Dans le but de réduire la consommation en carburant, les émissions de CO2 et les polluants tout en maintenant le haut rendement des moteurs, de nouveaux modes de combustions ont été étudiés et sont d’excellents candidats pour remplacer les moteurs conventionnels. En particulier, le mode HCCI a montré une excellente aptitude pour répondre à ces objectifs. Néanmoins, en dépit de ses avantages, de nombreux challenges sont à surmonter avant de permettre le développement de tels moteurs. Parmi eux, obtenir un contrôle efficace de la totalité de ce processus de combustion sur un large domaine d’utilisation demeure le principal défi. Ces travaux de thèse s’intéressent à l’utilisation des espèces chimiques oxydantes comme un moyen robuste de contrôle de la combustion HCCI. En raison de ces fortes propriétés oxydantes, l’ozone a été la principale molécule étudié. De plus, son intérêt est renforcé par le fait que l’ozone peut être produit au sein d’un véhicule au moyen de petits générateurs, mais cela peut aussi produire des oxydes d’azote. Ces recherches ont été effectuées au moyen d’un banc moteur monocylindre HCCI et couplées avec des simulations de cinétique chimique. Les deux principaux objectifs ont été : (1) Evaluer le potentiel d’utilisation d’un générateur d’ozone pour contrôler la combustion HCCI. L’impact de plusieurs espèces chimiques oxydantes, ozone and NOx, a été étudié sur la combustion de l’isooctane. De plus, un contrôle dynamique a été mis en place avec succès. (2) Comparer l’influence de l’ozone sur la combustion de l’isooctane et de carburants alternatifs. Des carburants à forte teneur en méthane et des alcools ont été étudiés en raison de leur forte résistance à l’autoinflammation et de leur structure chimique. / To reduce the fuel consumption, CO2 emissions and pollutant emissions while keep improving thermal efficiency of engines, alternative combustion modes are being investigated as good candidates to replace spark-ignited and diesel engines. In particular, Homogeneous Charge Compression Ignition (HCCI) engines have proven their potential to meet these requirements. However, despite of these advantages, several challenges remain to be addressed prior to the widespread implementation of HCCI engines. Among them, the control of the overall combustion process in such an engine over the full operating range is still considered as the main challenge to overcome. The present work introduces the use of oxidizing chemical species seeded in the intake system as a robust control technique for HCCI combustion process. In particular, ozone was examined due to its strong oxidizing characteristics. Moreover, ozone can be easily produced on-board a real vehicle from the intake oxygen thanks to small ozone generators, but can also lead to the production of NOx. Investigations were carried out using a single-cylinder HCCI engine and kinetics computation analysis. The two main objectives of this work are: (1) Evaluate the potential of using ozone generator to control the HCCI combustion. Along these lines, the interaction between NOx and ozone was investigated for isooctane as fuel and a real time control of the HCCI combustion was implemented and successfully tested. (2) Compare the influence of ozone on the combustion of isooctane and alternative fuels. Methane-based fuels (methane/propane and methane/hydrogen mixtures) and alcohols (methanol, ethanol, n-butanol) were selected due to their higher resistance to autoignition and their different chemical structure.

