Le procédé de refusion sous laitier électroconducteur (ESR =Electro Slag Remelting) permet de produire des alliages à haute valeur ajoutée utilisés pour des applications critiques. Les mesures in-situ sur les fours industriels étant coûteuses, la simulation numérique est essentielle à la maitrise et à la compréhension de ce procédé complexe. L’Institut Jean Lamour a développé depuis plusieurs années un modèle 2D axisymétrique qui permet de simuler la refusion d’une électrode consommable au sein d’une lingotière considérée comme totalement isolée électriquement du reste du système. Sont alors décrit en régime transitoire les transferts couplés de chaleur et de quantité de mouvement, ainsi que le passage du courant électrique dans le laitier et le lingot lors de la croissance et de la solidification de ce dernier. Les connaissances acquises au cours des dernières années sur le procédé ESR remettent en cause l’hypothèse d’isolation électrique du moule au cours de la refusion. L’objet de cette thèse est d’intégrer et d’étudier la possibilité de passage de courant entre le laitier et la lingotière au cours de la refusion. Un premier modèle a été développé. Il consiste en un calcul électromagnétique complet dans l'ensemble du système pour une géométrie simplifiée. Il a permis de simplifier la mise au point du modèle global, tout en fournissant de premiers résultats. Par la suite, un modèle totalement couplé a été finalisé puis les modifications du code ont fait l’objet de validations avec des mesures expérimentales. Des études de sensibilité ont été menées pour tester l’influence des propriétés du laitier et des paramètres opératoires sur la qualité du lingot final. / The ElectroSlag Remelting process (ESR) is widely used to produce high added value alloys for critical applications (aerospace industry, nuclear plants, etc.). Trial-and-error based approaches being expensive, numerical simulation is fundamental to improve the knowledge and the understanding of this complex process. The Institut Jean Lamour has been developing for several years a numerical code to simulate the melting of a consumable electrode, supposedly perfectly cylindrical, within a mold assumed to be perfectly electrically insulated from the electrode-slag-ingot system. Based on these assumptions, the 2-D axisymmetrical transient-state numerical model accounts for electromagnetic phenomena and coupled heat and momentum transfers, to simulate the continuous growth of the electroslag remelted ingot and the solidification of the metal and slag. Recent studies on the ESR process are challenging the insulated mold hypothesis. Therefore, the main objective of the thesis is to acknowledge and study the existence of a mold current during an ESR remelting. A first model has been set-up, aimed to simulate the electromagnetic phenomena in the whole system for a simplified geometry. The possibility of the existence of such a mold current was confirmed. Based on this work, a fully-coupled model has then been developed and the results have been compared with experimental data to check the validity of the modifications. The influence of slag properties and operating parameters on the final quality of the ingot has been tested.

Historicamente a radioterapia é divida em radioterapia externa, braquiterapia e radioisotopoterapia sistemática. As diferenças entre as três está no posicionamento da fonte de radiação com respeito ao corpo humano. Na radioterapia externa a fonte fica a uma certa distância do paciente, já no caso da braquiterapia as fontes podem ser inseridas dentro de cavidades do corpo ou implantadas diretamente nos tecidos. Na radioisotopoterapia sistemática isótopos radiativos são administrados por via oral ou venosa. Dessas três a radioterapia externa é a mais usada pois, ela permite realizar planejamentos de radioterapia em três dimensões (3D), partindo inicialmente de uma tomografia computadorizada da região do tumor. O planejamento baseado na tomografia computadorizada permite que a distribuição da radiação nos tecidos seja feito com mais precisão evitando assim, que os tecidos sadios sejam afetados. Nesse trabalho a radioterapia externa convencional, foi implementada e executada para um tratamento de próstata com implantes metálicos, usando 4 campos de irradiação (0, 90, 180, 270 graus) e uma dose total planejada de 70 Gy fracionada em 35 sessões, cada uma com 2 