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

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.

arXiv comment17 pages, 18 figures, supplementary material (see ancillary directory), to appear in the Journal of Non-Newtonian Fluid Mechanics

References in corpus (4)

• Radial distribution function of semiflexible polymers
• Universal dynamics of dilute and semidilute solutions of flexible linear polymers
• Shear thinning in dilute and semidilute solutions of polystyrene and DNA
• Rheological consequences of wet and dry friction in a dumbbell model with hydrodynamic interactions and internal viscosity

Cited by in corpus (4)

• Dilute polymer solutions under shear flow: comprehensive qualitative analysis using a bead-spring chain model with a FENE-Fraenkel spring
• Shear viscosity for finitely extensible chains with fluctuating internal friction and hydrodynamic interactions
• Rouse model with fluctuating internal friction
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