Abstract

We show that a suspension of non-Brownian calcite particles in glycerol-water mixtures can be tuned continuously from being a yield-stress suspension to a shear-thickening suspension—without a measurable yield stress—by the addition of various surfactants. We interpret our results within a recent theoretical framework that models the rheological effects of stress-dependent constraints on inter-particle motion. Bare calcite particle suspensions are found to have finite yield stresses. In these suspensions, frictional contacts that constrain inter-particle sliding form at an infinitesimal applied stress and remain thereafter, while adhesive bonds that constrain inter-particle rotation are broken as the applied stress increases. Adding surfactants reduces the yield stress of such suspensions. We show that, contrary to the case of surfactant added to colloidal suspensions, this effect in non-Brownian suspensions is attributable to the emergence of a finite onset stress for the formation of frictional contacts. Our data suggest that the magnitude of this onset stress is set by the strength of surfactant adsorption to the particle surfaces, which therefore constitutes a new design principle for using surfactants to tune the rheology of formulations consisting of suspensions of adhesive non-Brownian particles.Graphical Impact of surfactants on the rheology of concentrated calcite suspensions. Black, schematic flow curve for bare particles. Low stress: adhesive contact, rolling and sliding between particles prevented (red). High stress: frictional contact, rolling allowed (green), constraints broken → shear thinning. Blue, with surfactant. Low stress: repulsion prevents contact, rolling and sliding allowed, removing yield stress entirely. High stress: surfactant displaced (see inset), particles bare and sliding prevented; constraints formed → shear thickening

Highlights

  • A transformation has recently occurred in our understanding of the rheology of suspensions of hard non-Brownian particles with repulsive interactions

  • Powder was dispersed in glycerol-water mixtures using vortex and high-shear mixing at φ ≤ 0.45, or manual stirring at φ > 0.45, until a smooth appearance was achieved

  • For systems where the shear rate may decrease with stress, we report the apparent stress, σapp = 2T /π R3

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Summary

Introduction

A transformation has recently occurred in our understanding of the rheology of suspensions of hard non-Brownian (nB) particles (size 2 μm ) with repulsive interactions Such suspensions shear thicken: their viscosity increases with applied shear rate (Barnes 1989). Particles in mechanical contact cannot freely slide past one another due to Coulomb friction (Seto et al 2013) or other mechanisms (Hsu et al 2018; James et al 2018). This happens when the stabilising repulsive force between particles fails to keep them separated when the applied stress increases beyond a critical threshold, σ ∗, the ‘onset stress’. The additional particle motion needed on the local level to accommodate any given macroscopic strain leads to extra dissipation, so that the viscosity rises (Lerner et al 2012)

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