<p>  </p> <p>Concentrated solar power (CSP) is a technology that utilizes focused sunlight to heat a high-temperature medium (such as a molten salt). Heat from this medium can be transferred to a working fluid (such as supercritical CO2) that is then used to drive a turbine to generate electricity. Alternatively, the hot medium/fluid can be pumped into tanks for thermal energy storage (TES), for heat extraction later to generate dispatchable electricity and/or for electricity production at night or on cloudy days. By increasing the fluid temperature to <u>></u>750oC and utilizing TES, CSP can become more cost competitive with fossil-based electricity production. Current CSP systems utilize molten nitrate salts for heat transfer and TES that are known to thermally degrade at temperatures >600oC. To achieve temperatures <u>></u>750oC, molten chloride salts, such as ternary MgCl2-KCl-NaCl compositions, are being considered as heat transfer and thermal energy fluids for next generation CSP plants due to their higher temperature stability, low cost, and availability. </p> <p>In this work, it was demonstrated that MgCl2-containing molten salts are prone to oxidation in ambient air at 750oC, which can enhance corrosion of the containment materials and alter the thermophysical properties of the fluid. An alternative, low-cost, earth-abundant, MgCl2-free, oxidation-resistant molten salt, a eutectic CaCl2-NaCl composition, was developed, along with a corrosion mitigation strategy, to enable the slow growth of protective oxide layers on metals that are resistant to dissolution by such MgCl2-free molten chloride salts. </p> <p>This strategy was expanded to other low-cost, oxidation resistant compositions, such as eutectic BaCl2-CaCl2-KCl-NaCl with tailored chemical and thermophysical properties for CSP and TES. The melting temperature, heat capacity, oxidation resistance, and crystallization behavior were measured for eutectic a BaCl2-CaCl2-KCl-NaCl(17.5-47.8-3.3-31.4 mol%) (BCKN) salt and a MgCl2-KCl-NaCl (40-40-20 mol%) salt. BCKN salt was shown to have a similar melting temperature while having a higher heat capacity and far better oxidation resistance. </p> <p>The corrosion of the nickel-based superalloy Haynes 214 was studied in molten MgCl2-KCl-NaCl (40-40-20 mol%) salt at 750oC under inert atmosphere conditions using a custom-built rotating-disc corrosion testing apparatus that maintained laminar fluid flow on the sample. Non-protective external Cr-, Al-, and Mg- oxide layers were formed on Haynes 214 that were prone to spallation. Internal oxidation of Al was also observed along with Cr depletion zones within Haynes 214.  Corrosion kinetics were evaluated to quantify the role of fluid flow for application of this alloy for use in containment and transportation of this molten chloride salt. </p>

No description available.

No description available.

Laser-material interaction of Nickel based superalloy Haynes 282 melt pools were studied for laser parameters similar to laser powder bed fusion (PBF-LB) without powder. The effect of power, speed, hatch distance and laser focus offset were analysed by characterizing different types of melt pool behaviour, including conduction, transition to keyhole, and keyhole mode. Focus offset parameter was found to modify the melting mode from keyhole to conduction type in experiments with and without powder. This change in melting mode is attributed to the variation in laser beam spot size for the same line energy. Such manipulation of type of melting with control of focus offset can be utilized as a method to optimize process parameters for novel materials in the PBF-LB process at high layer thickness. Based on the above study, cubes were built with refined process parameters utilizing powder layer thicknesses of 60- and 90-microns for improved productivity, using partial factorial design of experiment. The conduction mode of melting helped reducing defects, minimizing lack of fusion and keyhole porosity in specimens built with powder at 60- and 90-microns layer thickness. Effect of process parameters and indirect measure like area energy, on the melt pool overlap, defect level and dominant shape of the defects are presented. Optimizing the process parameters to identify the boundaries for building cubes with reduced porosity is also discussed. / Den Ni-baserade superlegeringen, Haynes 282, skannades med laserparametrar liknande de som används i laserpulverbäddfusion (PBF-LB), men utan pulver.Studien undersökte inverkan av effekt, hastighet, avstånd mellan två intilliggandeskanningspass och laserfokusförskjutning, vilket karakteriserades genom olikatyper av beteenden hos smältbadet, inklusive värmeledning, övergång frånvärmeledning till nyckelhål, och nyckelhål. Fokusförskjutningen visade sig ändrasmältbadets läge från nyckelhål till värmeledning. Denna förändring observeradesbåde i experiment utan pulver och i de med pulver. Förändringen beror påbreddningen av laserstrålens punktstorlek samtidigt som samma linjeenergibibehålls. Denna förändring i smältningstyp genom fokusförskjutning kananvändas som en metod för att optimera utforskningen av nya material i PBFLB-processen. Baserat på detta byggdes kuber med pulver med lagertjocklekar på 60 och 90mikrometer, användande olika processparametrar enligt en experimentell designbaserad på en central sammansatt design. Smältning genom värmeledning bidrogtill att minska defekter, minimera bindningsfel och nyckelhålsporositet i proversom byggts med pulver med lagertjocklekar på 60 och 90 mikrometer. Inverkanav processparametrarna och indirekta mått såsom areaenergi på smältbadetsöverlappning, defektnivå och den dominerande formen på defekter presenteras.Optimering av processparametrarna samt identifiering av parameterrymden föratt bygga kuber med minskad porositet undersöks också. / <p>Paper A is to be submitted, and paper C is acceptet and are not included in this licentiate thesis. We do  not have permission to publish paper B in the digital version.</p>

