O objetivo do trabalho foi o de avançar na compreensão dos mecanismos envolvidos no comportamento óptico de diferentes materiais cerâmicos em função da espessura, utilizados para restauração dentária, determinar os coeficientes de absorção e espalhamento e correlacioná-los às características microestruturais de cada material. Além disso, foi avaliada a capacidade de mascaramento e a razão de contraste do material cerâmico nas formas monolítica, em duas camadas e como restauração cimentada. Para tanto, foram analisadas quatro cerâmicas odontológicas, uma porcelana de cobertura (vítrea) e três compósitos cerâmicos infiltrados com vidro do Sistema InCeram (alumina/vidro, alumina/zircônia/vidro e espinélio/vidro), além de uma resina composta odontológica empregada como substrato resinoso e um cimento resinoso para cimentação. Os coeficientes de espalhamento e absorção foram determinados por meio dos modelos de Beer-Lambert e Kubelka-Munk a partir das curvas espectrais de transmitância e reflectância (com fundos branco e preto) geradas em um espectrofotômetro na faixa de comprimento de onda entre 300 e 800 nm. A microestrutura de cada material foi analisada por meio de microscopia eletrônica de varredura com mapeamento elementar, difração de raios X e análise química por fluorescênica de raios X. O comportamento óptico dos materiais estudados foi influenciado pelas características microestruturais do material e a pela espessura. Os valores do coeficiente de espalhamento, S, das cerâmicas avaliadas foram significativamente maiores do que os valores do coeficiente de absorção, K, na região do visível. Foram propostas equações para prever as curvas espectrais de reflectância e transmitância de bilayers e de restaurações cimentadas. / The aim of this work was to advance in the understanding of the mechanisms related to the optical behavior of different ceramic materials as a function of thickness, used for dental restoration, to determine the absorption and scattering coefficients and to correlate them to the microstructural characteristics of each material. The masking ability and the contrast ratio of ceramic material as monolith, bilayer and cemented restoration were also evaluated. For this, four dental ceramics, one porcelain and three glass-infiltrated ceramic composites of InCeram System (alumina/glass, alumina/zirconia/glass, and spinell/glass), besides one dental composite resin used as resinous substrate and one resinous cement for luting. The scattering and absorption coefficients were determined by the Beer-Lambert and Kubelka-Munk models using spectral curves of transmittance and reflectance (with white and black backs) generated in a spectrophotometer in the 300 to 800 nm wavelength range. The microstructure of each material was analyzed by scanning electron microscopy with elemental mapping, X-ray diffraction, and chemical analysis by X-ray fluorescence. The optical behavior of studied materials was affected by the microstructural characteristics and thickness of the material. The values of scattering coefficient, S, of evaluated ceramics were significantly higher than the values of absorption coefficient, K, in the visible range. Equations for the prediction of reflectance and transmittance spectral curves of bilayer and cemented restorations were proposed.

Existe um amplo debate sobre as influências culturais remotas nos Andes e o surgimento da cerâmica nesses contextos. Nosso estudo não pretende retroceder aos períodos Formativo ou Cerâmico Inicial, mas apenas situar a coleção de cerâmica chimu do MAE/USP em relação ao debate atual sobre as relações de continuidade ou descontinuidade na costa norte peruana, através do estudo da tecnologia de produção cerâmica. O sistema tecnológico que caracteriza essa produção geralmente aparece na bibliografia com ênfase nas características de moldagem de seus artefatos e a vasta produção cerâmica desse período raramente é estudada a partir de sua variabilidade tecnológica. Este estudo busca enxergar possíveis diferenças tecnológicas que possam existir por trás dessa mensagem de unicidade e homogeneidade, explícita na cerâmica chimu, e investigar a respeito do significado das escolhas tecnológicas que caracterizam esse processo. A escolha de uma coleção de peças inteiras, de um estilo cerâmico monocromático, coletadas provavelmente aleatoriamente e carente de informação contextual impôs a necessidade de pensarmos numa metodologia diferenciada para a investigação das escolhas tecnológicas. A combinação da análise macroscópica de aspectos morfológicos e iconográficos, com a investigação sistemática através de técnicas físico-químicas não destrutivas permitiu o aprofundamento no conhecimento da tecnologia e especificidades do processo de produção dos artefatos, ao fornecer dados que foram fundamentais para inferências dos aspectos culturais das escolhas tecnológicas associadas a essa coleção. / There is a wide debate on the remote Andes cultural influences and the appearance of ceramics in these contexts. Our study does not intend to go back to Formative periods, but only to retrieve the collection of Chimu pottery MAE / USP with respect to the current debate regarding the relative continuity or discontinuity in Peru\'s northern coast, through the study of ceramic production technology. The technological system that characterizes this production usually appears in the literature with emphasis on the characteristics of molding and the vast production and ceramic artifacts from this period is rarely studied from its technological variability. This study aims to see the future technological differences that may exist behind this message of unity and homogeneity, explicit in Chimu ceramics, and inquiring into the meaning of technology choices that characterize this process. The choice of a collection of whole pieces of a ceramic style monochrome, probably collected at random and lacking in contextual information imposed the need to devise a methodology for the investigation of different technology choices. The combination of macroscopic analysis of morphological and iconographic, with the systematic investigation by physico-chemical techniques non destructive has allowed the depth knowledge of technology and the particularities of the production of the artifacts, to provide data that were fundamental to infer cultural aspects of technology choices associated with this collection.

