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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 241-244 
    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
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    International Journal for Numerical Methods in Fluids 17 (1993), S. 463-475 
    ISSN: 0271-2091
    Keywords: Finite elements ; Streamline upwind ; Quadratic elements ; Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: A direct streamline upwind method has been developed for convection-dominated flow problems utilizing quadratic elements. The approach presented retains the curve-sidedness feature offered by these elements. This facilitates the use of boundary conforming elements in domains that possess extreme curvature such as turbomachinery bladed components, for which the method is particularly suited. Three test cases are solved to evaluate the stability and diffusive characteristics of the numerical solution. The results presented clearly demonstrate that the proposed method does not exhibit any non-physical spatial oscillations, nor does it suffer from the traditional problem of excessive numerical diffusion.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    International Journal for Numerical Methods in Fluids 20 (1995), S. 169-185 
    ISSN: 0271-2091
    Keywords: Finite elements ; Multiblock ; Quadratic elements ; Equal-order ; Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: A new multiblock pressure-based finite element algorithm has been developed. This methodology implements quadratic interpolation for both the elemental velocity and pressure fields. A direct streamline upwinding scheme previously developedby the authors is used to model the non-linear inertia effects. Details of the algorithm and its multiblock foundation are provided along with validating test cases. The results presented clearly demonstrate the accuracy of this new approach and the differences in the pressure field for an element using quadratic versus the traditional bi linear approximation of the pressure field.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2439-2454 
    ISSN: 0887-624X
    Keywords: radiation ; nitrile rubber ; NMR ; ESR ; radicals ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of radiation-induced structural changes in nitrile rubber with different acrylonitrile contents were investigated by ESR, NMR, and FTIR. To investigate new structures solid-state NMR methods had to be used due to crosslinking of the irradiated rubbers, and higher probe temperatures were used to obtain better resolution. The radicals generated on the acrylonitrile groups were found to abstract hydrogen from the adjacent butadiene units resulting in the formation of allylic radicals. These allylic radicals reacted to form intermolecular crosslinks and cyclisation. Cyclisation of the butadiene units were found to occur in the initial stages of the irradiation. Radiation yields of radicals increased with acrylonitrile content from 1.42, 1.58, to 2.42 for 18, 30, and 45% acrylonitrile rubbers. The radiation yields for intermolecular crosslinking were higher in rubbers with higher acrylonitrile contents, giving G values of 17.8, 21.3, and 24.5 for 18, 30, and 45% acrylonitrile rubbers, respectively. However, the crosslink clustering was found to be less in the rubbers with a higher acrylonitrile content. © 1996 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 851-863 
    ISSN: 0887-624X
    Keywords: polymerization ; kinetics ; free radical ; transfer ; photolysis ; propagation ; rate coefficients ; termination ; EPR ; copolymerization ; initiation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problems of determining reliable, well-characterized values of kinetic parameters in free-radical polymerizations are discussed. The origins of the fact that experimental determinations of rate coefficients of ostensibly identical systems often result in quite different values being reported can be ascribed to subtle mechanistic assumptions made in data interpretation, which are considered in detail. A series of recommendations to assist in overcoming these problems, and to highlight their origins, are presented, with emphasis placed on new techniques including those employing laser photolysis and EPR.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previously used procedures for processing the amino acids from 6N hydrochloric acid hydrolysis of poly[N5-(4-hydroxybutyl)-L-glutamine], poly[N5-(3-hydroxypropyl)-L-glutamine], and several random copolymers derived from these, led to the formation of spurious products. These have been isolated and characterized as the γ-ester of glutamic acid and the hydroxyalkyl amine, and chloro-alkyl amine hydrochloride. The former reduces the observed values for glutamic acid, but the latter has no effect on them. A method is used to avoid formation of these artifacts in the amino-acid analysis. Of all the copolymers studied previously in this series, the compositions of only those containing L-serine are in error as a result of the formation of the γ-ester. A redetermination of the amino-acid compositions of the copolymer fractions studied earlier leads to slightly revised values for the Zimm-Bragg parameters σ and s of serine.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water-soluble, random copolymers containing L-methionine and N5-(3-hydroxypropyl)-L-glutamine have been prepared, fractionated, and characterized. The thermally induced helix-coil transitions of these copolymers in water have been investigated, and it has been found that incorporation of L-methionine increases the helix content of the polymers at all temperatures in the range of 0-60°C. The Zimm-Bragg parameters σ and s for the helix-coil transition in poly(L-methionine) in water were deduced from an analysis of the melting curves of the copolymers using the methods described in earlier papers.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2469-2480 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amino-acid-sequence distribution in poly(γ-benzyl-L-glutamate, L-methionine) prepared by polymerization of the respective N-carboxyanhydrides has been investigated. This copolymer was converted first to poly(L-glutamic acid, L-methionine), which was subsequently cleaved by treatment with cyanogen bromide. The resulting material was fractionated into oligomers of (glutamic acid)n-homoserine whose relative molar amounts were determined quantitatively. The results have been compared with those for a random incorporation of the methionine in a γ-benzylglutamate host polymer. Fairly close agreement has been found.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 57 (1995), S. 1155-1171 
    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 mechanism of radiation vulcanization of natural rubber with 2-ethyl hexyl acrylate (2EHA) monomer was investigated using electron spin resonance spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. The primary radicals formed in the arcylate molecule were found to abstract the allylic hydrogens of the polyisoprene. Crossliking may occur through the allylic radicals and/or main chain radicals formed on the polyacrylate. Acrylate was found to concentrate in the rigid regions of the crosslinked rubber indicating heterogeneity and a nonuniform distribution of the acrylate in the latex particles. The addition of the acrylate and the irradiation seems to effect the Brownian motion of the latex particles. Both the viscosity and the NMR peak widths are effected by the irradiation. Addition of 5% 2EHA increases the crosslinking by a factor of 3.6. The thermal stability of the rubber first increases with the dose in the presence of acrylate, but drops at higher doses due to peroxide formation. © 1995 John Wiley & Sons, Inc.
    Additional Material: 22 Ill.
    Type of Medium: Electronic Resource
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