Objective: The goal of the present study was to investigate the effect of chairside surface treatments on biaxial flexural strength and subsurface damage of monolithic zirconia ceramics. Methods: Specimens (15x15x1.2 mm3) were prepared by sectioning from commercially available zirconia blanks (BruxZirTM) and sintering according to manufacturer's recommendations. Fully dense specimens were randomly divided into five groups (n=30) and treated as follows; 1) as-sintered (AS) 2) air abraded with 50 μm alumina fine particles (AAF), 3) air abraded with 250 μm coarse alumina particles (AAC), 4) ground (G), and 5) ground and polished (GP) to mimic chairside and dental laboratory treatments. Microstructural changes were thoroughly characterized by optical and scanning electron microscopy, surface profilometry and atomic force microscopy. Crystalline phases and their depth profile were investigated by x-ray diffraction (XRD) and grazing incidence x-ray diffraction (GIXRD). Results were analyzed by Kruskal-Wallis test and Tukey's adjustment for multiple comparisons. A 0.05 level of significance was used. Reliability was evaluated by Weibull analysis. Results: All treatment groups exhibited a significant difference in mean surface roughness (Rq) compared to the as-sintered group (p<0.05). The AAC group showed the highest surface roughness at 1.08 ± 0.17 μm, followed by the G, AAF and AS groups. The GP group exhibited the lowest surface roughness. The group air abraded with fine particles showed the highest mean biaxial flexural strength (1662.62 ± 202.58 MPa), but was not different from the ground and polished group (1567.19 ± 209.76 MPa). The groups air abraded with coarse particles or ground with diamond bur exhibited comparable mean biaxial flexural strength at 1371.37 ±147.62 MPa and 1356.98 ±196.77 MPa, respectively. The as-sintered group had the lowest mean biaxial flexural strength at 1202.29 ±141.92 MPa. The depth of compressive stress layer, measured by GIXRD was approximately 50 μm in the AAF group, followed by the AAC group with ~35 μm, ~10 μm for the ground group and ~5 μm for the ground and polished group. Deep subsurface cracks were observed in the AAC group (~80 μm in depth) and G group (~25 μm in depth), whereas shallower flaws were present in the AAF and GP groups at 10 and 3 μm, respectively. Weibull analysis represented a greater reliability in zirconia specimens treated with air abrasion groups. Conclusions: Surface treatments induced the t-m transformation in 3Y-TZP and associated development of compressive stresses to a depth that varied with the severity of the treatment performed. GIXRD revealed that AAF led to the thickest compressive stress layer, followed by AAC, G and GP. SEM revealed that subsurface damage was most severe with AAC, followed by G, AAF and GP. We propose that the flexural strength results can be explained by the difference between the depth of the compressive stress layer induced by the transformation and the depth of the subsurface flaws.

Martensitic phase transformation in NiTi shape memory alloys (SMA) occurs over a hierarchy of spatial scales, as evidenced from observed multiscale patterns of the martensitic phase fraction, which depend on the material microstructure and on the size of the SMA specimen. This paper presents a methodology for the multiscale tracking of the thermally induced martensitic phase transformation process in NiTi SMA. Fine scale stochastic phase field simulations are coupled to macroscale experimental measurements through the compound wavelet matrix method (CWM). A novel process for obtaining CWM fine scale wavelet coefficients is used that enhances the effectiveness of the method in transferring uncertainties from fine to coarse scales, and also ensures the preservation of spatial correlations in the phase fraction pattern. Size effects, well-documented in the literature, play an important role in designing the multiscale tracking methodology. Molecular dynamics (MD) simulations are employed to verify the phase field simulations in terms of different statistical measures and to demonstrate size effects at the nanometer scale. The effects of thermally induced martensite phase fraction uncertainties on the constitutive response of NiTi SMA is demonstrated.

