Computational Fluid Dynamics (CFD) simulations are presented within this study for super-cooled liquid oxygen atomisation and gasification in a subcritical chamber operating at 1MPa. Relatively low cost simulation techniques have been used and their accuracy evaluated. Gasification efficiency expected from theory is compared with simulation results and physical limitation in addition to modelling limitations are discussed. Impinging jets have been used within the simulations with the intent of atomising the incoming liquid oxygen, followed by injection of hot water vapour perpendicularly, to increase turbulent mixing, residence time and in turn expected gasification efficiency. A computational fluid dynamics heating analysis is also included in order to highlight constraints on the chamber geometry imposed by transient rapid oxidation material limits. 316 stainless steel and 3D printed Inconel 718 were investigated experimentally to identify their transient macroscopic rapid oxidation limits. This information supplements existing published literature for operation at high temperatures for a transient period of time in oxygen rich environments. ANSYS Fluent 2020R1, and its newly included Volume of Fluid to Discrete Particle (VOF-DPM) Model, is used for CFD simulation of LOx atomisation and vaporisation. The CFD simulation technique is discussed in detail in order to allow the reader to gain knowledge into areas where computational power can be saved while still allowing assessment of trends for conducting relatively quick feasibility reviews e.g. for different chamber configurations. The CFD simulation results are compared with published experimental data and its accuracy when extended to this application is discussed. Results indicate that gasification of LOx within a compact chamber may be feasible if sufficient turbulence, resulting in longer residence times is present providing sufficient time for heat and mass transfer from the continuous phase. Simulations indicate that due to the mixing and gasification process the LOx particles within the chamber that have not entered the gaseous phase are smaller than that from pure atomisation and therefore more susceptible to gasification if injected into the main motor combustion chamber. Results hint at the potential benefit of swirl injection of hot gases to increase residence time and in turn the gasification efficiency, therefore, this is recommended for the topic of future research. / Computational Fluid Dynamics (CFD) simuleringar presenteras i denna studie för superkyld flytande syreförstoftning och förgasning i en underkritisk kammare som arbetar vid SI 1 MPa. Relativt billiga simuleringstekniker har använts och deras noggrannhet utvärderats. Förgasningseffektivitet som förväntas från teorin jämförs med simuleringsresultat och fysisk begränsning utöver detta diskuteras modelleringsberäkningarna. Stötstrålar har använts inom simuleringarna med avsikt att finfördela det inkommande flytande syret, följt av injektion av varm vattenånga vinkelrätt, för att öka turbulent blandning, uppehållstid och i sin tur förväntad förgasningseffektivitet. En beräkningsenhetsanalys för uppvärmningsdynamik ingår också för att belysa begränsningar för kammargeometri som införs genom övergående gränser för snabb oxidation. 316 rostfritt stål och 3D-printad Inconel 718 undersöktes experimentellt för att identifiera deras övergående makroskopiska snabba oxidationsgränser. Denna information kompletterar befintlig publicerad litteratur för drift vid höga temperaturer under en kort tid i syrgasrika miljöer. ANSYS Fluent 2020R1, och dess nyligen inkluderade volym av vätska till diskret partikel (VOF-DPM) -modell, används för CFD-simulering av LOxatomisering och förångning. CFD-simuleringstekniken diskuteras i detalj för att göra det möjligt för läsaren att få kunskap om områden där beräkningskraft kan sparas medan man fortfarande tillåter bedömning av trender för att göra relativt snabba genomförbarhetsgranskningar, t.ex. för olika kammarkonfigurationer. CFD-simuleringsresultaten jämförs med publicerade experimentella data och dess noggrannhet när den utvidgas till denna applikation diskuteras. Resultaten indikerar att förgasning av LOx i en kompakt kammare kan vara möjlig vid tillräcklig turbulens, vilket resulterar i längre uppehållstider är närvarande som ger tillräcklig tid för värme och massöverföring från den kontinuerliga fasen. Simuleringar indikerar att på grund av blandnings- och förgasningsprocessen är LOx-partiklarna i kammaren som inte har gått in i gasfasen mindre än den från ren förgasning och därför mer mottagliga för förgasning om de injiceras i huvudmotorns förbränningskammare. Resultat antyder den potentiella fördelen med virvelinjektion av heta gaser för att öka uppehållstiden och i sin tur förgasningseffektivitet, därför rekommenderas detta för ämnet för framtida forskning.

By structural health monitoring (SHM) of composite structures, their sustainability, safety and economics can be improved. On one hand, it enables using components to their full life or having them replaced early before otherwise unforeseen failure. On the other hand, it may make structures lighter as designs with smaller safety margins would be possible. Cryogenic liquid hydrogen tanks for aircraft would need to become lighter to enable such fossil-free aviation, which could require SHM. Vertically aligned carbon nanotubes (VACNT) have been used as embedded sensors in composites for temperature and strain sensing while other architectures of nanotubes have been used to detect fatigue damage. In this work, VACNT embedded in carbon fibre/epoxy composites are cycled both thermally and mechanically to investigate their suitability to detect damage in composite cryogenic tanks. It was found VACNT retain their strain sensing ability after cycling to cryogenic temperatures and that a relationship of increasing electrical resistance to increased cycling and damage is possible. That indicates VACNT are suitable for SHM of cryogenic tanks, but more testing and better electrical insulation of the VACNT is needed to confirm this. / Genom att övervaka kompositstrukturers livslängd med structural health monitoring (SHM), kan miljöhållbarheten, säkerheten och ekonomin i att använda dem förbättras. Å ena sidan möjliggör det att komponenter används sin fulla livslängd eller ersätts innan annars oförutsedda skador leder till kollaps. Å andra sidan kan det göra strukturer lättare eftersom designer med mindre säkerhetsmarginaler vore möjliga. Kryotankar för flytande väte i flygplan behöver bli lättare för att möjliggöra sådant fossilfritt flygande, vilket skulle kunna kräva SHM. Vertikalt riktade kolnanorör (vertically aligned carbon nanotubes, VACNT) har använts som inbäddade temperatur- och töjningssensorer i kompositer och andra kolnanorörsmaterial har använts för att detektera utmattningsskador. I detta arbetet har VACNT inbäddat i kolfiber och epoxi cyklats både termiskt och mekaniskt för att undersöka dess lämplighet som sensorer för skadedetektering i kryotankar. Det konstaterades att VACNT behåller sin töjningsdetekteringsförmåga efter termisk cykling till kryotemperatur och att det är möjligt att ett förhållande om ökande resistans med ökande cykling och skada kan finnas. Det indikerar att VACNT vore lämpliga för SHM i kryotankar, men mer provning och bättre elektrisk isolering av VACNT behövs för att bekräfta det.

