The predictions of non-equilibrium radiation for a Titan aerocapture aeroshell vary significantly amongst Computational Fluid Dynamics (CFD) analyses and are limited by the physical models of the non-equilibrium flow. Of particular interest are the non-equilibrium processes associated with the cyanogen (CN) molecule which is known to be a strong radiator. It is therefore important to have experimental data for these radiating shock layers which will allow for validation of CFD models. Furthermore, a more detailed understanding of the chemical processes that lead to the formation of CN above equilibrium concentration is required. This thesis describes the modelling of the radiation behind a shock using a collisional-radiative (CR) model and presents measurements of radiation intensity behind a shock in simulated Titan and Martian atmospheres. The uncertainties in radiation is more significant at lower speeds (around 5-8 km/s) with these atmospheres when compared to Earth entry. This is due to the formation of CN and because of the highly non-equilibrium nature of the flow. The motivation for this work began with the successful landing of the Huygens probe on the surface of Titan which led to the renewed interest in inter-planetary missions. Thus radiative heating during atmospheric entry to Titan and Mars was the subject of several experimental campaigns and extensive computational analyses. In order to better understand the formation of CN, and the nonequilibrium radiation emitted under such atmospheric conditions, NASA Ames Research Center conducted a series of experiments on their Electric Arc Shock Tube facility, EAST. Furthermore, several research groups in Europe and the United States independently developed CR models to predict the measured levels of radiation. The results from these simulations showed some ma jor discrepancies and highlighted a lack of knowledge and understanding about the fundamental physics behind the formation and decay of the CN molecule and its associated excited states. Based on a comparison of the various simulations with the CR models and the EAST experimental data, it was concluded that the absolute level of peak radiation was well predicted, however, there was a significant discrepancy related to the decay rate of the radiation. Therefore, to add to the relatively small amount of experimental data for these highly non-equilibrium radiating flow conditions, experiments were performed on the X2 shock tube at The University of Queensland with the aim of producing a comprehensive set of benchmark data for Titan entry. The data obtained from these experiments have been used to validate the results from the NASA Ames testing, and due to the large parametric variation, as a source for code validation. In addition to the experimental component of this thesis, an investigation into the simulation of CN non-equilibrium radiation was conducted. It has been previously concluded that there was a significant discrepancy between the experimentally measured radiation decay rate and the predicted value from CR models. Therefore, the primary aim of the simulation work presented in this thesis is to explain the reason behind this discrepancy. Through a parametric study of important reactions combined with an analysis of the reaction set, it was concluded that the coupling between the dissociation of N2 and the formation of CN (through the reaction N2 + C ↔ CN + N) controlled the radiation decay rate. The reason for the super equilibrium concentrations was identified to be a result of the N2 + C ↔ CN + N reaction continuing to over-produce CN after nominal equilibrium values are reached. This is due to the slow build up of N to drive the reverse reaction. Thus it has been shown in this thesis that the behaviour of the CN concentration is controlled by the rate of N2 dissociation. This led to the implementation of a more thorough method for simulating the dissociation process of molecular nitrogen. Therefore, a mono-quantum vibration state specific model that includes excitation and de-excitation reactions for all the vibrational states of nitrogen was incorporated into the CR model developed by Magin et al. The nitrogen vibration state specific model that was implemented was developed by Pierott and is based on SSH theory. The model developed in this thesis is known as the ViSpeN CR model (Vibrationally Specific Nitrogen). The ViSpeN results show significantly better agreement with experimental data in terms of the decay rate, initial rise of the radiation and the overall trends in the data. However, the work in this thesis has shown there are still discrepancies in predicting the absolute level of radiation measured in shock tunnel experiments. This led to the development of a modification to the ViSpeN model (known as ViSpeN-L) which includes a proposed new value for the radiative lifetime of the CN violet transition. The agreement between the experimental data and the ViSpeN-L model is excellent for conditions relevant to Titan entry.

