Abstract: Soot from combustion emissions has a negative impact on human health and the environment. Understanding and controlling soot formation is desirable to reduce this negative impact, especially as energy demands continue to increase. In this work, a range of fundamental combustion experiments are performed to better understand the soot formation process, and to develop diagnostics for measuring soot properties. First, studies on the effects of doping the flame with different polycyclic aromatic hydrocarbons (PAHs) was performed to investigate soot nucleation mechanisms. Soot formation was found to be most sensitive to phenylacetylene addition and nucleation through physical dimerization appears to be unlikely. Next, the effects of ammonia addition, a possible future fuel, on soot formation in laminar nonpremixed ethylene counterflow flames was performed. A reduction in soot volume fraction was observed and attributed to chemical effects of ammonia addition. Second, the investigation and development of several types of diagnostics was performed. Soot is typically reported to scale with pressure as Pn where P is pressure and n is a scaling factor. A wide range of scaling factors for ethylene coflow flames have been reported using different types of diagnostics. In this work, a comparison between a light extinction technique and PLII was performed and differences between reported values was explored. Next, the time resolved laser induced incandescence (TiRe-LII) diagnostic was advanced by exploring the effects of SVF on local gas heating. Errors introduced into this model by neglecting local gas heating are explored. Finally, a new diagnostic was developed for 3 dimensional measurements of SVF and velocity in turbulent flames using a technique known as diffuse-backlight illumination extinction imaging. Third, the application of gated 2D TiRe-LII was assessed in pressurized environments on laminar coflow flames. Comparisons between TiRe-LII and thermophoretically captured soot imaged by transmission electron microscopy (TEM) was performed. TiRe-LII was found to have reasonable agreement with TEM measurements if the SNR was high, but due to the large disparity in primary particle size in pressurized environments errors in 2D TiRe-LII can be significant.

The concurrent spreading of a boundary layer type diffusion flame is studied. The impossibility of obtaining a low velocity laminar flow without any perturbation induced by buoyancy has lead to the development of an experimental apparatus for use in micro-gravity facilities. Based on previous experimental observations, an original numerical approach has been developed showing, first the dominating role of the radiative heat transfer on the structure of the flame and second the major role of the soot on the extinction phenomenon at the flame trailing edge. The influence of the forced flow velocity, the fuel injection velocity and oxygen concentration on the geometry of the flame has been examined by imaging of CH* and OH* radicals spontaneous emission. Laser-Induced Incandescence (LII) is used to determine the soot field concentration in the flame. The soot formation has been studied by Laser Induced Fluorescence (LIF) of Polycyclic Aromatic Hydrocarbons (PAHs). The interaction between the reaction zone and the field of soot formation/oxidation is taken into account to analyze the flame length. These results can be used as the experimental input data for a future complete validation of numerical model simulating the soot formation and oxidation in this kind of flame.

Ce travail contribue à la quasi-in-situ détection des nanoparticules par la technique d’incandescence induite par laser (LII) pendant le dépôt chimique en phase vapeur avec catalyseur flottant (FCCVD) de nanotubes de carbone. Premièrement, la microscopie électronique en transmission (MET) à haute résolution était utilisé pour caractériser la nature et la taille des nanoparticules. Le signal théorique de LII a été simulé en considérant la densité des nanoparticules, la capacité thermique et la distribution de taille, etc. La sensibilité et l’incertitude concrètes des paramètres clés sur la taille évaluée des particules pour ce modelé ont été estimées. Le modèle LII a été validé par la comparaison des résultats évalués avec ceux obtenus par la MET. Ensuite, la technique mature LII combinée avec MET a été appliquée pour étudier l’évolution des nanoparticules dans la phase gazeuse le long de l’axe du réacteur. L’influence de la température, de la concentration de ferrocène, de la source de carbone et de la proportion hydrogène sur la taille des nanoparticules a également été démontrée. Enfin, les rôles des nanoparticules dans la phase gazeuse au cours du processus de synthèse des NTC ont été discutés en corrélant les informations sur l’évolution axiale des nanoparticules et la morphologie des NTC synthétisés sur le substrat le long de l’axe du réacteur. Un modèle basé sur la thermodynamique de la nucléation des nanoparticules a été proposé pour décrire le processus de