Ces dernières années un nouveau type de décharges hors équilibre thermodynamique, aptes à générer des micro jets de plasma se propageant en atmosphère libre, a suscité beaucoup d’intérêt dans la communauté scientifique. Ces micro jets, produits dans des structures type décharge à barrière diélectrique, ont des propriétés particulièrement intéressantes, tant sur le plan de la physique des plasmas que sur celui des applications, en particulier pour des applications biomédicales ou de traitement de surface.Dans ce travail de thèse il est démontré que ces jets de plasma correspondent à la propagation à grande vitesse d'un front d'ionisation sans déplacement de matière. Une caractérisation des propriétés des jets (vitesse et distance de propagation) a été effectuée en fonction de la tension appliquée, du débit, de la composition du gaz, et de la géométrie de la décharge. La distribution spatio-temporelle des espèces réactives produites par le jet a été mesurée, et en particulier celle de l'état métastable He (2³S) mesuré par absorption laser. Des densités comprises entre 1.10¹² et 5.10¹³ cm-³ ont été obtenues pour l’état He (2³S). Sa distribution est annulaire à la sortie de la structure de la décharge et se referme le long du jet. La densité maximale est obtenue à une distance correspondant à la moitié de la zone où les atomes métastables sont présents, ce qui est en contradiction avec les modèles actuels. De plus, afin de mieux comprendre la physique des jets de plasma, nous avons fait interagir deux jets placés l’un en face de l’autre. L'étude de la contre propagation de deux jets révèle qu’il existe une distance minimale d'approche laissant entre eux une zone exempte de plasma. Après l’extinction des deux plasmas, une seconde décharge s’amorce exactement dans cette zone. Une étude détaillée couplant diagnostics électrique, imagerie ultra-rapide et spectroscopie d'émission nous a permis de montrer que cette décharge secondaire est due à une inversion de polarité conduisant à la création transitoire d'un piège à électrons.Dans le but d'aborder l'étude des applications des jets de plasma au domaine biologique, nous avons également étudié la dégradation de l’ADN plasmidique par un jet de plasma. Nous avons mis en évidence que ce type de plasma induit majoritairement des cassures simples et doubles brins, alors que très peu d’oxydations de base ou de sites abasiques sont observés, ceci même avec l’ajout de quelques pourcents d’oxygène dans le gaz. / Micro plasma jets operating at atmospheric pressure in free atmosphere have recently attracted great attention because of their numerous advantages. In fact, micro plasma jets can be operated stably at atmospheric pressure and propagated over some centimeters in a free atmosphere. Moreover, these jets are non-thermal plasmas and create numerous reactive species. These properties allow to use this kind of plasma in many applications, such as surface treatment, decontamination, and plasma medicine.In this work it is shown that these micro plasma jets correspond to the fast propagation of an ionization front with no displacement of matter. A characterization of the plasma proprieties (e.g. distance and velocity of propagation) has been done as a function of the applied voltage, gas flow, gas composition and discharge geometry. The spatiotemporal distribution of the reactive species created by the plasma has been measured, with a special focus on the helium metastable atoms which have been measured by absorption laser spectroscopy. The helium metastable atom densities obtained are in the range of 1.10¹² to 5.10¹³ cm-³. Thanks to a very good spatiotemporal resolution, we have done a time-resolved full cartography of the plasma. This allowed us to show that the helium metastable atom distribution is annular near the nozzle and becomes circular as the plasma propagates. The maximum helium metastable atoms density has been measured at about half of the distance where the helium metastable atoms are present. This observation is in contradiction with results reported by numerical models. To gain further insight into the physical processes of the plasma, we have placed two micro plasma jets face to face. This study showed that both plasmas interact in such a way that they never come into contact, letting a space free of plasma between them. Moreover, we revealed that after the extinction of the plasmas, a second discharge is ignited in the previously free space. Fast imaging, spectroscopy diagnostics and electrical measurements showed that this second discharge is due to a polarity reversal, which creates an electron trap. Aiming the study of the application of micro plasma jets in the plasma medicine field, we have studied the degradation of plasmid DNA by our plasma jet. We observed that the plasma treatment leads mostly to single and double strands breaks, and to very little base oxidation and abasite site, even when oxygen is added into the gas mixture.

