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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.
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.
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.