Living Growth Kinetics of Polymeric Micelles on a Substrate

Living growth of micelles on the substrate is an intriguing phenomenon; however, little is known about its growth kinetics, especially from a theoretical viewpoint. Here, we examine the living growth kinetics of polymeric micelles on a hydrophobic substrate immersed in an aqueous solution. The block copolymers first assemble into short cylinder seeds anchored on the substrate. Then, the small aggregates of block copolymers in the solutions fuse onto the active ends of the anchored seeds, leading to micelle growth on the substrate. A theoretical model is proposed to interpret such living growth kinetics. It is revealed that the growth rate coefficient on the substrate is independent of the copolymer concentration and the multistep feedings; however, it is significantly affected by the surface hydrophobicity. Brownian dynamics simulations further support the proposed growth mechanism and the kinetic model. This work enriches living assembly systems and provides guidance for fabricating bioinspired surface nanostructures.