On the universality in the extensional rheology of monodisperse polymer melts and oligomer dilutions thereof

Abstract

The startup and steady extensional viscosities were measured on two narrow molar mass distributed (NMMD) poly(methyl methacrylates) (PMMA) diluted in 57% 2.1 kg/mole oligomer methyl methacrylates. The oligomer is short enough to be random configured and un-entangled though it is still a Kuhn chain. The weight-based average molecular weights of the PMMAs are 86 kg/mole and 270 kg/mole with polydispersites of 1.08 and 1.09 respectively. The extensional viscosities were in theoretical agreement with a constant ‘interchain pressure’ model, representing the maximal level of strain hardening in a Kuhn fluid. This has been observed for similar (styrene) oligomer diluted NMMD polystyrenes before, when the styrene oligomers were Kuhn chains. The original ‘interchain pressure’ model by Marrucci and Ianniruberto (Macromolecules 37(10):3934–3942, 2004), represents the minimal level of strain hardening in a Kuhn fluid. It has been shown previously to predict the extensional viscosities of NMMD polystyrene melts, and it is also in agreement with the extensional viscosities of the 86 kg/mole NMMD PMMA melt as well.