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The presentation gives an overview of BAM's activities on processing influences and application properties of MPEAs in the form of joined and machined high and medium entropy alloys (CoCrFeMnNi and CoCrNi). In the case of welding, the focus is on defect-free welded joints with sufficient mechanical properties. In the case of machining, the focus is on the possible influence on the surface quality of the materials through adequate milling parameters. In addition, the hydrogen absorption and diffusion properties as well as the electrochemical corrosion behavior are fundamentally examined.
The development of hydrogen technologies entails high safety requirements in distribution and dispensing infrastructure. Therefore, it is necessary to pursue research on material compatibility in hydrogen, especially for critical parts with tribological issues.
The focus of this study is to evaluate the influence of hydrogen on a wider range of commercially available polymer materials. Thereby, the friction and wear behavior of different grades of TPE, POM, PA66, PA12, PPA, PEEK, PPS, PTFE, PAI, PI and PBI were investigated against a rotating steel disk (AISI 304). Filled and unfilled polymers from different suppliers were evaluated at room temperature in air, vacuum and hydrogen gas (H2) as well as in liquid hydrogen at - 253°C (LH2).
The sliding behavior of the polymer materials is discussed by means of surface analyses, whereby special attention is paid to the formation of a transfer film.
According to the results at ambient temperature, the effect of hydrogen environment on the tribological behavior of neat polymers may be related to lack of moisture, but also to saturated hydrocarbons in gaseous hydrogen. In liquid hydrogen, the best tribological performances were achieved with neat PA polymers as well as PPS and PI composites.
Effect of high-pressure hydrogen environment on the physical and mechanical properties of elastomers
(2024)
This study presents the influence of high-pressure hydrogen environment on the physical and mechanical properties of two types of cross-linked hydrogenated acrylonitrile butadiene rubbers. Based on the CSA/ANSI standard, static exposures in hydrogen experiments were performed up to 100 MPa at 120 °C. Characterization before and after exposure was conducted by means of density and hardness measurements, dynamic mechanical analysis (DMA), tensile tests, compression set, FT-IR and AFM analyses to assess effects after decompression. While the effect of high-pressure exposure is significant immediately after exposure, most of the physical and mechanical properties recover after 48 hours. FT-IR, AFM, SEM and compression set results indicate, however, permanent effects.
Offshore wind turbines continuously increase in size and weight and demand adequate offshore foundations concepts like monopiles, tripods, or jackets. These components are typically constructed using submerged arc welding (SAW) with high-strength thick steel plates like the S420ML. During welding, the occurrence of delayed hydrogen-assisted cracking (HAC) must be anticipated. HAC is a critical combination of the local hydrogen concentration within a susceptible microstructure under certain mechanical load, i.e., the occurring (welding) residual stresses. The welding sequence of the thick-walled plates complicates the residual stress distribution due to the necessary repeated thermal cycling, i.e., welding seam/layer deposition to fill the joint. For that purpose, SAW with two-wire-technique was used to weld a specially designed and prototype-like mock-up of a real component with a thickness of 50 mm, filled with over 20 passes and a seam length of 1000 mm. Additional welded stiffeners simulated the effect of a high restraint, to achieve critical HAC conditions. The necessity of a minimum waiting time (MWT) before the NDT can be conducted (to exclude HAC) was critically verified by the application of ultrasonic testing of the welded joint at different time-steps of the NDT of up to 48 h after the completion welding. The residual stresses were determined by a robot XRD goniometer. Tensile residual stresses up to the yield limit are found both in the weld metal and in the heat-affected zone. Numerical modeling allowed the qualitative estimation of the hydrogen diffusion in the weld. No noticeable HAC occurrence was identified and confirms the high cracking resistance of the investigated material. Finally, the applicability of the MWT concept should be critically discussed.
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.
Multi-principal element alloys (MPEAs) are innovative materials that have attracted extensive research attention within the last decade. MPEAs are characterized by a solid solution of equiatomic metallic elements. Depending on the number of elements, they are also referred as high entropy alloys (HEAs with n ≥ 4 elements like CoCrFeMnNi) and medium-entropy alloys (MEA with n = 3 elements CoCrNi). Depending on the alloy concept, MPEAs show exceptional properties in terms of mechanical performance or corrosion resistance at extreme environments. In that connection, hydrogen and its challenges for the most metallic materials gets more and more important. MPEAs are candidate materials for the substitution of conventional materials like austenitic stainless steels e.g., at very high-pressure up to 1000 bar. Those pressures are typically reached in valves or compressors for refueling of tanks with operational pressure of 700 bar. So far, the susceptibility of HEA/MEAs to hydrogen assisted cracking (if any) and the especially the underlying hydrogen uptake and diffusion was not within the scientific scope and not investigated in detail yet. For that reason, we focused on the hydrogen absorption the characterization of the hydrogen diffusion and trapping at elevated temperatures in a CoCrFeMnNi-HEA (each element with 20 at.-%) and CoCrNi-MEA, each element with 33.3 at.-%). As reference grade, the commercially available austenitic stainless steel AISI 316L was investigated. High-pressure hydrogen charging was conducted at different pressures in autoclave environment with maximum value of 1,000 bar. Thermal desorption analysis (TDA) via carrier gas hot extraction with coupled mass spectrometry was used with a max. heating rate of 0.5 K/s up to 650 °C. The measured desorption spectra of the different samples were deconvoluted into a defined number of individual peaks. The individually calculated peak temperatures allowed the definition of activation energies for predominant trap sites in the respective materials as well as the percentage share of the totally absorbed hydrogen concentration. The results present for the first time the complex interaction of both MPEAs and high-pressure hydrogen charging. A deconvolution of four peaks was selected and a main desorption peak was identified the dominant hydrogen trap containing the biggest share of the absorbed hydrogen concentration. The chemical composition an austenitic phase of both MPEAs is responsible for delayed hydrogen diffusion and strong, but mostly reversible, trapping. The comparison with the 316L samples showed significantly higher activation energies in the MPEAs, whereas hydrogen was also trapped at very high extraction temperatures. The absorbed maximum hydrogen concentration at 1,000 bar was 130 ppm for the CoCrFeMnNi-HEA, 50 ppm for the CoCrNi-MEA and 80 ppm for the 316L. It is interesting that the CoCrFeMnNi-HEA has obviously a way higher trapping capability compared to the conventional austenitic 316L, which could be a major advantage in terms of resistance to hydrogen assisted cracking.
The study provides an overview of the aspects of joining and its importance in manufacturing of components for the more and more important field of hydrogen as key factor for the energy transition to a decarburized future. To this end, the fundamentals of the technology fields of hydrogen production, storage, transport, and application are presented and the state of the art of manufacturing of components for hydrogen technologies by joining is summarized. Based on representative examples from practice, research and development, the importance of joining technology in hydrogen technologies is clearly highlighted and perspectives for the future are derived. From a macroeconomic perspective, the focal points, or trends of joining technologies here include: the erection of new infrastructure for hydrogen storage and transport, and the safe conversion of existing natural gas infrastructure and its challenges for welded materials. In addition, we show the problems that are anticipated with in-service repair welding of hydrogen pipelines. In hydrogen applications, the efficient mass production of fuel cells and electrolysers is becoming increasingly important. For that reason, the importance of additive manufacturing is highlighted. Finally, the challenges for technical regulations and standardization by using hydrogen are shown.
