Resumo: O objetivo deste projeto foi estudar o efeito da segregação de dopantes em cerâmicas à base de SnO2 obtidas pelo método de mistura de óxidos para verificar como a segregação dos dopantes para o contorno de grão influencia as propriedades elétricas que são, basicamente, uma propriedade do contorno de grão nas cerâmicas de SnO2. Estes resultados foram comparados com os resultados obtidos para as cerâmicas preparadas pelo método de precipitação com uréia. As características morfológicas dos pós foram correlacionadas às características elétricas e microestruturais das cerâmicas. As características de microestrutura e de segregação foram acompanhadas por microscopia eletrônica de varredura e por microscopia eletrônica de transmissão. As características elétricas incluíram medidas de impedância complexa e de tensãocorrente. Os valores de energia de barreira de potencial aumentaram com a concentração de Cr2O3 para os sistemas à base de SnO2. Observou-se que a resistividade elétrica, dos sistemas dopados com cromo, aumentou com sua concentração e este comportamento pode ser atribuído à diminuição do tamanho médio de grão que acompanha o aumento da concentração de cromo. A partir das concentrações ≥ 0,10 % mol de Cr2O3 observou-se forte diminuição nos tamanhos de grão das amostras. O circuito equivalente é do tipo 'arco de Cole' que apresenta um elemento de fase constante atribuído às depressões dos semicírculos. Através da aproximação de Mukae, calculou-se os valores de densidade de doadores de carga, densidade de estados de superfície e tensão por barreira. Observou-se que estes parâmetros aumentaram com a concentração de cromo e que os valores de coeficiente não-linear apresentaram tendência de acompanhar o aumento desses valores nos sistemas estudados. Os sistemas preparados pelo...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The objective of this project was to study the effect of dopant segregation in SnO2-based ceramics obtained by the method of oxide mixture in order to verify how the segregation of the dopants into the grain boundary influences the electrical properties which are, basically, a property of the grain boundary in SnO2 ceramics. These results have been compared with the results obtained for ceramics prepared by the precipitation method with urea. The powder morphological characteristics have been correlated to the electrical and microstructural characteristics of the ceramics. The microstructure and segregation characteristics have been followed by scanning electronic microscopy and transmission electronic microscopy. The electrical characteristics included complex impedance and current-voltage measurements. The values of potential energy barrier increased with the Cr2O3 concentration for the SnO2-based systems. It was observed that the electrical resistivity of the chromium doped systems increased with its concentration and this behaviour can be attributed to the reduction of the mean grain size, which accompanies the increase of chromium concentration. From concentrations ≥ 0,10 % mol de Cr2O3 it was observed a strong reduction in the grain sizes of the samples. The equivalent circuit is of the 'Cole arc' type which presents a constant phase element attributed to the depressions of the semicircles. By using Mukae's approximation, the values of charge donors density, surface states density and barrier voltage were calculated. It was observed that these parameters increased with the chromium concentration and that the values of the nonlinear coefficient had a tendency to follow the increase of these values in the studied systems. The systems prepared by the method of conventional oxide mixture presented precipitates, in the grain ...(Complete abstract, click electronic access below) / Orientador: Wanda Cecília Las. / Coorientador: Mario Cilense. / Doutor

Les aubes de turbines haute pression des turboréacteurs sont soumises à des chargements thermomécaniques sévères en service. Elles sont actuellement fabriquées par solidification dirigée sous forme de monocristaux orientés suivant la direction <001> le long de la direction principale de l'aube. La solidification peut entrainer dans certains cas l'apparition de défauts, notamment la formation de deux grains : l'aube est alors constituée de deux grains d'orientations différentes. L'objectif de cette thèse est d'étudier l'influence de la présence d'un joint de grains sur la durée de vie de l'aube en superalliage AM1. Dans un premier temps, nous avons réalisé une étude expérimentale sur aubes réelles afin de déterminer l'influence du joint de grains sur la rupture par fatigue en flexion à différentes températures. Pour cela, des entailles ont été usinées dans les aubes pour solliciter de façon préférentielle le joint de grains au sein de l'aube dans des essais de type flexion. Cette étude a permis de mettre en évidence le rôle