This thesis contains detailed study of a newly discovered effect of quench switch- ing in thin films of antiferromagnetic CuMnAs. This effect can be used to induce highly reproducible resistance switching behaviour in response to electrical or optical laser pulsing. The resistance changes reach up to GMR-like values of 20 % at room temperature and 100 % at low temperatures. We attribute these changes to the nano-fragmentation of magnetic domain structure. After CuMnAs is pulsed into a high resistance state, a characteristic period of time follows, during which the resistance relaxes back to the original value. This relaxation can be described by Kohlrausch stretched exponential function. This type of relaxation is characteristic for behaviour of correlated complex systems, which goes well with the idea of highly fragmented and correlated magnetic states of quenched CuMnAs. The quench switching effect is studied in detail on devices with different geometries, for various parameters of the writing pulse, as well as growth pa- rameters of the CuMnAs films. The switching is demonstrated in CuMnAs films prepared on GaP, GaAs and Si substrates, where the quality of the film differs. This illustrates robustness and application potential of the effect. 1

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付記する学位プログラム名: 京都大学卓越大学院プログラム「先端光・電子デバイス創成学」 / 京都大学 / 新制・課程博士 / 博士(工学) / 甲第23903号 / 工博第4990号 / 新制||工||1779(附属図書館) / 京都大学大学院工学研究科電気工学専攻 / (主査)教授 雨宮 尚之, 准教授 掛谷 一弘, 講師 美舩 健, 教授 松尾 哲司 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Study of quench cooling is very important in nuclear reactor safety for limiting the extent of core damage during the early stages of severe accidents after Loss of Coolant Accidents (LOCA). Quench of a hot dry surface involves the rapid decrease in surface temperature resulting from bringing the hot surface into sudden contact with a coolant at a lower temperature. The quench temperature is the onset of the rapid decrease in the surface temperature and corresponds to the onset of destabilization of a vapor film that exists between the hot surface and the coolant. Re-wetting the surface is the establishment of direct contact between the surface and the liquid at the so-called re-wetting temperature. Re-wetting is characterized by the formation of a wet patch on the surface which then spreads to cover the entire surface. Situations involving quench and re-wetting heat transfer are encountered in a number of postulated accidents in Canada Deuterium Uranium (CANDU) reactors, such as re-wetting of a hot dry calandria tube in a critical break LOCA. This accident results in high heat transfer from the calandria tube to the surrounding moderator liquid which can cause the calandria tube surface to experience dryout and a subsequent escalation in the surface temperature. If the calandria tube temperature is not reduced by initiation of quench heat transfer, then this may lead to subsequent fuel channel failure. In literature very limited knowledge is available on quench and re-wetting of hot curved surfaces like the calandria tubes. In this study, a Water Quench Facility (WQF) has been constructed and a series of experiments were conducted to investigate the quench and re-wetting of hot horizontal tubes by a vertical rectangular water multi-jet system. The tubes were heated to a temperature between 380-800°C in a controlled temperature furnace then cooled to the jet temperature. The temperature variation with time in the circumferential and the axial directions of the tubes has been measured. The twophase flow behavior and the propagation of the re-wetting front around and along the tubes were simultaneously observed by using a high-speed camera. The effects of several parameters on the cooling process have been investigated. These parameters include: initial surface temperature, water subcooling (in the range 15- 800C), jet velocity (in the range 0.15-1.60 m/s), tube solid material (brass, steel and Alumina), surface curvature, tube wall thickness, jet orientation and number of jets. The variables studied include the re-wetting delay time (time to quench after initiating the cooling process), there-wetting front propagation velocity, the quench and re-wetting temperatures, the quench cooling rates and the boiling region size. The quench and the re-wetting temperatures as well as the re-wetting delay time were found to be a strong function of water subcooling. The quench and re-wetting temperatures increase with increasing water subcooling. The rewetting delay time decreases with increasing the water subcooling, decreasing initial surface temperature, increasing liquid velocity and decreasing the surface curvature. There-wetting front velocity is mainly dependent on the initial surface temperature and water subcooling. The re-wetting velocity increases by decreasing the initial surface temperature and by increasing the water subcooling. Decreasing the surface curvature was found to also increase the re-wetting front velocity. Correlations of the phenomena studied have been developed and provided good prediction of the experimental data collected in this study and data available from literature. The. results of this study provide novel knowledge and an experimental database for mechanistic modeling of quench heat transfer on calandria tube surfaces that experience dryout and film boiling. / Thesis / Doctor of Philosophy (PhD)

