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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).
The chapter starts with a brief introduction about corrosion, which is defined as the interdependency between a metal, a corrosive environment, and the respective component design. The second section introduces the most important forms of aqueous electrochemical corrosion (uniform corrosion, galvanic corrosion, selective and intergranular corrosion, and finally pitting and crevice corrosion in the case of passive layer forming metals). In addition, electrochemical corrosion under applied mechanical load is introduced (stress corrosion cracking, hydrogen-assisted cracking, corrosion fatigue), as well as special forms of corrosion (erosion, fretting, and microbiologically induced corrosion). The third section of this chapter introduces (mostly dry) chemical corrosion and high-temperature corrosion (oxidation, carburization, high-temperature hydrogen attack, sulfurization, nitriding, halogenation). As in the case of electrochemical corrosion, chemical corrosion can also be superimposed by mechanical loads. Finally, general facts on the testing of corrosion are introduced.
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.
Due to their excellent combination of ductility, strength and corrosive resistance, austenitic stainless steels (ASS) are widely used in many industrial applications. Thus, these steel grades can be found as structural components in the (petro-)chemical industry, in offshore applications and more recent for storage and transport of hydrogen fuel. Steels employed for these applications are exposed to aggressive environments and hydrogen containing media. The ingress and accumulation of hydrogen into the microstructure is commonly observed during service leading to a phenomenon called “hydrogen embrittlement”. A loss in ductility and strength, the formation of cracks and phase transformations are typical features of this hydrogen-induced degradation of mechanical properties.
Although, great efforts are made to understanding hydrogen embrittlement, there is an ongoing debate of the underlying mechanisms. This knowledge is crucial for the safe use and durability of components on the one side and the development of new materials on the other.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a powerful tool for depicting the distribution of the hydrogen isotope deuterium in the microstructure of austenitic and duplex steels. The combination with imaging techniques such as electron backscatter diffraction (EBSD) and scanning electron microscopy (SEM), delivering structural and morphological information, creates a comprehensive picture of the hydrogen/deuterium-induced effects in the materials. All the gathered data is treated with principal component analysis (PCA) and data fusion to enhance the depth of information.
The mobility of hydrogen and deuterium in a steel microstructure is affected by external mechanical stress. To investigate the behaviour of deuterium in a strained microstructure, a new in situ experimental approach was developed. This gives the possibility of analysing samples in the SIMS instrument simultaneously to four-point-bending-tests.
Specimens made from ASS AISI 304L were electrochemically charged with deuterium instead of hydrogen. This necessity stems from the difficulty to separate between artificially charged hydrogen and hydrogen existing in the pristine material or adsorbed from the rest gas in the analysis chamber. Nonetheless, similar diffusion, permeation and solubility data allow to draw qualitative conclusions from the experiments, which are relevant for the application addressed.
The degradation effect of hydrogen on the mechanical properties of steels is well known, but still not sufficiently understood. The fast and safe market ramp up of hydrogen technologies makes it evident to evaluate a wider understanding of this topic. In general it is often described as hydrogen embrittlement. Therefore it is desirable to achieve a test method which is able to provide material properties under hydrogen atmosphere in an easy way. Currently mechanical tests under hydrogen atmosphere are executed in autoclaves. For this technique complex hardware is needed, therefore tests are expensive and test capacities are only available in a small scale. The shown test method promises a trendsetting approach for reducing costs and machine time by using hollow specimen.
Hybrid laser-arc welding (HLAW) was applied for butt welding of 14.5 mm thick plates of ferritic cryogenic steel X8Ni9 containing 9% Ni, which is used for manufacturing storage and transport facilities of liquefied natural gas (LNG). The weld seam formation and the achievable metallurgical and mechanical properties of the hybrid welds were investigated experimentally for two types of filler wire, an austenitic wire dissimilar to the base metal (BM) and an experimentally produced matching ferritic wire. Safe penetration and uniform distribution of the austenitic filler metal in the narrow hybrid weld could only be achieved in the upper, arcdominated part of the weld. The pronounced heterogeneous distribution of the austenitic filler metal in the middle part and in the root area of the weld could not ensure sufficient notched impact toughness of the weld metal (WM). As a result, a decrease in the impact energy down to 17±3 J was observed, which is below the acceptance level of ≥34 J for cryogenic applications. In contrast, the use of a matching ferritic filler wire resulted in satisfactory impact energy of the hybrid welds of up to 134±52 J at the concerned cryogenic temperature of -196 °C. The obtained results contribute to an important and remarkable conversion in automated manufacturing of LNG facilities. In other words, the results will help to develop a new laser-based welding technology, where both quality and productivity are considered.The efficiency of the developed welding process has been demonstrated by manufacturing a prototype where a segment of the inner wall of large size LNG storage tank was constructed. In this concern, hybrid laser arc welding was conducted in both horizontal (2G) and vertical (3G) positions as a simulation to the actual onsite manufacturing. The prototype was fabricated twice where its quality was confirmed based on non-destructive and destructive examinations.
