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Made available in DSpace on 2014-10-09T12:38:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:43Z (GMT). No. of bitstreams: 1 05682.pdf: 7598679 bytes, checksum: 0a8e36b4d2b6ba00958df86a2415829e (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

This diploma work is focused on exploitation of high-temperature dilatometry in sintering of advanced ceramic materials. Newly developed software is presented in this diploma work. This software is able to calculate activation energy of sintering process via concept of Master Sintering Curve. In the second part of diploma work the software was verified by evaluation of sintering of four different ceramics materials. The following activation energies of sintering were calculated: 990kJ/mol for tetragonal ZrO2 (3mol% Y2O3), 620kJ/mol for cubic ZrO2 (8mol% Y2O3) and 640kJ/mol resp. 720kJ for Al2O3 with two different particle size.

Les conditions nécessaires pour obtenir des céramiques transparentes (absence de porosité, absence de seconde phase) requièrent une totale maitrise de chacune des étapes (synthèse, mise en forme, frittage) intervenant dans le processus, ce qui rend encore difficile l'industrialisation d'un procédé d'élaboration reproductible. Dans ce contexte, ce travail de thèse s’est focalisé à développer et évaluer la capacité du procédé de frittage micro-ondes à améliorer la robustesse du processus d'élaboration de spinelle transparent. La mise en place d'un dispositif de dilatométrie optique et une nouvelle technique de calibration originale, basée sur la fusion d'oxyde, ont permis de caractériser le frittage micro-ondes du spinelle pur avec une plus grande confiance. Même si aucun effet lié au procédé micro-onde n’a pu être mis en évidence pour le frittage du spinelle pur (trajectoire de frittage, mécanisme de densification et évolution de la porosité identiques), ces travaux ont démontré que l’impact de dopants pouvait être amplifié en présence du rayonnement micro-ondes. Ainsi, un décalage des courbes de retrait vers les basses températures a été observé lors du frittage micro-ondes du spinelle dopé avec TiO2 et MgO. L'existence d'un couplage particulier entre les défauts ponctuels chargés (lacunes, cations interstitiels) et le champ électrique pourrait être à l'origine de ce phénomène. Ces travaux de thèse ont également démontré la faisabilité de fritter des pièces de spinelle carrées de grandes dimensions (< 65 mm) compatibles avec un post-traitement HIP, en vue d'obtenir des pièces transparentes. Pour cela, un four micro-ondes monomode 915 MHz a été automatisé et une cellule de frittage adaptée a été développée. A l'issue du traitement HIP, les pièces ont présenté une transparence et des propriétés mécaniques (dureté; ténacité) comparables à celles des pièces pré frittées par voie conventionnelle. / The elaboration of transparent ceramics (no porosity, no second phase) requires a strict control of all steps of the process (synthesis, shaping, sintering). As a result, the industrialization of a reproducible process is still difficult to achieve. In this context, this thesis has focused on developing and evaluating the ability of the microwave sintering process to improve the robustness of the transparent spinel elaboration process.The set-up of an optical dilatometer and a new original calibration method, based of melting of different oxides, allowed to characterize the microwave sintering with a greater confidence. Even if no microwave effect has been observed on the sintering of pure spinel (identical sintering trajectory, densification mechanism and porosity evolution), this work has shown an amplification of the impact of dopants during microwave sintering. A shift of the shrinkage curves towards the low temperatures was observed during the microwave sintering of the spinel doped with TiO2 and MgO. The existence of a particular interaction between charged point defects (vacancies, interstitial cations) and the electric field could explain this phenomenon.This work thesis has shown also the feasibility of sintering of large square spinel pieces (< 65 mm) compatible with post treatment HIP in order to produce transparent ceramics. For this purpose, the microwave system working at 915 MHz was automatized and a new sintering configuration was developed. After a post-treatment, the transparency and mechanical properties (hardness; tenacity) of microwave pre-sintered samples were comparable with those of samples sintered by conventional heating.

Yes / Abstract Höganäs Astaloy CrM powder was used to prepare mixtures with 0.3-1.6 % carbon contents, both with and without 1 wt.% manganese additions. The carbon was added in three ways: as a graphite powder, as a solid CnHm hydrocarbon powder, and as a mixture of both. Green compacts were pressed at 300 - 800 MPa and sintered isothermally at temperatures in the range 1170 - 1295°C under flowing high purity nitrogen or nitrogen/hydrogen (9:1) atmosphere. Compressibility of the powder mixtures was investigated. Carbon loss occurring during sintering was carefully monitored. Sintering behaviour of numerous combinations of carbon content was investigated by dilatometry. For high carbon contents and high sintering temperatures, densification resulted from controlled generation of a liquid phase. Advantages of using solid hydrocarbon as a carbon donor and of Mn addition in powder metallurgy processing of steels are indicated.

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.

