Hard anodising on aluminium and its alloys has been widely practised for many years in order to improve the resistance of the otherwise poor wear characteristics of aluminium. In recent years there has been an increasing interest in other treatments and coatings, on both aluminium and other base metals. The aim of this investigation is to explain the tribological performance and wear mechanism(s) of an uncoated aluminium alloy, four anodic coated alloys, and also an electroless nickel alloy. All of the coatings are produced on three different aluminium alloys. The thickness of the anodic films is 30-35 micron, as this thickness falls within the range commonly used by industry. In an endeavour to explain the role of coating thickness on wear life, electroless nickel alloy has been produced in a range of thicknesses of 10, 20 and 30 micron. To evaluate abrasive and adhesive wear, the samples were rubbed against a single point diamond and steel ball, respectively, in a reciprocating movement at room temperature and 65-75% relative humidity, under a wide range of load and sliding distance. Some tests continued to run until a breakdown of the coatings occurred, whilst other tests were interrupted at intermediate stages. This enabled the initiation and propagation of failure mechanisms to be studied. Abrasive wear was performed under dry conditions, whereas, adhesive wear was evaluated under both dry and lubricated conditions. Wear of these coatings was proportional to the applied load and sliding distance, but there was no direct relationship between wear and hardness. The tribological performance of these coatings appears to be dictated by a) the composition of the substrate, b) the chemical and physical nature of the coatings and c) the test conditions. Under boundary lubricated conditions there was a considerable increase in the wear life of the coatings. A three dimensional surface texture is superior to a machined surface, in controlling contact conditions. There is an approximate linear relationship between coating thickness and wear life for electroless nickel alloys. These coatings predominantly fail by adhesion, plastic deformation and brittle fracture. A microscopic model for fracture of brittle materials, under both static and dynamic conditions for abrasive and adhesive wear correlates very well with the behaviour of these coatings. Analytical interpretation of adhesive wear was made by separately calculating the coefficient of wear "K" of the counterbodies. This information enables an improved understanding of the wear test itself to be added to the model of the wear mechanisms involved.

The increased demand in stringent requirements on engineered surfaces in the aerospace and manufacturing industries drove the need for developing advanced surface engineering techniques such as chemical etching, plasma etching, corona discharge and laser surface texturing in order to alter material surface physical and chemical properties. Among these techniques, laser surface texturing has been identified as one of the most efficient and effective surface treatment/ texturing techniques which utilizes laser ablation to meet the demand of practical engineering requirements. This thesis details three practical engineering challenges in the field of paint adhesion, dust adhesion and tribology performance of SPF sheet forming dies in which case the problems and motivation for development came from projects by industrial partner collaborations with BAe Systems, Rolls-Royce and Dyson Ltd. The proposed solutions to these challenges are formulated around laser surface texturing techniques using excimer and femtosecond lasers on three engineering materials which are CFRP, ABS polymer and HR4 nickel alloy. As ablation is the main mechanism used in laser surface texturing techniques in achieving surface property changes, the understanding of laser beam interaction with materials is crucial. The fundamental understanding of laser beam interaction with different materials has been researched since the use of lasers in practical engineering applications by which laser material interaction parameters such as ablation threshold, incubation coefficient and optical penetration depth are of primary interest in addition to the ablation rate. Currently the published literatures are either material specific or laser specific with minimal or zero comparison between different types of lasers and materials as such which limits the understanding of laser beam interaction with materials. In addition, laser beam interaction with polymers has always been done using ultraviolet wavelength lasers. In this thesis, the interaction between two types of lasers and three types of materials which includes metals and polymers are presented through comparison and discussion between different interactions. It has been discovered that the ablation threshold value is lower for ABSinteraction with excimer laser as compared to the interaction with femtosecond laser due to the difference in the ablation mechanism. The optical penetration depth value is higher for ABS interaction with the excimer laser as compared to the interaction with the femtosecond laser due to differences in the photon energy of the laser beam of different wavelength. Two ablation rate curves were identified on ABS interaction with infrared wavelength femtosecond laser beams