Titania (Titanium dioxide, TiO2) has been researched as a promising biomaterial due to its excellent biocompatibility. However, the main limitation of titania is its poor mechanical properties which limit its use in many load-bearing applications. In this thesis report, the properties of titania were improved by doping with small quantities of MgO, ZnO and SiO2 as sintering additives. Nanocrystalline powder was selected, as it possesses outstanding properties over conventional coarse-grained powders due to reduced grain size. Nanocrystalline anatase powder of size 5-15 nm was synthesized via a simple sol-gel technique. Small quantities of dopants were introduced into pure titania powder, through homogeneous mixing. The doped powder compositions were compacted uniaxially and sintered at 1300°C and 1500°C, separately, in air. The effects of sintering cycle and temperature on the microstructure, densification and mechanical properties of the sintered structures were studied. Mg doped structures recorded maximum sintered density of 3.87 g.cm-3. Phase analysis was carried out using powder XRD technique using Cu K[alpha] radiation. Microstructural analysis was performed using Scanning electron microscopy. The mechanical properties were assessed by evaluating hardness and biaxial flexural strength (ASTM F-394) of the structures. Results showed 12% increase in hardness and 18% increase in biaxial flexural strength in structures doped with ZnO and SiO2, respectively. Further, simulated body fluid maintained at 36.5°C was used to study the bioactivity and degradation behavior of the structures. The second part of the work aimed in the processing of porous titania scaffolds using polyethylene glycol as the pore-former. The green structures were sintered at 1400°C and 1500°C, separately in air and their properties have been studied. Microstructural analysis was carried out using Scanning electron microscope (SEM). Porosity was evaluated using the immersion technique. Vickers hardness and biaxial flexural tests were used to carry out the mechanical characterization. Further, the biomechanical/biodegradation behavior of the structures was assessed in simulated body fluid (SBF). Biodegradation and change in biomechanical properties as a function of time were studied in terms of weight change, change in Vickers hardness and biaxial flexural strength. The mechanical properties of porous titania scaffolds doped separately with MgO and ZnO have also been studied to investigate the influence of these additives on the properties of porous structures. The Vickers hardness and biaxial flexural strength were seen to improve with the addition of these sintering additives.

The introduction of ceramics into the market of wood cutting tools has failed so far due to the generally low toughness of ceramics which is causing brittle failure of the cutting edge. A feasibility study showed that Si3N4/SiC composites with fine elongated β-Si3N4 grains are a promising material for industrial wood machining and outperform commercial standard tungsten carbide tools in terms of lifetime. However, they were produced by hot pressing followed by very costly diamond cutting and grinding. The costs associated with the above production route are too high for an industrial viability. In this thesis Si3N4/SiC composites suitable for industrial wood milling are produced by a near net shape processing route including gas pressure sintering. These newly developed tools show less abrasive wear and consequently twice as long lifecycles than commercial standard tungsten carbide tools. Microscopic properties determine the performance of the Si3N4/SiC cutting tools. Therefore, an adequate selection of sintering additives is crucial. 12 wt% sintering additives are included in the composite as a combination of Al2O3 and the refractory oxides La2O3 and Y2O3. Important for the production of effective Si3N4/SiC wood cutting tools is the formation of a partly crystalline silicate phase within the multiple grain junctions during the final treatment by hot isostatic pressing. The use of MgO as a sintering additive for facilitating the densification of the Si3N4 ceramics inhibits the formation of the favourable silicate phase and must be avoided for the production of these wood cutting tools.

