Dissertationen zum Thema „Chamba Masks“

Surgical masks are intended to be used to prevent transmission of disease from a health care worker to a patient. Often times, they are relied upon by health care workers for their own protection. In light of recent developments regarding preparation for health care worker response to global infectious diseases such as H1N1 Influenza, health care workers may experience a false sense of security when wearing surgical masks. The goal of this study was to evaluate the filtration efficiency of a double strap tie-on surgical mask. The manufacturer asserts a >95% efficiency with a 0.1 um challenge aerosol under FDA testing procedures. The NIOSH Title 42 CFR Part 84 certification criteria call for testing at a rate of 85 lpm representing a human moderate to heavy work load breathing rate. Three sizes of monodispersed aerosols (polystyrene latex beads: 0.5 um, 1.0 um, 2.0 um) were used. The specific aims were to measure the collection efficiencies of this mask for the various particle sizes. Two tests were performed. In the first, masks were affixed to a dummy head and the edges of the mask were not sealed. In the second, the edges of the masks were sealed to the head using silicone sealant, so all penetration was through the filtering material of the mask. Differences in upstream and downstream particle concentrations were measured. Thus, penetration by leakage around the mask and through the filtering material was measured. The experimental set up involved passing the aerosol from the nebulizer through a diffusion dryer and Kr-85 charge equilibrator ensuring a dry charge neutralized aerosol cloud for detection by a LASAIR particle counter. The analysis revealed that the filtration efficiency for 0.5 um particles ranged from 3% to 43% for the unsealed masks and 42% to 51% for the sealed. For 1.0 um particles, the efficiency was 58% to 75% for unsealed and 71% to 84% for sealed masks. For 2.0 um, the efficiency was 58% to 79% for unsealed masks and 69% to 85% for the sealed masks. The data were statistically significant and indicated that surgical masks were associated with very low filtration efficiency. This suggests that they may be inadequate against airborne viruses and bacteria.

Magma chambers are a fundamental component of crustal magma transport modulating erupted volumes, compositions, and timing of eruptions. However, we understand little about how eruption episodicity relates to magma chamber evolution. A sizable amount of research has been done on the thermo-mechanical and chemical evolution of a chamber, but little has been done in combining the two. The many influences on composition make inference of crustal processes from erupted compositions dicult, but there are patterns of eruptive evolution in well- characterized systems that suggest something systematic is occurring. We have developed a coupled thermo-mechanical-chemical model in order to characterize melt evolution through cycles of chamber filling, rupture, and drainage in a thermally evolving, viscoelastic crust. We consider a deeply seated oblate spheroidal chamber, calculating pressure, temperature, volume, elemental concentration, partitioning between crystals and melt, and crustal temperature through time. We characterize the time dependence of chamber failure, thermal longevity, and melt elemental concentrations on mechanical parameters and influx rates, exploring the dependence on depth, primary and crustal compositions. These results should be important for constraining physical controls on eruption episodicity and predictions of instability at magmatic centers.

Les nombres magiques ou fermetures de couche sont une des caractéristiques importantes de la structure nucléaire, mais qui sont modifiés loin de la vallée de stabilité. La détermination de l'énergie de liaison, via des mesures de masse sur les noyaux exotiques, représente un des plus grands challenge dans l'étude de la structure nucléaire à cause de la précision importante qui est nécessaire, et du faible taux de production, ainsi que les courtes durées de vie. Afin de résoudre le problème, deux spectromètres de masse ISOLTRAP et MISTRAL peuvent être utilisés, tous les deux situés à ISOLDE/CERN (Genève). MISTRAL est un spectromètre de masse à transmission pour les noyaux de courtes durées de vie, et ISOLTRAP est un spectromètre de masse basé sur l'utilisation de pièges de Penning, qui effectue des mesures de masses de haute précision. Cette thèse décrit les techniques pour repousser les limites de ces deux instruments complémentaires: un système de refroidissement de faisceau pour améliorer la sensibilité de MISTRAL et une procédure d'optimisation pour améliorer la définition des champs de piégeage d'ISOLTRAP. Des mesures très précises ont été effectuées avec ISOLTRAP afin d'augmenter le nombre de noyaux très bien connus dans la table de masse, et afin d'examiner le cas de deux nouveauxnombres magiques N = 32 et N = 40. Les résultats montrent un surplus d'énergie de liaison pour le 56Cr32 dû à la présence d'une probable déformation. Pour le 68Ni40, il n'y a pas d'effet de liaison supplémentaire bien qu'un faible effet apparaisse, peut-être dû à une compétition avec la demi-couche à N = 39
Magic numbers or shell closures, are an important feature of nuclear structure, but now found to be modified far from stability. Determination of the nuclear binding energy via mass measurements of exotic nuclides represents one of the greatest challenges in the study of nuclear structure due to the high precision required and the low production rates and short half-lives. To solve the problem, the complementary spectrometers MISTRALand ISOLTRAP may be used, both located at ISOLDE/CERN (Geneva). MISTRAL is a transmission mass spectrometer for very short-lived nuclides, and ISOLTRAP a Penningtrap mass spectrometer providing exceptional precision. This thesis describes improvements in the limitations of these complementary instruments: a beam cooler to increase the sensitivity of MISTRAL and an optimization procedure to improve the definition ofthe ISOLTRAP trapping fields. High-precision mass measurements were performed at ISOLTRAP to extend the backbone of well-known nuclides in the mass table, and to finely examine the case for new magic numbers N = 32 and 40. The results illustrate a subtle effect of extra binding energy for 56Cr32 in the presence of a probable deformation. Practically no additional binding is found for 68Ni40 though a small effect is visible, perhaps in conjunction with a competitive mid-shell effect at N = 39

The research in this dissertation explored the sources and chemistry of organic nitrogen aerosols in the atmosphere. Two approaches were employed: field measurements and laboratory experiments. In order to characterize atmospheric aerosol, two ambient studies were conducted in Cache Valley in Northern Utah during strong winter inversions of 2004 and 2005. The economy of this region is heavily dependent on agriculture. There is also a fast growing urban population. Urban and agricultural emissions, aided by the valley geography and meteorology, led to high concentrations of fine particles that often exceeded the national ambient air quality standards. Aerosol composition was dominated by ammonium nitrate and organic species. Mass spectra from an aerosol mass spectrometer revealed that the organic ion peaks were consistent with reduced organic nitrogen compounds, typically associated with animal husbandry practices. Although no direct source characterization studies have been undertaken in Cache Valley with an aerosol mass spectrometer, spectra from a study at a swine facility in Ames, Iowa, did not show any evidence of reduced organic nitrogen species. This, combined with temporal and diurnal characteristics of organic aerosol peaks, was a pointer that the organic nitrogen species in Cache Valley likely formed from secondary chemistry. Application of multivariate statistical analyses to the organic aerosol spectra further supported this hypothesis. To quantify organic nitrogen signals observed in ambient studies as well as understand formation chemistry, three categories of laboratory experiments were performed. These were calibration experiments, smog chamber studies, and an analytical method development. Laboratory calibration experiments using standard calibrants indicated that quantifying the signals from organic nitrogen species was dependent on whether they formed through acid-base chemistry or via secondary organic aerosol pathway. Results from smog chamber reactions of amines with ozone, nitrogen oxides, nitrate radical, and nitric acid showed that the secondary organic aerosol pathway was more plausible than acid-base chemistry, thus making the contribution of the organic nitrogen species to the total aerosol mass in Cache Valley significant. Gas phase and aerosol products formed from the smog chamber reactions were identified and used to devise reaction mechanisms. Finally, an ion chromatographic method for detecting and quantifying some key organic nitrogen species in aerosol was developed and tested.

The different technologies of passive cooling concepts have to rely on a good thermal coupling between a building's thermal mass and indoor air. In many cases, the ceiling is the only surface remaining for a good coupling. Further research is necessary to investigate discrepancies between existing correlations. Therefore, the overall aim of the work described in this thesis is the investigation of heat transfer at a heated ceiling in an experimental chamber. Acoustic baffles obstruct the surface of the ceiling and impede heat transfer. However, there is nearly no published data about the effect of such baffles on heat transfer. Available results from simulations should be verified with an experimental investigation. Consequently, one of the primary aims of this work was to experimentally determine the influence of such acoustic baffles. A suitable experimental chamber has been built at Biberach University of Applied Sciences. The thesis describes the experimental chamber, the experimental programme as well as results from five different test series. With a value of ±0.1Wm⁻²K⁻¹ for larger temperature differences, uncertainty in resulting convective heat transfer coefficients for natural convection is comparable to that of results from an existing recent experimental work often recommended for use. Additionally, total heat transfer (by convection and radiation) results are presented. Results are given for natural, forced and mixed convection conditions at an unobstructed heated ceiling. Furthermore, results for acoustic baffles in both an unventilated and a ventilated chamber are shown. Natural convection results show a very good agreement with existing correlations. Under mixed convection conditions, convective heat transfer at an unobstructed ceiling decreases to the limiting case described by natural convection. Installation of acoustic baffles leads to a reduction in total heat transfer (convection and radiation) between 20% and 30% when compared to the case of an unobstructed ceiling.

