Les turbomachines actuelles ont atteint un niveau de maturité technique très élevé. De nouvelles architectures reposant sur des cycles thermodynamiques basés sur une combustion à gain de pression, comme la combustion à volume constant (CVC), ont le potentiel d’augmenter leur efficacité. Dans cette étude,une solution qui repose sur l’intégration dans une turbomachine de chambres de combustion à volume constant sans piston (CVCSP) est considérée. Les objectifs de ces travaux de thèse sont doubles : dans un premier temps de développer et de caractériser extensivement un nouveau dispositif (CV2) dédié à la Combustion à volume constant sans piston sur un cas de référence et, dans un second temps, de proposer à travers plusieurs études, une analyse de l’influence de l’aérodynamique et de la dilution sur les processus d’allumage et, plus généralement de combustion. Le dispositif CV2 permet la combustion aérobie en allumage commandé d’un mélange de propane ou de n-décane, injecté directement dans la chambre. Un point de référence est caractérisé en détail via : des mesures de champs de vitesse par PIV, de chimiluminescence pendant la combustion, une analyse 0D développée dans cette étude. La caractérisation détaillée de ce point de référence montre que le dispositif CV2 reproduit correctement une combustion à volume constant turbulente dans un mélange faiblement hétérogène en température et stratifié en composition, et ce sur un nombre de cycles permettant d’établir une convergence statistique raisonnable. Ces diagnostics et analyses sont employés dans 2 cas d’études pour caractériser successivement : l’influence de l’aérodynamique, via une variation de l’instant d’allumage, l’influence des gaz brûlés résiduels sur la combustion en allumage commandé et la stabilité cyclique, via une variation de la pression d’échappement.Dans un fonctionnement sans balayage, on montre que cette variabilité cyclique est liée au premier ordre à la variation de la dilution en gaz brûlé résiduel du mélange et à la vitesse locale. On montre notamment que, pour un mélange donné, il existe une corrélation statistique entre une vitesse statistique limite et la probabilité d’allumage moyenne. Pour représenter l’effet de pression dans un plénum en amont d’une turbine, on réalise une étude paramétrique sur la pression d’échappement. La dilution résultante, croissant avec la pression d’échappement, diminue la vitesse fondamentale de flamme et ralentit donc la combustion. Les niveaux de températures des gaz brûlés résiduels résultent des échanges de chaleur qui ont lieu sur toute la durée du cycle, de l’allumage du cycle N à celui du cycle N+1 suivant. Des extrapolations sur des cycles à température de paroi plus élevée et à échappement plus court montrent que l’adiabaticité du cycle est améliorée (de 20 %) et que l’effet de dilution en température est alors favorable à une vitesse de flamme turbulente qui est alors plus élevée. Un phénomène d’allumage par gaz brûlé résiduel est observé sur certains cycles de combustion. Ce phénomène est caractérisé dans des conditions favorables, i.e. faible richesse (0.66), allumage tardif et cycle plus court. Lors d’un allumage par gaz brûlés résiduels, un noyau de flamme se développe dans les zones présentant des gaz brûlés résiduels chauds et à basse vitesse autour du jet d’admission et se propage ensuite au reste du mélange identiquement à celui qui serait généré par allumage commandé.Ce travail prend place dans le cadre de la chaire industrielle CAPA sur la combustion alternative pour la propulsion aérobie financée par SAFRAN Tech, MBDA et l’ANR. / Current turbomachines have reached a very high level of technical maturity. Thermodynamic cycles based on pressure-gain combustion, such as constant volume combustion (CVC), feature a clear potential for efficiency improvement. The present study considers the integration in a turbomachine of piston-lessCVC chambers. The thesis work is twofold. First, a new experimental setup (CV2) dedicated to cyclic piston-less CVC is developed and thoroughly characterized on a reference operating point. Second, the influence of the aerodynamics and dilution on the processes of ignition and, in a larger sense, on combustion is discussed through dedicated studies. The CV2 device allows for the spark-ignited air-breathing combustion of a mixture of either propane orn-decane, directly injected into the chamber. A reference condition is characterized in details using: PIV velocity field measurements, chemiluminescence of combustion and a 0D modeling of the device. This detailed characterization