Structure and dynamics of polymer melt confined between two solid surfaces: A molecular dynamics study.

Using large scale molecular dynamics simulations we investigate the static and dynamic properties of a linear polymer melt confined between two solid surfaces. One of the walls is repulsive and the other is attractive wall. The bottom attractive wall is characterized by different degrees of roughness which is tuned by an array of short perpendicular rigid pillars with variable grafting density. We demonstrate that the conformations of polymers at the interfaces do not depend on substrate-polymer interactions, rather they show similar conformations of a single end-grafted chain under critical adsorption condition, consistent with the Silberberg's hypothesis. This observation is found to be in a good agreement with the analysis of the size distributions of trains, loops, and tails of melt chains at the walls known from the theoretical prediction of the end-grafted single chains at critical adsorption. Furthermore, we find that the pressure of the melt PN decreases as PN - P∞ ∝ N-1 with growing length of the chains N (where P∞ is the extrapolated pressure for N → ∞). Moreover, the surface tension γ near both walls is found to follow γN∝N(-2/3). Eventually, the lateral dynamics near rough surface drops suddenly when the separation between the neighboring pillars becomes smaller than 2Rg, where Rg is the bulk radius of gyration.