Dissertationen zum Thema „Porosité hydrogène“

Cette thèse s’inscrit dans le cadre d’une collaboration entre le CEA et ORANO Mining avec pour objectif de développer une nouvelle sonde diagraphique basée sur l’interrogation neutronique active, dans le cadre de l’exploration et de l’exploitation de l’uranium dont une part importante de la production provient aujourd’hui de mines utilisant la lixiviation in situ. L’extraction chimique du minerai s’effectue directement dans le sol, sur plusieurs centaines de mètres, par injection et collection de solutions chimiques. Pour évaluer la rentabilité du puits, il est non seulement nécessaire de connaitre la quantité d’uranium disponible, mais aussi la perméabilité du milieu géologique. Cette dernière est déterminée en mesurant la « porosité hydrogène », à savoir la fraction volumique de la roche occupée par de l’eau, à l’aide de sondes qui émettent puis mesurent des neutrons ayant diffusé sur les noyaux d’hydrogène. L’uranium, et plus précisément son isotope 235, est aussi mesurable à l’aide de sondes équipées d’un générateur de neutrons pulsé. Ces travaux de recherche ont abouti à la conception d’une sonde permettant de réaliser ces deux mesures avec un unique compteur proportionnel à hélium 3 entouré de polyéthylène et blindé avec du cadmium. Des impulsions de neutrons de durée 50 µs sont émises par le générateur toutes les 5 ms (à 200 Hz). Puis, au cours des 800 µs qui suivent l’arrêt de chaque tir, on mesure les neutrons diffusés dans la formation qui ne sont pas thermalisés entièrement et peuvent encore franchir le blindage en cadmium. On obtient un comptage inversement proportionnel à la quantité d’hydrogène présente dans l’environnement. Sur les millisecondes qui suivent, les neutrons thermiques encore présents dans la roche font fissionner des noyaux d’235U, ce qui émet en moyenne 2.5 neutrons prompts par fission. Une partie de ces derniers sont mesurés par le bloc de détection, tandis que les neutrons du générateur, devenus thermiques 800 µs après l’arrêt du tir, ne peuvent plus franchir le blindage en cadmium. Grace à cette double discrimination, temporelle et énergétique, on peut mesurer le signal des neutrons prompts de fission qui est proportionnel à la concentration en uranium. Le flux de neutrons thermiques interrogateurs étant absorbé par l’hydrogène présent dans l’environnement, on utilise la porosité hydrogène mesurée pour corriger le signal des neutrons prompts de fission. Après avoir étudié par simulation Monte-Carlo les grandeurs affectant les performances de ces deux mesures (diamètre de forage, décentrage de la sonde, épaisseur et matériau de tubage, gangue de boue, lithologie), nous avons validé expérimentalement leur faisabilité en laboratoire. Tout d’abord, plusieurs chaines d’acquisition ont été testées pour pouvoir mesurer des taux de comptage instantanés de l’ordre de 106 s-1, pendant et juste après chaque tir du générateur de neutrons. D’autre part, une sonde maquette de laboratoire a été réalisée et testée dans un fût d’étalonnage rempli de 1.6 t de sable de Fontainebleau, spécialement conçu pour ces essais. Un bon accord entre l’expérience et les simulations a permis de valider la mesure de teneur en uranium et d’appréhender de nouveaux phénomènes, notamment l’activation de l’oxygène 17 responsable d’un bruit d’un fond actif significatif dans les formations siliceuses saturées en eau. La qualification des méthodes de calcul du signal et du bruit a été menée à bien, ce qui a permis d’estimer les performances prévues en situation réelle, notamment des limites de détection entre 10 et 200 ppm en 3 min de mesure pour des porosité hydrogènes respectives de 0 et 40%
This PhD in the frame of CEA - ORANO Mining collaboration, aims to develop a new logging tool, based on neutron active interrogation, in the scope of uranium exploration and exploitation. A large amount of its production comes from In situ recovery mines, by leaching chemically the ore in the ground over hundreds of meters. It is mandatory to determine the amount of uranium available, but also the permeability of the sand, to evaluate the profitability. This geological quantity can be assessed from the measurement of the porosity hydrogen that is the volume fraction of water in the rock formation. It is possible to measure this one by using neutron probes. Uranium, and especially its 235 isotope, can also be measured with that kind of logging tools, if they rely on a pulsed neutron generator. This research leads to a new probe design that allows performing the both measurements with a unique cadmium-shielded-helium 3-proportional counter. The generator emits a 50 µs neutron burst every 5 ms (at 200 Hz). In the 800 µs after the salvo we can measure the not-fully-thermalised neutrons, thanks to the cadmium shield acting like a filter. The obtained count is inversely proportional to the hydrogen, and water, environment content. Over the following milliseconds, thermal neutrons of the rock formation will lead to 235U nuclei fissions, which emit in average 2.5 prompt fission neutrons. A chunk of these neutrons is emitted toward our counter, as the neutrons from the generator, fully thermalized after 800 µs, cannot cross the cadmium. Thanks to that double energy-time discrimination, it is possible to measure the prompt fission neutron signal contribution, which is proportional to the uranium concentration. As thermal neutrons are absorbed by the hydrogen content in the environment, we can use the porosity hydrogen measurement to correct the prompt fission neutrons signal from its effect. Furthermore, a parametric study has been conducting, using the Monte-Carlo simulation code MCNP 6.1, to compare the quantities that affect the measurements performances (e.g. diameter, standoff, casing thickness, casing, mudcake thickness, lithology). Finally, the new measurement methods feasibility has been validated through two experimental campaigns: in one hand, the capability of the electronics to handle input count rates in the 106 s-1 yield, during and right after a pulse of the neutron D-T generator. In the other hand, a laboratory model of the neutron probe has been built and tested in a dedicated calibration drum, filled with 1.6 t Fontainebleau sand. An agreement between experiment and computer simulations has been found, which validates the uranium concentration measurement and allows the understanding of the main components of the active background. This study highlighted the contribution of the oxygen 17 activation delayed neutrons, in the water saturated sandstone environments. The signal and noise analysis method were qualified, leading to the first estimations of in situ performances, like the detection limit of the uranium concentration measurement, from 10 to 200 ppm for 3 min of acquisition, for hydrogen porosities ranging respectively from 0 to 40%