Made available in DSpace on 2014-12-17T14:57:45Z (GMT). No. of bitstreams: 1 EduardoGR.pdf: 1635946 bytes, checksum: 593244cdda721eea4684ae85323cfee4 (MD5) Previous issue date: 2006-06-28 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The calcium phosphate ceramics have been very investigated as material for bone implants. The tricalcium phosphate (β-TCP) had a great potential for application in temporary implants like a resorbable bioceramic. This material presents a limitation in its sintering temperature due to occurrence of the allotropic transformation β → α at temperatures around 1200?C, not allowing the attainment of dense ceramic bodies. This transformation also causes cracks, what diminishes the mechanical strength, limiting its use to applications of low mechanical requests. This work studies the influence of the addition of manganese oxide in the sintering of β-TCP. Two processing routes were investigated. The first was the powder metallurgy conventional process. The test bodies (samples) were pressed and sintering at temperatures of 1200 and 1250?C. The second route was uniaxial hot pressing and its objective was to obtain samples with high relative density. The samples were physically characterized through density and porosity measurements. The thermal behavior was studied through dilatometric, thermal differential and thermogravimetric analysis. The mechanical properties were characterized by three point flexure test and Vickers microhardness measurements. The microstructure was analyzed by scanning electron microscopy. The addition of manganese oxide caused an improvement of the mechanical strength in relation to the material without additive and promoting the stabilization of β-TCP to greater temperatures / As cer?micas de fosfato de c?lcio t?m sido intensamente investigadas como materiais para implantes ?sseos. O fosfato tric?lcico (β-TCP) possui um grande potencial para aplica??o em implantes tempor?rios por ser uma biocer?mica absorv?vel. Entretanto, este tipo de material apresenta uma limita??o na sua temperatura de sinteriza??o devido ? ocorr?ncia da transforma??o alotr?pica β → α em torno de 1200?C. Isto impede a obten??o de corpos cer?micos densos e provoca trincas, diminuindo a resist?ncia do material e limitando a sua utiliza??o a aplica??es de baixa solicita??o mec?nica. A influ?ncia da adi??o de ?xido de mangan?s na sinteriza??o do β-TCP foi estudada neste trabalho. Duas rotas de processamento foram investigadas. A primeira utilizou o processo convencional de metalurgia do p?. Os corpos de prova foram prensados, sendo posteriormente sinterizados nas temperaturas de 1200 e 1250?C. O segundo m?todo de processamento utilizou a rota de prensagem uniaxial a quente, e tinha como objetivo obter corpos de prova com alta densidade relativa. As amostras foram caracterizadas fisicamente por meio de medidas de porosidade e densidade e termicamente por dilatometria e an?lise termogravim?trica e t?rmica diferencial. Os corpos sinterizados foram caracterizados mecanicamente por resist?ncia a flex?o em 3 pontos e microdureza Vickers, sendo tamb?m sua microestrutura analisada por microscopia eletr?nica de varredura. A adi??o do ?xido de mangan?s ocasionou uma melhoria da resist?ncia mec?nica em rela??o ao material sem aditivo, al?m de promover uma estabiliza??o do β-TCP em temperaturas mais elevadas

Ultra high temperature ceramics (UHTC) are candidate materials for high temperature applications such as leading edges for hypersonic flight vehicles, thermal protection systems for spacecraft, and rocket nozzle throat inserts due to their extremely high melting points. Tantalum and Niobium Carbide (TaC and NbC), with melting points of 3950°C and 3600°C, respectively, have high resistivity to chemical attack, making them ideal candidates for the harsh environments UHTCs are to be used in. The major setbacks to the implementation of UHTC materials for these applications are the difficulty in consolidating to full density as well as their low fracture toughness. In this study, small amounts of sintering additive were used to enhance the densification and Graphene Nanoplatelets (GNP) were dispersed in the ceramic composites to enhance the fracture toughness. While the mechanisms of toughening of GNP addition to ceramics have been previously documented, this study focused on the anisotropy of the mechanisms. Spark plasma sintering was used to consolidate both bulk GNP pellets and near full relative density TaC-NbC ceramic composites with the addition of both sintering aid and GNP and resulted in an aligned GNP orientation perpendicular to the SPS pressing axis that allowed the anisotropy to be studied. In situ high load indentation was performed that allowed real time viewing of the deformation mechanisms for enhanced analysis. The total energy dissipation when indenting the bulk GNP pellet in the in-plane GNP direction was found to be 270% greater than in the out-of-plane orientation due to the resulting deformation mechanisms that occurred. In GNP reinforced TaC-NbC composites, the projected residual damaged area as a result of indentation was 89% greater when indenting on the surface of the sintered compact (out-of-plane GNP orientation) than when indenting in the orthogonal direction (in-plane GNP orientation) which is further evidence to the anisotropy of the GNP reinforcement.

The introduction of ceramics into the market of wood cutting tools has failed so far due to the generally low toughness of ceramics which is causing brittle failure of the cutting edge. A feasibility study showed that Si3N4/SiC composites with fine elongated β-Si3N4 grains are a promising material for industrial wood machining and outperform commercial standard tungsten carbide tools in terms of lifetime. However, they were produced by hot pressing followed by very costly diamond cutting and grinding. The costs associated with the above production route are too high for an industrial viability. In this thesis Si3N4/SiC composites suitable for industrial wood milling are produced by a near net shape processing route including gas pressure sintering. These newly developed tools show less abrasive wear and consequently twice as long lifecycles than commercial standard tungsten carbide tools. Microscopic properties determine the performance of the Si3N4/SiC cutting tools. Therefore, an adequate selection of sintering additives is crucial. 12 wt% sintering additives are included in the composite as a combination of Al2O3 and the refractory oxides La2O3 and Y2O3. Important for the production of effective Si3N4/SiC wood cutting tools is the formation of a partly crystalline silicate phase within the multiple grain junctions during the final treatment by hot isostatic pressing. The use of MgO as a sintering additive for facilitating the densification of the Si3N4 ceramics inhibits the formation of the favourable silicate phase and must be avoided for the production of these wood cutting tools.