Effects of electrolyte concentration and counterion valence on the microstructural flow regimes in dilute cetyltrimethylammonium tosylate micellar solutions

Generalized flow diagram that allows identifying the mechanisms that control the shear thickening transition. [Display omitted] ► Behavior of dilute micellar solutions depends strongly on ionic strength. ► A critical deformation is required in order to develop shear thickening. ► Macroscopic behavior is controlled by electrostatic screening and chemical equilibrium. ► Rheological behavior of such systems can be summarized in a generalized flow diagram. The shear thickening behavior and the transition to shear thinning are examined in dilute cetyltrimethylammonium tosylate (CTAT) micellar solutions as a function of surfactant concentration and ionic strength using electrolytes with different counterion valence. Newtonian behavior at low shear rates, followed by shear thickening and shear thinning at higher shear rates, are observed at low and intermediate surfactant and electrolyte concentrations. Shear thickening diminishes with increasing surfactant concentration and ionic strength. At higher surfactant or electrolyte concentration, only a Newtonian region followed by shear thinning is detected. A generalized flow diagram indicates two controlling regimes: one in which electrostatic screening dominates and induces micellar growth, and another, at higher electrolyte and surfactant concentrations, where chemical equilibrium among electrolyte and surfactant counterions controls the rheological behavior by modifying micellar breaking and reforming. Analysis of the shear thickening behavior reveals that not only a critical shear rate is required for shear thickening, but also a critical deformation, which appears to be unique for all systems examined, within experimental error. Moreover, a superposition of the critical shear rate for shear thickening with surfactant and electrolyte concentration is reported.