Des gaz vont être générés par corrosion des conteneurs de déchets radioactifs au niveau d'un stockage en couche géologique profonde. Une bulle de gaz se crée et monte en pression. Si le gaz pénètre difficilement la formation géologique, l'augmentation de pression pourra la fissurer et créer des chemins préférentiels à la migration de radionucléides. Les argilites du Callovo-Oxfordien sont ici caractérisées. Un dispositif permettant de mesurer de très faibles perméabilités à l'hydrogène/hélium a été utilisé couplé au Dusty Gas Model. Les argilites proches de la saturation ont une porosité accessible au gaz inférieure à 1% voire 0,1% de la porosité totale. A partir de l'étude de l'effet Knudsen cette porosité pourrait être due à des pores de 50 à 200 nm de diamètre mis en évidence lors de la caractérisation des réseaux. En intégrant ces résultats dans un modèle opérationnel de l'ANDRA, la pression maximale atteinte au sein d'une alvéole de stockage serait de 83 bar.

Des gaz vont être générés par corrosion des conteneurs de déchets radioactifs au niveau d'un stockage en couche géologique profonde. Une bulle de gaz se crée et monte en pression. Si le gaz pénètre difficilement la formation géologique, l'augmentation de pression pourra la fissurer et créer des chemins préférentiels à la migration de radionucléides. Les argilites du Callovo-Oxfordien sont ici caractérisées. Un dispositif permettant de mesurer de très faibles perméabilités à l'hydrogène/hélium a été utilisé couplé au Dusty Gas Model. Les argilites proches de la saturation ont une porosité accessible au gaz inférieure à 1% voire 0,1% de la porosité totale. A partir de l'étude de l'effet Knudsen cette porosité pourrait être due à des pores de 50 à 200 nm de diamètre mis en évidence lors de la caractérisation des réseaux. En intégrant ces résultats dans un modèle opérationnel de l'ANDRA, la pression maximale atteinte au sein d'une alvéole de stockage serait de 83 bar
Gases will be generated by corrosion of high radioactive waste containers in deep geological repositories. A gas phase will be generated. Gas pressure will build up and penetrated the geological formation. If gases do not penetrate the geological barrier efficiently, the pressure build up may create a risk of fracturation and of creation of preferential pathways for radionuclide migration. The present work focuses on Callovo-Oxfordian argillites characterisation. An experiment, designed to measure very low permeabilities, was used with hydrogen/helium and analysed using the Dusty Gas Model. Argillites close to saturation have an accessible porosity to gas transfer that is lower than 0,1% to 1% of the porosity. Analysis of the Knudsen effect suggests that this accessible network should be made of 50 nm to 200 nm diameter pores. The permeabilities values were integrated to an ANDRA operating model. The model showed that the maximum pressure expected near the repository would be 83 bar

The oxide level of an A356 aluminium alloy will be controlled by (i) melting, casting and remelting A356 aluminium alloy for increasing the bi-films levels in the melt, and by (ii) additions of an extruded aluminium oxide rod directly to the melt. A clean A356 melt (no additions of any particulates) will be used as reference material. The melting experiments will be conducted in an electric resistance furnace under carefully controlled conditions. The three crucible experimental set-up, designed by SINTEF Materials and Chemistry, will be adopted to secure identical conditions for all three melts to be investigated. From each of the melts a series of reproducible castings will be made for tensile test measurements, as well as bend tests. The results from these tests will be statistically analysed. For the assessment of melt quality, in terms of inclusion count and bi-films index, the Porous Disc Filtration Apparatus (PoDFA) and the Reduced Pressure Test (RPT) will be adopted. For the analysis of fracture behaviour Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDX) will be use. The dissolved hydrogen level will be measured by adopting an ALSPEC H probe.If time is given, the data generated in the present work will be compared with results previously obtained by SINTEF Materials and Chemistry for experiments conducted under similar conditions. It is believed that the results from the present study will provide a sound basis for understanding the fundamentals of the key issues involve in the production of high quality aluminium castings.

