The effect of thixotropy on the yield transition in reversible, colloidal gels

Abstract

Thixotropic yield-stress fluids (TYSFs) are a unique class of materials whose properties are affected by both shear rate and shear history. When sheared, these materials undergo a transition from an elastic solid to a viscoelastic fluid, which is accompanied by a structural transition that slowly recovers upon the cessation of shear. The strong interdependence between structure, dynamics, and rheological properties in TYSFs make it challenging to identify the fundamental physics controlling these phenomena. In this study, we vary the ionic strength of a suspension of cellulose nanocrystals (CNC) to generate model TYSFs with tunable moduli and thixotropic kinetics. We use a novel rheological protocol—serial creep divergence—to identify the physics underlying the yield transition and recovery of CNC gels. Our protocol identifies a critical transition that bifurcates the solid-like and fluid-like regimes of the gels to precisely determine the yield stress of these materials even in the presence of thixotropic effects. Additionally, the thixotropic kinetics collapse onto a single master curve, which we fit to a transient solution to a coupled diffusion–aggregation model. Our work thereby identifies the underlying physicochemical mechanisms driving yielding and thixotropic recovery in attractive colloidal gels.