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For the hydrogen-based energy economy of tomorrow, the construction of the necessary infrastructure will play a central role. Most materials used to date, such as welded steels, can be prone to hydrogen embrittlement under certain conditions. This includes the classic delayed cold cracking during welding as well as degradation phenomena during service of components in hydrogen-containing environment. For the evaluation of any hydrogen effect, for example, on the mechanical properties of a welded metallic material, the hydrogen content must be precisely determined. In the case of weld seams, the carrier gas hot extraction (CGHE) according to ISO 3690 is meanwhile state-of-the-art. CGHE is based on accelerated hydrogen degassing due to the thermal activation of hydrogen at elevated temperatures. In addition to the quantification of hydrogen, thermal desorption analysis (TDA) with varying heating rates can be used to determine and evaluate the hydrogen trapping at microstructural defects in the material. For both techniques, experimental and metrological influences must be considered, which have a major effect on the result. For example, ISO 3690 suggests different sample geometries and minimum extraction times for CGHE. This study summarizes the results and experiences of numerous investigations at the Federal Institute for Materials Research and Testing (BAM) with different sample temperatures and geometries (ISO 3690 type B and cylindrical TDA samples) regarding the influence of the sample surface (polished/welded), measurement accuracy depending on the sample volume and the insufficient monitoring of the effect of PI control on the extraction temperature. A deviating extraction temperature from the target temperature can significantly falsify the measurement results. Based on the results, methods are shown which allow the desired extraction temperature to be reached quickly without physically interfering with the measuring equipment. This serves to significantly improve the reliability of the hydrogen measurement through increased signal stability and accelerated hydrogen desorption. In general, an independent temperature measurement with dummy samples is recommended for the heating procedure of choice to exclude possible undesired temperature influences before the measurement. The methods described can be transferred directly to industrial applications
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.
Die Umstellung der Wirtschaft auf wasserstoffbasierte Energieversorgung soll in Deutschland vor allem auf Basis der Umstellung des bestehenden Erdgasnetzes erfolgen. Dabei sollen ca. 90 % dieser Fernleitungsnetze auf dem bestehenden Erdgasnetz basieren. Die Beimischung von Wasserstoff zum Erdgas als auch der reine Wasserstofftransport werfen jedoch die Frage auf, ob und wie kompatibel die eingesetzten Materialien sind. Die Reparatur- und Erweiterungsfähigkeit von Erdgas-Bestandspipelines ist zu klären, wenn diese auf Wasserstoff umgestellt werden. Denn gerade Gashochdruckleitungen müssen regelmäßig gewartet und erweitert werden, um einen ordnungsgemäßen Betrieb sicherzustellen. Insbesondere das Schweißen unter Betriebsdruck bzw. an in Betrieb befindlichen Gasleitungen ist eine der wichtigsten Instandhaltungstechnologien, unabhängig von der Zusammensetzung des geförderten Mediums. Es ist daher dringend notwendig, eine geeignete Teststrategie zu erarbeiten, welche die nötigen Vorrausetzungen für sicheres Schweißen an in Betrieb befindlichen Druckwasserstoffleitungen schafft und entsprechende Kriterien für die Praxis liefert. Im Projekt H2-SuD - Einfluss des Schweißens auf die Wasserstoffaufnahme und Degradation im Betrieb befindlicher H2-Ferngasleitungen - soll geklärt werden, ob und wie stark mit einer Eigenschaftsdegradation geschweißter Rohrstähle in Gasnetzen in Folge einer Wasserstoffaufnahme zu rechnen ist. Die Präsentation gibt dazu einen kurzen Überblick über den aktuellen Status des Projektes. Die Förderung erfolgt im Rahmen der DVGW-Innovationsprogammes Wasserstoff (Nr. G 202131).
Joining and welding technologies are of high importance for the manufacturing of components and parts used in sustainable energy generation, conversion, and transport. In that connection, offshore and on-shore installed wind turbines are of high interest for the generation of electrical energy as well as photo-voltaic systems (solar cells). The electricity can be either directly transported or conversed via power-to-gas e.g., to hydrogen. In that scope, electrolyzer up to MW-range are of interest as well as the conver-sion back to electricity via fuel cells. In addition, hydrogen is a key element of the decarburization of in-dustries as well as the mobility sector encompassing sea, air and land transportation driven by hydrogen or its derivates. Well-known examples cover the direct reduction of iron ore to replace the conventional blast furnace process up to gas turbines or fuel cells for home-end use. All mentioned technologies re-quire reliable components, which are to a high extend dependent on joining and especially welding pro-cessing of materials. Especially, the (petro-) chemical industry has many years of experience with both materials used in hydrogen applications. The challenge is e.g., the transition to mass production of sys-tem components of electrolyzers/fuel cells and for distribution grids. At this point, the scalability of cur-rently applied joining processes often limits the economic efficiency, whereas especially laser welding or additive manufacturing will be of high interest. In that connection, it is very important to provide answers by joint research of universities, institutes, and industrial companies. Very often, solutions are already available and “just” have to be investigated and adapted for the new application, like repair welding of NG pipelines. For that reason, we want to set up a series of comprehensive papers with the aforementioned title. The idea is to get an in-depth but manageable overview of the importance of joining technologies in sustaina-ble energy generation, conversion, and transport encompassing current processes, limitations, and fur-ther perspectives. In that connection, the additive manufacturing is gaining more and more attention. If applicable, current challenges in the adaption or creation of new standards/regulations shall be addressed.
Microalloying elements such as Nb and Ti play a decisive function in achieving the desired mechanical strength of quenched and tempered, high-strength fine-grain structural steels with a nominal yield strength ≥ 690 MPa. The current specifications for the chemical composition only provide manufacturers with upper limits. However, even minor deviations in the alloy concept can have a significant impact on the mechanical properties. Consequently, accurate prediction of weldability and the integrity of welded joints becomes difficult or even impossible due to differences in composition and the resulting microstructures. Undesirable consequences include a possible softening of the heat-affected zone (HAZ) or, conversely, hardening effects. In view of these challenges, various microalloying strategies with different Ti and Nb contents are being systematically investigated for the first time using specially developed laboratory casting alloys. Each alloying route is based on the common S690QL, maintaining both the chemical composition and the heat treatment parameters. To analyse the weldability, three-layer welds were performed using gas metal arc welding (GMAW) and critical microstructures, such as areas of the heat-affected zone (HAZ) that exhibit significant softening or hardening, were identified. The effect of the softened HAZ region on failure was evaluated using transverse tensile specimens. Digital image correlation (DIC) is used to image changes in local strains in different HAZ regions in situ. Using a specially developed mirror system, the local strains of the microstructure zones on the top and bottom of the weld are recorded simultaneously. This makes it possible to analyse how the weld seam geometry (e.g., V-seam) influences the strain gradients. In addition, the analysis of the local deformation helps to understand the effects of the softened HAZ on the global strain, the fracture constriction, the fracture position, and the overall fracture behavior.
