Effect of the surface polarity, through employing nonpolar spacer groups, on the glass-transition dynamics of poly(phenyl methylsiloxane) confined in alumina nanopores

Abstract

Broadband dielectric spectroscopy and differential scanning calorimetry were used to study the effect of changes in the surface conditions on the segmental dynamics of poly(phenylmethylsiloxane) confined in alumina nanopores. Functionalization was done using highly polar propyl phosphoric units separated by the assumed concentration of triethoxysilane groups (from N = 0 to N = 24). By adjusting the proportion between polar units and nonpolar spacers, it was possible to control the surface polarity. Modification of the surface conditions does not inhibit the formation of the adsorbed layer, as revealed by the presence of two Tg’s in calorimetric results. However, changes in the surface polarity will prevent the growth of the additional interlayer in between the core volume and the interfacial layer. Finally, we also found that the changes in the surface polarity affect the equilibration kinetics and can be used to control the time scale of the structural recovery toward the equilibrium state.