The dissociation of hydrogen molecules at surfaces is the first step in the absorption process. If the absorbing material is covered by an oxide, this layer will determine the effective uptake rate of an underlying absorbing material. This effect is illustrated when determining the rate of transport of hydrogen through amorphous aluminium oxide layers. The transport rate was determined to be strongly thickness dependent. Hydrogen absorbed in a transition metal causes a volume expansion generated by a strain field around the absorbed hydrogen. This strain field causes a self-trapping of the hydrogen and a temperature dependent distribution in the atomic distances. The local strain field generated by the self-trapping process is found to be crucial for understanding both the hydrogen induced volume expansion as well as the diffusion of hydrogen. Ab-initio molecular dynamics simulations were used to reveal the temperature dependence of the unbinding of the hydrogen and the local strain field and its influence on the diffusion rate. The symmetry of the local strain field is also important for phase formation in metallic films and superlattices which are clamped to a substrate. As the thicknesses reduced from 50 to 10 nm thick vanadium films, substantial finite size effects become apparent in the phase diagrams. The volume change associated with the strain field cannot be accurately measured using x-ray diffraction because of its sensitivity to local arrangements of atoms. X-ray and neutron reflectivity were found to be more reliable probes of global effects of the sumof the local strainfields. Finite size effects in extremely thin V layers were also explored in metallic superlattices composed of iron and vanadium. The co-existence region, composed of a hydrogen gas and a solid-like phase, was found to be suppressed by at least 100 K to below 300 K. The hydrogen-hydrogen interaction can also be influenced by the electronic states in the non hydrogen absorbing layers, as demonstrated when comparing hydrogen absorption in Fe/V and Cr/V superlattices. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 728

Hydrogen embrittlement is a problem that offers challenges both to technology and to the theory of metallurgy. In the presence of a hydrogen rich environment, applications such as rolling bearings display a significant decrease in alloy strength and accelerated failure due to rolling contact fatigue. In spite of these problems being well recognised, there is little understanding as to which mechanisms are present in hydrogen induced bearing failure. The objective of this thesis are twofold. First, a novel alloy combining the excellent hardness of bearing steels, and resistance to hydrogen embrittlement, is proposed. Second, a new technique to identify the nature of hydrogen embrittlement in bearing steels is suggested. The new alloy was a successful result of computer aided alloy design; thermodynamic and kinetic modelling were employed to design a composition and heat treatment combining (1) fine cementite providing a strong and ductile microstructure, and (2) nano-sized vanadium carbide precipitates acting as hydrogen traps. A novel technique is proposed to visualise the migration of hydrogen to indentation-induced cracks. The observations employing this technique strongly suggest that hydrogen enhanced localised plasticity prevails in bearing steels. While proposing a hydrogen tolerant bearing steel grade, and a new technique to visualize hydrogen damage, this thesis is expected to aid in increasing the reliability of bearings operating in hydrogen rich environments.

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Une approche couplée prenant en compte l’interaction de la plasticité cristalline et de la diffusion d’hydrogène a été établie et utilisée pour étudier le transport de l’hydrogène dans les agrégats polycristallins synthétiques de l’acier 316L avec des géométries de grains and des orientations cristallographiques différentes. Les champs mécaniques calculés à l’aide du code ZeBuLoN sont transférés dans un code de diffusion développé dans le cadre de ce travail. Une nouvelle formulation associée à un nouveau schéma numérique permet un calcul qui présente une bonne convergence. Les résultats des simulations montrent la redistribution de l’hydrogène dans les polycristaux due à la présence des hétérogénéités des contraintes hydrostatiques à l’échelle intragranulaire. L’effet de la vitesse de déformation a été quantitativement obtenu. Afin d’enrichir l’approche continue, un intérêt particulier est porté sur le rôle des joints de grains. Des simulations numériques d’un modèle atomique plan par plan ont été développées et appliquées aux bicristaux et aux structures de type ”bambou”. Les effets de puits ou de barrière induits par la présence des joints de grains sont clairement démontrés dans le cas du nickel pur. Pour reproduire ces effets dans les simulations de diffusion avec le modèle continue, une approche originale de simulation”multi-échelles” de la diffusion au joint de grain a été développée, et un nouveau régime de diffusion au joint de grain a été modélisé. / In the present work, we establish a one-way coupled crystal plasticity – hydrogen diffusion analysis and use this approach to study the hydrogen transport in artificial polycrystalline aggregates of 316L steel with different grain geometries and crystallographic orientation. The data about stress/strain fields computed at the microstructure scaleutilizing the crystal plasticity concept are transferred to the in-house diffusion code which was developed using a new numerical scheme for solving parabolic equations. In the case of initial uniform hydrogen content, the heterogeneity of the mechanical fields is shownto induce a redistribution of hydrogen in the microstructure. The effect of strain rate is clearly revealed. In the second part, hydrogen transport across grain boundaries is investigatedconsidering the specific diffusivity and segregation properties of these interfaces. Using a discrete atomic layer model, the retarding impact of grain boundaries is demonstrated on bicrystals and bamboo type membranes with and without external mechanical loading. To reproduce the effects observed in the atomistic simulations into the crystal plasticity – hydrogen diffusion model, a new physically based multi-scale method is proposed. Using this new approach we study the effect of grain boundary trapping kinetics on hydrogen diffusion and reveal a new grain boundary diffusion regime which has notbeen reported before.