É crescente a aplicação dos cimentos à base de resina em próteses em cerâmica por exibirem propriedades estéticas e biomecânicas superiores aos cimentos convencionais. O presente estudo teve por objetivo avaliar o grau de conversão (GC) de quatro cimentos resinosos, sendo um com modo de polimerização físico (ChoiceTM 2/Bisco Inc), 2 com modo de polimerização dual (DuolinkTM/ Bisco Inc; VariolinkII®/Ivoclar-Vivadent) e um cimento com modo de polimerização químico (C&BTM/Bisco Inc), empregados na cimentação de coroas confeccionadas em cerâmica. Foram utilizados 42 pré-molares humanos que foram preparados para receber coroas totais confeccionadas com 2 sistemas cerâmicos: cerâmica de dissilicato de lítio (IPS e.MaxPress/Ivoclar-Vivadent®) e cerâmica de óxido de Zircônia estabilizada por Itrio (IPS e.maxZirCAD/Ivoclar-Vivadent®) para confecção dos copings, tendo uma cerâmica a base de fluorapatita como cobertura (IPS e.maxZirPresss/Ivoclar-Vivadent). Para a cimentação os dentes/coroas/cimento foram subdivididos aleatoriamente e, a foto ativação dos cimentos dual e físico, foi realizada com dois protocolos: foto-ativação nas faces vestibular, oclusal e lingual, com o tempo de exposição de 20s sequencialmente e foto-ativação somente por oclusal pelo tempo de 60s. O cimento químico foi mantido sem aturdimento por 15 minutos. Após a cimentação, os espécimes foram armazenados em água deionizada em estufa com temperatura de ±36oC e seccionados transversalmente após 7 dias em 3 regiões: cervical, no centro da coroa e 2mm aquém da face oclusal. O grau de conversão foi determinado pela técnica da espectroscopia Micro-Raman ao longo da linha de cimento nas face vestibular, mesial, lingual e distal. Os resultados foram submetidos a uma análise estatística ANOVA os quais mostraram que o GC dos cimentos com ativação em três faces sequencialmente depende da interação entre o tipo da cerâmica e da marca comercial do cimento; o GC sob a cerâmica de dissilicato de lítio é maior do que sob as cerâmicas de zircônia; em relação as faces e terços, o GC mostrou ser material dependente. Conclui-se que, o protocolo de ativação e a composição da cerâmica tem influência no GC dos cimentos analisados. / There is a growing application of resin-based cements in ceramic prostheses for displaying aesthetic and biomechanical properties superior to conventional cements. The present study aimed to evaluate the degree conversion (DC) of four resin cements, one with physical curing mode (ChoiceTM 2/Bisco Inc), two dualcuring mode (DuolinkTM / Bisco Inc; VariolinkII® / Ivoclar-Vivadent) and one chemical curing mode (C&BTM / Bisco Inc) employed in the cementation of crowns made of ceramic. We used 42 human premolars were prepared to receive full crowns made with two ceramic systems: lithium disilicate ceramic (IPS eMaxPress/Ivoclar- Vivadent®) and Yttrium oxide stabilized zirconia (IPS e.maxZirCAD / Ivoclar - Vivadent®) for the fabrication of copings, with a ceramic veneer as fluorapatite based (IPS e.maxZirPresss / Ivoclar-Vivadent). For cementation, teeth/crowns/cement were randomly divided, and the photo activation of dual cements and physical, was performed with two protocols: photo-activation in the buccal, occlusal and lingual, with an exposure time of 20s in each face and photo-activation only by occlusal for 60s. The cement chemical was maintained for 15 minutes without stunning. After cementation, specimens were stored in deionized water in an oven at a temperature of 37°C and sectioned after 7 days in three regions : cervical, in the center of the crown and 2 mm below the occlusal surface. The degree of conversion was determined along the cement line in the buccal, mesial, lingual and distal by micro- Raman spectroscopy. The results were submitted to statistic analysis by ANOVA which showed that the DC of cements with activation in three sequentially faces depends on the relationship by ceramic composition and cement trademark; the DC under lithium dissilicate ceramic is greater than in the zirconia; regarding the faces and thirds, DC proved to be material dependent. In conclusion, curing protocol and ceramic composition has a influence on DC of the cements analyzed.

