Nonmonotonic Glass Transition Temperature of Polymer Films Supported on Polymer Brushes

Abstract

We modulated the grafting density (σ) and chain length of polystyrene (PS) brushes on substrates to probe their effect on the glass transition temperature (Tg) in overlaying PS thin films. The Tg of PS films was analyzed as a function of brush thickness (or σRg 2), where Rg is the radius of gyration of PS brushes. Our results indicate that PS films below 90 nm exhibit a nonmonotonic dependence of Tg on grafting density with the maximum Tg occurring near the regime of wetting-dewetting transition of the overlaying melt. The maximum Tg was found to be higher than the value of bulk PS system. Computer simulation results suggest that such trends arise as a consequence of the environment of enhanced friction presented by the brush layer and the overlap between the polymer film and the grafted layer.