Les matériaux céramiques poreux présentent des propriétés de grand intérêt grâce à leur potentiel dans les applications de l'énergie. L'objectif général de cette thèse concerne le développement de matériaux (carbo)nitrures pour la production et le stockage de l'hydrogène (synthèse, caractérisation, propriétés et applications). La voie polymère précéramique, offrant un grand nombre de possibilités dans la chimie et la science des céramiques, est utilisée pour élaborer ces matériaux. Tout d'abord, nous avons préparé les systèmes binaires poreux tels que AlN et BN en répliquant la structure du CMK-3 et du charbon actif. Après pyrolyse, nous avons démontré la faisabilité de produire des nitrures avec une porosité adaptée. Par ailleurs, en couplant la voie polymère précéramique avec la technologie des aérogels, nous avons réussi à préparer des aérogels AlN et BN avec une porosité relativement élevée. Nous avons évalué le potentiel de ces matériaux poreux pour le nanoconfinement de deux hydrures chimiques, l'alanate de sodium et l'ammoniaborane, respectivement. Dans les deux cas, la nanoconfinement a déstabilisé le réseau de l'hydrure et a permis la libération de H2 à de basses températures ; en outre, dans le cas de l'ammoniaborane confiné, aucun sous-produit gazeux indésirable n'a été détectée, ce qui confirme la pureté du H2 dégagé. Deuxièmement, nous avons préparé des systèmes quaternaires poreux par association de AlN/BN avec des céramiques à base de silicium. En particulier, nous avons élaboré des céramiques SiAlCN en utilisant deux approches: la voie à « 2 sources » et la voie à « source unique ». En ce qui concerne la première, nous avons préparé des matériaux mésoporeux ordonnés qui ont été utilisés comme supports catalytiques pour l'hydrolyse d'une solution alcaline de borohydrure de sodium. Nous avons réussi à générer du H2 avec des cinétiques élevées. En ce qui concerne la seconde approche, le travail a porté sur l'étude de la chimie de matériaux SiAlCN et SiBCN. Des mousses cellulaires SiAlCN ont été préparées par l'utilisation de charges sacrificielles
Porous inorganic materials are of great interest owing to their potential in energy applications. The general objective of the present thesis concerns the development of functional (carbo)nitrides for hydrogen generation and storage (material design, elaboration, properties and applications). The PDCs route, which offers a large number of opportunities in chemistry and ceramic sciences, has been applied to produce functional (carbo)nitrides materials. Firstly, we prepared porous binary systems such as AlN and BN by replicating the structure of CMK-3 and that of activated carbon. After pyrolysis and removal of the template, we demonstrated the feasibility of producing nitrides with tailored porosity. Moreover, by coupling the PDCs route with the aerogel technology, we succeeded in preparing polymer-derived AlN and BN aerogels. We assessed the potential of these porous AlN and BN materials in nanoconfinement of two chemical hydrides, namely sodium alanate and ammoniaborane, respectively. In both cases, the nanoconfinement destabilized the network of the hydride and favored the release of H2 at low temperature. Besides, in the case of nanoconfined ammoniaborane, no evolution of undesired gaseous by-products was observed, which means that pure hydrogen was produced in our conditions. Secondly, we prepared porous quaternary systems through the association of AlN/BN with Si-based ceramics. In particular, we investigated the preparation of SiAlCN with tailored porosity by using two approaches: the “molecular building block” and “single-source precursor” approaches. Concerning the former, we investigated the preparation of ordered mesoporous materials to be used as catalytic supports for hydrolysis of alkaline solution of sodium borohydride. We succeeded in generating high amounts of H2 with attractive kinetics. Concerning the latter approach, the work was focused on the investigation of the chemistry of SiAlCN and SiBCN materials with a particular focus on the elaboration of SiAlCN microcellular foams by a sacrificial processing route

We present an analysis of the properties of HI holes detected in 20 galaxies that are part of “The HI Nearby Galaxy Survey” (THINGS). We detected more than 1000 holes in total in the sampled galaxies. Where they can be measured, their sizes range from about 100 pc (our resolution limit) to about 2 kpc, their expansion velocities range from 4 to 36 km/s, and their ages are estimated to range between 3 and 150 Myr. The holes are found throughout the discs of the galaxies, out to the edge of the HI disc; 23% of the holes fall outside R25. We find that shear limits the age of holes in spirals; shear is less important in dwarf galaxies which explains why HI holes in dwarfs are rounder, on average than in spirals. Shear, which is particularly strong in the inner part of spiral galaxies, also explains why we find that holes outside R25 are larger and older. We derive the scale height of the HI disc as a function of galactocentric radius and find that the disc flares at large radii in all galaxies. We proceed to derive the surface and volume porosity (Q2D and Q3D) and find that this correlates with the type of the host galaxy: later Hubble types tend to be more porous. The size distribution of the holes in our sample follows a power law with a slope of a=−2.9. Assuming that the holes are the result of massive star formation, we derive values for the supernova rate (SNR) and star formation rate (SFR) which scales with the SFR derived based on other tracers. If we extrapolate the observed number of holes to include those that fall below our resolution limit, down to holes created by a single supernova, we find that our results are compatible with the hypothesis that HI holes result from star formation. We use HI data from THINGS, 8μm, 24μm, 70μm and HI maps from SINGS, CO(2–1) data from HERACLES and FUV data from NGS to present a visual comparison of these maps with respect to the locations of HI holes. We find that the vast majority of HI holes are also prominent in the 8μm map and to some extent in the 24μm map. There is a lack of molecular gas from the interior of nearly all the holes, which is consistent with the idea that the latter are filled with hot gas. About 60% of young holes have FUV emission detected in their interiors highlighting the presence of the parent OB association. In addition, FUV is detected on the rims of some of the older HI holes, presumably due to the dispersion of the OB association with respect to the gas. We describe the development of a 2–D cross-correlation method to compare multi-wavelength maps in a quantitative way (quantified by Ccoef ) and give some first results from the application of this method to the nearby galaxy NGC2403. We find that the all the dust tracers are well correlated (Ccoef > 0.7) with the 8μm–24μm correlation being the highest (Ccoef > 0.88). Similarly all the star formation tracers are well linked as expected (Ccoef > 0.6). With respect to the relations between star formation and dust tracers we found that most are well matched (Ccoef > 0.7) as dust grains are heated by radiation in star forming regions. At smaller scales (15") FUV correlates poorly (Ccoef ~ 0.3) with the dust tracers, a direct consequence of the absorption of FUV photons by dust. We find that the HI is reasonably well correlated with the 8μm emission (Ccoef ~ 0.6) illustrating the fact that HI is mixed with PAH’s. Interestingly, the HI map shows some correlation with the SF map (Ccoef ~ 0.4) even though FUV and HI emissions were found to be completely uncorrelated (Ccoef ~ 0).

