<p>An atom or ion can change quantum state, usually through emission or absorption of a photon. The photon has the same energy as the energy difference between the states of the transition. The states, or energy levels, of an atom are quantized and light emitted, or absorbed, from the atom is therefore of specific wavelengths, giving spectral lines. The spectrum of an atomic ion is unique and contains information of the structure and energy levels of the ion. The spectrum of an atom can be used as a fingerprint in determinations of the abundance of the element in different objects.</p><p>This thesis is focused on some weak effects observed by spectroscopy. Although the effects are weak, they turn out to be of great importance. According to quantum mechanics transitions between certain states are not allowed. Here the weak effects open the possibility for transitions. Spectral lines from forbidden transitions are very weak and difficult to observe under ordinary laboratorial conditions, but they are commonly observed from astrophysical objects and can be very useful for diagnostics of astrophysical plasmas. The first reported observation of forbidden lines was from an astrophysical object and at that time supposed to be from new, previous unknown, elements. If all possible decay channels from an energy level are forbidden, the energy level is metastable and has usually a lifetime 10$^8$ times longer than an ordinary excited state. Measurements of such long lifetimes are difficult since the ion need to be confined during the observation time. Confinement of ions can be achieved with a storage device, such as a storage ring or a trap, where the ions are stored without interacting with each other or the surroundings.</p><p>A laser probing technique has been developed at the storage ring CRYRING, for measurements of lifetimes of metastable states. The technique has now been improved for measurement of longer lifetimes. The technique has also been modified to fit when measuring on negative ions. Results of lifetime measurements are reported and the techniques and methods used are described.</p><p>Another weak effect is hyperfine interaction, which splits the energy levels of an atom or ion. Hyperfine splitting is very small and usually special spectral techniques are needed to resolve such structure. A laser can, in combination with an electromagnetic radio-frequency field, be used for accurate determination of hyperfine structures in atomic ions. Such measurements are also important for evaluation of astrophysical properties, since hyperfine structure can broaden the spectral lines. An experimental setup for such double resonance measurements has been developed and constructed. Results of experimental measurements are reported and the technique is described.</p>

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Este trabalho experimental tem por objetivo apresentar os estudos experimentais realizados com jatos de líquidos evaporativos (\"flash boiling\") de iso-octano. Nos estudos, o jato emergia de um diminuto bocal que descarrega em uma grande câmara de baixa pressão. O líquido ao passar pelo bocal sofria uma expansão interna alcançando elevados graus de superaquecimento ou de metaestabilidade, já que se mantinha na fase líquida. Nos experimentos, eram controladas as condições de pressão e temperatura de injeção durante um período de alguns poucos segundos suficientes para que as condições de regime permanente fossem estabelecidas. Um dos métodos para a visualização do escoamento do jato evaporativo foi o \"Schlieren\", o qual permitia visualizar elevados gradientes de densidade como normalmente ocorrem com ondas de choque, presentes nesta investigação. Também foi empregada a técnica de visualização de \"iluminação por detrás\" para que fossem comparadas as imagens obtidas por este método com o do \"Schlieren\", bem como mostrar detalhes do fenômeno em estudo. Com isso, foi possível estudar a estrutura do processo evaporativo do jato e, com o auxílio de ferramentas de filtragem matemática e manipulação das imagens obtidas, os fenômenos compressíveis envolvidos. Os perfis dos jatos observados foram: (1) filete contínuo de líquido sem evaporação, (2) jato com fragmentações ou atomizado e (3) abrupta evaporação seguida por expansão com formação de ondas de choque. Neste último caso, a inspeção das fotografias indicou que a evaporação do líquido se dava externamente ao bocal, a partir de um núcleo metaestável de líquido, o qual apresentava o formato aproximado de um cone. Também foi aplicada a teoria de ondas oblíquas de evaporação para estudar o comportamento deste cone líquido. Os ensaios foram conduzidos com três bocais cônico-convergentes de dimensões e materiais diferentes, quais sejam: bocal de aço com diâmetro de saída de 0,3 mm, bocal de aço com 0,8 mm e bocal de vidro com 0,35 mm. / The main goal of this thesis is to present results of experiments with flashing liquid jets of iso-octane. The experiments were carried out with a liquid jet issuing from a small nozzle into a low-pressure chamber. High degrees of metastability were obtained as the liquid jet expanded within the nozzle. Injection pressure and temperature were controlled to the desired testing values for a few seconds, which were found long enough to reach and keep the steady state regime. The photographic documentation of the phenomenon was obtained from a \"Schlieren\" set up using CCD camera. The \"back-lightening\" visualization technique was also used in order to compare both image techniques and to unveil some flashing phenomenon details. Analyses of these images with the help of mathematical filters as well as other image manipulating techniques enabled a qualitative visualization of the flashing liquid jet structure and geometry leaving the nozzle. Three liquid jet regimes were observed: (1) continuous liquid jet (2) partially atomized, and (3) evaporation with the presence of shock waves. In this latter case, we speculate that the evaporation took part on the liquid jet surface, which had the approximate shape of a cone. Also it was employed the oblique evaporation wave theory to explain some of the behavior of the overall evaporation process. The tests were carried out using three conical-converging nozzles made of different materials: a 0.3 mm exit diameter steel nozzle, a 0.8 mm exit diameter steel nozzle, and a 0.35 mm exit diameter glass nozzle.

