Activation free energy gradient controls interfacial mobility gradient in thin polymer films

We examine the mobility gradient in the interfacial region of substrate-supported polymer films using molecular dynamics simulations and interpret these gradients within the string model of glass-formation. No large gradients in the extent of collective motion exist in these simulated films, and an analysis of the mobility gradient on a layer-by-layer basis indicates that the string model provides a quantitative description of the relaxation time gradient. Consequently, the string model indicates that the interfacial mobility gradient derives mainly from a gradient in the high-temperature activation enthalpy ΔH₀ and entropy ΔS₀ as a function of depth z, an effect that exists even in the high-temperature Arrhenius relaxation regime far above the glass transition temperature. To gain insight into the interfacial mobility gradient, we examined various material properties suggested previously to influence ΔH₀ in condensed materials, including density, potential and cohesive energy density, and a local measure of stiffness or u²(z)^-3/2, where u²(z) is the average mean squared particle displacement at a caging time (on the order of a ps). We find that changes in local stiffness best correlate with changes in ΔH₀(z) and that ΔS₀(z) also contributes significantly to the interfacial mobility gradient, so it must not be neglected.