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Hydrocarbons fuel our economy. Furthermore, intermediate goods and consumer products are often hydrocarbon-based. Beside all the progress they made possible, hydrogen-containing substances can have severe detrimental effects on materials exposed to them. Hydrogen-assisted failure of iron alloys has been recognised more than a century ago. The present study aims to providing further insight into the degradation of the austenitic stainless steel AISI 304L (EN 1.4307) exposed to hydrogen. To this end, samples were electrochemically charged with the hydrogen isotope deuterium (2H, D) and analysed by scanning electron microscopy (SEM), electron back-scatter diffraction (EBSD) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). It was found that deuterium caused a phase transformation from the original γ austenite into ε- and α’-martensite. Despite their low solubility for hydrogen, viz. deuterium, the newly formed phases showed high deuterium concentration which was attributed to the increased density of traps. Information about the behaviour of deuterium in the material subjected to external mechanical load was gathered. A four-point-bending device was developed for this purpose. This allowed to analyse in-situ pre-charged samples in the ToF-SIMS during the application of external mechanical load. The results indicate a movement of deuterium towards the regions of highest stress.
Welded components of P91 9% Cr steel demand for careful welding fabrication with necessary post weld heat treatment (PWHT). Before the PWHT, a hydrogen removal heat treatment is necessary for avoidance of hydrogen assisted cracking (HAC). In this context, the microstructure and temperature-dependent hydrogen diffusion is important, and reliable diffusion coefficients of P91 weld metal are rare. For that reason, the diffusion behavior of P91 multi-layer weld metal was investigated for as-welded (AW) and PWHT condition by electrochemical permeation experiments at room temperature and carrier gas hot extraction (CGHE) from 100 to 400 °C. Hydrogen diffusion coefficients were calculated, and the corresponding hydrogen
concentration was measured. It was ascertained that both heat treatment conditions show significant differences. At room
temperature the AW condition showed significant hydrogen trapping expressed by to seven times lower diffusion coefficients. A preferred diffusion direction was found in perpendicular direction expressed by high permeability. The CGHE experiments
revealed lower diffusion coefficients for the AW condition up to 400 °C. In this context, a hydrogen concentration of approximately 21 ml/100 g was still trapped at 100 °C. For that reason, a certain HAC susceptibility of as-welded P91 weld metal cannot
be excluded, and hydrogen removal should be done before PWHT.
Supermartensitic stainless steels (SMSS) are a commonly used material nowadays for building offshore structures, i.e. pipelines in the oil and gas industry. The harsh and corrosive environments in oil and gas applications require the correct combination of alloys to attain the desired properties of steel, including high strength and good corrosion properties, even in severe sour service conditions. Welding is the most commonly used method in joining offshore components, depending on requirements requiring strength or fitting. It has been shown that the heat affected zone (HAZ) is more susceptible to certain types of corrosion, including pitting corrosion, especially during severe sour service where a high pH and lower H2S values in the flow medium can lead to pitting corrosion in the HAZ of welded structures. Subsequent hydrogen uptake in the pits can cause cracks to initiate and propagate, leading to rupture of pipelines or catastrophic failures of structures, even at low mechanical loads. Offshore standards allow a certain amount of corrosion, including pitting, to be present before action is required, however the extent of pitting corrosion is not identified by performing visual inspection alone as the subsurface pit diameter may be vastly greater than the pit diameter at the surface. The critical conditions which lead to crack initiation and propagation from a pit with hydrogen uptake are currently not known. Therefore, pitting corrosion and subsequent crack initiation are a danger to the safety of structures. The interest in this phenomenon has resulted in many experimental studies and numerical simulations.
Several numerical models of pitting corrosion and hydrogen uptake resulting in crack initiation are already in existence, but these two phenomena are regularly modelled individually. Thus, a model enabling simulation of both phenomena simultaneously would be of great benefit. Hence, the goal of this study is to develop a model enabling simulation of pit growth and crack initiation, considering hydrogen uptake in the pit from a corrosive environment.
As a first step, this paper presents an investigation into various parameters, which influence crack initiation at pits. These crack critical parameters include: pit geometry, pit location, mechanical load and hydrogen transport into the microstructure. The results will help to identify critical conditions for crack initiation starting at the pit and developing measures to avoid hydrogen assisted cracking (HAC).
Aircraft main landing gear (MLG) components are commonly manufactured from low-alloyed, martensitic, ultra-high strength steels (UHSS) that have to be coated for corrosion protection, representing an expensive and environmentally harmful production step. To avoid already partly banned corrosion protection plating, the new high-alloyed UHSS, Ferrium S53 (UNS S10500), has been designed to replace lowalloyed legacy materials and has been subjected to a limited field test over five years. As with the legacy alloys, UNS S10500 has a fully hardened martensitic microstructure known to be susceptible to hydrogen assisted cracking, per se. Containing about 10 wt% Cr, steels such as S10500 are at the lower limit for corrosion resistant alloys. Similar to super-martensitic stainless steels used in the oil and gas industry, a common failure sequence in marine environments represents pitting and subsequent hydrogen assisted stress corrosion cracking (HASCC). For addressing such phenomena quantitively, as required for respective lifetime assessments of MLG components and systems, the tolerance of such materials dependent on the absorbed hydrogen concentration must be evaluated quantitatively. However, there is a lack of such valuable materials data, as well as of the fractographic behavior dependent on the hydrogen concentration that might be absorbed during HASCC. To provide an improved understanding of the hydrogen dependent mechanical and fractographic behavior, samples of the legacy AISI 4340 and the new S10500 MLG steels have electrochemically been hydrogen-saturated and subjected to tensile testing. In contrast to a previous study, this contribution for the first time focuses on materials that have been salvaged from real service used landing gear components. In this study, it has been demonstrated that the service-applied S10500 steel has not only a higher strength, but also an improved ductility in comparison to the legacy AISI 4340 steel after similar service durations that provides a higher tolerance against hydrogen concentrations that might be absorbed during potential pitting and HASCC in marine environments. In addition, it has been found that the absorbed hydrogen concentration significantly affects the fracture behavior. Interestingly, hardening of the hydrogen charged low-alloyed AISI 4340 steel changes the fracture topography from trans- toward intergranular, while hardening of the S10500 steel turned the fracture topography from inter- to transgranular at respectively high hydrogen concentrations.