A discussion is provided on demands that must be met in order to apply fracture mechanics to the determination of overall fatigue lifetime and strength, i.e., S-N curves and fatigue limits. These comprise the determination of the cyclic crack driving force for all stages of fatigue crack propagation, in particular for the short crack stage where the crack driving force has to be determined for elastic-plastic deformation and the gradual build-up of the crack closure phenomenon. Special emphasis is put on a fatigue damage relevant specification of the initial crack size. Different approaches in the literature are discussed. Another important aspect is the adequate treatment of multiple crack propagation. Finally, the discussion is illustrated by an example of a butt weld made of a medium strength steel.
Mikrolegierungselemente wie Nb und Ti sind entscheidend für die erwünschte mechanische Festigkeit von vergüteten Feinkornbaustählen mit einer Nennstreckgrenze von ≥ 690 MPa. Aktuelle Spezifikationen geben lediglich Obergrenzen für die chemische Zusammensetzung vor, allerdings können geringfügige Abweichungen erhebliche Auswirkungen auf die mechanischen Eigenschaften haben. Die Vorhersage der Schweißbarkeit und Integrität von Schweißverbindungen stellt aufgrund der variierenden Zusammensetzung und Mikrostrukturen Herausforderungen dar. Unerwünschte Effekte wie Erweichung der Wärmeeinflusszone (WEZ) oder Verfestigung können auftreten. Um dies zu untersuchen, wurden verschiedene Mikrolegierungsrouten mit variierenden Ti- und Nb-Gehalten an Laborschmelzen erforscht. Die Basis jeder Route entsprach der üblichen S690QL in Zusammensetzung und Wärmebehandlung. Dreilagenschweißungen wurden mittels Metallaktivgasschweißens (MAG) durchgeführt, um kritische Gefügebereiche zu identifizieren. Die Analyse konzentrierte sich auf Phasenumwandlungen während der Abkühlung und metallurgisches Ausscheidungsverhalten. Die mechanischen Eigenschaften der Schweißnähte wurden durch Zugversuche ermittelt. Die Ergebnisse zeigen einen bedeutenden Einfluss der Mikrolegierungsroute und Schweißwärmezufuhr auf die Ausscheidungskinetik, trotz insgesamt guter Schweißbarkeit der Werkstoffe.
Due to its low mass and high diffusivity in presence of compositional, thermal and mechanical gradients, hydrogen within a metallic microstructure can result in severe loss in ductility even at low concentrations and might lead eventually to a catastrophic and unpredictable failure of structural components during service. In this context, hydrogen mapping at the microscale is still considered among the most important challenges on the pathway towards a better understanding of the hydrogen transport and assisted cracking phenomena in metals, specifically in structural components, e.g. steels.
Among the very few available techniques to localize hydrogen at the microscale, Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a reliable tool. Based on the assumption that deuterium influence the microstructure similarly to hydrogen, in the following contribution ToF-SIMS was applied as the main technique to detect and locally map the deuterium distribution in several alloys: lean 2101 and standard 2205 duplex stainless steel (DSS), AISI 304L austenitic stainless steel and titanium 6Al-4V alloy. These alloys were selected as case studies in this work due to the wide use of them in many applications and environments which frequently provide critical conditions for hydrogen absorption and assisted degradation.
The innovative design of in-situ and ex-situ experiments enabled us to elucidate the permeation, transport and trapping of deuterium in the microstructure in sub-micron resolution for the first time. In addition to the novel experimental setups, further progress was gained by applying computational multivariate data analysis (MVA) on the raw data and data fusion with high resolution structural characterization methods (scanning electron microscopy and electron back-scattered diffraction – SEM/EBSD). This combination allowed us to correlate the deuterium distribution and the influence on the microstructure.
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.
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.
The following presentation provides an overview on some of the challenges with metallic materials used as structural materials in the energy sector for the transport and storage of hydrogen. The presentation contains explanations about the methodologies utilized to characterize the susceptibility of these materials for hydrogen.
Increasing environmental problems with conventional energy technology are stimulating the demand for alternative energy solutions. With air quality reaching catastrophic levels in large cities worldwide, Fuel Cell Electric Vehicles offer the ideal combination of clean power with the amenities of electric drives. Hydrogen use on vehicles, nevertheless, also raises some issues about safe handling. As fuel cells and hydrogen applications, including vehicles, approach technological maturity, developing their business cases becomes crucial in introducing them to the consumer markets.
