Beyond the Conventional Paradigm of Radial (Normal) Stretching of Tethered Chains. Do Theories of Micellization in Solutions of Block Copolymers Need to Be Revised?

We have studied conformations of a single tethered chain, chains in a planar brush, and corona-forming blocks in diblock copolymer micelles using dissipative particle dynamics. Interactions of all components of the systems were considered explicitly. In addition to the conventionally studied normal elongation of the chains in the brush and micellar corona, we detect regimes of partial or full adsorption of the tethered chains. They are realized for compatible with the substrate (interface) chains (blocks) and solvophobic surfaces (strongly selective solvent for the copolymer). The physical reason for the adsorption is shielding of unfavorable solvent–substrate (or micellar core–solvent) contacts by polymers. In the case of block copolymer micelles, adsorption–desorption of the corona-forming blocks can induce morphology transformation which cannot be predicted/described by traditional theories.