5 Werkstofftechnik
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High-entropy alloys (HEAs) and compositionally complex alloys (CCAs) represent new classes of materials containing five or more alloying elements (concentration of each element ranging from 5 to 35 at. %). In the present study, HEAs are defined as single-phase solid solutions; CCAs contain at least two phases. The alloy concept of HEAs/CCAs is fundamentally different from most conventional alloys and promises interesting properties for industrial applications (e.g., to overcome the strength-ductility trade-off). To date, little attention has been paid to the weldability of HEAs/CCAs encompassing effects on the welding metallurgy. It remains open whether welding of HEAs/CCAs may lead to the formation of brittle intermetallics and promote elemental segregation at crystalline defects. The effect on the weld joint properties (strength, corrosion resistance) must be investigated. The weld metal and heat-affected zone in conventional alloys are characterized by non-equilibrium microstructural evolutions that most probably occur in HEAs/CCAs. The corresponding weldability has not yet been studied in detail in the literature, and the existing information is not documented in a comprehensive way. Therefore, this study summarizes the most important results on the welding of HEAs/CCAs and their weld joint properties, classified by HEA/CCA type (focused on CoCrFeMnNi and AlxCoCrCuyFeNi system) and welding process.
This work investigates the effect of the tribotesting parameters (temperature, atmosphere, and third body chemical composition) on the coefficient of friction (CoF) during pin-on-disc dry (PoD) sliding tribotests using artificial third bodies. The third body comprised nanometric Fe3O4-based binary to quaternary chemical compositions containing copper, graphite, and zirconia. These mixtures were manually or ball-milled prepared, and pin-on-disc tribotests were conducted at 23 °C and 400 °C under air or nitrogen atmospheres. Combining PoD and artificial third body to create synthetic tribofilms might be useful for testing new formulations of Cu-free friction materials. Microstructural characterisation of the tribofilms was used to study the stability of the Fe3O4, copper, and graphite nanoparticles under different testing conditions to understand their effects on the CoF. For the Fe3O4-C-ZrO2-X systems, the ball milling mixing promoted the formation of turbostratic graphite in the tribofilm, impairing the lubricating effect of the graphite under air atmosphere at 23 °C. The formation of monoclinic CuO in the tribofilms during tribotests at 400 °C under air and N2 atmospheres promoted a lubricating effect.
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.
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.
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.
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.
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.
The manufacturability of metallic alloys using laser-based additive manufacturing methods such as laser powder bed fusion has substantially improved within the last decade. However, local melting and solidification cause hierarchically structured and crystallographically textured microstructures possessing large residual stress. Such microstructures are not only the origin of mechanical anisotropy but also pose metrological challenges for the diffraction-based residual stress determination. Here we demonstrate the influence of the build orientation and the texture on the microstructure and consequently the mechanical anisotropy of as-built Inconel 718. For this purpose, we manufactured specimens with [001]/[011]-, [001]- and [011]/[111]-type textures along their loading direction. In addition to changes in the Young’s moduli, the differences in the crystallographic textures result in variations of the yield and ultimate tensile strengths. With this in mind, we studied the anisotropy on the micromechanical scale by subjecting the specimens to tensile loads along the different texture directions during in situ neutron diffraction experiments. In this context, the response of multiple lattice planes up to a tensile strain of 10% displayed differences in the load partitioning and the residual strain accumulation for the specimen with [011]/[111]-type texture. However, the relative behavior of the specimens possessing an [001]/[011]- and [001]-type texture remained qualitatively similar. The consequences on the metrology of residual stress determination methods are discussed.
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.
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.
Signal optimization for transmission Kikuchi diffraction (TKD) measurements in the scanning electron microscope is investigated by a comparison of different sample holder designs. An optimized design is presented, which uses a metal shield to efficiently trap the electron beam after transmission through the sample. For comparison, a second holder configuration allows a significant number of the transmitted electrons to scatter back from the surface of the sample holder onto the diffraction camera screen. It is shown that the secondary interaction with the sample holder leads to a significant increase in the background level, as well as to additional noise in the final Kikuchi diffraction signal. The clean TKD signal of the optimized holder design with reduced background scattering makes it possible to use small signal changes in the range of 2% of the camera full dynamic range. As is shown by an analysis of the power spectrum, the signal-to-noise ratio in the processed Kikuchi diffraction patterns is improved by an order of magnitude. As a result, the optimized design allows an increase in pattern signal to noise ratio which may lead to increase in measurement speed and indexing reliability.
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.
This study reports on the stress relaxation potential of stress-relieving heat treatments for laser powder bed fused 316L. The residual stress is monitored non-destructively using neutron diffraction before and after the heat treatment. Moreover, the evolution of the microstructure is analysed using scanning electron microscopy. The results show, that a strong relaxation of the residual stress is obtained when applying a heat treatment temperature at 900°C. However, the loss of the cellular substructure needs to be considered when applying this heat treatment strategy.
To set up recommendations on how to define “reasonable minimum composition thresholds” for CO2 streams to access CO2 pipeline networks, we investigated potential impacts of CO2 streams with different and temporally variable compositions and mass flow rates along the CCS chain. All investigations were based on a generic “CCS cluster scenario” in which CO2 streams captured from a spatial cluster of eleven emitters (seven fossil-fired power plants, two cement plants, one refinery and one steel mill) are collected in a regional pipeline network. The resulting CO2 stream (19.78 Mio t impure CO2 per year) is transported in a trunk line (onshore and offshore) and injected into five generic replicate storage structures (Buntsandstein saline aquifers) offshore. Experimental investigations and modeling of selected impacts revealed beneficial as well as adverse impacts of different impurities and their combinations. Overall, no fundamental technical obstacles for transporting, injecting and storing CO2 streams of the considered variable compositions and mass flow rates were observed. We recommend to define minimum composition thresholds for each specific CCS project through limiting
i) the overall CO2 content,
ii) maximum contents of relevant impurities or elements,
iii) acceptable variability of concentrations of critical impurities, and defining impurity combinations to be avoided.
A great amount of material properties is strongly influenced by dislocations, the carriers of plastic deformation. It is therefore paramount to have appropriate tools to quantify dislocation substructures with regard to their features, e.g., dislocation density, Burgers vectors or line direction. While the transmission electron microscope (TEM) has been the most widely-used equipment implemented to investigate dislocations, it usually is limited to the two-dimensional (2D) observation of three-dimensional (3D) structures. We reconstruct, visualize and quantify 3D dislocation substructure models from only two TEM images (stereo pairs) and assess the results. The reconstruction is based on the manual interactive tracing of filiform objects on both images of the stereo pair. The reconstruction and quantification method are demonstrated on dark field (DF) scanning (S)TEM micrographs of dislocation substructures imaged under diffraction contrast conditions. For this purpose, thick regions (> 300 nm) of TEM foils are analyzed, which are extracted from a Ni-base superalloy single crystal after high temperature creep deformation. It is shown how the method allows 3D quantification from stereo pairs in a wide range of tilt conditions, achieving line length and orientation uncertainties of 3% and 7°, respectively. Parameters that affect the quality of such reconstructions are discussed.
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.
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 .
The effect of two types of scanning strategies on the grain structure and build-up of Residual Stress (RS) has been investigated in an as-built IN718 alloy produced by Laser Powder Bed Fusion (LPBF). The RS state has been investigated by X-ray diffraction techniques. The microstructural characterization was performed principally by Electron Backscatter Diffraction (EBSD), where the application of a post-measurement refinement technique enables small misorientations (< 2°) to be resolved. Kernel average misorientation (KAM) distributions indicate that preferably oriented columnar grains contain higher levels of misorientation, when compared to elongated grains with lower texture. The KAM distributions combined with X-ray diffraction stress maps infer that the increased misorientation is induced via plastic deformation driven by the thermal stresses, acting to self-relieve stress. The possibility of obtaining lower RS states in the build direction as a consequence of the influence of the microstructure should be considered when envisaging scanning strategies aimed at the mitigation of RS.
