Order and disorder in sodium silicate glasses and melts at 10 GPa

We report experimental evidence, in conjunction with quantum chemical calculation, supporting chemical ordering among network polyhedra (e.g. [5]Si and [6]Si) in sodium silicate glasses quenched from melts at 10 GPa by using 17O 3QMAS (triple quantum magic angle spinning) NMR, which resolves new oxygen sites at high pressure, including [5,6]Si‐O‐[4]Si and Na‐O‐[5,6]Si. The distribution of network polyhedra at 10 GPa, a controlling factor for transport and melting processes in the mantle, is not completely random but favors formation of oxygen linking dissimilar Si pairs such as [5,6]Si‐O‐[4]Si. The presence of non‐bridging oxygens (NBOs) in highly coordinated units at 10 GPa, Na‐O‐[5,6]Si, indicates that the formation of highly coordinated Si can also occur at initially depolymerized silicon tetrahedra such as Q3 or Q2. The methods and results given here yield improved prospects for understanding melt structures at high pressure and the atomistic origin of magmatic processes in the Earth's interior.

[1]  J. Stebbins,et al.  Nature of cation mixing and ordering in Na-Ca silicate glasses and melts , 2003 .

[2]  J. Stebbins,et al.  Extent of intermixing among framework units in silicate glasses and melts , 2002 .

[3]  Karl E. Vermillion,et al.  Relationships between bridging oxygen 17O quadrupolar coupling parameters and structure in alkali silicates , 1998 .

[4]  P. McMillan,et al.  Silicon and Oxygen Self-Diffusivities in Silicate Liquids Measured to 15 Gigapascals and 2800 Kelvin , 1997 .

[5]  Y. Fei,et al.  Mineralogy of the Martian interior up to core‐mantle boundary pressures , 1997 .

[6]  A. Pines,et al.  Triple-Quantum Two-Dimensional 27Al Magic-Angle Spinning Nuclear Magnetic Resonance Spectroscopic Study of Aluminosilicate and Aluminate Crystals and Glasses , 1996 .

[7]  J. Yarger,et al.  Al Coordination Changes in High-Pressure Aluminosilicate Liquids , 1995, Science.

[8]  L. Frydman,et al.  Isotropic Spectra of Half-Integer Quadrupolar Spins from Bidimensional Magic-Angle Spinning NMR , 1995 .

[9]  J. Stebbins,et al.  Correlations between 17O NMR parameters and local structure around oxygen in high-pressure silicates: Implications for the structure of silicate melts at high pressure , 1994 .

[10]  P. McMillan,et al.  Pressure-induced silicon coordination and tetrahedral structural changes in alkali oxide-silica melts up to 12 GPa: NMR, Raman, and infrared spectroscopy , 1991 .

[11]  B. Mysen Effect of pressure, temperature, and bulk composition on the structure and species distribution in depolymerized alkali aluminosilicate melts and quenched melts , 1990 .

[12]  T. Ahrens,et al.  On the nature of pressure‐induced coordination changes in silicate melts and glasses , 1987 .

[13]  N. Shimizu,et al.  Diffusivity of oxygen in jadeite and diopside melts at high pressures , 1984 .

[14]  Sucheta Sharma,et al.  Raman study of the coordination of aluminum in jadeite melts as a function of pressure , 1979 .

[15]  I. Kushiro Changes in viscosity and structure of melt of NaAlSi2O6 composition at high pressures , 1976 .