Current research in CI combustion aims to reduce PM and NOx emissions by controlling mixture homogeneity. Low CN fuels are suitable due to their auto-ignition resistance, but the in-cylinder mixture stratification level must be carefully visualised and controlled. Numerous diagnostic techniques exist for imaging the in-cylinder hydrocarbon species concentration. Tomographic techniques based on spectroscopic modalities are minimally-intrusive and able to target species of interest even in multi-component fuel blends. The high-speed CST technique applied in this work is based on the NIRAT modality. A number of collimated LASER beams at 1700nm traverse the optically accessible engine combustion chamber and are spectroscopically absorbed by the first overtone of the C-H stretch bond. Non species-specific attenuation mechanisms are suppressed by a DWR scheme utilising a reference wavelength at 1651nm. Ratiometric data is used to tomographically reconstruct the spatially-varying fuel concentration. In this work the first application of NIRAT on a commercial CI engine is presented, using instrumentation capable of imaging 13 frames/CAD at 1200rpm using a 31-beam array. A novel method was developed to experimentally quantify the tomography system’s non-uniform spatial resolution. The method was applied in laboratory experiments involving free-space propane plumes and a map of the spatial resolution was created. The spatial resolution varies between 4mm and 14mm. The mean of 9mm is 72% better than previous estimates in the literature. Regions of poor performance correlated with non-uniformities in the sensitivity matrix, indicating that a regular beam array may contribute towards more accurate and objective reconstructions of unknown concentrations. The characterised tomography system was installed on an optically-accessible Volvo D5 CI engine. The optically-inaccessible CAD region achieved was ±18CAD, a reduction of ±12° from previous works. The vibration-tolerance of the optical access system was verified, concluding that the initial alignment of the beams is the dominant factor that determines beam integrity after prolonged engine operation. The behavior of individual beams was studied, finding strong cycle-to-cycle correlation of the anomalies present. This was exploited to develop a novel, robust analysis algorithm to process the engine data. The algorithm achieved a standard deviation of <10% of the maximum pk-pk magnitude of the transmission signal in the fuel vapour phase. The system was applied to qualitatively visualise the mixing of a 50/50% blend of iso-/n-dodecane in a motored, nitrogen-aspirated engine under a range of operating conditions. A study by simulation of the decomposition of n-dodecane concluded that only 0.492% of the quantity injected is pyrolytically converted during a compression stroke. Spray-phase imaging was not possible due to severe reduction of the optical throughput, lasting for 8-15 CAD for a lean mixture and for 15-30 CAD for a rich mixture. Vapour-phase reconstructions using the enhanced iterative Landweber algorithm were successful in resolving rich fuel pockets consistent with the injection pattern. It was shown that the degree of mixture homogeneity at TDC is dependent upon the initial intake temperature. PLIF was used to cross-validate the NIRAT reconstructions. Localisation of the features reconstructed with NIRAT was excellent, with a maximum angular deviation of ±10°. A swirl motion of the mixture by 1°/CAD was observed using both techniques, confirming the features previously observed in the NIRAT reconstructions. In conclusion, NIRAT has been, for the first time, successfully applied for in-cylinder fuel distribution imaging in a CI engine. The results, created using an original data analysis algorithm, were successfully cross-validated using PLIF. A novel spatial resolution quantification method was formulated and used to characterise the tomography system. The numerous findings and learning points from the individual stages of this work will be used to advance the field of combustion diagnostics as well as contribute towards the development of advanced in-cylinder tomographic imaging systems.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20393号 / 工博第4330号 / 新制||工||1671(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 村田 靖次郎, 教授 小澤 文幸, 教授 近藤 輝幸 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

De nombreux travaux indiquent qu’il est important d’étudier les impacts physico-chimiques de la convection profonde tropicale. Nous avons utilisé le modèle méso-échelle 3D non-hydrostatique CATT-BRAMS pour étudier le transport de traceurs dans la troposphère tropicale au-dessus de l’Amérique du Sud. J’ai effectué une validation de l’outil en complément d’une étude en saison sèche et dans les basses couches menée au CPTEC (Brésil). Les résultats obtenus dans ces travaux indiquent un comportement météorologique globalement correct. Le transport en résultant montre une sur-estimation du transport d’espèces chimiques dans la moyenne troposphère et une sous-estimation dans la haute troposphère. Cela vient d’un déclenchement trop fréquent de la convection restreinte, de la paramétrisation de la convection profonde et de la représentation de leurs interactions. Une adaptation du modèle pour la saison humide est nécessaire. A l’échelle locale des difficultés venant d’une sensibilité importante de la paramétrisation au relief sont rencontrées. Le CATT-BRAMS évolue vers un modèle avec chimie, le C-CATT-BRAMS. Les premiers résultats obtenus indiquent un fort impact de l’initialisation et des conditions aux limites pour les espèces NO et O3. Quelques soient l’initialisation ou les conditions aux limites utilisées, on observe une augmentation du rapport de mélange de ces espèces au cours du temps. Cela peut provenir d’une sur-estimation des émissions `a la surface dans le modèle, en particulier pour les méga-cités. Il est important de poursuivre la validation de cet outil afin de pouvoir étudier l’impact physico-chimique de la convection profonde tropicale avec ce modèle. / Many works show it is important to study the phyical and chemical impacts of tropical deep convection. We used the 3D mesoscale non-hydrostatic model CATT-BRAMS to study the tracers transport in the tropical troposphere above South America. I validated the tool parallel to a study done in CPTEC (Brazil) for the dry season and in the lower troposphere. The results obtained in this work indicate a globaly correct meteorological behaviour. The associated transport show an over estimation of the chemical species transport in mid-troposphere and an under estimation in the upper troposphere.This comes from a to frequent triggering of shallow convection, from the deep convection scheme and from the representation of their interactions. An adaptation of the model for the wet season is necessary. At local scale, difficulties because of a high deep convection scheme sensitivity to the orography are encountered. The CATT-BRAMS model evolve to a model with chemistry, the C-CATT-BRAMS. The first results obtained indicate a strong impact of initialisation and boudary conditions on species NO and O3. Whatever be the initialisation or the boundary conditions, we observe an increase of the mixing ratio along time for these species. This can come from an over estimation of surface emissions in the model, especialy for megacities. It is important to continue the validation of this tool in order to be able to study the physical and chemical impacts of tropical deep convection with this model.

