La mobilité de l’hydrogène dans les métaux est un paramètre clef pour la compréhension des mécanismes de base de la fragilisation par l’hydrogène (FPH). Cette problématique est directement associée aux mécanismes de diffusion et de piégeage de l’hydrogène au sein d’un réseau cristallin. Ces derniers dépendent des diverses hétérogénéités microstructurales et en particulier des défauts cristallins présents au sein du matériau. Dans le cadre de nos travaux nous nous sommes restreints à étudier la diffusion et le piégeage de l’hydrogène au sein de deux systèmes élémentaires : des monocristaux et des bi-cristaux de nickel. Nous avons développé une méthodologie associant des outils expérimentaux (Perméation électrochimique/TDS, METHR, EBSD) et numériques (FEM-COMSOL/EAM-LAMMPS). Les résultats obtenus sur monocristaux montrent une dépendance du coefficient de diffusion de l’hydrogène avec l’orientation cristallographique et la teneur en hydrogène. L’analyse thermodynamique du système nickel-hydrogène-lacune démontre une dépendance du potentiel chimique de l’hydrogène à l’état de contrainte induit par la formation d’amas de lacunes associés à la présence de l’hydrogène. Le caractère anisotrope de la diffusion est alors expliqué par l’anisotropie des propriétés d’élasticité du réseau cristallin et la présence de ces amas. D’autre part nous avons caractérisé les processus de diffusion et de piégeage de l’hydrogène pour des bi-cristaux de nickel présentant différents volumes libres. L’énergie de ségrégation de l’hydrogène dépend de la nature du site (volume libre local et énergie mécanique associée à l’incorporation du soluté). La diffusion de l’hydrogène est influencée directement par la nature de joint de grain (excès de volume et distribution des sites). Nos résultats, à l’échelle atomique, montrent une corrélation entre la solubilité et le volume libre du joint de grain. Les joints de grains avec un volume libre important présentent des chemins de diffusion plus favorables pour l'hydrogène que dans le réseau cristallin et dans le même temps un nombre plus important de sites de ségrégation. / The mobility of hydrogen in metals is a key parameter for understanding the basic mechanisms of hydrogen embrittlement (HE). This problem is directly related to the mechanisms of diffusion and trapping of hydrogen within a crystal lattice. These mechanisms depend on the various microstructural heterogeneities and in particular the crystalline defects. In our work, we have focused on the diffusion and trapping of hydrogen in two elementary systems: nickel single crystals and bi-crystals. We developed a methodology combining experimental tools (electrochemical permeation / TDS, HRTEM, EBSD) and numerical methods (FEM-COMSOL / EAM-LAMMPS). The results obtained on the single crystals show a dependence of the diffusion coefficient of hydrogen with the crystallographic orientation and the hydrogen content. The thermodynamic analysis of the nickel-hydrogen-vacancy system shows a dependence of the chemical potential of hydrogen with the stress state induced by the formation of clusters of vacancies associated with the presence of hydrogen. The anisotropic character of the diffusion is then explained by the anisotropy of the elastic properties of the crystal lattice and the presence of these clusters. Moreover, we have characterized the processes of diffusion and trapping of hydrogen for nickel bi-crystals with different free volumes. The segregation energy of hydrogen depends on the nature of the site (the local free volume and the mechanical energy associated with the incorporation of solute). The diffusion of hydrogen is directly influenced by the nature of the grain boundary (the free volume and the distribution of the segregation sites). Our results, at the atomic scale, show a correlation between the solubility and the free volume of the grain boundary. The grain boundaries with a higher free volume have more favorable diffusion paths for hydrogen than in the crystal lattice and at the same time more segregation sites.