Photocrystallography is a relatively new and continuously developing technique used in the structure determination of metastable and transient species in the crystalline state. This thesis contains a description of investigations into photo-induced linkage isomerism reactions in the solid state with the use of single crystal and powder X-ray diffraction experiments to monitor structural changes at low temperature.

The research presented within this thesis is concerned with the design, synthesis, characterisation, and analysis of a series of new compounds of platinum (II), with aims to produce compounds possessing switchable optical properties, and with potential applications as "smart-materials" for use as highly selective sensors.

Cette thèse de doctorat s’intéresse aux écoulements diphasiques métastables typiques de certains transitoires accidentels qui pourraient intervenir dans les centrales nucléaires. Ces phénomènes sont difficiles à traiter en raison de la complexité topologique de l’écoulement, des transferts entre phases et du couplage fort entre les caractéristiques thermodynamiques et les aspects mathématiques.Les méthodes aujourd’hui en usage dans l’industrie ne décrivent pas complétement la complexité de ces écoulements car elles s’appuient sur des modèles trop simples. En fait ces méthodes ne prennent pas en compte le déséquilibre thermo-chimique entre l’eau liquide et sa vapeur. Par ailleurs, les méthodes hyperboliques proposées récemment dans la littérature pour la simulation des écoulements métastables ne peuvent pas être appliquées dans l’industrie car elles utilisent des lois d’état simples qui ne sont pas adaptées pour les calculs industriels.Le but de cette thèse est de développer une nouvelle approche qui couple les méthodes hyperboliques modernes à des équations d’état précises. Le produit final de ce travail est un nouveau modèle pour l’analyse industrielle des écoulements diphasiques métastables qui associe de nouvelles techniques pour le calcul des transferts interfaciaux et des propriétés de l’eau et de sa vapeur. De plus, cette approche est d’un coût abordable pour les configurations industrielles.Les méthodes développées dans cette thèse ont été systématiquement vérifiées avec des solutions exactes et validées en utilisant des données expérimentales de la littérature. / This Ph.D. thesis deals with the metastable two-phase flows typical of accidental transients that could occur in nuclear power plants. Those phenomena are of difficult treatment due to the topological difficulty of the flow, the interphase transfers and the strong coupling between thermodynamic features and mathematical aspects.The methods today in use in industry do not fully describe the complexity of these flows because based on too simple models. In fact, they do not take into account the thermo-chemical disequilibrium between liquid and vapor water. On the other hand, the hyperbolic methods recently proposed in the literature for the simulation of metastable flows can not be used in the industry because based on simple equations of state that are not adequate for industrial calculations.The purpose of this Ph.D. thesis is to develop a new approach that couples the modern hyperbolic methods to accurate equations of state. The final product of this work is a new model for the industrial analysis of metastable two-phase flows that incorporates novel techniques for the calculation of interfacial transfers and of steam-water properties. Moreover, it is computationally affordable for its use in industrial configurations.The methods developed in this thesis have been sistematically verified against exact solutions and validated using experimental data of the literature.

