A priori Determination of the Extensional Viscosity of Polymer Melts

TL;DR

This paper extends a Monte Carlo simulation algorithm to accurately predict the extensional viscosity of dense polymer melts across various deformation regimes, offering a computationally efficient and comprehensive a priori method.

Contribution

The extension of the COMOFLO Monte Carlo algorithm enables the first a priori simulation of steady-state extensional rheology of dense polymer melts in three dimensions.

Findings

Extensional viscosity increases with deformation rate, then plateaus and decreases.

The algorithm captures the physics of polymer melts in extensional flow accurately.

It provides computational advantages over molecular dynamics methods.

Abstract

The COMOFLO dynamic Monte Carlo algorithm is extended to enable the simulation of steady-state extensional rheology of dense melts for the first time ever. This significant advancement provides the ability to accurately capture the extensional viscosity of entangled polymer melts from low deformation rates, throughout the strain hardening regime, and into the region of viscosity thinning To do so, the purely extensional flow field associated with a four roll mill experiment is implemented in three dimensions. Periodic boundary conditions exist in all directions to enable a uniform deformation rate throughout the simulation domain. As expected, the extensional viscosity is four times the zero shear viscosity at low deformation rates. As the deformation rate increases, the extensional viscosity increases, plateaus, and then decreases. The algorithm thus correctly captures the physics of polymer melts in extensional flow in a fully a priori manner while providing significant computational advantages over molecular dynamics methods. Because the technique is applicable to polydisperse systems, the ability to predict in an a priori manner both shear and elongational rheology for linear polymer melts of arbitrary molecular weight distribution can now be considered a solved problem.