Atomization of arsine in a novel hydride atomizer for atomic absorption spectrometry (HG-AAS) was thoroughly optimized. This plasma atomizer is based on a dielectric barrier discharge (DBD). Sensitivity and detection limit reached 0.48 s ng-1 As and 0.16 ng ml-1 As, respectively, under optimum atomization conditions (Ar discharge using a flow rate of 60 ml min-1 Ar, DBD power 17 W). Analytical figures of merit reached in DBD are comparable to those found in an externally heated quartz tube multiatomizer (MMQTA) that was chosen as a model of conventional approach to hydride atomization in HG-AAS. An extent of interferences (Se, Sb, Bi) during As determination was investigated comparing both MMQTA and DBD atomizers. The later one was found to be more resistant towards interferences. A simple preconcentration of As in a DBD atomizer was reached after oxygen introduction into the Ar plasma in the DBD resulting in analyte retention in the atomizer followed by its volatilization once the oxygen flow is switched off. Preconcentration efficiency of 100 % was reached and detection limit improvement by a factor of ten was achieved (0.01 ng ml-1 As, preconcentration period 300 s).

Le plasma hors-équilibre est l’un des outils les plus attrayants et prometteurs pour de nombreuses applications assistées par plasma. La production d’espèces actives (espèces excitées, radicaux, photons de hautes énergies couvrant les spectres UV et IR) est importante pour le contrôle des gaz polluants, le traitement de surface, les actionneurs de plasma en aérodynamique, certaines applications biomédicales et, plus récemment, en médecine du plasma. Pour des densités de gaz atmosphérique et élevée, les applications des plasmas non-thermiques sont essentiellement l’allumage des mélanges combustibles ou, soi-disant, l’Allumage Assistée par Plasma (AAP). Les Décharges à Barrière Diélectrique de Surface (DBDS), largement utilisées pour le contrôle de l’écoulement aérodynamique, ont été récemment suggérées comme déclencheur de la combustion distribué dans différents systèmes. La possibilité d’utiliser les DBDS, comme allumeurs à des pressions allant jusqu’à plusieurs dizaines de bar, a été démontrée au cours des 4-5 dernières années. Au début de la thèse, l’ensemble des données expérimentales sur la décharge et l’allumage des combustibles par DBDS était assez pauvre, et insuffisant pour une analyse détaillée. Par conséquent, l’étude expérimentale de la DBDS à des densités atmosphérique et élevée de gaz, ainsi que l’étude du déclenchement de la flamme par DBDS nanoseconde (DBDSn) ont fait l’objet de cette thèse. Les résultats de la thèse sont présentés en trois parties. Dans la première partie, la DBDSn en mode mono-pulse est étudiée. Pour cela, l’analyse du dépôt d’énergie, du courant de la décharge, de la distribution de l’intensité et de la libération d’énergie qui en découle est effectuée. Les impulsions à polarités positive et négative sont utilisées pour générer la décharge surfacique, et la physique des streamers à polarités positive et négative y est discutée. Pour les deux polarités, la densité électronique et le champ électrique réduit sont estimés puis comparés avec des calculs et/ou des résultats obtenus par modélisation 2D. La deuxième partie est consacrée à l’étude des DBDSn à pression élevée (jusqu’à 12 bar) dans différents mélanges de gaz : N2, air, N2:CH4, N2:H2, Ar:O2, etc. Deux aspects morphologiquement différents de la DBDSn sont considérés : une DBD streamer « classique » à des pressions et tensions relativement basses, et une DBD filamentaire à des pressions et/ou tensions élevées. Les données quantitatives sur la décharge à haute pression (de 1 à 12 bar) sont obtenues par spectroscopie d’émission. Une description possible de la nature de cette filamentation est donnée. Enfin, la troisième partie présente les expériences d’allumage assistée par plasma utilisant des DBDSn à haute pression. Les morphologies de la décharge dans les mélanges combustibles pauvres (H2:air) et de l’allumage engendré sont étudiées. Puis, la comparaison entre allumage par décharge filamentaire et par streamer à la pression 1-6 bar est effectuée. Les données expérimentales sont analysées grâce à une modélisation de la cinétique de l’allumage assisté par plasma dans des champs électriques typiques des DBDSn (E/N = 100 Td). Une étude complexe des décharges à pression atmosphérique, à haute pression et de l’allumage permet d’obtenir une description détaillée de l’allumage à haute pression, distribué dans l’espace par le plasma hors-équilibre. / Non–equilibrium plasma is one of the most attractive and promising tool for many plasma–assisted applications. Production of active species (excited species, radicals, high energetic photons covering UV and IR spectral range) is important for gas pollution control, surface treatment, plasma actuators for aerodynamics application, biomedical applications and more recently the field of plasma medicine. For atmospheric and elevated gas densities the mainstream of the non–thermal plasma applications is the ignition of combustible mixtures or so–called Plasma–Assisted Ignition (PAI). Surface dielectric barrier discharges (SDBD), widely used for aerodynamic flow control, were recently suggested as distributed initiators of combustion in different systems. A principal possibility of using the SDBD ignitors at as high pressure as tens of bars has been demonstrated during the last 4-5 years. At the moment of the beginning of the thesis, the set of experimental data on the discharge and of ignition of fuels with SDBD was quite poor and insufficient for detailed analysis. Therefore, the experimental study of the surface DBD at atmospheric and elevated gas densities and the study of flame initiation with nanosecond SDBD were the object of the presented thesis. The results in the Thesis are presented in three parts. In the first part the nSDBD in a single shot regime at atmospheric air is investigated. The analysis of energy deposition, discharge current, intensity distribution and consequent energy release is performed. The positive and negative polarity pulses are used to produce surface discharge. The physics of anode and cathode–directed streamers is discussed. For both polarities of the applied pulses the electron density and reduced electric field are estimated and compared with calculations and/or 2D modeling results. The second part is devoted to the study of nSDBD at elevated pressures, up to 12 bar, in different gas mixtures ( N2, air, N2:CH4, N2:H2, Ar:O2, etc.). Two morphologically different forms of the nSDBD are considered: a “classical” streamer DBD at relatively low pressures and voltages, and a filamentary DBD at high pressures and/or voltages. The emission spectroscopy is used to obtain quantitative data about the discharge at high pressures (1-12 bar). The possible nature of the discharge filamentation is described. Finally, the third part describes the experiments of plasma–assisted ignition with nanosecond SDBD at elevated pressures. The discharge morphology in lean combustible ( H2:air) mixtures and following ignition of the mixtures are studied. The comparison of ignition by filamentary and streamer discharge at the pressures 1-6 bar is performed. Kinetic modeling of plasma assisted ignition for the electric fields typical for nSDBD, E/N = 100 − 200 Td is used for analysis of experimental data. Complex study of the discharges at atmospheric pressure, discharge at high pressures and ignition allow detailed description of the high-pressure distributed in space ignition by non--equilibrium plasma.