Gy. Em qualquer tipo de tratamento que envolva a radiação ionizante é exigido um controle de qualidade para assim, determinar se a dose inicialmente planejada será entregue ou não ao tumor. Idealmente deveria ser implementado um controle de qualidade em três dimensões mas, até o momento não há um dosímetro 3D consolidado na rotina clinica. No entanto, o uso de géis poliméricos associados à técnica de leitura de dose com imagem de ressonância magnética (IRM) possibilita a dosimetria tridimensional. Nesse contexto, é aplicada a dosimetria 3D usando para isso, o gel magic com formaldeído (magic-f). Além da dosimetria 3D, foram realizadas medidas de dose absorvida por meio de dosimetria pontual, para tal fim são utilizados dosímetros termoluminescentes e de alanina. Na avaliação da distribuição de dose feita pelo planejamento e a medida com o gel é usado a análise gama (3%/3mm), neste caso, a distribuição de dose medida concorda com a distribuição de dose planejada TPS. A análise gama apresenta um porcentagem de aprovação do 93%. Os valores de dose absorvida na interface osso-metal determinados pelos dosímetros TL apresentam um aumento de 1,73 Gy na região do osso sacro e outros aumentos entre o 0,16 e 0,33 Gy foram encontrados em regiões como a cabeça do fêmur e quadril. Esses aumentos na dose foram só para duas sessões com doses entregadas ao fantom de 2 Gy. De igual maneira para os dosímetros de alanina se encontro um aumento na dose de 1,22 e 2,42 Gy na região do osso sacro. O planejamento feito nesse caso foi de 6 Gy. Os resultados evidentemente mostram como as inomogeneidades de um material com número atómico alto, gera perturbações sobre as distribuições de dose inicialmente planejadas. / Historically, Radiotherapy is divided into external radiotherapy, brachytherapy and systemic radioisotopotherapy. The difference between the three lies in the position of the radiation source regarding the human body. In external radiotherapy the source is at a certain distances of patient, and in the case of brachytherapy, this source can be inserted into cavities of body or implanted directly in the tissues. In systemic radiotherapy radioisotopes are administered orally or intravenously. Of these three, external radiotherapy is the most used because it allows planning of radiotherapy in three dimensions (3D), starting from a CT scan of the tumor region. Computed tomography planning allows the distribution of radiation in the tissues to be more accurate thus avoiding, that healthy tissues are affected. In our case, conventional external radiotherapy was implemented and executed for a prostate treatment with metal implants, using 4 irradiation fields (0, 90, 180, 270 degrees) and a total planned dose of 70 Gy fractioned in 35 sessions each with 2 Gy. In any type of treatment involving ionizing radiation, quality control (QC) is required to determine if the dose initially planned is delivered or not to the tumor. Ideally, a quality control should be implemented in three dimensions but to date there is no consolidated 3D dosimeter system in the clinic routine. However, the used of polymeric gels associated with magnetic resonance image (IRM) allow three-tridimensional dosimetry. In this context, the 3D dosimetry is applied using the magic gel with formaldehyde (magic-f). In addition to 3D dosimetry, absorbed dose measurements were performed by means of a dose in a point, using thermoluminescent and alanine dosimeters. The comparison of dose distributions calculated by TPS and measured in the gel was made using by gamma analysis (3% / 3mm), in this case, the distribution of dose measurement agrees with the distributions expected by TPS. The analysis shows a percentage of approval of 93%. The absorbed dose values at the bone-metal interface determined by the TL dosimeters, presented a 1.73 Gy increase in the region of the sacral bone, and another increases between 0,16 and 0,33 Gy were found in the regions as the head of the femur and the hip. These dose increases were only for two sessions with doses delivered to the phanton of 2 Gy. Similarly for alanine dosimeters were found increases in the dose of 1.22 and 2.42 Gy in the region of sacral bone. The planning done in this case was 6 Gy. The results evidently show how the inomogeneities of a material with a high atomic number generate disturbances over the initially planned dose distributions.

