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J Chem Phys ; 144(4): 044502, 2016 Jan 28.
Article in English | MEDLINE | ID: mdl-26827221

ABSTRACT

Aluminoborosilicate glasses containing relatively high field strength modifiers (Ca, La, and Y) have been compressed at pressures up to 3 GPa and near the glass transition temperature (Tg) and quenched to room temperature at high pressure followed by decompression. Structural changes were quantified with high-resolution (27)Al and (11)B MAS nuclear magnetic resonance at 14.1-18.8 T. The changes with pressure in Al and B coordinations in the recovered samples are quite large with more than 50% decreases in tetrahedral aluminum ((IV)Al) and 200%-300% increases in tetrahedral boron ((IV)B). Glasses with higher field strength modifiers (La and Y) contain more high coordinated aluminum ((V,V I)Al) at all pressures studied. More high coordinated boron also correlates with higher field strength modifier if all three compositions are compared on an isothermal basis. Although lowering fictive temperature and increasing pressure both increase Al and B coordinations, our study shows that the actual mechanisms for structural changes are most probably different for temperature and pressure effects. Using a rough thermodynamic model to extrapolate to higher pressures, it appears that a simple non-bridging oxygen (NBO) consumption mechanism is not sufficient to convert all the aluminum to octahedral and boron to tetrahedral coordination, suggesting other mechanisms for structural changes could occur at high pressure as NBO becomes depleted.

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