Mechanical fatigue testing has shown that MEAs (membrane electrode assemblies) fail at lower stresses than PEMs (proton exchange membranes) at comparable times under load. The failure of MEAs at lower stresses is influenced by the presence of mud cracks in the catalyst layers acting as stress concentrators. Fatigue testing of MEAs has shown that smaller-scale cracking occurs in the membrane within these mud cracks, leading to leaking during mechanical fatigue testing and the failure of the membrane. In addition, this testing of MEAs has further established that the cyclic pressurization pattern, which affects the viscoelastic behavior of the membranes, has a significant effect on the relative lifetime of the MEA. To investigate this behavior, pressure-loaded blister tests were performed at 90 °C to determine the biaxial fatigue strength of Gore-Primea® Series 57 MEAs. In these volume-controlled tests, the leak rate was measured as a function of fatigue cycles. Failure was defined as occurring when the leak rate exceeded a specified threshold. Post-mortem characterization FESEM (field emission scanning electron microscopy) was conducted to provide visual documentation of leaking failure sites. To elucidate the viscoelastic behavior of the MEA based on these results, testing was conducted using a DMA to determine the stress relaxation behavior of the membrane. This data was then used in a FEA program (ABAQUS) to determine its effect on the mechanical behavior of the MEAs. A linear damage accumulation model used the ABAQUS results to predict lifetimes of the membrane in the MEAs. The models showed that under volume-controlled loading, the stress decays with time and the stress dropped towards the edges of the blisters. The lifetimes of the MEAs varied depending on the cycling pattern applied. This is important for understanding failure mechanisms of MEAs under fatigue loading, and will help the fuel cell industry in designing membranes that better withstand imposed hygrothermal stresses experienced during typical operating conditions. / Master of Science

Este trabalho apresenta o estudo do efeito do refletor sobre o tempo de vida neutrônico do Reator IPEN/MB-01. O método empregado requer uma abordagem que leve em conta tanto o núcleo quanto o refletor, de modo que as equações de cinética pontual, as quais constituem a base teórica de todo desenvolvimento matemático, contemplem ambas as regiões do reator. A partir dessas equações, conhecidas como equações de cinética pontual do modelo duas regiões, são obtidas as expressões teóricas para as APSDs (Auto Power Spectral Densities), as quais são utilizadas para o ajuste por mínimos quadrados aos dados das APSDs experimentais obtidas em vários estados subcríticos. O tempo de geração de nêutrons prontos, o tempo de vida dos nêutrons no refletor e a fração desses nêutrons que retornam ao núcleo, são obtidos como parâmetros do ajuste. / The aim of this study is to present the reflector effect on the neutron lifetimes in the IPEN/MB-01 reactor. The proposed method requires an approach which takes into account both the reflector and the core, so that the point kinetics equations, which constitute the theoretical basis of all mathematical development, contemplate both regions of the reactor. From these equations, as known as two regions kinetics point equations, theoretical expressions are obtained for the Auto Power Spectral Densities (APSD), which are used for least squares fit of the experimental data of APSD obtained in several subcritical states. The prompt neutron generation time, the neutron lifetimes in the reflector and the neutron return fraction from the reflector to the core are derived from the fitting.

