5 Werkstofftechnik
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Optimizing the properties of next-generation high-temperature and corrosion-resistant alloys is rooted in balancing structure-property relationships and phase chemistry. Here, we implement a complementary approach based on transmission electron microscopy (TEM) and atom probe tomography (APT) to ascertain aspects of hierarchical phase separation behavior, by understanding the microstructural evolution and the three-dimensional (3D) nanochemistry of a single crystal Fe79.5Si15.5V5.0 (at%) alloy. A maze-like hierarchical microstructure forms, in which a complex network of metastable disordered α plates (A2 phase) emerges within ordered α1 precipitates (D03 phase). The supersaturation in α1 (D03) precipitates with Fe and V drives the formation of α (A2) plates. The morphology of α (A2) plates is discussed concerning crystal structure, lattice misfit, and elastic strain. Phase compositions and a ternary phase diagram aid the thermodynamic assessment of the hierarchical phase separation mechanism via the Gibbs energy of mixing. A perspective on the stabilization of hierarchical microstructures beyond Fe79.5Si15.5V5.0 is elaborated by comparing hierarchical alloys. We find that the ratio of elastic anisotropy (Zener ratio) serves as a predictor of the hierarchical particles’ morphology. We suggest that the strengthening effect of hierarchical microstructures can be harnessed by improving the temporal and thermal stability of hierarchical particles. This can be achieved through phase-targeted alloying aiming at the hierarchical particles phase by considering the constituents partitioning behavior. Beyond Fe79.5Si15.5V5.0, our results demonstrate a potential pathway for improving the properties of high-temperature structural materials.
Irradiation assisted stress corrosion cracking (IASCC) is a form of intergranular stress corrosion cracking that occurs in irradiated austenitic alloys. It requires an irradiated microstructure along with high temperature water and stress. The process is ubiquitous in that it occurs in a wide range of austenitic alloys and water chemistries, but only when the alloy is irradiated. Despite evidence of this degradation mode that dates back to the 1960s, the mechanism by which it occurs has remained elusive. Here, using high resolution electron backscattering detection to analyze local stress-strain states, high resolution transmission electron microscopy to identify grain boundary phases at crack tips, and decoupling the roles of stress and grain boundary oxidation, we are able to unfold the complexities of the phenomenon to reveal the mechanism by which IASCC occurs. The significance of the findings impacts the mechanical integrity of core components of both current and advanced nuclear reactor designs worldwide.
The precise analysis of cation diffusion profiles through corrosion scales is an important aspect to evaluate corrosion phenomena under multicomponent chemical load, as during high‐temperature corrosion under deposits and salts. The present study shows a comprehensive analysis of cation diffusion profiles by electron microprobe analysis and microbeam X‐ray absorption near edge structure (µ‐XANES) spectroscopy in mixed oxide/sulfide scales grown on Fe–Cr model alloys after exposing them to 0.5% SO2. The results presented here correspond to depth‐dependent phase identification of oxides and sulfides in the corrosion scales by µ‐XANES and the description of oxidation‐state‐dependent diffusion profiles. Scales grown on low‐ and high‐alloyed materials show both a well‐pronounced diffusion profile with a high concentration of Fe3+ at the gas and a high concentration of Fe2+ at the alloy interface. The distribution of the cations within a close‐packed oxide lattice is strongly influencing the lattice diffusion phenomena due to their different oxidation states and therefore different crystal‐field preference energies. This issue is discussed based on the results obtained by µ‐XANES analysis.
Gypsum (CaSO4∙2H2O) and anhydrite (CaSO4) are among the dominant evaporite minerals in the Atacama Desert [1]. They are distributed ubiquitously, and play a key role in local landscape evolution.
