Thesis is focused on plasma modification of materials. The work has the character of a search of available literature, especially the papers presented in impacted journals. The aim is to provide a broader overview of the subject. The first section describes the most commonly modified powdered materials. The second part is focused on the plasma modification, the reasons for its use, capabilities and benefits respectively and disadvantages of these processes. The following sections are devoted to plasma discharges, plasma reactors, aspects of plasma modification and companies engaged in production, or modification of powders. Each chapter is intended to provide an overview of the modified powder materials, processes within the plasma discharges, construction and use of plasma reactors, plasma modification of aspects and the market situation in the context of powdered materials and companies dealing with the plasma modification.

This thesis deals with the plasma functionalization of nanofiber materials for biomedical applications. Nanofibers of SiO2 and PCL was functionalized using a microwave plasma in order to establish amine functional groups. The work includes theoretical assumptions selection of these materials, their properties and current use with emphasis on biomedical applications. The paper also presents the theoretical foundations of plasma technology, their principles and practical applications. The experimental part of the work includes the optimization of process parameters for each nanofiber materials, review hydrophilisation surface and material degradation through SEM and private functionalization. In conclusion outlines proposals for further action beyond the experiments of this work.

Les plasmas d’air à pression atmosphérique ont de nombreuses applications. Nous pouvons par exemple citer les applications biomédicales, le traitement des matériaux, la bio-décontamination environnementale et la combustion assistée par plasma. La polyvalence des décharges plasma résulte de leur capacité à produire des densités élevées d’espèces actives, sans toutefois chauffer substantiellement le gaz. Les décharges nanosecondes répétitivement pulsées (NRP) ont particulièrement reçu une grande attention en raison de leur capacité à produire des densités électroniques élevées, qui conduisent à la création de fortes densités d’espèces actives telles que l’oxygène atomique (O). Par ailleurs, des mesures de spectroscopie d’émission ont montré que des états excités du monoxyde d’azote (NO) sont produits par les décharges NRP opérant dans l’air ou dans des mélanges combustibles. Bien que les décharges NRP aient déjà fait l’objet de plusieurs investigations, les mécanismes cinétiques conduisant à la production de NO sont toujours incertains. C’est la motivation première des travaux menés dans le cadre de cette thèse. En outre, les décharges NRP se sont avérées produire une grande quantité d’oxygène d’atomique, espèce de grande importance pour la combustion assistée par plasma. Il a été en particulier démontré que grâce à la production élevée d’espèces actives, les décharges NRP peuvent stabiliser efficacement des flammes pauvres, à pression atmosphérique. Cependant la production de NO par les décharges NRP et les flammes stabilisées à l’aide des décharges NRP reste à étudier. Cela constitue le second objectif de cette thèse. Les mesures in-situ de densités absolues de NO dans les décharges plasmas et/ou en combustion sont très difficiles. Les techniques de fluorescence telle que la fluorescence induite par laser (LIF) nécessitent de complexes méthodes de calibration. Ces techniques requièrent également la connaissance des taux de quenching des états excités (en particulier à pression atmosphérique). Or ces taux de quenching sont très fortement dépendants de la température, de la nature des espèces en présence et de leur densité, et peuvent donc énormément différer entre un plasma opérant dans l’air et en combustion. D’autres techniques telles que l’utilisation des sondes à chimiluminescence sont tout aussi sujettes aux problèmes de calibration et de quenching des états excités tandis que les mesures ex-situ à l’aide d’analyseurs à gaz réalisant de l’absorption dans l’UV et l’IR peuvent conduire à des erreurs, surtout lorsqu’il s’agit de mesurer des radicaux. Dans cette étude, nous avons développé la spectroscopie d’absorption par laser à cascade quantique (QCLAS), pour des mesures in-situ de densités de NO dans l’air et en combustion. Cette technique permet de surmonter les difficultés des autres méthodes par utilisation d’une spectroscopie rotationnelle-vibrationnelle de haute résolution spectrale (10-3 cm-1). La QCLAS a les avantages d’être spectralement sélective, d’avoir une grande sensibilité et de ne pas nécessiter de calibration. Deux dispositifs expérimentaux ont été développés pour mesurer des densités de NO et des températures (1) dans une décharge NRP dans l’air, avec une résolution spatiale de 300-µm, et (2) en aval de la décharge NRP opérant dans l’air et dans des flammes méthane/air assistée par plasma, par utilisation d’une cellule multi-passages. [...] / Atmospheric pressure plasmas have numerous potential applications. These applications include for instance biomedicine, material processing, environmental biodecontamination and plasma-assisted combustion. The versatility of plasma discharges results from their ability to produce high quantities of active species without increasing the temperature of the gas appreciably. Nanosecond Repetitively Pulsed discharges (NRP) have received great attention owing to their capacity to generate high electron densities, which lead to the creation of a high density of active species such as atomic oxygen. Optical Emission Spectroscopy (OES) showed that excited nitric oxide (NO) was released by NRP discharges in air or in air/fuel mixtures.Although NRP discharges have already been the object of several investigations, the kinetic mechanisms of NO production by NRP discharges at atmospheric pressure remain somewhat unclear. This is one of the motivations for the investigations conducted in this thesis. In addition, NRP discharges were found to produce large amounts of atomic oxygen, which is of great interest for applications such as plasma-assisted combustion. It was shown in particular that thanks to this high production of active species, NRP discharges can effectively stabilize lean flames at atmospheric pressure. However, the production of NO in NRP discharges and in plasma-stabilized flames remains to be investigated. This is the second purpose of this thesis.Absolute and in-situ NO density measurements in atmospheric pressure plasma or/and flame environments are very challenging. Fluorescence-based techniques such as Laser Induced Fluorescence (LIF) require complex calibration methods. These techniques also require the knowledge of the quenching rates of the excited states (particularly at atmospheric pressure), which strongly depend on the temperature, density and nature of the species and can be very different for plasma or/and flame environments. Other techniques, such as chemiluminescence probe sampling also have quenching and calibration issues, and ex-situ UV and IR absorption-based gas analyzers can lead to errors, in particular for radicals.In this study, we developed Quantum Cascade Laser Absorption Spectroscopy (QCLAS) for in-situ nitric oxide absolute density measurements in open-air and in combustion environments. This technique overcomes the difficulties of the previous ones by using high-resolution (10-3 cm-1) rotational-vibrational absorption spectroscopy. This technique presents the advantages of high spectral selectivity, no calibration requirement, and high sensitivity. Two experimental setups were developed to measure NO densities and temperature, (1) within a NRP discharge in air, with 300-µm spatial resolution, and (2) downstream of NRP discharges in air and in plasma-assisted methane/air flames, using multi pass cell. [...]