Carbon emissions are one of the primary drivers of climate change and the transport sector accounts for 24% of the global carbon emissions. A shift within the automobile industry towards more eco-friendly modes of transportation is hence needed. Vehicles powered by hydrogen are a carbon emissions-free mode of transportation and have been identified as a viable approach to de-carbonize the transport sector, yet, the number of hydrogen-powered vehicles on the roads in Sweden as of 2022 is relatively low compared to the rest of the world. The aim of this study was both to identify factors that are important for actors to invest in hydrogen technology within the transport sector, and to identify how the collaboration between different actors was formed during the adoption process. The study uses a multiple-case study research design where the five cases of Storuman, Mariestad, Sandviken, Trelleborg and Ljungby were selected. Data was collected through eleven semi-structured interviews over video calls. The study has examined the diffusion process of hydrogen technology within the transport sector of each case according to the diffusion of innovations theory. An analysis of the diffusion of hydrogen technology has not, to the best of my knowledge, been conducted in the examined cases. Gaining an understanding of these processes can provide guidance for other municipalities or actors who aims to reduce their emissions and can play an important role in achieving Sweden´s objective of becoming the world´s first fossil-free welfare nation. The findings of the study were that investments in hydrogen technology within the transport sector are currently not economically profitable. However, investments in the innovation were still motivated in terms of a relative environmental advantage, reception of financial funding, the will to take a leading role in the energy transition, geographical location, long-term economic benefits and indirect economic benefits which mainly include that the municipality can market themselves as green and progressive in order to attract competent workforce and business opportunities. The study also concluded that local political support is an important pre-condition for a successful adoption of the innovation.

Indiana University-Purdue University Indianapolis (IUPUI) / Based on plane wave DFT calculation, we carried out micro level investigation of hydrogen storage in nanoporous silicon (npSi). One quarter of a hexagonal pore with Palladium catalyst placed at the surface has been studied for hydrogen dissociation, spillover, bond hopping, and diffusion for both single catalyst atom and small catalyst cluster consisting of multiple catalyst atoms. All the DFT computations were done in one of the biggest research supercomputer facilities of the world, Big Red II. We opted ABINIT, an open source DFT tool for our computations. Our calculation revealed low dissociation, spillover, and bond hoping energy barrier. The energy required to be provided from external sources to fully recharge the storage medium from a gaseous source at a completely empty state has also been evaluated. Hydrogen diffusion along the inner surface of the pore as a means of bond hopping and the possibility of quantum tunneling, a low temperature phenomena used to spontaneously go over an otherwise less likely high energy barrier have been studied as well. Using these micro level parameter values evaluated from the DFT study, the performance of any potential hydrogen storage material can be compared to a set of characteristics sought in an efficient storage media. Thus, the micro scale feasibility of this novel npSi material based hydrogen storage technology was studied as a part of a STTR Phase I project.