Volatile organic compounds (VOCs) are organic compounds which exist in the gas phase at room temperature and atmospheric pressure. The lifespan of VOCs in the Earth's atmosphere ranges from a few minutes to months. Many VOCs are dangerous to human health and can undergo oxidation mediated aggregation to form secondary organic aerosols which are equally detrimental to human health. VOCs come from biogenic and anthropogenic sources, however, in cities, anthropogenic sources are dominant. A significant portion of these anthropogenic VOCs are coming from diesel vehicle emissions. Chemical composition of VOCs from diesel exhaust is complex and varies with the engine technology, driving conditions and fuel used. Previously, VOCs have been measured using offline methods which required sample collection over a period (making it difficult to capture their temporal variability) and sample preparation (making the whole process time-consuming). The development of online mass spectrometrybased measurement techniques enabled monitoring VOCs in real time. Real time measurement of VOCs from the atmosphere is based on chemical ionisation mass spectrometry with hydronium ions as reagent ions. This was because hydronium ion allows the instrument to detect compounds that have proton affinity (PA) higher than that of water. Normal air components like N2 and O2 all have PA lower than water, however most of the saturated and unsaturated volatile organic compounds emitted from diesel exhaust have PA higher than water. The most commonly used instruments for atmospheric VOC measurement are Proton Transfer Reaction-Mass Spectrometer (quadrupole and Time of Flight), Selective Ion Flow Tube-Mass Spectrometer. The Aerodyne Chemical Ionisation Mass Spectrometer (CIMS) is a more recent instrument that allows the use of different reagent ions including hydronium ion H3O+. While both PTR-MS and SIFT-MS ionise samples at relatively low pressure (1-2 mbar) and their ionisation chambers been extensively studied, ion-Molecule Reaction (IMR) chamber in H3O+-CIMS operates at substantially higher pressure (~100 mbar) and, therefore, reagent ion distribution and ionisation chemistry are likely to be significantly different from the ones in PTR-MS and SIFT-MS. However, performance of the H3O+-CIMS has not been characterised in detail yet nor has this instrument been applied to investigate VOCs coming from diesel exhaust. This study is, therefore, aimed at characterising the performance of Aerodyne TOF-CIMS with H3O+ as reagent ions, herein referred to as H3O+-CIMS and later using the same for characterisation of diesel exhaust VOCs. In characterising the H3O+-CIMS, the influence of the pressure inside the IMR chamber and SSQ (small sequential quadrupole) chamber on the intensity of reagent ions was explored. It was found that the optimum pressures for IMR and SSQ were ≥ 160 mbar and ≥ 2.3 mbar respectively. Exploration of radio frequency (RF) voltages of quadrupole ion guides inside the atmospheric pressure interface showed that 200V for the SSQ and 350V for the big sequential quadrupole (BSQ) are the optimum RF voltages for obtaining a maximum reagent ion signal intensity. The sensitivity of the instrument towards some common VOCs was determined using a custom-made VOC mixture. It was found that H3O+-CIMS was more sensitive to oxygenated VOCs compared to non-oxygenated VOCs. The sensitivity to oxygenated VOCs was comparable to PTR-MS and SIFT-MS while it was lower for non-oxygenated VOCs. It was also observed that relative humidity of the incoming air influences VOCs signal intensity with different compounds showing different RH dependence. Hydrate formation was explored as PTR-MS and SIFT-MS have both shown the formation of hydrate with increase in humidity. In dry conditions with RH of 5%, hydrates were not formed for both non-oxygenated and oxygenated VOCs (NO-VOCs and O-VOCs respectively) except for acetonitrile with hydrate composition of ~7 – 25%. However, as RH increased to ~90%, hydrate composition was 10% 60% for NO-VOCs and ~ 3% to 4% for oxygenated VOCs. The instrument was tuned using 2 different tuning approaches - one aimed at maximising m/z 19 signal (H3O+) relative to the m/z 37 signal (H5O2 +) which maximises ion declustering and the other aimed at maximising m/z 37 signal (H5O2 +) relative to m/z 19 signal (H3O+) which minimises ion declustering. It was found that reagent ions and VOC signals were the highest with m/z 19 tuning approach. After characterisation, the H3O+-CIMS was used to investigate VOCs from diesel exhaust. A total of 256 peaks were identified within a m/z range 15Th – 200Th, could not go beyond m/z 200 because peak resolution becomes very difficult beyond this point. 179 VOCs remained after the background had been subtracted, 44 of these VOCs were non-oxygenated hydrocarbon species, 79 were oxygenated species, 50 were nitrogen containing species and 9 were sulphur containing species. VOC emissions from 3 diesel engines (Perkins, Kubota and Cummins) running on neat diesel fuel were compared. Cummins engine was found to emit the least number of VOCs in m/z 15 – 200 range which might be because it uses a common rail injection system unlike the other two engines, which utilise direct injection. When VOC emissions from neat diesel (D100) were compared with neat biodiesel (B100) using 3 diesel engines, benzene, toluene and xylene emissions were higher in B100 compared to D100 in all the engines. Similar trend was observed for CH5O+, C2H5O+, C4H5O+ and C5H9O+. This may be due to higher oxygen content in biodiesel compared to diesel fuel. However, a set of measurements was conducted where oxygen content of the fuel was varied by the use of biodiesel blends and it was shown that increasing the oxygen content of the fuel does not necessarily translate to increase in emissions of oxygenated VOCs. The role of oxygen content in the fuel was found to be compound dependent instead. It was also found that benzene, toluene and xylene emissions generally decreased with increase in oxygen content. The contribution of this study to knowledge is that H3O+ -CIMS with IMR inlet is a useful tool in analysing VOCs emitted from diesel exhaust. This study is among the few studies that have identified hydrogen cyanide to be among the VOCs emitted from diesel exhaust. It also showed that neat biodiesel had the highest number of oxygenated VOCs peaks despite the diesel engine used. Lastly, it was shown that increasing the oxygen content of the fuel does not necessarily mean that oxygenated VOC emissions will increase.

The literature identifies several models that describe inter-phase mass transfer, key to the emission process. While the emission process is complex and these models may be more or less successful at predicting mass transfer rates, they identify three key variables for a system involving a liquid and an air phase in contact with it: • A concentration (or partial pressure) gradient driving force; • The fluid dynamic characteristics within the liquid and air phases, and • The chemical properties of the individual components within the system. In three applied research projects conducted prior to this study, samples collected with two well-known sampling devices resulted in very different odour emission rates. It was not possible to adequately explain the differences observed. It appeared likely, however, that the sample collection device might have artefact effects on the emission of odorants, i.e. the sampling device appeared to have altered the mass transfer process. This raised the obvious question: Where two different emission rates are reported for a single source (differing only in the selection of sampling device), and a credible explanation for the difference in emission rate cannot be provided, which emission rate is correct? This research project aimed to identify the factors that determine odour emission rates, the impact that the characteristics of a sampling device may exert on the key mass transfer variables, and ultimately, the impact of the sampling device on the emission rate itself. To meet these objectives, a series of targeted reviews, and laboratory and field investigations, were conducted. Two widely-used, representative devices were chosen to investigate the influence of various parameters on the emission process. These investigations provided insight into the odour emission process generally, and the influence of the sampling device specifically.

L’aérosol organique secondaire (AOS), fraction majoritaire de l’aérosol submicronique, joue un rôle important sur la santé, l’environnement et le climat. L’évaluation de son impact constitue un véritable enjeu pour la communauté scientifique. Toutefois, nos connaissances actuelles sur les processus de formation d’AOS et sa composition chimique sont encore très lacunaires, et en l’occurrence, limitent le développement des modèles atmosphériques permettant de quantifier les impacts des AOS sur la qualité de l’air et le système climatique. Ainsi, l’objectif de ce travail est de produire un ensemble de données expérimentales fournissant des points de contrainte afin d’évaluer et d’améliorer les modèles. Pour ce faire, la formation d’AOS a été étudiée à partir de la photooxydation d’un précurseur modèle, le n-dodécane, dans la chambre de simulation atmosphérique CESAM. La composition chimique a été élucidée par des techniques spectrométriques et chromatographiques permettant d’identifier les différentes espèces constituant la phase gazeuse et particulaire. En particulier, de nouveaux mécanismes en phase condensée ont été proposés afin d’expliquer la formation des acides carboxyliques et des lactones, identifiés pour la première fois dans l’AOS d’un alcane. Ces derniers pourront être implémentés dans les modèles. Une grande diversité de conditions environnementales, telles que la température, l’humidité relative et la présence/absence de particules préexistantes, a été prise en compte dans ces travaux. Notamment, l’étude de l’influence de la température a mis en évidence une faible sensibilité de ce paramètre sur les rendements de production d’AOS. Tandis que l’étude sur l’effet de l’humidité relative, elle, a montré que l’ajout d’eau dans le système réactionnel au-delà de 5% abaisse les rendements d’AOS de près d’un facteur 2 en comparaison à des conditions sèches. Ainsi, la formation potentielle d’AOS sous ces différentes conditions a permis d’aboutir à des paramétrisations directement utilisables par les modélisateurs. Une caractérisation des effets de paroi dans CESAM, i.e. les pertes en phase gazeuse et particulaire, a également été menée
Secondary Organic Aerosol (SOA), the major fraction of the submicron aerosol, plays a key role on health, environment and climate. The evaluation of its impacts is a real challenge for the scientific community. Our current knowledge of SOA formation processes and chemical composition is still very deficient and limit the development of atmospheric models to quantify the impacts of SOA on air quality and climate system. Therefore, the aim of this work is to produce a set of experimental data to use to constrain and improve the models. To do that, the SOA formation has been studied from the photooxidation of a model precursor, n-dodecane, in the CESAM environmental chamber. The chemical composition has been investigated by spectrometric and chromatographic techniques which allowed us to identify the reaction products constituting the gaseous and particulate phases. In particular, new condensed phase mechanisms have been proposed to explain the formation of carboxylic acids and lactones, identified for the first time. These could be implemented in the models. A wide variety of environmental conditions, such as temperature, relative humidity and the presence/absence of preexisting particles, have been taken into account in this work. The study of the temperature influence has shown a low sensitivity of this parameter on the SOA production. While the study relative humidity effect has shown that adding water to the reaction system beyond 5% lowers SOA yields by almost a factor of 2 in comparison to dry conditions. The SOA formation potential, under these conditions, has been evaluated, and resulted in parameterizations which could be useful for modelers. Furthermore, a characterization of the wall effects in CESAM, i.e. gas and particulate phase wall losses, has been carried out

Organic aerosols represent one of the main sources of uncertainty affecting attempts to quantify anthropogenic climate change. The diverse physical and chemical properties of organic aerosols and the varied pathways involved in their formation and aging form the basis of this uncertainty, preventing extensive and accurate representation within regional and global scale models. This inability to constrain the radiative forcings produced by organic aerosols within the atmosphere consequently acts as a limitation to the wider objective of providing reliable projections of future climate. Biomass burning constitutes one of the main anthropogenic contributions to the global atmospheric organic aerosol (OA) burden, particularly in tropical regions where the potential for perturbations to the climate system is also enhanced due to higher average levels of solar irradiance. Emissions from biomass burning have been the subject of an intense research focus in recent years, involving a combination of field campaigns and laboratory studies. These experiments have aimed to improve the limited understanding of the processes involved in the evolution of biomass burning organic aerosol (BBOA) and contribute towards the development of more robust parameterisations for climate and chemical transport models. The main objective of this thesis was to use datasets acquired from several different global regions to perform a broad analysis of the BBOA fraction, with the extensive temporal and spatial scales provided by such measurements enabling investigation of a number of key uncertainties, including regional variability in emissions and the role of secondary organic aerosol (SOA) formation in aging smoke plumes. Measurements of BBOA mass concentration obtained using Aerodyne Research Inc. Aerosol Mass Spectrometers (AMS) were used to calculate characteristic ΔOA/ΔCO ratios for different environments, accounting for the effects of dilution and contrasting fire sizes to give a proportional representation of OA production. High levels of variability in average ΔOA/ΔCO were observed both between and within different regions. The scale of this variability consistently exceeded any differences between plumes of different ages, while a widespread absence of any sustained increase in ΔOA/ΔCO with aging indicates that SOA formation does not provide a net increase in OA mass. Despite this lack of OA enhancement, increasing proportions of oxygenated OA components in aged plumes highlight the chemical transformations occurring during the evolution of BBOA, and the additional influence of OA loss through evaporation or deposition. Potential drivers of variability in ΔOA/ΔCO at source, such as changes in fuel types and combustion conditions, were investigated for controlled fires carried out within a combustion chamber. These laboratory experiments revealed a number of complex relationships between BB emissions and source conditions. Although ΔOA/ΔCO was shown to be influenced by both fuel properties and transitions between flaming and smouldering combustion phases, the extent of these effects was limited, while variability between fires exceeded levels observed for ambient measurements. These findings emphasise the complexity of the BBOA lifecycle and the need to address the extensive uncertainties associated with its various constituent processes, in order to improve understanding of eventual climate impacts from biomass burning.

