V33F-04
Glasses and Melts under Compression and Surface Confinement

Wednesday, 16 December 2015: 14:25
310 (Moscone South)
Sung Keun Lee, Seoul National University, Seoul, South Korea
Abstract:
Upon compression and confinement (near surfaces), glasses are expected to be subject to successive structural transitions with multiple densification and confinement mechanisms. Experimental verification of these phenomena remain a major target of glass-melt studies. Here, we provide an overview of the recent progress by solid-state NMR and inelastic x-ray scattering (IXS) into structures of multi-component silicate and oxide glasses with varying pressure, composition (with fluid contents), and confinement [e.g., Lee et al. Rev. Min. Geochem. 2014, 78, 139; Lee and Ahn, Sci. Report, 2014, 4, 4200; Lee and Kim, J. Phys. Chem. C. 2015, 119 748].

O-17 NMR studies reveal the presence of metal-bridging oxygen in orthosilicate glasses (an analogue to peridotite melts) and allow direct quantification of the degree of Metal/Si disorder with composition and pressure. Despite the pronounced paramagnetic effect, detailed structural changes in iron-bearing silicate glasses can now be probed using solid-state NMR techniques. NMR results for the multi-component silicate glasses melts at high pressure highlight the moderate deviation from the degree of Al avoidance among framework cations (Si and Al) and preferential proximity between non-network cations and non-bridging oxygen. In contrast to an expected complexity in densification, experimental NMR and IXS results for glasses demonstrate that the pressure-induced changes in melt structures show a simple trend where the effect composition and pressure can be predicted with network flexibility.

Solid-state NMR techniques revealed the unknown structural details of oxide glasses and melts near surfaces and interfaces: the coordination environments in the surface confined oxide glasses are distinct from those of bulk, highlighted by a decrease in the fractions of high-energy clusters (and thus the degree of disorder) near interface. The structure of glass surfaces is also affected by the types of interfaces (e.g. crystalline vs. melts), demonstrating that a wide range of variations in structure of glasses and melts in contact with other coexisting phases can be experimentally identified.