Le monoxyde d'azote est exclusivement synthétisé chez les mammifères par une famille d’hémoprotéines, les NO-Synthases. Le cœur de l’activité des NO-Synthases est l’activation de l’oxygène c'est-à-dire l’activation de l’intermédiaire réactionnel FeIIO2. Cette étape est contrôlée par la réactivité intrinsèque du fer, par les transferts de proton et les transferts d’électron. Elle doit être parfaitement maîtrisée car elle contrôle le chemin catalytique emprunté et la nature du produit final. Comprendre l’étape d’activation de l’oxygène est essentiel à la compréhension du rôle biologique et/ou pathologique de la NO-Synthase de mammifère. Cette question s'étend aux NO-Synthases bactériennes pour lesquelles on ne connait ni le mécanisme moléculaire ni la fonction biologique. Ce manuscrit propose une analyse approfondie de l’étape d’activation de l’oxygène de la NO-Synthase. Dans un premier temps, nous avons étudié l’influence de l’environnement proximal sur la réactivité intrinsèque du fer et l’activation de l’oxygène. Nous avons généré des protéines mutées qui modifient les propriétés électroniques de la liaison proximale de l’hème. Ces protéines mutées ont été caractérisées par différentes spectroscopies (résonance paramagnétique électronique, Raman de résonance). Dans un second temps nous avons directement étudié le complexe FeIIO2, en présence d’analogues de substrat, grâce à des analyses de cinétique rapide en flux continu et en flux arrêté (stopped-flow). Dans un troisième temps, le rôle du cofacteur tetrahydrobioptérine dans le transfert de proton et d’électron a été étudié par une méthode de piégeage à des temps très courts : le freeze-quench. L'ensemble de nos résultats montrent que l’activation de l’oxygène est régulée par les propriétés électro-donneuses du ligand proximal et par le réseau de liaisons H distal. Nous mettons en évidence des différences dans le rôle redox du cofacteur tetrahydrobioptérine entre la NO-Synthase de mammifère et la NO-Synthase bactérienne. La difficulté majeure pour comprendre l’étape d’activation de l’oxygène de la NO-Synthase réside dans la complexité et la rapidité de la réaction catalytique. Dans ce contexte, nous avons cherché à adapter une méthodologie qui a prouvé son efficacité dans le cas des cytochromes P450 : la cryo-réduction couplée à des sauts en température. / Nitric oxide is exclusively synthesized by NO-Synthases in mammals. The heart of the NO-synthase activity is oxygen activation, which corresponds to the activation of the FeIIO2 intermediate. This step depends on the heme electronic properties and on the electron and proton transfers. Oxygen activation has to be well mastered to control exactly the nature of the end-product. Understanding the oxygen activation step is necessary to better understand the biological/pathological role of the mammalian NO-Synthases. Furthermore, bacterial NO-Synthases function and oxygen activation mechanism are unknown. This PhD work proposes a deep analysis of the oxygen activation step in NO-Synthases. First, proximal environment has been studied with mutated proteins. These mutations impact the electronic properties of the heme proximal bond. Spectroscopic analyses of these mutants have been done by electron paramagnetic resonance and resonance Raman. Then, we have studied the FeIIO2 intermediate with substrate analogs which has necessitated continuous flow and stopped-flow analyses. Finally, the role of the tetrahydrobiopterin cofactor in the electron and proton transfer has been studied and clarified thanks to a very fast trapping method : the freeze-quench. Our results show that the oxygen activation step is elaborately controlled by the proximal bond electron donation and the distal H bond network. At the same time we show some differences between mammalian and bacterial NO-Synthases concerning the redox role of the tetrahydrobiopterin cofactor. The major obstacle to understand the oxygen activation step resides in the complexity of the active site chemistry and the rate of catalytic reactions. For this reason, we propose to adapt an already successful protocol to trap some intermediates in the cytochromes P450 mechanism : cryo-reduction coupled with temperature jumps.