du joint de grains sur la durée de vie de l'aube selon la température d'essai, l'orientation cristallographique relative des grains, la position du joint de grains et le type de sollicitation. Parallèlement, une étude exprimentale sur éprouvettes bi-cristallines de type fatigue oligocyclique a été conduite en traction compression, avec une contrainte principale de traction suivant la normale au plan moyen du joint. Ces essais ont permis de quantifier la réduction de durée de vie induite par la présence du joint de grains par rapport à une éprouvette monocristalline. Un critère de rupture a été ainsi introduit dans la loi d'endommagement développée par l'Onera pour le superalliage monocristallin d'AM1. Ce critère de durée de vie a été appliqué dans les simulations numériques des aubes remaillées et permet de faire une première estimation de la nocivité du joint de grains dans les aubes. / The high pressure turbine blade of aeroengine are submitted to severe thermomechanical loading in service. The turbine blade are curently manufactured by directionnal solidification with oriented single crystal on the direction <001>, along the principal direction of the blade.The solidification process can induce different defects in the structure.This study is focused on a particular defect: the formation of two crystals in a blade. Defective turbine blades are composed of two grains with different orientation.The aim of this present thesis is to study the influence of the grain boundary on AM1 superalloy blade fatigue life. First, experimental investigations have been performed to understand at different temperatures, the influence of grain boundaries on fatigue fracture due to bending loadings. Notches have been introduced on turbine blades in order to accentuate solicitations on grain boundary. These experiments have evidenced the major role of grain boundary and grains orientations on turbine blade fatigue life.Then another experimental investigation has been carried out under low cycle fatigue on bicrystal specimens with tension/compression loading; the tensile principal stress is along the normal direction of the grain boundary mean plane. These tests allowed quantification of the fatigue life decrease due to the presence of grain boundary compared to the fatigue life of single crystal specimens.A failure criterion have been introduced in the damage constitutive behavior of single crystal AM1 developped by the Onera. This lifetime prediction model have been implemented in FE simulations. It allows the evaluation of the sensivity of grain boundary on turbine blade.

Ce travail de thèse s’est focalisé sur les interactions entre bandes de glissement - localisant la déformation plastique dans les matériaux métalliques polycristallins - et joints de grains. Le matériau choisi comme support de l’étude est un superalliage base Nickel (UdimetTM 720Li). De récents travaux ont montré que les bandes arrêtées aux joints de grains peuvent induire dans les grains voisins des rotations cristallines concentrées au sein de régions appelées micro-volumes. Ce phénomène est observé aux températures faibles et intermédiaires (T < 500°C), sous chargement monotone et cyclique. Il est responsable des premiers stades d’endommagement et conduit à la formation des fissures fatales en fatigue.Une analyse statistique d’un grand nombre d’interactions bandes de glissement – joints de grains via des observations MEB sur éprouvettes pré-déformées a été menée en relation avec les configurations cristallographiques locales afin d’identifier celles qui favorisent ou inhibent la formation des microvolumes.Un rôle particulier de l’angle de twist traduisant l’alignement des systèmes de glissement de part et d’autre du joint de grains a été mis en évidence notamment dans le cas des joints de macle.Ensuite, le travail a porté sur l’établissement de deux stratégies de simulation numérique en champs complets par éléments finis de l’interaction d’une bande de glissement avec un grain voisin. L’étude de la réponse élastique du grain voisin et notamment l’analyse des distributions des rotations cristallines,des contraintes et scissions résolues au sein du grain en tête de la bande de glissement ont permis de mieux comprendre les conditions favorisant la transmission du glissement au joint de grains et celles conduisant à l’arrêt des bandes de glissement avec ou sans formation de micro-volumes. / This thesis research focused on interactions between slip bands – manifestation of plastic strain localization in polycrystalline metallic materials – and grain boundaries. The material chosen for the study is a nickel based superalloy (UdimetTM 720Li). Recent investigations have shown that slip bands blocked at grain boundaries can induce significant crystalline elastic rotation in highly localized regions – referred to as micro-volumes – in neighboring grains. This