evidenced that the CV2 combustion chamber successfully replicates, on a number of cycles allowing a reasonable statistical convergence, a turbulent deflagrative constant-volume combustion in a mixture stratified in composition. Those diagnostics and analyses are applied to 2 cases of study to characterize successively : the influence of the aerodynamics, through a variation of the ignition timing, the influence of the residual burnt gases on spark-ignited combustion and the cyclic stability, through a variation of the exhaust backpressure.Operating the device without scavenging of the combustion chamber, we show that the cyclic variability correlates strongly with both the variation of residual burnt gases dilution and the local velocity. Particularly, we show that for a given mixture, a correlation exists between a statistical velocity limit and the average probability of ignition. The effect of a plenum backpressure upstream of a turbine, downstream of the combustion chamber, is simulated by varying the exhaust system backpressure. The resulting dilution, which increases with the exhaust backpressure, diminishes the fundamental flame velocity of the mixture and slows down the combustion. The residual burnt gases temperature results from the integrated heat exchanges that happen during the total cycle duration starting from the end of combustion of cycle N, to the ignition of cycle N+1. Enhanced cycles, with an increased wall temperature and reduced exhaust duration, are extrapolated by 0D analysis. Those cycles evidence a reduction of the cumulated heat exchanges of up to 20 %. The resulting dilutionis more favorable to higher turbulent flame velocity thus to shorter combustion duration. A phenomenon of ignition induced by the residual burnt gases is observed on certain combustion cycles. This phenomenon is characterized in favorable conditions, i.e. fuel-lean equivalence ratio (0.66), late ignition and shortcycles. During an ignition by residual burnt gases, a flame kernel is ignited in areas where the still hot residuals burnt gases meet fresh gases in low-velocity areas around the intake jet. The ignition kernel then propagates to the rest of the mixture in a similar manner as if it was spark-ignited.This work is part of the CAPA Chair research program on Alternative Combustion modes for Air-breathing Propulsion supported by SAFRAN Tech, MBDAFrance and ANR (French National Research Agency).

No description available.

The goal of this study was to characterize the binding sites on the surface of wheat roots, Triticum turgidum, involved in the adsorption of protons and metals, and quantify the thermodynamic constants needed for a surface complexation model to predict metal binding. The adsorption of protons, Cd(II), Cu(II), and Ni(II) to the root surface as a function of pH and ionic strength in single metal exposure scenarios was quantitatively described using potentiometric titrations, batch metal adsorption experiments, and the least squares fitting program FITEQL. Model predictions from single metal exposures were compared to measured metal adsorption concentrations when roots were exposed to binary and ternary combinations of the metals. Proton dissociation was a function of three discrete monoprotic acid sites on the root surface with log proton dissociation constants of -4.50, -6.23, and -7.37 respectively, upon which varied ionic strength had no effect. The total proton binding capacities for the three sites were 2.58 x 10-4, 1.29 x 10-4, and 2.58 x 10-4 M, respectively. Metal complexation was best described by a two-site model having conditional stability constant log values of 3.04 and 3.30 for Cd(II), 3.21 and 3.25 for Cu(II), and 2.83 and 2.84 for Ni(II) at ionic strength 0.01M. At ionic strength 0.1 M the conditional stability constants log values were 2.37 and 3.36 for Cd(II), 3.11 and 2.56 for Cu(II), and 2.18 and 3.00 for Ni(II). When roots were exposed to binary or ternary mixtures of the metals, the two monoprotic acid single metal model did not provide ideal fits to the data indicating that adsorption in a metal mixture scenario cannot be considered additive and is dependent on the combination of metals present in the exposure environment. The experimentally determined proton dissociation constants and metal stability constants could be used in commercial geochemical speciation programs such as Visual MINTEQ to predict metal adsorption to plants. / Natural Sciences and Engineering Research Council of Canada, The Mining Association of Canada, Ontario Power Generation, Environment Canada.