L’apparition ces dernières années de supraconducteurs réalisés industriellement utilisant des composés à haute température de transition offre la possibilité de nouveaux développements en magnétisme supraconducteur. En effet ils permettent d’augmenter le champ magnétique généré en conservant une cryogénie classique à 4,2K d’une part, et ils ouvrent la voie à des développements d’aimants supraconducteurs fonctionnant entre 10 et 30K d’autre part. Les matériaux supraconducteurs à haute température critique sont alors indispensables pour dépasser les inductions magnétiques de 16 T (cas de l’insert dipolaire HTc pour le Large Hadron Collider du CERN) ou augmenter la densité spécifique d’énergie stockée dans un SMES (Superconducting Magnetic Energy Storage, cas du projet ANR SuperSMES).Les atouts incontestables (température critique, champ magnétique critique, résistance mécanique) apportés par l’utilisation des matériaux supraconducteurs à haute température critique tels que l’YBaCuO dans les aimants supraconducteurs demandent de relever quelques défis. Leur comportement est encore mal compris, surtout lors des transitions résistives. Arriver à protéger ces conducteurs requiert une réflexion nouvelle sur les systèmes de protection destinés à éviter les dégradations thermiques et mécaniques. La réponse à la question « peut-on utiliser ces matériaux de manière pérenne dans les aimants supraconducteurs ? » est incontournable.Des éléments de réponse sont donnés ici. L’utilisation des conducteurs est abordée à travers différentes études expérimentales permettant de mieux connaître le conducteur (caractérisation électrique et modélisation de la surface critique) d’une part et de définir les étapes clés de la fabrication des aimants supraconducteurs à haute température de transition (étude des jonctions entre conducteurs ou entre galettes) d’autre part. Cette étude a abouti à la réalisation de deux prototypes d’aimants ayant permis d’identifier les difficultés liées à l’utilisation des rubans d’YBaCuO. Un modèle thermoélectrique des supraconducteurs à haute température de transition est développé et un code numérique basé sur le logiciel de calcul par Eléments Finis CASTEM permet d’étudier le phénomène de transition résistive, ou quench, dans un conducteur et dans un aimant. Le code a été validé sur des essais réalisés au Laboratoire National des Champs Magnétiques Intenses de Grenoble. Les résultats obtenus ont permis la définition des conducteurs pour les deux projets liés à la thèse et la validation de la protection. / The new industrial superconductors using high critical temperature compounds offer new possibilities for superconducting magnetism. Indeed they allow higher magnetic field with the same classical cryogenics at 4.2 K on one hand, and on the other hand they also pave the way for superconducting magnets working between 10 K and 30 K. The high temperature superconductors are then needed in order to produce magnetic fields higher than 16 T (case of HTS dipole insert for Large Hadron Collider at CERN) or to increase the specific density stored in one SMES (Superconducting Magnetic Energy Storage, in the case of the SuperSMES ANR Project).Nevertheless the indisputable assets (critical temperature, critical magnetic field, mechanical stresses) brought by the use of High critical temperature superconductors like YBCO, used in superconducting magnets, require to solve some challenges. Their behavior is still badly understood, especially during the resistive transitions. To succeed in protecting these conductors we need a new reflection on protection schemes designed to avoid the thermal and mechanical damages. The answer to the question: “Can we use those materials in the long run inside superconducting magnets?” is now inescapable.Some answers are given here. The use of the conductors is approached through various experimental studies to understand the material (electrical characterization and modeling of the critical surface) and to define the key stages of high critical temperature superconducting magnets manufacturing (work on the junctions between conductors and pancakes). This study led to the creation of two coils in order to identify the issues related to the use of YBCO tapes. A numerical thermo-electrical model of the high critical temperature superconductor has been developed and a numerical code based on the CEA software CASTEM (Finish Elements Model) allowed to study the resistive transition (or quench) behavior of those conductor and coil. The code has been confirmed by comparison with some experimental data obtained by the Laboratoire National des Champs Magnétiques Intenses in Grenoble. The results have allowed to define the conductors for the two projects of this thesis and to validate the feasibility of the protection of those conductors.

