Scanning Laser Epitaxy (SLE) is a new layer-by-layer additive manufacturing process being developed in the Direct Digital Manufacturing Laboratory at Georgia Tech. SLE allows for the fabrication of three-dimensional objects with specified microstructure through the controlled melting and re-solidification of a metal powder placed atop a base substrate. This dissertation discusses the work done to date on assessing the feasibility of using SLE to both repair single crystal (SX) turbine airfoils and manufacture functionally graded turbine components. Current processes such as selective laser melting (SLM) are not able to create structures with defined microstructure and often have issues with warping of underlying layers due to the high temperature gradients present when scanning a high power laser beam. Additionally, other methods of repair and buildup have typically been plagued by crack formation, equiaxed grains, stray grains, and grain multiplication that can occur when dendrite arms are separated from their main dendrites due to remelting. In this work, it is shown that the SLE process is capable of creating fully dense, crack-free equiaxed, directionally-solidified, and SX structures. The SLE process, though, is found to be currently constrained by the cumbersome method of choosing proper parameters and a relative lack of repeatability. Therefore, it is hypothesized that a real-time feedback control scheme based upon a robust offline model will be necessary both to create specified defect-free microstructures and to improve the repeatability of the process enough to allow for multi-layer growth. The proposed control schemes are based upon temperature data feedback provided at high frame rate by a thermal imaging camera. This data is used in both PID and model reference adaptive control (MRAC) schemes and drives the melt pool temperature during processing towards a reference melt pool temperature that has been found to give a desired microstructure in the robust offline model of the process. The real-time control schemes will enable the ground breaking capabilities of the SLE process to create engine-ready net shape turbine components from raw powder material.

Pour un réacteur à eau pressurisée, la contamination radioactive du circuit primaire constitue un problème majeur pour les opérations de maintenance. La principale source de cette contamination est le relâchement des produits de corrosion des tubes GV en alliages base nickel représentant environ les trois quarts de la surface totale du circuit primaire. L’oxydation des alliages base nickel en milieu primaire, à l’origine du relâchement, a fait l’objet de nombreuses études. Certaines pistes d’amélioration ont d’ailleurs d’ores et déjà été explorées comme la métallurgie des tubes et plus précisément leur état de surface, la pré-oxydation, l’addition de zinc au sein du milieu primaire. Cependant, la compréhension du phénomène demeure lacunaire. La nature et la structure de la couche d’oxyde formée sur les alliages base nickel est relativement bien connue, mais pas sa cinétique de formation et de relâchement ou de façon bien moins précise. L’objet principal de cette étude est donc le développement et la mise en œuvre d’un dispositif expérimental innovant permettant de suivre l’épaisseur d’oxyde formée par une mesure optique de réflectométrie in situ, ainsi que le relâchement en ligne par mesure de concentration par ICP – MS. Les échantillons utilisés lors des différents essais expérimentaux ont également été analysés par diverses techniques notamment l’XPS et le MET afin d’apporter de nouveaux éléments sur la nature ou la structure des couches d’oxyde. En outre, ces analyses, permettant également d’évaluer les épaisseurs d’oxyde ont contribué à valider les résultats d’oxydation obtenus par réflectométrie. L’utilisation de ce moyen expérimental a permis d’obtenir des résultats, certes peu nombreux mais aux perspectives prometteuses. / The radioactive contamination is a significant issue for the maintenance of the primary loop of a water pressurized reactor. The corrosion products released by steam generators tubes made of nickel base alloys, which represent seventy five percent of the whole primary loop surfaces, are highly responsible for this pollution. The oxidation of nickel base alloys in primary water is thus a widely studied subject. Besides, some mitigation means have already been performed like the control of tube manufacturing and of their surface state in particular, a pre-oxidation process, the injection of zinc into primary water. However, the phenomenon remains deficiently understood. The oxide layer nature and structure, formed on nickel base alloys is relatively well known, but this knowledge is far less precise about the layer formation and release kinetics. The main subject of this study is thus to develop an innovative experimental facility which permits to obtain the layer thickness by in situ optical reflectometry measurements, and the corrosion products release by concentration ICP – MS in line measurements. The implementation of these two techniques has needed lots of theoretical and technical adjustments, especially in situ way of using the reflectometry. Some analyses, XPS and MET in particular, have been performed on the different used samples to bring new facts about the nature and structure of oxide layers. Moreover, these analyses have contributed to validate the oxidation results, by measuring the oxide layer thickness and comparing it to the reflectometric results. The different tests realized with this new experimental device are quite promising and should be used and improved to perform others valuable tests.