Both LiCoO2 and LiNi1/3Mn1/3Co1/3O2 layered cathode materials are investigated in our studies. P3 phase of CoO2, the end member of the LixCoO2, is found in both chemically and electrochemically delithiated materials. Delithiated LixCoO2 specimens decompose into fine Co3O4 and LiCoO2 particles starting at around 200 °C. This decomposing reaction is proved by in-situ X-ray diffraction and in-situ transmission electron microscopy investigations. The structures of pristine and cycled LiNi1/3Mn1/3Co1/3O2 are investigated by electron diffraction. Single and polycrystalline crystals are found in this material. The partial substitution of Co by Ni and Mn in LiNi1/3Mn1/3Co1/3O2 opens up the possibility of different cation configurations in the crystal lattice. Both 3Rm symmetry and superlattices are identified in this material. The number of particles with superlattices in pristine material (40%) is much bigger than cycled material at discharge state (10%).

Les matériaux ODS (Oxide Dispersion Strengthened), mis au point par métallurgie des poudres, sont la solution de référence pour le gainage du combustible nucléaire des nouveaux réacteurs de génération IV à fort taux de combustion. Ils présentent une résistance au gonflement sous irradiation augmentée par rapport aux aciers austénitiques et une grande stabilité dimensionnelle en fluage induite par une dispersion homogène de nano-particules stables à haute température. Après co-broyage de la poudre d'alliage maître avec une poudre d'oxydes d'yttrium, le matériau est consolidé par filage à chaud, puis mis en forme à froid par laminage à pas de pèlerin. Les matériaux ODS sont caractérisés par une faible ductilité et une dureté élevée à température ambiante. Les passes de laminage doivent être entrecoupées par des traitements thermiques intermédiaires afin de restaurer le tube et éviter tout endommagement pendant la gamme de transformation.Cette étude vise à identifier les points clés pour la maîtrise de la gamme de transformation à froid de deux nuances ODS : une nuance ferritique Fe-14Cr-1W et une nuance martensitique Fe-9Cr-1W. Les relations entre les traitements thermomécaniques et la microstructure sont étudiées à partir de caractérisations multi-échelles. La compréhension des mécanismes d'évolution de la microstructure permet de proposer, pour chaque nuance, une gamme de transformation à froid robuste. Pour la nuance ferritique Fe-14Cr-1W, la déformabilité est assurée par une croissance des grains à haute température suivant un mécanisme de type Strain Induced Boundary Migration (SIBM). Des optimisations s'appuyant sur une recristallisation primaire sont envisagées. Pour la nuance martensitique Fe-9Cr-1W, la gamme mise en œuvre permet d'obtenir un matériau dont la déformabilité et les caractéristiques mécaniques à chaud sont équivalentes voire meilleures que celles des nuances de la littérature. Des évolutions des gammes et de la composition chimique sont proposées pour améliorer la résistance à la corrosion et au fluage. / Oxide dispersion strengthened steels, elaborated by powder metallurgy, are considered as reference materials for high burn up cladding tubes for future Sodium Cooled Fast reactors. They present superior radiation resistance compared with austenitic steels and high creep strength due to reinforcement by the homogeneous dispersion of hard nano-sized particles. After mechanical alloying of the matrix powder and the yttrium oxides, ODS steels are consolidated by hot extrusion and manufactured by using cold pilgerin process. ODS steels are usually characterized by a low ductility and a high hardness at room temperature. The cold-rolling passes have to be punctuated by intermediate heat treatments in order to soften the raw tube and avoid any damage in the course of manufacturing.The aim of this study is to identify the key points for the control of the manufacturing of two grades: a Fe-14Cr-1W ferritic grade and a Fe-9Cr-1W martensitic grade. The relationship between thermomechanical treatments and microstructure is studied by multi-scale characterizations. The understanding of the microstructure evolution permits the determination of robust fabrication routes for both grades. The deformability of the ODS Fe-14Cr-1W ferritic grade is ensured by grain growth at high temperature following a Strain Induced Boundary Migration (SIBM) mechanism. Optimizations through primary recrystallization are proposed. Fabrication route of ODS Fe-9Cr-1W martensitic grade permits to obtain a material characterized by deformability and high temperature mechanical properties similar or even better than those of literature grades. Fabrication routes evolutions and chemical composition optimization are proposed to improve the corrosion and thermal creep resistance.

