Viscosity of Colloidal Suspensions

Simple expressions are given for the Newtonian viscosity $\eta_N(\phi)$ as well as the viscoelastic behavior of the viscosity $\eta(\phi,\omega)$ of neutral monodisperse hard sphere colloidal suspensions as a function of volume fraction $\phi$ and frequency $\omega$ over the entire fluid range, i.e., for volume fractions $0 < \phi < 0.55$. These expressions are based on an approximate theory which considers the viscosity as composed as the sum of two relevant physical processes: $\eta (\phi,\omega) = \eta_{\infty}(\phi) + \eta_{cd}(\phi,\omega)$, where $\eta_{\infty}(\phi) = \eta_0 \chi(\phi)$ is the infinite frequency (or very short time) viscosity, with $\eta_0$ the solvent viscosity, $\chi(\phi)$ the equilibrium hard sphere radial distribution function at contact, and $\eta_{cd}(\phi,\omega)$ the contribution due to the diffusion of the colloidal particles out of cages formed by their neighbors, on the P\'{e}clet time scale $\tau_P$, the dominant physical process in concentrated colloidal suspensions. The Newtonian viscosity $\eta_N(\phi) = \eta(\phi,\omega = 0)$ agrees very well with the extensive experiments of Van der Werff et al and others. Also, the asymptotic behavior for large $\omega$ is of the form $\eta_{\infty}(\phi) + A(\phi)(\omega \tau_P)^{-1/2}$, in agreement with these experiments, but the theoretical coefficient $A(\phi)$ differs by a constant factor $2/\chi(\phi)$ from the exact coefficient, computed from the Green-Kubo formula for $\eta(\phi,\omega)$. This still enables us to predict for practical purposes the visco-elastic behavior of monodisperse spherical colloidal suspensions for all volume fractions by a simple time rescaling.