Carmo Lança

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.

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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.

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 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.

Opposite results concerning the sign of the parasitic charge accumulated at the metal dielectric contact in RF microelectromechanical systems (MEMS) capacitive switches are found in the literature. The mechanism concerning charge injection/extraction at the metal-dielectric contact and its influence on the pull-in voltage needs to be further clarified. A model-switch, for which only one dimension is in the microns range, is used to study the behaviour of a capacitive RF MEMS switch. The aim is to analyze how the electric charge is injected/extracted into or from the dielectric material under the applied field and to obtain realistic data to understand how this parasitic charge influences the pull-in voltage V-pi and the pull-off voltage V-po. A triangle voltage is employed to measure V-pi and V-po by measuring the isothermal charging/discharging currents. Our results demonstrate that V-pi is strongly dependent on the injected/extracted charge on the free surface of the dielectric. The charge injected/extracted at the bottom side of the dielectric has no influence on the actuation voltage. The charge injected/extracted on the free surface of the dielectric determines an increase of the modulus of V-pi and, eventually, the switch can fail to actuate. An estimation of the charge stored into the material was obtained (i) by measuring the charging current and the discharging current and (ii) from the value of the V-pi. The parasitic charge necessary to keep the bridge stick to the insulator is 5.3 x 10(-4) cm(-2) for our experimental conditions. The modification of the V-pi determined by the stored charge in the dielectric is analyzed. An increase of the relative dielectric permittivity by a factor of 2 produces a decrease of the actuation voltage of 10%. A variation of 30% in the elastic constant determines a variation of about 20% in the V-pi. A voltage threshold for charge injection/extraction was not observed.

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.

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 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 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.

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.