Background and Objective: Nickel-base superalloys, strengthened by a high volume fraction of Ni3Al precipitates, have been the undisputed choice for turbine discs in gas turbines as they exhibit the best available combination of elevated temperature tensile strength and resistance to low cycle fatigue (LCF), which are essential for a disc alloy. Alloy 720LI is a wrought nickel-base superalloy developed for disc application and exhibit superior elevated temperature tensile strength and LCF properties. It is distinct from contemporary disc alloys because of its chemistry, (especially Ti, Al and interstitial (C and B) contents), processing and heat treatment. However, literature available in open domain to develop an understanding of these properties in alloy 720LI is rather limited. This study was taken up in this background with an objective of assessing the tensile and LCF properties exhibited by alloy 720LI within a temperature regime of interest and understand the structure-property correlations behind it. Tensile Behavior: The effect of temperature and strain rate on monotonic tensile properties were assessed at different temperature in the range of 25 – 750°C (0.67 Tm) at a strain rate of 10-4 s-1 and strain rate effects were explored in detail at 25, 400, 650 and 750°C at different strain rates between 10-5 s-1 and 10-1 s-1. Yield and ultimate tensile strength of the alloy remains unaffected by temperature till about 600°C (0.58Tm) and 500°C (0.51Tm), respectively, beyond which both decreased drastically. Negligible strain rate sensitivity exhibited by the alloy at 25 and 400°C indicated that flow stress is a strong function of strain hardening rather than strain rate hardening. However at 650 and 750°C, especially at low strain rates, strain rate sensitivity is relatively high. TEM studies revealed that heterogeneous planar slip involving shearing of precipitates by dislocation pairs was prevalent under strain rate insensitive conditions and more homogeneous slip was evident when flow stresses were strain rate sensitive. The planarity of slip is also considered responsible for the deviation in experimental data from the Ludwick–Hollomon power-law at low plastic strains in regimes insensitive to strain rate. Irrespective of strain rate sensitivity and degree of homogeneity of slip, fracture mode remained ductile at almost all the conditions studied. Dynamic Strain Ageing: Alloy 720LI exhibits jerky flow in monotonic tension at intermediate temperatures ranging from 250-475°C. After considering all known causes for serrated flow in materials, the instability in flow (Portevin-LeChatelier (PLC) effect) is considered attributable to dynamic strain ageing (DSA), arising from interactions between diffusing solute atoms and mobile dislocations during plastic flow. As the temperature range of DSA coincided with typical bore and web temperatures of turbine discs, its possible influence on tensile properties is considered in detail. No significant change in tensile strength, ductility, or work hardening is observed, due to DSA, with increase in temperature from smooth to serrated flow regime. However strain rate sensitivity, which is positive in smooth flow regime turned negative in the serrated flow regime. Analysis of serrated flow on the basis of critical plastic strain for onset of serrations revealed that in most of the temperature-strain rate regimes studied, alloy 720LI exhibits ‘inverse’ PLC effect which is a phenomenon that has not been fully understood in contrast to ‘normal’ PLC effect observed widely in dilute solid solutions. Other characteristics of serrated flow viz., stress decrement and strain increment between serrations are also analyzed to understand the mechanism of DSA. Though the activation energy determined using stress decrements suggest that carbon atoms could be responsible for locking of dislocations, based on its influence on mechanical properties and also on its temperature regime of existence, weak pinning of dislocations by substitutional solute atoms are considered responsible for DSA in alloy 720LI. LCF Behavior: LCF studies were carried out under fully reversed constant strain amplitude conditions at 25, 400 and 650°C with strain amplitudes ranging from 0.4-1.2%. Different cyclic stress responses observed depending on the imposed conditions are correlated to the substructures that evolved. Low level of dislocation activity and interactions observed in TEM is considered the reason behind stable cyclic stress response at low strain amplitudes at all temperatures. TEM studies also show that secondary γ’ precipitates that are degraded through repeated shearing are