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In order to reduce the human footprint of CO2 emissions and limit global warming effects hydrogen combustion is becoming increasingly important. To enable fuel cells and gas turbines to operates this carbon free fuel, unprecedently large amounts of hydrogen need to be produced and safely transported and stored. The investigation of the effects of accidents involving hydrogen is therefore becoming of outmost importance. Since hydrogen is usually stored and transported under pressure, one scenario to be considered is the release of hydrogen from a leakage with subsequent ignition. The resulting jet flame must be characterized with respect to the thermal radiation emitted into the environment to define safety regulations. Various models that characterize the resulting flame shape and radiation already exist in the literature, but these are mainly based on empirical data from hydrocarbon jet flames.[1-4] To verify these models, a H2 Jet Flame project conducted at BAM, is investigating the safety of momentum driven hydrogen jet flames. For this purpose, large-scale tests are carried out at the Test Site Technical Safety (BAM-TTS). The object of the investigations is to assess the effects of real scale release scenarios regarding flame geometry and the thermal radiation emitted. Parameters such as release angle, leakage diameter (currently 1 mm to 10 mm), pressure (currently up to max. 250 bar) and mass flow (up to max. 0.5 kg/s) are varied. In addition, influences such as the type of ignition, ignition location as well as delayed ignition can also be investigated. The gained knowledge will be compared with existing jet flame models, to validate these and identify a possible need for further development. In particular, the focus will be laid on the thermal radiation of hydrogen flames. The challenge here is the visualization and characterization of the flame geometry in an open environment. Visualization is performed using infrared (IR) camera systems from at least two viewing angles. Measurements of the heat radiation of jet flames, which can be found in the literature, are mostly based on unsteady outflow conditions.The experimental setup used here allows for the generation of a steady-state outflow for several minutes and thus a direct comparability with existing (steady-state) models. Furthermore, the tests can be carried out for comparative measurements with hydrocarbons (methane, etc.) as well as mixtures of hydrogen and hydrocarbons.
In order to reduce the human footprint of CO2 emissions and limit global warming effects hydrogen combustion is becoming increasingly important. To enable fuel cells and gas turbines to operates this carbon free fuel, unprecedently large amounts of hydrogen need to be produced and safely transported and stored. The investigation of the effects of accidents involving hydrogen is therefore becoming of outmost importance. Since hydrogen is usually stored and transported under pressure, one scenario to be considered is the release of hydrogen from a leakage with subsequent ignition. The resulting jet flame must be characterized with respect to the thermal radiation emitted into the environment to define safety regulations. Various models that characterize the resulting flame shape and radiation already exist in the literature, but these are mainly based on empirical data from hydrocarbon jet flames.[1-4] To verify these models, a H2 Jet Flame project conducted at BAM, is investigating the safety of momentum driven hydrogen jet flames. For this purpose, large-scale tests are carried out at the Test Site Technical Safety (BAM-TTS). The object of the investigations is to assess the effects of real scale release scenarios regarding flame geometry and the thermal radiation emitted. Parameters such as release angle, leakage diameter (currently 1 mm to 10 mm), pressure (currently up to max. 250 bar) and mass flow (up to max. 0.5 kg/s) are varied. In addition, influences such as the type of ignition, ignition location as well as delayed ignition can also be investigated. The gained knowledge will be compared with existing jet flame models, to validate these and identify a possible need for further development. In particular, the focus will be laid on the thermal radiation of hydrogen flames. The challenge here is the visualization and characterization of the flame geometry in an open environment. Visualization is performed using infrared (IR) camera systems from at least two viewing angles. Measurements of the heat radiation of jet flames, which can be found in the literature, are mostly based on unsteady outflow conditions. The experimental setup used here allows for the generation of a steady-state outflow for several minutes and thus a direct comparability with existing (steady-state) models. Furthermore, the tests can be carried out for comparative measurements with hydrocarbons (methane, etc.) as well as mixtures of hydrogen and hydrocarbons.
