Process dependent properties of glassy polymer films revealed by molecular dynamics simulations

Abstract

A molecular dynamics (MD) framework has been proposed to systematically simulate process (but not cooling rate) dependent properties of glassy polymer films. With the coarse-grained (CG) polylactide (PLA) of low molecular weight (MW), the simulated thermal properties of glassy films are confirmed to be surely decided by the routes to prepare them. While the glassy films initially prepared from the melt bulk are stable, the glassy film initially constructed from the glassy bulk appears to be unstable, featuring highest potential energy among those films and different averaged heat capacity from the bulk counterparts. Inspired by physical vapour deposition (PVD), a surface formation process is further applied to the unstable film to generate stable glassy polymer films. Similar to the PVD, an optimal temperature at which the film is most stable can be identified with lower potential energy than the conventional films, for which free surface and enhanced order of the middle layer are responsible. This work paves a way for obtaining simulated models of stable glassy films and experimentally preparing advanced glassy films for high MW polymers, which otherwise are hard to be realized by the PVD process.