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Effect of Tensile Loading and Temperature on the Hydrogen Solubility of Steels at High Gas Pressure
(2023)
The hydrogen solubility in ferritic and martensitic steels is affected by hydrostatic stress, pressure, and temperature. In general, compressive stresses decrease but tensile stresses increase the hydrogen solubility. This important aspect must be considered when qualifying materials for high‐pressure hydrogen applications (e.g., for pipelines or tanks) by using autoclave systems. In this work, a pressure equivalent for compensating the effect of compressive stresses on the hydrogen solubility inside of closed autoclaves is proposed to achieve solubilities that are equivalent to those in pipelines and tanks subjected to tensile stresses. Moreover, it is shown that the temperature effect becomes critical at low temperatures (e.g., under cryogenic conditions for storing liquid hydrogen). Trapping of hydrogen in the microstructure can increase the hydrogen solubility with decreasing temperature, having a solubility minimum at about room temperature. To demonstrate this effect, the generalized law of the hydrogen solubility is parameterized for different steels using measured contents of gaseous hydrogen. The constant parameter sets are verified and critically discussed with respect to the high‐pressure hydrogen experiments.
The Tsumeb Mine in Namibia represents one of the best-preserved mining sites in the world and is rapidly gaining cross-disciplinary interest among cultural and engineering scientists. Most of the open pit and the shaft mining equipment are still in place, including the ore processing units and the local power plant. The mining area thus deserves recognition as an industrial world heritage site, especially due to the rarity of such locations on the African continent. The Shaft #1 headgear, built in 1924, represents one of the oldest known riveted steel headgears of the Promnitz design worldwide. In contrast to similar steel structures located in the northern hemisphere, it has been exposed to a different rural semi-arid climate since it is located in the Otavi Mountain Land, characterized by semi-annual change of rainy and dry seasons. Parts of the Shaft #1 headgear have remained largely untouched for more than 70 years. Besides its outstanding heritage value, it thus also represents an interesting object for studying the composition of corrosion layers formed on mild steel surfaces when exposed to continental and industrial mining atmospheres. To find a suitable transparent corrosion prevention coating, various on-site coating samples were evaluated after 11 months of outdoor exposure, including Owatrol Oil®, which is based on natural oil and alkyd resin with strong wicking potential. The substance is frequently applied for the conservation of single components but is not yet widely used on large steel structures in the field of industrial heritage conservation. However, it represented the most stable anti-corrosion coating under the local atmospheric conditions in the on-site tests. Thus, the suitability of Owatrol Oil® as a transparent coating for corrosion protection of riveted mild steel structures in such climates was further investigated as a more recent approach for the conservation of large steel structures. Since the protective coatings are exposed to strong UV radiation in the local climate, the addition of a specific UV stabilizer mixture was also tested. For such laboratory tests, two mild steel samples were taken. The first one originated from a diagonal strut of the 1920s and the second one from a handrail mounted in the early 1960s. Using corresponding high-resolution scanning electron microscopy (HR-SEM) and energy-dispersive X-ray spectroscopy (EDX) it was found that the corrosion layers are predominantly composed of lepidocrocite and goethite. A weathering program simulating the specific environmental conditions at Tsumeb in a UV climate chamber was developed and the corrosion resistance of the mild steel surface was subsequently evaluated by potentiodynamic measurements. Such tests proved to be a fast and reliable procedure for ranking the corrosion resistance of the old mild steels. It was found that the long-term corrosion layers already provide significant protection against further corrosion in the simulated environment. However, the study also showed that this can be further improved by the application of the Owatrol Oil® as a protective coating that also seals crevices. The addition of the UV stabilizers, however, led to a significant deterioration in corrosion protection, even in comparison to that of the uncoated long-term corrosion layers on the surface. Regular overcoating seems more advisable for the long-term preservation of the Shaft #1 headgear than modifying the Owatrol Oil® Coating with the tested UV-stabilizing additives.
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.
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.
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.
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.
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).
The damaging impact of hydrogen on the austenitic stainless steel AISI 304 L was analysed.