All-optical time-resolved measurement techniques provide a powerful tool for investigating critical parameters that determine the performance of infrared photodetector and emitter semiconductor materials. Narrow-bandgap InAs/GaSb type-II superlattices (T2SLs) have shown great promise as a next generation source of these materials, due to superior intrinsic properties and versatility. Unfortunately, InAs/GaSb T2SLs are plagued by parasitic Shockley-Read-Hall recombination centers that shorten the carrier lifetime and limit device performance. Ultrafast pump-probe techniques and time-resolved differential transmission measurements are used here to demonstrate that Ga-free InAs/InAsSb T2SLs and InAsSb alloys do not have this same limitation and thus have significantly longer carrier lifetimes. Measurements at 77 K provided minority carrier lifetimes of 9 μs and 3 μs for an unintentionally doped mid-wave infrared (MWIR) InAs/InAsSb T2SL and InAsSb alloy, respectively; a two order of magnitude increase compared to the 90 ns minority carrier lifetime measured in a comparable MWIR InAs/GaSb T2SL. Through temperature-dependent lifetime measurements, the various carrier recombination processes are differentiated and the dominant mechanisms identified for each material. These results demonstrate that these Ga-free materials are viable options over InAs/GaSb T2SLs for potentially improved infrared photodetectors. In addition to carrier lifetimes, the drift and diffusion of excited charge carriers through the superlattice growth layers (i.e. vertical transport) directly affects the performance of photodetectors and emitters. Unfortunately, there is a lack of information pertaining to vertical transport, primarily due to difficulties in making measurements on thin growth layers and the need for non-standard measurement techniques. However, all-optical ultrafast techniques are successfully used here to directly measure vertical diffusion in MWIR InAs/GaSb T2SLs. By optically generating excess carriers near one end of a MWIR T2SL and measuring the transit time to a thin, 2 lower-bandgap superlattice placed at the other end, the time-of-flight of vertically diffusing carriers is determined. Through investigation of both unintentionally doped and p-type superlattices at 77 K, the vertical hole and electron diffusion coefficients are determined to be 0.04±0.03 cm2/s and 4.7±0.5 cm2/s, corresponding to vertical mobilities of 6±5 cm2/Vs and 700±80 cm2/Vs, respectively. These measurements are, to my knowledge, the first direct measurements of vertical transport properties in narrow-bandgap superlattices. Lastly, the widely tunable two-color ultrafast laser system used in this research allowed for the investigation of nonlinear optical properties in narrow-bandgap semiconductors. Time-resolved measurements taken at 77 K of the nondegenerate two-photon absorption spectrum of bulk n-type GaSb have provided new information about the nonresonant change in absorption and two-photon absorption coefficients in this material. Furthermore, as the nondegenerate spectrum was measured over a wide range of optical frequencies, a Kramers-Kronig transformation allowed the dispersion of the nondegenerate nonlinear refractive index to be calculated.

<p>In this dissertation is exemplified how different laser based methods are applied in high-resolution spectroscopic studies of internal properties of diatomic molecules.</p><p>A molecular beam apparatus assembly is described, where a laser ablation source is combined with a time-of-flight mass spectrometer. Compounds investigated with this equipment are hafnium sulfide and hafnium oxide. The molecules are excited and ionized applying the resonant two-photon ionization (R2PI) scheme, which is a sensitive absorption and detection technique for probing the population of an excited state.</p><p>By means of the DC Stark effect, permanent electric dipole moments of HfS in the <i>D</i> ¹Π state and HfO in the <i>b</i> ³Π₁ state are determined while the molecules are exposed to a static electric field. Under field-free conditions low temperature rotationally resolved spectra are recorded, generating line positions from which molecular parameters are derived.</p><p>The R2PI method, modified with an adjustable delay time, is also used in lifetime measurements of individual rotational levels of the HfS <i>D</i>¹Π and HfO<i> b</i> ³Π₁ states. Oscillator strengths for transitions from the ground state are calculated, and in this connection basic concepts like Einstein coefficients, line strengths and Hönl-London factors, are surveyed. Theoretical calculation of lifetimes is discussed in view of the fact that a commonly available computer program (LEVEL 7.5 by Le Roy) gives erroneous output.</p><p>Some coherence and quantum interference related phenomena, such as electromagnetically induced transparency (EIT) and Autler-Townes (AT) splitting, are presented in the latter part of this thesis. Fundamental concepts and relations are introduced and explained. The driven three-level cascade system is elucidated, including some of its experimental applications to alkali metal dimers, Na₂ and Li₂.</p><p>A triple resonance spectroscopy experiment is described in terms of a three-laser, four-level inverted-Y excitation scheme, implemented in Na₂. The accompanying density matrix formalism, providing the basis for theoretical simulations, is accounted for. From analysis of the results an absolute value of the electric dipole moment matrix element (transition moment) is extracted, using the AC Stark effect.</p><p>Some recently reported unexpected experimental results and unforeseen features, occurring in Doppler broadened samples and related to the open character of molecular systems, are briefly commented.</p>