Aluminum alloys are having more attention due to their high specific stiffness and processing advantages. 7075 aluminum alloy is a wrought composition aluminum alloy in the Al-Zn-Mg-Cu series. Due to the significant addition of these alloying elements, 7075 has higher strength compared to all other aluminum alloys and effective precipitation hardenability characteristic. On the other hand, aluminum alloys have some drawbacks, which hinder the widespread application of them. One of the most commonly encountered defects in aluminum alloys is the hydrogen porosity. Additionally, in case of 7075, another problem is the lack of fluidity. Magnesium addition is thought to be effective in compensating this deficiency. Accordingly, in this study, die cast 7075 aluminum alloy samples with hydrogen porosity and additional magnesium content were investigated. The aim was to determine the relationship between hydrogen content and hydrogen porosity, and the effects of hydrogen porosity, additional magnesium and T6 heat treatment on ultimate tensile and flexural strength properties of pressure die cast 7075 aluminum alloy. 7075 aluminum alloy returns were supplied from a local pressure die casting company. After spectral analysis, pressure die casting was conducted at two stages. In the first stage, 7075 aluminum alloy with an increase in magnesium concentration was melted and secondly 7075 aluminum alloy was cast directly without any alloying addition. While making those castings, hydrogen content was measured continuously before each casting operation. As a final operation T6 heat treatment is carried out for certain samples. Finally, in order to accomplish our aim, mechanical and microstructural examination tests were conducted.

En centrales nucléaires, un accident grave est une séquence très peu probable d’événements durant laquelle des composants du réacteur sont significativement endommagés, par interactions chimiques et/ou fusion, à cause de très hautes températures. Cela peut mener à des rejets radiotoxiques dans l’enceinte et à une entrée d’air dans le réacteur. Dans ce contexte, ce travail de thèse mené chez EDF R&D visait à modéliser la détérioration du gainage combustible, en alliages de zirconium, en conditions accidentelles : haute température et soit vapeur soit mélange air-vapeur. L’objectif final était d’améliorer la simulation par le code MAAP de l’oxydation du gainage et de la production d’hydrogène, en particulier pendant un renoyage avec de l’eau. Dû à l’épaississement progressif d’une couche de ZrO2 dense et protectrice, la cinétique d’oxydation du Zr en vapeur à hautes températures est généralement (sous-)parabolique. Cependant, à certaines températures, cette couche d’oxyde peut se fissurer, devenant poreuse et non protectrice. Par ce processus de « breakaway », la cinétique d’oxydation devient plus linéaire. De plus, l’augmentation de température peut mener les matériaux du réacteur à fondre et à se relocaliser dans le fond de cuve dont la rupture peut induire une entrée d’air dans le réacteur. Dans ce cas, l’oxygène et l’azote réagissent avec les gaines pré-oxydées, successivement par oxydation du Zr (épaississant la couche de ZrO2), nitruration du Zr (formant des particules de ZrN) et oxydation du ZrN (créant de l’oxyde et relâchant de l’azote). Ces réactions auto-entretenues relancent la fissuration du gainage et de sa couche de ZrO2, induisant une hausse de sa porosité ouverte. Afin de quantifier cette porosité du gainage, un protocole expérimental innovant en deux étapes a été défini et appliqué : il consistait à soumettre des échantillons de gainage en ZIRLO® à diverses conditions accidentelles pendant plusieurs durées puis à des mesures de la porosité ouverte par porosimétrie par intrusion de mercure. Les conditions de corrosion comprenaient plusieurs températures allant de 1100 à 1500 K ainsi que de la vapeur et un mélange air-vapeur 50-50 mol%. Pour les échantillons de ZIRLO® oxydés en vapeur, sauf à 1200 et 1250 K, les transitions de cinétique n’ont pas lieu et la porosité ouverte reste négligeable au cours de l’oxydation. Cependant, pour les autres échantillons, corrodés en air-vapeur ou oxydés en vapeur à 1200 ou 1250 K, des transitions « breakaway » sont observées et les résultats de porosimétrie montrent que la porosité ouverte augmente au cours de la corrosion, proportionnellement au gain en masse. De plus, il a été mis en évidence que la distribution de tailles de pores des échantillons de ZIRLO® s’étend significativement pendant la corrosion, en particulier après « breakaway ». En effet, ces tailles vont de 60 μm à environ : 2 μm avant la transition, 50 nm juste après et 2 nm plus longtemps après. Enfin, un modèle numérique en deux étapes a été développé dans le code MAAP pour améliorer sa simulation de l’oxydation du gainage. D’abord, grâce à la proportionnalité entre porosité ouverte et gain en masse des échantillons, des corrélations de porosité ont été implémentées pour chaque condition de corrosion. Ensuite, les valeurs de porosité calculées sont utilisées pour augmenter proportionnellement la vitesse d’oxydation du gainage. Ce modèle amélioré simule ainsi non seulement les réactions chimiques des gaines en Zr (oxydation et nitruration) mais aussi leur dégradation mécanique et son impact sur leur vitesse d’oxydation. Ceci a été validé en simulant des essais QUENCH (-06, -08, -10 et -16), conduits au KIT pour étudier le comportement de gaines dans des conditions accidentelles avec un renoyage final. Ces simulations montrent un meilleur comportement thermique du gainage et une production d’hydrogène significativement plus haute et donc plus proche des valeurs expérimentales, en particulier pendant le renoyage
In nuclear power plants, a severe accident is a very unlikely sequence of events during which components of the reactor core get significantly damaged, through chemical interactions and/or melting, because of very high temperatures. This may potentially lead to radiotoxic releases in the containment building and to air ingress in the reactor core. In that context, this thesis work led at EDF R&D aimed at modeling the deterioration of the nuclear fuel cladding, made of zirconium alloys, in accidental conditions: high temperature and either pure steam or air-steam mixture. The final objective was to improve the simulation by the MAAP code of the cladding oxidation and of the hydrogen production, in particular during a core reflooding with water. Due to the progressive thickening of a dense and protective ZrO2 layer, the oxidation kinetics of Zr in steam at high temperatures is generally (sub-)parabolic. However, at certain temperatures, this oxide layer may crack, becoming porous and not protective anymore. By this “breakaway” process, the oxidation kinetics becomes rather linear. Additionally, the temperature increase can lead core materials to melt and to relocate down to the vessel lower head whose failure may induce air ingress into the reactor core. In this event, oxygen and nitrogen both react with the pre-oxidized claddings, successively through oxidation of Zr (thickening the ZrO2 layer), nitriding of Zr (forming ZrN particles) and oxidation of ZrN (creating oxide and releasing nitrogen). These self-sustained reactions enhance the cracking of the cladding and of its ZrO2 layer, inducing a rise of its open porosity.In order to quantify this cladding porosity, an innovative two-step experimental protocol was defined and applied: it consisted in submitting ZIRLO® cladding samples first to various accidental conditions during several time periods and then to measurements of the open porosity through porosimetry by mercury intrusion. The tested corrosion conditions included numerous temperatures ranging from 1100 up to 1500 K as well as both pure steam and a 50-50 mol% air-steam mixture. For the ZIRLO® samples oxidized in pure steam, except at 1200 and 1250 K, the “breakaway” kinetic transitions do not occur and the open porosity remains negligible along the oxidation process. However, for all other samples, corroded in air-steam or oxidized in pure steam at 1200 or 1250 K, “breakaway” transitions are observed and the porosimetry results show that the open porosity increases along the corrosion process, proportionally to the mass gain. Moreover, it was evidenced that the pore size distribution of ZIRLO® samples significantly extends during corrosion, especially after “breakaway” transitions. Indeed, the detected pore sizes ranged from 60 μm down to around: 2 μm before the transition, 50 nm just after and 2 nm longer after. Finally, a two-step numerical model was developed in the MAAP code to improve its simulation of the cladding oxidation. First, thanks to the proportionality between open porosity and mass gain of cladding samples, porosity correlations were implemented for each tested corrosion condition. Second, the calculated porosity values are used to proportionally enhance the cladding oxidation rate. This improved model thus simulates not only chemical reactions of Zr-based claddings (oxidation and nitriding) but also their mechanical degradation and its impact on their oxidation rate. It was validated by simulating QUENCH tests (-06, -08, -10 and -16), conducted at KIT to study the behavior of claddings in accidental conditions with a final reflooding. These simulations show a better cladding thermal behavior and a hydrogen production significantly higher and so closer to experimental values, in particular during the reflooding

