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.

The thesis describes effect of long-time ageing on the microstructure and properties of the Eurofer´97 steel. The ferritic-martensitic reduced activation steel Eurofer´97 is candidate structural material for in-core components of proposed fusion reactors. Thesis is focused on examination and description of brittle-fracture behaviour of the steel. Properties of the steel were investigated in as-received state and state after long-time ageing. Detailed microstructure studies were carried out by means of optical and electron microscopy and also by means of quantitative electron microscopy. Mechanical properties were evaluated also in both states by means of hardness tetsing, tensile testing and Charpy impact testing. Fractography analysis of fracture surfaces was carried out on samples after Charpy impact testing.

Orientador: Roberto Zenhei Nakazato / Resumo: O hidrogênio ocasiona a fragilização que é um fenômeno observado em alguns tipos de metais, principalmente o aço, quando expostos a ambientes com presença do sulfeto de hidrogênio (H2S). A difusão dos átomos de hidrogênio no aço se dá através da interação hidrogênio-metal, onde devido ao seu pequeno tamanho atômico esse pode ser difundido para o interior do aço, resultando na fragilização e redução das suas propriedades mecânicas. A susceptibilidade dos aços à fragilização por hidrogênio depende principalmente de fatores ambientais do meio como a temperatura, pressão parcial de H2S e pH do ambiente, além de fatores metalúrgicos como a microestrutura e propriedades mecânicas. O objetivo deste trabalho foi estudar as propriedades mecânicas, químicas e microestruturais dos aços API 5L X70MS (sour service) e API 5L X70MO (aço off-shore utilizado como comparativo para o API 5L X70MS), utilizados na fabricação de tubos para a indústria de petróleo e gás, bem como avaliar susceptibilidade à fragilização por hidrogênio desses materiais quando expostos à diferentes ambientes contendo H2S. A avaliação das propriedades mecânicas do material foi feita com base nos resultados de ensaio de tração, dureza e impacto. A microestrutura foi avaliada por meio de microscopia óptica e a análise das inclusões (MnS) feita por microscopia eletrônica de varredura. A composição química dos aços foi determinada por espectrometria e análise gasométrica. Para avaliação da susceptibilidade dos aços ao proc... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

Gegenstand des Vorhabens im Rahmen der WTZ mit Russland ist die Versprödung des Reaktordruckbehälters infolge der Strahlenbelastung mit schnellen Neutronen im kernnahen Bereich. Um den Einfluss von bestrahlungsinduzierten Gitterdefekten auf die mechanischen Eigenschaften zu ermitteln, wurden analytische Berechnungen zum Einfluss von Hindernissen auf die Beweglichkeit von Versetzungen und damit auf die Ausbildung einer plastischen Zone an der Rissspitze durchgeführt. Es wird demonstriert, dass sich die an der Rissspitze entstehenden Versetzungen an dem Hindernis (bestrahlungsinduzierte Punktdefekte) aufstauen. In Abhängigkeit der Rissbelastung KI und der Entfernung des Hindernisses von der Rissspitze werden die Versetzungsdichte und das durch den Versetzungsstau verursachte Spannungsfeld berechnet. Mit Hilfe von Experimenten zur Neutronenkleinwinkelstreuung (SANS - small angle neutron scattering) an verschiedenen WWER-Stählen und Modelllegierungen wurden Größenverteilungen und die Volumenanteile der strahleninduzierten Defekte für verschiedene Bestrahlungszustände (Fluenzen, Bestrahlungstemperaturen) ermittelt. Es wurde gezeigt, dass sich die strahleninduzierte Werkstoffschädigung durch Wärmebehandlung weitgehend wieder ausheilen lässt. Nach der thermischen Ausheilung ist der Werkstoff bei erneuter Bestrahlung weniger anfällig für strahleninduzierte Defekte. Die Ergebnisse der SANS-Untersuchungen wurden mit der Änderung der mechanischen Eigenschaften (Härte, Streckgrenze und Sprödbruchübergangstemperatur) korreliert. Mit der kinetischen Gitter-Monte-Carlo-Methode wurden numerische Sensitivitätsstudien zum Einfluss des Cu-Gehalts auf die Stabilität von Defekt-Clustern durchgeführt. Die Berechnungen zeigen, dass die Anwesenheit von Cu-Atomen zur Bildung von langlebigen Defekten führt. Dabei werden Leerstellen in Cu/Leerstellen-Cluster eingefangen. Leerstellen in reinem Eisen sind bei Bestrahlungstemperaturen von 270 °C dagegen nicht stabil, die Lebensdauer liegt zwischen 0.01 s und 1 s. Die kritische Cu-Konzentration, ab welcher stabile Defekte entstehen, beträgt ca. 0.1 Masseprozent.

Water Stuff & Sun are developing a hydrogen battery based on a technology called SFEER’s. The SFEER’s are spherical high-pressure gas storage containers that are the size of a tennis ball. They consist of a carbon fiber-shell that is lined on the inside with a polymer called PA6. The aim of this literature review is to present suitable materials that can be utilized as a coating on the PA6 liner in the SFEER’s to minimize the hydrogen permeability. The metallic coatings that were investigated are compounds based on chromium, boron, alu- minum and titanium. The non-metallic coatings that were investigated are lamellar inorganic components (LIC) in combination with PA6 and modified graphene oxide (GO). The coating methods that were investigated are some different PVD and CVD methods (sputter deposition, plasma enhanced CVD, ALD), electrodeposition and cold spray. The lowest permeability out of all the coatings was observed for alumina, Al2O3. Titanium nitride, TiN, was also found to have very low permeability. Since these two coatings had the lowest permeabilities they were further compared considering other factors. This resulted in alumina being chosen as the final recommendation for coating the SFEER’s. A comparison was also made to find the most suitable coating method for alumina. Cold spray was found to be very promising but if it can not be used the PVD and CVD methods are other potential candidates.