In this dissertation is exemplified how different laser based methods are applied in high-resolution spectroscopic studies of internal properties of diatomic molecules. A molecular beam apparatus assembly is described, where a laser ablation source is combined with a time-of-flight mass spectrometer. Compounds investigated with this equipment are hafnium sulfide and hafnium oxide. The molecules are excited and ionized applying the resonant two-photon ionization (R2PI) scheme, which is a sensitive absorption and detection technique for probing the population of an excited state. By means of the DC Stark effect, permanent electric dipole moments of HfS in the D 1Π state and HfO in the b 3Π1 state are determined while the molecules are exposed to a static electric field. Under field-free conditions low temperature rotationally resolved spectra are recorded, generating line positions from which molecular parameters are derived. The R2PI method, modified with an adjustable delay time, is also used in lifetime measurements of individual rotational levels of the HfS D 1Π and HfO b 3Π1 states. Oscillator strengths for transitions from the ground state are calculated, and in this connection basic concepts like Einstein coefficients, line strengths and Hönl-London factors, are surveyed. Theoretical calculation of lifetimes is discussed in view of the fact that a commonly available computer program (LEVEL 7.5 by Le Roy) gives erroneous output. Some coherence and quantum interference related phenomena, such as electromagnetically induced transparency (EIT) and Autler-Townes (AT) splitting, are presented in the latter part of this thesis. Fundamental concepts and relations are introduced and explained. The driven three-level cascade system is elucidated, including some of its experimental applications to alkali metal dimers, Na2 and Li2. A triple resonance spectroscopy experiment is described in terms of a three-laser, four-level inverted-Y excitation scheme, implemented in Na2. The accompanying density matrix formalism, providing the basis for theoretical simulations, is accounted for. From analysis of the results an absolute value of the electric dipole moment matrix element (transition moment) is extracted, using the AC Stark effect. Some recently reported unexpected experimental results and unforeseen features, occurring in Doppler broadened samples and related to the open character of molecular systems, are briefly commented.

Este trabalho apresenta o estudo do efeito do refletor sobre o tempo de vida neutrônico do Reator IPEN/MB-01. O método empregado requer uma abordagem que leve em conta tanto o núcleo quanto o refletor, de modo que as equações de cinética pontual, as quais constituem a base teórica de todo desenvolvimento matemático, contemplem ambas as regiões do reator. A partir dessas equações, conhecidas como equações de cinética pontual do modelo duas regiões, são obtidas as expressões teóricas para as APSDs (Auto Power Spectral Densities), as quais são utilizadas para o ajuste por mínimos quadrados aos dados das APSDs experimentais obtidas em vários estados subcríticos. O tempo de geração de nêutrons prontos, o tempo de vida dos nêutrons no refletor e a fração desses nêutrons que retornam ao núcleo, são obtidos como parâmetros do ajuste. / The aim of this study is to present the reflector effect on the neutron lifetimes in the IPEN/MB-01 reactor. The proposed method requires an approach which takes into account both the reflector and the core, so that the point kinetics equations, which constitute the theoretical basis of all mathematical development, contemplate both regions of the reactor. From these equations, as known as two regions kinetics point equations, theoretical expressions are obtained for the Auto Power Spectral Densities (APSD), which are used for least squares fit of the experimental data of APSD obtained in several subcritical states. The prompt neutron generation time, the neutron lifetimes in the reflector and the neutron return fraction from the reflector to the core are derived from the fitting.