In many technological applications of structured metallic alloys, hydrogen embrittlement (HE) is a major concern as it can penetrate in most metals, degrade their properties and lead to premature failures. Despite numerous efforts in the past decades during which many microscopic mechanisms were proposed, a clear understanding of H embrittlement mechanisms has not been achieved yet. Since HE processes occur on an atomic-scale, the exact mechanisms leading to HE are not easily identified experimentally. One possible improvement would be to use atomic-scale simulations to try to capture details of deformation and fracture processes at the atomic level, enabling the investigation of relevant microscopic mechanism. In such context, the goal of this PhD work is to understand and quantify H interactions with defects like vacancies, dislocations and cracks in fcc metals through multi-scale modeling. The study is organized in four main parts. In the first part, we employed first principle calculations (based on density functional theory) to describe H interaction with a vacancy in Nickel. More specifically, the segregation energies of multiple H atoms in a single and di-vacancies were computed. Two characteristic energies were found which clarify the experimental peaks observed in Thermal Desorption Spectra in the literature. The equilibrium concentrations of H-vacancy clusters was then evaluated, under conditions relevant to HE and stress corrosion cracking (SCC) of Ni based alloys (nuclear industry),by Monte Carlo simulations and a thermodynamic model developed from our DFT data. In the second part, we quantified the trapping effect of vacancies on H diffusion in Nickel. With DFT computed jump barriers, related to H trapping and detrapping in vacancies, we employed accelerated Kinetic Monte Carlo (KMC) simulations to evaluate the H diffusion coefficient as a function of vacancy concentration and temperature. In the third part, we studied the diffusion of H-vacancy clusters in Ni, based on the combination of DFT and a statistical method. DFT calculations of vacancy jump barriers were performed for clusters containing from one to six H inside the vacancy. With these computed barriers and previous calculated concentrations of H-vacancy clusters, a simple stochastic model similar to the KMC procedure was developed to estimate the diffusion coefficient of H-vacancy clusters as a function of H concentration and temperature. In the last part, we studied the interaction of hydrogen with a blunted crack tip in Aluminum by combined EAM (semi-empirical interatomic potential) and DFT calculations. Embedded atom method (EAM) potential simulations were performed to evaluate the H effect on dislocation emission from a blunted crack tip under mixed mode loading. This phenomenon can be understood by the H induced change of the unstable stacking fault energy (γus ) in Rice’s model. Therefore, DFT and EAM calculations of γus were performed including the effects of H and of the mixed mode loads. It is shown that the effect of the load perpendicular to the glide plane is very strong, contrary to the effect of sub-surface H, which is negligible

Neste trabalho se realiza a síntese e caracterização de nanofios de óxido de zinco. Adicionalmente se apresenta o processo de montagem de um dispositivo para medidas elétricas deste material. Estuda-se complementarmente o efeito do tratamento de plasma sobre as propriedades de fotoluminescência do material. Nanofios foram sintetizados pelo mecanismo vapor-líquido-sólido (VLS), utilizando ouro como catalizador e safira c-plane como substrato. As amostras foram caracterizadas utilizando microscopia eletrônica de varredura, fotoluminescência a temperatura ambiente, difração de raios X, e microscopia eletrônica de transmissão. Os nanofios obtidos têm seção transversal com formato quase hexagonal, e larguras de aproximadamente 46 nm. O comprimento deles varia de 3 a 10 μm. Os resultados de difração de raios x e microscopia eletrônica de transmissão mostram que eles são monocristalinos com rede cristalina tipo wurtzita, e com direção de crescimento no eixo c. Foram estudados os efeitos da potência de plasma de oxigênio (O2) na fotoluminescência dos nanofios a temperatura ambiente. A diferença na fotoluminescência após diferentes tratamentos de plasma de O2 mostra que a razão entre a emissão da região do band gap e da banda do visível pode ser modificada pelo tratamento. Este efeito corrobora com a hipótese de que a banda verde de luminescência está relacionada às vacâncias de zinco. A variação percentual da razão entre as duas regiões apresenta uma dependência linear com a potência do plasma. / In this work, we performed the synthesis and characterization of zinc oxide nanowires. We also report an assembly process to measure the electrical properties of this material. We study the plasma treatment effect on the photoluminescence spectra of the nanowires. Nanowires were synthesized via vapor-liquid-solid mechanism, using gold as catalyst and c-plane sapphire as substrate. The samples were characterized using scanning electron microscopy, room temperature photoluminescence, x-rays diffraction and transmission electron microscopy. Our nanowires show a quasi-hexagonal cross section, with diameters of approximately 46 nm. Their lengths ranged from 3 to 10 μm. Our results show monocrystalline wurtzite crystal nanowires with c growth direction. We also study the plasma power effect of oxygen (O2) plasma treatment on the room temperature photoluminescence spectra of the nanowires. Our results show that the deep level emission to near band emission ratio decreases with the plasma treatment. This effect supports the hypothesis that claims the green band luminescence is related to the oxygen vacancies. Furthermore, the relative ratio change depends linearly on the plasma power.

