Sodium migration pathways in multicomponent silicate glasses: Car–Parrinello molecular dynamics simulations

Abstract

The mechanism of sodium migration in low-silica alkali-alkaline earth silicate glasses is investigated through Car-Parrinello molecular dynamics (MD) simulations. The transport of sodium to the glass surface and its subsequent release is critical for the use of these glasses in biomedical applications. The analysis of the MD trajectory, mainly through a combination of space and time correlation functions, reveals a complex mechanism, with some common features to the migration in mixed-alkali silicate glasses and several important differences. The low site selectivity of Na cations in this glass allows them to use both Na and Ca sites in the migration process. The high fragmentation and the corresponding flexibility of the silicate network enable an additional mechanism for ion migration, not favorable in the more rigid network of common higher-silica glasses, involving the creation of empty transient sites through the correlated forward-backward motion of an Na or a Ca cation. We also show that because sodium migration must involve an undercoordinated intermediate, sharing of oxygen atoms in the initial and final coordination shells is a way to reduce the energetic cost of losing favorable Na-O interactions and Na migration proceeds between corner-sharing NaO(x) polyhedra, where x=5-7. For these low-silica compositions, the present simulations suggest that due to the participation of calcium in the Na migration, the latter will not be significantly hampered by extensive mixing with less mobile Ca ions, or, in any event, the effect will be less marked than for higher-silica glasses.