The FT-Raman techniques were developed to quantify reactions that follow on mixing aqueous solutions of bis-(1,3-diaminopropane)diaquacobalt( III) ion ([Co(tn)2(0H)(H20)]2+) and p-nitrophenylphosphate (PNPP). For the development and validation of the kinetic modelling technique, the well-studied inversion of sucrose was utilized. Rate constants and concentrations could be estimated using calibration solutions and modelling methods. It was found that the results obtained are comparable to literature values. Hence this technique could be further used for the [Co(tn)2(0H)(H20)]2+ assisted hydrolysis of PNPP. It was found that rate constants where the pH is maintained at 7.30 give results which differ from those where the pH is started at 7.30 and allowed to change during the reaction. The average rate constant for 2:1 ([Co(tn)2(0H)(H20)]2+:PNPP reactions was found to be approximately 3 x 104 times the unassisted PNPP hydrolysis rate. / Chemistry / M. Sc. (Chemistry)

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / FundaÃÃo de Amparo à Pesquisa do Estado do Amazonas / Esta tese està composta de quatro partes distintas. Na primeira parte, vamos dar uma nova caracterizaÃÃo da esfera euclidiana como a Ãnica variedade Riemanniana compacta com curvatura escalar constante e admitindo um campo de vetores conforme nÃo trivial que à tambÃm Ricci conforme. Na segunda parte, provaremos algumas propriedades dos quase sÃlitons de Ricci, as quais permitem estabelecer condiÃÃes de rigidez desses objetos, bem como caracterizar as estruturas de quase sÃlitons de Ricci gradiente na esfera euclidiana. ImersÃes isomÃtricas tambÃm serÃo consideradas; classificaremos os quase sÃlitons de Ricci imersos em formas espaciais, atravÃs de uma condiÃÃo algÃbrica sobre a funÃÃo sÃliton. AlÃm disso, vamos caracterizar, atravÃs de uma condiÃÃo sobre o operador de umbilicidade, as hipersuperfÃcies n-dimensionais de uma forma espacial, com curvatura mÃdia constante, tendo duas curvaturas principais distintas e com multiplicidades p e n - p. Na terceira parte, provaremos um resultado de rigidez e algumas fÃrmulas integrais para uma mÃtrica m-quasi-Einstein generalizada compacta. Na Ãltima parte, vamos apresentar uma relaÃÃo entre a curvatura gaussiana e o Ãngulo de contato de superfÃcies imersas na esfera euclidiana tridimensional,a qual permite concluir que a superfÃcie à plana, se o Ãngulo de contato for constante. AlÃm disso, deduziremos que o toro de Clifford à a Ãnica superfÃcie compacta com curvatura mÃdia constante tendo tal propriedade. / This thesis is composed of four distinct parts. In the first part, we shall give a new characterization of the Euclidean sphere as the only compact Riemannian manifold with constant scalar curvature carrying a conformal vector eld non-trivial which is also Ricci conformal. In the second part, we shall prove some properties of almost Ricci solitons, which allow us to establish conditions for rigidity of these objects, as well as characterize the structures of gradient almost Ricci soliton in Euclidean sphere. Isometric immersions also will be considered, we shall classify almost Ricci solitons immersed in space forms, through algebraic condition on soliton function. Furthermore, we characterize under a condition of the umbilicity operator, n-dimensional hypersurfaces in a space form with constant mean curvature, admitting two distinct principal curvatures with multiplicities p and n - p. In the third part, we prove a result of rigidity and some integral formulae for a compact generalized m-quasi-Einstein metric. In the last part, we present a relation between the Gaussian curvature and the contact angle of surfaces immersed in Euclidean three-dimensional sphere, which allows us to conclude that such a surface is at provided its contact angle is constant. Moreover, we deduce that Clifford tori are the unique compact surfaces with constant mean curvature having such property.

