Origins of the anomalous stress behavior in charged colloidal suspensions under shear.

Numerical simulations are conducted to determine microstructure and rheology of sheared suspensions of charged colloidal particles at a volume fraction of ϕ=0.33. Over broad ranges of repulsive force strength F0 and Péclet number Pe, dynamic simulations show coexistence of ordered and disordered stable states with the state dependent on the initial condition. In contrast to the common view, at low shear rates, the disordered phase exhibits a lower viscosity (μ(r)) than the ordered phase, while this behavior is reversed at higher shear rates. Analysis shows the stress reversal is associated with different shear induced microstructural distortions in the ordered and disordered systems. Viscosity vs shear rate data over a wide range of F0 and Pe collapses well upon rescaling with the long-time self-diffusivity. Shear thinning viscosity in the ordered phase scaled as μ(r)∼Pe(-0.81) at low shear rates. The microstructural dynamics revealed in these studies explains the anomalous behavior and hysteresis loops in stress data reported in the literature.