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  • 1
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 29 (1989), S. 1733-1737 
    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: The hydrolytic stability of a new commercial polycarbonate (Calibre 300, Dow Chemical USA) was investigated and compared with that of other commercial polycarbonates. The tests were conducted between 56% and 95% relative humidity (R. H.) at 100°C. Also performed were water immersion tests at 80 and 100°C. The water diffusivity was found to be 8.7 × 10-7 cm2/s at 100°C with an activation energy of 7.9 kcal/mole. These values are similar to other glassy polymers. The equilibrium water sorption, C∞, was found to increase with temperature and R.H. The isotherm at 100°C was determined to be: C∞ = 0.005945 [R.H.]. When samples immersed in a water bath at 100°C were transferred into room-temperature water, visible aqueous microcavities were formed due to the condition of super-saturation, and under stress may become crack initiation sites. For the polycarbonate investigated here, it was found that the decrease in weight-average molecular weight (M̄)w was a first-order process under a constant R.H. and temperature, and that hydrolytic embrittlement, i. e., (M̄)w 〈34,000, was reached after ca. 188, 143, 99, and 66 days under 56%, 73%, 87%, and 95% R.H., respectively, at 100°C. A comparison with reported hydrolytic stability data for other polycarbonates showed large differences in their stability which are believed to be due to the extent of end-group capping (over 95% in Calibre 300) and resin purity: both phenolic end-groups and some additives (i.e., fire retardants, thermal stabilizers) are known to accelerate hydrolytic degradation.
    Additional Material: 8 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 35 (1988), S. 2001-2008 
    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 hydrolysis of polyarylate in water between 55 and 98°C was found to be a zero-order process with an activation energy of 19.2 kcal/mol, determined by changes in molecular weight. The equation for the effect of temperature on the rate of hydrolysis is ln k = 34.1 - 104/T, where k is in day-1. The decrease in molecular weight is accompanied by a loss in ductility. The transition from a ductile to brittle failure in tension occurs at M̄w of about 35,000 and M̄n of 12,700. At 27°C (80°F) and high humidity environment this would occur after 21 years. But during injection molding, the material, if not properly dried, would embrittle in a matter of seconds.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 786-791 
    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: The hydrolytic degradation of polycarbonate resins is a first-order process in terms of the decrease in average molecular weights under a relative humidity (RH) and temperature. Two analysis procedures have been developed for making life-cycle predictions of polycarbonate at any combination of humidity and temperature. The first prediction procedure uses an Arrhenius equation derived for determination of the activation energy of polycarbonate hydrolysis tested at various temperatures under a constant RH. The rate constants at any combination of temperature and RH can be determined for a new resin tested at three or more RHs under a temperature, since the logarithm of the Arrhenius intercept has a linear empirical relationship with RH. The second prediction procedure uses a linear relationship between the logarithm of the rate constant and RH derived from the humid-aging of polycarbonate tested at various RHs under a constant temperature. The rate constants at any combination of temperature and RH can be determined for a new resin tested at three or more temperatures under a RH, since the intercept of the above linear relationship has another linear empirical relationship with temperature.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 39 (1990), S. 189-197 
    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 influence of relative humidity (RH), between 55 and 100%, on the rate of hydrolytic degradation of polyarylate was investigated at 100°C. The equilibrium water sorption in weight percent, C∞, was determined to be C∞ = 0.0043 X (RH)1.2. For specimens 0.32 cm thick, it takes about 24 h to reach 0.9C∞ at 100°C. The decrease in molecular weight (M̄w) due to the hydrolytic attack of water was linear with time, suggesting a zero-order process with respect to M̄w. The rate of decrease was found to be proportional to C∞. A 30% decrease in M̄w was observed after 21 days at 55% RH and 100°C and, at that point, the material has become brittle.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 61 (1996), S. 2065-2073 
    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 role of an accelerator in the nucleophilic cure of fluorocarbon compounds was further examined by preparing materials without a crosslinker. Under the previously used curing conditions, ODR reveals the formation of a secondary, accelerator-induced network that is unstable at slightly higher temperature, i.e., ≥190°C. Increased crosslink density and color are observed with the cure time, indicating slow curing reactions and likely formation of conjugated unsaturation. SEC of selective solvent-soluble fractions derived from specimens obtained from the key cure stages shows initially a falling refractive-index response. However, this change is followed by a shift in MWDs toward lower average molecular weights. On the other hand, infrared examination shows a continuous increase in the 1718 cm-1 absorption, but no major presence for the 1680 cm-1 absorption seen in the previous study in the presence of a crosslinker. The concurrent increase in the 3114 cm-1 peak confirms the presence of a —CF=CH— double bond. The solvent-soluble portions and bulk specimens have very similar infrared features. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 41 (1990), S. 835-843 
    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: Extender oil bloomed on the surface of ethylene-propylene-diene rubber (EPDM) vulcanizates has been analyzed by a dissolution/size exclusion chromatographic (SEC) method. Dissolution is here defined as the quantitative and selective removal of bloomed extender oil from the vulcanizates. The rate of migration of three potentially useful extender oils for windshield-wiper materials has been determined by the method. In this work a bloomed oil includes both an excluded oil surfaced during the process of vulcanization and a migrated oil surfaced during the course of aging or weathering. Typical initial rates of oil migration in the presence and absence of an excluded oil on the surface of compression-set EPDM vulcanizates were ca. 0.8 and 2.2 μg/cm2/h at 25°C, respectively. The rate of migration at an attained uniform oil concentration was found to be ca. 0.5 μg/cm2/h for the three extender oils.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1095-1107 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic and mechanistic investigations of liquid phase autoxidation of hexadecane at 120 to 190°C have shown that, in the early stages of oxidation, the initiation process involves homolytic decomposition of hydroperoxides. The values of a composite first order rate constant for this decomposition, k1, have been determined in stirred flow reactor experiments from the rate of formation of termination products and in batch reactor studies using inhibitor methods. Arrhenius parameters derived from these studies (log (A/s-1) = 8.5 and Ea = 26 kcal mol-1) allow calculation of k1 as a function of temperature. This permits determination of the rate of initiation as a function of hydroperoxide concentration and facilitates determination of absolute rate constants for other oxidation reactions occurring in this system.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 673-680 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constants for the intermolecular hydrogen abstraction reactions of secondary hydrogens by secondary alkylperoxy radicals in hexadecane autoxidation, k3, have been determined in the temperature range of 120-190°C using the stirred flow reactor technique. Absolute rate constants determined in this study for hexadecane are in good agreement with those determined for other hydrocarbons in liquid phase, on a per hydrogen basis, at lower temperatures. Arrhenius parameters for k3/H derived from this study are A = 108.6 M-1 s-1 and Ea = 16.0 kcal/mol. The values of these parameters provide experimental confirmation for previous estimates made from both lower temperature reactions in the liquid phase and higher temperature reactions in the gas phase. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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