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Wetting and Capillary Condensation in Symmetric Polymer Blends: A comparison between Monte Carlo Simulations and Self-Consistent Field Calculations

M. Mueller·K. Binder
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Abstract

We present a quantitative comparison between extensive Monte Carlo simulations and self-consistent field calculations on the phase diagram and wetting behavior of a symmetric, binary (AB) polymer blend confined into a film. The flat walls attract one component via a short range interaction. The critical point of the confined blend is shifted to lower temperatures and higher concentrations of the component with the lower surface free energy. The binodals close the the critical point are flattened compared to the bulk and exhibit a convex curvature at intermediate temperatures -- a signature of the wetting transition in the semi-infinite system. Investigating the spectrum of capillary fluctuation of the interface bound to the wall, we find evidence for a position dependence of the interfacial tension. This goes along with a distortion of the interfacial profile from its bulk shape. Using an extended ensemble in which the monomer-wall interaction is a stochastic variable, we accurately measure the difference between the surface energies of the components, and determine the location of the wetting transition via the Young equation. The Flory-Huggins parameter at which the strong first order wetting transition occurs is independent of chain length and grows quadratically with the integrated wall-monomer interaction strength. We estimate the location of the prewetting line. The prewetting manifests itself in a triple point in the phase diagram of very thick films and causes spinodal dewetting of ultrathin layers slightly above the wetting transition. We investigate the early stage of dewetting via dynamic Monte Carlo simulations.

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M. Mueller, K. Binder. 1998-05-26. Wetting and Capillary Condensation in Symmetric Polymer Blends: A comparison between Monte Carlo Simulations and Self-Consistent Field Calculations. https://doi.org/10.1021/ma980052x

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