Neste trabalho se realiza a síntese e caracterização de nanofios de óxido de zinco. Adicionalmente se apresenta o processo de montagem de um dispositivo para medidas elétricas deste material. Estuda-se complementarmente o efeito do tratamento de plasma sobre as propriedades de fotoluminescência do material. Nanofios foram sintetizados pelo mecanismo vapor-líquido-sólido (VLS), utilizando ouro como catalizador e safira c-plane como substrato. As amostras foram caracterizadas utilizando microscopia eletrônica de varredura, fotoluminescência a temperatura ambiente, difração de raios X, e microscopia eletrônica de transmissão. Os nanofios obtidos têm seção transversal com formato quase hexagonal, e larguras de aproximadamente 46 nm. O comprimento deles varia de 3 a 10 μm. Os resultados de difração de raios x e microscopia eletrônica de transmissão mostram que eles são monocristalinos com rede cristalina tipo wurtzita, e com direção de crescimento no eixo c. Foram estudados os efeitos da potência de plasma de oxigênio (O2) na fotoluminescência dos nanofios a temperatura ambiente. A diferença na fotoluminescência após diferentes tratamentos de plasma de O2 mostra que a razão entre a emissão da região do band gap e da banda do visível pode ser modificada pelo tratamento. Este efeito corrobora com a hipótese de que a banda verde de luminescência está relacionada às vacâncias de zinco. A variação percentual da razão entre as duas regiões apresenta uma dependência linear com a potência do plasma. / In this work, we performed the synthesis and characterization of zinc oxide nanowires. We also report an assembly process to measure the electrical properties of this material. We study the plasma treatment effect on the photoluminescence spectra of the nanowires. Nanowires were synthesized via vapor-liquid-solid mechanism, using gold as catalyst and c-plane sapphire as substrate. The samples were characterized using scanning electron microscopy, room temperature photoluminescence, x-rays diffraction and transmission electron microscopy. Our nanowires show a quasi-hexagonal cross section, with diameters of approximately 46 nm. Their lengths ranged from 3 to 10 μm. Our results show monocrystalline wurtzite crystal nanowires with c growth direction. We also study the plasma power effect of oxygen (O2) plasma treatment on the room temperature photoluminescence spectra of the nanowires. Our results show that the deep level emission to near band emission ratio decreases with the plasma treatment. This effect supports the hypothesis that claims the green band luminescence is related to the oxygen vacancies. Furthermore, the relative ratio change depends linearly on the plasma power.

