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

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 deltafunction potential—it tends to the delta-function potential in the limit of the width parameter μ 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 μ, 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 nonequilibrium distribution function, are found to be accurate above a threshold value of μ, for a given value of the strength of excluded volume interaction, z. A first order perturbation expansion reveals that the Gaussian approximation is exact to first order in z. 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.