0.10, and appears to exist as FeO4 structural units incorporated into the network of silicate chemical groupings, with their negative charge being balanced by Na+ network-modifying cations. The remaining Fe3+ cations (fraction 0.48 ± 0.10) are thought to be predominantly octahedrally co-ordinated and associatedwith BO33 orthoborate anions in FeBO3 chemical groupings, which become non-stoichiometric due to the reduction of some of the Fe3+ cations to Fe2+.
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