Comparison of Physical Aging and Glass Transition in Glassy-Rubbery Polymer Bilayer Films

In the present work, we use ellipsometry to extract the physical aging response of thin glassy polystyrene (PS) layers from rubbery-glassy bilayer films of poly(n-butyl methacrylate) (PnBMA) atop PS. How the soft interface between rubbery and glassy polymer domains can impact the physical aging response of glassy domains is unclear. Measurements in the literature have shown that the local glass transition temperature T_g of PS is strongly reduced near a PnBMA/PS interface with a magnitude twice as large compared to that imparted by a free surface. As the free surface is known to reduce physical aging, we anticipated large changes in the physical aging response of PS within PnBMA/PS bilayer films. However, surprisingly the aging response remained equivalent to bulk down to 75 nm PS layer thicknesses that were the thinnest we found could be accurately measured given the optical limits of dispersion. With complementary fluorescence measurements, we show that the average T_g(h_PS) of such PS layers within 150 nm PnBMA/75 nm PS bilayer films are also still bulk. These findings demonstrate that films with finite domain sizes have interfacial dynamical gradients that are significantly altered from those previously measured in systems with semi-infinite domain sizes.