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The experimental results obtained in a wide range of temperatures, for polyethylene terephthalate, demonstrate that the apparent activation energy changes when the charging (polarization) time or the isothermal discharging time, prior to the final thermally stimulated discharge current measurement, are used as variable parameters. Consequently, the charging and/or discharging time can be used as a variable parameter to investigate the landscape of the apparent thermal activation energies. A continuous distribution of the traps in the range from 0.4 to 3 eV was observed. The experimental results demonstrate that there is a range of experimental conditions for which the thermal activation energy is independent of the experimental parameter values. This is the activation energy value which should be used to characterize a certain mechanism.

The experimental results obtained in a wide range of temperatures, for polyethylene terephthalate, demonstrate that the apparent activation energy changes when the charging (polarization) time or the isothermal discharging time, prior to the final thermally stimulated discharge current measurement, are used as variable parameters. Consequently, the charging and/or discharging time can be used as a variable parameter to investigate the landscape of the apparent thermal activation energies. A continuous distribution of the traps in the range from 0.4 to 3 eV was observed. The experimental results demonstrate that there is a range of experimental conditions for which the thermal activation energy is independent of the experimental parameter values. This is the activation energy value which should be used to characterize a certain mechanism.

Polyethylene is one of the most widely used polymeric insulators in medium and high voltage power cables. However the importance of space charge distribution and its influence on the electrical aging in this polymer is not fully understood. The very good insulating properties of the material implying very long relaxation times (few days and even longer are usual) and low currents (few pA or below) make individual measurements of isothermal charge/discharge currents and thermostimulated currents difficult to analyze and reproduce. A single type of measurements does not take into account the space charge that remains trapped for long times. A combined procedure of isothermal and non-isothermal current measurements developed for high insulating polymers was used for low density polyethylene (LDPE) and crosslinked polyethylene (XLPE) films electrically aged. The press-molded LDPE and XLPE films were electrically aged under similar conditions using an AC electric field while immersed in a sodium chloride aqueous solution at constant temperature (electro-thermal aging). The use of the combined procedure for current measurement allowed obtaining information about space charge traps, activation energies and relaxation times for both LDPE and XLPE. This data was used to compare electrical aging under similar conditions for the two types of polyethylene.

Polyethylene is one of the most widely used polymeric insulators in medium and high voltage power cables. However the importance of space charge distribution and its influence on the electrical aging in this polymer is not fully understood. The very good insulating properties of the material implying very long relaxation times (few days and even longer are usual) and low currents (few pA or below) make individual measurements of isothermal charge/discharge currents and thermostimulated currents difficult to analyze and reproduce. A single type of measurements does not take into account the space charge that remains trapped for long times. A combined procedure of isothermal and non-isothermal current measurements developed for high insulating polymers was used for low density polyethylene (LDPE) and crosslinked polyethylene (XLPE) films electrically aged. The press-molded LDPE and XLPE films were electrically aged under similar conditions using an AC electric field while immersed in a sodium chloride aqueous solution at constant temperature (electro-thermal aging). The use of the combined procedure for current measurement allowed obtaining information about space charge traps, activation energies and relaxation times for both LDPE and XLPE. This data was used to compare electrical aging under similar conditions for the two types of polyethylene.

The dielectric breakdown of thin films of low-density polyethylene (LDPE) electrically aged in an aqueous solution of NaCl under an AC electric field was investigated. A two-parameter Weibull function was used for the dielectric breakdown time to failure. The probability of failure for a sample was obtained by the White method for progressively censored data. Samples aged at different temperatures were compared. The results show that initially the samples aged at lower temperature (approximate to25degreesC) are more prone to fail, while those aged at higher temperature (50degreesC) fail at longer times. This was attributed to a competition between oxidation and diffusion.

