<p dir="ltr">Ceramic/metal composites are being explored as potential replacements for conventional metal alloys in high-temperature components used in aerospace and power generation applications. Co-continuous ceramic/metal composites can offer attractive combinations of properties, such as improved mechanical toughness and thermal conductivity (relative to monolithic ceramics) and enhanced stiffness and corrosion/erosion resistance (relative to monolithic metals). However, development of cost-effective and scalable manufacturing routes to dense, complex-shaped ceramic/metal composites is a non-trivial challenge.</p><p dir="ltr">Chapter 1 of this dissertation is focused on the fabrication of WC/Cu composites using pressureless Cu liquid infiltration. The microstructure, density, porosity, phase content and properties of the resulting WC/Cu composites have been investigated. Mechanical properties, such as flexural strength and Vickers hardness have been evaluated, and the thermal cycling behavior of the WC/Cu composites have been examined. This study successfully demonstrates the fabrication of near-net-shape WC/Cu composites and provides insights into potential applications for such composites.</p><p dir="ltr">In Chapter 2, the limitations of metal alloy-based heat exchangers are discussed, leading to the exploration of alternative materials such as composite of zirconium carbide (ZrC) and tungsten (W). The favorable properties of ZrC/W composites, such as chemical compatibility, low vapor pressure, high thermal conductivity, stiffness, and thermal cyclability are highlighted. The fabrication of ZrC/W composites using reactive infiltration processes, emphasizing the importance of scalable fabrication methods, is also demonstrated.</p><p dir="ltr">Chapter 3 is focused on the fabrication and characterization of functionally graded ZrC/W – WC/Cu composites. These composites have been prepared by immersing WC/Cu preforms in Zr – Cu liquid at different temperatures, and the microstructures and phase distributions have been evaluated. It is observed with the same immersion time, the thickness of the ZrC/W reaction zone decreases with increasing immersion temperature due to the rapid reaction between WC and Zr at higher temperatures. Additionally, a model has been developed to describe the thermal conductivity of the composites as a function of the distance from the external surface. These findings provide insights into the fabrication and properties of functionally-graded composites for potential heat dissipation applications.</p><p dir="ltr">In Chapter 4, the development of a Ti-bearing, Ni-based active metal braze for joining Al₂O₃/Cr composites to Ni-based alloys is discussed. Joining ceramic components to metal parts poses challenges due to material property mismatches and ceramic brittleness. Conventional brazing materials often suffer from oxidation at high temperatures in air which compromises joint integrity. The focus of this chapter is the evaluation of the oxidation behavior of the developed brazing material to assess the suitability of this braze for reliable joining of ceramic-based composites to Ni-based alloys for use in air at high temperatures. Differential scanning calorimetry (DSC) has also been used to evaluate the solidus and liquidus temperatures of the Ni-19Cr-10Si and Ni-18Cr-10Si-4Ti alloys.</p><p><br></p>

Dynamic abnormal grain growth (DAGG) is a phenomenon by which single crystals up to centimeters in length are produced at elevated temperature during the application of strain. DAGG was previously demonstrated in commercial-purity molybdenum (Mo) materials. This is the first investigation to confirm DAGG in another material, tantalum (Ta). Previous experiments initiated and propagated DAGG using constant true-strain rate tensile tests, but this study demonstrates that DAGG can also occur under constant true-stress tensile conditions. A Mo material was tested under constant true stress, and two Ta materials were tested under constant true-strain rate. The effects of temperature, stress, strain rate, initial microstructure and texture on tensile test data and the resulting microstructures are examined. The microstructures of the Ta materials are analyzed using electron backscatter diffraction (EBSD) data to quantify the orientation, deformation, grain boundary character, and slip properties of the DAGG grains and unconsumed microstructure. The DAGG grains were found to be relatively undeformed compared to the unconsumed microstructure following DAGG and to not be oriented favorably, or unfavorably, for slip. The grain boundaries between DAGG grains in one Ta material were found to commonly have [sigma]3 character. This was likely due to a strong initial <111>-fiber texture. Previous investigations of DAGG in Mo indicated that DAGG grains commonly grow along the surface of the specimen, but this was not observed with significant frequency in Ta. Results suggest that the distance the DAGG grain boundary travels is proportional to the accumulated strain during DAGG, and the velocity of the DAGG grain boundary is proportional to the applied strain rate but is not related to the orientation of the DAGG grain or its slip properties. / text