Os objetivos deste trabalho foram: 1) avaliar o efeito do envelhecimento por ciclagem mecânica (1 milhão de ciclos a uma freqüência de 2 Hz) sobre a resistência à flexão biaxial de três materiais cerâmicos utilizados para a construção infra-estruturas de próteses parciais fixas: a) uma zircônia tetragonal policristalina estabilizada por ítria (Y-TZP); b) uma alumina policristalina (AL) e c) um compósito de alumina e zircônia infiltrado por vidro (ICZ) e 2) determinar a influência da tensão gerada durante a ciclagem sobre a degradação da resistência das cerâmicas estudadas, já que para cada material a ciclagem foi realizada com dois níveis diferentes de tensão. Material e método: Espécimes em forma de disco (12 mm x 2 mm e 12 mm x 1 mm) foram confeccionados conforme as recomendações dos fabricantes. A resistência à flexão desses materiais foi determinada por meio do ensaio de flexão biaxial. Para o grupo controle de todos os materiais estudados (espécimes de 1 mm de espessura), foi realizada estatística de Weibull para determinação da resistência característica (0) e módulo de Weibull (m). Após o envelhecimento por ciclagem mecânica, realizado para todos os materiais nas duas espessuras, os espécimes foram fraturados e os valores obtidos foram comparados com seus respectivos grupos controle. Resultados: O valor de m foi estatisticamente semelhante para todos os materiais, o ICZ (12,2) apresentou o maior valor comparado ao do Y-TZP (9,0) e do AL (8,4). Os valores de resistência característica, 0, apresentaram diferenças significantes para todos os materiais, 828 MPa para a Y-TZP, 405,8 MPa para a AL e 328 MPa para o ICZ. Não houve diferenças estatisticamente significantes entre as resistências medidas para os grupos controle e ciclado para nenhum dos materiais nas duas espessuras avaliadas. Conclusão: O envelhecimento por ciclagem mecânica não causou alterações significativas nos valores de resistência à flexão de nenhuma das cerâmicas testadas. O aumento no nível de tensão aplicada na ciclagem mecânica não gerou um aumento na degradação da resistência dos materiais estudados. / The objectives of this study were: 1) To evaluate the effect of aging by mechanical cycling (1 million cycles at a frequency of 2 Hz) on the biaxial flexural strength of three dental ceramics used as framework materials for fixed partial dentures (FPDs): a) yttria partially stabilized zirconia tetragonal polycrystals (Y-TZP), b) alumina polycrystals (AL) and c) alumina-based zirconia-reinforced glass infiltrated ceramic (ICZ) and 2) determine the influence of stress level generated during mechanical cycling on the flexural strength degradation of the studied ceramics. Materials and Methods: Disc-shaped specimens (12 mm x 2 mm and 12 mm x 1 mm) were prepared according to manufacturer\'s recommendations. The flexural strength of these materials was determined by biaxial flexure test for the control group of all materials. The Weibull statistics was performed to determine the characteristic strength (0) and Weibull modulus (m). After mechanical aging, the specimens were fractured and the values obtained were compared with their respective control groups. Results: No statistically significant differences were founded between the strength obtained for the control and cycled groups for any of the materials in the two thicknesses tested. The m value was similar for all materials, ICZ (12.2) which showed the highest value, followed by the Y-TZP (9) and AL (8.4). The values for characteristic strength (0) showed significant differences for all materials, 828 MPa for Y-TZP, 405.8 MPa for AL and 328 MPa for ICZ. Conclusion: Aging by mechanical cycling did not cause significant changes in the values of flexural strength for all the ceramics tested. The increase in the stress level during cyclic loading did not cause an increase in the strength degradation of the materials studied.

