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In order to study the rheology of long chain branched polymers, branches have been added on linear polypropylene precursors in varying amounts using reactive modification with peroxydicarbonates. The branched polypropylene samples show distinct strain hardening, something absent from the linear melt; this considerably improves the melt strength of the modified polymer. The zero shear viscosity and the elasticity measured by the relaxation spectrum also increase with the number of branches per molecule. Two models are applied to describe strain hardening of the viscosity during the course of elongation. The model parameters were found to vary systematically with the degree of branching and, therefore, their values can be used as a measure of this. Consequently, fluidity, elasticity, strain hardening, and melt strength are all related to the degree of long chain branching.

Linear polypropylene was modified by reaction with peroxydicarbonates in a twin screw extruder to obtain varied degrees of long chain branching. The melt strength and the elasticity of the modified polymers were found to increase with the modification. The processability in foaming and thermoforming processes improved with branching and showed an optimum, beyond which higher degrees of long chain branching appeared not to help any further. The branched PP samples showed distinct strain hardening in the elongational viscosity, which was absent from the original linear melts. Melt strength, elasticity and strain hardening increased with the increase of the number of long chain branches on the main chain. The effect of molecular weight and molecular weight distribution of the precursor on the improvement of the processability of the polymer was examined. Polym. Eng. Sci. 44:973–982, 2004. © 2004 Society of Plastics Engineers.

The fragmentation of high-density polyethylene (HDPE) films from single-use supermarket plastic bags to microplastics under laboratory-simulated onshore and nearshore conditions was investigated for a period of 6 months. The weathering process of the plastic strips either on beach sand or in seawater under direct natural sunlight was monitored by tensile strength, molecular weight measurements, FTIR, weight loss, and image processing of photographs of the plastic strips before and after mild mechanical stress was applied. The latter represents a novel method proposed for determining the onset of fragmentation through the application of mild mechanical stress on the weathered plastic samples emulating the action of sand and wind on a beach. It was found that 12 h of application of mild mechanical stress in rotating glass bottles filled partially with sand was sufficient time to reach the maximum degree of fragmentation that could occur for the weathered plastics samples being tested. For example, applied mechanical stress yielded an area loss of almost 14% for samples weathered for a period of 5 months and about 16.7% after 5.5 months. While tensile strength tests and molecular weight measurements were rather inconclusive till the very last month when the onset of fragmentation was identified; FTIR measurements revealed that samples under ultraviolet irradiation were gradually modified chemically until fragmentation commenced. After 6 months of weathering, molecular weight measurements showed a 60% reduction for sample SMB-1 whereas for sample SMB-2 the measurement was not possible due to extensive fragmentation. The onset of fragmentation for SMB-1 and SMB-2 samples occurred at a cumulative luminance of 5.3 × 10 6 lux•d and in the presence of atmospheric oxygen whereby the polymer films broke down partially to microplastics. When the UV exposure reached 7.2 × 10 6 lux•d the weathered plastic strips broke down fully to microplastics with the application of a mild mechanical stress. Samples placed in seawater proved to be resistant to fragmentation compared to those on sand over the 6-month period of the weathering experiment. The direct implication of this work is that beached macroplastic debris should be regularly collected from the seashore before they are weathered by sunlight and returned to the sea as microplastics by the action of high waves or strong winds.

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