Interplay of surface and confinement effects on the molecular relaxation dynamics of nanoconfined poly(methyl...

The thermally stimulated current (TSC) signatures of the primary (alpha) transition and its precursor, the Johary-Goldstein (beta) relaxation, are used to probe effects of nanoconfinement on the dielectric relaxation dynamics of poly(methyl methacrylate) (PMMA) radically polymerised in situ 50 angstroms mean pore size silica-gel. Nanoconfinement leads to a broadened and low-temperature-shifted beta band (peaking at Tbeta, with deltaTbeta = T(conf.)beta - T(bulk)beta = -15 degrees C for a heating rate of 5 deg/min), signifying the occurrence of faster relaxing moieties compared to the bulk-like PMMA film. Furthermore, both TSCs and differential scanning calorimetry (DSC) estimate a rise of the glass transition temperature for the confined phase ([Formula: see text]= +13 degrees C) and an increased width for the corresponding transition signals, relative to the signals in the bulk. Simple free-volume and entropy models seem inadequate to provide a collective description of the above perturbations. The observation of a spatial heterogeneity regarding the relaxation dynamics is discussed in terms of the presence of a motional gradient, with less mobile segments near the interface and more mobile segments in the core, and the interplay of adsorption ( e.g., strong physical interactions that slow down molecular mobilities) and confinement effects ( e.g., lower entanglements concentration and local density fluctuations that provide regions of increased free space). The results suggest that in the case of high-molecular-weight polymers confined in small-pore systems, adsorption effects have considerable bearing on the glass transition phenomenon whereas confinement primarily influences side-chains' rotational mobilities. The confinement effect is expected to dominate over adsorption for PMMA phases occluded in higher pore sizes and silanised walls.