The Joint European Summer School JESS 2021 addresses these issues by offering high quality graduate level courses on selected topics of vehicle technology, innovation & business development, safe handling of hydrogen, and modelling. This series of summer schools has been ongoing since 2004 and targets an audience of university students (MSc and PhD levels) and post-doctoral researchers. We also welcome more experienced researchers and engineers wishing to expand their general knowledge, for instance, to suit a newly acquired position or collect credits for Continuous Professional Development (CPD). The course content is tailored to the needs of a diverse audience: newcomers to the field, experienced students, and young professionals working at the forefront of fuel cell and hydrogen applications.
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.
Characterization of Hydrogen Diffusion in a Thick-walled Submerged Arc Multi-Layer Weld Joint
(2021)
The energy production of the future will be dominated by CO2-emission free techniques like wind turbines and become essential in scope of the planned hydrogen economy. As onshore installation capacity is limited, the in-crease of the number of offshore wind turbines (OWT) is a major goal. In that connection, the OWTs continuously increase in size and weight and demand adequate foundations concepts like monopiles or tripods. These compo-nents are typically manufactured from welded mild steel plates with thickness up to 200 mm. The predominant welding technique is submerged arc welding (SAW) with up to five wires. In accordance with the standards, the occurrence of delayed hydrogen assisted cracking is anticipated by either a hydrogen removal heat treatment (HRHT) or a so-called minimum waiting time (MWT) before non-destructive testing (NDT) of the respective weld joint is allowed. The reason for the MWT is the necessary time for the hydrogen diffusion at ambient temperature due the high plate thickness. Both the effectiveness of a HRHT at elevated temperatures or the MWT at ambient temperature can be estimated by calculation of the diffusion time. This time depends on reliable hydrogen diffu-sion coefficients and these are rare in literature. For that reason, this study presents the hydrogen diffusion coef-ficients obtained from a multi-layer SAW joint of an offshore steel grade. Two different experimental techniques were used to identify the respective diffusion behavior: (1) hydrogen desorption experiments with a carrier gas hot extraction analyzer at elevated temperatures for the characterization of a HRHT and (2) the electrochemical permeation technique at ambient temperature for the characterization of an MWT. From both experiments, the respective diffusion coefficients were calculated. The obtained DCs are different from those reported in literature, i.e., the duration or applicability of a HRHT or MWT must be critically discussed.
As onshore installation capacity is limited, the increase in the number of offshore wind turbines (OWT) is a major goal. In that connection, the OWTs continuously increase in size and weight and demand adequate foundations concepts like monopiles or tripods. These components are typically manufactured from welded mild steel plates with thickness up to 200 mm. The predominant welding technique is submerged arc welding (SAW). In accordance with the standards, the occurrence of hydrogen-assisted cracking is anticipated by either a minimum waiting time (MWT, before non-destructive testing of the welded joint is allowed) at ambient or a hydrogen removal heat treatment (HRHT) at elevated temperatures. The effectiveness of both can be estimated by calculation of the diffusion time, i.e., diffusion coefficients. In this study, these coefficients are obtained for the first time for a thick-walled S420G2+M offshore steel grade and its multi-layer SAW joint. The electrochemical permeation technique at ambient temperature is used for the determination of diffusion coefficients for both the base material and the weld metal. The coefficients are within a range of 1025 to 1024 mm2/s (whereas the weld metal had the lowest) and are used for an analytical and numerical calculation of the hydrogen diffusion and the related MWT. The results showed that long MWT can occur, which would be necessary to significantly decrease the hydrogen concentration. Weld metal diffusion coefficients at elevated temperatures were calculated from hydrogen desorption experiments by carrier gas hot extraction. They are within a range of 1023 mm2/s and used for the characterization of a HRHT dwell-time. The analytical calculation shows the same tendency of long necessary times also at elevated temperatures. That means the necessary time is strongly influenced by the considered plate thickness and the estimation of any MWT/HRHT via diffusion coefficients should be critically discussed.
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.
Multielement-Legierungen (MPEA - Multiple Principal Element Alloys, gemeinhin 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 diese 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 von 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 bis Ende 2022 nur äußert wenig Aufmerksamkeit zuteil. Erfahrungen zu Mischverbindungen (sogenannte 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 CoCrFeMnNi (Hochentropie-) und CoCrNi (Mittelentropielegierung) mittels WIG- und Rührreibschweißen mit einem konventionellen, hochlegierten und austenitischen Cr-Ni-Stahl (1.4301) 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 WEZ der MPEAs sowie eine geringfügig verminderte Zugfestigkeit. 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 zielgerichtete weitere Betrachtungen dieser höchst innovativen Werkstoffe.
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.
Competence Centre H2Safety@BAM – Safeguarding the Quality Infrastructure in the Hydrogen Economy
(2022)
Hydrogen is a central component of the energy transition and the European Green Deal for a climate-neutral Europe. To achieve the goals defined for 2050, the EU and the German government have developed a framework for action and are making long-term investments in research, development, and the rapid implementation of innovative hydrogen technologies.
