Efficient Determination of Slip-Link Parameters from Broadly Polydisperse Linear Melts

We investigate the ability of a coarse-grained slip-link model and a simple double reptation model to describe the linear rheology of polydisperse linear polymer melts. Our slip-link model is a well-defined mathematical object that can describe the equilibrium dynamics and non-linear rheology of flexible polymer melts with arbitrary polydispersity and architecture with a minimum of inputs: the molecular weight of a Kuhn step, the entanglement activity, and Kuhn step friction. However, this detailed model is computationally expensive, so we also examine predictions of the cheaper double reptation model, which is restricted to only linear rheology near the terminal zone. We report the storage and loss moduli for polydisperse polymer melts and compare with experimental measurements from small amplitude oscillatory shear. We examine three chemistries: polybutadiene, polypropylene and polyethylene. We also use a simple double reptation model to estimate parameters for the slip-link model and examine under which circumstances this simplified model works. The computational implementation of the slip-link model is accelerated with the help of graphics processing units, which allow us to simulate in parallel large ensembles made of up to 50,000 chains. We show that our simulation can predict the dynamic moduli for highly entangled polymer melts over nine decades of frequency. Although the double reptation model performs well only near the terminal zone, it does provide a convenient and inexpensive way to estimate the entanglement parameter for the slip-link model from polydisperse data.

The molecular weight distribution problem and reptation mixing rules

Mixing rules model how the physical properties of a polymer, such as its relaxation modulus G(t), depend on the distribution w(m) of its molecular weights m. They are of practical importance because, among other things, they allow estimates of the molecular weight distribution (MWD) w(m) of a polymer to be determined from measurements of its physical properties including the relaxation modulus. The two most common mixing rules are “single” and “double” reptation. Various derivations for these rules have been published. In this paper, a conditional probability formulation is given which identifies that the fundamental essence of “double” reptation is the discrete binary nature of the “entanglements”, which are assumed to occur in the corresponding topological model of the underlying polymer dynamics. In addition, various methods for determining the MWD are reviewed, and the computation of linear functionals of the MWD motivated and briefly examined.