formation des nanoparticules au cours du processus DCVCF. Il est constaté que les nanoparticules asformé en phase gazeuse présentent des structures cœur-coquille avec un noyau de α-Fe et la coque de carbone. Ainsi, les nanoparticules de fer en phase gazeuse ne pourraient pas contribuer à la croissance de NTC sur le substrat à cause de l’encapsulation de carbone. En même temps, la taille des nanoparticules évaluée par LII est en bon accord avec celle-ci déterminée par MET. Cette étude, montrant les relations potentielles entre les nanoparticules flottantes et les NTCs sur le substrat, révèle une perspective importante de l’application de LII pour comprendre et améliorer le processus DCVCF. / This work contributes to the quasi-in-situdetection of nanoparticles by laser induced incandescence(LII) technique during the floating catalytic chemicalvapor deposition (FCCVD) synthesis of Carbonnanotubes.First, high resolution transmission electron microscopy(TEM) was used to characterize the nanoparticlenature and size. The theoretical LII signal was simulatedby considering the nanoparticle density, heatcapacity and size distribution, etc. A detailed sensitivityand uncertainty of the key parameters on the evaluatedparticle size for this model was estimated. TheLII model was validated by a comparison of the evaluatedresults with the ones obtained by TEM measurements.Then, the developed LII technique combinedwith TEM was applied to investigate the evolutionof nanoparticles in the gas phase along thereactor axis. The influence of the temperature, ferroceneconcentration, carbon source and hydrogen ratioon the nanoparticle size was also demonstrated. Finally,the roles of nanoparticles in the gas phase duringCNT synthesis process were discussed by correlatinginformation on the axial nanoparticle evolutionand the morphology of CNTs synthesized on thesubstrate along the reactor axis. And a model basedon the thermodynamics of the nanoparticle nucleationwas proposed to describe the nanoparticle formationprocess during the FCCVD process. It is found thatthe as-formed nanoparticles in the gas phase exhibitcore-shell structures with an α-Fe core and a carbonshell. Hence iron nanoparticles in the gas phasecould not contribute to the CNT growth on the substratebecause of the carbon encapsulation. Meanwhilethe evaluated size of nanoparticles by LII is ingood agreement with the TEM determined one. Thisstudy, showing potential relations between the floatingnanoparticles and the CNTs on the substrate, revealsthe important LII application prospect to understandand to improve the FCCVD process.

De par leurs propriétés remarquables, les nanotubes de carbone (NTCs) reçoivent beaucoup d’attention et de nombreuses recherches sont menées sur ces matériaux depuis les dernières décennies. Le nombre d'applications envisagées mais aussi la quantité demandée de NTCs augmentent chaque année. Pour atteindre une production à grande échelle et contrôlée, il est nécessaire d'avoir une bonne compréhension des mécanismes de croissance des NTCs. Dans ce manuscrit, la formation ainsi que l'activité catalytique de nanoparticules (NPs) par dépôt chimique en phase vapeur assisté par aérosol (CVD) sont étudiées expérimentalement, pour analyser le processus d'évolution des NPs et leur relation avec les NTCs.Dans le chapitre 1, nous présentons une introduction générale sur des structures, les méthodes de synthèse, les propriétés et les applications envisagées des NTCs, ainsi que l’état de l’art concernant l’étude des mécanismes de croissance des NTCs.Dans le chapitre 2, nous décrivons le système de dépôt chimique en phase vapeur avec catalyseur flottant, ainsi que les méthodes de diagnostic in-situ/ex-situ utilisées dans cette étude. La technique d’incandescence induite par laser (LII) est particulièrement importante dans ce chapitre, car cette technique nous permet de réaliser un diagnostic in situ sur la quantité/taille des NPs déposées pendant le processus de synthèse.Dans le chapitre 3, nous présentons l'évolution des NPs lors de la synthèse ainsi que les influences des différents paramètres de CVD (température, quantité de carbone/catalyseur, composition du gaz, etc.) sur les gouttelettes et les NPs respectivement. Un modèle pour la formation de NPs est proposé à la fin de ce chapitre.Dans le chapitre 4, les résultats des expériences sur l'évolution de la composition du gaz sont révélés. Ces résultats donnent des informations concernant les réactions chimiques ayant lieu dans la phase gazeuse lors de la synthèse des NTCs.Dans le chapitre 5, une étude détaillée de l'influence des paramètres de CVD sur les produits NTCs est menée, et les relations entre les NPs et les NTC sont discutées.Pour finir, des conclusions générales ainsi que les perspectives prévues pour les travaux futurs sont présentées. / Due to the outstanding properties in various aspects, carbon nanotubes (CNTs) received worldwide attentions and intensive investigations are carried out in the last decades. While the number of applications as well as the quantity