Quantification of five- and six-coordinated aluminum ions in aluminosilicate and fluoride-containing glasses by high-field, high-resolution 27Al NMR

Abstract

Aluminum cation sites with five ( [5]Al) or six ( [6]Al) anion neighbors are minor species in aluminosilicate glasses that are interesting in models of structure, diffusion, and viscous flow. Using 27Al NMR, we present the first direct evidence for [5]Al in a calcium-aluminosilicate glass without excess aluminum over charge-balancing cations, and quantify small concentrations of both [5]Al and [6]Al in several fluoride-containing aluminosilicate glasses. NMR techniques that enhance resolution by decreasing the effects of second-order quadrupolar broadening, including triple-quantum magic-angle spinning (3QMAS), analysis of spinning sidebands, and data collection at very high external magnetic fields (14.1 and 18.8 T), are particularly effective in accurately observing such species.