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  • Polymer and Materials Science  (2)
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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 877-886 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several important aspects of the flow in polymer melts through capillaries remain unexplored. This paper examines experimentally one such effect associated with the radial shear-stress gradient in capillaries. During capillary melt flow of a polymer with a wide molecular weight distribution, migration of the large molecules away from the region of highest shear stress, i.e., at the capillary wall, has been predicted but only modestly investigated. This effect has the potential to produce a molecular weight spectrum over the cross section of extruded polymer. Studies of distribution in shear were conducted on a well-characterized wide-distribution polystyrene (M̄w = 234,000). An Instron Rheometer equipped with a long capillary (length/diameter ratio of 66.7) was used to perform the extrusion at temperatures of 160-250°C. A solvent coring procedure was used to dissolve away concentric layers of polymer from the extrudate for molecular weight analyses. The method has been shown to cut clean sections without selective extraction. Values of M̄w, M̄n and M̄w/M̄n were calculated from complete molecular weight distribution data obtained by calibrated gel permeation chromatography. For a wide range of shear rates and temperatures, no evidence for molecular fractionation was observed. Shear degradation of this polymer was found to be small. However, at high shear rates at 250°C, evidence indicating extensive shear-induced thermal degradation was found. No evidence for oxidative degradation at the extrudate surface was found at either low or high shear rates at this temperature.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 17 (1973), S. 2761-2770 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The nature and magnitude of mechanical reactions of polystyrene in capillary flow has been examined in a model extrusion process. Studies on polystyrene quantify the sensitive increase in shear degradation tendency with increasing polymer molecular weight. A molecular weight spectrum caused by the shear stress profile was measured across the extrudate radius by the new technique of solvent coring. It was further determined that an appreciable fraction of the mechanical reaction is shear induced in the capillary reservoir. This is confirmed by precision determinations of molecular weights and distributions by gel permeation chromatography on samples taken from concentric layers in the capillary reservoir after 50% sample extrusion. These results, involving traces of oxygen as a chemical probe, describe the stress profile in the reservoir and in the capillary during the pressure extrusion of high molecular weight polystyrene. Thus, changes in molecular weight and distribution may be attributable to changes in different portions of the shear geometry rather than the uniform changes generally considered. Clear evidence is also presented showing the dramatic effects of oxygen on these shear-induced changes in molecular weight and distribution.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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