In this study, Ca K-edge X-ray absorption spectroscopy (XAS) has been employed to study the Ca structural role in a set of silicate glasses. For the first time the accurate analysis of the Ca pre-edge peak has been performed, providing information about the different Ca local environments, and on its structural role.

This approach was tested on Ca-aluminosilicate glasses (CAS system) with constant SiO2 content (50 and 76 mol%), ranging from percalcic to peraluminous domains. In alkali-earth aluminosilicate glasses Al and Si are network formers in a large range of compositions, whereas calcium should act either as network modifier and charge compensator. The results obtained show a different Ca behavior as a function of Al content, which in turn is related to the Al local environment. For example, we observe changes in the pre-edge peak centroid energies depending on the changes in the role of Ca as a network modifier (Al = 0 mol%) to charge compensator (aluminosilicate join) to a more complex role in the peraluminous domain, depending on the fraction of [4],[5],[6]Al. This approach was further applied to study Fe-bearing glasses and, a diopside (CaMgSi2O6) composition at different temperatures. It was possible to correlate the variations occurring in the Ca pre-edge peak centroid positions with both redox state and crystal nucleation mechanism.

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