The Cold-Electron Bolometer (CEB) is a sensitive detector of millimeter-wave radiation, in which tunnel junctions are used as temperature sensors of a nanoscale normal metal strip absorber. The absorber is fed by an antenna via two Superconductor-Insulator-Normal metal (SIN) tunnel junctions, fabricated at both ends of the absorber. Incoming photons excite electrons, heating the whole electron system. The incoming RF power is determined by measuring the tunneling current through the SIN junctions. Since electrons at highest energy levels escape the absorber through the tunnel junctions, it causes cooling of the absorber. This electron cooling provides electro-thermal feedback that makes the saturation power of a CEB well above that of other types of millimeter-wave receivers. The key features of CEB detectors are high sensitivity, large dynamic range, fast response, easy integration in arrays on planar substrates, and simple readout. The high dynamic range allows the detector to operate under relatively high background levels. In this thesis, we present the development and successful operation of CEB, focusing on the fabrication technology and different implementations of the CEB for efficient detection of electromagnetic signals. We present the CEB detector integrated across a unilateral finline deposited on a planar substrate. We have measured the finline-integrated CEB performance at 280-315 mK using a calibrated black-body source mounted inside the cryostat. The results have demonstrated strong response to the incoming RF power and reasonable sensitivity. We also present CEB devices fabricated with advanced technologies and integrated in log-periodic, double-dipole and cross-slot antennas. The measured CEB performance satisfied the requirements of the balloon-borne experiment BOOMERANG and could be considered for future balloon-borne and ground-based instruments. In this thesis we also investigated a planar phase switch integrated in a back-to-back finline for modulating the polarization of weak electromagnetic signals. We examine the switching characteristics and demonstrate that the switching speed of the device is well above the speed required for phase modulation in astronomical instruments. We also investigated the combination of a detector and a superconducting phase switch for modulating the polarization of electromagnetic radiation.

Este estudo teve por finalidade estudar os efeitos da fototerapia com laser em baixa intensidade (Low Level Laser Therapy LLLT) sobre a inflamação e reparação após lesão criogênica realizada no sitema nervoso central (SNC) de ratos. Foram realizados 3 experimentos. Em todos os experimentos foi utilizado um modelo de deformação cortical direta induzida por lesão criogênica. A LLLT foi realizada com laser de diodo em baixa intensidade emitindo no vermelho visível (InGaAlP, 660 nm) ou no infravermelho (AlGaAr, 780 nm). Os parâmetros de irradiação foram: potência de 40 mW, área do feixe de 0,04 cm2, densidades de energia de 3 J/cm2 (3 s) ou 5 J/cm2 (5 s) determinando energias por ponto de 0,12 J e 0,20 J, respectivamente. Foram realizadas 2 irradiações com intervalo de 3 h, no modo contato e em 2 pontos por lesão. No experimento 1, 50 ratos da linhagem Wistar foram utilizados para determinar os parâmetros de LLLT capazes de influenciar na dinâmica da produção de citocinas proinflamatórias (TNF-a, IL-1b, IL-6) e antiinflamatória (IL-10). As citocinas foram mensuradas pelo teste ELISA no cérebro e no sangue dos animais, 6 e 24h após a lesão. Os grupos experimentais foram: controle (não irradiado) e 4 grupos irradiados com 3 J/cm2 ou 5 J/cm2 para cada comprimento de onda (n=10 por grupo). Para os experimentos 2 e 3 foram utilizados 40 ratos (20 não irradiados controles e 20 irradiados). A LLLT foi realizada somente com o parâmetro de irradiação do laser no infravermelho e a densidade de energia de 3 J/cm2. Nestes experimentos o processo de reparação das lesões criogênicas no SNC foi acompanhado em 6 h, 1, 7 e 14 dias após a última irradiação (n=5 por grupo por tempo experimental). No experimento 2 foi realizada a análise morfométrica da região lesionada do SNC. No experimento 3 foi analisada a distribuição das células inflamatórias (linfócitos T, leucócitos e macrófagos). Os dados de cada experimento foram comparados estatísticamente por análise de variância (ANOVA) ou Kruskal-Wallis seguido dos testes de Tukey ou de Dunn, respectivamente (F=5%). O trauma criogênico foi capaz de criar lesões focais no córtex representadas por necrose, edema, hemorragia e infiltrado inflamatório. Os achados mais marcantes foram: no experimento 1 com a irradiação do laser no infravermelho e 3 J/ cm2, o TNF- a e a IL-6 se mantiveram nos mesmos níveis em 6 e 24 h, enquanto no controle houve aumento significativo. Experimento 2: as lesões não tratadas apresentaram maior perda tecidual em 6 h que as irradiadas. Experimento 3: as lesões irradiadas apresentaram menor quantidade de leucócitos e linfócitos T nas primeiras 24 h do que nas lesões controle. A quantidade de macrófagos foi similar nos dois grupos. Conclusões: Levando em consideração as condições experimentais deste estudo concluiu-se que LLLT exerce efeitos nos processos de inflamação e reparação diminuindo a concentração de citocinas próinflamatórias (TNF-F e IL-6) no sangue e mantendo a de IL-1I no cérebro. Adicionalmente, diminui a perda tecidual inicial pós- lesão criogênica e a infiltração inicial de leucócitos e linfócitos T. / This study aimed to study the effects of phototherapy with low-intensity laser (Low Level Laser Therapy - LLLT) on inflammation and repair after cryogenic injury held in central nervous system (CNS) of rats. There were 3 experiments. In all experiments a model of deformation induced by direct cortical cryogenic injury was used. The LLLT was carried out with a low intensity diode laser emitting in the visible red (InGaAlP, 660 nm) or infrared (AlGaAs, 780 nm). The irradiation parameters were: power of 40 mW, beam area of 0.04 cm2, energy densities of 3 J/cm2 (3 s) or 5 J/cm2 (5 s) providing energy per point of 0.12 