Appearances and first impressions are deceiving. My figurines represent the twisted world where everything on the surface appears to be perfect, but there are skeletons in everyone's closet.

My background in clay has emphasized the development of technical considerations in functional ceramics as well as the search for personal images. The past two years have seen an emphasis on the exploration of technical areas chosen to lead to the development of a familiarity with techniques and a solidification of statement. The process has nurtured in me the realization that the objects I produce do not represent an attempt to attain an axiom of art but are personal statements developed through an empirical use of forms and images.

The influence of drying parameters namely residence time before drying, drying temperature, drying time, relative humidity, and slip recipe on the drying rate of slip cast sanitary wares, predominantly lavatories and toilet closets, was studied. The drying temperatures were changed from 80 oC to 110 oC with an increment of 10 oC. The drying time was changed from 10 to 7 h with a decrease of 1 hour. Relative humidity of the environment was changed from 60 to 75 %. The percent weight loss, percent residual moisture and the percent shrinkage of the samples were determined by weighing and measuring the samples before and after the tests. The percent weight loss was within the range of 6.5 to 6.6 % after holding the as cast samples for 6 hours at ambient casting shop conditions while it was within the range of 17.96 to 18.10 % when subsequently dried for 10 hours at 110 oC in the dryer. The percent shrinkage was within the range of 2.9 - 3.0 % after holding the as cast samples 6 h at ambient laboratory conditions. No shrinkage was observed in the sample when it was subsequently dried for 10 hours at 110 oC in the dryer. Optimum moisture content of dried wares was obtained after drying for 8 hours at 100 oC in the dryer. It has been seen that the relative humidity of the dryer at the beginning of the drying should be lower than 75 %. As the non-plastic content in the recipe of the sanitary ware slip increased, drying shrinkage and residual moisture content decreased. The results of this study showed that through increasing the residence time up to 6h with a casting shop environment of approximately 30 oC and 60 % relative humidity, the drying time could be safely reduced from 10 h to 8 h with a drying temperature of 100 oC for the test plates. The same approach can be used for more complex shapes, e.g., WC closets, basins, tanks etc. in EczacibaSi Vitra plant. Once the drying time was reduced, the amount of natural gas per ware would be reduced to a certain extent. Aside from that the reduction in the drying time would increase the quantity of the drying cycles per week so that more wares could be dried. When all these observations were taken into account, this thesis study could also be utilized by other sanitary ware producing companies whose processes require slip cast drying.

This masters’s thesis contains literary research about basic shaping methods of ceramic materials concerning the slip casting method. In addition, stabilization of ceramic slips, drying of ceramic green bodies and their subsequent sintering are described. This thesis also includes a description of plasma technology, including DCBD (Diffuse Coplanar Barrier Discharge) technology. In experimental part of this thesis the Al2O3 powder was treated with DCBD technology. From the prepared powder, the green body was prepared by the slip casting method, which was subsequently sintered by one-step and two-step sintering. The thesis describes the methods of preparation of ceramic samples and their evaluation. Evaluated experiments have shown that plasma technology has a positive effect on the treatment of ceramic powder Al2O3. Alumina ceramic samples of high relative density ( 99%) and low grain size (

Extensive attention has been paid to consolidate nanoparticles into nanocrystalline components that possess better properties than their coarse-grained counterparts. Nanocrystalline monolithic tungsten (W) has been envisaged to possess better properties than coarse-grained tungsten and to improve the performance of many military components. Commercially available nano-W powders were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and Brunauer, Emmett, and Teller (BET) measurement. While the bulk of nano-W powders consisted of bcc-W as confirmed by XRD and TEM, much of their surface consisted of WO3 with traces of WO2 and WC. Despite the irregular morphology and agglomerates greater than 1 m in size, the diameter of individual nano-W powders ranged from 30 to 100 nm with a surface area of 10.4 m2/g. To obtain green bodies of higher densities and more homogeneous microstructures after consolidation, W nanopowders were de-agglomerated in water and slip cast in plaster molds. De-agglomeration in water was conducted by repeated ultrasonication, washing, centrifuge and pH adjustment. The change in particle size and morphology was examined via SEM. After the initial surface oxide was removed by repeated washing, the reactivity of W nanoparticles to water was somewhat inhibited. Increasing the number of cycles for ultrasonication and washing increased the pH, the degree of de-agglomeration and the stability of W suspension. The zeta potential was more negative with increasing pH and most negative at pH values close to 5. Viscosity also decreased with increasing pH and reached a minimum at a pH 5. To obtain the highest solid loading with the lowest viscosity, the pH value of W suspension was adjusted to 5 using aqueous tetramethylammonium hydroxide solutions. The relative density of the slip cast increased with longer ultrasonic time, increasing slurry pH up to 5, and consequent increase in solids loading. Smaller particles were separated from larger ones by ultrasonication, washing with water and centrifugation. At a 27.8 vol.% solids loading, the size-separated fine W slurry was slip cast into pellets with relative green densities up to 41.3 % and approximate particle sizes of 100 nm. W powders were also ultrasonicated in aqueous poly (ethyleneimine) (PEI) solutions with various concentrations. SEM examinations of particle sizes showed that 1 wt.% PEI led to the optimum dispersion and ultrasonication for longer time with a low power resulted in better dispersion. 0.5 g of W powders were ultrasonicated in 10 ml aqueous poly (allylamine hydrochloride) (PAH) solutions with molar concentrations ranging from 0.01 to 0.05 M. W suspensions with 0.03 M and 0.04 M PAH after two washing cycles showed improved dispersion. Cold isostatic pressing can further increase the green density following slip casting. Sintered slip casts made from de-agglomerated nanoparticle W showed a lower density, more uniform microstructure, smaller grains and smaller pores than the sintered dry pressed pellets.

