Long-range effects on polymer diffusion induced by a bounding interface

We have measured the diffusion of deuterated polystyrene of molecular weight 90 × 10³ in various matrices of hydrogenated polystyrene as a function of distance from an attractive interface, oxide-covered silicon. Surprisingly long-range effects are observed. Diffusion rates an order of magnitude slower than bulk persist up to 10R_g (radius of gyration) from the interface of either the diffusant or matrix polymers. The slowdown is independent of matrix molecular weight over a broad range. However, mixing of polymers within the matrix strongly influences the rates of diffusion.