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  • Physics  (55)
  • 1970-1974  (55)
  • 1935-1939
  • 1972  (55)
  • 1
    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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  • 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-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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  • 4
    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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  • 5
    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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  • 6
    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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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 1077-1092 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The surface oxidation of polypropylene films which occurs during ultraviolet irradiation in air was found to result in extensive surface restructuring. This restructuring was detected by changes in surface infrared spectra, as measured by attenuated total reflection spectroscopy, and by electron microscopy. The 997 cm-1/974 cm-1 absorbance ratio of the film surfaces increased steadily during ultraviolet degradation and was interpreted as an increase in helical ordering which resulted from backbone scission during irradiation. This scission probably also results in the increase in crystallinity detected by density changes. Electron microscopy of direct surface replicas and replicas of material detached from the oxidized film surfaces showed that surface cracking resulted during photo-oxidation, and that this oxidation penetrated selectively into the polymer structure. The replicas of detached, oxidized material showed periodic structures related to the interior morphology of the films. The observed restructuring is believed to be entirely responsible for the decrease in percentage elongation at break which results from photodegradation.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2135-2153 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is assumed that the intensity of the vibrational Raman scattering from each of the structural units (molecular segments or crystallites) in an oriented polymer solid is determined by a symmetric second-rank tensor. The distribution of orientations of the principle axes of the tensors is expanded in a series of generalized spherical harmonics, Zlmn(θ)e-imψe-inφ, and it is shown that relations among the coefficients in this expansion can be obtained from suitable intensity measurements using polarized radiation. If the orientation of the tensor axes within the structural unit is known (in the general case, for several Raman lines), then the coefficients Mlmn of a similar expansion for axes fixed in the units can be obtained for l, m, and n even and l ≤ 4. The limitation to even m follows from the assumption that the solid has at least orthotropic statistical symmetry but the limitations on n and l arise from the nature of the Raman effect. Some simple special cases are considered and some orientation-independent intensity sums are derived. It is shown that, with the simplifying assumption usually made, the theory of the polarized fluorescence method for determining molecular orientations is a special case of the theory for the Raman method.
    Additional Material: 3 Tab.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2461-2473 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of a phenol-formaldehyde polymer with a deliberately introduced flaw were fractured in tension. The appearance of the fracture surface near the flaw suggested the disruption of particles pre-existing in the polymer. At a greater distance from the flaw, a featureless surface was observed which was succeeded by one showing interference colors. At still greater distances, linear features were observed to be lying in the direction of crack propagation which, in most areas, were regular and evenly spaced. There were indications that these features were formed by the curling of a surface film. The above observations are interpreted as providing evidence that tensile fracture is accompanied by plastic defórmation at the fracture surface.
    Additional Material: 12 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2259-2280 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photocurrents induced by ultraviolet illumination of poly(ethylene terephthalate) (Mylar) and polyethylene specimens supplied with aluminum electrodes in a sandwich configuration have been studied in the wavelength range 380-180 nm. A description is given of the precautions taken to ensure that artefacts such as photoelectric emission external to the specimen do not influence the measurements. In both materials, a fast and a slow transient are present. Measurements on polyethylene show that the magnitude of the response is linearly dependent on the light intensity and is essentially thickness independent. This behavior leads to difficulties in interpretation in terms of known conduction processes. In Mylar it is shown that hole injection from the positive electrode into the polymer is responsible for the observed currents, and evidence to associate a similar process with the effects in polyethylene is presented.
    Additional Material: 8 Ill.
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