This thesis focuses on the study of UV light-generated zinc complexes with cadmium and organic molecules SAM, SAH, CYS, HCYS and GSSG, specifically at 375 nm. Furthemore, the aim of the work is to characterize the precursors spectrally and temporally before and after irradiation in the transilluminator at 250 nm. Study of genesis these complexes was performed by FLIM. Thanks to this method, it was found that the formation of complexes occurs only with Zn:SAH, Zn:GSSG and Zn:Cd. The formation of complexes is influenced by the method of preparation. The spectral characteristic was performed on a fluorimeter where the increase in fluorescence intensity of the irradiated solution with the precursors was expected. These were turbid solutions where sedimentation of the particles was observed and the intensity of fluorescence was changed. In the Zn:SAM and Zn:CYS sample, the sedimentation increased in intensity, while in Zn:SAH and Zn:HCYS decreased. The Zn:Cd precursor solution was clear and there was no change in intensity. Zn:Cd showed the best spectral properties, while the Zn:SAM sample, whose excitation and emission maxima are very close to each other, appeared to be the worst. A sample with Zn:CYS and Zn:HCYS showed almost the same spectra and respective peak results. Based on lifetime characteristics by TCSPC, the sample with Zn:CYS, Zn:HCYS and Zn:GSSG, which showed 3 lifetimes, was best treated. Lifetime could not be unambiguously determined for SAM and SAH samples. Zn:Cd had 4 lifetimes

Four types of astrochemically relevant radiative processes are studied: bound-bound, bound-free, free-bound and free-free. The former two together determine radiative lifetimes, which are calculated for the HeLi+ molecular ion. Free-bound processes, also called radiative association, are studied on two systems: He in collisions with Li+ , and O in collision with C+. Collisions of He and Li+ are believed to have occurred during the recombination era of the Universe, while collisions of O with C+ are considered to be relevant in SN 1987A. Altogether, 17 radiative association cross sections and rate coefficients are calculated for radiative association, and the effect of a stimulated emission is also illustrated. A free-free process, also called radiative charge transfer, is studied in collisions of He with Li+.

