The effect of increasing pressure and two-dimensional (2D) confinement on the dynamics of glass-forming polymer poly­(methylphenylsiloxane) (PMPS) was investigated with the use of dielectric spectroscopy. We demonstrate that the glass-forming polymer confined to nanoporous alumina might obey the density scaling relation similar to that in the bulk and that the same value of the scaling exponent is used to superimpose the α-relaxation time measured under different thermodynamic conditions. Our comprehensive analysis of the relaxation processes detected in the dielectric loss spectra of PMPS allows us to identify the Johari–Goldstein β-relaxation which for a bulk polymer shows up as a well-resolved peak while under 2D nanoconfinement only as an excess wing. In contrast to previous studies, we provide dielectric evidence of an additional α′-relaxation, slower than the segmental (α-) dynamics, which is related to the chain dynamics of PMPS.

No 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.