The mechanism of cavitation-induced polymer scission; experimental and computational verification

In this paper we describe qualitatively and quantitatively the non-random scission of polymers by ultrasound. Scission experiments have been performed using monodisperse polymethyl methacrylate dissolved in methyl methacrylate, showing that fracture occurs close to the center of the polymer chain. A mechanism is proposed for this non-random fracture, from which it can be concluded that complete stretching of the polymer chains is required before breakage can occur. The developed model, which is a combination of strain rate and drag force calculations, predicts a limiting molecular weight, which has experimentally been confirmed. The scission rate depends almost quadratically on the molecular weight, which is derived by modeling the experimental time-dependent molecular weight distributions. This dependence supports the requirement of complete stretching of the polymer chain before breakage. The developed degradation model is also capable to describe the effects of various process variables on cavitation-induced polymer scission. (C) 2004 Elsevier Ltd. All rights reserved.