Effects of polydispersity on confined homopolymer melts: a Monte Carlo study

New insight into the molecular scale details of polymer melts under confined conditions is obtained from the first dynamic Monte Carlo study incorporating polydispersity. While confinement effects on polymers have been widely explored, little work exists on the effects of polydispersity. This is surprising given the near universal presence of polydispersity in physical systems. To address this shortcoming, a new variation of on-lattice dynamic Monte Carlo simulation is used to provide an understanding of how polydispersity alters confinement effects on polymer melts. Polymer melts of varying polydispersity are simulated between two hard walls (surface interaction parameter, χ(s) = 0) of variable spacing. As plate spacing decreases, polymer chains adopt conformations in which the end-to-end vector is parallel to the hard walls. However, polydisperse melts with the same length average molecular weight, N(w) (which is analogous to the weight average molecular weight, M(w)) show reduced orientation effects. Polydispersity provides greater degrees of freedom; that is, there are more configurations for the system to adopt to accommodate confinement without ordering. At plate spacings of four radii of gyration and only modest polydispersity index values (polydispersity index, PDI = 1.42), the order parameters are reduced by 15% compared to the monodisperse case. The same PDI value corresponds to a 10% reduction in the perturbations of the end-to-end vector and Rouse time. Interestingly, length-based migration effects are observed. Longer chains reside away from the walls and the shorter chains are found nearer the walls; at equilibrium there is a molecular weight based fractionation across the gap. Confinement also leads to a "speeding up" of the polymer dynamics. Altered dynamic phenomena include a reduction of the Rouse time for the same average molecular weight and an altered scaling behavior with plate spacing. Reptation times are also reduced and polydispersity smoothes out the transitions between different scaling regimes. The overall picture that emerges is not unexpected—polydispersity profoundly affects the behavior of confined homopolymers.