The dielectric breakdown of thin films of low-density polyethylene (LDPE) electrically aged in an aqueous solution of NaCl under an AC electric field was investigated. A two-parameter Weibull function was used for the dielectric breakdown time to failure. The probability of failure for a sample was obtained by the White method for progressively censored data. Samples aged at different temperatures were compared. The results show that initially the samples aged at lower temperature (approximate to25degreesC) are more prone to fail, while those aged at higher temperature (50degreesC) fail at longer times. This was attributed to a competition between oxidation and diffusion.

Using a recently developed procedure combining isothermal and non-isothermal current measurements space charge trapping and transport in LDPE was successfully studied. Unaged, thermally and electrically aged samples were investigated. The samples were conditioned before each measurement in order to obtain reproducible results. In the non-isothermal measurements appeared a broad peak (40degreesC to 50degreesC) that was possible to decompose into two or three peaks (35, 45 and 65degreesC). At even higher temperature another peak was sometimes present (85degreesC) depending on the prior sample conditioning. The space charge is trapped near the surface in deep traps (maximum depth of approximate to 15 mum). Relaxation times, mobilities and activation energies have been calculated for different charging/discharging conditions. For unaged samples the reproducibility of the results was poor while for the aged polyethylene it was quite good, meaning that aging helps conditioning. In the electrically aged LDPE there is a decrease of conductivity and the broad peak of the non-isothermal spectra shows a slight shift towards higher temperatures when compared with the data found in the thermally aged polymer.

Using a recently developed procedure combining isothermal and non-isothermal current measurements space charge trapping and transport in LDPE was successfully studied. Unaged, thermally and electrically aged samples were investigated. The samples were conditioned before each measurement in order to obtain reproducible results. In the non-isothermal measurements appeared a broad peak (40degreesC to 50degreesC) that was possible to decompose into two or three peaks (35, 45 and 65degreesC). At even higher temperature another peak was sometimes present (85degreesC) depending on the prior sample conditioning. The space charge is trapped near the surface in deep traps (maximum depth of approximate to 15 mum). Relaxation times, mobilities and activation energies have been calculated for different charging/discharging conditions. For unaged samples the reproducibility of the results was poor while for the aged polyethylene it was quite good, meaning that aging helps conditioning. In the electrically aged LDPE there is a decrease of conductivity and the broad peak of the non-isothermal spectra shows a slight shift towards higher temperatures when compared with the data found in the thermally aged polymer.

Low-density polyethylene (LDPE) films were thermally aged in a sodium chloride aqueous solution at constant temperature (thermal aging). Some of the samples were simultaneously immersed in solution and subjected to an electric AC field (electrical aging). The dielectric relaxation spectra at 30 degreesC in the range of 10(-5) Hz to 10(5) Hz were obtained for unaged and aged samples. For the low frequency (LF) region (10(-5) Hz to 10(-1) Hz) the time domain technique was used. A lock-in amplifier was used for the 10(-1) Hz to 10(1) Hz medium frequency (MF) region. While for the high frequency (HF), 10(-1) Hz to 10(5) Hz, RLC bridge measurements were performed. The main differences can be seen between electrically, thermally aged and unaged LDPE in the HF and LF regions. The LF peak is a broad peak related to localized space charge injection driven by the electric field. For electrically aged samples this peak increases in an earlier stage of electrical aging, decreasing afterwards. While in thermally aged samples the peak amplitude always increases with aging time. Finally the HF shows the beginning of a peak due to the gamma and beta transitions. This peak decreases with aging disappearing for the most aged samples.

Low-density polyethylene (LDPE) films were thermally aged in a sodium chloride aqueous solution at constant temperature (thermal aging). Some of the samples were simultaneously immersed in solution and subjected to an electric AC field (electrical aging). The dielectric relaxation spectra at 30 degreesC in the range of 10(-5) Hz to 10(5) Hz were obtained for unaged and aged samples. For the low frequency (LF) region (10(-5) Hz to 10(-1) Hz) the time domain technique was used. A lock-in amplifier was used for the 10(-1) Hz to 10(1) Hz medium frequency (MF) region. While for the high frequency (HF), 10(-1) Hz to 10(5) Hz, RLC bridge measurements were performed. The main differences can be seen between electrically, thermally aged and unaged LDPE in the HF and LF regions. The LF peak is a broad peak related to localized space charge injection driven by the electric field. For electrically aged samples this peak increases in an earlier stage of electrical aging, decreasing afterwards. While in thermally aged samples the peak amplitude always increases with aging time. Finally the HF shows the beginning of a peak due to the gamma and beta transitions. This peak decreases with aging disappearing for the most aged samples.