A formação dos monoalquil carbonatos (MACs) em meio aquoso - produzidos pela reação de um álcool e bicarbonato foi investigada por eletroforese capilar (CE) com detecção condutométrica sem contato (C4D). Foram estudadas ao todo 29 substâncias, das quais 25 apresentaram formação de adutos aniônicos monocarregados e 2 delas, adutos aniônicos com dupla carga. A eletroforese capilar proporcionou a obtenção de medidas de propriedades físico-químicas. Através do tempo de migração, foram obtidos mobilidade, coeficiente de difusão e raio iônico hidratado. Para os n-álcoois de 1 a 5 átomos de carbono, os adutos apresentaram raio iônico hidratado entre 216 pm e 310 pm. Os MACs têm raio iônico proporcional ao do álcool gerador, sendo sistematicamente maiores devidos à anexação do grupo carbonato. Quando comparado a ácidos carboxílicos de cadeia carbônica similar, os MACs possuem menor raio iônico hidratado. A obtenção dos valores da cinética de formação e hidrólise foi possível pela utilização de dupla detecção condutométrica, a qual permitia determinar a concentração do MAC em dois momentos diferentes ao longo da coluna. Devido à impossibilidade de uma calibração direta - já que os sais de MACs se decompõem em água - foi introduzida uma nova técnica de calibração que dispensa o uso de uma solução padrão do analito em favor de uma com espécie de mobilidade similar. As constantes cinética e termodinâmica foram comparadas com aquelas disponíveis na literatura, mostrando boa concordância, como no caso dos adutos para o metanol e etanol (a 25 ºC em meio aquoso), cujos valores da constante termodinâmica sugeridos pela literatura são de 3,57 e 1,80, respectivamente, enquanto que os valores calculados em nosso trabalho são de 4,2 e 2,3, a 25ºC. De forma similar ao ácido carbônico, os ácidos alquilcarbônicos (ACAs) se decompõem em meio ácido, o que dificulta a determinação da verdadeira constante de dissociação. Ainda assim, estudos em pH de 3 a 9, permitiram estimar os valores de pKa dos ácidos derivados de metanol, etanol e propanol como estando algo abaixo de 4, o que estaria em acordo com o valor de 3,6 do ácido carbônico. A formação de MACs também foi observada para dióis, como o etileno glicol e polióis, como o glicerol e manitol. Foi também possível observar, por eletroforese capilar, a formação de adutos aniônicos monovalentes para açúcares, tais como a sacarose, glicose e frutose. Por fim, a pesquisa revelou a possibilidade da formação de adutos com dupla carga - os bis(carbonatos) - para alguns dióis: o 1,4-butanodiol e o 1,6-hexanodiol. Esta é a primeira vez que estas espécies foram observadas. Estes resultados sugerem a formação de adutos aniônicos para várias outras classes de compostos, as quais possuam a hidroxila na cadeia carbônica. Embora, em meio predominantemente aquoso, estas espécies não estejam em alta concentração, trata-se de um novo conjunto de espécies a serem consideradas quando se trabalha em condições propícias. / The formation of monoalkyl carbonates (MACs) in aqueous medium - resulting from an alcohol and bicarbonate - was investigated by using capillary electrophoresis with capacitively coupled contactless conductivity detection (C4D). Twenty nine substances were studied. The mono-charged anionic adducts were observed for 25 of them and double-charged species were observed for 2. Capillary electrophoresis allowed us to obtain some physical-chemical properties. The migration time was used to calculate the ionic mobility, coefficient of diffusion, and hydrodynamic radius. The radii ranged from 216 to 310 pm for the adducts formed from the n-alcohols of 1 to 5 carbon atoms, respectively. The MACs have radii proportional to the size of the alcohol, being systematically greater because of the attached carbonate group. When compared to carboxylic acids of similar carbonic chain, the MACs have smaller radii. The calculation of the kinetic constants was possible due to the double C4D detection, which allows quantitation of the MAC at two different moments along the capillary. Due to the decomposition of the MAC salt in water, a direct quantitation was not possible. Thus an indirect calibration approach was introduced, where the analyte is substituted by a stable species of similar mobility. Good agreement was obtained between the kinetic and thermodynamic constants obtained by this method and those ones available in literature. For instance, the methanol and ethanol adducts were 4.2 and 2.3 (at 25 ºC), respectively, while the literature\'s values are 3.57 and 1.80. Similarly to carbonic acid, the alkyl carbonic acids (ACAs) decompose in acid medium, which impairs the determination of the dissociation constant. Even so, studies from pH between 3 and 9 allowed us to estimate that the pKa values of the adducts for methanol, ethanol, and propanol are somewhat below 4, which is in agreement with the value 3.6 for the carbonic acid. MACs were also observed for diols and polyols as well as for sugars. Finally, double-charged species bis(carbonates) were formed with 1,4-butanediol and 1,6-hexanediol. This is the first time that these species are reported. Although the concentrations of these species are not high in an aqueous medium, they form a new set of substance to be considered in aqueous solution when the conditions are favorable.

