Having gained popularity in the last decade, the dielectric barrier discharge (DBD) has been studied in numerous ways as a device for air acceleration. A major interest of all these works has been concentrated on achieving higher efficiency and producing higher jet velocities. These studies considered alternative geometries, different voltage waveforms etc., yet none of these studies tackle the inherently inefficient process of force creation and actuation in a DBD. Air acceleration has been attributed to the electric force that switches direction on each voltage half cycle (that is due to the nature of the discharge mechanism) yet has a forward resulting force. The present thesis considers the phenomenon of memory charge accumulation on the dielectric surface and reasons that the backward force in the second half cycle can be reversed by further migration of the memory charges to an added exposed anode. Hence a novel 3-electrode configuration is presented. Flow velocity investigations showed a 27% improvement in efficiency in comparison with the traditional 2-electrode actuator. This meant a 0.4m/s gain along the velocity profile. During the investigation process, a new discharge mechanism was encountered. This was characterized by the double discharge lines along the exposed electrode edges while in the presence of a \"floating\" encapsulated electrode. / Tendo ganho popularidade na última década, a descarga de barreira dielétrica (DBD) foi estudada de várias maneiras como um dispositivo para aceleração do ar e controle aerodinâmico. Um grande interesse de todos esses trabalhos foi concentrado em alcançar maior eficiência e produzir maiores velocidades de jato. Alguns desses estudos consideraram geometrias alternativas, diferentes formas de onda de tensão, etc., mas nenhum desses estudos aborda o processo inerentemente ineficiente de criação e atuação da força em um DBD. A Aceleração do ar tem sido atribuída à força elétrica que muda de direção em cada meio ciclo (que é devido à natureza do mecanismo de descarga), mas que tem uma força resultante para a frente. A presente tese considera o fenômeno de acumulação de carga de memória na superfície dielétrica e raciocina que a força contraria no segundo meio ciclo da descarga pode ser revertida por migração dessas cargas de memória para um ânodo adicional exposto. Assim, uma nova configuração de 3 eletrodos é apresentada. Investigações de velocidade do fluxo mostraram uma melhoria de 27% na eficiência em comparação com o tradicional atuador de 2 eletrodos. Isso significou um ganho de 0,3 m/s ao longo do perfil de velocidade. Durante o processo de investigação, foi encontrado um novo mecanismo de descarga. Isso foi caracterizado por uma dupla descarga ao longo das bordas do eletrodos expostos, enquanto na presença de um eletrodo encapsulado \"pendurado\".

The field of ambient desorption/ionization mass spectrometry (ADI-MS) has existed for over a decade. ADI-MS is a technique that offers benefits including fast analysis time, simple ionization sources that are easily constructed, and little to no required sample preparation. The research presented here describes efforts to better understand plasma-based ADI-MS sources and to explore the use of hydrogen-doped plasma gases with these sources. The use of hydrogen-doped argon (H2/Ar) and hydrogen-doped helium (H2/He) as plasma gases for a dielectric barrier discharge (DBD) and an AC glow discharge is presented first. When using the DBD, the intensity of the signal obtained when analyzing organic molecules in positive ion mode was increased by factors up to 37 times. In negative ion mode, only H2/Ar was shown to enhance the signal of an organic analyte. The limits of detection for caffeine when using hydrogen-doped plasma gases were found to decrease by factors of 78 and 1.9 for H2/Ar and H2/He respectively. The same phenomenon was observed when using H2/Ar with the AC discharge, but no signal enhancement was observed when using hydrogen-doped helium with the AC discharge. Similarly, if the DBD was allowed to ground through a wire rather than through the air, no signal enhancement was observed for H2/He. Using H2/Ar with metal samples is presented second. By using the metal sample as the grounded electrode for the AC glow discharge, many different metals could be detected directly with a time-of-flight mass spectrometer (TOF-MS) in the form of atomic ions both on their own and in combination with water and ammonia from the discharge. Any refractory metals tested did not yield signal. In addition to direct analysis with a TOF-MS, the AC discharge was used as a sampling method for an inductively coupled plasma mass spectrometer (ICP-MS). When coupled with an ICP-MS, the AC glow discharge was found capable of sampling even refractory elements, though the power of the ICP was required for ionization and detection. Scanning electron microscope (SEM) images of a copper surface exposed to the plasma discharge showed signs of melting when using the H2/Ar. Finally, a computer simulation of the chemistry and flow dynamics of a DC glow discharge generated in helium is presented. The simulation explores many of the fundamental processes at work and how they depend on the composition of the plasma gas. The generation of important species in the plasma was found to depend more on the amount of N2 and H2O impurities in the plasma gas rather than on the humidity or air pressure.

