This study considers the effect, on plasma ion oscillations, of various lengths of discharge tubes as well as various cross sections of discharge tubes. Four different gases were used in generating the plasma. Gas pressure and discharge voltage and current were varied to obtain a large number of signals. A historical survey is given to familiarize the reader with the field. The experimental equipment and procedure used in obtaining data is given. An analysis of the data obtained is presented along with possible explanations for the observed phenomena. Suggestions for future study are made.

Os filmes micrométricos contendo óxido misto de lantânio, estrôncio, cobalto e ferro (La0,60Sr0,40)(Co0,20Fe0,80)O3-δ - LSCF, misturado com (Ce0,90Gd0,10)O1,95 - CGO, são relevantes para a utilização como camada funcional para o cátodo da Célula a Combustível de Óxido Sólido de Temperaturas Intermediárias. Estes filmes foram depositados no um substrato cerâmico e denso de CGO ou CGO sobre (ZrO2)0.92(Y2O3)0.08 - YSZ. O estudo deste cátodo é fundamental, pois é nele que ocorre a reação de redução do gás oxigênio, e o seu desempenho eletroquímico depende da interface destes dois materiais. Neste sentido, o presente trabalho contribui para a síntese dos particulados de LSCF para o processamento de filmes, utilizando a técnica de deposição com uso de aerógrafo e para sua conformação em camadas contendo porosidade com espessuras entre 30 e 50 μm. Inicialmente, os particulados de LSCF foram sintetizados pela técnica do citratos e de LSCFCGO obtidos por mistura mecânica, sendo caracterizados por DRX para a confirmação da formação da estrutura cristalina ortorrômbica para o LSCF e cúbica para CGO. Em seguida, foram preparadas suspensões orgânicas de LSCF, LSCFCGO e CGO que foram alimentadas por gravidade em um aerógrafo manual para deposição sobre substrato do eletrólito. Para a conformação dos substratos de CGO ou YSZ, utilizou-se prensa uniaxial e isostática, sinterização e retificação. Verificaram-se, pelas micrografias, que os substratos CGO e YSZ apresentaram densidades (> 92%) suficientes para serem utilizados como eletrólitos. Os filmes de LSCF e LSCFCGO apresentaram-se com porosidades adequadas (> 30%) e espessura total de aproximadamente 40 μm, com boa aderência ao eletrólito. A presença do cátodo compósito contendo eletrólito de CGO sobre YSZ possibilitou aumento de 25% no desempenho eletroquímico (2,50 Ω.cm2 para 650ºC) em decorrência da melhora na reação de redução do oxigênio na interface cátodo/eletrólito. / The study of micrometrics films of (La0.60Sr0.40)(Co0.20Fe0.80)O3-δ - LSCF mixture with (Ce0.90Gd0.10)O1.95 - CGO is relevant for use as functional cathode of Intermediate Temperature Solid Oxide Fuel Cells (ITSOFC). These films were deposited on the CGO or CGO and YSZ dense ceramic substrate, used as electrolyte, structural component of the module. The study of this cathode is fundamental, because is there that occurs oxygen reduction reaction, and the electrochemical performance depends on the interface of these two materials. In this sense, this work contributes for the synthesis of LSCF particulates, for processing films using the wet powder spraying technique, adopted for the conformation of the ceramic films for allowing the attainment porous layers with thicknesses between 30 and 50 μm. Initially, the LSCF particulates were synthesized by the citrate technique and the LSCFCGO produced by solid mixture were characterized by XRD to confirm the formation of LSCF orthorhombic structure and CGO cubic structure. In the stage of formation were prepared organic suspensions of LSCF, LSCFCGO and CGO fed by gravity in a manual airbrush for electrolyte substrate deposition, sintering and grinding for thickness reduction. The micrographs showed that the CGO and YSZ substrates were dense (> 92%) enough to be used as solid electrolyte. The LSCF and LSCFCGO films presented with adequate porosity (> 30%) and total thickness of approximately 40 μm, with good adhesion to electrolyte. The presence of the composite cathode containing CGO or YSZ electrolyte allowed the increase of 25% in the electrochemical performance (2.50 Ω.cm2 to 650ºC) due to improvement in the oxygen reduction reaction at the interface cathode/electrolyte.

