Nonlinear rheology of a concentrated spherical silica suspension:

Time-dependent nonlinear flow behavior was investigated for a model hard-sphere suspension, a 50 wt% suspension of spherical silica particles (radius = 40 nm; effective volume fraction = 0.53) in a 2.27/1 (wt/wt) ethylene glycol/glycerol mixture. The suspension had two stress components, the Brownian stress ^B and the hydrodynamic stress ^H After start-up of flow at various shear rates , the viscosity growth function ₊ (t, ) was measured with time t until it reached the steady state. The viscosity decay function _– (t, ) was measured after cessation of flow from the steady as well as transient states. At low where the steady state viscosity ( ) exhibited the shear-thinning, the _– (t, ) and ⁺ (t, ) data were quantitatively described with a BKZ constitutive equation utilizing data for nonlinear relaxation moduli G (t, ). This result enabled us to attribute the thinning behavior to the decrease of the Brownian contribution ^B = ^B / (considered in the BKZ equation through damping of G (t, )). On the other hand, at high where ( ) exhibited the thickening, the BKZ prediction largely deviated from the ₊ (t, ) and ₊ (t, ) data, the latter obtained after cessation of steady flow. This result suggested that the thickening was due to an enhancement of the hydrodynamic contribution ^H = ^H / (not considered in the BKZ equation). However, when the flow was stopped at the transient state and only a small strain (<0.2) was applied, ^H was hardly enhanced and the _– (t, ) data agreed with the BKZ prediction. Correspondingly, the onset of thickening of ₊ (t, ) was characterized with a -insensitive strain ( 0.2). On the basis of these results, the enhancement of ^H (thickening mechanism) was related to dynamic clustering of the particles that took place only when the strain applied through the fast flow was larger than a characteristic strain necessary for close approach/collision of the particles.