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Uniaxial mechanical properties of face‑centered cubic singleand multiphase high‑entropy alloys
(2022)
Since the high entropy concept was proposed at the beginning of the millennium, the research focus of this alloy family has been wide ranging. The initial search for single-phase alloys has expanded with the aim of improving mechanical properties. This can be achieved by several strengthening mechanisms such as solid-solution hardening, hot and cold working and precipitation hardening. Both single- and multiphase high- and medium-entropy alloys can be optimized for mechanical strength via several processing routes, as is the case for conventional alloys with only one base element, such as steels or Ni-based superalloys.
High‐temperature KCl‐induced corrosion of high Cr and Ni alloys investigated by in‐situ diffraction
(2024)
High‐temperature KCl‐induced corrosion in laboratory air was observed in situ utilizing X‐ray diffraction. High Cr‐containing model alloys (Fe‐13Cr, Fe‐18Cr‐12Ni, and Fe‐25Cr‐20Ni) were coated with KCl and exposed to dry air at 560°C. KCl‐free alloys were studied in the equivalent atmosphere as a reference. After exposure to KCl‐free environments, all alloys showed the formation of very thin oxide layers, indicating good corrosion resistance. In contrast, KCl‐bearing alloys showed distinct damage after exposure.
High‐temperature corrosion was studied under multiple chemical loads on ferritic‐austenitic model alloys (Fe–13Cr, Fe–18Cr–12Ni, and Fe‐25Cr–20Ni) with KCl deposit under 0.5% SO2/99.5% Ar gas atmosphere at 560°C. Postexposure characterization was done by X‐ray diffraction and scanning electron microscopy. In a pure SO2/Ar environment a protective Cr2O3 scale was formed by all samples. The introduction of KCl deposits causes the scale to be nonprotective and multilayered, consisting of CrS, FeS, Cr2O3, Fe3O4, and Fe2O3. The impact of the microstructure and alloying elements is discussed.
Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms.
Development and characterization of starch film and the incorporation of silver nanoparticles
(2020)
Starch is one of the biopolymers being used for bioplastic synthesis. For production, starch can be combined with different plasticizers, starches from different plant sources and even with nanomaterials to improve or to add film properties. The challenge of adding these, e.g. in the form of silver nanoparticles (AgNp) is to determine the concentration so as to avoid impairing the properties of the film, agglomeration or altering the visual characteristics of the film. In this study, a starch film synthesis route and the incorporation of silver nanoparticles has been proposed in order not to alter the properties of the film while maintaining the transparency and a clear colour of the starch film. The results showed that the proposed synthesis route is promising, efficient, reproducible, fast and the film has good mechanical properties.
Recherche verschiedener jeweils nationaler/internationaler Regelwerke
und Prozeduren für die Systematische Schadensanalyse
• Literaturrecherche zu Methoden der systematischen interdisziplinären Schadensanalyse
• Vergleich der Regelwerke VDI 3822, ASTM, ASM sowie der Methoden
• Anwendung der Regelwerke/Prozeduren und Methoden am Beispiel
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
Interfacial properties related to wettability and corrosion in CO2 transport pipelines are experimentally determined by the sessile and the pendant drop methods. The contact angle of a water drop in a compressed CO2 atmosphere is analyzed on an X70 pipeline carbon steel and compared to that on a martensitic steel S41500 to elucidate the effect of corrosion process on active wetting behaviour. The measurements are performed with liquid CO2 at 278 K and pressures ranging from 5 to 20 MPa. The results show that the contact angle (CA) increases with pressure from 132 ° to 143 ° for S41500 and from 117 ° to 137 ° for X70 and decreases with drop age by 20 ° to 24 ° regardless of the pressure and of the fact that corrosion only occurs on X70, which is confirmed by scanning electron microscopy, element mapping and energy dispersive x-ray spectrometry (EDS) analysis. At higher pressure, the contact angles on both materials converge. Further, related properties like density and interfacial tension were determined. CO2 - saturated water has a higher density than pure water: At 5 MPa saturated water reaches a density of 1017 kg⋅m^(-3) and at 20 MPa 1026 kg⋅m^(-3) compared to pure water with a density of 1002 kg⋅m^(-3) and 1009 kg⋅m^(-3), respectively. In this pressure range the IFT drops from 33 mN⋅m^(-1)at 5 MPa to 23 mN⋅m^(-1) at 20 MPa.
Our research focused on Inconel 625 weld overlays on 16Mo3 steel boiler pipes. The Investigation focused on the characterization of changes in the microstructure and chemical composition after annealing. The annealing was performed for ten hours at temperatures from 600 to 1000°C. Changes in the microstructure were observed with a scanning and transmission electron microscope (SEM and TEM). The investigation was supplemented by hardness measurements.
The ferritic steel 13CrMo4-5 due to good properties with relation to attractive price is frequently use in power plants industry. According EN10028-2 this steel can be used up to 570 °C because of its creep behavior but its corrosion resistance limits the use frequently to lower temperatures, depending on gas temperature and slag formation. The corrosion test were performed in environment containing mixture of gases like: O2, COx, SOx and ashes, with elements e.g. Na, Cl, Ca, Si, C, Fe, Al. Exposure time was respectively 240 h, 1000 h and 4500 h in temperature 600 °C. The oxide scale on the 13CrMo4-5 steel was significant thicker than for In686 coating and the difference increase according for longer exposure time.
The microstructure, chemical and phase composition of the oxide scales were investigated by means of a light microscope, the electron scanning and transmission microscopes (SEM,TEM) equipped with the EDS detectors.
The 13CrMo4-5 ferritic steel is commonly used in power plants, due to its favorable mechanical properties. According to EN 10028-2, this steel can be used at temperatures up to 570°C because of its creep behavior. The inefficient corrosion resistance limits the application of this steel to lower temperatures depending on the gas temperature and slag formation. Therefore, the application of a highly resistant Ni-based coating is proposed to extend the corrosion resistance of elements made of ferritic steel. The corrosion test was performed in an environment containing a mixture of gases, like O2, COx, and SOx, and deposited ashes with elements, e.g., Na, Cl, Ca, Si, C, Fe, and Al. The exposure time was, respectively, 240 h, 1000 h and 4500 h at a temperature of 600°C. The oxide scale formed on the 13CrMo4-5 steel was significantly thicker than on the IN686 coating. The microstructure and chemical and phase compositions of the oxide scale were investigated using light optical microscopy together with scanning and transmission electron microscopy techniques. Energy dispersive x-ray analyses were performed when appropriate.
This work presents the microstructure and chemical composition of oxide scales created on Ni – base coating after corrosion experiments in aggressive gases and ashes. The Inconel 686 coating applied on the low carbon steel 13CrMo4-5 was performed by a CO2 laser cladding process. The experiments were carried out in oxidizing gas atmospheres containing O2, COx, SOx. The second Variation of corrosion experiments were performed in a reducing atmosphere with ashes containing elements such as: Na, Cl, Ca, Si, C, Fe, Al etc. After 240 h and 1.000 h corrosion experiments the oxide scales on the substrate and overlay were created in both cases.
The sulfur compounds were found on the top of the coating surface (EPMA) and also higher contents of silica compounds were revealed on specimens covered by ashes during the experiments. The microstructure and chemical composition of the clad and scales were investigated by means of a light microscope and an electron microscope (SEM)equipped with an EDS detector.
The work presents the microstructure, chemical composition and mechanical properties of Inconel 686 coatings after high - temperature corrosion in environment of aggressive gases and ashes. To produce the Ni - based coatings the QS Nd:YAG laser cladding process was carried out. As the substrate used 13CrMo4-5 boilers plate steel. Ni - base alloys characterize the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. Formed clad were characterized by high quality of metallurgical bonding with the substrate material and sufficiently low amount of the iron close to the clad layer surface. After corrosion experiment the oxide scale on the substrate and clad created. The scale on 13CrMo4-5 steel had 70 μm thickness while the scale of the clad had less than 10 μm. The microstructure, chemical composition of the obtained clad and scales were investigated by scanning electron microscope (SEM) and electron probe microanalyzer (EPMA) equipped with the EDS detectors.
The Ni-Cr-Mo-W alloy is characterized by the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. To protect the surface of the substrate 13CrMo4-5 steel against aggressive environments the Inconel 686 as clad layer was used. The corrosion process was performed in oxidizing mixture of gases like O2, COx, SOx. The second part of corrosion Experiment concerned the corrosion test of the coating in reducing atmosphere of the specified gases with ashes, which contained e.g. Na, Cl, Ca, Si, C, Fe, Al.
The Ni-Cr-Mo-W alloy is characterized by the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. To protect the surface of the substrate 13CrMo4-5 steel against aggressive environments the Inconel 686 as clad layer was used. The corrosion process was performed in oxidizing mixture of gases like O2, COx, SOx. The second part of corrosion Experiment concerned the corrosion test of the coating in reducing atmosphere of the specified gases with ashes, which contained e.g. Na, Cl, Ca, Si, C, Fe, Al.
As more industrial interests focusing on using salt caverns and repurposed gas or petroleum reservoirs for alternative fuel storage, i.e. CO2/H2, the question raises whether microorganisms may impact the infrastructure, gas purity and storage condition over time.
Environments with high salinity (> 1.5 Meq of NaCl) are resided by halophiles (salt-loving microorganisms). To compensate for the intensive osmotic stress, they have resorted to two main adaptation strategies: 1) production of compatible solutes and 2) accumulation of intracellular KCl. Microbial community analysis of several high salinity environments revealed a number of recurring genera, including Halomonas and Halanaerobium. However, the impact of halophiles on the overall integrity and stability of the storage facilities remain largely unknown.
To evaluate the suitability and stability of saline storage facilities, several model halophilic microorganisms, such as members of Halomonas, will be selected as testing subjects. First, the impact of halophiles on the infrastructure will be determined using an integrative approach by combining a number of techniques, including electrochemistry, TOF-SIMS, SEM/FIB/EDS and FIB-TEM. Second, the abilities of halophiles to alter the fuel composition (i.e. increase/decrease the fractions of H2) will be monitored using gas chromatography by growing them under high pressure.
As a result of climate change and the accompanying mandatory shift to renewable energy resources, microorganisms will continue to play an important role in the energy sector, both to their benefit and detriment. Thus, it is important to achieve a certain level of understanding regarding the activities and mechanisms of halophiles prior to large-scaled excursions.
Alkali and alkaline earth chlorides are discussed as heat storage media and are characterized by their low price and high availability. Disadvantages are a high corrosion rate and formation of Cr6+ ions in the melt, as observed in various binary chlorine salt melts. In our work the system NaCl-KCl-MgCl2 is considered. The storage capacity in this salt system is between 2 and 3 MWh per 10 t salt, depending on composition, melting temperature and working temperature. At the same time the system offers a eutectic line, which allows a high variance of the composition and possibly different corrosion rates can be observed. Corrosion tests in melts were carried out and the corrosion layers investigated. The tests with chloride melts on 12% Cr steel show an inner corrosion zone of up to 40 µm depth after 96 hours. The corrosion mechanisms and potential solutions are discussed.