J and 0.20 J, respectively. Two irradiations were performed at 3 h-intervals, in contact mode and in 2 points for lesion. In experiment 1, 50 Wistar rats were used to determine the parameters of LLLT able to influence the dynamics of production proinflammatory cytokines (TNF-, IL-1 and IL-6) and antiinflammatory cytokine (IL- 10). Cytokines were measured by ELISA in the brain and blood of animals, 6 and 24 hours after injury. The experimental groups were: control (non-irradiated) and 4 irradiated groups [3 J/cm2 and 5 J/cm2 for each wavelength (n = 10 per group)]. For experiments 2 and 3 40 rats (20 non-irradiated - controls and 20 irradiated).were used. The LLLT was performed only with the parameter of laser irradiation on the infrared and the energy density of 3 J/cm2. In these experiments, the process of repair of cryogenic injury in the CNS was followed in 6 h, 1, 7 and 14 days after the last irradiation (n = 5 per group and time trial). In experiment 2 a morphometric analysis of the injured area of the CNS was done. In experiment 3 the distribution of inflammatory cells (lymphocytes, leukocytes and macrophages) was analyzed. Data from each experiment were compared statistically by analysis of variance (ANOVA) or Kruskal-Wallis followed by tests of Tukey or Dunn, respectively ( = 5%). Cryogenic trauma was able to create focal lesions in the cortex represented by necrosis, edema, hemorrhage and inflammatory infiltrate. The most striking findings were: in experiment 1 with the laser irradiation in the infrared and 3 J/cm 2, TNF- and IL-6 remained at the same levels at 6 and 24 h, while in the control there was a significant increase. Experiment 2: untreated lesions showed greater tissue loss than irradiated lesions in 6 h. Experiment 3: lesions irradiated had fewer leukocytes and lymphocytes in the first 24 h than control lesions. The amount of macrophages was similar in both groups. Conclusions: Considering the experimental conditions of this study it was concluded that LLLT has effects in the processes of inflammation and repair by decreasing the concentration of proinflammatory cytokines (TNF- and IL-6) in blood and holding the IL-1 in the brain. Additionally, decreases the initial tissue loss after cryogenic injury and the initial infiltration of leukocytes and lymphocytes T.

Os hidrocarbonetos policíclicos aromáticos nitrados (nitro-HPAs) são potencialmente genotóxicos, por isso existe um grande interesse na determinação analítica desses compostos no material particulado no ar. Os nitro-PAHs são emitidos diretamente para a atmosfera pela combustão incompleta ou podem ser formados in situ a partir dos HPAs precursores. Neste trabalho, são apresentados os resultados obtidos no desenvolvimento de um método de análise de nitro-HPAs (1-nitronaftaleno, 2-nitronaftaleno, 1-nitropireno, 2-nitropireno, 2-nitrofluoranteno, 3-nitrofluoranteno, 1,3-dinitropireno, 1,6- dinitropireno, 2-nitrofluoreno, 6-nitrocriseno, 7-nitrobenzo(a)antraceno, 9- nitroantraceno e 9-nitrofenantreno) por GCxGC. A separação destes compostos por GCxGC pode simplificar a etapa de pré-tratamento do extrato orgânico oriundo do material particulado no ar. A GCxGC promove a separação em duas colunas com mecanismos de separação diferentes, conectadas em série, o que resulta em uma capacidade de separação maior. O sistema GCxGC empregado neste trabalho possui um injetor com programação de temperatura (PTV), um modulador criogênico de dois jatos de CO2 líquido (Dual Jet) e um detector por ionização em chama (FID). A separação foi feita empregando a fase estacionária apolar 5% fenil polisilfenilene siloxano na primeira coluna (30 m / 0,25 mm / 0,25 µm) e a semipolar 14% cianopropilfenil polisiloxano na segunda coluna (1 m / 0,10 mm / 0,10 µm). Diferentes condições cromatográficas foram testadas, como: programação de temperatura no PTV, de 40-90ºC até 350ºC, com taxa de aquecimento de 2,2 e 14,5ºC/s; programação de temperatura no forno, de 40-90ºC até 300ºC, com taxa de aquecimento de 2, 2,5 e 3ºC/min; períodos de modulação de 3, 4 e 5s. O volume injetado foi 2µL, no modo splitless; a vazão do gás de arraste (He) foi constante e igual a 1 mL/min e o detector FID foi operado em 120 Hz. As larguras de pico medidas em 10% da altura variaram de 167 a 350ms para 1- nitronaftaleno e 6-nitrocriseno, respectivamente, e a capacidade de pico para o conjunto de colunas de separação usado foi estimada em cerca de 9800. Parâmetros de validação, tais como os limites de detecção (200 a 500 ng/mL) e de quantificação (650 a 1600 ng/mL) para alguns nitro-HPAs foram determinados. Para a quantificação, foram testados os métodos por padronização interna e externa, sendo que, através dos resultados deste trabalho, pode-se mostrar que a determinação de nitro-HPAs por GCxGC com o modulador empregado é possível se for feita através do método de padronização interna. O sistema GCxGC empregado causou dificuldades operacionais, principalmente na conexão das colunas e na modulação. Perdas de massa de analito foram detectadas nas análises por GCxGC, muito provavelmente causadas por uma conexão parcial das colunas. Isso poderia ser evitado se a conexão fosse feita pela fusão das colunas a um conector de vidro adequado a essa finalidade. Picos modulados divididos foram observados com frequência, o que comprometeu a precisão e exatidão dos resultados. A divisão dos picos ocorreu de modo aleatório dificultando a identificação da causa mais provável para a sua ocorrência. Cromatogramas GCxGC de extratos orgânicos não fracionados de particulados no ar, oriundos de queima direta de palha de cana-de-açúcar, de região afetada pela queima de cana-de-açúcar e de área urbana da cidade de São Paulo, mostraram a potencialidade do método / Nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) are potentially genotoxic, so there is a great interest in the analytical determination of these compounds in airborne particulate matter. The nitro-PAHs are emitted directly into the atmosphere by incomplete combustion or may be formed in situ from PAHs. In this work, results obtained from the development