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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.
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.
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.
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