Die Arbeit befasst sich mit der Elektronenspinresonanz (ESR) stark korrelierter Elektronensysteme mit ferromagnetischen Wechselwirkungen. Es wurden dafür Messungen an den Kondogitter-Systemen CeRuPO und CeOsPO, der Dotierungsreihe CeFeAs1-xPxO, den niederdimensionalen frustrierten Quadratgittern AA’VO(PO4)2 sowie in dem schwach ferromagnetischen Metall Nb1-yFe2+y durchgeführt. Alle Verbindungen zeigen entweder eine ferromagnetische Ordnung oder befinden sich in der Nähe einer ferromagnetischen Instabilität, die die Eigenschaften des stark korrelierten Systems beeinflusst.

Die Elektronenspinresonanz (ESR) untersucht die im quasistatischen Magnetfeld resonante Absorption eines an die Probe angelegten Mikrowellenmagnetfeldes. Es wurde das System Yb1-w A1-w (Rh1-x Cox)2 (Si1-y Gey) 2 mit A=La, bzw. Lu, sowie das System YbIr2Si2 mittels ESR untersucht. Unter Kondo-Wechselwirkung vieler Leitungselektronen mit einem lokalen 4f-Moment des Kondo-Ions bildet sich ein nicht-magnetisches Grundzustands-Singlett, was zur Abschirmung des magnetischen Moments führt. YbRh2Si2 ist das erste Schwere-Fermionen-System mit Kondo-Ionen, das ohne Dotierung zusätzlicher ESR-Sonden ein ESR-Signal unterhalb der Kondo-Temperatur aufweist. Es zeigt sich, dass das ESR-Signal nicht mittels gängiger ESR-Theorien konsistent beschrieben werden kann. Die Messungen, die im Rahmen dieser Arbeit angestellt wurden, flossen in die Entwicklung von weiterführenden Theorien (z.B. [1], [2]) ein. Die Temperaturabhängigkeit des ESR-g-Faktors konnte damit erfolgreich beschrieben werden, womit erstmals der Nachweis einer Kondo-Wechselwirkung in Kondo-Gitter-Systemen mittels ESR gelang. Ferner konnte die Bedeutung von ferromagnetischen Fluktuationen für eine kleine, beobachtbare Linienbreite beschrieben werden. Der ESR-Methode ist somit die Kondo-Spindynamik direkt zugänglich. Dieser Zugang ist neu und einzigartig, denn andere Methoden (NMR, inelastische Neutronenstreuung) charakterisieren die Kondo-Spindynamik auf indirekte Weise. [1] P. Wölfle und E. Abrahams. Phenomenology of esr in heavy-fermion systems: Fermi-liquid und nicht-fermi-liquid regimes Phys. Rev. B, 80(23): 235112, 2009. [2] B. I. Kochelaev, S. I. Belov, A. M. Skvortsova, A. S. Kutusov, J. Sichelschmidt, J. Wykhoff, C. Geibel und F. Steglich. Why could electron spin resonance be observed in a heavy fermion kondo lattice? Eur. Phys. J. B, 72(4): 485, 2009.

Historicamente a radioterapia é divida em radioterapia externa, braquiterapia e radioisotopoterapia sistemática. As diferenças entre as três está no posicionamento da fonte de radiação com respeito ao corpo humano. Na radioterapia externa a fonte fica a uma certa distância do paciente, já no caso da braquiterapia as fontes podem ser inseridas dentro de cavidades do corpo ou implantadas diretamente nos tecidos. Na radioisotopoterapia sistemática isótopos radiativos são administrados por via oral ou venosa. Dessas três a radioterapia externa é a mais usada pois, ela permite realizar planejamentos de radioterapia em três dimensões (3D), partindo inicialmente de uma tomografia computadorizada da região do tumor. O planejamento baseado na tomografia computadorizada permite que a distribuição da radiação nos tecidos seja feito com mais precisão evitando assim, que os tecidos sadios sejam afetados. Nesse trabalho a radioterapia externa convencional, foi implementada e executada para um tratamento de próstata com implantes metálicos, usando 4 campos de irradiação (0, 90, 180, 270 graus) e uma dose total planejada de 70 Gy fracionada em 35 sessões, cada uma com 2 Gy. Em qualquer tipo de tratamento que envolva a radiação ionizante é exigido um controle de qualidade para assim, determinar se a dose inicialmente planejada será entregue ou não ao tumor. Idealmente deveria ser implementado um controle de qualidade em três dimensões mas, até o momento não há um dosímetro 3D consolidado na rotina clinica. No entanto, o uso de géis poliméricos associados à técnica de leitura de dose com imagem de ressonância magnética (IRM) possibilita a dosimetria tridimensional. Nesse contexto, é aplicada a dosimetria 3D usando para isso, o gel magic com formaldeído (magic-f). Além da dosimetria 3D, foram realizadas medidas de dose absorvida por meio de dosimetria pontual, para tal fim são utilizados dosímetros termoluminescentes e de alanina. Na avaliação da distribuição de dose feita pelo planejamento e a medida com o gel é usado a análise gama (3%/3mm), neste caso, a distribuição de dose medida concorda com a distribuição de dose planejada TPS. A análise gama apresenta um porcentagem de aprovação do 93%. Os valores de dose absorvida na interface osso-metal determinados pelos dosímetros TL apresentam um aumento de 1,73 Gy na região do osso sacro e outros aumentos entre o 0,16 e 0,33 Gy foram encontrados em regiões como a cabeça do fêmur e quadril. Esses aumentos na dose foram só para duas sessões com doses entregadas ao fantom de 2 Gy. De igual maneira para os dosímetros de alanina se encontro um aumento na dose de 1,22 e 2,42 Gy na região do osso sacro. O planejamento feito nesse caso foi de 6 Gy. Os resultados evidentemente mostram como as inomogeneidades de um material com número atómico alto, gera perturbações sobre as distribuições de dose inicialmente planejadas. / Historically, Radiotherapy is divided into external radiotherapy, brachytherapy and systemic radioisotopotherapy. The difference between the three lies in the position of the radiation source regarding the human body. In external radiotherapy the source is at a certain distances of patient, and in the case of brachytherapy, this source can be inserted into cavities of body or implanted directly in the tissues. In systemic radiotherapy radioisotopes are administered orally or intravenously. Of these three, external radiotherapy is the most used because it allows planning of radiotherapy in three dimensions (3D), starting from a CT scan of the tumor region. Computed tomography planning allows the distribution of radiation in the tissues to be more accurate thus avoiding, that healthy tissues are affected. In our case, conventional external radiotherapy was implemented and executed for a prostate treatment with metal implants, using 4 irradiation fields (0, 90, 180, 270 degrees) and a total planned dose of 70 Gy fractioned in 35 sessions each with 2 Gy. In any type of treatment involving ionizing radiation, quality control (QC) is required to determine if the dose initially planned is delivered or not to the tumor. Ideally, a quality control should be implemented in three dimensions but to date there is no consolidated 3D dosimeter system in the clinic routine. However, the used of polymeric gels associated with magnetic resonance image (IRM) allow three-tridimensional dosimetry. In this context, the 3D dosimetry is applied using the magic gel with formaldehyde (magic-f). In addition to 3D dosimetry, absorbed dose measurements were performed by means of a dose in a point, using thermoluminescent and alanine dosimeters. The comparison of dose distributions calculated by TPS and measured in the gel was made using by gamma analysis (3% / 3mm), in this case, the distribution of dose measurement agrees with the distributions expected by TPS. The analysis shows a percentage of approval of 93%. The absorbed dose values at the bone-metal interface determined by the TL dosimeters, presented a 1.73 Gy increase in the region of the sacral bone, and another increases between 0,16 and 0,33 Gy were found in the regions as the head of the femur and the hip. These dose increases were only for two sessions with doses delivered to the phanton of 2 Gy. Similarly for alanine dosimeters were found increases in the dose of 1.22 and 2.42 Gy in the region of sacral bone. The planning done in this case was 6 Gy. The results evidently show how the inomogeneities of a material with a high atomic number generate disturbances over the initially planned dose distributions.

In this thesis we used ESR to investigate magnetic properties of low D vandium and copper oxides in which small quantum spins are arranged in 1D chains and 2D layers. The thesis covers five different low dimensional spin systems. They turned out to be experimental reliazation of some of the most intersiting theoritical models in the field of quantum magnetism.