responsible for the continuous softening, observed after a short initial hardening phase, at higher strain amplitudes. Studies at 400°C show manifestation of DSA on LCF behavior at 400°C in the form increased cyclic hardening which tends to offset softening effects at higher strain amplitudes. Plastic strain dependence of fatigue lives exhibited bilinearity in Coffin-Manson plots at all temperatures. TEM substructures revealed that planar slip with deformation concentrated on slip bands is the major deformation mode under all the conditions examined. However, homogeneity of deformation increases with increase in strain and temperature. At 25°C, with increasing strain, increased homogeneity manifested in the form of increased number of slip bands. At 650°C, with increase in strain, increased dislocation activity in the inter-slip band regions lead to increased homogeneity. It is also seen that fine deformation twins that form at 650°C and low strain amplitudes play a role in aiding homogenization of deformation. Unlike other alloy systems where an environmental effect or a change in deformation mechanism leads to bilinearity in Coffin – Manson (CM) plots, our study shows that differences in distribution of slip is the reason behind bilinear CM plots. While the properties and behavior of alloy 720LI under monotonic and cyclic loading conditions over a range of temperatures could be rationalized on the basis of deformation substructures, the thesis opens up the door for further in-depth studies on deformation mechanisms in 720LI as well as other disc alloys of similar microstructure.

The area of research dealing with joining of dissimilar metals has been active in recent time. Although fusion and non-fusion techniques of joining have been effectively used for manufacturing components, a comprehensive scientific understanding of the process is lacking. This void exists both in fusion and non-fusion welding methods. The present investigation addresses some of these aspects. The investigation consists of two sections - Part A and Part B. Part A is on Friction welding and Part B deals with Fusion welding using laser. Each section has two chapters each. Following an introductory chapter, basic aspects of friction welding is presented in chapter 2. Chapter 3 deals with the work on friction welding of Fe-Cu couple. Fe-Cu couple is a system with positive heat of mixing. After a brief introduction on various non-equilibrium processes that can occur in this system, experimental details and results are presented. Using the results an attempt is made to understand the flash formation, formation of pores at the interface and the formation of chemically altered zone. It is observed that a chemically altered layer forms predominantly on the Cu side of the interface. It consists of Fe entrapped as fragments/fine crystals and as solid solution in Cu matrix. This zone has higher thickness at the edges than at the center. The mechanism of formation of this interfacial layer which is central to the joining process is related to the fracture and transport of fragments during plastic deformation. Fe forms solid solution in copper under non-equilibrium conditions promoted by shear energy. Using the concept of ballistic mixing, the formation of solid solution is explored. Using nano-indentation experiments mechanical properties of the weldment is estimated and an attempt is made to correlate mechanical properties with the amount of second element present in that location. The chapter 4 in part A deals with the friction welding of Ni-Ti couple. Ni-Ti system has negative heat of mixing and it forms a number of intermetallics. After a brief introduction to the chapter, various experimental techniques and strategies followed to carry out the experiments are explained. Following these, the results are presented. It is observed that TiNi3 formed at initial stage. Theories based on effective heat of formation and surface energy also predict the nucleation of TiNi3. With the continuation of frictional processes, the formation of TiNi and Ti2Ni phases were also observed. Formation of Ti2Ni was shown to greatly accelerate due to shear process. In this system two complementary processes like ballistic mixing and thermal assisted diffusion accelerate Ti2Ni formation. From mechanical tests it is found that Ti2Ni layer in the weldment is weak and hence formation of Ti2Ni in the weldment is detrimental. In chapter 5 an introduction to fusion welding of dissimilar metals is presented as background materials for the subsequent chapters. Chapter 6 deals with nature of segregation of Ag during laser welding of Fe-Ni couple. Ag is