Extension of electrochemically active sites in SOFCs and SOECs

Solid oxide fuel (SOFCs) and electrolyzer (SOECs) cells have been promoted as promising technologies for the stabilization of fuel supply and usage in future green energy systems. SOFCs are devices that produce electricity by the oxidation of hydrogen or hydrocarbon fuels with high efficiency. Conversely, SOECs can offer the reverse reaction, where synthetic fuels can be generated by the input of renewable electricity. Due to this similar but inverse nature of SOFCs and SOECs, these devices have traditionally been constructed from comparable materials. Nonetheless, several limitations have hindered the entry of SOFCs and SOECs into the marketplace. One of the most debilitating is associated with chemical interreactions between cell components that can lead to poor longevities at high working temperatures and/or depleted electrochemcial performance. Normally such interreactions are countered by the introduction of thin, purely ionic conducting, buffer layers between the electrode and electrolyte interface. The objective of this thesis is to assess if possible improvements in electrode kinetics can also be obtained by modifying the transport properties of these buffer layers by the introduction of multivalent cations. The introduction of minor electronic conductivity in the surface of the electrolyte material has previously been shown to radically enhance the electrochemically active area for oxygen exchange, reducing polarization resistance losses. Hence, the current thesis aims to extend this knowledge to tailor a bi-functional buffer layer that can prevent chemical interreaction while also enhancing electrode kinetics.The thesis selects a typical scenario of an yttria stabilized zirconia electrolyte combined with a lanthanide containing oxygen electrode. Gadolinium, terbium and praseodymium doped cerium oxide materials have been investigated as potential buffer layers. The mixed ionic electronic conducting (MIEC) properties of the doped-cerium materials have been analyzed and collated. A detailed analysis is further presented of the impact of the buffer layers on the kinetics of the oxygen electrode in SOFC and SOEC devices. Special focus is made to assess for potential links between the transport properties of the buffer layer and subsequent electrode performance. The work also evaluates the electrochemical performance of different K2NiF4 structure cathodes deposited onto a peak performing Pr doped-cerium buffer layer, the influence of buffer layer thickness and the Pr content of the ceria buffer layer. It is shown that dramatic increases in electrode performance can be obtained by the introduction of MIEC buffer layers, where the best performances are shown to be offered by buffer layers of highest ambipolar conductivity. These buffer layers are also shown to continue to offer the bifunctional role to protect from unwanted chemical interactions at the electrode/electrolyte interface.

Tissue healing of immediate implant placement in extraction sockets with titanium versus zirconium oxide implants : an experimental study in the beagle dog

Tese de doutoramento, Medicina Dentária (Periodontologia), Universidade de Lisboa, Faculdade de Medicina Dentária, 2016

Projecto de execução de uma obra de arte

Trabalho de Projecto para obtenção do grau de Mestre em Engenharia na Área de Especialização em Estruturas

Pontes integrais: estado da arte

Dissertação para obtenção do grau de mestre em Engenharia Civil

Studies on Catalysis by Vanadia Supported On Metal Oxides

Catalysis is an essential technology in manufacturing industries. The investigation based on supported vanadia catalysts and it’s sulfated analogues. Vanadia is a transition metal oxide and is used in oxidation reactions in chemical industry. It is more active and selective catalysts on suitable supports. The work deals with preparation of vanadia incorporated tin oxide and zirconia systems by wet impregnation. Physico-chemical characterization using instrumental techniques like BET etc. The surface acidic properties were determined by the ammonia TPD studies, Perylene absorption studies and Cumene conversion reaction. The catalytic activities of the prepared systems are tested by Friedel-Crafts benzylation of arenes and Bechmann rearrangement of Cyclohexanol oxime. Here the rector reactions are relatively rare. So to test the application of the catalyst systems for the selective oxidation of cyclohexanol to cyclohexanone and finally evaluate the catalytic activity of the systems for the vapour phase oxidative dehydrogenation of Ethylbenzene, which leads to the formation of Industrially important compound ‘styrene’ is another objective of this work

Acid-Base, Surface electron donating and catalytic properties of binary oxides of Zr with rare earth elements