Το έργο αφορά στη μελέτη ενός πλάσματος Αζώτου εκκένωσης διηλεκτρικού φράγματος σε ατμοσφαιρική πίεση με διπλό στόχο: Πρώτον, την καλύτερη κατανόηση των φυσικοχημικών μηχανισμών που διέπουν αυτές τις εκκενώσεις, και στη συνέχεια την εφαρμογή αυτών στην επεξεργασία της επιφάνειας μεταλλικών υλικών. Συνεπώς η προσέγγιση στο πρόβλημα θα αναλυθεί λεπτομερώς με βάση δύο συμπληρωματικούς τομείς: - Μοντελοποίηση και Αριθμητική Εξομοίωση - Πειραματική Μελέτη. Το ψυχρό πλάσμα μιας εκκένωσης σε ατμοσφαιρική πίεση παρέχει μια σημαντική τεχνολογική καινοτομία: σπάει το φράγμα της τεχνολογίας κενού στην οποία βασίζονται οι τεχνικές πλάσματος χαμηλής πίεσης. Έτσι το ψυχρό πλάσμα μιας εκκένωσης σε ατμοσφαιρική πίεση παρουσιάζει σημαντικό βιομηχανικό ενδιαφέρον στο πλαίσιο της επεξεργασίας υλικών χαμηλής προστιθέμενης αξίας. Σε αυτή τη μελέτη, η επεξεργασία λαμβάνει χώρα υπό συνθήκες χωρικής μετα-εκκένωσης. Έτσι τα προϊόντα της εκκένωσης (και ιδιαίτερα τα ενεργά σωμάτια) αποστέλλονται, με βάση τη γεωμετρία του αντιδραστήρα και τη ροή του αερίου, εκτός του χώρου μεταξύ των ηλεκτροδίων.Μια τέτοια διάταξη επιτρέπει την επεξεργασία τμημάτων μεγάλων διαστάσεων ή ακόμα και τμημάτων που παρουσιάζουν καμπυλότητες. Επιτρέπει επίσης μια συνεχή βιομηχανική διεργασία κατά τα πρότυπα μιας γραμμής παραγωγής. Τα υλικά που μελετήθηκαν είναι κράματα μετάλλων Αl-2024 και TiA6V4, με βάση το αλουμίνιο και το τιτάνιο αντίστοχα. Χρησιμοποιούνται ευρέως στη βιομηχανία της αεροναυπηγικής που αντιπροσωπεύει ένα σημαντικό μέρος της οικονομικής δραστηριότητας στη Νοτιοδυτική Γαλλία και ειδικά στην περιοχή του Pau. ο σκοπός της επεξεργασίας είναι να καταστεί συμβατή η επιφάνειa με τις βιομηχανικές διεργασίες κολλήσεων και βαφών. / This work deals with an atmospheric pressure dielectric barrier discharge (DBD) plasma in Nitrogen in a double goal: To give insight into the physicochemical mechanisms that dominate in such a discharge and to apply such a discharge in the surface treatment of metal-alloy samples. This thesis investigates the aforementioned topic via two complementary approaches: Συνεπώς η προσέγγιση στο πρόβλημα θα αναλυθεί λεπτομερώς με βάση δύο συμπληρωματικούς τομείς: - Numerical Modeling and Simulation - Experimental Study The cold plasma generated by an atmospheric pressure electrical discharge holds a significant technological advantage: it breaks the vacuum technology barrier which is the cornerstone of traditional low pressure plasma techniques. Thus, the atmospheric pressure cold plasma appears interesting for industrial surface treatment applications and especially in the case of low added value materials. In this thesis, the surface treatment application takes place in spatial afterglow conditions: the dielectric barrier discharge’s effluents are guided, based on the dedicated reactor design and the elevated gas flow values here used out, of the inter-electrode space. These experimental features permit the surface treatment of large samples or even the treatment of pieces of arbitrary geometries (eg. concave, …). Such a set-up also makes possible a continuous industrial process under the production line standards. The materials that were investigated in the framework of this thesis are the metallic alloys Αl-2024 and TiA6V4, on the basis of Aluminum and Titanium respectively. They are used frequently in aerospace and aeronautical design and engineering which represent an important part of the industrial activity in the South – West part of France and especially in the region of Pau. The purpose of their surface treatment by the atmospheric pressure DBD plasma spatial afterglow was to render them compatible with the industrial processes related to adhesion and painting.

