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.

Orientador: Cecília Amélia de Carvalho Zaváglia / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-27T01:43:48Z (GMT). No. of bitstreams: 1 Almeida_FabianoCosta_D.pdf: 3772112 bytes, checksum: cb918f5ac800f74bbb146bf9c3e50a84 (MD5) Previous issue date: 2015 / Resumo: Os bráquetes são suportes utilizados pelos ortodontistas para controlar o posicionamento dos dentes nos tratamentos ortodônticos. Por eles, mais precisamente por seus slots, passam os fios ortodônticos e ambos são responsáveis pela biomecânica dos movimentos. O bráquete pode ser confeccionado por diversos materiais, sendo o mais comum o metal pela praticidade, preço e resistência. Recentemente, com a maior demanda por aparelhos estéticos, devido ao aumento de adultos utilizando estes dispositivos, aumentou o uso de bráquetes estéticos, feitos geralmente de polímeros ou cerâmicas. As maiores dificuldades encontradas estão relacionadas a estética, resistência, capacidade de coloração por alimentos e maior atrito com o fio. O propósito deste estudo foi a obtenção de compósitos cerâmicos de alumina e zircônia (ZTA) a partir de pós finamente cominuídos em diferentes proporções 70/30, 80/20 e 90/10 provenientes de materiais cerâmicos de alumina e zircônia separadamente. Os compósitos cerâmicos (ZTA) foram submetidos a processos de análises do tamanho de partículas, moagens, prensagens, conformações de corpos de provas (c.p.), difração de raio X, ensaios de compressão diametral, análises das propriedades mecânicas, avaliações das microestruturas e análises de propagação de trincas. Os resultados demonstraram tamanhos de partículas de 0,3µ, os valores da compressão diamentral de 296,64 MPa, 262,60 MPa, 220,30 MPa, os valores de microdureza de 13,12 GPa, 13,42 GPa, 13,81 GPa, os valores de tenacidade à fratura de 8,91 MPa m½, 9,37 Mpa m½, 9,65 Mpa m½, os tamanhos de grãos em torno de 0,6µ e uma redução significativa nas propagações das trincas em relação à alumina. Estes compósitos cerâmicos de alumina e zirconia (ZTA) demonstraram resultados superiores em seus valores de tenacidade à fratura de aproximadamente 68% em relação a alumina, atualmente utlizados em bráquetes comerciais. Ocorreu uma redução do tamanho de grãos e modificações no comportamento de propagação das trincas resultando na diminuição da ocorrência de trincas. A conclusão, diante dos resultados apresentados nas análises, foi que os materiais compósitos cerâmicos de alumina e zircônia (ZTA), nos quesitos avaliados, foram adequados para serem aplicados em bráquetes estéticos de Ortodontia, porém novos trabalhos foram sugeridos para avaliação desses materiais em relação ao desgaste, a fricção e a coloração. Palavras-chave Aparelhos ortodonticos estéticos, bráquetes cerâmicos, compósitos cerâmicos, compósitos ZTA / Abstract: The brackets are used by orthodontists to control the tooth positions on orthodontic treatments. Inside the brackets, in the slots, are the orthodontic wire and both are responsible for the biomechanical movement. The brackets can be made of different materials and the most common is the metallic by practically, price and resitance. Recently, with the greatest demand of aesthetic devices, because a adult demand, increased use of aesthetic brackets made of polymers and ceramics. The greatest aesthetic difficulties are the resitence, staining for food and the wire friction. This work aims to contribute to the development of new aesthetic orthodontic brackets. Thereby was proposed in this study the obtainment of ceramic composites alumina and zirconia (ZTA) powder finely comminuted in different proportions 70/30, 80/20 and 90/10 from alumina and zirconia separately. These ceramic composites alumina and zirconia (ZTA) were submitted to particle analysis, milling process, pressing, specimens conformations, X ray diffraction, diametral compression, mechanical properties analysis, evaluation of microstructured and crack propagation analysis. The results showed particle size 0,3µ, the diametral compression values of 296,64 MPa, 262,60 MPa, 220,30 Mpa, the hardness values of 13,12 GPa, 13,42 GPa, 13,81 GPa, the fracture toughtness values of 8,91 MPa m½, 9,37 Mpa m½, 9,65 Mpa m½, the grain size of 0,6µ and a significant reduction in crack propagation compared to alumina. These ceramic composites alumina and zirconia (ZTA) demonstrated superior results in their fracture toughness values of approximately 68% compared to alumina, currently used in commercial brackets. There was a reduction in grain size and changes in the behavior of propagation of cracks resulting in a decrease of occurance of cracks. The conclusion on the results presented was that ceramic composites alumina and zirconia (ZTA), on the variables evaluated, were suitable for application in Orthodontic aesthetic brackets however new studies have been suggested for the evaluation of these materials in relation to wear, friction and staining. Key Words Aesthetic orthodontic devices, ceramic brackets, ceramic composites, ZTA composites / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

This thesis is focused on ceramics materials in terms of their partition, properties, structure, manufacture and methods of their possible machining. The first part of this thesis is devoted to the distribution of ceramics materials, their structure, properties, and methods of production. Currently, ceramics materials are increasingly used in structural (engineering) applications therefore we deal with methods of effective machining of ceramic materials, to achieve part of the required shape, dimensions and surface quality. The evaluation of ceramic grinding test from the point of view of cutting forces and surface quality of the machined faces are presented in the last part of the thesis. The tested materials have been provided by company SEEIF Ceramics a.s.