of an analytical method for nitro-PAHs by GCxGC are presented. The nitro-PAHs studied were: 1- nitronaphthalene, 2-nitronaphthalene, 1-nitropyrene, 2-nitropyrene, 2- nitrofluoranthene, 3-nitrofluoranthene, 1,3-dinitropyrene, 1,6-dinitropyrene, 2- nitrofluorene, 6-nitrochrysene, 7-nitrobenzo(a)anthracene, 9-nitroanthracene and 9- nitrophenanthrene. The separation of these compounds by GCxGC should simplify the pretreatment step of the airborne particulate organic extract. In GCxGC two capillary columns of different mechanisms of separation are coupled by an interface called modulator, which increase significantly the chromatographic resolution. The GCxGC system used in this work is equipped with a PTV injector, a dual-stage double jets CO2 cryogenic modulator and a flame ionization detector (FID). The separation was carried out using a nonpolar stationary phase 5% methyl phenyl polysiloxane in the first column (30 m / 0.25 mm / 0.25 µm) and a semipolar 14% cyanopropyl phenyl dimethyl polysiloxane in the second column. Different chromatographic conditions were tested: the PTV was programmed from 40-90ºC to 350ºC at 2.2 and 14.5ºC/s; the oven was programmed from 40-90ºC to 350ºC at 2.0, 2.5 and 3.0ºC/min; the modulation periods tested were 3, 4 and 5s. The injected volume was 2µL in splitless mode, the carrier gas (He) flow rate of 1 mL/min was constant and the FID detector was operated at 120 Hz. Validation parameters, such as the limit of detection (200 - 500 ng/mL) and quantitation (650 - 1600 ng/mL) were determined. For quantification, the internal and external standardization methods were tested, and through the results of this study, it can be shown that the determination of nitro-PAHs by GCxGC with the modulator used is possible if made by internal standardization method. The GCxGC system presented operational difficulties, particularly in the column connection and in the modulation zone. A partial connection of the columns resulted in mass loss of the analytes. The connection of the columns could be more effective if it was made by fusing the columns to a glass connector suitable for this purpose. Divided modulated peaks were frequently observed, which compromised the precision and accuracy of the results. The division of the peaks occurred randomly hindering the identification of the most likely cause for its occurrence. GCxGC chromatograms corresponding to unfractionated organic extracts of airborne particulate material from the sugarcane straw burning, from an area impacted by sugar cane burning emissions and from an urban area of São Paulo City showed the capability of the method.

Le développement des technologies de communication et de l’information nécessite des composants semi-conducteurs ultrarapides et à faible niveau de bruit. Les transistors bipolaires à hétérojonction (TBH) sont des dispositifs qui visent des applications à hautes fréquences et qui peuvent satisfaire ces conditions. L’objet de cette thèse est l’étude expérimentale et la modélisation du bruit haute fréquence des TBH Si/SiGe:C (technologie STMicroelectronics) et InP/InGaAs (III-V Lab Alcatel-Thales).Accompagné d’un état de l’art des performances dynamiques des différentes technologies de TBH, le chapitre I rappelle brièvement le fonctionnement et la caractérisation des TBH en régime statique et dynamique. La première partie du chapitre II donne la description des deux types de TBH, avec l’analyse des performances dynamiques et statiques en fonction des variations technologiques de ceux-ci (composition de la base du TBH SiGe:C, réduction des dimensions latérales du TBH InGaAs). Avec l’aide d’une modélisation hydrodynamique, la seconde partie montre l’avantage d’une composition en germanium de 15-25% dans la base du TBH SiGe pour atteindre les meilleurs performances dynamiques. Le chapitre III synthétise des analyses statiques et dynamiques réalisées à basse température permettant de déterminer le poids relatif des temps de transit et des temps de charge dans la limitation des performances des TBH. L’analyse expérimentale et la modélisation analytique du bruit haute fréquence des deux types de TBH sont présentées en chapitre IV. La modélisation permet de mettre en évidence l’influence de la défocalisation du courant, de l’auto-échauffement, de la nature de l’hétérojonction base-émetteur sur le bruit haute fréquence. Une estimation des performances en bruit à basse température des deux types de TBH est obtenues avec les modèles électriques. / In order to fulfil the roadmap for the development of telecommunication and information technologies (TIC), low noise level and very fast semiconductor devices are required. Heterojunction bipolar transistor has demonstrated excellent high frequency performances and becomes a candidate to address TIC roadmap. This work deals with experimental analysis and high frequency noise modelling of Si/SiGe:C HBT (STMicroelectronics tech.) and InP/InGaAs HBT (III-V Lab Alcatel-Thales).Chapter I introduces the basic concepts of HBTs operation and the characterization at high-frequency. This chapter summarizes the high frequency performances of many state-of-the-art HBT technologies. The first part of chapter II describes the two HBT sets, with paying attention on the impact of the base composition (SiGe:C) or the lateral reduction of the device (InGaAs) on static and dynamic performances. Based on TCAD modelling, the second part shows that a 15-25% germanium composition profile in the base is able to reach highest dynamic performances. Chapter III summarizes the static and dynamic results at low temperature, giving a separation of the intrinsic transit times and charging times involved into the performance limitation. Chapter IV presents noise measurements and the derivation of high frequency noise analytical models. These models highlight the impact of the current crowding and the self-heating effects, and the influence of the base-emitter heterojunction on the high frequency noise. According to these models the high frequency noise performances are estimated at low temperature for both HBT technologies.