A new experimental procedure combining usual isothermal DC charging and discharging with non-isothermal current measurements has been recently proposed. It is mainly suitable for very high insulating polymers and it was successfully applied to the study of space charge trapping and transport in low-density polyethylene. The analysis of the isothermal currents revealed the presence of different traps whose characteristic (de)trapping times can be deduced. The isothermal procedures allowed the selective charging of the sample. By choosing the charging field and the ratio of charge/discharge times, non-isothermal analysis permitted the differentiation of three or four peaks (at approximate to50degreesC, approximate to65degreesC, approximate to70degreesC and approximate to85degreesC) associated with charge detrapping from surface or near-surface (<20 mum) traps. These traps have activation energies between 0.21 and 1.54 eV. The mobility at 30degreesC is around 5 x 10(-16) m(2) V-1 s(-1). Samples had to be conditioned before each experiment in order to obtain reproducible results.

A new experimental procedure combining usual isothermal DC charging and discharging with non-isothermal current measurements has been recently proposed. It is mainly suitable for very high insulating polymers and it was successfully applied to the study of space charge trapping and transport in low-density polyethylene. The analysis of the isothermal currents revealed the presence of different traps whose characteristic (de)trapping times can be deduced. The isothermal procedures allowed the selective charging of the sample. By choosing the charging field and the ratio of charge/discharge times, non-isothermal analysis permitted the differentiation of three or four peaks (at approximate to50degreesC, approximate to65degreesC, approximate to70degreesC and approximate to85degreesC) associated with charge detrapping from surface or near-surface (<20 mum) traps. These traps have activation energies between 0.21 and 1.54 eV. The mobility at 30degreesC is around 5 x 10(-16) m(2) V-1 s(-1). Samples had to be conditioned before each experiment in order to obtain reproducible results.

Low density polyethylene (LDPE) films kept in a sodium chloride aqueous solution, were aged under a high AC electrical field. The films were prepared from press moulding of LDPE pellets with small amounts of antioxidants. The dielectric spectra at 30 degreesC in the range of 10(-5) Hz to 105 Hz were obtained prior and after ageing. Three different experimental techniques were used to obtain the full spectrum. For the low frequency (LF) region (10(-5) Hz to 10(-1) Hz) the time domain technique was used (charge and discharge currents were also measured). The measuring device used for the 10(-1) Hz to 10(1) Hz medium frequency (MF) region was a lock-in amplifier. While for the high frequency (HF), 10(-1) Hz to 10(5) Hz, RLC bridge measurements were performed. Differences can be seen between aged and unaged PE. The region showing less changes with ageing is the MF region where the peak of the unaged samples seems to become less defined with ageing time. This peak is probably due to additives and impurities (such as antioxidants) that will tend to slowly diffuse out with time. The LF peak is a broad peak related to localised space charge injection driven by the electric field. This peak increases in an earlier stage of ageing decreasing afterwards possibly when the polymer becomes more conductive. Finally the HF shows the beginning of a peak due to gamma and beta transitions. The later is related to dipolar rotation of carbonyl groups in amorphous polymer regions, while the former is associated to crankshaft motions in the main polymer chain. This peak decreases with ageing disappearing for the most aged samples. This could also be explained if the sample becomes more conductive.