Le monoxyde d’azote (NO) est connu pour ses nombreuses actions afin de maintenir l’homéostasie de la barrière intestinale, régulant la sécrétion de mucus, le stress oxydant, le système immunitaire… Le S-nitrosoglutathion (GSNO), donneur de NO naturellement produit par l’organisme, a montré une action bénéfique sur le renforcement de la barrière intestinale. L’enjeu est aujourd’hui de comprendre les mécanismes inhérents à cette observation. Pour ce faire une étude en Chambre de Ussing a été menée. Une fois le modèle d’étude validé par le suivi de marqueurs de perméabilité, les études histologiques et d’expression des protéines de jonctions cellulaires, le métabolisme du GSNO administré dans la lumière de l’intestin ont été explorés. Également, l’effet du GSNO sur la perméabilité de la barrière intestinale a été étudié. Les résultats permettent aujourd’hui d’envisager le GSNO comme une piste thérapeutique intéressante et prometteuse aux multiples applications possibles : intestinales, cardiovasculaires ou encore cérébrales
Nitric oxide is known for its many actions to maintain intestinal barrier homeostasis, regulating mucus secretion, oxidative stress, immune system… S-nitrosoglutathione (GSNO), a nitric oxide donor naturally produced by the organism, has shown a beneficial effect on the intestinal barrier reinforcement. Nowadays, challenge is to understand the mechanisms inherent to this observation. For that, a Ussing chamber study was performed. After the model validation, by following permeability markers, histological studies, and cell junction proteins expression study, the GSNO metabolism administered in the intestinal lumen was explored. Also, GSNO effect on the intestinal barrier permeability was evaluated. Results allow today to consider GSNO as an interesting and promising drug candidate, in the context of intestinal, cardiovascular or cerebral pathologies

Le champ électrique d'une puissance suffisante peut provoquer une augmentation de conductivité et perméabilité de la membrane cellulaire. L'effet est connu comme l'électroporation, attribuée à la création de voies aqueuses dans la membrane. Quantifier le transport de la matière dans le cadre d'électroporation est un objectif important. Comprendre ces processus a des ramifications dans l’extraction du jus ou l’extraction sélective des composés de cellules végétales, l'amélioration de l'administration de médicaments, et des solutions aux défis environnementaux. Il y a un manque de modèles qui pourraient être utilisés pour modéliser le transport de la matière dans les structures complexes (tissus biologiques) par rapport à l'électroporation. Cette thèse présente une description mathématique théorique (un modèle) pour étudier le transport de la matière et le transfert de la chaleur dans tissu traité par l’électroporation. Le modèle a été développé en utilisant les lois de conservation et de transport et permet le couplage des effets de l'électroporation sur la membrane des cellules individuelles au transport de la matière ou la chaleur dans le tissu. Une solution analytique a été trouvée par une simplification, mais le modèle peut être étendu avec des dépendances fonctionnelles supplémentaires et résolu numériquement. La thèse comprend cinq articles sur l'électroporation dans l'industrie alimentaire, la création de modèle pour le problème de diffusion, la traduction du modèle au problème lié à l’expression de jus, validation du modèle, ainsi que des suggestions pour une élaboration future du modèle. Un chapitre supplémentaire est dédié au transfert de la chaleur dans tissu
An electric field of sufficient strength can cause an increase of conductivity and permeability of cell membrane. Effect is known as electroporation and is attributed to creation of aqueous pathways in the membrane. Quantifying mass transport in connection with electroporation of biological tissues is an important goal. The ability to fully comprehend transport processes has ramifications in improved juice extraction and improved selective extraction of compounds from plant cells, improved drug delivery, and solutions to environmental challenges. While electroporation is intensively investigated, there is a lack of models that can be used to model mass transport in complex structures such as biological tissues with relation to electroporation. This thesis presents an attempt at constructing a theoretical mathematical description – a model, for studying mass (and heat) transfer in electroporated tissue. The model was developed employing conservation and transport laws and enables coupling effects of electroporation to the membrane of individual cells with the resulting mass transport or heat transfer in tissue. An analytical solution has been found though the model can be extended with additional dependencies to account for the phenomenon of electroporation, and solved numerically. Thesis comprises five peer-reviewed papers describing electroporation in the food industry, model creation for the problem of diffusion, translation of the model to the mathematically-related case of juice expression, model validation, as well as suggestions for possible future development, extension, and generalization. An additional chapter is dedicated to transfer of heat in tissue

O objetivo desta tese é o estudo de formação de fuligem em chamas laminares de difusão. Para o modelo de formação de fuligem é escolhido um modelo semi-empírico de duas equações para prever a fração mássica de fuligem e o número de partículas de fuligem. O modelo descreve os processos de nucleação, de crescimento superficial e de oxidação das partículas. Para o modelo de radiação, a perda de calor por radiação térmica (gás e fuligem) é modelada considerando o modelo de gás cinza no limite de chama opticamente fina (OTA - Optically Thin Approximation). São avaliados diferentes modelos de cálculo das propriedades de transporte (detalhado e simplificado). Em relação à cinética química, tanto modelos detalhados quanto reduzidos são utilizados. No presente estudo, é explorada a técnica automática de redução conhecida como Flamelet Generated Manifold (FGM), sendo que esta técnica é capaz de resolver cinética química detalhada com tempos computacionais reduzidos. Para verificar o modelo de formação de fuligem foram realizados uma variedade de experimentos numéricos, desde chamas laminares unidimensionais adiabáticas de etileno em configuração tipo jatos opostos (counterflow) até chamas laminares bidimensionais com perda de calor de etileno em configuração tipo jato (coflow). Para testar a limitação do modelo os acoplamentos de massa e energia entre a fase sólida e a fase gasosa são investigados e quantificados para as chamas contra-corrente Os resultados mostraram que os termos de radiação da fase gasosa e sólida são os termos de maior importancia para as chamas estudas. Os termos de acoplamento adicionais (massa e propriedade termodinâmicas) são geralmente termos de efeitos de segunda ordem, mas a importância destes termos aumenta conforme a quantidade de fuligem aumenta. Como uma recomendação geral o acoplamento com todos os termos deve ser levado em conta somente quando a fração mássica de fuligem, YS, for igual ou superior a 0.008. Na sequência a formação de fuligem foi estudada em chamas bi-dimensionais de etileno em configuração jato laminar usando cinética química detalhada e explorando os efeitos de diferentes modelos de cálculo de propriedades de transporte. Foi encontrado novamente que os termos de radiação da fase gasosa e sólida são os termos de maior importância e uma primeira aproximação para resolver a chama bidimensional de jato laminar de etileno pode ser feita usando o modelo de transporte simplificado. Finalmente, o modelo de fuligem é implementado com a técnica de redução FGM e diferentes formas de armazenar as informações sobre o modelo de fuligem nas tabelas termoquímicas (manifold) são testadas A melhor opção testada neste trabalho é a de resolver todos os flamelets com as fases sólida e gasosa acopladas e armazenar as taxas de reação da fuligem por área de partícula no manifold. Nas simulações bidimensionais estas taxas são então recuperadas para resolver as equações adicionais de formação de fuligem. Os resultados mostraram uma boa concordância qualitativa entre as predições do FGM e da solução detalhada, mas a grande quantidade de fuligem no sistema ainda introduz alguns desafios para a obtenção de bons resultados quantitativos. Entretanto, este trabalho demonstrou o grande potencial do método FGM em predizer a formação de fuligem em chamas multidimensionais de difusão de etileno em tempos computacionais reduzidos.
The objective of this thesis is to study soot formation in laminar diffusion flames. For soot modeling, a semi-empirical two equation model is chosen for predicting soot mass fraction and number density. The model describes particle nucleation, surface growth and oxidation. For flame radiation, the radiant heat losses (gas and soot) is modelled by using the grey-gas approximation with Optically Thin Approximation (OTA). Different transport models (detailed or simplified) are evaluated. For the chemical kinetics, detailed and reduced approaches are employed. In the present work, the automatic reduction technique known as Flamelet Generated Manifold (FGM) is being explored. This reduction technique is able to deal with detailed kinetic mechanisms with reduced computational times. To assess the soot formation a variety of numerical experiments were done, from one-dimensional ethylene counterflow adiabatic flames to two-dimensional coflow ethylene flames with heat loss. In order to assess modeling limitations the mass and energy coupling between soot solid particles and gas-phase species are investigated and quantified for counterflow flames. It is found that the gas and soot radiation terms are of primary importance for flame simulations. The additional coupling terms (mass and thermodynamic properties) are generally a second order effect, but their importance increase as the soot amount increases As a general recommendation the full coupling should be taken into account only when the soot mass fraction, YS, is equal to or larger than 0.008. Then the simulation of soot is applied to two-dimensional ethylene co-flow flames with detailed chemical kinetics and explores the effect of different transport models on soot predictions. It is found that the gas and soot radiation terms are also of primary importance for flame simulations and that a first attempt to solve the two-dimensional ethylene co-flow flame can be done using a simplified transport model. Finally an implementation of the soot model with the FGM reduction technique is done and different forms for storing soot information in the manifold is explored. The best option tested in this work is to solve all flamelets with soot and gas-phase species in a coupled manner, and to store the soot rates in terms of specific surface area in the manifold. In the two-dimensional simulations, these soot rates are then retrieved to solve the additional equations for soot modeling. The results showed a good qualitative agreement between FGM solution and the detailed solution, but the high amount of soot in the system still imposes some challenges to obtain good quantitative results. Nevertheless, it was demonstrated the great potential of the method for predicting soot formation in multidimensional ethylene diffusion flames with reduced computational time.

Se compararon dos experiencias de inducción anestésica en seis gatos premedicados con acepromacina y buprenorfina: cámara (exp. 1) o mascarilla (exp. 2). En cada experiencia se empleó isofluorano o sevofluorano vehiculados en oxígeno o en una mezcla de oxígeno y óxido nitroso según grupo. Se valoró la calidad de forma subjetiva y la velocidad de inducción en base a distintos tiempos medidos durante esta fase. Tras un mantenimiento de treinta minutos en el que se registraron distintos parámetros cardiorrespiratorios y la temperatura corporal, se evaluó la calidad y velocidad de recuperación anestésica. No se observaron diferencias en cuanto a los tiempos o calidad de inducción o recuperación anestésica entre isofluorano o sevofluorano con o sin óxido nitroso. Los parámetros cardiorrespiratorios durante el mantenimiento fueron similares entre grupos. En conclusión, a pesar de las mejores propiedades del sevofluorano, el isofluorano sigue siendo un anestésico de elecció n para procedimientos de corta duración en gatos.

