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- 9.0 Abteilungsleitung und andere (24) (entfernen)
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The application of implants e.g. for osteosynthesis or substitution of worn out joints is common practice since decades. Successes in surgery and orthopedics are highly dependent on the use of artificial parts for implanting into the human body. Over the years the number of surgical procedures and the number of different implants were growing rapidly. Implants, however, are exposed to complex mechanical, corrosive and tribological loads along with restriction in geometric dimension. While being essentially successful, the sheer number of cases leads to a rising number of implant failures. Such failures are painful for the affected patients and are very costly.
The failure cases presented in this paper occurred from 1981 to 2016. The predominant failure mechanism of all kinds of implants is fatigue fracture. Fatigue cracks are initiated due to a whole bunch of reasons: Material defects and fabrication defects are rare events. The main factors are cyclic overload due to improper fitting with delayed bone healing, corrosion and unauthorized modification of the implant during surgery
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.
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.
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.
In the presented research, the high potential and abilities of secondary ion mass spectrometry (ToF-SIMS) to detect and locally map the hydrogen distribution in two types of duplex stainless steels are shown. The research validates certain proposed mechanisms by combining ToF-SIMS with high-resolution scanning electron microscopy and electron-backscattered diffraction. The combination of data from several techniques on the same region was conducted in this field for the first time by applying data treatment of the ToF-SIMS raw data and data fusion approach. This powerful combination of methods allows reviewing of the occurring processes related to hydrogen assisted cracking. The step beyond the state of the art in this field was gained here by developing permeation and mechanical loading experiments within the ToF-SIMS during chemometric imaging of the hydrogen distribution in the microstructure. The research presents the necessary correlation between the hydrogen distribution and the resulted structural changes, the diffusion behavior in a duplex microstructure and stress induced diffusion of hydrogen by applying external load at the microscale.
The interaction of hydrogen with various tungsten-inert-gas-welded austenitic stainless steels’ (AUSS) microstructure is studied by means of desorption/absorption analysis and microstructure observations. One of the limitations of welding is created by the presence of hydrogen in the weld, which can shorten the steel’s service life. The local hydrogen concentration, trapping, and its distribution along the welded samples were studied by thermal desorption spectrometry and were supported by X-ray diffraction (XRD) and electronic microstructural observations. Hydrogen content demonstrated a dependence on the welding zone. It was found that hydrogen distribution, and accepted microstructure during welding, played a significant role in the trapping mechanism of 316L AUSS. XRD analysis revealed residual stresses which were caused due to the presence of hydrogen in c-phase. It was shown that the austenite microconstituents inside 316L can have a crucial effect in preventing hydrogen-assisted cracking phenomenon. The effects of AUSS microstructure on hydrogen absorption and desorption behavior are discussed in detail.
Among the very few techniques to localize hydrogen (H) at the microscale in steels, Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a reliable tool. The necessity to detect hydrogen stems from its deleterious effects in metals, that are often used as structural components and to obtain better understanding of the underlying metallurgical mechanisms of hydrogen embrittlement (HE) which are still unclear.
Austenitic stainless steels are nowadays commonly used in a wide variety of application, from hydrogen transport and storage facilities to petrochemical and offshore applications where they are exposed to aggressive environments and therefore prone to HE. One of the greater risks in the austenitic class is the embrittlement of the material due to the instability of the γ austenite and its transformation into a brittle α martensitic phase. This transformation takes place due to the local stresses that are induced by the uptake of hydrogen during service. Nonetheless, it was shown that this transformation can occur as an artefact during SIMS analysis itself where Cs-sputtering is necessary not only to remove surface contaminations but mainly to enhance H/D secondary ion yield.
In the following contribution we show the influence of different sputtering conditions on AISI 304L austenitic stainless steel in order to distinguish the artefact from the hydrogen induced transformation. The material was charged electrochemically in a deuterium based electrolyte. Deuterium (D) must be in these experiments as a replacement for hydrogen which cannot be used because adsorbed hydrogen superimposes hydrogen originating from charging the sample in the SIMS images. ToF-SIMS analyses were conducted by ToF SIMS IV (IONTOF GmbH, Münster, Germany). The experiments were carried out on deuterium charged and non-charged samples. The structural characterization was carried out by SEM and EBSD examinations before and after charging, both with a Leo Gemeni 1530VP field-emission scanning electron microscope and a Zeiss Supra 40 instrument (Carl Zeiss Microscopy GmbH, Oberkochen, Germany). The results showed that the use of 1keV Cs+ beam induces stacking faults while higher sputter beam energies results in γ→α transformation.