Die Elektronenspinresonanz (ESR) untersucht die im quasistatischen Magnetfeld resonante Absorption eines an die Probe angelegten Mikrowellenmagnetfeldes. Es wurde das System Yb1-w A1-w (Rh1-x Cox)2 (Si1-y Gey) 2 mit A=La, bzw. Lu, sowie das System YbIr2Si2 mittels ESR untersucht. Unter Kondo-Wechselwirkung vieler Leitungselektronen mit einem lokalen 4f-Moment des Kondo-Ions bildet sich ein nicht-magnetisches Grundzustands-Singlett, was zur Abschirmung des magnetischen Moments führt. YbRh2Si2 ist das erste Schwere-Fermionen-System mit Kondo-Ionen, das ohne Dotierung zusätzlicher ESR-Sonden ein ESR-Signal unterhalb der Kondo-Temperatur aufweist. Es zeigt sich, dass das ESR-Signal nicht mittels gängiger ESR-Theorien konsistent beschrieben werden kann. Die Messungen, die im Rahmen dieser Arbeit angestellt wurden, flossen in die Entwicklung von weiterführenden Theorien (z.B. [1], [2]) ein. Die Temperaturabhängigkeit des ESR-g-Faktors konnte damit erfolgreich beschrieben werden, womit erstmals der Nachweis einer Kondo-Wechselwirkung in Kondo-Gitter-Systemen mittels ESR gelang. Ferner konnte die Bedeutung von ferromagnetischen Fluktuationen für eine kleine, beobachtbare Linienbreite beschrieben werden. Der ESR-Methode ist somit die Kondo-Spindynamik direkt zugänglich. Dieser Zugang ist neu und einzigartig, denn andere Methoden (NMR, inelastische Neutronenstreuung) charakterisieren die Kondo-Spindynamik auf indirekte Weise. [1] P. Wölfle und E. Abrahams. Phenomenology of esr in heavy-fermion systems: Fermi-liquid und nicht-fermi-liquid regimes Phys. Rev. B, 80(23): 235112, 2009. [2] B. I. Kochelaev, S. I. Belov, A. M. Skvortsova, A. S. Kutusov, J. Sichelschmidt, J. Wykhoff, C. Geibel und F. Steglich. Why could electron spin resonance be observed in a heavy fermion kondo lattice? Eur. Phys. J. B, 72(4): 485, 2009.

<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>Ispitan je uticaj heksanskih, etanolnih i etil-acetanih ekstrakata zrna soje i punomasnih hraniva od zrna soje, ekstrudiranog sojinog griza i hidrotermički tretiranog zrna soje, na termičku i katalitičku oksidaciju metil-linoleata primenom ESR spektroskopije i &quot;spin- traping&quot; tehnike. Utvrđeno je da ispitivani ekstrakti inhibiraju termičku i katalitičku oksidaciju metil-linoleata različitim mehanizmima antioksidativnog delovanja. Ustanovljeni antioksidativni efekti dovedeni su u vezu sa vrstama i sadržajem liposolubilnih (a-tokoferol, P-karotin, ukupni ksantofili) i neliposolubilnih antioksidanata (izoflavoni i fitinska kiselina) soje, odnosno u vezu sa termičkim tretmanima primenjenim u proizvodnji ovih hraniva. Ispitani su i uticaji primene različitih rastvarača (etil-acetat, etanol, acetonitril) na antioksidativne efekte ekstrakata neliposolubilnih antioksidanata punomasnih hraniva od zrna soje tokom termičke i katalitičke oksidacije sojinog ulja primenom ESR.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>The influence of hexane, ethanol and ethyl acetate extracts of soybean grain and full-fat feeds of soybean grain, fullfat extruded soybean grits and hydrothermal treated soybean grain on the thermal and catalytic oxidation of methyl linoleate has been studied by ESR spectroscopy and spin-trapping method. It has been found that the investigated extracts inhibit the thermal and catalytic oxidation of methyl linoleate through different mechanisms of antioxidation action. The antioxidative effects found were related to the kinds and contents of soybean liposolubile (a-tocopherol, P-carotene, total xanthophyls) and nonliposolibile antioxidants (isoflavones, phytic acid), that is, they were put in relation to thermal treatments used in production of these feeds. The effects of the application of different solvents on the antioxidative actions of the extracts of nonliposolubile antioxidants of full-fat soybean feeds during thermal and catalytic oxidation of soybean oil have been studied by ESR.</p>