No presente trabalho, foi realizado um estudo sobre a influência da adição do boro em um aço C-Mn, nas transformações de fases por resfriamento contínuo, através da técnica dilatométrica. Para este estudo, utilizou-se dois aços de composição química semelhante: o aço 10B22 com 30 ppm de boro e o aço sem boro é o E1522, equivalente. Foram traçadas as curvas de CCT dos dois aços, onde analisou-se o efeito de temperabilidade do boro através das curvas de resfriamento. Os materiais foram ensaiados em um dilatômetro de resfriamento rápido, utilizando corpos de prova cilíndricos, resfriados por injeção de ar e hélio. Os resultados gráficos dos processos de resfriamento foram comparados com análises metalográficas ótica estruturais e quantitativas e também por medidas de dureza. Detalhes microestruturais, tais como, contagem de fases formadas em função das taxas de resfriamento, tamanho de grão, distribuição de inclusões e precipitados, foram extraídos, através de um sistema de análise de imagens. Complementando o trabalho, foi realizado uma completa documentação fotográfica das microestruturas, com uma indicação final do tratamento térmico mais adequado aos aços C-Mn microligados ao boro. / This work presents a study about the influence of boron on phase transformation by continuous cooling in a C-Mn steel using the dilatometric technique. For this study two close chemical composition steels were applied: a 10B2 steel with 30 ppm of boron and a E1522 steel without boron. For both steels the CCT curves were obtained, where the effect of boron on hardenability was analysed throughout continuous cooling curves. Both materials were testedcin a high speed quenching dilatometer, using cilindricals samples quenched by helium blow on their surfaces. The graphics results of cooling processes were compared with microstructural and quantitative optical metallographic analysis and hardness measurements. Microstructural features as such phases fraction as a function of cooling rates, grain size, and distributions of inclusions and precipitates were obtained through an image analysis system. In addition, complete microstructural photography documentation was carried out where it was possible to indicate the best heat treatment to boron microalloyed C-Mn steels.

Alumina é um material amplamente aplicado em diversas áreas. Uma dessas aplicações utiliza a alumina amorfa e a alumina gama, como suporte catalítico devido suas elevadas áreas de superfície específica e defeitos em suas estruturas cristalinas. Porém, problemas com a estabilidade das aluminas metaestáveis em altas temperaturas se tornaram um desafio. Assim a combinação da alumina com alguns óxidos emergiu como uma nova classe de materiais catalíticos com melhor estabilidade quando comparada com a alumina gama ou alumina amorfa convencional. Entretanto, entender como se dá à estabilização das fases através desses aditivos se tornou outro desafio. Assim, este trabalho teve como objetivo avaliar os possíveis efeitos de aditivos nas propriedades termodinâmicas da alumina. Além de sua influência sobre a transição de fases amorfo-gama, ou seja, a influência sobre o balanço energético através da evolução do tamanho de partícula. Para isto foram sintetizadas aluminas com diferentes concentrações de Mg2+ e Zr4+ através do método proposto por Pechini. As amostras foram calcinadas e caracterizadas por Calorimetria Diferencial de Varredura, Análise de Superfície Específica pelo método de Adsorção-Desorção de Gases, Difração de Raios X, Espectrometria de Infravermelho por Transformada de Fourier e Picnometria. Os resultados das análises mostraram um aumento da estabilidade para as amostras dopadas com os aditivos, porém com distintas evoluções de área de superfície específica, evidenciando que o caminho adotado pelo aditivo quando inserido em um material matriz independe de sua concentração. / Alumina is a material applied in several areas. One such application uses the gamma alumina and amorphous alumina as catalyst support. The use of alumina as the catalyst support is because of their high specific surface areas and defects in their crystal structures. However, problems with the stability of metastable aluminas at high temperatures have become a challenge. To solve this problem, we use a combination of some oxides to alumina improves the stability of the material when compared with conventional catalytic aluminas. However, a new challenge, to understand the performance of these oxides in the stabilization of alumina. This work aimed to evaluate the possible effects of additives on the thermodynamic properties of alumina, through its influence on the amorphous-phase transition range. The assessment of influence on the energy balance was made by the evolution of particle size. For this alumina powders were synthesized with different concentrations of Mg2+ and Zr4+ using the method proposed by Pechini. The samples were calcined and characterized by Differential Scanning Calorimetry, Surface Analysis by the method of Specific Adsorption-Desorption of Gases, X-Ray Diffraction, Infrared Spectroscopy Fourier Transform and Picnometry. The analysis results showed an increased stability for the samples doped with additives, but with different evolutions of specific surface area, showing the path taken by the additive when inserted into a matrix material depend on its concentration.