The formation mechanism of especially anhydrite has been a matter of scientific debate for more than a century [2]. To date, there exists no model that can reliably predict anhydrite formation at earth’s surface conditions. While thermodynamics favor its formation [3], it is hardly achieved on laboratory time scales at conditions fitting the Atacama Desert. Long induction times for nucleation have recently been modeled by Ossorio et al. [4]. However, anhydrite can be readily found in the Atacama Desert. Recently, the mineral was synthesized in flow-through reactors as a byproduct of K-jarosite dissolution at high water activity (aw=0.98) and room temperature [5], even-though the thermodynamic stability field begins only under a value of ~0.8. Additionally, recent studies investigated the nano-structure of various calcium-sulfates, which advocate for highly non-classical crystallization behavior [6]. The specific roles of particulates, ionic or organic reagents working as catalysts for the non-classical crystallization pathway remain to be determined.
Here, we present recent results from flow-through experiments as well as analyses of anhydrite samples from the Atacama Desert. Flow-through experiments were performed to systematically explore the domains of flow rate, composition, ionic-strengths and starting materials. Neither primary, nor secondary anhydrite was produced in any of these experiments. Analyses on Atacama samples reveal the existence of at least three distinct anhydrite facies, with differing mineralogy and micro- to nano-structures. The facies are (1) aeolian deposits with sub-µm grain sizes, (2) (sub-)surface nodules that formed from aeolian deposits and (3) selenites with secondary anhydrite rims. Possible mechanisms of their formation will be discussed.
Gypsum (CaSO4∙2H2O), bassanite (CaSO4∙0.5H2O), and anhydrite (CaSO4) are essential evaporite minerals for the evolution of hyper-arid surface environments on Earth and Mars (Voigt et al. 2019; Vaniman et al. 2018). The formation mechanism of especially anhydrite has been a matter of scientific debate for more than a century (van’t Hoff et al. 1903). To date, there exists no model that can reliably predict anhydrite formation at earth’s surface conditions. While thermodynamics favor its formation, it is hardly achieved on laboratory time scales at conditions fitting either the Atacama Desert on Earth, or the surface of Mars (Wehmann et al. 2023). In light of most recent developments (e.g. Stawski et al. 2016), that advocate for a complex, non-classical nucleation mechanism for all calcium sulphates, we present an analysis of natural samples from the Atacama Desert to identify key features that promote the nucleation and growth of anhydrite under planetary surface conditions. Our analyses reveal at least three distinct anhydrite facies, with differing mineralogy and micro- to nano-structures. The facies are (1) aeolian deposits with sub-μm grain sizes, (2) (sub-)surface nodules that formed from aeolian deposits and (3) selenites with secondary anhydrite rims. Possible mechanisms of their formation will be discussed.
Several studies have been shown that the electron beam can be used to create nanomaterials from microparticle targets in situ in a transmission electron microscope (TEM). Here, we show how this method has to be modified in order to synthesize plasmonic gold nanoparticles (NPs) on insulating silicon oxide substrate by employing a scanning electron microscope with a comparatively low acceleration voltage of 30 kV. The synthesized NPs exhibit a random distribution around the initial microparticle target: Their average size reduces from 150 nm to 3 nm with growing distance to the initial Au microparticle target. Similarly, their average distance increases. The synthesized NP assemblies therefore show distinctly different plasmonic behaviour with growing distance to the target, which allows to study consequences of random hybridization of surface plasmon in disordered system, such as Anderson localization. To reveal the surface plasmons and their localization behaviour we apply electron energy loss spectroscopy in the TEM.
Several studies have shown that the electron beam (e-beam) can be used to create nanomaterials from microparticles in situ in a TEM. However, attempts to produce gold nanoparticles (NPs) on silicon oxide substrate remained to be accomplished. Here, we show that the production of gold NPs is possible by using the e-beam in a SEM, under a set of parameters. The NPs produced present a size gradient along the radial direction. A parameter study shows that the microparticles may: 1) flicker away without producing NPs, 2) fragment to form NPs and/or 3) react with the silicon oxide substrate, depending on the applied current. A hypothesis regarding the driving physical phenomena that lead the microparticles to fragment into NPs is discussed. Fabrication of gold NPs in the SEM provides a more cost-effective option as compared to the established method in the TEM.
