Atomistic understanding of the network dilation anomaly in ion-exchanged glass

Chemically strengthened glasses are of increasing technological importance for personal electronic devices, tablet computers, and a variety of other applications. However, there are many unexplained phenomena associated with the physics of the ion exchange process used for strengthening. One of the most puzzling of these is the anomalous behavior of the network dilation coefficient, i.e., the parameter governing the amount of linear strain of the glass per unit of alkali ions exchanged, which is inevitably a factor of 2–4 higher for as-melted glasses as compared to chemically strengthened versions of the same glass compositions prepared via ion exchange. In this paper, we investigate the atomistic origin of this discrepancy between as-melted and ion-exchanged glasses based on molecular dynamics simulations of a series of alkali tetrasilicate glasses, viz., xNa2O·(20−x)K2O·80SiO2 (mol%). The network dilation coefficient of the ion-exchanged glasses is dependent on composition and ranges from 30% to 54% of the ideal value obtained from the as-melted glasses. This anomalous behavior of the network dilation coefficient is explained in terms of different local environments between sodium and potassium sites in the glass network and a two-stage relaxation process of the local potassium environment after ion exchange. ► Network dilation coefficient describes the amount of strain per unit change in alkali. ► Network dilation of ion-exchanged glass is less than that of as-melted glasses. ► Molecular dynamics simulations reveal the atomic origin of the network dilation anomaly. ► Network dilation anomaly due to K+ coordination in as-melted vs. ion-exchanged glasses.