Department of Applied Chemistry, Cochin University of Science and Technology

Characterization of Selected Photonic Materials and Systems Using Photoacoustic Technique

The photoacoustic investigations carried out on different photonic materials are presented in this thesis. Photonic materials selected for the investigation are tape cast ceramics, muItilayer dielectric coatings, organic dye doped PVA films and PMMA matrix doped with dye mixtures. The studies are performed by the measurement of photoacoustic signal generated as a result of modulated cw laser irradiation of samples. The gas-microphone scheme is employed for the detection of photoacoustic signal. The different measurements reported here reveal the adaptability and utility of the PA technique for the characterization of photonic materials.Ceramics find applications in the field of microelectronics industry. Tape cast ceramics are the building blocks of many electronic components and certain ceramic tapes are used as thermal barriers. The thermal parameters of these tapes will not be the same as that of thin films of the same materials. Parameters are influenced by the presence of foreign bodies in the matrix and the sample preparation technique. Measurements are done on ceramic tapes of Zirconia, Zirconia-Alumina combination, barium titanate, barium tin titanate, silicon carbide, lead zirconate titanateil'Z'T) and lead magnesium niobate titanate(PMNPT). Various configurations viz. heat reflection geometry and heat transmission geometry of the photoacoustic technique have been used for the evaluation of different thermal parameters of the sample. Heat reflection geometry of the PA cell has been used for the evaluation of thermal effusivity and heat transmission geometry has been made use of in the evaluation of thermal diffusivity. From the thermal diffusivity and thermal effusivity values, thermal conductivity is also calculated. The calculated values are nearly the same as the values reported for pure materials. This shows the feasibility of photoacoustic technique for the thermal characterization of ceramic tapes.Organic dyes find applications as holographic recording medium and as active media for laser operations. Knowledge of the photochemical stability of the material is essential if it has to be used tor any of these applications. Mixing one dye with another can change the properties of the resulting system. Through careful mixing of the dyes in appropriate proportions and incorporating them in polymer matrices, media of required stability can be prepared. Investigations are carried out on Rhodamine 6GRhodamine B mixture doped PMMA samples. Addition of RhB in small amounts is found to stabilize Rh6G against photodegradation and addition of Rh6G into RhB increases the photosensitivity of the latter. The PA technique has been successfully employed for the monitoring of dye mixture doped PMMA sample. The same technique has been used for the monitoring of photodegradation ofa laser dye, cresyl violet doped polyvinyl alcohol also.Another important application of photoacoustic technique is in nondestructive evaluation of layered samples. Depth profiling capability of PA technique has been used for the non-destructive testing of multilayer dielectric films, which are highly reflecting in the wavelength range selected for investigations. Eventhough calculation of thickness of the film is not possible, number of layers present in the system can be found out using PA technique. The phase plot has clear step like discontinuities, the number of which coincides with the number of layers present in the multilayer stack. This shows the sensitivity of PA signal phase to boundaries in a layered structure. This aspect of PA signal can be utilized in non-destructive depth profiling of reflecting samples and for the identification of defects in layered structures.

Thermal characterization of ceramic tapes using photoacoustic effect

Thermal characterization of alumina–zirconia and zirconia ceramic tapes using a photoacoustic technique is presented. A transmission-mode geometry is employed for the measurement of thermal diffusivity while a reflection-mode geometry is used for the measurement of thermal effusivity. In both these geometries, the same open photoacoustic cell is used. From the measured values of thermal diffusivity and thermal effusivity, the thermal conductivity value has also been evaluated.

Katalizatory złotowo-miedziowe na nośnikach cerowych, cyrkonowych i cerowo-cyrkonowych – preparatyka, charakterystyka i zastosowanie w procesach utleniania

Wydział Chemii

Immobilisation of phenanthroline-bis triazine(c1-btphen) on magnetic nanoparticles for co-extraction of americium(III) and europium(III)

The present work reports a convenient route for the immobilisation of a phenanthroline-bis triazine (C1-BTPhen) group on the surface of zirconia-coated maghemite (γ-Fe2O3) magnetic nanoparticles. The magnetic nanoparticles functionalized with C1-BTPhen were able to co-extract Am(III) and Eu(III) from nitric acid (HNO3). The extraction efficiency of these C1-BTPhen-functionalized magnetic nanoparticles for both Am(III) and Eu(III) was 20% at 4M HNO3. The interaction between C1-BTPhen and metal cations is reversible. These functionalized magnetic nanoparticles can be used for the co-extraction of traces of Am(III) and Eu(III).