The aim of the diploma thesis is generation of active particles in plasma activated water (PAW) using a low-temperature plasma discharge. In this work I focus on the determination of hydrogen peroxide, nitrites and nitrates as active particles. The practical part is focused on a specific case of use of a plasma discharge in selected electrolytes dissolved in an aqueous solution. Here, three phosphates, differing in the number of acidic hydrogens, were selected for each experiment, and sodium chloride and tap water were compared for comparison. Phosphates were selected for their stable pH during plasma discharge in solution to monitor the effect of pH. The experiments were focused on investigating the stability of active particles in PAW, under which conditions is the highest production rate of these particles and what effect the pH value has on the result. It was found that hydrogen peroxide is generated the most in an alkaline environment but shows better stability in neutral. The concentration of generated nitrites is not high, but it shows stability, regardless of the polarity of the main electrode used for PAW generation. Nitrites were generated the most in alkaline environment and nitrates in acidic environment. One of the conclusions is that nitrates are not a very stable particle in PAW. Thanks to the activation and oxidation properties of plasma activated water, this method can be used in medicine or agriculture

In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and the pyrimidine is reported here. The effect of substituents on substituted-benzene cations on their solvation by an HCN solvent was also investigated using ion mobility mass spectrometry and DFT computations were also investigated. We looked at the effect of the presence of electron-withdrawing substituents in fluorobenzene, 1,4 di- fluorobenzene, and benzonitrile on their solvation by up to four HCN ligands, and compared it to previous work done to determine the solvation chemistry of benzene and phenylacetylene by HCN. We report here the observed increase in the binding of the HCN molecule to the aromatic ring as the electronegativity of the substituent increased. We also show in this dissertation, DFT calculations that reveal the formation of both hydrogen-bonded and electrostatic isomers, of similar energies for each addition to the ions respectively. The catalytic activity of the 1st and 2nd row TM ions towards the polymerization of acetylene done using the reflectron time of flight mass spectrometry and DFT calculations is also reported in this dissertation. We explain the variation in the observed trend in C-H/C-C activity of these ions. We also report the formation of carbide complexes by Zr+, Nb+, and Mo+, with the acetylene ligands, and show the thermodynamic considerations that influence the formation of these dehydrogenated ion-ligand complexes. Finally, we show in this dissertation, a novel ionization technique that we employed to generate ions that could be relevant to the interstellar and circumstellar media using the reflectron time of flight mass spectrometry.

