Adding salt to a surfactant solution: Linear rheological response of the resulting morphologies

The micellar system composed of Cetylpyridinium Chloride-Sodium Salicylate (CPyCl-NaSal) in brine aqueous solutions has been studied by systematically changing the salt concentration, in order to investigate the rheology of the arising morphologies. In particular, the zero-shear viscosity and the linear viscoelastic response have been measured as a function of the NaSal concentration (with [CPyCl] = 100 mM). The Newtonian viscosity shows a nonmonotonic dependence upon concentration, passing through a maximum at NaSal/CPyCl approximate to 0.6, and eventually dropping at higher salt concentrations. The progressive addition of salt determines first a transition from a Newtonian to a purely Maxwell-like behavior as the length of the micelles significantly increases. Beyond the peak viscosity, the viscoelastic data show two distinct features. On the one hand, the main relaxation time of the system strongly decreases, while the plateau modulus remains essentially constant. Calculations based on the rheological data show that, as the binding salt concentration increases, there is a decrease in micelles breaking rate and a decrease in their average length. On the other hand, in the same concentration region, a low-frequency elastic plateau is measured. Such a plateau is considered as the signature of a tenuous, but persistent branched network, whose existence is confirmed by cryo-transmission electron microscopy images.