A cluster approach to rationalize shear thinning: Application to polymer solutions and suspension fluids

Abstract

This paper calculates for liquid mixtures of high and low molecular weight components, how many solute molecules flow on the average conjointly. The application of the approach to solutions of poly(dimethyl siloxane) in its pentamer, to suspensions of gibbsite (Al(OH)3) in dimethyl sulfoxide, and to human blood testifies that the approach is applicable without restrictions regarding the chemical nature of the high molecular weight compound. The shear thinning of the systems under investigation can be understood in terms of a reduction of the shear-overlap parameter Σ, where the generalized intrinsic viscosity {η} constitutes the central property governing the composition and shear rate dependence of the viscosities. Furthermore, the present analysis demonstrates that intrinsic viscosities can be determined for all solutes and that they decrease with rising shear rates according to a Boltzmann sigmoid for the systems DMS5/PDMS and blood. The comparison of the hydrodynamic specific volumes of the solutes (i.e., of [η]) with the corresponding specific volumes in the pure state leads to the conclusion that solutes that cannot interpenetrate carry a considerable amount of solvent piggyback with them when flowing. In addition to the pure description of the observations, the approach was able to point to new phenomena, e.g., the solidification of the gibbsite suspensions beyond a characteristic solute concentration, which shifts to higher values with increasing shear rates. Because of its general nature, the present approach should become helpful, above all in the areas of technology (reactions in flowing systems) and health (rheology of blood).