The electrodeless plasma discharge is typically driven by radio frequency (RF) power supply within the range (0.2 &iexcl / 40 MHz). The applied power is coupled into the plasma inductively called inductively coupled plasma (ICP). RF ICP technique has achieved significance importance in a diversity of research and industrial applications for over the last threes decades. It is still required to undertake both theoretical and experimental research. In this work, RF ICP technique is applied on the torch modeling in 2D. Based on extended electromagnetic vector potential representation, an axisymmetric model in 2D is proposed for the calculations of the electromagnetic fields in an RF ICP torch. The influence of axial vector potential is included to the vector potential formulations. This is achieved by imposing a helical current carrying wire configuration. The corresponding governing equations are solved numerically by applying finite element method (FEM) using commercial partial differential equation solver (Flex PDE3). Based on this model, the plasma behavior and properties are examined in terms of plasma parameters. Besides, a comparative iii analysis is made between proposed model called helical configuration and the one currently available in the literature called circular configuration. This study shows relatively little difference between temperature fields predicted by two models. However, significant difference is observed between corresponding flows and electromagnetic fields. Especially, tangential flow which is observed in helical configuration vanishes in circular configuration. The proposed model offers an effective means of accounting for the variations of the helical coil geometry on the flow and temperature fields and achieving a better representation of the electromagnetic fields in the discharge. Finally, it is concluded that minimum number of turns (n = 2) yields significant difference between two models whereas, maximum allowable number of turns yield no distinctions on the results of two models in terms of azimuthally applied current. However, axial effect of current still exists but very small with respect to the result obtained with minimum number of turns.

This thesis presents Photocatalytic TiOx layers created by own PECVD reactor assembled in the building of Department of Applied Physics and Technics. Parameters of depositions were optimalized as well as the PECVD reactor itself. Final layers are compared to layers made by Degussa P25. As a result based on the included measurements, this thesis tries to answer the question whether PECVD is the suitable method for depositions of photocatalytic layers.

This diploma thesis deals mainly with utilization of plasma in technological aplications. The introductory part is apllied to the theoretical description of plasma generated by the surfatron. This launcher works with the frequency of 2,45 GHz and it is able to excite the surface wave, that sustains plasma column in a quartz tube. Plasma generated by surfatron was used for modification of surface properties of polyethylen to change its surface energy. By changing of surface energy it was reached of higher hydrophilicity. Plasma generated by surfatron was diagnosed in detail during experiments in a continual regime as well as in a pulse one with a help of a single {--} probe and a double {--} probe Langmuir measurement. In this diploma thesis there is discussed influence of pressure, power and other experimental options.

This thesis deals with the study of parameters of diaphragm discharge in liquids. NaCl solution of different conductivity was used as a conductive medium. Conductivities were adjusted in the range from 220 to 1000 µS cm-1. Two diagnostic methods were used for the study of plasma parameters. The first one was employed in the laboratory of plasma chemistry at Faculty of Chemistry, Brno University of Technology, namely the optical emission spectroscopy. The second method used for plasma diagnostics was the time resolved ICCD camera at the Laboratoire de Physique des Plasmas at the École Polytechnique in Paris. The reactor for the diagnostics by optical emission spectroscopy had the volume of 4 l, and it was made of polycarbonate. PET diaphragm was placed in the barrier separating the cathode and the anode space. Electrodes were made of titanium coated with platinum. Electric power source supplied a constant DC voltage of maximum 5 kV and electric current up to 300 mA. Spectrometer Jobin Yvon TRIAX 550 with CCD detector was used during the experiments in order to measure overview spectra within the range from 200 to 900 nm as well as OH molecular spectra and Hß line spectra. All spectra were scanned in both discharge polarities, i.e. at the cathode and the anode part of reactor. The basic parameters of the discharge plasma were calculated from the spectra, that means rotational and electron temperature and electron density. Another part of experiment consisted of measurements by the ICCD camera iStar 734. Two types of reactors were used. The first one was the same as the reactor for the measurements by the optical emission spectroscopy. The second one was also made of polycarbonate, but the volume of conductive solution was 110 ml, only. HV electrodes made of stainless steel were placed in this reactor. Ceramic diaphragm (Shapal-MTM) was used in both reactors. Diaphragms had different thickness and diameter of holes. ICCD camera acquired photographs with details of processes of the bubbles generation and discharge operation (propagation of plasma channels), depending on solution conductivity, dimensions of the diaphragm, and with respect to the electrode part of the reactor.