To this aim, samples were charged electrochemically with the hydrogen isotope deuterium (2H, D) and examined with time-of-flight secondary ion mass spectrometry (ToF-SIMS) and electron backscatter diffraction (EBSD). The fusion of the obtained chemical and structural information revealed local enrichment of deuterium in austenite, transformation into martensite, crack formation and severe roughening of the specimen surface. The results indicated that martensite was not only formed during charging but also during Desorption and ToF-SIMS examinations. Furthermore, cross-sections of deuterium-charged samples revealed that in preferred deformation bands a g/ε/a 0 evolution is taking place.
By means of microscopic analyses and carrier gas hot extraction (CGHE), it was found that the use of NaAsO2 as recombination poison decreased the uptake of hydrogen significantly and resulted in severe precipitation on the specimen surfaces. This is in contrast to the popular presumption that NaAsO2 enhances the uptake of hydrogen (and
deuterium) during electrochemical charging by hampering its recombination from Atoms to molecules.
Carrier gas hot extraction (CGHE) is a commonly applied technique for determination of hydrogen in weld joints using a thermal conductivity detector (TCD) for hydrogen measurement. The CGHE is based on the accelerated hydrogen effusion due to thermal activation at elevated temperatures. The ISO 3690 standard suggests different specimen geometries as well as necessary minimum extraction time vs. temperature. They have the biggest influence on precise hydrogen determination. The present study summarizes the results and experience of numerous test runs with different specimen temperatures, geometries (ISO 3690 type B and small cylindrical samples), and factors that additionally influence hydrogen determination. They are namely specimen surface (polished/as-welded), limited TCD sensitivity vs. specimen volume, temperature measurement vs. effects of PI-furnace controller, as well as errors due to insufficient data assessment. Summarized, the temperature is the driving force of the CGHE. Two different methods are suggested to increase the heating rate up to the desired extraction temperature without changing the experimental equipment. Suggestions are made to improve the reliability of hydrogen determination depended on the hydrogen signal stability during extraction accompanied by Evaluation of the recorded data. Generally, independent temperature measurement with dummy specimens is useful for further data analysis, especially if this data is used for calculation of trapping kinetics by thermal desorption analysis (TDA).
The interaction of hydrogen with various tungsten-inert-gas-welded austenitic stainless steels’ (AUSS) microstructure is studied by means of desorption/absorption analysis and microstructure observations. One of the limitations of welding is created by the presence of hydrogen in the weld, which can shorten the steel’s service life. The local hydrogen concentration, trapping, and its distribution along the welded samples were studied by thermal desorption spectrometry and were supported by X-ray diffraction (XRD) and electronic microstructural observations. Hydrogen content demonstrated a dependence on the welding zone. It was found that hydrogen distribution, and accepted microstructure during welding, played a significant role in the trapping mechanism of 316L AUSS. XRD analysis revealed residual stresses which were caused due to the presence of hydrogen in c-phase. It was shown that the austenite microconstituents inside 316L can have a crucial effect in preventing hydrogen-assisted cracking phenomenon. The effects of AUSS microstructure on hydrogen absorption and desorption behavior are discussed in detail.
A two-dimensional numerical mesoscale model has been created representing a microstructure of a typical 2205/1.4462 duplex stainless steel to further elucidate the mechanisms of hydrogen-assisted crack initiation and propagation in multiphase non-hydride forming metallic microstructures. Hydrogen-assisted cracking (HAC) was simulated by considering different stress and strain behavior as well as different diffusion behavior in both phases. For simulation of crack initiation and propagation, the element elimination technique has been applied. The model allows the simulation of path-free crack propagation which contributes to a better understanding of the HAC process in two-phase microstructures. As a particular result, the analyses revealed that a global macroscopic elastic deformation might already cause plastic deformation in both phases entailing respective HAC.
Due to the increasing global demand for pure silver, native wire silver aggregates in very high purities are gaining more industrial attention. Up to the present, no substantial metallurgical Investigation of natural wire silver exists in the accessible literature. To convey urgently needed cross-disciplinary fundamental knowledge for geoscientists and metallurgical engineers, twenty natural wire silver specimens from eight different ore deposits have been investigated in detail for the first time by EBSD (Electron Back Scattering Diffraction), supported by light microscopy and micro-probe analyses. The improved understanding of the natural silver wire microstructure provides additional Information regarding the growth of natural silver aggregates in comparison to undesired artificial growth on electronic devices. Clear evidence is provided that natural silver curls and hairs exhibit a polycrystalline face-centered cubic microstructure associated with significant twinning. Although the investigated natural wire silver samples have relatively high purity (Ag > 99.7 wt.-%), they contain a variety of trace elements such as, S, Cu, Mn, Ni, Zn, Co and Bi, As and Sb. Additionally, Vickers micro-hardness measurements are provided for the first time which revealed that natural silver wires and curls are softer than it might be expected from conversion of the general Mohs hardness of 2.7.
