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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 71 (1967), S. 4573-4575 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Industrial and engineering chemistry 8 (1969), S. 54-57 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 365-375 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: This paper presents the development of a novel in-line extrusion rheometer based on the flow of polymer through a wedge (vertically tapered slit). This rheometer is suitable for measuring changes in rheological properties on-line during reactive extrusion, because it can be used to estimate the viscosity for a range of shear rates without the need to change the polymer flow rate (i.e., extruder throughput). Equations have been developed to estimate the parameters of the power-law equation, used to describe the viscosity-shear rate relationship, from measurements of pressure drops along the wedge. An experimental in-line wedge rheometer has been built and used to measure the viscosity for a series of polypropylenes prepared via reactive extrusion. Viscosity measurements from the experimental in-line wedge rheometer are compared with measurements from a capillary rheometer. Good agreement is found between the capillary and wedge rheometer measurements.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 598-612 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: This paper presents the development of a model for free radical initiated polypropylene degradation during reactive extrusion that combines a kinetic model of the polypropylene degradation reaction with a simplified model of the melting mechanism in the extruder. The free radical initiated degradation of polypropylene is characterized by a narrowing of the molecular weight distribution (MWD) and a decrease in the molecular weight averages. A high temperature SEC is used to determine MWD's for three different commercially available polypropylenes degraded at various initiator concentrations in a 1.5 inch single screw extruder (L/D = 24:1). The predictions of the kinetic model alone and the combined kinetic-melting model are compared with the experimentally determined MWD's and molecular weight averages for the degraded polypropylenes. The predictions of a modified kinetic model that includes the possibility of termination by combination are also examined. The kinetic-melting model is found to provide significantly improved predictions of the experimentally determined MWD's and molecular weight averages in comparison to the original kinetic model. A viscosity-molecular weight relationship is also developed, which is then used to determine the gain of the degradation process as a function of the initiator concentration from the molecular weight averages predicted by the kinetic-melting model. Earlier work has shown such prior knowledge of the process gain can be used to significantly improve the performance of process control schemes for the degradation process.
    Additional Material: 11 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 1381-1419 
    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: A new-method of interpreting GPC chromatograms which accounts for skewing and symmetrical axial dispersion has been developed. General relationships for a symmetrical axial dispersion correction and for a skewing correction are derived.The method has been verified experimentally for unimodal chromatograms and linear calibration curves over a wide range of GPC operating conditions, polymer molecular weights and polydispersities. Measurements of h and skewing factors were obtained by a once-through technique. The need for performing reverse flow experiments has been eliminated. Artificial oscillations in the corrected chromatogram due to step size (Method of Pierce-Armonas), and to number of terms in a polynomial expansion (Method of Tung and Method of Smith) are eliminated.The method has yet to be evaluated for nonlinear calibration curves and multi-modal distributions. However, suggestions for its application in these circumstances are presented.
    Additional Material: 21 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 35 (1988), S. 1019-1032 
    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: Polypropylene was degraded by injection of a free-radical initiator during extrusion. Molecular weight distribution, molecular weight averages, and melt flow index were measured to see the effect of initiator concentration (0.00 to 0.04 wt%), temperature (200 and 220°C), and screw rpm (31 and 44). Initiator concentration was the most significant variable. In all cases, increased initiator concentration degraded the high molecular weight tail of the polypropylene and narrowed the molecular weight distribution. Melt flow index varied linearly with initiator concentration beyond 0.01 wt% initiator. Reaction temperature had no effect on the measured properties of the extrudate. This was attributed to the minimum residence time in the extruder being sufficient for all degradation reactions to be completed. It also implied that the same reactions occurred at both temperatures. Increased screw rpm slightly increased molecular weight. No interaction among initiator concentration, temperature, and screw rpm was observed.
    Additional Material: 10 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 35 (1988), S. 1033-1048 
    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: A kinetic model for the free-radical-initiated molecular weight degradation of polypropylene was further developed. The model has a single variable parameter, the initiator efficiency, f. Assumptions were detailed, new comparisons with experimental data presented, and model sensitivity to the value of f evaluated. The model was found to provide a good description of both molecular weight distribution and molecular weight average data from degradations carried out in a single-screw extruder at 200 and 220°C. Data at 0.04 wt% initiator feed concentration were fit and the resulting f value used to predict results at 0.01 wt% and 0.02 wt%. In accordance with observation, the model predicted that temperature would have no effect on the molecular weight of the extrudate because the comparatively long (≥ 2.8 min) residence time in the extruder permitted degradation reactions to go to completion. The model predictions were found to depend upon the change in molecular weight distribution rather than the absolute value of the distribution data. Predictions were therefore unaffected by concentration correction in size exclusion chromatography interpretation. The model was determined to have a low sensitivity to the value of f. Hence, f was estimated to only ± 25% and it is anticipated that attempts to use the model for comparing different initiators would be limited by this characteristic. Also, because the minimum residence time in the extruder was 2.8 min, the model has yet to be tested against data at times less than this value.
    Additional Material: 8 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 35 (1988), S. 1065-1084 
    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: Quantitative size exclusion chromatography (SEC) was considered a system with the following components: sample preparation, fractionation, detection, calibration, and resolution correction. Four systems were evaluated: I was 3 columns with “conventional single detector interpretation”; II was 4 columns with concentration correction and detector assessment; III was concentration correction applied to the data of I; IV was two development “mixed bed” columns. Analysis of polystyrene standards included calculation of their molecular weight averages and use of the Glöckner “T” measure of resolution as well as “specific resolution index.” Systems I and III provided the best high molecular weight results. System IV allowed 12-20 min analysis times and provided a highly linear calibration curve with very good reproducibility; however, it showed significantly worse resolution at high molecular weights. Plots of molecular weight averages determined from SEC versus their known true values were particularly useful. Concentration correction using the Rudin model moved different concentration data toward a common universal calibration curve and generally lowered molecular weight averages. Narrow polystyrene standards required relatively high concentrations for precise molecular weight averages and therefore, their averages were not good indicators of the need for concentration correction. Analysis of polypropylene samples corroborated the lower high molecular weight resolution of System III. Concentration correction did significantly change the polypropylene molecular weight distribution but did not affect the result of the kinetic model fitting.
    Additional Material: 14 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 35 (1988), S. 1049-1063 
    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: Polypropylene was analyzed by size exclusion chromatography (SEC) at 145°C using a single-differential refractometer detector. The objective was to provide data for characterization of polypropylene degradation during a reactive extrusion process. Two antioxidants [tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) methane (I) and octadecyl 3,5-di-tert-butyl-4-hydroxyhydro cinnamate (II)] were tested for their ability to prevent thermal degradation of the polypropylene during sample preparation. The use of 0.20 wt% of (I) was effective during the 36-48 h required to completely dissolve the samples in trichlorobenzene for SEC analysis. “Reshaping” of the chromatograms by resolution correction demonstrated that, while the molecular weight averages were changed by 8% because of axial dispersion, most of the individual heights of the distributions were changed by less then 2%. Tail heights of the distributions were more affected but were also shown to be highly imprecise. Selecting individual heights of the distributions rather than molecular weight averages therefore minimized axial dispersion error and also circumvented errors in molecular weight averages originating from dilution of distribution tails below detector sensitivity limits. Various forms of distributions were examined and the equations linking the chain length distribution predicted by polymerization kinetic models to the SEC chromatogram are presented. The analytical method developed provided precise data for kinetic modeling. However, absolute accuracy requires further assessment.
    Additional Material: 10 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 25 (1987), S. 313-320 
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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