Some aspects of linear and nonlinear viscoelastic behaviour of polymer melts in shear

In linear viscoelastic investigations the frequency dependence of the phase shift between stress and strain appears to be very characteristic of the molecular structure of the material. This function is also a good approximation of the slope of the double logarithmic plot of the absolute value of the shear modulusG_d vs. the angular frequency. The product (G_d/) sin 2 comes very close to the relaxation spectrumH(), with = 1/, in all physical states of the material.The experimentally observed separability of time and strain effects in nonlinear viscoelasticity of highly viscous isotropic polymer fluids imposes restraints to the form of the constitutive equation. A single integral superposition equation of the Boltzmann type containing the product of a time function and a nonlinear strain function gives good results in describing experimental data in shear as well as in elongation. The molecular structure affects both functions in a different way. A universal definition of the nonlinear tensorial strain measure has not yet been developed. There are some indications that a definition on the basis of the principal stretch ratios may be fruitful.Invited paper, presented at the First Conference of European Rheologists at Graz (Austria), April 14–16, 1982.