Latent heat during recalesence and nucleation and post-recalesence temperature was analysed for refractory metals. An effect on latent heat was found by alloying the pure elements with other refractories. Latent heat was found to be 15-65% of tabulated values. Interface energy was evaluated from undercooling experiments. It was found that the dimensionless numbers β (σLs/ σLv) and α can be used to classify elements into distinctive groups and crystallographic structure. The phase diagrams for Al-Ti, Al-Ti-B and Al-Ti-C as well as inoculation were analysed. It was found that Al nucleates on Al3Ti which nucleates on TiB2. TiC was found to decompose into Al4C3 and Al3Ti. The inoculation of nodular cast iron with Mg, Ce; Ca and the formation of sulphides and oxides was analysed. The formation of new inclusions during the solidification as well as the formation of graphite is discussed. / QC 20100602

Out of the known refractory metals and alloys, molybdenum (Mo) and its alloys are very important due to their unique combination of properties which render them suitable for various applications. Owing to their good creep properties, minimum damage from neutron irradiation and good compatibility with the liquid alkali metals, molybdenum and its alloys are well suited candidates for structural components in the newly developed Compact High Temperature Reactor (CHTR). However, to fabricate components for structural application from molybdenum and its alloys, the processing response needs to be established. The present thesis is an attempt to address this issue in a more generic manner. The study have been specifically aimed to examine the hot deformation behaviour of molybdenum and two of its alloys (Mo-TZM and Mo-TZC) over a high temperature range, for obtaining stable microstructure with good mechanical properties. The thesis basically addresses the following (i) the thermos-mechanical response of the material with change in deformation conditions, and (ii) the evolution of microstructure during hot deformation, and identification of associated mechanisms. Chapter 1 of the thesis includes an introduction of the material system and alloys with a detailed survey of the literature on the deformation behaviour of refractory metals and alloys that are used as structural materials in nuclear reactors. More emphasis is given to molybdenum and two of its alloy Mo-TZM and Mo-TZC. Chapter 2 includes the detail of the experimental techniques and analysis procedures that are followed in the course of investigation. The hot deformation behaviour of molybdenum in temperature range 1400 - 1700°C and strain rate range 0.001 - 10.0s-1 is discussed in chapter 3. The stress - strain behaviour has been further analysed to obtain strain rate sensitivity maps. The micro-mechanisms operative in different deformation domain has been analysed extensively by Electron Back Scatter Diffraction (EBSD) technique. Different restoration processes which include dynamic recrystallization, recovery and grain growth have been identified in different domains of deformation conditions. Chapter 4 of this thesis is dedicated to the hot deformation behaviour of Mo-TZM alloy. Deformation behaviour was studied under identical conditions as molybdenum. Mo-TZM showed higher strain rate sensitivity and high temperature strength than molybdenum. Dynamic recovery is the most predominant mechanism in Mo-TZM alloy as revealed through the analysis of stress strain curve as well as EBSD based investigation. At higher temperature and strain rates dynamic recrystallization has also been observed. The effect of excess carbon which results in Mo-TZC alloy, deformation behaviour has been investigated in chapter 5. The analysis of stress – strain curves in this case indicates the predominance of dynamic recrystallization over a range of deformation conditions. The mechanism has been identified as particle simulated nucleation (PSN). The significant growth of the deformed grains is observed at the highest temperature of deformation. A comparison of deformation behaviour of alloying addition in molybdenum alloys has been discussed in chapter 6. The results of deformation behaviour of molybdenum and its alloys has been compared vis-a-vis with another similar class of alloys based on Niobium (Nb) and apparent similarities and differences in the deformation behaviour has also been discussed in chapter 6. Finally, the overall summary of the thesis has been presented in chapter 7.