Neste trabalho, foi desenvolvida e caracterizada a cerâmica à base de zircônia tetragonal aditivada com biovidro para aplicações em implantes ou próteses. Essa zircônia (Y-TZP) tem conteúdo de 3% em mol de Y2O3, com objetivo de estabilizar a fase metaestável tetragonal, a qual possui características de conferir características tenacificantes ao material. O Biovidro utilizado como aditivo de sinterização, e, supressor de interstícios foi de composição (em peso) 52,75% CaOP2O5, 30% SiO2 e 17,25% MgO.Na preparação do Biovidro os pós foram moídos, misturados e peneirados a 63 um. Misturas contendo pós de Y-TZP e Biovidros foram preparadas nas propoções (em peso) de 0, 3, 5 e 10%. As misturas destes pós foram moídas e homogeneizadas em meio úmido, utilizando moinho planetário e, em seguida, secadas, desaglomeradas e peneiradas a 63 um. Foram feitos estudos sobre o comportamento dos compactados durante a sinterização, utilizando dilatometria. As misturas foram compactadas por prensagem uniaxial à frio e submetidas à sinterização em 1300ºC, a uma taxa de aquecimento de 10ºC/min, patamar de 120 min e taxa de resfriamento de 5ºC/min. As amostras sinterizadas depois de retificadas, foram cortadas em hastes nas dimensões (mm) 3x4x45, seguindo as especificações ditadas pela norma DIN EM 843-1 (ASTM C 1161-90) e polidas. Os corpos de prova tiveram analisada a densidade relativa, identificação das fases por difração de raios X, e microestrutura por microscopia eletrônica de varredura (MEV), determinando-se o tamanho e a morfologia (razão de aspecto) média dos grãos. A dureza e a tenacidade à fratura, desses corpos sinterizados, foram avaliados utilizando método de identação Vickers. Quanto à resistência mecânica foram aplicados ensaios de flexão estática e de fadiga, utilizando dispositivo de flexão em 4 pontos. Os resultados indicaram que as amostras com maiores teores de biovidro (10%), apresentam baixa densidade relativa, enquanto as amostras com 3 e 5% possuem alta densificação, sendo indicadas para aplicações estruturais. Esses resultados são relacionados ao aumento da quantidade de fase monoclínica das amostras com 10%, o que gera microtrincamento e, consequente aumento da porosidade. Esse efeito interfere diretamente nas propriedades mecânicas, as quais indicam que amostras com 3 e 5% de biovidro possuem dureza próxima a 1150 HV, tenacidade à fratura de 6,1 a 6,3 MPam1/2, e resistência a flexão de 360 a 450 MPa. Esses resultados são superiores aos relatados a zircônica monolítica (sem adição de biovidro) e, ao material aditivado com 10% de biovidro, os quais apresentaram resultados sensivelmente inferiores da ordem de 900 HV, tenacidade máxima de 4 a 5 MPam1/2 e resistência a fratura média de 125MPa (Y-TZP) e 300MPa (Y-TZP-10% biovidro). Os resultados dos testes de fadiga indicaram que as amostras sofrem grande espalhamento de valores, os quais são inerentes das características microestruturais do material. Estas se devem principalmente ao espalhamento heterogêneo dos vidros (fase líquida) pela matriz de ZrO2 durante o processo de sinterização, promovendo regiões com diferentes quantidades de fase intergranular, o que ocasiona formação de campos com diferentes concentrações de tensão, que são, possivelmente, responsáveis pelo aparecimento das trincas e, seu respectivo crescimento subcrítico durante os testes de fadiga. Com a diminuição da tensão aplicada nos testes de fadiga, foi encontrado que o limite de resistência a fadiga destes materiais está na ordem de 220 MPa, para ambas as composições com 3 e 5% de Biovidro. / Not avaliable.

