On the startup behavior of wormlike micellar networks: The effect of different salts bound to the same surfactant molecule

Abstract

We report on shear startup data for two wormlike micellar solutions, differing only in concentration and type of two binding aromatic sodium salts. The surfactant molecule is cetylpiridinium chloride at a fixed concentration (100 mM). Sodium salicylate (NaSal) and diclofenac sodium (Diclo) are used as binding salts at concentrations 68 mM NaSal and 52 mM Diclo such that both systems are fully entangled and their linear viscoelastic response is essentially identical. Both systems show the linear response typical of a wormlike micellar solution, with terminal behavior at low frequencies, a well-defined moduli crossover, and a plateau modulus. In the nonlinear regime, however, the behavior of the two systems is totally different, suggesting that the molecular structure difference of the salts and their binding activity to the surfactant molecule are both crucial to determine the fast flow behavior. The NaSal solution shows a very complex rheological response, with strain hardening and very sharp stress peaks, whereas the solution containing Diclo behaves much like ordinary linear polymers, exhibiting pronounced overshoots as well as moderate undershoots in the transient shear viscosity, before approaching the steady state. This polymerlike behavior has also been proved by successfully comparing data with predictions of a constitutive equation recently adopted for both entangled polymers and linear wormlike micelles. As far as NaSal is concerned, a phenomenological model based on rubber network theory is developed, which describes the flow singularities. A physical interpretation of the different behavior in the nonlinear regime is also suggested.