Carmo Lança

Lately the electrical and dielectric properties of cork and some cork-based materials (commercial and non-commercial) have been studied in order to understand their ability to store electrical charge. The main problem found so far is related to the water content in cork, only of a few % weight. but large enough to influence greatly the conductivity of cork and, consequently, the charge storage capability. To overcome this problem cork has been combined with hydrophobic materials. In this work a commercial wax (paraffin wax) was used to produce a cork/paraffin composite by hot pressing. After milled and mixed natural cork. TetraPak (R) containers waste and paraffin were pressed to make plaques of a new composite. Different concentrations of cork. TetraPak (R) and paraffin, different granules sire, different temperature and pressure were used to produce the samples. The electrical properties of the new composite were measured by the isothermal charging and discharging current method and the results compared to previously ones obtained for natural cork and other derivative products. The new composite has shown to have lower conductivity than the commercial agglomerate. which makes it a better material for charge storage.

Space charge in electrically aged LDPE was studied using a recently developed technique combining isothermal charging and discharging with non-isothermal measurements. Samples were aged in a NaCl aqueous solution at 40degreesC for 1500h under an AC field of 6MV/m (50Hz). The samples were then isothermally DC charged and discharged (both currents recorded). Next a non-isothermal experiment with constant heating rate was performed. Finally the sample was kept at the highest temperature and the final isothermal discharge current registered. The last step has to be carried on for long time to ensure an almost complete discharge of the remnant charge so that results become reproducible and possible to analyze. Selective charging (careful choice of the field, temperature and the ratio of charging/discharging times) revealed the presence of different trapping sites. From the analysis of the isothermal and non-isothermal data the relaxation times and activation energies could be obtained.

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.

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.

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.

Space charge in electrically aged LDPE was studied using a recently developed technique combining isothermal charging and discharging with non-isothermal measurements. Samples were aged in a NaCl aqueous solution at 40degreesC for 1500h under an AC field of 6MV/m (50Hz). The samples were then isothermally DC charged and discharged (both currents recorded). Next a non-isothermal experiment with constant heating rate was performed. Finally the sample was kept at the highest temperature and the final isothermal discharge current registered. The last step has to be carried on for long time to ensure an almost complete discharge of the remnant charge so that results become reproducible and possible to analyze. Selective charging (careful choice of the field, temperature and the ratio of charging/discharging times) revealed the presence of different trapping sites. From the analysis of the isothermal and non-isothermal data the relaxation times and activation energies could be obtained.

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.

Water trees result from ac electrical aging of the polymeric insulation of medium and HV power cables in a humid or wet environment. As suggested by their name, they arise from penetration of water in the polymer. Visual observation with the help of an optical microscope shows tree (bush) type structures. This suggests that water trees might be fractal objects. Calculation of the fractal dimension from experimental samples may confirm the fractal characteristics and also give information on the damage caused to the polymer. In this work images of water trees taken under the optical microscope, dyed by methylene blue and etched for scanning electron microscopy (SEM), were studied in order to estimate the fractal dimension using a box-counting algorithm. The photographs, made using an optical microscope (scale of 100 mum), of the dyed samples were obtained from laboratory-aged low-density polyethylene (LDPE) specimens using accelerated techniques. Different field amplitude and frequency and also time of aging were used and the dimension values were compared. SEM images resulting from aged cross-linked polyethylene (XLPE) cables revealed a structure at a different scale (similar to 3 mum). Each photograph was analyzed to compare regions with and without water trees.

An understanding of space charge build-up in the polymeric insulation of power cables is important in determining how aging occurs and progresses and, also in predicting cable lifetime. In this investigation electric-field induced space charge in peelings from XLPE (cross-linked polyethylene) cables was measured using two different methods: the pulsed electro-acoustic technique (PEA) and the combined procedure of isothermal and non-isothermal charging/discharging currents (FTSDC). These two methods allow the study of space charge in highly insulating materials. Also, since electric fields of different orders of magnitude are applied to the sample in the two methods, it is possible to analyze different characteristics of the space charge traps. Prior to the measurements the samples were subjected to conditioning to remove volatiles. Cable peelings from various brands aged under different conditions (including field aged and thermally aged samples) were studied as received from the manufacturers. Some of the samples have undergone further ageing in AC electric field (50Hz) for 1000h to see the influence of further ageing on space charge build-up. The results for the different types of samples are compared in an attempt to correlate different ageing parameters.

Cork is a natural cellular and electrically insulating material which may have the capacity to store electric charges on or in its cell walls. Since natural cork has many voids, it is difficult to obtain uniform samples with the required dimensions. Therefore, a more uniform material, namely commercial cork agglomerate, usually used for floor and wall coverings, is employed in the present study. Since we know from our previous work that the electrical properties of cork are drastically affected by absorbed and adsorbed water, samples were protected by means of different polymer coatings (applied by spin-coating or soaking). Corona charging and isothermal charging and discharging currents were used to study the electrical trapping and detrapping capabilities of the samples. A comparison of the results leads to the conclusion that the most promising method for storing electric charges in this cellular material consists of drying and coating or soaking with a hydrophobic, electrically insulating polymer such as polytetraflouroethylene (Teflon (R)). (c) 2007 Elsevier B.V. All rights reserved.

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.

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.

In PE films aged under electric field the crystallisation of water (and melting of ice) has been studied by quadrupolar NMR, this technique allows one to determine the concentration of water as low as 10(-4). It is shown that the pore dimensions of the tracks forming the water trees of the order of 2.5 nm, are independent of the ageing time. The mobility of water in these water trees and in porous glass, of similar pore dimensions, are compared. (C) 2000 Elsevier Science Ltd. All rights reserved.

In PE films aged under electric field the crystallisation of water (and melting of ice) has been studied by quadrupolar NMR, this technique allows one to determine the concentration of water as low as 10(-4). It is shown that the pore dimensions of the tracks forming the water trees of the order of 2.5 nm, are independent of the ageing time. The mobility of water in these water trees and in porous glass, of similar pore dimensions, are compared. (C) 2000 Elsevier Science Ltd. All rights reserved.