Early Stage of Corrosion Formation on Pipeline Steel X70 Under Oxyfuel Atmosphere at Low Temperature
(2020)
The early stage of corrosion formation on X70 pipeline steel under oxyfuel atmosphere was investigated by applying a simulated gas mixture (CO2 containing 6700 ppmv O2, 100 ppmv NO2, 70 ppmv SO2 and 50 ppmv H2O) for 15 h at 278 K and ambient pressure. Short-term tests (6 h) revealed that the corrosion starts as local spots related to grinding marks progressing by time and moisture until a closed layer was formed. Acid droplets (pH 1.5), generated in the gas atmosphere, containing a mixture of H2SO4 and HNO3, were identified as corrosion starters. After 15 h of exposure, corrosion products were mainly X-ray amorphous and only partially crystalline. In-situ energy-dispersive X-ray diffraction (EDXRD) results showed that the crystalline fractions consist primarily of water-bearing iron sulfates. Applying Raman spectroscopy, water-bearing iron nitrates were detected as subordinated phases. Supplementary long-term tests exhibited a significant increase in the crystalline fraction and formation of additional water-bearing iron sulfates. All phases of the corrosion layer were intergrown in a nanocrystalline network. In addition, numerous globular structures have been detected above the corrosion layer, which were identified as hydrated iron sulphate and hematite. As a type of corrosion, shallow pit formation was identified, and the corrosion rate was about 0.1 mma−1. In addition to in-situ EDXRD, SEM/EDS, TEM, Raman spectroscopy and interferometry were used to chemically and microstructurally analyze the corrosion products.
In context of CLUSTER project, impacts of impurities (SO2, NO2, O2, CO, H2S, H2, N2, Ar and H2O) in CO2 streams captured from different sources in a regional cluster on transport, injection and storage were investigated. Corrosion studies of oxidizing, reductive or mixed atmospheres towards transport pipeline steel X70 were carried out applying high pressure (10 MPa) at low temperatures (278 K or 313 K).
Specific amounts of oxidizing and reductive impurities as well as some moisture were added to dense phase CO2 to replicate CO2 streams from sources in a CCS pipeline network. Due to the moisture content being only 50 ppmV no visible acid condensation took place. To simulate stress conditions at the inside pipeline surface due to fluid pressure (10 MPa) specimens were preloaded using a load frame. Experiments conducted at 278 K and at 313 K revealed the highest corrosion rate at lower temperature. Corrosive effect of impurities was strongest applying mixed atmosphere, containing oxidizing and reductive components, closely followed by CO2 streams with pure oxidizing character. By far, the lowest corrosion rate (10x lower) resulted from reductive atmosphere. In general, at constant temperature and pressure the CO2 stream composition strongly influences the morphology, thickness and composition of the corrosion products. Applying oxidizing or mixed impurities, iron hydroxides or oxides (e.g. goethite, hematite) occur as dominating corrosion products, capable to incorporate different amounts of sulfur. In contrast, using reductive atmosphere very thin corrosion layers with low crystallinity were developed, and phase identification by XRD was unfeasible. SEM/EDX analysis revealed the formation of Fe-O compounds, most likely attributed to the oxygen partial pressure in the system induced by CO2 (≥0.985 volume fraction) and volatile H2O. In addition to the surface covering corrosion layer, secondary phases had grown locally distributed on top of the layer. These compounds are characteristic for the applied atmosphere and vary in number, shape and chemical composition.
In this work, the focus was set on the corrosion process of condensate as drops on the surface of carbon steels (X52, X70), martensitic steel UNS S41500, and superaustenite UNS 08031 in CO2 atmosphere with impurities at 278 K (to simulate the transportation condition in a buried pipeline). Exposure tests were performed at both normal pressure and high pressure where CO2 is supercritical or in dense phase. The drop, 1 ‑ 10 µL in volume, was prepared by dropping CO2 saturated ultra-pure water onto the surface of steel coupons in a one-liter-autoclave. The CO2 gas stream, simulating the oxyfuel flue gas with varying concentration of impurities (SO2 and O2), was then pumped into the autoclave to observe the condensation and corrosion impacts of impurities. Comparable exposure tests were carried out with the same gas mixture and the same volume of water as vapor to observe the drop formation and the corrosion process that follows. The wettability and stability of drops on the surface of steel coupons in CO2 supercritical/dense phase environment was evaluated additionally by contact angle measurement.
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost-effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells, the corrosion resistance of the materials used needs to be determined.
In this study, representative low-cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were investigated in simulated pore water at 333 K and under CO2 saturation condition to represent the worst-case scenario: CO2 diffusion and aquifer fluid penetration. These simulated pore waters were made from relevant cement powder to mimic the realistic casing-cement interface. Electrochemical studies were carried out using the pore water made of cement powder dissolved in water in comparison with those dissolved in synthetic aquifer fluid, to reveal the effect of cement as well as formation water on the steel performance. Two commercially available types of cement were investigated: Dyckerhoff Variodur® and Wollastonite. Variodur® is a cement containing high performance binder with ultra-fine blast furnace slag which can be used to produce high acid resistance concrete. On the other hand, Wollastonite is an emerging natural material mainly made of CaSiO3 which can be hardened by converting to CaCO3 during CO2 injection.
The results showed the pH-reducing effect of CO2 on the simulated pore water/aquifer (from more than 10 to less than 5) leading to the active corrosion process that happened on both 1.8977 and 1.7225. Electrochemical characterization showed negative free corrosion potential and polarisation curves without passive behaviors. The tested coupons suffered from pitting corrosion, which was confirmed by surface analysis. Interestingly, basing on the pit depth measurements from the tested coupons and the hardness of cement powder, it is suggested that Variodur® performed better than Wollastonite in both aspects. The electrochemical data was compared to that resulted from exposure tests to give a recommendation on material selection for bore-hole construction.
Carbon Capture Utilization and Storage (CCUS) is a promising technology to reach the target for reduction of CO2 emissions. Crucial points for a sustainable and future-proof CCUS system are reliability and cost efficiency of the whole process chain, including separation of CO2 from the source, compression of CO2, its subsequent transportation to the injection site and injection into geological formations, e.g. aquifers. Recent studies have shown that even at a very low concentration of impurities, condensation of sulfuric and nitric acids in dense phase CO2 are possible and observable. Thus, impact of impure CO2 stream toward corrosion susceptibility of materials to be used in CCUS system need to be considered. In this talk, basing on results achieved from two German long-term projects (COORAL and CLUSTER), the dominating impurities of the CO2 stream and corrosion mechanisms are addressed. Investigations cover the whole CCUS process chain and provide a material recommendation for certain parts.
Die Analyse von Bruchflächen wird in der Schadensanalyse meist auf der Basis von Erfahrungswissen vorgenommen, welches aus vorliegenden Untersuchungen, eigenen Vergleichsversuchen und aus der Literatur stammt. Durch Vergleiche mit bereits vorliegenden Bildern werden qualitativ Bruchmechanismen ermittelt. Grundlage sind zumeist zweidimensionale Bilder aus licht- und elekt-ronenoptischen Verfahren. Quantitative Aussagen beziehen sich bislang beispielsweise auf makroskopische Anteile von Bruchmechanismen oder die Ausmessung von Schwingstreifen. In jüngerer Zeit gibt es vermehrt Ansätze, Computer-Algorithmen einzusetzen, die in der Lage sind, unterschiedlich strukturierte Bruchmerkmale zu finden und zu klassifizieren. Im hier vorgestellten IGF-Vorhaben „iFrakto“, IGF Vorhaben Nr.: 21477 N, werden licht- und elektronenoptisch Topographie-Bilder erzeugt und die gewonnenen 3D-Informationen zusammen mit den klassischen 2D-Bildern ausgewertet.
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells the corrosion resistance of the materials used needs to be determined.
In this study, representative low cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were embedded in cement to mimic the realistic casing-cement interface. Electrochemical studies were carried out using these metal-cement specimens in comparison with those made of metal only in CO2 saturated synthetic aquifer fluid, at 333 K, to reveal the effect of cement on the steel performance. The results showed the protective effect of cement on the performance of pipeline metals during polarisation process. However, the corrosion current density was high in all cases, with and without cement, indicating that the corrosion resistance of these materials is low. This conclusion was supported by the surface analysis of the polarized specimens, which revealed both homogenous and pitting corrosions. Furthermore, to reveal the possible protective performance of FeCO3, the pipeline steels were pre-carbonated and then tested in the same condition as freshly polished specimens.
In this work, the focus was set on the corrosion process of condensate as drops on the surface of carbon steels (X52, X70), martensitic steel UNS S41500, and superaustenite UNS 08031 in CO2 atmosphere with impurities at 278 K (to simulate the transportation condition in a buried pipeline). Exposure tests were performed at both normal pressure and high pressure where CO2 is supercritical or in dense phase. The drop, 1 ‑ 10 µL in volume, was prepared by dropping CO2 saturated ultra-pure water onto the surface of steel coupons in a one-liter-autoclave. The CO2 gas stream, simulating the oxyfuel flue gas with varying concentration of impurities (SO2 and O2), was then pumped into the autoclave to observe the condensation and corrosion impacts of impurities. Comparable exposure tests were carried out with the same gas mixture and the same volume of water as vapor to observe the drop formation and the corrosion process that follows. The wettability and stability of drops on the surface of steel coupons in CO2 supercritical/dense phase environment was evaluated additionally by contact angle measurement.
Die „auffälligen großen Streifen“ sind von echten Schwingstreifen nur sehr schwer zu trennen, weil sie parallel zu den Schwingstreifen verlaufen und meistens ebenfalls nicht sehr groß sind. Die im Labor getesteten Proben zeigten, dass diese großen Streifen zusammen mit Verreibungen auftraten und „tire tracks“ („Reifenspuren“) verursachten. Dies wurde durch eine hochauflösende REM-Untersuchung bestätigt, die „tire tracks“ auf den „großen Streifen“ zeigte. Ein weiterer Hinweis ist die Änderung des R-Werts von -1 auf 0,1, was zu einer Bruchfläche ohne große Streifen und „tire tracks“ führt.
To study the effects of condensed acid liquid, hereafter referred to as condensate, on the CO2 transport pipeline steels, gas mixtures containing a varying concentration of H2O, O2, NO2, and SO2, were proposed and resulted in the condensate containing H2SO4 and HNO3 with the pH ranging from 0.5 to 2.5. By exposing the pipeline steel to the synthetic condensate with different concentration of acidic components, the corrosion kinetic is significantly changed. Reaction kinetic was studied using electrochemical methods coupled with water analysis and compared with surface analysis (scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffractometry (XRD)) of corroded coupons. The results showed that, although the condensation of NO2 in the form of HNO3 causes faster general corrosion rate, it is the condensation of SO2 in the form of H2SO4 or the combination of SO2 and NO2 that may cause much more severe problems in the form of localized and pitting corrosions. The resulting corrosion forms were depended on the chemical nature of acids and their concentration at the same investigated pH. The effects of changing CO2 flow rate and renewing condensate on pitting corrosion were further studied.
To reveal the corrosion resistance of casing steel/mortar interface in CO2 injection condition, sandwich samples were prepared and exposed up to 20 weeks in aquifer fluid under 10 MPa and 60 °C. Cross section analysis revealed the crevice corrosion as main mechanism instead of pitting corrosion, which would be expected to happen in the extremely high Chloride concentration. Detailed analysis using EDS line scan shown the slow diffusion of Chloride, suggesting why pitting did not happen after 20 weeks. To mimic the passivated steel surface, the steel coupon was passivated in simulated pore solution having pH 13.5 for 42 days. The passivated coupon was further exposed to NGB solution for 28 days. Electrochemical characterization was performed along the exposure processes to reveal the change in impedance, indicating the corrosion resistance of steel casing/mortar interface.