Ce travail porte sur l'étude du comportement sous sollicitation de fretting sirnple à haute température de superalliages monocristallins à base de nickel MC2 et CMSX-4. Il trouve son application dans le domaine aéronautique, plus précisément au niveau de la turbine haute pression des moteurs d'hélicoptère. Celle-ci a pour fonction de convertir l'énergie cinétique des gaz brûlés en un couple qui entraîne en rotation le compresseur. Elle participe ainsi directement à l'entretien du cycle de combustion du moteur ce qui fait d'elle un organe clé. Située directement en aval de la chambre de combustion, la turbine haute pression (HP) est composée d'un disque central polycristallin et d'aubages monocristallins rapportés, liés au disque par une liaison dite pied de sapin. La rotation de la turbine et la température élevée des gaz de combustion va générer sur les aubes, le disque et l'attache qui les relie，des sollicitations thermomécaniques importantes. Du fait de la force centrifuge et du défilement des aubes devant les étages fixes des distributeurs, l'attache pied de sapin est la cible d 'oscillations dynamiques à l'origine de phénomènes d'endommagement par fretting. Ce fretting,, l'interface de contact entre l'aube et le disque fait l'objet d'une attention toute particulière，ce qui a motivé la conduite de ces travaux. Après une première phase et développement et de validation d'un banc d'essai innovant qui a nécessité la mise en place d'un dispositif de chauffage par induction, un soin tout particulier est apporté à la préparation des échantillons. La nature monocristalline du matériau constitutif des aubes nécessite en effet de respecter précisément l'orientation de la microstructure par rapport aux axes de sollicitation et la surface de contact. Pour cela une mesure systématique de la désorientation des axes primaires et secondaires des barreaux bruts est réalisée. La désorientation relevée est ensuite compensée au cas par cas lors du prélèvement par électroérosion des échantillons. Le lot d'échantillons obtenu peut dès lors être considéré comme homogène en terme d'orientation, malgré le fait que les barreaux bruts présentent des désorientations différentes. [...] / The aim of this work is to study the behavior of MC2 and CMSX-4 nickel based superalloys when subjected to fretting load at high temperature. Since it drives the compressor shaft, the high pressure turbine is a key part of the helicopter engine. 1n order to increase the global reliability and efficiency of the engine, single crystal nickel based superalloys are employed for turbine blades while disk parts are made of polycrystalline materials. Each turbine blade is attached to the central disk via a special link called fir tree root. Due to high temperature and dynamic oscillations, the contact zone between blades and disk is subjected to high thermomechanical stresses. 1t causes fretting phenomena that can lead to wear and cracking damage. This work focuses on both the partial slip and gross slip regime in order to study the damage process of single crystal MC2 and CMSX-4 materials. To perform the mechanical tests, an innovative fretting device is designed to fit the specifications. The use of an induction heat system allows an accurate control of high temperatures. To be consistent with the real flying parts,，the specific orientation of the microstructure of the material with respect to the contact loading direction is taken into account. The microstructure misalignement of raw material bars is measured and compensated as the specimens are machined for extraction. Consequently the obtained set of samples is considered to be of homogeneous microstructure orientation even if their source material contains deviations in orientation. Four material states are investigated: precision grinding conventional shot-peening ultrasonic shot-peening and nitriding process. The results show that for the partial slip régime, shot peening processes are very useful for turbine blade applications. As a matter of fact, the risk for crack nucleation and extension are reduced by the introduction of residual stresses beneath the surface in spite of the high temperature. 1nvestigating the gross slip regime results show that wear of material leads to the formation of a third body and then to the formation of a thin layer called "glaze layer)) with low friction coefficient. To describe the formation process of the "glaze layer)) halted trials are performed. The results allow the drafting of a scenario in which wear debris are stuck and sintered beneath the contact.

