Rheology of viscoelastic mixed surfactant solutions: effect of scission on nonlinear flow and rheochaos

The linear and nonlinear rheology of viscoelastic mixed anionic-zwitterionic surfactant solutions has been systematically investigated. In the linear viscoelastic regime, these systems display nearly Maxwellian behavior with a unique relaxation time, tau0, and a characteristic elastic plateau modulus, G0. Linear rheological data were used to calculate the repitation and breaking times of the micelles, tau(rep) and tau(b), respectively. Surprisingly, the elastic modulus G0 significantly increases with salt concentration c(s), whereas tau(b) decreases by 1 order of magnitude. The strong effect of c(s) on the material parameters and microstructure of rodlike micelles allowed for the systematic investigation of the effect of these parameters on nonlinear flow. For samples with relatively long tau(b), the quasi-static flow diagram (stress vs shear rate) shows a stress peak followed by a metastable branch (a region of decreasing shear stress), whereas for samples with relatively short tau(b), this phenomenon is not observed. Transient flow responses corroborate quasi-static flow findings and further reveal the significance of microscopic dynamic parameters on flow behavior. Shear stress time series were recorded at constant shear rates, and above a critical shear rate, gamma(c2), stress fluctuations are observed. The amplitude of these stress fluctuations, Delta sigma, was found to scale as Delta sigma approximately equal to G0(tau(b)| gamma - gamma(c2)|)beta with beta approximately 0.5. This scaling is observed for micellar systems with tau(b) ranging from 0.12 to 0.01 s and G0 ranging from 1 x 10(3) to 7 x 10(3) dyn/cm2.