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.
Climate change and related energy policies, exacerbated by unforeseen geopolitical developments, pose new challenges for gas analytics, such as the use of hydrogen, hydrogen-containing alternative gaseous fuels (NH3, etc.), the use of alternative methane-based energy gases (LNG, LPG, etc.) or decarbonisation via CCSU. In all topics, the quality, i.e. the actual chemical composition of the gases, naturally plays a decisive role. BAM is meeting this strategic importance with the further development of hydrogen analytics and is continuing to develop the methods used in order to support the German economy and research landscape with traceability, reference materials and analytical procedures as quickly as possible.
Mass spectrometry plays an important role for trace analysis in hydrogen matrix. The presentation shows first experimental results from the application of PTR-TOF-MS (Proton Transfer Reaction Time-of-Flight Mass Spectrometry).
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.
The prerequisites for a successful energy transition and the economic use of hydrogen as a clean green energy carrier and for H2 readiness are a rapid market ramp-up and the establishment of the required value chains. Reliable quality and safety standards for innovative technologies are the prerequisite for ensuring supply security, for environmental compatibility and sustainable climate protection, for building trust in these technologies and thus enable product and process innovations.
With the Competence Centre "H2Safety@BAM", BAM is creating the safety-related prere-quisites for the successful implementation of hydrogen technologies at national as well as European level. BAM uses decades of experience in dealing with hydrogen technologies to develop the necessary quality and safety standards.
The presentation will draw a bow from the typical basic tasks of BAM in the field of competence "Sensors, analytics and certified reference materials", such as maintenance and dissemination of the national gas composition standards for calorific value determination as Designated Institute for Metrology in Chemistry within the framework of the Metre Convention, to the further development of measurement and sensor technology for these tasks. For the certification of reference materials, a mostly slow and time-consuming but solid reference analysis is common. With hydrogen and its special properties, completely new requirements are added. In addition, fast and simple online analysis is required for process control, for example to register quality changes, e.g., during load changes or refuelling processes.
Ultrasonic measurement technology has become indispensable in NDT. In order to reduce measurement time and extend the application to other materials, contactless ultrasound is the subject of many different research groups. Department 8 has been researching successfully in this field for years. A novel approach is based on so-called fluidic devices. These devices can be used to perform binary logic operations with the help of natural flow instabilities. Hence the abbreviated name, Fluidic (FLUID+LogIC). Only a pressure reservoir of the used fluid is required as energy supply. This enables the production of very robust actuators that generate ultrasonic signals in an extremely energy efficient way.
The presentation includes the research results of the ZIM innovation project OsciCheck. The original idea will be presented and its application on different building materials is validated. Beyond this, the possible application areas are much larger and a detailed outlook is given to discuss the future potential of fluidic ultrasonic actuators.
Mixed copper and titanium hydride powder was hot-pressed and characterized by Carrier Gas Hot Extraction, XRay Diffraction, Thermal Gravimetric Analysis coupled with Mass Spectrometry, and Scanning Electron Microscopy.
The hot-pressed and five conventional samples were applied for calibration of hydrogen in Glow Discharge Optical Emission and Mass Spectrometry. Up to the introduction of 15 ng/s hydrogen the Emission yield model is useful in Glow Discharge Optical Emission Spectrometry. A correlation between saturation and even reversal of the emission yield of the spectral lines H121, H486 and H656 and low sputtering rates was found. Hydrogen effects exist for the spectral lines of Cu(II) 219 and Ti(I) 399. In Glow Discharge Mass Spectrometry, a linear dependency of the 1H ion current on the sputtered mass per time exists over the total range of hydrogen content investigated. Hydrogen effects also exist for the sensitivity of 48Ti and 63Cu. The sputtering rate of two-phase materials depends linearly on the sputtered mass per time of one phase, which allows the sputtering rate of two-phase materials with known composition to be predicted.
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 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