Supermartensitic stainless steels (SMSS) are a commonly used material nowadays for building offshore structures, i.e. pipelines in the oil and gas industry. The harsh and corrosive environments in oil and gas applications require the correct combination of alloys to attain the desired properties of steel, including high strength and good corrosion properties, even in severe sour service conditions. Welding is the most commonly used method in joining offshore components, depending on requirements requiring strength or fitting. It has been shown that the heat affected zone (HAZ) is more susceptible to certain types of corrosion, including pitting corrosion, especially during severe sour service where a high pH and lower H2S values in the flow medium can lead to pitting corrosion in the HAZ of welded structures. Subsequent hydrogen uptake in the pits can cause cracks to initiate and propagate, leading to rupture of pipelines or catastrophic failures of structures, even at low mechanical loads. Offshore standards allow a certain amount of corrosion, including pitting, to be present before action is required, however the extent of pitting corrosion is not identified by performing visual inspection alone as the subsurface pit diameter may be vastly greater than the pit diameter at the surface. The critical conditions which lead to crack initiation and propagation from a pit with hydrogen uptake are currently not known. Therefore, pitting corrosion and subsequent crack initiation are a danger to the safety of structures. The interest in this phenomenon has resulted in many experimental studies and numerical simulations.
Several numerical models of pitting corrosion and hydrogen uptake resulting in crack initiation are already in existence, but these two phenomena are regularly modelled individually. Thus, a model enabling simulation of both phenomena simultaneously would be of great benefit. Hence, the goal of this study is to develop a model enabling simulation of pit growth and crack initiation, considering hydrogen uptake in the pit from a corrosive environment.
As a first step, this paper presents an investigation into various parameters, which influence crack initiation at pits. These crack critical parameters include: pit geometry, pit location, mechanical load and hydrogen transport into the microstructure. The results will help to identify critical conditions for crack initiation starting at the pit and developing measures to avoid hydrogen assisted cracking (HAC).
Die Energiewirtschaft ist bereits jetzt in massivem Umbruch. Herausforderungen der Energiewende sind u.a. die Einbindung von regenerativen Energiequellen und deren Speicherung. Dieses stellt auch die Fügetechnik, als zentrale Produktionstechnologie für die Komponentenfertigung, vor neue Aufgaben. Der Vortrag gibt zu ausgewählten Themen einen kurzen Überblick.
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.
Submerged arc welded (SAW) components of creep-resistant low-alloyed Cr-Mo-V steels are used for thick-walled heavy petrochemical reactors (wall-thickness up to 475 mm) as well as employed in construction of modern high-efficient fossil fired power plants. These large components are accompanied by significant restraints during welding fabrication, especially at positions of different thicknesses like welding of nozzles. As a result, residual stresses occur, playing a domi-nant role concerning so-called stress relief cracking (SRC) typically during post weld heat treat-ment (PWHT). Besides specific metallurgical factors (like secondary hardening due to re-precipitation), high tensile residual stresses are a considerable influence factor on SRC. For the assessment of SRC susceptibility of certain materials mostly mechanical tests are applied which are isolated from the welding process. Conclusions regarding the influence of mechanical factors are rare so far. The present research follows an approach to reproduce loads, which occur during welding of real thick-walled components scaled to laboratory conditions by using tests designed on different measures. A large-scale slit specimen giving a high restraint in 3 dimensions by high stiffness was compared to a medium-scale multi-pass welding U-profile specimen showing a high degree of restraint in longitudinal direction and a small-scale TIG-re-melted specimen. The small-scale specimens were additionally subjected to mechanical bending to induce loads that are found during fabrication on the real-scale in heavy components. Results show for all three cases compa-rable high tensile residual stresses up to yield strength with high gradients in the weld metal and the heat affected zone. Those high tensile stresses can be significant for cracking during further PWHT.
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).