Apresentamos os resultados de medidas espectroscópicas feitas em átomos de elementos contidos em uma descarga elétrica do tipo catodo oco, usando um laser sintonizável de emissão contínua. Com experiências de absorção ótica foi possível determinar a densidade populacional e a temperatura dos átomos de 238U no estado fundamental, em função dos vários parâmetros que caracterizam a descarga. Desenvolvemos um método para a determinação da potência de saturação e calculamos o valor do produto para a transição 0 16.900cm-1 do 238UI. De forma alternativa às medidas óticas oudemos estudar a interação fóton-átomo analisando o sinal optogalvânico induzido na descarga pela radiação laser, com frequência sintonizada na mesma transição atômica do urânio e em função dos parâmetros anteriormente considerados. Os resultados obtidos com as experiências de absorção ótica e espectroscopia optogalvânica / The results of spectroscopic measurements obtained with atomic species present in a hollow cathode type discharge are reported. Using laser optical absorption techniques it was possible to get the population density and the atomic temperature of the 238UI ground state as a function of some discharge parameters. A method to determine the laser saturation intensity was developed, so the value of the product for the 0 16.900cm-1 238UI transition could be calculated. It was also possible to study the photon-atom interaction through the analysis of the optogalvanic signal induced in the laser radiation as a function of the same parameters considered before. Optogalvanic spectroscopy and optical absorption experiments showed the spatial distribution of the atoms in the ground state and excited states inside the cathode. In another set of experiments, a new way of inducing optogalvanic effect was investigated without using a tunable dye laser as the axcitation source. Measurements were done with two copper hollow cathode tubes filled with different gases, that were used as excitation source radiation and as signal detector. The results suggest that it is possible to use the new spectroscopy tecnique for qualitative and quantitative material analysis.

Apresentamos os resultados de medidas espectroscópicas feitas em átomos de elementos contidos em uma descarga elétrica do tipo catodo oco, usando um laser sintonizável de emissão contínua. Com experiências de absorção ótica foi possível determinar a densidade populacional e a temperatura dos átomos de 238U no estado fundamental, em função dos vários parâmetros que caracterizam a descarga. Desenvolvemos um método para a determinação da potência de saturação e calculamos o valor do produto para a transição 0 16.900cm-1 do 238UI. De forma alternativa às medidas óticas oudemos estudar a interação fóton-átomo analisando o sinal optogalvânico induzido na descarga pela radiação laser, com frequência sintonizada na mesma transição atômica do urânio e em função dos parâmetros anteriormente considerados. Os resultados obtidos com as experiências de absorção ótica e espectroscopia optogalvânica / The results of spectroscopic measurements obtained with atomic species present in a hollow cathode type discharge are reported. Using laser optical absorption techniques it was possible to get the population density and the atomic temperature of the 238UI ground state as a function of some discharge parameters. A method to determine the laser saturation intensity was developed, so the value of the product for the 0 16.900cm-1 238UI transition could be calculated. It was also possible to study the photon-atom interaction through the analysis of the optogalvanic signal induced in the laser radiation as a function of the same parameters considered before. Optogalvanic spectroscopy and optical absorption experiments showed the spatial distribution of the atoms in the ground state and excited states inside the cathode. In another set of experiments, a new way of inducing optogalvanic effect was investigated without using a tunable dye laser as the axcitation source. Measurements were done with two copper hollow cathode tubes filled with different gases, that were used as excitation source radiation and as signal detector. The results suggest that it is possible to use the new spectroscopy tecnique for qualitative and quantitative material analysis.

