Simulation of polymer chains in elongational flow. Kinetics of chain fracture and fragment distribution

Abstract

In this paper the Brownian dynamics technique for computer simulation of the fracture of polymer chains in a dilute solution subjected to elongational flow was used. Individual randomly coiled chains are placed at the stagnation point of a steady, uniaxial flow, and their evolution with time is monitored for chain fracture. The chains are modeled either as Rouse chains with a cutoff spring length, or as chains of springs obeying a Morse potential. Kinetic parameters are the first-order kinetic constant and the half-life time. The dependence of these parameters with elongational rate and chain length is expressed in the form of scaling laws, and the results are compared for the two models. Also studied was the size distribution of the resulting fracture fragments, finding that it may vary from sharply peaked to uniform, depending on the strength of the flow.