High-pressure experiments as a novel perspective to study the molecular dynamics of glass-forming materials confined at the nanoscale

Herein, we report the pioneering high-pressure dielectric studies on the dynamics of a model van der Waals glass-forming liquid bisphenol-A diglycidyl ether (DGEBA) infiltrated into anodic aluminum oxide (AAO) templates of the mean pore sizes, d = 150 and d = 18 nm. It was found that although the shape of the structural relaxation process varies with the confinement, it remains constant under varying thermodynamic conditions for a given pore diameter. Consequently, the time-temperature-pressure (TTP) rule satisfied for the majority of bulk substances is also obeyed for the spatially restricted liquid. We have also shown for the first time that there is a decoupling between the core and interfacial mobility at elevated pressure. Moreover, it was noted that the structural dynamics of the former fraction of molecules becomes systematically shorter with respect to the bulk DGEBA during the compression. The enhanced structural dynamics of the core material, as well as the varying pressure coefficients of the glass transition temperature of the interfacial and core molecules, have been discussed in the context of a distinct evolution in their free volume/density packing with respect to the bulk DGEBA, and a change in the interfacial tension, which may lead to the enhanced wettability of the liquid adsorbed onto the pore walls under different thermodynamic conditions. The performed high-pressure measurements offer novel perspectives to explore the combination of two different effects, compression and confinement, which might be a breakthrough in the study of the glass transition phenomenon and the behavior of soft materials confined at the nanoscale.