Este trabalho procurou identificar o defeito que ocorria no teste de estanqueidade de uma peça e apresentar a correlação entre o nível de porosidade encontrado no produto fundido com a liga de alumínio A356 e os processos de fusão e de manutenção sob temperaturas controladas, o teor de hidrogênio, o sistema de enchimento e de alimentação, obedecendo ao princípio de solidificação direcional e o posicionamento do modelo em relação à linha de divisão. Foram efetuadas algumas experiências com diferentes tempos de introdução de nitrogênio para a purificação do metal, com a inversão do modelo em relação ao plano de partição do molde, com a modificação das dimensões do sistema de enchimento, com a substituição dos massalotes laterais por outros com luvas exotérmicas e utilizando-se resfriadores. Tentou-se verificar os benefícios que os filtros cerâmicos proporcionam aos fundidos, principalmente quanto à diminuição do nível de porosidade, menor turbulência e maior capacidade de reter as inclusões e parte dos filmes de óxidos. Para comprová-los, propôs-se a fundição de peças, em moldes confeccionados pelo processo de areia à verde, com diferentes tipos de filtros cerâmicos nos canais de distribuição. As amostras foram analisadas no Laboratório Metalográfico do Departamento de Engenharia Metalúrgica e de Materiais da Escola Politécnica da Universidade de São Paulo e no Laboratório de Metalurgia e de Materiais Cerâmicos do Instituto de Pesquisas Tecnológicas de São Paulo. Após a análise dos resultados em microscópio óptico, microscópio eletrônico de varredura e em espectrômetro por emissão de energia observou-se que o problema está relacionado principalmente com a alimentação e a solidificação direcional e não somente com o teor de hidrogênio.
The objective of this work is to study the type of defect identified during the pressure tightness test of aluminum parts and to establish a relationship between porosity level of an A356 aluminum alloy and the production processes, hydrogen level, feeding system, and directional solidification. Different nitrogen blowing times, inversion of the mould pattern, relative to the partition line, changing of the feeding system dimensions, replacement of the lateral feeding by exothermic gloves and the use of chills where tested. Ceramic filters were also tested, in order to evaluate their influence on the formation of porosities and on the porosity level, through a decrease of turbulence and an increase in the capacity of retaining non-metallic inclusions and part of the oxide films. Casting was performed by the green sand process using different ceramic filters. The obtained parts were metallographicaly analyzed through optical and scanning electronic microscopy using also EDS analysis. The results showed that porosity is related with the feeding conditions and directional solidification besides the hydrogen content of the alloys.

This master thesis will cover the possibility of using directed gassing of Al-Si alloys in a high pressure die casting foundry. As a control gas, rotary degasser with gaseous 20 % H2 in N2 as a medium was used. Castings were casted via high pressure die casting machine. The aim of this research is to compare internal defect such as porosity or shrinkage of a casts made from degassed and control gassed melt.

Products manufactured by aluminium casting have become very popular and already replaced many parts that were once produced by iron and steel casting. This trends upwards especially in the automotive industry as it has become extremely important to reduce vehicle weight due to environmental requirements and economical aspects. This popularity of aluminium alloys could be ascribed to their light weights and many other advantages including excellent castability, good corrosion resistance, good thermal and electrical conductivity, good machinability, low melting temperatures and minimal gas solubility with the exception of hydrogen. The most important alloy group among casting alloys is Aluminium Silicon (Al - Si).   Al-Si alloys must undergo a specific melt treatment procedure prior to casting. This treatment consists of several steps including degassing of hydrogen, grain refinement and eutectic modification. The aim of this study is to make an assessment of the metal treatment process of an (Al-Si) casting alloy at Unnaryd Modell AB for the purpose of improving the melt conditions and thus the quality of the final product. A rotary degasser provided by Foseco is also tested instead of the traditional tablet degassing method to see if this technique would result in any significant improvement of the melt quality. The results show that Unnaryd modell AB follows a proper treatment routine. It shows moreover that the rotary degassing is superior to the tablet degassing in many aspects including the level of degassing achieved, time efficiency, environmental consideration and personnel security.