1. Introduction
A normally unwanted process that can arise when converging an electron beam onto, e.g. microparticles, has been called "damage induced by electric field" (DIEF) [1]. By DIEF, the convergent electron beam (CEB) imparts a high amount of energy to the microparticle locally and strongly interacts with its atoms. At a specific current density J, which can be controlled by the convergence angle α, the irradiated material begins to transform. The phenomenon of expelling nanomaterial from microparticles under the influence of a convergent electron beam (CB) in a transmission electron microscope (TEM) has been largely studied [2]. Several types of nanoparticles (NPs) have been observed for different metallic materials and metal oxides after specific CB protocols (P) in the TEM. Thus, DIEF can be used as a promising synthesis method controlled changes of micrometric material to create new nanometric material compositions and morphologies.
While these reactions have been observed in situ at the high acceleration voltages associated with TEM, it remains unclear whether the SEM can also be used to fabricate NPs via DIEF. In contrast to TEM there is no possibility to statically convert the electron beam to a range of α to reach the needed J as in TEM. Instead, the scanning parameters and the magnification can be manipulated so as to find an integrated J. Considering that the scanning electron microscope (SEM) is easier to use, more accessible and cheaper than a TEM, here we explore the possibility to transfer the concepts of DIEF known to operate in the TEM for in situ NP generation SEM.
2. Objectives
The main goal is to determine whether DIEF can be translated to the SEM perform to controlled in situ fabrication of nanoparticles from microparticles, using gold microparticles on amorphous SiO substrate as precursors. We determine what experimental parameters must be taken into account to create SEM-based CBPs for NP creation in the SEM with these materials.
3. Materials & methods
Gold microparticles with diameter of around 1 to 3 µm were deposited on electron transparent amorphous SiO/SiO2 substrate. Using a convergent electron beam protocol (CBP) in a scanning electron microscope (SEM) at an acceleration voltage of 30 kV, the gold microparticles were irradiated until a production of NPs takes place as shown in figure 1. The beam current varied between 16 and 23 nA.
4. Results
Depending on the CBP parameters, either only Au NPs or a mixture of Au and Si NPs are produced. The particle size ranges from a few nm up to 100 nm, and it depends on the distance of the NP to the initial position of the microparticle. Further beam parameters such as the dwell time, the effective irradiated volume and particle size determine whether NPs are produced or if the microparticles only are expelled from the substrate without reacting.
5. Conclusion
The SEM can be used as an instrument for synthesizing nanomaterials via DIEF. Different CBP protocols can be applied for obtaining either gold nanoparticles or silicon + gold nanoparticles
Several studies have shown that the electron beam (e-beam) can be used to create nanomaterials from microparticles in situ in a TEM. However, attempts to produce gold nanoparticles (NPs) on silicon oxide substrate remained to be accomplished. Here, we show that the production of gold NPs is possible by using the e-beam in a SEM, under a set of parameters. To understand the physical mechanisms leading to the gold NPs, the mechanisms of e-beam induced charging as well as e-beam induced heating of the MPs were discussed. Several hints point to heating as the driving mechanism.
The phenomenon of expelling nanomaterial from microparticles of different materials, such as Au, WO3 or B2O3 under the influence of a convergent electron beam (CB) of a transmission electron microscope (TEM) was reviewed by Ignacio Gonzalez-Martinez [1]. Converging the e-beam in a TEM means that a high amount of energy enters the microparticle at a very local place and interact with the matter. Obviously, during the convergent beam protocol, no imaging with the electron beam is possible, but at the end, nanoparticles with different appearances lie down next to the microparticle while its size is reduced.
Hence, there is a blind spot in the observation, which we want to fill, as we want to help clarify the nature of the expelling phenomenon. One hypothesis that explains the phenomenon is the so-called damage (of the microparticle) induced by an electric field (DIEF). Within this theory, the material is ionized and expelled in form of ionic waves. Our aim is therefore to fabricate specimens with artificial microlandscapes, as schematically exemplified in figure 1a), using the focused ion beam (FIB) and micromanipulators, as experimental setups to follow the paths of the expelled material.