which has not been reported before. Chemical composition of the laser treated layer changes through chain scission process, creating free radical carbons that reacted with oxygen, nitrogen and water vapour in air creating oxygen and nitrogen rich functional groups which increased with increasing laser fluence and number of pulses. Laser ablation is known for its capability of altering surface morphology and surface chemistry of materials through excitation of electrons causing bond scission or melt where materials are vaporised, ejected or undergo chemical compositional changes. In the case of polymers, addition of oxygen and nitrogen rich functional groups are identified whereas in the case of metals, changes in crystallographic, orientation and oxidation states are identified. Such changes are deemed ideal for applications such as adhesion where it is mainly used for bonding and joining of similar or dissimilar materials. In this research, excimer laser surface treatment showed improvement in CFRP paint adhesion where a better adhesion is achieved than sand-papered surfaces. Paint adhesion of CFRP surfaces is affected by surface contaminants, surface chemical composition and surface roughness where the degree of inuence is in the respective order. In addition, excimer and femtosecond laser surface treated ABS also improved dust adhesion. The main factors that affect the ABS surface dust adhesion performance are surface roughness and surface chemical composition. The increase in surface roughness increases the surface area available for dust to adhere to. In addition, it also increases the drag coefficient of the air flow results in a higher removal force exerted by the air flow onto the dust particles through changes in the localised aerodynamic flow. The increase in polar functional groups increases the adhesion of the dust particles onto the surface due to an induced dipole moment by the charged dust particles. Laser micro-dimpled surfaces have been reported to be effective in reducing friction coefficient and wear rate of surfaces under oil lubricated conformal contact conditions where the dimples act as reservoirs to store lubricant and wear particles. But such surfaces have not been extensively researched under non-conformal contact conditions for different lubricated environments. In addition, there are contradictory results found between published literatures which observe under similar wear environments and conditions but with different dimple geometry. Hence a detailed investigation on dimpled surfaces under non-conformal contact conditions is being carried out. Laser surface texturing of 100 μm size dimples shows a reduction in nickel alloy wear rate under dry and oil lubricated environments. A higher dimple area ratio reduces the wear rate under dry condition with abrasive wear as the main wear mechanism. Under oil lubricated environments, the friction coefficient is dependent on the surface contact pressure, sliding speed and the viscosity of the lubricant and the wear rate is dependent on the film thickness which correlates to the friction coefficient. The wear rate of a dimpled surface is dependent on three factors which are the dimple diameter to contact area diameter ratio, depth of the dimple produced and the density of the dimples. Positive results are obtained in all three engineering applications indicating the feasibility of laser surface texturing techniques in providing suitable material surface properties for these applications.

CuNi nanoparticles were synthesized using a new polyol synthesis method. Three different CuxNi1-x catalysts were synthesized where x = 20, 50 and 80. The nanoparticles were deposited on carbon, C, gamma-alumina, γ-Al2O3, yttria-stabilized zirconia, YSZ, and samariumdoped ceria, SDC. Each set of catalysts was tested using the Reverse Water Gas Shift, RWGS, reaction under atmospheric pressure and at temperatures ranging from 400°C-700°C. The experiments were repeated 3 times to ensure stability and reproducibility. Platinum nanoparticles were also deposited on the same supports and tested for the RWGS reaction at the same conditions. The CuNi nanoparticles were characterized using a variety of different techniques. Xray diffraction, XRD, measurements demonstrate the resence of two CuNi solid solutions: one Cu rich solid solution, and the other a Ni rich solid solution. X-ray photo electron spectroscopy, XPS, measurements show Cu enrichment on all catalytic surfaces. Scanning electron microscopy, SEM, measurements show CuNi nanoparticles ranging in size from 4 nm to 100 nm. Some agglomeration was observed. SDC showed the best yield with all catalysts. Furthermore, high oxygen vacancy content was shown to increase yield of CO for the RWGS reaction. Cu50Ni50/SDC shows the combination of highest yield of CO and the best stability among CuNi catalysts. It also has similar yields (39.8%) as Pt/SDC at 700°C, which achieved the equilibrium yield at that temperature (43.9%). The catalyst was stable for 48 hours when exposed to high temperatures (600-700°C). There was no CH4 observed during any of the experiments when the partial pressure of the reactant gases was fed stoichiometrically. Partial pressure variation experiments demonstrated the presence of CH4 when the partial pressure of hydrogen was increased to twice the value of the partial pressure of CO2.