In this thesis, we focused on understanding the synthesis of titanium dioxide (TiO2) films and nitrogen doped TiO2 films using an atmospheric pressure Dielectric Barrier Discharge (DBD). The first part of the work was dedicated to the deposition of TiO2 films by cold plasma DBD with titanium tetraisopropoxide as precursor in a single-step process at room temperature. The deposition rate was about 70 nm·min-1. The photocatalytic degradation rate for the degradation of methylene blue (MB) under ultra violet (UV) irradiation of the TiO2 film after annealing was close to a reference anatase TiO2 spin coated film. Moreover, the TiO2 films showed a good photocatalytic stability. The second part of the study focused on the optimization and the understanding of the effect of the plasma parameters (gas flow rate and power) on the morphology of the TiO2 films and on the investigation of the deposition mechanisms. The morphology of the film changed from granular to compact film by either increasing the total flow rate or decreasing the plasma power. In other words, adapting the energy density in the plasma allowed the control of the morphology of the TiO2 films. To our knowledge, it was the first time that the energy density parameters of the plasma were used to control the morphology of TiO2 films. The photocatalytic degradation rate for the degradation of MB under UV irradiation of the annealed TiO2 film turned out to be about 2 and 15 times higher than the one of the commercial TiO2 film and the as-deposited TiO2 films, respectively. In order to extend the light utilization to the visible light range, TiO2 films were doped with nitrogen using a room temperature argon/ammonia plasma discharge. XPS and SIMS results confirmed that the nitrogen has been incorporated in the TiO2 lattice mostly in Ti-N state. This was further confirmed by Raman spectroscopy and XRD. The plasma properties and the doping mechanism were studied by Optical Emission Spectroscopy. It is suggested that the NH radicals played a key role in the doping of TiO2. The concentration of nitrogen in the N-TiO2 coatings could be tuned by adapting the ratio of NH3 in the plasma or the plasma power. The band gap of our N-TiO2 coatings is lower than the one of undoped TiO2 coating. The photocatalytic degradation rate for N-TiO2 coating was more than 4 times higher than the one of the undoped TiO2 coating. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Forças eletro-hidrodinâmicas apresentam boas qualidades para a utilização como meio de produzir e manipular escoamentos. Um de seus grandes méritos consiste na falta de partes móveis para a introdução de quantidade de movimento em escoamentos. Foi realizado um estudo experimental para a investigação e comparação de três diferentes configurações dos eletrodos usados para a produção de dispositivos eletro-hidrodinâmicos gerados por descarga de barreira dielétrica. Uma configuração é composta de eletrodos retangulares planos e a outra de um fio e um eletrodo retangular plano. A outra configuração usa uma nova configuração com um eletrodo plano de borda serrilhada, como eletrodo ativo, e um eletrodo retangular plano isolado. Todas as configurações foram investigados para entender o comportamento na produção de escoamento. Medições de tubo Pitot dos perfis de velocidade dos jatos de parede foram feitas em várias distâncias a partir da região da descarga elétrica. Na sequência, a medição do escoamento ao longo do eletrodo serrilhado foi realizada. Assim, pretende-se determinar as características de escoamento tridimensionais produzidas por esta configuração. Os resultados mostram melhores características da configuração serrilhado para ser utilizado na produção de escoamento mais intensos. / Electro-hydrodynamic forces have good qualities to be used to produce and manipulate flows. One of its great merits is the lack of moving parts to introduce momentum in flows. An experimental study for measure and comparing three different configurations of electrodes used for the production of electro-hydrodynamic devices generated by dielectric barrier discharge was performed. One configuration is composed of rectangular at electrodes and the other of a wire electrode and a rectangular at electrode. The other uses a new configuration with a serrated edge flat plane electrode, as the active electrode and an isolated rectangular flat. All configurations are investigated to understand the behavior in the production of the flow. Pitot tube measurements of velocity profiles of the wall jets are made at various distances away from the electrical discharge region. Further, the measurement of the flow along the serrated electrod is performed. Thus, it is intended to determine the three-dimensional flow characteristics produced by this configuration. The results show the best features of serrated configuration to be used in the production of more intense flow.