With the Competence Centre "H2Safety@BAM", BAM is creating the safety-related prerequisites for the successful implementation of hydrogen technologies at national as well as European level.
To this end, BAM conducts research, testing and consulting in a holistic and inter-disciplinary manner under one roof – in the Competence Centre H2Safety@BAM. The activities of the competence centre focus on ensuring the safety of infra-structures, plants, and processes as well as innovative hydrogen transport and storage systems based on digital quality testing and the experimental testing of components and systems. It thus creates the prerequisites for the implementation and adaptation of legal framework conditions as well as for standardization. Closely related to this are investigations into the properties and compatibility of metallic materials and polymers as well as friction systems for the safe operation of components, plants, processes, and systems. This interdisciplinary and holistic approach is complemented by the development of gas analytics and suitable sensors, online measurements of gas properties in process control, test scenarios under real conditions as well as impact assessments of accidents and risk assessments and risk management systems derived from them. With its portfolio of tasks and competences, BAM builds trust in the safety and reliability of technical system solutions for hydrogen.
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.
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.
The damaging impact of hydrogen on the austenitic stainless steel AISI 304 L was analysed.
To this aim, samples were charged electrochemically with the hydrogen isotope deuterium (2H, D) and examined with time-of-flight secondary ion mass spectrometry (ToF-SIMS) and electron backscatter diffraction (EBSD). The fusion of the obtained chemical and structural information revealed local enrichment of deuterium in austenite, transformation into martensite, crack formation and severe roughening of the specimen surface. The results indicated that martensite was not only formed during charging but also during Desorption and ToF-SIMS examinations. Furthermore, cross-sections of deuterium-charged samples revealed that in preferred deformation bands a g/ε/a 0 evolution is taking place.
By means of microscopic analyses and carrier gas hot extraction (CGHE), it was found that the use of NaAsO2 as recombination poison decreased the uptake of hydrogen significantly and resulted in severe precipitation on the specimen surfaces. This is in contrast to the popular presumption that NaAsO2 enhances the uptake of hydrogen (and
deuterium) during electrochemical charging by hampering its recombination from Atoms to molecules.
The Tsumeb Mine in Namibia represents one of the best-preserved mining sites in the world and is rapidly gaining cross-disciplinary interest among cultural and engineering scientists. Most of the open pit and the shaft mining equipment are still in place, including the ore processing units and the local power plant. The mining area thus deserves recognition as an industrial world heritage site, especially due to the rarity of such locations on the African continent. The Shaft #1 headgear, built in 1924, represents one of the oldest known riveted steel headgears of the Promnitz design worldwide. In contrast to similar steel structures located in the northern hemisphere, it has been exposed to a different rural semi-arid climate since it is located in the Otavi Mountain Land, characterized by semi-annual change of rainy and dry seasons. Parts of the Shaft #1 headgear have remained largely untouched for more than 70 years. Besides its outstanding heritage value, it thus also represents an interesting object for studying the composition of corrosion layers formed on mild steel surfaces when exposed to continental and industrial mining atmospheres. To find a suitable transparent corrosion prevention coating, various on-site coating samples were evaluated after 11 months of outdoor exposure, including Owatrol Oil®, which is based on natural oil and alkyd resin with strong wicking potential. The substance is frequently applied for the conservation of single components but is not yet widely used on large steel structures in the field of industrial heritage conservation. However, it represented the most stable anti-corrosion coating under the local atmospheric conditions in the on-site tests. Thus, the suitability of Owatrol Oil® as a transparent coating for corrosion protection of riveted mild steel structures in such climates was further investigated as a more recent approach for the conservation of large steel structures. Since the protective coatings are exposed to strong UV radiation in the local climate, the addition of a specific UV stabilizer mixture was also tested. For such laboratory tests, two mild steel samples were taken. The first one originated from a diagonal strut of the 1920s and the second one from a handrail mounted in the early 1960s. Using corresponding high-resolution scanning electron microscopy (HR-SEM) and energy-dispersive X-ray spectroscopy (EDX) it was found that the corrosion layers are predominantly composed of lepidocrocite and goethite. A weathering program simulating the specific environmental conditions at Tsumeb in a UV climate chamber was developed and the corrosion resistance of the mild steel surface was subsequently evaluated by potentiodynamic measurements. Such tests proved to be a fast and reliable procedure for ranking the corrosion resistance of the old mild steels. It was found that the long-term corrosion layers already provide significant protection against further corrosion in the simulated environment. However, the study also showed that this can be further improved by the application of the Owatrol Oil® as a protective coating that also seals crevices. The addition of the UV stabilizers, however, led to a significant deterioration in corrosion protection, even in comparison to that of the uncoated long-term corrosion layers on the surface. Regular overcoating seems more advisable for the long-term preservation of the Shaft #1 headgear than modifying the Owatrol Oil® Coating with the tested UV-stabilizing additives.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in two different electrolyte systems (NaCl and H2SO4 c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively. To analyze the semiconducting properties of the passive film Mott-Schottky analysis was conducted.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX, ICP-MS and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance due to the higher concentration of chromium in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize our results on the mechanistical aspects of the observed high corrosion resistance.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in three different electrolyte systems (NaCl, H2SO4 and NaClO4; c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance due to the higher concentration of Chromium in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize our results on the mechanistical aspects of the observed high corrosion resistance.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in three different electrolyte systems (NaCl, H2SO4 and NaClO4; c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance due to the higher concentration of Chromium in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize our results on the mechanistical aspects of the observed high corrosion resistance.