The thermo-chemical relaxation of nitrogen hypersonic flows behind strong shocks and in nozzle expansions is investigated with 1D flow simulations and detailed vibrational kinetics. This work aims at deriving from detailed vibrational models accurate reduced models easy to implement in multidimensional reentry flow codes. First, nonequilibrium couplings between vibrational excitation, dissociation and recombination reactions are considered. Vibrational kinetics is described using accurate vibrational state-to-state rate constant databases of the literature completed with the forced harmonic oscillator model. The key role of multiquanta vibration-translation processes on the relaxation of the vibrational distribution function and the dissociation/recombination processes is put forward behind shocks and in nozzles. The vibrational distributions, which deviate strongly from equilibrium for nozzle expansions, are driven by vibration-translation processes and dissociation/recombination processes. A macroscopic model using groups of vibrational levels is developed to derive consistently the chemical and vibrational energy source terms from the vibrational state-to-state database.This model successfully reproduces the thermal, chemical and vibrational distribution function dynamics predicted by the state-to-state model with one group of levels behind a shock wave, and with three groups of levels in nozzle expansions. In a second step, the detailed vibrational model is extended to ionized nitrogen flows, including in particular a detailed modeling of the resonant electronvibration processes. Behind shocks, these processes control the rate of ionization by feeding energy to the electrons, up until the time when the elastic electron-ion exchanges takes over. It is shown that the widely used assumption of equilibrium between the electron and vibration temperatures predicts a too fast relaxation behind shock waves. In nozzle expansions, it is shown that for low electron concentration, the electron temperature is driven by electronvibration processes. Moreover, it is found that electrons are strongly coupled to low vibrational levels, and that more levels are coupled when the electron temperature increases. Coupling of the flow field with radiation is performed using the tangent slab approximation, and it is shown that the population of a metastable and two higher electronic levels are strongly impacted. Finally, the macroscopic model is extended to ionized nitrogen flows and is successfully applied on shock waves with one group of levels and with three groups of levels in nozzle expansions. In particular, the proposed macroscopic model represents more accurately the electron-vibration coupling than the widely used Landau-Teller model.

Title: Recombination study of ions with electrons at temperatures below 300 K Author: Tomáš Kotrík Department: Department of Surface and Plasma Science Supervisor of the doctoral thesis: Prof. RNDr. Juraj Glosík, DrSc. Department of Surface and Plasma Science Abstract: Presented is the study of recombination of ions with electrons performed at low temperatures using the Flowing afterglow with Langmuir probe experimental technique. Studied was the dissociative recombination of H and D ions at temperatures 77 - 300 K. Apart from a two-body also a three-body recombination channel assisted by neutral He atoms was identified and studied. The obtained temperature dependence of the two-body recombination rate coefficient is in a good agreement with findings of other experimental and theoretical works. The dissociative recombination of HCO and DCO ions with electrons was studied in the temperature range 150 - 300 K. The observed temperature dependence of measured recombination rate coefficient for HCO and DCO ions (~T -1.3 and ~T -1.1 , respectively) is in agreement with the majority of previous experimental works and evokes that indirect mechanism governs the recombination process. The electron- assisted collisional-radiative recombination of Ar ions was for the first time studied at temperatures 50 - 300 K. The...