Quasi-one-dimensional quantum models are ideal for theoretically exploring the physical phenomena associated with strong correlations. In this thesis we study three examples where strong correlations play an important role in the static or dynamic properties of the system. Firstly, we examine the behaviour of a doped fermionic two-leg ladder in which umklapp interactions are present. Such interactions arise at special band fillings and can be induced by the formation of charge density wave order in an array of two-leg ladders with long-range (three-dimensional) interactions. For the umklapp which arises from the half-filling of one of the bands, we show that the low-energy theory has a number of phases, including a strong coupling regime in which the dominant fluctuations are superconducting in nature. These superconducting fluctuations carry a finite wave vector – they are the one-dimensional analogue of Fulde-Ferrell-Larkin-Ovchinnikov superconductivity. In a second example, we consider a quantum spin model which captures the essential one-dimensional physics of CoNb₂O₆, a quasi-one-dimensional Ising ferromagnet. Motivated by high-resolution inelastic neutron scattering experiments, we calculate the dynamical structure in the paramagnetic phase and show that a small misalignment of the transverse field can lead to quasi-particle breakdown – a surprising broadening in the single particle mode observed in experiment. Finally, we study the out-of-equilibrium dynamics of a model with tuneable integrability breaking. When integrability is broken by the presence of weak interactions, we show that the system relaxes to a non-thermal state on intermediate time scales, the so-called “prethermalization plateau”. We describe the approximately stationary behaviour in this regime by constructing a generalised Gibbs ensemble with charges deformed to leading order in perturbation theory. Expectation values of these charges are time-independent, but interestingly the charges do not commute with the Hamiltonian to leading order in perturbation theory. Increasing the strength of the integrability breaking interactions leads to behaviour compatible with thermalisation. In each case we use a combination of perturbative analytical calculations and non-perturbative numerical computations to study the problem at hand.

O presente trabalho de pesquisa avalia os efeitos das temperaturas de austenitização plena e intercrítica, associado ao tratamento térmico de têmpera interrompida e partição, realizada em banho de sais fundidos e sua influência no comportamento mecânico e microestrutural do aço de alta resistência e baixa liga AISI300M. Para os ensaios de caracterização mecânica foram realizados ensaios de dureza cujos resultados variaram de (35HRC a 55HRC) dependendo do tratamento; ensaios de tração, que atingiram o limite de resistência máximo de 2272 MPa com 6% de alongamento; ensaios de tenacidade ao impacto Charpy que superaram os tratamentos convencionais de têmpera atingindo 38J de energia absorvida; além dos ensaios de tenacidade à fratura linear-elástica, método (KIC) que ficaram entre (35 e 67 MPa√m). Para a caracterização microestrutural foram realizadas análises por microscopia óptica, microscopia eletrônica de varredura (MEV), além da investigação microestrutural pela técnica de microscopia eletrônica de transmissão (MET) que elucidaram os microconstituintes multifásicos presentes como martensita, ferrita e bainita. Para quantificar as frações de fases presentes utilizou-se a técnica de difração por raios-X e método de refinamento Rietveld, mostrando até 20% de austenita retida na condição de partição em 400ºC. Para auxiliar e mapear as fases presentes foram utilizadas as técnicas de MEV-EBSD e EBSD acoplada ao microscópio eletrônico de transmissão MET-EBSD com indexação via software ASTAR. Após os ensaios mecânicos, as superfícies de fratura foram examinadas via MEV e exibiram em geral um modo misto de fratura om a presença de dimples, coalescimento de microcavidades e quase-clivagem. / The present research work evaluates the effects of the complete and intercritical austenitization temperatures associated with interrupted quenching and partitioning performed in molten salt baths and its influence in the mechanical behavior and microstructural of AISI 300M high strength low alloy steel. Hardness tests with range from 55HRC to 35HRC were obtained depending on the heat treatment. Tensile tests have shown maximum strength limit of 2272 MPa and 6% elongation. Toughness parameters by instrumented Charpy impact tests exceeded values obtained in the conventional heat treatments providing 38J of absorbed energy. In addition, results from linear-elastic fracture toughness tests (KIC), values among 67 and 35MPa√m were found. Microstructure characterization was performed by optical microscopy, scanning electron microscopy (SEM) and microstructural research by transmission electron microscopy (TEM), which optimized the multiphase microconstituents with the presence of martensite, ferrite and bainite. In order to quantify the phases volume fractions present, it was used a X-ray diffraction technique and \"Rietveld\" refinement method that obtained up to 20% of retained austenite in the partitioning condition at 400°C. To assist and map the present phases, it was used MEV-EBSD and EBSD techniques coupled to the transmission electron microscope MET-EBSD with indexing via ASTAR software. After the mechanical tests, fracture surfaces were analyzed by SEM and showed in general, a mixed mode of fracture with the presence of dimples, microcoalescence and quasi-cleavage.