L'objectif de cette thèse est de mettre en évidence l'influence de la microstructure initiale sur le glissement intergranulaire lors du fluage à haute température d'un superalliage polycristallin à base de nickel. Dans ce but, plusieurs microstructures sont obtenues à partir de la microstructure de référence de l'alliage NR6, par application de traitements thermiques spécifiques. L'influence des paramètres microstructuraux sur les déformations locales est ensuite étudiée à l'aide d'une technique de microextensométrie couplée à une analyse par diffraction des électrons rétrodiffusés. Il est ainsi possible de relier microstructure, déformations locales et comportement macroscopique en fluage. Pour la microstructure de référence de l'alliage NR6, la déformation opère principalement par cisaillement des phases γ et γ'. Ce mécanisme est favorable au glissement intergranulaire. L'absence de précipités tertiaires de phase γ' favorise le contournement des précipités secondaires par les dislocations. Ceci permet de réduire le glissement intergranulaire mais est également néfaste pour la résistance à la déformation de l'alliage. La présence de joints de grains dentelés augmente la résistance au glissement intergranulaire mais diminue la résistance à la déformation intragranulaire en favorisant le contournement des précipités. Ainsi la résistance globale à la déformation n'est pas affectée. Enfin, l'augmentation de la taille de grains n'a d'influence ni sur les mécanismes de déformation mis en jeu ni sur l'amplitude du glissement. Cependant, la fraction moins élevée de joints de grains induit une diminution de la contribution du glissement intergranulaire à la déformation globale. / The aim of this study is to highlight the influence of initial microstructure on grain boundary sliding during high-temperature creep of a polycrystalline nickel-based superalloy. To reach this goal, several microstructures are produced from the reference microstructure of NR6 alloy by adequate heat treatments. The influence of microstructural parameters on local deformations is then studied thanks to a microextensometry technique coupled with an electron back-scattered diffraction analysis. It thereby enables linking microstructure, local deformations and macroscopic creep behaviour. In the case of NR6 alloy reference microstructure, deformation occurs mainly by γ and γ' phases cutting by dislocations. This mechanism is grain boundary sliding-favourable. The absence of tertiary γ' phase precipitates promotes secondary precipitates bypassing by dislocations. This results in a reduction of grain boundary sliding but is also harmful to the alloy creep resistance. Grain boundary serration improves grain boundary sliding resistance but diminishes intragranular deformation resistance by favouring precipitate bypassing. Then global deformation resistance is not changed. Finally, grain size increase has influence neither on activated deformation mechanisms nor on sliding amplitude. However, the decrease of grain boundary fraction leads to a reduction of grain boundary sliding contribution to overall strain.

La Corrosion Haute Température (HTC), en environnements divers et sévères, d'alliages métalliques toujours plus élaborés en termes de composition et micro-structure, est un sujet industriel et scientifique très complexe. La PhotoElectroChimie (PEC) est une technique de choix pour caractériser les propriétés physico-chimiques et électroniques des couches d'oxydation très hétérogènes formées en HTC. Sur des exemples d'alliages modèles mais représentatifs de la réalité industrielle (aciers duplex, base-Nickel 690), ce travail présente le développement et la validation d'un dispositif expérimental permettant d'appliquer pour la première fois tout l'arsenal des techniques PEC à l'échelle mésoscopique (typiquement 30 µm), ainsi que la validation d'une modélisation originale développée au SIMaP des spectres de photocourants en énergie, qui permet de les décrire et ajuster finement et d'en extraire notamment avec précision les gaps des oxydes semiconducteurs présents dans la couche thermique. / High Temperature Corrosion (HTC), in various and severe atmospheres, of continually more elaborated (composition, micro–structure) metallic alloys, is a rather complex industrial and scientific topic. PhotoElectroChemistry (PEC) acquired a special place in the characterization of physico–chemical and electronic properties of the highly heterogeneous oxidation layers formed in HTC. Through studies of model but industrially representative samples (duplex stainless steel, Ni–base alloy 690), this work presents the development and validation of an experimental set–up allowing for the first time to use the whole set of PEC techniques at the mesoscopic level (typically 30 µm), as well as the validation of an original model of photocurrent energy spectra, developed at SIMaP, allowing to well describe, and accurately fit the latter spectra, and thus yielding, notably, precise bandgap values for the semiconducting components of the thermal scale.