The Topic of the presentationis a discussion on defects which can cause failure in cyclically loaded metallic components. Although also touching Features such as material defects such as pores or micro-shrinkages, etc. and geometric defects such as surface roughness and secondary notches (which are not considered in the design process) which origin in manufacturing, and others the presentation concentrates on non-metallic inclusions. It is prefaced by an introduction to the life cycle of a fatigue crack from initiation up to fracture. Special emphasis is put on the fact that only cracks which are not arrested during one of their distinct Propagation stages can grow to a critical size.
According to the definition of the ASM handbook [1,3], a defect is "an imperfection. that can be shown to cause failure by a quantitative analysis and that would not have occurred in the absence of the imperfection". The topic of the present three-part review is a discussion of defects which can cause failure in cyclically loaded structures. The features discussed comprise material defects such as non-metallic inclusions, pores or micro-shrinkages, etc. and geometric defects such as surface roughness and secondary notches which have their origin in manufacturing, and defects such as surface damage due to scratches, impact events or contact fatigue as well as corrosion pits which arise in service. In this first part, the discussion is prefaced by an introduction to basic aspects which are essential for a deeper understanding of the characteristics and mechanisms how the defects influence fatigue crack initiation and propagation. These include the life cycle of a fatigue crack from initiation up to fracture, crack arrest, multiple crack initiation and coalescence, and the material and geometrical properties affecting these.
Defects as a root cause of fatigue failure of metallic components. II: Non-metallic inclusions
(2019)
This second part of the review on defects as root cause of fatigue failure comprises the origin, the nature and the effects of non-metallic inclusions. Topics addressed are the different kinds of inclusions formed during the manufacturing process, various types of mis-match causing local stresses and, as a consequence, fatigue crack initiation, and effects of characteristics such as size, morphology, localization, spatial distribution and orientation of the defects on the fatigue behavior. Methods for inclusion counting and sizing are discussed along with statistical aspects necessary to be considered when evaluating structural components.
This third part of the review on defects as root cause of fatigue failure addresses cavities (pores, micro-shrinkages, unmelted regions), defective microstructures and microcracks as material defects and defects due to local damage during manufacturing, service and maintenance such as dents, scratches and localized corrosion. In addition, damage due to contact fatigue and the effect of surface roughness are discussed in the context of fatigue failure. Also addressed is the competition between different kinds of defects in controlling the initiation and early growth of fatigue cracks.
Ein Defekt ist „eine Imperfektion …, für die in einer quantitativen Analyse gezeigt werden kann, dass sie Versagen verursacht hat, welches ohne die Imperfektion nicht aufgetreten wäre“. Defekte in diesem Sinn können einerseits Werkstoffimperfektionen wie nichtmetallische Einschlüsse, Poren und Porennester, Nichtdurchschweißungen oder Bereiche defekter Mikrostruktur, andererseits unbeabsichtige geometrische Imperfektionen wie Kratzer, Eindrücke, Korrosionsgrübchen, Einbrandkerben, zu große Oberflächenrauheit u.a. sein. Sie können in der Fertigung, im Betrieb oder auch bei der Wartung entstehen. Nicht jede Imperfektion ist ein Defekt im oben genannten Sinn. Entscheidend ist zumeist nicht, dass an ihr ein oder mehrere Risse initiiert werden, sondern dass wenigstens ein Riss wachstumsfähig bleibt und so innerhalb der projektierten Lebensdauer zum Bruch oder anderweitigem Versagen führt. Aufgrund des begrenzten Umfangs bleibt die vorliegen-de Übersicht beschränkt.