phenomenon is observed from room to intermediate temperatures (T < 500°C), under monotonic or cycling loading. It is responsible for the first stages of damage initiation and is at the origin of fatigue fatal cracks.A statistical analysis was carried out over a large data set of slip bands – grain boundaries interactions through SEM observations performed on pre-deformed samples. Local crystallographic configurations were investigated in order to identify those that favor or inhibit the formation of micro-volumes. A peculiar role of the twist angle - related to the alignment of slip systems on both sides of the grain boundary – was evidenced, particularly in the case of twin boundaries.Then, two strategies of numerical modeling of the interaction between a slip band and a neighboring grain using full-field finite element simulation were developed. In this work, the elastic regime only is considered and distributions of crystalline rotations, stresses and resolved shear stresses at the tip of theim pinging slip band in the neighboring grain were analyzed in order to better understand the conditions leading to the transmission of slip through the grain boundary and those leading to the termination of slip bands with or without formation of micro-volumes.

A simple method for increasing the stable temperature range of the liquid crystalline blue phase is demonstrated, by mixing a non-mesogenic polymer of low molecular weight into the blue phase material. In a mixture of cholesteryl benzoate and cholesteryl nonanoate the addition of polystyrene increased the stable blue phase range from 0.5K to 12K. This was measured strictly on heating from the chiral nematic phase through the blue phase in order to minimise non-equilibrium effects, and is one of the largest ranges so measured. The stability range can be closely tuned by changing the polymer concentration and molecular weight. The maximum range found by adding a particular compound seems only to depend on its saturation point in the liquid crystal, and the dependence of the range on concentration is non-linear. These features were explained by a numerical model of a blue phase unit cell incorporating the mean field Flory-Huggins and Maier-Saupe theories where the polymer could fill the high energy defect regions. Two of the oligomers which are shown to stabilise the blue phase are fluorescent, at 450nm and 500nm respectively, and it is proposed that tests on these mixtures could reveal photonic effects caused by the concentration of the fluorophores in the blue phase defect regions. The twist-grain boundary (TGB) phase is present in mixtures of cholesteryl oleyl carbonate and cholesteryl nonanoate over a range of up to 0.3K. The addition of polystyrene has no effect on the stability of the TGB phase. Conventional, in situ UV-initiated polymer stabilisation does not appear to stabilise the TGB phase, but is capable of stabilising over at least 30K the micron-size filaments which appear in the TGB phase when it is heated from the smectic phase in a cell with homeotropic alignment. Some notes are made on the causes and structure of this filament texture, and it is observed that the filaments tend to grow with a characteristic curvature. It is shown theoretically that the correct material could stabilise the TGB phase similarly to the polymers in the blue phase, by extending the previous model to include the Kobayashi-McMillan theory of smectic ordering. A second theoretical model of chirality around the transition to the smectic phase is then presented which takes account of fluctuations, based on an analogy with the state of a smectic-forming material infiltrated into an aerogel. A phase resembling the TGB phase emerges from this model. The model gives two first order transitions in accordance with experiments on the TGB phase, and reflects other experimental pitch and calorimetry measurements too. The electrochemical polymerisation of an acrylate monomer in the nematic and smectic-C* phases is investigated. 30-100V is applied across a cell containing the liquid crystal-monomer mixture, with no additional initiating compound. In both phases, the texture during polymerisation is frozen in by the polymer formed. In a nematic phase in a cell with initially planar alignment, the director in the field off state can be observed to tilt toward the homeotropic over a number of hours. In the ferroelectric case, as well as the textural freezing there is a somewhat reversible agglomeration of polymer strands into micron-scale structures. Scanning electron microscopy reveals a range of structures on both electrode surfaces, including in the nematic case corrugations with a periodicity of 500-750nm. There is no evidence of a polymer network spanning the thickness of the cell - rather the liquid crystal seems to be realigned by a polymer film at the electrode surfaces.