Having gained popularity in the last decade, the dielectric barrier discharge (DBD) has been studied in numerous ways as a device for air acceleration. A major interest of all these works has been concentrated on achieving higher efficiency and producing higher jet velocities. These studies considered alternative geometries, different voltage waveforms etc., yet none of these studies tackle the inherently inefficient process of force creation and actuation in a DBD. Air acceleration has been attributed to the electric force that switches direction on each voltage half cycle (that is due to the nature of the discharge mechanism) yet has a forward resulting force. The present thesis considers the phenomenon of memory charge accumulation on the dielectric surface and reasons that the backward force in the second half cycle can be reversed by further migration of the memory charges to an added exposed anode. Hence a novel 3-electrode configuration is presented. Flow velocity investigations showed a 27% improvement in efficiency in comparison with the traditional 2-electrode actuator. This meant a 0.4m/s gain along the velocity profile. During the investigation process, a new discharge mechanism was encountered. This was characterized by the double discharge lines along the exposed electrode edges while in the presence of a \"floating\" encapsulated electrode. / Tendo ganho popularidade na última década, a descarga de barreira dielétrica (DBD) foi estudada de várias maneiras como um dispositivo para aceleração do ar e controle aerodinâmico. Um grande interesse de todos esses trabalhos foi concentrado em alcançar maior eficiência e produzir maiores velocidades de jato. Alguns desses estudos consideraram geometrias alternativas, diferentes formas de onda de tensão, etc., mas nenhum desses estudos aborda o processo inerentemente ineficiente de criação e atuação da força em um DBD. A Aceleração do ar tem sido atribuída à força elétrica que muda de direção em cada meio ciclo (que é devido à natureza do mecanismo de descarga), mas que tem uma força resultante para a frente. A presente tese considera o fenômeno de acumulação de carga de memória na superfície dielétrica e raciocina que a força contraria no segundo meio ciclo da descarga pode ser revertida por migração dessas cargas de memória para um ânodo adicional exposto. Assim, uma nova configuração de 3 eletrodos é apresentada. Investigações de velocidade do fluxo mostraram uma melhoria de 27% na eficiência em comparação com o tradicional atuador de 2 eletrodos. Isso significou um ganho de 0,3 m/s ao longo do perfil de velocidade. Durante o processo de investigação, foi encontrado um novo mecanismo de descarga. Isso foi caracterizado por uma dupla descarga ao longo das bordas do eletrodos expostos, enquanto na presença de um eletrodo encapsulado \"pendurado\".