Hydrogen absorption and diffusion in T24 steel weld joints and effect on mechanical properties
(2018)
The present contribution summarizes results obtained from experiments with low-alloyed boiler steel grades T24 (CrMoV alloy), T22 (CrMo) and thermally simulated T24 HAZ microstructure and pure weld metal. The hydrogen absorption and diffusion behavior was investigated by permeation experiments and thermal desorption analysis (TDA). The results showed significant weld microstructure influence on diffusion by hydrogen trapping. Trapped hydrogen was determined in the T24 BM at temperatures up to 120 °C compared to 75 °C in the T22. In addition, the T24 HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the BM. For the mechanical properties, tensile tests were conducted with electrochemically hydrogen charged specimens and compared to results obtained from slow strain rate tests (SSRT) in high-temperature water up to 200 °C. The as-welded HAZ had remarkably increased susceptibility compared to the BM already at low hydrogen concentration of 1-2 ppm. The SSRT were conducted for free corrosion and acidic environment and confirmed this behavior at elevated temperatures for both HAZ microstructures of T24 and T22. Summarized, each weld microstructure has specific diffusion coefficients and shows different susceptibility to degradation of the mechanical properties, i.e. delayed hydrogen assisted cracking or stress corrosion cracking.
During the energy transformation from fossil fuels to renewable energy sources, the use of hydrogen as fuel and energy storage can play a key role. This presents new challenges to industry and the scientific community alike. The storage and transport of hydrogen, which is nowadays mainly realized by austenitic stainless steels, remains problematic, which is due to the degradation of mechanical properties and the possibility of phase transformation by hydrogen diffusion and accumulation. The development of materials and technologies requires a fundamental understanding of these degradation processes. Therefore, studying the behavior of hydrogen in austenitic steel contributes to an understanding of the damage processes, which is crucial for both life assessment and safe use of components in industry and transportation. As one of the few tools that is capable of depicting the distribution of hydrogen in steels, time-of-flight secondary ion mass spectrometry was conducted after electrochemical charging. To obtain further information about the structural composition and cracking behavior, electron-backscattered diffraction and scanning electron microscopy were performed. Gathered data of chemical composition and topography were treated employing data fusion, thus creating a comprehensive portrait of hydrogen-induced effects in the austenite grade AISI 304L. Specimens were electrochemically charged with deuterium instead of hydrogen. This arises from the difficulties to distinguish between artificially charged hydrogen and traces existing in the material or the rest gas in the analysis chamber. Similar diffusion and permeation behavior, as well as solubility, allow nonetheless to draw conclusions from the experiments.
The phase transformation under various cooling rates and in different HAZ regions for high-strength armour steel was analysed by dilatometry. To develop a continuous cooling transformation (CCT) diagram, the samples were heated up to a peak temperature of 1250 °C to achieve a coarse-grained microstructure and then cooled down with a cooling time t 8/5 varying from 3 to 240 s. Analysis of dilatation curves revealed the austenite decomposition process, during which transformation temperatures were determined. The results showed martensitic transformations for all welding-relevant cooling times. Furthermore, to analyse different heat-affected subzones of the weld, the peak temperature was varied between 550 and 1250 °C at a constant cooling time t 8/5 of 6 s. The simulated coarse-grained heat-affected zone (CGHAZ) and fine-grained-heat affected zone (FGHAZ) showed only martensitic transformations with transformation temperatures below 400 °C. The steel exhibited an inhomogeneous hardness with hardening in the CGHAZ and FGHAZ and softening in the intercritical and subcritical HAZ. The physically simulated microstructure was validated by a real hybrid laser-arc weld microstructure.