Foram realizados ensaios de dilatometria em ligas não comerciais que apresentam microestrutura bainítica após o resfriamento contínuo. As variações de composição química foram realizadas sobre o aço destinado para construção mecânica AISI 5120 com adições de molibdênio, boro e nióbio. Os ensaios foram conduzidos no dilatômetro com atmosfera e temperatura controlada. No dilatômetro, foram aplicados resfriamentos contínuos em diferentes velocidades a partir da temperatura em que normalmente peças forjadas são reaquecidas. Tradicionalmente, a classe dos aços apresentados neste trabalho é exposta ao tratamento térmico de têmpera e revenimento e apresentam microestrutura martensítica. Com o objetivo de eliminar o tratamento térmico realizado pós conformação, foi proposto como substituição os aços bainíticos. Aços bainíticos não exigem tratamento térmico pós conformação e, apenas com a aplicação de um resfriamento controlado, é possível obter uma microestrutura que apresenta propriedades (tensão de escoamento e tenacidade) iguais ou melhoradas em relação ao material temperado e revenido. As microestruturas obtidas nas diferentes ligas resfriadas de maneira contínua foram caracterizadas de modo a estabelecer relações entre a velocidade de resfriamento e produtos formados, morfologia e fração de microconstituíntes. A caracterização microestrutural foi realizada de maneira intensiva de modo a relacionar desde propriedades magnéticas com padrões de difração de raios X das amostras para medição da fração de austenita retida. O objetivo deste trabalho foi investigar qual é a influência do molibdênio, boro e nióbio no resfriamento contínuo de aços bainíticos, bem como estabelecer o intervalo de velocidades de resfriamento em que é possível obter de maneira homogênea a estrutura bainítica. Após o resfriamento, os corpos de prova foram caracterizados por metalografia (microscopia óptica e eletrônica de varredura), dureza, saturação magnética, difração de raios x e EBSD. De fato foi verificado o efeito do molibdênio, boro e nióbio na cinética de decomposição da austenita no resfriamento contínuo e estabelecido relações entre a microestrutura obtida, velocidade de resfriamento e composição química. Foi observado também o efeito do molibdênio, boro e nióbio em evitar a transformação ferrítica para baixas velocidades de resfriamento de modo a obter uma estrutura bainítica sob um maior intervalo de resfriamento. / Dilatometry tests were carried out in a non commercial alloy that showed bainitic microstructure after continuous cooling from the austenitization temperature. The chemical composition variations were performed on a base chemical composition of a commercial steel (AISI 5120), additions were of molybdenum, boron and niobium. The tests were conducted on the dilatometer with atmosphere and temperature control. In the dilatometer, continuous cooling was carried out at different rates from the temperature in which the reheating of forged parts is usually performed. Traditionally, the steels used for this application are quenched and tempered and present a predominantly tempered martensite microstructure; bainitic steels were proposed as a substitution in order to eliminate further heat treatments after forging. The bainitic steels do not require post-conformation heat treatment: only with the application of a controlled continous cooling is possible to obtain a homogenous bainitic microstructure which has equal or improved properties (yield strength and toughness) comparing to quenched and tempered material. The microstructures obtained from the different alloys continuously cooled were characterized in order to establish relations between the cooling rate and formed products, morphology and volume fraction of phases. The microstructural characterization was carried out intensively and correlated with magnetic properties and X-ray diffraction patterns of the samples. The objectives of this work were to investigate the influence of molybdenum, boron and niobium on the continuous cooling of bainitic steels, as well as to establish the range of cooling rates needed in order to obtain an homogeneous bainitic structure. After cooling, the specimens were characterized by metallography (optical and scanning electron microscopy), hardness, magnetic saturation, x-ray diffraction and EBSD. The effect of molybdenum, boron and niobium on the kinetics of austenite decomposition in the continuous cooling was verified and relationships established between the microstructure, cooling rate and chemical composition. It was also observed the effect of molybdenum, boron and niobium in avoiding ferritic transformation at low cooling rates in order to obtain a bainitic structure under a longer cooling interval.

