A novel biodegradable ammonia control material was developed from steam exploded corn cob and its adsorption capacity was studied by packed column and titration method. The packed column studies showed that the maximum absorption capacities of the raw corn cob (RCC) and the steam exploded corn cob (SECC) were 10.45 mg NHB3B/gRCC and 59.80 mg NHB3B/gSECC respectively. However, the titration of the water slurries with a NHB4BOH showed that the capacity of the SECC was 14.4 times that of RCC. The large difference between the packed column (SECC/RCC = 5.7) and the slurry titration (SECC/RCC = 14.4) was probably because: (1) the initial ammonia reaction products blocked the pores of the SECC and reduced diffusion into the pore structure; (2) the ammonia gas flow rates were too high and therefore the gas did not penetrate the pores; (3) the gas contact time was below the equilibrium value; and (4) since interior pore surface area is usually larger than the external surface area of a particle, it appears the low column SECC/RCC ratio is due to reactions on the SECC particle surface whereas the slurry result was a combination of both. Fourier Transform Infrared, FTIR spectroscopy was conducted on RCC, SECC, ammonia adsorbed on RCC and ammonia adsorbed on SECC in the range 4000–700 cmP-1P. The FTIR bands in the region between 1500 and 2000 cmPâ 1P showed a considerable difference between RCC and SECC. When SECC was treated with ammonia, the carboxylic functional group peak at 1700 cmP-1P was reduced and a new peak was observed at 1584 cmP-1P. The adsorption, desorption test and the heat of adsorption results suggested combined physisorption and chemisorption of ammonia on SECC but chemisorption was found to play an important role in ammonia removal. The BET specific surface area of RCC was 3.4 m2/g whilst that SECC was less than 1 m2/g. Although SECC had a low surface area compared with RCC its adsorption capacity was found to be greater than that of RCC meaning the adsorption process is chemically controlled. Also, the pore size distribution showed that RCC exhibited both macroporosity and mesoporosity whilst SECC showed only mesoporosity. It is interesting to note that upon steam exploding RCC, the macropores within RCC collapsed to form more mesopores in SECC. The high uptake of SECC was determined to be its small pore width compared to that RCC. Simultaneous Differential Scanning Calorimetry, DSC and Thermal Gravimetric Analyzer, TGA, was used to determine the heat of adsorption of ammonia on SECC. The heat of adsorption of ammonia on SECC was 33.00 kJ per mole of NHB3B. This study shows that SECC could be potentially used to remove NHB3B from various emission sources. / Master of Science

This thesis presents an analysis method for determining the whipping response of a hull girder to underwater explosion (UNDEX) bubble pulse loading. A potential flow-based UNDEX bubble model capable of calculating the behavior of a migrating bubble for up to three pulses is developed. An approximate vertical plane ship vibration model is derived using fundamental beam theory by representing the ship as a free-free beam with varying cross-sectional properties along its length. The fluid-structure interaction is approximated using strip theory and the distant flow assumption. The most severe predicted whipping load conditions are applied to a MAESTRO finite element model of the ship as a quasi-static load case to determine the response of the structure to the whipping loads. The calculated hull girder bending moments are compared to the ultimate bending strength of the hull girder to determine if the girder will collapse. The analysis method is found to be a useful method for determining preliminary UNDEX-induced whipping design load cases for early-stage ship design. However, more detailed and accurate data is needed to validate and verify the predicted whipping responses. It is found that the most severe whipping loads occur as the result of an UNDEX event that occurs under the keel near midship and produces a bubble with a pulsation frequency similar to the natural vibration frequency of the ship in its third mode. Significant damage to the ship structure and hull girder collapse is possible as a result of these loads. / Master of Science