In the course of tomorrow's hydrogen-based energy transition, the construction of the corresponding infrastructure will play a central role. In that context, large diameter long-distance transmission pipelines for hydrogen will be the backbone in the European Union with service pressures from 70 to 90 bar (e.g., depending on national regulations). It is a major goal to rededicate the existing LNG infrastructure despite the necessity of new pipelines. From that point of view repairing of such transmissions pipelines via welding can be necessary. For the LNG infrastructure, it is state of the art that repair welding is conducted at pipelines under service, i.e., the LNG is still flowing as pressurized gas in the steel pipes. The reason is that a shut-down of large diameter pipelines is not so easy or sometimes impossible. In fact, as long no oxygen enters the pipeline, there would be any combustion or (in the worst case) explosion. At the moment, it is entirely open if current repair welding procedures for LNG pipelines can be transferred to pure hydrogen pipelines. In opposite to LNG, hydrogen can be way easier absorbed to the pipeline steels and diffuses through the material. If it accumulates in susceptible regions, i.e., in the welded joint, hydrogen assisted embrittlement could occur. The planned welding procedure requires a so-called preheating and maintenance of the weld joint of up to 300°C for several hours. This temperature is way higher compared to the typical service temperature of max. 40 to 50°C at operational pressures of 100 bar. In accordance to API 941, these low-alloyed pipeline steels are subjected to short-term service loads, which they are not designed for. For that reason, a collaborative project between BAM and DVGW (German Association for Gas and Water professions) was initiated in 2022 to answer the following questions by experiments and numerical simulation of: (1) How many hydrogen is additionally absorbed during the heating of the material to max. 300°C under remaining operational pressures? (2) Is the hydrogen concentration sufficient to reach a critical condition? (3) Which material and weld microstructure is the most susceptible? (4) Is there a significant difference in the repair welding behavior of LNG pipelines that had been already in use for long-term? (5) Which welding parameters and joint dimensions must be ensured for safe repair welding repair of typical pipelines? For that reason, the present study gives an overview on the current practice in repair welding of in-service pipelines, the industrial importance of this topic for the hydrogen-based energy transition and summarizes first results.
In the course of tomorrow's hydrogen-based energy transition, the construction of the corresponding infrastructure will play a central role. The majority of materials used to date are typically welded for component fabrication. In that context, steels are widely applied and can be prone to hydrogen embrittlement. For the evaluation of any hydrogen effect on, for example, the mechanical properties of a welded metallic material, the hydrogen content must be precisely determined. According to ISO 3690, carrier gas hot extraction (CGHE) can be used. In addition to the pure quantification of hydrogen, thermal desorption analysis (TDA) with varied heating rates can be used to determine and evaluate the bonding state at microstructural defects in the material. For both techniques, experimental and measurement influences have to be considered, which have a great effect on the result. For CGHE, for example, ISO 3690 suggests different sample geometries as well as minimum extraction times. The present study summarizes results and experiences of numerous investigations with different sample temperatures and geometries (ISO 3690 type B and cylindrical TDA samples) regarding: the influence of the sample surface (polished/welded), measurement accuracies depending on the sample volume. In particular, a deviating extraction temperature to the set temperature, can significantly falsify the measurement results. Based on the results, methods are shown to quickly reach the desired extraction temperature without having to physically interfere with the measurement equipment. This serves to substantially improve the reliability of hydrogen measurement through increased signal stability and accelerated hydrogen desorption. In general, an independent temperature measurement with dummy samples for the selected heating procedure is advisable to exclude possible unwanted temperature influences already before the measurement. In addition (and way more important), the methods described can be transferred directly to industrial applications.
The hydrogen economy requires large-scale storage and transportation options like long-distance transmission pipelines. The applied materials (typically steels) must be carefully tested under different conditions (pressure, temperature, impact of impurities, etc.) for their suitability and service with hydrogen. In combination with mechanical load, as occurs in every gas network, hydrogen can induce degradation of the mechanical properties and promote finally resulting in embrittlement, i.e., the formation of cracks. The conventional testing procedures consist of autoclaves in which samples are strained under pressurized hydrogen. The test apparatus requires large amounts of hydrogen and thus a high level of safety and costs. In very specific cases, these tests might be replaced by simplified electrochemical charging. However, these test alternatives raise several questions regarding the equivalency of both testing scenarios. In the early 1980’s the idea of a so-called hollow tensile sample raised and was reinitiated 2021 in ISO TC 164 by T. Ogata (NIMS, Japan) and further developed (e.g. by Fraunhofer IWM, Germany). The idea was: the sample itself represents the autoclave instead of charging a sample from outside. For that reason, a hole is drilled through the sample and the inner surface is pressurized by hydrogen gas during the mechanical testing. Indeed, this represents the main advantage as no expensive pressure-resistant autoclave equipment for large H-volumes is necessary, which significantly reduces the safety-related issues and thus the high costs. In the following, we show recent activities at BAM Berlin on adaption of the hollow-specimen technique for slow strain rate testing (SSRT). The current research activities are focussed on macroscopic influences like the sample geometry, minimum necessary dimensions, and microscopic influences e.g., on the surface by the processing method (drill hole quality and geometric precision) as well as the gas pressure effect (mechanical deformation of surface in different media).
This contribution briefly summarizes the standardization activities in accordance with the "Nationale Roadmap Wasserstofftechnologien" and presents selected results on the activities in Germany with scope on hydrogen transport in pipelines. The talk was given during a panel discussion to set-up a steering committee for standardization for hydrogen pipelines and welding , coordinated by the International Institute of Welding.
In the course of tomorrow's hydrogen-based energy transition, the construction of the corresponding infrastructure will play a central role. In that context, large diameter long-distance transmission pipelines for hydrogen will be the backbone in the European Union with service pressures from 70 to 90 bar (e.g., de-pending on national regulations). It is a major goal to repurposing the existing natural gas (NG) infrastructure despite the necessity of new pipelines. From that point of view repair welding or further welding of branch pipe etc. can be necessary during in-service, i.e., permanent flow of pressurized hydrogen. The reason is that a shut-down of large diameter pipelines is not easy or sometimes merely impossible. At the moment, it is entirely open if current repair welding procedures for NG pipe-lines can be transferred to pure hydrogen pipelines. For that reason, a collaborative project between BAM, DVGW (German Association for Gas and Water Professions) and a large number of gas grid operators, pipeline manufacturers and construction companies was initiated in 2023 to answer questions on: (1) How many hydrogen is additionally absorbed during the preheating and maintaining at interpass temperature under remaining operational pressures? (2) Is the hydrogen concentration sufficient to reach a critical condition? (3)Which material and weld microstructure are the most susceptible? (4) Is there a difference in the repair welding behavior of NG pipelines with materials in “used” condition? (5) Which welding parameters and joint dimensions must be ensured for safe repair welding? The final aim of this project is the publication of a recommended practice for repair welding of in-service hydrogen pipelines. For that reason, the present study gives an overview on: (A) current practice in repair welding of in-service pipelines and (b) plans for hydrogen pipelines and first results of international research projects.
With the introduction of a hydrogen-based energy and national economy, safety-relevant components for hydrogen technologies are becoming increasingly important. Characteristic of hydrogen technologies are, for example, harsh environmental conditions such as cryogenic or high-pressure storage, corrosion issues in fuel cells and electrolyzers, turbines, and many more. Additive manufacturing of components is becoming increasingly important and irreplaceable for the production of complex technical systems. Using the case studies of burners for gas turbines and electrodes and membranes for polymer (PEMFC) and solid oxide (SOFC) fuel cells, this article shows the potential of additive manufacturing of components. At the same time, however, the challenge of considering divergent mechanical properties depending on the direction of assembly in a "hydrogen-compatible" manner is also highlighted. Finally, the challenges posed by additive manufacturing and hydrogen for materials testing are highlighted under scenarios that are as realistic as possible.
High-entropy alloys (HEAs) are innovative high-performance materials that have attracted more and more research attention. HEAs are characterized by a solid solution of typically five equiatomic metallic elements. In addition, medium-entropy alloys (MEA, with three elements) are of interest and become more and more important. Depending on the alloy concept, HEAs and MEAs show exceptional mechanical properties, especially high-strength and ductility combinations at both cryogenic and elevated temperatures combined with excellent corrosion resistance. Future structural HEA/MEA components can be exposed to potential applications with hydrogen containing environments like high-temperature water in pressurized nuclear reactors or aerospace structures. Other potential applications could be in materials for vessel walls in the field of cryogenic and high-pressure hydrogen storage. So far, the susceptibility of HEAs/MEAs to hydrogen assisted cracking (if any) and the hydrogen diffusion is not investigated in detail yet and can limit or extend possible applications of HEA/MEA as structural materials. In our work, we focused on the hydrogen absorption, diffusion, and distribution in a HEA (CoCrFeMnNi the original Cantor-alloy) and a MEA (CoCrNi). Cathodic hydrogen charging was carried out for the hydrogen ingress, and thermal desorption analysis (TDA) revealed complex hydrogen trapping in both alloy types up to 300 °C. The absorbed total hydrogen concentrations were > 100 ppm for the HEA and > 40 ppm for MEA. In addition, the assessment of the peak deconvolution is not trivial and must consider both experimental and microstructure influences.