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.
The impact of the microstructure of Fe-16Cr-0.2C on high-temperature oxidation – sulphidation in SO2
(2021)
This study elucidates the impact of the microstructure of Fe-16Cr-0.2C on oxide layer formation at 650 ◦C in Ar-0.5 % SO2. A cold-rolled and two heat-treated states of the alloy were exposed for up to 1000 h. The samples were characterised in detail from microstructural and chemical perspectives using scanning electron microscopy (SEM), X-ray diffraction (XRD) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The microstructural modification of the alloy by heat-treatment was advantageous. It was found that Cr-carbides support chromia formation and reduce sulphidation when their area fraction is low and diameter is small.
The unusual behavior observed in the coefficient of thermal expansion and specific heat capacity of CrFeNi, CoCrNi, and CoCrFeNi medium/high-entropy alloys is commonly referred to as the K-state effect. It is shown to be independent of the Curie temperature, as demonstrated by temperature-dependent magnetic moment measurements. CoCrFeNi alloy is chosen for detailed characterization; potential reasons for the K-state effect such as texture, recrystallization, and second-phase precipitation are ruled out. An examination of the electronic structure indicates the formation of a pseudo-gap in the Density of States, which suggests a specific chemical interaction between Ni and Cr atoms upon alloying. Hybrid Monte Carlo/Molecular Dynamic (MC/MD) simulations indicate the presence of non-negligible chemical short-range order (CSRO). Local lattice distortions are shown to be negligible, although deviations around Cr and Ni elements from those expected in a fully disordered structure are experimentally observed by X-ray absorption spectroscopy. The determined bonding distances are in good agreement with MC/MD calculations. A mechanism is proposed to explain the anomalies and calorimetric experiments and their results are used to validate the mechanism.
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.
Detailed microstructural characterization of the AlMo0.5NbTa0.5TiZr refractory high entropy superalloy in the as-cast state is reported for first time and compared with the state annealed at 1400 oC for 24 h. The former shows a dendritic structure, with a mixture of A2/B2 phases < 20 nm in both the dendritic and interdendritic regions. A mostly amorphous phase, rich in Al and Zr, is found within the interdendritic region. The annealed state reproduced the combination of A2/B2/Al-Zr-rich phases reported previously. Calculations from two relevant ThermoCalc databases were compared with the experimental results. Equilibrium calculations were compared with results for the annealed alloy, whereas solidification paths calculated using Scheil-Gulliver model were used for comparison with the as-cast alloy. A previously hypothesized spinodal decomposition during cooling as the mechanism responsible for the patterned A2/B2 microstructure is confirmed via the CALPHAD calculations, pointing to its use as an efficient design tool for such alloys. Finally, the comparison between the experimental and computational findings allowed better understanding the solidification path and equilibrium stability of this alloy, giving a base to make better decisions on the field of new refractory superalloy design.
Although layer-based additive manufacturing methods such as laser powder bed fusion (PBF-LB) offer an immense geometrical freedom in design, they are typically subject to a build-up of internal stress (i.e. thermal stress) during manufacturing. As a consequence, significant residual stress (RS) is retained in the final part as a footprint of these internal stresses. Furthermore, localized melting and solidification inherently induce columnar-type grain growth accompanied by crystallographic texture. Although diffraction-based methods are commonly used to determine the RS distribution in PBF-LB parts, such features pose metrological challenges in their application. In theory, preferred grain orientation invalidates the hypothesis of isotropic material behavior underlying the common methods to determine RS. In this work, more refined methods are employed to determine RS in PBF-LB/M/IN718 prisms, based on crystallographic texture data. In fact, the employment of direction-dependent elastic constants (i.e. stress factors) for the calculation of RS results in insignificant differences from conventional approaches based on the hypothesis of isotropic mechanical properties. It can be concluded that this result is directly linked to the fact that the {311} lattice planes typically used for RS analysis in nickel-based alloys have high multiplicity and less strong texture intensities compared with other lattice planes. It is also found that the length of the laser scan vectors determines the surface RS distribution in prisms prior to their removal from the baseplate. On removal from the baseplate the surface RS considerably relaxes and/or redistributes; a combination of the geometry and the scanning strategy dictates the sub-surface RS distribution.
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.
This study investigates the room‐ and high‐temperature (650 °C) tensile and low‐cycle‐fatigue behavior of Inconel 718 produced by laser powder bed fusion (PBF‐LB/M) with a four‐step heat treatment and compares the results to the conventional wrought material. The microstructure after heat treatment is characterized on different length scales. Compared to the wrought variant, the elastic and yield properties are comparable at both test temperatures while tensile strength, ductility, and strain hardening capacity are lower. The fatigue life of the PBF‐LB/M variant at room temperature is slightly lower than that of the wrought material, while at 650 °C, it is vice versa. The cyclic stress response for both material variants is characterized by cyclic softening, which is more pronounced at the higher test temperature. High strain amplitudes (≥0.7%) at room temperature and especially a high testing temperature result in the formation of multiple secondary cracks at the transitions of regions comprising predominantly elongated grain morphology and columns of stacked grains with ripple patterns in the PBF‐LB/M material. This observation and pronounced crack branching and deflection indicate that the cracks are controlled by sharp micromechanical gradients and local crystallite clusters.
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.
The main difference between high entropy alloys and conventional alloys is the solid solution strengthening effect, which shifts from a single element to a multi-element matrix. Little is known about the effectiveness of this effect at high temperatures. Face-centered cubic, equiatomic, and single crystalline high entropy alloy CrMnFeCoNi was pre-alloyed by arc-melting and cast as a single Crystal using the Bridgman process. Mechanical characterization by creep testing were performed at temperatures of 700, 980, 1100, and 1200°C at different loads under vacuum and compared to single-crystalline pure nickel. The results allow a direct assessment of the influence of the chemical composition without any disturbance by grain boundary sliding or diffusion. The results indicate different behaviors of single crystalline pure nickel and CrMnFeCoNi. At 700°C CrMnFeCoNi is more creep-resistant than Ni, but at 980°C both alloys show a nearly similar creep strength. Above 980°C the creep behavior is identical and the solid solution strengthening effect of the CrMnFeCoNi alloy disappears.
Kirkendall porosity that forms during interdiffusion in a diffusion couple of nickel-base superalloy CMSX-10 with pure nickel is investigated. The diffusion experiments are conducted at a temperature of 1250 °C, where the strengthening ƴ'-phase ist partially dissolved. The porosity is studied by X-ray sub-μ tomography with a spatial resolution of about 0.35³ μm³ at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. It is found that depending on the distance from the interface the Kirkendall pores take different shapes: octahedral, rounded pyramidal, drop shaped, dendritic, pear shaped, and joint shapes. Such a variety of pore morphologies indicates a complex multistage process of porosity nucleation and growth under vacancy supersaturation of different degrees. The experimental findings are interpreted on the basis of the results of diffusion modeling. It is shown that the kinetics of porosity growth is essentially influenced by the dissolution of the ƴ'-phase.
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.