This study aims at tackling some of the problems often encountered in photostability testing and liquid formulation development. Three anti-cancer drugs will be employed as models; Dacarbazine (DBZ) has well established photostability issues, Axitinib (AXI) and Sunitinib (SUT) are two new drugs only commercially available in solid dosage forms. In ethanol, the photokinetics of these drugs were well described by the newly proposed Φ-order kinetic mathematical model. This has confirmed the photoreversible character of AXI and SUT’s and unimolecular photoreaction of DBZ’s photodegradations. Also, the Φ-order kinetics is proven to describe them better than the usually used classic thermal reaction orders. In aqueous solution, the drugs were found to undergo thermal and photochemical complex degradations, involving at least 3 photoproducts. A new photokinetic approach has been proposed in this work to solving and unravelling the attributes of such complex mechanisms. For the first time, the quantum yields (QY) of the three drugs were determined and found to increase with irradiation wavelength. SUT’s QY were comparable in ethanol and water (QY460 = 0.02), DBZ was found to be more photoefficient in water (QY330 = 0.04 and 0.1, respectively) and AXI in water (QY330 = 0.06 and 0.03). Φ-order kinetics’ potential for the development of reliable actinometers of the three drugs, without prior knowledge of unknown reaction parameters, has also been established. A general equation to describe the isotherm of a (Gn:Hm) guest-host multicomponent complex was proposed in this work to palliate the lack of a strategy for characterising nanosponge-drug complexes. It provides information on both stiochiometry and association constant of the complex. The results indicate that hydrophobic AXI forms a 1:0.8 complex, indicating the possibility of multiple association sites and/or different types of binding. The newly developed AXI/nanosponge liquid formulation has significantly increased solubility (5000-fold) and thermal stability. Furthermore, the photostability of DBZ and SUT were considerably improved by using a strategy based on light-absorption competitors. Their initial velocities reduced from 10 and 3 s-1 (respectively) to 1 and 0.13 s-1. The successful application of these methods to the model anti-cancer drugs has set out new approaches that might be found useful for future treatments of photodegradation data, development of drug-actinometers and liquid formulations of drugs.

La pollution atmosphérique est une problématique urbaine majeure, avec des concentrations de polluants dépassant fréquemment les seuils de recommandations pour la santé. Les véhicules participent fortement à la pollution atmosphérique malgré l’intégration de systèmes de dépollution dans leur ligne d’échappement. L’objectif de ce travail de recherche était de caractériser les émissions primaires à l’échappement des véhicules ainsi que leur évolution physique en champ proche pour mieux comprendre la contribution des émissions primaires liées au trafic à la pollution atmosphérique urbaine. L’évolution des émissions a été étudiée dans une chambre de simulation atmosphérique qui a permis de simuler des conditions atmosphériques contrôlées.La première partie de ce travail était centrée sur les mesures d’émissions à l’échappement des véhicules récents qui sont ou seront majoritaires dans le parc automobile français dans les prochaines années. Pour cela, un échantillon de véhicules regroupant les principales technologies de dépollution commercialisées a été testé. Les gaz d’échappement émis par les véhicules ont été analysés lors de tests sur un banc à rouleau suivant différentes conditions de conduites. Les polluants soumis aux réglementations Européennes ont été mesurés, ainsi que certains composés non-réglementés par les normes Européennes mais dont la dangerosité a été mise en évidence par la communauté scientifique.La deuxième partie de ce travail se concentre sur l’évolution en champ proche des polluants particulaires dans les heures qui suivent leur rejet dans l’atmosphère. L’effet de la dilution soudaine des gaz en sortie de pot d’échappement a été étudié en utilisant une méthodologie innovante de prélèvement directement à l’échappement. Ensuite l’évolution des particules dans les premières heures après leur rejet a été étudiée dans une chambre de simulation atmosphérique de 8 m3, construite spécifiquement dans le cadre de cette thèse pour être couplé au banc à rouleau. / Air pollution is a major urban issue, with pollutant concentrations frequently exceeding health recommendations. Vehicles are highly involved in air pollution despite the integration of pollution control systems. The objective of this research is to characterise the primary exhaust emissions of vehicles and their physical evolution in the near field to better understand the impact of primary emissions related to traffic on urban air pollution. Emissions evolution was studied in an atmospheric simulation chamber with controlled atmospheric conditions. The first part of this work aims to determine the exhaust emissions of recent vehicles that are or will be major in the French car fleet in the coming years. A sample of vehicles grouping the main commercialised depollution technologies was tested on a chassis dynamometer according to different driving conditions and the emissions from their exhaust gas were analysed. The pollutants subject to European regulations were taken into account, as well as compounds not regulated by European standards but whose toxicity has been highlighted by the scientific community.The second part of this work focuses on the near-field evolution of particulate pollutants in the hours following their release into the atmosphere. The effect of the abrupt gas dilution at the end of the exhaust has been studied using an innovative sampling methodology directly at the exhaust of the vehicles. Then the evolution of the particles in the first hours after their rejection was studied in an atmospheric simulation chamber of 8 m3, built specifically within the framework of this thesis to be coupled with the dynamometer.

