Denser fluids of charge-stabilized colloids form denser sediments

Abstract

Granular matter, where solid-like elasticity emerges in the absence of crystalline order, has been actively studied over the last few decades, targeting fundamental physical understanding of granular packings and glasses, abundant in everyday life and technology. We employ charge-stabilized sub-micron particles in a solvent, known as colloids, to form granular packings through a well-controlled process, where initially homogeneous and thermodynamically equilibrated colloidal fluids form solid sediments, when subjected to an effective gravity in a centrifuge. We demonstrate that particles' volume fraction φ_j in these sediments increases linearly with that in the initial fluid φ₀, setting an upper limit φ_RCP ≈ 0.64 on both φ_j and φ₀, where φ_RCP coincides with the well-known, yet highly controversial, ‘random close packing’ density of spheres, providing new insight into the physics of granular packings. The observed φ_j(φ₀) dependence is similar to the one recently reported for colloidal hard spheres, sterically stabilized by surface-linked polymer combs (S. R. Liber, et al., Proc. Natl. Acad. Sci. U. S. A., 2013, 110, 5769–5773). However, the lower limit on sediment densities drops to φ_j ≈ 0.49 in the present work, suggesting that sedimented charge-stabilized silica are able to overcome mutual electrostatic repulsions, forming gel-like structures stabilized by occasional van der Waals contacts. Finally, by introducing particle size polydispersity, which significantly modifies fluid structure and sedimentation dynamics, we almost completely diminish the φ_j(φ₀) dependence, bringing φ_j(0) close to its value in frictionless systems.