Elongational-flow predictions of the Leonov constitutive equation

Abstract

The basic thermodynamic ideas from rubber-elasticity theory which Leonov employed to derive his constitutive model are herein summarized. Predictions of the single-mode version are presented for homogeneous elongational flows including stress growth following start-up of steady flow, stress decay following sudden stretching and following cessation of steady flow, elastic recovery following cessation of steady flow, energy storage in steady-state flow, and the velocity profile in constantforce spinning. Using parameters of the multiple-mode version which fit the linearviscoelastic data, the Leonov-model predictions of elongational stress growth during, and elastic recovery following, steady elongation are calculated numerically and compared to the experimental results for Melt I and to the Wagner model. It is found that the Leonov model, as originally formulated, agrees qualitatively with the data, but not quantitatively; the Wagner model gives quantitative agreement, but requires much nonlinear data with which to fit model parameters. Quantitative agreement can be obtained with the Leonov model, if the nonequilibrium potential which relates recoverable strain to strain rate is adjusted empirically. This can most simply be done by making each relaxation time dependent upon the recoverable strain. The Leonov model, unlike the Wagner model, is derived from an entropic constitutive equation, which is advantageous for calculating stored elastic energy or viscous dissipation. The Leonov model also has an appealingly simple differential form, similar to the upper-convected Maxwell model, which, in numerical calculations, may be an important advantage over the integral Wagner model.