Structure and mechanical properties of compressed sodium aluminosilicate glasses: Role of non-bridging oxygens

• Sodium aluminosilicate glasses with varying NBO content are subjected to hot compression at 1 GPa.
• Raman and 27Al NMR spectroscopy, density, and indentation measurements are performed.
• High-NBO glasses exhibit larger change in density and mechanics upon compression.
• 27Al NMR data show a surprising presence of five-fold aluminum in the as-made high-NBO glasses.
• Larger pressure-induced generation of AlV, and in one case AlVI, in glasses with NBOs.

Clarifying the effect of pressure on the structure of aluminosilicate glasses is important for understanding the densification mechanism of these materials under pressure and the corresponding changes in macroscopic properties. In this study, we examine changes in density, network structure, indentation hardness, and crack resistance of sodium aluminosilicate glasses with varying Al/Si ratio and thus non-bridging oxygen (NBO) content before and after 1 GPa isostatic compression at elevated temperature. With increasing NBO content, the silicate network depolymerizes, resulting in higher atomic packing density, lower hardness, and higher crack resistance. The ability of the glasses to densify under isostatic compression is higher in the high-NBO glasses, and these glasses also exhibit more pronounced pressure-induced changes in mechanical properties. The 27Al NMR data show a surprising presence of five-fold aluminum in the as-made high-NBO glasses, with additional formation upon compression. Our study therefore provides new insights into the complicated relationship between Al coordination and NBO content in aluminosilicate glasses and how it affects their densification behavior.