In sub-millimeter sheets of wrought H-X750 Nickel-base superalloy, aluminum-rich coatings are bonded to matrix with a vapor phase aluminization process. If an appropriate amount of aluminum is bonded to matrix with homogenization treatment, the resulting diffusion couple will diffuse into coherent (g/g’) heterogeneous phases creating matrix that is both precipitation and solid solution strengthened. The diffusional mechanisms for solid solution mass transport involved with the growth and dispersion of bonded aluminum-rich coatings in the aluminization process only differ from the no external mass flow homogenization process with annealing treatment in that the boundary conditions are different. In each case these forces that activate diffusion at the macroscopic level are connected to the activation energies of random walks of atoms on a wide scale at the angstrom level. An overview of wrought Nickel-base superalloy is presented. Starting with thin sheets the alloy will be aluminized and homogenized. The research from this study will determine the parameters for the movement of the phase boundaries, mass transport, and the time variant concentration fields for both the aluminization and homogenization processes. This is predictable for both single dimension fluxes assuming the interdiffusivities and fluxes at the phase boundaries are known. Because mass-transport is related to the movement of the phase boundaries through density, an investigation into the less dense aluminum-rich coatings and resultant matrix is also included.

The continuing quest for higher performance levels of modern gas turbine engines has been accompanied by the demand for higher engine operating temperatures. The use of Thermal Barrier Coatings (TBCs) enabled gas turbines to operate at higher temperatures by protecting the blade material (nickel superalloy) while operating in extreme environments. The TBC system typically consists of a bond coat for protection of the nickel–based superalloy against oxidation followed by a top coat consisting of a thermally insulating zirconia-yttria. In addition to the complex gradation in phases, the coatings are subjected to continuous oxidation with service exposure, mechanical loading on rotating parts, fatigue, thermal mis-match and temperature gradients. Hence, the study of failure mechanisms of TBCs become important in deciding operational reliability and service life of the coating. As there are many systems in which the operating temperatures are not high enough to warrant the use of the top coat (ceramic layer), the study of failure mechanisms in superalloys coated with only the bond coat continue to be of great interest. The present work concentrates on the fracture behavior of NiAl bond coats on nickel superalloy and seeks to evaluate the fracture toughness of the coating through the use of micro-machined samples. A review of the relevant literature indicated that while a considerable body of work exists on bulk tests of failure (spalling, splitting, etc.), not much has been reported in the open literature on the evaluation of basic quantities such as the toughness of the coating itself. The present thesis seeks to establish a protocol for the evaluation of toughness and crack propagation mechanisms in coatings through a combination of micro-sample testing that allows fracture to be correlated with location in the film and the use of an analytical model to quantitatively evaluate stress intensity factors in a bi-material system. A system of NiAl coating produced by pack aluminizing is studied for the fracture properties of the coating. Specimen geometries are optimized to enable micro-cracks to be machined and propagated in a low load testing system, such as a depth sensing indenter, so that crack lengths (and position relative to the interface) can be correlated with load. To enable linear elastic theory to be used, dimensions are determined that allow fracture before general yielding. A three point bending test using miniaturized micro-beam specimens of ~ 4 X 0.3 X 0.3 mm is found to be suitable for the above purpose. The technique is a challenging one that requires focused ion beam machining (FIB) along with careful handling and alignment of small samples. The coatings are characterized for their microstructure by electron microscopy to identify compositional variation across the thickness and to determine the thickness of the coating and inter diffusion zone (IDZ). The crack advancement is monitored with increments of loading and the stress intensity factor is evaluated using a program written in “MAPLE” for an edge crack subjected to bending in a bilayered material. Surprisingly, fracture in this system is found to be stable owing to a gradual increase in toughness from the coating surface to the interface. Such an increase from less than 2 to more than 9 MPa m0.5 may be due to the increasing Ni/Al ratio across the thickness of the bond coat. Crack branching is observed as the crack approaches the IDZ and the reasons for such behaviour are not fully understood. This work establishes the viability of this technique to determine fracture properties in highly graded coated systems and may be readily extended to more complex coating architectures and other forms of loading such as cyclic, mixed mode, etc.

