[ES] El proceso de combustión en llamas de difusión de combustible atomizado es un fenómeno multifásico altamente complejo que a día de hoy no se comprende en su totalidad, ya que involucra varios eventos simultáneos, como atomización, vaporización y cinética química. A lo largo de los años, los investigadores han estudiado a fondo la combustión en llamas de combustibles líquidos, con el fin de comprender los procesos fundamentales como clave para reducir las emisiones contaminantes y mejorar la eficiencia de la propulsión de las aeronaves. En los últimos años, la evolución tanto en la tecnología de inyección como en la de combustión ha permitido mejorar el proceso de mezcla por aspersión y la eficiencia del motor y, por tanto, reducir las emisiones contaminantes. Por lo que, diferentes configuraciones de tipo de inyector y distribución de aire dentro de la cámara de combustión han demostrado ser capaces de reducir el consumo de combustible, así como las emisiones de óxidos de nitrógeno y hollín sin afectar el rendimiento del motor. Esta tesis proporciona una metodología experimental para estudiar los efectos de las condiciones de co-flujo, el caudal másico de combustible, el tipo de combustible y el diámetro de salida del quemador sobre la atomización y la combustión de la llama producida en un quemador anular bajo condiciones de operación pobres. La caracterización del chorro sin combustión se realizó mediante dos técnicas ópticas diferentes. Por un lado, se utilizó velocimetría de imagen de partículas para medir los campos de velocidad del espray. Por otro lado, retroiluminación microscópica difusa (MDBI) para medir el tamaño y la velocidad de las gotas. Los resultados mostraron que ambos están controladas principalmente por el tipo de combustible y el caudal másico del mismo. Sin embargo, la variación de la velocidad de co-flujo no mostró un efecto significativo en las características de las gotas (tamaño y velocidad), lo que probablemente se deba a que el campo de visión de la técnica MBDI estaba muy cerca de la punta del inyector. Adicionalmente, al incrementar la temperatura de co-flujo se observó que el diámetro promedio de gota disminuía, lo cual es causado por la evaporación del combustible. Finalmente, las variaciones en los perfiles de tamaño y velocidad de las gotas al variar el diámetro de salida de aire se relacionaron con la variación de la velocidad del co-flow, lo que afectaba la evaporación y el arrastre de las gotas. Para el estudio de la llama en condiciones reactivas, se probó en condiciones de operación que permitan llama estabilizadas, utilizando tres técnicas ópticas diferentes, las cuales se activaron simultáneamente. La extinción de luz difusa se utilizó para determinar el espesor óptico del hollín. Además, se emplearon las técnicas de quimioluminiscencia OH* y MDBI para medir la altura de despegue de la llama y las características de las gotas, respectivamente. Los resultados mostraron que la velocidad y temperatura del co-flujo, y el tipo de combustible influyen fuertemente en la altura de despegue de la llama. Mientras que en la formación hollín los parámetros más influyentes fueron la velocidad del co-flujo y el tipo de combustible. Con respecto a los resultados de la evaporación de las gotas, se observó que el tamaño inicial y las propiedades del combustible controlan su evaporación. El combustible n-Dodecano es el menos volátil y tiene un tamaño de gota inicial más grande y, por lo tanto, las gotas tardaron más en evaporarse, lo que resultó en una mayor longitud de despegue de la llama y una mayor formación de hollín debido a su mayor tendencia a formar hollín. Por el contrario, las gotas de n-Heptano se evaporaron más rápido, lo que resultó en una altura de despegue de la llama más corta y también en una menor formación de hollín. Finalmente, el combustible n-Decano mostró resultados intermedios para la evaporación de gotas, la altura de despegue de la llama y la formación de hollín. / [CA] El procés de combustió en flames de difusió de combustible atomitzat és un fenomen multifásico altament complex que a hores d'ara no es comprén en la seua totalitat, ja que involucra diversos esdeveniments simultanis, com a atomització, vaporització i cinètica química. Al llarg dels anys, els investi- gadors han estudiat a fons la combustió en flames de combustibles líquids, a fi de comprendre els processos fonamentals com a clau per a reduir les emissions contaminants i millorar l'eficiència de la propulsió de les aeronaus. En els últims anys, l'evolució tant en la tecnologia d'injecció com en la de combustió ha permés millorar el procés de mescla per aspersió i l'eficiència del motor i, per tant, reduir les emissions contaminants. Pel que, diferents configuracions de tipus d'injector i distribució d'aire dins de la cambra de combustió, han demostrat ser capaços de reduir el consum de combustible, així com les emissions d'òxids de nitrogen i sutja sense afectar el rendiment del motor. Aquesta tesi proporciona una metodologia experimental per a estudiar els efectes de les condicions de co-flux, el cabal màssic de combustible, el tipus de combustible i el diàmetre d'eixida del cremador sobre l'atomització i la combustió de la flama produïda en un cremador anul·lar sota condicions d'operació pobres. La caracterització del doll sense combustió es va realitzar mitjançant dues tècniques òptiques diferents. D'una banda, es va utilitzar velocimetría d'imatge de partícules per a mesurar els camps de velocitat de l'esprai. D'altra banda, retroil·luminació microscòpica difusa (MDBI) per a mesurar la grandària i la velocitat de les gotes. Els resultats van mostrar que tots dos estan controlades principalment per la mena de combustible i el cabal màssic d'aquest. No obstant això, la variació de la velocitat de co-flux no va mostrar un efecte significatiu en les característiques de les gotes (grandària i velocitat), la qual cosa probablement es deu al fet que el camp de visió de la tècnica MBDI estava molt prop de la punta de l'injector. Addicionalment, en incrementar la temperatura de co-flux es va observar que el diàmetre mitjà de gota disminuïa, la qual cosa és causat per l'evaporació del combustible. Finalment, les variacions en els perfils de grandària i velocitat de les gotes en variar el diàmetre d'eixida d'aire es van relacionar amb la variació de la velocitat del co-flux, la qual cosa afectava l'evaporació i l'arrossegament de les gotes. Per a l'estudi de la flama en condicions reactives, es va provar en condicions d'operació que permeten flama estabilitzades, utilitzant tres tècniques òptiques diferents, les quals es van activar simultàniament. L'extinció de llum difusa es va utilitzar per a determinar la grossària òptica del sutge. A més, es van emprar les tècniques de quimioluminescència OH* i MDBI per a mesurar l'altura d'enlairament de la flama i les característiques de les gotes, respectivament. Els resultats van mostrar que la velocitat i temperatura del co-flux, i el tipus de combustible influeixen fortament en l'altura d'enlairament de la flama. Mentre que en la formació sutge els paràmetres més influents van ser la velocitat del co-flux i el tipus de combustible. Respecte als resultats de l'evaporació de les gotes, es va observar que la grandària inicial i les propietats del combustible controlen la seua evaporació. El combustible n-Dodecano és el menys volàtil i té una grandària de gota inicial més gran i, per tant, les gotes van tardar més a evaporar-se, la qual cosa va resultar en una major longitud d'enlairament de la flama i una major formació de sutge degut a la seua major tendència a formar sutge. Al contrari, les gotes de n-Heptano es van evaporar més ràpid, la qual cosa va resultar en una altura d'envol de la flama més curta i també en una menor formació de sutja. Finalment, el combustible n-Decano va mostrar resultats intermedis per a l’evaporació de gotes, l’altura d’envol de la flama i la formació de sutja / [EN] The combustion process in spray flames is a highly complex multi-phase phenomenon that is still not completely understood since it involves several simultaneous events, such as atomization, vaporization, and chemical kinetics. Over the years, researchers have studied the combustion in spray flames thoroughly, in order to understand the fundamental processes as key to re- duce pollutant emissions and improve the efficiency of aircraft propulsion. In recent years, the evolution in both injection and combustion technology has allowed to improve the spray mixing process and engine efficiency and hence, reducing pollutant emissions. Therefore, different configurations of injector type and air distribution inside the combustion chamber have proved capable of reducing fuel consumption, as well as emissions of nitrogen oxides and soot without affecting the engine performance. This thesis provides an experimental methodology to study the effects of co-flow conditions, fuel mass flow rate, fuel type and air outlet diameter at the burner exit on the atomization and combustion behavior of the spray flame produced on an annular spray burner under lean conditions. The characterization of the liquid spray without combustion was carried out using two different optical techniques. On the one hand, particle image velocimetry was used to characterize the global velocity fields of the spray. On the other hand, Microscopic diffused back-illumination (MDBI) to measure the size and droplet velocity at a field of view close to the injector tip. The results exhibited that both droplet size and droplet velocity are mainly controlled by the fuel type and fuel mass flow rate. Nevertheless, the variation of the co-flow velocity did not show a significant effect on droplet characteristics (size and velocity), which is likely due to the fact that the field of view of the MDBI technique was located very close to the injector tip. Additionally, by increasing the co-flow temperature, it was observed that the mean droplet size decreased, which is caused by the fuel evaporation process. Finally, the variations in the droplet size and velocity profiles when varying the air outlet diameter were related to the velocity variation when modifying the cross-sectional area at the burner outlet, which affects the evaporation and drag of the drops. On the spray development in reactive conditions, it was investigated in the operating conditions that promote stabilized flames, using three different optical techniques, all of which were triggered simultaneously. The light extinction was used to determine the optical thickness through the soot cloud. In addition, OH* chemiluminescence and the MDBI techniques were employed to measure the flame lift-off height and droplet characteristics, respectively. The results exhibited that the co-flow velocity, co-flow temperature and fuel type strongly influence the flame lift-off height. While in the soot formation the most influential parameters were the co-flow velocity and the type of fuel. Regarding the results of the droplet evaporation, it was observed that the initial droplet sizes and the fuel properties control the droplet evaporation process. n-Dodecane fuel is the least volatile and also exhibited a larger initial droplet size and thus, the droplets took more time to evaporate than the other two fuels, resulting in a longer flame lift-off height and likewise higher soot formation by its greater tendency to form soot. Contrary, n-Heptane droplets evaporated faster, resulting in a shorter flame lift-off height and also less soot formation. Finally, n-Decane showed intermediate results for droplet evaporation, flame lift-off height, and soot formation. / Cardona Vargas, S. (2021). Development of a test rig for the study of the atomization and combustion of a spray flame in an atmospheric annular spray burner at lean conditions [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/179994 / TESIS

