Interchain tube pressure effect in extensional flows of oligomer diluted nearly monodisperse polystyrene melts

Abstract

We have derived a constitutive equation to explain the extensional dynamics of oligomer-diluted monodisperse polymers, if the length of the diluent has at least two Kuhn steps. These polymer systems have a flow dynamics which distinguish from pure monodisperse melts and solutions thereof, if the solvent has less than two Kuhn steps, e.g. is not a chain. The constitutive equation is based on a phenomenological tube-based model within the methodology of the molecular stress function approach. The nonlinear dynamics have been explained as a consequence of a constant thermal interchain pressure originating from the short polymer chains (e.g. the oligomers) on the wall of the tube containing the long chains. The nonlinear dynamics are uniquely defined by the Rouse time and the maximal extensibility of the long polymer chains. Both are linked to the entanglement length. The relation between the Rouse times and entanglements have been established based on published extensional experiments on nearly monodisperse polystyrene melts. The constitutive equation has shown agreement with the experimental startup of and steady extension data from Huang et al. (Macromolecules 46:5026–5035, 2013a) based on 285 and 545 kg/mol polystyrenes diluted in styrene oligomers containing 3.3 (1.92 kg/mol) and 7.3 (4.29 kg/mol) Kuhn steps.