used as a tracer to probe fluid flow in the Fe-Ni couple during laser welding. Ag is immiscible both in Fe and Ni whereas Fe and Ni form a complete solution at an elevated temperature and in liquid state. Besides the experimental work, numerical simulation of the weld pool were carried out using homogeneous mixture model using SIMPLER algorithm. Experiments and simulations indicate that fluid flow is asymmetrical and in the deep penetration welding strong convection in the pool drives the tracer to the top of the pool. Overall distribution of the tracer is due to the combined effect of convection and diffusion. In shallow welding there exists a boundary region where tracer does not penetrate. In chapter 7 the results of instrumented indentation experiments on laser welded Fe-Cu weldment has been presented. It was earlier reported that during laser welding of Fe-Cu couple, a variety of microstructures evolves at various locations in the weldment and hardness of the weldment were found to be very high. Here an attempt has been made to explore in details the origin of such a high hardness. The chapter starts with a description of various microstructures that are observed in this weldment followed by the various procedures used for extracting data from instrumented indentation tests. It is followed by the presentation of the experimental results. It is found that rule of mixture along with Hall-Petch strengthening explains the observed increase in hardness of the weldment. The fine scale microstructure consisting of alternate Fe rich and Cu rich layers increases the hardness of the weldment. On copper side of the weldment, composition and scale of microstructure fluctuates and so also the hardness. Finally in chapter 8 overall conclusions of the various chapters in the thesis have been summarised.

NiTi based shape memory alloys (SMA) cover most of the commercially produced shape memory devices and components. The reversible martensitic transformation between the phases B2 (austenite) and B19′ (martensite) is responsible for the shape memory effect in these alloys. The amount of strain which can be regained after a permanent deformation through thermal activation, known as the recoverable strain, is a strong function of crystallographic texture and microstructure. Texture influences the activation of a specific martensite variant during stress induced martensitic (SIM) transformation and also the re-orientation of twinned variants during further deformation. The variant selection decides the amount of recoverable strain. Since the NiTi based shape memory alloys inevitably undergo thermo-mechanical processing in the course of component design, the consequent evolution of texture and microstructure regulate the shape memory behavior. The present thesis is aimed to address this issue in some NiTi alloys that are technologically important for different applications, namely a binary Ni-rich NiTi alloy, a copper containing NiTi alloy and a hafnium containing NiTi alloy. The Ni rich NiTi alloy displays pseudoelastic behavior that can be used for couplings, the NiTiCu alloy provides a controlled thermal hysteresis suitable for actuator applications and the NiTiHf alloy can be used for high temperature applications. The first Chapter of the thesis provides a detailed overview of the existing knowledge related to evolution of microstructure and texture during processing, the transformation texture and its role on the shape memory behavior in NiTi alloys. The second chapter includes the experimental procedure followed to generate different textures, namely unidirectional and cross rolling with and without a subsequent annealing and also the details of the techniques used to characterize the structure, microstructure, texture and mechanical properties. The evolution of texture during thermo-mechanical processing of a Ni rich NiTi alloy and its impact on shape memory behavior is addressed in Chapter 3. The two modes of rolling employed at higher temperature led to the formation of different textures. The texture of unidirectionally rolled samples was characterized by a strong <111>||ND fiber, while a strong Goss {100}<110> component along with <111>||ND fiber was observed in the texture of the cross rolled samples. Annealing of the unidirectionally rolled samples generated a strong <100>||ND fiber, and a weak <111>||ND fiber was observed for the cross rolled samples. Microtexture analyses indicated that dynamically recrystallized grains had significantly different texture compared to the statically annealed material. One of the salient features of this study is the analysis of different twin boundaries with