In vielen Bereichen des modernen Stahlbaus kommen geschweißte Vollwandträger, wie I-Träger zum Einsatz. Im Gegensatz zu Walzprofilen können die Bauhöhe, die Querschnittsform und die Blechdicken an die Beanspruchung angepasst werden, wodurch sich wirtschaftliche Vorteile erzielen lassen. Dabei werden heutzutage immer häufiger hochfeste Feinkornbaustähle mit (Mindest-) Fließgrenzen bis 690 MPa eingesetzt. Zur verbesserten Ausnutzung des Tragfähigkeitspotenzials geschweißter Profile aus diesen Stählen existieren keine geeigneten Modelle zur Erfassung der schweißfertigungsbedingten Eigenspannungen an realen Komponenten. Diese Daten werden durch konservative Annahmen angenähert. Die potentielle Tragfähigkeit geschweißter Konstruktionen wird daher in der Regel unterschätzt. Die Eigenspannungsannahmen in DIN EN 1993 basieren auf starken Vereinfachungen, bspw. im Rahmen sog. „Ersatzstabnachweise“. Diese setzen die Proportionalität der Eigenspannungsamplituden zur Fließgrenze voraus. Vergleichsrechnungen mit einem parametrisierten Eigenspannungsmodell zeigten mögliche Abweichungen in den berechneten Tragfähigkeiten über mehrere Knicklinien. Die Festlegungen hinsichtlich der anzuwendenden Knicklinie beeinflussen jedoch die Blechdicken und somit in erheblichem Maße auch die Fertigungskosten.
Als Optimierungsstrategie wurden in diesem Forschungsprojekt deswegen unterschiedliche anwendungsorientierte Modellansätze entwickelt, welche mithilfe nichtlinearer Traglastberechnungen, die höhere Ausnutzung von Tragfähigkeitsreserven ermöglichen sollen.
Forschungsziel war somit primär die Entwicklung und Bereitstellung entsprechender Berechnungsansätze. Experimentell wurde hierzu der Eigenspannungszustand von konventionell geschweißten Strukturen am Beispiel der im Stahlbau besonders häufig verwendeten I-Träger aus zwei gängigen Baustählen, einem unlegierten Baustahl S355J2+N und einem Feinkornbaustahl S690QL, erfasst und durch numerische Schweißstruktursimulationen ergänzt. Anschließend erfolgte die Ableitung eines vereinfachten Berechnungsmodells zur weiteren Berücksichtigung in nichtlinearen Tragfähigkeitsberechnungen. Die Erkenntnisse sollen in einen entsprechenden Anwenderleitfaden, herausgegeben durch das Technical Committee 8 der Europäischen Konvention für Stahlbau, einfließen und diesbezüglich als Orientierung einer möglichen zukünftigen Anpassung der Knicklinien in DIN EN 1993-1-1 dienen.
Im Projekt wurden die genannten Stähle in zwei typischen Dickenkombinationen von 25/15 mm und 20/10 mm (Gurt- und Stegbleche) zu Großprobekörpern „I-Träger“ unter industrienahen Fertigungsbedingungen mittels Metall-Aktivgasschweißen gefügt. Diese erzeugten die typischen Eigenspannungen, die in solchen Trägern nach der Fertigung vorliegen. Während des Schweißens wurden die Temperaturfelder durch Thermoelemente aufgezeichnet. Die Eigenspannungen wurden nach dem Schweißen experimentell durch eine Kombination aus mechanischem Zerlegen (Zerlegemethode) und anschließender mobiler Röntgendiffraktometrie (XRD) festgestellt. Der Einfluss der industriell üblichen Brennschnittkantenvorbereitung der Bleche auf die finalen
Eigenspannungszustände wurde experimentell zusätzlich an kleinmaßstäblichen Proben untersucht. Metallographische Analysen (Schliffbilder und Härtemessungen) komplettierten das experimentelle Programm der FE 2 (BAM, Berlin).