Low density polyethylene (LDPE) films kept in a sodium chloride aqueous solution, were aged under a high AC electrical field. The films were prepared from press moulding of LDPE pellets with small amounts of antioxidants. The dielectric spectra at 30 degreesC in the range of 10(-5) Hz to 105 Hz were obtained prior and after ageing. Three different experimental techniques were used to obtain the full spectrum. For the low frequency (LF) region (10(-5) Hz to 10(-1) Hz) the time domain technique was used (charge and discharge currents were also measured). The measuring device used for the 10(-1) Hz to 10(1) Hz medium frequency (MF) region was a lock-in amplifier. While for the high frequency (HF), 10(-1) Hz to 10(5) Hz, RLC bridge measurements were performed. Differences can be seen between aged and unaged PE. The region showing less changes with ageing is the MF region where the peak of the unaged samples seems to become less defined with ageing time. This peak is probably due to additives and impurities (such as antioxidants) that will tend to slowly diffuse out with time. The LF peak is a broad peak related to localised space charge injection driven by the electric field. This peak increases in an earlier stage of ageing decreasing afterwards possibly when the polymer becomes more conductive. Finally the HF shows the beginning of a peak due to gamma and beta transitions. The later is related to dipolar rotation of carbonyl groups in amorphous polymer regions, while the former is associated to crankshaft motions in the main polymer chain. This peak decreases with ageing disappearing for the most aged samples. This could also be explained if the sample becomes more conductive.

Thin films of low density polyethylene (LDPE) and crosslinked polyethylene (XLPE) were aged under an AC electric field while kept in sodium chloride aqueous solution. After aging the samples showed water trees (localized damaged with the appearance of hydrophilic ramified structures whose size ranges from a few microns to I mm). Some of the samples suffered dielectric breakdown showing small channels (1-2 mm. diameter) crossing the film and sometimes also signs of carbonization. In order to identify the oxidation mechanisms contributing to aging, FTIR was used to analyze both unaged and aged specimens. Comparing between unaged and aged LDPE an increase in the FTIR spectrum for bands at 1720 cm(-1), 1640 cm(-1) and 1590 cm(-1) was visible for the aged samples. The first region corresponds to carbonyl groups (C=O bonds) resulting from oxidation (most probably ketones). While the second one is related to carbon double bonds formed due to chain scission. Finally the third one is due to carboxylates. For the XLPE the analysis is more difficult. Besides aging it needs to be taken into account the by-products of crosslinking that will tend also to diffuse out with time. The main effect of aging is an increase in the concentration of 1640 cm(-1) band (C=C bonds). For the water treed regions dry and wet samples were compared. In the wet ones the absorbance is larger for the 3380 cm(-1) exhibiting, as expected, water absorption in the water treed regions (hydrophilic characteristics were increased).

Thin films of low density polyethylene (LDPE) and crosslinked polyethylene (XLPE) were aged under an AC electric field while kept in sodium chloride aqueous solution. After aging the samples showed water trees (localized damaged with the appearance of hydrophilic ramified structures whose size ranges from a few microns to I mm). Some of the samples suffered dielectric breakdown showing small channels (1-2 mm. diameter) crossing the film and sometimes also signs of carbonization. In order to identify the oxidation mechanisms contributing to aging, FTIR was used to analyze both unaged and aged specimens. Comparing between unaged and aged LDPE an increase in the FTIR spectrum for bands at 1720 cm(-1), 1640 cm(-1) and 1590 cm(-1) was visible for the aged samples. The first region corresponds to carbonyl groups (C=O bonds) resulting from oxidation (most probably ketones). While the second one is related to carbon double bonds formed due to chain scission. Finally the third one is due to carboxylates. For the XLPE the analysis is more difficult. Besides aging it needs to be taken into account the by-products of crosslinking that will tend also to diffuse out with time. The main effect of aging is an increase in the concentration of 1640 cm(-1) band (C=C bonds). For the water treed regions dry and wet samples were compared. In the wet ones the absorbance is larger for the 3380 cm(-1) exhibiting, as expected, water absorption in the water treed regions (hydrophilic characteristics were increased).