Microscopic structure and dynamics of shear-thinning suspensions of polydisperse, repulsive vesicles

We investigate the rheology, microscopic structure, and dynamics of an industrially relevant dispersion made of charged vesicles, from dilute to concentrated conditions. We find that these suspensions exhibit a shear-thinning behavior at relatively low volume fractions. At the microscale, this corresponds to a well-defined transition in both the structure, marked by a sudden increase of the scattered intensity, and the dynamics, which slow down and develop a two-step decay in the correlation functions. This low-concentration transition is particularly surprising in light of experiments showing that for surfactant vesicles of similar composition the interactions should be purely repulsive. This leads us to suggest that the observed structural and dynamic transition could arise, as an entropic effect, from the large sample polydispersity coupled to crowding. The shear-thinning behavior is thus interpreted as the nonlinear response of this transient structure to the imposed flow. Our work suggests that similar effects might be a generic feature of dense, highly polydisperse charged suspensions.