Structure, conformation and dynamics of polymer chains at solid melt interfaces

We have performed molecular dynamics, and lattice Monte Carlo simulations of polymeric melts in the vicinity of solid surfaces. The structural features of the solid‐melt interface were very simple. The interfacial width was comparable to the segment size. Inside this narrow interface the segment density profile was oscillatory. The density oscillations were much less pronounced than those present at solid‐atomic liquid interfaces. On a scale much larger than the segment size, chain conformations were found to be identical with those of ideal chains next to a reflective barrier. In particular, the number of surface‐segment contacts scaled like the square root of the molecular weight. Extensive molecular dynamics simulations showed that chain desorption times increase with molecular weight but at a rate much slower than the longest relaxation time of Rouse chains. Therefore, sufficiently long chains desorbed almost freely from the surface despite the presence of attractive surface‐segment interactions. A study of chain relaxation dynamics confirmed that the Rouse modes constitute an appropriate set of normal coordinates for chains in the melt interacting with a solid surface. The effect of the surface on mode relaxation was significant. All relaxation processes of chains located within a couple of radii of gyration from the surface were slowed down considerably. This effect, however was approximately the same for fast and slow modes and independent of molecular weight for sufficiently long chains.