A B S T R A C T Title: Recombination of Ions in Plasma at 50 − 300 K Author: Peter Rubovič Supervisor: Prof. RNDr. Juraj Glosík, DrSc. Abstract: Main part of this doctoral thesis lies in a study of recom- bination of atomic and molecular ions in low temperature plasmatic environment with emphasis on effect of third bodies. Stationary After- glow equipped with Cavity Ring Down Spectrometer and Cryogenic Flowing Afterglow with Langmuir Probe II were used to obtain recom- bination rate coefficients. Electron assisted collisional radiative recom- bination of Ar+ ion was studied in the temperature range of 50−100 K and helium assisted collisional radiative recombination was observed too. Both H+ 3 and its isotopologue D+ 3 were studies in flowing after- glow and spectroscopically in stationary afterglow as well. Binary re- combination rate coefficients and ternary recombination rate coeffi- cients for helium assisted ternary recombination were determined in the temperature range of 50 − 250 K. These coefficients were deter- mined also for pure ortho- and para- nuclear spin configurations of H+ 3 in the temperature range of 80 − 200 K. Keywords: dissociative recombination, collisional radiative recombi- nation, H+ 3 , D+ 3 , Ar+ viii

La relaxation thermo-chimique d’écoulements hypersoniques d’azote derrière des chocs forts et pour des détentes en tuyères est étudiée en effectuant des simulations d’écoulements 1D basées sur une cinétique vibrationnelle détaillée. Ces modèles vibrationnels détaillés sont utilisés pour développer des modèles macroscopiques précis et peu coûteux en temps de calcul pour les codes multidimensionels d’écoulements de rentrée. On considère d’abord les couplages hors équilibre entre l’excitation vibrationnelle et les réactions de dissociation / recombinaison. La cinétique vibrationnelle est décrite en utilisant des bases de constantes de réaction vibrationnelles précises de la littérature, complétées par le modèle de l’oscillateur harmoniques forcé. Le rôle prépondérant des processus vibration-translation multiquanta sur la relaxation de la distribution vibrationnelle et les processus de dissociation / recombinaison est mis en évidence derrière les chocs et dans les tuyères. Les distributions vibrationnelles, qui dévient fortement de l’équilibre dans les détentes en tuyères, résultent des processus vibration-translation et de dissociation / recombinaison. Un modèle macroscopique utilisant des groupes de niveaux vibrationnels est développé pour calculer de manière consistante les termes sources de chimie et d’énergie vibrationnelle à partir de la base de constantes de réaction vibrationnelles. Ce modèle reproduit précisément les dynamiques des températures, de la chimie et des distributions vibrationnelles avec un groupe de niveaux derrière un choc et trois groupes de niveaux pour les détentes. Dans un second temps, le modèle détaillé est généralisé aux écoulements d’azote ionisé en adoptant en particulier un modèle détaillé des processus résonants électron-vibration. Derrière les chocs, ces processus contrôlent la dynamique d’ionisation en alimentant les électrons en énergie, jusqu’à ce que les échanges élastiques électron-ion prennent le relais. Il est montré que l’hypothèse couramment utilisée d’équilibre entre les températures des électrons et de vibration conduit à une relaxation trop rapide derrière les chocs. Dans les détentes en tuyère pour lesquelles la concentration en électrons est faible, la température des électrons est contrôlée par les processus électron-vibration. On observe que les électrons sont fortement couplés aux bas niveaux vibrationnels, et que le nombre de niveaux couplés augmente avec la température des électrons. Le couplage de l’écoulement avec le rayonnement, modélisé dans l’approximation des plans tangents, impacte fortement la population du second métastable et de deux états électroniques plus élevés de N. Finalement, le modèle macroscopique est généralisé à l’azote ionisé. Un bon accord avec le modèle détaillé est obtenu avec un groupe de niveaux derrière un choc et trois groupes de niveaux pour les détentes en tuyère. En particulier, le modèle macroscopique proposé décrit plus précisément les échanges électron-vibration que le modèle de Landau-Teller couramment utilisé. / The thermo-chemical relaxation of nitrogen hypersonic flows behind strong shocks and in nozzle expansions is investigated with 1D flow simulations and detailed vibrational kinetics. This work aims at deriving from detailed vibrational models accurate reduced models easy to implement in multidimensional reentry flow codes. First, nonequilibrium couplings between vibrational excitation, dissociation and recombination reactions are considered. Vibrational kinetics is described using accurate vibrational state-to-state rate constant databases of the literature completed with the forced harmonic oscillator model. The key role of multiquanta vibration-translation processes on the relaxation of the vibrational distribution function and the dissociation/recombination processes is put forward behind shocks and in nozzles. The vibrational distributions, which deviate strongly from equilibrium for nozzle expansions, are driven by vibration-translation processes and dissociation/recombination processes. A macroscopic model using groups of vibrational levels is developed to derive consistently the chemical and vibrational energy source terms from the vibrational state-to-state database.This model successfully reproduces the thermal, chemical and vibrational distribution function dynamics predicted by the state-to-state model with one group of levels behind a shock wave, and with three groups of levels in nozzle expansions. In a second step, the detailed vibrational model is extended to ionized nitrogen flows, including in particular a detailed modeling of the resonant electronvibration processes. Behind shocks, these processes control the rate of ionization by feeding energy to the electrons, up until the time when the elastic electron-ion exchanges takes over. It is shown that the widely used assumption of equilibrium between the electron and vibration temperatures predicts a too fast relaxation behind shock waves. In nozzle expansions, it is shown that for low electron concentration, the electron temperature is driven by electronvibration processes. Moreover, it is found that electrons are strongly coupled to low vibrational levels, and that more levels are coupled when the electron temperature increases. Coupling of the flow field with radiation is performed using the tangent slab approximation, and it is shown that the population of a metastable and two higher electronic levels are strongly impacted. Finally, the macroscopic model is extended to ionized nitrogen flows and is successfully applied on shock waves with one group of levels and with three groups of levels in nozzle expansions. In particular, the proposed macroscopic model represents more accurately the electron-vibration coupling than the widely used Landau-Teller model.