The design of functional materials for specific applications has been an ongoing challenge for scientists aiming to resolve present and future societal needs. A burgeoning interest was awarded to developing methods for the design and synthesis of hybrid materials, which encompass superior functionality via their multi-component system. In this context, Metal-Organic Materials (MOMs) are nominated as a new generation of crystalline solid-state materials, proven to provide attractive features in terms of tunability and versatility in the synthesis process. In strong correlation with their structure, their functions are related to numerous attractive features, with emphasis on gas storage related applications. Throughout the past decade, several design approaches have been systematically developed for the synthesis of MOMs. Their construction from building blocks has facilitated the process of rational design and has set necessary conditions for the assembly of intended networks. Herein, the focus is on utilizing the single-metal-ion based Molecular Building Block (MBB) approach to construct frameworks assembled from predetermined MBBs of the type MNx(CO2)y. These MBBs are derived from multifunctional organic ligands that have at least one N- and O- heterochelate function and which possess the capability to fully saturate the coordination sphere of a single-metal-ion (of 6- or higher coordination number), ensuring rigidity and directionality in the resulting MBBs. Ultimately, the target is on deriving rigid and directional MBBs that can be regarded as Tetrahedral Building Units (TBUs), which in conjunction with appropriate heterofunctional angular ligands are capable to facilitate the construction of Zeolite-like Metal-Organic Frameworks (ZMOFs). ZMOFs represent a unique subset of MOMs, particularly attractive due to their potential for numerous applications, arising from their fully exploitable large and extra-large cavities. The research studies highlighted in this dissertation will probe the validity and versatility of the single-metal-ion-based MBB approach to generate a repertoire of intended MOMs, ZMOFs, as well as novel functional materials constructed from heterochelating bridging ligands. Emphasis will be put on investigating the structure-function relationship in MOMs synthesized via this approach; hydrogen and CO2 sorption studies, ion exchange, guest sensing, encapsulation of molecules, and magnetic measurements will be evaluated.

Coalbed methane (CBM) is basically naturally fractured, and the cleat network plays the main role in providing the fluid flow path, hence the permeability measure in CBM relies principally on the characteristics of this network. However, the permeability of the cleat network in coals is typically low. Moreover, fractures in coal seams might be partially to fully filled with minerals, a process called mineralization, as the result of which the permeability measure would decrease, sometimes leading to the total blockage of fractures. Therefore, to provide a promising cleat network permeability, reservoir stimulation is an important part in development of low permeability CBM to induce new fractures and demineralize the original cleat network. The current study, in general, focuses on two stimulation techniques aiming at enhancing the permeability and connectivity of coal cleat network, namely liquid nitrogen (LN2) fracturing, and acid stimulation. Several techniques and equipment were used to conduct this research, such as Micro Computed Tomography (μ-CT) scanning, medical CT scanning, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), flooding set-ups, etc. Although LN2 fracturing has been studied previously, there are some gaps in the research in this field. The first matter to consider in LN2 fracturing is to investigate the mechanism of this technique in fracturing coals. Therefore, the research presented in the third chapter of the current study, examines and quantifies the pore structure and connectivity evolution of a bituminous coal frozen in LN2, based on the in-situ morphological analysis through μ-CT scanning. This helps us to investigate the associated in-situ fracturing mechanisms, and measure the extent of induced fractures and damage to the rock in 3D at micrometre-scale. The results of this study shows the considerable potential of LN2 freezing in coal cleat network permeability enhancement. The μ-CT results clearly demonstrate that the cleat network is boosted following the treatment, where thoroughgoing fractures with a maximum opening of 13 μm appear, some of which are rooted in the original cleat network. While this application increases the porosity measure of the bituminous coal by 11%, core flooding tests and Lattice Boltzmann simulations show over double increase in the coal’s permeability value after liquid nitrogen exposure. This noticeable permeability enhancement is not only due to generation of new fractures, but also is attributed to the connection establishment of the cleat network with originally isolated pores and micro-cleats following the freezing, thereby increasing pore network connectivity. Following conducting the above study, which revealed encouraging results in permeability and connectivity enhancement of the coal and illustrated the discovering mechanisms of LN2 fracturing approach, another research in this work focuses on examining the performance of this stimulation technique in different coal ranks. This research is presented in chapter 4 of the current study. This research thus is aimed at exploring the potential of this thermal shock in fracturing three main coal ranks, namely sub-bituminous, bituminous and anthracite. The 3D X-ray computed tomography results in μ-CT and macroscale (medical-CT) reveal a poor performance of LN2 fracturing in anthracite. On the contrary, the in-situ 3D visualization of the other two coal ranks suggests a promising fracturing performance. The porosity evolutions of bituminous and sub-bituminous coals through the treatment are 14% and 119% in microscale, respectively. Thus, this work suggests that LN2 fracturing approach may not be a reliable stimulation technique for high rank coals, although performs encouragingly in medium to low rank coals. In addition to the above studies on LN2 fracturing potential and mechanism as well as its performance in different coal ranks, another research completed in this study focuses on the potential of several cycles of LN2 freezing/unfreezing, a process called freeze-thaw, which is presented in chapter 5 of the current study. This research is aimed at comparing the performance of this fracturing technique in one freezing cycle with up to three freeze-thaw cycles, and quantifies the efficiency of each cycle in cleat network evolution. μ-CT images revealed a promising efficiency in cleat network evolution after three freezing cycles, where the number of pores increased by 50% (92715 142650), and the number of interconnected pores almost doubled (42060 78905). SEM along with μ-CT images highlight more encouraging efficiency of second and third freezing cycles, particularly in terms of enhancing fractures interconnection. Mechanical properties analysis reveals more significant damage in the coal in the latter freezing cycles, where the indentation modulus was initially 3.49 GPa and decreased to 2.81, 2.11 and 1.52 GPa through three freezing cycles. Finally, the permeability of the coal under 1000 kPa confining pressure increased from 0.035 mD to 0.18 mD, with larger increments in later cycles. Therefore, this research highlights the superiority of LN2 freeze-thaw cycling over single freezing of coals with LN2 through conducting a quantitative comparison on the efficiency of each freezing cycle. In addition to LN2 fracturing technique, this study works on acid stimulation of coals, and evaluates the potential of a combination of these two recovery enhancement approaches in coal’s permeability evolution, the results of which is presented in the form of a research article in chapter 6. This work suggests that a combination of these two techniques have a considerable potential for recovery enhancement in coals. In case where acidizing is performed first, in addition to the permeability enhancement because of cleat demineralization, a more promising LN2 fracturing application is expected, because the coal’s strength decreases following acidizing, and the coal is more prone to freezing. In the other sequence of applications, where LN2 freezing is accomplished first, not only the cleat network is extended and boosted due to the fracturing application, but also the following acidizing process benefits because of a better accessibility of the acid to remote mineralised fractures. The findings in the above research articles show how a coalbed methane could be treated to provide an enhanced cleat network, where fluid flow is facilitated, and the coalbed methane is extracted. Such coalbed methane reserve would be depleted from gas at this stage. Generally, underground reservoirs might have a potential for gas storage following depletion from gas/oil. This could be beneficial from environmental aspect, for example unwanted gases such as carbon dioxide could be injected into these reservoirs. Additionally, in the recent years, depleted underground reservoirs have attracted the attention of energy sector as a possible storage site for generated hydrogen, as it is not a safe practice to store massive amount of this gas in surface reservoirs. Indeed, hydrogen has become a significant topic recently due to its dramatic potential as an energy carrier as well as environmental friendliness, while its storage is a challenge, thus the viability of storing this gas into a depleted coal seam was investigated in this study. In this application, coal permeability is a key parameter which determines how fast H2 can be injected and withdrawn again. However, it is expected to observe coal swelling when subjected to several gases, as a result of which coal permeability reduces significantly. Therefore, chapter 7 presents a research article, in which H2 gas is injected into a coal core and dynamic permeability is measured, while imaging the core via x-ray micro-tomography at reservoir conditions. Importantly, no changes in coal cleat morphology or permeability were observed in this study. This research thus suggests that H2 geo-storage in deep coal seams is feasible from a fundamental petro-physical perspective.

