The aim of this research project was to investigate the microstructural changes of MCrAlY coated Ni-based superalloys that are routinely used in industrial gas turbine engines for power generation. One of the main aims of the characterisation was to understand ageing time and temperature effects on the microstructural evolution so that a methodology could be developed where the characterisation of a thermally exposed microstructure can be used to estimate unknown service exposure conditions.

Ce travail est consacré à l'étude de l'ingénierie des joints de grains dans les superalliages à base de Nickel pour disques de turbines aéronautiques. L'ingénierie des joints de grains a montré son efficacité dans l'amélioration des propriétés en fatigue et en fluage dans certains alliages de cuivre et de nickel. Cette amélioration est obtenue en réalisant une succession de déformations à température ambiante séparées par des traitement thermiques. Ce traitement a pour objectif de modifier la distribution du réseau de joints de grains. L'objectif de l'étude est d'adapter ces traitements au procédé du forgeage à haute température des superalliages. Une étude expérimentale est menée pour mettre en évidence l'influence des paramètres de forgeage sur les caractéristiques du réseau de joints de grains. La caractérisation de ce réseau est faite grâce à la réalisation de cartographies d'orientations cristallographiques par EBSD. Une méthode de caractérisation innovante basée sur la discrétisation des cartographies en réseaux de points triples est proposée. Cette méthode permet d'analyser la connectivité du réseau de joints de grains en vue d'une corrélation avec les propriétés mécaniques. / This work is dedicated to the study of Grain Boundary Engineering in Ni-based superalloys for aircraft turbine disk. The grain boundary engineering has proven its efficiency for the improvement of the fatigue and creep properties of copper and nickel alloys. This improvement is achieved by performing a succession of room temperature deformations interspaced by heat treatments to modify the distribution of the grain boundary network. The aim of the study is to adapt these processes to high temperature forging of superalloys. An experimental study is achieved to highlight the influence of forging parameters on the grain boundary network. The characterization of the grain boundary network is made through the completion of crystallographic orientation mapping by EBSD. An innovative characterization method based on the discretization of orientation maps in a triple junction network is proposed. This method allows to analyze the connectivity in the grain boundary network with the objective of a correlation with mechanical properties.

<p>Ni-based superalloys have been widely used for high temperature applications such as turbine blades for jet propulsion and power plants due to their excellent creep, fatigue, and corrosion resistance. But as the demand for higher temperature capability and strength increases, there remains a need to better understand high temperature deformation mechanisms and improve and strengthen superalloys at these elevated temperatures. Recently, a correlation has been observed between solute segregation at planar defects (stacking faults, antiphase boundaries, etc) and enhanced high temperature creep properties – known colloquially as phase transformation strengthening. Experimentally, regardless of alloy composition, strong Co segregation at planar defects along with Cr has been observed. In addition, it has been suggested by density functional theory work that Co would promote Cr concentration at stacking faults by forming strong Cr-Co bonds. Based on these findings, it was hypothesized the presence of Co provides a significant thermodynamic driving force for segregation to planar defects. </p><p>In order to further investigate the correlation between solute segregation and deformation mechanisms the fabrication of a planar front single crystal Ni-based superalloy and its microstructure, alloy composition, and microhardness properties of the as-zone melted and solution heat treated states were investigated and compared to the directionally-solidified state to study the effect of microsegregation on these alloy characteristics. Next, new Co-containing, Cr-free alloys are designed to optimize g-g’ volume fraction, size, and morphology to mimic microstructures observed in single crystal superalloys. The general alloy design strategy and approach are outlined, and the composition, microstructure, phase transformation temperatures, and mechanical properties of new Cr-free and Co-containing alloys are reported. A new set of Cr-free alloys have thus been designed, with modifications of Nb, Ta, and Ti additions ranging from 3 to 7 at.% to investigate the role of these elements on the phase transformation strengthening mechanism at elevated temperatures.</p><p></p>