Al2O3 has been widely used as a coating in industrial applications due to its excellent chemical and thermal resistance. Considering high temperatures and aggressive mediums exist in geothermal systems, Al2O3 can be a potential coating candidate to protect steels in geothermal applications. In this study, γ-Al2O3 was used as a coating on martensitic steels by applying AlOOH sol followed by a heat treatment at 600 °C. To evaluate the coating application process, one-, two-, and three-layer coatings were tested in the artificial North German Basin (NGB), containing 166 g/L Cl−, at 150 °C and 1 MPa for 168 h. To reveal the stability of the Al2O3 coating in NGB solution, three-layer coatings were used in exposure tests for 24, 168, 672, and 1296 h, followed by surface and cross-section characterization. SEM images show that the Al2O3 coating was stable up to 1296 h of exposure, where the outer layer mostly transformed into boehmite AlOOH with needle-like crystals dominating the surface. Closer analysis of cross-sections showed that the interface between each layer was affected in long-term exposure tests, which caused local delamination after 168 h of exposure. In separate experiments, electrochemical impedance spectroscopy (EIS) was performed at 150 °C to evaluate the changes of coatings within the first 24 h. Results showed that the most significant decrease in the impedance is within 6 h, which can be associated with the electrolyte penetration through the coating, followed by the formation of AlOOH. Here, results of both short-term EIS measurements (up to 24 h) and long-term exposure tests (up to 1296 h) are discussed.
This work presents an X-ray absorption spectroscopy study on a single-phase state of the Al8Cr17Co17Cu8Fe17Ni33 compositionally complex alloy, focused on the local crystal structure around each alloying element. The comparison of 1st shell bond lengths, obtained by the analysis of extended X-ray absorption fine structure (EXAFS) measured at the K-edges of each alloying element, indicates that Al8Cr17Co17Cu8Fe17Ni33 crystallizes in a distorted arrangement of an fcc lattice. A modest bond length dependence of the alloying elements with increasing atomic number is observed, with minima and maxima at Cr/Co, and Al/Cu, respectively. 1st shell bond lengths spread over ~0.03 Å; consequently, such variations cannot result in lattice distortions greater than ~0.04 Å. EXAFS results clearly indicate short-range order in the alloy: pairing of Al with Ni and Cu is favored, correlating well with a g’ precipitate composition (Al-Ni-Cu rich) reported in previous work, while Al-Cr bonding is unfavored and no Al-Al pairs are observed. Electronic structure information was obtained through comparison between near-edge regions of alloying Elements and corresponding pure metals. Intensity comparison of K-edge features agree with a charge variation of p states in Al8Cr17Co17Cu8Fe17Ni33, where Ni and Cu act as p states electron acceptors, suggesting an orbital hybridization with Al, responsible for a shrinkage in Al metallic radius in the alloy by 0.17 Å.
Understanding the interaction between boehmite and epoxy and the formation of their interphases with different mechanical and chemical structures is crucial to predict and optimize the properties of epoxy-boehmite nanocomposites. Probing the interfacial properties with atomic force microscopy (AFM)-based methods, especially particle-matrix long-range interactions, is challenging. This is due to size limitations of various analytical methods in resolving nanoparticles and their interphases, the overlap of interphases, and the effect of buried particles that prevent the accurate interphase property measurement. Here, we develop a layered model system in which the epoxy is cured in contact with a thin layer of hydrothermally synthesized boehmite. Different microscopy methods are employed to evaluate the interfacial properties. With intermodulation atomic force microscopy (ImAFM) and amplitude dependence force spectroscopy (ADFS), which contain information about stiffness, electrostatic, and van der Waals forces, a soft interphase was detected between the epoxy and boehmite. Surface potential maps obtained by scanning Kelvin probe microscopy (SKPM) revealed another interphase about one order of magnitude larger than the mechanical interphase. The AFM-infrared spectroscopy (AFM-IR) technique reveals that the soft interphase consists of unreacted curing agent. The long-range electrical interphase is attributed to the chemical alteration of the bulk epoxy and the formation of new absorption bands.
Rapid cooling rates and steep temperature gradients are characteristic of additively manufactured parts and important factors for the residual stress formation. This study examined the influence of heat accumulation on the distribution of residual stress in two prisms produced by Laser Powder Bed Fusion (LPBF) of austenitic stainless steel 316L. The layers of the prisms were exposed using two different border fill scan strategies: one scanned from the centre to the perimeter and the other from the perimeter to the centre. The goal was to reveal the effect of different heat inputs on samples featuring the same solidification shrinkage. Residual stress was characterised in one plane perpendicular to the building direction at the mid height using Neutron and Lab X-ray diffraction. Thermography data obtained during the build process were analysed in order to correlate the cooling rates and apparent surface temperatures with the residual stress results. Optical microscopy and micro computed tomography were used to correlate defect populations with the residual stress distribution. The two scanning strategies led to residual stress distributions that were typical for additively manufactured components: compressive stresses in the bulk and tensile stresses at the surface. However, due to the different heat accumulation, the maximum residual stress levels differed. We concluded that solidification shrinkage plays a major role in determining the shape of the residual stress distribution, while the temperature gradient mechanism appears to determine the magnitude of peak residual stresses.
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°.
In the current study, the 3D nature of the melt pool boundaries (MPBs) in a 316 L austenitic steel additively manufactured by laser-based powder bed fusion (L-PBF) is investigated. The change of the cell growth direction and its relationship to the MPBs is investigated by transmission electron microscopy. A hitherto unreported modulated substructure with a periodicity of 21 nm is further discovered within the cell cores of the cellular substructure, which results from a partial transformation of the austenite, which is induced by a Ga+ focused ion beam. While the cell cores show the modulated substructure, cell boundaries do not. The diffraction pattern of the modulated substructure is exploited to show a thickness ≥200 nm for the MPB. At MPBs, the cell walls are suppressed, leading to continuously connecting cell cores across the MPB. This continuous MPB is described either as overlapping regions of cells of different growing directions when a new melt pool solidifies or as a narrow planar growth preceding the new melt pool.
Fractography plays a critical role in failure analysis of engineering components and has a considerable importance for safety investigations. Usually, the interpretation of fracture surfaces is done by experts with the help of literature and experimental data, that requires a lot of experience. The use of deep learning (DL) with neural networks in failure analysis becomes more and more relevant with the rapidly developing possibilities. Especially, the modern network architectures can assist fractographers in determining various fracture features on SEM images of the fracture surfaces. The basis for the best possible evaluation is the understanding of the influence of the input data used for training deep neural networks (DNN). Therefore, this study discusses the influence of the selection of the input data used for the prediction quality of these networks in order to take this into account for future data acquisition. Specimens of various metallic materials were subjected to fatigue cracking experiment under laboratory conditions. The fractured surfaces were then imaged using various modes or detectors (such as SE, BSE and topography) in SEM, and those captured images were used to create a training data set. The relevance of the individual data for the quality of the prediction is determined by a specific combination of the different detector data. For the training, the well-established architecture of a UNet-ResNet34 with a fixed set of hyperparameters is used. It has been found in this present study that the combination of all input data significantly increases the prediction accuracy, whereby even the combination of SE and BSE data provides considerable advantages over the exclusive use of SE images.
For the precise determination of orientations in polycrystalline materials, electron backscatter diffraction (EBSD) requires a consistent calibration of the diffraction geometry in the scanning electron microscope (SEM). In the present paper, the variation of the projection center for the Kikuchi diffraction patterns which are measured by EBSD is calibrated using a projective transformation model for the SEM beam scan positions on the sample. Based on a full pattern matching approach between simulated and experimental Kikuchi patterns, individual projection center estimates are determined on a subgrid of the EBSD map, from which least-square fits to affine and projective transformations can be obtained. Reference measurements on single-crystalline silicon are used to quantify the orientation errors which result from different calibration models for the variation of the projection center.
Real-time observation of high- temperature gas corrosion in dry and wet SO2-containing atmosphere
(2019)
Sulfur and water have a fundamental impact on the corrosion rate and potential failure of materials. It is therefore necessary to understand the mechanisms, rates, and potential means of transport, as well as the reactions of these elements with an alloy. This paper investigates the effect of water vapor in the initial stages of SO2 corrosion of an Fe-9Cr-0.5Mn model alloy at 650°C in situ under laboratory conditions using energy-dispersive x-ray diffraction analysis. Two separate experiments were run, one with a 99.5% Ar + 0.5% SO2 atmosphere and one with a 69.5% Ar + 0.5% SO2 + 30% H2O atmosphere. With a wet atmosphere, the alloy formed a scale with decreasing oxygen content towards the scale–alloy interface. Sulfides were identified above and below a (Fe, Cr)3O4 layer in the inner corrosion zone. In contrast to this, the overall scale growth was slower in a dry SO2 atmosphere.