Ceramic materials are natural or synthetic, inorganic, non-metallic materials incorporating ionic and covalent bonding. Most ceramics in use are polycrystalline materials where grains are connected by a network of solid-solid interfaces called grain boundaries. The structure of the grain boundaries and their arrangement play a key role in determining materials properties. Developing a fundamental understanding of the formation, structure, migration and methods of control grain boundaries have drawn the interest of scientists for over a century.<br> While grain boundaries were initially treated as isotropic, advances in materials science has expanded to include energetically anisotropic boundaries. The orientation and structure of a grain boundary, determined by this anisotropy, controls the mobility of a grain boundary. The mobility is the controlling factor during grain growth impacting the microstructural evolution of a material.<br> This thesis covers fundamental research to model how a materials’ equilibrium crystal shape can be used as a grain growth control mechanism. First an overview of ceramic processing and microstructural development is presented with a focus on the role of grain boundaries in determining the properties of a material. The role of anisotropy and related recent work is highlighted setting the foundation for the link between the equilibrium crystal shape and grain growth. A discussion on the selection of the NiO-MgO system for all experimental work is included.<br> A novel production and processing route for NiO-MgO was developed. Mechanical alloying and milling resulted in significant impurity contamination therefore a chemical production route was used. A modified amorphous citrate process was developed where metal salts containing Ni and Mg were mixed with a polyfunctional organic acid. Rapid dehydration and calcination at 500°C resulted in chemically homogeneous powders. The amorphous citrate production route produced powder with crystallites ranging from 244-393 nm and agglomerates ranging from 20-300 μm with plate-like morphology.<br> NiO-MgO powders produced via the amorphous citrate method were sintered using various techniques. Conventional sintering was unable to produce fully dense samples peaking with relative densities from 95-96%. The introduction of pressure through spark plasma sintering and hot pressing improved the relative sample density to 97-100%. It was discovered that exposure to the vacuum required for spark plasma sintering and hot pressing resulted in the reduction of NiO. Spark plasma sintering created oxygen depleted regions and hot pressing further reduced NiO to pure nickel metal which precipitated out at the grain boundaries.<br> Due to the poor sintering behavior of NiO-MgO grain growth experiments were carried out on the large agglomerates formed during the amorphous citrate process. Agglomerates with more than 50 grains with a thickness of at least 1 μm were selected. Grain growth was measured across five compositions with Ni:Mg ratios of 100:0, 75:25, 50:50, 25:75, 0:100. The average grain size and growth rate increased with increasing nickel content with a significant jump between 50% and 75%. Increasing nickel content was also observed to correspond with a higher number of grains exhibiting surface faceting.<br> The NiO-MgO equilibrium crystal shape as a function of composition was measured previously. To make the equilibrium crystal shape a more viable control for grain growth a quantitative microstructural characterization technique was developed to measure a materials equilibrium crystal shape. Topographic surface information (surface facets measured by atomic force microscopy, AFM) and grain crystallographic orientation (measured by electron back-scattered diffraction, EBSD) were combined to produce the crystallographic topography of a sample surface. Surface crystallographic topography was used to identify the faceting behavior of grains with a range of orientations. Using the combined data, facet stability maps (n diagrams) for NiO-MgO were developed.<br> Controlling grain growth via the equilibrium crystal shape offers the potential to produce microstructures with a high frequency of desirable grain boundaries (grain boundary engineering) and therefore properties. The combination of using AFM and EBSD to create crystallographic topographical surface data and n-diagrams has been demonstrated. N-diagrams for most materials do not exist, but the technique used here can be applied to a wide range of materials and will expand the ability to control microstructures of ceramic materials.<br><br>