É crescente a preocupação com o desenvolvimento de materiais adequados a trabalharem interagindo com o corpo humano. Diversas pesquisas têm sido realizadas no desenvolvimento de biomateriais aplicáveis na odontologia, este empenho é justificável pelo grande número de intervenções cirúrgicas para extração de dentes realizadas em todo o mundo. Durante o processo de fabricação de reconstruções dentárias, que utilizam sistemas metalocerâmicos, é utilizado um tratamento térmico que tem a função de promover a adesão da porcelana ao metal. Entretanto, sabe-se que tratamentos térmicos podem alterar a microestrutura do material metálico, modificando suas propriedades. Este trabalho avaliou as modificações causadas em propriedades mecânicas e microestruturais da liga à base de níquel (FIT CAST-SB) utilizada para fins odontológicos, quando a mesma é submetida ao tratamento térmico para adesão da porcelana (denominado de queima). A liga foi inicialmente fundida através da técnica de centrifugação e cera perdida. Posteriormente, um grupo de amostras (grupo TT) foi submetido ao tratamento térmico de queima para adesão da porcelana e o outro grupo (grupo F), permaneceu apenas submetido ao processo de fundição. Os grupos F e TT foram submetidos a ensaio de tração. Nos grupos F e TT, e no material como recebido pelo fabricante (grupo CR), foram realizados ensaios de microdureza e caracterização microestrutural, esta ultima através da técnica de microscopia eletrônica de varredura (MEV). Os grupos F e CR foram submetidos à análise química quantitativa (em um espectrômetro de emissão atômica) e semi-quantitativa por um sistema de Energy Dispersive Spectroscopy (EDS) acoplado ao MEV, sendo que esta ultima técnica também foi aplicada ao grupo TT. A técnica de tratamento digital de imagem foi aplicada às micrografias dos grupos F e TT, para a determinação de possíveis modificações quantitativas nas fases presentes, antes e após o tratamento térmico. Todos os resultados dos ensaios foram submetidos ao teste de hipótese nula (H0), para a distribuição t de Student. Concluiu-se que, para as amostras testadas, o limite de resistência foi superior ao fornecido pelo fabricante, respectivamente 559,39 e 545,55 MPa para os grupos F e TT, contra 306 MPa do fabricante. Enquanto o limite de escoamento foi ligeiramente inferior, 218,71 e 240,58 MPa para os grupos F e TT, respectivamente, contra 258 MPa do fabricante. Os resultados de microdureza ficaram entorno de 70HV, superior aos 21HV fornecido pelo fabricante. Pode-se afirmar, com 95% de confiabilidade, que não houve variação nas propriedades mecânicas e na microestrutura (quantidades de fases presentes e tamanho) antes e após a queima para adesão da porcelana, para os corpos de prova testados. A microestrutura da liga, quando observada em MEV no modo elétrons retroespalhados (modo BSE), é formada por uma matriz de estrutura dendrítica e coloração cinza, uma segunda fase interdendrítica de coloração branca e aspecto rendilhado, e precipitados de coloração preta, apresentando também porosidades. / There is a growing concern with the development of suitable materials for interactive working with the human body. Many searchs have been carried in the development of biomaterials for odontology applications and this dedication is justifiable for the large number of surgical interventions for tooth extractions in the entire world. During the manufacturing process of dental reconstructions, which use metal-ceramic systems, a heat treatment is used to promote adhesion of the porcelain in the metal. However, it is known that heat treatment can change the metallic materials microstructure, changing their properties. This work evaluated the mechanical properties and microstructural changing of the nickel base alloy (FIT CAST-SB) used in odontology, when the alloy is submitted to the heat treatment for the porcelain adhesion (demented of firing). First the alloy was cast using the technical of centrifugation and lost-wax. After that, one samples group (TT group) was submitted for porcelain firing heat treatment and another group (F group), remained only cast. The F and TT groups were submitted to tensile test. The F and TT groups, and the material as received by the manufacturer (CR group), were submitted to microhardness test and microstructural characterization, this latter using scanning electron microscopic. The F and CR groups