demanded of CNTs are increasing year after year, to achieve large scale production of the desired structures in a controlled way, it is highly required having a clear understanding about the CNTs growth mechanism. In this study, the formation and catalytic activity of nanoparticles (NPs) under aerosol-assisted chemical vapor deposition (CVD) is experimentally investigated, aiming to study the NPs evolution process and their relation with the CNTs products.In chapter 1, we provide a general review of CNTs structures, synthesis methods, properties as well as applications. Moreover, the current situation of CNTs growth mechanism study is presented.In chapter 2, the floating catalyst chemical vapor deposition synthesis system, and the in-situ/ex-situ diagnostic methods used in this study are introduced. Laser induced incandescence technique (LII) is particularly explained in this chapter, which permits to achieve an in-situ diagnostic of the NPs quantity/size during the synthesis process.In chapter 3, the evolution of NPs during the synthesis is presented, in which the influences of different CVD parameters (temperature, carbon/catalyst quantity, gas composition etc.) on the droplets as well as on the NPs are investigated respectively. A NPs formation model is proposed based on the NPs variation information at the end of this chapter.In chapter 4, the experimental results of the gas composition evolution in chemical vapor deposition reactor are revealed, which reflect the gas phase chemical reactions information during the CNTs synthesis.In chapter 5, a detailed investigation about the influence of CVD parameters on the CNTs products is explained. And the relation between the NPs and CNTs is discussed.In the end, general conclusions are formed according to works and perspectives are provided for the improvement of the future work.

[pt] Entender o processo de produção de fuligem é crucial para o projeto de novos queimadores, como os de fornos industriais. Estes queimadores, que utilizam processos de combustão turbulenta, dependem de transferência de calor via radiação das partículas de fuligem para as paredes do forno para seu bom funcionamento. A fuligem formada na região de radiação deve ser oxidada para evitar problemas de saúde e meio ambiente. Mesmo tendo havido significativo progresso no decorrer das duas últimas décadas em relação às chamas laminares, a interação entre a turbulência e a produção de fuligem ainda é um problema em aberto. Este trabalho apresenta resultados experimentais recentes da distribuição instantânea e média da distribuição de fuligem em chamas turbulentas de etileno/ar não prémisturadas estabilizadas em um queimador do tipo bluff-body. A intensidade de turbulência na região de esteira deste queimador é muito alta, levando a uma presença de fuligem intermitente e a estruturas de fuligem altamente distorcidas. A distribuição de fuligem é medida usando incandescência induzida por laser (LII), com uma excitação em 266 nm a 10 Hz e fluência de 0,8 J/cm2 e medição em 400 nm por uma câmera intensificada. Os resultados da técnica LII são comparados à técnica clássica de extinção da luz. Resultados da distribuição de hidrocarbonetos aromáticos policíclicos também são apresentados. Os resultados obtidos permitem caracterizar a distribuição da função de densidade de probabilidade de fuligem. Nas situações de escoamento onde a turbulência da esteira é controlada pelo escoamento de ar, demonstra-se que a PDF da fração volumétrica de fuligem corresponde a uma distribuição lognormal. / [en] Understanding the soot production process is crucial to the design of new burners, such as those in industrial furnaces. Indeed, these burners, which use turbulent combustion processes, rely on radiative heat transfer from the soot particles to the furnace walls to operate properly. The soot formed within the radiation region must the be oxidized in order to avoid health and environment issues. Although there has been significant progress over the past two decades in relation to laminar flames, the interaction between turbulence and soot production is still an open problem. This works presents recent experimental results of the instantaneous and mean soot distribution on non-premixed turbulent ethylene/air flames stabilized at a bluff-body burner. The turbulence intensity in the wake region of this burner is very high, leading to a soot intermittent presence and to highly distorted soot structures. The soot distribution is measured using laserinduced incandescence (LII), with 266 nm excitation at 10 Hz, 0.8 J/cm2 fluence and collected at 400 nm by an intensified camera. The results of the LII technique are compared to those of a classical of light extinction technique. Polyciclic aromatic hydrocarbon distribution results are also presented. The results obtained allow to characterize the soot probability density function distribution. In flow situations where the wake turbulence is controlled by the air flow, the soot volume fraction PDF is shown to correspond to a lognormal distribution.