Scandate cathode under various processing stages: scandia nano-powder, tungsten scandia mix powder, sintered and impregnated pellets, were characterized with techniques that included electron microscopy, EDS, XPS, and work function measurements. The size and shape uniformity of nano-scale scandia particles changed from round to square and polyhedron during heat treatment. Reduction in size and improvement in size uniformity as heat treating temperature increased were observed. When determining the highest Sc coverage, three assessment methods were used and with their combined results, it was concluded that set VII had the highest Sc at%. In the sintered pellets, it was observed with SEM that more initial scandia coverage in the mix powder sets corresponded to a larger number of scandia particles distributed over the tungsten surface. The structure of the cross section made on pellet surface was porous which was expected in any functional cathode. Kelvin probe measurements revealed that work function values of sintered pellets were similar and decreased by approximately 0.6 eV after the impregnation. A cross section on the impregnated pellet surface revealed that the pores that existed in sintered pellets were gone and filled with impregnated materials that emerged to the surface during impregnation.

Fundamental thermodynamic investigations have been carried out regarding the phase equilibria of La0.8Sr0.2MnO3±δ (LSM), a cathode of a solid oxide fuel cell (SOFC), utilizing the CALculation of PHAse Diagram (CALPHAD) approach. The assessed thermodynamic databases developed for LSM perovskite in contact with YSZ fluorite and the other species have been discussed. The application of computational thermodynamics to the cathode is comprehensively explained in detail, including the defect chemistry analysis as well as the quantitative Brouwer diagrams, electronic conductivity, cathode/electrolyte interface stability, thermomechanical properties of the cathode and the impact of gas impurities, such as CO2 as well as humidity, on the phase stability of the cathode. The quantitative Brouwer diagrams for LSM at different temperatures are developed and the detailed analysis of the Mn3+ charge disproportionation behavior and the electronic conductivity in the temperature range of 1000-1200°C revealed a good agreement with the available experimental observations. The effects of temperature, CO2 partial pressure, O2 partial pressure, humidity level and the cathode composition on the formation of secondary phases have been investigated and correlated with the available experimental results found in the literature. It has been indicated that the CO2 exposure does not change the electronic/ionic carriers’ concentration in the perovskite phase. The observed electrical conductivity drop is predicted to occur due to the formation of secondary phases such as LaZr2O7, SrZrO3, SrCO3 and Mn oxides at the LSM/YSZ interface, resulting in the blocking of the electron/ion transfer paths. For the thermo-mechanical properties of LSM, a new weight loss Mechanism for (La0.8Sr0.2)0.98MnO3±δ using the La-Sr-Mn-O thermodynamic database is modeled with respect to the compound energy formalism model. This newly proposed mechanism comprehensively explains the defect formation as a result of volume/weight change during the thermal cycles. According to the proposed mechanism the impact of cation vacancies regarding the volume change of cathode was explained.

京都大学 / 新制・課程博士 / 博士(人間・環境学) / 甲第23995号 / 人博第1047号 / 新制||人||245(附属図書館) / 2022||人博||1047(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 中村 敏浩, 教授 陰山 洋, 教授 雨澤 浩史 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Le développement des piles à combustible à oxyde solide SOFC est conditionné par un abaissement de la surtension cathodique mesurée à 600-700°C. Dans cette optique, une sélection de nouveaux matériaux de cathode a été réalisée au laboratoire depuis quelques années. Ainsi, les oxydes sur-stoechiométriques en oxygène de type A2MO4+¤ (structure K2NiF4) possèdent des propriétés électrocatalytiques et de conduction de l'oxygène particulièrement intéressantes. Une étude approfondie a été menée sur les composés Nd2¤xNiO4+¤ (x = 0 et 0,05) : la réduction de l'oxygène a été caractérisée par spectroscopie d'impédance électrochimique et par voltamétrie (cellule en configuration symétrique placée sous air). Les mesures réalisées sous différentes pressions partielles d'oxygène et diverses surtensions cathodiques ont permis d'identifier les diverses contributions du mécanisme de réduction du dioxygène. L'utilisation de poudres de morphologie contrôlée (issues de différentes voies de synthèse) a conduit à réduire fortement les phénomènes de polarisation d'électrode, le transfert ionique à l'interface cathode / électrolyte restant l'étape limitante du processus. Par ailleurs, suite aux résultats particulièrement encourageants obtenus pour les cellules symétriques (faibles résistances spécifiques et surtensions cathodiques minimisées), les premiers tests en configuration de pile complète ont pu être réalisés. Après une optimisation des paramètres de mise en forme, i.e. sélection de la méthode de dépôt et du cycle thermique de frittage adapté, des densités de courant de l'ordre de 1,3 A/cm2 ont été mesurées à 0,7 V pour une température de fonctionnement de 800°C.

