| Abstract: | Shear modification treatment represents a special shearing history affecting mainly the elastic behavior of polymer melts. This process has been attributed to reversible physical changes in the entanglement structure of the polymer chain network. Shear modification studies were performed for two well-characterized low-density polyethylene (LDPE) grades differing in molecular weight distribution and degree of long chain branching. The shear working of the material was carried out using a specially designed shearing unit producing definable amounts of pure shear in a continuous process. Measurements of the dynamic storage modulus, G′, steady-state shear compliance; Je, extrudate swell, melt flow index, and the extensional behavior (Rheotens test) indicate that primarily properties associated with the elasticity of the melt are reduced in value. The observed reduction is found to correlate with the mean specific energy dissipated during sample preparation. Comparing the two LDPE grades showed that higher degrees of modification can be obtained at lower energy input levels for the more highly branched grade. Reversibility tests were performed and complete recovery of the initial material behavior was observed. Comparison of measurement results for samples prepared using the shearing unit presented here and a Brabender Plasticorder indicates that the degree of modification depends not only on the molecular structure of the polymer but also on the manner in which the shearing history is imposed upon the material. |