Laboratory based temperature-dependent kinetics and product yields for alkene ozonolysis and the reaction of CH3O2 with ClO and BrO have been measured via chamber studies and a turbulent flow tube coupled to CIMS (Chemical Ionisation Mass Spectrometry). In order to gain a better understanding of the fate of the products formed during hydrocarbon oxidation and their subsequent impact on the ozone budget (and so the oxidising capacity of the atmosphere) it is imperative to know the rate at which these reactions proceed and to identify their product yields. As tropospheric temperature varies, Arrhenius parameters were determined during the ozonolysis of selected alkenes. The temperature dependent kinetic database was extended and the activation energies for the ozonolysis of selected alkenes were correlated with an existing SAR (Structure Activity Relationship). Given the myriad organic species in the atmosphere, SARs are useful tools for the prediction of rate coefficients. Inclusion of Arrhenius parameters into the SAR allows for prediction over a range of temperatures, improving the conditions reflected in models. Achieving mass balance for alkene ozonolysis has proven to be a difficult challenge considering the numerous pathways of the Criegee Intermediate (CI). The product yield of formic acid – an organic acid with significant atmospheric implications which is under predicted by models – was determined as a function of relative humidity during ethene ozonolysis. This reaction exhibited a strong water dependence which lead to the prediction of the reaction rate of the CI with water which ranges between 1 × 10-12 – 1 × 10-15 cm3 molecule-1 s-1 and will therefore dominate its loss with respect to bimolecular processes in the atmosphere. Peroxy radicals, strongly influence the total oxidising capacity of the troposphere. The reaction of peroxy radicals with halogen oxides is recognised to be responsible for considerable ozone depletion in the atmosphere, exacerbated by reactive halogens (X, XO) taking part in catalytic cycles. Arrhenius parameters were determined for ClO + CH3O2 and BrO + CH3O2. Temperature is an important parameter affecting rate, exemplified here as the reaction involving ClO exhibited a positive temperature dependence whereas for BrO a negative temperature dependence was evident. As a consequence, the impact of ClO + CH3O2 with respect to ozone loss is diminished. Global modelling predicts a reduction in ozone loss by a factor of around 1.5 and implicates regions such as clean marine environments rather than the polar stratosphere. Conversely, a more pronounced temperature dependence for the reaction of BrO with CH3O2 placed particular importance on lower stratospheric chemistry where the modelled CH3O2 oxidation is doubled. The main products for this reaction were identified to be HOBr and CH2O2. The decomposition of CH2O2 could enhance HOx in the lower and middle stratosphere and contribute to a significant source of HOx in the upper troposphere. Bimolecular reaction of CH2O2 with water could also provide a none negligible source HC(O)OH in the upper troposphere. Alkenes and peroxy radicals undergo chemical processing in the atmosphere whilst acting as a source and sink of ozone and thus can impose detrimental effects on the biosphere, climate and air quality of the Earth.

Le travail présenté dans ce mémoire consiste à adapter la méthode de corrélation d'images numériques (CIN) pour la gestion des discontinuités du milieu et de la transformation. Le cadre d'utilisation des méthodes optiques de mesure i.e. celui de la mécanique des milieux continus, impose une continuité matérielle : i) du domaine et ii) de la transformation. Pour traiter les discontinuités en question, on peut reconsidérer la continuité (milieu et transformation) par morceaux. Dans le cadre de la CIN, cela se traduit par la possibilité d'adapter localement la forme et la taille des fenêtres de corrélation à la zone d'intérêt et à sa cinématique. Pour ce faire, il est possible d'utiliser des masques : un masque-objet pour traiter les discontinuités du milieu et un masque-discontinuité pour traiter les discontinuités de la transformation. Cependant, avant l'implémentation des masques dans la procédure de corrélation, plusieurs essais expérimentaux de déplacement sur des modèles comportant les deux types de discontinuité, ont été conduits. Ces essais ont permis de prouver l'influence des discontinuités sur la dégradation de la précision de mesure par CIN. Ensuite, des essais de traction ont été menés sur une éprouvette en polycarbonate conduisant à un mode I d'ouverture ou de fermeture de fissure. Après l'implémentation des masques dans le logiciel de corrélation Correla, le calcul des champs de déplacement et de déformation a été opéré avec succès à la surface de cette éprouvette, démontrant ainsi l'efficacité de la CIN adaptée
The development of the digital image correlation method (DIC) for the management of discontinuities of the material and the transformation is discussed in this thesis. As we know, the framework for the use of the optical measurement methods i.e. of continuum mechanics requires a continuity of: i) domain and ii) transformation. To treat those discontinuities, we can consider a piecewise continuity (material and transformation). In the case of DIC method, this can be done by adapting locally the shape and size of the correlation subsets to the zone of interest and its kinematics. A novel way to do it, is by using masks: an object mask to process material discontinuities and a discontinuity mask to process transformation discontinuities. However before the implementation of masks in the correlation process, several experimental displacement tests on models reproducing the two types of discontinuity at small scale were performed. Those tests proved the influence of discontinuities on the degradation of the measurement accuracy by DIC. Then, tensile tests were conducted on a polycarbonate made specimen knowing a mode I opening or closing crack. After implementing masks in the correlation software Correla, the calculation of displacement and deformation fields was successfully performed on the surface of this specimen for all its edges, demonstrating the effectiveness of the adapted DIC

In many instances, television news is the primary outlet through which people gain knowledge on climate change. Both the perceived threat of climate change and American news media have grown politically divided since the 1980s. I make the argument that American news media influences the partisan divide over climate change. In addition to the political landscape of news media, focus on political events and figures in climate coverage further contributes to a partisan divide. Supporting these claims are research displaying how climate change news is processed in a partisan manner and a selection of three case study periods in which climate change coverage spiked among MSNBC, CNN, and Fox News in the last twenty years (2000-2019). I collected news footage from all three case studies using the online database archive.org. Using this footage, an accompanying documentary short was produced that focused on the Paris Climate Accord Withdrawal in 2017. Presented in the documentary and the three case study periods, Fox News held a consistently hands-off and dismissive tone towards climate change, while MSNBC and CNN implemented climate science into coverage while advocating for collective climate action. I report that media is selected and processed via partisanship among viewers; these case studies illustrate the ways in which news media drives the political divide on climate change. I conclude by offering some future ways climate coverage can be more unifying, such as more emphasis on the economic benefits of “a green economy” in news coverage.

Les pertes thermiques d'une chambre froide s'ouvrant par glissement lateral sont mesurees a l'aide d'un thermoanemometre a fil chaud, ayant seize capteurs de mesure de la vitesse du courant d'air. Les resultats experimentaux sont correles par une loi qui exprime le debit massique en fonction de l'ecart de temperature. Des rideaux d'air protecteurs sont experimentes. Ils permettent un gain de 38% sur le debit massique d'air chaud entrant en chambre froide

Malgré la découverte des rayons cosmiques il y a plus de cent ans, de nombreuses questions restent aujourd’hui sans réponse : que sont les rayons cosmiques, comment sont-ils créés et d’où viennent-ils ? Depuis 2002, l’instrument CODALEMA, basé sur le site de l’Observatoire de radio-astronomie de Nançay, étudie les rayons cosmiques d’ultra haute énergie (RCUHE, au delà de 1017 eV) qui arrivent dans l’atmosphère terrestre. Leur faible flux rend impossible une détection directe à ces énergies. Ces rayons cosmiques vont cependant interagir avec les atomes de l’atmosphère, engendrant une cascade de particules secondaires chargées communément appelée gerbe de particules, détectable depuis le sol, et dont on va extraire des informations sur le rayon cosmique primaire. L’objectif est de remonter aux caractéristiques du primaire ayant engendré la gerbe de particules, donc de déterminer sa direction d’arrivée, sa nature et son énergie. Lors du développement de la gerbe, les particules chargées en mouvement engendrent notamment l’émission d’une impulsion de champ électrique très brève, que CODALEMA détecte au sol avec des antennes radio dédiées, sur une large bande de fréquences (entre 1 et 200 MHz). L’avantage majeur de la radio-détection est sa sensibilité au profil complet de la gerbe et son cycle utile proche des 100 %, qui pourrait permettre d’augmenter le nombre d’évènements détectés à très haute énergie, et donc de mieux contraindre les propriétés des RCUHE. Au fil des ans, des efforts importants ont été consacrés à la compréhension de l’émission radio-électrique des grandes gerbes de particules dans la gamme [20-80] MHz mais, malgré certaines études menées jusqu’aux années 90, la bande [1-10] MHz est restée inutilisée pendant près de 30 ans. L’une des contributions de cette thèse porte sur l’expérience EXTASIS, adossée à CODALEMA, qui vise à ré-investiguer cette bande et à étudier la contribution dite de ”mort subite”, impulsion de champ électrique créé par les particules de la gerbe lors de leur arrivée et de leur disparition au sol. Nous présentons la configuration instrumentale d’EXTASIS, composée de 7 antennes basses fréquences exploitées dans [1.7-3.7] MHz, couvrant environ 1 km2. Nous rapportons l’observation, sur 2 ans, de 25 évènements détectés en coïncidence par CODALEMA et EXTASIS et estimons un seuil de détection de 23±4 μV/m à partir de comparaisons avec des simulations. Nous rapportons également une forte corrélation entre l’observation du signal basse fréquence et le champ électrique atmosphérique. L’autre contribution majeure de cette thèse porte sur l’étude du champ électrique émis par les gerbes et l’amélioration des performances du détecteur dans la bande [20-200] MHz. Nous proposons dans un premier temps une méthode de calibration des antennes de CODALEMA en utilisant l’émission radio de la Galaxie. Nous investiguons aussi plusieurs algorithmes de réjection de bruit afin d’améliorer la sélectivité des évènements enregistrés. Nous présentons ensuite une méthode de reconstruction des paramètres du rayon cosmique primaire, mettant en oeuvre des comparaisons combinant des informations de polarisation et fréquentielles entre les données enregistrées et des simulations, nous menant enfin à une proposition de composition en masse des rayons cosmiques détectés
Despite the discovery of cosmic rays there are more than one hundred years ago, many questions remain unanswered today: what are cosmic rays, how are they created and where do they come from ? Since 2002, the CODALEMA instrument, located within the Nançay Radio Observatory, studies the ultra-high energy cosmic rays (UHECR, above 1017 eV) arriving in the Earth atmosphere. Their low flux makes it impossible to detect them directly at these energies. These cosmic rays, however, will interact with the atoms of the atmosphere, generating a cascade of secondary charged particles, commonly known as extensive air shower (EAS), detectable at ground level, and from which we will extract information on the primary cosmic ray. The objective is to go back to the characteristics of the primary that generated the EAS, thus to determine its direction of arrival, its nature and its energy. During the development of the shower, these charged particles in movement generate a fast electric field transient, detected at ground by CODALEMA with dedicated radio antennas over a wide frequency band (between 1 and 200 MHz). The major advantage of radio-detection is its sensibility to the whole profile of the shower and its duty cycle close to 100 %, which could increase the number of events detected at very high energy, and thus to better constrain the properties of the RCUHE. Over the years, significant efforts have been devoted to the understanding of the radio emission of extensive air shower (EAS) in the range [20-80] MHz but, despite some studies led until the nineties, the[1-10] MHz band has remained unused for nearly 30 years. One of the contributions of this thesis concerns the EXTASIS experiment, supported by the CODALEMA instrument, which aims to reinvestigate the [1-10] MHz band and to study the so-called ”sudden death” contribution, which is the expected impulsive electric field created by the particles at their arrival and their disappearance on the ground. We present the instrumental set up of EXTASIS, composed of 7 low frequency antennas exploited in [1.7-3.7] MHz, covering approximately 1 km2. We report the observation, over 2 years, of 25 low-frequency events detected in coincidence by CODALEMA and EXTASIS and estimate a detection limit of 23±4 μV/m from comparisons with simulations. We also report a strong correlation between the observation of the low frequency signal and the atmospheric electric field. The other major contribution of this thesis concerns the study of the electric field emitted by the EAS and the improvement of the detector’s performances in the [20-200] MHz band. First, we propose a calibration method for CODALEMA antennas using the radio emission of the Galaxy. We are also investigating several noise rejection algorithms to improve the selectivity of recorded events. We then present a method for reconstructing the parameters of the primary cosmic ray, implementing systematic comparisons combing polarization and frequency information between the recorded data and simulations, leading finally to a proposal for a mass composition of cosmic rays detected