Offshore wind turbines are an important goal in national energy strategies worldwide. Foundation structures are manufactured from submerged arc welded (SAW) plates with thicknesses up to 200 mm. In that connection, high-strength steels like the S420G2+M are more and more applied offering the possibility for increased stability and load-bearing capacity of the foundations. These offshore steel grades can show a susceptibility for delayed hydrogen assisted cold cracking of the weld joints. For that purpose, a minimum waiting time (MWT) of up to 48 h (dependent on applied standards) is recommended before non-destructive testing is allowed and conducted. But this concept is based on older steel grades that have been used for three or more decades. Nowadays, the metallurgical improvements (clean steels, proper rolling, and heat treatment) of base materials and well as welding consumables must be anticipated. Hence, the MWT concept should be critically discussed as it is assumed to be very conservative. For that reason, the focus of this study was to investigate the diffusion behavior in S420G2+M steel and its multi-layer SAW joint. Electrochemical permeation experiments were carried at room temperature. Boundary conditions were anticipated in terms of using different sample thicknesses. From the experimental data, hydrogen diffusion coefficients and absorbed diffusible hydrogen concentrations had been calculated. It was shown that hydrogen diffusion in the base material is increased compared to the weld metal. In addition, the sample thickness had a significant on the calculated diffusion coefficients. The minimum and maximum diffusion coefficients had been used for numerical modelling of the hydrogen diffusion in the welding joint. It became clear that a MWT must be always regarded together with a critical initial diffusible hydrogen concentration for the evaluation of a possible delayed cracking as diffusion times were mostly > 48 h due to the thick plates.
Safety and reliability are the major challenges to face for the development and acceptance of hydrogen technology. It is therefore crucial to study deeply material compatibility, in particular polymer materials that are directly in contact with hydrogen. This paper presents an experimental study on the fretting wear behavior of two types of cross-linked hydrogenated acrylonitrile butadiene rubbers against 316L steel ball in hydrogen environment. Furthermore, aging experiments were conducted for 7 days under static conditions in 100 MPa hydrogen. the influences of hydrogen pressure as well as the aging exposure on the fretting behavior are discussed by means of surface analyses along with the material properties.
The degradation effect of hydrogen on the mechanical properties of steels is well known, but still not sufficiently understood. The fast and safe market ramp up of hydrogen technologies makes it evident to evaluate a wider understanding of this topic. In general it is often described as hydrogen embrittlement. Therefore it is desirable to achieve a test method which is able to provide material properties under hydrogen atmosphere in an easy way. Currently mechanical tests under hydrogen atmosphere are executed in autoclaves. For this technique complex hardware is needed, therefore tests are expensive and test capacities are only available in a small scale. The shown test method promises a trendsetting approach for reducing costs and machine time by using hollow specimen.
Future structural components made of the novel high-entropy (HEA) or medium-entropy alloys (MEA) components can be potentially exposed to hydrogen containing environments like high-temperature water in pressurized nuclear reactors or aerospace structures. Further applications are vessels wall materials for cryogenic or high-pressure hydrogen storage. So far, the susceptibility of HEA/MEAs to hydrogen assisted cracking (if any) and the hydrogen diffusion is not investigated in detail yet and can limit or extend possible applications of HEA/MEA as structural materials. In our work, we focused on the hydrogen absorption, diffusion, and distribution in a HEA (Co20Cr20Fe20Mn20Ni20, the original Cantor-alloy) and a MEA (Co33.3Cr33.3Ni33.3). Conventional cathodic hydrogen charging was carried out for the hydrogen ingress in the materials. Thermal desorption analysis (TDA) via carrier gas hot extraction with coupled mass spectrometry revealed complex hydrogen trapping in both alloy types up to 300 °C. The absorbed total hydrogen concentrations were ≥ 70 ppm for the HEA and approximately 40 ppm for the MEA-type. Although both materials have different chemical composition, the TDA spectra were comparable. In addition, it was shown that the consideration of the sample geometry is an important influence on the sample temperature. It decreases the effective applied heating rate, which must be anticipated for each hydrogen peak after deconvolution of the spectra. This increases the activation energy and shifts the peak to lower temperatures. As a result, microstructure effects can be separated from experimental boundary conditions like the concentration gradient due to the charging process and later thermal activation.
Metals that are exposed to high pressure hydrogen gas may undergo detrimental failure by embrittlement. Understanding the mechanisms and driving forces of hydrogen absorption on the surface of metals is crucial for avoiding hydrogen embrittlement. In this study, the effect of stress-enhanced gaseous hydrogen uptake in bulk metals is investigated in detail. For that purpose, a generalized form of Sievert's law is derived from thermodynamic potentials considering the effect of microstructural trapping sites and multiaxial stresses. This new equation is parametrized and verified using experimental data for carbon steels, which were charged under gaseous hydrogen atmosphere at pressures up to 1000 bar. The role of microstructural trapping sites on the parameter identification is critically discussed.
Joining processes for components in hydrogen technologies: Current need and future importance
(2022)
This presentation gives an overview on the importance of joining processes for component fabrication in hydrogen technologies. For that reason, the current need and future research and developement activites are highlighted for the three technological fields: hydrogen storage, transport and use (in terms of the emerging field of additive manufacturing). Finally, some remarks are given for necessary changes in the standardization.
This lecture deals with the sliding behaviour of polymer materials in hydrogen environment. After a short introduction of the hydrogen activities at BAM, the tribological performances of polymer materials in gaseous hydrogen are presented and compared with air and vacuum environment. The second part focusses on the influence of the counterface materials in hydrogen. Finally, the last section is dedicated to experiments liquid hydrogen.
The focus of this study is to evaluate of hydrogen on the friction and wear behavior of a wide range of polymer materials. Thereby, the tribological performance of filled and unfilled polymers from different suppliers were compared at room temperature in air and hydrogen gas (H2) as well as in liquid hydrogen at -253°C (LH2).
This study gives an overview on the important field of joining processes for component fabrication in hydrogen technologies. For that reason, the current need and future research and developement activites are highlighted for the different technological field of hydrogen generation, storage, transport and use. In addition, the emerging field of additive manufacturing is included. Finally, some remarks are given for necessary changes in the standardization and its challenges.
Martensitic 9 %-Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. The small number of available diffusion coefficients varies already at room temperature by several orders of magnitude (mostly regarded as result of present microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. The diffusion coefficients are calculated by two methods (time-lag and inflection point method) were performed. The results show that, despite of microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
As more industrial interests focusing on using salt caverns and repurposed gas or petroleum reservoirs for alternative fuel storage, i.e. CO2/H2, the question raises whether microorganisms may impact the infrastructure, gas purity and storage condition over time.
Environments with high salinity (> 1.5 Meq of NaCl) are resided by halophiles (salt-loving microorganisms). To compensate for the intensive osmotic stress, they have resorted to two main adaptation strategies: 1) production of compatible solutes and 2) accumulation of intracellular KCl. Microbial community analysis of several high salinity environments revealed a number of recurring genera, including Halomonas and Halanaerobium. However, the impact of halophiles on the overall integrity and stability of the storage facilities remain largely unknown.
To evaluate the suitability and stability of saline storage facilities, several model halophilic microorganisms, such as members of Halomonas, will be selected as testing subjects. First, the impact of halophiles on the infrastructure will be determined using an integrative approach by combining a number of techniques, including electrochemistry, TOF-SIMS, SEM/FIB/EDS and FIB-TEM. Second, the abilities of halophiles to alter the fuel composition (i.e. increase/decrease the fractions of H2) will be monitored using gas chromatography by growing them under high pressure.
As a result of climate change and the accompanying mandatory shift to renewable energy resources, microorganisms will continue to play an important role in the energy sector, both to their benefit and detriment. Thus, it is important to achieve a certain level of understanding regarding the activities and mechanisms of halophiles prior to large-scaled excursions.
