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  • Physics  (96)
  • 2020-2023
  • 2010-2014
  • 1970-1974  (55)
  • 1965-1969  (41)
  • 1935-1939
  • 1972  (55)
  • 1966  (41)
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  • 2020-2023
  • 2010-2014
  • 1970-1974  (55)
  • 1965-1969  (41)
  • 1935-1939
Year
  • 1
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) was exposed in vacuo γ-radiation from a Co60 source at a dose rate of 0.02 Mrad/min., and an ambient temperature of 47°C. Gaseous products were analyzed in a mass spectrometer and carboxyl groups estimated by titration with NaOH and by infrared analysis. Initial G values were —COOH = 0.77, CO2 = 0.17, CO = 0.11, H2 = 0.015, and CH4 = 0.003. All these values decreased markedly with increasing dose except G(CO)2, which, roughly, was maintained up to 5000 Mrad. It was considered whether the dependence on dose of the yields of the major reaction products could be accounted for by the following set of first-order reactions: It was found that the rate of formation of —COOH groups at low doses was much too high to fit this simple reaction scheme. However, a better fit was obtained over a range of higher doses (ca. 100-5000 Mrad). A final conclusion could not be reached concerning the validity of the above reaction scheme.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3267-3277 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated preparation of equimolar copolymers of styrene and diethyl fumarate is described. The reaction medium consisted of these monomers dissolved in a methanol-zinc bromide solution. Rates of polymerization increased with increasing applied current and the copolymer yield increased linearly with the total number of Faradays transferred. The copolymer composition is 1:1 and is essentially invariant with the degree of conversion (〈15%), electroinitiation rate, and monomer feed ratios. A reaction mechanism involving donor-acceptor complexes and electroinitiated excitation of these complexes at the electrode is postulated.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3253-3265 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparative analysis of photoinitiation and electroinitiation can help elucidate initiation processes in donor-acceptor charge-transfer copolymerization. The technique has been applied to the zinc bromide-catalyzed copolymerization of styrene and diethyl fumarate in methanol. The photocopolymer product was analyzed by GPC, NMR, and elemental analysis. The results showed that 1:1 copolymers were formed initially, but changes occurred in both the kinetics and products after the early stages of the reaction. Significant correlations found between the two initiation methods included the initial kinetic order with respect to the initiating process and the effect on product yield of equivalent increases in total initiation energy. The limiting value of zinc bromide for both initiation methods was found to be the same. The data obtained support the contention that the copolymerization proceeds through a donor-acceptor process and that photoactivation of the preformed complex, inducing electron transfer, is a likely initiation process.
    Additional Material: 9 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1555-1564 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization kinetics of a range of fractions of poly(ethylene oxide) are presented and analyzed. It is concluded that deviations from the Avrami equation with exponent of 3 are mainly due to rejection of low molecular weight molecules for the low molecular weight fractions (M̄n 〈 6,000) and to a process of crystal perfecting for the high molecular weight fractions (M̄n 〉 6,000).
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1811-1836 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model for the crystallization kinetics of polymers is outlined and is used to interpret observations of the crystallization of polyethylene at high pressures. This model introduces a distinction between σe the lamellar surface energy which controls the lamellar thickness, and σe′, the surface nucleus surface energy which controls the growth rate. Differential scanning calorimetry and electron microscopy data for several polyethylenes crystallized at pressures of up to 8 kb are presented. From the dependence of lamellar thickness on the crystallization undercooling at 5 kb, it is found that σe increases markedly with pressure leading to the formation of very thick crystals at high pressures. The magnitude of the increase in σe is in agreement with σe values calculated from the dependence of melting temperatures on pressure. The nucleus surface energy σe′ is not expected to vary significantly with pressure, and estimates of growth rates of 5 kb which indicate that the growth rate does not vary significantly with pressure at constant under-cooling confirm this. Fractionation effects and the differences in behavior between different polyethylenes are also discussed.
    Additional Material: 11 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 863-875 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Folded-chain crystals of certain polyamides present some novel diffraction effects due to the small number of repeat units within the lamellar thickness. X-ray diffraction evidence is available in the complete range from low to wide angles. This information is interpreted in terms of the structure factor of an individual lamella together with the lattice factor appropriate for the stacking of lamellae. When due account is taken of the lattice factor, whose effect can be detected even at large angles, three features of the lamellar structure can be deduced. First, the evidence is in favor of the straight-chain stems traversing almost the total thickness of each lamella, implying sharp folds at the lamellar surfaces. Some consequences of this result on the interpretation of data obtained from annealed mats are mentioned. Second, the detailed determination of the stem structure demands that the majority of the folds in nylon 66 lie in the acid group. Third, there are regions of depleted electron density at the lamellar surfaces, though features of the crystal structure are still retained. This indicates the presence of some folds deeper in the crystal than the majority.
    Additional Material: 7 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 252-254 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 1637-1654 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular core binding energies of the polymers formed by copolymerization of CF3NO with CF2=CF2, CF2=CFCl, and CF2=CFH, respectively, have been studied by means of ESCA. The results are interpreted in terms of CNDO/2 SCF MO calculations on some model systems. Some evidence for structural irregularity is found for the copolymers with CF2=CFCl and with CF2=CFH. The reaction mechanism for the polymerization is also discussed in terms of the experimental results and INDO SCF MO calculations.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2253-2265 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Aryl- and 2-alkyl-2-oxazolines have been polymerized to poly-(N-aroyl)aziridines and poly(N-acyl)aziridines, respectively, in the presence of boron trifluoride. The polymers obtained were glassy, light yellow resins with molecular weights ranging from 3500 to 7500 (35-50 oxazoline units per chain). The polymerization rates have been determined for several of these monomers. A polymerization mechanism is proposed.
    Additional Material: 4 Ill.
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  • 10
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free radicals formed by γ-irradiation of oriented samples of poly(ethylene terephthalate) (PET) were studied at 25°C. by ESR spectroscopy. The G value for trapped free radicals is 0.02. The predominant radical is identified as $\text{O} - \text{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{C} H} - \text{CH}_\text{2} - \text{O} -$, and a minor component of the spectrum is tentatively assigned to the radical —CO—Ċ6H3—CO—. The absence of cyclohexadienyl type radicals is discussed. Previously reported dose rate effects in PET are explained by reference to a chain reaction involving β-bond scission of the radical $\text{O} - \text{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{C} H} - \text{CH}_\text{2} - \text{O} -$.
    Additional Material: 7 Ill.
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