For reliability and safety issues of injection wells, corrosion resistance of materials used needs to be determined. Herein, representative low-cost materials, including carbon steel X70/1.8977 and low alloyed steel 1.7225, were embedded in mortar to mimic the realistic casing-mortar interface. Two types of cement were investigated: (1) Dyckerhoff Variodur commercial Portland cement, representing a highly acidic resistant cement and (2) Wollastonite, which can react with CO2 and become stable under a CO2 stream due to the carbonation process. Exposure tests were performed under 10 MPa and at 333 K in artificial aquifer fluid for up to 20 weeks, revealing crevice corrosion and uniform corrosion instead of expected pitting corrosion. To clarify the role of cement, simulated pore water was made by dispersing cement powder in aquifer fluid and used as a solution to expose steels. Surface analysis, accompanied by element mapping on exposed specimens and their crosssections, was carried out to trace the chloride intrusion and corrosion process that followed.
Recent studies have shown that even at a very low concentration of impurities (less than 100 ppmv of SO2, NO2, O2 and H2O) the droplet formation and condensation of sulfuric and nitric acids in dense phase CO2 are possible and observable. To reveal the mechanism of droplet corrosion in dense phase CO2 at high pressure and low temperature, further studies on factors that affect wettability and resulting corrosion behaviors of transport pipeline steels are needed. In this study, effects of surface morphology were investigated by varying surface roughness of carbon steel coupons exposed to CO2 stream containing impurities to measure the wettability by contact angle and to observe the condensation as well as possible droplet corrosion that followed. Other considered factors were: pH of the droplet, temperature, droplet volume, and exposure time.
The research focus of this study was set on the corrosion process of condensate as droplets on the surface of carbon steels (X52, X70) martensitic steel UNS S41500, and super austenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the offshore transportation condition in a buried pipeline). The possibility of dew/droplet formation on the steel surface and wetting behavior of corresponding materials were evaluated by contact angle measurement in dense CO2 at 278 K. To observe the effect of impurities (SO2 and O2) on droplet corrosion process, exposure tests were carried out in the mixed atmosphere with a drop, 1 ‑ 10 µL in volume, of CO2 saturated ultra-pure water on steel surface. Comparable exposure tests were carried out with the same gas mixture and the same volume of water, as vapor, to observe the droplet formation and the corrosion process that follows. Effects of surface roughness on the droplet formation and its corrosion process were further studied and showed no significant role upon long time exposure. The results from droplet experiments were compared to those from the bulk electrolyte for the further recommendation on the quality control of gas stream along with the use of carbon steels as transport pipelines in CCS - Carbon Capture and Storage system.
This work examined the droplet corrosion of CO2 pipeline steels caused by impurities in CO2 supercritical/dense phase at 278 K, simulating the underground transport condition. The wetting properties of carbon steels (X52 and X70) as well as martensitic steel UNS S41500, and superaustenite UNS N08031 were studied by contact angle measurement, revealing reactive wetting behavior of carbon steels. Exposure tests with CO2 saturated water droplet on steel surface showed that the impurities (220 ppmv SO2 and 6700 ppmv O2) diffused into the droplet and then reacted with metal coupons in supercritical/dense phase condition, forming the corrosion product instantly during pumping process. Due to the active wetting behavior, the carbon steels suffered from heavily attack, while negligible corrosion product was observed in cases of martensitic steel UNS S41500 and superaustenite UNS 08031 coupons. Condensation experiments that were carried out on fresh polished coupons in CO2 with 1200 ppmv H2O showed that the formation and aggregation of droplet is dependent on the presence of impurities. Without SO2 and O2, the same concentration of H2O did not cause observable corrosion process after a week of exposure. With 220 ppmv SO2 and 6700 ppmv O2 even low water concentration (5-30 ppmv) still resulted in heterogeneous nucleation and subsequent growth of droplets, leading to corrosive process on carbon steel surface albeit to a lesser extent.
In this work, the focus was set on the corrosion process of condensate as drops on the surface of carbon steels (X52, X70), martensitic steel UNS S41500, and superaustenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the transportation condition in a buried pipeline). Exposure tests were performed at both normal pressure and high pressure where CO2 is supercritical or in dense phase. The drop, 1 ‑ 10 μL in volume, was prepared by dropping CO2 saturated ultra-pure water onto the surface of steel coupons in a one-liter-autoclave. The CO2 gas stream, simulating the oxyfuel flue gas with varying concentration of impurities (SO2 and O2 ), was then pumped into the autoclave to observe the condensation and corrosion impacts of impurities. Comparable exposure tests were carried out with the same gas mixture and the same volume of water as vapor to observe the drop formation and the corrosion process that follows. The wettability and stability of drops on the surface of steel coupons in CO2 supercritical/dense phase environment was evaluated additionally by contact angle measurement.
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells the corrosion resistance of the materials used needs to be determined.
In this study, representative low cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were embedded in cement to mimic the realistic casing-cement interface. Electrochemical studies were carried out using these metal-cement specimens in comparison with those made of metal only in CO2 saturated synthetic aquifer fluid, at 333 K, to reveal the effect of cement on the steel performance. The results showed the protective effect of cement on the performance of pipeline metals during polarisation process. However, the corrosion current density was high in all cases, with and without cement, indicating that the corrosion resistance of these materials is low. This conclusion was supported by the surface analysis of the polarized specimens, which revealed both homogenous and pitting corrosions.
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost-effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells, the corrosion resistance of the materials used needs to be determined.
In this study, representative low-cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were investigated in simulated pore water at 333 K and under CO2 saturation condition to represent the worst-case scenario: CO2 diffusion and aquifer fluid penetration. These simulated pore waters were made from relevant cement powder to mimic the realistic casing-cement interface. Electrochemical studies were carried out using the pore water made of cement powder dissolved in water in comparison with those dissolved in synthetic aquifer fluid, to reveal the effect of cement as well as formation water on the steel performance. Two commercially available types of cement were investigated: Dyckerhoff Variodur® and Wollastonite. Variodur® is a cement containing high performance binder with ultra-fine blast furnace slag which can be used to produce high acid resistance concrete. On the other hand, Wollastonite is an emerging natural material mainly made of CaSiO3 which can be hardened by converting to CaCO3 during CO2 injection.
The results showed the pH-reducing effect of CO2 on the simulated pore water/aquifer (from more than 10 to less than 5) leading to the active corrosion process that happened on both 1.8977 and 1.7225. Electrochemical characterization showed negative free corrosion potential and polarisation curves without passive behaviors. The tested coupons suffered from pitting corrosion, which was confirmed by surface analysis. Interestingly, basing on the pit depth measurements from the tested coupons and the hardness of cement powder, it is suggested that Variodur® performed better than Wollastonite in both aspects. The electrochemical data was compared to that resulted from exposure tests to give a recommendation on material selection for bore-hole construction.
Impact of acid condensation on wetting and corrosion behavior of CO2 transport-pipeline steel
(2018)
Es ist allgemein akzeptiert, das Korrosion in CO2-Transport-Pipelines vernach¬lässigbar ist, solange der Wassergehalt des CO2-Stroms deutlich unter der maximal löslichen Menge liegt. Bisher gibt es keinen allgemeinen Konsens darüber, welcher maximale Wassergehalt in zu transportierendem CO2 zugelassen werden sollte. Bei einem Druck von 100 bar und im Temperaturbereich von 277 K bis 298 K beträgt die Löslichkeit von Wasser in CO2 ca. 1.900 bis 3.200 ppmv, aber die Korrosionsrate von Stählen steigt schon ab einem Wassergehalt von 500 ppmv deutlich an. Bei Anwesenheit von Begleitstoffen wie SO2, NO2 und O2, können sich HNO3, H2SO3 und H2SO4 bilden. Menge und Zusammensetzung von kondensierter Säure sind von der Gaszusammensetzung abhängig, und der Korrosionsmechanismus und die Korrosionsform sind vom Kondensationsverhalten abhängig.
Many microstructural features exhibit non-trivial geometries, which can only be derived to a limited extent from two-dimensional images. E.g., graphite arrangements in lamellar gray cast iron have complex geometries, and the same is true for additively manufactured materials and three-dimensional conductive path structures. Some can be visualized using tomographic methods, but some cannot be due to weak contrast and/or lack of resolution when analyzing macroscopic objects. Classic metallography can help but must be expanded to the third dimension. The method of reconstructing three-dimensional structures from serial metallographic sections surely is not new. However, the effort required to manually assemble many individual sections into image stacks is very high and stands in the way of frequent application. For this reason, an automated, robot-supported 3D metallography system is being developed at BAM, which carries out the steps of repeated preparation and image acquisition on polished specimen.
Preparation includes grinding, polishing and optionally etching of the polished surface. Image acquisition comprises autofocused light microscopic imaging at several magnification levels. The image stacks obtained are then pre-processed, segmented, and converted into 3D models, which in the result appear like microtomographic models, but with high resolution at large volume. Contrasting by classical chemical etching reveals structures that cannot be resolved using tomographic methods. The integration of further imaging and measuring methods into this system is underway. Some examples will be discussed in the presentation.
Die klassische Metallographie basiert auf Abbildungen einzelner Schliffebenen und kann auf räumliche Formen und Anordnungen des Gefüges nur bedingt schließen. Die Idee, aus metallographischen Serienschliffen dreidimensionale Gefügestrukturen zu rekonstruieren, ist daher naheliegend und nicht neu. Allerdings ist der Aufwand, in Handarbeit viele Einzel-Schliffe zu präparieren und zu Bildstapeln zusammenzusetzen, sehr hoch und steht einer häufigen Anwendung entgegen.
Deshalb wird an der BAM ein Roboter-gestütztes 3D-Metallographie-System entwickelt, das an einer Schliffprobe die Schritte Präparation und Bildeinzug vollautomatisch mit vielen Wiederholungen ausführt. Die Präparation umfasst Schleifen, Polieren und optional Ätzen der Schlifffläche, der Bildeinzug autofokussierte lichtmikroskopische Aufnahmen bei mehreren Vergrößerungsstufen. Der erhaltene Bildstapel wird anschließend vorverarbeitet, segmentiert und in ein 3D-Modell umgesetzt, das einer mikrotomographischen Aufnahme ähnelt, allerdings mit besserer lateraler Auflösung bei großem Volumen. Im Gegensatz zu tomographischen Verfahren besteht die Möglichkeit der Kontrastierung durch klassische chemische Ätzung. Die Integration eines REMs ist geplant. Bislang durchgeführte Arbeiten verdeutlichen die Möglichkeiten der Darstellung von Heißgas-Korrosionsschichten, Grauguss-Werkstoffen und Keramik-basierten mikroelektronischen Strukturen (Vias).
Thermal cycling of a Ni-excess NiTi alloy was conducted between 50 °C and liquid nitrogen temperature to induce martensitic transformations and to reverse them after. The starting point was an annealed and slowly cooled state, the end point a sample thermally cycled 1500 times. Positron annihilation lifetime spectra and Coincidence Doppler Broadening profiles were obtained in various states and at various tem- peratures. It was found that the initial state was low in defects with positron lifetimes close to that of bulk NiTi. Cycling lead to a continuous build-up of a defect structure up to 20 0 −50 0 cycles after which saturation was reached. Two types of defects created during cycling were identified, namely pure dislo- cations and vacancies attached to dislocations.
