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The avoidance of failures during the fabrication or operation of petrochemical reactors made of creep-resistant, low-alloy steels as 13CrMoV9-10 requires still research despite over 60 years of international investigations in the field of stress relief cracking. The quality of modern base materials and filler metals leads to the fact that previously known crack causes, such as impurities of S or P, recede into the background. Rather, the causes are increasingly to be found in the fabrication process. Investigations on the influence of heat control on the stresses in welded components and thus on the stress relief cracking sensitivity under realistic manufacturing conditions are not yet available. This work is subdivided in two parts. Part 1 of this study focused on the effect of heat control during submerged arc welding on the stresses. For this purpose, a testing facility was applied, which allows to observe the forces and moments accumulating during welding or heat treatment in a component-like specimen under shrinkage restraint. The stress acting in the specimen increases with higher preheat/interpass temperatures and higher heat input. During the heat treatment, the stresses are relieved. Nevertheless, cracks are formed already during heating. The total crack length correlates with the heat input.
Welding of 13CrMoV9-10 vanadium steel requires care due to an increased susceptibility to stress relief cracking during post weld heat treatment. Previous research into the crack formation in creep-resistant steels has focused on thermal and metallurgical factors; however, little knowledge has been gathered regarding the crack formation during post weld heat treatment considering real-life restraint conditions. This work is subdivided in two parts. Part I showed that an increasing heat input during submerged arc welding under restraint led to an increasing stress level in the joint prior to the post weld heat treatment. The magnitude of stress relief cracking observed in the heat-affected zone after the post weld heat treatment is affected by the heat input. In Part II of this work, the cracks and the associated microstructure which occurred under restraint were studied. The application of a Special acoustic emission analysis indicated that the cracks formed in a temperature range between 300 and 500 °C during the post weld heat treatment. The toughness in the heat-affected zone of the restrained welds was affected by the welding heat input.
Microstructural analyses of all specimens revealed accelerated aging due to precipitation of carbides during post weld heat treatment under restraint.
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.
High-entropy alloys (HEAs) and compositionally complex alloys (CCAs) represent new classes of materials containing five or more alloying elements (concentration of each element ranging from 5 to 35 at. %). In the present study, HEAs are defined as single-phase solid solutions; CCAs contain at least two phases. The alloy concept of HEAs/CCAs is fundamentally different from most conventional alloys and promises interesting properties for industrial applications (e.g., to overcome the strength-ductility trade-off). To date, little attention has been paid to the weldability of HEAs/CCAs encompassing effects on the welding metallurgy. It remains open whether welding of HEAs/CCAs may lead to the formation of brittle intermetallics and promote elemental segregation at crystalline defects. The effect on the weld joint properties (strength, corrosion resistance) must be investigated. The weld metal and heat-affected zone in conventional alloys are characterized by non-equilibrium microstructural evolutions that most probably occur in HEAs/CCAs. The corresponding weldability has not yet been studied in detail in the literature, and the existing information is not documented in a comprehensive way. Therefore, this study summarizes the most important results on the welding of HEAs/CCAs and their weld joint properties, classified by HEA/CCA type (focused on CoCrFeMnNi and AlxCoCrCuyFeNi system) and welding process.
High-entropy alloys (HEAs) are characterized by a solid solution of minimum five and medium-entropy alloys (MEAs) of minimum three principal alloying elements in equiatomic proportions. They show exceptional application properties, such as high-strength and ductility or corrosion resistance. Future HEA/MEA-components could be exposed to hydrogen containing environments like vessels for cryogenic or high-pressure storage where the hydrogen absorption and diffusion in these materials is of interest. In our study, we investigated the HEA Co20Cr20Fe20Mn20Ni20 and the MEA Co33.3Cr33.3Ni33.3. For hydrogen ingress, cathodic charging was applied and diffusion kinetic was measured by high-resolution thermal desorption spectros-copy using different heating rates up to 0.250 K/s. Peak deconvolution resulted in high-temperature desorption peaks and hydrogen trapping above 280 °C. A total hydrogen concentration > 40 ppm was identified for the MEA and > 100 ppm for HEA. This indicates two important effects: (1) delayed hydrogen diffusion and (2) considerable amount of trapped hydrogen that must be anticipated for hydrogen assisted cracking phenomenon. Local electrochemical Volta potential maps had been measured for the hydrogen free condition by means of high-resolution Scanning Kelvin Probe Force Microscopy (SKPFM).
Medium and High Entropy Alloys (MEA/HEA) are recently developed material classes, providing manifold applications, e.g., due to extraordinary structural properties. In that connection, the machinability as important issue for the processing of these materials was not in the scientific focus. This study focusses on experimental analysis of milling process conditions including ultrasonic assisted milling (USAM) and their effects on the resulting surface integrity of equiatomic CoCrFeNi-MEA specimens. For that reason, milling parameters (cutting speed, feed per cutting edge) were systematically varied for both conventional milling and USAM. The surface integrity was analyzed in terms of topography, defects, and residual stresses. Especially USAM leads to a decrease of occurring cutting forces and, hence, to an improvement of the surface integrity. Beneficial effects were observed in terms of lower tensile residual stresses at high cutting speed and feed per cutting edge.