BCC metals are commonly used throughout the world and understanding their deformation behavior, especially at the sub-grain level, is essential for their continued use in technological advancements. Correctly and confidently characterizing the active slip systems in BCC materials has been a difficult task throughout past research. The research described in this thesis utilizes high resolution digital image correlation (HRDIC) and relative displacement ratio (RDR) analysis to accurately characterize active slip systems in large grained BCC tantalum and provides new insights into dislocation nucleation sites, relative CRSS values for {110} and {112} slip systems, the correlation between GB transmission factors and strain gradients, the relative length of NBGZs, and slip transmission. A 99.99% pure tantalum oligo sample was sputtered with gold and remodeled to provide high resolution data points to be used in HRDIC. The high resolution of the gold remodeled samples combined with a RDR analysis made it possible to confidently identify active slip systems during tensile deformation at room temperature. One of the observations from this analysis was the discrepancy between the observed active slip systems and those predicted from a simple single-CRSS Schmid's Law. By considering the active systems observed in grains with a range of orientation, it was concluded that the {112} slip systems have a higher CRSS than the {110} by 6.7%. Independent CPFE simulations and experiments on single crystal samples of the same material, agreed with our findings establishing a range of increased CRSS for {112} of 3.9%-7.1%. These conclusions are compared with the small number of available estimates of the CRSS ratio, and lie in between the value of equal CRSS used by most modelers, and experimental estimates of 15-25% higher for {112}. The identified active slip systems were also used in the Luster and Morris equation to calculate each GBs transmissivity factor - an estimate of strain incompatibility between neighboring grains. Results indicate that there is an inverse correlation between GB transmissivity and strain gradient slope, as well as a positive correlation between GB transmissivity and slip trace reorientation for some GBs. Only one instance of slip transmission was observed from the 24 GBs analyzed, suggesting it is an uncommon occurrence in BCC tantalum. An analysis of the length of the NBGZ in relation to slip and strain gradients was compared to previous studies and suggests the relative and absolute length of the NBGZ changes with grain size, at least for large length scales. Strain gradients for each side of the GB were measured and results indicated steep negative strain gradient slopes that suggest dislocation nucleation in the GBs and propagation towards the interior of the grain. When compared against the transmissivity factor, an inverse relationship was found to exist between strain gradients and high transmissivity factors.

A highly resolving micro-light beam-induced current (µLBIC)-system is presented in this work. Based on the laser excitation via an optical microscope, current values can be measured with sub-micron precision. We show, that this non-destructive, light-based approach delivers superior results to a reference electron microscope based electron beam induced current method concerning contrast and robustness towards reflection differences, whereas no vacuum is needed, no charging effects can occur and equal resolution is achieved. µLBIC allows therefore mapping of pn-junctions at silicon solar cell cross sections. By combination of µLBIC with other measurement methods in the same setup, such as micro-Raman spectroscopy, complementary microscopic information about material stress or crystallinity and electronic properties at the same region of interest on the sample is revealed. By applying µLBIC for analyzing silicon solar cross sections, two characterization examples of current technological relevance are presented: enhanced dopant diffusion along grain boundaries between grains with different orientations is quantified and the impact of a nickel silicide spike on local charge collection quality is studied.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21767号 / 工博第4584号 / 新制||工||1714(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 乾 晴行, 教授 安田 秀幸 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Understanding microstructural evolution in Friction Stir Welding (FSW) of steels is essential in order to understand and optimize the process. Ferritic steels undergo an allotropic phase transformation. This makes microstructural evolution study very challenging. An approach based on Electron Backscattered Diffraction (EBSD) and phase transformation orientation relationships is introduced to reconstruct pre-transformed grain structure and texture. Reconstructed pre-transformed and post-transformed grain structures and textures were investigated in order to understand microstructural evolution. Texture results show that there is evidence of shear deformation as well as recrystallization in the reconstructed prior austenite. Room temperature ferrite exhibits well-defined shear deformation texture components. Shear deformation texture in the room temperature microstructure implies that FSW imposes deformation during and after the phase transformation. Prior austenite grain boundary analysis shows that variant selection is governed by interfacial energy. Variants that have near ideal BCC/FCC misorientation relative to their neighboring austenite and near zero misorientation relative to neighboring ferrite are selected. Selection of coinciding variants in transformed prior austenite Σ3 boundaries supports the interfacial-energy-controlled variant selection mechanism.