Damage tolerance counts as one of the most widespread approach to fatigue assessment and surely as one of the most promising in understanding the process-structure-property-performance relationships in additively manufactured metallic materials. Manufacturing defects, surface roughness, microstructural features, short and long crack fatigue propagation, residual stresses and applied loads can be taken into consideration in a fracture mechanics-based fatigue assessment. Many aspects are crucial to the reliable component life prediction. Among those a prominent role is played by an accurate measurement and modelling of the short crack fatigue behavior, and reliable statistical characterization of defects and residual stresses.
This work aims at addressing the issues related to both experimental testing, fatigue and fatigue crack propagation, and fracture mechanics-based modelling of fatigue lives. Examples will be provided on an additively manufactured AISI 316 L.
This paper presents the results of a study of the morphology and structure at the weld interface in a brass–Invar bimetal, which belongs to the class of so-called thermostatic bimetals, or thermobimetals. The structure of the brass–Invar weld interface was analyzed using optical microscopy and scanning electron microscopy (SEM), with the use of energy-dispersive X-ray (EDX) spectrometry and back-scattered electron diffraction (BSE) to identify the phases. The distribution of the crystallographic orientation of the grains at the weld interface was obtained using an e-Flash HR electron back-scatter diffraction (EBSD) detector and a forward-scatter detector (FSD). The results of the study indicated that the weld interface had the wavy structure typical of explosive welding. The wave crests and troughs showed the presence of melted zones consisting of a disordered Cu–Zn–Fe–Ni solid solution and undissolved Invar particles. The pattern quality map showed that the structure of brass and Invar after explosive welding consisted of grains that were strongly elongated towards the area of the highest intensive plastic flow. In addition, numerous deformation twins, dislocation accumulations and shear bands were observed. Thus, based on the results of this study, the mechanism of Cu–Zn–Fe–Ni structure formation can be proposed.
The high-temperature corrosion behaviors of the equimolar CrCoNi medium- and CrMnFeCoNi high-entropy alloy were studied in a gas atmosphere consisting of a volumetric mixture of 10% H2O, 2% O2, 0.5% SO2, and 87.5% Ar at 800 °C for up to 96 h. Both alloys were initially single-phase fcc structured and showed a mean grain size of ~50 µm and a homogeneous chemical composition. The oxide layer thickness of the Cantor alloy CrMnFeCoNi increased linearly with exposure time while it remained constant at ~1 µm for CrCoNi. A Cr2O3 layer and minor amounts of (Co,Ni)Cr2O4 developed on CrCoNi while three layers were detected on the Cantor alloy. These layers were a thin and continuous chromium rich oxide layer at the oxide/alloy interface, a dense (Mn,Cr)3O4 layer in the center and a thick and porous layer of Mn3O4 and MnSO4 at the gas/oxide interface. Additionally, a few metal sulfides were observed in the CrMnFeCoNi matrix. These results were found to be in reasonable agreement with thermodynamic calculations.
The importance of high-entropy alloy (HEAs) in the field of materials research is increasing continuously and numerous studies have been published, recently. These are mainly focused on manufacturing of different alloy systems having excellent structural properties from low to high temperatures. Therefore, HEAs are of high potential for many applications in very demanding conditions. However, this is so far limited by poor knowledge and experience regarding economic and reliable component manufacturing. The processability of HEAs has hardly been investigated so far, indicated by the small number of publications worldwide: welding <30 and machining <5.
Hence, this contribution provides an overview about the current state of the art on processing of HEAs. Fundamental principles are shown for safe weld joints while ensuring high component integrity. For safe welding, the combined consideration of complex interactions of material, construction and process is necessary. Recent studies on different HEAs showed the influence of heat input by means of different welding processes on the microstructure and respective properties. Based on intensive literature survey and on our initial study, the main research objectives of processing HEAs are presented.
Trace elements W and Hf have different influence on the microstructure and the mechanical properties when added to the Al10Co25Cr8Fe15Ni36Ti6 compositionally complex alloy. The addition of both can thus merge both element’s beneficial influences when combined with the appropriate heat treatment: Hf enhances the cubicity of the γ’ particles in the γ matrix while the W reduces the negative influence of the Heusler phase: this phase can be completely dissolved when W is present in the alloy.
The discovery of the high entropy concept at the beginning of the 3rd millennium lead to a worldwide increase in metallurgical research, as the possible element combinations seemed nearly endless and the range of applications wide. In the early years of research, one of the main goals was the discovery of a single-phase high entropy alloy. As research evolved, it was found that properties could be enhanced by opening the HE-concept towards multiphase alloys, and from the wide area of possibilities our group chose a tuning of the properties towards high temperature application.
Compositionally complex Al10Co25Cr8Fe15Ni36Ti6 alloy, which is single-phase at high temperature, around 1200°C, shows a three phase morphology at intermediate temperatures, around 800°C. A high temperature homogenization procedure has to be applied in order to decrease the segregation induced by the dendritic growth. Subsequent annealing promotes the formation of the strengthening γ' precipitates. The alloy shows a positive lattice misfit between the γ and the γ' phase, which can be an indicator for good creep properties.
The microstructure can be optimized by adding trace elements such as Mo and Hf, known as γ and γ' strengtheners in Ni-based superalloys, respectively. Atom probe measurements show that Mo segregates into the γ matrix, and Hf prefers the γ' precipitates, where it increases the lattice parameter and thus also the lattice misfit, by about 50%. The alloy family shows interesting mechanical properties, especially the Al9.5Co25Cr8Fe15Ni36Ti6Hf0,5 alloy – its tensile properties are better than those of commercial Alloy 800H and IN617 at temperatures up to 700°C.
The multi-phase approach has proven to widen the application properties of high entropy alloys. After a decade of testing different alloys in the Al-Co-Cr-Cu-Fe-Ni-Ti family the Al10Co25Cr8Fe15Ni36Ti6 was found to be a solid base for more fine-tuned microstructural optimization. Following the example of superalloys, the Al10Co25Cr8Fe15Ni36Ti6 alloy aims for a γ/γ' microstructures in order to guarantee a good microstructural stability at high temperatures. The shape and volume fraction of the γ' particles is known to influence the mechanical properties of superalloys, and they do so in the high entropy family as well [1]. Shape, misfit and creep properties of several modified versions of the Al10Co25Cr8Fe15Ni36Ti6 alloy are compared and discussed in this talk.
The surface corrosion behaviour is a key issue which determines whether the material is applicable at a given atmosphere. Medium-entropy alloy FeCrNi alloy was exposed to synthetic air at 1000°C, 1050°C, and 1100 °C for up to 1000 h using a thermobalance. The oxidation rate was parabolic at 1000 and 1050°C, but breakaway occurred at 1100°C after 5 h of aging time. The whole oxide scales formed under the isothermal oxidation tests spalled off and additional oxidation tests were carried out at 1000 °C and 1050°C for 24 h and up to 100 h at 1000°C in a tubular furnace. The corrosion behaviour of the MEA was analysed by scanning electron microscope, energy-dispersive X-ray spectroscopy, and X-ray diffraction and compared to the behaviour of 316 L. The experimental results showed that under all conditions chromium is the main diffusion element resulting in the formation of a Cr2O3 layer at the MEA surface. Spallation of the layer induces the formation of additional oxidation products under the surface of the (spalled off) chromia layer.
High entropy alloys (HEA) are a new class of materials that have been investigated since the early 2000s and offer great potential to replace conventional alloys. However, since they sometimes have significant contents of expensive alloying elements such as Co or Ni, their use is only conceivable in highly stressed areas of components. For this purpose, the weldability with conventional alloys such as high-alloy austenitic steels must be investigated. In addition to the resulting microstructure, the mechanical properties are also fundamental for the usability of HEAs in DMWs. For this purpose, TIG welds of CoCrFeMnNi HEA (cold rolled and recrystallized state) with AISI 304 austenitic steel are investigated. These mechanical properties are analyzed in this work by means of tensile tests and local hardness measurement. The local strain behavior of the welded joints is also characterized by means of Digital Image Correlation (DIC). The results of the local hardness measurement show a clear influence of the initial condition of the HEA on the HAZ. Thus, the HEA in the cold-rolled condition shows a clear softening because of recrystallization processes in the HAZ. On the other hand, there is no influence on the hardness of the weld metal, which is approx. 200 HV0.1 in both cases. The tensile tests show a consistent failure of the weld in the weld metal. However, regardless of the HEA condition, strengths in the range of the recrystallized HEA (RM ~ 550–600 MPa) are achieved, although with significantly reduced fracture elongations.
Early Material Damage in Equimolar CrMnFeCoNi in Mixed Oxidizing/Sulfiding Hot Gas Atmosphere
(2022)
The challenges to use more varied fuels at medium and high temperatures above 500 °C need to be addressed by tuning the materials towards a better resistance against increased corrosion. As a first step the corrosion processes need to be better understood, especially in the case of the unavoidable and highly corrosive sulfur-based gases. In this work oxidation/sulfidation of an equimolar CrMnFeCoNi high entropy alloy is studied at an early stage after hot gas exposure at 600 °C for 6 h in 0.5% SO2 and 99.5% Ar. The oxidation process is studied by means of x-ray diffraction, scanning and transmission electron microscopy and supported by thermodynamic calculations. It is found that the sulfur does not enter the bulk material but interacts mainly with the fast-diffusing manganese at grain boundary triple junctions at the alloy surface. Sub-micrometer scaled Cr-S-O rich phases close to the grain boundaries complete the sulfur-based phase formation. The grains are covered in different Fe, Mn and Cr based spinels and other oxides.
Early Material Damage in Equimolar CrMnFeCoNi in Mixed Oxidizing/Sulfiding Hot Gas Atmosphere
(2022)
The use of more and more varied fuels implies an increased list of criteria that need to be addressed when choosing a material for a combustion chamber and its supply pipes. The materials must be very resistant against corrosion, especially when the process takes place at temperatures above 500°C. In this work the influence of SO2 on the surface of the “Cantor alloy” is investigated.
While a lage amount of research on high entropy alloys is oriented towards mechanical properties and the microstructural improvement it is also necessary to keep an eye on the environment that potential application materials will be submitted to. The Co-Cr-Fe-Ni based high entropy family has shown great potential over the years of high entropy research and some candidate alloys are chosen for an insight into their corrosion behaviour. Several atmospheres are studied, i.e. O2, H2O, SO2 and a mix thereof in argon as well as synthetic air. Just as for classic alloys, the chromium is the most important element in terms of protection agains further corrosion. The addition of manganese, as in case of the “Cantor alloy” CrMnFeCoNi, overpasses Cr when it comes to oxygen affinity and thus counteracts the layer formation of Cr2O3. Even without Mn, a temperature chosen too high will also affect the formation of the chromium oxide layer and spall it off, annulling its protective potential. We can also observe how trace elements influence the layer formation. These effects and their mechanisms will be discussed for the alloys CrFeNi, CoCrNi, CrMnFeCoNi and variations of Al10Co25Cr8Fe15Ni36Ti6 using a combination of electron microscopy, thermodynamic calculations and x-ray diffraction.
