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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 Tg 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 Tg(hPS) 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. 

Recent studies suggest chain adsorption in the melt may be responsible for a number of property changes in thin films by making correlations between the residual adsorbed layer thickness h ads ( t ) measured after a given solvent washing procedure as a function of annealing time t of the film at an elevated temperature prior to this solvent rinse. This procedure, frequently called “Guiselin's experiment”, refers to the thought experiment proposed in a 1992 theoretical treatment by Guiselin that assumed chain segments in contact with the surface are irreversibly adsorbed whereby unadsorbed chains could be washed away by solvent without disturbing the adsorbed substrate contact points in the melt. In the present work, we review this recent literature, identifying and experimentally testing a common protocol for forming adsorbed layers h ads ( t ) from solvent washing melt films. We find h ads ( t ) curves to be far less reproducible and reliable than implied in the literature, strongly dependent on solvent washing and substrate cleaning conditions, and annealing at elevated temperatures is unnecessary as densification of films sitting at room temperature makes the glassy film harder to wash off, leaving behind h ads of comparable thickness. This review also summarizes literature understanding developed over several decades of study on polymer adsorption in solution, which experimentally demonstrated that polymer chains in solution are highly mobile, diffusing and exchanging on the surface even in the limit of strong adsorption, contradicting Guiselin's assumption. Preformed adsorbed layers of different thicknesses h ads are shown to not affect the average glass transition temperature or physical aging of 30 nm thick films. In summary, a number of open questions and implications are discussed related to thin films and polymer nanocomposites.