Rheology of Wormlike Micelles with Varying Hydrophobicity of the Counterion

Abstract

Dynamic viscoelastic experiments were performed on mixtures of cetyl trimethylammonium tosylate (CTAT) and cetyl trimethylammonium 3-hydroxy naphthalene 2-carboxylate (CTAHNC) to understand the effect of hydrophobicity of the counterions on the structure of aggregates formed. The total surfactant concentration is fixed at 100 mM, and the ratio of the two counterions HNC- to tosylate- (x2) is varied from 0 to 0.7. The zero shear viscosity (η) and the terminal time of stress relaxation (τR) initially increases slowly with x2 and then decreases drastically for x2 > 0.5. The initial increase of both η and τR can be explained by an increase of the micellar length owing to the more hydrophobicity of HNC-, which reduces the scission energy of the micelles due to the decrease of the electrostatic contribution. A decrease of the η and τR above x2 = 0.5 is attributed to the formation of intermicellar connections, which is favored at very high salt content. The presence of intermicellar branching speeds up the repta...