<p dir="ltr">Antennas are used to transmit communication signals for many applications including for the navigation of aircraft. To protect the antennas from environmental conditions electromagnetic transparent structures called radomes are used. Advancements in technology have led to the development of hypersonic flight vehicles. These aircraft travel at speeds of Mach 5 and greater subjecting them to extreme environmental conditions. These aircraft require precise navigation making it important to have radome materials that can withstand the extreme conditions of high-speed flight while maintaining transparency to the incoming and outgoing signals of the antenna. Silicon nitride is a ceramic material of interest for high temperature radomes due to its mechanical properties, temperature stability, and satisfactory dielectric properties. Incorporating porosity into silicon nitride further enhances the transmission performance making porous silicon nitride a leading candidate material for high temperature radomes. In this dissertation slip casting with pressureless sintering is proposed as a route to fabricate porous silicon nitride ceramics for radomes. Modification of sintering aids and sintering temperatures are explored as a method to control the amount of porosity. Mechanical properties and dielectric properties of these materials are investigated. </p><p dir="ltr">First, an aqueous silicon nitride suspension developed for slip casting was optimized by investigating the rheological properties, zeta potential, and sedimentation behavior. It was determined that a suspension with 30 vol% solids, 0.5 wt% dispersant (PEI), and a pH of 7 was the optimized condition that resulted in uniform cast parts. This optimized suspension was used to fabricate silicon nitride samples with yttria and alumina sintering aids. An average density of 93% with an average strength of 659 MPa at room temperature and a strength of 472 MPa maintained up to 1200°C was achieved. Dielectric constant and loss tangent were measured on samples with 4-17% porosity to be 5.85-7.70 and <0.02, respectively. </p><p dir="ltr">To create samples with higher levels of porosity and therefore lower dielectric constants the yttria and alumina sintering aids were replaced with ytterbium oxide. Ytterbium oxide assists in forming porous silicon nitride due to the high melting temperature and high viscosity of the resulting glassy phase. Slip cast samples with 5% Yb₂O₃ were sintered at temperatures of 1700-1850°C resulting in porosities of 21-32% and strengths of 267-445 MPa. The dielectric constants of these materials were measured to be 4.56-5.80 with average loss tangents <0.006. The amount of ytterbium oxide was also studied to determine the effects on density, microstructure, mechanical properties, and dielectric properties. Slip-cast samples with 5-15% Yb₂O₃ were made having average porosities of 23-36% and strengths of 275-421 MPa. The dielectric constants of these materials were measured to be 4.13-4.65 with average loss tangents of <0.007. </p><p dir="ltr">Lastly, slip casting using the previously developed and evaluated suspensions was done to fabricate various radome shapes as well as layered structures. The processing method presented in this dissertation shows the potential for fabricating porous silicon nitride for high temperature radome applications with controlled porosity and relatively high strengths.</p>

