Long chain branching and polydispersity effects on the rheological properties of polyethylenes

The rheological behavior of linear, and branched polyethylenes is studied as a function of the weight average molecular weight (M-W) and its distribution (MWD) as well as the level of long chain branching in an attempt to identify correlations between long chain branching, polydispersity and rheological properties. It is found that a need for vertical shift of the viscoelastic moduli data to obtain the master curves using the time-temperature superposition principle is associated with the existence of long chain branching in the structure of the polymer. The degree of vertical shift is found to correlate with the level of long chain branching. This correlation corroborates with the observation that long chain branching correlates with the horizontal flow energy of activation. Plots of atan(G " /G') vs. G* (known as Van Gurp plots) also reveal some important features that can be used as signs of specific features in the structure of polymers. More specifically, the area included below the Van Gurp curves correlates with the level of long chain branching and polydispersity index. The correlations are presented in graphical form and they can be used to associate rheological properties with the presence of long chain branching and/or polydispersity.