As energy carrier of the future, green hydrogen can make a decisive contribution to a sustainable energy supply. Particularly important is the decarbonization of heavy industry. Therefore, a reliable supply of hydrogen must be guaranteed. A hydrogen pipeline grid can achieve this purpose. In Europe concrete plans for a hydrogen pipeline grid already exist, as the so called “European Hydrogen backbone”. As building a completely new pipeline grid is economically not justifiable, a dual-way strategy of repurposing natural gas (NG) pipelines and newly built pipelines is intended. Long distance pipeline grids require regular maintenance and repairs. For natural gas (NG) pipelines in-service welding is state of the art. Concepts such as hot-tapping (drilling into pressurized pipelines) and “stoppling” (sealing off pipeline sections after installing bypasses or pressure relieves) allow the repair of damaged pipeline sections or the installation of new branches without shutting the pipeline down, which in most cases isn’t possible from an economic standpoint. The EIGA 121/14 guideline already pointed out in 2014 that “a hydrogen hot-tap shall not be considered a routine procedure”. This shows that the determination of the transferability of these repair concepts to hydrogen pipelines is of utmost importance. Due to the degrading effects of hydrogen on mechanical proper-ties, commonly referred to as “hydrogen embrittlement” it is necessary to understand and investigate the occurring effects. In the special case of repair welding on in-service hydrogen pipelines an increased hydro-gen uptake due to a large heat input and microstructural changes in the material needs to be considered. Therefore, material degradation must be investigated to determine whether modifications of repair procedures are necessary to ensure a reliable and safe hydrogen transportation via pipelines. For this reason, this paper gives an overview on existing weld repair concepts and its risks and limitations in terms of hydrogen absorption and possible embrittlement effects when transferred to hydrogen pipelines. The complexity lies in a large variety of materials (low alloyed steels), pipeline diameters and corresponding welded joints. The material compatibility of materials in used (repurposed NG-pipelines) and new condition must be investigated. Particularly for repurposed/used pipelines the effect of a pre-matured/corroded inner surface and sometimes insufficient documentation of the material “history” needs to be considered. An overview on ongoing and completed R&D-projects with respect to repair concepts for hydrogen pipelines and hydrogen effects on pipeline materials is given. The focus hereby lies on possible methods of material testing and modeling. Its current difficulties, limits and possible solution will be discussed.
Contemporary steels creep-resistant steels like the 13CrMoV9-10 are used as thick plates e.g., for applications in hydrocrackers. The large plate thickness requires high efficiency welding processes like submerged arc welding (SAW) and a mandatory post weld heat treatment (PWHT). The PWHT-parameters stem from a combination of empirical knowledge and traditional experiments on free shrinking (FS) welds. In that connection, the formation of so-called stress-relief cracking (SRC) must be anticipated. The SRC susceptibility of a welded component is a complex combination and interaction of com-ponent specific, thermal, and metallurgical factors. Many of which have to date not been conclusively researched. For example, it is well known that SRCs develop during PWHT due to formation and growth of carbides on prior austenite grain boundaries, resulting in a significant hardness increase (secondary hardening) and toughness decrease. This leads to a high SRC susceptibility of the coarse grain heat-affected zone (CGHAZ) of the last weld bead during PWHT. This is intensified in case of high residual stresses from the component-specific, structurally induced stiffness. In combination with multi-layer welding this leads to a multiaxial stress distribution. Nonetheless, the combined effect of PWHT and high-residual stresses on the SRC formation is merely unknown. For that reason, this study presents the effect of different heating rates in conjunction with a certain component stiffness. For that reason, SAW joints of 13CrMoV9-10 steel were investigated under FS and defined external restraint condition.
Multiple principal element alloys encompass the well-known high entropy alloys (HEA). The alloy system represents a new class of materials consisting of at least three alloying elements, each containing 5 to 35 at.%. Thus, this alloying concept differs fundamentally from conventional materials such as steel or nickel alloys. For this purpose, the alloying elements are specifically selected, the microstructures are adjusted in a single-phase and, in some cases, multi-phase manner. In particular, conflicting goals, such as the trade-off between strength and ductility in conventional steels, are overcome. However, in the last 20 years, the focus has been on material synthesis. With the increase in available material quantities, the focus is now on processing issues such as joining and welding processes. The weldability of HEAs has received very little attention so far. The experience with dissimilar metal welds is completely lacking but is essential for the application of these materials in combination with conventional materials. The present study presents comprehensive experimental results on the weldability of an equimolar CoCrFeMnNi-HEA in cold-rolled and heat-treated condition, which was joined by tungsten inert gas welding to an austenitic steel AISI 304. The mechanical properties of the dissimilar metal welds were characterized by cross-weld tensile samples, whereas the local deformation in the weld of the different welding zones was measured by digital image correlation. In accordance with the respective initial HEA condition (cold-rolled vs. heat-treated), the local strain behavior was divergent and influenced the global mechanical properties of both DMW types. Nonetheless, the experiments provided proof in principle of the weldability for dissimilar joints of the CoCrFeMnNi-HEA welded to conventional materials like austenitic stainless steels ensuring a corresponding capability for mechanical loading. This allows further considerations on the application of these innovative materials.
Mikrolegierungselemente, wie Nb und Ti, sind für die signifikante Festigkeitssteigerung von vergüteten, hochfesten Feinkornbaustählen mit einer Nominalstreckgrenze ≥ 690 MPa unerlässlich. Normvorgaben zur chemischen Zusammensetzung geben dabei nur obere Grenzwerte für die Hersteller vor. Weiterhin wirken sich bereits kleine Abweichungen in der Legierungsroute teilweise drastisch auf die mechanischen Eigenschaften aus. Somit wird eine adäquate Vorhersage der Schweißeignung und der Integrität der Schweißverbindung aufgrund der variierenden Mikrogefüge erschwert bis unmöglich. Unerwünschte Nebeneffekte sind die mögliche Erweichung der Wärmeeinflusszone (WEZ) als auch der gegenteilige Effekt der Aufhärtung. Vor diesem Hintergrund werden erstmals systematisch die unterschiedlichen Mikrolegierungsrouten mit variierenden Ti und Nb-Gehalten an Versuchsschmelzen untersucht. Die Stahlgüte S690QL bildet dabei die Grundlage der chemischen Zusammensetzung sowie der entsprechenden Wärmebehandlung. Zur Untersuchung der jeweiligen Schweißeignung wurden Dreilagen-Schweißungen mittels moderner MAG-Hochleistungsschweißprozesse durchgeführt und kritische Gefügebereiche mit hoher Erweichung/Aufhärtung identifiziert. Der Fokus der analytischen Betrachtungen lag hier auf der Identifikation der Phasenumwandlungen beim Abkühlen und auf dem metallurgischen Ausscheidungsverhalten. Zusätzlich wurden isotherme und nicht-isotherme Phasenberechnungen mit der Software Thermo-Calc durchgeführt. Mechanisch-technologische Untersuchungen zur Kerbschlagzähigkeit mittels Kerbschlagbiegeversuchen durchgeführt wurden, bestätigen dabei die Ergebnisse der thermodynamischen Simulation bezüglich des Ausscheidungsverhaltens während der Temperatur-Zeit Schweißzyklen. Daraus lässt sich der Einfluss der Wärmeeinwirkung beim Schweißen auf die Gefügeausbildung in der WEZ und der korrespondierenden mechanischen Eigenschaften qualitativ beschreiben.