Foram coletadas amostras de uma chapa grossa temperada, de aço microligado ao boro com 8 mm de espessura. O aço foi produzido em aciaria do tipo LD, laminado na forma de chapa grossa em laminador de cadeira única reversível e finalmente recebeu tratamento de têmpera em forno de tubos radiantes e máquina de têmpera com fluxo de água. Todas as etapas de produção tiveram os parâmetros de processo controlados para obtenção das melhores propriedades possíveis. As amostras foram retiradas da região situada a um quarto da largura da chapa e submetidas a diversos ciclos térmicos em aparelho de dilatometria. Com auxílio de técnicas de microscopia ótica, microscopia eletrônica de varredura e medidas de dureza, o aço pôde ser caracterizado e foi possível levantar as curvas de resfriamento contínuo (TRC). As microestruturas revelaram a presença de múltiplos microconstituintes, principalmente em resfriamentos a partir de resfriamentos 25°C/s, quando surgem elementos aciculares como ferrita acicular e bainita misturados com ferrita poligonal e perlita. Acima desta taxa de resfriamento o campo perlítico é suprimido e a partir de 45°C/s surge a martensita. A 100°C/s a microestrutura é dominada predominantemente por martensita. As amostras resfriadas nas 3 taxas mais severas também revelaram a presença de austenita retida e constituinte MA, detectados por meio de difração de raios-x e ataque com reagente de Klemm. / Samples were taken from a quenched plate with 8mm thickness and chemical composition consisting of carbon, manganese, silicon, aluminum, niobium, titanium and boron. The steel was produced in LD converter, rolled in a reversible single chair rolling mill and quenched in a radiating tube furnace and quenching machine with water flow. All production stages had the process parameters controlled to obtain the best possible properties. The samples were extracted from a position situated at one quarter of the plate´s width and submitted to various thermal cycles in dilatometry device. With the aid of optical microscopy, scanning electron microscopy and hardness measurements, the steel could be characterized and the continuous cooling transformation curves could (CCT) be plotted. The microstructures revealed the presence of multiple components, especially when cooling rates reach 25°C/s, where acicular elements, like acicular ferrite and bainite, are found along with polygonal ferrite and pearlite. Above this cooling rate the pearlite field is suppressed and starting at 45°C/s martensite was found. At 100°C/s the microstructure is mainly martensitic. The samples cooled at the 3 most severe rates also revealed the presence of retained austenite and MA constituent, which were detected by x-ray diffraction and attack using Klemm reagent.

A proposta de desenvolvimento deste trabalho de dissertação veio de encontro com o objetivo de adaptar um laboratório para pesquisas em transformações de fases, utilizando o método dilatométrico, onde foram estudadas as reações no estado sólido que sofrem os materiais submetidos a ciclos térmicos. Para atingir este objetivo, instalou-se recentemente um dilatômetro de resfriamento rápido, modelo DT 1000 da Adamel Lhomargy. Completada a etapa de instalação do equipamento, o passo seguinte consistiu em explorar, através de ciclos térmicos variados, todos os recursos manipuláveis do dilatômetro. Aplicando a técnica dilatometrica em um aço de características termomecânicas conhecidas - SAE 1070 - possibilitou-se, a partir deste trabalho, que pesquisas mais complexas pudessem ser executadas com tal equipamento ou que o mesmo servisse como um instrumento complementar para estudos de transformações de fases. Nessa fase inicial de investigações estudou-se as curvas dilatométricas a fim de verificar os tempos de início e fim de transformação isotérmica em várias temperaturas de decomposição da austenita. Traçou-se as curvas de transformação isotérmica - curvas TTT - para o aço ensaiado (tratado termicamente), onde analisou-se a influência desse tratamento térmico prévio (recozimento) sobre a transformação \'alfa\' para \'gama\'. Finalizando a parte prática deste trabalho, comprovou-se as transformações de fases isotérmicas nas várias temperaturas ensaiadas, através de análise metalográfica e de medidas de microdureza dos produtos obtidos. A fim de solucionar eventuais problemas relacionados ao manuseio e manutenção do equipamento, com base na experiência adquirida ao longo do desenvolvimento deste trabalho, são dadas sugestões de possíveis aplicações do dilatômetro de têmpera rápida DT 1000 em pesquisas de transformações de fases. / The purpose of this work comes together with the objective to adapt a phase transformation research laboratory using dilatometric method, where it will be possible to study the solid state reactions of materials submited to thermal cycles. To fulfil this purpose, it was installed a high speed quenching dilatometer, model DT 1000 manufactured by Adamel Lhomargy. After this stage, our next step was to explorer all equipment resources through variable thermal cycles. Appling dilatometric method to a well known thermomechanical steel - SAE 1070 - it becomes possible the accomplishment of more complex experiments with this equipment. This equipment, itself, may be a powerfull auxilliary instrument to phase transformations studies. In this first investigation, it was studied the dilatometric curves to find the beginning and the end times of isothermal phase transformation for several austenite decomposition temperatures - TTT diagram - for the tested steel (thermal treated). The effect of this previous heat treatment (annealing) on the \'alfa\' for \'gama\' transformation were observed. Finally, the isothermal phase transformation at the different tested temperatures could be confirmed through metallographic and microhardness analysis. In order to solve possible problems associated to the equipment use or maintenance, some suggestions of applications of the high speed quenching dilatometer are indicated for further works.