Hochentropie Legierungen (engl. High Entropy Alloys, HEAs) sind eine relativ neue Werkstoffklasse. Seit ersten Veröffentlichungen im Jahr 2004, steigt das Forschungsinteresse an diesem Werkstoffkonzept stetig an. Im Gegensatz zu herkömmlichen Legierungen bestehen HEAs aus fünf Legierungselementen in äquiatomaren Gleichgewicht. Der Hochentropie-Effekt ist dabei u.a. auf die erhöhte Konfigurationsentropie zurückzuführen, der die Mischkristallbildung fördert. Viele HEAs weisen aufgrund hervorragender struktureller Eigenschaftskombinationen von sehr tiefen bis zu hohen Temperaturen enormes Anwendungspotential auf. Für ihre Anwendung als reale Bauteile stellt sich aber die zentrale Frage der Anwendbarkeit von trennenden Fertigungstechnologien für HEAs. Dies findet in der bisherigen weltweiten Materialforschung bisher kaum Beachtung. Für die Forderung nach wirtschaftlicher Bauteilfertigung ist für potenzielle Anwendungsbereiche, bspw. in der Energietechnik, eine zuverlässige und sichere Verarbeitung von wesentlicher Bedeutung. Fräsen ist dabei ein Standardprozess für die zerspanende Bearbeitung von Metallen. Der vorliegende Beitrag stellt Ergebnisse durchgeführter Zerspanbarkeitsanalysen vor. Diese konzentriert sich auf die aus dem Fräsprozesse resultierende Oberflächenintegrität an einem sogenannten „Cantor-HEA“ (mit der Zusammensetzung Co20Cr20Fe20Mn20Ni20). Hierfür wurden Untersuchungen mit konventionellem Kugelkopffräsen durchgeführt und mit dem an der BAM Berlin verfügbaren innovativen Hybridverfahren, dem ultraschallunterstützten Fräsen (engl. Ultrasonic Assisted Milling, USAM), verglichen. USAM verspricht dabei eine geringere Degradation der Oberflächeneigenschaften aufgrund geringerer Belastungen auf die Werkstückoberfläche beim Spanen. Dazu wurden grundlegende Fräsparameter (Schnittgeschwindigkeit und Zahnvorschub) systematisch variiert und während der Fräsexperimente die Zerspankräfte gemessen, deren anschließende Analyse ein Verständnis für die mechanischen Beanspruchungen ermöglicht, die auf Werkzeug und Bauteiloberfläche wirken. Diese Beanspruchungen bedingen eine topographische, mechanische und mikrostrukturelle Beeinflussung der Oberfläche und letztlich der Oberflächenintegrität. Zur deren Charakterisierung wurden Licht- und Rasterelektronen-mikroskopie eingesetzt, sowie die Rauheit mittels 3D-Mikroskop und die Eigenspannungen mittels Röntgendiffraktion gemessen. Die Ergebnisse belegen einen signifikanten den positiven Effekt beim USAM, insbesondere durch reduzierte Zerspankräfte im Vergleich zum konventionellen Kugelkopffräsen. Dies führt zu geringerer mechanischer Beanspruchung von Werkzeug und Oberfläche verbunden mit geringeren Zugeigenspannungen an und unter der Oberfläche und bewirkt schließlich eine wesentlich höhere Oberflächenintegrität.
Die schädigende Wirkung von Wasserstoff auf die mechanischen Eigenschaften von Stählen ist zwar bekannt, aber noch immer nicht ausreichend erforscht. Die schnelle und sichere Markteinführung von Wasserstofftechnologien macht es erforderlich, dieses Thema genauer zu untersuchen. Im Allgemeinen wird dies oft als Wasserstoffversprödung bezeichnet. Daher ist es wünschenswert, eine Prüfmethode zu entwickeln, die auf einfache Weise die Materialeigenschaften unter Wasserstoffatmosphäre ermitteln kann. Derzeit werden mechanische Prüfungen unter Wasserstoffatmosphäre in Autoklaven durchgeführt. Für diese Technik ist eine aufwendige Hardware erforderlich, daher sind die Prüfungen teuer und die Prüfkapazitäten nur in geringem Umfang verfügbar. Die hier vorgestellte Prüfmethode verspricht einen zukunftsweisenden Ansatz zur Reduzierung von Kosten und Bearbeitungszeiten durch die Verwendung von Hohlkörpern, d.h. die Probe selbst stellt den Autoklav dar.
Das Thema Wasserstoff ist an der BAM seit mehr als hundert Jahren aktuell und steht auch gegenwärtig im Zentrum zahlreicher Forschungs- und Kooperationsaktivitäten. Mit der aktuellen Wasserstoff-Strategie der BAM werden wichtige Voraussetzungen dafür geschaffen, dass der Markthochlauf gelingt und die technische Sicherheit und Überwachung der Infrastrukturen und Anlagen gewährleistet ist – von der Erzeugung, über den Transport bis zur Speicherung und Bereitstellung von Wasserstoff als Energieträger der Zukunft.
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.