A numerical study has been performed to investigate the mechanics of the turbulent wake of a circular cylinder that is controlled by a plasma actuator. The numerical investigation implements a straightforward moving wall boundary condition to model the actuator's effects on the flow. Validations of the moving wall for this simulation are set forth with the understanding that the moving wall can model the plasma actuator bulk flow effects at a distance downstream and not in a region near or on the plasma actuator. The moving wall boundary condition is then applied to a circular cylinder at a Reynolds number of 8,000. At this unsteady transitional flow regime, a large eddy simulation solver is utilized to resolve flow features. The moving walls are placed at the top and bottom ninety degree points of the cylinder and alternately activated at a frequency to produce lock-in behavior. Investigation into the flowfield mechanics reveals that a harmonic frequency of the forced frequency occurs from the creation of sub-vortices from the instantaneous starting and stopping of the moving-wall actuators. With the forcing frequency close to the natural shedding frequency it is found that the aerodynamic drag increases due to the moving wall creating an average low pressure region on to the downstream side of the cylinder. It is also found that drag can be reduced when the forcing frequency is closer to half the natural shedding frequency. This happens because of a decrease in the average pressure on the downstream side of the cylinder.

Recently there has been a surge in the field of mass spectrometry centered around the concept of rapid analysis of target analytes with minimal or no sample preparation. The target analyte undergoes desorption from its surface of origin and is subsequently ionized under ambient conditions. The technique is termed ambient desorption/ionization mass spectrometry (ADI-MS). Since the introduction of ADI-MS in 2004, there has been an explosion of research based around the development of novel ambient desorption/ionization (ADI) sources with the capability of desorbing and ionizing a variety of target analytes from various sampling surfaces. One type of ADI source uses the properties of an electrical discharge, typically a helium gas plasma, for desorption and ionization. For electrical-discharge-based sources, ionization is the result of an atmospheric pressure chemical ionization (APCI) process. The initiation of the APCI process it generally attributed to the Penning ionization of atmospheric nitrogen (N2) by highly energetic helium metastable species (Hem). In this work, I describe the direct imaging of the densities of helium metastable atoms in atmospheric pressure plasma jet (APPJ) of a helium-based dielectric-barrier discharge (DBD) using collisionally-assisted laser-induced fluorescence. Axial Hem distributions are compared to the emission of excited helium (He*) and nitrogen ion (N2+*) species in the plasma. A correlation is found between Hem densities and the performance of the ionization source in ADI-MS. Fluorescence images also show that Hem densities increase substantially when a glass slide is placed 10 mm from the discharge capillary in a geometry typical for desorption/ionization experiments. Advantage is taken of the time-varying nature of the plasma to produce axial profiles of temporally and spectrally resolved fluorescence images of Hem atoms and ground state nitrogen ions in the plasma jet. The axial distribution and similarities in the temporal behavior of the helium metastable and ground state nitrogen ion species give strong evidence that nitrogen ion species are created via Penning ionization by helium metastable atoms. Although axial distributions of He*,N2+*, and N2* emission support the fluorescence data, temporally-resolved emission measurements show that emission from key plasma species is almost entirely the result of excitation by a temporal energy wave. The effect that hydrogen (H2) has on the helium metastable atom densities is also presented. The addition of hydrogen to the discharge gas severely quenches the metastable state, leaving it virtually undetectable. The addition of 0.9% H2 to the helium in the source provides an order of magnitude increase in ADI-MS signal for target analytes despite the quenching of the Hem population.

