Carmo Lança

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.

The Thermally Stimulated Discharge Current (TSDC) method is a very sensitive technique to analyze the movement of dipoles and of space charge (SC). To increase the selectivity of the method we have proposed a variant of the TSDC method, namely the final thermally stimulated discharge current (FTSDC) technique. The experimental conditions can be selected so that the FTSDC is mainly determined by SC de-trapping. The aim of this paper is to analyze if the elementary peaks obtained by using the two methods can be assumed as elementary Debye peaks and to determine the best experimental conditions to obtain a narrow experimental peak which means to increase the selectivity of the method.

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.

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)).

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).