Corrosion fatigue (CF) of duplex stainless steel (DSS) X2CrNiMoN22-5-3 was investigated in in-situ geothermal conditions of the Northern German Basin (NGB). The influence of the load type on CF behavior of the alloy was examined by applying push/pull and rotating bending cyclic load to failure. The hour-glass shaped specimens with both polished and precisely turned surface finish were tested in corrosion chambers allowing for the permanent circulation of Northern German Basin electrolyte heated to 369 K. Additionally, the influence of a protective cathodic potential on the CF life expectancy was investigated by employing a potentiostat. The rotating bending cyclic load led to a higher CF life expectancy, which decreased with increasing duration of the experiment due to a higher deterioration rate of the material. The application of a cathodic potential caused a significant increase of the CF lifespan from 4.7 x 105 (open-circuit potential (OCP)) to 107 cycles (preset threshold cycle number) for the potential range from USHE = – 450 to – 900 mV. Microstructural analysis of the CF damage revealed horizontal grain attack within corrosion pit cavities, multiple fatigue cracks and preferable deterioration of the austenitic phase.
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.
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.
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.
Materials used in military applications have to withstand multiple threats like ballistics and explosions. Thus, high-strength low alloyed (HSLA) steels are used. The main joining technique for metals is welding. Therefore, analysing the dynamic impact behaviour of high-strength welds is very important to fulfil these demands.
Investigation of welds at high strain rates has rarely been conducted in the past. To determine the dynamic impact behaviour of hybrid laser-arc welds, the Split Hopkinson Pressure Bar (SHPB) technique was used. The base material was a quenched and tempered fine-grained armour steel with yield strength of 1100 MPa.
First, a full hybrid laser-arc weld was investigated by extracting specimens consisting of weld metal and heat affected base material. The influence of two variables, the cooling time between 800 °C and 500 °C (t8/5) and strength of filler material, on the impact behaviour was studied. The cooling time t8/5 was varied by preheating to influence the microstructure in the HAZ and to analyse the effect on the hardness and dynamic compressive strength.
Subsequent analysis to detail the original Investigation was carried out by dilatometer heat treatment of specimens to create homogenous subzones of the weld. These specimens have a homogenous microstructure of HAZ and were tested by SHPB to determine the stress-strain characteristics for the different microstructures of HAZ.
The results of the weld specimen showed the effect of preheating and filler material strength on the dynamic compressive behaviour. The analysis of the different microstructures of the HAZ indicated that especially the tempered microstructure caused a reduction in dynamic compressive strength.
X5CrNiCuNb16-4 has been proven to be sufficient resistant in corrosive environments, but shows rather unusual corrosion behaviour in CCS environment. Therefore a series of 30 specimens was tested at stress amplitudes between 150 MPa and 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ∼ 30 Hz). Due to the rather heterogeneous fine machined surfaces (Rz=4) the specimens are comparable with prefabricated parts. X5CrNiCuNb16-4 reached the maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa and lies 60% below the stress amplitude measured in air. The scatter range TN = 1:34 is disproportionately large. Although the fracture surface exhibited the typical striations and corroded surface areas no significant differences were found. The hardness was found to be homogeneous in all specimens tested at 335 HV10. Non-metallic inclusions were found within the microstructure, but no correlation could be found between the inclusions and early rupture. Still specimens that showed inclusions at the fracture surface and its cross section endured lower number of cycles. Additionally Aluminium was analysed in specimens with low number of cycles and may be cause for early rupture during corrosion fatigue tests. These findings reveal a very high sensitivity on a homogeneous microstructure upon the corrosion and corrosion fatigue behaviour of X5CrNiCuNb16-4 and needs to be taken into account when regarding this steel as pipe steel during injection of CO2 into saline aquifers.
As an approach towards more rough industrial laser welding applications, the Nd:YAG laser welding process has been coupled to the plasma powder welding process for the first time. Process stabilities have been achieved by such hybrid welding which are even better than those known from previous coupling of the laser process with gas metal arc welding (GMAW), for instance.
The present contribution focuses on the technology and potentials of the novel laser hybrid welding technique and addresses the realisation and the perspectives for practical applications. The experimental results demonstrate that the new process coupling enables welding of austenitic stainless steels in the thickness range between 3 mm and 8 mm at various weld geometries and joint configurations and at welding speeds exceeding 2 m/min. In addition it has been proven that the laser plasma powder arc welding (LPPAW) technique can also be applied to out-of-position conditions. Continuous advancement of the welding equipment ensures a high gap bridging ability and levelling of misalignment due to higher powder feeding rates. The recent development of a new plasma powder torch even provides a higher efficiency of powder feeding and guarantees smoth weld surfaces. Up to the present, the investigations demonstrated that the novel laser plasma powder hybrid welding technique offers all perspectives for application in pipe fabrication, ship building and offshore as well as transportation industry.
