Viscometric Functions for a Dilute Solution of Polymers in a Good Solvent

TL;DR

This paper models dilute polymer solutions with excluded volume effects using a narrow Gaussian potential, deriving viscometric functions through analytical and simulation methods, revealing swelling and shear thinning behaviors.

Contribution

It introduces a regularized Gaussian potential to incorporate excluded volume effects and provides exact and approximate predictions of viscometric functions in shear flow.

Findings

Excluded volume causes polymer swelling at equilibrium.

Shear thinning occurs due to excluded volume effects.

Gaussian approximation is accurate above a certain width parameter.

Abstract

A dilute polymer solution is modeled as a suspension of non-interacting Hookean dumbbells and the effect of excluded volume is taken into account by incorporating a narrow Gaussian repulsive potential between the beads of each dumbbell. The narrow Gaussian potential is a means of regularising a delta-function potential---it tends to the delta-function potential in the limit of the width parameter going to zero. Exact predictions of viscometric functions in simple shear flow are obtained with the help of a retarded motion expansion and by Brownian dynamics simulations. It is shown that for relatively small non-zero values of the width parameter, the presence of excluded volume causes a swelling of the dumbbell at equilibrium, and shear thinning in simple shear flow. On the other hand, a delta function excluded volume potential does not lead to either swelling or to shear thinning. Approximate viscometric functions, obtained by assuming that the bead-connector vector is described by a Gaussian non-equilibrium distribution function, are found to be accurate above a threshold value of the width parameter, for a given value of the strength of excluded volume interaction. A first order perturbation expansion reveals that the Gaussian approximation is exact to first order in the strength of excluded volume interaction. The predictions of an alternative quadratic excluded volume potential suggested earlier by Fixman (J. Chem. Phys., 1966, 45, 785; 793) are also compared with those of the narrow Gaussian potential.