Les particules de suie, issues de la combustion incomplète, peuvent, en fonction des conditions de combustion, contenir une part plus ou moins importante de composés organiques (OC/TC). Par ailleurs, dès lors que ces nanoparticules sont émises dans l'atmosphère, des composés organiques volatiles peuvent s'adsorber, formant une gangue autour de ces agrégats fractals. L'impact de cette composition initiale ou de ce « vieillissement atmosphérique » sur les propriétés morphologiques et radiatives de ces particules n'est pas bien connu. Ceci a un impact sur les modèles radiatifs climatiques mais aussi sur l'interprétation des signaux délivrés par les différents diagnostics optiques pouvant être utilisés pour la métrologie des aérosols. En particulier, ce travail vise à juger de la pertinence de l'usage de diagnostics optiques pour caractériser les particules de suie en conditions atmosphériques. Afin d'étudier l'impact des composés organiques initialement présents dans la particule ou adsorbés en post-combustion sur leurs propriétés radiatives, nous avons étudié en laboratoire des suies produites par une flamme de diffusion (miniCAST) pour différentes richesses globales et avons ajouté un revêtement organique d'acide. Dans le but de générer en laboratoire une couche d'acide oléique sur des particules de référence, un dispositif de « coating » a été mis en œuvre et qualifié. Les particules ainsi générées et recouvertes ou non, ont été caractérisées en masse (mesures TEOM), en taille (mesures SMPS) et morphologiquement (densité effective). L'épaisseur de coating ainsi que la restructuration morphologique causée par l'ajout d'une gangue de matière organique ont ainsi été quantifiées. Les propriétés radiatives, ont été mesurées par extinction spectrale (Turbidimétrie) et diffusion (diffusion angulaire et spectrale). Un effort particulier a été mené pour que des mesures expérimentales puissent valider des résultats de calculs numériques préexistants. Par ailleurs, ces différentes techniques de mesures (optiques et non optique) ont conduit à la généralisation de la théorie Rayleigh Debye Gans for Fractal Aggregates (RDG-FA) à des particules de type agrégats fractals polydispersés recouverts d'un revêtement organique (RDG-CFA). Ceci permettant d'appréhender de façon phénoménologique l'impact du coating sur les propriétés radiatives et d'entrevoir une implantation plus aisée dans les codes de simulation climatique ou pour l'interprétation des mesures optiques dans l'atmosphère. Enfin, une attention particulière a été portée sur la technique d'incandescence induite par laser (LII) afin d'étudier la faisabilité de l'application de cette technique aux particules organiques ou ayant interagi avec les composés atmosphériques au cours de leur vieillissement. / Soot particles resulting from incomplete combustion may contain a more or less important part of organic compounds (OC / TC), depending on the combustion conditions. Moreover, once these nanoparticles are emitted into the atmosphere, volatile organic compounds can adsorb, forming a coating around these fractal aggregates. The impact of the initial composition or the atmospheric aging on the morphological and radiative properties of these particles is not well known. This has an impact on the radiative climate models but also on the interpretation of the signais delivered by the different optical diagnostics that can be used for aerosol metrology. In particular, this work aims to evaluate the relevance of the use of optical diagnostics to characterize soot particles in atmospheric conditions. In order to study the impact of organic compounds initially present in the particle or adsorbed in post-combustion on their radiative properties, we have studied soot produced by a diffusion flame (miniCAST) for different global richnesses and added an organic acid coating. In order to produce an oleic acid layer on reference particles, a coating device has been implemented and qualified. Particles thus generated, coated or not, were characterized in mass (TEOM measurements), in size (SMPS measurements) and morphologically (effective density). The coating thickness as well as the morphological restructuring caused by the addition of an organic coating was thus quantified. The radiative properties were measured by spectrally resolved light extinction and scattering (angular and spectrally resolved). A special effort was made to allow experimental measurements to validate pre-existing numerical results. Moreover, these different measurement techniques (optical and non-optical) have led to the generalization of the Rayleigh Debye Gans for Fractal Aggregates (RDG-FA) theory to particles of the polydispersed fractal aggregate type coated with an organic layer (RDG-CFA). This allows to understand phenomenologically the impact of a coating on the radiative properties and to permit an easier implementation in climate simulation codes or for the interpretation of optical measurements in the atmosphere. Finally, special attention was paid to the laser induced incandescence technique (LII), to study the applicability of this technique to organic particles or having interacted with atmospheric compounds during their aging processes.