Offshore-Windenergieanlagen bilden einen zentralen Bestandteil der zukünftigen Energieerzeugung. Hierzu notwendige Gründungs- und Turmstrukturen werden vorrangig aus UP-geschweißten Blechen aus hochfesten niedriglegierten Stählen mit Dicken bis zu 200 mm hergestellt. Die großen Blechdicken begünstigen hohe Schweißeigenspannungen und lange Diffusionswege für z. B. über den Schweißprozess eingebrachten Wasserstoff. Damit steigt das Risiko für eine wasserstoffunterstützte Kaltrissbildung (WKB) an. Zum sichereren Ausschluss von WKB in den geschweißten Komponenten wird in Abhängigkeit der Nahtgröße, Wärmeeinbringung und Stahlsorte eine Mindestwartezeit (MWZ) von bis zu 48 h empfohlen, bevor die zerstörungsfreie Prüfung durchgeführt wird. Es ist allerdings offen, ob die empfohlene MWZ zu konservativ ist. Einflüsse sind hier bspw. die schwierige Bewertung des Wasserstoffdiffusionsverhaltens im heterogenen UP-Mehrlagen-Schweißgut (SG) im Vergleich zum Grundwerkstoff (GW).
Zudem sind nur sehr begrenzt H-Diffusionskoeffizienten für UP-Mehrlagen-SG als Grundlage zur Abschätzung des Zeitintervalls einer möglichen verzögerten Kaltrissbildung (somit MWZ) oder auch für Nachwärmprozeduren zur Wasserstoffreduktion (keine MWZ) verfügbar. Verlässliche H-Diffusionskoeffizienten sind daher ein adäquates Tool zur Bewertung des Risikos einer verzögerten WKB. Dieser Beitrag beschreibt Untersuchungen zur Charakterisierung der Wasserstoffdiffusionsverhalten in UP-Mehrlagen-SG eines 60 mm dicken Bleches einer Offshore-Stahlgüte.
Dazu wurden Proben unterschiedlicher Dicke aus dem reinen Schweißgut extrahiert und über elektrochemische Permeation und Trägergasheißextraktion im Temperaturbereich bis 400 °C sehr interessante Ergebnisse zu den korrespondierenden Diffusionskoeffizienten erarbeitet.
Offshore-Windenergieanlagen bilden einen zentralen Bestandteil der zukünftigen Energieerzeugung. Hierzu notwendige Gründungs- und Turmstrukturen werden vorrangig aus UP-geschweißten Blechen aus hochfesten niedriglegierten Stählen mit Dicken bis zu 200 mm hergestellt. Die großen Blechdicken begünstigen hohe Schweißeigenspannungen und lange Diffusionswege für z.B. über den Schweißprozess eingebrachten Wasserstoff. Damit steigt das Risiko für eine wasserstoffunterstützte Kaltrissbildung (WKB) an. Zum sichereren Ausschluss von WKB in den geschweißten Komponenten wird in Abhängigkeit der Nahtgröße, Wärmeeinbringung und Stahlsorte eine Mindestwartezeit (MWZ) von bis zu 48 h empfohlen, bevor die zerstörungsfreie Prüfung durchgeführt wird. Es ist allerdings offen, ob die empfohlene MWZ zu konservativ ist. Einflüsse sind hier bspw. die schwierige Bewertung des Wasserstoffdiffusionsverhaltens im heterogenen UP-Mehrlagen-Schweißgut (SG) im Vergleich zum Grundwerkstoff (GW). Zudem sind nur sehr begrenzt H-Diffusions-koeffizienten für UP-Mehrlagen-SG als Grundlage zur Abschätzung des Zeitintervalls einer möglichen verzögerten Kaltrissbildung (somit MWZ) oder auch für Nachwärmprozeduren zur Wasserstoffreduktion (keine MWZ) verfügbar. Verlässliche H-Diffusionskoeffizienten sind daher ein adäquates Tool zur Bewertung des Risikos einer verzögerten WKB. Dieser Beitrag beschreibt Untersuchungen zur Charakterisierung der Wasserstoffdiffusionsverhalten in UP-Mehrlagen-SG eines 60 mm dicken Bleches einer Offshore-Stahlgüte. Dazu wurden Proben unterschiedlicher Dicke aus dem reinen Schweißgut extrahiert und über elektrochemische Permeation und Trägergasheißextraktion im Temperaturbereich bis 400 °C sehr interessante Ergebnisse zu den korrespon-dierenden Diffusionskoeffizienten erarbeitet. Es zeigte sich, dass:
1. Diffusionskoeffizienten bei Umgebungstemperatur als Tool zur Bewertung einer MWZ geeignet sind. Jedoch veränderte sich der Diffusionskoeffizient mit der untersuchten Probendicke um bis zu einer Größenordnung, d. h. daraus abgeleitete Wartezeiten differieren dementsprechend.
2. Dies deutet darauf hin, dass MWZs von bis zu 48 h einerseits möglicherweise zu konservativ gewählt sind, da der Wasserstoff schneller aus der Naht diffundiert. Andererseits muss aber auch die schnellere Diffusion in weitere potenziell risskritische Nahtbereiche, wie die WEZ, berücksichtigt werden. Daher ist noch keine direkte Aussage auf eine verallgemeinerte WKB-Anfälligkeit (ja/nein) innerhalb der MWZ möglich.