This thesis examines the modeling of the shock-layer radiative heating associated with hypersonic vehicles entering the atmospheres of Earth and Titan. For Earth entry, flight conditions characteristic of lunar-return are considered, while for Titan entry, the Huygens probe trajectory is considered. For both cases, the stagnation region flowfield is modeled using a two-temperature chemical nonequilibrium viscous shock layer (VSL) approach. This model is shown to provide results that are in agreement with the more computationally expensive Navier-Stokes solutions. A new radiation model is developed that applies the most up-to-date atomic and molecular data for both the spectrum and non-Boltzmann modeling. This model includes a new set of atomic-lines, which are shown to provide a significant increase in the radiation (relative to previous models) resulting from the 1 - 2 eV spectral range. A new set of electronic-impact excitation rates was compiled for the non-Boltzmann modeling of the atomic and molecular electronic states. Based on these new rates, a novel approach of curve-fitting the non-Boltzmann population of the radiating atomic and molecular states was developed. This new approach provides a simple and accurate method for calculating the atomic and molecular non-Boltzmann populations. The newly-developed nonequilibrium VSL flowfield and nonequilibrium radiation models were applied to the Fire II and Apollo 4 cases, and the resulting radiation predictions were compared with the flight data. For the Fire II case, the present radiation-coupled flowfield model provides intensity values at the wall that predicted the flight data better than any other previous study, on average, throughout the trajectory for the both the 0.2 - 6.0 eV and 2.2 - 4.1 eV spectral ranges. The present results over-predicted the calorimeter measurements of total heat flux over most of the trajectory. This was shown to possibly be a result of the super-catalytic assumption for the wall boundary condition, which caused the predicted convective heating to be too high. For the Apollo 4 case, over most of the trajectory the present model over-predicted the flight data for the wall radiative intensity values between 0.2 - 6.2 eV. For the analysis of Huygens entry into Titan, the focus of the radiation model was the CN violet band. An efficient and accurate method of modeling the radiation from this band system was developed based on a simple modification to the smeared rotational band (SRB) model. This modified approach, labeled herein as SRBC, was compared with a detailed line-by-line (LBL) calculation and shown to compare within 5% in all cases. The SRBC method requires many orders-of-magnitude less computational time than the LBL method, which makes it ideal for coupling to the flowfield. The non-Boltzmann modeling of the CN electronic states, which govern the radiation for Huygens entry, is discussed and applied. The radiation prediction resulting from the non-Boltzmann model is up to 70% lower than the Boltzmann result. A new method for treating the escape factor in detail, rather than assuming a value equal to one, was developed. This treatment is shown to increase the radiation from the non-Boltzmann model by about 10%. / Ph. D.

No description available.