Le sujet de ce mémoire de thèse concerne l’usure des inserts en carbure de tungstène soumis à des sollicitations d’impact-glissement. Ces inserts situés sur la tête de coupe de tunneliers permettent d’excaver le sol. Ces carbures sont caractérisés par une dureté élevée et une résistance à l’usure importante ; néanmoins, ils sont soumis à des conditions d’excavation sévères qui finissent par les endommager. Il est donc primordial d’augmenter leur résistance à l’usure afin d’augmenter leur durée de vie dans le but de réduire les opérations de remplacement et les coûts. Une étude expérimentale avec un banc d’impact-glissement permet de solliciter les carbures de tungstène dans des conditions proches de celles rencontrées lors de l’excavation. Nous analysons trois carbures de tungstène avec des propriétés et des compositions différentes. Un des trois carbures sert de référence et est utilisé industriellement. Les deux autres carbures ont été développés récemment. Une bille, en acier 100Cr6 ou en carbure de silicium, est soumise à un déplacement vertical, et vient impacter l’échantillon en carbure de tungstène. Le déplacement de deux lames flexibles, situées sous l’échantillon impacté, permet de générer le glissement au moment de l’impact. L’abrasion et l’adhésion sont les principaux mécanismes d’usure, accompagnés de la formation de fissures dans le cas du carbure le plus fragile. Le volume d’usure dépend fortement de l’énergie d’impact, du nombre d’impacts, de l’angle d’impact, de la nature des matériaux au contact et de l’environnement de contact. Le carbure de référence s’use le plus parmi les trois carbures. De plus, le glissement contribue à augmenter l’usure et la bille en SiC forme une couche sacrificielle avec l’un des carbures développé récemment. La présence d’argon au contact tend à réduire l’adhésion et, par conséquent, l’usure est moins sévère. Parallèlement aux tests expérimentaux, une analyse numérique par éléments finis sous Abaqus/Explicit est réalisée. Un modèle 3D représentant le contact entre la bille et le plan incliné a été développé en mettant en avant la dynamique du contact. Cela nous donne accès à des grandeurs non déterminées expérimentalement (distance glissée, énergie dissipée par frottement, énergie de déformation plastique, contraintes au contact) et permet ainsi de mieux comprendre les mécanismes mis en jeu lors du contact. Les coefficients énergétiques d’usure obtenus expérimentalement sont mis en corrélation avec les énergies dissipées par frottement et les énergies de déformation plastique. La distribution des contraintes de traction et de compression permet d’établir un lien avec la formation des fissures pour le carbure le plus fragile. Cette approche expérimentale combinée à la simulation numérique nous permet de mieux comprendre les phénomènes d’endommagement qui se déroulent au contact de l’insert. / Tungsten carbide cutting tools are very frequently used for tunnel boring machines, as inserts on the drag bits at the front face. With their high toughness, hardness and their wear resistance, they are highly suitable for this kind of application. During excavation, those tools are subjected to important mechanical stresses mostly represented as repetitive impacts combined with the sliding motion induced by the rotation of the cutting wheel. In this regard, their lifetime should be optimized in order to reduce the maintenance operations cost. This thesis highlights the wear mechanisms associated to the impact-sliding motion of tungsten carbide cutting tools. An experimental approach is presented with an impact-sliding test rig allowing to represent the contact dynamics closed to the one observed during the excavation. The test rig is developed with a ball/flat configuration. The ball undergoes a vertical sinusoidal motion derived by an electromagnetic shaker and impacts the inclined tungsten carbide sample. There are two vertical foils underneath the tungsten carbide, which slide backward during the impact: this induces the sliding motion. Three types of tungsten carbides with different chemical compositions, production processes and mechanical properties have been tested. AISI 52100 and SiC balls are considered in this study. Abrasion and adhesion are mainly observed on wear scars, with cracks initiation for the more brittle tungsten carbide. Wear volume depends on many factors : the impact energy, the number of impacts, the impact angle, the ball material, the hardness of materials and the environment under which they are tested. The reference material wears out the most with larger wear scars. The sliding motion contributes greatly on the wear and SiC ball tends to create a sacrificial layer in some conditions. Tests run under argon showed that adhesion is less likely to occur at the contact. Besides, a 3D finite element dynamic model has been developed with the use of ABAQUS/Explicit. Experimental data are taken into account in order to obtain simulation conditions analogous to those in the experimental study. This numerical approach gives an insight on wear phenomena involved in this impact-sliding contact. In addition to this, parameters that were unreachable experimentally could be calculated (sliding distance, friction dissipated energy, plastic deformation energy). Energetic wear coefficient, calculated experimentally, can be correlated with the dissipated energy and the plastic deformation energy. Cracking features are linked to the contact stress distribution. Numerical results provide an input on experimental data and help in understanding complex wear processes entailed in this impact-sliding conditions.