The focus of this study is to evaluate the influence of hydrogen on the friction and wear behavior of a wide range of polymer materials. Thereby, the tribological performance of filled und unfilled polymers from different suppliers were compared at room temperature in air and hydrogen gas (H2) as well as in liquid hydrogen at -235°C (LH2).
Offshore wind turbines (OWT) are a major goal of the energy strategy of Germany encompassing the increase of the installed wind power. OWT components are manufactured from welded steel plates with thicknesses up to 200 mm. The underlying standards and technical recommendations for construction of OWTs encompass specifications of so-called minimum waiting time (MWT) before non-destructive testing of the weld joints is allowed. Reason is the increased risk of time-delayed hydrogen assisted cold cracking as hydrogen diffusion is very slow due to the very thick plates. The strict consideration of those long MWT up to 48 h during the construction of OWTs leads to significant financial burden (like disproportionately high costs for installer ships as well as storage problems (onshore)). In this study, weld joints made of S355 ML were examined in comparison with the offshore steel grade S460 G2+M. The aim was to optimize, i.e., reduce, the MWT before NDT considering varied heat input, hydrogen concentration and using self-restraint weld tests. This would significantly reduce the manufacturing time and costs of OWT construction. To quantify the necessary delay time until hydrogen-assisted cold cracks appear, acoustic emission analysis was applied directly after welding for at least 48 h.
Martensitic 9 %-Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. The small number of available diffusion coefficients varies already at room temperature by several orders of magnitude (mostly regarded as result of present microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. The diffusion coefficients are calculated by two methods (time-lag and inflection point method) were performed. The results show that, despite of microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
High-entropy alloys (HEAs) are characterized by a solid solution of minimum five and medium-entropy alloys (MEAs) of minimum three principal alloying elements in equiatomic proportions. They show exceptional application properties, such as high-strength and ductility or corrosion resistance. Future HEA/MEA-components could be exposed to hydrogen containing environments like vessels for cryogenic or high-pressure storage where the hydrogen absorption and diffusion in these materials is of interest. In our study, we investigated the HEA Co20Cr20Fe20Mn20Ni20 and the MEA Co33.3Cr33.3Ni33.3. For hydrogen ingress, cathodic charging was applied and diffusion kinetic was measured by high-resolution thermal desorption spectros-copy using different heating rates up to 0.250 K/s. Peak deconvolution resulted in high-temperature desorption peaks and hydrogen trapping above 280 °C. A total hydrogen concentration > 40 ppm was identified for the MEA and > 100 ppm for HEA. This indicates two important effects: (1) delayed hydrogen diffusion and (2) considerable amount of trapped hydrogen that must be anticipated for hydrogen assisted cracking phenomenon. Local electrochemical Volta potential maps had been measured for the hydrogen free condition by means of high-resolution Scanning Kelvin Probe Force Microscopy (SKPFM).
Hydrogen-charged supermartensitic steel samples were used to systematically investigate imaging artifacts in neutron radiography. Cadmium stencils were placed around the samples to shield the scintillator from excessive neutron radiation and to investigate the influence of the backlight effect. The contribution of scattered neutrons to the total detected intensity was investigated by additionally varying the sample-detector distance and applying a functional correlation between distance and intensity. Furthermore, the influence of the surface roughness on the edge effect due to refraction was investigated.
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.
Effect of weld penetration depth on hydrogen-assisted cracking of high-strength structural steels
(2019)
The need for steels with highest mechanical properties is a result of the increasing demands for energy and resource efficiency. In this context, high-strength structural (HSS) steels are used in machine, steel and crane construction with yield strength up to 960 MPa. However, welding of HSS steels requires profound knowledge of three factors in terms of avoidance of hydrogen-assisted cracking (HAC): the interaction of (1) microstructure, (2) local stress/strain and (3) local hydrogen concentration. In addition to the three main factors, the used weld-arc process is also important for the performance of the welded joint, especially when using modern arc variants. In the past, the conventional transitional arc process (Conv. A) was mainly used for welding of HSS grades. In the past decade, the so-called modified spray arc process (Mod. SA) has been used increasingly for welding production. This modified process enables reduced seam opening angles with increased deposition rates compared to the conventional process. Economic benefits of using this arc type are: a reduced number of necessary weld beads and a lower weld seam volume, which result in decreased total welding time and costs. Nonetheless, investigations on a high-strength S960QL showed significantly higher hydrogen concentrations in the weld metal at a reduced seam opening angle with Mod. SA. This indicates an increased susceptibility of the welded component to HAC. Hence, existing recommendations on HAC-avoidance cannot be transferred directly to the Mod. SA-process. In the present study, the susceptibility to HAC of the HSS steel S960QL with same type of filler material was investigated. For that purpose, both Conv. A and Mod. SA were used with same heat input at different deposition rates. For assessment of the HAC susceptibility, the externally loaded implant test was used. Both conducted test series with Conv. A and Mod. SA showed similar crack critical stress of about 280 MPa. Below this value, no delayed fracture appeared. The welds with Mod. SA showed higher hydrogen concentrations. The fracture occurred in the heat-affected zone (HAZ) or in the weld metal (WM). However, the test series with Mod. SA showed a significant extension of the time to failure of several hours compared to tests carried out with Conv. A.
9 %-Cr steel P91 is widely used in power plants due to the excellent creep-resistance. Components of this steel are typically welded and demand for careful welding fabrication, whereas a so-called post weld heat treatment (PWHT), must be conducted to increase the toughness and decrease the hardness of the martensitic as-welded (AW) microstructure. Before the PWHT, a hydrogen removal (or dehydrogenation) heat treatment is necessary as hardened AW martensitic microstructure is generally prone to delayed hydrogen assisted cracking (HAC). The microstructure and temperature dependent hydrogen diffusion is an important issue as it determines how long a potential crack-critical hydrogen concentration could remain in the microstructure. In this context, reliable hydrogen diffusion coefficients of P91 weld metal are rare. Hence, the diffusion behavior of P91 multi-layer weld metal was investigated in two different microstructure conditions: AW and further PWHT (760 °C for 4 h). Two different experimental techniques were used to cover a wide range of hydrogen diffusion temperatures: the electrochemical permeation technique (PT) at room temperature and the carrier gas hot extraction (CGHE) for a temperature range from 100 to 400 °C. From both techniques typical hydrogen diffusion coefficients were calculated and the corresponding hydrogen concentration was measured. It was ascertained that both heat treatment conditions show significant differences in hydrogen diffusivity. The biggest deviations were identified for room temperature. In this case, the AW condition shows significant hydrogen trapping and up to seven times lower diffusion coefficients. Additionally, PT investigations showed a preferred diffusion direction of hydrogen in the weld metal expressed by the diffusion coefficients and the permeability for both heat treatment conditions. The CGHE generally revealed lower diffusion coefficients for the AW microstructure up to 200 °C. In addition, the AW condition showed hydrogen concentrations up to 50 ml/100 g (considering electrochemical charging). Nonetheless, this hydrogen was not permanently (reversibly) trapped. Nonetheless, this temperature is approximately 100 °C below recommended dehydrogenation heat treatment (DHT). This has two main consequences: (I) in case of welding is interrupted or no DHT is conducted, a HAC susceptibility of hardened martensitic P91 weld metal cannot be excluded and (II) DHT can be conducted at temperatures around 200 °C below the recommended temperatures.
9 %-Cr steels like P91 and P92 are widely used in power plants due to the excellent creep-resistance. Components of this steel are typically welded and demand for careful welding fabrication, whereas a so-called post weld heat treatment (PWHT), must be conducted to increase the toughness and decrease the hardness of the martensitic as-welded (AW) microstructure. Before the PWHT, a hydrogen removal (or dehydrogenation) heat treatment is necessary as hardened AW martensitic microstructure is generally prone to delayed hydrogen assisted cracking (HAC). The microstructure and temperature dependent hydrogen diffusion is an important issue as it determines how long a potential crack-critical hydrogen concentration could remain in the microstructure. In this context, reliable hydrogen diffusion coefficients of P91 and P92 weld metal are rare.