Das Afterglow tritt am Übergang vom Plasma zur Gasphase auf. Die dominierende aktive Spezies im Afterglow sind metastabil angeregte Neutralteilchen. Der Abbau der Metastabilen erfolgt in drei verschiedenen Prozessen: dem radiativen Zerfall, den Quenching-Stößen sowie der Relaxation in Stößen mit Oberflächen. Potentielle Anwendungsmöglichkeiten des Afterglows für Schichtabscheidung und Oberflächenmodifizierung werden diskutiert. Zur theoretischen Beschreibung des strömenden Afterglows wurde ein Collisional Radiative Modell entwickelt, welches die Reflexion angeregter Spezies an Oberflächen berücksichtigt. Als Diagnostikmethoden wurden die optische Emissionsspektroskopie (OES), die Chemolumineszenz sowie die Langmuir-Sondenmessungen eingesetzt, um die Konzentration metastabil angeregter Spezies zu bestimmen. Es wurde der Einfluß von konstruktiven und äußeren Paramentern auf die Konzentration metastabil angeregter Spezies im Afterglow untersucht. Es zeigt sich, daß unter den gegebenen Bedingungen die Quenching-Stöße der dominierende Verlustprozeß im Afterglow sind. Die Parameter Druck, Strömungsgeschwindigkeit und Länge des Afterglows können zu einem Skalierungsparameter zusammengefaßt werden, der zur online-Prozeßregulierung verwendet werden kann. Es werden

Cette thèse étudie le transfert de chaleur par rayonnement observé dans les conditions d'écoulement raréfié, en régime hypersonique qui seraient rencontrés au cours d'une mission d'aérocapture dans l'atmosphère de Titan. Des estimations précises du rayonnement hors-équilibre dans des écoulements à grande vitesse tels que ceux autour des corps de re-entrée, sont indispensables pour la conception de systèmes de protection thermique plus efficace. Parce que la masse du système de protection thermique est une fraction importante de la masse totale du véhicule, il ya un grand intérêt dans la conception de systèmes plus légers et plus efficaces. Les expériences en vol sont coûteuses et contraignantes, c'est pourquoi l'essai en laboratoire dans des installations capables de produire des écoulements hypersoniques est nécessaire. Malheureusement, les échelles de longueur généralement impliquées dans les expériences en vol sont trop grandes pour être testées dans des installations expérimentales et donc des modèles réduits de véhicules 'aeroshells' sont généralement testés. Les tubes d'expansion de l'université de Queensland - X1, X2 et X3 - ont été largement utilisés pour la modélisation à l'échelle réduite des écoulements hypersoniques (Morgan 2001). Pour les installations d'essais au sol telle que la soufflerie X2, une mise à l'échelle binaire est utilisée pour tester des modèles à échelle réduite de véhicules de vol, ce qui constitue le paramètre le plus important à respecter afin de reproduire un vol à haute vitesse. La mise à l'échelle binaire, appelé aussi 'mise à l'échelle 'ƒÏL', exige que le produit de la densité et de la longueur caractéristique du véhicule soit conservé entre le vol et les conditions expérimentales. Toutefois, il a été montré par Capra (2007) que le transfert de chaleur par rayonnement ne suit pas cette même loi de mise à l'échelle, et la similitude n'est pas crée pour les cas en vol où le transfert de chaleur par rayonnement et par convection sont fortement couplés. Cela peut entraîner d'importantes erreurs dans les estimations des propriétés d'écoulement associée et l'estimation du transfert de chaleur due au rayonnement. L'installation X2 a été modifiée en 2006 pour permettre l'expérimentation à basse pression en mode tube à choc non-réfléchi. L'utilisation d'un tube à choc non-réfléchi a permis la mesure du transfert de chaleur par rayonnement à la densité réelle en vol et supprimé les problèmes d'échelle liés à la mesure des rayonnements sur les véhicules en modèle réduit, au moins pour une partie de l'écoulement. Des mesures ont été effectuées dans la région immédiatement située derrière le choc et le long de la ligne médiane de l'écoulement de base, où le choc reste plan. Les écoulements externes, tels que ceux entourant une capsule de re-enntrée, n'ont pas été reproduits. La limite de basse pression d'exploitation était d'environ 10 Pa, limitée par la croissance de la couche limite sur les murs. / This thesis investigates the radiative heat transfer encountered in rarefied, hypervelocity flow conditions such as would be experienced during an aerocapture mission to Titan. Accurate estimates of the nonequilibrium radiation involved in high speed operations such as reentry are essential in order to design these thermal protection systems more efficiently. Because the mass of the thermal protection system is a large fraction of the overall vehicle mass, there is great interest in designing lighter and more efficient systems. Flight experiments are expensive and restrictive, hence