Spurenelemente spielen eine wichtige Rolle bei der Verfeinerung der Eigenschaften von komplexen Materialien. Diese Arbeit zeigt die Korrelation zwischen der Mikrostruktur, der Gitterfehlpassung und den Kriecheigenschaften. Die Legierung Al10Co25Cr8Fe15Ni36Ti6 (in at. %) mit komplexer Zusammensetzung wurde mit den Elementen Hf und W verstärkt. Die Zugabe von Hf bewirkt eine eckigere Form der würfelförmigen gamma'-Ausscheidungen und einen erhöhten Anteil der Heusler-Phase. Die Zugabe von W wiederum formt die Würfelchen rundlicher und löst die Heusler-Phase auf. Eine Mischung der beiden Spurenelemente zeigt einen Übergang zwischen den beiden Extremen, sowohl in Hinsicht auf die Form der Ausscheidungen als auch in Bezug auf die Gitterfehlpassung und die Kriecheigenschaften.
Superalloy inspired Al10Co25Cr8Fe15Ni36Ti6 compositionally complex alloy is known for its gamma-gamma' microstructure and the third Heusler phase. Variations of this alloy, gained by replacing 0.5 or 1 at. pct Al by the equivalent amount of Mo, W, Zr, Hf or B, can show more phases in addition to this three-phase morphology. When the homogenization temperature is chosen too high, a eutectic phase formation can take place at the grain boundaries, depending on the trace elements: Mo and W do not form eutectics while Hf, Zr and B do. In order to avoid the eutectic formation and the potential implied grain boundary weakening, the homogenization temperature must be chosen carefully by differential scanning calorimetry measurements. A too low homogenization temperature, however, could impede the misorientation alignment of the dendrites in the grain. The influence of grain boundary phases and incomplete dendrite re-orientation are compared and discussed.
A new race for high performance structural materials has started since the discovery of high entropy alloys at the beginning of the 21st century. The possible combination of several elements in an, until then, unknown composition space opened the ground for discovering new materials. Solid solution strengthening remains the most prominent mechanisms that is active in this family of materials, but it is supported by all other strengthening mechanism on the path to better and better performing materials. Chemical, thermal and mechanical approaches are combined to optimize these alloys. Optimum performances can be reached by using a high number of different strengthening mechanisms, induced both by composition and processing. The most prominent with composition induced mechanism is precipitation hardening, and on the processing side it is cold working such as cold-rolling, torsion or extrusion. The contribution uses tensile test data at room temperature solely for comparison – high temperature and cryogenic data are omitted because it would lead beyond the scope of this manuscript.
Misfits of γ- γ’ based Al10Co25Cr8Fe15Ni36Ti6 and its Mo- and Hf-variations are studied up to a temperature of 980 °C and compared with Ni- and Co-based superalloys. The trace elements decrease (Hf) or increase (Mo) the edge radii of the γ’ cuboids without changing their sizes. Atom probe measurements revealed that the Hf alloy prefers the γ’ phase while Mo prefers the γ matrix, leading to a lattice parameters enhancement of both phases, as could be revealed by synchrotron X-ray diffraction. The misfit is influenced in opposite ways: Hf increases the positive misfit, while Mo reduces it at all investigated temperatures.
Early material damage in equimolar CrMnFeCoNi in mixed oxidizing/sulfiding hot gas atmosphere
(2022)
The challenges to use more varied fuels at medium and high temperatures above 500 °C need to be addressed by tuning the materials toward a better resistance against increased corrosion. As a first step the corrosion processes need to be better understood, especially in the case of the unavoidable and highly corrosive sulfur-based gases. Herein, oxidation/sulfidation of an equimolar CrMnFeCoNi high-entropy alloy is studied at an early stage after hot gas exposure at 600 °C for 6 h in 0.5% SO2 and 99.5% Ar. The oxidation process is studied by means of X-ray diffraction, scanning and transmission electron microscopy, and supported by thermodynamic calculations. It is found that the sulfur does not enter the bulk material but interacts mainly with the fast-diffusing manganese at grain boundary triple junctions at the alloy surface. Submicrometer scaled Cr–S–O-rich phases close to the grain boundaries complete the sulfur-based phase formation. The grains are covered in different Fe-, Mn-, and Cr-based spinels and other oxides.
We investigated the effect of water vapor in the initial stages of SO2 corrosion of an Fe-9Cr-0.5Mn model alloy at 650 °C. Two separate experiments were run, one with 99.5%-Ar + 0.5%-SO2 and one with 69.5%-Ar + 0.5%-SO2 with 30%-H2O atmosphere. During the experiment the scale growth was observed in-situ, using energy dispersive X-ray diffraction (EDXRD). Our results confirm an increased speed of oxygen transport into the material, with the addition of water, while the transport of sulfur appears to be less affected.
Undetected and undesired microstructural variations in components produced by laser powder bed fusion are a major challenge, especially for safety-critical components. In this study, an in-depth analysis of the microstructural features of 316L specimens produced by laser powder bed fusion at different levels of volumetric energy density and different levels of inter layer time is reported. The study has been conducted on specimens with an application relevant build height
(>100 mm). Furthermore, the evolution of the intrinsic preheating temperature during the build-up of specimens was monitored using a thermographic in-situ monitoring set-up. By applying recently determined emissivity values of 316L powder layers, real temperatures could be quantified. Heat accumulation led to preheating temperatures of up to about 600 °C. Significant differences in the preheating temperatures were discussed with respect to the individual process parameter combinations, including the build height. A strong effect of the inter layer time on the heat accumulation was observed. A shorter inter layer time resulted in an increase of the preheating temperature by more than a factor of 2 in the upper part of the specimens compared to longer inter layer times. This, in turn, resulted in heterogeneity of the microstructure and differences in material properties within individual specimens. The resulting differences in the microstructure were analyzed using electron back scatter diffraction and scanning electron microscopy. Results from chemical analysis as well as electron back scatter diffraction measurements indicated stable conditions in terms of chemical alloy composition and austenite phase content for the used set of parameter combinations. However, an increase of the average grain size by more than a factor of 2.5 could be revealed within individual specimens. Additionally, differences in feature size of the solidification cellular substructure were examined and a trend of increasing cell sizes was observed. This trend was attributed to differences in solidification rate and thermal gradients induced by differences in scanning velocity and preheating temperature. A change of the thermal history due to intrinsic preheating could be identified as the main cause of this heterogeneity. It was induced by critical combinations of the energy input and differences in heat transfer conditions by variations of the inter layer time. The microstructural variations were directly correlated to differences in hardness.
AbstractThe high-temperature corrosion behaviors of the equimolar CrCoNi medium-entropy alloy and CrMnFeCoNi high-entropy alloy were studied in a gas atmosphere consisting of a volumetric mixture of 10% H2O, 2% O2, 0.5% SO2, and 87.5% Ar at 800 °C for up to 96 h. Both alloys were initially single-phase fcc with a mean grain size of ~ 50 μm and a homogeneous chemical composition. The oxide layer thickness of CrMnFeCoNi increased linearly with exposure time while it remained constant at ~ 1 μm for CrCoNi. A Cr2O3 layer and minor amounts of (Co,Ni)Cr2O4 developed on the latter while three oxide layers were detected on the former, i.e., a thin and continuous chromium rich oxide layer at the oxide/alloy interface, a dense (Mn,Cr)3O4 layer in the center and a thick and porous layer of Mn3O4 and MnSO4 at the gas/oxide interface. Additionally, a few metal sulfides were observed in the CrMnFeCoNi matrix. These results were found to be in reasonable agreement with thermodynamic calculations.
The steam side oxidation of ferritic–martensitic VM12-SHC steel was investigated under thermo-cyclic conditions in water steam at 620/320 °C and 30 bar with a focus on assessing the influence of pre-oxidation time, specimen geometry and surface finish. The specimens were pre-oxidized under isothermal conditions in water steam at 620 °C and 30 bar for 500 h or 1500 h. After pre-oxidation treatment, all specimens were subjected up to 258 thermal cycles. Three different geometries—rectangular coupons, U-shaped ring segments and ring samples—were investigated to evaluate the influence of open/closed shape, and flat/curved surface on corrosion rate. At the same time, two types of surface finish were considered: “as received” and “ground.” The formation of a protective scale by pre-oxidation was investigated. EBSD and ESMA analyses revealed that the Cr-content of the alloy appeared to be insufficient for obtaining a protective oxide scale under studied conditions, at the same time the anayses confirmed that initial oxidation depends on presence of minor alloying elements as Si and Mn, strong oxide formers which can alter the kinetics and morphology of the corrosion reaction. Moreover, rectangular coupons with small wall thickness and flat surface exhibited the highest corrosion rate, while “ground” curved samples showed only local oxidation. This indicates that for same pre-oxidation time, oxidation kinetics is controlled by curvature.
Subsurface characterization of high-strength high-interstitial austenitic steels after impact wear
(2018)
The microstructure of the subsurface after impact wear of three high-strength high interstitial austenitic steels has been analysed using transmission electron microscopy (TEM) in alloys with C and N as interstitial elements. In all cases, a nanocrystalline region followed by a transition zone and a cold-worked area are present. Additionally, microhardness and nano-scratching tests were conducted to study the wear-related properties of the impact subsurface and the base material. The results of the microstructural analysis reveal that the following mechanisms are involved during impact wear: abrasion (ploughing), microcrack formation associated with contact fatigue, entrapment and adhesion of SiO2 particles. The analysis of the wear-related properties indicates that the subsurface acts as a self-protective layer that prevents the deterioration of the substrate.
Influence of support configurations on the characteristics of selective laser-melted Inconel 718
(2018)
Samples fabricated using two different support configurations by following identical scan strategies during selective laser melting of superalloy Inconel 718 were characterized in this study. Characterization methods included optical microscopy, electron back-scattered diffraction and x-ray diffraction residual stress measurement. For the scan strategy considered, microstructure and residual stress development in the samples were influenced by the support structures. However, crystallographic texture intensity and the texture components formed within the core part of the samples were almost independent of the support. The formation of finer grains closer to the support as well as within the columnar grain boundaries resulted in randomization and texture intensity reduction by nearly half for the sample built on a lattice support. Heat transfer rates dictated by the support configurations in addition to the scan strategy influenced the microstructure and residual stress development in selective laser-melted Inconel 718 samples.
Understanding the origins of intrinsic stress in Si nanowires (NWs) is crucial for their successful utilization as transducer building blocks in next-generation, miniaturized sensors based on anoelectromechanical systems (NEMS). With their small size leading to ultrahigh-resonance frequencies and extreme surface-to-volume ratios, silicon NWs raise new opportunities regarding sensitivity, precision, and speed in both physical and biochemical sensing. With silicon optoelectromechanical properties strongly dependent on the level of NW intrinsic stress, various studies have been devoted to the measurement of such stresses generated, for example, as a result of harsh fabrication processes. However, due to enormous NW surface area, even the native oxide that is conventionally considered as a benign surface condition can cause significant stresses. To address this issue, a combination of nanomechanical characterization and atomistic simulation approaches is developed. Relying only on low-temperature processes, the fabrication approach yields monolithic NWs with optimum boundary conditions, where NWs and support architecture are etched within the same silicon crystal. Resulting NWs are characterized by transmission electron microscopy and micro-Raman spectroscopy. The interpretation of results is carried out through molecular dynamics simulations with ReaxFF potential facilitating the incorporation of humidity and temperature, thereby providing a close replica of the actual oxidation environment - in contrast to previous dry oxidation or self-limiting thermal oxidation studies. As a result, consensus on significant intrinsic tensile stresses on the order of 100 MPa to 1 GPa was achieved as a function of NW critical dimension and aspect ratio. The understanding developed herein regarding the role of native oxide played in the generation of NW intrinsic stresses is important for the design and development of silicon-based NEMS.