Insights into early damage mechanisms during high-temperature gas corrosion provide important aspects for the prediction of the long-term stability of hightemperature materials exposed to a hot and corrosive environment. The current work presents a real time study concerning the combined oxidation and sulfidation of ferritic model alloys in a hot SO2 containing atmosphere using energy dispersive X-ray diffraction. The applied high temperature reactor allows the transmittance of high energetic X-rays in order to collect X-ray diffraction pattern of the sample surface in situ during the reaction with the reactive environment. The results revealed that the first phases crystallizing on iron with 2 wt% chromium and with 9 wt% chromium are oxides. The aging experiments at T = 650° C with 0.5% SO2 and 99.5% Ar were followed in situ and caused an external mixed oxide-sulfide layer on top of iron with 2 wt% chromium. On the higher alloyed material the external scale consists of iron oxides and the inner scale of mixed (Fe,Cr)-oxides and chromium-sulfides. The oxide content continuously increases parallel to an increase of the sulfide amount. Thus, the initially formed (Fe,Cr)-oxides do not have a protective character and support the transport of sulfur through the growing oxide scale.
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.
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.
The morphology of pores partially shrunk during a half-hour HIP at temperature of 1288 °C and pressure of 103 MPa has been investigated in nickel-based superalloy CMSX-4. The investigation resulted in the following findings: surrounding the shrinking pores by a c¢-shell (Ni3Al), faceting of the pores surface by {023} and {011} planes, and formation the submicroscopic satellite pores connected by channels with the neighboring larger pores. It is assumed that the formation of the c¢-shell around the pores and the faceting of the pore surface is due to diffusion processes occurring during pore shrinkage, and therefore these findings can be considered as arguments supporting the vacancy model of pore annihilation. The submicroscopic satellite pores are expected to be the result of dividing the casting pores of a complex initial shape during their shrinking. The connecting channels are probably required for the gas to escape from the rapidly shrinking small satellite pores into the slowly shrinking large pore. Thus, it is reasonable to assume that the casting pores may contain some amount of gas.
On the influence of crystallography on creep of circular notched single crystal superalloy specimens
(2020)
The present work contributes to a better understanding of the effect of stress multiaxiality on the creep behavior of single crystal Ni-base superalloys. For this purpose we studied the creep deformation and rupture behavior of double notched miniature creep tensile specimens loaded in three crystallographic directions [100], [110] and [111] (creep conditions: 950 °C and 400 MPa net section stress). Crystal plasticity finite element method (CPFEM) was used to analyze the creep stress and strain distributions during creep. Double notched specimens have the advantage that when one notch fails, the other is still intact and allows to study a material state which is close to rupture. No notch root cracking was observed, while microstructural damage (pores and micro cracks) were frequently observed in the center of the notch root region. This is in agreement with the FEM results (high axial stress and high hydrostatic stress in the center of the notched specimen). Twinning was observed in the notch regions of [110] and [111] specimens, and <112> {111} twins were detected and analyzed using orientation imaging scanning electron microscopy. The present work shows that high lattice rotations can be detected in SXs after creep fracture, but they are associated with the high strains accumulated in the final rupture event.
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.
The determination of residual stresses becomes more complicated with increasing complexity of the structures investigated. Additive manufacturing techniques generally allow the production of ‘lattice structures’ without any additional manufacturing step. These lattice structures consist of thin struts and are thus susceptible to internal stress-induced distortion and even cracks. In most cases, internal stresses remain locked in the structures as residual stress.
The determination of the residual stress in lattice structures through nondestructive neutron diffraction is described in this work. It is shown how two difficulties can be overcome: (a) the correct alignment of the lattice structures within the neutron beam and (b) the correct determination of the residual stress field in a representative part of the structure. The magnitude and the direction of residual stress are discussed. The residual stress in the strut was found to be uniaxial and to follow the orientation of the strut, while the residual stress in the knots was more hydrostatic. Additionally, it is shown that strain measurements in at least seven independent directions are necessary for the estimation of the principal stress directions. The measurement directions should be chosen according to the sample geometry and an informed choice on the possible strain field. If the most prominent direction is not measured, the error in the calculated stress magnitude increases considerably.
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.
Shear testing can contribute to a better understanding of the plastic deformation of Ni-base superalloy single crystals. In the present study, shear testing is discussed with special emphasis placed on its strengths and weaknesses. Key mechanical and microstructural results which were obtained for the high-temperature (T ≈ 1000 °C) and low-stress (τ ≈ 200 MPa) creep regime are briefly reviewed. New 3D stereo STEM images of dislocation substructures which form during shear creep deformation in this regime are presented. It is then shown which new aspects need to be considered when performing double shear creep testing at lower temperatures (T < 800 °C) and higher stresses (τ > 600 MPa). In this creep regime, the macroscopic crystallographic [11−2](111) shear system deforms significantly faster than the [01−1](111) system. This represents direct mechanical evidence for a new planar fault nucleation scenario, which was recently suggested (Wu et al. in Acta Mater 144:642–655, 2018). The double shear creep specimen geometry inspired a micro-mechanical in-situ shear test specimen. Moreover, the in-situ SEM shear specimen can be FIB micro-machined from prior dendritic and interdendritic regions. Dendritic regions, which have a lower γ′ volume fraction, show a lower critical resolved shear stress.
To increase efficiency, modern steam plants are pushing their operational regime from super-critical (600 °C/300 bar) to ultra-super-critical (740/760 °C/350 bar) stretching existing turbine materials to their limits. The focus is on new generation functional materials and technologies which complement the inherent properties of existing materials.
Current work proposes a novel High Power Impulse Magnetron Sputtering (HIPIMS) Deposition technology, for the first time, for deposition of a ceramic based CrN/NbN coating with a nanoscale multilayer structure (bi-layer thickness Δ = 1.9 nm) with superior adhesion (LC2 = 80 N) to protect low Chromium P92 steel widely used in steam power plants. Thermodynamic calculations predict the equilibrium phases and aggressive gaseous compounds generated by the interaction of steam with the coating. CrN/NbN coated P92 steel samples oxidised at 600 °C in a high pressure (50 bar) 100% steam atmosphere for up to 1000 h reveal the coating's superior oxidation resistance and protective mechanisms, especially against the detrimental effect of Hydrogen. High temperature (650 °C) Tensile Strength, Low Cycle Fatigue and Creep tests confirm that, unlike other state-of-the-art PVD technologies, HIPIMS is not detrimental to the mechanical properties of the substrate material. Water droplet erosion tests confirm no measurable weight loss after 2.4 X 10⁶ impacts.
Low cost, high-efficiency catalysts towards water splitting are urgently required to fulfil the increasing demand for energy. In this work, low-loading (<20 wt%) Ni-confined in layered metal oxide anode catalysts (birnessite and lepidocrocite titanate) have been synthesized by facile ion exchange methodology and subjected to systematic electrochemical studies. It was found that Ni-intercalated on K-rich birnessite (Ni-KMO) presents an onset overpotential (ηonset) as low as 100 mV and overpotential at 10 mA cm−2 (η10) of 206 mV in pH = 14 electrolyte. By combining electrochemical methods and X-ray absorption and emission spectroscopies (XAS and XES), we demonstrate Ni sites are the active sites for OER catalysis and that the Mn3+ sites facilitate Ni intercalation during the ion-exchange process, but display no observable contribution towards OER activity. The effect of the pH and the nature of the supporting electrolyte on the electrochemical performance was also evaluated.