The surface behavior of biologically or atmospherically relevant chemical compounds in aqueous solution has been studied using surface-sensitive X-ray photoelectron spectroscopy (XPS). The aim is to provide information on the molecular-scale composition and distribution of solutes in the surface region of aqueous solutions. In the first part, the distribution of solutes in the surface region is discussed, where in particular single molecular species are studied. Concentration-dependent studies on succinic acid and various alkyl-alcohols, where also parameters such as pH and branching are varied, are analyzed using different approaches that allow the quantification of surface concentrations. Furthermore, due to the sensitivity of XPS to the chemical state, reorientation of linear and branched alkyl-alcohols at the aqueous surface as a function of concentration is observed. The results are further discussed in terms of hydrophilic and hydrophobic interactions in the interfacial region, where the three-dimensional hydrogen bonded water structure terminates. In the second part, mixed solutions of compounds, both ionic and molecular, are inspected. Again concentration, but also co-dissolution of other chemical compounds, are varied and differences in the spatial distribution and composition of the surface region are discussed. It is found that the guanidinium ion has an increased propensity to reside at the surface, which is explained by strong hydration in only two dimensions and only weak interactions between the aromatic π-system and water. Ammonium ions, on the other hand, which require hydration in three dimensions, are depleted from the surface region. The presence of strongly hydrated electrolytes out-competes neutral molecules for hydrating water molecules leading to an enhanced abundance of molecules, such as succinic acid, in the interfacial region. The partitioning is quantified and discussed in the context of atmospheric science, where the impact of the presented results on organic loading of aerosol particles is emphasized.

A body in a hypersonic flow field will experience very high heating especially during re-entry. Conventionally this problem is tackled to some extent by the use of large angle blunt cones. At the cost of increased drag, the heat transfer rate is lower over most parts of the blunt body, except in a region around the stagnation point. Thus even with blunt cones, management of heat transfer rates and drag on bodies at hypersonic speeds continues to be an interesting research area. Various thermal protection systems have been proposed in the past, like heat sink cooling, ablation cooling and aerospikes. The ablative cooling system becomes extremely costly when reusability is the major concern. Also the shape change due to ablation can lead to issues with the vehicle control. The aerospikes themselves may become hot and ablate at hypersonic speeds. Hence an alternate form of cooling system is necessary for hypersonic flows, which is more feasible, cost effective and efficient than the conventional cooling systems. Injection of a mass of cold fluid into the boundary layer through the surface is one of the potential cooling techniques in the hypersonic flight corridors. These kinds of thermal protection systems are called mass transfer cooling systems. The injection of the mass may be through discrete slots or through a porous media. When the coolant is injected through a porous media over the entire surface, the coolant comes out as a continuous mass. Such a cooling system is also referred as “transpiration cooling system”. When the fluid is injected through discrete slots, the system is called as “film cooling system”. In either case, the coolant absorbs the incoming heat through its rise in enthalpy and thus modifies the boundary layer characteristics in such a way that the heat flow rate to the surface is less. Injection of a forward facing jet (opposite to the freestream direction) from the stagnation point of a blunt body can be used for mitigating both the aerodynamic drag and heat transfer rates at hypersonic Mach numbers. If the jet has enough momentum it can push the bow shock forward, resulting in reduced drag. This will also reduce heat transfer rate over most part of the body except around the jet re-attachment region. A reattachment shock impinging on the blunt body invariably increases the local heat flux. At lower momentum fluxes the forward facing jet cannot push the bow shock ahead of the blunt body and spreads easily over the boundary layer, resulting in reduced heat transfer rates. While the film cooling performance improves with mass flow rate of the jet, higher momentum flow rates can lead to a stronger reattachment leading to higher heat transfer rate at the reattachment zone. If we are able to reduce the momentum flux of the coolant for the same mass flow rate, the gas coming out can easily spread over the boundary layer and it is possible to improve the film cooling performance. In all the reported literature, the mass flow rate and the momentum flux are not varied independently. This means, if the mass flow rate is increased, there is a corresponding increase in the momentum flux. This is because the injection (from a particular orifice and for a particular coolant gas) is controlled only by the