Made available in DSpace on 2016-12-12T20:25:12Z (GMT). No. of bitstreams: 1 Diego da Silva.pdf: 2316377 bytes, checksum: 8cdc8aef19b579ce777e88c236323f74 (MD5) Previous issue date: 2015-12-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In practical applications related to the drying process is absolutely essential to understand the basic echanism of mass transfer of chemical species by convection. Once understood this physical phenomenon, it is possible to propose techniques to increase the convective mass transfer coefficient of the chemical species in order to enhance or control the drying. Within this context, the main objective of this study was to develop, validate and apply a numerical simulation tool for the study of the turbulent flow of a binary mixture (air-water vapor) inside the channels. The numerical method was developed using finite difference equations being discretized by central differences in co-located mesh. Artificial dissipation terms have been introduced to control the roblem of odd-even decoupling and minimize numerical instabilities. Because the flow is turbulent, the turbulence model type high Reynolds_ &#603;, since the industrial applicability of the model was used. The physical study was to evaluate drying important parameters, namely: (i) determining the rates of mass transfer of chemical species on the surface of the channels (solid / gas interface) in problems of forced convection; (ii) analyzing the effects of parameters / important characteristics of the flow of the mixture over a drying process. The results established that the mass transfer of the chemical species to the flow channel wall is directly affected by parameters considered, particularly in the entrance region and the channel region resulting in recirculation. / Em aplicações práticas relacionadas ao processo de secagem é absolutamente essencial compreender o mecanismo básico da transferência de massa da espécie química por convecção. Uma vez compreendido este fenômeno físico, é possível propor técnicas para aumentar o coeficiente convectivo de transferência de massa de forma a intensificar ou controlar a secagem. Dentro deste contexto, o principal objetivo deste trabalho foi desenvolver, validar e aplicar uma ferramenta de simulação numérica para o estudo do escoamento turbulento de uma mistura binária (ar-vapor d água) no interior de canais. O método numérico foi desenvolvido em diferenças finitas, sendo as equações de governo discretizadas em diferenças centrais em malha co-localizada. Foram introduzidos termos de dissipação artificial para controlar o problema do desacoplamento par-ímpar e minimizar instabilidades numéricas. Devido o escoamento ser turbulento, foi utilizado o modelo de turbulência do tipo k &#8722; &#603; alto Reynolds, visto a aplicabilidade industrial do modelo. O estudo físico realizado consistiu em avaliar parâmetros importantes da secagem, a saber: (i) determinação das taxas de transferência de massa da espécie química na superfície dos canais (interface sólido/gás) em problemas de convecção forçada; (ii) análise dos efeitos de parâmetros/características importantes do escoamento da mistura sobre um processo de secagem. Os resultados obtidos estabeleceram que a transferência de massa da espécie química das paredes do canal é diretamente afetada pelos parâmetros considerados, principalmente na região de entrada do canal e em regiões que resultam em recirculação.