La forme d’un noyau, ou la déviation de la distribution en masse par rapport à une forme sphérique, est une des propriétés fondamentales du noyau. Elle est gouvernée à la fois par des effets macroscopiques et microscopiques, tels que l'énergie de liaison donnée par le modèle de la goutte liquide ou la structure en couche du noyau, respectivement. L’étude de la forme des noyaux exotiques par spectrométrie gamma permet de tester finement différents modèles théoriques initialement développés pour les noyaux stables. L’objectif de cette thèse est l’étude de l’évolution de la forme des noyaux exotiques riches en neutrons dans les chaînes isotopiques allant du Zr (Z=40) au Pd (Z=46). Le plus souvent, la forme des noyaux évolue lentement de la forme sphérique, près des fermetures de couche ou des noyaux magiques (ou doublement magiques), à des formes allongées (prolate), pour des noyaux avec de nombreux nucléons de valence. Cependant, Les noyaux auxquels nous nous intéressons ont tendance à avoir des états excités qui évoluent rapidement en fonction du nombre de neutrons, ce qui peut être interprété comme des variations rapides de la forme du noyau. Ceci inclue dans de rares cas l'observation d'états de forme aplatie (oblate) et triaxiale. Jusqu'à présent, les propriétés connues de ces noyaux se limitent (principalement) aux énergies d'excitation. Les informations sur le degré de collectivité nucléaire (que l'on peut déduire de la durée de vie des états excités) sont rares, tandis que les informations directes de forme sont pratiquement inexistantes. L'estimation la plus simple de la déformation nucléaire dans les noyaux pairs peut être obtenue à partir de l'énergie du premier état 2⁺. Pour les isotopes du Sr (Z = 38) et du Zr (Z = 40), il a été observé que cette énergie diminue considérablement à N = 60, alors que son évolution est beaucoup plus progressive pour les isotopes du Mo (Z = 42). Des mesures précises de durée de vie constituent un élément clé de l'étude systématique de l'évolution de la déformation nucléaire et du degré de collectivité dans cette région. Des noyaux riches en neutrons dans la région de masse A = 100-120 ont été peuplés par la réaction de fusion-fission d'un faisceau de ²³⁸U à 6,2 MeV/u sur une cible ⁹Be. Le noyau composé ²⁴⁷Cm était produit à une énergie d'excitation de ∼45 MeV avant de fissionner. Le dispositif expérimental utilisé pour cette étude comprenait le spectromètre de masse de haute résolution VAMOS pour l'identification les noyaux en Z et A, le réseau de 35 détecteurs au germanium AGATA (Advanced γ-ray Tracking Array) AGATA, pour la spectroscopie de rayons γ, ainsi qu'un mécanisme de "plunger" pour mesurer la durée de vie jusqu'à quelques ps par la méthode RDDS (Recoil Distance Doppler Shift). De plus, la cible était entourée de 24 détecteurs LaBr₃ (Bromure de lanthane) pour mesurer des durées de vie plus de 100 ps avec la méthode du "fast-timing". La combinaison de spectromètres sophistiqués utilisée dans cette expérience a permis de mesurer des durées de vie d'états nucléaires allant de 100 picosecondes à quelques picosecondes. Dans cette thèse, nous exposerons de nouveaux résultats pour les états à courte durée de vie dans les noyaux riches en neutrons A∼100, en mettant l'accent sur les chaînes des Zr, Mo et Ru. Nous discuterons des techniques expérimentales utilisées pour évaluer les durées de vie ainsi que l'interprétation de celles-ci à l'aide de modèles de structures nucléaires récents. / The shape of an atomic nucleus, ie. the deviation of its mass distribution from sphericity, is a fundamental property and governed by a delicate interplay of macroscopic and microscopic effects, such as the liquid-drop like binding energy and the nuclear shell structure, respectively. Studying nuclear shape properties using gamma ray spectroscopic methods allows detailed tests of different nuclear models, which were originally developed for stable nuclei. We proposed a project to study the evolution of nuclear shapes in exotic nuclei, far from the valley of stability, specifically in neutron-rich nuclei in the isotopic chains from Zr (Z=40) to Pd (Z=46). Usually, nuclear shapes are slowly evolving from spherical shapes around closed-shell or (doubly-) magic nuclei to elongated (prolate) shapes in nuclei with many valence nucleons. The nuclei of interest, however, show rapidly evolving patterns of excited states, which can be interpreted as rapid variations of the nuclear shape, including the rare observation of oblate (disk-like) and triaxial shapes. So far the known properties for these nuclei are (mainly) limited to excitation energies. Information on the nuclear collectivity, which can be deduced from the lifetime of the excited states, are sparse, while direct information of the shape is practically non existing. The simplest estimate of nuclear deformation in even-even nuclei can be obtained from the energy of the first 2⁺ state. For Sr (Z = 38) and Zr (Z = 40) isotopes this energy is observed to decrease dramatically at N = 60, while its evolution is much more gradual in Mo nuclei (Z = 42). Precise lifetime measurements provide a key ingredient in the systematic study of the evolution of nuclear deformation and the degree of collectivity in this region. Neutron-rich nuclei in the mass region of A = 100-120 were populated through the fusion-fission reaction of a ²³⁸U beam at 6.2 MeV/u on a ⁹Be target. The compound nucleus ²⁴⁷Cm was produced at an excitation energy of around 45 MeV before undergoing fission. The setup used for this study comprised the high-resolution mass spectrometer VAMOS in order to identify the nuclei in Z and A, the Advanced gamma ray Tracking Array AGATA of 35 germanium detectors to perform gamma ray spectroscopy, as well as a plunger mechanism to measure lifetimes down to a few ps using the Recoil Distance Doppler Shift method (RDDS). In addition, the target was surrounded by 24 Lanthanum Bromide (LaBr₃) detectors for a fast-timing measurement of lifetimes longer than 100 ps. The sophisticated set of spectrometers used in this experiment allowed measurement of nuclear lifetimes in a range from 100’s of picoseconds down to a few picoseconds. In this thesis, we will report on new lifetime results for short-lived states in neutron-rich (A ~ 100) nuclei, with an emphasis on the Zr, Mo and Ru chains. We will discuss the experimental techniques used to evaluate the lifetimes as well as their interpretation in terms of state-of-the-art nuclear structure models.

No description available.