Polyelectrolyte complexes: Bulk phases and colloidal systems

Complex formation between oppositely charged polyelectrolytes and its application to making colloidal systems are reviewed. [Display omitted] ► Understanding polyelectrolyte complexes: the state of the art. ► Driving forces, cohesive energy and phase behavior. ► Dynamics of polyelectrolyte complexes. ► From phase behavior to controlled microphases: micelles and micellar networks. ► Polyelectrolyte complexes on surfaces: multilayers and brushes. When aqueous solutions of polycations and polyanions are mixed, polyelectrolyte complexes form. These are usually insoluble in water, so that they separate out as a new concentrated polymer phase, called a complex coacervate. The behavior of these complexes is reviewed, with emphasis on new measurements that shed light on their structural and mechanical properties, such as cohesive energy, interfacial tension, and viscoelasticity. It turns out that stoichiometric complexes can be considered in many respects as pseudo-neutral, weakly hydrophobic polymers, which are insoluble in water, but become progressively more soluble as salt is added. In fact, the solubility-enhancing effect of salt is quite analogous to that of temperature for polymers in apolar solvents. Since two-phase systems can be prepared in colloidal form, we also discuss several kinds of colloids or ‘microphases’ that can arise due to polyelectrolyte complexation, such as thin films, ‘zipper’ brushes, micelles, and micellar networks. A characteristic feature of these charge-driven two-phase systems is that two polymeric ingredients are needed, but that some deviation from strict stoichiometry is tolerated. This turns out to nicely explain how and when the layer-by-layer method works, how a ‘leverage rule’ applies to the density of the ‘zipper brush’, and why soluble complexes or micelles appear in a certain window of composition. As variations on the theme, we discuss micelles with metal ions in the core, due to incorporation of supramolecular coordination polyelectrolytes, and micellar networks, which form a new kind of physical gels with unusual properties.