Este estudo tem como objetivo estudar o fósforo total e as especiações de fósforo nos sedimentos superficiais associados aos processos biogeoquímicos em dois sistemas estuarinos, na plataforma continental sudeste e na região polar antártica. Amostras de água de fundo foram coletadas em dois períodos sazonais (verão-inverno) nos estuários sob diferentes graus de impacto ambiental antrópico. A metodologia de extração das frações de (SEDEX) aplicada para obter as especiações químicas de fósforo foi testada com padrões certificados antes das análises. Os resultados foram reprodutivos e a eficiência da extração foi aceitável. As concentrações das espécies químicas de fósforo sedimentar nos dois estuários mostraram diferenças entre os setores seguindo as características granulométricas, influência da maré, condições redox das águas de fundo bem como, as ações antrópicas reveladas pelos dados quantitativos e qualitativos. Uma influência sazonal mínima foi observada. No caso da plataforma sudeste, altos valores de matéria orgânica foram observados em núcleos ao longo da plataforma, junto às estações externas das radiais de Santos e Ilha Grande mostrando uma diferenciação acompanhada pelas frações de fósforo orgânico e carbono orgânico. Nas demais radiais, altos valores de CaCO3 foram observados nas estações mais externas. Na Baía do Almirantado as frações predominantes foram P mineral, P detrítico, P-ligado à apatita autigênica, sendo que a forma orgânica foi baixa e associada a baixos valores de carbono orgânico. A quantificação e distribuição das espécies de fósforo nos sedimentos constituem importante ferramenta para compreender o ciclo biogeoquímico do fósforo e dos demais nutrientes nos ecossistemas marinhos. / This work aims to study the total and chemical species of phosphorus in the surface sediments associated to the biogeochemical processes in two estuarine systems, the southeastern continental shelf and Antarctic polar region. Bottom water samples were collected in two seasonal periods (summer-winter) in the estuaries under different degrees of environmental anthorpic impacts. The fraction extraction methodology (SEDEX) applied to obtain the chemical phosphorus species was tested in relation to the certified standards before analyses. The results were reproductive and the extraction efficiency was acceptable. The chemical species concentrations of sedimentary phosphorus in the two estuarine systems showed differences between sectors following the granulometric characteristics, tide influence, redox conditions of the bottom waters as well as anthropic actions revealed by quantitative and qualitative data. A minimum seasonal influence was observed. In the case of eastern continental shelf, high values of organic matter were found in nuclei distribution along the platform in the external stations of Santos and Ilha Grande radials showing a differentiation accompanied by organic phosphorus and C org., fractions. In the other radials high CaCO3 values were observed in the external stations. In the Admiralty Bay the predominant fractions were detrital apatite and authigenic/biogenic apatite, being that organic form was low, linked to low values of organic carbon. The quantification and distribution of P species in the sediments constitute important tools to understand the P and the other nutrient biogeochemical cycles in the sea ecosystems

Este estudo tem como objetivo estudar o fósforo total e as especiações de fósforo nos sedimentos superficiais associados aos processos biogeoquímicos em dois sistemas estuarinos, na plataforma continental sudeste e na região polar antártica. Amostras de água de fundo foram coletadas em dois períodos sazonais (verão-inverno) nos estuários sob diferentes graus de impacto ambiental antrópico. A metodologia de extração das frações de (SEDEX) aplicada para obter as especiações químicas de fósforo foi testada com padrões certificados antes das análises. Os resultados foram reprodutivos e a eficiência da extração foi aceitável. As concentrações das espécies químicas de fósforo sedimentar nos dois estuários mostraram diferenças entre os setores seguindo as características granulométricas, influência da maré, condições redox das águas de fundo bem como, as ações antrópicas reveladas pelos dados quantitativos e qualitativos. Uma influência sazonal mínima foi observada. No caso da plataforma sudeste, altos valores de matéria orgânica foram observados em núcleos ao longo da plataforma, junto às estações externas das radiais de Santos e Ilha Grande mostrando uma diferenciação acompanhada pelas frações de fósforo orgânico e carbono orgânico. Nas demais radiais, altos valores de CaCO3 foram observados nas estações mais externas. Na Baía do Almirantado as frações predominantes foram P mineral, P detrítico, P-ligado à apatita autigênica, sendo que a forma