Hydrogen was once called “the versatile embrittler” [1], which summarizes very well the effect on reduction of ductility and/or toughness in technical alloys like steel. In that connection, welding is one of the most important component fabrication technologies. During welding, hydrogen can be transferred to the weld pool from manifold sources (like contaminations, residuals at the surface, etc.). As hydrogen embrittles a material, the safety of welded components with hydrogen is always a critical issue. Weld heat input causes additional changes in the microstructure like grain growth or partial dissolution of precipitates and many more. All these things influence the mechanical properties and also represent hydrogen traps. These traps decrease the hydrogen diffusion compared to the ideal lattice. The result can be so-called delayed hydrogen assisted cracking (HAC) of the weld joint due to the significantly decreased diffusivity by trapped hydrogen. This is often an underestimated risk as those cracks can appear in the weld joint even after some days!
It is essential to know about hydrogen ingress during welding and the microstructure specific hydrogen diffusion. Both are depended on weld parameter influence and the chemical composition of the base material and weld metal. For that purpose, gas analytic methods like solid-state carrier gas hot extraction (CGHE) are useful tools to: (1) identify detrimental hydrogen concentrations from weld joints, (2) binding energies from hydrogen traps by thermal desorption analysis or (3) high-temperature diffusion coefficients. Those values are extremely important for welding practice in terms of recommendations on realistic hydrogen removal heat treatment (HRHT) after welding. Considering the increasing use of “digital” experiments, the data is also needed for reliable numerical simulations of HAC process or HRHT-effectiveness.
The present contribution gives an overview on the influence of hydrogen on weld joints, the necessity, methods and standards for hydrogen determination (CGHE) with the aim of fabrication of safe welded and crack-free components.
[1] R. A. Oriani (1987), Corrosion 43(7):390-397. doi: 10.5006/1.3583875
The development of hydrogen technologies is a key strategy to reduce greenhouse gas emission worldwide. Power-to-Gas is a challenging solution, in which hydrogen and methane can be used in mobility, industry, heat supply and electricity generation applications. This presentation deals with the tribological behaviour of polymer materials in hydrogen and methane, both in gas and in liquefied form.
High-strength low-alloyed (HSLA) steels with yield strength ≥ 690 MPa are gaining popularity in civil engineering and construction of heavy vehicles. With increasing yield strength, the susceptibility for degradation of the mechanical properties in the presence of diffusible hydrogen, i.e., hydrogen-assisted cracking (HAC), generally increases. HAC is a result of the critical interaction between local microstructure, mechanical load, and hydrogen concentration. In existing standards for welding of HSLA-steels, recommendations including working temperatures and dehydrogenation heat treatment (DHT) are given to Limit the amount of introduced hydrogen during welding. These recommendations are based on investigations into conventional arc welding processes. In the past decade, modern weld technologies were developed to enable welding of narrower weld seams with V-grooves of 30°, e.g., the modified spray arc process. In that connection, a reduced number of weld runs and weld volume are important technical and, economic benefits. In the present study, the hydrogen distribution in S960QL multi-layer welds with thickness of 20 mm was analyzed. The influence of different weld seam opening angles, heat input, working temperature and DHT were investigated. The results show that weldments with narrow grooves contained an increased amount of diffusible hydrogen. Hydrogen concentration has been reduced by decreasing both the heat input and working temperature. Hydrogen-free weldments were only achieved via subsequent DHT after welding. Furthermore, hydrogen distribution was experimentally determined across the weld seam thickness in HSLA gas metal arc welded multi-layer welds for the first time.
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).
Among the very few techniques to localize hydrogen (H) at the microscale in steels, Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a reliable tool. The necessity to detect hydrogen stems from its deleterious effects in metals, that are often used as structural components and to obtain better understanding of the underlying metallurgical mechanisms of hydrogen embrittlement (HE) which are still unclear.
Austenitic stainless steels are nowadays commonly used in a wide variety of application, from hydrogen transport and storage facilities to petrochemical and offshore applications where they are exposed to aggressive environments and therefore prone to HE. One of the greater risks in the austenitic class is the embrittlement of the material due to the instability of the γ austenite and its transformation into a brittle α martensitic phase. This transformation takes place due to the local stresses that are induced by the uptake of hydrogen during service. Nonetheless, it was shown that this transformation can occur as an artefact during SIMS analysis itself where Cs-sputtering is necessary not only to remove surface contaminations but mainly to enhance H/D secondary ion yield.
In the following contribution we show the influence of different sputtering conditions on AISI 304L austenitic stainless steel in order to distinguish the artefact from the hydrogen induced transformation. The material was charged electrochemically in a deuterium based electrolyte. Deuterium (D) must be in these experiments as a replacement for hydrogen which cannot be used because adsorbed hydrogen superimposes hydrogen originating from charging the sample in the SIMS images. ToF-SIMS analyses were conducted by ToF SIMS IV (IONTOF GmbH, Münster, Germany). The experiments were carried out on deuterium charged and non-charged samples. The structural characterization was carried out by SEM and EBSD examinations before and after charging, both with a Leo Gemeni 1530VP field-emission scanning electron microscope and a Zeiss Supra 40 instrument (Carl Zeiss Microscopy GmbH, Oberkochen, Germany). The results showed that the use of 1keV Cs+ beam induces stacking faults while higher sputter beam energies results in γ→α transformation.
Due to their excellent combination of ductility, strength and corrosive resistance, austenitic stainless steels (ASS) are widely used in many industrial applications. Thus, these steel grades can be found as structural components in the (petro-)chemical industry, in offshore applications and more recent for storage and transport of hydrogen fuel. Steels employed for these applications are exposed to aggressive environments and hydrogen containing media. The ingress and accumulation of hydrogen into the microstructure is commonly observed during service leading to a phenomenon called “hydrogen embrittlement”. A loss in ductility and strength, the formation of cracks and phase transformations are typical features of this hydrogen-induced degradation of mechanical properties.
Although, great efforts are made to understanding hydrogen embrittlement, there is an ongoing debate of the underlying mechanisms. This knowledge is crucial for the safe use and durability of components on the one side and the development of new materials on the other.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a powerful tool for depicting the distribution of the hydrogen isotope deuterium in the microstructure of austenitic and duplex steels. The combination with imaging techniques such as electron backscatter diffraction (EBSD) and scanning electron microscopy (SEM), delivering structural and morphological information, creates a comprehensive picture of the hydrogen/deuterium-induced effects in the materials. All the gathered data is treated with principal component analysis (PCA) and data fusion to enhance the depth of information.
The mobility of hydrogen and deuterium in a steel microstructure is affected by external mechanical stress. To investigate the behaviour of deuterium in a strained microstructure, a new in situ experimental approach was developed. This gives the possibility of analysing samples in the SIMS instrument simultaneously to four-point-bending-tests.
Specimens made from ASS AISI 304L were electrochemically charged with deuterium instead of hydrogen. This necessity stems from the difficulty to separate between artificially charged hydrogen and hydrogen existing in the pristine material or adsorbed from the rest gas in the analysis chamber. Nonetheless, similar diffusion, permeation and solubility data allow to draw qualitative conclusions from the experiments, which are relevant for the application addressed.
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.
High-strength low-alloyed (HSLA) steels with yield strength ≥ 690 MPa are gaining popularity in civil engineering and construction of heavy vehicles. With increasing yield strength, the susceptibility for degradation of the mechanical properties in presence of diffusible hydrogen, i.e. hydrogen-assisted cracking (HAC) generally increases. HAC is a result of the critical interaction of local microstructure, mechanical load and hydrogen concentration. In existing standards for welding of HSLA steels, recommendations like working temperatures and dehydrogenation heat treatment (DHT) are given to limit the amount of introduced hydrogen during welding. The recommendations are based on investigations with conventional arc welding processes. In the past decade, modern weld technologies were developed to enable welding of narrower weld seams with V-grooves of 30°, e.g. the modified spray arc process. In that connection, a reduced number of weld runs and weld volume are important technical and, hence, economic benefits. In the present study, the hydrogen distribution in S960QL multi-layer welds with thickness of 20 mm was analyzed. The influence of different weld seam opening angles, heat input, working temperature and DHT was investigated. The results show that weldments with narrow groove contained increased diffusible hydrogen amount. Hydrogen concentration has been reduced by decreasing both the heat input and working temperature. Hydrogen free weldments were only achieved via subsequent DHT after welding. Furthermore, hydrogen distribution was experimentally determined across the weld seam thickness in HSLA GMA welded multi-layer welds for the first time.
