NETWORK RUPTURE AND FLOW OF CONCENTRATED POLYMER SOLUTIONS

Entanglement theories for polymer solutions resemble those developed for solid rubbers. These rubberlike theories are extremely successful qualitatively; they give a good indication of the type of response observed experimentally in concentrated solutions. Quantitatively the theories are not so useful; in general they predict constant viscosities in simple shearing motions and ever‐increasing tensile stress in steady elongational flow. If it is supposed that the lifetime of the entanglements is limited partly by a maximum allowable strain magnitude, and that the network ruptures locally whenever this magnitude is exceeded, greatly improved quantitative predictions are observed. For polyisobutylene‐cetane solutions, where the critical strain magnitude appears to be about 3, excellent prediction of the steady shearing viscosity curve is available starting from the measured dynamical response to small sinusoidal strains and the critical strain magnitude. Normal stress effects are also well represented; in elongational flow the tensile stress shows a slight maximum. It thus appears that the notion of network rupture is useful in guiding the selection of continuum theories for polymer fluid description. Copyright © 1969 American Institute of Chemical Engineers