The new multi-element alloying concept of systems with defined entropy (HEA — high-entropy alloy or MEA — medium-entropy alloy) is increasing in material research interest. Improved properties or combinations of properties are shown by several systems. Thus, the resulting microstructures and production of HEA/MEA as well as properties have been primarily investigated so far. Furthermore, processing is a key issue to transfer HEA/MEA systems to real components. Since welding is the most important joining process for metals, it is crucial to investigate the influence of welding to guarantee component integrity. Since most HEA are made of expensive alloying elements such as Co or Ni, they will not be used entirely as structural materials. Thus, it can be advantageous to weld conventional alloys such as austenitic stainless steels with the HEA and MEA to produce components that are both application-oriented and economically viable. Therefore, in this paper, first results of dissimilar metal welding, by tungsten inert gas (TIG) and friction stir welding (FSW), of a CoCrFeMnNi HEA as well as a CoCrNi MEA with a conventional AISI 304 austenitic stainless steel are presented. The focus is on the microstructure formation due to the two welding processes. The results of TIG welding show a dendritic microstructure, whereas in FSW both materials are stirred but still coexist.
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.
Die Wasserstofftechnologien der näheren Zukunft erfordern sichere Komponenten. Die Füge- und Schweißtechnik ist hier von zentraler Bedeutung, insbesondere für die Transportinfrastruktur (wie Pipelines). Der vorliegende Vortrag gibt hierzu einen umfassenden Überblick, beginnend bei der Erzeugung, Speicherung über Transport und Nutzung. Zusätzlich wird die zunehmende Bedeutung der additiven Fertigung beleuchtet und ein kurzer Ausblick auf die aktuelle Normungsroadmap der Wasserstofftechnologien gegeben.
Offshore-Windenergieanlagen erfordern Gründungskonzepte aus unterpulver-(UP-)geschweißten Dickblechen (bspw. der Güte S420ML). Während der Schweißfertigung kann eine zeitverzögerte wasserstoffunterstützte Kaltrissbildung auftreten, deren Bewertung aufgrund der Bauteilgröße von Offshore-Strukturen sehr komplex ist. Deswegen wurde eine bauteilähnliche Geometrie (Mock-Up) entwickelt, um reale Steifigkeitsverhältnisse auf den Labormaßstab zu übertragen. Zusätzliche Versteifungen simulieren die Wirkung einer Einspannung bzw. Schrumpfbehinderung der Schweißnaht. Über die Verwendung von Schweißpulvern mit definierter Feuchte wurden zudem ein Extremszenario der Wasserstoffaufnahme simuliert. Entsprechend der vorgegebenen Mindestwartezeit für die ZfP von bis zu 48 h wurde die Schweißnaht zerstörungsfrei mit Phased-Array-Ultraschall-Prüfung (PAUT) geprüft und die Eigenspannungen über Röntgendiffraktometrie (XRD) bestimmt. Zusätzlich wurde die Wasserstoffverteilung in der Schweißverbindung numerisch simuliert. Außer zulässigen Defekten (wie Poren), wurde keine verzögerte Kaltrissbildung in den Mock-Ups festgestellt, was auf hohe Rissbeständigkeit hindeutet.
Offshore-Windenergieanlagen erfordern Gründungskonzepte aus unterpulver-(UP-)geschweißten Dickblechen (bspw. der Güte S420ML). Während der Schweißfertigung kann eine zeitverzögerte wasserstoffunterstützte Kaltrissbildung auftreten, deren Bewertung aufgrund der Bauteilgröße von Offshore-Strukturen sehr komplex ist. Deswegen wurde eine bauteilähnliche Geometrie (Mock-Up) entwickelt, um reale Steifigkeitsverhältnisse auf den Labormaßstab zu übertragen. Zusätzliche Versteifungen simulieren die Wirkung einer Einspannung bzw. Schrumpfbehinderung der Schweißnaht. Über die Verwendung von Schweißpulvern mit definierter Feuchte wurden zudem ein Extremszenario der Wasserstoffaufnahme simuliert. Entsprechend der vorgegebenen Mindestwartezeit für die ZfP von bis zu 48 h wurde die Schweißnaht zerstörungsfrei mit Phased-Array-Ultraschall-Prüfung (PAUT) geprüft und die Eigenspannungen über Röntgendiffraktometrie (XRD) bestimmt. Zusätzlich wurde die Wasserstoffverteilung in der Schweißverbindung numerisch simuliert. Außer zulässigen Defekten (wie Poren), wurde keine verzögerte Kaltrissbildung in den Mock-Ups festgestellt, was auf hohe Rissbeständigkeit hindeutet.
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.
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. This includes the classical delayed cold cracking during welding processing as well as embrittlement phenomena during operation. 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. In the case of welds, for example, according to ISO 3690, this is the isothermal carrier gas hot extraction (CGHE). CGHE is based on accelerated hydrogen degassing due to thermal activation of hydrogen at elevated temperatures. 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 as well as the insufficient monitoring of the effect of the PI controller on the extraction temperature. 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.
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.
Offshore wind turbines (OWT) are a key factor of the sustainable energy generation of tomorrow. The continuously increasing installation depths and weight of the OWTs require suitable foundation concepts like monopiles or tripods. Typically, mild steels like the S420ML are used with plate thicknesses up to several hundreds of mm causing high restraints in the weld joints. Due to the large plate thickness, submerged arc welding (SAW) with multiple wires is the state-of-the-art welding procedure. As a result of the very high stiffness of the construction, a certain susceptibility for time-delayed hydrogen-assisted cracking (HAC) may occur. The evaluation of crack susceptibility is very complex due to the component size and stiffness of real offshore structures. For this purpose, a near-component test geometry was developed to transfer the real stiffness conditions to laboratory (i.e., workshop) scale. The investigated mock-up, weighing 350 kg, comprised heavy plates (thickness 50 mm, seam length 1,000 m) joined by a 22-pass submerged arc weld. Additional stiffeners simulated the effect of high restraint or shrinkage restraint of the weld. Extreme scenarios of hydrogen absorption during welding were simulated via the use of welding fluxes in dry (HD < 5 ml/100g Fe) and moisture condition (HD > 15 ml/100g Fe). The residual stresses were determined by a robot X-ray diffractometer. Areas of critical tensile residual stress (at the level of the yield strength) were found in the weld metal and heat affected zone. To identify possible delayed cracking, the welds were tested by phased array ultrasonic testing (PAUT) after 48 h. Summarized, no significant occurrence of HAC was detected, indicating the high crack resistance of the welded joint, i.e., a suitable combination of base material, welding consumable and welding parameters.
Der Vortrag gibt einen tiefen Überblick über die Bedeutung der Füge- und Schweißtechnik in Wasserstofftechnologien. Dazu gliedert sich der Vortrag in die Komplexe H2-Erzeugung, Speicherung, Transport, Anwendung auf und gibt jeweils repräsentative Industriebeispiele für den heutigen Anwendungsstand. Insbesondere werden hier Fertigungstechnologien für Brennstoffzellen vorgestellt, sowie Herausforderungen beim Reparaturschweißen von Wasserstoffpipelines. Zeitgleich wird in einem eigenen Kapitel die Bedeutung der additiven Fertigung ebenso erläutert, wie die aktuellen und umfassenden Tätigkeiten auf dem Gebiet der Normung zu H2-Technologien.