En 1972, Skumanich découvre une relation empirique unique entre la période de rotation de surface des étoiles G et leur âge sur la séquence principale. Cette découverte ouvrit alors une nouvelle voie pour la datation stellaire : la gyrochronologie. Dès lors, bon nombre d'auteurs, entre la fin des années 80 et 90, se sont intéressés à l'évolution de la vitesse de rotation de surface des étoiles de faible masse ($M_*$ = 0.4 $M_{odot}$- 1.1 $M_{odot}$). Les premiers modèles phénoménologies sur le sujet été nés.L'évolution de la vitesse de rotation de ces étoiles commence à être raisonnablement bien reproduite par la classe de modèle paramétrique que je présente dans cette thèse. Par manque de descriptions théoriques satisfaisantes, seuls les effets globaux des mécanismes physiques impliqués sont ici décris. Le principal enjeu est d'étudier le cadre et la façon dont le moment cinétique stellaire est impacté par ces processus tout en contraignant leurs principales caractéristiques.Au cours de ma thèse, j'ai modélisé les trajets rotationnels des enveloppes externes et médianes des distributions de période de rotation de 18 amas stellaire entre 1 Myr et 1 Gyr. Ceci m'a permis d'analyser la dépendance temporelle des mécanismes physiques impliqués dans l'évolution du moment cinétique des étoiles de type solaire. Les résultats que j'ai obtenus montrent que l'évolution de la rotation différentielle interne impact fortement la convergence rotationnelle (relation empirique de Skumanich), l'évolution de l'abondance de surface en lithium, et les intensités du champ magnétique généré par effet dynamo. En plus de reproduire ces enveloppes externes, le modèle que j'ai développé fournit des contraintes sur les mécanismes de redistribution interne du moment cinétique et sur les durées de vie des disques circumstellaires, supposés responsables de la régulation rotationnelle observée durant les quelques premiers millions d'années de la pré-séquence principale. L'extension du modèle aux étoiles moins massives (0.5 et 0.8 $M_{odot}$) que j'ai réalisé, a également fournis la dépendance en masse de ces différents processus physiques.Cette étape à notamment ajoutée de fortes contraintes sur les temps caractéristiques associés au transport de moment cinétique entre le coeur et l'enveloppe, sur l'efficacité du freinage magnétique vraisemblablement reliée à un changement de topologie des étoiles de type solaire vers celles de 0.5 $M_{odot}$, et sur l'histoire rotationnelle, interne comme de surface, des étoiles entre 1 Myr à 1 Gyr
In 1972, Skumanich discovers a unique empirical relationship between the rotation period of the surface of G star and their age on the main sequence. This discovery then opened a new path for stellar dating: the gyrochronology. Therefore, many authors in the late 80's and the begenning 90's, were interested in the evolution of the surface angular velocity of low-mass stars ($M_*$ = 0.4 $M_{odot}$- 1.1 $M_{odot}$). The first phenomenological models on the subject were born.The angular velocity evolution of these stars begins to be reasonably well reproduced by the class of parametrical model that I present in this thesis. Because of the lack of adequate theoretical descriptions, only the overall effects of the physical mechanisms involved are described here. The main issue is to study the framework and how the stellar angular momentum is affected by these processes and to constrain their main characteristics.Over the course of my thesis, I modelled the rotational tracks of external and median envelopes and median of rotation period distributions of 18 stellar clusters between 1 Myr and 1 Gyr. This allowed me to analyse the time dependence of the physical mechanisms involved in the angular momentum evolution of solar-type stars. The results I obtained show that the evolution of the internal differential rotation significantly impact the rotational convergence (empirical Skumanich's relationship), the evolution of the surface lithium abundance, and the intensity of the magnetic field generated by dynamo effect. In addition to the reproduction of these external envelopes, the model I developed provides constraints on the mechanisms of internal redistribution of angular momentum and the lifetimes of circumstellar disks, that are held responsible for the rotational regulation observed during the first few million years of pre-main sequence. The extension of the model to less massive stars (0.5 et 0.8 $M_{odot}$) that I performed also provided the mass dependence of these physical processes. Most specifically, this step added strong constraints on the characteristic time associated to the transport of angular momentum between the core and the envelope, on the efficiency of magnetic braking likely related to a change of topology from solar-type stars to those of 0.5 $M_{odot}$, and on the internal and external rotational history of stars from 1 Myr to 1 Gyr

L’élevage des vins et spiritueux en barrique en chêne modifie leurs qualités organoleptiques par deux phénomènes principaux. D’une part, le bois libère des composés volatiles et non volatiles qui enrichissent la boisson, et, d’autre part, les propriétés du bois permettent une légère oxydation tout au long du vieillissement. Dans ce dernier cas, les modes de transfert d’oxygène ainsi que les facteurs limitants sont aujourd’hui peu connus alors qu’ils sont d’une grande importance dans la qualité du produit final. Cette thèse vise à mieux comprendre la dynamique des transferts d'oxygène dans le chêne, et ce, en présence du front d'imbibition du liquide dû au contact entre le contenu et la surface interne de la barrique. À cette fin, plusieurs montages expérimentaux originaux ont été développés.Dans un premier temps, à l’échelle macroscopique, 4 barriques instrumentées dans un chai ont permis d’étudier ces transferts en conditions réelles. Il se produit une perte de liquide au cours de l’élevage du vin, ce qui génère une dépression interne. Ainsi, à la diffusion d’oxygène à travers la barrique, s’ajoute un phénomène de percolation de l’air vers l’intérieur de la barrique à partir d’un certain seuil de dépression. Ce seuil de percolation peut être atteint lors de variations des conditions en humidité relative et en température du chai, ce qui est expliqué par le changement dimensionnel de la barrique. On constate des apports d’oxygène entre 10 et 100 µg/L par événement de percolation. Ces apports ne sont pas négligeables par rapport à la quantité d’oxygène que le vin reçoit durant son élevage.Dans un second temps, à l’échelle microscopique, chaque mécanisme est traité de façon découplée : diffusion d’oxygène d’une part et suivi du front d’imbibition d’autre part. La diffusion d’oxygène est étudiée pour le chêne sessile (Quercus petraea (Matt.) Liebl.) et le chêne pédonculé (Quercus robur L.) de largeurs de cerne différentes grâce à un dispositif expérimental innovant. Un modèle numérique fondé sur la méthode des volumes finis est employé pour identifier le coefficient de diffusion. On constate une bonne représentation de la diffusion via la simulation. Ensuite, le suivi du front d’imbibition est réalisé par un système d’imagerie à rayons X sur des échantillons de merrains en contact avec de l’eau et de l’éthanol. Un algorithme de corrélation d’images non supervisé est développé pour suivre l’avancée du front de liquide, et ce sur plusieurs mois.Enfin, l’étude des transferts simultanés est réalisée en combinant les deux dernières expériences. On observe alors une forte diminution de la diffusion de l’oxygène avec l’avancée du front d’imbibition dans le bois. Ces résultats nous permettent de mieux appréhender la complexité de la dynamique des transferts d'oxygène lors du vieillissement des vins et spiritueux en barrique en chêne
The aging of wines and spirits in oak barrels modifies their organoleptic qualities by two main phenomena. Firstly, the wood releases volatile and non-volatile compounds that enrich the beverage, and secondly, the wood properties allow a slight oxidation throughout the aging process. In the latter case, the modes of oxygen transfer as well as the limiting factors are little known today, although they are of great importance in the quality of the final product. This thesis aims to provide a better understanding of the dynamics of oxygen transfer in oak, in the presence of the liquid impregnation front due to the contact between the liquid and the internal surface of the barrel. To this end, several original experimental set-ups have been developed.Initially, at the barrel scale, 4 instrumented barrels were placed in a cellar to study the transfers in real conditions. The loss of liquid during aging generates an internal underpressure. Thus, in addition to the diffusion of oxygen through the wood thickness, there is a phenomenon of air percolation towards the inside of the barrel from a certain threshold of the pressure gap. This percolation threshold can be reached during variations in relative humidity and temperature conditions in the cellar, which provoke dimensional changes of the barrel. Oxygen inputs between 10 and 100 µg/L per percolation event are observed. These contributions are not negligible compared to the quantity of oxygen that the wine receives during its aging.Secondly, at the stave scale, each mechanism is treated in a decoupled way: diffusion of oxygen on the one hand and monitoring of the imbibition front on the other. Oxygen diffusion is studied for sessile oak (Quercus petraea (Matt.) Liebl.) and pedunculate oak (Quercus robur L.) with various ring widths using an innovative experimental device. A numerical model based on the finite volume method is used to identify the diffusion coefficient. A good representation of the diffusion via simulation is observed. Next, the imbibition front is monitored by an X-ray imaging system on stave samples in contact with water and ethanol. An unsupervised image correlation algorithm is developed to monitor the progress of the liquid front over several months.Finally, the study of simultaneous transfers is carried out by combining the last two experiments. A strong decrease in oxygen diffusion is then observed with the advance of the imbibition front in the stave thickness. These results allowed us to better apprehend the complexity of the dynamics of oxygen transfer during the aging of wines and spirits in oak barrels

La these porte sur la mesure de la masse du boson w a lep2 par la methode de la reconstruction directe de ses produits de desintegration dans le canal hadronique. Des outils specifiques necessaires a l'extraction de la valeur de la masse du boson w a partir des donnees collectees avec l'appareillage delphi en 1997 ont ete developpes (recherche de variables optimales pour selectionner les evenements ww, mise au point d'une methode specifique de reconstruction cinematique). La valeur observee de la masse du boson w a ete interpretee dans le cadre du modele standard, notamment pour contraindre la masse du boson de higgs. Une partie importante est consacree aux effets systematiques provenant des interactions entre les produits de desintegration hadronique des bosons w (reconnection de couleur et correlations de bose-einstein), qui peuvent notoirement influer sur la mesure de leur masse.

