Structural properties of concave cylindrical brushes interacting with free chains

Abstract

We present a self-consistent field theoretical study of the microstructure of concave cylindrical brushes as a function of the cylinder radius, grafting density, grafted chain length, and the solvent quality. We show that the results for the radial monomer density profile and the distribution of the free ends are in good agreement with the corresponding molecular dynamics results. Part of the investigation is focused on the conformational behavior of a free macromolecule in a cylindrical brush. A central result is the observed non-monotonous variation of the size of a free chain in a brush-coated tube when the tube radius is systematically changed. An interpretation of this behavior which differs qualitatively from that of a polymer in cylindric confinement is suggested in terms of scaling theory and rationalized by considering the overlap between the free polymer and the grafted chains as a function of the tube radius.