Multielement-Legierungen (MPEA - Multiple Principal Element Alloys), gemeinhin und partiell fälschlicherweise auch als Hochentropielegierungen bezeichnet) stellen eine neue Klasse von Werkstoffen dar, die aus mindestens drei Legierungselementen mit jeweils 5 bis 35 Atom-% bestehen. Somit unterscheidet sich dieses Legierungskonzept fundamental von konventionellen Werkstoffen wie Stahl oder Nickellegierungen. Hierzu werden die Legierungselemente gezielt ausgewählt und die Mikrostrukturen ein- und zum Teil auch mehrphasig eingestellt. Das Ziel ist dabei, hochinnovative MPEA mit individuell einstellbaren Eigenschaften für die industrielle Anwendung zu identifizieren. Dabei werden insbesondere Zielkonflikte, wie bspw. der Trade-off zwischen Festigkeit und Duktilität bei konventionellen Stählen, überwunden. Insbesondere die hohe mechanische Festigkeit bei höchster Korrosionsbeständigkeit sind bei bestimmten Legierungssystemen von hohem Interesse. Hier kann u.a. die Substitution klassischer hochlegierter Stähle oder Ni-Basislegierungen perspektivisch erfolgen. In den letzten 20 Jahren lag der Fokus jedoch auf der reinen Materialsynthese. Mit der Zunahme verfügbarer Werkstoffquantitäten, stehen Verarbeitungsfragen, wie werkstoff- und beanspruchungsgerechte Füge- bzw. Schweißverfahren jetzt im Mittelpunkt. Der Schweißeignung von MPEA wurde bisher nur äußert wenig Aufmerksamkeit zuteil. Erfahrungen zu Mischverbindungen
(DMWs - Dissimilar Metal Welds) fehlen dabei vollständig, sind jedoch essenziell für die Anwendung dieser Werkstoffe in Verbindung mit konventionellen Werkstoffen. Die vorliegende Studie präsentiert erstmals im deutschen Sprachraum, die umfassenden experimentellen Ergebnisse zur Schweißeignung von MPEA-Mischverbindungen und der resultierenden Mikrostruktur. Dazu wurden zwei äquiatomare MPEAs in Form einer Co20Cr20Fe20Mn20Ni20 (Hochentropie-) und Co33.3Cr33.3Ni33.3 (Mediumentropielegierung) mittels WIG und Rührreibschweißen mit einem konventionellen, korrosionsbeständigem Cr-Ni-Stahl AISI 304 (1.4301 bzw. X5CrNi18-10) gefügt. Die erstmals untersuchten DMWs resultierten dabei in sehr interessanten Mikrostrukturen, mechanisch-technologische Eigenschaften wurden durch instrumentierte Zugversuche gewonnen, die gleichzeitig der Ermittlung der lokalen Verformung im Schweißnahtbereich dienten (durch Verwendung der berührungslosen DIC-Digital Image Correlation-Technik). Dabei zeigt sich für beide Schweißverfahren eine Erweichung in der Wärmeeinflusszone (WEZ) der MPEAs sowie eine geringfügig verminderte Zugfestigkeit, bei einer deutlichen Abnahme der Bruchdehnung. Durch die Experimente konnte der prinzipielle Nachweis der Schweißeignung der MPEAs für DMWs mit konventionellen Werkstoffen erbracht werden, die auch eine dementsprechende mechanische Beanspruchbarkeit ermöglichen. Dies ermöglicht weitere Betrachtungen zur Anwendung dieser innovativen Werkstoffe.
Im Zuge der wasserstoffbasierten Energiewirtschaft von morgen, kommt der Errichtung der dementsprechenden Infrastruktur die zentrale Rolle zu. Der überwiegende Teil bisher eingesetzter und meist geschweißter Werkstoffe, wie Stähle, kann unter bestimmten Bedingungen zur Wasserstoffversprödung neigen. Dies umfasst die klassische verzögerte Kaltrissbildung während der Schweißverarbeitung als auch Versprödungsphänomene während des Betriebs. Für die Bewertung eines jeden Wasserstoffeffektes auf bspw. die mechanischen Eigenschaften eines geschweißten metallischen Werkstoffes, muss der Wasserstoffgehalt präzise bestimmt werden, Im Fall von Schweißnähten ist die beispielsweise nach der ISO 3690, die klassische isotherme Trägergas-Heißextraktion (TGHE). Die TGHE basiert dabei auf der beschleunigten Wasserstoffentgasung aufgrund der thermischen Aktivierung des Wasserstoffs bei erhöhten Temperaturen. Neben der reinen Quantifizierung des Wasserstoffs, kann über die thermische Desorptionsanalyse (TDA) mit variierten Heizraten, der Bindungszustand an mikrostrukturellen Defekten im Material festgestellt und bewertet werden. Für beide Techniken sind experimentelle und messtechnische Einflüsse zu beachten, die großen Effekt auf das Ergebnis haben. Für die TGHE schlägt die ISO 3690 schlägt beispielswiese verschiedene Probengeometrien sowie Mindestextraktionszeiten vor. Die vorliegende Studie fasst Ergebnisse und Erfahrungen zahlreicher Untersuchungen an der Bundesanstalt für Materialforschung und -prüfung (BAM) mit unterschiedlichen Probentemperaturen und Geometrien (ISO 3690 Typ B und zylindrische TDA-Proben) zusammen hinsichtlich: Einfluss der Probenoberfläche (poliert/geschweißt), Messgenauigkeiten in Abhängigkeit des Probenvolumens sowie die unzureichende Überwachung des Effektes des PI-Reglers auf die Extraktionstemperatur. Insbesondere eine abweichende Extraktionstemperatur zur eingestellten Temperatur, kann die Messergebnisse wesentlich verfälschen. Basierend auf den Ergebnissen werden Methoden aufgezeigt, um schnell die gewünschte Extraktionstemperatur zu erreichen, ohne physisch in das Messequipment eingreifen zu müssen. Dies dient der wesentlichen Verbesserung der Zuverlässigkeit der Wasserstoffmessung durch erhöhte Signalstabilität und beschleunigte Wasserstoffdesorption. Im Allgemeinen ist eine unabhängige Temperaturmessung mit Dummy-Proben für die gewählte Heizprozedur angeraten, um mögliche unerwünschte Temperatureinflüsse bereits vor der Messung auszuschließen. Die beschriebenen Methoden können ohne großen Aufwand direkt in die industrielle Anwendung überführt werden.