The aim of this thesis is to increase our knowledge and understanding of trace water concentrations in nominally anhydrous minerals (NAMs). Special focus is put on the de- and rehydration mechanisms of clinopyroxene crystals in volcanic systems, how these minerals can be used to investigate the volatile content of mantle rocks and melts on both Earth and other planetary bodies (e.g., Mars). Various analytical techniques for water concentration analysis were evaluated. The first part of the thesis focusses on rehydration experiments in hydrogen gas at 1 atm and under hydrothermal pressures from 0.5 to 3 kbar on volcanic clinopyroxene crystals in order to test hydrogen incorporation and loss from crystals and how their initial water content at crystallization prior to dehydration may be restored. The results show that extensive dehydration may occur during magma ascent and degassing but may be hindered by fast ascent rates with limited volatile loss. De- and rehydration processes are governed by the redox-reaction OH- + Fe2+ ↔ O2- + Fe3+ + ½ H2. Performing rehydration experiments at different pressures can restore the water contents of clinopyroxene at various levels in the volcanic systems. Subsequently water contents of magmas and mantle sources can be deduced based on crystal/melt partition coefficients. This thesis provides examples from the Canary Islands, Merapi volcano in Indonesia and the famous Nakhla meteorite. Using NAMs as a proxy for magmatic and mantle water contents may provide a very good method especially for planetary science where sample material is limited. The thesis’ second part focusses on analytical methods to measure the concentration of water in NAMs. Specifically the application of Raman spectroscopy and proton-proton scattering are tested. The hydrated mineral zoisite is thoroughly analyzed in order to be used as an external standard material. Polarized single crystal spectra helped to determine the orientation of the OH-dipole in zoisite. Further, Transmission Raman spectroscopy and a new method for the preparation of very thin samples for proton-proton scattering were developed and tested. The results provide new possibilities for the concentration analysis of water in NAMs such as three dimensional distribution and high spatial resolution.

