POLYELECTROLYTE COMPLEXATION

This chapter reviews the theoretical and experimental description of complexes and complex-based hybrid self-assemblies composed of flexible polyelectrolytes, with a special emphasis on thermodynamics, equilibrium structure, and properties of liquid complex coacervates. It discusses the theoretical frameworks that have been employed to describe complexation and properties of complexes, which is followed by a survey of computer simulations studies. It expores the experimental studies on the thermodynamics, structure, and bulk and interfacial properties of both coacervates and precipitates. Liquid-state (LS) theory has been recently used to explore a complete description of the correlations between the oppositely charged polyelectrolyte chains and the counterions in polyelectrolyte complexes. Perry and Sing [96] employed the polymer reference interaction site model (PRISM) to incorporate chain connectivity into a modified LS theory framework. The chapter discusses the bulk and interfacial properties, including polymer diffusion, viscoelastic behavior, and interfacial tension, of liquid polyelectrolyte complexes.