La chimie supramoléculaire est un domaine qui suscite depuis quelques années un intérêt grandissant. Le domaine s’appuie sur les interactions intermoléculaires de façon à contrôler l’organisation moléculaire et ainsi moduler les propriétés des matériaux. La sélection et le positionnement adéquat de groupes fonctionnels, utilisés en combinaison avec un squelette moléculaire particulier, permet d’anticiper la façon dont une molécule interagira avec les molécules avoisinantes. Cette stratégie de construction, nommé tectonique moléculaire, fait appel à la conception de molécules appelées tectons (du mot grec signifiant bâtisseur) pouvant s’orienter de façon prévisible par le biais d’interactions faibles et ainsi générer des architectures supramoléculaires inédites. Les tectons utilisent les forces intermoléculaires mises à leur disposition pour s’orienter de façon prédéterminée et ainsi contrecarrer la tendance à s’empiler de la manière la plus compacte possible. Pour ce faire, les tectons sont munies de diverses groupes fonctionnels, aussi appelés groupes de reconnaissance, qui agiront comme guide lors de l’assemblage moléculaire. Le choix du squelette moléculaire du tecton revêt une importance capitale puisqu’il doit permettre une orientation optimale des groupes de reconnaissance. La stratégie de la tectonique moléculaire, utilisée conjointement avec la cristallisation, ouvre la porte à un domaine de la chimie supramoléculaire appelé le génie cristallin. Le génie cristallin permet l’obtention de réseaux cristallins poreux soutenus par des interactions faibles, pouvant accueillir des molécules invitées. Bien que toutes les interactions faibles peuvent être mises à contribution, le pont hydrogène est l’interaction prédominante en ce qui a trait aux réseaux cristallins supramoléculaires. La force, la directionnalité ainsi que la versatilité font du pont hydrogène l’interaction qui, à ce jour, a eu le plus grand impact dans le domaine du génie cristallin. Un des groupements de reconnaissance particulièrement intéressants en génie cristallin, faisant appel aux ponts hydrogène et offrant plusieurs motifs d’interaction, est l’unité 2,4-diamino-1,3,5-triazinyle. L’utilisation de ce groupement de reconnaissance conjointement avec un cœur moléculaire en forme de croix d’Onsager, qui défavorise l’empilement compact, permet l’obtention de valeurs de porosités élevées, comme c’est le cas pour le 2,2’,7,7’-tétrakis(2,4-diamino-1,3,5-triazin-6-yl)-9,9’-spirobi[9H-fluorène]. Nous présentons ici une extension du travail effectué sur les cœurs spirobifluorényles en décrivant la synthèse et l’analyse structurale de molécules avec une unité dispirofluorène-indénofluorényle comme cœur moléculaire. Ce cœur moléculaire exhibe les mêmes caractéristiques structurales que le spirobifluorène, soit une topologie rigide en forme de croix d’Onsager défavorisant l’empilement compact. Nous avons combiné les cœurs dispirofluorène-indénofluorényles avec différents groupements de reconnaissance de façon à étudier l’influence de l’élongation du cœur moléculaire sur le réseau cristallin, en particulier sur le volume accessible aux molécules invitées.
Supramolecular chemistry is a field of rapidly increasing interest in recent years. The field uses weak intermolecular interactions to control molecular organisation and therefore modulate the properties of materials. Adequate selection and positioning of functional groups, combined with a carefully selected molecular core to which the groups are attached, allows for the creation of molecules with a high degree of predictability in the way they will interact with their neighbours. This approach to the design and construction of materials, called molecular tectonics, is based on subunits called tectons (derived from the Greek word for builder), which use weak interactions to organise themselves in a predictable manner and generate novel supramolecular architectures. In favorable cases, the interactions can counter the general tendency shown by molecules to pack together in a compact manner. Instead, specific functional groups direct molecular recognition and help guide the process of auto-assembly. At the same time, the molecular core of the tecton is also of capital importance as it must allow an optimal orientation of the recognition groups. The molecular tectonics approach, used jointly with crystallisation, opens the door to new opportunities in crystal engineering. For example, crystal engineering now allows the logical creation of porous crystalline networks that can accept guest molecules. Although any type of weak interaction can hold such networks together, the hydrogen bond is favored for constructing porous supramolecular networks. The strength, directionality and versatility of the hydrogen bond accounts for its special importance in the domain of crystal engineering. A recognition group of particular interest in crystal engineering is the 2,4-diamino-1,3,5-triazinyl unit. This unit forms hydrogen bonds according to various standard motifs. The use of this recognition group, joined to molecular cores specifically designed to inhibit close packing, such as Onsager crosses, allows for the construction of supramolecular networks with high porosity, as shown by the behaviour of 2,2’,7,7’-tetrakis(2,4-diamino-1,3,5-triazin-6-yl)-9,9’-spirobi[9H-fluorene]. We present here an extension of previous studies of spirobifluorenyl cores by describing the synthesis and structural analysis of molecules with related dispirofluorene-indenofluorenyl cores. This new core offers the same characteristics as the spirobifluorenyl core, namely rigid topology and an Onsager cross molecular shape which are known to inhibit close packing. We have combined this core with a variety of recognition groups to verify the influence of the molecular core on the crystalline networks generated, particularly on the volume accessible to guest molecules.

