Macromolecular architecture and complex viscosity

Abstract

General rigid bead-rod theory [O. Hassager, “Kinetic theory and rheology of bead-rod models for macromolecular solutions. II. Linear unsteady flow properties,” J. Chem. Phys. 60(10), 4001–4008 (1974)] explains polymer viscoelasticity from macromolecular orientation. By means of general rigid bead-rod theory, we relate the complex viscosity of polymeric liquids to the architecture of axisymmetric macromolecules. In this work, we explore the zero-shear and complex viscosities of 24 different axisymmetric polymer configurations. When nondimensionalized with the zero-shear viscosity, the complex viscosity depends on the dimensionless frequency and the sole dimensionless architectural parameter, the macromolecular lopsidedness. In this work, in this way, we compare and contrast the elastic and viscous components of the complex viscosities of macromolecular chains that are straight, branched, ringed, or star-branched. We explore the effects of branch position along a straight chain, branched-chain backbone length, branched-chain branch-functionality, branch spacing along a straight chain (including pom-poms), the number of branches along a straight chain, ringed polymer perimeter, branch-functionality in planar stars, and branch dimensionality.