A coarse-grained molecular dynamics study of segmental structure and mobility in capped crosslinked copolymer films

T Davris and AV Lyulin, JOURNAL OF CHEMICAL PHYSICS, 143, 074906 (2015).

DOI: 10.1063/1.4928961

We present results from molecular-dynamics simulations of a generic bead-spring model of copolymer chains confined between solid walls and report on the glass-transition temperature and segmental dynamics as a function of film thickness and mesh size (the end-to-end distance of the subchains in the crosslinked polymer networks). Apparently, the glass- transition temperature displayed a steep increase for mesh-size values much smaller than the radius of gyration of the bulk chains, otherwise it remained invariant to mesh-size variations. The rise in the glass- transition temperature with decreasing mesh size and film thickness was accompanied by a monotonic slowing-down of segmental dynamics on all studied length scales. This observation is attributed to the correspondingly decreased width of the bulk density layer that was obtained in films whose thickness was larger than the end-to-end distance of the bulk polymer chains. To test this hypothesis, additional simulations were performed in which the crystalline walls were replaced with amorphous or rough walls. In the amorphous case, the high polymer density close to the walls vanished, but the dynamic response of the film was not affected. The rough walls, on the other hand, only slightly decreased the density close to the walls and led to a minor slowing-down in the dynamics at large length-scales. (C) 2015 AIP Publishing LLC.

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