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  • Polymer and Materials Science  (21)
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  • 1
    Electronic Resource
    Electronic Resource
    Evaluation of crosslinking and scission yields in the degradation of polystyrene by γ-irradiation in air (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2919-2933 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A sample of polystyrene with narrow molecular weight distribution (M̄w/M̄n = 1.03) has been formed into a 3-mm sheet and subjected to γ-irradiation at 25°C in air. Simultaneous crosslinking and scission of polymer chains resulted. Analyses by velocity and equilibrium sedimentation, gelpermeation chromatography, and osmometry of the polystyrene subjected to doses in the range 0-90 Mrad, all within the pre-gel region, have yielded average values of G(S) = G(X) = 0.022 ± 0.002 for the complete sample. Combination of these various experimental techniques has been successful in yielding consistent values of G(S) and G(X) and should be applicable with advantage to other polymers, particularly when neither G(S) nor G(X) is zero. The wide variation in literature values of G(S) and G(X) for irradiation of polystyrene under vacuum precludes any unequivocal conclusion on the effect of air on the radiation yields.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170151208
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  • 2
    Electronic Resource
    Electronic Resource
    A simplified data treatment for dead-end and high conversion polymerization kinetics (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 241-244 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simplified approximation method for the treatment of dead-end and high conversion polymerization kinetics is presented. The method is based on the treatment of dead-end polymerization first described by Tobolsky. In appropriate circumstances, by contrast with Tobolsky's method, this method provides measurements of kd and kp/kt1/2 without recourse to the measurement of the monomer conversion at infinite time.Kinetic studies of free radical polymerizations are normally confined to measurements of initial rates. At low conversions the predictions of the general mechanism for chain-growth polymerization involving initiation, propagation, and termination steps are generally obeyed. Thus the polymerization rate should be first order in the vinyl monomer and half-order in the initiator concentrations.At high conversions, however, large deviations which can be ascribed to various effects can occur; for example, (1) the effect of the increasing viscosity of the polymerization medium on the termination rate constant kt, and possibly also on the propagation rate constant kp, which have been considered by North1 and Cardenas and O'Driscoll,2 or (2) depletion of the initiator as the polymerization progresses. This depletion will occur in all polymerizations but its significance will depend on the magnitude of the rate constant for initiator decomposition (kd) and the period of polymerization. Appropriate conditions will lead to limiting monomer conversion even after infinite polymerization time; this phenomenon has been called dead-end polymerization by Tobolsky.3Free radical polymerizations to high conversion are particularly important in the industrial context when initial kinetics are obviously inadequate. Suitable treatment of the conversion/time relationship is highly desirable.Senogles and Woolf4 have examined the polymerization of n-lauryl methacrylate at 60°C with 2-azobisisobutyronitrile as initiator under dead-end conditions.Here we propose a modification of Tobolsky's treatment of such polymerizations by using an approximation for the exponential decay in the initiator concentration. This method permits easy manipulation of the experimental data and the estimation of values for the kinetic parameters in favorable circumstances without recourse to the measurement of the conversion at infinite time or the evaluation of complicated functions of the monomer conversion. The method thus allows the duration of the laboratory experimentation to be significantly shortened and the complexity of the subsequent data analysis to be considerably reduced.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200126
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  • 3
    Electronic Resource
    Electronic Resource
    Monomer and configurational sequence regularity in the 2:1 copolymer of vinyl chloride with sulfur dioxide (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 14 (1976), S. 263-272 
    Details
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.130140503
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  • 4
    Electronic Resource
    Electronic Resource
    Evidence of crosslinking and chain scission in the degradation of poly(tert-butyl crotonate) by γ-irradiation (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 131-139 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of γ-irradiation on poly(tert-butyl crotonate) has been investigated by velocity sedimentation and solubility studies. Evidence of significant crosslinking as well as of chain scission has been obtained, the estimates of G(X) and G(S) being 0.66 and 0.59, respectively.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150113
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  • 5
    Electronic Resource
    Electronic Resource
    Crosslinking and scission yields for polystyrene subjected to γ irradiation in vacuo (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 4081-4088 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of molecular weight averages and distributions have been made on three samples of narrow molecular size distribution polystyrene with molecular weights from 100, 000 to 400, 000 subjected to 60Co γ irradiation in vacuo for various doses within the pregel region+ G(X), the radiation chemical yield of crosslinking, has been determined as 0.043 ± 0.002 and G(S)/G(X), the ratio of scission to crosslinking, as 0.02; no effect of molecular weight was observed. By comparison with previous experimental results for polystyrene irradiated in air it has been established unequivocally that an oxygen environment leads to enhanced scission at the expense of crosslinking. Literature values of G(X) and G(S)/G(X) are reviewed in the light of these results and explanations are offered to account for major discrepancies.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170171227
