Abstract

We study the ageing and ultimate gravitational collapse of colloidal gels in which the interparticle attraction is induced by non-adsorbing polymers via the depletion effect. The gels are formed through arrested spinodal decomposition, whereby the dense phase arrests into an attractive glass. We map the experimental state diagram onto a theoretical one obtained from computer simulations and theoretical calculations. Discrepancies between the experimental and simulated gel regions in the state diagram can be explained by the particle size and density dependence of the boundary below which the gel is not strong enough to resist gravitational stress. Visual observations show that gravitational collapse of the gels falls into two distinct regimes as the colloid and polymer concentrations are varied, with gels at low colloid concentrations showing the onset of rapid collapse after a delay time. Magnetic resonance imaging (MRI) was used to provide quantitative, spatio-temporally resolved measurements of the solid volume fraction in these rapidly collapsing gels. We find that during the delay time, a dense region builds up at the top of the sample. The rapid collapse is initiated when the gel structure is no longer able to support this dense layer.

Highlights

  • Many industrial products contain colloids at intermediate volume fractions in which the particles are denser than the liquid

  • We study the ageing and ultimate gravitational collapse of colloidal gels in which the interparticle attraction is induced by non-adsorbing polymers via the depletion effect

  • We have delineated in detail the gel region in a model colloidal suspension: a dispersion in decalin of hard-spherelike sterically stabilised PMMA particles in which an interparticle attraction is induced via the depletion effect caused by added non-adsorbing polystyrene polymers

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Summary

Introduction

Many industrial products contain colloids at intermediate volume fractions (say, E5–40%) in which the particles are denser than the liquid. A key requirement is that the particles must not sediment appreciably during a ‘shelf life’ of months to years, but, when required, the products must flow under moderate applied stresses. These seemingly contradictory requirements can be met by formulating the product as a colloidal gel: a space-spanning network of attractive particles with a yield stress high enough to bear the material’s own weight, but low enough to be overcome in use to give flowability. The first is formed when the system phase separates through spinodal decomposition into this arrested glass phase at high volume fraction.[3,4,5,6,7,8] The second class of systems form ‘equilibrium gels’ without phase separating.[9,10,11,12,13,14,15]

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