laboratory testing is needed in facilities that are capable of producing hypervelocity flow. Unfortunately, as the size of a typical flight vehicle is too large to reasonably test in experimental facilities, subscale models of the aeroshell vehicles are generally tested. The University of Queensland's expansion tube facilities - X1, X2 and X3 - have been widely used for subscale modelling of hypersonic flowfields (Morgan 2001). Ground testing facilities such as the X2 facility take advantage of binary scaling to test small scale models of flight vehicles, which is the most important parameter to match in order to reproduce high speed flight. Binary scaling, also called 'ƒÏL' scaling, requires that the multiplication of density and the characteristic length of the vehicle be balanced between flight and experimental conditions. However, it was shown by Capra (2007) that radiative heat transfer does not follow this same scaling factor, and true similarity with flight is not created for flows where the radiative and convective heat transfer are strongly coupled. This can result in significant errors in the estimates of the associated flow properties and the estimation of the heat transfer due to radiation. The X2 facility was modified in 2006 to allow experimentation at low pressures in nonreflected shock tube mode. Nonreflected shock tube operation allowed the taking of true-flight density measurements of the radiative heat transfer and removed the scaling problems involved in radiation measurements for model vehicles, at least for part of the flowfield. Measurements were made in the region immediately behind the shock along the centreline of the core flow, where the shock remained planar. External flow fields, such as those surrounding a reentry capsule, were not reproduced. The low density operating limit was approximately 10 Pa, limited by boundary layer growth on the walls.

Dans les plasmas chauds denses, la distribution spatiale des électrons libres et des ions peut affecter fortement la structure atomique. Pour tenir compte de ces effets, nous avons implémenter un potentiel plasma fond´ sur le modèle d’un gaz d’électron uniforme et sur une approche de type Thomas-Fermi dans le Flexible Atomic Code (FAC). Ce code a été utilisé, pour obtenir les énergies, les fonctions d’onde, et les taux radiative modifiés par l’environnement plasma. Dans des ions hydrogénoides, les résultats numériques ont été comparés avec succès à un calcul analytique basé sur la théorie des perturbations du premier ordre. Dans le cas des ions multi-électronique, on observe un décalage des niveaux, en accord avec d’autre calcul récent. Diverses méthodes pour les calculs de section efficace de collision sont examinées. L’influence de la densité du plasma sur ces sections est analysée en détail. Certaines expressions analytiques sont propos´es pour les ions hydrogénoides comme dans la limite où l’approximation de Born ou Lotz s’applique et sont comparés aux résultats numériques du code de FAC. Enfin, à partir de ce travail, nous étudions l’influence de l’environnement de plasma sur notre modèle collisionel-radiatif nommé -Foch-. En raison de cet environnement, la charge moyenne du plasma augmente, ceci est principalement due a l’abaissement du continuum. Nous observons également, le décalage des raies sur les spectres d’émission lié-lié. Un bon accord est trouvé entre notre travail et les données expérimentales sur un plasma de titane. / In hot dense plasmas, the free-electron and ion spatial distribution may strongly affect the atomic structure. To account for such effects we have implemented a potential correction based on the uniform electron gas model and on a Thomas-Fermi Approach in the Flexible Atomic Code (FAC). This code has been applied to obtain energies, wave-functions and radiative rates modified by the plasma environment. In hydrogen-like ions, these numerical results have been successfully compared to an analytical calculation based on first-order perturbation theory. In the case of multi-electron ions, we observe level crossings in agreement with another recent model calculation. Various methods for the collision cross-section calculations are reviewed. The influence of plasma environment on these cross-sections is analyzed in detail. Some analytical expressions are proposed for hydrogen-like ions in the limit where Born or Lotz approximations apply and are compared to the numerical results from the FAC code. Finally, from this work, we study the influence of the plasma environment on our collisional-radiative model so-called -Foch-. Because of this environment, the mean charge state of the ions increases. The line shift is observed on the bound-bound emission spectra. A good agreement is found between our work and experimental data on a Titanium plasma.