Understanding the mechanisms that control the mechanical behavior of microscale actuators is necessary to design an actuator that responds to an applied actuation force with the desired behavior. Micro actuators which employ a diaphragm supported by torsional hinges which deform during actuation are used in many applications where device stability and reliability are critical. The material response to the stress developed within the hinge during actuation controls how the actuator will respond to the actuating force. A fully recoverable non-linear viscoelastic response has been observed in electrostatically driven micro actuators employing torsional hinges of silicon covered with thin metal films. The viscoelastic response occurs over a time period of 50 minutes at an operating temperature of 35°C. This viscoelastic phenomenon is similar to that reported in articles addressing anelastic behavior associated with viscous grain boundary slippage and dislocation bowing. In order to investigate this viscoelastic response as a function of metal film composition and thickness, bi-layer torsional hinge actuators consisting of Si with a deposited metal layer were designed to exhibit similar stress levels as the electrostatically driven micro actuators. The test devices were fabricated using common semiconductor fabrication techniques. The actuators were micromachined by deep etching 100mm diameter, 425µm thick, double side polished, single crystal (100) wafers to create a 4.5µm thick device layer. Subsequent etching of the device layer released the fixed-fixed torsional hinge test actuators. Physical vapor depositions of Au, Al and Al-Ti in two different thicknesses (100nm, and 150nm) were deposited in order to investigate the impact of metal film thickness and composition on the viscoelastic response. Grain sizes of the deposited films were estimated using backscattered electron images. Rotational actuation of the test actuators was achieved by using a modified Ambios XP-1 surface profiler that applies a constant force of 0.28mN while measuring the displacement of the actuator with respect to time. The viscoelastic response was observed in the test devices with Au and Al thin films indicating that this phenomenon is attributable to the stresses induced on the torsional hinge. Results indicate that the viscoelastic response was not observed in AlTi thin films consisting of 0.3at% titanium. Two theoretical models are presented that discuss the mechanism associated with the viscoelastic response as well as a method for inhibiting these mechanisms by the addition of an alloying element to form a second phase precipitate.

<p> The room-temperature fracture behaviour of calcia partially stabilized zirconia (PSZ) was investigated. Fracture energy measurements were made using the standard stress intensity calibration and work to fracture techniques. The detailed nature of the PSZ microstructure was studied using scanning electron microscopy, qualitative X-ray analysis and T.E.M, surface replication. The grain structure was detenninod to be bimodal with small grains of pure zirconia dispersed along the boundaries of large grains. These large grains consist of a binary pure-zirconia/stabilized zirconia mixture. An attempt was made to relate the fracture properties to the nature of the inherent flaws present in the material. </p> <p> The strength of calcia partially stabilised zirconia was observed to depend on the size and distribution of the grain boundary precipitate of pure zirconia. It is postulated that this grain boundary precipitate causes decohesion and weakening of some of the grain boundaries due to the large internal stresses associated with its martensitic phase transformation. This phenomena of grain boundary decohesion leads to elastic nonlinearity and hysteresis. Crack propagation was always observed to proceed in a slow controlled fashion in this material. A model is proposed to explain theses observations based on the formation of a microcrack zone at the tip of a propagation crack. The occurrence of continued stable crack propagation is believed associated with increasing microcrack zone size with increasing crack length. Evidence supporting this model is presented. </p> / Thesis / Master of Science (MSc)