Carrier gas hot extraction (CGHE) is a commonly applied technique for determination of hydrogen in welded joints using a thermal conductivity device (TCD) for quantitative 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 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 PID-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 the reach 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 calibration specimens is useful for further data analysis, especially if this data is used for calculation of trapping kinetics by thermal desorption analysis (TDA).
Neutron cameras allow visualizing hydrogen distributions with radiographic or tomographic imaging methods in iron and steel. The necessary contrast between hydrogen and iron stems from the high difference in the total neutron cross section of both elements. This allows e.g. the in situ measurement of hydrogen mass flow inside cm thick steel samples with a temporal resolution of 20 s using neutron radiography as well as the quantitative measurement of hydrogen accumulations at the crack’s inner surfaces in hydrogen embrittled iron samples with neutron tomography. We could detect directly gaseous hydrogen in the crack cavities and we measured the gas pressure. This new quality of the information on a micrometer scale allows new insights for the analysis of hydrogen-induced damage mechanisms. Further, this method is non-destructive and provides local information in situ and in three dimensions with a spatial resolution of 20-30 µm. In this contribution, we show examples that demonstrate the spatial and temporal resolution of the neutron radiography and tomography methods in order to visualize and quantify hydrogen accumulations at cracks. The measurements were performed at the research reactor BER II of the HZB in Berlin and at the FRM II reactor of the neutron source Heinz Maier-Leibnitz in Garching.
Neutron cameras allow visualizing hydrogen distributions with radiographic or tomographic imaging methods in iron and steel.
The necessary contrast between hydrogen and iron stems from the high difference in the total neutron cross section of both elements. This allows e.g. the in situ measurement of hydrogen mass flow inside cm thick steel samples with a temporal resolution of 20 s using neutron radiography as well as the quantitative measurement of hydrogen accumulations at the crack’s inner surfaces in hydrogen embrittled iron samples with neutron tomography. We could detect directly gaseous hydrogen in the crack cavities and we measured the gas pressure. This new quality of the information on a micrometer scale allows new insights for the analysis of hydrogen-induced damage mechanisms. Further, this method is non-destructive and provides local information in situ and in three dimensions with a spatial resolution of 20-30 μm.
In this contribution, we show examples that demonstrate the spatial and temporal resolution of the neutron radiography and tomography methods in order to visualize and quantify hydrogen accumulations at cracks. The measurements were performed
at the research reactor BER II of the HZB in Berlin and at the FRM II reactor of the neutron source Heinz Maier-Leibnitz in
Garching.
The reduction of harmful emissions to the environment is one of the most urgent challenges of our time. To achieve this goal, it is inevitable to shift from using fossil fuels to renewable energy sources. Within this transition, hydrogen can play a key role serving as fuel in transportation and as means for energy storage.
The storage and transport of hydrogen using austenitic stainless steels as the infrastructure, as well as the use of these grades in hydrogen containing aggressive environments, remains problematic. The degradation of the mechanical properties and the possibility of phase transformation by ingress and accumulation of hydrogen are the main drawbacks. Advanced studies of the behaviour of hydrogen in austenite is necessary to fully understand the occurring damage processes. This knowledge is crucial for the safe use of components in industry and transportation facilities of hydrogen.
A powerful tool for depicting the distribution of hydrogen in steels, with high accuracy and resolution, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). We here present a comprehensive research on the hydrogen degradation processes in AISI 304L based on electrochemical charging and subsequent ToF-SIMS experiments. To obtain furthermore information about the structural composition and cracking behaviour, electron-backscattered diffraction (EBSD) and scanning electron microscopy (SEM) were performed afterwards. All the gathered data was treated employing data fusion, thus creating a thorough portrait of hydrogen diffusion and its damaging effects in AISI 304L.
Specimens were charged with deuterium instead of hydrogen. This necessity stems from the difficulty to separate between artificially charged hydrogen and traces existing in the material or adsorbed from the rest gas in the analysis chamber. Similar diffusion and permeation behaviour, as well as solubility, allow nonetheless to draw onclusions from the experiments.
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.
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.
High-strength low-alloyed (HSLA) steels with yield strength ≥ 690 MPa have increasing im-portance in steel construction and civil engineering. However, weld processing of those steels is a major challenge. The susceptibility for degradation of mechanical properties of weld joints sig-nificantly increases in presence of hydrogen and can result in hydrogen assisted cracking (HAC). Generally, risk for HAC increases with increasing yield strength of HSLA steels. To min-imize the incidence of HAC, it is essential to gain knowledge about both the (1) absorbed hydro-gen amount and its distribution in the weld seam and (2) options to lower the amount of intro-duced hydrogen. Existing standards recommend heat treatment procedures (interpass tempera-ture or post weld heat treatment) to reduce the diffusible hydrogen concentration in weldments. In this context, different weld seam geometries should be considered. For HSLA steel fabrication weld processing with seam opening angles of 45° to 60° is typical. Modern weld technologies allow welding with seam opening angles of 30° - reduced welding time and costs. In the present study, the hydrogen distribution in multi-layer welds of a 960 MPa HSLA steel was analysed. Influence of different seam opening angles as well as heat input, interpass temperature and post weld heat treatments were investigated. The welded samples were quenched in ice water imme-diately after welding and subsequently stored in liquid nitrogen. After defined warming up, small specimens were machined from the weld seam by water jet cutting. The diffusible hydrogen concentration was measured by carrier gas hot extraction with coupled mass spectrometer. The results showed, that low heat input and post weld heat treatment procedures can lower hydrogen concentrations in welds. Furthermore, a gradient of the hydrogen concentration was identified with increasing weld pool depth. By varying the seam opening angles different hydrogen concen-trations were measured.
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 development of hydrogen technologies is a key strategy to reduce greenhouse gas emission worldwide. Power-to-Gas is a challenging solution, in which hydrogen and methane can be used in mobility, industry, heat supply and electriity generation applications. This presentation deals with the tribological behaviour of polymer materials in hydrogen and methane, both in gas and in liquid form.
Hydrogen determination in weld seams is standardized in ISO 3690. In accordance to this standard, a defined time for hydrogen collection has to be anticipated for different extraction temperatures. In other words, the temperature is the most important value that has to be monitored in addition to the aimed hydrogen determination.
The specimen geometry has influence on the real sample temperature during CGHE vs. the adjusted furnace temperature. This presentation gives a short summary on possible influences on the "correct" hydrogen determination temperature during carrier gas hot extraction (CGHE) using infrared radiation driven furnace. The main findings are: (1) specimen surface is important in terms of polished or oxidized condition, (2) specimen geometry is important for fast heating, (3) PID-values of control software are a considerable influence to accelerate the heating process depite thick specimens and (4) independent sample temperature determination before CGHE is strongly recommended.
The tribological characteristics of pure and graphite filled polymers were investigated in gaseous hydrogen at ambient temperatures and in LH2 at -253°C. It could be shown that the tribological properties of PI and PEEK materials is related to the formation of a transfer film. The influence of both hydrogen and cryogenic temperatures will be discussed in the presentation.
The tribological characteristics of pure and graphite filled polymers were investigated in gaseous hydrogen at ambient temperatures and in LH2 at -253°C. It could be shown that the tribological properties of PI and PEEK materials is related to the formation of a transfer film. The influence of both hydrogen and cryogenic temperatures will be discussed in the presentation.
In order to satisfy the growing requirements towards lightweight design and resource efficiency in modern steel constructions, e.g., mobile cranes and bridges, high-strength steels with typical yield strength ≥ 690 MPa are coming into use to an increasing extent. However, these steels require special treatment in welding. The susceptibility for degradation of the mechanical properties
in the presence of hydrogen increases significantly with increasing yield strength. In case of missing knowledge about how and the amount of hydrogen that is uptaken during welding, hydrogen-assisted cracking (HAC) can be a negative consequence.
