Structural changes in aluminosilicate glasses up to 164 GPa and the role of alkali, alkaline earth cations and alumina in the densification mechanism

Abstract

Pressure induced structural changes in silicate melts have a great impact on their physico-chemical properties and hence on their behaviour in the deep Earth's interior. In order to gain a deeper understanding we have studied the densification mechanism in multicomponent aluminosilicate glasses (albitic and albit-diopside composition) by means of extended X-ray absorption fine structure spectroscopy coupled to a diamond anvil cell up to 164 GPa. We have monitored the structural modifications from the network-former Ge as well as the network-modifier Sr. Notably, we tracked the evolution of Ge-O and Sr-O bond lengths (RGe-O, RSr-O) and their coordination number with pressure. We show that RGe-O increases strongly up to about 32 GPa, whereas RSr-O increases only slightly up to ~26 GPa. We assign these extensions to the increase of the coordination number from 4 to 6 (Ge) and from ~6 to at least 9 (Sr). Upon further compression RGe-O and RSr-O exhibit a continuous decrease to the highest probed pressure. These bond contractions, notably of RGe-O, that are continuous and exceed the one observed in pure SiO2 and GeO2, reflect a higher structural flexibility of multi-component glasses compared to those simple systems. Particularly, the high fraction of non-bridging oxygen atoms due to the presence of Na, Sr, Ca, Mg in the studied glasses, favours the simple compression of the highly-coordinated polyhedra of Si and Ge at pressure greater than 30 GPa. This is in strong contrast to pure oxides where cation polyhedral distortions govern the densification mechanism of the glass. The results of this study demonstrate that low field-strength alkali and alkaline earth cations, ubiquitous in deep Earth's melts, have a profound influence on the densification mechanism of glasses. Our results provide important constrains for interpreting the observed low velocity anomalies at the Earth's core-mantle boundary that have been, beyond others, referred to the presence of high-density melts. The hypothesis that non-buoyant melts at the Earth's core-mantle boundary can be formed by peculiar structural transformations in melts leading to higher coordination numbers compared to their crystalline equivalents is not supported from the present observations. The present results rather suggest that if velocity anomalies are to be explained by melts, these likely have considerable differences in chemical composition to the surrounding crystalline phase assemblage.