Journal of Chemical Physics, Vol.106, No.23, 9799-9809, 1997
New Statistical-Mechanical Treatment of Systems Near Surfaces .3. Polydisperse Linear and Branched Polymers in an Interacting Solution
We apply a recently developed analytical but approximate method to study the behavior of polydisperse linear and branched polymers in a solution with interaction and near various kinds of surfaces. We consider equilibrium polydispersity controlled by a set of activities. The method allows us to account for polymer connectivity and excluded-volume effects and goes beyond the random mixing approximation. The method also allows us to probe the entire density range, which is not possible in a Monte Carlo simulation. The density profiles show oscillations for bulk densities phi(mb) larger than some threshold value phi(mt), the amplitudes of those oscillations being a strong function of the solvent-monomer interaction parameter w. The behavior of linear and branched polymers is almost identical for the same bulk densities phi(mb), except when the solvent-monomer interaction is repulsive and the surface-monomer interaction is not attractive. In this case, the effect of branching is to increase the correlation length xi describing the approach of a density profile to its bulk value. We also compute the surface thermodynamic functions (the entropy and the free energy). While the surface free energies are identical for linear and branched polymers, the surface entropies are very different.