Cette thèse vise à évaluer le potentiel d'un nouveau couple cathode / électrolyte pour une application en IT-SOFC (700°C), par le biais de l’élaboration et du test de cellules à anode support de configuration planaire. Les matériaux concernés sont l'électrolyte BaIn0.3Ti0.7O2.85 (BIT07), de structure perovskite, et les nickelates de terres rares Ln2-xNiO4+ (LnN, Ln = La, Nd, Pr) en tant que cathodes ; ces matériaux ont montré des propriétés prometteuses dans des travaux préliminaires effectués à l'IMN et l'ICMCB. La première partie de cette thèse porte sur la mise en place d'un protocole d'élaboration de cellules complètes utilisant des techniques bas coûts et industrialisables (cellules de taille 3 x 3 cm2) : l’anode Ni / BIT07 a été élaborée par coulage en bande, l'électrolyte BIT07 par vacuum slip casting et les cathodes par sérigraphie. Les mesures électrochimiques réalisées sur une première génération de cellules ont mis en évidence la nécessité d'ajouter une couche barrière de GDC entre les cathodes LnN et l'électrolyte BIT07. Les meilleures performances ont été obtenues pour une cellule BIT07 / Ni | BIT07 | GDC | PrN, avec une densité de puissance à 700°C et 0.7 V de 176 mW cm-2 pour une faible résistance de polarisation de 0. 29 Ω cm2. La principale limitation des performances a été identifiée comme étant la résistance interne du banc de test, donnant lieu à des valeurs de résistances séries anormalement élevées. Cette cellule a été opérée avec succès durant plus de 500 heures sous courant, avec néanmoins une vitesse de dégradation extrapolée élevée de l’ordre de 27% / kh. / This thesis aimed at assessing the potential of a novel cathode / electrolyte couple for IT-SOFC applications (700°C), through the elaboration and testing of planar anode-supported cells. The materials involved were the perovskite-structured BaIn0.3Ti0.7O2.85 (BIT07) electrolyte and the rare earth nickelate Ln2-xNiO4+ (LnN, Ln = La, Nd, Pr) cathodes, both materials having shown promising properties in preliminary work done at the IMN and the ICMCB. The first part of this thesis concerned the implementation of a cell elaboration protocol using low-cost and scalable shaping techniques (cell size 3 x 3 cm2); namely, the Ni / BIT07 anodes were elaborated by tape casting, the BIT07 electrolyte by vacuum slip casting and the cathodes by screen printing. Comparison of electrochemical results for a first and second generation of cells highlighted the usefulness of adding a GDC buffer layer in between the LnN cathodes and the BIT07 electrolyte. The best performance has been obtained for a cell BIT07 / Ni | BIT07 | GDC | PrN, with a power density at 700°C and 0.7 V of 176 mW cm-2 for a competitive polarisation resistance of 0.29 Ω cm2. The main limitation of the performance has been determined to be related to the internal resistance of the test setup, giving anomalously high series resistances. This cell has been successfully operated beyond 500 hours under current, although with a fairly high extrapolated degradation rate of 27% / kh.

Novel ceramic membrane cells of BaCe₀.₅Zr₀.₃Y₀.₁₆Zn₀.₀₄O[subscript(3-δ)] (BCZYZ), a proton-conducting oxide, have been developed for electrocatalytic ammonia synthesis. Unlike the industrial Haber-Bosch process, in this work an attempt to synthesise ammonia at atmospheric pressure has been made. The membrane cell fabricated by tape casting and solution impregnation comprises of a 200 μm-thick BCZYZ electrolyte and impregnated electrode composites. Electrocatalysts for anode and cathode were investigated. For the anode, the co-impregnation of Ni and CeO₂ provided excellent electrode performance including high catalytic activity, sintering stability and compatibility with the BCZYZ electrolyte. The best composition was the mixture of 25 wt% NiO and 10 wt% CeO₂. A symmetrical cell prepared with this electrode composition revealed low polarisation resistances of 1.0 and 0.45 Ωcm² in humidified 5% H₂/Ar at 400 and 500 °C, respectively. For the cathode, 25 wt% of impregnated Fe oxide provided a satisfactory performance in non-humidified N₂ atmosphere. Significant amounts of ammonia were produced from the single cell with Ni-CeO₂ anode and Fe oxide cathode at 400-500 °C under atmospheric pressure. Ammonia formation rate was enhanced by Pd catalyst addition and electrochemical performance was improved by Ru addition. The highest ammonia formation rate of 4 x 10⁻⁹ mols⁻¹cm⁻² was attained using the cell with a Pd-modified Fe cathode at 450 °C. The formation reaction of ammonia typically consumed around 1-2.5 % of total applied current while most of the applied current was employed in H⁺ reduction. The total current efficiency of around 90-100 % could be obtained from the membrane cells.

