Structure-rheology relationship for a homogeneous colloidal gel under shear startup.

The structural anisotropy and shear rheology of colloidal gels under startup of shear flow are calculated by Brownian dynamics simulations modified to include particle surface-mediated attractions, which is a model for thermoreversible colloidal gels. Shear-induced structural changes are analyzed in both real and reciprocal space through computation of the pair distribution function and structure factor. A distinct structural anisotropy is evident as alignment along the compressional and vorticity axes. A spherical harmonics expansion of pair distribution function is calculated to analyze structural anisotropy. In reciprocal space, structural anisotropy is quantified through an alignment factor, which shows overshoot behavior similar to the stresses. Based on the microstructure analysis, the evolution of the structural anisotropy is explained by the anisotropic rupture of the colloidal gel microstructure. This result provides evidence for how shearing creates structural anisotropy. The structural anisotropy during flow startup is quantitatively related to rheological behavior via a stress-small angle neutron scattering (SANS) rule that is modified to consider the influence of the rupture of the colloidal gel structure. A simple structure kinetic equation accounting for bond creation and rupture provides a unifying view of the results. This new, modified stress-SANS rule quantitatively links the shear-induced structural anisotropy to the nonlinear rheology. [ABSTRACT FROM AUTHOR]