Though Ni-base superalloys show a high oxidation and corrosion resistance, coatings could still improve these properties, especially if used at temperatures up to 1000 °C. Here, a coating was prepared by applying a boehmite-sol via dip-coating and a subsequent heat treatment at 600 °C for 30 minutes. To evaluate the coating, the oxidation behavior of bare and alumina coated Ni-base alloy Inconel 625 in air at 900 °C was studied for up to 2000 h. Electron microscopic studies of sample surfaces and cross-sections showed that (i) in the 3.5 µm – 6.3 mm thick scale formed on the bare alloy, Fe and Ni are located as fine precipitates at the grain boundaries of the chromia-rich scale, (ii) Ni and Ti are concentrated to a minor degree at the grain boundaries of the scale, too; and for the coated sample: (iii) the only 1.8 µm thick sol-gel alumina coating slows down the formation of chromia on the alloy surface and reduces the outward diffusion of the alloy constituents. The protective effect of the coating was evidenced by (i) diminished chromium diffusion at grain boundaries resulting in less pronounced string-like protrusions at the outer surface of the coated IN 625, (ii) formation of a Cr-enriched zone above the alloy surface which was thinner than the scale on the uncoated sample, (iii) no detectable Cr-depleted zone at the alloy surface, and (iv) a narrower zone of formation of Kirkendall pores.
Thin Sol-Gel Alumina Coating as Protection of a 9% Cr Steel Against Flue Gas Corrosion at 650 °C
(2018)
Samples of sol-gel alumina coated and uncoated P92 steel were exposed to flue gas at 650 °C for 300 h. As result of this treatment a 50 µm thick bi-layered oxide scale had formed on the surface of the uncoated sample. Below the scale a 40 µm thick inner oxidation zone was detected. In contrast, the porous, micron thick alumina coating enabled the formation of a chromium oxide scale with a thickness of some nanometers at the interface between steel substrate and coating. In this case high temperature corrosion of the steel was prevented so far.
CALM is software for determining the Bravais lattice type and the resulting lattice parameters from a single Kikuchi pattern. It requires the definition of 4 bands and a single bandwidth from which all other band positions as well as bandwidths are derived. For band detection, it uses the Funk transform, which allows detection of twice as many bands as usual. CALM works for any symmetry and requires low-noise patterns of at least 320x240 pixels. The resulting errors are <2% even for such small patterns, assuming good quality. The relative errors are <0.5%. However, this requires a projection centre position best derived from a sample of a cubic phase in CALM. However, this must have been recorded under identical conditions. Hundreds of Kikuchi patterns of phases with different symmetries were examined.
CALM is software for determining the Bravais lattice type and the resulting lattice parameters from a single Kikuchi pattern. It requires the definition of 4 bands and a single bandwidth from which all other band positions as well as bandwidths are derived. For band detection, it uses the Funk transform, which allows detection of twice as many bands as usual. CALM works for any symmetry and requires low-noise patterns of at least 320x240 pixels. The resulting errors are <2% even for such small patterns, assuming good quality. The relative errors are <0.5%. However, this requires a projection centre position best derived from a sample of a cubic phase in CALM. However, this must have been recorded under identical conditions. Hundreds of Kikuchi patterns of phases with different symmetries were examined.
The Bravais lattices and their lattice parameters are blindly determined using electron backscatter diffraction (EBSD) patterns of materials with cubic or tetragonal crystal structures. Since the geometric relationships in a single EBSD pattern are overdetermined, the relative errors of determining the lattice parameters as well as the axial ratios are confined to about 0.7 ± 0.4% and 0.07 ± 0.03%, respectively, for ideal simulated EBSD patterns. The accuracy of the crystal orientation determination reaches about 0.06 ± 0.03°. With careful manual band detection, the accuracy of determining lattice parameters from experimental patterns can be as good as from simulated patterns, although the results from simulated patterns are often better than expermental patterns, which are lower quality and contain uncertain systematic errors. The reasonably high accuracy is obtained primarily because the detection of the diffracting-plane traces and zone axes is relatively accurate. The results here demonstrate that the developed procedure based on the EBSD technique presents a reliable tool for crystallographic characterization of the Bravais lattices of unknown phases.
Roaldite – Fe4N – has been identified in the São Julião de Moreira iron meteorite using electron backscatter diffraction (EBSD) and simultaneously acquired energy-dispersive x-ray spectroscopy (EDS). Mean-periodic-number images derived from raw EBSD patterns confirm this phase by an even higher spatial resolution compared to EDS.
Roaldite appears in the form of systematically and repetitively aligned plates. Despite the locally heavy plastic deformation, it is shown that the origin of the oriented precipitation of roaldite is linked to the orientation of the kamacite matrix. Roaldite can be considered to be precipitated from kamacite using an inverse Kurdjumov-Sachs (K-S) or Nishiyama-Wassermann (N-W) orientation relationship. A more accurate discrimination is impossible due to the accumulated shock deformation, which blurs the local reference orientation of kamacite. The habit plane of roaldite is found to be {112}R, which is most likely parallel to {120}K of kamacite. Some of the roaldite plates contain two orientation variants which repeatedly alternate. Their misorientation angle is about 12°.
We use pattern matching of experimental and dynamically simulated backscattered Kikuchi diffraction (BKD) patterns to increase the orientation precision of electron backscatter diffraction (EBSD) measurements. In order to quantify the improvement in orientation precision, we analyze the experimental distribution of the kernel average misorientation (KAM) angles. We find that for the same raw data, i.e. the same EBSD data acquisition time budget, the pattern matching approach improves the KAM resolution by an order of magnitude compared to orientation data delivered from the conventional Hough-transform based data analysis. This quantitative improvement enables us to interpret small orientation changes in plastically deformed materials which are hidden in noisy orientation data delivered from the reference EBSD system.
As an application example, we analyze a ferritic-martensitic steel (P92) sample before and after low-cycle fatigue (LCF) loading (±0.3% strain) at 620 °C. Whereas the low precision of the EBSD orientation data from the manufacturer software does not allow a reliable discrimination of the gradually changing microstructure, we find very clear systematic differences of the local microstructure after the pattern matching orientation refinement of the initial, raw pattern data. For the investigated P92 sample, the KAM-angle histograms are well described by two log-normal distributions indicating the already tempered and the remaining and mostly untempered martensite.
Gold and platinum-group-metals (PGM) are cycled through Earth's environments by interwoven geological, physical, chemical and biological processes leading to the trans/neoformation of metallic particles in placers.
The placer deposit at Corrego Bom Successo (CBS, Brazil) is one of the few localities worldwide containing secondary gold- and PGM-particles. Placer gold consists of detrital particles from nearby hydrothermal deposits that were transformed in the surface environment. Processes that have affected these particles include shortdistance transport, chemical de-alloying of the primary Gold silver, and (bio)geochemical dissolution/reprecipitation of Gold leading to the formation of pure, secondary gold and the Dispersion of gold nanoparticles. The latter processes are likely mediated by non-living organic matter (OM) and bacterial biofilms residing on the particles. The biofilms are largely composed of metallophillic β- and γ-Proteobacteria. Abundant mobile gold and platinum nanoparticles were detected in surface waters, suggesting similar mobilities of these metals. Earlier hydrothermal processes have led to the formation of coarsely-crystalline, arborescent dendritic potarite (PdHg). On potarite surfaces, biogeochemical processes have then led to the formation of platinum- and palladium-rich micro-crystalline layers, which make up the botryoidal platinum palladium aggregates. Subsequently potarite was dissolved from the core of many aggregates leaving voids now often filled by secondary anatase (TiO2) containing biophilic elements. The presence of fungal structures associated with the anatase suggests that fungi may have contributed to ist formation. For the first time a primary magmatic PGM-particle comprising a mono-crystalline platinum palladium-alloy with platinum iridium osmium inclusions was described from this locality, finally defining a possible primary source for the PGM mineralisation. In conclusion, the formation of modern-day placer gold- and PGM-particles at CBS began 100s ofmillions of years ago bymagmatic and hydrothermal processes. These provided the metal sources for more recent biogeochemical cycling of PGEs and gold that led to the trans/neoformation of gold- and PGM-particles.
A historical tool for crystallographic analysis is provided by the Hilton net, which can be used for manually surveying the crystal lattice as it is manifested by the Kikuchi bands in a gnomonic projection. For a quantitative analysis using the Hilton net, the projection centre as the relative position of the signal source with respect to the detector plane needs to be known. Interplanar angles are accessible with a precision and accuracy which is estimated to be ≤0.3o. Angles between any directions, e.g. zone axes, are directly readable. Finally, for the rare case of an unknown projection-centre position, its determination is demonstrated by adapting an old approach developed for photogrammetric applications.
It requires the indexing of four zone axes [uvw]i in a backscattered Kikuchi diffraction pattern of a known phase collected under comparable geometric conditions.
A pseudosymmetric description of the crystal lattice derived from a single wideangle Kikuchi pattern can have several causes. The small size (<15%) of the sector covered by an electron backscatter diffraction pattern, the limited precision of the projection centre position and the Kikuchi band definition are crucial. Inherent pseudosymmetries of the crystal lattice and/or structure also pose a challenge in the analysis of Kikuchi patterns. To eliminate experimental errors as much as possible, simulated Kikuchi patterns of 350 phases have been analysed using the software CALM [Nolze et al. (2021). J. Appl. Cryst. 54, 1012–1022] in order to estimate the frequency of and reasons for pseudosymmetric crystal lattice descriptions. Misinterpretations occur in particular when the atomic scattering factors of non-equivalent positions are too similar and reciprocal-lattice points are systematically missing. As an example, a pseudosymmetry prediction depending on the elements involved is discussed for binary AB compounds with B1 and B2 structure types. However, since this is impossible for more complicated phases, this approach cannot be directly applied to compounds of arbitrary composition and structure.
The derivation of a crystal structure and its phase-specific parameters from a single wide-angle backscattered Kikuchi diffraction pattern requires reliable extraction of the Bragg angles. By means of the first derivative of the lattice profile, an attempt is made to determine fully automatically and reproducibly the band widths in simulated Kikuchi patterns. Even under such ideal conditions (projection centre, wavelength and lattice plane traces are perfectly known), this leads to a lattice parameter distribution whose mean shows a linear offset that correlates with the mean atomic number Z of the pattern-forming phase. The consideration of as many Kikuchi bands as possible reduces the errors that typically occur if only a single band is analysed. On the other hand, the width of the resulting distribution is such that higher image resolution of diffraction patterns, employing longer wavelengths to produce wider bands or the use of higher interference orders is less advantageous than commonly assumed.
