Rheology of diblock copolymer micellar systems

Abstract

This article summarizes rheological features of moderately concentrated, diblock copolymer micellar solutions in selective solvents. In solvents of monomeric sizes, spherical micelles (with glassy cores) are arranged on cubic lattices to exhibit elasto-plastic responses. These lattices are formed due to an osmotic constraint for the conformation of solvated corona blocks of the micelles. In polymeric solvents (homopolymers) chemically identical to the corona blocks, this constraint is screened and the micelles are randomly dispersed in the systems. In this type of blends (micellar dispersions) in short, nonentangling matrices the micelles have no plasticity but exhibit two-step viscoelastic relaxation: The fast relaxation process corresponds to relaxation of individual corona blocks while the slow process is attributable to diffusion of the micelles. Corresponding to these molecular mechanisms, the fast process exhibits modest damping of the nonlinear relaxation modulus against large step strains while the slow process exhibits much stronger damping. Under steady flow, the micellar dispersion exhibits two-step shear-thinning with the molecular origin identical to that for the nonlinear damping. All these rheological features of the micellar lattices and dispersions are strikingly similar, in many aspects, to the features of colloidal crystals and hard-sphere suspensions of solid particles.