Effect of Surface Modification on the Glass Transition Dynamics of Highly Polar Molecular Liquid S-Methoxy-PC Confined in Anodic Aluminum Oxide Nanopores

Abstract

In the presence of nanoscale confinement, the role of surface effects come to the fore in determining the glass-transition dynamics of the molecular liquids and polymers. Therefore, by playing with the surface chemistry it is possible to understand better the mechanism which governs the behavior of glass-forming systems at the nanoscale. In this work, we have combined dielectric and calorimetric data to study surface and confinement effects for highly polar glass-forming liquid S-Methoxy-PC constrained within anodic aluminum oxide membranes of different pore sizes. The inner surface of the pores was modified either by silanization or atomic layer deposition (ALD) coatings. For the tested substance in native nanopores, we have observed two glass transition events in the calorimetric response accompanied by a characteristic deviation of the temperature dependence of the α-relaxation time from the Vogel–Fulcher–Tamman law. We found that depending on the hydrophobicity of the ALD layer the glass transition temperature of the interfacial layer tends to decrease, the α-relaxation peak broadens, and the molecular mobility slows down compared to the native pores. These changes are more visible with increasing hydrophobicity of the surface. Silanization was also found to eliminate at least partially the effects caused by nanopore confinement. However, in this study the most pronounced effects were observed only for pores with large diameters.