O principal objetivo dessa dissertação de mestrado é o estudo das propriedades estruturais e eletrônicas de umdosmateriaismais promissores para a nanoeletrônica, os nanotubos de carbono, na presença de defeitos do tipo vacâncias. Os defeitos estudados neste trabalho são as monovacâncias e multivacâncias em nanotubos de carbono armchair (5, 5). Para isso, realizamos cálculos quânticos de primeiros princípios baseados na teoria do funcional da densidade. Primeiramente, foi realizado um estudo sistemático das monovacâncias variando a sua concentração, para que possamos entender qual é a influência da distância entre esses defeitos no sistema. A partir de 14.784Å o efeito do potencial inserido pela vacância praticamente é desprezível. Seguindo essa sistemática, observamos também que a partir de 19.712Å a interação elástica entre defeitos é desprezível. Em todas as estruturas de bandas ocorre o surgimento de bandas de impureza, caracterizadas por uma localização de carga no defeito, principalmente no \"dangling bond\". Utilizando o procedimento NEB (nudge elastic band) obtivemos um valor de 0.55eV para a barreira de migração da vacância. Esse valor fornece um tempo aproximado de 0.156ms a 300K, para que a vacância salte de um sítio para outro na rede do nanotubo. Tendo isso, determinamos que a monovacância é um defeito que apresenta uma grande mobilidade no sistema, o que pode eventualmente ocorrer de uma encontrar-se com outras, formando sistemas maiores, como clusters de monovacâncias ou multivacâncias. Seguindo o nosso objetivo, realizamos um estudo sistemático das multivacâncias. Determinamos todas as reconstruções desses defeitos, nas quais observamos que as multivacâncias de índice par, apresentavam somente pentágonos e uma região central, e em contrapartida as de índice ímpar apresentavam pentágonos, uma região central e um dangling bond na sua estrutura final. Definidas as estruturas e as energias das multivacâncias, calculamos suas propriedades eletrônicas, onde é notório que a influência desses defeitos é muito mais drástica que as monovacâncias, devido a sua grande extensão no sistema. Realizamos cálculos de transporte eletrônico para todos os sistemas, utilizando o método de funções de Green fora do equilíbrio (NEGF-DFT), desenvolvido no nosso grupo. A partir desses cálculos, observamos que todos os defeitos modificam a estrutura eletrônica do sistema, uns mais outros menos, mas até para as multivacâncias maiores como a hexavacância, o sistema mantém o seu caráter metálico. Através das técnicas de funções de Green, mostramos que quando estamos utilizando condições periódicas de contorno há uma surgimento de minigap\'s espúrios. Estes não aparecem quando o vínculo de simetria translacional é quebrado via técnicas de funções de Green. / The main purpose of this dissertation is the study of the electronic and structural properties in the presence of different types of vacancies, in one of the most promising materials for nanoelectronics, carbon nanotubes. The defects studied in this work are monovacancy and multivacancies in (5, 5) armchair carbon nanotubes. For that purpose perform quantum ab initio calculations based on density functional theory (DFT). Firstly, was made a systematic study of monovacancies varying its concentration, so we can understand what is the influence of the distance between these defects in the system. Undergoes reconstruction pentagon nonagon from14.784Å on words the effect of the potential created by the vacancy is practically negligible. Following this systematic approach, we also found that from 19.712Å the structural interaction between the defects tends to zero. In all band structures one observes impurity bands, characterized by charge localization in the defect, mainly in the dangling bond. Using the NEB (nudge elastic band) procedure we obtained a value of 0.55eV for the migration barrier of the monovacancy. This value provides an approximate time of 0.156ms at 300K for the vacancy to jump from one site to another on the nanotube network. Hence, we determined that the monovacancy presents a great mobility in the system, which may possibly inccur in two ore more vacancies merging with others to form a larger defect, such as clusters of monovacancies or a hole multivacancy. Following our goal, we conducted a systematic study of multivacancies. We determined all reconstructions of these defects. We observed that multivacancies with and even number of carbon atoms removed had only pentagons and a central region. In contrast the CNT with and odd numbers of carbon atoms removed have pentagons, a central region and a dangling bond in its final structure. Once we have defined the structures and the energies of the multivacancies, we calculated their electronic properties. It is clear that the influence of these defects is much more drastic than the monovacancy, due to the size of the defect in the system. We calculated the electronic transport for all systems, using a non-equilibrium Green\'s functions method (NEGF-DFT), developed in our group. From these calculations, we observed that all the defects alter the electronic structure of the system, but even for the largest multivacancy, the system maintains its metallic character. Using the Green\'s functions techniques, we show that the use of periodic boundary conditions leads to the emergence of spurious mini-gap\'s. These do not appear when the translational symmetry is broken using Green\'s function approach and a true open system is considered.