Use of checkerboard DNA-DNA hybridization to evaluate the internal contamination of dental implants and comparison of bacterial leakage with cast or pre-machined abutments

To evaluate the checkerboard DNA-DNA hybridization method for detection and quantitation of bacteria from the internal parts of dental implants and to compare bacterial leakage from implants connected either to cast or to pre-machined abutments. Nine plastic abutments cast in a Ni-Cr alloy and nine pre-machined Co-Cr alloy abutments with plastic sleeves cast in Ni-Cr were connected to Branemark-compatible implants. A group of nine implants was used as control. The implants were inoculated with 3 mu l of a solution containing 10(8) cells/ml of Streptococcus sobrinus. Bacterial samples were immediately collected from the control implants while assemblies were completely immersed in 5 ml of sterile Tripty Soy Broth (TSB) medium. After 14 days of anaerobic incubation, occurrence of leakage at the implant-abutment interface was evaluated by assessing contamination of the TSB medium. Internal contamination of the implants was evaluated with the checkerboard DNA-DNA hybridization method. DNA-DNA hybridization was sensitive enough to detect and quantify the microorganism from the internal parts of the implants. No differences in leakage and in internal contamination were found between cast and pre-machined abutments. Bacterial scores in the control group were significantly higher than in the other groups (P < 0.05). Bacterial leakage through the implant-abutment interface does not significantly differ when cast or pre-machined abutments are used. The checkerboard DNA-DNA hybridization technique is suitable for the evaluation of the internal contamination of dental implants although further studies are necessary to validate the use of computational methods for the improvement of the test accuracy. To cite this article:do Nascimento C, Barbosa RES, Issa JPM, Watanabe E, Ito IY, Albuquerque Junior RF. Use of checkerboard DNA-DNA hybridization to evaluate the internal contamination of dental implants and comparison of bacterial leakage with cast or pre-machined abutments.Clin. Oral Impl. Res. 20, 2009; 571-577.doi: 10.1111/j.1600-0501.2008.01663.x.

Correlation between vertical misfits and stresses transmitted to implants from metal frameworks

An inappropriate prosthetic fit could cause stress over the interface implant/bone. The objective of this study was to compare stresses transmitted to implants from frameworks cast using different materials and to investigate a possible correlation between vertical misfits and these stresses. Fifteen one-piece cast frameworks simulating bars for fixed prosthesis in a model with five implants were fabricated and arranged into three different groups according to the material used for casting: CP Ti (commercially pure titanium), Co-Cr (cobalt-chromium) or Ni-Cr-Ti (nickel-chromium-titanium) alloys. Each framework was installed over the metal model with all screws tightened to a 10 N cm torque and then, vertical misfits were measured using an optical microscope. The stresses transmitted to implants were measured using quantitative photoelastic analysis in values of maximum shear stress (T), when each framework was tightened to the photoelastic model to a 10 N cm standardized torque. Stress data were statistically analyzed using one-way ANOVA and Tukey`s test and correlation tests were performed using Pearson`s rank correlation (alpha = 0.05). Mean and standard deviation values of vertical misfit are presented for CP Ti (22.40 +/- 9.05 mu m), Co-Cr (66.41 +/- 35.47 mu m) and Ni-Cr-Ti (32.20 +/- 24.47 mu m). Stresses generated by Co-Cr alloy (tau = 7.70 +/- 2.16 kPa) were significantly higher than those generated by CP Ti (tau = 5.86 +/- 1.55 kPa, p = 0.018) and Ni-Cr-Ti alloy (tau =5.74 +/- 3.05 kPa, p = 0.011), which were similar (p = 0.982). Correlations between vertical misfits and stresses around the implants were not significant as for any evaluated materials. (C) 2011 Elsevier Ltd. All rights reserved.