Les alliages à base de Nickel constituent les meilleurs matériaux actuellement développés pour répondre aux sollicitations sous hautes températures dans les domaines de l’aéronautique du nucléaire etc… L’objectif de ce travail de thèse est d’étudier leur comportement en température sous sollicitations de fretting usure. Dans cette étude, on s’intéresse à un contact René125/Waspaloy représentatif d’une application aéronautique. Dans un premier temps nous avons étudié l’effet de la température. On montre qu’à partir de 400°C, l’interface génère la formation d’une glaze layer lubrifiante qui réduit considérablement la cinétique de l’usure. En fixant la température à 700°C (température de l’application industrielle), nous avons étudié la stabilité de ces couches protectrices vis-à-vis de la pression de contact, de l’amplitude de glissement, de la fréquence et du nombre de cycle appliqués. Cette analyse montre une évolution bilinéaire de l’usure avec une usure initiale rapide liée à la formation de la « glaze layer » puis une usure additionnelle quasiment nulle dès que la « glaze layer » est formée. Ces travaux montrent que le volume d’usure associée à la formation de la « glaze layer » est fonction de la vitesse de glissement. Au dessus d’une vitesse seuil de glissement, la formation de la « glaze layer » protectrice devient plus difficile. Une courbe maîtresse est ainsi établie. Des analyses chimiques des interfaces associées à des essais interrompus ont permis d’établir le scénario de formation de ces glaze layers. Pour finir, une étude comparative des revêtements développés dans le cadre du projet INNOLUB a été menée de façon à sélectionner le revêtement offrant les meilleures propriétés tribologiques pour l’application étudiée. / Nickel based alloys are the most developed materials nowadays for applications at high temperature, as in aeronautics, nuclear…The aim of this study is to understand their behavior at high temperature under fretting wear solicitations. Thereby, we had focused on a tribosystem formed of Waspaloy/René 125, which represent the crankcase/blade contact of the low pressure Turbine. We started studying the temperature effect, it is been noticed that above T = 400°C, a lubricant tribofilm, called the Glaze Layer is generated at the interface of the contact, which enable an abrupt reduction in friction and wear rate. The temperature was than fixed at 700°C (service temperature), so the glaze layer stability was analyzed as a function of contact pressure, sliding amplitude, frequency and number of cycles imposed. This analysis shows a bilinear wear evolution, characterized by a fast initial wear related to the formation of the glaze layer, followed by almost no wear once the glaze layer is formed. This study showed that the wear rate related to the glaze layer formation is dependent of the sliding velocity. Above a sliding velocity threshold, the formation of a stabilized glaze layer is quite difficult. A Master curve is here established. Microscopic and spectroscopic investigations are conducted to analyze the interface based on interrupted tests of a very short duration. Leading to a precise description of the glaze layer formation mechanisms. At the end of this study, a comparative analysis of different coatings developed to improve these components behavior, in the framework of INNOLUB project was established, allowing choosing the coating offering the best tribological properties and lifetime.