Understanding the mechanical behavior of silicon nanowires is essential for the implementation of advanced nanoscale devices. Although bending tests are predominantly used for this purpose, their findings should be properly interpreted through modeling. Various modeling approaches tend to ignore parts of the effective parameter set involved in the rather complex bending response. This oversimplification is the main reason behind the spread of the modulus of elasticity and strength data in the literature. Addressing this challenge, a surface-based nanomechanical model is introduced in this study. The proposed model considers two important factors that have so far remained neglected despite their significance: (i) intrinsic stresses composed of the initial residual stress and surface-induced residual stress and (ii) anisotropic implementation of surface stress and elasticity. The modeling study is consolidated with molecular dynamics-based study of the native oxide surface through reactive force fields and a series of nanoscale characterization work through in situ threepoint bending test and Raman spectroscopy. The treatment of the test data through a series of models with increasing complexity demonstrates a spread of 85 GPa for the modulus of elasticity and points to the origins of ambiguity regarding silicon nanowire properties, which are some of the most commonly employed nanoscale building blocks. A similar conclusion is reached for strength with variations of up to 3 GPa estimated by the aforementioned nanomechanical models. Precise consideration of the nanowire surface state is thus critical to comprehending the mechanical behavior of silicon nanowires accurately. Overall, this study highlights the need for a multiscale theoretical framework to fully understand the size-dependent mechanical behavior of silicon nanowires, with fortifying effects on the design and reliability assessment of future nanoelectromechanical systems.
Wood treated with nano metal fluorides is found to resist fungal decay. Sol−gel synthesis was used to synthesize MgF2 and CaF2 nanoparticles. Electron microscopy images confirmed the localization of MgF2 and CaF2 nanoparticles in wood. Efficacy of nano metal fluoride-treated wood was tested against brown-rot fungi Coniophora puteana and Rhodonia placenta. Untreated wood specimens had higher
mass losses (∼30%) compared to treated specimens, which had average mass loss of 2% against C. puteana and 14% against R. placenta, respectively. Nano metal fluorides provide a viable alternative to current wood preservatives.
Morphology and structure of TixOy nanoparticles generated by femtosecond laser ablation in water
(2018)
In this work femto-second pulsed laser ablation in liquid (PLAL) procedure for the generation of titanium oxide nanoparticles (NP) is reported with the purpose of understanding morphology and structure of the newly generated NPs. Ablation duration was varied for optimization of NP generation processes between 10 and 90 min. Surface morphology of NPs as well as their size and shape (distribution) were analysed by various complementary electron microscopy techniques, i.e. SEM, TSEM and TEM. The crystalline structure of titanium oxide particles was investigated byXRD(two instruments operated in different geometries) and HR-TEM. Concentration of generated titanium oxide NPs in liquid was analysed by ICP-MS. A mix of crystalline (mainly anatase), partly crystalline and amorphous spherical titanium oxide NPs can be reported having a mean size between 10 and 20 nm, which is rather independent of the laser ablation (LA) duration. A second component consisting of irregularly shaped, but crystalline titanium oxide nanostructures is co-generated in the LA water, with more pronounced occurrence at longer LA times. The provenance of this component is assigned to those spherical particles generated in suspension and passing through the converging laser beam, being hence subject to secondary irradiation effects, e. g. fragmentation.
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 sliding behavior of an amorphous silica sample between two rigid surfaces is in the focus of the present paper. Molecular Dynamics using a classical Tersoff’s potential and a recently developed ReaxFF potential was applied for simulating sliding within a thin film corresponding to a tribofilm formed from silica nanoparticles. The simulations were performed at different temperatures corresponding to moderate and severe tribological stressing conditions. Simulations with both potentials revealed the need of considering different temperatures in order to obtain a sound interpretation of experimental findings. The results show the striking differences between the two potentials not only in terms of magnitude of the resistance stress (about one order of magnitude) but also in terms of friction mechanisms. The expected smooth sliding regime under high temperature conditions was predicted by both simulations, although with Tersoff’s potential smooth sliding was obtained only at the highest temperature. On the other hand, at room temperature Tersoff-style calculations demonstrate stick-slip behavior, which corresponds qualitatively with our experimental findings. Nevertheless, comparison with a macroscopic coefficient of friction is not possible because simulated resistance stresses do not depend on the applied normal pressure.
An analytical model for forecasting the temperature dependence of γ/γ' misfit in heat-resistant nickel alloys is proposed. The model accounts for the concentration dependences of the periods of crystalline lattices of the γ and γ' phases (Vegard law), thermal expansion of the γ and γ' lattices, and dissolution of the γ' phase at high temperatures. Adequacy of calculations of misfit is confirmed by comparison with the results of measurements using methods of X-ray and neutron diffraction. The model is applied for development of a nickel alloy with positive misfit.
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.
Inconel 718 is a precipitation strengthened, nickel-based super alloy of interest for the Additive Manufacturing (AM) of low volume, complex parts to reduce production time and cost compared to conventional subtractive processes. The AM process involves repeated rapid melting, solidification and reheating, which exposes the material to non-equilibrium conditions that affect elemental segregation and the subsequent formation of solidification phases, either beneficial or detrimental. These variations are difficult to characterize due to the small length scale within the micron sized melt pool. To understand how the non-equilibrium conditions affect the initial solidification phases and their critical temperatures, a multi-length scale, multi modal approach has been taken to evaluate various methods for identifying the initial phases formed in the as-built Inconel 718 produced by laser-powder bed fusion (L-PBF) additive manufacturing (AM). Using a range of characterization tools from the bulk differential thermal analysis (DTA) and x-ray diffraction (XRD) to spatially resolved images using a variety of electron microscopy tools, a better understanding is obtained of how these minor phases can be properly identified regarding the amount and size, morphology and distribution. Using the most promising characterization techniques for investigation of the as-built specimens, those techniques were used to evaluate the specimens after various heat treatments. During the sequence of heat treatments, the initial as-built dendritic structures recrystallized into well-defined grains whose size was dependent on the temperature. Although the resulting strength was similar in all heat treated specimens, the elongation increased as the grain size was refined due to differences in the precipitated phase distribution and morphology.
T92 steel was oxidized at 650 °C for 1000 h in dry and wet oxyfuel gases. The microstructure of inner oxide layer was investigated using scanning transmission electron microscopy and energy dispersive spectroscopy on thin lamellas of oxide cross-sections. The oxides were composed of fine equiaxed grains and separated into Fe-rich and Cr-rich regions. Fe-rich regions were wustite and iron sulphide while Cr-rich regions consisted of Fe-Cr spinel with different stoichiometries. Precipitates of (W,Mo)-rich oxides were formed within the oxide scale and beneath the oxide/alloy interface. Often iron sulphide and (W,Mo)-rich oxide were surrounded by Cr-rich spinel.
Due to the increasing global demand for pure silver, native wire silver aggregates in very high purities are gaining more industrial attention. Up to the present, no substantial metallurgical Investigation of natural wire silver exists in the accessible literature. To convey urgently needed cross-disciplinary fundamental knowledge for geoscientists and metallurgical engineers, twenty natural wire silver specimens from eight different ore deposits have been investigated in detail for the first time by EBSD (Electron Back Scattering Diffraction), supported by light microscopy and micro-probe analyses. The improved understanding of the natural silver wire microstructure provides additional Information regarding the growth of natural silver aggregates in comparison to undesired artificial growth on electronic devices. Clear evidence is provided that natural silver curls and hairs exhibit a polycrystalline face-centered cubic microstructure associated with significant twinning. Although the investigated natural wire silver samples have relatively high purity (Ag > 99.7 wt.-%), they contain a variety of trace elements such as, S, Cu, Mn, Ni, Zn, Co and Bi, As and Sb. Additionally, Vickers micro-hardness measurements are provided for the first time which revealed that natural silver wires and curls are softer than it might be expected from conversion of the general Mohs hardness of 2.7.