Global warming and the high energy demands of fossil fuel in industries have led governments to implement legislation aimed towards developing more energy efficient and sustainable processes. In the brickwork industry, the burning of coal and natural gas provides the energy to fire clay bricks in the 900-1200 oC range into high quality building materials. Microwaves powered by renewable energy sources have been suggested as a sustainable alternative to fossil fuels. Microwave heating has been considered a promising technique for the processing of clays due to the potential energy consumption and carbon footprint reductions, and for its volumetric heating nature, which enables the fast and uniform heating of a load. This could result in improving the mechanical properties of the fired products. The aims of this project were to develop an understanding of how microwaves interact with clays in order to show whether they could be used to fire clay-based building materials, and to understand how this could be achieved and the parameters that affect it. The composition of Danish clays was quantified, i.e. quartz, calcite, albite, orthoclase, kaolinite, montmorillonite and muscovite, and their thermal evolution was studied across the firing range. The dielectric properties of clays were measured at 912-2470 MHz and 20-950 oC in order to investigate the microwave/clay interaction, assess the effects of changing composition, temperature, frequency and material's density on their potential for microwave processing, and provide critical information on the design and scale up of this technology. Relating the mineralogy of a material and its evolution during heating to changes on the dielectric property trends, and thus microwave processability, was examined for the first time in this thesis. Insight into the influence of individual components on the potential for microwave heating was gained from an analogous study on clay constituents. While the dielectric constants of clays were found to be relatively stable during heating, their loss factors fluctuated with temperature. Free and physically bound water were the dominant dielectric species near room temperature, while their removal halved the loss factors until 350 oC. Beyond this temperature, a steady increase in the loss factors concurred with the mineral dehydroxylations. The loss factors sharply rose beyond 800 oC due to sintering effects, while calcite decomposition partially counteracted this growth. Montmorillonite and muscovite were the most microwave absorbing mineral species due to their water affinity and interlayer cation content, enabling the microwave treatment of the whole clay. On the other hand, a frequency shift from 2470 MHz to 912 MHz resulted in a loss factors increase. This is mainly due to the frequency shifting towards the dipolar dispersion area of physically bound water and the zone in which ionic conductivity heating effects dominate. Mixing rules were used to relate each single mineral to dielectric property variations, and thus rapidly gain knowledge of the microwave processability of any clay across the firing range based on its composition. Böttcher model provided accurate estimations when compared to experimental measurements, and with the same degree of uncertainties at the 912-2470 MHz frequencies and 0.56-0.37 void fraction ranges. The model was expanded for different compositions with clays from Spain, England and Netherlands. This was the first time that mixing rules were successful in estimating mixtures of more than three constituents. A microwave system was developed with the aim of firing clay products of comparable quality to conventional specimens. The basis of design focused on maximising the thermal uniformity of the clay load. The process design steps involved remodelling the clay load, building heat transfer models of the load, carrying out trials to study whether clays behave as expected from their dielectric properties, i.e. volumetric or selective heating, minimising thermal gradients, and assessing alternative methods for the control of the holding stage. Microwave firing cycles manufactured clays with a thermal uniformity at the height of firing of 1050±55 oC and reduced processing times to < 3 h. This is 92% faster than in brickworks, where conventional samples could not match the heating rates without cracking. High temperature (>800 oC) mineral reactions went unfinished due to the reduced holding time of the microwave treatment (30 min), which resulted in dimmer surface colorations. Enhanced thermal uniformity and reduced time for densification resulted in specimens with a 12% higher compressive strength, 38% larger water absorption and 7% higher void fraction. Clay samples three times as big were fired to gain an insight into the scale up of the technique. A tighter process control and higher reproducibility were reported, which is promising for potentially allowing longer holding times in scaled up processes, but the product quality improvement did not change. Looking into an industrial scale up, further work would be required to assess possible design concepts, and an optimal microwave firing process may require complete redesign of the furnace configuration, where several challenges need to be considered, such as brick arrangement, power availability and applicator size and shape. For the purposes of assessing the possible economic and environmental impact of implementing microwave clay firing at industrial scale, one of the most straightforward designs, i.e. retrofitting of an industrial tunnel kiln for microwave processing, was considered. Although energy expenditures would decrease from 11.6 GJ fuel/h to 6.1 GJ electricity/h when using a microwave system for the same throughput, the higher cost of electricity and microwave equipment over conventional burners made the conventional technique more economically feasible. The substitution of natural gas by electricity powered by green energy sources resulted in carbon footprint reductions of >95%, and agreed with the energy policies of numerous countries and supranational organisations worldwide.