This thesis describes and assesses a simplified tool for modeling underwater explosion shock effects during early naval ship concept design. A simplified fluid model using Taylor flat-plate theory is incorporated directly into the OpenFSI module code in Nastran and used to interface with the structural solver in Nastran to simulate a far-field shockwave impacting the hull. The kick-off velocities and the shock spectra captured in this computationally efficient module is compared to results from a high-fidelity CASE (Cavitating Acoustic Spectral Element) fluid model implemented with the ABAQUS/Nastran structural solver to validate the simplified framework and assess the sufficiency of this very simple but, fast approach for early stage ship design. / Master of Science

Depuis plusieurs années déjà, nombre d’applications industrielles impliquant des nanomatériaux ont vu le jour mais les connaissances relatives aux dangers de ces nouveaux matériaux sont actuellement assez restreintes. Le développement de ces nouveaux produits ne pouvant se poursuivre sans une évaluation approfondie des risques pour l’environnement et au poste de travail, les dangers relatifs aux nanoparticules doivent être évalués. La toxicité potentielle de ces nouveaux matériaux est souvent mise en avant. Néanmoins, les risques d’incendie et d’explosion ne doivent pas être négligés. Centrées essentiellement sur les poudres de taille micrométrique, les données de la littérature ne permettent pas, en effet, à l’heure actuelle, d’évaluer la probabilité et la gravité d’une explosion de nanopoudres. Dans ce contexte, la sensibilité à l’inflammation et la sévérité d’explosion de nanomatériaux pulvérulents typiques ont été évaluées ainsi que la validité des appareillages et procédures standards, habituellement utilisés lors d’une telle démarche. Enfin, la méthodologie adoptée afin d’évaluer les risques d’inflammation et d’explosion d’une installation de production de nanopoudres et de sécuriser au mieux la santé des travailleurs exposés aux nanoparticules est illustrée aux travers de deux exemples. Cette démarche pourra servir de base à de futures analyses de risques concernant les produits nanostructurés, exercice qui va devenir indispensable et de plus en plus fréquent au vu du contexte économique et réglementaire / In the industrial and research fields, nanomaterials provides a growing interest and many industrial applications have already been developed in the last years. However, knowledge about the hazards related to these new materials is currently limited. As safe nanomaterial production cannot be permitted without a deeper evaluation of environmental and occupational hazards, hazards related to nanoparticles have to be evaluated. One often thinks about the potential toxicity of nanoparticles. However, dust fire and explosion should not be neglected when the dusts are combustible, which may often be the case. So far, literature studies concerning the evaluation of explosion and flammability risks of powders were essentially carried out on micron-sized materials and do not enable in fact to evaluate fire and explosion risk probabilities and gravities of nanopowders. The main goal of this work is to study explosion and ignition risks related to nanopowders. In particular, the evaluation of the explosion sensitivity and severity of typical nanomaterials has been studied as well as the validity of the existing analytical and methodological tools designed to evaluate dust ignition and explosion hazards. This work also deals with the methodology applied to a plant and to a laboratory in order to define the best safety barriers which were positioned to ensure the best occupational safety level to all workers and evaluate in a good way the ignition and explosion risks related to the use and production of fluffy nanomaterials. This work will certainly help risk engineers concerned about the handling and the production of combustible nanopowders.

