High pressure effects on liquid viscosity and glass transition behaviour, polyamorphic phase transitions and structural properties of glasses and liquids

Since the pioneering work of Bridgman it has been known that pressure affects the glass transition of polymers and liquid state viscosities. Usually the Tg and viscosity both increase as a function of pressure as expected from ‘free volume’ theories. However, H2O provided a notable exception in that the viscosity passes through a minimum at low temperature. It was thought that this might be linked to the anomalous thermal expansion behavior. However further research on geologically important aluminosilicate liquids revealed that they could show anomalous viscosity decreases with increasing pressure and this behavior is given a structural interpretation as five-fold coordinated Si4+ and Al3+ species are formed. Also the existence of polyamorphism or density-driven liquid–liquid phase transitions in certain systems can lead to anomalies in the Tg or η vs. P relations. This may be the case for H2O, for example. Current research is focusing on investigating structural changes in liquids and glasses at high pressure as the rich variety of behavior is becoming recognized. Both experimental studies and computer simulations are important as the underlying phenomonology is linked to changes in the glass or liquid structure as a function of densification.