In the field of modelling hydrogen assisted cracking (HAC) phenomenon, hydrogen diffusivity is an important input parameter for numerical simulation. In terms of hydrogen diffusion coefficients, they have great impact on realistic assessment of the evolution of possible crack critical hydrogen concentrations. In addition, the chemical compositions of steels can have a strong effect on hydrogen diffusion. Unfortunately, literature provides a wide range of available hydrogen diffusion coefficients even for similar microstructures and equal temperatures. The scattering of the data can lead to significant deviations in the results of simulating the evolving hydrogen concentrations due to hydrogen uptake (by fabrication or service). Thus, the application of such data to crack-models or for component life tie predictions can be realized up to the present only by considering envelope curves of such value, corresponding to a work or bench case scenario, respectively. For improved reliability of numerical simulaitons, it is necessary to minimize the mentioned deviation of these data. Hence, this work focuses on the validation of hydrogen diffusion coefficients obtained from permeation experiments at room temperature. Two baintic steels with different alloying concepts were investigated, the creep-resistant 7CrMoVTiB10-10 and the reactor pressure vessel grade 20MnMoNi4-5. A numerical model is presented for simulation of the corresponding hydrogen diffusion during permeation experiments using the finite element software ANSYS. Three different diffusion coefficients (obtained from different common calculation methods) are considered and compared to numerical results. The vases of thes calculation methods are permeation transients which are a direct measure for hydrogen. The results of the simulated hydrogen diffusion coefficients show that only one procedure for calculation of diffusion coefficitnes is suitable in comparision to the experimental values. Thus, it is suggested to use this method for analysis of experimental results in case of hydrogen diffusion during permeation experiments. Furthermore, this work supplies validated values for the hydrogen diffusion coefficients of both steel grades.
This paper describes austenitic-ferritic duplex stainless steels, SAF 2205, in the presence of hydrogen. The duplex stainless steels (DSS) properties include excellent resistance to stress corrosion cracking, high strength and good weldability. Those steels are preferably used in industries combining hydrogen and loads. Hydrogen location in addition to hydrogen binding energy with the steel's defects are of great importance for the analysis of hydrogen embrittlement model in that steel. It is known from previously published works that the susceptibility to hydrogen embrittlement will depend on the competition between reversible and irreversible traps; meaning a direct relation to the hydrogen's state and position in the steel. In this work, we examine the local hydrogen concentration, trapping and distribution by two modern and advanced techniques: thermal desorption spectrometry (TDS) and we support it by time of flight-secondary ion mass spectrometer (ToF-SIMS). In this paper, we support and give for the first time new insights and better understanding to the hydrogen embrittlement mechanism in SAF 2205. The trapping energies levels were calculated using TDS and Lee and Lee's model. This model revealed reversible in addition to irreversible trapping sites. Also the trapping controlling mechanism was found to be a combination of detrapping controlled mechanism and diffusion controlled mechanism. The use of ToF-SIMS for local imaging the distribution of hydrogen species supports the discussion of the different hydrogen traps in this type of steel. The hydrogen embrittlemet phenomenon in SAF 2205 will be discussed in details in that paper.
Deuterium permeation and cracking in duplex steels as viewed by ToF-SIMS and HR-SEM with data fusion
(2016)
Better understanding of hydrogen assisted degradation and trapping mecha-nisms requires sufficient imaging techniques for respective hydrogen-microstructure interaction studies, in particular with multi-phase metallic micro-structures [1]. The present work is focusing on the elucidation of deuterium be-havior in two austenitic-ferritic duplex stainless steels (DSS) under the assumption that deuterium behaves in many ways similarly to hydrogen [2]. For case studies standard 2205 and lean 2101 DSSs were chosen due to the extensive use of these steels in industry [3]. The analyses were conducted by using a novel in-situ permeation and Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) imaging technique or by ex-situ ToF-SIMS imaging following electrochemical charging experiments. Another pioneering procedure was data fusion (including chemometry) of results of powerful laterally resolved chemical analysis and high resolution structural characterization techniques .