Les superalliages monocristallins à base de nickel sont utilisés en aéronautique pour les aubes de turbines. Cette étude est consacrée à la modélisation du comportement en fluage du superalliage monocristallin AM1 après mise en radeaux, au cours d’essais isothermes à contrainte variable. Des diffractogrammes (200) ont été obtenus in situ par diffractométrie trois axes en rayonnement synchrotron, à haute température (950-1150°C) pour des paliers de contrainte entre 0 et 300MPa. Pour chaque phase, les déformations élastiques se déduisent de la position des pics et les contraintes, déformations plastiques et vitesses de déformation sont obtenues par la mesure du désaccord paramétrique, en utilisant un modèle composite en série. Ces résultats sont combinés à une caractérisation post mortem en microscopie électronique : morphologie des phases, densité et nature des dislocations. La mesure in situ du désaccord paramétrique donne accès à la densité instantanée de dislocations aux interfaces y/y’. Dans la phase ylors d’incréments de la contrainte appliquée, la contrainte de Von Mises augmente, puis se relaxe jusqu’à une contrainte seuil. Cette contrainte est en accord avec la contrainte d’Orowan et les largeurs des couloirs mesurées post mortem. La déformation plastique de la phase y’ est produite par montée de dislocations de vecteur de Burgers perpendiculaire à l’axe de traction sous l’action de la seule contrainte transverse et contrôlée par l’entrée de dislocations depuis les interfaces. Une simulation des pics de diffraction permet de reproduire l’évolution de leur largeur en fonction de la nature et de la répartition des dislocations aux interfaces et dans la phase y' / Nickel-based superalloys are used in aeronautics for turbine blades. This study aims at modelling the creep behaviour of single-crystalline AM1 superalloy with a rafted γ/γ’ microstructure during isothermal tests under variable applied stresses. (200) diffraction profiles are obtained with a triple crystal diffractometer and high energy synchrotron radiation at high temperature (950-1150°C) with an applied stress varying between 0 and 300 MPa. For each phase, the elastic strain is deduced from the peaks’ positions and the stress, plastic strain rate from the lattice mismatch, assuming a model lamellar composite material. Post mortem characterizations by electronic microscopy completes the results: morphology of each phase, dislocations densities and nature. The measurement of lattice mismatch leads to an in situ estimation of the dislocations’ density at the γ/γ’ interfaces. For the γ phase, during successive jumps of the applied stress, the Von Mises stress increases and then relaxes down to a threshold stress. This stress is in agreement with Orowan stress deduced from the post mortem measurements of the γ channels’ width. Plastic strain of the γ' phase is produced by climb of dislocations with Burgers’ vectors perpendicular to the tensile axis under the mere transversal stress and is controlled by the entrance of dislocations into the rafts from the interfaces. The distribution of elastic strains was simulated by assuming two main contributions: dislocations at the γ/γ’ interfaces and within the γ’ rafts. The simulation reproduces the absolute magnitude of the peaks’ width, as well as their increase with dislocation densities

Nickel-based alloys are used in components such gas turbines within the aerospace industry and electric power generation due to its high tensile, rapture and creep strength. Increasing the efficiency of gas turbines are crucial to reduce emissions within the aerospace industry and increasing power gain for electric power generation. Innovation to increase the efficiency relies in part on the development of new nickel-based alloys with beneficial material properties. But also on stable and predictable material behavior during processing and post-processing of the components in the gas turbine. In two prominent material processing fields of precipitation hardened nickel-based alloys, additive manufacturing and welding, strain-age cracking (SAC) is a common phenomenon. SAC is a solid state phenomenon that generally occurs in alloys strengthened with 𝛾′, L12(Pm3m), or 𝛾′′, D022(I4/mmm), phase precipitates during post weld heat treatment or reheating where it manifests as intergranular cracking. Even though the existence of SAC has been known for several decades, its dominant mechanisms are still under considerable debate and the undertaken modeling efforts to gain insight on the phenomenon are virtually non-existent. This study aims to clarify the dominant mechanisms behind strain-age cracking. Breaching this gap would allow for new development for nickel-based alloys within both additive manufacturing and welding. To that extent the goal of this study is to provide tools to aid in clarifying the dominant mechanisms behind strain-age cracking. This is done by implementing the recently developed structural phase-field crystal (XPFC) model and examining the capabilities to model a precipitation event during reheating for a reference binary alloy in two dimensions. To evaluate the strain because of precipitation, a simple method based on the principles of neutron and synchrotron strain scanning is outlined and tested on the limited precipitation event achieved within the study. The XPFC model is capable of modeling precipitation with some restrictions that need further development with extended computational recourses. Lastly, the possibilities to extend the implemented XPFC model to cover nickel-based alloys is discussed.