Cette thèse présente deux axes de recherches pour améliorer les performances de la cathode d'une pile SOFC. 1) Des films minces mésostructurés de CGO ont été réalisés par le procédé sol-gel, incluant l'utilisation de copolymères à bloc, associé à du dip-coating. Ce type de film, de porosité contrôlée, a ensuite été intégré à l'interface cathodique d'un dispositif complet. L'efficacité de ces films a été testée en pile complète et se traduit par une diminution de la chute ohmique dans la pile, améliorant ainsi ses performances. 2) Une nouvelle architecture de cathode composite LSC-CGO a ensuite été étudiée pour le fonctionnement d'une ITSOC à 600°C. Nous avons choisi d'élaborer ce composite par infiltration de nanoparticules de LSC dans une couche poreuse de CGO. Une matrice de CGO, présentant des mésopores et des macropores, a été réalisée par infiltration d'un sol de précurseurs de CGO dans une couche poreuse formée de billes de PMMA. La matrice à porosité hiérarchique a été obtenue après calcination du film hybride : les macropores sont issus de la décomposition thermique de grosses billes de PMMA et les mésopores sont obtenus par décomposition soit de plus petites billes de PMMA soit d'un copolymère initialement présent dans le sol de CGO. La réalisation de nanoparticules de LSC en milieu polyol a également été étudiée : des nanoparticules ont été obtenues après un traitement thermique à haute température et une étude complémentaire de la synthèse à basse température de nanoparticules de plus petites tailles est nécessaire pour réaliser le composite. Ce travail présente l'intérêt de la synthèse par infiltration pour la réalisation de cathodes de SOFC à porosité contrôlée

Ces travaux s'inscrivent dans le cadre des recherches menées sur l'évaluation des procédés pyrochimiques pour la séparation actinides-lanthanides. Ils concernent plus précisément un coeur de procédé consistant en la réduction, sur cathode liquide, des actinides dissous en milieu sel fondu. Cette technique présente un certain potentiel pour un scénario de « gestion groupée ». L'objectif de ces travaux est de proposer un procédé de séparation électrolytique qui améliorait, à la fois, les performances d'extraction des An, et de séparation An-Ln. L'amélioration de la sélectivité passe par la mise en oeuvre d'autres solvants que ceux explorés jusqu'à présent. Une étude méthodologique et thermodynamique nous a conduits à sélectionner une combinaison solvant/substrat cathodique prometteuse : fluorures fondus et bismuth liquide. Cette étape a été suivie d'une validation expérimentale (sur néodyme), permettant de s'assurer aussi bien de la faisabilité de mise en oeuvre des systèmes, que de la pertinence de nos prévisions. Les performances d'extraction pourraient, quant à elles, se voir améliorées par la mise en oeuvre d'un renouvellement de l'interface sel/cathode liquide. Il s'agit alors de répondre à la faisabilité d'une électrolyse dynamique sur gouttes de métal liquide. L'étude de la transposition de cette technologie aux milieux présélectionnés nous a conduits à mettre au point un petit dispositif dédié aux études d'écoulement, ainsi qu'une méthode de détermination des tensions interfaciales à haute température. Ces travaux démontrent que le principe de séparation sur cathode liquide à surface renouvelée ne présente pas de point rédhibitoire. Néanmoins, une validation en actif et une optimisation de la technologie sont nécessaires pour compléter l'évaluation de cette technique séparative innovante.