Results for the ex-situ observations showed a different influence of deuterium loading on the two steel grades as well as different damage mechanisms in each phase. Formation of sub-surface blisters between the ferrite and austenite were obtained in both the standard and the lean DSS. In both steels, an increased deuterium concentration was observed around deformed regions such as cracks, confirming that they originate from the presence of deuterium [4]. The formation of parallel cracks was obtained only in the austenite within the standard duplex whereas in the lean duplex the highest intensity of deuterium was obtained in the austenite along the ferrite-austenite interphase.
In comparison, application of the novel in-situ permeation technique enabled to register and record the deuterium permeation through the material and the respective saturation sequence of the two phases as well as the interfaces. Faster diffusion of the deuterium was observed in the ferrite and a direct proof for deuterium enrichment at the austenite-ferrite interface has been given [1]. The integration of the specified techniques gives a better insight into the processes leading to hydrogen induced failure. These two experimental techniques provide very valuable tools for elucidation of respective metallurgical failure mechanisms that can be used for the validation of respective numerical models for hydrogen assisted cracking (HAC).
Modeling of Hydrogen-Assisted Cracking (HAC) in Duplex Stainless Steels (DSS):
- Hydrogen causes significant degradation in DSS and consequently HAC
- Mechanisms of HAC have not been fully understood in two-phase microstructures
- Mesoscale numerical modeling for HAC in DSS was created, coupled to the macroscale, enabling simulation of HAC in both phases independent from predefined crack paths
In the present work, the influence of deuterium on the microstructure of a duplex stainless steel type EN 1.4462 has been characterized by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) supported by scanning electron microscopy (SEM), focused ion beam (FIB), electron back scattered diffraction(EBSD) and energy dispersive x-ray (EDX) investigations. Characterization has been carried out before and after electrochemical charging with deuterium which has been used as a tracer, due to its similar behavior to hydrogen in the steel microstructure. In a first approach, the distribution of the deuterium occurring at temperatures above 58 °C has been visualized. Further it turned out that sub-surface micro blisters are formed in the ferrite-austenite interface, followed by the formation of needle shaped plates and subsequent cracking at the ferrite surface. In the austenite phase, parallel cracking alongside twins and hexagonal close packed (martensitic) regions has been observed. In both phases and even in the apparent interface, cracking has been associated with high deuterium concentrations, as compared to the surrounding undamaged microstructure. Sub-surface blistering in the ferrite has to be attributed to the accumulation and recombination of deuterium at the ferrite-austenite interface underneath the respective ferrite grains and after fast diffusing through this phase. Generally, the present application of chemometric imaging and structural analyses allows characterization of hydrogen assisted degradation at a sub-micron lateral resolution.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and high-resolution scanning electron microscopy are well-acknowledged tools in materials characterization. The ability to map chemical species on the surface of an investigated sample with often low mass detection limits makes ToF-SIMS an essential tool in fields where many question marks concerning Degradation processes and damage mechanisms exist. The aim of this paper is to describe the power of data fusion of ToF-SIMS and high-resolution scanning electron microscopy results employing computational methods for multivariate data Analysis such as principal component analysis. As a case study the investigation of hydrogen distribution in an artificially charged Duplex stainless steel microstructure is presented aiming on a better understanding of hydrogen embrittlement.
As consequence for increasing threats by IEDs (Improvised Explosive Devices) on vehicles, the blast resistance of the welded frames and bodies becomes increasingly important. Considering vehicle welds subjected to blasting, the real configurations of the joints in the structure and the position of the blast loads have to be considered. The present contribution thus focuses on a weld joint at the explosion endangered wheel well of a tactical truck. The high-strength steel welds were subsequently impacted by explosion loads within the upper range from those experienced in practical military operation to cause not only deformation, but also to investigate the ultimate fracture behaviour of the high-strength weld. The interaction between cooling time t8/5 and displacement, crack path as well as fracture surface was analysed. The analyses of the fracture surfaces revealed ductile overload failure and also the size of the dimples was influenced by the cooling time t8/5. As a prominent feature, these investigations showed that the crack path of such high-strength steel welds under blasting is less influenced by the final hardness level in the respective weld microstructures but much more affected by the hardness gradient at the fusion line and inside the Heat Affected Zone (HAZ).
