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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).
Carrier gas hot extraction (CGHE) is a commonly applied technique for determination of hydrogen in welded joints using a thermal conductivity device (TCD) for quantitative measurement. The CGHE is based on the accelerated hydrogen effusion due to thermal activation at elevated temperatures. The ISO 3690 standard suggests different specimen geometries as well as necessary minimum extraction time vs. temperature. They have the biggest influence on precise hydrogen determination. The present study summarizes the results and experience of numerous test runs with different specimen temperatures, geometries and factors that additionally influence hydrogen determination. They are namely: specimen surface (polished/as-welded), limited TCD sensitivity vs. specimen volume, temperature measurement vs. effects of PID-furnace controller as well as errors due to insufficient data assessment. Summarized, the temperature is the driving force of the CGHE. Two different methods are suggested to increase the heating rate up the reach the desired extraction temperature without changing the experimental equipment. Suggestions are made to improve the reliability of hydrogen determination depended on the hydrogen signal stability during extraction accompanied by evaluation of the recorded data. Generally, independent temperature measurement with calibration specimens is useful for further data analysis, especially if this data is used for calculation of trapping kinetics by thermal desorption analysis (TDA).
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 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.
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.
Dieses Dokument fasst den Projekfortschritt des BAM-Projektes "Entwicklung von Wärmenachbehandlungsstrategien zur Vermeidung von Spannungsrelaxationsrissen" im Rahmen des Fachausschusses 1 "Schweißmetallurgie" des DVS e.V. für das Projektjahr 2021 zusammen und stellt die wichtigsten Ergebnisse in Kurzform vor.
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.
Bewertungsmethode zur Interaktion von Metallurgie und Reaktionskräften beim PWHT warmfester Stähle
(2022)
Die Präsentation fasst die Entwicklung einer Ersatzprüfmethode für sogenannte Stress-Relief-Cracks (SRC) bei dickwandigen und kriechfesten geschweißten Stahlkomponenten zusammen. Über die Kombination von gezielter mechanischer Beanspruchung unter hoher Temperaturbeanspruchung werden die Effekte des Post Weld Heat Treatments auf SRC realistisch erstmal auf Laborskala nachgebildet.
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.
Multi-element systems with defined entropy (HEA - High Entropy Alloy or MEA - Medium Entropy Alloy) are rather new material concepts that are becoming increasingly important in materials research and development. Some HEA systems show significantly improved properties or combinations of properties, e.g., the overcome of the trade-off between high strength and ductility. Thus, the synthesis, the resulting microstructures, and properties of HEA have been primarily investigated so far. In addition, processing is crucial to achieve a transfer of potential HEA/MEA materials to real applications, e.g. highly stressed components. Since fusion welding is the most important joining process for metals, it is of vital importance to investigate the weldability of these materials. However, this has rarely been the subject of research up to date. For that reason, in this work the weldability depending on the surface preparation of a CoCrFeMnNi-HEA and a CoCrNi-MEA for TIG welding is investigated. The fusion welding of longer plates is described here for the first time for the CoCrNi alloy. The welds of both materials showed distinct formation of cracks in the heat affected zone (HAZ). Optical and scanning electron microscopy analysis clearly confirmed an intergranular fracture topography. But based on the results, the crack mechanism cannot be conclusively clarified as either a liquid metal embrittlement (LME) or hot cracking like liquid film separation occurred.
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.
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.
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.
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.
High entropy alloys (HEA) are a new class of materials. In contrast to conventional alloys, HEA are single-phase alloys with at least five alloying elements. HEAs have enormous application potential due to (postulated) excellent structural property combinations from low to high temperatures. For HEA-application as structural materials in real components, a key issue is the suitability for joining processing. Requirements for the reliable and safe joining of these materials are crucial regarding economical component manufacture for future applications. In this context, friction stir welding (FSW) is a promising joining process due to the welding process temperature below the material melting point avoiding major issues, e. g. formation of (hard and brittle) intermetallic phases, which may have detrimental influences on the weld joint properties.
This study presents elementary research about the FSW process influences on a CoCrFeMnNi-HEA with focus on the microstructure and mechanical properties. For that purpose, the FSW joint of the HEA is compared to that of an austenitic stainless steel AISI 304. The microstructures of the welds were investigated and characterized by means of light microscopy, SEM, EBSD and XRD. Hardness and tensile testing were applied to determine influences on the mechanical properties. Generally, a comparable weldability of HEA and AISI 304 in terms of metallurgical characteristics and resulting mechanical properties exhibited. For the weld joints of both materials typical characteristics regarding FSW were observed within the weld metal and thermo-mechanically influenced zone: fine-grained stirred zone with increased hardness and reduced fracture elongation compared with the respective base material.
Die Studie gibt einen kurzen Überblick über die jetzige Bedeutung der Fügetechnik in Wasserstofftechnologien und über zukünftige Forschungsbedarfe für die Branche in den einzelnen Technologiefeldern Wasserstofferzeu-gung, -speicherung, -transport und -nutzung. Fügetechnologien haben dabei wesentliche Bedeutung für die er-folgreiche Umsetzung von technischen Komponenten der Wasserstofftechnologien. Die Schwerpunkte bzw. For-schungsbedarfe ergeben sich bspw. durch die Erstellung neuer Infrastruktur für Wasserstoffspeicherung und -transport sowie durch Umnutzung der bestehenden Erdgasinfrastruktur. Bei der Wasserstofferzeugung und -anwendung wird z.B. die Entwicklung effiziente Massenproduktionsmethoden von Elektrolyseuren und Brennstoff-zellen einen wichtigen Meilenstein bilden und laserbasierte Fügetechnologien sind hier zum Teil schon etabliert. Die additive Fertigung nimmt dabei eine Querschnittsposition ein und besitzt hohes Anwendungspotential für die Zukunft z.B. für die Fertigung von Komponenten in Gasturbinen. Aus den technischen Fragestellungen und For-schungsbedarfen ergeben sich zudem Herausforderungen für die notwendige Neu- und Weiterentwicklung von technischen Regelwerken und Normen und den Eingang in die Aus- und Weiterbildung von fügetechnischem Fachpersonal.
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.
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.