Hydrodynamic interaction and complex viscosity of multi-bead rods

Abstract

One good way to explain the elasticity of a polymeric liquid is to just consider the orientation distribution of the macromolecules. When exploring how macromolecular architecture affects the elasticity of a polymeric liquid, we find the general rigid bead–rod theory to be both versatile and accurate. This theory sculpts macromolecules using beads and rods. Whereas beads represent points of Stokes flow resistances, the rods represent rigid separations. In this way, how the shape of the macromolecule affects its rheological behavior in suspension is determined. Until recently, general rigid bead–rod theory has neglected interferences of the Stokes flow velocity profiles between nearby beads. We call these hydrodynamic interactions, and we here employ our new method for exploring how these interactions affect the complex viscosity of suspensions of multi-bead rods. These multi-bead rods are also called shish-kebabs. We use the center-to-center distance between adjacent beads as the characteristic length. We proceed analytically, beginning with a geometric expression for the shish-kebab bead positions. Our analytical solution for the complex viscosity presents as one for N=3,5,6,7,8,…, one for N=4, and another for the rigid dumbbell, N=2. We find that for shish-kebabs, hydrodynamic interactions (i) increase zero-shear viscosity, (ii) increase zero-shear first normal stress coefficient, (iii) decrease the real part of the dimensionless complex viscosity, and (iv) increase minus the dimensionless imaginary part. We find that the combination of (iii) and (iv) explains crossovers of the parts of the complex viscosity. We further find that for a monodisperse polystyrene solution, the general rigid bead–rod theory with hydrodynamic interaction, for both parts of the complex viscosity, provides stunning improvement over without.