Nonlinear rheology of concentrated spherical silica suspensions: 3. Concentration dependence

Abstract

Nonlinear rheology was examined for concentrated suspensions of spherical silica particles (with radius of 40 nm) in viscous media, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture and pure ethylene glycol. The particles were randomly and isotropically dispersed in the media in the quiescent state, and their effective volume fraction φ_eff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σ_B due to their diffusion. For large step strains γ, the nonlinear relaxation modulus G(t,γ) exhibited strong damping and obeyed the time-strain separability. This damping was related to γ-insensitivity of strain-induced anisotropy in the particle distribution that resulted in decreases of σ_B/γ. The damping became stronger for larger φ_eff. This φ_eff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for larger φ_eff. Under steady/transient shear flow, the particles exhibited thinning and thickening at low and high γ˙, respectively. The thinning behavior was well described by a BKZ constitutive equation using the G(t,γ) data and attributable to decreases of a Brownian contribution, σ_B/γ˙. The thickening behavior, not described by this equation, was related to dynamic clustering of the particles and corresponding enhancement of the hydrodynamic stress at high γ˙. In this thickening regime, the viscosity growth η₊ after start-up of flow was scaled with a strain γ˙t. Specifically, critical strains γ_d and γ_s for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φ_eff. This φ_eff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger φ_eff.