Probing Medium-Range Order in Oxide Glasses at High Pressure.

Densification in glassy networks has traditionally been described in terms of short-range structures, such as how atoms are coordinated and how the coordination polyhedron is linked in the second coordination environment. While changes in medium-range structures beyond the second coordination shells may play an important role, experimental verification of the densification beyond short-range structures is among the remaining challenges in the physical sciences. Here, a correlation NMR experiment for prototypical borate glasses under compression up to 9 GPa offers insights into the pressure-induced evolution of proximity among cations on a medium-range scale. Whereas amorphous networks at ambient pressure may favor the formation of medium-range clusters consisting primarily of similar coordination species, such segregation between distinct coordination environments tends to decrease with increasing pressure, promoting a more homogeneous distribution of dissimilar structural units. Together with an increase in the average coordination number, densification of glass accompanies a preferential rearrangement toward a random distribution, which may increase the configurational entropy. The results highlight the direct link between the pressure-induced increase in medium-range disorder and the densification of glasses under extreme compression.