In the diploma thesis dividing of ceramic materials is made, their bonds and other attributions, which define ceramic materials. There is also described how ceramic materials are manufactured and the thesis is including information about machining ceramic materials. In the experimental part sample of ceramic material R-S67K was machined by milling. During the experiment cutting forces were measured and roughness of surface after finishing, these data were finally evaluated.

Ceramic manufacturing is an expensive process with long lead times between the initial design and final manufactured part. This limits the use of ceramic as a viable material unless there is a large project budget or high production volume associated with the part. Ceramic stereolithography is an alternative to producing low cost parts through the mixing of a photo curable resin and ceramic particles. This is an additive manufacturing process in which each layer is built upon the previous to produce a green body that can be sintered for a fully dense ceramic part. This thesis introduces a new approach to ceramic stereolithography with a top mask projection light source which is much more economical compared to current vector scanning methods. The research goes through the design and development of a stereolithography printer prototype capable of handling ceramics and the testing of different mixtures to provide the best printing results with varying viscosities. The initial testing of this printer has created a starting point for top mask projection as an economical alternative to current ceramic manufacturing techniques.

This dissertation is focus on the study of solid-electrolyte interphases (SEIs) on advanced lithium ion battery (LIB) anodes. The purposes of this dissertation are to a) develop a methodology to study the properties of SEIs; and b) provide guidelines for designing engineered SEIs. The general knowledge gained through this research will be beneficial for the entire battery research community.

Piezoelectric materials in the forms of both bulk and thin-film have been widely used as actuators and sensors due to their electromechanical coupling. The characterization of piezoelectric materials plays an important role in determining device performance and reliability. Instrumented indentation is a promising method for probing mechanical as well as electrical properties of piezoelectric materials. The use of instrumented indentation to characterize the properties of piezoelectric materials requires analytical relations. Finite element methods are used to analyze the indentation of piezoelectric materials under different mechanical and electrical boundary conditions. For indentation of a piezoelectric half space, a three-dimensional finite element model is used due to the anisotropy and geometric nonlinearity. The analysis is focused on the effect of angle between poling direction and indentation-loading direction on indentation responses. For the indentation by a flat-ended cylindrical indenter, both insulating indenter and conducting indenter without a prescribed electric potential are considered. The results reveal that both the indentation load and the magnitude of the indentation-induced potential at the contact center increase linearly with the indentation depth. For the indentation by an insulating Berkovich indenter, both frictionless and frictional contact between the indenter and indented surface are considered. The results show the indentation load is proportional to the square of the indentation depth, while the indentation-induced potential at the contact center is proportional to the indentation depth. Spherical indentation of piezoelectric thin films is analyzed in an axisymmetric finite element model, in which the poling direction is anti-parallel to the indentation-loading direction. Six different combinations of electrical boundary conditions are considered for a thin film perfectly bonded to a rigid substrate under the condition of the contact radius being much larger than the film thickness. The indentation load is found to be proportional to the square of the indentation depth. To analyze the decohesion problem between a piezoelectric film and an elastic substrate, a traction-separation law is used to control the interfacial behavior between a thin film and an electrically grounded elastic substrate. The discontinuous responses at the initiation of interfacial decohesion are found to depend on interface and substrate properties.