coincident site lattice (CSL) relations that has been observed in the hot rolled material. The origin of these twins has been attributed to deformation. The evolution of twin boundaries with CSL relation has strong influence on texture formation. A few of the important texture components have been found to have CSL relation amongst them. The origin of different texture components were found using intra-grain misorientation parameters. In-situ transformation studies in a scanning electron microscope have confirmed the formation of different types of twins at very low amount of strain in the Ni rich NiTi alloy. A Schmid factor based criterion was used to identify the activation of a particular variant. Trace analysis of the surface relief due to SIM transformation was utilized to confirm the theoretically predicted variant. Schmid criterion has been found to be valid in all the cases. Modulus variation with temperature and strain was studied using dynamical mechanical analysis. Microstructural changes during thermal and thermo-mechanical cycling revealed higher orientation gradient along grain boundaries compared to grain interior. The compatibility condition at the grain boundaries were attributed to higher misorientation development. Misorientation development during cycling loading process is also found to be a strong function of texture. Processing condition and texture has a strong influence on the recoverable strain. Particularly, the strength of <111>||ND fiber is influential in deciding the recoverable strain. Study of microstructure and texture evolution in the TiNiCu SMA and subsequent study on its impact on recoverable strain is presented in Chapter 4. Convincing evidences for the mechanisms operating during different dynamic restoration processes have been presented through microstructural investigation. Texture analysis of the austenite phase showed the formation of <111>||ND fiber. Despite the weakening of texture at larger strain, strength of certain deformation texture components like S {123}<634> and Cu {112}<111> increased, which suggested that texture evolution in TiNiCu alloy deviates from the texture of binary NiTi at large strains. Transformation texture analysis was carried out through electron back scattered diffraction technique, using an in-situ heating stage. The analysis of the results showed predominant activation of <011> type II as well as {11 1 } type I twins. A comparison of martensite and austenite pole figures indicated strong variant selection during phase transformation. Like the binary NiTi alloy, cross rolling of TiNiCu alloy also showed ample changes in the texture of martensite phase through the formation of different texture components. Annealing of both unidirectionally and cross rolled samples led to the weakening of texture. The change in volume fraction of Ti2NiCu precipitates, resulting from different processing conditions, influenced the transformation temperature. In this case also, texture and large intra-grain misorientation governed the recoverable strain. Chapter 5 is dedicated to the study of high temperature NiTiHf alloy. X-ray diffraction and differential scanning calorimetric studies confirmed a two step martensitic transformation, a B19` monoclinic and rhombohedral R-phase martensite in the studied alloy (Ni49.4Ti38.6Hf12). Microstructural investigations showed the formation of dendritic (Ti,Hf)2Ni precipitates along the grain boundary. Evolution of R-phase martensite was always observed along with (Ti,Hf)2Ni precipitates, irrespective of the processing condition. Dissolution of (Ti,Hf)2Ni precipitates by solution treatment suppressed the R phase formation. Strong texture of R-phase martensite confirmed variant selection during martensitic transformation. On the contrary, texture of B19` martensite was always weak, suggesting no preference for variant selection. Rolled material with a relatively strong texture exhibited higher recoverable strain compared to annealed material. Finally, all the significant outcomes of the present investigation are summarized in Chapter 6. Based on the conclusions, suggestions for future work have been mentioned.