Doctor of Philosophy(PhD) / This body of research uses numerical and experimental investigative techniques to further the understanding of autoignition. Hydrogen/nitrogen and methane/air fuel configurations of turbulent lifted flames in a vitiated coflow burner are used as model flames for this investigation. Characterisation was undertaken to understand the impact of controlling parameters and the overall behaviour of the flames, and to provide a body of data for modelling comparisons. Modelling of the flames was conducted using the PDF-RANS technique with detailed chemistry incorporated using In-situ Adaptive Tabulation (ISAT) within the commercial CFD package, FLUENT 6.2. From these investigations, two numerical indicators for autoignition were developed: convection-reaction balance in the species transport budget at the mean flame base; and the build-up of ignition precursors prior to key ignition species. These indicators were tested in well defined autoignition and premixed flame cases, and subsequently used with the calculated turbulent lifted flames to identify if these are stabilised through autoignition. Based on learnings from the modelling, a quantitative, high-resolution simultaneous imaging experiment was designed to investigate the correlations of an ignition precursor (formaldehyde: CH2O) with a key flame radical (OH) and temperature. Rayleigh scattering was used to measure temperature, while Laser Induced Fluorescence (LIF) was used to measure OH and CH2O concentrations. The high resolution in the Rayleigh imaging permitted the extraction of temperature gradient data, and the product of the OH and CH2O images was shown to be a valid and useful proxy for peak heat release rate in autoigniting and transient flames. The experimental data confirmed the presence of formaldehyde as a precursor for autoignition in methane flames and led to the identification of other indicators. Sequenced images of CH2O, OH and temperature show clearly that formaldehyde exists before OH and peaks when autoignition occurs, as confirmed by images of heat release. The CH2O peaks decrease later while those of OH remain almost unchanged in the reaction zone.