As a first step towards the fabrication of such specimen, we make experimental feasibility studies for each fabrication method, FIB structuring with Ga+ ion beam and micromanipulated microparticle deposition. Bridges (gray regions in Fig. 1) are created by milling a commercially available electron transparent membrane (silicon oxide or carbon) of a Cu-TEM grid. Platinum or carbon walls (blue features in Fig. 1) are built to stand on those bridges. Microparticles (yellow sphere in Fig. 1) of gold or other material are deposited in the center of the bridges.
Figure 2a) shows four square holes (black area) and between them the residual silicon oxide membrane bridges (dark grey). On top of the bridges, walls (light grey) are deposited. The width of the bridges is different, the walls overlap the holes as well as the distance between the walls is very small, so these and other parameters need to be optimized. Figure 2b) shows a square hole (black) with bridges (white) on the right side on top of a carbon membrane (grey). There are still some obstacles which needs to be eliminated. For instance, the deposition process of the walls is not reliable as visible at the wall on top where a hole arises instead of a wall.
These studies are still in progress and the results are further discussed in terms of the applicability for the DIEF experiment in the TEM.
Damage induced by electric field (DIEF) that happens in the transmission electron microscope (TEM) when converging the electron beam (e-beam) on microparticles (MPs) can be used to synthesis new nanomaterial and nanomaterial compositions. The research questions are to clarify the limits and possibilities of the method regarding materials that can be produced, systems to which it is applicable and working beam parameters. Synthesis of nano-objects from microparticles using DIEF in TEM could be shown for different materials. Additionally, DIEF using the e-beam in a scanning electron microscope (SEM) can also be used to synthesis nano-objects. A deeper material analysis of this nano-objects was done using TEM and shows that the material of the nanoparticles (NPs) can be gold or/and silicon. Furthermore, the size of the NPs depends on the distance to the center of DIEF whereby the larger NPs are closer to the center. The areas of gold NPs are promising candidates for plasmonic or photonic devices for energy storage or transport.
Fracture mechanics is a key to fatigue assessment in AM metal components. Short fatigue cracks are initiated at defects and pronounced surface roughness intrinsic to AM. The subsequent crack-propagation is strongly influenced by microstructural interactions and the build-up of crack-closure. The aim of the present study is to give an insight into short-crack propagation in AM-metals. Fatigue crack propagation resistance curves were determined experimentally for AISI 316L manufactured by Laser Powder Bed Fusion (L-PBF) which was heat treated at three different temperatures. Differences in the build-up of the fatigue-crack propagation threshold in between the L-PBF specimens and compared to wrought material are due to the residual stress states, a pronounced roughness of the crack-faces in the L-PBF specimens and phase transformation in the vicinity of the crack-tip, resulting in increased crack-closure. This, together with crack-branching found along the crack path, enhances the resistance to the propagation of fatigue cracks.
