Degradation of semidilute polymer solutions in elongational flows

Abstract Elongational flow techniques are applied to the examination of flow-induced chain scission of macromolecules in solution. An opposed jets apparatus is used both to produce mechanical scission and to monitor the molecular-weight distribution of the scission products. Gel permeation chromatography is also used to complement the latter. In dilute solutions of almost monodisperse high-molecular-weight atactic polystyrene (aPS), degradation occurs as closely central scission of the molecules beyond a critical strain rate. As the concentration is increased to the semidilute regime, this preferential breaking near the centre of the molecule disappears (for 1.5% aPS/decalin solutions, M p = 5.8 × 10 6 ). Therefore, according to expectation, the scission is randomized as the number of entanglements per chain is greatly increased. The results also indicate that, once entanglements are present, the parameter that seems to be most relevant to the process of molecular fracture is the applied stress.