The role of the binding salt sodium salicylate in semidilute ionic cetylpyridinium chloride micellar solutions: a rheological and scattering study

The micellar system based on cetylpyridinium chloride (CPyCl) and sodium salicylate (NaSal) in brine solution is investigated on both macro- and micro-length scales through rheology and scattering measurements. The linear viscoelasticity of the system and its structural parameters are explored by systematically changing the amount of NaSal over an extremely wide range of concentrations, thus producing salt-to-surfactant molar ratios from zero to about 8.5. As a result, the well-known non-monotonic behaviour of the zero-shear rate viscosity as a function of salinity can be connected to micellar morphological changes, whose driving force is represented by the simultaneous binding and screening actions of NaSal. The viscosity behaviour can be seen as a direct consequence of consecutive lengthening/shortening of the contour length, where the micelles attempt to minimize the electrostatic charge density on their surface. Along similar lines, the scattering measurements of the semidilute solutions show that the local stiffness of the micellar chain changes with increasing salt content influencing the elasticity of the resulting network. Within this general view, the branching of the micelles can be seen as a side effect attributable to the main character of the play, namely, the binding salt NaSal, whereas the overall dynamics of the system is driven by the considerable changes in the entanglement density of the micellar network.