Os hidrocarbonetos policíclicos aromáticos nitrados (nitro-HPAs) são potencialmente genotóxicos, por isso existe um grande interesse na determinação analítica desses compostos no material particulado no ar. Os nitro-PAHs são emitidos diretamente para a atmosfera pela combustão incompleta ou podem ser formados in situ a partir dos HPAs precursores. Neste trabalho, são apresentados os resultados obtidos no desenvolvimento de um método de análise de nitro-HPAs (1-nitronaftaleno, 2-nitronaftaleno, 1-nitropireno, 2-nitropireno, 2-nitrofluoranteno, 3-nitrofluoranteno, 1,3-dinitropireno, 1,6- dinitropireno, 2-nitrofluoreno, 6-nitrocriseno, 7-nitrobenzo(a)antraceno, 9- nitroantraceno e 9-nitrofenantreno) por GCxGC. A separação destes compostos por GCxGC pode simplificar a etapa de pré-tratamento do extrato orgânico oriundo do material particulado no ar. A GCxGC promove a separação em duas colunas com mecanismos de separação diferentes, conectadas em série, o que resulta em uma capacidade de separação maior. O sistema GCxGC empregado neste trabalho possui um injetor com programação de temperatura (PTV), um modulador criogênico de dois jatos de CO2 líquido (Dual Jet) e um detector por ionização em chama (FID). A separação foi feita empregando a fase estacionária apolar 5% fenil polisilfenilene siloxano na primeira coluna (30 m / 0,25 mm / 0,25 µm) e a semipolar 14% cianopropilfenil polisiloxano na segunda coluna (1 m / 0,10 mm / 0,10 µm). Diferentes condições cromatográficas foram testadas, como: programação de temperatura no PTV, de 40-90ºC até 350ºC, com taxa de aquecimento de 2,2 e 14,5ºC/s; programação de temperatura no forno, de 40-90ºC até 300ºC, com taxa de aquecimento de 2, 2,5 e 3ºC/min; períodos de modulação de 3, 4 e 5s. O volume injetado foi 2µL, no modo splitless; a vazão do gás de arraste (He) foi constante e igual a 1 mL/min e o detector FID foi operado em 120 Hz. As larguras de pico medidas em 10% da altura variaram de 167 a 350ms para 1- nitronaftaleno e 6-nitrocriseno, respectivamente, e a capacidade de pico para o conjunto de colunas de separação usado foi estimada em cerca de 9800. Parâmetros de validação, tais como os limites de detecção (200 a 500 ng/mL) e de quantificação (650 a 1600 ng/mL) para alguns nitro-HPAs foram determinados. Para a quantificação, foram testados os métodos por padronização interna e externa, sendo que, através dos resultados deste trabalho, pode-se mostrar que a determinação de nitro-HPAs por GCxGC com o modulador empregado é possível se for feita através do método de padronização interna. O sistema GCxGC empregado causou dificuldades operacionais, principalmente na conexão das colunas e na modulação. Perdas de massa de analito foram detectadas nas análises por GCxGC, muito provavelmente causadas por uma conexão parcial das colunas. Isso poderia ser evitado se a conexão fosse feita pela fusão das colunas a um conector de vidro adequado a essa finalidade. Picos modulados divididos foram observados com frequência, o que comprometeu a precisão e exatidão dos resultados. A divisão dos picos ocorreu de modo aleatório dificultando a identificação da causa mais provável para a sua ocorrência. Cromatogramas GCxGC de extratos orgânicos não fracionados de particulados no ar, oriundos de queima direta de palha de cana-de-açúcar, de região afetada pela queima de cana-de-açúcar e de área urbana da cidade de São Paulo, mostraram a potencialidade do método / Nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) are potentially genotoxic, so there is a great interest in the analytical determination of these compounds in airborne particulate matter. The nitro-PAHs are emitted directly into the atmosphere by incomplete combustion or may be formed in situ from PAHs. In this work, results obtained from the development of an analytical method for nitro-PAHs by GCxGC are presented. The nitro-PAHs studied were: 1- nitronaphthalene, 2-nitronaphthalene, 1-nitropyrene, 2-nitropyrene, 2- nitrofluoranthene, 3-nitrofluoranthene, 1,3-dinitropyrene, 1,6-dinitropyrene, 2- nitrofluorene, 6-nitrochrysene, 7-nitrobenzo(a)anthracene, 9-nitroanthracene and 9- nitrophenanthrene. The separation of these compounds by GCxGC should simplify the pretreatment step of the airborne particulate organic extract. In GCxGC two capillary columns of different mechanisms of separation are coupled by an interface called modulator, which increase significantly the chromatographic resolution. The GCxGC system used in this work is equipped with a PTV injector, a dual-stage double jets CO2 cryogenic modulator and a flame ionization detector (FID). The separation was carried out using a nonpolar stationary phase 5% methyl phenyl polysiloxane in the first column (30 m / 0.25 mm / 0.25 µm) and a semipolar 14% cyanopropyl phenyl dimethyl polysiloxane in the second column. Different chromatographic conditions were tested: the PTV was programmed from 40-90ºC to 350ºC at 2.2 and 14.5ºC/s; the oven was programmed from 40-90ºC to 350ºC at 2.0, 2.5 and 3.0ºC/min; the modulation periods tested were 3, 4 and 5s. The injected volume was 2µL in splitless mode, the carrier gas (He) flow rate of 1 mL/min was constant and the FID detector was operated at 120 Hz. Validation parameters, such as the limit of detection (200 - 500 ng/mL) and quantitation (650 - 1600 ng/mL) were determined. For quantification, the internal and external standardization methods were tested, and through the results of this study, it can be shown that the determination of nitro-PAHs by GCxGC with the modulator used is possible if made by internal standardization method. The GCxGC system presented operational difficulties, particularly in the column connection and in the modulation zone. A partial connection of the columns resulted in mass loss of the analytes. The connection of the columns could be more effective if it was made by fusing the columns to a glass connector suitable for this purpose. Divided modulated peaks were frequently observed, which compromised the precision and accuracy of the results. The division of the peaks occurred randomly hindering the identification of the most likely cause for its occurrence. GCxGC chromatograms corresponding to unfractionated organic extracts of airborne particulate material from the sugarcane straw burning, from an area impacted by sugar cane burning emissions and from an urban area of São Paulo City showed the capability of the method.