Die Ergebnisse zeigten, dass beim mechanischen Zerlegen bereits ein Großteil der Eigenspannungen herausgelöst wurde. Eine Aussage zu den nahtnahen Zugeigenspannungen war allerdings erst durch die Überlagerung mit der XRD möglich. Dabei zeigte der S690QL überwiegend ein besseres Verhalten als der S355J2+N, welches sich unter anderem in abgesenkten Zugeigenspannungen im Verhältnis zur jeweiligen Fließgrenze äußerte. Die maximalen Eigenspannungen wurden dabei zumeist in der Wärmeeinflusszone (WEZ) der Schweißnaht gemessen, unabhängig von der eingebrachten Streckenenergie oder der Festigkeit des Grundwerkstoffs. Die baupraktische Annahme, dass die maximalen Eigenspannungen in Höhe der Fließgrenze vorliegen können, wurde nur in Einzelfällen und nur für den S355J2+N bestätigt. Die experimentellen Ergebnisse zeigten für die Druckeigenspannungen ebenfalls reduzierte relative Eigenspannungswerte des S690QL. Dies zeigt die notwendige weitere Optimierung bei der Wahl der Bewertungsansätze für Eigenspannungen auf die Tragfähigkeit.
Die erzeugten Messwerte dienten im weiteren Verlauf als Eingangswerte für die Modellentwicklung und die numerischen Simulationen an I-Trägern durch die FE 1 (LSH, Cottbus). Die numerischen Schweißsimulationen erfolgten in Simufact.Welding® für die Simulationsmodelle mit „klassischem“ Schweißsimulationsansatz sowie in Ansys® für vereinfachte Simulationen und Näherungsansätze. Die Modelle lieferten insgesamt vergleichbare Ergebnisse für die Längseigenspannungen mit teils jedoch erheblichen Unterschieden in den Rechenzeiten. Durch eine angepasste Vernetzung konnte die Rechenzeit in allen Fällen deutlich reduziert werden. Aufgrund der verwendeten Bauteilgrößen ist die Anwendung der Modellierung mit Volumenelementen allerdings meistens nicht praktikabel. Für typische Trägerschweißungen bieten stattdessen Querschnittsmodelle mit der Annahme eines verallgemeinerten ebenen Verzerrungszustands eine mögliche Alternative. Der Abgleich der Ergebnisse mit den Experimenten lieferte zusammenfassend überwiegend gute bis befriedigende Übereinstimmungen. Die experimentell festgestellten Tendenzen wurden dabei in allen Fällen richtig vorhergesagt.
Eine umfassende Bewertung der erzielbaren Genauigkeiten war bisher nicht möglich. Dies lag einerseits daran, dass die Datendichte der mit der durch die Zerlegung gewonnen Ergebnisse gering war. Anderseits lieferten die überlagerten Ergebnisse mit der XRD in Teilen, insbesondere in den interessierenden Druckbereichen, widersprüchliche Aussagen zum Eigenspannungseinfluss, was bisher nicht abschließend geklärt werden konnte. Darüber hinaus entstanden etwaige Abweichungen in den Simulationen auch durch die zugrunde gelegten Materialdaten selbst. Diese entsprachen Standarddatensätzen aus Materialbibliotheken. Die Skalierung dieser erfolgte gleichmäßig über den gesamten Temperaturbereich. Insbesondere für den S690QL existierten zu wenige belastbare Materialkennwerte.
Entsprechende Versuche konnten im Rahmen dieses Vorhabens nicht mit durchgeführt werden.
Dennoch konnten hinsichtlich eines vereinfachten Berechnungsvorgehens zur Berücksichtigung der Schweißeigenspannungen in Tragfähigkeitsberechnungen einige wichtige Erkenntnisse gewonnen werden. Auf Basis der in den numerischen Schweißsimulationsmodellen ermittelten plastischen Dehnungsmuster, auch „Eigenspannungsquellen“, wurde eine vereinfachte Simulationsvorgehensweise vorgeschlagen und verifiziert. Die dabei eingeführten Vereinfachungen wurden im Hinblick auf die Berechnung ausschließlich der plastischen Längsdehnungen bzw. der Längseigenspannungen gewählt. Die Anwendbarkeit ist daher auf ausreichend lange Schweißträger mit Längsnähten beschränkt. Einige Modellmodifikationen zur weiteren Vereinfachung bzw. Modellimplementierung in die strukturmechanische Berechnung an großen Komponenten wurden vorgestellt. Abschließend erfolgt die Einstufung in eine mögliche Knicklinie auf Basis eines mittels GMNIA (geometrisch und materiell nichtlineare Analyse mit Imperfektionen) Berechnungen simulierten Streubands der Tragfähigkeiten mittels Abaqus® und Ansys®. Die anfängliche Hypothese einer günstigeren Knicklinie eines S690QL im Vergleich zum S355J2+N wurde dabei rechnerisch bestätigt. Der experimentelle Nachweis mittels entsprechender Trägerfähigkeitsversuche ist allerdings noch ausstehend.
