Structural rearrangements during sub-Tg relaxation and nucleation in lithium disilicate glass revealed by a solid-state NMR and MD strategy

Abstract

Structural rearrangements taking place during relaxation and crystal nucleation in lithium-disilicate (LS2) glass have been investigated by a comprehensive set of solid-state nuclear magnetic resonance (NMR) experiments, supported by molecular dynamics (MD) simulations. Samples were subjected to heat treatments at 435 °C, i.e., 20 K below the laboratory glass transition temperature (Tg). Raman and NMR data indicate that under these conditions both relaxation and nucleation occur without detectable changes in the network former unit distribution of the glassy silicon-oxide network. Instead, relaxation of the frozen supercooled melt and nucleation of LS2 crystals occur principally in terms of a changing lithium local environment: 7Li spin-echo decay NMR indicates average Li-Li distances, characterized by homonuclear dipolar second-moment measurements, are reduced after very short heat treatments and approach those found in the isochemical crystal. This finding is supported by molecular dynamics (MD) simulations predicting a dependence of the Li+ ion distribution on the melt-cooling rate. In addition, the structural reorganization also impacts the distribution of electric field gradients as detected by 7Li satellite transition NMR spectroscopy. Finally, crystal nucleation becomes most evident by the appearance of minor amounts of sharp 29Si MAS resonances and a significant change in the 7Li NMR satellite transitions, as visualized by difference spectroscopy. This study defines a new NMR strategy, generally applicable for investigating the structural relaxation process accompanying the internal crystallization of ion-conducting frozen supercooled melts containing suitable NMR active nuclear probes (7Li, 23Na, 133Cs, etc.).