Plusieurs types d’applications industrielles complexes, relèvent du domaine multidisciplinaire de l’Electro-Hydro-Dynamique (EHD) où les interactions entre des particules chargées et des particules neutres sont étudiées dans le contexte couplé de la dynamique des fluides et de l’électrostatique. Dans cette thèse, nous avons étudié par voie de simulation numérique certains phénomènes Electro-Hydro-Dynamiques comme l’injection unipolaire, le phénomène de conduction dans les liquides peu conducteurs et le contrôle d’écoulement avec des actionneurs plasma à barrières diélectriques (DBD). La résolution de tels systèmes physiques complexes exige des ressources de calculs importantes ainsi que des solveurs CFD parallèles dans la mesure où ces modèles EHD sont mathématiquement raides et très consommateurs en temps de calculs en raison des gammes d’échelles de temps et d’espace impliquées. Cette thèse vise à accroitre les capacités de simulations numériques du groupe Electro-Fluido-Dynamique de l’Institut Pprime en développant un solveur parallèle haute performance basé sur des modèles EHD avancés. Dans une première partie de cette thèse, la parallélisation de notre solveur EHD a été réalisée avec des protocoles MPI avancés comme la topologie Cartésienne et les Inter-communicateurs. En particulier, une stratégie spécifique a été conçue pour prendre en compte la caractéristique multi-blocs structurés du code. La nouvelle version parallèle du code a été entièrement validée au travers de plusieurs benchmarks. Les tests de scalabilité menés sur notre cluster de 1200 cœurs ont montré d’excellentes performances. La deuxième partie de cette thèse est consacrée à la simulation numérique de plusieurs écoulements EHD typiques. Nous nous sommes intéressés entre autres à l’électroconvection induite par l'injection unipolaire entre deux électrodes plates parallèles, à l’étude des panaches électroconvectifs dans une configuration d'électrodes lame-plan, au mécanisme de conduction basé sur la dissociation de molécules neutres d'un liquide faiblement conducteur. Certains de ces nouveaux résultats ont été validés avec des simulations numériques entreprises avec le code commercial Comsol. Enfin, le contrôle d’écoulements grâce à un actionneur DBD a été simulé à l’aide du modèle Suzen-Huang dans diverses configurations. Les effets de l’épaisseur du diélectrique, de l’espacement inter-électrodes, de la fréquence de la tension appliquée et sa forme d’onde, sur la vitesse maximale du vent ionique induit ainsi que sur la force électrique moyenne ont été étudiés. / Several intricately coupled applications of modern industries fall under the multi-disciplinary domain of Electrohydrodynamics (EHD), where the interactions among charged and neutral particles are studied in context of both fluid dynamics and electrostatics together. The charge particles in fluids are generated with various physical mechanisms, and they move under the influence of external electric field and the fluid velocity. Generally, with sufficient electric force magnitudes, momentum transfer occurs from the charged species to the neutral particles also. This coupled system is solved with the Maxwell equations, charge transport equations and Navier-Stokes equations simulated sequentially in a common time loop. The charge transport is solved considering convection, diffusion, source terms and other relevant mechanisms for species. Then, the bulk fluid motion is simulated considering the induced electric force as a source term in the Navier-Stokes equations, thus, coupling the electrostatic system with the fluid. In this thesis, we numerically investigated some EHD phenomena like unipolar injection, conduction phenomenon in weakly conducting liquids and flow control with dielectric barrier discharge (DBD) plasma actuators.Solving such complex physical systems numerically requires high-end computing resources and parallel CFD solvers, as these large EHD models are mathematically stiff and highly time consuming due to the range of time and length scales involved. This thesis contributes towards advancing the capability of numerical simulations carried out within the EFD group at Institut Pprime by developing a high performance parallel solver with advanced EHD models. Being the most popular and specific technology, developed for the distributed memory platforms, Message Passing Interface (MPI) was used to parallelize our multi-block structured EHD solver. In the first part the parallelization of our numerical EHD solver with advanced MPI protocols such as Cartesian topology and Inter-Communicators is undertaken. In particular a specific strategy has been designed and detailed to account for the multi-block structured grids feature of the code. The parallel code has been fully validated through several benchmarks, and scalability tests carried out on up to 1200 cores on our local cluster showed excellent parallel speed-ups with our approach. A trustworthy database containing all these validation tests carried out on multiple cores is provided to assist in future developments. The second part of this thesis deals with the numerical simulations of several typical EHD flows. We have examined three-dimensional electroconvection induced by unipolar injection between two planar-parallel electrodes. Unsteady hexagonal cells were observed in our study. 3D flow phenomenon with electro-convective plumes was also studied in the blade-plane electrode configuration considering both autonomous and non-autonomous injection laws. Conduction mechanism based on the dissociation of neutral molecules of a weakly conductive liquid has been successfully simulated. Our results have been validated with some numerical computations undertaken with the commercial code Comsol. Physical implications of Robin boundary condition and Onsager effect on the charge species were highlighted in electro-conduction in a rectangular channel. Finally, flow control using Dielectric Barrier Discharge plasma actuator has been simulated using the Suzen-Huang model. Impacts of dielectric thickness, gap between the electrodes, frequency and waveform of applied voltage etc. were investigated in terms of their effect on the induced maximum ionic wind velocity and average body force. Flow control simulations with backward facing step showed that a laminar flow separation could be drastically controlled by placing the actuator at the tip of the step with both electrodes perpendicular to each other.