Ni-based superalloys are the important materials for gas turbines in advancedaeroplane engines . The addition of refractory elements to these superalloys,such as rhenium and tungsten, can significantly improve the hightemperatureperformance by so-called solid-solution hardening. Although thestrengthening effect of refractory elements in Ni-based superalloys have beenknown for a long time, the effective interactions among alloying componentsas well as the atomic ordering in the alloy systems are still under investigationand even under debate. In this work, we study these interactions and thisordering for two binary alloys, Ni-rich Ni-Re and Ni-rich Ni-W, by means ofab initio simulations and statistical mechanics simulations based on the IsingHamiltonian. For the Ni-rich Ni-Re alloys, we show that the effective cluster interactionsvary substantially depending on the temperature, concentration of the componentsand the magnetic state of the matrix. The strain-induced interactionshave large contribution to the nearest-neighbor pair-interactions and some multisitecluster-interactions in the ferromagnetic and nonmagnetic states. Theordering tendency of binary Ni-Re alloy systems can be predicted in terms ofordering energy and enthalpy of formation. We show that the D1a orderedstructure should be stable at the concentration of 20 at.% Re in the Ni-rich Ni–Re alloy system. The Monte Carlo simulations of Ni-Re random alloysshow the existence with the D1a-Ni4Re ordered structure at low temperatures. We also calculated lattice parameters for different compositions of Ni-rich Ni-W alloys, and we find that lattice parameters of random Ni-W alloys increaselinearly with the concentration of W. This is in good agreement withthe Vegard’s law predictions and experimental data. We investigated phasestability of Ni-rich Ni-W alloys in terms of the enthalpies of formation andordering energies. We find the chemical pair interactions are sensitive to themagnetic state and concentration. The calculated strain-induced interactionsare quite large for the first coordination shell, which is due to a large sizemismatch of Ni and W. Taking local lattice relaxation into account, the Ni-Wsystems were modeled by Monte Carlo method. The D1a-Ni4W ordered structurecan be observed up to 22 at.% W. In higher concentrations of W, in ourMC calculations, the DO22-Ni3W and Pt2Mo-Ni2W ordered structures can beobserved in Ni-25 at.% W alloy and Ni-33 at.% W alloy, respectively. / <p>QC 20160721</p>

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<blockquote><div><div>Methods and techniques for tailoring the surface morphology of metallic surfaces are determined in part by the complex behavior of elemental interactions in conjunction with electrochemical reactions. In this work, we show how the surface morphology can be predicted based on experimental data resulting from polarization curves and compositional differences of Fe- and Ni-based superalloys. Electrochemical treatments utilizing NaCl as the electrolyte were adapted using parameters such as the pitting resistance equivalent (PRE) number and polarization curves to obtain both rough and smooth surfaces. Utilizing these metrics, we electrochemically etched Inconel 600, SS304, Inconel 718 and Inconel 625 obtaining average surface roughness values that ranged from 0.05 to 57.4 μm indicating the success of tailoring the technique to obtaining rough and smooth surfaces. The effect of current density, current pulsing, and temperature were varied to elucidate roughness and pitting behavior, and strong correlations to the PRE number and polarization curve properties of the alloy were observed. Heat treatments and subsequent evolution to the microstructure in the form of grain growth and precipitation altered the etching behavior. These techniques can be used in preventing corrosion failure and enhancing electrochemical machining</div></div></blockquote>

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19730号 / 工博第4185号 / 新制||工||1645(附属図書館) / 32766 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Dry reforming of methane is an important reaction to generate syngas from two greenhouse gases. The syngas can be used in Fishcher-Tropsch synthesis to produce valueded chemicals. Chapter I reviews the catalytic conversion of methane and carbon dioxide to syngas, including DRM reaction chemistry, catalysts used in this process, catalyst deactivation, and the kinetics of DRM reaction. Chapter II discusses the development of bimodal pore NiCeMgAl catalysts for DRM reaction. Bimodal pore NiCeMgAl catalysts were synthesized via the refluxed co-precipitation method and systematically investigated the influence of active metal loading, calcination temperature, reduction temperature and gas hourly space velocity (GHSV) on the catalytic performance of DRM reaction. The Ni15CeMgAl sample with 15 wt% NiO loading was found to be active enough at 750 °C with a high CH4 conversion of 96.5%. The proper reduction temperature for the NiCeMgAl catalyst is either 550–650 °C or 850 °C. Higher calcination temperature favors the formation of NiAl2O4 and MgAl2O4 spinel structures. Compared with non-bimodal pore NiCeMgAl catalyst, bimodal pore NiCeMgAl catalyst has a longer stability in the feed gas without dilution. In chapter III, the kinetic behavior of bimodal pore NiCeMgAl catalyst for DRM reaction was investigated after the elimination of external and internal diffusion effects in a fixed-bed reactor as a function of temperature and partial pressures of reactants and products. A Langmuir-Hinshelwood model was developed assuming that the carbon deposition is ignorable but the RWGS reaction is non-ignorable and the removal of adsorbed carbon intermediate is the rate-determining step. A nonlinear least-square method was applied to solve the kinetic parameters. The derived kinetic expression fits the experimental data very well with a R2 above 0.97, and predicts the products flow rate satisfactorily. Chapter IV documents the results of in situ XRD study on the NiMgAl catalyst for DRM reaction. The phase evolution of a NiMgAl oxide catalyst at the reduction stage was qualitatively analysed and quantitatively determined by employing the continuous changes in XRD intensity and TPR information. The stable crystallite size of both active metal and spinel support is responsible for the long stability of NiMgAl catalyst without carbon deposition during the DRM reaction.

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