Plusieurs évènements astrophysiques comme les novae, les supernovae de type Ia (SNeIa) et les sursauts X sont le résultat d'une combustion thermonucléaire explosive dans un plasma stellaire. Les supernovae comptent parmi les objets astrophysiques les plus fascinants tant sur le plan théorique que sur celui des observations. Au moment de l'explosion, la luminosité d'une supernova peut égaler celle de l'intégralité des autres étoiles de la galaxie. On admet aujourd’hui que les SNeIa résultent de l'explosion thermonucléaire d'une étoile naine blanche, un objet dense et compact composé de carbone et d'oxygène. Divers chemins évolutifs peuvent conduire à l’explosion de la naine blanche si celle-ci est membre d’un système stellaire binaire. Néanmoins, la nature du système binaire, les mécanismes d'amorçage et de propagation de la combustion thermonucléaire ainsi que le rapport carbone/oxygène au sein de l'étoile compacte ne sont pas encore clairement identifiés à ce jour. En ce qui concerne l’écoulement réactif, on invoque ainsi une détonation (Modèle sub-Chandrasekhar), une déflagration ou la transition d'une déflagration vers une détonation (Modèle Chandrasekhar). La détonation semble donc jouer un rôle prépondérant dans l'explication des SNeIa. Les difficultés de modélisation des détonations proviennent essentiellement (i) de la libération d'énergie en plusieurs étapes, de l’apparition d’échelles de temps et de longueurs caractéristiques très différentes (ii) des inhomogénéités de densité, de température et de composition du milieu dans lequel se propage le front réactif et qui donnent naissance aux structures cellulaires et autres instabilités de propagation du front (extinctions et réamorçages locaux). En plus de celles citées ci-dessus, deux autres difficultés majeures inhérentes à l'étude de ce mode de propagation dans les plasmas stellaires sont rencontrées : la complexité de l’équation d’état astrophysique et la cinétique nucléaire pouvant impliquer plusieurs milliers de nucléides couplés par plusieurs milliers de réactions. Ainsi, les premiers travaux impliquant une combustion thermonucléaire explosive ont été réalisés sur bases d'hypothèses simplificatrices comme l'équilibre nucléaire statistique instantané des produits de réactions ou l'utilisation d'un réseau réduit à une dizaine d'espèces nucléaires. Dans tous ces travaux, la détonation est assimilée à une discontinuité totalement réactive (détonation de Chapman-Jouguet ou CJ). La résolution de l'onde de détonation nécessite l'étude détaillée du processus nucléaire se déroulant dans la zone de réaction. Malheureusement, les supports de calculs actuels ne permettent pas encore ce type de simulations pour les détonations astrophysiques. Le modèle ZND qui constitue une description unidimensionnelle stationnaire de l’écoulement (plan ou courbé) constitue une excellente approximation de la réalité. Notre travail réexamine les résultats des calculs des structures des ondes de détonations stellaires dans les conditions de température, de densité et de composition envisagées dans les travaux de ce type (détonation CJ et ZND) réalisés jusqu’à présent mais avec une équation d’état appropriée aux plasmas stellaires et une cinétique nucléaire nettement plus riche ; le plus grand réseau jamais utilisé pour ce genre d’études (333 noyaux couplés par 3262 réactions), prenant en compte les données les plus récentes de la physique nucléaire (vitesses de réaction et fonctions de partition)./Several astrophysics events like novae, supernovae and X burts, result from an explosive thermonuclear burning in stellar plasma. Type Ia Supernovae (SNeIa) count amoung the most fascinating stellar objects, they can be more brighter than an entire galaxy. Astrophysic works show that SNeIa may result from a thermonuclear explosion of a compact and dense star called carbon-oxygen white dwarf. The ignition stage and the propagation mode of the thermonuclear combustion wave are not identified yet. The Deflagration-to-Detonation Transition process (or "delayed detonation") sims to give the best overall agrements with the observations : detonations can play appart in SNeIa events. Simulating thermonuclear detonations count same difficults. The most important are the burning length scales that spent over more than ten oders of magnitud, the nuclear kinetics that involve thousands of nuclids linked by thousands of nuclear reactions and the stellar plasma equation of state (EOS). Hydrodynamical simulations of detonation use very simplified ingedients like reduced reactions network and asymptotic EOS of completely electron degenerate stellar plasma. Our work is the modelling of these detonations using more representative EOS of the stallar plasma that includs ions, electrons, radiation and electron-pistron pairs. We also use a more detailed kinetic network, comprising 331 nuclids linked by 3262 capture and photodisintegration reactions, than those usualy employed.