β-Ti alloys are widely used in airframe and biomedical applications due to their high ductility, high hardenability, and low elastic modulus. The phase transformations in β-Ti alloys are rather complex due to formation of metastable phases during various thermo-mechanical treatments. One such critical metastable phase, the hexagonal omega (ω) phase, can form in β-Ti alloys under quenching from the high temperature β phase and/or isothermal aging at intermediate temperature. Despite a substantial amount of reported works on the ω phase, there are several critical issues related to the ω formation need to be resolved, e.g. role of alloying elements and oxygen content. Therefore, this dissertation has attempted to provide insights into ω transformation in low misfit (Ti-Mo) and high misfit (Ti-V) binary systems as well as multicomponent (Ti-Nb-Zr-Ta) alloys. The evolution of ω structure, morphology and composition from the early stage (β-solution+quenched) to later stages after prolonged aging are systematically investigated by coupling transmission electron microscopy (TEM), atom probe tomography (APT) and high-energy synchrotron X-ray diffraction techniques. The influence of aging temperature and duration on characteristic of ω phase in Ti-Mo, and Ti-V alloys is addressed in details. It is found that compositional changes during aging can alter the structure, size and morphology of ω precipitates. In low misfit alloys, the ellipsoidal morphology of ω phase was retained during isothermal aging, while in high misfit alloys it changed from ellipsoidal to cuboidal morphology after prolonged aging. Secondly, ω transformation in biomedical Ti-Nb-Zr-Ta alloy is probed in which the micro-hardness was sensitive to microstructural changes. Furthermore, the evolution of oxygen concentration in ω precipitates during various aging conditions in binary Ti-Mo and Ti-V alloys are reported. It has been accepted that interstitial elements such as oxygen can largely alter mechanical behavior and the microstructure of Ti-alloys. Recently, oxygen is intentionally added to some biomedical alloys to improve their performances. However, a careful understanding of the effect of oxygen on ω phase transformation is still lacking in the literature. In this work, the role of oxygen on ω phase formation in biomedical TNTZ alloys is investigated. Although it is traditionally accepted that oxygen suppresses ω transformation, our observations revealed contradictory results during isothermal aging of TNZT alloys. The results of our investigations provide a novel insight into understanding the effect of interstitial elements on metastable phase transformation in β-Ti alloys. It is concluded that depending upon the nature of alloying elements and/or the applied thermo-mechanical treatments, oxygen may play a different role in ω transformations.

Este trabalho experimental tem por objetivo apresentar os estudos experimentais realizados com jatos de líquidos evaporativos (\"flash boiling\") de iso-octano. Nos estudos, o jato emergia de um diminuto bocal que descarrega em uma grande câmara de baixa pressão. O líquido ao passar pelo bocal sofria uma expansão interna alcançando elevados graus de superaquecimento ou de metaestabilidade, já que se mantinha na fase líquida. Nos experimentos, eram controladas as condições de pressão e temperatura de injeção durante um período de alguns poucos segundos suficientes para que as condições de regime permanente fossem estabelecidas. Um dos métodos para a visualização do escoamento do jato evaporativo foi o \"Schlieren\", o qual permitia visualizar elevados gradientes de densidade como normalmente ocorrem com ondas de choque, presentes nesta investigação. Também foi empregada a técnica de visualização de \"iluminação por detrás\" para que fossem comparadas as imagens obtidas por este método com o do \"Schlieren\", bem como mostrar detalhes do fenômeno em estudo. Com isso, foi possível estudar a estrutura do processo evaporativo do jato e, com o auxílio de ferramentas de filtragem matemática e manipulação das imagens obtidas, os fenômenos compressíveis envolvidos. Os perfis dos jatos observados foram: (1) filete contínuo de líquido sem evaporação, (2) jato com fragmentações ou atomizado e (3) abrupta evaporação seguida por expansão com formação de ondas de choque. Neste último caso, a inspeção das fotografias indicou que a evaporação do líquido se dava externamente ao bocal, a partir de um núcleo metaestável de líquido, o qual apresentava o formato aproximado de um cone. Também foi aplicada a teoria de ondas oblíquas de evaporação para estudar o comportamento deste cone líquido. Os ensaios foram conduzidos com três bocais cônico-convergentes de dimensões e materiais diferentes, quais sejam: bocal de aço com diâmetro de saída de 0,3 mm, bocal de aço com 0,8 mm e bocal de vidro com 0,35 mm. / The main goal of this thesis is to present results of experiments with flashing liquid jets of iso-octane. The experiments were carried out with a liquid jet issuing from a small nozzle into a low-pressure chamber. High degrees of metastability were obtained as the liquid jet expanded within the nozzle. Injection pressure and temperature were controlled to the desired testing values for a few seconds, which were found long enough to reach and keep the steady state regime. The photographic documentation of the phenomenon was obtained from a \"Schlieren\" set up using CCD camera. The \"back-lightening\" visualization technique was also used in order to compare both image techniques and to unveil some flashing phenomenon details. Analyses of these images with the help of mathematical filters as well as other image manipulating techniques enabled a qualitative visualization of the flashing liquid jet structure and geometry leaving the nozzle. Three liquid jet regimes were observed: (1) continuous liquid jet (2) partially atomized, and (3) evaporation with the presence of shock waves. In this latter case, we speculate that the evaporation took part on the liquid jet surface, which had the approximate shape of a cone. Also it was employed the oblique evaporation wave theory to explain some of the behavior of the overall evaporation process. The tests were carried out using three conical-converging nozzles made of different materials: a 0.3 mm exit diameter steel nozzle, a 0.8 mm exit diameter steel nozzle, and a 0.35 mm exit diameter glass nozzle.

