Lattice theory for binding of linear polymers to a solid substrate from polymer melts. II. Influence of van der Waals interactions and chain semiflexibility on molecular binding and adsorption.

The polymeric Langmuir theory, developed in Paper I [J. Dudowicz et al., J. Chem. Phys. 151, 124706 (2019)], is employed to investigate the influence of van der Waals interactions and chain rigidity on the thermodynamics of the reversible molecular binding to interfaces in one component polymer fluids (polymer melts). Both van der Waals interactions and chain stiffness are found to influence the temperature variation of the surface coverage Θ, the binding transition itself, and the cooperativity of molecular binding. Re-entrancy of the surface coverage Θ(T) is found to arise when the intermolecular interactions are sufficiently attractive to cause a liquid-vapor like phase separation in the interfacial region, a phenomenon that can occur in the binding of both small molecules and polymer chains to surfaces. [ABSTRACT FROM AUTHOR]