Cette étude est dédiée à l'amélioration du design des microréacteurs gaz-liquide. Le terme de microréacteur correspond à des appareils composés de canaux dont les dimensions sont de l’ordre de quelques dizaines à quelques centaines de microns. Grâce à la valeur importante du ratio surface/volume, ces appareils constituent une issue prometteuse pour contrôler les réactions rapides fortement exothermiques, souvent rencontrées en chimie fine et pharmaceutique. Dans le cas des systèmes gaz-liquide, on peut citer par exemple les réactions de fluoration, d’hydrogénation ou d’oxydation. Comparés à des appareils conventionnels, les microréacteurs permettent de supprimer le risque d’apparition de points chauds, et d’envisager le fonctionnement dans des conditions plus critiques, par exemple avec des concentrations de réactifs plus élevées. En même temps, la sélectivité peut être augmentée et les coûts opératoires diminués. Ainsi, les technologies de microréacteurs s’inscrivent bien dans les nouveaux challenges auxquels l'industrie chimique est confrontée ; on peut citer en particulier la réduction de la consommation énergétique et la gestion des stocks de produits intermédiaires. Les principaux phénomènes qui doivent être étudiés lors de la conception d’un microréacteur sont le transfert de matière et le transfert thermique. Dans les systèmes diphasiques, ces transferts sont fortement influencés par la nature des écoulements, et l'hydrodynamique joue donc un rôle central. Par conséquent, nous avons focalisé notre travail sur l’hydrodynamique de l’écoulement diphasique dans les microcanaux et sur les couplages constatés avec le transfert de masse. Dans ce contexte, nous nous sommes dans un premier temps intéressés aux régimes d’écoulement et aux paramètres contrôlant la transition entre les différents régimes. Au vu des capacités de transfert de matière et à la flexibilité offerte en terme de conditions opératoires, le régime de Taylor semble le plus prometteur pour mettre en œuvre des réactions rapides fortement exothermiques et limitées par le transfert de matière. Ce régime d'écoulement est caractérisé par des bulles allongées entourées par un film liquide et séparées les unes des autres par une poche liquide. En plus du fait que ce régime est accessible à partir d’une large gamme de débits gazeux et liquide, l'aire interfaciale développée est assez élevée, et les mouvements de recirculation du liquide induits au sein de chaque poche sont supposés améliorer le transport des molécules entre la zone interfaciale et le liquide. A partir d'une étude de l’hydrodynamique locale d’un écoulement de Taylor, il s’est avéré que la perte de charge et le transfert de matière sont contrôlés par la vitesse des bulles, et la longueur des bulles et des poches. Dans l’étape suivante, nous avons étudié l'influence des paramètres de fonctionnement sur ces caractéristiques de l’écoulement. Une première phase de notre travail expérimental a porté sur la formation des bulles et des poches et la mesure des champs de vitesse de la phase liquide dans des microcanaux de section rectangulaire. Nous avons également pris en compte le phénomène de démouillage, qui joue un rôle important au niveau de la perte de charge et du transfert de matière. Des mesures du coefficient de transfert de matière (kLa) ont été réalisées tandis que l'écoulement associé était enregistré. Les vitesses de bulles, longueurs de bulles et de poches, ainsi que les caractéristiques issues de l’exploitation des champs de vitesse précédemment obtenus, ont été utilisées afin de proposer un modèle modifié pour la prédiction du kLa dans des microcanaux de section rectangulaire. En mettant en évidence l'influence du design du microcanal sur l’hydrodynamique et le transfert de matière, notre travail apporte une contribution importante dans le contrôle en microréacteur des réactions rapides fortement exothermiques et limitées par le transfert de matière. De plus, ce travail a permis d'identifier certaines lacunes en termes de connaissance, ce qui devrait pouvoir constituer l'objet de futures recherches
The present project deals with the improvement of the design of gas-liquid microreactors. The term microreactor characterizes devices composed of channels that have dimensions in the several tens to several hundreds of microns. Due to their increased surface to volume ratios these devices are a promising way to control fast and highly exothermic reactions, often employed in the production of fine chemicals and pharmaceutical compounds. In the case of gas-liquid systems, these are for example direct fluorination, hydrogenation or oxidation reactions. Compared to conventional equipment microreactors offer the possibility to suppress hot spots and to operate hazardous reaction systems at increased reactant concentrations. Thereby selectivity may be increased and operating costs decreased. In this manner microreaction technology well fits in the challenges the chemical industry is continuously confronted to, which are amongst others the reduction of energy consumption and better feedstock utilization. The main topics which have to be considered with respect to the design of gasliquid μ-reactors are heat and mass transfer. In two phase systems both are strongly influenced by the nature of the flow and thus hydrodynamics play a central role. Consequently we focused our work on the hydrodynamics of the two-phase flow in microchannels and the description of the inter-linkage to gas-liquid mass transfer. In this context we were initially concerned with the topic of gas-liquid flow regimes and the main parameters prescribing flow pattern transitions. From a comparison of flow patterns with respect to their mass transfer capacity, as well as the flexibility offered with respect to operating conditions, the Taylor flow pattern appears to be the most promising flow characteristic for performing fast, highly exothermic and mass transfer limited reactions. This flow pattern is characterized by elongated bubbles surrounded by a liquid film and separated from each other by liquid slugs. In addition to the fact that this flow regime is accessible within a large range of gas and liquid flow rates, and has a relatively high specific interfacial area, Taylor flow features a recirculation motion within the liquid slugs, which is generally assumed to increase molecular transport between the gas-liquid interface and the bulk of the liquid phase. From a closer look on the local hydrodynamics of Taylor flow, including the fundamentals of bubble transport and the description of the recirculation flow within the liquid phase, it turned out that two-phase pressure drop and gas-liquid mass transfer are governed by the bubble velocity, bubble lengths and slug lengths. In the following step we have dealt with the prediction of these key hydrodynamic parameters. In this connection the first part of our experimental study was concerned with the investigation of the formation of bubbles and slugs and the characterization of the liquid phase velocity field in microchannels of rectangular cross-section. In addition we also addressed the phenomenon of film dewetting, which plays an important rôle concerning pressure drop and mass-transfer in Taylor flow. In the second part we focused on the prediction of gas-liquid mass transfer in Taylor flow. Measurements of the volumetric liquid side mass transfer coefficient (kLa-value) were conducted and the related two-phase flow was recorded. The measured bubble velocities, bubble lengths and slug lengths, as well as the findings previously obtained from the characterization of the velocity field were used to set-up a modified model for the prediction of kLa-values in μ-channels of rectangular cross-section. Describing the interaction of channel design hydrodynamics and mass transfer our work thus provides an important contribution towards the control of the operation of fast, highly exothermic and mass transfer limited gas-liquid reactions in microchannels. In addition it enabled us to identify gaps of knowledge, whose investigation should be items of further research

Les manipulateurs industriels collaboratifs ouvrent une nouvelle ère dans la fabrication flexible, où les robots et les humains sont capables de coexister et de travailler ensemble. Cependant, divers défis persistent pour parvenir à une collaboration complète entre les robots et les humains en milieu industriel. Dans cette thèse, deux défis principaux - la sécurité et la collaboration - sont abordés pour atteindre cet objectif. Concernant la sécurité, la thèse présente une méthode d'évitement des collisions en temps réel qui permet au robot d'ajuster les chemins générés hors ligne pour une tâche industrielle, tout en évitant les collisions avec les humains à proximité. En outre, la thèse a présenté une nouvelle méthode pour effectuer un mouvement d'évitement de collision réactif, en utilisant la méthode de Newton du second ordre qui offre divers avantages par rapport aux méthodes traditionnelles utilisées dans la littérature. Sur la collaboration, la thèse présente un mode de guidage manuel précis comme alternative au mode de guidage actuel pour effectuer des opérations de positionnement précis de l'effecteur terminal du robot d’une manière simple et intuitive. La thèse présente également de nouvelles contributions à la formulation mathématique de la dynamique des robots, y compris un algorithme récursif pour calculer la matrice de masse des robots sériels avec un coût minimal du second ordre et un algorithme récursif pour calculer efficacement les symboles de Christoffel. Tous les algorithmes présentés sont validés soit en simulation, soit dans un scénario réel
Collaborative industrial manipulators are ushering a new era in flexible manufacturing, where robots and humans are allowed to coexist and work side by side. However, various challenges still persist in achieving full human robot collaboration on the factory floor. In this thesis two main challenges - safety and collaboration - for achieving that goal are addressed. On safety, the thesis presents a real-time collision avoidance method which allows the robot to adjust the offline generated paths of the industrial task in real-time for avoiding collisions with humans nearby. In addition, the thesis presented a new method for performing the reactive collision avoidance motion using second order Newton method which offers various advantages over the traditional methods in the literature. On collaboration, the thesis presents the precision hand-guiding as an alternative to the teach-pendant for performing precise positioning operations of the robot’s end-effector in a simple and intuitive manner. The thesis also presents new contributions into the mathematical formulation of robot dynamics, including a recursive algorithm for calculating the mass matrix of serially linked robots with a minimal second order cost, and a recursive algorithm for calculating Christoffel symbols efficiently. All the presented algorithms are validated either in simulation or in a real-world scenario

