Aging, rejuvenation and thixotropy in complex fluids. Time-dependence of the viscosity at rest and under constant shear rate or shear stress

TL;DR

This paper introduces a new model for complex fluids that unifies aging and thixotropy, predicts bifurcations in viscosity behavior under different conditions, and aligns with experimental data on laponite gels.

Contribution

A novel thixotropic model incorporating aging, defining conditions for viscosity changes, and predicting bifurcations under various shear conditions.

Findings

Viscosity bifurcation at critical volume fraction PHIc2.

Different flow behaviors modeled by Herschel-Bulkley and Bingham models.

Model predictions align with experimental data on laponite gels.

Abstract

Complex fluids exhibit time-dependent changes in viscosity that have been ascribed to both thixotropy and aging. However, there is no consensus for which phenomenon is the origin of which changes. A novel thixotropic model is defined that incorporates aging. Conditions under which viscosity changes are due to thixotropy and aging are unambiguously defined. Viscosity changes in a complex fluid during a period of rest after destructuring exhibit a bifurcation at a critical volume fraction PHIc2. For volume fractions less than PHIc2, the viscosity remains finite in the limit t => infinite. For volume fractions above critical the viscosity grows without limit, so aging occurs at rest. At constant shear rate there is no bifurcation, whereas under constant shear stress the model predicts a new bifurcation in the viscosity at a critical stress sB, identical to the yield stress sy observed under steady conditions. The divergence of the viscosity for stress s sB is best defined as aging. However, for s > sB, where the viscosity remains finite, it seems preferable to use the concepts of restructuring and destructuring, rather than aging and rejuvenation. Nevertheless, when a stress sA (sB) is applied during aging, slower aging is predicted and discussed as true rejuvenation. Plastic behaviour is predicted under steady conditions when s > sB. The Herschel-Bulkley model fits the flow curve for stresses close to sB, whereas the Bingham model gives a better fit for s >> sB. Finally, the model's predictions are shown to be consistent with experimental data from the literature for the transient behaviour of laponite gels.