Rheologica Acta, Vol.45, No.5, 755-764, 2006
Dependence of the zero shear-rate viscosity and the viscosity function of linear high-density polyethylenes on the mass-average molar mass and polydispersity
Linear high-density polyethylenes with molar masses M-w between 240 and 1,000,000 g/mol, obtained by metallocene catalysts, were characterized in shear using oscillatory and creep tests. The polydispersities of the molar mass distributions (MMDs) lay between 1 and 16. The resulting zero shear-rate viscosities n(0) covered a range from 2.5 x 10(-3) to around 10(8) Pas. Above a critical molar mass of M-c approximate to 2,900 g/mol, the experimental results can be described by the relation n0 similar to M-w(3.6), independently of the MMD. The oscillatory data were fitted with a Carreau-Yasuda equation. The resulting parameters were correlated to molecular structure. The parameter a, being a quantity for the width of the transition between the Newtonian and the non-Newtonian regime, showed a dependence on the molar mass M-w but not on M-w/M-n. The parameter lambda of the Carreau-Yasuda equation was found to be the reciprocal crossover frequency for all samples with a log-Gaussian MMD. lambda depends on the molar mass Mw and also on M-w/M-n.
Keywords:high-density polyethylene;zero shear-rate viscosity;mass-average molar mass;polydispersity;viscosity function;Carreau-Yasuda model