The new multi-element alloying concept of systems with defined entropy (HEA — high-entropy alloy or MEA — medium-entropy alloy) is increasing in material research interest. Improved properties or combinations of properties are shown by several systems. Thus, the resulting microstructures and production of HEA/MEA as well as properties have been primarily investigated so far. Furthermore, processing is a key issue to transfer HEA/MEA systems to real components. Since welding is the most important joining process for metals, it is crucial to investigate the influence of welding to guarantee component integrity. Since most HEA are made of expensive alloying elements such as Co or Ni, they will not be used entirely as structural materials. Thus, it can be advantageous to weld conventional alloys such as austenitic stainless steels with the HEA and MEA to produce components that are both application-oriented and economically viable. Therefore, in this paper, first results of dissimilar metal welding, by tungsten inert gas (TIG) and friction stir welding (FSW), of a CoCrFeMnNi HEA as well as a CoCrNi MEA with a conventional AISI 304 austenitic stainless steel are presented. The focus is on the microstructure formation due to the two welding processes. The results of TIG welding show a dendritic microstructure, whereas in FSW both materials are stirred but still coexist.
Influence of Surface Preparation on Cracking Phenomena in TIG-Welded High and Medium Entropy Alloys
(2022)
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 overcoming 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 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. However, based on the results, the crack mechanism cannot be conclusively identified as either a liquid metal embrittlement (LME) or hot cracking-like liquid film separation.
Multielement-Legierungen (MPEA – multiple pricipal element alloys) stellen eine neue Klasse von Werkstoffen dar, die aus mindestens drei äquiatomaren Legierungselementen mit jeweils einem Gehalt von 5–35 Atom-% bestehen. Somit unterscheidet sich das Legierungskonzept fundamental von konventionellen bspw. Stahl- oder Al-basierten Legierungen. In jüngster Zeit lag der Schwerpunkt auf dem Legierungs-Design der MPEA und der Überprüfung bzw. Erreichung der gewünschten Eigenschaften bzw. -kombinationen. Hierzu werden die egierungselemente gezielt ausgewählt und die Mikrostrukturen ein- und zum Teil auch mehrphasig eingestellt. Ziel sind hochinnovative MPEA mit angepassten Eigenschaften für die industrielle Anwendung. Dabei sollen insbesondere die bei konventionellen Legierungen wesentlichen Zielkonflikte, wie bspw. der Trade-off zwischen Festigkeit und Duktilität, überwunden werden. Darüber hinaus sind mechanische Eigenschaften bei sehr hohen sowie kryogenen Temperaturen bei gleichzeitig höchster Korrosionsbeständigkeit von hohem Interesse. Die Herstellung von Bauteilen erfordert dazu werkstoff- und beanspruchungsgerechte Füge- bzw. Schweißverfahren. Der Schweißeignung von MPEA wurde bis Ende 2021 nur äußert wenig Aufmerksamkeit zuteil. Die Auswirkungen durch Schweißprozesse auf die Metallurgie und die gewünschten Eigenschaften sind bisher kaum bekannt und limitieren die potenzielle Anwendbarkeit als Funktions- oder Konstruktionswerkstoffe.
In einem interdisziplinären BAM-Forschungsprojekt werden aktuell grundlegende Untersuchungen zur Schweißverarbeitung und resultierender Mikrostruktur-Anwendungseigenschafts-Beziehung verschiedener MPEA durchgeführt. Insbesondere Wärmeeinflusszone und Schweißgut sind geprägt durch eine Mikrostruktur, die aus Ungleichgewichtszuständen resultiert. Im Falle von MPEA wurde dies bisher nicht systematisch untersucht. Dazu erfolgte im Rahmen des Projektes eine umfassende Literaturauswertung zum Schweißen von MPEA und Zusammenfassung in einer umfassenden, systematischen Datenbasis. Aus diesem Grund sollen in der vorliegenden Studie die bisher bedeutsamsten Erkenntnisse zur Schweißbarkeit von MPEA systematisch nach MPEA-Typ und Schweißverfahren geordnet und mit eigenen aktuellen Forschungsergebnissen verglichen werden. Durch WIG- und Rührreibschweißversuche an den MPEA-Systemen CoCrNiFeMn bzw. CoCrNi konnten im Projektverlauf bereits wesentliche Fragestellungen beantwortet werden. Dazu zählen Auftreten bzw. Verhinderung intermetallischer Phasen/Seigerungen oder deren Auswirkung auf die Eigenschaften der Schweißverbindung (bspw. Festigkeit oder Korrosionsbeständigkeit).
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.