total pressure of injection and free stream conditions. The present investigation is mainly aimed at demonstrating the effect of reduction in momentum of the coolant (injected opposing a hypersonic freestream from the stagnation point of a blunt cone), keeping the mass flow rate the same, on the film cooling performance. This is achieved by splitting a single jet into a number of smaller jets of same injection area (for same injection total pressure and same free stream conditions). To the best of our knowledge there is no report on the use of forward facing micro-jet array for film cooling at hypersonic Mach numbers. In this backdrop the main objectives of the present study are: • To experimentally demonstrate the effect of splitting a single jet into an array of closely spaced smaller micro-jets of same effective area of injection (injected opposite to a hypersonic freestream from the stagnation zone), on the reduction in surface heat transfer rates on a large angle blunt cone. · Identifying various parameters that affect the flow phenomenon and doing a systematic investigation of the effect of the different parameters on the surface heat transfer rates and drag. Experimental investigations are carried out in the IISc hypersonic shock tunnel on the film cooling effectiveness. Coolant gas (nitrogen and helium) is injected opposing hypersonic freestream as a single jet (diameter 2 mm and 0.9 mm), and as an array of iv micro jets (diameter 300 micron each) of same effective area (corresponding to the respective single jet). The coolant gas is injected from the stagnation zone of a blunt cone model (58o apex angle and nose radius of 35 mm). Experiments are performed at a flow freestream Mach number of 5.9 at 0o angle of attack, with a stagnation enthalpy of 1.84 MJ/Kg, with and without injections. The ratios of the jet stagnation pressure to the pitot pressure (stagnation pressure ratio) used in the present study are 1.2 and 1.45. Surface convective heat transfer measurements using platinum thin film sensors, time resolved schlieren flow visualization and aerodynamic drag measurements using accelerometer force balance are used as flow diagnostics in the present study. The theoretical stagnation point heat transfer rate without injection for the given freestream conditions for the test model is 79 W/cm2 and the corresponding aerodynamic drag from Newtonian theory is 143 N. The measured drag value without injection (125 N) shows a reasonable match with theory. As the injection is from stagnation zone it is not possible to measure the surface heat transfer rates at the stagnation point. The sensors thus are placed from the nearest possible location from the stagnation point (from 16 mm from stagnation point on the surface). The sensors near the stagnation point measures a heat transfer rate of 65 W/cm2 on an average without any injection. Some of the important conclusions from the study are: • Up to 40% reduction in surface heat transfer rate has been measured near the stagnation point with the array of micro jets, nitrogen being the coolant, while the corresponding reduction was up to 30% for helium injection. Considering the single jet injection, near the stagnation point there is either no reduction in heat transfer rate or a slight increase up to 10%. · Far away from stagnation point the reduction in heat transfer with array of micro-jets is only slightly higher than corresponding single jet for the same pressure ratio. Thus the cooling performance of the array of closely spaced micro jets is better than the corresponding single jet almost over the entire surface. • The time resolved flow visualization studies show no major change in the shock standoff distance with the low momentum gas injection, indicating no major changes in other aerodynamic aspects such as drag. · The drag measurements also indicate that there is virtually no change in the overall aerodynamic drag with gas injection from the micro-orifice array. · The spreading of the jets injected from the closely spaced micro-orifice array over the surface is also seen in the visualization, indicating the absence of a region of strong reattachment. · The reduction in momentum flux of the injected mass due to the interaction between individual jets in the case of closely spaced micro-jet array appears to be the main reason for better performance when compared to a single jet. The thesis is organized in six chapters. The importance of film cooling at hypersonic speeds and the objectives of the investigation are concisely presented in Chapter 1. From the knowledge of the flow field with counter-flow injection obtained from the literature, the important variables governing the flow phenomena are organized as non-dimensional parameters using dimensional analysis in Chapter 2. The description of the shock tunnel facility, diagnostics and the test model used in the present study is given in Chapter 3. Chapter 4 describes the results of drag measurements and flow visualization studies. The heat transfer measurements and the observed trends in heat transfer rates with and without coolant injection are then discussed in detail in Chapter 5. Based on the obtained results the possible physical picture of the flow field is discussed in Chapter 6, followed by the important conclusions of the investigation.