No description available.

Ce travail traite de la conception de générateur alimentant une lampe DBD destinée à la production de rayonnement UV. Cette alimentation doit permettre un contrôle efficace du rayonnement, grâce aux degrés de liberté apportés par le contrôle du générateur (fréquence, amplitude du courant injecté dans la lampe). Le modèle électrique de la lampe est utilisé pour prédire l’impact des caractéristiques du générateur sur le rayonnement UV produit. Une synthèse des interrupteurs de puissance du convertisseur statique permettant le contrôle du courant injecté est proposée et des solutions d’implémentation sont étudiées. Une démarche de conception en vue de l’optimisation du transformateur haute tension est proposée, notamment en ce qui concerne la valeur de ses éléments parasites. L’ensemble de ces travaux est étayé par des réalisations expérimentales. / This work presents the concept of a generator supplying a DBD lamp for UV radiation production purpose. This supply permits effective control of radiation based on degree-of-freedom provided by generator control system (lamp current frequency and ampli-tude). Lamp electrical model is used to predict the impact of power source characteristics on the produced UV radiation. A synthesis of the switching devices of power converter for current lamp control is pro-posed and the implemented solutions are studied. A design procedure for high voltage transformer optimization is proposed in particular concerning parasitic elements. The entire work is supported by experimentations.

L'absorption des biomolécules, en particulier des protéines, sur les implants médicaux joue un rôle important dans le processus d'acceptation de l'implant dans le corps humain. L'activation des surfaces polymères par polymérisation plasma à pression atmosphérique et traitement plasma sont des méthodes utilisées dans les laboratoires des recherches pour modifier la cinétique d'adsorption et la quantité d'adsorbant. Le but de cette thèse est de mieux comprendre les mécanismes d'absorption des molécules biologiques sur des surfaces polymères modifiées par plasma à pression atmosphérique ou par autoassemblage, d'établir les mécanismes à l'interface et aussi d'établir la liaison entre la conformation des molécules adsorbées et les propriétés de biocompatibilité. / The objective of this thesis is to better understand the absorption mechanisms of biological molecules on surfaces obtained in plasma at atmospheric pressure or by self-assembly, to establish mechanisms at the interface and also establish the link between conformation of proteins adsorbed and the properties of biocompatibility.We studied a discharge at atmospheric pressure to obtain thin films of polyethylene glycol (PEG) and polyethylene glycol (PEG) with polystyrene copolymer. The characterization of thin polymer films was made using techniques atomic force microscopy (AFM), scanning electron microscopy (SEM), the contact angle measurements, infrared spectroscopy with Fourier transform (FTIR ) and X-ray photoelectron spectroscopy (XPS). The surfaces were analyzed in terms of biomolecules absorption with atomic force spectroscopy and quartz crystal microbalance.Studies of the ions and amino acids diffusion through functionalized mesoporous structures by low-pressure plasma are presented. After functionalization, we demonstrate the selectivity of the membrane for a particular class of amino acid, those which have a hydrophilic character.The mechanisms of self-assembly and stabilization of the G type molecules inside of the porous silicon are shown. Because the optical properties of these types of surfaces it can be observed the differences in stability of these molecules on the ionic strength of the different ion which form the structures.

