Correlation of viscoelastic properties with the molar mass distribution for aqueous polyacrylamide solutions

The dependence of viscous and elastic rheological functions on molar mass and molar mass distribution was investigated under shear flow conditions using concentrated solutions of polyacrylamides and polyacrylamide mixtures. The zero-shear viscosity η₀ correlates with the weight-average molar mass M?_w; with increasing shear rate the corresponding controlling molar mass average tends to change to the number-average molar mass M?_n. It is shown that the analysis of the shape of the whole flow curve is a simple way to obtain qualitative information about molar mass distribution. Elastic forces are influenced mainly by the high-molar-mass tail of a molar mass distribution. The zero normal stress coefficient ψ₀ depends on a molar mass average between M?_w and z-average molar mass M?_z·ψ₀ increases with the 7,4th power of the molar mass for the polyacrylamides (not for the mixtures). The steady-state compliance J_e⁽⁰⁾ is, for the investigated system, independent of the absolute molar mass, but increases with the 5,5th power of the ratio M?_z/M?_w. The elasticity modulus G₀^(A) can be correlated with M?_n of the polyacrylamide samples and their mixtures. These investigations show that the analysis of various rheological functions can lead to a wealth of information about the molar mass distribution of a polymer.