Im Zuge der wasserstoffbasierten Energiewirtschaft von morgen, kommt der Errichtung der dementsprechenden Infrastruktur die zentrale Rolle zu. Der überwiegende Teil bisher eingesetzter und meist geschweißter Werkstoffe, wie Stähle, kann unter bestimmten Bedingungen zur Wasserstoffversprödung neigen. Dies umfasst die klassische verzögerte Kaltrissbildung während der Schweißverarbeitung als auch Versprödungsphänomene während des Betriebs. Für die Bewertung eines jeden Wasserstoffeffektes auf bspw. die mechanischen Eigenschaften eines geschweißten metallischen Werkstoffes, muss der Wasserstoffgehalt präzise bestimmt werden, Im Fall von Schweißnähten ist die beispielsweise nach der ISO 3690, die klassische isotherme Trägergas-Heißextraktion (TGHE). Die TGHE basiert dabei auf der beschleunigten Wasserstoffentgasung aufgrund der thermischen Aktivierung des Wasserstoffs bei erhöhten Temperaturen. Neben der reinen Quantifizierung des Wasserstoffs, kann über die thermische Desorptionsanalyse (TDA) mit variierten Heizraten, der Bindungszustand an mikrostrukturellen Defekten im Material festgestellt und bewertet werden. Für beide Techniken sind experimentelle und messtechnische Einflüsse zu beachten, die großen Effekt auf das Ergebnis haben. Für die TGHE schlägt die ISO 3690 schlägt beispielswiese verschiedene Probengeometrien sowie Mindestextraktionszeiten vor. Die vorliegende Studie fasst Ergebnisse und Erfahrungen zahlreicher Untersuchungen an der Bundesanstalt für Materialforschung und -prüfung (BAM) mit unterschiedlichen Probentemperaturen und Geometrien (ISO 3690 Typ B und zylindrische TDA-Proben) zusammen hinsichtlich: Einfluss der Probenoberfläche (poliert/geschweißt), Messgenauigkeiten in Abhängigkeit des Probenvolumens sowie die unzureichende Überwachung des Effektes des PI-Reglers auf die Extraktionstemperatur. Insbesondere eine abweichende Extraktionstemperatur zur eingestellten Temperatur, kann die Messergebnisse wesentlich verfälschen. Basierend auf den Ergebnissen werden Methoden aufgezeigt, um schnell die gewünschte Extraktionstemperatur zu erreichen, ohne physisch in das Messequipment eingreifen zu müssen. Dies dient der wesentlichen Verbesserung der Zuverlässigkeit der Wasserstoffmessung durch erhöhte Signalstabilität und beschleunigte Wasserstoffdesorption. Im Allgemeinen ist eine unabhängige Temperaturmessung mit Dummy-Proben für die gewählte Heizprozedur angeraten, um mögliche unerwünschte Temperatureinflüsse bereits vor der Messung auszuschließen. Die beschriebenen Methoden können ohne großen Aufwand direkt in die industrielle Anwendung überführt werden.
Dissimilar metal TIG weld joints of multiple principal element alloys (MPEA) to austenitic steel 304
(2023)
Multi-element alloys (MPEA - Multiple Principal Element Alloys) represent a new class of materials consisting of at least three alloying elements, each with 5 to 35 atomic %. This material class includes high-entropy alloys (HEA, with n ≥ 4 elements). The underlying alloying concept differs fundamentally from conventional materials such as the Fe-based steel. For this purpose, the alloying elements are specifically selected, and the microstructures are adjusted in a single-phase and, in some cases, multi-phase manner. The aim is to identify highly innovative MPEA with individually adjustable properties for industrial applications. In the last 20 years, however, the focus has been on pure material synthesis. With the increase in available material quantities, the focus is on processing issues such as joining and welding processes. In that connection, the weldability of MPEAs has received very little attention so far. Experience with dissimilar metal welds (DMWs) is completely lacking but is essential for the application of these materials if joint to conventional materials. This study presents selected experimental results on the weldability of MPEA-DMWs and the resulting microstructures. For this purpose, the equiatomic CoCrFeMnNi (HEA) was investigated in cold-rolled (CR) and heat-treated (HT) condition and joined by tungsten inert gas (TIG) welding to an austenitic stainless steel 304. The DMWs showed defect-free conditions (no lack of fusion, cracks and so on), whereas the cold-rolling increases the microhardness. The global mechanical properties were obtained by instrumented tensile tests of cross-weld samples and showed sufficient yield and tensile strength comparable to that of the individual base materials (BM). The local strain conditions were determined by digital image correlation and showed the highest local strains to occur in the intermixed weld metal. Indeed, the preferred fracture location of the cross-weld tensile samples was in the weld metal. Finally, the experiments proofed the weldability of the MPEAs to conventional 304. This enables targeted further considerations for example as structural materials.
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).
Microalloying elements, such as Nb and Ti, are essential for the targeted mechanical strength of quenched and tempered, high-strength fine-grained structural steels with a nominal yield strength ≥ 690 MPa. Current specifications for chemical composition only provide upper limits for manufacturers. But even small deviations in the alloying route can have a drastic effect on the mechanical properties. Thus, an adequate prediction of the weldability and the integrity of the welded joint becomes difficult or even impossible due to the varying composition and, hence, the microstructures. Undesirable side effects are the possible softening of the heat-affected zone (HAZ) as well as the opposite effect of hardening. Against this background, different microalloying routes with varying Ti and Nb contents are systematically investigated for the first time on specially designed lab-cast alloys. The basis of each alloy route was the common S690QL in terms of both the chemical composition as well as the heat treatment. To investigate the weldability, three-layer welds were performed using metal active gas welding (MAG) and critical microstructural areas with high softening/hardening were identified. The scope was here on the identification of phase transformations during cooling and on the respective metallurgical precipitation behavior. Isothermal and non-isothermal phase calculations were performed using Thermo-Calc® and showed that the prediction of the non-equilibrium precipitation characteristics during welding is not trivial, especially for this relatively complex chemical composition. The mechanical properties of the welded joints were identified by both Charpy tests (toughness) and tensile tests (strain and strength). During the test, the local straining behavior of the welded joints, was identified using a digital image correlation (DIC) system, see Figure 1. Despite the generally good weldability of the materials, the results show a significant influence of the microalloying route as well as the welding heat input on the different precipitation kinetics.
Mikrolegierungselementen, wie Nb und Ti sind für eine signifikante Festigkeitssteigerung von vergüteten, hochfesten Feinkornbaustählen mit einer Nominalstreckgrenze ≥ 690 MPa unerlässlich. Normvorgaben zur chemischen Zusammensetzung dieser Stähle geben zur Erzielung der vorgeschriebenen Eigenschaften dabei oft nur Grenzgehalte für die Hersteller vor. Die Wirkung der Mikrolegierungselemente bzw. ihrer Karbide und/oder Nitride ist teilweise komplett konträr, insbesondere bei Auflösung und Wiederausscheidung in der WEZ bei identischem Schweißzusatz. Somit wird eine adäquate Vorhersage der Chargenabhängigkeit hinsichtlich der Schweißeignung und des Tragverhaltens der Schweißverbindung erschwert. Eine unerwünschte Eigenschaft ist dabei die Erweichung der WEZ, wie auch u.U. der gegenteilige Effekt der Aufhärtung.
