Tunable Adhesion and Interfacial Structure of Layer‐by‐Layer Assembled Block co‐polymer Micelle and Polyelectrolyte Coatings

Abstract

AbstractUnderstanding and tuning nanoscale structure is critical in developing new coatings and adhesives. In this work layer‐by‐layer assembly of block co‐polymer (BCP) micelles and oppositely charged polyelectrolytes produces structurally unique coatings with wet adhesion comparable to that of mussel adhesive proteins. Cationic (CAT) and anionic (ANI) BCPs, synthesized by atom transfer radical polymerization (ATRP), are used to create colloidally stable, self‐assembled, spherical BCP micelles. The assembly of BCP micelle and polyelectrolyte multilayers is monitored in situ where CAT‐ and ANI‐BCP micelles exhibit linear and super‐linear growth, respectively. Imaging of the surfaces reveals that CAT‐BCP micelles yield flat, uniform layers whereas ANI‐BCP micelle assemblies form islands that increase in surface area with each additional layer. The adhesion of these layers, measured by colloidal probe atomic force microscopy (CP‐AFM), shows that the distinct layers of CAT‐BCP micelle assemblies produce alternating high and low adhesion surfaces whereas ANI‐BCP micelle assemblies continually increase in adhesion with each additional bilayer. The unique behavior of each assembly demonstrates that both composition and structure play important roles in wet adhesion of submicron layers and that each can be tuned to target performance for different applications.