Microscopic Activated Dynamics Theory of the Shear Rheology and Stress Overshoot in Ultra-Dense Glass-Forming Fluids and Colloidal Suspensions

TL;DR

This paper develops a microscopic activated dynamics theory to understand the shear rheology and stress overshoot in ultra-dense glass-forming fluids and colloidal suspensions, linking microscopic relaxation processes to macroscopic flow behavior.

Contribution

It introduces a new quantitative model for the transient stress overshoot, explicitly capturing the coupled evolution of structure, elasticity, and stress relaxation under shear.

Findings

Model predictions match experimental stress overshoot data.

Activated motion is essential for both transient and steady-state responses.

The theory explains the dependence of stress overshoot on shear rate and packing fraction.

Abstract

We formulate a microscopic, force-level, activated dynamics-based statistical-mechanical theory for the continuous startup nonlinear shear-rheology of ultra-dense glass-forming hard-sphere fluids and colloidal suspensions in the context of the ECNLE approach. Activated structural relaxation is described as a coupled local-nonlocal event involving caging and longer-range collective elasticity which controls the characteristic stress relaxation time. Theoretical predictions for the deformation-induced mobility enhancement, onset of relaxation acceleration at low values of stress, strain, or shear-rate, apparent power-law thinning of the steady-state structural relaxation time and viscosity, a non-vanishing activation barrier in the shear-thinning regime, an apparent Herschel-Bulkley form of the rate dependence of the steady-state shear stress, exponential growth of different measures of a dynamic yield or flow-stress with packing fraction, and reduced fragility and dynamic heterogeneity under deformation were previously shown to be in good agreement with experiment. The central new question addressed here is the defining feature of the transient response - the stress-overshoot. In contrast to the steady-state flow regime, understanding the transient response requires an explicit treatment of the coupled nonequilibrium evolution of structure, elastic modulus, and stress relaxation time. We formulate a new quantitative model for this aspect in a physically motivated and computationally tractable manner. Theoretical predictions for the stress-overshoot are shown to be in good agreement with experimental observations in the metastable ultra-dense regime of hard-sphere colloidal suspensions as a function of shear-rate and packing fraction, and accounting for deformation-assisted activated motion is crucial for both the transient and steady-state responses.