A band width determination using the first derivative of the band profile systematically underestimates the true Bragg angle. Corrections are proposed to compensate for the resulting offset Δa/a of the mean lattice parameters derived from as many Kikuchi band widths as possible. For dynamically simulated Kikuchi patterns, Δa/a can reach up to 8% for phases with a high mean atomic number Z, whereas for much more common low-Z materials the offset decreases linearly. A predicted offset Δa/a = f(Z) is therefore proposed, which also includes the unit-cell volume and thus takes into account the packing density of the scatterers in the material. Since Z is not always available for unknown phases, its substitution by Zmax, i.e. the atomic number of the heaviest element in the compound, is still acceptable for an approximate correction. For simulated Kikuchi patterns the offset-corrected lattice parameter deviation is Δa/a < 1.5%. The lattice parameter ratios, and the angles α, β and γ between the basis vectors, are not affected at all.1.5%. The lattice parameter ratios, and the angles , and between the basis vectors, are not affected at all.
A new software is presented for the determination of crystal lattice parameters from the positions and widths of Kikuchi bands in a diffraction pattern. Starting with a single wide-angle Kikuchi pattern of arbitrary resolution and unknown phase, the traces of all visibly diffracting lattice planes are manually derived from four initial Kikuchi band traces via an intuitive graphical user interface. A single Kikuchi bandwidth is then used as reference to scale all reciprocal lattice point distances. Kikuchi band detection, via a filtered Funk transformation, and simultaneous display of the band intensity profile helps users to select band positions and widths. Bandwidths are calculated using the first derivative of the band profiles as excess-deficiency effects have minimal influence. From the reciprocal lattice, the metrics of possible Bravais lattice types are derived for all crystal systems. The measured lattice parameters achieve a precision of <1%, even for good quality Kikuchi diffraction patterns of 400 x 300 pixels. This band-edge detection approach has been validated on several hundred experimental diffraction patterns from phases of different symmetries and random orientations. It produces a systematic lattice parameter offset of up to ±4%, which appears to scale with the mean atomic number or the backscatter coefficient.
An extensive set of information about the diffracting volume is carried by EBSD patterns: the crystal lattice, the reciprocal lattice, the crystal structure, the crystal symmetry, the mean periodic number of the diffracting phase, the source point from where it has been projected (projection centre), the crystal orientation, the sample topography (local tilt), the (preparation) quality of defect density of the crystal, and possible pattern overlaps. Some of this information is used regularly in conventional EBSD analyses software while others are still waiting for a more widespread application. Despite the wealth of information available, the accuracy and precision of the data that are presently extracted from conventional EBSD patterns are often well below the actual physical limits. Using a selection of example applications, we will demonstrate the gain in angular resolution possible using relatively low-resolution patterns of approximately 20k pixels in combination with pattern matching (PM) approaches. In this way, fine details in a microstructure can be revealed which would otherwise be hidden in the orientation noise.
Electron backscatter diffraction (EBSD) is a technique to obtain microcrystallographic information from materials by collecting large-angle Kikuchi patterns in the scanning electron microscope (SEM). An important fundamental question concerns the scattering-angle dependent electron energy distribution, which is relevant for the formation of the Kikuchi diffraction patterns. Here we review the existing experimental data and explore the effective energy spectrum that is operative in the generation of backscatter Kikuchi patterns from silicon. We use a full pattern comparison of experimental data with dynamical electron diffraction simulations. Our energy-dependent cross-correlation based pattern matching approach establishes improved constraints on the effective Kikuchi pattern energy spectrum, which is relevant for high-resolution EBSD pattern simulations and their applications.
The locally varying tetragonality in martensite grains of a high-carbon steel (1.2 mass percent C) was resolved by electron backscatter diffraction (EBSD) with a spatial resolution in the order of 100 nm. Compared to spatially integrating X-ray diffraction, which yielded an average tetragonality fo c/a=1.05, the EBSD measurements in the scanning electron microscope allowed to image a local variation of the lattice papameter ration c/a in the range of 1.02 ≤ c/a ≤ 1.07. The local variation of tetragonality is confirmed by two different EBSD data analysis approaches based on the fitting of simulated to experimental EBSD patterns. The resulting EBSD-based tetragonality maps are pointing to a complex interaction of carbon concentration and local lattice distortions during the formation process of martensitic structures.
Ferritic-martensitic Fe-Cr alloys are widely utilised as materials for high temperature applications such as super heater tubes in coal, biomass or co-fired power plants. Various corrosive gases are produced in combustion processes, but especially SO2 is known to cause catastrophic application failure. In order to understand the effect of orientation and grain size of the alloy on the initial corrosion processes we analysed metal coupons of Fe-Cr- alloys (2-13 wt. % Cr) by electron backscattered diffraction (EBSD) before and after exposure to SO2 containing atmospheres in 650°C for short time spans (2 min – 12 h). An infra red heated furnace with integrated water-cooling was used for the ageing procedures to conduct short time experiments and to keep the reaction products in a ‘frozen’ state.
EBSD characterization of oxides formed on the surface of the alloys showed a topotactic relationship between grain orientation of the alloys and the oxides. With increasing scale thickness this relation diminishes possibly due to lattice strain. There appears to be no correlation between oxide growth and absolute, initial orientation, grain size, or the quality of polishing. An initially topotactic relationship between scale and steel had been already described for the formation of magnetite in hot steam environments, indicating that the initial corrosion mechanisms are mainly depending on the presence of Oxygen, and not changed by the presence of Sulphur. However, Sulphur is incorporated into the oxide scale in the low Cr alloy, and mainly observable in the inner corrosion zone for the higher alloyed material. Furthermore, oxides formed directly on grain boundaries in higher Cr alloyed materials are enriched in Cr compared to oxides on grain faces.
Comprehensive insights into the early stages of corrosion mechanisms provide fundamental knowledge to further understand and model long time material behaviour. The present work studies the early stages of combined oxidation and sulphidation of ferritic model alloys for time scales up to 250 h at 650 °C to observe the influence of chromium during the corrosion under SO2. Model alloys were used to focus on the reaction of the intended elements: Fe, Cr, S, and O. Pure iron simultaneously forms magnetite and iron sulphide in an early stage of corrosion, covered by a pure oxide layer after 100 h. Iron with 13 wt% Cr shows hematite and mixed Fe-Cr-oxides first, before sulphides nucleate in the inner corrosion zone. With increasing ageing time a magnetite layer is observed below the hematite layer. Quantitative phase fractions of all corrosion products observed were determined from cross section images. Characterization of the Fe13Cr corrosion scale by FIB revealed a highly porous structure in the inner corrosion zone where Cr-rich (Fe, Cr)-sulphides are present, and caused the scale to spall easily.
Metal sulfide grain boundary precipitates of a ferrous model alloy with 13 wt.% chromium formed at 650°C under a gas atmosphere containing 0.5% SO2 and 99.5% Ar were investigated after ageing for 3 h, 6 h, and 12 h. The precipitates formed along grain boundaries were identified as Cr5S6 using energy-dispersive x-ray spectroscopy in transmission electron microscopy and electron backscatter diffraction analysis. Serial focused ion beam slicing was conducted followed by three-dimensional reconstruction to determine the number, size, and penetration depth of the precipitates evolved at the different time steps. There was a linear increase in the number of precipitates with time, while their average size increased only for the initial aging time but became constant after 6 h. Based on these results, a model for grain boundary sulfidation of ferritic alloys is discussed.
9-12% Cr ferritic-martensitic stainless steels are widely used as high temperature construction materials in power plants due to their excellent creep and oxidation resistance. The growing share of renewable energy sources in power generation forces many of these plants into more flexible operation with frequent load shifts or shutdowns. These cyclic operation profiles constitute a major lifetime issue.
The present contribution reports on current findings obtained in a multidisciplinary project which combines cyclic mechanical and cyclic oxidation testing with detailed microstructural analyses. Mechanical analyses are carried out on P92 and P91 steel grades to give an overview of softening phenomena and lifetimes obtained in isothermal cyclic loading (low cycle fatigue, LCF), non-isothermal cyclic loading (thermo-mechanical fatigue, TMF), and service-like combinations of creep and fatigue periods (creep-fatigue interaction).
Oxidation testing focuses on the grades P92 and VM12 with the intention of clarifying the impact of frequent passes through intermediate temperature levels on the kinetics of steam-side oxidation and the characteristics of the evolving oxide scales. An attempt is made to evaluate their composition, strength, integrity and adhesion after up to 250 temperature cycles. Flat coupons as well as curved tube sections are tested to assess the mutual influence of geometry on oxide scale integrity.
Complementary microstructural investigations by scanning and transmission electron microscopy plus EBSD are used for phase identification and substrate/oxide interface characterisation. The evolutions of grain size and dislocation density under different test conditions are quantified.
9-12% Cr ferritic-martensitic stainless steels are widely used as high temperature construction materials in power plants due to their excellent creep and oxidation resistance. The growing share of renewable energy sources in power generation forces many of these plants into more flexible operation with frequent load shifts or shutdowns. These cyclic operation profiles constitute a major lifetime issue. The present contribution reports on current findings obtained in a multidisciplinary project which combines cyclic mechanical and cyclic oxidation testing of different 9-12% Cr grades with detailed microstructural analyses.
Mechanical analyses are carried out on P92 and P91 steel grades to give an overview of softening phenomena and lifetimes obtained in isothermal cyclic loading (low cycle fatigue, LCF), non-isothermal cyclic loading (thermo-mechanical fatigue, TMF), and service-like combinations of creep and fatigue periods.
Complementary microstructural investigations by scanning and transmission electron microscopy plus EBSD are used for phase identification, substrate/oxide interface characterization and quantification of the microstructure evolution under cyclic conditions.
Cyclic mechanical performance and microstructure evolution of P92 under LCF and TMF conditions
(2019)
9-12% Cr ferritic-martensitic stainless steels are widely used as high temperature construction materials in fossil fueled power plants due to their excellent creep and oxidation resistance, but changes in electricity markets during the last two decades have considerably changed the typical working conditions of these facilities. The growing contribution of renewable energy sources in power generation forces most of these plants into flexible operation with frequent load shifts or shutdowns. These cyclic operation profiles constitute a major lifetime issue, raising the question which fundamental processes govern the reaction of ferritic-martensitic steels to cyclic load and temperature variations.
The present contribution reports on current findings obtained in a multidisciplinary project funded by German Ministry of Education and Research (BMBF) which combines cyclic mechanical and cyclic oxidation testing of different 9-12% Cr grades with detailed microstructural analyses and related micromechanical modeling.
In this contribution, an overview will be given on the results obtained in the mechanical testing programme of the project. Mechanical analyses were carried out on P91 and (mainly) P92 steel grades, particularly looking at softening phenomena and lifetimes obtained in isothermal cyclic loading (low cycle fatigue, LCF), non-isothermal cyclic loading (thermo-mechanical fatigue, TMF), and service-like combinations of fatigue and creep/relaxation periods. For this purpose, cylindrical specimens were extracted from thick-walled steam pipes, orthogonal to the pipe axis, and subjected to strain controlled cyclic loading (± 0.2 to ±0.5 % mechanical strain). Temperature intervals of TMF tests were chosen as either 300-620°C or 500-620°C, resembling so-called warm or hot start conditions of a power plant.
The test results will be presented and discussed with a focus on the impact of hold periods during testing (combined creep/relaxation-fatigue conditions) on mechanical softening, lifetime and formation of cracks. The findings will be complemented by results on the modification of the hierarchical ferritic-martensitic microstructure under different loading scenarios.