Atmospheric monitoring of radionuclides as part of the International Monitoring System requires the capability to differentiate between a radionuclide signature emanating from peaceful nuclear activity and one emanating from a well-contained underground nuclear explosion. While the radionuclide signatures of nuclear weapons are generally well known, radionuclides must first pass through hundreds of meters of earth to reach the surface where they can be detected and analyzed. Less well known is the affect that subsurface vertical transport has on the isotopic signatures of nuclear explosions. In this work, a model is developed, and tested, simulating the detonation of a simple underground nuclear explosion and the subsequent vertical transport of resulting radioxenon to the surface. First, the fast-fission burn of a fissile spherical core surrounded by a layer of geologic media is modeled, normalized to 1 kton total energy. The resulting source term is then used in the testing and evaluation of the constructed vertical transport model, which is based on the double-porosity model of underground fluid transport driven by barometric pumping. First, the ability of the vertical transport code to effectively model the underground pressure response from a varying surface pressure is demonstrated. Next, a 100-day simulation of the vertical migration of a static source is examined, and the resulting cumulative outflow of roughly 1% initial inventory outflow per cycle is found to closely follow the analytical predictions. Finally, calculated radioxenon source terms are utilized to model the resulting vertical transport and subsequent surface outflow. These results are found to be consistent with the physical expectations of the system, and lastly a cursory sensitivity analysis is conducted on several of the physical parameters of the model. The result is that the vertical transport model predicts isotopic fractionation of radioxenon that can potentially lie outside of currently accepted standard bounds. / text

On s'intéresse à la fragmentation d'objets cohésifs au travers d'un ensemble d'expériences modèles. Dans une première expérience, on force l'extension radiale d'un anneau formé de grains cohésifs (billes magnétiques ou billes de polymères liées par des ponts liquides). Sous l'effet de l'extension, les grains se séparent, puis, à cause de la cohésion, ils entament une dynamique d'agrégation qui conduit à la formation de fragments de tailles diverses. On montre que la distribution des tailles de fragments ainsi formés converge vers une loi de distribution Gamma et on propose un modèle expliquant l'évolution auto-similaire de la distribution. Dans un deuxième temps, on introduit une distribution d'intensité des liaisons entre les grains. La fragmentation en présence de ces "défauts" conduit à une distribution des tailles de fragments plus large, mais dont la loi est conservée. Dans une dernière étude, une coque sphérique composée de liquide est forcée à s'étendre par la combustion d'un mélange de gaz réactif emprisonné à l'intérieur de celle-ci. La distribution des tailles des gouttes qui en résulte obéit à la même famille de lois de distribution que celles observées pour les anneaux composés de grains cohésifs. Dans cette dernière expérience, le rôle des défauts est joué par les instabilités hydrodynamiques se développant sur la surface de la coque liquide au cours de son extension. Ainsi la largeur de la distribution des tailles de gouttes dépend de la vigueur de l'extension de la coque liquide. / We are studying the fragmentation of cohesive objects through a set of model experiments. In a first experiment, we force the radial extension of a ring made of cohesive grains (magnetic beads or polymer beads bonded with liquid bridges). Because of the extension, the grains separate from each other, then, because of the cohesion, start an aggregation dynamic leading to the formation of fragments of different sizes. We show that the distribution of the fragment sizes formed in this way converge to a Gamma law distribution and we propose a model explaining the self-similar evolution of the distribution. On a second part we introduce a distribution of intensities of the bonds between the grains. The fragmentation in the presence of "defects" leads to a broader size distribution, with the same law. In a last study, a spherical shell composed with liquid is forced to extend by the combustion of a reagent mixture of gas confined inside. The drop size distribution observed is conform to the same family of distribution laws found for the rings composed with cohesive grains. In this last experiment the role of defects is played by the hydrodynamic instabilities developing on the surface of the liquid shell under extension. Thus the broadness of the drop size distribution depends on the strength of extension of the liquid shell.