Carmo Lança

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.

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.

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.

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.

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.

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.

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.

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.

The use of orthopaedic and dental implants is expanding as a consequence of an ageing population and also due to illness or trauma in younger age groups. The implant must be biocompatible, bioactive and interact favourably with the recipient's bone, as rapid osseointegration is key to success. In this work, Ti-6Al-4V plates were coated using the CoBlastTM technique, with hydroxyapatite (HAp) and HAp/BaTiO3 (barium titanate, BT) non-piezoelectric cubic nanopowders (HAp/cBT) and piezoelectric tetragonal micropowders (HAp/tBT). The addition of BT, a piezoelectric ceramic, is a strategy to accelerate osseointegration by using surface electric charges as cues for cells. For comparison with commercial coatings, plates were coated with HAp using the plasma spray technique. Using XRD and FTIR, both plasma spray and CoBlastTM coatings showed crystalline HAp and no presence of by-products. However, the XRD of the plasma-sprayed coatings revealed the presence of amorphous HAp. The average surface roughness was close to the coatings' thickness (≈5 $μ$m for CoBlastTM and ≈13 $μ$m for plasma spray). Cytotoxicity assays proved that the coatings are biocompatible. Therefore, it can be concluded that for HAp-based coatings, CoBlastTM is a viable alternative to plasma spray, with the advantage of facilitating room temperature addition of other ceramics, like piezoelectric BaTiO3.

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.

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)).

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.

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).

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.

The physical properties of the cubic and ferrimagnetic spinel ferrite LiFe5O8 has made it an attractive material for electronic and medical applications. In this work, LiFe5O8 nanosized crystallites were synthesized by a novel and eco-friendly sol-gel process, by using powder coconut water as a mediated reaction medium. The dried powders were heat-treated (HT) at temperatures between 400 and 1000 °C, and their structure, morphology, electrical and magnetic characteristics, cytotoxicity, and magnetic hyperthermia assays were performed. The heat treatment of the LiFe5O8 powder tunes the crystallite sizes between 50 nm and 200 nm. When increasing the temperature of the HT, secondary phases start to form. The dielectric analysis revealed, at 300 K and 10 kHz, an increase of $ε$′ (≈10 up to ≈14) with a tan$δ$ almost constant (≈0.3) with the increase of the HT temperature. The cytotoxicity results reveal, for concentrations below 2.5 mg/mL, that all samples have a non-cytotoxicity property. The sample heat-treated at 1000 °C, which revealed hysteresis and magnetic saturation of 73 emu g−1 at 300 K, showed a heating profile adequate for magnetic hyperthermia applications, showing the potential for biomedical applications.

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.