The underlying cause of mechanical anisotropy in additively manufactured (AM) parts is not yet fully understood and has been attributed to several different factors like microstructural defects, residual stresses, melt pool boundaries, crystallographic and morphological textures. To better understand the main contributing factor to the mechanical anisotropy of AM stainless steel 316L, bulk specimens were fabricated via laser powder bed fusion (LPBF). Tensile specimens were machined from these AM bulk materials for three different inclinations: 0◦, 45◦, and 90◦ relative to the build plate. Dynamic Young’s modulus measurements and tensile tests were used to determine the mechanical anisotropy. Some tensile specimens were also subjected to residual stress measurement via neutron diffraction, porosity determination with X-ray micro-computed tomography (μCT), and texture analysis with electron backscatter diffraction (EBSD). These investigations revealed that the specimens exhibited near full density and the detected defects were spherical. Furthermore, the residual stresses in the loading direction were between −74 ± 24 MPa and 137 ± 20 MPa, and the EBSD measurements showed a preferential ⟨110⟩ orientation parallel to the build direction. A crystal plasticity model was used to analyze the elastic anisotropy and the anisotropic yield behavior of the AM specimens, and it was able to capture and predict the experimental behavior accurately. Overall, it was shown that the mechanical anisotropy of the tested specimens was mainly influenced by the crystallographic texture.
Molten salt containing systems gain in importance for sustainable energy use and production. For research and development, interactions of molten salts with potential container materials are of major interest. This article introduces preparation procedures to display an intact metal and salt microstructure and their interface using light optical microscopy and scanning electron microscopy. The exemplary material combination is the ternary salt mixture NaCl-KCl-MgCl2 and the low alloyed steel 1.4901 (T92) with a maximum service temperature of 550 °C. These are potential elements/materials for use in latent heat thermal energy storages.
We describe a lattice-based crystallographic approximation for the analysis of distorted crystal structures via Electron Backscatter Diffraction (EBSD) in the scanning electron microscope. EBSD patterns are closely linked to local lattice parameter ratios via Kikuchi bands that indicate geometrical lattice plane projections. Based on the transformation properties of points and lines in the real projective plane, we can obtain continuous estimations of the local lattice distortion based on projectively transformed Kikuchi diffraction simulations for a reference structure. By quantitative image matching to a projective transformation model of the lattice distortion in the full solid angle of possible scattering directions, we enforce a crystallographically consistent approximation in the fitting procedure of distorted simulations to the experimentally observed diffraction patterns. As an application example, we map the locally varying tetragonality in martensite grains of steel.
To visualize the varying tetragonal distortions in high carbon martensitic steels by EBSD, two different approaches have been applied on backscattered Kikuchi diffraction (BKD) patterns. A band-edge refinement technique called Refined Accuracy (RA) (Oxford Instruments) is compared with a technique called Pattern Matching (PM), which optimizes the fit to a simulated BKD signal. RA distinguishes between hypothetical phases of different fixed 𝑐∕𝑎, while PM determines a best fitting continuous 𝑐∕𝑎 by projective transformation of a master pattern. Both techniques require stored BKD patterns.
The sensitivity of the 𝑐∕𝑎-determination was tested by investigating the microstructure of a ferritic steel with an expected 𝑐∕𝑎 = 1. The influence of the Kikuchi pattern noise on 𝑐∕𝑎 was compared for a single or 40 averaged frames per measuring point, and turned out to be not significant. The application of RA and PM on the martensitic microstructure delivered qualitatively similar maps of 𝑐∕𝑎. The comparison of RA and PM shows that RA is suitably fast and precise during mapping the martensite 𝑐∕𝑎 ratio in analyses of high carbon martensite, especially for fast initial surveys. As RA leads quantitatively to higher noise in 𝑐∕𝑎, the PM analysis can be used for higher precision results.
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.
Friction stir welding (FSW) of high-melting temperature alloys, such as steel and Inconel, requires tooling that can survive under the applied loads at the elevated temperatures. Tungsten-Rhenium (W-Re) alloys are a suitable candidate for this application; however, the costs typically associated with achieving the required densities and grain structure for the tooling are high due to the lengthy traditional processing required. Further costs are incurred in machining the starting bar stock to the final FSW tooling configuration. An alternate processing method is used in this study to shorten the fabrication time using direct current sintering which rapidly consolidates the starting powders at lower temperatures than used in traditional powder metallurgy. Although this process enables retention of the fine grain size, the sintering time is too short to form the desired single, solid phase. Therefore, the specimens were subjected to a post-consolidation heat treatment to fully solutionize the W matrix. Once the desired density and solid solution phase was verified in coupons, the final processing parameters were used to consolidate a net shape tool for FSW.
Extended X-ray absorption fine structure (EXAFS) conducted on an equiatomic MoNbTaW bcc medium-entropy alloy that was annealed at 2273 K reveals unexpectedly small 1st and 2nd shell element-specific lattice distortions. An experimental size-mismatch parameter, δexp, is determined to be ca. 50% lower than the corresponding calculated value. Around W, short-range order (SRO) preferring 4d elements in the 1st and 2nd shells persists. A Nb-W ordering is found, which is reminiscent of ordering emerging at lower temperatures in the B2(Mo,W;Ta,Nb)- and B32(Nb,W)-phases. With high-temperature ordering preferences in fcc also foreshadowing low-temperature phase, these findings suggest a general feature of high-temperature SRO.
Carbon Capture and Storage (CCS) is well acknowledged to mitigate climate change. Therefore, pipe Steels suitable for CCS technology require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe Steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Main corrosion products analysed on pits are FeCO3 and FeOOH. The carbon content does not show significant influence on the pitting behaviour. Generally, higher chromium Content results in better corrosion resistance. Although X35CrMo17-1 and X5CrNiCuNb16-4 show low surface corrosion rates, their resistance against local corrosion in CCS environment is not significantly better compared to the much less costly Steels X20Cr13 and X46Cr13.
We discuss a refined simulation approach which treats Kikuchi diffraction patterns in electron backscatter diffraction (EBSD) and transmission Kikuchi diffraction (TKD). The model considers the result of two combined mechanisms: (a) the dynamical diffraction of electrons emitted coherently from point sources in a crystal and (b) diffraction effects on incoherent diffuse intensity distributions. Using suitable parameter settings, the refined simulation model allows to reproduce various thickness- and energy-dependent features which are observed in experimental Kikuchi diffraction patterns. Excess-deficiency features are treated by the effect of gradients in the incoherent background intensity. Based on the analytical two-beam approximation to dynamical electron diffraction, a phenomenological model of excess-deficiency features is derived, which can be used for pattern matching applications. The model allows to approximate the effect of the incident beam geometry as a correction signal for template patterns which can be reprojected from pre-calculated reference data. As an application, we find that the accuracy of fitted projection centre coordinates in EBSD and TKDcan be affected by changes in the order of 10−3–10-2 if excess-deficiency features are not considered in the theoreticalmodel underlying a best-fit pattern matching approach. Correspondingly, the absolute accuracy of simulation-based EBSD strain determination can suffer frombiases of a similar order of magnitude if excess-deficiency effects are neglected in the simulation model.
