Evidence for Al/Si tetrahedral network in aluminosilicate glasses from AlK-edge x-ray-absorption spectroscopy

Abstract

The structure of aluminosilicate melts and/or glasses plays a key role in the earth sciences for the understanding of rock-forming igneous processes, as well as in the materials sciences for their technical applications. In particular, the alkaline-earth aluminosilicate glasses are an extremely important group of materials, with a wide range of commercial application, as well as serving as an analog for natural basaltic melts. However, definition of their structure and properties is still controversial, and in particular the role and effect of Al has long been a subject of debate. Here we report a series of experimental x-ray absorption near-edge structure spectra at the Al K edge on a series of synthetic glasses of peralkaline composition in the $\mathrm{CaO}\ensuremath{-}{\mathrm{Al}}_{2}{\mathrm{O}}_{3}\ensuremath{-}{\mathrm{SiO}}_{2}$ system, together with a general theoretical framework for data analysis based on an ab initio full multiple-scattering theory. We propose an Al/Si tetrahedral network model for aluminosilicate glasses based on distorted polyhedra, with varying both the $T\ensuremath{-}\mathrm{O} (T=\mathrm{Al}$ or Si) bond lengths and the $T\ensuremath{-}\mathrm{O}\ensuremath{-}T$ angles, and with different Al/Si composition. This model achieves a significant agreement between experiments and simulations. In these glasses, experimental data and theoretical results concur to support a model in which Al is network former with a comparatively well ordered local medium-range order (up to 5 \AA{}).