Equicrestal and Subcrestal Dental Implants: A Histologic and Histomorphometric Evaluation of Nine Retrieved Human Implants

Background: Stability of pen-implant crestal bone plays a relevant role relative to the presence or absence of interdental papilla. Several factors can contribute to the crestal bone resorption observed around two-piece implants, such as the presence of a microgap at the level of the implant abutment junction, the type of connection between implant and prosthetic components, the implant positioning relative to the alveolar crest, and the interimplant distance. Subcrestal positioning of dental implants has been proposed to decrease the risk of exposure of the metal of the top of the implant or of the abutment margin, and to get enough space in a vertical dimension to create a harmoniously esthetic emergence profile. Methods: The present retrospective histologic study was performed to evaluate dental implants retrieved from human jaws that had been inserted in an equicrestal or subcrestal position. A total of nine implants were evaluated: five of these had been inserted in an equicrestal position, whereas the other four had been positioned subcrestally (1 to 3 mm). Results: In all subcrestally placed implants, preexisting and newly formed bone was found over the implant shoulder. In the equicrestal implants, crestal bone resorption (0.5 to 1.5 mm) was present around all implants. Conclusion: The subcrestal position of the implants resulted in bone located above the implant shoulder. J Periodontol 2011;82:708-715.

Effects of Early Functional Loading on Maintenance of Free Autogenous Bone Graft and Implant Osseointegration: An Experimental Study in Dogs

Purpose: The aim of the present study was to investigate the healing, integration, and maintenance of autogenous onlay bone grafts and implant osseointegration either loaded in the early or the delayed stages. Materials and Methods: A total of 5 male clogs received bilateral blocks of onlay bone grafts harvested from the contralateral alveolar ridge of the mandible. On one side, the bone block was secured by 3 dental implants (3.5 mm x 13.0 mm, Osseospeed; Astra Tech AB, Molndal, Sweden). Two implants at the extremities of the graft were loaded 2 clays after installation by abutment connection and prosthesis (simultaneous implant placement group); the implant in the middle remained unloaded and served as the control. On the other side, the block was fixed with 2 fixation screws inserted in the extremities of the graft. Four weeks later, the fixation screws were replaced with 3 dental implants. The loading procedure (delayed implant placement group) was performed 2 clays later, as described for the simultaneous implant placement sites. The animals were sacrificed 12 weeks after the grafting procedure. Implant stability was measured through resonance frequency analysis. The bone volume and density were assessed on computed tomography. The bone to implant contact and bone area in a region of interest were evaluated on histologic slides. Results: The implant stability quotient showed statistical significance in favor of the delayed loaded grafts (P=.001). The bone-to-implant contact (P=.008) and bone area in a region of interest (P=0.005) were significantly greater in the delayed group. Nevertheless, no difference was found in terms of graft volume and density between the early loaded and delayed-loaded approaches. Conclusions: The protocol in which the implant and bone graft were given delayed loading allows for effective quality of implant osseointegration and stabilization, with healing and remodeling occurring in areas near the implant resulting in denser bone architecture. (C) 2010 American Association of Oral and Maxillofacial Surgeons J Oral Maxillofac Sing 68:825-832, 2010

Influence of Post and Resin Cement on Stress Distribution of Maxillary Central Incisors Restored with Direct Resin Composite

The current study evaluated the influence of two endodontic post systems and the elastic modulus and film thickness of resin cement on stress distribution in a maxillary central incisor (MCI) restored with direct resin composite using finite element analysis (FEA). A three-dimensional model of an MCI with a coronary fracture and supporting structures was performed. A static chewing pressure of 2.16 N/mm(2) was applied to two areas on the palatal surface of the composite restoration. Zirconia ceramic (ZC) and glass fiber (GF) posts were considered. The stress distribution was analyzed in the post, dentin and cement layer when ZC and GF posts were fixed to the root canals using resin cements of different elastic moduli (7.0 and 18.6 GPa) and different layer thicknesses (70 and 200 mu m). The different post materials presented a significant influence on stress distribution with lesser stress concentration when using the GF post. The higher elastic modulus cement created higher stress levels within itself. The cement thicknesses did not present significant changes.