Philosophiae Doctor - PhD / Emerging micropollutants such as bisphenol-A and 2-nitrophenol present a great threat in drinking water due to their adverse effects. Most conventional technologies in water and wastewater treatment are not designed to eliminate these xenobiotics; instead pollutants are merely transferred from one phase to another. Advanced oxidation technologies (AOTs) however, have been identified as suitable routes for the degradation of these potential damaging substances based on free radical mechanisms and use of less expensive chemicals. Moreover, due to the structural complexity of wastewater and the existence of pollutants as mixtures, no single advanced oxidation technology can convincingly remove all forms of contaminants and then most often than not, a combination of treatment processes is required for an effective purification process. Besides, the problem of adequate degradation of emerging contaminants in the environment, when AOT(s) are used individually, they present inherent problems. For instance, powder TiO₂ photocatalysts obstruct light penetration, thus prevent effective interaction of UV light with the target pollutants, and particulates present problems of post-filtration and recovery of catalyst particles after treatment. Additionally, TiO₂ has a high band gap energy, high electron-hole recombination rate, and is prone to aggregation of the suspended particles. Similarly, the dielectric barrier discharge (DBD) system produces ultra violet light and hydrogen peroxide within the plasma zone which is not fully maximised for the mineralization of persistent organic pollutants. Rapid oxidation and aggregation of nano zero valent iron particles in photo-Fentons process reduce the particles mobility and affect its performance. In the same vein, the jet loop reactor (JLR) system is characterised by low impingement yield, which is responsible for low mineralization rate. In light of this background, this research investigated the degradation of bisphenol-A and 2- nitrophenol in aqueous solution using the following combined advanced oxidation methods: DBD/supported TiO₂ or Ag doped TiO₂ photocatalysts, DBD/photo-Fenton induced process and JLR/UV/H₂O₂. The target was to assess the performance of each single system and then identify the best combined AOTs capable of significantly mineralizing the target compounds. Firstly, two materials were developed namely supported TiO₂ and stabilized nano zero valent Fe. The TiO₂ photocatalyst supported on a stainless steel mesh was synthesised using sol-gel solution of 8 % PAN/DMF/TiCl₄. The influence of calcination temperature and holding time on the formation of nanocrystals was investigated. Afterwards, various amounts of metallic silver were deposited on the (optimum) supported TiO₂ photocatalyst using thermal evaporation. The catalysts were characterized by several analytical methods; HRSEM, HRTEM, EDS, SAED, FTIR, TGA-DSC, UV-vis/diffuse reflectance spectroscopy, XRD, BET, and XPS. The photocatalytic activity of the prepared catalysts was determined using methylene blue as a model pollutant under ultra-violet light irradiation. Secondly, the TiO2 photocatalyst and 2.4 % Ag doped TiO₂ nanocomposites obtained as optimums (in section 1) were combined with the DBD to decompose BPA or 2-NP in aqueous solution. Moreover, the photo-Fenton process was applied for degradation of the model pollutants, and different dosages of stabilized nZVI (in the range of 0.02 -1.00 g) were added to the DBD system to induce the photo-Fenton process and improve BPA or 2-NP degradation efficiency. Finally, a jet loop reactor (JLR) presenting advanced mixing by the “impinging effect” was explored to decompose BPA or 2-NP in aqueous solution as a function of inlet applied pressure, solution pH, and initial concentration of BPA or 2-NP. Subsequently, different concentrations of hydrogen peroxide (H₂O₂) were added to the JLR to enhance the mineralization process. Furthermore, a combination of JLR with in-line UV light and H₂O₂ were further utilised to decompose BPA or 2-NP in aqueous solution. The residual concentration of the model compounds and intermediates were analysed using high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LCMS). The concentration of the ozone, hydrogen peroxide and hydroxyl radicals generated by the DBD in the presence or absence of a catalyst was monitored using Ultraviolet-visible spectroscopy and Photoluminescence spectroscopy. The results revealed that the optimal thermal conditions to obtain well supported uniformly grown, highly active crystalline TiO₂ catalysts with high specific surface area was 350 ºC at a 3 h holding time in N2 atmosphere with a flow rate of 20 mL/min. Pyrolysis temperature and holding time played an important role on the crystalline nature and photocatalytic activity of the catalyst. Moreover, 2.4 % Ag doped TiO₂ nanocomposites exhibited higher photocatalytic activity for methylene blue degradation than the undoped supported TiO₂ nanocrystals. The results indicated that combining DBD with 2.4 % Ag doped TiO₂ nanocomposites achieved 89 % and 81 % removal efficiency for BPA or 2-NP compared to 67.22 % or 