Anomalous Enthalpy Relaxation in Vitreous Silica

It is a challenge to calorimetrically determine the glass transition temperature (Tg) of vitreous silica. Here, we demonstrate that this challenge mainly arises from the extremely high sensitivity of the Tg to the hydroxyl content, but also from decrease of the Tg with repeating the calorimetric scans. It is known that the liquid fragility (i.e., the speed of the viscous slow-down of a supercooled liquid at its Tg during cooling) has impact on enthalpy relaxation in glass. Here, we find that vitreous silica (as a strong system) exhibits striking anomalies in both glass transition and enthalpy relaxation compared to fragile oxide systems. The anomalous enthalpy relaxation of vitreous silica is discovered by performing the hyperquenching-annealing-calorimetry experiments. We argue that the strong systems like vitreous silica and vitreous Germania relax in a structurally cooperative manner, whereas the fragile ones do in a structurally independent fashion. We discuss the origin of the anomalous enthalpy relaxation in the HQ vitreous silica.