We discuss a refined simulation approach which treats Kikuchi diffraction patterns in electron backscatter diffraction (EBSD) and transmission Kikuchi diffraction (TKD). The model considers the result of two combined mechanisms: (a) the dynamical diffraction of electrons emitted coherently from point sources in a crystal and (b) diffraction effects on incoherent diffuse intensity distributions. Using suitable parameter settings, the refined simulation model allows to reproduce various thickness- and energy-dependent features which are observed in experimental Kikuchi diffraction patterns. Excess-deficiency features are treated by the effect of gradients in the incoherent background intensity. Based on the analytical two-beam approximation to dynamical electron diffraction, a phenomenological model of excess-deficiency features is derived, which can be used for pattern matching applications. The model allows to approximate the effect of the incident beam geometry as a correction signal for template patterns which can be reprojected from pre-calculated reference data. As an application, we find that the accuracy of fitted projection centre coordinates in EBSD and TKDcan be affected by changes in the order of 10−3–10−2 if excess-deficiency
features are not considered in the theoreticalmodel underlying a best-fit pattern matching approach. Correspondingly, the absolute accuracy of simulation-based EBSD strain determination can suffer frombiases of a similar order of magnitude if excess-deficiency effects are neglected in the simulation model.
The alloying system Co-Al-W-Ta is comprehensively investigated in the vicinity of the compositional point Co-9Al-10W-2Ta, at. pct. These investigations provided a large amount of quantitative information, which can be used for alloy development, namely, the compositional dependences of the The alloying system Co-Al-W-Ta is comprehensively investigated in the vicinity of the compositional point Co-9Al-10W-2Ta, at. pct. These investigations provided a large amount of quantitative information, which can be used for alloy development, namely, the compositional dependences of the γ‘-solvus, solidus, and liquidus temperatures; fraction of the extrinsic phases after casting; the compositional dependence of the γ/γ‘-lattice misfit; the element partitioning between γ- and γ‘-phases; and the two Phase compositional area γ/γ‘ in the Co-rich part of the Co-Al-W-Ta phase diagram at 900°C. It is shown that additions of Ta elevate the γ‘-solvus temperature and increase the γ/γ‘-lattice misfit, but adding more than about 3 at. pct Ta results in a large amount of undissolvable extrinsic phases. Additionally, two Co-Al-W-Ta alloys with lower content of W were developed and solidified as [001] single crystals for mechanical testing in a temperature range between 20 and 1200°C. These tests included measurement of the Young modulus, tensile tests with constant strain rate, and stress rupture tests. It was found that at temperatures up to about 750°C the ultimate tensile strength of Co-Al-Ta-W alloys can be at the same level or even higher than of Ni-based superalloys.
In this work, we employed glow discharge optical emission spectrometry (GD-OES) depth profiling as a fast and semi-quantitative method to investigate the aluminum (Al) current collector degradation in commercial lithium cobalt oxide (LCO) pouch cells with no Al2O3 pretreatment. After battery aging, a heterogeneous deposit was found on the surface of the cathode. Gray hotspot areas within an extensive pale white region were formed. Consistent with energy dispersive X-ray (EDX) analysis of micro-cross sections milled via targeted focused ion beam (FIB), an Al-containing layer of approximately 3 µm can be observed using GD-OES. We attribute one main cause of this layer is the degradation of the Al current collector. The nonuniform growth of this layer was investigated by performing GD-OES depth profiling at different in-plane positions. We found that the gray area has a higher mass concentration of Al, probably in metallic form, whereas the white area was probably covered more homogeneously with Al2O3, resulting from the inhomogeneous distribution of the pitting positions on the current collector. Compared to FIB-EDX, GD-OES enables a faster and more convenient depth profile analysis, which allows the more productive characterization of lithium-ion batteries (LIBs), and consequently benefits the development of preferable battery materials.
Interdiffusion in the Face-Centered Cubic Phase of the Co-Al-W-Ta System Between 1090 and 1240 °C
(2018)
Interdiffusion of Al, W, Ta and Co in a Co-base alloy at temperatures between 1090 and 1240 °C has been investigated. The interdiffusion coefficients were found to be close to those reported for these elements in Ni-base alloys. Combining the diffusion simulation software DICTRA with the Ni-base diffusion databases TCNi5 and MobNi3, the interdiffusion profiles of Co, Al W, and Ta were modeled for Co9Al8W2Ta/Co diffusion couples annealed at different temperatures and for different times. The results show that interdiffusion in the Co-Al-W-Ta alloys can be modeled reasonably well using the available commercial databases for thermodynamics and kinetics of Ni-base systems.
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).
This study examines the relationship between the magnetic mesostructure with the microstructure of low carbon steel tungsten inert gas welds. Optical microscopy revealed variation in the microstructure of the parent material, in the heat affected and fusion zones, correlating with distinctive changes in the local magnetic stray fields measured with high spatial resolution giant magneto resistance sensors. In the vicinity of the heat affected zone high residual stresses were found using neutron diffraction.
Notably, the gradients of von Mises stress and triaxial magnetic stray field modulus follow the same tendency transverse to the weld. In contrast, micro-X-ray fluorescence characterization indicated that local changes in element composition had no independent effect on magnetic stray fields.
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.
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.
Iron aluminides, already reported in the late 19th century, did not cease to attract the interest of scientists and engineers ever since. Besides good oxidation resistance, low density and resource availability, potentials for hightemperature strengths that compete with high-alloy steels were unlocked by low alloy contents. Still, research on alloy design continues, as alloying usually comes at the price of brittleness in low-temperature regimes. A potential candidate is the quinary Fe–Al–Mo–Ti–B system which is strengthened by solid solution and eutectic borides. It was shown to have good strength and outstanding creep resistance under compressive loading up to elevated temperatures. Although the individual effect of alloy additions is well understood in iron aluminides, little is known about the combined effects of alloying concentrations on microstructure, phase stability and mechanical properties. Therefore a systematic study of two Ti-doped near-Fe3Al alloys with varying contents of Mo (2–4 at.%) and B (0.5–1 at.%) was conducted. In total eight different alloys were fabricated by investment casting into ceramic shell molds. Alloys were characterized and compared by grain size, phase transitions, microstructure evolution as well as elemental compositions and volume fractions of phases. For mechanical characterization, macrohardness and microhardness tests as well as tensile tests at ambient and high tempera tures were conducted. Independent of alloy additions, alloys with 24–25 at.% Al exhibit superior proof strength due to a higher matrix hardness. Decreasing B content generally decreases strength by lower secondary phase fractions which contribute via particle hardening. Reducing Mo content decreases both the solute concentration in the matrix and secondary phase fractions. Surprisingly, strength is similar or even superior to alloys with higher Mo content. Strength relations are discussed with a focus on solid-solution hardening theory and other competing strengthening mechanisms.
Fatigue tests were performed on the forged aluminum alloy EN AW-2618A in the T61 state. Different stress ratios (R = -1, R = 0.1) were selected to study the influence of mean stress on fatigue life. Two overaged states (10 h/230 ◦C, 1000 h/230 ◦C) were also tested to investigate the influence of overaging on fatigue life. Transmission electron microscopy (TEM) was used to characterize the precipitates (S-phase), which are mainly responsible for the strength of the alloy. A fractographic analysis was also performed to determine the failure mode. Overaging reduces the fatigue life compared to the T61 state. The longer the aging time, the lower the fatigue resistance. The reason is the decrease in (yield) strength, which correlates with the radius of the S-phase: the precipitate radius increases by a factor of approximately two for the overaged states compared to the initial state. The analysis of the fracture surfaces showed crack initiation occurs predominantly on the outer surface and is
associated with the primary phases.