A demanda do silício de grau solar (SiGS) utilizado na indústria fotovoltaica cresce atualmente em uma média de 35% ao ano e a projeção para a próxima década é de constante crescimento. Entretanto, a disponibilidade de matéria-prima para a produção do SiGS não tem crescido na mesma taxa, resultando em uma elevação de seu custo. Logo, a obtenção de rotas alternativas menos onerosas para a produção do SiGS torna-se crucial, principalmente sendo o Brasil o 3o maior produtor mundial de silício de grau metalúrgico. Tendo como objetivo a purificação do silício, o presente trabalho de pesquisa apresenta um estudo detalhado da solidificação direcional do silício, que é uma das etapas utilizadas em todas as rotas alternativas atualmente pesquisadas com o objetivo de purificação. Este estudo foi realizado em um forno do tipo Bridgman vertical, onde o silício líquido contido em um molde foi extraído da região quente do forno, resultando em uma solidificação direcional controlada e ascendente. Dois tipos de silício foram escolhidos como material de entrada para o processo de refino: o silício de grau metalúrgico e o silício de grau metalúrgico pré-refinado por lixiviação. Quatro velocidades de extração do molde entre 5 a 110 mm/s foram empregadas nos ensaios. A macrossegregação de impurezas nos lingotes obtidos foi medida através de análises químicas e a estrutura metalúrgica observada através de macro e micrografias. Os lingotes solidificados com menor velocidade de extração, onde se observa evidências de uma interface sólido-líquido plana, apresentam um grau de refino superior aos de maior velocidade, que mostram evidências de uma interface celular ou dendrítica. As análises químicas mostram que, após a solidificação direcional, os teores de Fe, Al, Cr e Ti medidos nas regiões da base e central dos lingotes atingem níveis especificados para o SiGS por alguns autores. / The demand for solar grade silicon (SiGS) in the photovoltaic industry has grown 35% per year and a constant growth rate is predicted for the next decade. The availability of feedstock to produce SiGS, however, has not grown at the same rate, resulting in increasing SiGS cost. Consequently, the development of less expensive alternative processing routes is of paramount importance to the photovoltaic industry in general, and particularly to Brazil, which is the 3rd largest producer of metallurgical grade silicon. The objective of the present work is to study the directional solidification of silicon, which is a step adopted in virtually all alternative processing routes under development to refine silicon. The directional solidification of silicon was carried out in a vertical Bridgman furnace, where liquid silicon was poured into a quartz mold, which was extracted at constant velocity from the hot region of the furnace, resulting in ascending directional solidification. Two types of feedstock silicon were used, namely, a metallurgical grade silicon that was refined by leaching prior to directional solidification and metallurgical grade silicon as-received from the manufacturer. The quartz molds with liquid silicon were extracted at four different velocities in the range from 5 to 110 mm/s. In the solidified silicon ingots, the macrosegregation of elements were measured using accurate analytical techniques, whereas the metallurgical structures were observed in macro and micrographs. The ingots solidified at lower extraction velocities, at which evidences of a planar solidliquid interface were observed, showed greater refining effect than those solidified at larger velocities, which showed evidences of a cellular or dendritic solid-liquid interface. The contents of Fe, Al, Cr, and Ti measured at the base and center portions of the solidified ingots comply with the specifications of SiGS proposed by some authors.