La décontamination bactériologique des surfaces par lumière pulsée est un enjeu de société qui requiert le développement de nouveaux outils. Une technique ayant prouvée son efficacité est l’utilisation de lumière pulsée dans le domaine de longueur d’onde 200-280 nm (bande d’absorption de l’ADN). Dans ce travail, nous avons étudié deux sources, Décharge à Barrière Diélectrique (DBD) et réseaux de microdécharges permettant de générer un rayonnement à 222 nm correspondant à l’émission de l’exciplexe KrCl*. Nos études ont permis de démontrer qu’il était possible de produire des décharges dans de nombreuses microcavités fonctionnant en parallèle sans aucun ballast résistif à condition d’employer une excitation impulsionnelle nanoseconde. Des études d’imagerie et de spectroscopie résolues temporellement ont démontré que l’ensemble des microdécharges s’initiaient en moins de 5 ns, ce qui permet d’envisager la réalisation de matrice de microdécharges rayonnant des puissances crêtes élevées. Dans le cas des DBD, les études ont couplé modèle et expérience, ce qui nous a permis de déterminer les étapes clés de la cinétique réactionnelle et de prédire les meilleures conditions de production d’un rayonnement intense à 222 nm. Par ailleurs, grâce aux microdécharges, nous avons pu réaliser une source de rayonnement VUV permettant de sonder la densité de chlore atomique dans des réacteurs de gravure plasma par spectroscopie d'absorption résonnante. / Bacteriological decontamination of surfaces by pulsed light is a society issue that requires the development of new tools. A technique that proved its efficiency was to use a pulsed light in the 200-280 wavelength range corresponding to the DNA absorption band.In this work, we studied two different sources, the so-called Dielectric Barrier Discharge (DBD) and microdischarges arrays, to generate a radiation at 222 nm corresponding to the KrCl* exciplex emission. By using nanosecond pulsed discharges, we demonstrated that many microdischarges operating in parallel can be triggered simultaneously without introducing any resistive ballast. High speed ICCD imaging and time resolved spectroscopic studies had shown that all the microdischarges were initiated in less than 5 ns, which allowed the produce arrays of microdischarges generating high peak power of UV light. In the DBD case, studies have coupled experience and simulation which allowed us to determine the key steps of the kinetic pathways and to predict the best conditions for producing an intense 222 nm radiation. Moreover, microdischarges were also used to realize a VUV source to probe the atomic chlorine density in plasma etching reactors through resonance absorption spectroscopy.

Fluidos em uma descarga brilhante à pressão atmosférica usando uma barreira de dielétrico DBD atraiu o interesse das comunidades de termo-dinâmica, fluido-dinâmica, e comunidades de controle. Este trabalho investiga os efeitos de um atuador de plasma operando numa voltagem e frequência de 8 kV e 4.4 kHz sobre a curva do Cp de um cilindro de PVC em baixa velocidade de escoamento. O experimento foi repetido com o atuador em vários ângulos no cilindro. Os resultados mostram uma aceleração do escoamento junto com um atraso da separação. Esses efeitos são maiores quando o atuador é posicionado num ângulo mais próximo da região da separação. / Fluids in a dielectric barrier DBD glow discharge at atmospheric pressure attracted the interest of the communities of thermo and fluid dynamics as well as control. This dissertation investigates the effects of a plasma actuator operating at 8 kV and 4.4 kHz, on the Cp curve of a PVC cylinder in a low velocity airflow. The experiment was repeated with the actuator at various angles. The results show an acceleration of the flow accompanied with a delay of the flow separation. These effects were shown to be larger when the actuator was positioned at an angle closer to the region of separation.

The aim of this thesis is to investigate the properties of a Radio Frequency capacitive discharge at atmospheric pressure in argon. In these conditions where the pressure x distance product is around 150 Torr.cm, the discharge usually consists of several locally hot filaments. By pulsing the RF generator with an appropriate width and period, it was found possible to control the filament to glow transition in order to obtain a diffused and stable plasma.¶ The 2 mm gap between the electrodes is open to the ambient air and fed with argon via one hundred submillimetric holes regularly spread on the surface of the top electrode. This configuration allows “on-line” surface treatment of polymer films without having to turn the discharge off between successive samples. An important and lasting improvement of the polymer wettability is quickly obtained without risk of damage. The plasma diagnostic methods are emission spectroscopy and electric measurements. The Stark broadening of the Balmer β transition line of atomic hydrogen is measured to determine a plasma density of 10^15/cm3 in the filamentary mode. The glow mode density estimation was based on power balance yielding a density of 5×10^11/cm3. Emission line ratios between neutrals and Ar+ ions are used in the Saha equation to calculate the electron temperature. It results in an approximation of 1.3 eV for the glow mode and 1.7 eV for the filaments.¶ A unidimensional self-consistent fluid model is developed to gain insight into the homogeneous discharge behaviour. Poisson’s equation for the electric field is coupled to the first moments of the Boltzmann equation (continuity equation, drift-diffusion equation and energy equation). Transport and reaction coefficients are obtained from the mean energy of the electrons.¶ The model is applied to a reduced argon kinetic with the main ionization and excitation processes. Simulation results are in agreement with experimental measurements. The atmospheric pressure RF discharge is similar to a lower pressure RF discharge for which the ionization occurs mainly inside the oscillating sheaths where electrons are the most energetic