Magister Legum - LLM / This research paper examines the different forms of employment patterns that have emerged as a result of globalisation as well as the mechanisms that have been used by the legislator to accommodate those in non-standard employment relationships. / South Africa

Les travaux présentés dans cette thèse relèvent principalement de la réactivité des surfaces et des interactions gaz-surface. Les champs d'application de ce travail sont variés et s'inscrivent principalement dans le domaine de la fusion nucléaire et du projet ITER.Dans ce cadre, la modélisation à l'échelle atomique est un outil important pour comprendre et interpréter les résultats expérimentaux. Notre domaine de compétences est celui du calcul de structures électroniques et des propriétés chimiques. Ces calculs sont principalement conduits dans le cadre de la Théorie de la Fonctionnelle de la Densité (DFT) et de la thermodynamique statistique.Bien que composé de six chapitres, ce manuscrit comporte trois parties principales. La première est dédiée à la présentation des méthodes de calculs utilisées tout au long de cette thèse. La deuxième partie est consacrée à l'étude de la formation du carbure de béryllium à partir d'un dépôt de béryllium sur une surface de graphite. Le degré de fiabilité des résultats DFT a été évalué et les principales étapes de la formation de carbure de béryllium ont été déterminées. La troisième partie développée sur deux chapitres est consacrée à l'étude de l'interaction entre l'hydrogène et le tungstène métallique. La dissolution, la diffusion ainsi que le piégeage de l'hydrogène dans le tungstène ont été étudiés. Un excellent accord a été obtenu entre les valeurs calculées et les résultats expérimentaux de référence. / The work herein presented deals with the reactivity of surfaces and the gas–surface interaction. This work is connected to different fields of applied science and more specifically to the field of nuclear materials for fusion devices like the International Thermonuclear Experimental Reactor (ITER).Numerical simulations at the atomic scale can provide an in depth understanding of the mechanisms at the origin of experimental observations. More specifically, our skills are about electronic structure calculations and chemical properties modelling; most of the work we produced has been conducted within the framework of the Density Functional Theory (DFT) and statistical thermodynamics. While made of six chapters, the manuscript can be cast in three main parts. The first one is dedicated to the methods used throughout this thesis. The second is devoted to the formation of beryllium carbide from deposited beryllium atoms on graphite surfaces; the reliability of the DFT results was benchmarked and the main steps of the beryllium carbide formation were determined. The third part explores the interaction between hydrogen and metallic tungsten. The formation of vacancies in the material, its impact on the solubility and diffusion of hydrogen in tungsten were investigated, and the results were compared with experiment; an excellent agreement was found.

Svensk fastighetsmarknad blomstrar med anledning av rekordlåga räntor, bostadsbrist och näst intill inga vakanser. De låga räntorna har lett till att fler tar sig an fastighetsmarknaden, samtidigt som den nämnda bostadsbristen kan tänkas öka incitamenten att investera i fastigheter. Riskerna för fastigheter bör vara snarlika oavsett läge om med beaktande av att belåning är billigt, bostadsbristen hög och vakanserna närapå obefintliga. Det är därför befogat att ställa frågan hur det kommer sig att fastighetsföretag har olika direktavkastningskrav på fastigheter belägna i olika lägen? Studiens syfte är att få förståelse för hur fastighetsägare tänker när de sätter sina avkastningskrav och försöka förklara vad det finns för motiv till att de uppställer skilda avkastningskrav beroende på var fastigheterna är belägna. Vi undersöker också hur fastighetsbolagen hanterar de risker som finns kopplade till fastighetsmarknaden. En kvantitativ enkät har besvarats av 31 fastighetsbolag som arbetar med hyreslägenheter runt om i Sveriges tre största städer, Stockholm, Malmö och Göteborg. Enkäten ska ha besvarats av företagets analytiker och/eller av de investeringsansvariga på företagen. Enkätsvaren gav en inblick i fastighetsföretagens bestånd, deras avkastningskrav, vakanser, omflyttningar, standardrisk och i vilket läge de anser att risken är störst att äga fastigheter. Arbetet har inte har inte tagit hänsyn till skillnader i företagens storlek utan enbart deras verksamhetsområde det vill säga hyresbostäder. Studiens resultat bekräftar att fastighetsföretagen har väldigt låga vakanser i sitt bestånd oberoende av fastigheternas läge. Vår regressionsmodell förklarar 54,7% av direktavkastningskraven