Carmo Lança

Cross-linked polyethylene (XLPE) is currently widely used as an insulating material for power cables due to its good physical properties, however when in use it undergoes an electrical ageing process. Its ability to trap electric charge can give rise to space charge accumulation in the bulk of the polymer and produce localised electric stresses that can lead to cable failure, since the electric field will be increased above the design stress in some regions favouring the initiation of degradation there. In this work the PEA (pulsed electro-acoustic) method was used to compare the charge dynamics in three samples (XLPE cable peelings) aged in different ways (electrothermally in the laboratory, field aged in service and thermally aged in the laboratory). Very different transient behavior was found depending upon the ageing history. This is related to differences in the migration of chemical species in the insulation layer, which are known to act as charge traps. All materials showed heterocharge peaks when the space charge reached stability, the magnitude of which seems to be related to the severity of the ageing.

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.

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.

The isothermal charging current and the isothermal discharging current in low mobility materials 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. 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 to charge injection or extraction at the metal-dielectric interface and a reverse current related to the charge trapped into the shallow superficial or near superficial states of the dielectric and which can move at the interface in the opposite way that occurring during injection. Two important parameters can be determined (i) the highest value of the relaxation time for the polarization mechanisms which are involved into the transient current and (ii) the height of the potential barrier W-0 at the metal-dielectric interface. The experimental data demonstrate that there is no threshold field for electron injection/extraction at a metal-dielectric interface.

During electric polarization charge is injected into the material. The structure is decorated with space charge and during the subsequent heating an apparent peak and the genuine peaks that are related to dipole randomization and charge detrapping are observed. The method is used here to analyze the molecular movements in polyimide in the temperature range from 293 to 623 K. Two weak relaxations have been observed around 337 K and around 402 K. The electrical conductivity changes with temperature in agreement with the Arrhenius law only below (W= (0.84 +/- 0.03) eV) and above ( W (0.82 +/- 0.03) eV) the temperature range where the beta relaxation is observed. The variation of the electrical conductivity with temperature, in the range of the beta relaxation, is controlled by the variation of the charge currier mobility with temperature and it shows a non-Arrhenius behavior. We suggest that the beta(1) sub-glass relaxation is related to the rotation or oscillation of phenyl groups and the beta(2) sub-glass relaxation is related to the rotation or oscillation of the imidic ring. At higher temperatures an apparent peak was observed. The relaxation time of the trapped charge, at 573 K, is high than 8895 s. (C) 2010 Elsevier B.V. All rights reserved.

The thermally stimulated discharge current (TSDC.) method is a very sensitive and a very selective technique to analyze dipole disorientation and the movement of de-trapped space charge (SC). We have proposed a variant of the TSDC method, namely the final thermally stimulated discharge current (FTSDC) technique. flee experimental conditions can be selected so that the FTSDC is mainly determined by the SC de-trapping. The temperatures of the maximum intensity of the fractional polarization peaks obtained at low temperature, in the range of the local (secondary) relaxation, are in general about 10 to 20 K above the poling temperature. Measurements of the FTSDC in a wide temperature range demonstrate the existence of an apparent peak at a temperature T-ma shifted with about 10 to 30 K above the charging temperature T-c. The shift of T-ma with respect to T-c depends on the experimental conditions. The peak width at the half maximum intensity decreases as T-c increases and the thermal apparent activation energy increases. The variations are not monotonous revealing the temperature range where the molecular motion is stronger and consequently the charge trapping and de-trapping processes are affected. Our results demonstrate that there is a strong similarity between the elementary peaks obtained by the two methods, and the current is mainly determined by SC de-trapping. Even the best elementary peaks are not fitted very well by the analytical equation, indicating that the hypothesis behind this equation have to be reconsidered.

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 measured isothermal charging and discharging 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. 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 through the dielectric materials. 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. By fitting the experimental data, 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 W-0 of the potential barrier at the metal-dielectric interface immediately after the step voltage is applied. Only the initial part of the measured isothermal charging or discharging current can be used to obtain information about the polarization processes. By transforming the time-domain data into the frequency domain, a maximum for the imaginary part of the dielectric permittivity is obtained, in good agreement with the data obtained from AC dielectric measurements and the finally thermally stimulated discharge current measurements. (C) 2009 Elsevier B.V. All rights reserved.

The electrical methods used to study the molecular movements are based on the movement of the dipoles under DC or AC electric field. We have proposed recently a combined measuring protocol to analyze charge injection/extraction, transport, trapping and de-trapping in polar or non-polar dielectric materials. The method is used here to analyze the molecular movements in polyimide in the temperature range from 293 to 572 K. A strong relaxation was observed around 402 K and a very weak relaxation around 345 K. This is the beta relaxation which is quite complex. As concern the behavior at high temperatures, above the beta relaxation, a high peak was observed that shifts continuously to higher temperatures as the charging temperature and/or the charging field increase. The maximum current of the peak increases and the temperature corresponding to the maximum current increases as the charging temperature and/or the charging field increase, given a direct observation of the so called cross-over effect related to current decay for sample charged at high fields and/or high temperatures.

The final thermally stimulated discharge current (FTSDC) technique can be used to analyze charge trapping and transport in insulating materials. The experimental conditions can be selected so that the FTSDC is mainly determined by the space charge detrapping. Measurements of the FTSDC in a wide temperature range including the local (secondary) beta relaxation and the non-local (primary) cc relaxation, for different polymers, demonstrate the existence of an apparent peak. The shift of peak temperature T-m with respect to the charging temperature T-p is analyzed. The interval T-m - T-p decreases from about 25 K to zero, as T-p approaches the glass transition T-g. T-m - T-p is lower for materials of lower conductivity. The peak width at the half maximum intensity decreases as Tp increases and the thermal apparent activation energy increases. The variations are not monotonous revealing the temperature range where the molecular motion is stronger and consequently the charge trapping and detrapping processes are affected by the strong thermal motion.

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.

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.