Simulation Study of the Effects of Polymer Network Dynamics and Mesh Confinement on the Diffusion and Structural Relaxation of Penetrants (2301.05356v2)

Abstract: The diffusion of small molecular penetrants through polymeric materials represents an important fundamental problem, relevant to the design of materials for applications such as coatings and membranes. Polymer networks hold promise in these applications, because dramatic differences in molecular diffusion can result from subtle changes in the network structure. In this paper, we use molecular simulation to understand the role that crosslinked network polymers have in governing the molecular motion of penetrants. By considering the local, activated alpha relaxation time of the penetrant and its long-time diffusive dynamics, we can determine the relative importance of activated glassy dynamics on penetrants at the segmental scale versus entropic mesh confinement on penetrant diffusion. We vary several parameters, such as the crosslinking density, temperature, and penetrant size, to show that crosslinks primarily affect molecular diffusion through modification of the matrix glass transition, with local penetrant hopping at least partially coupled to the segmental relaxation of the polymer network. This coupling is very sensitive to the local activated segmental dynamics of the surrounding matrix, and we also show that penetrant transport is affected by dynamic heterogeneity at low temperatures. To contrast, only at high temperatures and for large penetrants or when the dynamic heterogeneity effect is weak does the effect of mesh confinement become significant, even though penetrant diffusion more broadly empirically follows similar trends as established models of mesh confinement-based transport.