were submitted to quantitative chemical analysis (atomic emission spectroscopy) and semi-quantitative by Energy Dispersive Spectroscopy (EDS) in the MEV, and this last technique was applied to TT group too. The digital images process technique was applied to micrographics of F and TT groups, to determine the changes in the material phases before and after heat treatment. All results were submitted to the hypothesis test of Students t-distribution. For the samples tested, it was concluded that the tensile strength was higher then the manufacturer information, respectively 559,39 and 545,55 MPa for F and TT groups, against 306 MPa informed by the manufacturer. However, the yield point was slightly lower, 218,81 and 240,58 MPa for F and TT groups, respectively, against 258 informed by the manufacturer. The microhardness results were about 70HV, higher than 21HV informed by the manufacturer. It was concluded, with 95% of confiability, that there was no mechanical properties and microstructure (percent and size of the phases) changes, before and after porcelain firing, in the specimens used. The alloy microstructure, when observed by scanning electron microscopy (SEM) in backscattered electron mode (BSE mode) is formed by a matrix with dendritc structure and gray color, a second phase interdendritc with white color and lacy appearance, and black precipitates, and porosity are also found.

É crescente a preocupação com o desenvolvimento de materiais adequados a trabalharem interagindo com o corpo humano. Diversas pesquisas têm sido realizadas no desenvolvimento de biomateriais aplicáveis na odontologia, este empenho é justificável pelo grande número de intervenções cirúrgicas para extração de dentes realizadas em todo o mundo. Durante o processo de fabricação de reconstruções dentárias, que utilizam sistemas metalocerâmicos, é utilizado um tratamento térmico que tem a função de promover a adesão da porcelana ao metal. Entretanto, sabe-se que tratamentos térmicos podem alterar a microestrutura do material metálico, modificando suas propriedades. Este trabalho avaliou as modificações causadas em propriedades mecânicas e microestruturais da liga à base de níquel (FIT CAST-SB) utilizada para fins odontológicos, quando a mesma é submetida ao tratamento térmico para adesão da porcelana (denominado de queima). A liga foi inicialmente fundida através da técnica de centrifugação e cera perdida. Posteriormente, um grupo de amostras (grupo TT) foi submetido ao tratamento térmico de queima para adesão da porcelana e o outro grupo (grupo F), permaneceu apenas submetido ao processo de fundição. Os grupos F e TT foram submetidos a ensaio de tração. Nos grupos F e TT, e no material como recebido pelo fabricante (grupo CR), foram realizados ensaios de microdureza e caracterização microestrutural, esta ultima através da técnica de microscopia eletrônica de varredura (MEV). Os grupos F e CR foram submetidos à análise química quantitativa (em um espectrômetro de emissão atômica) e semi-quantitativa por um sistema de Energy Dispersive Spectroscopy (EDS) acoplado ao MEV, sendo que esta ultima técnica também foi aplicada ao grupo TT. A técnica de tratamento digital de imagem foi aplicada às micrografias dos grupos F e TT, para a determinação de possíveis modificações quantitativas nas fases presentes, antes e após o tratamento térmico. Todos os resultados dos ensaios foram submetidos ao teste de hipótese nula (H0), para a distribuição t de Student. Concluiu-se que, para as amostras testadas, o limite de resistência foi superior ao fornecido pelo fabricante, respectivamente 559,39 e 545,55 MPa para os grupos F e TT, contra 306 MPa do fabricante. Enquanto o limite de escoamento foi ligeiramente inferior, 218,71 e 240,58 MPa para os grupos F e TT, respectivamente, contra 258 MPa do fabricante. Os resultados de microdureza ficaram entorno de 70HV, superior aos 21HV fornecido pelo fabricante. Pode-se afirmar, com 95% de confiabilidade, que não houve variação nas propriedades mecânicas e na microestrutura (quantidades de fases presentes e tamanho) antes e após a queima para adesão da porcelana, para os corpos de prova testados. A microestrutura da liga, quando observada em MEV no modo elétrons retroespalhados (modo BSE), é formada por uma matriz de estrutura dendrítica e coloração cinza, uma segunda fase interdendrítica de coloração branca e aspecto rendilhado, e precipitados de