Carmo Lança

Using a recently developed procedure combining isothermal and non-isothermal current measurements space charge trapping and transport in LDPE was successfully studied. Unaged, thermally and electrically aged samples were investigated. The samples were conditioned before each measurement in order to obtain reproducible results. In the non-isothermal measurements appeared a broad peak (40degreesC to 50degreesC) that was possible to decompose into two or three peaks (35, 45 and 65degreesC). At even higher temperature another peak was sometimes present (85degreesC) depending on the prior sample conditioning. The space charge is trapped near the surface in deep traps (maximum depth of approximate to 15 mum). Relaxation times, mobilities and activation energies have been calculated for different charging/discharging conditions. For unaged samples the reproducibility of the results was poor while for the aged polyethylene it was quite good, meaning that aging helps conditioning. In the electrically aged LDPE there is a decrease of conductivity and the broad peak of the non-isothermal spectra shows a slight shift towards higher temperatures when compared with the data found in the thermally aged polymer.

Using a recently developed procedure combining isothermal and non-isothermal current measurements space charge trapping and transport in LDPE was successfully studied. Unaged, thermally and electrically aged samples were investigated. The samples were conditioned before each measurement in order to obtain reproducible results. In the non-isothermal measurements appeared a broad peak (40degreesC to 50degreesC) that was possible to decompose into two or three peaks (35, 45 and 65degreesC). At even higher temperature another peak was sometimes present (85degreesC) depending on the prior sample conditioning. The space charge is trapped near the surface in deep traps (maximum depth of approximate to 15 mum). Relaxation times, mobilities and activation energies have been calculated for different charging/discharging conditions. For unaged samples the reproducibility of the results was poor while for the aged polyethylene it was quite good, meaning that aging helps conditioning. In the electrically aged LDPE there is a decrease of conductivity and the broad peak of the non-isothermal spectra shows a slight shift towards higher temperatures when compared with the data found in the thermally aged polymer.

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.

Bone grafting and surgical interventions related with orthopaedic disorders consist in a big business, generating large revenues worldwide every year. There is a need to replace the biomaterials that currently still dominate this market, i.e., autografts and allografts, due to their disadvantages, such as limited availability, need for additional surgeries and diseases transmission possibilities. The most promising replacement materials are biomaterials with bioactive properties, such as the calcium phosphate-based bioceramics group. The bioactivity of these materials, i.e., the rate at which they promote the growth and directly bond with the new host biological bone, can be enhanced through their electrical polarization.In the present work, the electrical polarization features of pure hydroxyapatite (Hap), pure β-tricalcium phosphate (β-TCP) and biphasic hydroxyapatite/β-tricalcium phosphate composites (HTCP) were analyzed by measuring thermally stimulated depolarization currents (TSDC). The samples were thermoelectrically polarized at 500. °C under a DC electric field with a magnitude of 5. kV/cm. The biphasic samples were also polarized under electric fields with different magnitudes: 2, 3, 4 and 5. kV/cm. Additionally, the depolarization processes detected in the TSDC measurements were correlated with dielectric relaxation processes observed in impedance spectroscopy (IS) measurements.The results indicate that the β-TCP crystalline phase has a considerable higher ability to store electrical charge compared with the Hap phase. This indicates that it has a suitable composition and structure for ionic conduction and establishment of a large electric charge density, providing great potential for orthopaedic applications.

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 623K. Two weak relaxations have been observed around 337K and around 402K. 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 β relaxation is observed. The variation of the electrical conductivity with temperature, in the range of the β relaxation, is controlled by the variation of the charge currier mobility with temperature and it shows a non-Arrhenius behavior. We suggest that the β1 sub-glass relaxation is related to the rotation or oscillation of phenyl groups and the β2 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 573K, is high than 8895s.

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.

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.