Grafted polymers inside cylindrical tubes: Chain stretching vs layer thickness

Abstract

We present a study of the detailed structure of grafted polymer chains and the layers they form inside cylindrical tubes, using the finitely extensible nonlinear elastic chain model and numerical self-consistent field theory. For very large tube radius, the chain stretching and layer thicknesses are the same as for polymers grafted to a planar surface. For decreasing radius, our calculations indicate that the layer almost always gets thinner, although there can be situations where it is very slightly thicker. However, we find that this thinning is not necessarily due to changes to the polymers: in fact, the root-mean-squared layer thickness would decrease even if the polymers themselves are completely unchanged. Furthermore, we find that the polymer stretching can increase at the same time that the layer thickness decreases. These apparent paradoxes are resolved by analyzing and distinguishing between the volume fraction profiles and monomer number distributions in these systems, including how they change and why. We also find that, in a given system, parts of each polymer move towards the curved surface and parts away from it, and that these differences are key to understanding the behavior.