화학공학소재연구정보센터
Journal of Applied Polymer Science, Vol.61, No.11, 1887-1897, 1996
Rheological Behavior of Degraded Polypropylene Melts - From MWD to Dynamic Moduli
The linear viscoelastic behavior of polydisperse polypropylenes in the melt is predicted using the molecular weight distribution (MWD) as determined from gel permeation chromatography, on the basis of simplified molecular dynamics : single exponential form of the relaxation modulus of narrow fractions, double reptation, tube renewal, and constraint release. Owing to a few approximations, the calculation only requires a few parameters, namely the scaling law for the zero shear viscosity of narrow fractions eta(0) = f(M), the plateau modulus G(N)(0), and the value of the molecular weight between entanglements M(e). Using this method a relaxation spectrum of Maxwellian contributions with a large number of modes is obtained. This spectrum well predicts the rheological behavior in the terminal zone of samples obtained by controlled peroxydic degradation of polypropylene with polydispersity ranging from 4 to 10. Attention is focused on the zero shear rate viscosity, frequency, and modulus of the crossover of the storage and loss moduli from experiments and calculations, because these parameters are generally thought to be sensitive to both average molecular weight and polydispersity and are relatively easy to get from dynamic experiments. How the initial spectrum can be conveniently reduced to a more simple spectrum with only a few modes, without significant loss of information, is shown. This spectrum may be useful and time saving in calculations, for example, to describe the memory function in nonlinear constitutive equations while keeping its physical meaning in relation to the MWD.