Sparse Long-chain Branching's Effect on the Film-casting Behavior of PE

Abstract

Abstract The degree of film-width reduction or necking during film-casting is analyzed for three metallocene-catalyzed linear low density polyethylenes, LLDPE, with varying degrees of sparse long-chain branching, LCB. The resins included three sparsely LCB polyethylene, PE, materials with varying LCB content ranging from linear to 0.57 LCB/10000 CH2 along with a Ziegler-Natta polymerized LLDPE and a tubular free-radical polymerized low density polyethylene, LDPE. The last two resins are used as reference materials. The primary objective of this analysis is to evaluate whether uniaxial extensional rheological characteristics, in particular strain-hardening, that are a result of LCB influence the film-necking properties. At the lowest drawdown ratio, necking is observed to be reduced with increasing LCB, and thus strain-hardening characteristics. At the higher drawdown ratios it is observed that LCB no longer reduces necking and the curves merge to the results found for linear PE, except in the case of LDPE, which shows reduced necking at all drawdown ratios. Furthermore, comparisons of film necking are also made to separate the effects of molecular weight distribution, MWD, and LCB. The results indicate that both broadening the MWD and the addition of sparse LCB reduce the degree of necking, but to a lesser degree in the case of broadening the MWD. Analysis of the uniaxial extensional and dynamic shear rheology with the pom-pom constitutive model reveals that a distribution of branches along shorter relaxation time modes is important in reducing necking at higher drawdown ratios. Factors such as shear viscosity effects, extrudate swell, and non-isothermal behavior were eliminated as contributing factors.