How Does Monomer Structure Affect the Interfacial Dynamics of Supported Ultrathin Polymer Films?
AN Storey and WG Zhang and JF Douglas and FW Starr, MACROMOLECULES, 53, 9654-9664 (2020).
We utilize recently introduced chemically specific but coarse-grained models of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) to explore the influence of monomer architecture on the dynamics of supported thin polymer films based on molecular dynamics simulations. In particular, we contrast differences in the molecular packing and mobility gradients in these materials near the substrate and "free" interface regions. As expected, relaxation is generally enhanced in the free surface region relative to the film interior (and bulk), and the degree of enhancement is similar for both PEO and PMMA. However, the dynamical changes near the substrate are more sensitive to monomer structure, and are enhanced with increasing polymer-substrate interaction strength, epsilon. PMMA is relatively stiff compared to PEO and has a side group of appreciable size, and we find that the dynamics of PMMA near the substrate are slowed significantly more in comparison to PEO for the same substrate. Substrate interactions lead to a notable difference of local fragility near the substrate that appears to arise from a higher cohesive interaction strength of the PMMA chains in this region. Our data also reveal the inadequacy of the these coarse-grained polymer models to reproduce the experimentally known differences in the fragility of these materials. However, this technical shortcoming is not expected to alter our qualitative conclusions regarding the comparative effect of substrate interactions on relatively flexible polymers such as PEO versus a relatively stiff polymer such as PMMA.
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