och för att signifikant kunna säkerställa vad som är bakgrunden till fastighetsbolagens direktavkastningskrav och riskbedömning krävs fler observationer och fler förklarande variabler. / Abstract Title: Can difference in yield be justified? Subject, Course: Real Estate Science, Bachelor Thesis 15 creditsAuthors: Hjalmar Åhman and Sebastian PeterssonAdvisor: Peter KarpestamKeywords: Risk, yield, vacancies, default risk, real estate housingSwedish real estate market is booming due to low interest rates, housing shortages and almost no vacancies. The low interest rates have made it more interesting to invest in real estate, while the mentioned housing shortage may conceivably increase the incentive to invest in real estate. The risks for real estate should be similar regardless of the situation if one looks at the above, where the borrowing is cheap, the housing shortage is high and the vacancies close to non-existing. It is therefore a fair question to ask why real estate companies have different direct yield requirements for housing properties in different locations?The purpose of the study is to gain an insight into how property owners think when they set their requirements for returns and understand why the yield requirements are different in different locations. In connection therewith, we will also study how the property companies handle the risks associated with the real estate market.A quantitative questionnaire has been answered by 31 real estate companies that manage rental apartments around Sweden's three largest cities, Stockholm, Malmö and Gothenburg. The survey was addressed to the company's analysts or investment managers. The questionnaire responses gave an insight into the companies' portfolios, their yield requirements, vacancies, relocations, standard risk and in what position they believe the risk is greatest to own real estate.The study's results confirm that the real estate companies have very low vacancies in their stock regardless of their location. Our regression model explains 54.7% of the direct yield requirements and in order to have substantially certain of the background to the property companies' direct yield requirements and risk assessment, more observations and more explanatory variables may be required.

Title: Investigation of vacancies in Fe-Al alloys Author: RNDr. František Lukáč Department: Department of Low Temperature Physics Supervisor: doc. Mgr. Jakub Čížek, Ph.D., Department of Low Temperature Physics, Faculty of Mathematics and Physics Abstract: Fe-Al alloys exhibit relatively high vacancy concentrations, which significantly influence the mechanical properties of these alloys. Positron annihi- lation spectroscopy was employed for investigations of vacancies in this work and the vacancy concentrations in Fe-Al alloys were determined by positron lifetime spectroscopy and measurements of positron diffusion length of implanted mono- genergetic positrons. The correlation of hardness with the vacancy concentration was characterized by determination of the vacancy hardening coefficient in Fe- Al alloys. The thermal evolutions of hardness and the vacancy concentration were compared during the annealing of the Fe-Al alloys with various composi- tions. Coincidence Doppler broadening of annihilation peak was employed for determination of the chemical composition of quenched-in vacancies in Fe-Al al- loys. Increased concentration of Al atoms in surrounding vacancies in Fe-Al alloys was related to the attractive interaction between the Al atoms and the vacancy. Quantum mechanical ab initio calculations were...

Catalysts based on cerium oxide are ubiquitous in industrial-scale chemical conversion. Here, a thorough study of their fundamental properties is undertaken via a model system ap- proach with the goal of furthering rational design in heterogeneous catalysis. A focus is put on understanding the behavior of oxygen vacancies in cerium oxide with respect to atomic co-ordination and electronic structure perturbations. Utilizing state-of-the-art probing tech- niques, a scalable model system framework is developed that allows for control over both the oxygen vacancy concentration and local co-ordination. High precision of the innova- tive approach facilitated observation of new phases of substoichiometric cerium oxide and lead to a first-of-a-kind investigation of the electronic structure of cerium oxide throughout isostructural transition from CeO2 to Ce2O3. The acquired results advance fundamental understanding of essential properties of cerium oxide that are relevant to its utilization in heterogeneous catalysis and open new pathways for functionalization of cerium oxide-based materials. Furthermore, the methodology developed in the thesis is transferable to other important reducible oxides. 1