Moreover, modern weld technology like the modified spray arc process enables welding of narrower weld seams. In this context,
a reduced number of weld beads, volume, and total heat input are technical and economical benefits. This work presents the influence of welding parameters on the diffusible hydrogen content in both (1) single-pass and (2) multi-layer welds. Different
hydrogen concentrations were detected by varied contact tube distance, wire feed speed, arc length, and varied arc type (transitional
arc and modified spray arc). The results show that all welding parameters have significant influence on the diffusible hydrogen concentration in the single-pass welds. By increasing the number of weld beads in case of multi-layer welding, the
hydrogen concentration has been reduced. Whereby, differences in hydrogen concentrations between both arc types are present.
Neutron imaging has become a valuable tool for measuring hydrogen distributions qualitatively and quantitatively in metals. Hydrogen mass flow can be measured inside cm thick Steel samples with 10 s temporal resolution. Hydrogen accumulations around craclcs in embrittled iron samples can be visualized three-dimensionally. The gas pressure of hydrogen in crack cavities has been measured to be in the ränge of 5 MPa to 15 MPa. This quality of information allows new insights for the analysis of damage mechanisms on a micrometer scale, e.g., of hydrogen blistering. Further, this method is nondestructive and provides local information in situ and in three dimensions with a spatial resolution of 20 µm - 30 µm.
Current interest in hydrogen gas as an energy source is growing due to its attractive properties such as high chemical energy density and the fact that its combustion produces water as by-product, qualifying this gas as an appealing clean energy source. In particular, the use of molecular hydrogen in automotive applications such as the hydrogen internal combustion engine (HICE) or hydrogen fuel cells is an excellent clean alternative.
Despite these promising opportunities, hydrogen gas has a distinct disadvantage as an everyday energy medium, that is, it is highly flammable. Hydrogen processing apparatuses should therefore be constantly monitored so that leaks are immediately detected. The implementation of direct sensing systems for H2(g) is thus a decisive factor for its application and acceptance as a clean energy source. Because the automotive market alone is already a mass market, these sensors do not only have to be reliable, robust and dimensionally small, but operation has to be simple and the device itself cost-effective. In addition, very low detection limits are a must as already escape of small quantities of H2(g) is directly related to public health and safety. Besides electrochemical or semiconductor sensors, optical sensors are especially appealing because the equipment is usually simple and accessible, easily miniaturized and measurements can be performed in situ and in real time.
If one cannot rely for instance on metallic palladium as interacting matrix, a major challenge for optochemical hydrogen sensors is to find a suitable material that fulfils all the requirements mentioned above and undergoes a dedicated indication reaction with H2(g). One such alternative can be Metal-Organic Frameworks (MOFs) which constitute a predefined, organized, mesoporous structure built up from metal ions and organic bridging ligands. With a myriad of building blocks being available, MOFs can be equipped with internal H2 reception sites that shall allow for selective and sensitive indication. For instance, if Pd ions are implemented in such a way that they express open metal sites (OMS), these OMS shall possess a strong affinity for hydrogen. If light absorbing and emitting organic ligands are additionally chosen, luminescent MOFs (LMOFs) can result that are perfect candidates for optical sensors, as changes at the analyte reception site can be effectively transduced into a measurable signal.
In this contribution, we intended to discuss the development of a new luminescent sensor material for the detection of the highly flammable H2(g). This sensor material is based on an LMOF assembled from Pd(II) and aromatic bridging ligands, the advent of hydrogen at the OMS in the LMOF producing distinct variations in the material’s optical properties.
In the course of 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 scientific community alike.
The storage and transport of hydrogen, which is nowadays mainly realised by austenitic stainless steels, remains problematic. That is due to the degradation of mechanical properties and the possibility of phase transformation by hydrogen diffusion and accumulation. Development of materials and technologies requires a fundamental understanding of these degradation processes. Therefore, studying the behaviour 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 (ToF-SIMS) was conducted after electrochemical charging. To obtain furthermore information about the structural composition and cracking behaviour, electron-backscattered diffraction (EBSD) and scanning electron microscopy (SEM) were performed. Gathered data of chemical composition and topography was 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 behaviour, as well as solubility, allow nonetheless to draw conclusions from the experiments.
Metallic organic frameworks are the materials stirring great interest by their large variety of structure types and chemical composition as well as low density and very high surface area, which are desirable properties for gas storage such as for hydrogen, methane or carbon dioxide. Using different so called secondary building units offer an opportunity to form tunable structures with channels of various geometry and allow in this way to study the absorption of the molecular hydrogen, methane or carbon dioxid in the systematic way.
In order to satisfy the growing requirements towards lightweight design and resource efficiency in modern steel constructions, e.g. mobile cranes and bridges, high-strength steels with typical yield strength ≥ 690 MPa are coming into use to an increasing extent. However, these steels require special treatment in welding. The susceptibility for degradation of the mechanical properties in presence of hydrogen increases significantly with increasing yield strength. In case of missing knowledge about how and which amount of hydrogen is uptaken during welding, hydrogen assisted cracking (HAC) can be a negative consequence. Moreover, modern weld technology like the modified spray arc process enables welding of narrower weld seams. In this context, a reduced number of weld beads, volume and total heat input are technical and economic benefits. This work presents the influence of welding parameters on the diffusible hydrogen content in both singlepass and multi-layer welds. Different hydrogen concentrations were detected by varied contact tube distance, wire feed speed, arc length as well as varied arc type (transitional arc and modified spray arc). The results show, that all welding parameters have significant influence on the diffusible hydrogen concentration in the single-pass welds. By increasing the number of weld beads in case of multi-layer welding, the hydrogen concentration have been substantially reduced. Whereby, differences in hydrogen concentrations between both arc types are present.
Trapping in T24 steel weld joints – Effects on activation energy for hydrogen diffusion during TDA
(2017)
Failure cases in the past decade exhibited severe cracking in T24 welds and showed that generally hydrogen-assisted cracking (HAC) occurring up to 200°C cannot be excluded. A basic understanding is necessary on how hydrogen diffusion is influenced by the weld process. In this regard, both weld microstructures HAZ and weld metal have particular influence on hydrogen diffusion compared to the base material. In general, hydrogen diffusion at a certain temperature is described by diffusion coefficients representing an effective value of combined lattice diffusion and effects of reversible hydrogen traps. Those traps are typically precipitates, interstitials, grain boundaries and so on. A common approach to describe the trap character and its effect on diffusion is the determination of so-called activation energy. This can be done by respective thermal desorption analysis (TDA) with linear heating. In the present study, different T24 as-welded microstructures (BM, HAZ, WM) were investigated. For that purpose, electrochemically hydrogen charged specimens were analyzed by TDA with linear heating using a mass spectrometer for detection of ultra-low hydrogen amounts. The results showed that typically the as-welded HAZ had higher energy traps than the tempered base material. Nonetheless two important effects were ascertained: (1) it is strictly necessary to monitor the sample temperature due to its great impact on the hydrogen desorption peak temperature and (2) the real heating rate in the specimen vs. the applied heating rate has to be considered. Both influence the calculated activation energy, i.e. the assigned hydrogen trap character (moderate or strong trap), which changed up to a factor of two in terms of the calculated activation energy. This effect can be much more important compared to the microstructure effect itself. Hence, suitable experimental boundary conditions should be mandatory for the determination of hydrogen trap kinetics.
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.
Molybdenum disulfide (MoS₂) is a well-known solid lubricant for tribosystems running in vacuum or dry gases. Problems arise due to its sensitivity to humidity, which is a drawback for its application under ambient conditions. However, by using a physical vapor deposition (PVD) process, deposition parameters can be optimized not only to gain a coatings structure with favorable frictional properties but also to minimize the sensitivity to attack by water molecules. Therefore, an improved tribological behavior even under moist conditions can be achieved. MoS₂coatings are also candidates for being applied at cryogenic temperatures. They already have proven their suitability, e.g., for sliding support elements between superconducting magnets of the nuclear fusion-experiment Wendelstein 7-X. However, these coatings were exclusively produced for this particular application and the utilization for more common tribosystems may be precluded due to cost considerations. In view of a wider range of applications, pure and Cr containing PVD-MoS₂ coatings with an optimized structure were tested under varying environments including hydrogen gas and cryogenic temperatures. Results of the most promising variant are presented in this paper.