Hydrogen assisted stress corrosion and cold cracking represent still a major topic regarding the safety of welded steel components against failure in many industrial branches. Hydrogen might be introduced during fabrication welding or might be taken up from an environment during sour service or at cathodic protection. Additionally, understanding and avoidance of hydrogen entry into weld microstructures from gaseous pressurized environments becomes increasingly important for renewable energy components. There are two types of metallurgical mechanisms associated with hydrogen assisted cracking, i.e. the cracking as well as hydrogen transport and trapping mechanisms. For numerical modelling, it has to be considered that both types are not independent of each other, that the mechanisms are not yet completely clarified and that validation of such models strongly depends on implementation of the correct hydrogen related materials properties. However, quite significant achievements have been made in modelling of hydrogen assisted cracking by indirect coupling of thermal, stress-strain as well as hydrogen uptake and diffusion analyses. After a brief introduction into the subject and by revisiting various proposed cracking mechanisms, the present contribution focuses on recent developments of a numerical model based on a comparison of actual hydrogen concentrations and mechanical loads with respective hydrogen dependent material properties as crack initiation and propagation criteria. The basic procedure for numerical simulation of crack initiation and propagation is outlined and it is shown how such numerical simulations can be validated experimentally. Furthermore, it is highlighted how such a procedure has been extended to a comprehensive model for life time prediction of welded steel pipeline components and experimentally verified. Finally, it is outlined how the model can be extended to simulate cracking in heterogeneous steel microstructures on the different scales.
Since the mid-nineties, supermartensitic stainless steels (SMSS) have increasingly been applied to welded subsea-pipeline systems in the North Sea oil and gas fields, especially to flowlines at mild sour service conditions. However, in 2001 cracking and leaks occurred during installation and service start-up of two SMSS flowlines in the Norwegian Tune gas condensate field, welded with a new developed matching filler wire. Brittle transgranular cracking started especially at inter-run lack of fusion and propagated brittle, predominantly through the weld metal. The present paper provides a brief overview of the original failure case and respective sequence of events leading to complete replacement of the SMSS by carbon steel flowlines in 2002. Then, detailed investigations of a circumferential weld sample of the failed Tune flowline are highlighted, targeted at comparison of the failure appearance to previous investigations of this filler material type and to search for possible explanations for the brittle fracture at the crack initiation area. SEM investigations of the fracture surface revealed brittle areas only in the direction towards the top side of the weld while the major part of the investigated surface exhibited ductile fracture. As an approach to clarify, if the fracture was a consequence of hydrogen assisted cracking, five small sized specimens have been cut out of the original sample. Cracking has been introduced parallel to the original fracture surface in these specimens at respective saw cuts and bending. The results show that brittle transgranular cracking appeared only in the specimen cooled down to very low temperatures by liquid nitrogen and in the sample charged with hydrogen to an average concentration of about 15 ml/100 g. However, a fracture similar to the original surface was observed only in the hydrogenized specimen. As a further result, very similar fracture surfaces of supermartensitic stainless steel weld metals had been observed on specimens subjected to hydrogen assisted cold cracking (HACC) as well as to hydrogen assisted stress corrosion cracking (HASCC). In total, the results indicate that brittle fracture starting at the inter-run lack of fusion were not initiated by high notch tip deformation rates, but rather influenced by hydrogen, probably taken up during welding.