orgânica foi baixa e associada a baixos valores de carbono orgânico. A quantificação e distribuição das espécies de fósforo nos sedimentos constituem importante ferramenta para compreender o ciclo biogeoquímico do fósforo e dos demais nutrientes nos ecossistemas marinhos. / This work aims to study the total and chemical species of phosphorus in the surface sediments associated to the biogeochemical processes in two estuarine systems, the southeastern continental shelf and Antarctic polar region. Bottom water samples were collected in two seasonal periods (summer-winter) in the estuaries under different degrees of environmental anthorpic impacts. The fraction extraction methodology (SEDEX) applied to obtain the chemical phosphorus species was tested in relation to the certified standards before analyses. The results were reproductive and the extraction efficiency was acceptable. The chemical species concentrations of sedimentary phosphorus in the two estuarine systems showed differences between sectors following the granulometric characteristics, tide influence, redox conditions of the bottom waters as well as anthropic actions revealed by quantitative and qualitative data. A minimum seasonal influence was observed. In the case of eastern continental shelf, high values of organic matter were found in nuclei distribution along the platform in the external stations of Santos and Ilha Grande radials showing a differentiation accompanied by organic phosphorus and C org., fractions. In the other radials high CaCO3 values were observed in the external stations. In the Admiralty Bay the predominant fractions were detrital apatite and authigenic/biogenic apatite, being that organic form was low, linked to low values of organic carbon. The quantification and distribution of P species in the sediments constitute important tools to understand the P and the other nutrient biogeochemical cycles in the sea ecosystems

Dans cette thèse, des structures MEMS de type micropoutre ont été conçues pour des applications capteurs. Un procédé de fabrication alternatif au silicium, associant la technique de sérigraphie à l'utilisation d’une couche sacrificielle (SrCO3), a été utilisé pour la réalisation de micropoutres piezoélectriques (PZT, matériau servant à la fois d’actionneur et de transducteur) dans un premier temps. Des tests de détection en phase gazeuse ont été réalisés avec et sans couche sensible avec succès à l’aide du mode de vibration non conventionnel 31-longitudinal. Le toluène a notamment pu être détecté à des concentrations voisines de 20ppm avec une couche sensible PEUT. D’autres espèces telles que l’eau, l’éthanol ou l’hydrogène ont été détectés sans couches sensibles afin de s’affranchir des contraintes liées à celle-ci (vieillissement notamment). Des tests préliminaires de caractérisation en milieu liquide ont également été réalisés avec dans l’optique la détection d’espèces en phase liquide. Par ailleurs, un capteur de force a été conçu et réalisé avec le même procédé de fabrication. Ce dernier est composé d’une micropoutre en matériau diélectrique sur laquelle est intégrée une piezorésistance servant à la transduction du signal associé à la déformation subie par la micropoutre. Des détections de force en mode statique (sans actionneurs) ont permis de caractériser les capteurs, notamment en termes de sensibilité, de gamme de force et de force minimale détectable ou encore de linéarité. / The project concerns the conception, fabrication and characterization of cantilever-type MEMS structures for sensors applications. An alternative process to silicon related ones, associating the screen-printing technique to a sacrificial layer (SrCO3), was used to realize piezoelectric cantilevers (PZT material utilized as actuator and transducer) in a first time. Detections in gas phase were performed successfully with and without sensitive layer thanks to the unusual 31-longitudinal vibration mode. Namely, we were able to detect toluene at concentrations as low as 20ppm with a PEUT sensitive layer. Other species like water, ethanol or hydrogen could be detected without sensitive layer in order to get rid of the sensitive layer-related issues (ageing for example). Preliminary characterizations were carried out in liquid phase in a view to perform liquid phase detection. Besides, a cantilever-based force sensor, fabricated thanks to the same fabrication process was designed. This last one integrates a piezoresistor allowing the transduction of the mechanical signal linked to the strain overcome by the microcantilever. Force detections in static mode (without any actuator) permitted the sensors’ characterization. Indeed, their sensitivity, force range, minimal detectable force and linearity were carried out.

PhDENV / Department of Ecology and Resource Management / See the attached abstract below