The tribological behaviour of polyetheretherketone (PEEK) and polyimide (PI) composites was investigated in air, vacuum and hydrogen environments. Polymers were filled with graphite, submicron particles or carbon nano-tubes. Experiments reveal that hydrogen environment has a major influence on both polymer structure and fillers during sliding. The sliding behaviour of these polymer composites is much improved in hydrogen compared to air. In particular, graphite and nano-particles have a remarkable effect on friction and wear, respectively.
Fatigue crack propagation investigations have been performed in austenitic-ferritic duplex stainless steel H22N5M3 in air and during hydrogen charging, using various frequencies of loading. Strong differences of crack propagation velocity depending on the test conditions were noticed. Lower frequency with applied hydrogen charging led to the huge increase of crack propagation velocity compared to the tests performed in air. To understand such a behaviour in each case and characterize crack mode, the samples were observed using electron back-scattered diffraction (EBSD). It was shown that in air, the fatigue crack propagation involved plastic deformation and the resulting cracks had ductile character. The presence of hydrogen led to more brittle mode of cracking. This effect was also connected with frequency of loading: lower frequency, which assured longer time for hydrogen-crack tip interaction, resulted in the highest crack propagation velocity and the brittle cracking mode with lower amount of plastic deformation. The performed observations indicated that the path of the crack went mostly transgranularly through both austenite and ferrite phases. Phase and grain boundaries were not the preferred paths for crack propagation.
The hydrogen influence on the microstructure of the austenitic-ferritic Cr22-Ni5-Mo3 stainless steel was investigated. Cathodic hydrogen charging was performed electrochemically from aqueous solution of 0.1M H2SO4 with hydrogen entry promoter addition. The aim of this study was to reveal microstructural changes appearing during the hydrogen charging and particularly to clarify the occurrence of phase transformations induced by hydrogen. The specific changes in both phases of steel were observed. In the ferritic phase, strong increase of dislocation density was noticed. Longer time of hydrogen charging leaded also to the strips and twin plates formation in ferrite phase. In the austenitic phase, the generation of stacking faults, followed by the formation of α' martensite was remarked.
Low-alloyed CrMoV steels, such as T24, are widely used for welded components in fossil power stations due to their excellent creep-strength. Spectacular failure cases in the recent years exhibited severe cracking in T24 welds. The results showed that hydrogen-assisted cracking (HAC) occurring up to 200 degree Celsius cannot be excluded. Hence, a basic understanding is necessary on how hydrogen affects the material properties of welded microstructures. In this regard, each weld microstructure (HAZ and weld metal) has influence on the HAC susceptibility and respective hydrogen diffusion. Thus, the present contribution summarizes different results obtained from experiments with grades T24 (CrMoV alloy) and T22 (CrMo) and thermally simulated HAZ. Tensile tests were conducted with hydrogen charged specimens and compared to hydrogen-assisted stress corrosion cracking results obtained from slow strain rate tests (SSRT) up to 200 degree Celsius. Electrochemical permeation and degassing experiments were performed to identify a particular weld microstructure influence on hydrogen diffusion and trapping (especially in the HAZ). The results showed that T24 base material has improved resistance to hydrogen-assisted degradation/cracking. In contrast, the as-welded HAZ had remarkably increased susceptibility (tesnile tests at hydrogen concentration of 1 to 2 ppm). SSRT experiments confirmed this at elevated temperatures for both the T24 and the T22. Hence, the evaluation of a particular degradation of the mechanical properties should be performed independently for each weld microstructure. In addition, the HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the base materials. Trapped hydrogen was determined in the T24 at temperatures up to 120 degree Celsius compared to 75 degree Celsius in the T22. This has to be considered in case of changing operational temperatures, e.g. in the case of start-up and shutdown processes of boiler components.
Hydrogen-assisted cracking (HAC) represents a significant failure risk for (high strength) creep resistant low-alloyed steel components in fossil-fired power plant applications at temperatures of up to and above 200 °C. This particularly applies to respective start-up and shut-down processes associated with alternating service-conditions in terms of load flexible power plants. For quantitative determination of localized crack critical hydrogen concentrations, the temperature dependent hydrogen diffusion coefficients have to be determined as exactly as possible.
However, available literature provides a wide range of hydrogen diffusion coefficients for low alloyed steels with similar microstructures. Additionally, the available diffusion data seem not to be very reliable and their scatter increases with decreasing temperature. One reason is that the experimental boundary conditions can have a major impact on the determination of respective effective diffusion coefficients. Hence, the scope of this study is to evaluate the influence of the experimental boundary conditions on the derived diffusion coefficients. In addition, different methods for calculating diffusion coefficients are discussed. To elucidate such influences and to draw a line to practical application, the diffusion and trapping behavior in the creep resistant steel 7CrMoVTiB10 10 has been studied.
For such purpose, hydrogen charged specimens were isothermally degassed at different temperatures using carrier gas hot extraction (CGHE). Based on experimental data, a numerical model has been developed by which the hydrogen transport behavior and the respective hydrogen distribution during CGHE can be assessed.
It is demonstrated that the specimen heating rate has a large influence on the calculated diffusion coefficients under assumption of isothermal degassing which elsewhere has been underestimated in the assessment of diffusion data in creep-resistant steels. The numerical results suggest that calculation methods for diffusion coefficients are limited if compared to experimental results. It also turned out that the sample preparation time before CGHE can enormously influence determined diffusion coefficients. Consequently, non-homogeneous hydrogen concentration profiles have to be anticipated in the simulations to arrive at characteristic effusion curves consistent to respective CGHE experiments. In turn, validated diffusion coefficients are now available for the low-alloyed Cr-Mo-V steel, which can be helpful to calculate appropriate hydrogen removal heat treatment procedures.
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
The steel grade 20MnMoNi5-5 (according to German DIN standard or 16MND5 according to French AFNOR standard) is widely applied in (weld) fabrication of reactor pressure vessel components. Thus, a wide range of welding technologies (like submerged arc welding (SAW) or tungsten inert gas (TIG)) is used resulting in different heat affected zone (HAZ) microstructures. During weld fabrication, the weld joints may take up hydrogen. Especially, the HAZ shows an increased susceptibility for a degradation of the mechanical properties in presence of hydrogen. In addition, the hydrogen-assisted degradation of mechanical properties is influenced by three main local factors: hydrogen concentration, microstructure, and load condition. Hence, the base material (BM) and two different simulated non-tempered as-quenched HAZ microstructures were examined using hydrogen-free and hydrogen-charged tensile specimens. The results indicate that the effect of hydrogen on the degradation is significantly increased in case of the HAZ compared to the BM. In addition, hydrogen has remarkable effect in terms of reduction of ductility. It was ascertained that the degradation of the mechanical properties increases in the order of BM, bainitic HAZ, and the martensitic HAZ. Scanning electron microscope (SEM) investigation showed a distinct change of the fracture topography depended on the microstructure with increasing hydrogen concentration in case of the as-quenched HAZ microstructures.
Neutron imaging
(2016)
Neutron imaging methods are appropriate to investigate hydrogen distributions in several metallic systems. The large total neutron cross section of hydrogen compared to those of elements or isotopes, respectively, in usual structural materials like steels or zirconium alloys allows the detection even of small amounts of hydrogen in such materials. The dependence of the total macroscopic neutron cross section of the sample or component on the hydrogen concentration can be determined experimentally by means of calibration specimens with known hydrogen concentrations. Such a calibration allows for a full quantitative determination of the local hydrogen concentration with a spatial resolution better than 20 μm. Because neutron radiography is fast and non-destructive, in situ investigations of time-dependent processes like hydrogen absorption and release or hydrogen bulk diffusion can be performed. This chapter gives an introduction into the main neutron imaging methods, radiography and tomography, and gives as examples results of neutron imaging investigations of hydrogen in different steels and in zirconium alloys,respectively.
The polymer chemical structure of the polyimide has a major influence on the tribological behaviour. The addition of graphite in PI2 has a beneficial effect in hydrogen on the friction and wear. The low friction of graphite is associated with a lubricant film in hydrogen. The influence of hydrogen on graphite is more effective than humidity. CNTs have a similar effect to that of graphite in PEEK composites. TiO2 particles improve significantly the wear rate both in vacuum and hydrogen environment. In LH2 friction and wear decrease for unfilled polymers. Friction of graphite filled composites increases slightly and wear rate is stable.