L'étude de la double désintégration bêta sans neutrinos joue un rôle important dans plusieurs questions en physique des particules et cosmologie. Ce processus nucléaire hypothétique viole la conservation du nombre leptonique par deux unités et jusqu'à présent il est le seule moyen pratique pour dévoiler la nature du neutrino : sa détection implique forcement que neutrino et antineutrino sont la même particule. En outre, le taux de décroissance est sensible à la masse efficace de Majorana du neutrino, du coup à l'échelle absolue des valeurs propres de la masse et leur hiérarchie. La marque expérimentale de la DDB0ν est un pic monochromatique dans le spectre énergétique de la somme des deux électrons émis. Le but des expériences de prochaine génération est une sensibilité sur la masse efficace du neutrino de l'ordre de dizaines de meV, c'est-à-dire demi-vies de l'ordre de 10²⁷-10²⁸ années : en pratique, il s'agit de construire des sources de quelques centaines de kg d'isotope candidat, au moins, et les sonder par des détecteurs très efficients, tout en gardant le bruit de fond dans la région énergétique d'intérêt au niveau d'un coup/tonne/an. Les bolomètres luminescents sont une technique prometteuse vu leur excellentes résolutions énergétiques, haute efficacité de détection, ample choix pour les matériaux et extensibilité modulaire à grande échelle; de plus, grâce à la détection simultanée de chaleur et lumière produites par l'interaction des particules, il est possible de discriminer les contaminations α, dangereuse source de bruit aux énergies d'intérêt pour plusieurs noyaux candidats à la DDB0ν. Cette thèse a été effectuée dans le contexte de l'expérience LUMINEU : une expérience pilote qui a pour but la construction d'une expérience de prochaine génération basée sur les bolomètres scintillants en molybdate de zinc, pour l'étude de l'isotope candidat ¹⁰⁰Mo. En vue de la construction d'une expérience à grande échelle, il est nécessaire d'effectuer des caractérisations systématiques pour s'assurer des performances et de la reproductibilité des détecteurs et leurs composantes. La disponibilité d'installations expérimentales en surface, facilement accessibles, est souhaitable pour des tests routiniers : j'ai mené la plupart des expériences au CSNSM, où j'ai aussi travaillé à l'installation d'un nouvel cryostat à dilution basé sur la technologie du Pulse-Tube. Une partie de ma thèse a concerné l'étude de détecteurs bolométriques de lumière aux absorbeurs en germanium et thermomètres NTD (thermistors Neutron Transmutation Doped) : une structure standard pour LUMINEU a été établie et on a mesuré les performances des bolomètres telles que sensibilité, résolution énergétique, bruit de base et reproductibilité. Les résultats sont satisfaisants en vue d'un emploi dans une expérience avec bolomètres scintillants, bien que la configuration soit très sensible à la microphonie. En outre, j'ai testé avec succès des détecteurs bolométriques de lumière exploitants l'effet Neganov-Luke, qui augmente le rapport signal-bruit au niveau compatible avec la détection de la lumière Cherenkov pour la discrimination des événements. Une autre partie a vu la caractérisation des bolomètres scintillants en molybdate de zinc avec masse allant jusqu'à environ 300 g : couplés aux capteurs de lumière susmentionnés et lus par thermistors NTD, ils ont été refroidis en surface au CSNSM et en endroit souterrain à Modane, dans l'installation de l'expérience EDELWEISS pour la Matière Noire. Grâce à la détection simultanée de lumière et chaleur, les interactions des particules β/γ sont séparées des contaminations α. Les résultats démontrent que la caractérisation de bolomètres massifs, presque la taille cible des détecteurs finaux, est possible même en surface, en dépit du rayonnement cosmique. En outre, ces tests ont permis d'optimiser la compatibilité de l'installation de Modane avec les exigences des bolomètres scintillants pour la recherche de la DDB0ν. / Neutrinoless Double Beta Decay (0νDBD) is regarded as an important key in the decryption of some hot astroparticle and cosmological enigmas: it violates lepton number by two units and it is currently the only known practical way to shed light on the neutrino nature, being possible only in case of a Majorana neutrino, identical to its antiparticle. Moreover, the 0νDBD rate is sensitive to the effective neutrino mass, so it would be useful to define the absolute neutrino mass scale and hierarchy. The experimental footprint of 0νDBD is a monochromatic peak in the sum energy spectrum of the two emitted electrons. Next-generation experiments aim at reaching a sensitivity on the effective neutrino mass of the order of ten meV, corresponding to half lives in the range 10²⁷-10²⁸ years: this means to be able to gather, at least, a few hundred kilograms of 0νDBD candidate isotope source and to efficiently scrutinize it with very sensitive detectors. Meanwhile, background levels in the energy region of interest of the 0νDBD signal should be lowered to less than one count/ton/y. Cryogenic luminescent bolometers are a promising technique for 0νDBD search, as they feature excellent energy resolutions, high detection efficiency, flexibility in the material choice and easy scalability to large modular experiments; furthermore, the simultaneous read-out of heat and light signals produced by particle interactions provides an active discrimination method against the dangerous α contaminations, populating the 0νDBD energy region of several interesting candidate isotopes. The work presented in