Segregation of chain ends to the surface of a polymer melt: Effect of surface profile versus chain discreteness.

Silberberg has argued that the surface of a polymer melt behaves like a reflecting boundary on the random-walk statistics of the polymers. Although this is approximately true, independent studies have shown that violations occur due to the finite width of the surface profile and to the discreteness of the polymer molecule, resulting in an excess of chain ends at the surface and a reduction in surface tension inversely proportional to the chain length, N . Using self-consistent field theory (SCFT), we compare the magnitude of these two effects by examining a melt of discrete polymers modeled as N monomers connected by Hookean springs of average length, a , next to a polymer surface of width [Formula: see text]. The effects of the surface width and the chain discreteness are found to be comparable for realistic profiles of [Formula: see text] ∼ a. A semi-analytical approximation is developed to help explain the behavior. The relative excess of ends at the surface is dependent on the details of the model, but in general it decreases for shorter polymers. The excess is balanced by a long-range depletion that has a universal shape independent of the molecular details. Furthermore, the approximation predicts that the reduction in surface energy equals one unit of kBT for every extra chain end at the surface.