Structural changes in borosilicate glasses as a function of Fe2O3 content: A multi-technique approach

EALES, J.D., BELL, A.M.T., CUTFORTH, D.A., KRUGER, A.A. and BINGHAM, Paul (2023). Structural changes in borosilicate glasses as a function of Fe2O3 content: A multi-technique approach. Journal of Non-Crystalline Solids, 622: 122664. [Article]

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Abstract
Three series of borosilicate glasses were prepared, ranging from simple ternary sodium borosilicate glasses (SCFe series), to complex borosilicate glasses (CCFe Series), to high-level radioactive waste analogue glasses (HAFe series). 57Fe Mössbauer and Fe K-edge XANES spectroscopies showed that the iron exists exclusively as Fe3+ in predominantly distorted tetrahedral structures ([4]Fe3+), with evidence for lower abundances of higher-coordinated [5 or 6]Fe3+. Raman, B K-edge XANES, and XPS spectroscopies qualitatively demonstrated that Fe3+ preferentially integrates into the borosilicate network through the silicate sub-network in the simple glasses, whereas in the complex glasses it preferentially integrates through the borate sub-network. The [4]B3+ fraction for the SCFe and CCFe glasses showed minimal changes as a function of Fe content, indicating that Fe concentration has no effect on boron coordination and is- therefore unlikely to be competing with [4]B3+ groups for charge compensation, qualitatively supporting the presence of competing tetrahedral avoidance hierarchies.
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