On a cherche a determiner la masse du meson bs, par la reconstruction complete de ses desintegrations a partir des donnees enregistrees par l'experience delphi entre 1991 et 1994 au collisionneur l. E. P. , situe au cern pres de geneve. Les previsions theoriques ont permis de situer le domaine de masse attendu pour le meson bs. Le resultat d'un calcul original base sur la theorie effective des quarks lourds a ete compare a d'autres previsions, obtenues precedemment par d'autres methodes. La coherence de la methode experimentale a ete verifiee sur les mesons bu et bd, de masses parfaitement connues, et abondamment produits. La masse moyenne des candidats bu et bd reconstruits etait en accord avec la valeur moyenne mondiale. Le nombre d'evenements bs attendus dans quatre canaux de desintegration, qui presentent les rapports d'embranchement les plus importants et qui conduisent a des etats finals comportant uniquement des particules chargees, a ete estime. L'analyse des donnees a permis de reconstruire entierement la chaine de desintegration de quatre evenements candidats bs. Pour chacun des candidats, les differentes sources de fond (reflexion, reconstruction incomplete ou association combinatoire) ont ete etudiees. Une methode maximum de vraisemblance a alors permis de determiner la valeur de la masse la plus probable du meson bs a partir des evenements selectionnes: 5382 mev, avec une erreur de 16 mev

Les dichalcogénures des métaux de transition sont constitués d'un empilement de monocouches atomiques liées entre elles par des liaisons faibles de type Van der Waals. Lorsqu'une monocouche de ce matériau est isolée, la symétrie d'inversion du cristal est brisée et la présence d'un couplage spin-orbite fort introduit une levée de dégénérescence des états électroniques ayant des spins différents. Le facteur de Landé effectif (g*) qui intervient dans l'énergie Zeeman est un paramètre qui caractérise, entre autres, la structure de bande du matériau. Il est exceptionnellement grand dans le système WSe_2 en raison de la présence de tungstène et des interactions électroniques. Sa détermination au travers des mesures de résistance électrique sous champ magnétique intense est l'objet de cette thèse. Dans un premier temps, des monocouches de WSe_2 sont produites par l'exfoliation mécanique du matériau massif et leur adressage électrique à l'échelle micrométrique est réalisé par des procédés technologiques de salle blanche impliquant la lithographie électronique. La magnétorésistance des échantillons produits est ensuite étudiée dans des conditions extrêmes de basse température et de champ magnétique intense. La densité de porteur de charges, des trous dans le cas cette thèse, peut être ajustée in-situ par effet de champ. Dans les monocouches de WSe_2, la quantification de l'énergie des niveaux de Landau modifiée par l'effet Zeeman est révélée par la présence d'oscillations complexes de la magnéto-résistance (oscillations de Shubnikov-de Haas). Le développement d'un modèle théorique dédié, où le désordre est pris en compte par un élargissement Gaussien des niveaux de Landau, est nécessaire afin d'interpréter quantitativement les résultats expérimentaux. Il simule l'évolution des composantes du tenseur de résistivité où les paramètres d'ajustement sont la mobilité électronique, l'énergie des bords de mobilité des niveaux de Landau ainsi que le facteur de Landé effectif. L'ajustement théorique aux résultats expérimentaux permet d'extraire l'évolution de g* des trous en fonction de leur densité dans une gamme variant de 5.10^12 à 7,5.10^12 cm^-2, qui s'inscrit dans la continuité des résultats issus de la littérature. Au-delà des approches novatrices sur le plan des conditions expérimentales et de modélisation, cette étude confirme l'importance des interactions électroniques dans la compréhension des propriétés électroniques de ce matériau
Transition metal dichalcogenides are made up of a stack of atomic monolayers bound together by weak Van der Waals interactions. When a single layer of this material is isolated, the crystal inversion symmetry is broken, leading to the degeneracy lifting of the electronic states having different spins in the presence of strong spin-orbit coupling. The effective Landé factor (g*) which arises in the Zeeman energy is a parameter which characterizes, among others, the band-structure of the material. It is exceptionally large in WSe_2 monolayers thanks to the presence of heavy tungsten atoms as well as electronic interactions. Its experimental determination through electrical resistance measurements under intense magnetic field constitutes the objective of this thesis. First, WSe_2 monolayers are produced by mechanical exfoliation of the mother material and their electrical addressing at the micrometric scale is achieved by clean room processes involving electron-beam lithography. Their magneto-resistance is studied under extreme conditions of low temperature and high magnetic field. The charge carrier density, holes in the thesis, can be varied in situ thanks to field effect. In WSe_2 monolayers, the quantization of the Landau level energy modified by the Zeeman effect is revealed by the presence of complex magneto-resistance oscillations (Shubnikov-de Haas oscillations). A dedicated theoretical model, where disorder is introduced through a Gaussian broadening of the Landau levels, is necessary for a quantitative understanding of the experimental results. The components of the resistivity tensor are simulated by this model where the main fitting parameters are the electronic mobility, the mobility edge of the Landau levels and the effective Landé factor. The fitting of the experimental results allows the extraction of g* for a hole density ranging from 5.10^12 to 7.5.10^12 cm^-2, which follows the trend reported in the literature. Beyond the innovative approaches in terms of experimental conditions and modelling, this study confirms the importance of electronic interactions in understanding the electronic properties of this material

Ce travail concerne la modélisation, à l’échelle moléculaire, de l’interaction entre des nanoparticules carbonées et le rayonnement électromagnétique. Le but est d’aider à la compréhension des propriétés optiques des particules de suie afin de mieux quantifier l’influence des suies sur l’atmosphère et le climat. L’étude de l’interaction rayonnement/particules de suie fraîche a été effectuée par la méthode PDI ; il a été montré que : i) le coefficient d’absorption massique (MAC) des particules de suie dépend de la répartition des atomes dans la particule et de leurs liaisons, en particulier entre 200 et 350 nm ; ii) le MAC diffère selon que le cœur de la particule carbonée est occupé ou non par des plans graphitiques ; iii) un modèle analytique n’est pas adapté pour calculer le MAC d’une nanoparticule carbonée présentant des défauts structuraux. De plus, des méthodes de chimie quantique ont été utilisées pour caractériser le vieillissement des suies. Les résultats montrent que : i) NO, Cl, et HCl sont physisorbées sur une surface carbonée parfaite alors que sur une surface défective, ces espèces sont chimisorbées et conduisent à une modification de la surface ; ii) la présence de Cl conduit à un piégeage fort des molécules d’eau supérieur à celui obtenu lorsqu’un site oxygéné est présent sur la surface carbonée, expliquant ainsi le caractère hydrophile des suies émises lors d’incendies dans des milieux industriels. Enfin, la méthode PDI a été appliquée au calcul de la polarisabilité de HAP afin d’interpréter des spectres d’absorption des grains carbonés du milieu interstellaire, en incluant des molécules pour lesquelles aucune donnée n’était actuellement disponible
This work concerns the modeling, at the molecular level, of the interaction between carbonaceous particles of nanometric size and the electromagnetic radiation. The goal is to improve our understanding of the optical properties of soot particles, to better quantify the influence of soot on the atmosphere and on climate change. The study of the interaction between radiation and fresh soot particles was carried out using the point dipole interaction method; it has been shown that: i) the mass absorption coefficient (MAC) of these soot nanoparticles may significantly depend on their atomistic details, especially between 200 and 350 nm; ii) the MAC depends on whether the heart of the carbonaceous particle is occupied or not by graphite planes; iii) an analytical model is not suitable for calculating the MAC of carbonaceous nanoparticles having structural defects. In addition, quantum chemical methods have been used to characterize the ageing of soot. The results obtained are i) NO, Cl, and HCl are physisorbed on a perfect carbonaceous surface whereas on a defective surface, these species are chemisorbed and lead to a modification of the surface; ii) on a carbonaceous surface, the presence of adsorbed Cl atoms leads to a strong trapping of the surrounding water molecules. This may be related to the highly hydrophilic nature of soot emitted during fires in industrial environments. Finally, the PDI method was applied to calculate the polarizability of PAHs to help at interpreting the absorption spectra of carbonaceous grains in the interstellar medium, including molecules for which no data was currently available

Malgré l'accord remarquable entre le modèle standard et les nombreuses mesures de précision effectuées depuis quelques décennies, la physique des particules a encore bien des mystères à éclaircir. L'un deux concerne la violation de la parité et la masse des neutrinos. Pour résoudre cette énigme, le modèle symétrique et le mécanisme du See-Saw prédisent l'existence de nouveaux bosons de jauge (W$_R$ et Z') et de neutrinos droits de Majorana N$_l$. Si ces nouvelles particules ont des masses voisines de quelques TeV/c2, le LHC et son détecteur ATLAS devraient en permettre la découverte, grâce aux processus qui sont décrits dans cette thèse : $pp \to W_(R) \to eN_(e) \to eejj$ et $pp \to Z' \to N_(e)N_(e) \to eejjjj$. Ceux-ci conduisent non seulement à des jets hadroniques mais aussi à des électrons dans l'état final. L'énergie et la position de ces derniers sont reconstruites dans un calorimètre électromagnétique à argon liquide. Avant d'y interagir, les électrons produits au point de collision rencontrent une certaine quantité de matière inerte, où il perdent une partie de leur énergie. Afin de compenser cet effet et ainsi maintenir la résolution en énergie à un niveau acceptable, on installe un pré-échantillonneur sur la face interne du calorimètre électromagnétique. Cette thèse en présente les principales performances.

abstract: This fifteen-minute cyclical mass uses excerpts from the text of the Mass Ordinary and is laid out into five movements and across three different languages: Kyrie (Latin), Gloria (Chinese), Credo (English), Sanctus (Chinese), and Agnus Dei (Latin). Rather than following the tradition of celebrating devotion, this mass tells the story of the abuse of power in political and religious leadership. Movements sung in Latin represent the devout Christian base whose motives and inspiration remain pure and divine. The English movement, Credo, has been altered from the original and represents the manipulation and distortion of scripture, truth, and facts by self-serving leaders and politicians. Finally, Chinese movements represent those who are persecuted for their convictions and their identity. The turmoil of the Chinese movements is characterized by atonality and fast tempos with contrasting, meditative, lyrical B sections. The outer Latin movements contain the familiar Kyrie and Agnus Dei texts in triple canon with the orchestra. The English middle movement is simultaneously familiar and awkward, with harmonies that almost function, under an altered Credo text. After an aria-like passage, the orchestra takes the “I believe” figure and manipulates it in a modal fugato, culminating in a climactic version of the main motive. A repeated double-dotted quarter note—sixteenth-note rhythm followed by a fast tremolo in the castanets make up the central “bangu motive.” This motive is derived from traditional Beijing Opera, in which the bangu is the principal percussion element. As a rhythmic motive, fragments of it appear in every movement and in several different instrument groups. These fragments undergo various transformations before a version of it arrives as the final Agnus Dei rhythmic figure.
Dissertation/Thesis
Masters Thesis Music 2018

A flux chamber is an effective and recognized means of sampling off gassing surfaces, such as landfills and settling ponds. Because there has been little discussion on the survey patterns used for deploying flux chambers. This thesis looks into developing a scalable survey pattern as part of a flux chamber test methodology that can accurately give a representative sample of the emission components and the emission rate of the entire area of interest. The test methodology evolved out of literature review and experiences of two case studies which are discussed within this thesis.