this dissertation was carried out in the context of the LUMINEU project: a pilot experiment focused on zinc molybdate scintillating bolometers, to define the strategies for the construction of a next-generation experiment based on the 0νDBD candidate ¹⁰⁰Mo. In view of the construction of a large 0νDBD experiment, involving hundreds of modules, systematic cryogenic measurements have to be performed to ensure good performance and reproducibility of the detectors and their components. Aboveground facilities are preferred for routinary tests because of their easier accessibility: most of the tests were carried out at CSNSM, where I also worked on the setup of a new cryogenic apparatus, based on the Pulse-Tube technology. One part of my thesis work saw the study of bolometric light detectors based on germanium absorbers and Neutron Transmutation Doped (NTD) thermometers: a proper design was developed in view of LUMINEU and the devices were characterized in terms of sensitivity, energy resolution, baseline noise and reproducibility. The results are compatible with a 0νDBD search final experiment, though this detector configuration is very sensitive to vibrational noise. In addition, the feasibility of bolometric light detectors based on NTD thermometers and Neganov-Luke amplification was investigated, demonstrating that this technique can actually boost the signal-to-noise gain to a level compatible with event discrimination based on Cherenkov light detection. Another part of my work dealt with the test of scintillating zinc molybdate bolometers of mass up to ~300 g, coupled to the aforementioned light detectors and operated both in the aboveground facilities at CSNSM and underground at Modane, in the cryostat of the EDELWEISS Dark Matter search experiment. Good event discrimination capability was achieved: thanks to double read-out of heat and light, it is possible to identify α particles, the threatening background for 0νDBD interests, against β/γ interactions. The results proved the possibility to pre-characterize aboveground detectors of mass close to the one of a final experiment module, despite the high cosmic rays rates. Besides, the measurements opened the way to the mutual compatibility of the underground setup, conceived for another kind of experiment, and LUMINEU 0νDBD search detectors.

Nous avons mis en place un dispositif permettant l’acquisition d'échos de photons stimulés infrarouges à l’échelle femtoseconde. Le but est d'examiner la dynamique vibrationnelle aux temps courts de métaux carbonyles (W(CO)₆ and Fe(CO)₅) piégés en matrice cryogénique (4-50 K). Cet environnement solide, issu de la condensation d'un mélange gazeux contenant une impureté et un gaz inerte (N₂, CH₄, Ar, etc.), est propice à l’étude de systèmes dans leur état fondamental. L’excitation d’une vibration moléculaire s’atténue toujours temporellement, ce qui correspond dans le domaine spectral à un élargissement des raies d’absorption. L’étude de la dynamique vibrationnelle vise à examiner les causes physiques à l’origine de cet élargissement spectral. Typiquement, elles sont de trois sortes : phénomènes intramoléculaires, interactions entre molécules piégées et interactions entre la molécule piégée et l’environnement. Les échos de photons permettent de distinguer les contributions homogènes et inhomogènes de l’élargissement spectral et de caractériser les processus de déphasage, de relaxation des populations et de diffusion spectrale. Parmi les résultats obtenus, nous avons mis en évidence l'influence des phonons spécifiques aux matrices moléculaires (ex : libration de N₂ et rotation de CH₄ ) sur le déphasage vibrationnel ainsi que l’influence de la transition de phase du méthane solide à 20 K sur la dynamique vibrationnelle. Nous avons également montré que la dynamique vibrationnelle était dépendante du site cristallographique dans lequel est piégée la molécule. Enfin, en excitant plusieurs modes de vibration simultanément, nous avons pu examiner les couplages intramoléculaires. / We built an experimental set-up in order to generate infrared stimulated photon echoes at the femtosecond timescale. The purpose is to examine the short time vibrational dynamics of metal carbonyls (W(CO)₆ and Fe(CO)₅) trapped in cryogenic matrices (4-50 K). This environment, resulting from the condensation of a gas mixture containing the impurity and an inert gas (N₂, CH₄, Ar, etc.), is well suited to study systems in their ground state. An excited molecular vibration is always damped in the time domain. It corresponds in the frequency domain to a broadening of the absorption line. The study of the vibrational dynamics aims at examining the physical causes of this spectral broadening. Typically, there are three kinds of causes: intramolecular phenomena, interactions between trapped molecules and interactions between the impurity and the environment. Photon echoes allow distinguishing between the homogeneous and the inhomogeneous contributions of the spectral broadening and characterizing dephasing process, population relaxation and spectral diffusion. Among the obtained results, we highlighted the influence of phonons that are specific to molecular matrices (ex: N₂ libration and CH₄ rotation) on the vibrational dephasing. Moreover, we observed the influence of the phase transition of solid methane at 20 K on the vibrational dynamics. We also showed that the vibrational dynamics depends on the site in which the molecule is trapped. Finally, when exciting several vibrational modes, we are also able to study intramolecular couplings.

