An Evaluation of Dilution Rheology for the Characterization of Long Chain Branching of Polyethylenes

The purpose of this paper was to re-evaluate the novel rheological method of Crosby et al. [J. Rheol. 46 (2002) 401] to characterise long chain branching (LCB) in polyethylenes (PE) using the rheology of concentrated solutions. The feasibility of this dilution method centred on knowing the class of branched material and the molecular tube theory-based technique for the determination of two topological parameters (n, bU), where n is the number of entanglements between branch points while bU is the probability of meeting a branch point when tracing along the molecule from a random monomer against the direction of polymerisation. This paper proposes new possible approaches to calculate the two topological parameters (n, bU) set for metallocene polyethylenes (mPE), and their ambiguity discussed, as the results are dependent on the approach taken, though the previous authors mentioned only one. In addition, their approach requires an input value of LCB/1000C obtained from the standard analytical solution (SEC-V or SEC-LALLS) methods, hence, until now, without proper demonstration of the potential advantage of the dilution rheology method for LCB characterisation, as the main premise of their published article was to characterise the degree of LCB via rheological measurements without recourse to other methods of LCB characterisation.