coloração preta, apresentando também porosidades. / There is a growing concern with the development of suitable materials for interactive working with the human body. Many searchs have been carried in the development of biomaterials for odontology applications and this dedication is justifiable for the large number of surgical interventions for tooth extractions in the entire world. During the manufacturing process of dental reconstructions, which use metal-ceramic systems, a heat treatment is used to promote adhesion of the porcelain in the metal. However, it is known that heat treatment can change the metallic materials microstructure, changing their properties. This work evaluated the mechanical properties and microstructural changing of the nickel base alloy (FIT CAST-SB) used in odontology, when the alloy is submitted to the heat treatment for the porcelain adhesion (demented of firing). First the alloy was cast using the technical of centrifugation and lost-wax. After that, one samples group (TT group) was submitted for porcelain firing heat treatment and another group (F group), remained only cast. The F and TT groups were submitted to tensile test. The F and TT groups, and the material as received by the manufacturer (CR group), were submitted to microhardness test and microstructural characterization, this latter using scanning electron microscopic. The F and CR groups were submitted to quantitative chemical analysis (atomic emission spectroscopy) and semi-quantitative by Energy Dispersive Spectroscopy (EDS) in the MEV, and this last technique was applied to TT group too. The digital images process technique was applied to micrographics of F and TT groups, to determine the changes in the material phases before and after heat treatment. All results were submitted to the hypothesis test of Students t-distribution. For the samples tested, it was concluded that the tensile strength was higher then the manufacturer information, respectively 559,39 and 545,55 MPa for F and TT groups, against 306 MPa informed by the manufacturer. However, the yield point was slightly lower, 218,81 and 240,58 MPa for F and TT groups, respectively, against 258 informed by the manufacturer. The microhardness results were about 70HV, higher than 21HV informed by the manufacturer. It was concluded, with 95% of confiability, that there was no mechanical properties and microstructure (percent and size of the phases) changes, before and after porcelain firing, in the specimens used. The alloy microstructure, when observed by scanning electron microscopy (SEM) in backscattered electron mode (BSE mode) is formed by a matrix with dendritc structure and gray color, a second phase interdendritc with white color and lacy appearance, and black precipitates, and porosity are also found.

[pt] A liga VAT46 foi desenvolvida para ser uma opção às ligas comumente utilizadas em motores de combustão interna, VAT80A e VAT751. A microestrutura da liga VAT46, após passar por tratamento térmico, é formada pelas fases y [Ni3(Al,Ti)], y (Ni3Nb), carbetos de nióbio (NbC) e a δ [Ni3(Al,Ti,Nb)]. A fase δ contribui para otimização da liga, porem pode ser um caminho para o hidrogênio causar fragilização. Os estudos de mecanismo de oxidação referentes a esta liga não analisaram a influência e as consequências do vapor d água e da fase δ nos estágios iniciais do processo de oxidação. Devido a insuficiência de dados, gerar informações inéditas sobre a influência do vapor d’água e da fase δ nos momentos iniciais de oxidação, torna este tipo de estudo relevante. Dois tipos de amostras da liga VAT46 foram submetidas a experiencia de oxidação, uma delas com a precipitação da fase δ, e foram utilizados como parâmetro a temperatura de 800ºC por 10 horas e dividido em duas etapas, uma com a presença de vapor d água e outro em ambiente seco. Apenas a amostra sem a fase δ foi oxidada nos dois ambientes. As amostras oxidadas foram analisadas por meio de microscópio ótico, microscópio eletrônico de varredura (MEV) e técnica de EDS. As análises microestruturais das amostras como recebida evidenciam a formação da fase δ com morfologia agulha e regiões adjacentes pobre em metais, como nióbio e níquel, o que pode significar a formação da desta fase pela dissolução da fase y. Os resultados relevaram que a nucleação de óxidos na superfície está relacionada com os carbeto e não com a fase δ e que a presença