Laun's rule for predicting the first normal stress coefficient in complex fluids: A comprehensive investigation using fractional calculus

Abstract

Laun's rule [H. M. Laun, “Prediction of elastic strains of polymer melts in shear and elongation,” J. Rheol. 30, 459–501 (1986).] is commonly used for evaluating the rate-dependent first normal stress coefficient from the frequency dependence of the complex modulus. We investigate the mathematical conditions underlying the validity of Laun's relationship by employing the time-strain–separable Wagner constitutive formulation to develop an integral expression for the first normal stress coefficient of a complex fluid in steady shear flow. We utilize the fractional Maxwell liquid model to describe the linear relaxation dynamics compactly and accurately and incorporate material nonlinearities using a generalized damping function of Soskey–Winter form. We evaluate this integral representation of the first normal stress coefficient numerically and compare the predictions with Laun's empirical expression. For materials with a broad relaxation spectrum and sufficiently strong strain softening, Laun's relationship enables measurements of linear viscoelastic data to predict the general functional form of the first normal stress coefficient but often with a noticeable quantitative offset. Its predictive power can be enhanced by augmenting the original expression with an adjustable power-law index that is based on the linear viscoelastic characteristics of the specific material being considered. We develop an analytical expression enabling the calculation of the optimal power-law index from the frequency dependence of the viscoelastic spectrum and the strain-softening characteristics of the material. To illustrate this new framework, we analyze published data for an entangled polymer melt and for a semiflexible polymer solution; in both cases our new approach shows significantly improved prediction of the experimentally measured first normal stress coefficient.