[pt] O presente trabalho apresenta um estudo experimental da distribuição da fuligem e de hidrocarbonetos aromáticos policíclicos (PAH) em chamas laminares não pré-misturadas de etileno e ar, mediante o uso de técnicas de diagnóstico espectroscópico, num queimador tipo co-flow. Para este fim são aplicadas as técnicas de fluorescência induzida por plano laser e incandescência induzida por plano laser, com excitação no espectro ultravioleta. Bandas espectrais de detecção centradas em 340, 400, 450, 500, 550 nm são empregadas para caracterizar diferentes PAH, aproveitado o fenômeno do deslocamento do espectros de fluorescência para o infravermelho, conforme se incrementa sua massa molecular. A técnica de extinção laser é utilizada para calibrar os resultados de incandescência e obter a fração volumétrica de fuligem. A radiação espontânea emitida pela fuligem é utilizada para medir a temperatura pela técnica de termometria em duas cores. A comparação dos resultados obtidos com uma detecção simultânea (0 ns) e atrasada (50 ns) com respeito ao pulso laser permite discriminar entre as regiões onde estão presentes PAHs e fuligem ou apenas fuligem. Os resultados mostram que na região mais fria, perto da entrada de combustível, apenas existem PAH. Seguindo esta região, numa zona de altura intermediária e mais quente, tanto a fuligem como o PAHs coexistem até a o ponto de máxima fração volumétrica integrada de fuligem. O deslocamento no sentido vertical da distribuição de fluorescência é observado com o aumento do comprimento de onda de detecção, o que é consistente com o crescimento do tamanho de PAH e sua progressiva transformação em fuligem. A distribuição de PAH e da fuligem é investigada como função da vazão de combustível. A fração volumétrica de fuligem apresenta uma distribuição clássica, cujo valor se incrementa com a vazão de combustível, enquanto que a temperatura medida diminui. / [en] This work presents an experimental study of soot and polycyclic aromatic hydrocarbons (PAH) distribution in axisymmetric ethylene-air non-premixe laminar flames using spectroscopic diagnostic in a co-flow target burner. For this purpose, are applied laser-induced fluorescence and laser-induced incandescence techniques with UV excitation. Spectral detection bands centered at 340, 400, 450, 500, 550 nm are employed to characterize PAH, using the infrared fluorescence spectra displacement phenomenon with the molecular mass increase. The incandescence is captured at 400 nm and the laser extinction technique is used to calibrate the signal, and, thus to obtain the soot volume fraction at the reaction zone. The soot spontaneous emitted radiation is used to measure the temperature by the two-color pyrometry technique. The comparison between results with prompt (0 ns) and delayed (50 ns) detection, with respect to the laser pulse, allows to discriminate the regions between soot precursors (PAH) and soot. The results show that, in the colder region, near the fuel inlet, PAH exist only. Following this region, in an intermediate warmer zone, both soot and PAH appear to coexist until the point of maximum integral soot volumetric fraction. A vertical displacement of the fluorescence distribution with increasing detection wavelength is observed, which is consistent with PAH size growth and with its progressive transformation into soot. PAH and soot distribution are investigated as a function of the fuel flow rate. The soot volumetric fraction exhibits a classical distribution, whose value increases with the fuel flow rate, whereas the measured temperature decreases, exhibiting a singular behavior in the region where the soot is formed.