56.8 % obtain when using the DBD system alone. The 2.4 % Ag doped TiO₂ nanocomposites demonstrated excellent activity and offered photochemical stability after four repeated applications.In the case of the photo-Fenton induced process, nano zero valent iron particles (nZVI) stabilized with polyethylene glycol were synthesised using a modified borohydride reduction method. The HRSEM, BET, XRD, and XPS analysis confirmed the formation of filamentous, high surface area iron nanoparticles in the zero valent state. Unlike combined DBD/Ag doped TiO2 nanocomposites, 100 % or complete removal of BPA or 2-NP in aqueous solution was achieved with DBD/nZVI system within 30 minutes compared to 67.9 % (BPA) or 56.8 % (2-NP) with DBD alone after 80 minutes. The removal efficiency was attributable to the production of an increased concentration of OH radicals as well as existence of a synergetic effect in the combined DBD/nZVI system. Five new transformation products namely: 4-nitrophenol (C₆H₅NO₃), 4-nitrosophenolate (C₆H₄NO₂), 4-(prop-1-en-2-yl) cyclohexa-3,5-diene-1,2-dione, (C₉H₈O₂), 4-(2- hydroxylpropan-2-yl)cyclohexane-3,5-diene-1,2-dione (C₉H₁₀O₃), and 1,2-dimethyl-4-(2- nitropropan-2-yl)benzene (C₉H₁₀NO₄) were identified during the degradation of BPA. While, three aromatic intermediate compounds such as 2-nitro-1,3,5-benzenetriolate (C₆H₂NO₅), 2- nitro-1,4-benzoquinone (C₆H₃NO₄), and 2,5-dihydroxyl-1,4-benzoquinone (C₆H₄O₄) respectively were identified during the degradation of 2-NP for the first time in the DBD with JT14 or JT17 using LC-MS. These intermediate compounds have never been reported in the literature, thereby expanding the number of BPA or 2-NP intermediates in the data base in the DBD/JT14 or DBD/nZVI system. BPA degradation proceeded via ozonation, hydroxylation, dimerization, and decarboxylation and nitration step, while 2-NP proceeded via hydroxylation, nitration and denitration respectively. Furthermore, maximum removal efficiency of BPA or 2-NP in aqueous solution using JLR alone under the optimum solution pH (3), inlet pressure (4 bar), flow rate (0.0007 m3/s) was 14.0 % and 13.2 % respectively after 80 minutes. A removal efficiency of 34.9 % was recorded for BPA while 33.2 % was achieved for 2-NP using combined JLR/UV under the same conditions as JLR alone. For the combined JLR/H₂O₂ under optimum conditions of inlet pressure (4 bar), solution pH (3) and peroxide dosage (0.34 g/L), a 51.3 % and 50.1 % removal efficiency was achieved for BPA and 2-NP respectively under same conditions relative to JLR alone. Combination of JLR/UV/H₂O₂ achieved 77.7 % (BPA) or 76.6 % (2- NP) removal efficiency under the same conditions. The combined JLR/UV/H₂O₂ process was found to be most effective combination under the optimized operating parameters due to existence of a synergetic index value of 6.42 or 6.84. This implies that JLR should be coupled with UV and H₂O₂ to achieve greater mineralization efficiency instead of using the system individually. The obtained experimental data of these combined treatment processes fitted the pseudo-first order kinetic models. The combination of the JLR/UV/H₂O₂ was found to be energy efficient and could effectively degrade BPA or 2-NP in aqueous solution to a greater extent than the JLR, JLR/UV or JLR/H₂O₂ system. However, the total organic carbon (TOC) reduction value by all combined DBD and JLR system recorded was not completely achieved due to the formation of recalcitrant intermediate compounds under the applied conditions. In conclusion, this study is reporting for the first time a combination of supported 2.4 % Ag doped TiO₂ nanocomposites with dielectric barrier discharge system for BPA/2-NP degradation in aqueous solution; a combination jet loop reactor based on impingement with in-line UV lamp and H2O2 for successfully decomposing BPA or 2-NP in aqueous solution; as well as a combination of dielectric barrier discharge system and stabilised nano zero valent iron particles, which induced a photo-Fenton process for highly effective removal of BPA or 2-NP in aqueous solution. This study conclusively supports the hypothesis that combined advanced oxidation technologies offer a sustainable and highly efficient means of achieving partial or complete removal of BPA or 2-NP in aqueous solutions. Considering all the combinations of AOTs investigated in this study, the novel DBD/photo-Fenton-induced process under optimised operating parameters was found to be the most efficient in the elimination of BPA or 2-NP in aqueous solutions. The combination of DBD with photo- Fenton like process offers a promising advanced waste water purification technology in the immediate future. Based on these findings, it is recommended that DBD should be redesigned to prevent loss of ozone and JLR system reconfigured to increase impingement and cavitational yield in order to have an effective combination treatment strategy for waste water purification especially in large scale waste water management. / National Research Foundation (NRF) and Water Research Commission, South Africa

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.

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.