High pressures and the structure of solids of geochemical and geophysical interest

Abstract

Pressures of 10 GPa and above can bring about phase transformations in many oxides, an effect of great interest to geochemists and geophysicists. We can interpret such behaviour as due to the differential compressibility of 'anion' and 'cation' leading to a progressive rise in radius ratio with pressure, and hence, on the classic crystallochemical picture, eventually to an increase in co-ordination number (though with complications which make prediction difficult). More generally, pressure affects Gibbs free energy G directly; for oxides a pressure of 5 GPa gives, very roughly, the same contribution to G as 100°C in temperature (though with opposite sign). Thus high pressure significantly affects the shape and structure of phase diagrams, showing increasingly important effects above, say, 10 GPa—but again prediction can be difficult. However these two complementary approaches to the effects of pressure, helpful though they can be conceptually, are 'crystal-based' and totally neglect another rather littleknown but potentially important effect--the formation of amorphous solids; 'polymers' and glasses. Since amorphous materials are 'non-equilibrium' they are not readily dealt with theoretically; also, since they are difficult to detect by standard crystallographic techniques, they can be overlooked experimentally. The pressure-induced formation of amorphous solids could have significant implications for both geochemistry and geophysics.