Vor diesem Hintergrund werden im Rahmen eines DFG-Vorhabens systematisch Mikrolegierungs-routen mit variierenden Ti- und Nb-Gehalten des hochfesten und vergüteten Feinkornbaustahls S690QL untersucht. Dazu wird das MAG-Schweißen mit modifizierten Sprühlichtbogen verwendet, welches durch hohe Abschmelzleistung gekennzeichnet ist und schmalere Nahtöffnungswinkel (α = 30°) ermöglicht. An Dreilagen-Schweißungen wird der Effekt der metallurgischen Zusammensetzung in Kombination mit hoher Wärmeeinwirkung auf die Ausbildung einer kritischen WEZ-Gefügezone mit Erweichung und/oder exzessiver Aufhärtung untersucht. Ein besonderes Augenmerk wird auf die Phasenumwandlungen und das Ausscheidungsverhalten im Gefüge der Wärmeeinflusszone gelegt. Neben umfangreichen metallographischen Untersuchungen einzelner WEZ-Bereiche wurden, unter Variation der chemischen Zusammensetzung,
thermodynamische Phasenberechnungen mittels Thermo-Calc durchgeführt. Hierdurch wird ein Verständnis zur Phasentransformation und Ausscheidungswachstum und -auflösung während des Schweißens in Abhängigkeit von Temperatur und Abkühlbedingungen geschaffen. Das Ziel ist es, den Einfluss der Wärmeeinwirkung auf die Gefügeausbildung in der WEZ und dessen mechanischer Eigenschaften zu analysieren. Insbesondere wird hier auf die Auswirkung der unterschiedlichen Mikrolegierungskonzepte (Ti oder Nb) geachtet.
For a significant increase in the strength of high-strength fine-grained structural steels with a nominal yield strength ≥690 MPa, the addition of microalloying elements such as Nb and Ti is required. The standard specifications for the chemical composition of these steels (e.g., in EN 10025-6) often only give the manufacturer limit contents to achieve the defined properties. The effect of the alloying elements in the heat affected zone (HAZ) is sometimes completely contrary.
This makes it difficult to adequately predict the batch dependency regarding weldability and the load-bearing behaviour of the welded joint. Three different micro-alloyed steels of the grade S690QL were produced on a laboratory scale, focusing on different Nb and Ti contents. To investigate the tempering effect, these were gas metal arc welded in three layers. In addition to metallographic investigations of individual HAZ areas, thermodynamic phase calculations were carried out using Thermo-Calc, following variations in the chemical composition. This provides an understanding of phase transformation, precipitation growth, and dissolution during welding as a function of temperature and cooling conditions. The results show
a divergent metallurgical behaviour in the HAZ of the three different micro-alloyed steels. Thereby, the Ti micro-alloyed grade showed a strong softening of the HAZ in contrast to the Nb micro-alloyed grade. This can be attributed to a contrary precipitation behaviour during welding.
Large scale hydrogen assisted cracking test for thick walled SAW joints for offshore applications
(2023)
Offshore wind turbines continuously increase in size and weight and demand adequate offshore foundations concepts like monopiles, tripods or jackets. These components are typically submerged arc welded (SAW) 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 complicate 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 22 passes and a seam length of 1,000 mm. Additional welded stiffeners simu-lated the effect of a high restraint, to stimulate 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 48 h after 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 modelling allowed the qualitative estimation of the hydrogen diffusion in the weld. A remarkable HAC occurrence was not identified and proves both, a certain resistance of the weld joint to HAC and the (questionable) duration of the MWT.
Multiple principal element alloys (MPEA) encompass the well-known high entropy alloys (HEAs). MPEA/HEA represent a new class of materials consisting of at least three alloying elements, each containing 5 to 35 at.-%. This alloying concept thus differs fundamentally from conventional materials such as steel or nickel alloys. For this purpose, the alloying elements are specifically selected, and the microstructures are adjusted in a single-phase and, in some cases, multi-phase manner. In particular, conflicting goals, such as the trade-off between strength and ductility in conventional steels, are overcome. In the last 20 years, however, the focus has been on material synthesis. With the increase in available material quantities, the focus is now on pro-cessing issues such as joining and welding processes. The weldability of MPEA has received very little atten-tion so far. Experience with dissimilar metal welds (DMWs) is completely lacking but is essential for the appli-cation of these materials in combination with conventional materials. The present study presents, comprehen-sive experimental results on the weldability of MPEA-DMWs. For that purpose, a Co20Cr20Fe20Mn20Ni20 HEA in cold-rolled and heat-treated condition was joined by means of tungsten inert gas welding (TIG) with the austenitic Cr-Ni steel AISI 304. The DMWs resulted in interesting mechanical properties. They were obtained by instrumented tensile tests as well as the local deformation in the weld area by using digital image correlation (DIC) technique. A significant softening in the heat-affected zone (HAZ) of the MPEAs as well as a slightly reduced tensile strength with a significant decrease of the elongation at fracture were found. The experiments provided proof in principle of the weldability of the MPEAs for DMWs with conventional materials that ensure a corresponding capability for mechanical loading. This allows further considerations on the application of these innovative materials.
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.
Die Wasserstoffinfrastruktur ist eine zentraler Bestandteil der erfolgreichen Umsetzung der wasserstoffbasierten Energiewende. Dabei bilden Ferngasleitungen quasi das "Rückgrat" der Transportinfrastruktur großer Gasmengen. Dabei müssen unter Umständen Reparaturen an den Pipelines durchgeführt werden. Dabei ist in der Erdgasinfrastruktur das Schweißen an in Betrieb befindlichen (d.h. von Gas durchflossenen) Pipelines Stand der Technik. Es ist jedoch vollkommen offen, inwieweit diese Technik auf die reine Wasserstoffpipelines übertragbar sind. Hierzu leistet das Projekt H2SuD wichtige Beiträge zur Aufklärung des Einfluss eines Reparaturschweißprozesses auf die Wasserstoffaufnahme und Degradation im Betrieb befindlicher H2 Gasleitungen.
Creep-resistant steels such as the 13CrMoV9-10, used in the construction of thick-walled pressure vessels, are most commonly submerged arc welded (SAW). These steels can develop stress relief cracks (SRC) if the mandatory post weld heat treatment (PWHT) is performed improperly. Current PWHT parameters, such as heating rate and holding time at a specific holding temperature, are based on both empirical experience and conventional free shrinking welding experiments to characterize the SRC-susceptibility of the weld. These cannot adequately depict the higher residual stresses caused by the structurally induced stiffness of the surrounding construction. This study discusses the development of a repeatable, precise, and time-efficient methodology to study the effects of different stress levels and heating rates on the SRC susceptibility of the coarse grain heat-affected zone (CGHAZ). For that purpose, samples were thermically treated to simulate a coarse grain heat-affected zone (CGHAZ) and subsequently exposed to representative levels of stress during the heating phase of a PWHT. The recorded stress and heating rate–dependent strains were mathematically analyzed via curve tracing/calculus to identify interdependent effects. This procedure facilitates the measurement of material characteristics such as carbide growth on grain boundaries at the µm-scale via an integrated value over the entire sample volume. The first and second derivatives show a slight, precipitate-dependent, increase in hardness of the sample, depending on the heating rate and applied stress. This new methodology generates an improved assessment of the SRC susceptibility of SAW microstructures of creep-resistant CrMoV steels.
Die vorliegende Präsentation fasst die Ergebnisse von drei laufenden bzw. beendeten AiF/IGF-Projekten zusammen, die über die Forschungsvereinigung Stahlanwendung FOSTA e.V. an der BAM bearbeitet wurden zum Thema: Bewertung und Vermeidung von schweißverarbeitungsbedingten Rissen in hochfesten Baustählen.
