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.

Broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC) are combined to study the effect of changes in the surface chemistry on the segmental dynamics of glass-forming polymer, poly(methylphenylsiloxane) (PMPS), confined in anodized aluminum oxide (AAO) nanopores. Measurements were carried for native and silanized nanopores of the same pore sizes. Nanopore surfaces are modified with the use of two silanizing agents, chlorotrimethylsilane (ClTMS) and (3-aminopropyl)trimethoxysilane (APTMOS), of much different properties. The results of the dielectric studies have demonstrated that for the studied polymer located in 55 nm pores, changes in the surface chemistry and thermal treatment allows the confinement effect seen in temperature evolution of the segmental relaxation time, τ α (T) to be removed. The bulk-like evolution of the segmental relaxation time can also be restored upon long-time annealing. Interestingly, the time scale of such equilibration process was found to be independent of the surface conditions. The calorimetric measurements reveal the presence of two glass-transition events in DSC thermograms of all considered systems, implying that the changes in the interfacial interactions introduced by silanization are not strong enough to inhibit the formation of the interfacial layer. Although DSC traces confirmed the two-glass-transition scenario, there is no clear evidence that vitrification of the interfacial layer affects τ α (T) for nanopore-confined polymer.

Under confinement, the properties of polymers can be much different from the bulk. Because of the potential applications in technology and hope to reveal fundamental problems related to the glass-transition, it is important to realize whether the nanoscale and macroscopic behavior of polymer glass-formers are related to each other in any simple way. In this work, we have addressed this issue by studying the segmental dynamics of poly­(4-chlorostyrene) (P4ClS) in the bulk and upon geometrical confinement at the nanoscale level, in either one- (thin films on Al substrate) or two- (within alumina nanopores) dimensions. The results demonstrate that the segmental relaxation time, irrespective of the confinement size or its dimensionality, can be scaled onto a single curve when plotted versus ργ/T with the same single scaling exponent, γ = 3.1, obtained via measurements at high pressures in bulk. The implication is that the macro- and nanoscale confined polymer dynamics are intrinsically connected and governed by the same underlying rules.