Viscosity of Polyelectrolyte Surfactant Complexes-The Importance of the Choice of the Polyelectrolyte Seen for the Case of PDADMAC Versus JR 400

Some oppositely charged polyelectrolyte (PE) surfactant mixtures show a remarkable increase in viscosity near charge equilibrium, while other very similar systems do not show any appreciable effect. The exact structural prerequisites to achieve a significant increase in viscosity are still unclear. In previous work, we investigated the structure and dynamics of oppositely charged polyelectrolyte surfactant complexes (PESCs) formed from sodium dodecylsulfate (SDS) and the cationically modified hydroxyethyl cellulose JR 400, which does enhance the viscosity around charge equilibrium enormously. Here, we study PESCs consisting of SDS and the cationic PE polydiallyldimethylammonium chloride (PDADMAC) which do not significantly increase the viscosity of solutions under similar conditions. Apparently very similar ingredients in PESCs can lead to largely different macroscopic behavior. Using small-angle neutron scattering, rheology, and neutron spin-echo spectroscopy, we gain insights into the system's mesoscopic structure and dynamics. Different from that in SDS/JR 400, no intermixed aggregates are formed but instead a cylindrical core-shell structure. In it, the PDADMAC is much less strongly bound and possesses much higher dynamics which explains the much lower viscosity.