Molecular dynamics study of crystallization of polymer systems confined in small nanodomains

Abstract

We study the ordering dynamics of polymer crystallization using molecular dynamics simulations, in which the polymers are confined to small nanodomains surrounded by a noncrystalline medium. Although the adsorption process and surface diffusion of polymer chains play a major role in the case of the crystalline interface, the domain interface which consists of noncrystalline medium does not have such a crystal substrate to induce the growth of a crystal layer, which may lead to different ordering dynamics. We found that existence of a noncrystalline domain interface has two opposite effects. In the case of semiflexible polymer systems, the domain interface accelerates crystallization in the initial period, whereas it suppresses crystallization in the intermediate or late period. When the rigidity of polymer chains increases, the acceleration effect of the initial crystallization induced by the domain interface is sometimes hidden by spontaneous homogeneous nucleation. These ordering behaviors can be explained by the restriction on the local chain direction near the domain surface in the crystal nucleation stage and the restriction of large orientation relaxation and coalescence in the crystal growth stage. Simulation results reveal that the confinement by the noncrystalline medium does not have a simple effect on the polymer crystallization dynamics, but has various conflicting effects combined with the time stage, the rigidity of polymer chains, and the strength of the surrounding domain interface.