Der Vortrag gibt einen kurzen Überblick über die Bedeutung der Fügetechnik in Wasserstofftechnologien und über zukünftige Herausforderungen. Fügetechnologien, insbesondere die Schweißtechnik, haben dabei wesentliche Bedeutung für die Umsetzung von technischen Komponenten der Wasserstofftechnologien. Forschungsschwerpunkte ergeben sich insbesondere für die Erzeugung und den Transport des Wasserstoffs.
Multi-Principal-Element or High-Entropy Alloys (MPEAs/HEAs) have gained increasing interest in the past two decades largely due to their outstanding properties such as superior mechanical strength and corrosion resistance. However, research studies on their processability are still scarce. This work assesses the effect of different machining conditions on the machinability of these novel alloys, with the objective of advancing the introduction of MPEA systems into industrial applications. The present study focuses on the experimental analysis of finish-milling conditions and their effects on the milling process and resulting surface finish of CoCrFeNi, Al0.3CoCrFeNi and Al0.3CoCrFeNiMo0.2 alloys fabricated via Spark Plasma Sintering. Ball-nose-end milling experiments have been carried out various milling parameters such as cutting speed, feed per cutting edge, and ultrasonic assistance. In situ measurements of cutting forces and temperature on the tool edge were performed during the experiments, and surface finish and tool wear were analyzed afterwards. The results exhibited decreasing cutting forces by means of low feed per cutting edge and reduced process temperatures at low cutting speed, with the use of ultrasonic-assisted milling. It was shown that the machinability of these modern alloys through conventional, as well as modern machining methods such as ultrasonic-assisted milling, is viable, and common theories in machining can be transferred to these novel MPEAs.
This work investigates the microstructure formed in friction stir welds of FCC alloys, focused on two multiprincipal alloys: a CoCrFeMnNi high-entropy alloy (HEA) and a CoCrNi medium-entropy alloy (MEA). A commercial stainless steel AISI 304 is used for comparison. The largest nugget was formed in the MEA, while the smallest was formed in the HEA. Grain refinement occurs in the stirred zone in all welds. Discontinuous dynamic recrystallisation is the predominant restoration mechanism during friction stir welding of the three investigated alloys. A sharp decrement in the Σ3 boundary fraction occurs in the stirred zone of the AISI 304 and HEA welds, while comparable values with the base metal are found for the MEA weld. The peak in the maximum index of crystallographic texture is observed on the advancing side of the stirred zone of the AISI 304 weld. A strong <001> θ-fibre texture is formed in the advancing side of the nugget in the AISI 304 from a well-established {123} <634> S-type texture in the base metal. Multiple crystallographic texture components without specific fibres are identified in most regions of the welds, indicating the complex shear path history during friction stir welding.
This study gives an overview on the important field of joining processes for component fabrication in hydrogen technologies. The current main issues and future perspectives are highlighted for the different technological field of hydrogen generation, storage, transport and use. In addition, the emerging field of additive manufacturing is included. Some remarks are given for standardization and regulations.
Wasserstoff erfüllt die zentrale Rolle für die Umwandlung der bisherigen fossil-basierten Energieerzeugung und -nutzung auf eine dekarbonisierte, nachhaltige Form. Dazu muss der Wasserstoff erzeugt, gespeichert, transportiert werden, bevor er wieder der Nutzung zugeführt wird. Hierzu sind entlang der gesamtem Prozesskette Wasserstofftechnologien notwendig, die einen sicheren Betrieb erfordern. Hierbei kommt dem schweißtechnischen Anlagen- und Behälterbau wesentliche Bedeutung zu, insbesondere (aber nicht ausschließlich) für Speicherung und Transport des Wasserstoffes. Der vorliegende Beitrag gibt einen kurzen Überblick, wo und wie die konventionelle Schweißtechnik hierzu wichtige Beiträge leistet. Die additive Fertigung, also das „Drucken“ von Bauteilen wird dabei zunehmend wichtiger, entlang der gesamtem Prozesskette der Wasserstofftechnologien. Gleichwohl darf nicht unterschätzt werden, dass auch wesentlicher Bedarf an der Erweiterung und teilweiser Neufassung von bestehenden Regel- und Normenwerken besteht.
Wasserstoff erfüllt die zentrale Rolle für die Umwandlung der bisherigen fossil-basierten Energieerzeugung und -nutzung auf eine dekarbonisierte, nachhaltige Form. Dazu muss der Wasserstoff erzeugt, gespeichert, transportiert werden, bevor er wieder der Nutzung zugeführt wird. Hierzu sind entlang der gesamtem Prozesskette Wasserstofftechnologien notwendig, die einen sicheren Betrieb erfordern. Hierbei kommt dem schweißtechnischen Anlagen- und Behälterbau wesentliche Bedeutung zu, insbesondere (aber nicht ausschließlich) für Speicherung und Transport des Wasserstoffes. Der vorliegende Beitrag gibt einen kurzen Überblick, wo und wie die konventionelle Schweißtechnik hierzu wichtige Beiträge leistet. Die additive Fertigung, also das „Drucken“ von Bauteilen wird dabei zunehmend wichtiger, entlang der gesamtem Prozesskette der Wasserstofftechnologien. Gleichwohl darf nicht unterschätzt werden, dass auch wesentlicher Bedarf an der Erweiterung und teilweiser Neufassung von bestehenden Regel- und Normenwerken besteht.
Der Vortrag gibt einen kurzen Überblick über die Bedeutung der Fügetechnik in Wasserstofftechnologien und über zukünftige FuE-Bereiche. Fügetechnologien haben dabei wesentliche Bedeutung für die Umsetzung von technischen Komponenten der Wasserstofftechnologien. Forschungsschwerpunkte ergeben sich insbesondere für die Erzeugung und den Transport des Wasserstoffs.
Für eine signifikante Festigkeitssteigerung von vergüteten, hochfesten Feinkornbaustäh-len mit einer Nominalstreckgrenze ≥ 690 MPa, ist die Zugabe von Mikrolegierungselementen, wie Nb und Ti, unerlässlich. Die Normvorgaben zur chemischen Zusammensetzung dieser Stähle (bspw. in DIN EN 10025-6) geben zur Erzielung der vorgeschriebenen Eigenschaften dabei oft nur Grenzgehalte für die Hersteller vor. Die Wirkung der Legierungselemente in der WEZ ist teilweise komplett konträr. Somit wird eine adäquate Vorhersage der Chargenabhängigkeit hinsichtlich der Schweißeignung und des Tragver-haltens der Schweißverbindung erschwert. Neben metallographischen Untersuchungen einzelner WEZ-Bereiche wurden unter Variation der chemischen Zusammensetzung, thermodynamische Phasenberech-nungen mittels ThermoCalc durchgeführt. Hierdurch wird ein Verständnis zur Phasentransformation, Aus-scheidungswachstum und -auflösung während des Schweißens in Abhängigkeit von Temperatur und Ab-kühlbedingungen geschaffen.