Devido à elevada razão superfície/volume dos nanomateriais, estes apresentam propriedades únicas que são consequência das propriedades de suas superfícies. Para estabilizar as nanopartículas, as quais tendem ao crescimento para reduzir o excesso de energia, uma estratégia é a introdução de aditivos que segreguem na superfície e reduzam a energia de superfície. Neste trabalho, o sistema de importância tecnológica SnO2-TiO2 foi estudado. Nanopartículas de Sn1-xTixO2 (0,00 x 1,00) foram sintetizadas pelo método dos precursores poliméricos. Difratogramas de raios X mostram que uma solução sólida com estrutura do tipo rutilo é obtida para x 0,90. A evolução dos parâmetros de rede, os espectros obtidos por perda de energia de elétrons (EELS) e os espectros no infravermelho coletados no modo de refletância difusa (DRIFT) sugerem a segregação do Ti4+ na superfície, que justifica a elevada solubilidade do Ti4+ no SnO2. Os espectros Raman são coerentes com a segregação, mostrando que, mesmo sem a formação de segunda fase, ocorrem regiões ricas em Ti. A segregação está relacionada também à redução do tamanho de cristalito e ao aumento da área de superfície específica devido à redução da energia de superfície (de 1,40 Jm-2 em x = 0,00 até 1,08 Jm-2 em x = 0,50) determinada por calorimetria de adsorção de água e coerente com os dados da calorimetria de dissolução. Para x 0,90, ocorre a formação da fase anatásio além do rutilo e os fenômenos de estabilização dos polimorfos podem ser explicados pela modificação da energia de superfície. Com base na caracterização feita, as atividades fotocatalíticas das nanopartículas foram avaliadas e foi verificado um aumento da eficiência devido à superior área de superfície das amostras aditivadas em relação às amostras puras. / Due to the high surface/volume ratio, nanomaterials have unique properties as a consequence of their surface properties. In order to stabilize the nanoparticles, which tend to grow to reduce their excess energy, one can introduce additives that are prone to segregate at the surfaces and reduce the surface energy. In this work, the technologically relevant SnO2-TiO2 system was studied. Sn1-xTixO2 (0.00 x 1.00) nanoparticles were synthesized by polymeric precursors method. X-ray diffraction patterns show that a rutile-structured solid solution is formed for x 0.90. Lattice parameters evolution, electron energy loss spectra (EELS) and diffuse reflectance infrared spectra (DRIFT) suggest a Ti4+ surface segregation, which explains the high Ti4+ solubility in SnO2. Raman spectra are in accord with the segregation, showing Ti-rich sites in the absence of a second crystalline phase. The segregation is also related to a decrease in the crystallite size and an increase in the surface area due to a decrease in the surface energy (from 1.40 Jm-2 for x = 0.00 to 1.08 Jm-2 for x = 0.50) determined by water adsorption calorimetry and consistent with drop solution calorimetry data. For x 0.90, the formation of anatase occurs in addition to rutile, and the polymorphic stability can be explained according to the surface energy modification. Based on these results, photocatalytic activity of the samples were evaluated, and an increase in the efficiency due to a higher surface area was observed for the samples containing additive compared to pure samples.

"Planar Solid Oxide Fuel Cell manufacturing can be considered in the pilot plant stage with efforts driving towards large volume manufacturing. The science of the solid oxide fuel cell is advancing rapidly to expand the knowledge base and use of material combinations and layer forming methods for the unit cell. Few of the many processing methods, over 15, reported in literature for layer formation are used today in high volume manufacturing. It is difficult to establish future market demand and cost levels needed to plan a course of action today. The need to select amongst different designs, materials and processes will require a tool to aid in these decisions. A modeling tool is presented to robustly compare the various process combinations and manufacturing variable to make solid oxide fuel cells in order to identify key trends prior to making strategic investment decisions. The ability to accurately forecast investment requirements and manufacturing cost for a given high volume manufacturing (HVM) process based on expected volume is critical for strategic decisions, product placement and investor communications. This paper describes the use of an updated process based cost model that permits the comparison of manufacturing cost data for various process combinations, production volumes, and electrolyte layer thickness tolerances. The effect of process yield is addressed. Processing methods discussed include tape casting, screen printing and sputtering."

The yttria-stabilized zirconia (YSZ) system has been extensively studied because of its critical applications, like solid oxide fuel cells (SOFCs), oxygen sensors, and jet engines. However, there are still important questions that need to be answered and significant thermodynamic information that needs to be provided for this system. There is no predictive tool for the ionic conductivity of the cubic-YSZ (c-YSZ), as an electrolyte in SOFCs. In addition, no quantitative diagram is available regarding the oxygen ion mobility in c-YSZ, which is highly effective on its ionic conductivity. Moreover, there is no applicable phase stability diagram for the nano-YSZ, which is applied in oxygen sensors. Phase diagrams are critical tools to design new applications of materials. Furthermore, even after extensive studies on the thermodynamic database of the YSZ system, the zirconia-rich side of the system shows considerable uncertainties regarding the phase equilibria, which can make the application designs unreliable. During this dissertation, the CALPHAD (CALculation of PHase Diagrams) approach was applied to provide a predictive diagram for the ionic conductivity of the c-YSZ system. The oxygen ion mobility, activation energy, and pre-exponential factor were also predicted. In addition, the CALPHAD approach was utilized to predict the Gibbs energy of bulk YSZ at different temperatures. The surface energy of each polymorph was then added to the predicted Gibbs energy of bulk YSZ to obtain the total Gibbs energy of nano-YSZ. Therefore, a 3-D phase stability diagram for the nano-YSZ system was provided, by which the stability range of each polymorph versus temperature and particle size are presented. Re-assessment of the thermodynamic database of the YSZ system was done by applying the CALPHAD approach. All of the available thermochemical and phase equilibria data were evaluated carefully and the most reliable ones were selected for the Gibbs energy optimization process. The results calculated by the optimized thermodynamic database showed good agreement with the selected experimental data, particularly on the zirconia-rich side of the system.