Viscometric Functions and Rheo-optical Properties of Dilute Polymer Solutions: Comparison of FENE-Fraenkel Dumbbells with Rodlike Models

TL;DR

This paper demonstrates that the FENE-Fraenkel dumbbell model can effectively replicate the behavior of rigid rodlike polymers, capturing both their rheological and optical properties through adjustable parameters.

Contribution

It introduces the FENE-Fraenkel spring as a versatile model capable of mimicking rodlike and springlike polymer behaviors, bridging the gap between different macromolecular models.

Findings

FENE-Fraenkel spring can imitate rod behavior with hydrodynamic interactions.

Adjusting stiffness and extensibility reproduces shear-thinning and normal stress differences.

Model shows improved accuracy over traditional rodlike models when fitted to experimental data.

Abstract

Rigid macromolecules or polymer chains with persistence length on the order of the contour length (or greater) have traditionally been modelled as rods or very stiff springs. The FENE-Fraenkel-spring dumbbell, which is finitely extensible about a non-zero natural length with tunable harmonic stiffness, is one such model which has previously been shown to reproduce bead-rod behaviour in the absence of hydrodynamic interactions. The force law for the FENE-Fraenkel spring reduces to the Hookean or FENE spring force law for appropriately chosen values of the spring parameters. It is consequently possible to explore the crossover region between the limits of bead-spring and bead-rod behaviour by varying the parameters suitably. In this study, using a semi-implicit predictor-corrector Brownian dynamics algorithm, the FENE-Fraenkel spring is shown to imitate a rod with hydrodynamic interactions when spring stiffness, extensibility and simulation timestep are chosen carefully. By relaxing the spring stiffness and extensibility, the FENE-Fraenkel spring can also reproduce spring-like behaviour, such as a crossover from $-1/3$ to $-2/3$ power-law scaling in the viscosity with shear rate, and a change from positive to negative second normal stress difference. Furthermore, comparisons with experimental data on the viscosity and linear dichroism of high aspect ratio, rigid macromolecules shows that the extensibility and stiffness of the FENE-Fraenkel spring allows for equal or improved accuracy in modelling inflexible molecules compared to rodlike models.