This work explores the feasibility of producing bead-on-plate welds of a CrCoNi medium entropy alloy and a CrMnFeCoNi high entropy alloy using electron beam welding. The alloys were welded in two states: one in an as-cold-rolled condition and the other in an annealed condition. In addition, the materials are welded with two different parameters. The FCC microstructure of the welds is investigated using scanning electron microscopy assisted by energy-dispersive X-ray spectroscopy and electron-backscattered diffraction. The impact of the weld on the microstructure is discussed. The heat-affected zone is negligible for the annealed condition of both medium and high entropy alloys since there is no driving force for recrystallisation and the exposure time to high temperature is insufficient for grain coarsening. The texture formed in the fusion zone is also discussed and compared to the texture in the base metal and the heat-affected zone. Although the grain growth along the (100) crystallographic direction is preferential in all cases, the crystallographic texture type differs from each weld. Higher hardness values are measured in the medium entropy alloy’s base metal and fusion zone than in the high entropy alloy.
The new alloying concept of multi-element systems with defined entropy (HEA—high-entropy alloy; MEA—medium-entropy alloy) is gaining increasing importance in materials research. Significantly improved properties or combinations of properties are shown by some HEA/MEA systems. Thus, primarily the production and resulting microstructures of HEA, as well as its properties, have been investigated so far. Furthermore, processing is a main issue in transferring HEA systems from the laboratory to real components. Since welding is the most important joining process for metals, it is crucial to investigate the influence of welding to guarantee component integrity. Welding leads to residual stresses, which significantly affect the component integrity. Hence, the focus of this study is the residual stress formation and distribution in a CoCrFeMnNi HEA and ternary CoCrNi MEA using two different welding processes: tungsten inert gas (TIG) welding and solid-state friction stir welding (FSW). As a pathway for the application of HEA in this investigation, for the first time, residual stress analyses in realistic near-component specimens were performed. The residual stresses were determined by X-ray diffraction (XRD) on the surfaces of top and root weld side. The results were correlated with the local welding microstructures. The results show that both FSW and TIG generate significant tensile residual stresses on the weld surfaces in, and transverse to, the welding direction. In the case of FSW of the CoCrFeMnNi HEA, the longitudinal residual stresses are in the range of the yield strength of approx. 260 MPa in the weld zone.
Multielement-Legierungen (MPEA – multiple pricipal element alloys) stellen eine neue Klasse von Werkstoffen dar, die aus mindestens drei äquiatomaren Legierungselementen mit jeweils einem Gehalt von 5–35 Atom-% bestehen. Somit unterscheidet sich das Legierungskonzept fundamental von konventionellen bspw. Stahl- oder Al-basierten Legierungen. In jüngster Zeit lag der Schwerpunkt auf dem Legierungs-Design der MPEA und der Überprüfung bzw. Erreichung der gewünschten Eigenschaften bzw. -kombinationen. Hierzu werden die egierungselemente gezielt ausgewählt und die Mikrostrukturen ein- und zum Teil auch mehrphasig eingestellt. Ziel sind hochinnovative MPEA mit angepassten Eigenschaften für die industrielle Anwendung. Dabei sollen insbesondere die bei konventionellen Legierungen wesentlichen Zielkonflikte, wie bspw. der Trade-off zwischen Festigkeit und Duktilität, überwunden werden. Darüber hinaus sind mechanische Eigenschaften bei sehr hohen sowie kryogenen Temperaturen bei gleichzeitig höchster Korrosionsbeständigkeit von hohem Interesse. Die Herstellung von Bauteilen erfordert dazu werkstoff- und beanspruchungsgerechte Füge- bzw. Schweißverfahren. Der Schweißeignung von MPEA wurde bis Ende 2021 nur äußert wenig Aufmerksamkeit zuteil. Die Auswirkungen durch Schweißprozesse auf die Metallurgie und die gewünschten Eigenschaften sind bisher kaum bekannt und limitieren die potenzielle Anwendbarkeit als Funktions- oder Konstruktionswerkstoffe.
In einem interdisziplinären BAM-Forschungsprojekt werden aktuell grundlegende Untersuchungen zur Schweißverarbeitung und resultierender Mikrostruktur-Anwendungseigenschafts-Beziehung verschiedener MPEA durchgeführt. Insbesondere Wärmeeinflusszone und Schweißgut sind geprägt durch eine Mikrostruktur, die aus Ungleichgewichtszuständen resultiert. Im Falle von MPEA wurde dies bisher nicht systematisch untersucht. Dazu erfolgte im Rahmen des Projektes eine umfassende Literaturauswertung zum Schweißen von MPEA und Zusammenfassung in einer umfassenden, systematischen Datenbasis. Aus diesem Grund sollen in der vorliegenden Studie die bisher bedeutsamsten Erkenntnisse zur Schweißbarkeit von MPEA systematisch nach MPEA-Typ und Schweißverfahren geordnet und mit eigenen aktuellen Forschungsergebnissen verglichen werden. Durch WIG- und Rührreibschweißversuche an den MPEA-Systemen CoCrNiFeMn bzw. CoCrNi konnten im Projektverlauf bereits wesentliche Fragestellungen beantwortet werden. Dazu zählen Auftreten bzw. Verhinderung intermetallischer Phasen/Seigerungen oder deren Auswirkung auf die Eigenschaften der Schweißverbindung (bspw. Festigkeit oder Korrosionsbeständigkeit).
Martensitic 9% Cr steels like P91 and P92 can show an increased susceptibility to delayed hydrogen-assisted cracking. The focus of this study was the microstructure and heat treatment efect on the mechanical properties of P92 base material and P91 multi-layer weld metal in both as-welded and post weld heat treated (PWHT) condition. Tensile tests with hydrogen free reference samples and electrochemically hydrogen charged samples were carried out; the mechanical properties were assessed and supported by detailed fractographic analysis. Finally, a hydrogen and microstructure-dependent fracture criterion is established. All investigated microstructures showed a hydrogen-infuenced degradation of the mechanical properties compared to the hydrogen-free reference samples. The as-welded martensitic P91 weld metal had the highest degree of degradation in the presence of hydrogen. The P91 PWHT weld metal and the P92 base material had comparable properties. From that point of view, a signifcantly increased risk for hydrogen-assisted cold cracking during welding fabrication of P91 weld joints must be considered before any heat treatment is conducted.
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.
Für eine signifikante Festigkeitssteigerung von vergüteten, hochfesten Feinkornbaustählen mit einer Nominalstreckgrenze ≥ 690 MPa, ist die Zugabe von Mikrolegierungselementen, wie Nb und Ti, unerlässlich. Die Normvorgaben zur chemischen Zusammensetzung dieser Stähle (bspw. in DIN EN 10025-6) geben zur Erzielung der vorgeschriebenen Eigenschaften dabei oft nur Grenzgehalte für die Hersteller vor. Die Wirkung der Legierungselemente in der WEZ ist teilweise komplett konträr. Somit wird eine adäquate Vorhersage der Chargenabhängigkeit hinsichtlich der Schweißeignung und des Tragverhaltens der Schweißverbindung erschwert. Neben metallographischen Untersuchungen einzelner WEZ-Bereiche wurden unter Variation der chemischen Zusammensetzung, thermodynamische Phasenberechnungen mittels ThermoCalc durchgeführt. Hierdurch wird ein Verständnis zur Phasentransformation, Ausscheidungswachstum und -auflösung während des Schweißens in Abhängigkeit von Temperatur und Abkühlbedingungen geschaffen.
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.