This thesis provides an in depth look at the application of Shot peening to three alloys that cover a wide range of stabilizer compositions (Ti-64, Ti-5553 and Ti21S). Here the effects of Shot peening on the material were studied by characterizing the changes to subsurface microstructres in a variety of starting microstructures across all alloys studied. the study also compared the evolution of residual stress across all conditions and its effect on precipitation during post shot peening heat treatments. <div>Additionally, the study developed a novel shot peening media providing proof of concept for the idea of self-peening a material. This being the practice of peening the target material with the same material as media. Here the production of hardened Ti media was achieved to then self peen titanium alloys. the results from conventional and self-peened samples are compared in terms of corrosion resistance, surface hardening, surface roughness, and residual stress evolution.</div>

La transformation de phase influence considérablement les propriétés thermomécaniques des matériaux métastables. Elle est prise en considération dans des modèles numériques qui simule le comportement de ces derniers dans des codes de calcul et qui nécessitent des résultats expérimentaux. Ainsi, ces travaux concernent la caractérisation du comportement axial et multiaxial de deux aciers iTRIP à savoir l’acier 301L et l’acier 304L ainsi qu’un alliage à mémoire de forme à base de CuAlBe. Cette caractérisation est couplée avec un suivi de la cinétique des transformation de phase entreprise par la mesure de la résistance électrique. Le premier chapitre est une étude bibliographique des deux classes de matériaux métastables cités précédemment ainsi que du phénomène de transformation de phase et les techniques permettant sa caractérisation. Le deuxième chapitre, s’intéresse aux essais uniaxiaux thermomécaniques réalisés sur un acier iTRIP afin de valider la méthode de dosage de phase. Aussi, les essais thermomécaniques multiaxiaux réalisés sur des éprouvettes tubulaires en acier iTRIP 304L y seront présentés. Le troisième chapitre est consacré aux essais uniaxiaux réalisés sur des éprouvettes de CuAlBe ainsi qu’au dosage de phase des cas biphasé et triphasé. Aussi, la validation de l’hypothèse de linéarité entre la fraction volumique de martensite et la déformation de transformation équivalente dans le cas de chargements multiaxiaux proportionnels et non proportionnels est faite. / Phase transformation considerably influences the thermomechanical properties of metastable materials. This is reflected in the numerical model that simulates the behavior of these materials for the calculation codes and require experiments.Thus, the present work concerns the characterization of the axial and multi-axial behavior of two iTRIP steels, 301L steel and 304L steel in addition to a shape memory alloy based on CuAlBe. This characterization is coupled with monitoring of phase transformation kinetics through the measurement of the electrical resistance.The first chapter is a bibliographic study of the two classes of metastable materials mentioned above as well as the phase transformation phenomenon and its characterization techniques. The second chapter deals with uniaxial thermomechanical tests on a steel iTRIP to validate the phase assay. The multiaxial thermomechanical testing performed on specimens tubular steel 304L iTrip will be presented.The third chapter is devoted to uniaxial tests performed on CuAlBe spicemens and realization phase doping in a three-phase case. Also, the validation of the assumption of linearity between the martensite volume fraction and the equivalent transformation strain in the case of proportional and non-proportional loading is done.