Diploma thesis is focused on mechanical properties testing by small punch test and comparison of these properties with mechanical properties obtained by conventional tensile test. Steels P92 and AISI 316L in a shape of discs were tested. There were determined values of mechanical properties, namely yield stress, and ultimate tensile stress, obtained by the small punch test – constant deflection rate in this thesis. Values of initial stress and residual stress were evaluated from relaxation small punch test. Mechanical properties obtained by small punch test – constant deflection rate, and small punch test – relaxation, respectively, are compared with mechanical properties obtained by conventional tensile test, and relaxation tensile test, respectively. There were proposed own empirical relationships for restatement of mechanical properties obtained by small punch test to mechanical properties obtained by conventional tensile test in the thesis. Relatively small agreement of results obtained by small punch test, and conventional tensile test was demonstrated by a comparison. Application of own empirical relationships resulted in better agreement. Very good agreement of results of small punch test – relaxation, and relaxation tensile test was shown by their comparison.

Proline-rich antimicrobial peptides (PrAMPs) are promising candidates to treat bacterial infections. The designer peptide ARV-1502 exhibits strong antimicrobial effects against Enterobacteriaceae both in vitro and in vivo. Since the inhibitory effects of ARV-1502 reported for the 70 kDa heat-shock protein DnaK do not fully explain the antimicrobial activity of its 176 substituted analogs, we further studied their effect on the bacterial 70S ribosome of Escherichia coli, a known target of PrAMPs. ARV-1502 analogues, substituted in positions 3, 4, and 8 to 12 (underlined) of the binding motif D3KPRPYLPRP12 with aspartic acid, lysine, serine, phenylalanine or leucine, were tested in a competitive fluorescence polarization (FP) binding screening assay using 5(6)-carboxyfluoresceinlabeled (Cf-) ARV-1502 and the 70S ribosome isolated from E. coli BW25113. While their effect on ribosomal protein expression was studied for green fluorescent protein (GFP) in a cell-free expression system (in vitro translation), the importance of known PrAMP transporters SbmA and MdtM was investigated using E. coli BW25113 and the corresponding knockout mutants. The dissociation constant (Kd) of 201 16 nmol/L obtained for Cf-ARV-1502 suggests strong binding to the E. coli 70S ribosome. An inhibitory binding assay indicated that the binding site overlaps with those of other PrAMPs including Onc112 and pyrrhocoricin as well as the non-peptidic antibiotics erythromycin and chloramphenicol. All these drugs and drug candidates bind to the exit-tunnel of the 70S ribosome. Substitutions of the C-terminal fragment of the binding motif YLPRP reduced binding. At the same time, inhibition of GFP expression increased with net peptide charge. Interestingly, the MIC values of wild-type and DsbmA and DmdtM knockout mutants indicated that substitutions in the ribosomal binding motif altered also the bacterial uptake, which was generally improved by incorporation of hydrophobic residues. In conclusion, most substituted ARV-1502 analogs bound weaker to the 70S ribosome than ARV-1502 underlining the importance of the YLPRP binding motif. The weaker ribosomal binding correlated well with decreased antimicrobial activity in vitro. Substituted ARV-1502 analogs with a higher level of hydrophobicity or positive net charge improved the ribosome binding, inhibition of translation, and bacterial uptake.