Due to the increasing global demand for pure silver, native wire silver aggregates in very high purities are gaining more industrial attention. Up to the present, no substantial metallurgical Investigation of natural wire silver exists in the accessible literature. To convey urgently needed cross-disciplinary fundamental knowledge for geoscientists and metallurgical engineers, twenty natural wire silver specimens from eight different ore deposits have been investigated in detail for the first time by EBSD (Electron Back Scattering Diffraction), supported by light microscopy and micro-probe analyses. The improved understanding of the natural silver wire microstructure provides additional Information regarding the growth of natural silver aggregates in comparison to undesired artificial growth on electronic devices. Clear evidence is provided that natural silver curls and hairs exhibit a polycrystalline face-centered cubic microstructure associated with significant twinning. Although the investigated natural wire silver samples have relatively high purity (Ag > 99.7 wt.-%), they contain a variety of trace elements such as, S, Cu, Mn, Ni, Zn, Co and Bi, As and Sb. Additionally, Vickers micro-hardness measurements are provided for the first time which revealed that natural silver wires and curls are softer than it might be expected from conversion of the general Mohs hardness of 2.7.
Duplex (DSS) and austenitic stainless steels (ASS) are frequently used in many energy related applications. The duplex grade is considered to have outstanding mechanical properties as well as good corrosion resistance. The austenitic phase combines high ductility, even at low temperatures, with sufficient strength, and therefore such materials are applied in storage and transport of high-pressure hydrogen. During service in acidic environments large amounts of hydrogen can ingress into the microstructure and induce many changes in the mechanical properties of the steel. Embrittlement of steels by hydrogen remains unclear even though this topic has been intensively studied for several decades. The reason for that lies in the inability to validate the proposed theoretical models in the sub-micron scale. Among the very few available methods nowadays, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) enables a highly accurate mapping of hydrogen in the microstructure in a spatial resolution below 100 nm. In the present work ToF-SIMS was used as a main tool in order to investigate the effect of deuterium on a duplex microstructure of lean and standard DSSs during and after the electrochemical charging process. Electrochemical charging simulates the service of a component in acidic environments under conditions of cathodic protection that are commonly applied to prevent corrosion reactions. ToF-SIMS after multivariate data analysis (MVA) was combined with high resolution topographic images and electron back-scattered diffraction (EBSD) data to characterize the structural changes. It was observed that the ferritic phase was affected almost identical in all steels whereas in the austenitic phase significant differences were obtained in the lean duplex in comparison to the standard DSS. The obtained results have been compared to similar investigations on a AISI 304L austenitic stainless steel. The advantage of the combined techniques is reflected by the ability to correlate the hydrogen distribution in the microstructure and the resulted phase transformation.
The reduction of harmful emissions to the environment is one of the most urgent challenges of our time. To achieve this goal, it is inevitable to shift from using fossil fuels to renewable energy sources. Within this transition, hydrogen can play a key role serving as fuel in transportation and as means for energy storage.
The storage and transport of hydrogen using austenitic stainless steels as the infrastructure, as well as the use of these grades in hydrogen containing aggressive environments, remains problematic. The degradation of the mechanical properties and the possibility of phase transformation by ingress and accumulation of hydrogen are the main drawbacks. Advanced studies of the behaviour of hydrogen in austenite is necessary to fully understand the occurring damage processes. This knowledge is crucial for the safe use of components in industry and transportation facilities of hydrogen.