Les “alliages à haute entropie (de mélange)” (AHE) sont une nouvelle famille de matériaux prometteurs. Ils sont caractérisés par la formation d'une solution solide à 5 éléments (en proportions équiatomiques) de structure cristalline simple. Dans cette thèse, la composition cubique centrée TiZrNbHfTa est étudiée, proposant une caractérisation en profondeur d’un alliage considéré « de référence » dans la famille des AHE réfractaires.Tout d'abord, la microstructure et la structure de l’alliage (dans son état brut de coulée ou recristallisé) sont étudiées. L’environnement local de sous-systèmes de TiZrNbHfTa est analysé par EXAFS. Le traitement des données est effectué par une double approche d’affinement EXAFS et de simulation Reverse Monte-Carlo couplée à une approche d’algorithme génétique. Un mélange quasi-parfait des différents éléments est obtenu à l’échelle locale et la distribution de distance des premiers voisins devient moins bien définie sous l’effet de l’augmentation des différences entre rayons atomiques.Ensuite, l’impact de la solution solide concentrée sur les propriétés mécaniques et les mécanismes de déformation de l’alliage est étudié. Des essais mécaniques spécifiques sont effectués, conduisant à l’obtention des volumes d’activation et à la partition de la contrainte d’écoulement. Une étude MET complémentaire permet d'analyser les microstructures de déformation. Une très haute limite d’élasticité est obtenue, mais la force de friction de Peierls contrôle de manière classique la déformation de cet alliage à la température ambiante, ce qui conduit à un taux d’écrouissage limité. Une nouvelle approche visant à augmenter cette propriété est finalement proposée / High entropy alloys (HEA) are a new promising type of materials. Breaking with the traditional alloying concepts, solid solution(s) based on 5 elements in equiatomic concentration with simple crystal structures are obtained. In this study, the equiatomic composition TiZrNbHfTa is investigated, in order to provide an in-depth characterization of a “reference” body centered cubic refractory HEA.First, the microstructure and structure of the alloy are studied. Thermomechanical treatments procedures are established to access recrystallized microstructures. The local environment is studied by EXAFS in sub-components of the TiZrNbHfTa system. The double approach used, based on EXAFS fit and reverse Monte-Carlo coupled with evolutionary algorithm allowed to quantify both the mixing of the elements at the atomic scale and the lattice distortion. For all the investigated compositions, good mixing is achieved, and the distance distribution of first nearest neighbors becomes less precise with increasing atomic size mismatch.Then, the impact of such concentrated multi-element solid solution on the mechanical properties and the deformation mechanism of the material is investigated by specific tests. The activation volumes and the flow stress partition are extracted. The mechanical results are coupled with a TEM study. This part evidences that the alloy displays an impressive yield strength. However, the high lattice friction controlling the dislocation glide does not differ from classical bcc structures, leading to a rather low work hardening. A new design approach aiming at increasing the work-hardening in such materials is finally proposed, and a proof of concept is given

Aluminum (Al) and its alloys are widely used in various technological applications, mainly due to the excellent thermal conductivity, non-magnetic, ecofriendly, easy formability and good recyclability. However due to the inferior corrosion resistance its applications are hampered in various engineering sectors. Besides, the corrosion related failures such as leakage of gas from pipeline, catastrophic breakdown of bridges and fire accidents in processing plants further puts the human life in jeopardy. Within the United States over $ 400 billion dollars per year are spent over research to understand and prevent the corrosion related failures. Recently, the development of transition metal(TM) aluminides (AlxTMy, where, TM = Mo, W, Ta, Nb, Cr, Zr and V) has received the global attention mainly due to high strength at elevated temperatures, light-weight, excellent corrosion and wear resistance. In light of this, surface modification via laser surface alloying (LSA) is a promising engineering approach to mitigate the corrosion and wear problems. In the present study the attempts are made to study the Al-Mo, Al-W, Al-Nb, and Al-Ta systems as a potential corrosion resistant coatings on aluminum. The refractory metal (Mo, W, Nb, Ta) precursor deposit was spray coated separately on aluminum substrate and was subsequently surface alloyed using a continuous wave diode-pumped ytterbium laser at varying laser energy densities. Microstructural analysis was conducted using scanning electron microscopy and further X-ray diffractometry was carried out to evaluate the various phases evolved during laser surface alloying. Corrosion resistance of laser alloyed coatings were evaluated using open circuit potential, cyclic potentiodynamic polarization, electrochemical impedance spectroscopy measurements were performed in 0.6 M NaCl solution (pH:6.9±0.2, 23˚C). Open circuit potential measurements indicate the more stable (steady state) potential values over long periods after laser surface alloying. Cyclic polarization results indicated reduction in the corrosion current density, enhancement in the polarization resistance, and increase in coating/protective efficiency with increase in laser energy density compared to untreated aluminum. Electrochemical impedance spectroscopy measurements also indicated an increase in charge transfer resistance after laser surface alloying of refractory metals on aluminum. Additionally, first principle calculations of thermodynamic, electronic and elastic properties of intermetallics evolved during LSA were also thoroughly investigated to correlate the corrosion performance of intermetallic coatings with these properties. The present study indicates that novel Al-Mo, Al-W, Al-Nb, and Al-Ta intermetallics has a great potential for light weight structural applications with enhanced corrosion resistance.