Nuclear reactor pressure vessels are constructed by welding low alloy steel forgings together. Welding processes can leave residual stresses which affect the RPV's resistance to fracture. Welding also induces microstructural changes and these changes have a number of associated consequences, including inelastic strains and altering mechanical properties. The extent to which these microstructural changes influence residual stress evolution during welding is not fully understood. The aim of this project is to characterise the microstructural and mechanical response of SA-508 Gr.3 Cl.1 pressure vessel steel to thermal cycles and develop representative models that can be used to determine how these effects influence stress predictions. There is insufficient materials data to inform the models used to predict how phase transformations influence residual stresses. Using the recently developed Gleeble thermo-mechanical simulator, previously unmeasured data characterising the response of the material to weld-like thermal cycles was generated. Variations in the kinetics of austenite formation and decomposition were investigated using dilatometry. It was found that when the steel is subjected to multiple thermal cycles that exceed the austenisation temperature, the behaviour during the first thermal cycle is different to that of subsequent cycles. In the subsequent thermal cycles, two observations were made: 1) the austenite formation rate increases on heating, and 2) for a given cooling rate, the austenite will decompose at lower temperatures into harder phases. It is explained how these changes in behaviour can affect the residual stress distribution in this thesis. Bainitic, austenitic and martensitic samples were generated. The stress-strain behaviour of these phases is presented and has been used to inform mechanical constitutive models. Finite element simulations of autogenous edge welded beams have shown how microstructural changes can affect the residual stress predictions. The extent of the transformed region of the HAZ and the yield stress of the material surrounding this region influences the location and magnitude of the peak tensile residual stress after a weld pass. Changes in mechanical properties induced by tempering bainitic and martensitic samples were quantified experimentally. The reductions in yield stress in bainite and martensite during short tempering heat treatments were found to be significant. A new approach to integrate the observed tempering behaviour into existing models is presented. The data and models presented in this thesis can provide guidance to structural integrity engineers and help produce more accurate and less conservative residual stress predictions for use in structural integrity assessments.

The work presented in this thesis detail the measurement of the thermal expansion coefficient of three magnetic spin materials. Thermal expansion coefficient values were measured by capacitive dilatometry in several key low (T < 250 K) temperature regions specific to each material. This thesis is separated into several key parts. The first part establishes the theory behind observing phase transitions through the thermal expansion coefficient. Beginning with the classical definitions of the specific heat, compressibility and thermal expansion coefficient, the three properties are related using a property known as the Grüneisen parameter. To first order, the parameter allows phase transitions to be observed by the thermal expansion coefficient. The second part introduces capacitive dilatometry; a technique used to measure the thermal expansion coefficient. Three capacitive dilatometer devices are presented in this section. The silver compact dilatometer, the fused quartz dilatometer and the copper dilatometer. Each device discusses merits and weaknesses to their designs. Particular focus is made on the fused quartz dilatometer which was built during the duration of this thesis. The third part presents research on three magnetic spin materials; LiHoF4, Tb2Ti2O7 and Ba3NbFe3Si2O14. These materials are studied individually focusing on specific aspects. LiHoF4, a candidate material for the transverse field Ising model, provides insight to quantum phase transitions. Thermal expansion coefficient and magnetostriction along the c-axis for T ≈ 1.3-1.8 K and transverse field Ht ≈ 0-4 T were measured extracting critical points for a Ht-T phase diagram. Existing thermal expansion coefficient measurements had evidence of possible re-entrant behaviour. With a high density of low transverse field critical points it was established that LiHoF4 showed no evidence of re-entrant behaviour. The highly debated material Tb2Ti2O7 has a rich, controversial low temperature behaviour. Originally believed to be a spin liquid, specific heat results propose a scenario involving a sample composition dependent ordered state. Still under considerably attention, thermal expansion coefficient measurements were performed for T < 1 K. The results are interpreted to either fit into the proposed scenario or provide evidence for an alternate scenario. The material Ba3NbFe3Si2O14 exhibits a magnetoelectric multiferroic phase below TN ≈ 27 K; a phase where magnetic and electric order simultaneously exist. The formation of this phase is believed to have a similar structural shift observed in hexagonal perovskite multiferroic materials. The ferroelectric ordering in those materials are brought about through a centrosymmetric to non-centrosymmetric structural shift. The thermal expansion and thermal expansion coefficient coefficient along the a and c axis are measured for T > TN searching for a displacive structural phase transition.