A powerful tool for depicting the distribution of hydrogen in steels, with high accuracy and resolution, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). We here present a comprehensive research on the hydrogen degradation processes in AISI 304L based on electrochemical charging and subsequent ToF-SIMS experiments. To obtain furthermore information about the structural composition and cracking behaviour, electron-backscattered diffraction (EBSD) and scanning electron microscopy (SEM) were performed afterwards. All the gathered data was treated employing data fusion, thus creating a thorough portrait of hydrogen diffusion and its damaging effects in AISI 304L.
Specimens were charged with deuterium instead of hydrogen. This necessity stems from the difficulty to separate between artificially charged hydrogen and traces existing in the material or adsorbed from the rest gas in the analysis chamber. Similar diffusion and permeation behaviour, as well as solubility, allow nonetheless to draw onclusions from the experiments.
Hydrogen absorption and diffusion in T24 steel weld joints and effect on mechanical properties
(2018)
The present contribution summarizes results obtained from experiments with low-alloyed boiler steel grades T24 (CrMoV alloy), T22 (CrMo) and thermally simulated T24 HAZ microstructure and pure weld metal. The hydrogen absorption and diffusion behavior was investigated by permeation experiments and thermal desorption analysis (TDA). The results showed significant weld microstructure influence on diffusion by hydrogen trapping. Trapped hydrogen was determined in the T24 BM at temperatures up to 120 °C compared to 75 °C in the T22. In addition, the T24 HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the BM. For the mechanical properties, tensile tests were conducted with electrochemically hydrogen charged specimens and compared to results obtained from slow strain rate tests (SSRT) in high-temperature water up to 200 °C. The as-welded HAZ had remarkably increased susceptibility compared to the BM already at low hydrogen concentration of 1-2 ppm. The SSRT were conducted for free corrosion and acidic environment and confirmed this behavior at elevated temperatures for both HAZ microstructures of T24 and T22. Summarized, each weld microstructure has specific diffusion coefficients and shows different susceptibility to degradation of the mechanical properties, i.e. delayed hydrogen assisted cracking or stress corrosion cracking.
Hydrogen absorption and diffusion in T24 steel weld joints and effect on mechanical properties
(2018)
The present contribution summarizes results obtained from experiments with low-alloyed boiler steel grades T24 (CrMoV alloy), T22 (CrMo) and thermally simulated T24 HAZ microstructure and pure weld metal. The hydrogen absorption and diffusion behavior was investigated by permeation experiments and thermal desorption analysis (TDA). The results showed significant weld microstructure influence on diffusion by hydrogen trapping. Trapped hydrogen was determined in the T24 BM at temperatures up to 120 °C compared to 75 °C in the T22. In addition, the T24 HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the BM. For the mechanical properties, tensile tests were conducted with electrochemically hydrogen charged specimens and compared to results obtained from slow strain rate tests (SSRT) in high-temperature water up to 200 °C. The as-welded HAZ had remarkably increased susceptibility compared to the BM already at low hydrogen concentration of 1-2 ppm. The SSRT were conducted for free corrosion and acidic environment and confirmed this behavior at elevated temperatures for both HAZ microstructures of T24 and T22. Summarized, each weld microstructure has specific diffusion coefficients and shows different susceptibility to degradation of the mechanical properties, i.e. delayed hydrogen assisted cracking or stress corrosion cracking.
A common approach to describe hydrogen traps is by their activation energy that is necessary to release hydrogen from the trap. In the present study, Cr-Mo-V steel T24 (7CrMoVTiB10-10) base material and TIG weld metal were investigated. Electrochemically hydrogen charged specimens were analyzed by thermal desorption analysis (TDA) with different linear heating rates. The results show two different effects. At first, the microstructure effect on trapping is evident in terms of higher hydrogen concentrations in the weld metal and increased activation energy for hydrogen release. Secondly, it is necessary to monitor the real specimen temperature. A comparison between the adjusted heating rate and the real specimen temperature shows that the calculated activation energy varies by factor two. Thus, the trap character in case of the base material changes to irreversible at decreased temperature. Hence, the effect of the experimental procedure must be considered as well if evaluating TDA results.