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21373号 / 工博第4532号 / 新制||工||1706(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 前 一廣, 教授 河瀬 元明, 教授 佐野 紀彰 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The use of lithium-ion batteries is something that is becoming more common in today’s society. They are found in a variety of electronic equipment such as mobile phones, laptops and tools. Several incidents have been reported due to lithium-ion batteries ending up in a state called thermal runaway. This in combination with the increasing demands for environmentally friendly and sustainable energy in the form of e.g. wind turbines and solar panels, can therefore lead to unforeseen consequences. Residual energy from wind or solar power can be stored in an energy storage, often a battery system of several interconnected lithium-ion batteries. In case of an incident in these storages where a large quantity of these batteries is located, there is a risk that an explosion will occur. This further leads to the interest if it’s possible to prevent an explosion with the help of mechanical ventilation.  The purpose of this report has been to investigate the reasons why these batteries are being able to cause an explosion, what gases are emitted in the event of a thermal runaway and how explosive they are. With the results given it’s possible to then perform calculations on ventilation capacity needed to maintain a non-explosive atmosphere. This was carried out through a literature study of currently available research combined with information from various authorities, hand calculations and calculations in Excel.  With the results of the literature study, it can be stated that the battery cell consisting of the cathode material lithium-nickel-manganese-cobalt oxide (NMC) is most reactive. The most common gases emitted from these cells during thermal runaway are hydrogen, carbon monoxide, carbon dioxide, methane, ethylene and ethane. These gases are also the most common gases during thermal runaway when the battery consists of a different cathode material, but the distribution may look different. All of these gases, with the exception of carbon dioxide, are flammable and can contribute to an explosive atmosphere.  Three different scenarios are developed where thermal runaway is assumed to take place at a battery cell inside battery storages of different sizes: two container-based energy storage and one battery storage for home use located in a garage space. In these respective scenarios, a certain number of cells are assumed to be in thermal runaway. The lower flammability limit for the ventilated gas mixture is determined to 8,53% based on the amount of emitted gas and the distribution of it due to thermal runaway. With the knowledge of the lower flammability limit of the emitted gas mixture, as well as other available data from each scenario, the desired capacity for ventilation is calculated at 0,23 m3/s for the two container-based battery storages and at 0,035 m3/s for the battery storage located in the garage space. If this capacity of the ventilation is present when thermal runaway occurs, it means that the concentration of combustible gases should remain below the lower flammability limit. It is worth noting that these calculations were performed to some extent based on assumptions and may therefore be judged more as approximate rather than exact.  The conclusions drawn by the performed calculations are that mechanical ventilation is a potential alternative to ensure that the atmosphere in a battery storage doesn’t become explosive if a thermal runaway occurs in the battery cells.

Les risques importants d'inflammation de "nuages de poussières" en milieu industriel ainsi que l'entrée en vigueur de nouvelles normes (telles que les directives ATEX) font qu'il est aujourd'hui essentiel, pour les exploitants, de quantifier le danger représenté par leurs activités. Cette étude traite le cas des poussières d'aluminium et plus particulièrement l'influence de leur état d'oxydation sur les seuils d'amorçage par arc électrique. Un dispositif d'inflammation comprenant un système original de génération d'arc électrique à puissance constante a été mis au point spécifiquement pour ce travail. Une méthode statistique de traitement a été adaptée et utilisée afin d'évaluer des énergies d'inflammation conduisant à une probabilité d'amorçage de 50%. Une procédure d'oxydation contrôlée des poudres d'aluminium, ainsi que leur caractérisation physico chimique, est présentée. La croissance des seuils d'inflammation avec le taux d'oxydation des produits testés a ainsi pu être mise en évidence. Dans un second temps, des mesures de vitesse apparente de flamme ainsi que des relevés de pression dans les premiers instants de l'explosion ont été réalisés. Ces mesures expérimentales seront confrontées aux résultats obtenus à l'aide d'un modèle numérique permettant de relier l'évolution de la pression dans la chambre à la vitesse de propagation de la flamme.