Une fraction significative de pesticides intègre le compartiment atmosphérique notamment durant les épandages agricoles. L'atmosphère est ainsi considérée comme un important vecteur de dissémination de ces composés dans l'environnement. Par conséquent, une bonne connaissance de leur comportement atmosphérique est indispensable à la compréhension de leur devenir environnemental. Actuellement, il existe une incohérence entre les brèves durées de vie atmosphérique estimées (à partir de la réactivité théorique en phase gazeuse) et les observations de terrain (prenant en compte les phases gazeuse et particulaire) qui révèlent souvent des transports sur de longues distances. L'objectif de ce travail a été d'aborder cette problématique par l'étude de la réactivité de trois pesticides (alachlore, trifluraline et terbuthylazine) adsorbés à la surface de particules de silice au sein d'un réacteur à écoulement et sous conditions simulées. Des protocoles expérimentaux ont été spécialement développés pour observer les cinétiques supposées lentes de ces herbicides vis-à-vis de l'ozone et des radicaux hydroxyles. Les résultats obtenus tendent à corroborer l'hypothèse suggérant que les temps de vie atmosphérique des pesticides actuellement utilisés sont sous-estimés, du moins pour les composés les moins volatils. Il paraît donc nécessaire de poursuivre les investigations sur la réactivité hétérogène des pesticides pour pouvoir obtenir une image plus complète de leur comportement vis-à-vis de la dégradation atmosphérique, ce qui permettrait à terme de déterminer des durées de vie atmosphériques plus réalistes.

Le microscope de photodétachement, construit au laboratoire Aimé Cotton au milieu des années 90, permet de visualiser les images d'interférences obtenues à partir d'électrons détachés d'ions négatifs par excitation laser, en présence d'un champ électrique uniforme. Après détachement, dans une première approximation, l'électron et l'espèce neutre précédemment liés n'interagissent plus : on a une source d'électrons libres. Or, selon les équations de la mécanique classique, un électron libre d'énergie cinétique donnée placé dans un champ électrique uniforme a deux trajectoires paraboliques différentes pour arriver en un même point. Quantiquement parlant, l'onde de matière électronique se divise et suit les deux chemins possibles. Du fait de la cohérence de l'onde électronique émise par photodétachement, les deux demi-ondes interfèrent. Les images d'interférences enregistrées sont très sensibles à l'énergie cinétique des électrons qui les composent. On peut ainsi mesurer cette énergie par comparaison entre les images expérimentales et celles prédites par le modèle théorique de l'électron libre, et faire de la spectroscopie de très haute résolution. L'étude quantitative des images a été utilisée pour tester la validité du modèle de l'électron libre pour le détachement de Si- et OH-, en recherchant d'éventuels effets d'interaction entre l'électron détaché et l'espèce neutre. L'anion Si- a permis de valider le modèle pour un atome plus lourd que ceux précédemment utilisés. L'anion moléculaire OH- a été choisi notamment pour examiner l'effet d'un potentiel dipolaire sur les interférences. Les résultats obtenus n'ont pas mis en évidence de modification des images, et ont donc validé cette méthode pour la mesure des énergies de détachement d'anions diatomiques. Ces travaux ont permis de proposer de nouvelles mesures des affinités électroniques de Si et de OH, avec une meilleure précision.