Este estudo teve por finalidade estudar os efeitos da fototerapia com laser em baixa intensidade (Low Level Laser Therapy LLLT) sobre a inflamação e reparação após lesão criogênica realizada no sitema nervoso central (SNC) de ratos. Foram realizados 3 experimentos. Em todos os experimentos foi utilizado um modelo de deformação cortical direta induzida por lesão criogênica. A LLLT foi realizada com laser de diodo em baixa intensidade emitindo no vermelho visível (InGaAlP, 660 nm) ou no infravermelho (AlGaAr, 780 nm). Os parâmetros de irradiação foram: potência de 40 mW, área do feixe de 0,04 cm2, densidades de energia de 3 J/cm2 (3 s) ou 5 J/cm2 (5 s) determinando energias por ponto de 0,12 J e 0,20 J, respectivamente. Foram realizadas 2 irradiações com intervalo de 3 h, no modo contato e em 2 pontos por lesão. No experimento 1, 50 ratos da linhagem Wistar foram utilizados para determinar os parâmetros de LLLT capazes de influenciar na dinâmica da produção de citocinas proinflamatórias (TNF-a, IL-1b, IL-6) e antiinflamatória (IL-10). As citocinas foram mensuradas pelo teste ELISA no cérebro e no sangue dos animais, 6 e 24h após a lesão. Os grupos experimentais foram: controle (não irradiado) e 4 grupos irradiados com 3 J/cm2 ou 5 J/cm2 para cada comprimento de onda (n=10 por grupo). Para os experimentos 2 e 3 foram utilizados 40 ratos (20 não irradiados controles e 20 irradiados). A LLLT foi realizada somente com o parâmetro de irradiação do laser no infravermelho e a densidade de energia de 3 J/cm2. Nestes experimentos o processo de reparação das lesões criogênicas no SNC foi acompanhado em 6 h, 1, 7 e 14 dias após a última irradiação (n=5 por grupo por tempo experimental). No experimento 2 foi realizada a análise morfométrica da região lesionada do SNC. No experimento 3 foi analisada a distribuição das células inflamatórias (linfócitos T, leucócitos e macrófagos). Os dados de cada experimento foram comparados estatísticamente por análise de variância (ANOVA) ou Kruskal-Wallis seguido dos testes de Tukey ou de Dunn, respectivamente (F=5%). O trauma criogênico foi capaz de criar lesões focais no córtex representadas por necrose, edema, hemorragia e infiltrado inflamatório. Os achados mais marcantes foram: no experimento 1 com a irradiação do laser no infravermelho e 3 J/ cm2, o TNF- a e a IL-6 se mantiveram nos mesmos níveis em 6 e 24 h, enquanto no controle houve aumento significativo. Experimento 2: as lesões não tratadas apresentaram maior perda tecidual em 6 h que as irradiadas. Experimento 3: as lesões irradiadas apresentaram menor quantidade de leucócitos e linfócitos T nas primeiras 24 h do que nas lesões controle. A quantidade de macrófagos foi similar nos dois grupos. Conclusões: Levando em consideração as condições experimentais deste estudo concluiu-se que LLLT exerce efeitos nos processos de inflamação e reparação diminuindo a concentração de citocinas próinflamatórias (TNF-F e IL-6) no sangue e mantendo a de IL-1I no cérebro. Adicionalmente, diminui a perda tecidual inicial pós- lesão criogênica e a infiltração inicial de leucócitos e linfócitos T. / This study aimed to study the effects of phototherapy with low-intensity laser (Low Level Laser Therapy - LLLT) on inflammation and repair after cryogenic injury held in central nervous system (CNS) of rats. There were 3 experiments. In all experiments a model of deformation induced by direct cortical cryogenic injury was used. The LLLT was carried out with a low intensity diode laser emitting in the visible red (InGaAlP, 660 nm) or infrared (AlGaAs, 780 nm). The irradiation parameters were: power of 40 mW, beam area of 0.04 cm2, energy densities of 3 J/cm2 (3 s) or 5 J/cm2 (5 s) providing energy per point of 0.12 J and 0.20 J, respectively. Two irradiations were performed at 3 h-intervals, in contact mode and in 2 points for lesion. In experiment 1, 50 Wistar rats were used to determine the parameters of LLLT able to influence the dynamics of production proinflammatory cytokines (TNF-, IL-1 and IL-6) and antiinflammatory cytokine (IL- 10). Cytokines were measured by ELISA in the brain and blood of animals, 6 and 24 hours after injury. The experimental groups were: control (non-irradiated) and 4 irradiated groups [3 J/cm2 and 5 J/cm2 for each wavelength (n = 10 per group)]. For experiments 2 and 3 40 rats (20 non-irradiated - controls and 20 irradiated).were used. The LLLT was performed only with the parameter of laser irradiation on the infrared and the energy density of 3 J/cm2. In these experiments, the process of repair of cryogenic injury in the CNS was followed in 6 h, 1, 7 and 14 days after the last irradiation (n = 5 per group and time trial). In experiment 2 a morphometric analysis of the injured area of the CNS was done. In experiment 3 the distribution of inflammatory cells (lymphocytes, leukocytes and macrophages) was analyzed. Data from each experiment were compared statistically by analysis of variance (ANOVA) or Kruskal-Wallis followed by tests of Tukey or Dunn, respectively ( = 5%). Cryogenic trauma was able to create focal lesions in the cortex represented by necrosis, edema, hemorrhage and inflammatory infiltrate. The most striking findings were: in experiment 1 with the laser irradiation in the infrared and 3 J/cm 2, TNF- and IL-6 remained at the same levels at 6 and 24 h, while in the control there was a significant increase. Experiment 2: untreated lesions showed greater tissue loss than irradiated lesions in 6 h. Experiment 3: lesions irradiated had fewer leukocytes and lymphocytes in the first 24 h than control lesions. The amount of macrophages was similar in both groups. Conclusions: Considering the experimental conditions of this study it was concluded that LLLT has effects in the processes of inflammation and repair by decreasing the concentration of proinflammatory cytokines (TNF- and IL-6) in blood and holding the IL-1 in the brain. Additionally, decreases the initial tissue loss after cryogenic injury and the initial infiltration of leukocytes and lymphocytes T.