Effect of pressure on structure of oxide glasses at high pressure: Insights from solid-state NMR of quadrupolar nuclides

Abstract

Revealing the structure of oxide glasses at high pressure remains a fundamental yet difficult problem in modern physical and chemical sciences. The recent advances in solid-state NMR techniques used for quadrupolar nuclides offer a considerably improved resolution of atomic sites, unveiling previously unknown structural details of oxides glasses at high pressure. Here, we present an overview of the recent progress and insights by high-resolution multi-nuclear triple quantum magic angle spinning (3QMAS) NMR into pressure-induced changes in coordination number, connectivity, and topological disorder in oxide glasses quenched from melts at high pressure. 11B and 27Al 3QMAS NMR studies of oxide glasses show that the formation of highly coordinated Al ( [5,6]Al) and four coordinated [4]B are prevalent at high pressure up to 8 GPa. The formation of oxygen clusters linking these highly coordinated framework units and Si (e.g., [5,6]Al–O– [4]Si, [5,6]Si–O– [4]Si, and Na–O– [5,6]Si) is observed in the 17O NMR spectra at higher pressure, leading to an overall increase in the degree of polymerization with pressure. 23Na MAS NMR spectra of diverse oxide glasses at high pressure and high magnetic field also indicate that the Na–O bond distance may decrease with pressure. Pressure-induced changes in structurally relevant NMR parameters such as the 17O quadrupolar coupling product ( P q ) for the Si–O–Si cluster and 27Al P q for Al sites in oxide glasses indicate the occurrence of pressure-induced reductions in the Si–O–Si angle and an increase in the Al–O bond length distribution with pressure, indicating an increase in the overall topological disorder in oxide glasses with pressure. All the pressure-induced changes in structure and topology are characterized by strong composition dependence. These experimental results highlight a new opportunity to investigate the molecular structures of silicate melts at high pressure and reveal connections between the microscopic signatures of anomalous and non-linear changes in the macroscopic properties of the corresponding liquids. While many challenges still remain in the synthesis of oxide glasses with wider range of melt composition at higher pressure above 12 GPa, recent progress in enhancement of sensitivity and resolution in the solid state NMR hold strong promise for study exploring additional details of connectivity among quadrupolar nuclides and medium-range order of the more complex, multi-components glasses at high pressure.