Cette thèse vise à évaluer le potentiel d'un nouveau couple cathode / électrolyte pour une application en IT-SOFC (700°C), par le biais de l'élaboration et du test de cellules à anode support de configuration planaire. Les matériaux concernés sont l'électrolyte BaIn0.3Ti0.7O2.85 (BIT07), de structure perovskite, et les nickelates de terres rares Ln2-xNiO4+ (LnN, Ln = La, Nd, Pr) en tant que cathodes ; ces matériaux ont montré des propriétés prometteuses dans des travaux préliminaires effectués à l'IMN et l'ICMCB. La première partie de cette thèse porte sur la mise en place d'un protocole d'élaboration de cellules complètes utilisant des techniques bas coûts et industrialisables (cellules de taille 3 x 3 cm2) : l'anode Ni / BIT07 a été élaborée par coulage en bande, l'électrolyte BIT07 par vacuum slip casting et les cathodes par sérigraphie. Les mesures électrochimiques réalisées sur une première génération de cellules ont mis en évidence la nécessité d'ajouter une couche barrière de GDC entre les cathodes LnN et l'électrolyte BIT07. Les meilleures performances ont été obtenues pour une cellule BIT07 / Ni | BIT07 | GDC | PrN, avec une densité de puissance à 700°C et 0.7 V de 176 mW cm-2 pour une faible résistance de polarisation de 0. 29 Ω cm2. La principale limitation des performances a été identifiée comme étant la résistance interne du banc de test, donnant lieu à des valeurs de résistances séries anormalement élevées. Cette cellule a été opérée avec succès durant plus de 500 heures sous courant, avec néanmoins une vitesse de dégradation extrapolée élevée de l'ordre de 27% / kh.

Orientador: Rubens Nisie Tango / Banca: Alexandre Luíz Souto Borges / Banca: Sebastião Ribeiro / Resumo: O objetivo deste estudo foi desenvolver um novo formato de pilar protético estético em zircônia (3Y-TZP) visando suprimir a utilização do parafuso trespassante utilizado no formato convencional de pilares protéticos em zircônia. Inicialmente foi feita a caracterização do material utilizado na técnica de colagem de barbotina (slip casting) através da confecção de uma barra que teve suas propriedades mecânicas, módulo de elasticidade (E) e coeficiente de Poisson (), grau de contração e dimensão de suas partículas após sinterização avaliados pelos métodos de frequências naturais de vibração e microscopia eletrônica de varredura (MEV), respectivamente. Previamente à confecção do pilar protótipo, este teve seu comportamento mecânico avaliado e comparado a um pilar de 3YTZP convencional com parafuso trespassante pela análise por elementos finitos (FEA) durante sua instalação em implante e recebendo carga oblíqua simulando força de mastigação (210,5 N). O protótipo foi confeccionado pela técnica de colagem de barbotina em um molde de gesso obtido a partir de uma duplicata ampliada em cera. A densidade final foi avaliada pelo método de Archimedes em água. Obteve-se o módulo de elasticidade de 187,97 ± 4,84 GPa e coeficiente de Poisson de 0,19 ± 0,04 para o material. O grau de contração de sinterização foi de 58 vol% e o tamanho do grão foi de 0,705 ± 0,424 μm. Na análise por FEA verificou-se concentrações de tensões na região inicial da rosca para ambos os pilares, e durante o carregamento foram observadas tensões de tração no lado em que incidiu a carga, com presença de tensões de compressão no lado oposto. Ainda, observou-se durante o carregamento do pilar protético convencional concentração de tensão na região do pescoço do parafuso trespassante. A densidade final obtida para o pilar protótipo em 3Y-TZP foi de 95,68% em ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The purpose of this study was to develop a new esthetic zirconia (3YYTZP) implant abutment shape to suppress the use of the fixing screw commonly used by the conventional zirconia abutments. A material characterization, Young's modulus (E), Poisson's rate (), shrinkage and particles dimensions after sintering was performed for a bar shape specimen obtained by slip casting evaluated by the natural torsional and flexural vibration frequencies and scanning electron microscope (SEM), respectively. Previously to the prototype abutment confection, its mechanical behavior was evaluated and compared to a conventional zirconia abutment with a fixing screw by finite element analisys (FEA) simulating the abutment installation and oblique loading (210.5 N). The prototype was confectioned by the slip casting technique using a gypsum mould obtained from a wax expanded replica. The abutment had its density measured by Archimedes' method. Through the natural vibration frequencies a Young's modulus of 187.97 ± 4.84 GPa and a Poisson's rate of 0.19 ± 0.04 were obtained for the material. The shrinkage was 58 vol% and the grain size was 0,705 ± 0,424 μm . The FEA showed stress concentration at the first thread pitch for both abutments, and tensile stress concentration were observed at the side that received the oblique load with compressive stress at the opposite side. Whereas, for the conventional abutment model a stress concentration was observed at the screw's stem. The final density for the zirconia prototype abutment was 95.68% from the theoretical density (6.12 g.cm-3). The zirconia abutment obtained by slip casting presented satisfactory physical properties. The suppressing of the fixing screw could provide better performance to the abutment due to the lack of stress concentration in the screw when an oblique load is applied, when evaluated by FEA / Mestre