de vapor d água aumentou a velocidade de crescimento lateral dos núcleos de óxidos formados inicialmente nos carbetos. / [en] The VAT46 alloy was developed to be an option to the alloys commonly used in internal combustion engines, VAT80A and VAT751. The microstructure of the VAT46 alloy, after undergoing heat treatment, is formed by the phases y [Ni3(Al,Ti)], y (Ni3Nb), niobium carbides (NbC) and δ [Ni3(Al,Ti,Nb)]. The δ phase contributes to alloy optimization, but may be a pathway for hydrogen to cause embrittlement. The oxidation mechanism studies for this alloy did not analyze the influence and consequences of water vapor and the δ phase in the initial stages of the oxidation process. Due to insufficient data, generating unpublished information on the influence of water vapor and the δ phase in the initial moments of oxidation makes this type of study relevant. Two types of samples of the VAT46 alloy were submitted to the oxidation experiment, one with the precipitation of the δ phase, and were used as a parameter the temperature of 800ºC for 10 hours and divided into two stages, one with the presence of water vapor and the other in a dry environment. Only the sample without the δ phase was oxidized in both environments. The oxidized samples were analyzed using an optical microscope, a scanning electron microscope (SEM) and an EDS technique. The microstructural analyses of the samples as received show the formation of phase δ with needle morphology and adjacent regions poor in metals such as niobium and nickel, which may mean the formation of this phase by the dissolution of phase y. The results showed that the nucleation of oxides at the surface is related to the carbides and not to the δ phase and that the presence of water vapour increased the lateral growth speed of the oxide nuclei initially formed in carbides.

Um dos principais mecanismos de falha que causam riscos de fratura a reatores de água pressurizada é a corrosão sob tensão de ligas metálicas em água do circuito primário (CSTAP). É causada por uma combinação das tensões de tração, meio ambiente em temperatura e microestruturas metalúrgicas susceptíveis. Ela pode ocorrer, dentre outros locais, nos bocais do mecanismo de acionamento das barras de controle. Essa fratura pode causar acidentes que comprometem a segurança nuclear através do bloqueio das barras de controle e vazamentos de água do circuito primário reduzindo a confiabilidade e a vida útil do reator. O objetivo desta Tese de Doutorado é o estudo de modelos e uma proposta de modelagem para fraturas por corrosão sob tensão em liga 75Ni15Cr9Fe (liga 600), em água de circuito primário de reator de água pressurizada nesses bocais. São superpostos modelos eletroquímicos e de mecânica da fratura e validados com dados obtidos em experimentos e na literatura. Na parte experimental foram utilizados resultados obtidos pelo CDTN no equipamento recém-instalado de ensaio por taxa de deformação lenta. Na literatura está proposto um diagrama que exprime a condição termodinâmica de ocorrerem diversos modos de CSTAP na liga 600: partiu-se de diagramas de potencial x pH (diagramas de Pourbaix), para a liga 600 imersa em água primária à alta temperatura (3000C a 3500C). Sobre ele, determinaram-se os submodos de corrosão, a partir de dados experimentais. Em seguida acrescentou-se uma dimensão adicional ao diagrama, correlacionando uma variável a que se denominou fração de resistência à corrosão sob tensão. No entanto, é possível acrescentar-se outras variáveis que exprimem a cinética de iniciação e/ou crescimento de trinca, provenientes de outras modelagens de CSTAP. A contribuição original deste trabalho se insere nessa fase: partindo-se de uma condição de ensaio de potencial versus pH, foram iniciadas as modelagens de um modelo empírico-comparativo, um semi-empírico-probabilístico, um de tempo de iniciação e um de taxa de deformação, a partir dos ensaios experimentais e superpostas a essa condição. Esses exprimem respectivamente a susceptibilidade à CSTAP, o tempo de falha, e nos dois últimos o tempo de iniciação de falha por corrosão sob tensão. Os resultados foram comparados com os da literatura e se mostraram coerentes. Através desse trabalho, obteve-se uma metodologia de modelagem a partir de dados experimentais. / One of the main failure mechanisms that cause risks to pressurized water reactors is the primary water stress corrosion