Structure and dynamics of polyelectrolyte surfactant mixtures under conditions of surfactant excess.

Oppositely charged polyelectrolyte (PE) surfactant mixtures can self-assemble into a large variety of mesoscopic structures, so-called polyelectrolyte surfactant complexes (PESCs). These structures directly affect the macroscopic behavior of such solutions. In this study, we investigated mixtures of the cationically charged PE JR 400 and the anionic surfactant SDS with the help of different neutron scattering and fluorescence methods. While an excess of PE charges in semi-dilute solutions causes an increase of viscosity, it has been observed that an excess of surfactant charges reduces the viscosity while precipitation is observed at charge equilibrium. The increase in viscosity had been investigated before and was attributed to the formation of cross links between PE chains. In this publication we focus our attention on the reduction of viscosity which is observed with an excess of surfactant charges. It is found that the PE chains form relatively large and densely packed clusters near the phase boundary on the surfactant rich side, thereby occupying less space and reducing the viscosity. For even higher surfactant concentrations, individual surfactant decorated PE chains are observed and their viscosity is found to be similar to that of the pure PE.