碩士
國立成功大學
材料科學(工程)研究所
83
Thermal measurements were used to explore the porosity formation in cast alloy. In sand casting, the dimension of riser, and mold temperature of the castings were systematically varied obtain a wide range of thermal variations during the The Thermal variables together with changes of hydrogen content were correlated with the porosity content in the casting. The results show that small or without riser can cause non- directional solidification and negative thermal gradient and velocity values. During solidification, thermal gradient and solidification time increase and solidus velocity decreases with increasing dimension of riser. The porosity content was found to increase with decreasing thermal gradient and increasing solidus velocity and hydrogen content. Previous criterion of soundness unsoundness as a function of volume and freezing ratios is also to be dependent on the hydrogen content. An increase of hydrogen content moves the regime boundary upward and causes to produce sound casting more difficult, even for a casting designed with volume ratio and low freezing ratio.

The increasing spread of nanotechnology has led to the design of new materials that represent a potential solution for several issues such as gas storage and gas separation, shape/size selective catalysis, drug storage and delivery. Among those materials, nanoporous structures have gradually aroused the attention of the scientific community. This interest is witnessed by the increasing number of publications about novel porous materials constructed from the assembly of molecular building blocks such as metal-organic frameworks. The most recent examples are supramolecular porous frameworks. These architectures are built up through traditional noncovalent interactions such as hydrogen bonds, π-π interactions. Most recent discoveries have found a novel type of bond that involves the participation of a halogen atom. This type of interaction assumes the name of halogen bond and is highly directional and hydrophobic. These features can be exploited for the design of defined structures. The present work is focused on the description of several halogen organic frameworks among which some of them present robust porous architectures. The structures were obtained by combining the tetrafunctional XB acceptor hexamethylenetetramine with different halogen bond donors. The work is divided into three parts. The literature part gives a background about nanoporous materials and their evolution with a section dedicated to the description of the halogen bond. The experimental section describes the methods used to obtain the supramolecular architectures. The final part discusses the structures and the noncovalent interactions that have driven their assembly.
O contínuo avanço da nanotecnologia potenciou o desenvolvimento de novos materiais que apresentam soluções para variadas problemáticas, das quais são exemplos o armazenamento de gases e sua separação, a catálise seletiva e o desenvolvimento e entrega de fármacos. Devido às suas propriedades, os materiais nanoporosos estão a ganhar destaque, o que levou a um aumento do número de publicações ao longo dos últimos anos, sendo um dos exemplos mais recentes as estruturas supramoleculares porosas. Estas arquiteturas são construídas através de interações não covalentes, como as ligações de hidrogénio e interações π-π. Descobertas mais recentes evidenciam um novo tipo de interação que envolve a participação de um átomo de halogénio, a qual assume o nome de “ponte de halogénio” e é altamente direcional e hidrofóbica. O presente trabalho teve como objetivo a síntese e caracterização de uma série de halogen organic frameworks, resultantes da combinação entre um aceitador hexametilenotetramina e diferentes dadores de halogénio. O trabalho encontra-se dividido em três partes. A revisão bibliográfica transmite informações básicas acerca dos materiais nanoporosos e a sua evolução, bem como o princípio por detrás da “ponte de halogénio”. Por sua vez, a parte experimental descreve a metodologia utilizada para obtenção das estruturas supramoleculares em estudo. Por fim, a terceira secção incide sobre a discussão acerca das referidas estruturas e respetivas interações não covalentes que levam à sua construção.