<p>Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. </p><p>In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings.</p><p>To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of >95% for all monoterpenes and formed products included in the investigation.</p><p>Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆³-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation.</p><p>Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene. </p>

Thesis (Ph. D.)--Miami University, Dept. of Chemistry and Biochemistry, 2007. / Title from second page of PDF document. Includes bibliographical references (p. 87-96).

Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings. To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of &gt;95% for all monoterpenes and formed products included in the investigation. Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆3-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation. Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene.

The vitamin D metabolite 1,25(OH)2D3 has long been known to inhibit growth of prostate cancer cells and this mainly through a VDR-mediated pathway controlling target gene expression, resulting in cell cycle arrest, apoptosis and differentiation. Another major way in which 1,25(OH)2D3 inhibits cell growth in prostate cancer is via membrane-initiated steroid signalling, which triggers activation of signal cascades upon steroid binding to a receptor complex, leading to induction of genes regulating cell growth, proliferation and apoptosis. The main prostate cancer inhibiting membrane-initiated route is the TGFβ signalling pathway, elicited by the protein TGFβ. In this experiment the activating effects of 1,25(OH)2D3 on TGFβ in prostate cancer cells, as well as two other important proteins downstream in this cascade, Smad2 and 3, were investigated. PC-3 cells were incubated for 3, 5, 10, 30 and 60 minutes as well as 38 hours both together with 1,25(OH)2D3 of the concentrations 10-10 and 10-7 M and without. As the downstream cascade protein JNK is a known activator of Smad2/3, this procedure was also repeated with a JNK inhibitor. An ELISA assay scanning for activated TGFβ was then performed on supernatants from the cells treated without JNK inhibitor. In addition, a Western Blot scanning for activated Smad2 and 3 was performed on supernatants from all groups of treatment. The analysis of the result values showed that 10-10 M 1,25(OH)2D3 significantly lowered the content of active TGFβ in PC-3 cells within 3 and 5 minutes. Unfortunately the Western Blot was unsuccessful and needs therefore be repeated.

The vitamin D metabolite 1,25(OH)2D3 has long been known to inhibit growth of prostate cancer cells and this has been attributed to a VDR-mediated pathway controlling target gene expression, resulting in cell cycle arrest, apoptosis and differentiation. New research has shown that another vitamin D metabolite, 24,25(OH)2D3, inhibits proliferation of prostate cancer cells as well, more specifically, cells of the line LNCaP. It is not clear exactly how 24,25(OH)2D3 exerts this cancer growth inhibition but it has been shown that it is to some extent regulated via G protein coupled signalling pathways. Catalase is a haem-containing redox enzyme found in the majority of animal cells, plant cells and aerobic microorganisms. This enzyme is very important because it prevents excessive accumulation of the strongly oxidizing agent H2O2 which otherwise can do damage to the cells. Because of this preventive effect of catalase, important cellular processes which generate H2O2 as by-product can proceed safely. Biochemical analysis of catalase has shown that it binds endogenously to 24,25(OH)2D3. The fact that 24,25(OH)2D3 has anti-proliferative effects on prostate cancer cells combined with the fact that it binds to catalase generates the hypothesis that this binding interferes with the essential task of catalase to keep the cell free from accumulation of destructive H2O2, and by means of this interference induces apoptosis. Finding out about the cancer growth inhibiting mechanism behind each vitamin D metabolite is important and may be a lead in the search for a new, better treatment of prostate cancer. The specific aim of this project was to study if and in what way 24,25(OH)2D3 affects the enzymatic activity of catalase in LNCaP cells and to do this with dose and time responses in focus. In this experiment LNCaP cells were incubated for 48 hours together with 24,25(OH)2D3 in five different concentrations, then a catalase assay was performed on the cells including fluorescence-mediated measuring of catalase activity in both treated and untreated cells. The analysis of the result values showed that regardless of dose or time, 24,25(OH)2D3 has no statistically significant effect on catalase activity in cells of the line LNCaP.