PALEOFLUID CHEMISTRY OF OROGENIC GOLD DEPOSITS: NOVEL ANALYTICAL METHODS AND CASE STUDIES FROM THE BOHEMIAN MASSIF Tomáš Hrstka1 1 Charles University in Prague, Faculty of Science, Institute of Geochemistry, Mineralogy and Mineral Resources, Albertov 6, Praha 2, CZ-128 43 Abstract of the Ph.D. Thesis Fluid inclusions represent a unique tool for understanding the processes leading to the formation of mineral deposits and fluid-rock interactions in general. Orogenic gold deposits in the central part of the Bohemian Massif (Libčice and Kasejovice deposits) were studied in order to provide a better understanding of their genesis. A multifaceted approach was adopted including a broad spectrum of micro-analytical methods. While traditional methods were used as the basis of this study (e.g., microthermometry, SEM and optical microscopy), the application and improvement/development of modern analytical methods (e.g., LA-ICP- MS and Raman spectroscopy) or introduction of alternative innovative techniques (CLSM, Nano- tomography, QEMSCAN) constituted a significant part of this study. This study reveals the importance of the HCO3 - species in hydrothermal fluids (i.e., >100 řC to ~350 řC). Previously, the prevalence of Cl- and other anions was reported for hydrothermal paleofluids and the majority of studies suggested...

Une dégradation des propriétés mécaniques des arcs surperélastiques en alliages à mémoire de forme à base NiTi, utilisés dans les traitements orthodontiques, a été observée après absorption d'hydrogène. L’effet de l’hydrogène a été étudié, dans un premier temps, sur le comportement global des arcs à l’aide des essais de traction et dans un deuxième temps, sur le comportement local à l’aide des essais de nanoindentation. Pour modéliser le comportement des AMFs après absorption d'hydrogène, une première approche a été proposée, en introduisant la dépendance des paramètres de la transformation martensitique à la concentration moyenne d'hydrogène, observée dans les courbes contrainte-déformation obtenues, dans un modèle existant dédié aux AMFs. Une deuxième approche consiste à proposer un modèle thermomécanochimique couplé. Pour ce faire, un nouveau potentiel thermodynamique est défini en introduisant la déformation chimique due à la présence de l'hydrogène et l'interaction de ce dernier avec les variantes de martensite. Des forces thermodynamiques sont déduites de ce potentiel et équilibrées en faisant intervenir les phénomènes dissipatifs : mécanique, thermique et chimique. L'exploitation du modèle proposé a nécessité le développement d'un élément fini spécifique adoptant la concentration d'hydrogène comme un degré de liberté supplémentaire qui prend en compte le couplage complet et la formulation proposée de l'équilibre thermique et chimique / A degradation of the mechanical properties of NiTi-based shape memory alloys superelastic archs, used in orthodontic treatments, was observed after hydrogen absorption. The effect of hydrogen was first investigated on the global behaviour of archs using tensile tests and secondly on the local behaviour using nanoindentation tests. A first approach to model the behavior of AMFs after hydrogen absorption has been proposed, by introducing the dependence of martensitic transformation parameters on the average hydrogen concentration, observed in the stress-strain curves obtained, in an existing dedicated model to SMA. A second approach is to propose a coupled thermomechanical model. A new thermodynamic potential is defined by introducing the chemical strain due to the presence of hydrogen and the interaction of the latter with martensite variants. Thermodynamic forces are deduced from this potential and balanced by involving mechanical, thermal and chemical dissipative phenomena. The exploitation of the proposed model required the development of a special finite element adopting the hydrogen concentration as an additional degree of freedom that takes into account the thermomechanical coupling and the proposed formulation of the thermal and chemical equilibrium