Diese Untersuchung beschäftigt sich mit der Charakterisierung von Kurzrisswachstum in mittels Laser-Pulverbett-Verschmelzen (LPBF - Laser Powder Bed Fusion) hergestelltem rostfreien austenitischen Stahl. Spezifischer wird die Ermittlung zyklischer R-Kurven untersucht. Diese beschreiben den Aufbau des Widerstands gegen Ermüdungsrisswachstum - d.h. des Schwellenwertes - aufgrund von Rissschließeffekten bei physikalisch kurzen Rissen. Mit Hilfe der zyklischen R-Kurven kann die Fähigkeit eines Bauteils, physikalisch kurze Risse zu arretieren, charakterisiert werden. Wir verfügen damit über eine Schnittstelle zwischen klassischer Ermüdung und Bruchmechanik. Das ist gerade auch für additiv gefertigte (AM – Additive Manufacturing) Materialien von Interesse. Diese weisen prozessintrinsische Defekte auf, die als Initiierungsstellen kurzer Ermüdungsrisse agieren. Im Rahmen der experimentellen Untersuchungen wurden zyklische R-Kurven für konventionellen und LPBF AISI-316L-Stahl ermittelt. Insbesondere wurde der Einfluss verschiedener Wärmebehandlungen (WB1: 450°C, WB2: 800°C und WB3: 900°C) auf das Wachstumsverhalten physikalisch kurzer Risse im LPBF-Material untersucht. Aufgrund hoher Eigenspannungen war die Ermittlung des Kurzrisswachstumsverhaltens bei WB1 nicht möglich. Für WB2 und WB3 ergaben sich sehr unterschiedliche zyklische R-Kurven. Untersuchungen der Eigenspannungen, der Bruchfläche (insbesondere der Rauheit) und der Mikrostruktur sollen die Ursachen für das unterschiedliche Verhalten erklären. Die Ergebnisse werden mit den Verhältnissen in konventionellem Material verglichen.
Additively Manufactured (AM) parts are still far from being used in safety-relevant applications, mainly due to a lack of understanding of the feedstock-process-propertiesperformance relationship. This work aims at providing a characterization of the fatigue behavior of the additively manufactured AISI 316L austenitic stainless steel and a direct comparison with the fatigue performance of the wrought steel. A set of specimens has been produced by laser powder bed fusion (L-PBF) and a second set of specimens has been machined out of hot-rolled plates. The L-PBF material shows a higher fatigue limit and better finite life performance compared to the wrought material, accompanied by an extensive amount of cyclic softening.
Das zyklische plastische Verformungsverhalten von additiv gefertigtem Edelstahl AISI 316L wurde in dehnungsgeregelten Kurzzeitfestigkeitsversuchen (LCF-Versuchen) untersucht. Dabei wurden zwei Wärmebehandlungszustände betrachtet: Beim ersten Zustand war die fertigungsbedingte zelluläre Struktur vorhanden, während sie durch die zweite Wärmebehandlung aufgelöst wurde. Untersuchungen im Transmissions-Elektronen-Mikroskop (TEM) zeigten, dass die zyklische Verformung die Zellstruktur lokal zerstörte und Gleitbänder entstanden, was die Entfestigung in diesem Fall erklärt. Für Material ohne Zellstrukturen resultierten nach zyklischer Verformung ähnliche Versetzungsstrukturen wie in konventionell gefertigtem (warmgewalzten) Material.
Lithium-ion batteries (LIBs) are one technology to overcome the challenges of climate and energy crisis. They are widely used in electric vehicles, consumer electronics, or as storage for renewable energy sources. However, despite innovations in batteries' components like cathode and anode materials, separators, and electrolytes, the aging mechanism related to metallic aluminum current collector degradation causes a significant drop in their performance and prevents the durable use of LIBs. Glow-discharge optical emission spectroscopy (GD-OES) is a powerful method for depth-profiling of batteries' electrode materials. This work investigates aging-induced aluminum deposition on commercial lithium cobalt oxide (LCO) batteries' cathodes. The results illustrate the depth-resolved elemental distribution from the cathode surface to the current collector. An accumulation of aluminum is found on the cathode surface by GD-OES, consistent with results from energy-dispersive X-ray spectroscopy (EDX) combined with focused ion beam (FIB) cutting. In comparison to FIB-EDX, GD-OES allows a fast and manageable depth-profiling. Results from different positions on an aged cathode indicate an inhomogeneous aluminum film growth on the surface. The conclusions from these experiments can lead to a better understanding of the degradation of the aluminum current collector, thus leading to higher lifetimes of LIBs.