During the energy transformation from fossil fuels to renewable energy sources, the use of hydrogen as fuel and energy storage can play a key role. This presents new challenges to industry and the scientific community alike. The storage and transport of hydrogen, which is nowadays mainly realized by austenitic stainless steels, remains problematic, which is due to the degradation of mechanical properties and the possibility of phase transformation by hydrogen diffusion and accumulation. The development of materials and technologies requires a fundamental understanding of these degradation processes. Therefore, studying the behavior of hydrogen in austenitic steel contributes to an understanding of the damage processes, which is crucial for both life assessment and safe use of components in industry and transportation. As one of the few tools that is capable of depicting the distribution of hydrogen in steels, time-of-flight secondary ion mass spectrometry was conducted after electrochemical charging. To obtain further information about the structural composition and cracking behavior, electron-backscattered diffraction and scanning electron microscopy were performed. Gathered data of chemical composition and topography were treated employing data fusion, thus creating a comprehensive portrait of hydrogen-induced effects in the austenite grade AISI 304L. Specimens were electrochemically charged with deuterium instead of hydrogen. This arises from the difficulties to distinguish between artificially charged hydrogen and traces existing in the material or the rest gas in the analysis chamber. Similar diffusion and permeation behavior, as well as solubility, allow nonetheless to draw conclusions from the experiments.
For almost 150 years it is known that hydrogen has a deleterious effect on the mechanical properties of metallic components. Nowadays, the problem of hydrogen assisted degradation is highly relevant in energy related fields due to the massive use of steel as a structural component in these applications and its sensitivity to hydrogen. Since the discovery of hydrogen assisted cracking (HAC), researchers studied intensively and suggested possible explanations and mechanisms in order to define how hydrogen is affecting the material. In general, it is considered that hydrogen changes the mechanical properties more in terms of ductility (deformation capacities) than in strength (load capacities). Hydrogen concentration is one of three crucial factors in the degradation process, together with the microstructure of the material and the internal/external mechanical load. The relatively high concentration of hydrogen resulting in this loss of ductility can originate during production or before service (e.g. welding processes) and during service (i.e. catholically protected systems to eliminate corrosion processes in sour environments).
In parallel to the theoretical work, tremendous efforts were, and are still, invested in searching for a proper method to elucidate, map and quantify the hydrogen in the microstructure, which is the basis for this work. For steels, the focus is mainly on the observations of diffusion processes and the interaction of hydrogen with the microstructure
in regions with high local stresses/strains (for example around evolving cracks). The challenge for reaching this goal arises from the fact that accurate indication of hydrogen by means of position, unlike heavier atoms, can be made only by mass spectrometry or by interaction with another element (e.g. silver decoration, special coating and resonant nuclear reaction by nitrogen). In addition to this, the difficulty recording the hydrogen behavior while it rapidly diffuses through the material, leaving only the unpredicted failure, should be taken into account.
Although using powerful characterization methods, models and computational simulations, the key to defining the mechanisms behind HAC is still under debate and not fully understood. The relationship between material and hydrogen is determined by three factors, i.e., the material structure and microstructure – determining the physical properties, the mechanical load applied on the material and the hydrogen concentration. It is well known that in order to have a complete definition of HAC these three factors must be examined locally with the minimal scale and the maximal resolution reachable. The major gap is the lack in such a characterization method or a technique by which one has the ability to detect and observe the hydrogen in the metallic microstructure. The commonly used techniques nowadays are capable of characterization of the microstructure without the ability to observe the hydrogen distribution. Global hydrogen concentration and localized hydrogen observation are possible by some techniques which are incapable of indicating a change in the structure or microstructure therefore a comprehensive overview can be gained only by combining several methods.
In the presented research, secondary ion mass spectrometry (SIMS) was adopted as the main tool to detect and locally map the hydrogen distribution in two types of duplex stainless steel grades: EN 1.4462 (standard 2205 duplex stainless steel) and EN 1.4162 (2101 lean duplex stainless steel). The term duplex stainless steel (DSS) refers to the austenitic-ferritic microstructure of the steel where the combination of physical and mechanical properties of the two phases is achieved. The DSS was selected as a case study for this work due to the wide use of this grade in many energy and the lack of knowledge on hydrogen behavior in two-phase containing microstructures. ToFSIMS was exploited in-situ and ex-situ in three experimental approaches during or following
an electrochemical charging procedure. This type of hydrogen charging was selected as it simulated a procedure of cathodic protection of most sub-water oil and gas extraction and delivery systems. The experimental procedures were:
1. Ex-situ charging followed by ToF-SIMS imaging for basic understanding of hydrogen distribution.
2. Ex-situ charging followed by in-situ mechanical loading to obtain information on hydrogen behavior around a propagating crack.