Nitrogen-alloyed tool steel is made at Uddeholms AB by adding high-nitrogen ferroalloy after vacuum degassing where introduced impurities are hard to remove. In this thesis two types of high-nitrogen ferrochromium are compared, a solid version and a powder cored wire. They are examined in crossection and 16 samples from four charges are examined with Pulse Distribution Analysis as well as systematic microscopy of polished cross sections. The PDA results missed smaller spinel inclusions shown in previous research to be detrimental. The wire form shows promise but more charges need to be evaluated before a conclusion is drawn. / Kvävelegerat verktygsstål tillverkas hos Uddeholms AB genom tillsats av kväverika ferrolegeringar efter vakumavgasning, och orenheter som introduceras i detta steg är svåra att avskilja. I den har uppsatsen jämförs två typer av kväverikt ferrokrom varav en i form av stycken och en i form av tråd med pulverkärna. De undersöks i tvärsnitt och totalt 16 prov från fyra charger undersöks med PDA (pulsfördelningsanalys) och systematisk mikroskopering i tvärsnitt. Resultaten från PDA missade mindre inneslutningar av spinell vilka tidigare har visat sig problematiska. Trådformen verkar lovande men fler charger behöver undersökas för att kunna dra en definitiv slutsats.

Im Mittelpunkt der vorliegenden Arbeit stehen Untersuchungen zur Analytik, Stabilität und Metabolisierung von Nitroxylradikalen, unter besonderer Berücksichtigung Ihrer Anwendung als ESR-Spinsonden im Rahmen der Bearbeitung pharmazeutisch-technologischer und biopharmazeutischer Fragestellungen. Neben der Entwicklung und Adaptierung geeigneter analytischer Methoden waren dabei Stabilitätsfragen unter den Bedingungen ihres Einsatzes, die Stabilität von Reaktionsprodukten und Metaboliten, das elektrochemische und chemische Reduktionsverhalten sowie die Biotransformation du rch Mikroorganismen, in subzellulären Fraktionen der Leber und in humanen Zellkulturen von besonderem Interesse. Als wichtigste Ergebnisse dieser Arbeit sind: (i) bisher unbekannte Metaboliten (wie z.B. sekundäreAmine) identifiziert, (ii) der Erkenntnisstand zu den Mechanismen der Biotransformation dieser stabilen Radikale erweitert, (iii) methodische Fortschritte wie die Entwicklung einer On-line HPLC-ESR-Kopplung und bei der Anwendung der Festphasenmikroextraktion (SPME) erreicht, (iv) die ESR als Methode für nichtinvasive Messungen des pH-Wertes und für die Erfassung der Stabilität und Hautpenetration von Liposomen erschlossen worden. / The present thesis was focused on the investigation of analytic, stability and metabolism of nitroxyl radicals used as esr spin probes in pharmaceutical, technological and biopharmaceutical applications. New analytical methods were developed and adapted for nitroxides and diamagnetic products. The stability of nitroxides was analysed and reaction products were cleared up. Furthermore there were in vestigated the electrochemical and chemical behaviour of reduction as well as the biotransformation by microorganisms, in subcellular liver fractions and in human cell cultures. The main results of this document are presented in the following: (i) the appearance of new dia- and paramagnetic metabolites (e.g. secondary amines), (ii) the latest findings about metabolic mechanisms of stable nitroxyl radicals, (iii) the development of online HPLC-ESR-couppling technique and the application of solid phase microextraction (SPME) as the greatest acquisition, (iv) the advantage of ESR technique for noninvasive measurement of pH and to register the stability and penetration of liposomes through skin layers.