The thermoelectric properties and microstructure of two families of misfit type layered structure cobaltites were investigated for thermoelectric applications. Firstly, Bismuth strontium cobaltite ceramics with the formulations Bi2+xSr2Co2Oy (x=0, 0.1 and 0.2), Bi1.74Sr2Co1.8Oy and Bi2Sr2Co1.8Oy were produced using solid-state reaction (MO) method. The same powders were also used to produce ceramics by Spark Plasma Sintering (SPS) fabrication technique. SEM, high resolution XRD and HRTEM techniques has been employed to characterise the microstructure and crystal structures of the ceramics. Figure of merit (ZT) was also determined from measurement of electrical resistivity, Seebeck coefficient and thermal conductivity. Together with the above, calcium cobaltite of formulation Ca3-xBixCo3O9 (x=0 and 0.3) was also produced via MO and SPS routes. The same characterisation techniques were used for characterisation of calcium cobaltite. For Bi2+xSr2Co2Oy ceramics, it was found that SPS fabrication is essential to obtain high density samples. Excess bismuth has a major role in the adjustment of the microstructure and thermoelectric properties. The room temperature microstructure contains two minor phases with compositions of CoO and Bi0.75Sr0.25O1.26. The crystal structure of the main phase was successfully indexed and refined as misfit type structure having monoclinic symmetry with I2/a space group. A high ZT of 0.12 was achieved in both x=0.1 and 0.2 MO samples. For Bi2Sr2Co1.8Oy ceramics, the microstructure contains only one minor phase, Bi0.75Sr0.25O1.26. A high ZT of 0.16 was obtained at 900 K for this composition. For Bi1.74Sr2Co1.8Oy, it was not possible to obtain high density ceramics by MO route and SPS fabrication was necessary. However, SPS sample showed a low ZT of 0.04 at 900 K.For ceramics of formulation Ca3-xBixCo3O9 (x=0 and 0.3), it was difficult to obtain high density calcium cobaltite ceramics by MO route and SPS fabrication was found to be essential. In addition to improved density, SPS produced textured microstructure. Similar to bismuth strontium cobaltite, excess bismuth played a major role in microstructure development and thermoelectric properties. Single phase and high density Ca3Co4O9 ceramics were obtained by SPS. A minor phase of Bi2Ca2Co2Oy was found in the microstructure of Ca3-xBixCo3O4 (x=0.3) samples. A high ZT of 0.25 was obtained for Ca3Co4O9 SPS samples at 900 K through improvement of power factor. In-situ synchrotron XRD in the temperature range of 300-1223 K was performed on both Bi2Sr2Co2Oy and Ca3Co4O9 to obtain their high temperature structural characteristics. The crystal structure of both compounds remains unchanged till 1223 K. For, Bi2Sr2Co2Oy the CoO and Bi0.75Sr0.25O1.26 minor phases disappear above 1073 K and a new minor phase containing (Bi-Sr-O) or (Bi-Co-O) starts forming. On heating, the lattice volume and coefficient of thermal expansion change linearly for both compounds. Thermal expansion coefficient was found to be 0.0000353-0.0000343 and 0.0000296-0.0000288 K-1 over the temperature range of 300-1223 K for Bi2Sr2Co2Oy and Ca3Co4O9 respectively.

This PhD project is focused on three lead-free ferroelectric solid solutions, which are specifically Na0.5Bi0.5TiO3-KNbO3(NBT-KN), Na0.5Bi0.5TiO3-NaNbO3(NBT-NN) and Na0.5Bi0.5TiO3-BaTiO3(NBT-BT), to evaluate the effects of composition, electric field and temperature on structural and electrical properties. Novel observations of both reversible and irreversible electric field-induced phase switching were made in both NBT-KN and NBT-NN ceramics. The NBT-KN solid solution is the primary focus of this thesis. All compositions were observed to be cubic in the as-sintered, unpoled state. However, a well-defined ferroelectric hysteresis P-E loop was obtained for compositions with low KN contents, indicating that an irreversible phase transition from a weak-polar relaxor ferroelectric (RF) to a long-range ordered metastable ferroelectric (FE) state had occurred during the measurement procedure. Both the unpoled and poled ceramic powders were examined using high resolution synchrotron XRD. For the poled state, a rhombohedral R3c structure was identified for compositions with low KN content, confirming the occurrence of the irreversible electric field-induced structural transformation from cubic to rhombohedral. In contrast, a cubic structure was retained for high KN contents, giving rise to reversible phase switching evidenced by constricted P-E hysteresis loops. Similar behaviour was observed for NBT-NN system. An 'in-situ' electric field poling experiment was conducted using high energy synchrotron XRD. In certain NBT-KN compositions the structural transformation, from cubic to mixed phase cubic+rhombohedral and finally single phase rhombohedral, occurred progressively with increasing cycles of a bipolar electric field. Similar behaviour was observed for NBT-NN compositions having low NN contents. Furthermore, the distributions of domain orientation and lattice strain over a range of orientations relative to the poling direction were determined for NBT-KN, NBT-NN and NBT-BT ceramics exhibiting the rhombohedral phase. By combining the structural information with the results of dielectric and ferroelectric measurements, a phase diagram was constructed to illustrate the influence of temperature and composition on the stability of the metastable ferroelectric and relaxor ferroelectric states for the NBT-KN system. Furthermore, the phase transition temperatures obtained from dielectric measurements were correlated with the ferroelectric and thermal depolarisation characteristics for each of the NBT-KN, NBT-NN and NBT-BT systems.