Ces dernières années un nouveau type de décharges hors équilibre thermodynamique, aptes à générer des micro jets de plasma se propageant en atmosphère libre, a suscité beaucoup d'intérêt dans la communauté scientifique. Ces micro jets, produits dans des structures type décharge à barrière diélectrique, ont des propriétés particulièrement intéressantes, tant sur le plan de la physique des plasmas que sur celui des applications, en particulier pour des applications biomédicales ou de traitement de surface.Dans ce travail de thèse il est démontré que ces jets de plasma correspondent à la propagation à grande vitesse d'un front d'ionisation sans déplacement de matière. Une caractérisation des propriétés des jets (vitesse et distance de propagation) a été effectuée en fonction de la tension appliquée, du débit, de la composition du gaz, et de la géométrie de la décharge. La distribution spatio-temporelle des espèces réactives produites par le jet a été mesurée, et en particulier celle de l'état métastable He (2³S) mesuré par absorption laser. Des densités comprises entre 1.10¹² et 5.10¹³ cm-³ ont été obtenues pour l'état He (2³S). Sa distribution est annulaire à la sortie de la structure de la décharge et se referme le long du jet. La densité maximale est obtenue à une distance correspondant à la moitié de la zone où les atomes métastables sont présents, ce qui est en contradiction avec les modèles actuels. De plus, afin de mieux comprendre la physique des jets de plasma, nous avons fait interagir deux jets placés l'un en face de l'autre. L'étude de la contre propagation de deux jets révèle qu'il existe une distance minimale d'approche laissant entre eux une zone exempte de plasma. Après l'extinction des deux plasmas, une seconde décharge s'amorce exactement dans cette zone. Une étude détaillée couplant diagnostics électrique, imagerie ultra-rapide et spectroscopie d'émission nous a permis de montrer que cette décharge secondaire est due à une inversion de polarité conduisant à la création transitoire d'un piège à électrons.Dans le but d'aborder l'étude des applications des jets de plasma au domaine biologique, nous avons également étudié la dégradation de l'ADN plasmidique par un jet de plasma. Nous avons mis en évidence que ce type de plasma induit majoritairement des cassures simples et doubles brins, alors que très peu d'oxydations de base ou de sites abasiques sont observés, ceci même avec l'ajout de quelques pourcents d'oxygène dans le gaz.

In spite of their high abundance and importance, aqueous systems are enigmatic on the microscopic scale. In order to obtain information about their geometrical and electronic structure, simple aqueous solutions have been studied experimentally by photo- and Auger electron spectroscopy using the novel liquid micro-jet technique in conjunction with synchrotron radiation. The thesis is thematically divided into three parts. In the first part we utilize the surface sensitivity of photoelectron spectroscopy to probe the distributions of solutes near the water surface. In agreement with recent theoretical predictions we find that large polarizable anions, such as I- and ClO4-, display enhanced surface propensities compared to smaller rigid ions. Surface effects arising from ion-ion interactions at higher electrolyte concentrations and as function of pH are investigated. Studies of linear mono-carboxylic acids and benzoic acid show that the neutral molecular forms of such weak acids are better stabilized at the water surface than their respective conjugate base forms. The second part examines what type of information core-electron spectra can yield about the chemical state and hydration structure of small organic molecules in water. We demonstrate that the method is sensitive to the protonation state of titratable functional groups and that core-level lineshapes are dependent on local water hydration configurations. Using a combination of photoelectron and X-ray absorption spectroscopy we also show that the electronic re-arrangement upon hydrolysis of aldehydes yields characteristic fingerprints in core-level spectra. In the last part of this thesis we study ultrafast charge delocalization dynamics in aqueous solutions using resonant and off-resonant Auger spectroscopy. Intermolecular Coulombic decay (ICD) is found to occur in a number of core-excited solutions where excess energy is transferred between the solvent and the solute. The rate of ultrafast electron delocalization between hydrogen bonded water molecules upon oxygen 1s resonant core-excitation is found to decrease upon solvation of inorganic ions. The presented work is illustrative of how core-level photoelectron spectroscopy can be valuable in the study of fundamental phenomena in aqueous solutions.

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