Um novo conceito para o desenvolvimento de ligas metálicas vem sendo estudado pela comunidade científica nos últimos anos, trata-se de ligas com elementos multiprincipais, também conhecidas como ligas de alta entropia (HEAs). HEAs constituídas de metais refratários e alumínio se destacam como possíveis ligas para utilização na indústria aeroespacial por apresentaram alta resistência específica. Dessa forma, torna-se necessário uma investigação das relações de fases envolvendo metais refratários e o alumínio. Para este trabalho, foi escolhido o sistema Al-Nb-V, uma vez que se encontrou apenas uma seção isotérmica experimental completa do sistema e nenhuma avaliação termodinâmica na literatura. Para o desenvolvimento do trabalho, foram produzidas ligas por fusão a arco. As amostras foram tratadas a 1200 °C por 10 dias para a determinação da seção isotérmica do sistema nessa temperatura. A caracterização microestrutural foi realizada por meio de difração de raios X (DRX), microscopia eletrônica de varredura (MEV) e microanálise eletrônica (EDS). Em relação à seção isotérmica disponível na literatura, foram observadas algumas diferenças. A seção da literatura, por exemplo, propõe a estabilidade do composto ternário NbVAl2, o qual não foi encontrado neste trabalho. Os resultados permitiram a determinação de boa parte da seção isotérmica a 1200 °C do sistema Al-Nb-V. Em paralelo, foi realizada uma revisão das avaliações termodinâmicas dos binários disponíveis na literatura. Os dados da literatura e os resultados experimentais obtidos foram utilizados para construir uma base de dados termodinâmicos pelo método Calphad. A modelagem termodinâmica apresenta boa consistência com os resultados experimentais obtidos. / A new concept for the development of metallic alloys has been studied by the scientific community in recent years, which deals with multi-principal element alloys, also known as High Entropy Alloys (HEAs). HEAs with refractory metals and aluminium as constituents are possible alloys for use in the aerospace industry mainly due to their high specific resistance. In this way, the investigation of phase equilibria involving refractory metals and aluminium is required. For this work, the Al-Nb-V system was chosen, since only one complete experimental isothermal section of this system and no thermodynamic assessments were found in the literature. For the development of this work, 23 alloys were produced by arc melting. The alloys were treated at 1200 °C for 10 days to determine the isothermal section of the system at this temperature. The microstructural characterization was performed via X-ray diffractometry (XRD) scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Some discrepancies were observed between the isothermal section available in the literature and the results of the present work. The isothermal section found in the literature, for example, proposes the stability of the ternary compound NbVAl2, which was not found in this work. Based on the present work, a new isothermal section at 1200 °C is proposed for the Al-Nb-V system. Also, a review of the thermodynamic descriptions of the binary systems available in the literature was performed. The literature data and the experimental results were used to build a thermodynamic database using the Calphad method. This preliminary thermodynamic modelling shows good consistency with the experimental results.

MoSiB alloys show promise as the next-generation turbine blade material due to their high-temperature strength and oxidation resistance afforded by a protective borosilicate surface layer. Powder processing and reactive synthesis of these alloys has proven to be a viable method and offers several advantages over conventional melt processing routes. Microstructures obtained have well-dispersed intermetallics in a continuous matrix of molybdenum solid-solution (Mo-ss). However, bend testing of pure Mo and Mo-ss samples has shown that, while the powder processing route can produce ductile Mo metal, the hardening effect of Si and B in solid-solution renders the matrix brittle. Testing at elevated temperatures (200°C) was performed in order to determine the ductile-to-brittle transition temperature of the metal as an indication of ductility. Methods of ductilizing the Mo-ss matrix such as annealing and alloying additions have been investigated.

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Made available in DSpace on 2014-10-09T12:49:13Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:43Z (GMT). No. of bitstreams: 1 09808.pdf: 15249724 bytes, checksum: 28b6b5cf9f351da89e42817bc182390d (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:00/00255-9