<p dir="ltr">Burst-mode lasers and burst-mode optical parametric oscillators (OPOs) are applied and developed for planar laser induced fluorescence (PLIF) measurements of key species for high-speed combustion measurements. OH-PLIF in the rotating detonation engine was performed for the first time at wave structure visualization in two different planes and was 10 times faster than any other burst mode OH-PLIF measurements at the time. The same system was used to perform another OH-PLIF experiment at 1 MHz for ~200 pulses to compare key features of the detonation wave structure with computational fluid dynamic simulations and a fundamental detonation tube experiment. The system was also used for seedless velocity measurements in the exhaust by tracking a pocket of OH with a technique called FLASH. A similar OPO was built, aligned, and tuned to perform 1 MHz NO PLIF in a Mach 10 hypersonic tunnel to visualize second mode instabilities and calculate the frequency in the boundary layer transition of a 7-degree cone. A high-efficiency OPO was developed and characterized utilizing the KTP crystal to provide narrow bandwidth pulses for the fluorescence of multiple species. The OPO was pumped at repetition rates up to 1 MHz and was calculated to have a 1.9% UV efficiency from the fundamental 1064 nm output. This is 3 – 5 times increase in efficiency from previous custom and commercial built OPOs. The OPO was applied to the RDC for OH PLIF in the combustor channel and NO PLIF for injector dynamics and response studies. Lastly, a burst-mode laser was used to perform LII on the post detonation blast flow field to measure explosively generated soot. The data was taken at 1 MHz and compared and corrected with a separate set of experiments and computational simulations.</p>

<p dir="ltr">Soot is a byproduct formed during incomplete combustion of hydrocarbon fuels. Atmospheric soot from aircraft emissions increases local air temperatures, drives cloud formation, and decreases albedo on snow and ice: three factors that promote global warming. It is also potentially harmful to humans and has been associated with negative effects on heart and lung health. Operationally, soot formation indicates an inefficiency in combustion and can cause deterioration in aircraft engines. Modeling soot formation in complex flow fields is difficult and has been largely unsuccessful. In-situ soot measurements at relevant conditions can inform the design and operation of aircraft engines with reduced soot emissions. Laser-induced incandescence (LII) is a diagnostic that allows for non-intrusive measurements of soot volume fraction and primarily particle size in combustion environments. It involves laser-heating soot particles to temperatures at which they incandescence and measuring the radiated signal. The strong absorption capabilities and high sublimation temperature of soot make this diagnostic highly selective against the detection of other species. A coupled set of differential equations can be used to model the change in temperature and mass of a soot particle over time. Methods for modeling the fundamental processes in LII were reviewed in this work and comparisons were made between several different models.</p><p dir="ltr">International Sooting Flame target conditions were used to form a laminar diffusion flame in a Yale burner with a range of soot levels. Soot volume fraction measurements were conducted and compared with other experimental values to validate the accuracy of the experimental setup and techniques used. A calibration was performed using a laser extinction measurement from a previous study. Results showed an overall increase in soot volume fraction with increasing percentages of ethylene, as well as a transition in the peak location. Time-resolved LII was conducted at 10 MHz to determine the primary particle size of soot particles. Larger primary particles were observed with increasing height for flames with higher ethylene content. Changes in the soot formation and surface growth rates are suspected factors in the observed trends in the data. </p><p dir="ltr">The overall objective of this study was to validate an experimental setup for Laser-Induced Incandescence using a laminar diffusion flame. LII measurements were successfully demonstrated using the same diagnostic setup in a liquid-fueled swirl-stabilized flame at aircraft engine-relevant conditions. This study sets the groundwork for further investigation into aircraft soot generation using LII. </p>