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T21:32:45Z No. of bitstreams: 1 JOÃO PAULO DANTAS DE CARVALHO - DISSERTAÇÃO PPGEQ 2015..pdf: 1534561 bytes, checksum: 93959f6eca85fa51565d250b6a984284 (MD5) / Made available in DSpace on 2018-03-23T21:32:45Z (GMT). No. of bitstreams: 1 JOÃO PAULO DANTAS DE CARVALHO - DISSERTAÇÃO PPGEQ 2015..pdf: 1534561 bytes, checksum: 93959f6eca85fa51565d250b6a984284 (MD5) Previous issue date: 2015-11-11 / CNPq / Desde a sua descoberta, em 1864 por Cailletet, a fragilização de metais por hidrogênio, foi sujeito a inúmeras investigações, sendo primeiramente estudado com a injeção de hidrogênio gasoso em metais e ligas. Devanathan e Stachurski (1962) desenvolveram a técnica eletroquímica de permeação de hidrogênio em metais e ligas, tornando o estudo mais prático, esta metodologia se baseia em uma dupla célula eletroquímica dispostas simetricamente onde o metal a ser estudado é inserido entre elas. Uma delas conhecida como célula de carga irá gerar o H2 a ser permeado através do corpo de prova e na outra, conhecida como célula de detecção, o mesmo será oxidado e quantificado seu fluxo. Toda a detecção é realizada potenciostaticamente, mas a geração pode ser realizada por meio galvanostático (método galvanostático-potenciostático), potenciostacamente (método duplo-potenciostático) ou por permeação em circuito aberto em meio ácido, chamado de „PCAA‟. As normas ASTM 148-97 (2003) e ISO 17081 (2004) padronizam os experimentos de permeação eletroquímica de hidrogênio. Como os diferentes métodos são baseados em soluções de contorno diferenciados para solução da segunda lei de Fick, tais normas não levam isto em consideração adotando o cálculo da difusividade do hidrogênio apenas pelo método duplo potenciostático, mesmo para aqueles que estudam o fenômeno, diga-se de passagem, em sua grande maioria, utilizando a metodologia galvanostático-potenciostático. Autores como McBreen et al (1966) e Boes & Zuchner (1972) descrevem o fenômeno de permeação de hidrogênio em metais de forma matemática, a partir da solução da segunda de lei de Fick, estes trabalhos atestam a diferença entre os métodos duplo-potenciostatico e galvanostático-potenciostático, porém nunca foi proposto um modelo que descreva o comportamento do método PCAA. Com isso, o trabalho tem como objetivo elucidar o emprego dos modelos matemáticos para determinação do coeficiente de difusão do hidrogênio em metais através das distintas técnicas eletroquímicas de permeação, utilizando os aços API 5L X70 e X65, além disto procurou-se um modelo matemático para o caso em que a geração de hidrogênio seja realizada pelo método PCAA. Neste trabalho atesta-se que que o uso das equações proposta pela norma, a princípio, subestimam o valor da difusividade. A equação proposta para o método PCAA, apresentou um perfeito ajuste de dados experimentais de permeação. A correlação proposta para o cálculo da difusividade mostrou-se coerente para estimar este parâmetro, não só para o caso PCAA, como também para todos os casos. / Since its discovery in 1864 by Cailletet, hydrogen embrittlement of metals, was subjected to numerous investigations, first being studied with the injection of gaseous hydrogen in metals and alloys. Devanathan and Stachurski (1962) developed the electrochemical technique of hydrogen permeation in metals and alloys, making it the study more practical this methodology is based on a dual symmetrically arranged electrochemical cell where the metal to be studied is inserted between them. One known as load cell will generate H2 to be permeated through the specimen and the other, known as the detection cell, it will be oxidized and its flow quantified. All detection is performed potentiostaticly, but the generation can be performed by galvanostatic (galvanostaticpotentiostatic method), potentiostaticly (double- potentiostatic method), or by hydrogen permeation on acid environment method known as a PCAA. The regulations ASTM 148-97 (2003) and ISO 17081 (2004) standardize the electrochemical hydrogen permeation experiments. How different methods are based on different workarounds for solution of the second Fick's law, such rules do not take this into account by adopting the calculation of the hydrogen diffusivity only by the dual voltage method, even for those who study the phenomenon, say passing for the most part, using the galvanostatic-potentiostatic methodology. Authors such as McBreen et al (1966) and Boes & Züchner (1972) describe the hydrogen permeation phenomenon in mathematical form of metal from the solution of the second Fick law, these works attest to the difference between the double-potentiostatic methods and galvanostatic-potentiostatic, but has never proposed a model that describes the behavior of the PCAA method. Thus, the study aims to elucidate the use of mathematical models to determine the hydrogen diffusion coefficient in metals through the different electrochemical techniques permeation using the API 5L steels X70 and X65, in addition sought a mathematical model for the case where the hydrogen generation is performed by the PCAA method. This work testifies that the use of the equations proposed by the standard at first underestimate the value of diffusivity. The equation proposed for the PCAA method, presented a perfect fit experimental permeation data. The proposed correlations for calculating the diffusivity was found to be consistent to estimate this parameter not only to the case PCAA, but also for all cases.