La transformation de phase influence considérablement les propriétés thermomécaniques des matériaux métastables. Elle est prise en considération dans des modèles numériques qui simule le comportement de ces derniers dans des codes de calcul et qui nécessitent des résultats expérimentaux. Ainsi, ces travaux concernent la caractérisation du comportement axial et multiaxial de deux aciers iTRIP à savoir l’acier 301L et l’acier 304L ainsi qu’un alliage à mémoire de forme à base de CuAlBe. Cette caractérisation est couplée avec un suivi de la cinétique des transformation de phase entreprise par la mesure de la résistance électrique. Le premier chapitre est une étude bibliographique des deux classes de matériaux métastables cités précédemment ainsi que du phénomène de transformation de phase et les techniques permettant sa caractérisation. Le deuxième chapitre, s’intéresse aux essais uniaxiaux thermomécaniques réalisés sur un acier iTRIP afin de valider la méthode de dosage de phase. Aussi, les essais thermomécaniques multiaxiaux réalisés sur des éprouvettes tubulaires en acier iTRIP 304L y seront présentés. Le troisième chapitre est consacré aux essais uniaxiaux réalisés sur des éprouvettes de CuAlBe ainsi qu’au dosage de phase des cas biphasé et triphasé. Aussi, la validation de l’hypothèse de linéarité entre la fraction volumique de martensite et la déformation de transformation équivalente dans le cas de chargements multiaxiaux proportionnels et non proportionnels est faite. / Phase transformation considerably influences the thermomechanical properties of metastable materials. This is reflected in the numerical model that simulates the behavior of these materials for the calculation codes and require experiments.Thus, the present work concerns the characterization of the axial and multi-axial behavior of two iTRIP steels, 301L steel and 304L steel in addition to a shape memory alloy based on CuAlBe. This characterization is coupled with monitoring of phase transformation kinetics through the measurement of the electrical resistance.The first chapter is a bibliographic study of the two classes of metastable materials mentioned above as well as the phase transformation phenomenon and its characterization techniques. The second chapter deals with uniaxial thermomechanical tests on a steel iTRIP to validate the phase assay. The multiaxial thermomechanical testing performed on specimens tubular steel 304L iTrip will be presented.The third chapter is devoted to uniaxial tests performed on CuAlBe spicemens and realization phase doping in a three-phase case. Also, the validation of the assumption of linearity between the martensite volume fraction and the equivalent transformation strain in the case of proportional and non-proportional loading is done.

Le travail consiste en l'optimisation de la microstructure d'un alliage usuel TA6V par obtention de phases métastables. Ces nouvelles microstructures, obtenues par traitements thermiques, permettent d'améliorer la tenue mécanique (statique et en fatigue) de l'alliage sans pour autant changer la biocompatibilité. / This PhD aims at optimizing the microstructure of the usual TA6V alloy by using metastable phases. These new microstructures, obtained by thermal treatments, permit to improve the mechanical strength (static but also the fatigue ones) without modifying the biocompatibility.