(50d) Effect of Sparse Long-Chain Branching On the Film-Casting Behavior for a Series of Well-Defined HDPEs

The effect of sparse long chain branching, LCB, on the film-casting process is analyzed using a molecular model for the rheological behavior for a series of well-characterized, high-density polyethylene (HDPE) resins and a low-density polyethylene (LDPE) resin at various drawdown ratios. A full rheological characterization in both shear and shear-free flows is also presented. At low drawdown ratios, the LDPE exhibited the least degree of necking at distances less than the HDPE frostline. The sparsely-branched HDPE resins films had similar final film-widths that were larger than those of the linear HDPE. As the drawdown ratio was increased, film width profiles separated based on branching level. Small amounts of LCB were found to reduce the amount of necking at intermediate drawdown ratios. At higher drawdown ratios, the sparsely-branched HDPE resins of lower LCB had content film-widths that mimicked that of the linear HDPE, while the sparsely-branched HDPE resins of higher LCB content retained a larger film width. Molecular structural analysis via the Pom-pom constitutive model suggested that branching that was distributed across a larger range of backbone lengths serve to improve resistance to necking. As the drawdown ratio increased, the length of the backbones dominating the response decreased, so that the linear chains were controlling the necking behavior of the sparsely-branched resins of lower LCB content while remaining in branched regime for higher LCB content HDPEs. Other processing variables such as shear viscosity magnitude, extrudate swell, and non-isothermal processing conditions were eliminated as contributing factors to the differences in the film width profile.