The current competitive situation on electricity markets forces power plants into cyclic operation regimes with frequent load shifts and starts/shutdowns. In the present work, the cyclic mechanical behavior of ferritic-martensitic 9-12 % Cr steels under isothermal and thermomechanical loading was investigated for the example of grade P92 material. A continuous softening was observed under all loading conditions. The introduction of hold periods to the applied cycles reduced material lifetime, with most prominent effects at technologically relevant small strain levels. The microstructural characterization reveals a coarsening of the original “martensitic” lath-type microstructure to a structure with polygonal subgrains and reduced dislocation density. The microstructural data forms the input for a physically-based modelling approach.
A round-robin study has been carried out to estimate the impact of the human element in small-angle scattering data analysis. Four corrected datasets were provided to participants ready for analysis. All datasets were measured on samples containing spherical scatterers, with two datasets in dilute dispersions and two from powders. Most of the 46 participants correctly identified the number of populations in the dilute dispersions, with half of the population mean entries within 1.5% and half of the population width entries within 40%. Due to the added complexity of the structure factor, far fewer people submitted answers on the powder datasets. For those that did, half of the entries for the means and widths were within 44 and 86%, respectively. This round-robin experiment highlights several causes for the discrepancies, for which solutions are proposed.
A Round Robin study has been carried out to estimate the impact of the human element in small-angle scattering data analysis. Four corrected datasets were provided to participants ready for analysis. All datasets were measured on samples containing spherical scatterers, with two datasets in dilute dispersions, and two from powders.
Most of the 46 participants correctly identified the number of populations in the dilute dispersions, with half of the population mean entries within 1.5 % and half of the population width entries within 40 %, respectively. Due to the added complexity of the structure factor, much fewer people submitted answers on the powder datasets.
For those that did, half of the entries for the means and widths were within 44 % and 86 % respectively. This Round Robin experiment highlights several causes for the discrepancies, for which solutions are proposed.
Small-angle Scattering Data Analysis Round Robin: anonymized results, figures and Jupyter notebook
(2023)
The intent of this round robin was to find out how comparable results from different researchers are, who analyse exactly the same processed, corrected dataset.
This zip file contains the anonymized results and the jupyter notebook used to do the data processing, analysis and visualisation. Additionally, TEM images of the samples are included
Using the method of directional solidification, single crystals of experimental nickel-based superalloys with negative, zero, and positive γ/γ' misfits are obtained. The γ' solvus, solidus, and liquidus temperatures of the alloys are determined, and the microstructures of the alloys after directional solidification, heat treatment, and creep tests are investigated. Creep tests are performed at temperatures of 800 and 1000°C. It is found that single crystals of the alloy with a negative γ/γ' misfit have the highest creep resistance and lifetime (the crystal lattice period of the γ' phase is smaller than that of the γ matrix).
Coupons of X5CrNiCuNb16-4 that may be used as injection pipe with 16% Chromium and 0.05% Carbon (1.4542, AISI 630) were exposed for 3000 h to CO2-saturated saline aquifer water similar to the conditions in the Northern German Basin at ambient pressure and 60 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness. Corrosion rates for polished and technical surfaces were below 0.005 mm/year compared to corrosion rates of 0.035 mm/year after shot peening.
Coupons of X5CrNiCuNb16-4 with different surface roughness that may be utilized as injection pipe with 16% Chromium and 0.05% Carbon (1.4542, AISI 630) were exposed for 3000 h to CO2-saturated saline aquifer water simulating the conditions in the Northern German Basin at ambient pressure and 60 °C. Additionally, corrosion fatigue experiments (ambient pressure, technically clean CO2, saline aquifer water of Stuttgart Aquifer) were performed using specimen of X46Cr13 (1.4043, AISI 420C) with regard to the influence of the roughness of technical surfaces on the number of cycles to failure at different stress amplitudes. Specimen of Duplex stainless steel X2CrNiMoN22-3-2 (1.4462) for corrosion fatigue experiments were provided with technical surfaces after machining as well as polished surfaces. Results were obtained at load amplitudes ranging from 175 MPa to 325 MPa in the geothermal brine of the Northern German Basin at 98 °C. The main precipitation phases on the surface as well as within pits reveal carbonates or hydroxides such as siderite (FeCO3) and ferrous hydroxide goethite (FeOOH) independent of the original surface roughness. Corrosion rates for polished and technical surfaces were below 0.005 mm/year compared to corrosion rates of 0.035 mm/year after shot peening. Specimen with technical surfaces tested at high stress amplitudes (>275 MPa) lasted longer (cycles to failure: P50% at Sa 300 MPa=5x105) than specimen with polished surfaces (cycles to failure: P50% at Sa 300 MPa=1.5x105). This behavior is emphasized by the slope coefficient (technical surfaces k = 19.006, polished surfaces k=8.78) meaning earlier failure for polished at high stress amplitude Sa. Although rather low scatter ranges (technical surface: TN=1:1.35, polished surface: TN=1.1.95) indicate no change in failure mechanism it may be assumed that at low stress pitting is the initiating crack growth process whereas at high stress amplitudes the formation of micro cracks is reason for crack propagation and failure.
To mitigate carbon dioxide emissions CO2 is compressed and sequestrated into deep geological layers (Carbon Capture and Storage CCS). The corrosion of injection pipe steels is induced when the metal is in contact with CO2 and at the same time the geological saline formation water. Stainless steels X35CrMo17 and X5CrNiCuNb16-4 with approximately 17% Cr show potential as injection pipes to engineer the Northern German Basin geological onshore CCS-site. Static laboratory experiments (T = 60 ◦C, p = 100 bar, 700–8000 h exposure time, aquifer water, CO2-flow rate of 9 L/h) were conducted to evaluate corrosion kinetics. The anomalous surface corrosion phenomena were found to be independent of heat treatment prior to exposure. The corrosion process is described as a function of the atmosphere and diffusion process of ionic species to explain the precipitation mechanism and better estimate the reliability of these particular steels in a downhole CCS environment.
During capture and storage technology (CCS) as well as in geothermal energy production Steels need to withstand the corrosive environment such as: heat, pressure, salinity of the aquifer and CO2-partial pressure. 1.4542 shows unusual corrosion phenomena, but is still sufficiently resistant in corrosive environments. To better understand its behaviour differently heat treated coupons of 1.4542 and for comparison X20Cr13 and X46Cr13 were kept in the artificial brine of the Northern German Basin at T=60 °C. Ambient pressure as well as p=100 bar for 700 h - 8000 h in water saturated supercritical CO2 and CO2-saturated synthetic aquifer Environment was applied. Fatigue tests were performed via push-pull tests with a series of 30 specimens from 150 MPa to 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). FeCO3 and FeOOH are corrosion products also after dynamic corrosion tests. Martensitic microstructure offers good corrosion resistance in geothermal environment. The S-N-curve showing no typical fatigue strength and very steep slopes of possible fatigue strength for finite life. Possible influencing artefacts, such as Al-inclusions could not be correlated to early rupture despite specimens containing inclusions at the fracture surface and cross section reached lower number of cycles. Applied potential proofed to enhance fatigue life tremendously.
During carbon sequestration the CO2-induced corrosion of injection pipe steels is a relevant safety issue when emission gasses are compressed into deep geological layers. The reliability of the high alloyed steel X35CrMo17 suitable as injection pipe for the geological onshore CCS-site (Carbon Capture and Storage) in the Northern German Basin, is demonstrated in laboratory experiments in equivalent corrosive environment (T = 60 °CC, p = 1–100 bar, aquifer water, CO2-flow rate of 9 L/h, 700–8000 h exposure time). Corrosion kinetics and microstructure were characterized and compared to other potential injection pipe steels (42CrMo4, X46Cr13, X20Cr13 and X5CrNiCuNb16-4).
Degradation of AISI 630 exposed to CO2-saturated saline aquifer at ambient pressure and 100 bar
(2018)
In general high alloyed steels are suitable as pipe steels for carbon capture and storage technology (CCS), because they provide sufficient resistance against the corrosive environment of CO2-saturated saline aquifer which serves as potential CCS-site in Germany. High alloyed martensitic steel AISI 630 has been proven to be sufficient resistant in corrosive environments, e.g. regarding heat, pressure, salinity of the aquifer, CO2-partial pressure), but reveals a distinct corrosion pattern in CCS environment. Therefore coupons of AISI 630 heat treated using usual protocols were kept at T=60 °C and ambient pressure as well as p=100 bar up to 8000 h in an a) water saturated supercritical CO2 and b) CO2-saturated synthetic aquifer environment similar to on-shore CCS-sites in the Northern German Basin. AISI 630 precipitates a discontinuous ellipsoidal corrosion layer after being exposed for more than 4000 hours. Best corrosion resistance in the CO2-saturated synthetic aquifer environment phase is achieved via normalizing prior to exposure. In water saturated supercritical CO2 tempering at medium temperatures after hardening gives lowest corrosion rates. Corrosion fatigue via push-pull tests with a series of 30 specimens was evaluated at stress amplitudes between 150 MPa and 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). The endurance limit of AISI 630 is reduced by more than 50% when exposed to CCS environment (maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa).
The commercial usage of latent thermal energy storages primarily depends on the development of a suitable phase change material (PCM). For industrial high temperature applications above 400 °C multicomponent chloride eutectics are promising and therefore discussed seriously. The profound thermodynamic investigation of such eutectics requires a much greater amount of specimen material than conventional calorimeter can handle. Therefore, a special adiabatic calorimeter was developed and designed. With a specimen mass of > 100 g the typical thermodynamic measurements with a commercial calorimeter can be extended by cycle stability measurements, which are often decisive for practical application of PCM. Furthermore, by implementing corrosion specimens inside the calorimeter high temperature corrosion experiments according to ISO 21608 can be performed inside the calorimeter. Adiabatic measuring conditions can be provided by using two separate heating systems. Therefore, the outer “protective system” follows the temperature curve of the inner “measuring system” minimizing the temperature difference between the heating systems and simultaneously preventing heat losses from the measuring systems.
Corrosion fatigue specimen with different surfaces (technical surfaces after machining and polished surfaces) of high alloyed martensitic stainless steel X46Cr13 (1.4043) and duplex stai nless steel X2CrNiMoN22 3 2 (1.4462) were compared at load amplitudes from 175 MPa to 325 MPa in the geothermal brine of the N orthern German Basin at 98 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO 3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness . At high stress amplitudes above 275 MPa technical surfaces (P50% at σa 300 MPa=5 × 10 5 ) resulted in more cycles to failure than polished (P50% at σa 300 MPa=1.5 × 10 5 ). The greater slope coefficient for technical surfaces k = 19.006 compared to polished surfaces k =8.78 demonstrate s earlier failure at given stress amplitude σa .
In CCS environment (carbon capture and storage) pipes are loaded statically and/or cyclically and at the same time exposed constantly to the highly corrosive hot thermal water. Experimental procedures such as ambient pressure immersions tests, in-situ corrosion fatigue experiments using a flexibly designed corrosion chamber at ambient pressure and a specially designed corrosion chamber at high pressure. Experimental set-ups for push/pull and rotation bending load are introduced. The corrosion behavior and lifetime reduction of high alloyed steels (X46Cr13, 1.4043), (X5CrNiCuNb16-4, 1.4542) and (X2CrNiMoN22-5-3, 1.4462) is demonstrated (T=60 °C, geothermal brine: Stuttgart Aquifer flow rate: 9 l/h, CO2 ).