3. Im Fall einer konservativen Prävention der WKB durch Wasserstoffarmglühen (Vermeidung der MWZ) sind die Diffusionskoeffizienten bei erhöhten Temperaturen bis 400 °C zur Abschätzung der notwendigen Haltezeiten geeignet, z. B. über die numerische Simulation der Wasserstoffdiffusion.
Multiple principal element alloys (MPEA) represent a class of materials consisting of at least three alloying elements, each with 5 to 35 atomic %. The MPEAs encompass the so-called high-entropy (HEA) and medium-entropy alloys (MEAs) and are fundamentally different from conventional materials like the Fe-based steel. Within the last 20 years, highly innovative MPEA with individually adjustable properties for industrial applications were identified. However, the focus has been on pure material synthesis. With the increase in available material quantities, the focus is now on processing issues such as joining and welding. In that connection, the weldability of MPEAs has received very little attention so far and experience in dissimilar metal welds (DMWs) is lacking so far but. The present study summarizes comprehensive experimental results on the weldability of MPEA-DMWs and their resulting microstructure. For this purpose, two equiatomic MPEAs, CoCrFeMnNi (HEA) and CoCrNi (MEA) in cold-rolled and annealed conditions were joined by solid-state friction stir welding (FSW) to an austenitic stainless steel 316L. The DMWs showed very interesting microstructure features. In addition, the mechanical-technological properties were obtained by instrumented tensile tests, and the local straining was determined in-situ by digital image correlation (DIC). A significant influence of the FSW processing on the mechanical performance was identified,in terms of the formation of FSW-specific defects like whitebands or tunnel defects. The experiments proofed the general (but currently limited) FS weldability of the MPEAs to conventional austenitic steel grade AISI 304. This enables targeted further considerations of these highly innovative MPEAs.
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.
Zinc oxide - polymer interfaces are known to exhibit interesting properties regarding molecular adhesion. This work is aimed at the investigation of the effect of the morphology and surface chemistry on the macroscopic adhesion of a model epoxy-based adhesive to nanorod (ZnO NR) and nanocrystalline (ZnO NC) ZnO-modified surfaces. Both ZnO films have been prepared using hydrothermal synthesis on hot-dip galvanized steel (HDG) surfaces by varying the precursor chemistry in order to control the film morphology. Poly (acrylic acid) (PAA) was used to improve the interfacial adhesion by modifying the morphology and surface chemistry of ZnO nanostructured films. The strong interaction of PAA from a dilute and neutral aqueous solution with the ZnO nanocrystallites was shown to significantly improve the interfacial adhesion by means of a nanoetching process.
It was shown that the wet peel-forces correlate well with the considered morphology and surface chemistry.
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.
Effect of weld penetration depth on hydrogen-assisted cracking of high-strength structural steels
(2019)
The need for steels with highest mechanical properties is a result of the increasing demands for energy and resource efficiency. In this context, high-strength structural (HSS) steels are used in machine, steel and crane construction with yield strength up to 960 MPa. However, welding of HSS steels requires profound knowledge of three factors in terms of avoidance of hydrogen-assisted cracking (HAC): the interaction of (1) microstructure, (2) local stress/strain and (3) local hydrogen concentration. In addition to the three main factors, the used weld-arc process is also important for the performance of the welded joint, especially when using modern arc variants. In the past, the conventional transitional arc process (Conv. A) was mainly used for welding of HSS grades. In the past decade, the so-called modified spray arc process (Mod. SA) has been used increasingly for welding production. This modified process enables reduced seam opening angles with increased deposition rates compared to the conventional process. Economic benefits of using this arc type are: a reduced number of necessary weld beads and a lower weld seam volume, which result in decreased total welding time and costs. Nonetheless, investigations on a high-strength S960QL showed significantly higher hydrogen concentrations in the weld metal at a reduced seam opening angle with Mod. SA. This indicates an increased susceptibility of the welded component to HAC. Hence, existing recommendations on HAC-avoidance cannot be transferred directly to the Mod. SA-process. In the present study, the susceptibility to HAC of the HSS steel S960QL with same type of filler material was investigated. For that purpose, both Conv. A and Mod. SA were used with same heat input at different deposition rates. For assessment of the HAC susceptibility, the externally loaded implant test was used. Both conducted test series with Conv. A and Mod. SA showed similar crack critical stress of about 280 MPa. Below this value, no delayed fracture appeared. The welds with Mod. SA showed higher hydrogen concentrations. The fracture occurred in the heat-affected zone (HAZ) or in the weld metal (WM). However, the test series with Mod. SA showed a significant extension of the time to failure of several hours compared to tests carried out with Conv. A.