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High‐density polyethylene melt elasticity—some anomalous observations on the effects of molecular structure
Author(s) -
Mendelson R. A.,
Finger F. L.
Publication year - 1975
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1975.070190414
Subject(s) - die swell , swell , rheology , polymer , elasticity (physics) , materials science , high density polyethylene , molar mass distribution , shear rate , polyethylene , annealing (glass) , polymerization , composite material , fractionation , thermodynamics , polymer chemistry , chemistry , extrusion , chromatography , physics
The die swell behavior of polymeric melts is a manifestation of melt elasticity of these materials and is of considerable commercial as well as fundamental importance. Hence, knowledge of the effect of such molecular variables as molecular weight (MW) and molecular weight distribution (MWD) on melt elasticity is important from both commercial and basic rheological points of view. The effect of these variables on melt elasticity of broad‐distribution polymers in the shear rate region of commercial interest is not unambiguously known, with most published theory and experiment being applicable to the low‐shear behavior of narrow‐distribution polymers and blends thereof. There is indication that die swell increases with increasing MW and broadening MWD. However, the current investigation of carefully characterized broad‐distribution HDPE materials prepared specifically to examine the effects of various molecular variables on melt elasticity does not support this contention and, in fact, provides consistent evidence for the opposite result, i.e., decreasing die swell with increasing MW or broadening distribution. The various samples studies were prepared by fractionation removal or addition of component molecular species or by polymerization designed to provide systematic variation of molecular species or by polymerization designed to provide systematic variation of molecular parameters. Overall MWD's of the samples were characterized, and die swell behavior was determined at 200°C over a wide shear rate region in a high L / D capillary both with and without annealing of extrudates. The results are presented showing effects of specific molecular variables.