One of the most important results emerging from string theory is the gauge gravity duality (AdS/CFT correspondence) which tells us that certain problems in particular gravitational backgrounds can be exactly mapped to a particular dual gauge theory a quantum theory very similar to the one explaining the interactions between fundamental subatomic particles. The chief merit of the duality is that a difficult problem in one theory can be mapped to a simpler and solvable problem in the other theory. The duality can be used both ways. Most of the current theoretical framework is suited to study equilibrium systems, or systems where time dependence is at most adiabatic. However in the real world, systems are almost always out of equilibrium. Generically these scenarios are described by quenches, where a parameter of the theory is made time dependent. In this dissertation I describe some of the work done in the context of studying quantum quench using the AdS/CFT correspondence. We recover certain universal scaling type of behavior as the quenching is done through a quantum critical point. Another question that has been explored in the dissertation is time dependence of the gravity theory. Present cosmological observations indicate that our universe is accelerating and is described by a spacetime called de-Sitter(dS). In 2011 there had been a speculation over a possible duality between de-Sitter gravity and a particular field theory (Euclidean SP(N) CFT). However a concrete realization of this proposition was still lacking. Here we explicitly derive the dS/CFT duality using well known methods in field theory. We discovered that the time dimension emerges naturally in the derivation. We also describe further applications and extensions of dS/CFT.

O presente trabalho de pesquisa avalia os efeitos das temperaturas de austenitização plena e intercrítica, associado ao tratamento térmico de têmpera interrompida e partição, realizada em banho de sais fundidos e sua influência no comportamento mecânico e microestrutural do aço de alta resistência e baixa liga AISI300M. Para os ensaios de caracterização mecânica foram realizados ensaios de dureza cujos resultados variaram de (35HRC a 55HRC) dependendo do tratamento; ensaios de tração, que atingiram o limite de resistência máximo de 2272 MPa com 6% de alongamento; ensaios de tenacidade ao impacto Charpy que superaram os tratamentos convencionais de têmpera atingindo 38J de energia absorvida; além dos ensaios de tenacidade à fratura linear-elástica, método (KIC) que ficaram entre (35 e 67 MPa√m). Para a caracterização microestrutural foram realizadas análises por microscopia óptica, microscopia eletrônica de varredura (MEV), além da investigação microestrutural pela técnica de microscopia eletrônica de transmissão (MET) que elucidaram os microconstituintes multifásicos presentes como martensita, ferrita e bainita. Para quantificar as frações de fases presentes utilizou-se a técnica de difração por raios-X e método de refinamento Rietveld, mostrando até 20% de austenita retida na condição de partição em 400ºC. Para auxiliar e mapear as fases presentes foram utilizadas as técnicas de MEV-EBSD e EBSD acoplada ao microscópio eletrônico de transmissão MET-EBSD com indexação via software ASTAR. Após os ensaios mecânicos, as superfícies de fratura foram examinadas via MEV e exibiram em geral um modo misto de fratura om a presença de dimples, coalescimento de microcavidades e quase-clivagem. / The present research work evaluates the effects of the complete and intercritical austenitization temperatures associated with interrupted quenching and partitioning performed in molten salt baths and its influence in the mechanical behavior and microstructural of AISI 300M high strength low alloy steel. Hardness tests with range from 55HRC to 35HRC were obtained depending on the heat treatment. Tensile tests have shown maximum strength limit of 2272 MPa and 6% elongation. Toughness parameters by instrumented Charpy impact tests exceeded values obtained in the conventional heat treatments providing 38J of absorbed energy. In addition, results from linear-elastic fracture toughness tests (KIC), values among 67 and 35MPa√m were found. Microstructure characterization was performed by optical microscopy, scanning electron microscopy (SEM) and microstructural research by transmission electron microscopy (TEM), which optimized the multiphase microconstituents with the presence of martensite, ferrite and bainite. In order to quantify the phases volume fractions present, it was used a X-ray diffraction technique and \"Rietveld\" refinement method that obtained up to 20% of retained austenite in the partitioning condition at 400°C. To assist and map the present phases, it was used MEV-EBSD and EBSD techniques coupled to the transmission electron microscope MET-EBSD with indexing via ASTAR software. After the mechanical tests, fracture surfaces were analyzed by SEM and showed in general, a mixed mode of fracture with the presence of dimples, microcoalescence and quasi-cleavage.