Polymer Engineering and Science, Vol.34, No.7, 570-579, 1994
Mechanism of Shear Modification of Low-Density Polyethylene
In this paper we address the aspects associated with shear modification of low density polyethylene by extrusion. By successive passes of the polymer through an extruder it can be shown that both the melt viscosity and melt elasticity are reduced by shear modification. These reversible variations are not accompanied by significant changes in molecular weight distribution. The major effects of extrusion are to decrease the amount of elastically effective material. Study of proton relaxation times at 150-degrees-C shows that the melt comprises regions of relatively ordered, entangled, and unentangled polymer. Shearing reduces the proportion of more ordered material. The elastically effective anchors that are reduced by shearing are regions with restricted segmental mobility rather than conventional entanglements or intermolecular knots. Successive extrusions produce a relatively small decrease in the number of such constraints to molecular motion. Repeated shearing has a diminishing effect on the proportion of more ordered material in the polyethylene melt. This parallels observations of the effects of repeated shear modification on the properties of polyethylene films and other extrudates.