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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1283-1296 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isotactic and atactic poly(methyl methacrylate) containing varying amounts of polymerization initiator and chain-transfer additives, and carefully purified radiation-polymerized material, were γ-irradiated in the dark at liquid nitrogen temperature. On warming to room temperature at a near-linear rate of 20°K./min., a glow peak having a maximum luminescence intensity at 162 ± 8°K. was observed in all samples; an additional peak at 239 ± 7°K. was resolved relatively infrequently. Low luminescence yields precluded an investigation of the spectral distribution of the glow peaks. It is shown that the electron traps associated with the lower temperature peak are most probably the main-chain methyl groups, while the higher temperature glow peak is tentatively associated with escape of electrons from structural defects in a few small crystalline regions of the samples. It is postulated that, for the peak at 162°K., the trapped electrons combine radiatively with luminescence centers when thermally induced rotational motion of the main-chain methyl groups permits sufficient wave-function overlap. Assuming that methods of glow curve analysis proposed for inorganic materials are applicable to organics, first-order recombination kinetics and an activation energy of 0.084 ± 0.006 e. v. are deduced for the intensity maximum at 162°K. This activation energy is in fair agreement with that obtained by Bordoni et al. for an unspecified side-chain motion occurring at similar temperatures, but is only about half the values quoted with some reservations by Powles and by Kawai on the basis of NMR experiments. It was not possible to determine the kinetics of the 239°K. peak with certainty, but an activation energy of 0.432 ± 0.085 e. v. follows from a first-order assumption. The additives present in the samples did not appear to play any significant part as electrontrapping agents; this observation contrasts with some recent work on the visible and ultraviolet absorption spectra of the same materials which showed a close correlation of additional bands developed following irradiation with the presence of specific additives.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1321-1336 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transient photocurrents in poly(vinyl chloride) films are shown to be due to photo-injection of electrons from metallic cathodes. Most of the injected electrons are promptly trapped, but some drift across the sample to the anode under the influence of an external electric field. The mobility of these electrons, determined by transient photoconductivity techniques, is 4.7 ± 0.5 × 10-4 cm2/V-sec at 27°C, and rises to 3.4 ± 0.5 × 10-3 cm2/V-sec at 43°C, the measuring cell having been evacuated to a pressure of 10-6 torr at both temperatures. Diffusion of helium into the samples appears to decrease the electron, mobility. It is suggested that electron transport is correctly described by using an energy-band model for intramolecular motion and an activated hopping model for intermolecular transfer. Oscillations observed in the transient photocurrents in the frequency range 103-105 Hz are attributed to electron avalanche formation at the anode, with photosuccessors.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 1713-1724 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence (TL) emission from low-density polyethylene has been investigated. The glow curves of gas-free samples x-irradiated at -190°C and heated to room temperature were found to contain three peaks numbered I, II, and III in order of increasing temperature, in agreement with earlier results. The sites of all traps are accessible to absorbed gases; in the presence of air, O2, N2 or Ar, “gas” traps are formed, resulting in the appearance of an additional peak IV in the glow curve at a temperature between peaks I and II, large reductions in the intensities of peaks II and III, and various changes in peak I. The peak I, II, and III traps are formed from particular chain configurations occurring in the chain-fold regions of the samples, these configurations being broken up by different forms of molecular motion within the chains. It is unlikely that the peak IV traps are just the gas molecules themselves; they are probably formed from new chain configurations occurring in the amorphous regions of the samples in the presence of the gas, the properties of the gas influencing the associated TL intensity and emission temperature. These traps are also broken up by molecular motion. The samples can be divided into two main types, differing mainly in the height of peak I relative to peak II, which is of nearly constant intensity in all samples. We suggest that two types of trap which are not interconvertible are associated with peak I, and that the dominant type in a given sample depends on the fine details of the sample fabrication process.
    Additional Material: 8 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 B: Polymer Physics 25 (1987), S. 1885-1895 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Further thermoluminescence data are presented supporting our earlier suggestion that the electron traps associated with the three peaks in the thermoluminescence glow curve of a low-density polyethylene sample from which absorbed air has been removed are formed by the polymer chains themselves in the chain-fold regions of the samples. These traps are shown to be sensitive to heating of the sample to temperature around its melting point; in particular, the lowest temperature peak disappears if the sample is held at 90°C in vacuum for 5 min. If the sample is maintained in vacuum at room temperature after such treatment, its modified glow curve remains unchanged for a period of at least 7 days; however, if the sample is exposed to air, nitrogen, or argon after such treatment, its gas-free glow curve begins to change within 3 days, evolving toward a three-peak form with the same peak temperatures but with relative intensities different from those observed before heating began. This suggests that the gas molecules “lubricate” the polymer chains, which then begin to move toward new equilibrium configurations. Immersion in n-hexane at room temperature has little effect on the luminescence centers but disables the electron traps. Immersion in fuming nitric acid at room temperature for 2 days appears to destroy the electron traps permanently, as would be expected if the chain folds are digested by the acid; its effect on the luminescence centers is still to be determined.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1979-1997 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence (TL) and thermally stimulated conductivity (TSC) glow curves in poly(vinyl chloride), polyethylene, polystyrene, polytetrafluoroethylene, and polyimide have been compared, and many similarities have been observed. Comparison with available NMR, dynamic mechanical loss, and dielectric loss, molecular mobility data shows that most TL and TSC peaks occur at temperatures similar to those assigned to the onset of specific molecular motions, suggesting that the peaks are due to the liberation of electrons from traps formed by the polymer chains themselves, e.g., potential wells or cavities due to chain entanglement in amorphous regions, or main-chain branching points. Peaks for which correlation with molecular motion is not apparent are tentatively assigned to liberation of electrons from traps centered on impurities. The TSC peak temperatures in PVC were not affected in any consistent fashion by the application of high-strength electric fields during the warming process, indicating that the electron traps are electrically neutral when empty and charged when filled; the direction of the TSC currents appears to be determined by temperature gradients existing within the samples. The TL glow-curves are generally in good agreement with the results of other workers. The dark dc conductivity of PVC not exposed to ionizing radiation rises sharply in the temperature region assigned to the β-relaxation process, suggesting that the electron mobility in that polymer is dominated by molecular chain motion, i.e., the interchain charge transport process is probably best described in terms of a hopping process.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1703-1704 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 9 (1971), S. 573-577 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 8 (1970), S. 217-224 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1691-1701 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When FEP-Teflon samples are electron irradiated at room temperature in open circuit and stored in that state for varying times following the end of irradiation, the temperature of the first current peak of the short-circuit TSC plot increases with increasing storage time. A new model is presented to explain this phenomenon, its main features being (i) a quasicontinuous distribution of hole-trap activation energies, the “center of mass” of the trapped hole population moving toward the deeper end of the distribution during the storage time, and (ii) an electron/hole recombination coefficient much smaller than that implied in an earlier model. It is shown that the assumption of a single dominant type of hole trap implies an unrealistically large frequency factor.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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