Slow Transients and Metastability in Wormlike Micelle Rheology

Abstract

The steady-state nonlinear rheology of wormlike micellar systems is thought to be subject to shear banding (the underlying shear stress vs. strain rate curve σ(γ) is nonmonotonic). Shear banding may result in a plateau (σ(γ) = σp) in the measured flow curve (at controlled mean strain rate γ). We present new rheological data for aqueous CPyCl/NaSal (100 mM /60 mM). Steady-state flow curves published previously for this system (Rehage H. and Hoffmann H., Mol. Phys. 74 (1991) 933) have since been interpreted as shear-banded flow with top-jumping, in which the steady-state shear rate γ1 in the low shear band is the largest possible (γ 1 = γ 1 max , σ p = σ max ). That would rule out the existence of a metastable branch with a stress larger than σp. We show that such a branch does, however, exist (for temperatures in the range 20 - 25 °C). Similar results are found for a 100 mM/75 mM system. The time scale for relaxation of a metastable state onto true steady state flow, τ ss , is far longer than the Maxwell time of the fluid; this is consistent with shear banding. We observe τ ss ∼ (γ - γ c ) -P in the metastable regime (γ > γ 1 ), with p an exponent that depends on composition and temperature. The critical shear rate γ c is in some cases less than γ 1 so that no actual divergence of τ ss occurs. In at least one case, though, there is evidence for a physical divergence (γ c > γ 1 ) accompanied by a small window of shear rates, γ 1 < γ < γ c , for which τ ss is effectively infinite. In some respects the observed behaviour resembles that reported previously (Berret J.-F., Roux D.C. and Porte G., J. Phys. II Prance 4 (1994) 1261) for equimolar CPyCl/NaSal in 0.5 M NaCl. Those results were interpreted in terms of nucleation and growth of a shear-induced nematic phase. However the same explanation is unlikely for the low weight fractions (Φ ≤ 5%) used in our study.