Accelerator Mass Spectrometry (AMS) is a single-atom counting technique that measures the abundance of rare, long-lived radioisotopes using only milligrams of sample. The astrophysical radioisotopes 53Mn and 60Fe have been utilised for many applications including meteoritics, exposure dating, and the search for near-Earth supernovae. 53Mn measurements at the ANU have been limited to sensitivities above 10^-13 by insufficient suppression of the stable isobar, 53Cr. To expand the applications accessible to 53Mn analysis, a new detector was commissioned that will improve the available sensitivity. This thesis covers the implementation of the new Flexible Anti-Scatter Multi-Anode (FASMA) detector. Simulations were conducted to determine the optimal placement of the detector inside the gas-filled magnet, and to assist with the design of a new multi-anode configuration. The FASMA detector was successfully tested and full spectra were recorded. These preliminary results indicate an improvement in the achievable sensitivity, even without the suppression of scattered particles. With further work, the FASMA detector should reach a sensitivity at or below 10^-14, which is competitive with the best reported level in the field. Long-lived radionuclides, such as 53Mn and 60Fe, are important for extracting the exposure history of meteorites, both in space and on Earth, as well helping to identify their origin. In light of this, cosmogenic 53Mn and 60Fe ratios were measured in ten meteorite samples. Since the available data on live 53Mn and 60Fe is scarce, these measurements will improve the constraints on current production rate models for meteorites.

Олійник Н. І. Моделювання температурних полів газів в робочих об’ємах камерних печей : кваліфікаційна робота магістра спеціальності 144 "Теплоенергетика" / наук. керівник Г. В. Карпенко. Запоріжжя : ЗНУ, 2021. 85 с.
UA : Робота викладена на 85 сторінках друкованого тексту, містить 2 таблиці, 29 рисунків. Перелік посилань включає 95 джерел з них на іноземній мові 23. Кваліфікаційна робота магістра присвячена моделюванню температурних полів газів в робочих об’ємах камерних печей. Виконано чисельне моделювання масових витрат пічних газів у камері реальної промислової печі. Проведені експериментальні дослідження на нагрівальній установці за умови створення електричного поля у її робочому просторі. Виконано розрахункову та промислову оцінки щодо доцільності подальшого використання результатів дослідження.
EN : The work is presented on 85 pages of printed text, contains 2 tables,29 figures.The list of references includes 95 sources, 23 of them in foreign language.The qualification work of the master is devoted to the modeling of temperature fields of gases in the working volumes of chamber furnaces. Numerical simulation of mass consumption of furnace gases in the chamber of a real industrial furnace was performed. Experimental studies on the heating plant were conducted provided that the electric field is created in its operating space. The calculation and industrial assessment on the expediency of further use of the results of the study were performed.

Камерная нагревательная печь усовершенствована путем реконструкции каркаса, применением новых теплоизоляционных материалов, использованием новых газовых горелок, работающих в импульсном режиме, и оснащенных системой автоматики. Решена задача нагрева массы металла до заданной температуры. Рассмотрен импульсный нагрев этой массы по заданной программе. Проведен тепловой расчет печи, гидравлические расчеты газопроводов, воздухопроводов, тракта дымовых газов, дана оценка экономической эффективности. Приведено описание системы автоматики.
A chamber furnace has been renovated with using some new technologies, as well as: reconstruction of the skeleton, using new thermoinsulation materials and installation of new gas burners operating at pulse mode with automatical control system. A task of metal mass heating up to the given temperature was solved. Heating processes at the pulse mode with set program was considered. The thermal calculation of furnace, hydraulic calculations of gas pipelines, air and flue gases supply systems were held. Economical efficiency estimation was given. Automatical control system was described.

La fumée du tabac est un aérosol extrêmement complexe constitué de milliers de composés répartis entre la phase particulaire et la phase vapeur. Il a été démontré que les effets toxicologiques de cette fumée sont associés aux composés appartenant aux deux phases. Plusieurs composés biologiquement actifs ont été identifiés dans la fumée du tabac; cependant, il n’y a pas d’études démontrant la relation entre les réponses biologiques obtenues via les tests in vitro ou in vivo et les composés présents dans la fumée entière du tabac. Le but de la présente recherche est de développer des méthodes fiables et robustes de fractionnement de la fumée à l’aide de techniques de séparation analytique et de techniques de détection combinés à des essais in vitro toxicologiques. Une étude antérieure réalisée par nos collaborateurs a démontré que, suite à l’étude des produits de combustion de douze principaux composés du tabac, l’acide chlorogénique s’est avéré être le composé le plus cytotoxique selon les test in vitro du micronoyau. Ainsi, dans cette étude, une méthode par chromatographie préparative en phase liquide a été développée dans le but de fractionner les produits de combustion de l’acide chlorogénique. Les fractions des produits de combustion de l’acide chlorogénique ont ensuite été testées et les composés responsables de la toxicité de l’acide chlorogénique ont été identifiés. Le composé de la sous-fraction responsable en majeure partie de la cytoxicité a été identifié comme étant le catéchol, lequel fut confirmé par chromatographie en phase liquide/ spectrométrie de masse à temps de vol. Des études récentes ont démontré les effets toxicologiques de la fumée entière du tabac et l’implication spécifique de la phase vapeur. C’est pourquoi notre travail a ensuite été focalisé principalement à l’analyse de la fumée entière. La machine à fumer Borgwaldt RM20S® utilisée avec les chambres d’exposition cellulaire de British American Tobacco permettent l’étude in vitro de l’exposition de cellules à différentes concentrations de fumée entière du tabac. Les essais biologiques in vitro ont un degré élevé de variabilité, ainsi, il faut prendre en compte toutes les autres sources de variabilité pour évaluer avec précision la finalité toxicologique de ces essais; toutefois, la fiabilité de la génération de la fumée de la machine n’a jamais été évaluée jusqu’à maintenant. Nous avons donc déterminé la fiabilité de la génération et de la dilution (RSD entre 0,7 et 12 %) de la fumée en quantifiant la présence de deux gaz de référence (le CH4 par détection à ionisation de flamme et le CO par absorption infrarouge) et d’un composé de la phase particulaire, le solanesol (par chromatographie en phase liquide à haute performance). Ensuite, la relation entre la dose et la dilution des composés de la phase vapeur retrouvée dans la chambre d’exposition cellulaire a été caractérisée en utilisant une nouvelle technique d’extraction dite par HSSE (Headspace Stir Bar Sorptive Extraction) couplée à la chromatographie en phase liquide/ spectrométrie de masse. La répétabilité de la méthode a donné une valeur de RSD se situant entre 10 et 13 % pour cinq des composés de référence identifiés dans la phase vapeur de la fumée de cigarette. La réponse offrant la surface maximale d’aire sous la courbe a été obtenue en utilisant les conditions expérimentales suivantes : intervalle de temps d’exposition/ désorption de 10 0.5 min, température de désorption de 200°C pour 2 min et température de concentration cryogénique (cryofocussing) de -75°C. La précision de la dilution de la fumée est linéaire et est fonction de l’abondance des analytes ainsi que de la concentration (RSD de 6,2 à 17,2 %) avec des quantités de 6 à 450 ng pour les composés de référence. Ces résultats démontrent que la machine à fumer Borgwaldt RM20S® est un outil fiable pour générer et acheminer de façon répétitive et linéaire la fumée de cigarette aux cultures cellulaires in vitro. Notre approche consiste en l’élaboration d’une méthodologie permettant de travailler avec un composé unique du tabac, pouvant être appliqué à des échantillons plus complexes par la suite ; ex : la phase vapeur de la fumée de cigarette. La méthodologie ainsi développée peut potentiellement servir de méthode de standardisation pour l’évaluation d’instruments ou de l’identification de produits dans l’industrie de tabac.
Tobacco smoke is an extremely complex aerosol composed of thousands of constituents distributed amongst the particulate and vapor phases. Toxicological effects have been linked to compounds present in both of these phases. Many biologically active compounds have been identified within tobacco smoke; however, there is a lack of studies correlating specific in vitro or in vivo biological responses to components within whole tobacco smoke. The goal of this research was to develop reliable and robust smoke fractionation methods using analytical separation and detection techniques in combination with in vitro toxicological assays. In a previous study by our collaborators, toxicological assessment of the particulate phase combustion products of twelve individual tobacco components revealed that the combustion products of chlorogenic acid were the most cytotoxic using the in vitro micronucleus test. Therefore, a preparative liquid chromatography method was developed in this work to fractionate the combustion products of chlorogenic acid to assess the bioactivity of these fractions and to identify the compounds responsible for the toxicity observed. The sub-fraction responsible for the most cytotoxic response comprised catechol, which was identified by liquid chromatography/time-of-flight mass spectrometry. Emerging studies have highlighted the toxicological significance of whole tobacco smoke and specifically the vapor phase, which shifted our focus to whole smoke analyses. The Borgwaldt RM20S® smoking machine in combination with British American Tobacco’s in vitro cell exposure chamber allow for the generation of fresh cigarette smoke in various doses and delivery to cell cultures. In vitro biological assays have a high degree of variability, thus, all other sources of variability must be accounted for to accurately assess toxicological endpoints; however, the reliability of dose delivery of the instrument had not been assessed until now. We have determined the reliability (RSD from 0.7-12%) of smoke generation and dilution by quantifying two reference standard gases (CH4 by flame ionization detection and CO by infrared absorption) and the tobacco particulate phase marker, solanesol (by high performance liquid chromatography-ultraviolet absorption detection). The relationship between dose and diluted vapor phase components found within the exposure chamber was then characterized by developing a headspace stir-bar sorptive extraction-gas chromatography/mass spectrometry method. The method repeatability gave an RSD from 10-13% for five reference compounds identified in the vapor phase of cigarette smoke. The maximal peak area response was obtained using the following experimental conditions: exposure-to-desorption time interval of 10  0.5 min, desorption temperature of 200 °C for 2 min, and a cryofocussing temperature of -75 °C. The dilution precision was found to yield a linear response of analyte abundance and was observed to be a function of concentration (RSD from 6.2-17.2 %) with quantities of 6-450 ng for the reference compounds. The findings obtained suggest the Borgwaldt RM20S® is a reliable tool to generate and deliver repeatable and linear doses of cigarette smoke to in vitro cell cultures. Our approach began with designing the methodology to work with an individual tobacco component, which could then be applied to a more complex sample, e.g., the vapor phase of cigarette smoke. The methodology developed can potentially serve as standardized methods for the assessment of instrumentation or screening of products for the Tobacco Industry.