Fluorescence studies of confinement in polymer films and nanocomposites: Glass transition temperature, plasticizer effects, and sensitivity to stress relaxation and local polarity

Confinement effects in polystyrene and poly(methylmethacrylate) films and nanocomposites are studied by fluorescence. The ability to employ an intensive measurable, the excited-state fluorescence lifetime, in defining the glass transition temperature, T_g, of polymers is demonstrated and compared to the use of an extensive measurable, fluorescence intensity. In addition, intrinsic fluorescence from the phenyl groups in polystyrene is used to determine the T_g-confinement effect in films as thin as ∼15 nm. The decrease in T_g with decreasing film thickness (below ∼60 nm) agrees well with results obtained by extrinsicpyrene fluorescence. Dye label fluorescence is used to quantify theenhancement in T_g observed with decreasing thickness (below ∼90 nm) in poly(methyl methacrylate) films; addition of 2-4 wt% dioctyl phthalate plasticizer reduces or eliminates the T_g-confinement effect in films down to 20 nm thickness. Intrinsic polystyrene fluorescence, which is sensitive to local conformation, is used to quantify the time scales (some tens of minutes) associated with stress relaxation in thin and ultrathinspin-coated films at T_g + 10 K. Finally, the shape of the fluorescence spectrum of pyrene doped at trace levels in polystyrene films and polystyrene-silica nanocomposites is used to determine effects of confinement on microenvironment polarity.