Carmo Lança

For the characterization of the new materials and for a better understanding of the connection between structure and properties it is necessary to use more and more sensible methods to study molecular movement at nanometric scale. This paper presents the experimental basis for a new electrical method to study the fine molecular movements at nanometric scale in dielectric materials. The method will be applied for polar and non-polar materials characterization. Traditionally, the electrical methods used to study the molecular movements are based on the movements of the dipoles that are parts of the molecules. We have proposed recently a combined protocol to analyze charge injection/extraction, transport, trapping and detrapping in low mobility materials. The experimental results demonstrate that the method can be used to obtain a complex thermogram which contains information about all molecular movements, even at nanoscopic level. Actually during the charging process we are decorating the structure with space charge and during the subsequent heating we are observing an apparent peak and the genuine peaks that are related to charge de-trapping determined by the molecular movement. The method is very sensitive, very selective and allows to determinate the parameters for local and collective molecular movements, including the temperature dependence of the activation energy and the relaxation time.

Hydroxyapatite [Hap; Ca10(PO4)6(OH)2) and b-tricalcium phosphate [b-TCP; Ca3(PO4)2] are biocompatible calcium phosphates used in skeletal surgery. The natural HAp is one of the main components of bone and, as a synthetic material, has been widely used for bone replacement presenting good bioactivity. Nevertheless synthetic HAp presents a slow in vivo degradation rate which is disadvantageous for bone’s reparative process. b-TCP has also good osteogenic characteristics presenting the ability to form strong bonds with the bone however, its degradation rate is too fast [1]. Therefore, a composite combining these two ceramics is valuable as it exhibits a suitable degradation rate. Because of the piezoelectric properties of bone it is known that electrical polarization of calcium phosphates can enhance the bioactivity and biointegration of implants [2]. Previous studies have already showed that HAp/b-TCP ceramics can be electrically polarized and that electrical polarization enhances osteogenesis in the early stage of the implantation process. However further studies are required to understand, optimize and improve the polarization technique [1]. In this work a commercial biphasic ceramic powders were pressed in a mold at 200 MPa to produce disc shaped samples. Afterwards, the samples were sintered at temperatures from 950ºC to 1150ºC and the influence of the heat treatment in the electrical polarization and subsequent bioactivity was investigated. The samples were polarized under a high DC electric field at relatively lower temperature (200oC) compared to previous studies and the stability of polarization was tested using TSDC (thermally depolarization currents) measurements. It was studied the influence of the water, initially present in the material, in the total charge deposited during polarization, its stability and its relation with heat treatment after pressing. The influence of the addition of b-TCP on sample’s stored charge was also evaluated. Finally bioactivity tests in a simulated body fluid solution were made taking into account the signal of the charge in each surface of the disc samples so that the results could be compared to previous ones.

The final thermally stimulated discharge current method allows a better selection of the experimental conditions for sample polarization. By decreasing the ratio between the charging time and the discharging time, the apparent peak is of the same order of magnitude as the genuine peaks and there is only a partial overlap between then. Two peaks have been identified for polyamide 11, one associated with the glass transition around 60 °C and the second associated with the Curie transition around 96 °C.

The final thermally stimulated discharge current method allows a better selection of the experimental conditions for sample polarization. By decreasing the ratio between the charging time and the discharging time, the apparent peak is of the same order of magnitude as the genuine peaks and there is only a partial overlap between then. Two peaks have been identified for polyamide 11, one associated with the glass transition around 60 degrees C and the second associated with the Curie transition around 96 degrees C.

Cork is a cellular biomaterial that has unique characteristics that make it suitable for many types of applications. Since it is also an electrical insulator, the study of its electrical and dielectric properties can lead to new interesting applications. The moisture present in cork and derivatives has a very important role on the dielectric properties. In this work a composite made of both recycled cork and TetraPak (R) used containers was studied and compared with other cork products. The dielectric relaxation spectra of natural cork (as received), commercial cork agglomerate and of a composite cork/Tetrapak (R) was investigated in the temperature range of -50 to 120 degrees C and in the frequency range of 10(-1) Hz-2 MHz. For some samples of the composite a small amount of paraffin was added. The highest values for the imaginary part of the dielectric permittivity were found for the commercial material and the composite without paraffin. The lowest was found for the cork/TetraPak (R)/paraffin composite. The influence of humidity content was investigated for the composite with wax. Natural cork shows a peak around 80 degrees C (not seen in the derivative materials). The commercial agglomerate and the cork/TetraPak (R)/paraffin composite show a peak around 40-50 degrees C. In the composite this peak becomes smaller as humidity is removed. (C) 2009 Elsevier B.V. All rights reserved.

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.

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.

There is a sustained interest both from theoretical and from practical points of view to understand the isothermal charging and the isothermal discharging currents in dielectrics. The measured currents are analyzed either in terms of polarization mechanisms or in terms of charge injection/extraction at the metal-dielectric interface and the conduction current through the dielectric material. As long as we do not know the nature of the origin of the current, it is not clear what information we can get by analyzing the experimental data. We propose to measure the open-circuit isothermal charging and discharging currents just to overpass the difficulties related to the analysis of the conduction mechanisms in dielectric materials. We demonstrate that besides a polarization current, there is a current related with charge injection or extraction at the metal-dielectric contact and a reverse current related to the charge trapped into the superficial trap states of the dielectric and that can jump at the interface in a reverse way. An analytical expression for the current is proposed. By fitting the experimental data to this analytical equation, two important parameters can be determined: (i) the highest value of the relaxation time for the polarization mechanisms still involved into the transient current and (ii) the height of the potential barrier W-0 at the metal-dielectric interface at the initial time when the step voltage is applied. The value obtained for Al-polyethylene terephthalate interface is (0.43 +/- 0.02) eV. For a charging voltage of 220 V there are 6x10(14) trapped electrons/m(2). (c) 2008 American Institute of Physics.

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.

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.