A seamless pipe made of AISI 321 stainless steel represented a part of a transportation Pipeline system for hydrogen-containing hot gas in a hydrocarbon cracking unit. After a service period of approximately 21 months, a segment of such pipe demonstrated the cracks, causing leakage and respective fire. For clarification of a failure root cause, various metallurgical investigations combined with numerical simulations have been applied. The results revealed that the rupture of seamless pipe was evidently influenced by hydrogen assisted cracking (HAC). An increased susceptibility of the alloy to HAC had to be attributed to its sensitive microstructure which was related to the occurrence of slip bands with a high quantity in austenite grains, particularly in the specific region underneath the outer wall surface. In addition, the intensity of restraint resulting from the T-joint weld configuration caused respectively higher triaxial stresses in the confined area on the outer wall surface where the crack started. The numerical simulations of hydrogen diffusion revealed that a uniform hydrogen concentration profile over the pipe wall thickness was reached when the service period was more than 20 months. This duration agreed well to the timeto-failure of the actual component. Considering additionally that the final stage of rupture by overload was preceded by severe HAC, as confirmed by the respective intergranular fracture topography.
Das Kapitel beginnt mit einer kurzen Einführung über die Korrosion (Wechselwirkung zwischen einem Metall, einer korrosiven Umgebung und der der jeweiligen Konstruktion). Im zweiten Abschnitt werden die wichtigsten Formen der wässrigen elektrochemischen Korrosion (Flächenkorrosion, galvanische, selektive und interkristalline Korrosion sowie Loch- und Spaltkorrosion) betrachtet. Darüber hinaus wird die elektrochemische Korrosion unter mechanischer Belastung betrachtet (Spannungsrisskorrosion, wasserstoffunterstützte Rissbildung, Korrosionsermüdung), sowie Sonderformen der Korrosion (Erosion, Fretting und mikrobiologisch induzierte Korrosion). Der dritte Abschnitt befasst sich mit der chemischen und Hochtemperaturkorrosion (Oxidation, Aufkohlung, Hochtemperatur-Wasserstoffangriff, Aufschwefelung, Nitrierung, Halogenierung). Zusätzlich enthält das Kapitel Maßnahmen zur Vermeidung der Korrosion.
The chapter starts with a brief introduction about corrosion, which is defined as the interdependency between a metal, a corrosive environment, and the respective component design. The second section introduces the most important forms of aqueous electrochemical corrosion (uniform corrosion, galvanic corrosion, selective and intergranular corrosion, and finally pitting and crevice corrosion in the case of passive layer forming metals). In addition, electrochemical corrosion under applied mechanical load is introduced (stress corrosion cracking, hydrogen-assisted cracking, corrosion fatigue), as well as special forms of corrosion (erosion, fretting, and microbiologically induced corrosion). The third section of this chapter introduces (mostly dry) chemical corrosion and high-temperature corrosion (oxidation, carburization, high-temperature hydrogen attack, sulfurization, nitriding, halogenation). As in the case of electrochemical corrosion, chemical corrosion can also be superimposed by mechanical loads. Finally, general facts on the testing of corrosion are introduced.
The effect of electrochemical charging of hydrogen on the structure of a lean duplex stainless steel LDX 2101® (EN 1.4162, UNS S32101) was examined by both Time-of-Flight secondary ion mass spectrometry and electron back-scatter diffraction. The goal is to correlate hydrogen concentration and induced structural changes. Chemical and structural characterizations were done for the same region at the sample's surface with sub-micron spatial resolution. Regions of interest were varying in size between 50 × 50 μm and 100 × 100 μm. The results show a phase transformation of austenite to mainly a defect-rich BCC and scarcely a HCP phase. The phase transformation occurred in deuterium rich regions in the austenite.
Literature provides a wide range of hydrogen diffusion coefficients for low alloyed steels used in power plants. In fact, experimental boundary conditions and calculation methods have influence on the determination of these coefficients. The diffusion and trapping behavior in creep-resistant steel 7CrMoVTiB10-10 has been studied. Based on experimental carrier gas hot extraction (CGHE) data, a numerical model has been developed to describe the hydrogen transport and respective hydrogen distribution at elevated temperatures. The numerical results suggest that common calculation methods for diffusion coefficients are limited for experimental data analysis. The sample preparation time before CGHE experiment influences the determined diffusion coefficients with the consequence that non-homogeneous hydrogen concentration profiles have to be considered in the simulations.
Quantitative investigations of hydrogen dependent properties of aircraft landing gear materials have only scarcely been carried out in the past. They are essential for respective component life time assessments. To better understand the behavior of these landing gear materials in a hydrogen rich environment, specimens were charged in the condition as delivered with known concentrations of hydrogen and then mechanically tested to evaluate the degradation effects. The present contribution is focused on evaluating the hydrogen concentration dependent material properties and the respective fracture topographies of the two investigated steels, and then continued by the comparison of the results with other previously investigated martensitic steels in order to better understand the thresholds for these materials to maintain structural integrity.