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T13:42:56Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T13:42:56Z (GMT). No. of bitstreams: 0 / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T13:42:56Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T13:42:56Z (GMT). No. of bitstreams: 0 / Eletrocatalisadores baseados em Pd/C, PdCu/C, PdNi/C e PdAg/C foram produzidos pelo método de micro-ondas para serem utilizados como cátodo na célula a combustível alcalina na ausência e presença de álcool. Este método se mostrou bastante efetivo para a produção dos materiais, uma vez que as partículas apresentaram boa dispersão no suporte de carbono e produziram eletrocatalisadores com tamanho de partícula em torno de 3,5 nm, de acordo com as análises de DRX e MET. A partir das voltametrias cíclicas observa-se que para os eletrocatalisadores de PdCu/C e PdNi/C quanto maior a quantidade de Cu ou Ni, respectivamente, maior a área ativa do material estudado. Análises de disco anel rotatório foram realizadas nos eletrocatalisadores demonstrando que, independente da composição estudada, a quantidade produzida de peróxido foi de no máximo 4%. Estes dados corroboram com as inclinação das retas nas análises de Koutecky-Levich, uma vez que em ambos os casos a RRO ocorre via 4 elétrons. Análises de estabilidade dos materiais demonstraram que todos eles mantiveram ou melhoraram seu desempenho diante da RRO, quando se compara os dados obtidos antes e depois de 1000 ciclos voltamétricos. Testes de tolerância ao metanol e etanol foram realizados em meia célula com todas as composições de eletrocatalisadores produzidos. Na presença tanto de metanol quanto de etanol as composições atômica de 50:50, para todos os materiais estudados, foram as que demonstraram menor influência da presença do álcool durante a varredura linear da RRO. Nas medidas realizadas em célula unitária, com relação à tolerância ao metanol durante a RRO, o eletrocatalisador que demonstrou melhor desempenho foi o PdAg/C 70:30 enquanto que na presença de etanol o eletrocatalisador que demonstrou melhor desempenho foi o PdNi/C 70:30. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Le grenaillage est souvent utilisé sur les pieds d’aube de turbine haute pression afin de retarder l’apparition des fissures dans les zones de concentration de contraintes. Ce traitement de surface génère des contraintes résiduelles et de l’écrouissage en surface de la pièce, ce qui influe sur sa durée de vie. L’enjeu de cette thèse est de mettre en place une méthodologie permettant de prendre en compte cet état mécanique initial, ainsi que son évolution en service, dans l’analyse de durée de vie d’une aube élaborée en superalliage monocristallin à base de nickel (AM1). Tout d’abord, cet état mécanique (contraintes résiduelles et écrouissage) est déterminé expérimentalement. Les contraintes résiduelles sont notamment évaluées par diffraction des rayons X en utilisant la méthode d’Ortner. Cet état mécanique est ensuite introduit dans les calculs de structure. Pour cela, on s’inspire de la méthode connue de l’introduction directe du champ d’eigenstrains qui est, ensuite, étendue afin d’introduire également les variables d’écrouissage ainsi que l’état mécanique anisotrope complet dans toute la structure. L’étape suivante a visé à suivre expérimentalement et à modéliser l’évolution de ces quantités sous sollicitations thermique, d’une part et cycliques à température constante (650°C), d’autre part. Enfin, la chaîne complète de calcul de durée de vie de l’AM1 est appliquée afin d’analyser la durée de vie des éprouvettes grenaillées. Les résultats obtenus sont discutés en regard des essais de fatigue effectués sur éprouvettes représentatives / Shot-peening is widely used on roots of high pressure turbine blade to postpone crack initiation in stress concentration area. This pre-stressing introduces compressive residual stress and strain hardening in a surface layer which will influence lifetime. The aim of this thesis is to propose a methodology which allows taking into account the impact of such pre-stressing and their evolution on the fatigue behaviour of a single crystal nickel-based superalloy (AM1) used for high pressure turbine blades. Firstly, the experimental work is devoted to the determination of the initial mechanical state (residual stresses and strain hardening). Residual stresses are namely determined using X-ray diffraction involving the use of a specific method developed by Ortner. This experimental initial mechanical state is then introduced as an input in structure calculation. The well-known method involving the direct introduction of eigenstrain profiles is used and improved to also introduce strain hardening variables and the complete anisotropic mechanical state in all the integration points of the structure. The next step consist in following experimentally and modeling the evolution of these quantities under thermal and mechanical loads under an uniform temperature (650°C). Finally, the complete lifetime assessment is carried out on representative shot-peened samples. Results are discussed with respect to experimental fatigue tests