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  • 6
    Electronic Resource
    Electronic Resource
    Depropagation reactions in the copolymerization of vinyl chloride and sulfur dioxide (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 15 (1977), S. 659-669 
    Details
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.130151104
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  • 7
    Electronic Resource
    Electronic Resource
    Radiation degradation of polystyrene/poly(methyl methacrylate) blends (1979)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 24 (1979), S. 2415-2418 
    Details
    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
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1979.070241210
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  • 8
    Electronic Resource
    Electronic Resource
    Effects of gamma radiation on two aromatic polysulfones (1975)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 19 (1975), S. 405-417 
    Details
    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: Two aromatic polysulfones, poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenyleneisopropylidene-1,4-phenylene) (I) and poly (oxy-1,4-phenylenesulfonyl-1,4-phenylene) (II), undergo crosslinking and chain scission at 30°C during γ-irradiation, the former being predominant in vacuum and the latter in air. Both processes occurred more readily in I, which contains isopropylidene linkages. Gel measurements gave G(crosslink) = 0.051, G(scission) = 0.012 for this polymer at 30°C in vacuum. Increased irradiation temperatures resulted in higher crosslinking and gas yields, especially above the glass transition temperature. The tensile strength, flexural strength, and modulus of I were unaffected by γ-irradiation up to about 50 Mrad in air, but the strength decreased markedly at higher doses. The elongation at break decreased progressively with dose. For both polymers, G(gas) = 0.04 at 30°C with the main products being SO2, H2, CO2, CH4, and H2O.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1975.070190208
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  • 9
    Electronic Resource
    Electronic Resource
    Effects of gamma radiation on two aromatic polysulfones. II. A comparison of irradiation at various temperatures in air-vacuum environmentsPresented in part at the First Chemical Congress of the North American Continent, Mexico City, December 1975. (1979)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 23 (1979), S. 2763-2775 
    Details
    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 aromatic polysulfone poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenyleneiso-propylidene-1,4-phenylene) (I) showed no change in flexural yield strength after doses of γ-radiation up to 600 Mrad in vacuum at 35,80, and 125°C (Tg = 190°C)). However, the flexural strength decreased markedly with doses above 100 Mrad on irradiation in air, to 40-60% of the initial value after 200-400 Mrad, depending on the sample and the irradiation conditions. Chain crosslinking was predominant over scission for irradiation in vacuum at all temperatures; (G(X), G(S), and G(S)/G(X) increased with the irradiation temperature, but G(S)/G(X) decreased to zero above Tg. Poly(oxy-1,4-phenylenesulfonyl-1,4-phenylene) (II) behaved similarly, except that the flexural strength was found to be very dependent on the thermal treatment of the sample. This polymer showed a remarkable retention of its mechanical properties on irradiation up to 200°C (Tg = 230°C) in the absence of air, the flexural strength being retained up to 500 Mrad. Radiation annealing occurred at 35°C in vacuum and air and combined radiation and thermal annealing at 125 and 220°C. Progressive removal of surface layers from flexural test bars of I irradiated in air showed that the decrease in flexural strength with dose could be explained by a decrease in the molecular weight towards the surface resulting from radiation-oxidation reactions.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1979.070230921
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  • 10
    Electronic Resource
    Electronic Resource
    Degradation of polystyrene by gamma irradiation: Effect of air on the radiation-induced changes in mechanical and molecular properties (1979)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 24 (1979), S. 425-439 
    Details
    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: Irradiation of 3 mm polystyrene sheet in air at 30°C with γ rays caused a rapid decrease in the tensile and flexural strengths and strains to fracture. These properties were decreased to 50% of their initial values after ca. 80 Mrads and to 25% after ca. 200 Mrads, beyond which dose the rate of change was relatively small. These results contrast with the negligible changes that are observed after 600 Mrads in vacuum. The effect of irradiation in air has been correlated with decreasing molecular weight at the surface, even though crosslinking predominated over the complete sample so that a gel point was reached at a dose slightly in excess of 100 Mrads. Scission and crosslinking yields, G(S) and G(X), were determined as a function of depth by gel permeation chromatography of layers removed progressively from the surface. G(S) decreased and G(X) increased with depth, in accord with the concepts of increased scission by reaction with oxygen and a diffusion effect. Unusual transverse cracking to a limited depth occurred during tensile measurements, a phenomenon that is attributed to the nonuniform molecular weight profile.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1979.070240211
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