cracking (PWSCC) occurring in alloys. It can occurs, besides another places, at the control reactor displacement mechanism nozzles. It is caused by the joint effect of tensile stress, temperature, susceptible metallurgical microstructure and environmental conditions of the primary water. These cracks can cause accidents that reduce nuclear safety by blocking the rods displacement and may cause leakage of primary water, reducing the reactors life. In this work it is proposed a study of the existing models and a modeling proposal to primary water stress corrosion cracking in these nozzles in a nickelbased Alloy 600. It is been superposed electrochemical and fracture mechanics models, and validated using experimental and literature data. The experimental data were obtained at CDTN-Brazilian Nuclear Technology Development Center, in a recent installed slow strain rate testing equipment. In the literature it is found a diagram that indicates a thermodynamic condition for the occurrence of some PWSCC submodes in Alloy 600: it was used potential x pH diagrams (Pourbaix diagrams), for Alloy 600 in high temperature primary water (3000C till 3500C). Over it, were located the PWSCC submodes, using experimental data. It was added a third parameter called stress corrosion strength fraction. However, it is possible to superpose to this diagram, other parameters expressing PWSCC initiation or growth kinetics from other models. Here is the proposition of the original contribution of this work: from an original experimental condition of potencial versus pH, it was superposed, an empiric-comparative, a semi-empiric-probabilistic, an initiation time, and a strain rate damage models, to quantify respectively the PWSCC susceptibility, the failure time, and in the two lasts, the initiation time of stress corrosion cracking. It was modeling from our experimental data. The results were compared with the literature and it showed to be coherent. From this work was obtained a modeling methodology from experimental data.

As ligas à base de níquel de alta resistência são utilizadas em uma infinidade de sistemas avançados, onde baixo peso e sistemas de transmissão mecânica de alta densidade de energia são necessários. Componentes, tais como, engrenagens, rolamentos e eixos poderiam ser consideravelmente menor e mais durável se uma grande melhoria em propriedades mecânicas de ligas à base de níquel for alcançada. Um refinamento significativo no tamanho de grão (incluindo nível nano) é um método promissor para a obtenção de melhorias fundamentais nas propriedades mecânicas. O tamanho de grão é conhecido por ter um efeito significativo sobre o comportamento mecânico dos materiais. Um dos métodos mais favoráveis de alcançar refinamento de grão extremo é submetendo os materiais à deformação plástica intensa. As principais variáveis microestruturais nas superligas são a quantidade de precipitados e sua morfologia, o tamanho e a forma do grão e a distribuição de carbonetos (Cr7C3 e Cr23C6) que poderão reduzir propriedades mecânicas da liga. Neste trabalho é apresentada análise por microscopia óptica e eletrônica de transmissão e também os dados de dureza após deformação plástica intensa (tensão de cisalhamento puro) e alguns tratamentos térmicos. / High strength nickel based alloys are used in a multitude of advanced systems where lightweight, high power density mechanical power transmission systems are required. Components such as gears, bearings and shafts could be made significantly smaller and more durable if a major improvement in nickel based alloy mechanical properties could be achieved. A significant refinement in grain size (includes nano level) is thought to be a promising method for achieving fundamental improvements in mechanical properties. Grain size is known to have a significant effect on the mechanical behavior of materials. One of the most favorable methods of achieving extreme grain refinement is by subjecting the materials to severe plastic deformation. The principal microstructural variations in superalloys are the precipitation amount and morphology, grain size and the distribution of carbide precipitation (Cr7C3 and Cr23C6) that could reduce the mechanical properties of the alloys. This work shows optical and transmission electron microscopy analysis and also hardness data after severe plastic deformation (pure shear stress) and some thermal treatments.