Investigation of degradation of the aluminum current collector in lithium-ion batteries by GD-OES
(2022)
Lithium-ion batteries (LIBs) are one technology to overcome the challenges of climate and energy crisis. They are widely used in electric vehicles, consumer electronics, or as storage for renewable energy sources. However, despite innovations in batteries' components like cathode and anode materials, separators, and electrolytes, the aging mechanism related to metallic aluminum current collector degradation causes a significant drop in their performance and prevents the durable use of LIBs. Glow-discharge optical emission spectroscopy (GD-OES) is a powerful method for depth-profiling of batteries' electrode materials. This work investigates aging-induced aluminum deposition on commercial lithium cobalt oxide (LCO) batteries' cathodes. The results illustrate the depth-resolved elemental distribution from the cathode surface to the current collector. An accumulation of aluminum is found on the cathode surface by GD-OES, consistent with results from energy-dispersive X-ray spectroscopy (EDX) combined with focused ion beam (FIB) cutting. In comparison to FIB-EDX, GD-OES allows a fast and manageable depth-profiling. Results from different positions on an aged cathode indicate an inhomogeneous aluminum film growth on the surface. The conclusions from these experiments can lead to a better understanding of the degradation of the aluminum current collector, thus leading to higher lifetimes of LIBs.
Introduction
Lithium-ion batteries (LIBs) are one key technology to overcome the climate crisis and energy transition challenges. Demands of electric vehicles on higher capacity and power drives research on innovative cathode and anode materials. These high energy-density LIBs are operated at higher voltages, leading to increased electrolyte decay and the current collectors' degradation. Even though this fundamental corrosion process significantly affects battery performance, insufficient research is being done on the aluminum current collector. Fast and convenient analytical methods are needed for monitoring the aging processes in LIBs.
Methods
In this work glow-discharge optical emission spectrometry (GD-OES) was used for depth profile analysis of aged cathode material. The measurements were performed in pulsed radio frequency mode. Under soft and controlled plasma conditions, high-resolution local determination (in depth) of the elemental composition is possible. Scanning electron microscopy (SEM) combined with a focused ion beam (FIB) cutting and energy dispersive X-ray spectroscopy (EDX) was used to confirm GD-OES results and obtain additional information on elemental distribution.
Results
The aging of coin cells manufactured with different cathode materials (LCO, LMO, NMC111, NMC424, NMC532, NMC622, and NMC811) was studied. GD-OES depth profiling of new and aged cathode materials was performed. Quantitative analysis was possible through calibration with synthetic standards and correction by sputter rate. Different amounts of aluminum deposit on the cathode surface were found for different materials. The deposit has its origin in the corrosion of the aluminum current collector. The results are compatible with results from FIB-EDX. However, GD-OES is a faster and less laborious analytical method. Therefore, it will accelerate research on corrosion processes in high energy-density batteries.
Innovative aspects
- Quantitative depth profiling of cathode material
-Monitoring of corrosion processes in high energy-density lithium-ion batteries
- Systematic investigation of the influence of different cathode materials
Lithium-ion batteries (LIBs) are one technology to overcome the challenges of climate and energy crisis. They are widely used in electric vehicles, consumer electronics, or as storage for renewable energy sources. However, despite innovations in batteries' components like cathode and anode materials, separators, and electrolytes, the aging mechanism related to metallic aluminum current collector degradation causes a significant drop in their performance and prevents the durable use of LIBs.[1] Glow-discharge optical emission spectroscopy (GD-OES) is a powerful method for depth-profiling of batteries' electrode materials. This work investigates aging-induced aluminum deposition on commercial lithium cobalt oxide (LCO) batteries' cathodes. The results illustrate the depth-resolved elemental distribution from the cathode surface to the current collector. An accumulation of aluminum is found on the cathode surface by GD-OES, consistent with results from energy-dispersive X-ray spectroscopy (EDX) combined with focused ion beam (FIB) cutting. In comparison to FIB-EDX, GD-OES allows a fast and manageable depth-profiling. Results from different positions on an aged cathode indicate an inhomogeneous aluminum film growth on the surface. The conclusions from these experiments can lead to a better understanding of the degradation of the aluminum current collector, thus leading to higher lifetimes of LIBs.