Experimental and Modeling Comparison of the Dynamics of Capped and Freestanding Poly(2-chlorostyrene) Films.

Proximity to a nonrepulsive wall is commonly considered to cause slower dynamics, which should lead to greater relaxation times for capped thin polymer films than for bulk melts. To the contrary, here we demonstrate that Al-capped films of poly(2-chlorostyrene) exhibit enhanced dynamics with respect to the bulk, similar to analogous freestanding films. To quantitatively resolve the impact of interfaces on whole film dynamics, we analyzed the experimental data via the Cooperative Free Volume rate model. We found that the interfacial region adjacent to a cap contains an excess of free volume (relative to the bulk) about half of that proximate to a free surface. Employing a useful analogy between confinement and pressure effects, we estimated that the effect of capping an 18 nm freestanding film would be equivalent to applying a pressure increase of 19 MPa.