Numerical investigations on hydrogen-assisted cracking in duplex stainless steel microstructures
(2016)
Duplex stainless steels (DSS) are used in various industrial applications, e.g. in offshore constructions as well as in chemical industry. DSS reach higher strength than commercial austenitic stainless steels at still acceptable ductility. Additionally, they exhibit an improved corrosion resistance against pitting corrosion and corrosion cracking in harsh environments. Nevertheless, at specific conditions, as for instance arc welding, cathodic protection or exposure to sour service environments, such materials can take up hydrogen which may cause significant property degradation particularly in terms of ductility losses which, in turn, may entail hydrogen-assisted cracking (HAC). The cracking mechanism in DSS is different from steels having only a single phase, because hydrogen diffusion, stress-strain distribution and crack propagation are different in the austenite or ferrite phase. Therefore, the mechanism of HAC initiation and propagation as well as hydrogen trapping in DSS have not been fully clarified up to the present, as for most of the two-phase microstructures. At this point the numerical simulation can bridge the gap to a better insight in the cracking mechanism regarding the stress-strain distribution as well as hydrogen distribution between the phases, both austenite and ferrite, of the DSS. For that purpose, a two dimensional numerical mesoscale model was created representing the microstructure of the duplex stainless steel 1.4462, consisting of approximately equal portions of austenite and ferrite. Hydrogen assisted cracking was simulated considering stresses and strains as well as hydrogen concentration in both phases. Regarding the mechanical properties of austenite and ferrite different statements can be found in the literature, dependent on chemical composition and thermal treatment. Thus, various stress-strain curves were applied for austenite and ferrite simulating the HAC process in the DSS microstructure. By using the element elimination technique crack critical areas can be identified in both phases of the DSS regarding the local hydrogen concentration and the local mechanical load. The results clearly show different cracking behavior with varying mechanical properties of austenite and ferrite. Comparison of the results of the numerical simulation to those of experimental investigations on DSS will improve understanding of the HAC process in two phase microstructures.
Spectacular failure cases of fossil power stations in the recent years exhibited severe cracking in T24 welds. The results show that hydrogen-assisted cracking up to 200 °C cannot be excluded. Hence, it is important to gain a basic understanding on how hydrogen might affect the basic material properties in the respective weld microstructures. The present study focuses on hydrogen degradation of the respective weld microstructures, i.e., the weld metal and the coarse grained heat affected zone, where actually cracking appeared in practice. Tensile tests were carried out for coarse grain heataffected zone (CGHAZ) and the weld metal in uncharged and electrochemically hydrogen-charged condition. It turned out that both microstructures show distinct tendency for gradual degradation of mechanical properties in the presence of increasing hydrogen concentration. Already for a hydrogen concentration about and above 2 ml/100 g Fe, a significant ductility reduction has been observed. SEM investigations revealed that the fracture topography changes from ductile topography in uncharged condition to intergranular topography for the CGHAZ and to ductile-brittle mix for the weld metal (WM) in hydrogen charged condition. Ti-rich inclusions were identified as central regions of quasi-cleavage fracture areas in the WM. An approximation procedure is applied to quantify the degradation intensity.
Real Time Imaging of Deuterium in a Duplex Stainless Steel Microstructure by Time-of-Flight SIMS
(2016)
For more than one century, hydrogen assisted degradation of metallic microstructures has been identified as origin for severe technical component failures but the mechanisms behind have not yet been completely understood so far. Any in-situ observation of hydrogen transport phenomena in microstructures will provide more details for further elucidation of these degradation mechanisms. A novel experiment is presented which is designed to elucidate the permeation behaviour of deuterium in a microstructure of duplex stainless steel (DSS). A hydrogen permeation cell within a TOF-SIMS instrument enables electrochemical charging with deuterium through the inner surface of the cell made from DSS. The outer surface of the DSS permeation cell exposed to the vacuum has been imaged by TOF-SIMS vs. increasing time of charging with subsequent chemometric treatment of image data. This in-situ experiment showed evidently that deuterium is permeating much faster through the ferrite phase than through the austenite phase. Moreover, a direct proof for deuterium enrichment at the austenite-ferrite interface has been found.
Duplex stainless steels have been used for a long time in the offshore industry, since they have higher strength than conventional austenitic stainless steels and they exhibit a better ductility as well as an improved corrosion resistance in harsh environments compared to ferritic stainless steels. However, despite these good properties the literature shows some failure cases of duplex stainless steels in which hydrogen plays a crucial role for the cause of the damage. Numerical simulations can give a significant contribution in clarifying the damage mechanisms. Therefore, a numerical model of a duplex stainless steel microstructure was developed enabling simulation of crack initiation and propagation in both phases. The phase specific stress strain analysis revealed that local plastic deformation occurs in both austenite and δ-ferrite already in the macroscopically elastic range. Altogether, phase specific hydrogen-assisted material damage was simulated for the first time taking into account all main factors influencing hydrogen assisted cracking process. The results agree well with experimental observations and thus allow a better insight in the mechanism of hydrogen-assisted material damage.