3. In-situ permeation of hydrogen through a steel membrane inside the ToF-SIMS to obtain information on diffusion behavior of hydrogen in a two-phase microstructure.
The comprehensive view of the effect of hydrogen on steel was gained by using supplementary methods, such as high resolution scanning electron microscopy (HR-SEM), focused ion beam (FIB) and electron back-scattered diffraction (EBSD). The state of the art in this work lies in applying both: in-situ experimental approaches and data treatment of the ToF-SIMS raw data. The data treatment includes the combination of data from several sources (data fusion).
The results for the ex-situ charging followed by static sample imaging and data fusion showed that when the analyzed surface is directly exposed to the electrolyte the degradation is pronounced differently in the ferrite, austenite and interface. The degradation mechanisms in the ferrite and austenite were reflected by the formation of cracks on the surface of both, where a high concentration of hydrogen was obtained. This result supports the assumption that hydrogen is attracted to highly deformed regions. The advantage of using in-situ charging/permeation in comparison to ex-situ charging is that the effect of hydrogen on the ferrite and austenite phases when the hydrogen is evolving from within the microstructure is realized, in comparison to when the analyzed surface is initially exposed directly to the electrolyte. In both experiments the ferrite was observed as a fast diffusion path for the hydrogen. The faster diffusion of hydrogen through the ferrite is expected due to the higher diffusion coefficient, however, a direct proof for the diffusion sequence in this scale was never shown. Most significant results were achieved by the ‘core’ experiments of this research. These experiments included the design of a novel dynamic mechanical loading device to apply an external load during SIMS imaging of a hydrogen precharged-notched sample. For the first time it was shown that plastic deformation induced by applying a mechanical load is resulting in a redistribution of hydrogen locally around the notch.
The phase transformation under various cooling rates and in different HAZ regions for high-strength armour steel was analysed by dilatometry. To develop a continuous cooling transformation (CCT) diagram, the samples were heated up to a peak temperature of 1250 °C to achieve a coarse-grained microstructure and then cooled down with a cooling time t 8/5 varying from 3 to 240 s. Analysis of dilatation curves revealed the austenite decomposition process, during which transformation temperatures were determined. The results showed martensitic transformations for all welding-relevant cooling times. Furthermore, to analyse different heat-affected subzones of the weld, the peak temperature was varied between 550 and 1250 °C at a constant cooling time t 8/5 of 6 s. The simulated coarse-grained heat-affected zone (CGHAZ) and fine-grained-heat affected zone (FGHAZ) showed only martensitic transformations with transformation temperatures below 400 °C. The steel exhibited an inhomogeneous hardness with hardening in the CGHAZ and FGHAZ and softening in the intercritical and subcritical HAZ. The physically simulated microstructure was validated by a real hybrid laser-arc weld microstructure.
Hydrogen determination in weld seams is standardized in ISO 3690. In accordance to this standard, a defined time for hydrogen collection has to be anticipated for different extraction temperatures. In other words, the temperature is the most important value that has to be monitored in addition to the aimed hydrogen determination.
The specimen geometry has influence on the real sample temperature during CGHE vs. the adjusted furnace temperature. This presentation gives a short summary on possible influences on the "correct" hydrogen determination temperature during carrier gas hot extraction (CGHE) using infrared radiation driven furnace. The main findings are: (1) specimen surface is important in terms of polished or oxidized condition, (2) specimen geometry is important for fast heating, (3) PID-values of control software are a considerable influence to accelerate the heating process depite thick specimens and (4) independent sample temperature determination before CGHE is strongly recommended.
Herausforderungen bei der schweißtechnischen Verarbeitung / Welche Rolle spielt der Wasserstoff beim Schweißen? / Vorgewärmt und doch ein Kaltriss? - Wärmeführung beim Schweißen / Abbildung bauteilspezifischer Beanspruchungen im Labormaßstab / Maßnahmen zur Kaltrissvermeidung / Moderne Lichtbogenschweißverfahren