In this work, Slow Strain Rate Test (SSRT) testing, Light Optical Microscopy (LOM) and Scanning Electron Microscopy (SEM) were used to study the effect of microstructure, corrosive environments and cathodic polarisation on stress corrosion cracking (SCC) of two grades of high strength steels, Type A and Type B. Type A is manufactured by quench and tempered (Q&T) method. Type B, a normalize steel was used as reference. This study also supports electrochemical polarisation resistance method as an effective testing technique for measuring the uniform corrosion rate. SSRT samples were chosen from base metal, weld metal and Heat Affected Zone (HAZ). SSRT tests were performed at room temperature under Open Circuit Potential (OCP) and cathodic polarisation using 4 mA/cm2 in 1 wt% and 3.5 wt% NaCl solutions. From the obtained corrosion rate measurements performed in 1 wt% and 3.5 wt% NaCl solutions it was observed that increased chloride concentration and dissolved oxygen content enhanced the uniform corrosion for all tested materials. Moreover, the obtained results from SSRT tests demonstrate that both Q&T and normalized steels were not susceptible to SCC in certain strain rate (1×10-6 s-1) in 1 wt% and 3.5 wt% NaCl solutions under OCP condition. It was confirmed by a ductile fracture mode and high reduction in area. The weld metal of Type A with acicular ferrite (AF), pro-eutectoid (PF) and bainite microstructure showed higher susceptibility to hydrogen assisted stress corrosion cracking compared to base metal and HAZ. In addition, typical brittle intergranular cracking with small reduction in area was observed on the fracture surface of the Type A due to hydrogen charging.

High hardness steels can be affected by delayed brittle cracking often attributed to hydrogen embrittlement. Improved resistance to hydrogen embrittlement would be beneficial to many industries including military, automotive, and high-rise construction. While other prevention methods include coating, trapping, and barriers, design efforts in this study were focused on improving intrinsic properties to be more resistant to hydrogen embrittlement. Four alloys targeting 477 – 534 HB were designed and produced in-house and compared against a commercial grade 500 HB alloy. Charpy V-notch (CVN) impact toughness and tensile specimens were made according to ASTM E23 and ASTM E8 to characterize mechanical properties. Hydrogen embrittlement testing was performed using ASTM E8 test samples electro-chemically charged in either sodium hydroxide or sulfuric acid with thiourea in solution. Results suggested that alloying for lower strength and better toughness by reducing C and Mn results in lower hydrogen embrittlement susceptibility.

No description available.

The effects of hydrogen on the fracture behavior of manual SMA welds in carbon steel plate was investigated utilizing modified ½T compact tension specimens. Tests performed on these specimens in the presence of hydrogen were compared to similar tests in helium. These tests showed that hydrogen lowers J_C in both the heat affected zone and the base metal. In 350 psi helium, the experimental value of J_C in the heat affected zone (2826 in.-lbs./in.²) was greater than that obtained in the base metal (1650 in.-lbs./in.²). The tests conducted in 350 psi hydrogen resulted in a reduction in J_C for both the heat affected zone (1425 in.-lbs./in.²) and the base metal (59 in.-lbs./in.²). Furthermore, when compared to specimens tested in helium, it was determined that the material tearing modulus for specimens tested in hydrogen was significantly reduced. Slow stable crack growth occurred in all helium tests and in tests performed on the heat affected zone in hydrogen. However, unstable crack growth (fast fracture) was obtained for base metal tests in hydrogen. Fractographic studies revealed that the mechanism for all slow stable crack growth was microvoid coalescence; whereas, the surface of base metal specimens tested in hydrogen showed that fast fracture occurred by cleavage. Optical microscopy revealed that the fracture path for all base metal tests remained in the base metal, but that the fracture path for all heat affected zone tests moved towards the base. These observations, in conjunction with microhardness readings and quantitative metallography, were used to develop explanations for the observed behavior. These explanations include the combined effects of hydrogen, weld defects, residual stresses, grain size, and test variables such as temperature and specimen size and geometry. / M. S.

The following dissertation is divided into two parts. Part I deals with the modeling of helium trapping at oxide-iron interfaces in nanostructured ferritic alloys (NFAs) using density functional theory (DFT). The modelling that has been performed serves to increase the knowledge and understanding of the theory underlying the prevention of helium embrittlement in materials. Although the focus is for nuclear reactor materials, the theory can be applied to any material that may be in an environment where helium embrittlement is of concern. In addition to an improved theoretical understanding of helium embrittlement, the following DFT models will provide valuable thermodynamic and kinetic information. This information can be utilized in the development of large-scale models (such as kinetic Monte Carlo simulations) of the microstructural evolution of reactor components. Accurate modelling is an essential tool for the development of new reactor materials, as experiments for components can span decades for the lifetime of the reactor. Part II of this dissertation deals with the development, and use of, kinetic Monte Carlo (KMC) simulations for improved efficiency in investigating catalytic chemical reactions on surfaces. An essential technique for the predictive development and discovery of catalysts relies on modelling of large-scale chemical reactions. This requires multi-scale modelling where a common sequence of techniques would require parameterization obtained from DFT, simulation of the chemical reactions for millions of conditions using KMC (requiring millions of separate simulations), and finally simulation of the large scale reactor environment using computational fluid dynamics. The tools that have been developed will aid in the predictive discovery, development and modelling of catalysts through the use of KMC simulations. The algorithms that have been developed are versatile and thus, they can be applied to nearly any KMC simulation that would seek to overcome similar challenges as those posed by investigating catalysis (such as the need for millions of simulations, long simulation time and large discrepancies in transition probabilities). / Ph. D.