In this work we instigated the fragmentation of Au microparticles supported on a thin amorphous carbon film by irradiating them with a gradually convergent electron beam inside the Transmission Electron Microscope. This phenomenon has been generically labeled as ‘‘electron beam-induced fragmentation’’ or EBIF and its physical origin remains contested. On the one hand, EBIF has been primarily characterized as a consequence of beam-induced heating. On the other, EBIF has been attributed to beam-induced charging eventually leading to Coulomb explosion. To test the feasibility of the charging framework for EBIF, we instigated the fragmentation of Au particles under two different experimental conditions. First, with the magnetic objective lens of the microscope operating at full capacity, i.e. background magnetic field 𝐵 = 2 T, and with the magnetic objective lens switched off (Lorenz mode), i.e. 𝐵 = 0 T. We observe that the presence or absence of the magnetic field noticeably affects the critical current density at which EBIF occurs. This strongly suggests that magnetic field effects play a crucial role in instigating EBIF on the microparticles. The dependence of the value of the critical current density on the absence or presence of an ambient magnetic field cannot be accounted for by the beam-induced heating model. Consequently, this work presents robust experimental evidence suggesting that Coulomb explosion driven by electrostatic charging is the root cause of EBIF.
In this work we instigated the fragmentation of Au microparticles supported on a thin amorphous carbon film by irradiating them with a gradually convergent electron beam inside the Transmission Electron Microscope. This phenomenon has been generically labeled as “electron beam-induced fragmentation” or EBIF and its physical origin remains contested. On the one hand, EBIF has been primarily characterized as a consequence of beam-induced heating. On the other, EBIF has been attributed to beam-induced charging eventually leading to Coulomb explosion. To test the feasibility of the charging framework for EBIF, we instigated the fragmentation of Au particles under two different experimental conditions. First, with the magnetic objective lens of the microscope operating at full capacity, i.e. background magnetic field B = 2 T, and with the magnetic objective lens switched off (Lorenz mode), i.e. B = 0 T. We observe that the presence or absence of the magnetic field noticeably affects the critical current density at which EBIF occurs. This strongly suggests that magnetic field effects play a crucial role in instigating EBIF on the microparticles. The dependence of the value of the critical current density on the absence or presence of an ambient magnetic field cannot be accounted for by the beam-induced heating model. Consequently, this work presents robust experimental evidence suggesting that Coulomb explosion driven by electrostatic charging is the root cause of EBIF.
High- and medium-entropy alloys (HEAs) are a quite new class of materials. They have a high potential for applications from low to high temperatures due to the excellent combination of their structural properties.
Concerning their application as components; processing properties, such as machinability, have hardly been investigated so far. Hence, machinability analyses with a focus on the influence of the milling process and its basic parameters (cutting speed, feed per cutting edge) on the resulting surface integrity of specimens from an equiatomic high- (CoCrFeMnNi) and a medium- (CoCrNi) entropy alloy have been carried out. A highly innovative milling process with ultrasonic assistance (USAM) was compared to conventional milling processes.
Recent studies have shown that USAM has a high potential to significantly reduce the mechanical load on the tool and workpiece surface during milling. In this study, the basic machining and ultrasonic parameters were systematically varied. After machining, the surface integrity of the alloys was analyzed in terms of topography, defects, subsurface damage, and residual stresses. It was observed that USAM reduces the cutting forces and increases the surface integrity in terms of lower tensile residual stresses and defect density near the surfaces for the CoCrFeMnNi alloy. It was shown that the cutting forces and the metallurgical influence in the sub surface region are reduced by increasing the cutting speed and reducing the feed rate per cutting edge. With the CoCrNi alloy, the tool revealed severe wear. As a result, for this alloy no influence of the parameters on the machinability could be determined.
Due to its matrix/γ′ structure, the compositionally complex alloy (CCA) Al10Co25Cr8Fe15Ni36Ti6 has excellent properties that fulfill the requirements for a high-temperature material. This base alloy is alloyed with small amounts of high melting elements to a further improvement of its properties, which results in different shapes, fractions and sizes of the two phases γ′ and Heusler after various homogenization and annealing steps. By correlating this microstructure with time independent and dependent mechanical properties, conclusions can be drawn about the effects of the individual phases. The needle-shaped Heusler-phase leads to bad mechanical behavior if its phase fraction is too high. A fraction below 3 vol% is not critical in tensile tests, but it reduces the creep resistance compared to a purely two-phase matrix/γ′-alloy. Sharp-edged cubic γ′-particles and a coarse Heusler-phase without sharp edges in case of the base alloy with 0.5 at.% hafnium lead to the best tensile and creep properties in the high temperature range. At 750 °C, the Hf-containing alloy clearly outperforms two commercially used alloys in the targeted area of application when it comes to creep resistance.
Refractory chemically complex alloys with bcc-based microstructures show great potential for high-temperature applications but most of them exhibit limited room-temperature ductility, which remains a challenge. One such example is the AlMo0.5NbTa0.5TiZr alloy, mainly consisting of a nano-scaled structure with an ordered B2 matrix and a high-volume fraction of aligned cuboidal and coherently embedded A2 precipitates. This work aims to investigate how the cooling rate after hot isostatic pressing of the AlMo0.5NbTa0.5TiZr alloy affects its microstructure and its resulting hardness and fracture toughness at room temperature. A slow cooling rate of 5 °C/min leads to a coarse microstructure consisting of aligned slabs (mean A2 precipitate ≈ 25 nm) with a nanohardness of about 8 GPa. In contrast, after the fastest cooling rate (30 °C/min), the A2 precipitates become more cubic with an edge length of ≈ 16 nm, resulting in an increase in nanohardness by 10 %. The fracture toughness is roughly independent of the cooling rate and its mean value (≈ 4.2 MPa∙m1/2) resembles that of some B2 intermetallics and other A2/B2 alloys. As the lattice misfit between the A2 and B2 phases is known to play a key role in microstructure formation and evolution, its temperature dependence between 20 and 900 °C was investigated. These findings offer insights into the evolution of the microstructure and room-temperature mechanical properties of the AlMo0.5NbTa0.5TiZr alloy, which could help the development of advanced chemically complex alloys.
Hydrocarbons fuel our economy. Furthermore, intermediate goods and consumer products are often hydrocarbon-based. Beside all the progress they made possible, hydrogen-containing substances can have severe detrimental effects on materials exposed to them. Hydrogen-assisted failure of iron alloys has been recognised more than a century ago. The present study aims to providing further insight into the degradation of the austenitic stainless steel AISI 304L (EN 1.4307) exposed to hydrogen. To this end, samples were electrochemically charged with the hydrogen isotope deuterium (2H, D) and analysed by scanning electron microscopy (SEM), electron back-scatter diffraction (EBSD) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). It was found that deuterium caused a phase transformation from the original γ austenite into ε- and α’-martensite. Despite their low solubility for hydrogen, viz. deuterium, the newly formed phases showed high deuterium concentration which was attributed to the increased density of traps. Information about the behaviour of deuterium in the material subjected to external mechanical load was gathered. A four-point-bending device was developed for this purpose. This allowed to analyse in-situ pre-charged samples in the ToF-SIMS during the application of external mechanical load. The results indicate a movement of deuterium towards the regions of highest stress.
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.
First year students especially with migration background and language deficiencies rate material science in mechanical engineering as one of the fundamental courses with high work load and necessity of language skills due to the descriptive nature of the course. Therefore a blended learning course structure using based on inverted classroom teaching scenarios was established. Heart of the self-study period are visualizing peer-to-peer lecture films supported by micro-lectures along with various online teaching materials. Although students with migration background generally scored lower in tests due to the lack of language skills improved learning outcomes are demonstrated in high quality class discussions and in overall understanding. This paper introduces the learning structure and graded activities, evaluates the course and compares results of native German-speaking students to those of students with migration background.
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.
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.
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.
Since the TEM has the capacity to observe the atomic structure of materials, in-situ TEM synthesis methods are uniquely suited to advance our fundamental understanding of the bottom-up dynamics that drive the formation of nanostructures. E-beam induced fragmentation (potentially identified as a manifestation of Coulomb explosion) and electron stimulated desorption (ESD) are phenomena that have received attention because they trigger chemical and physical reactions that can lead to the production of various nanostructures. Here we report a simple TEM protocol implemented on WO2.9 microparticles supported on thin amorphous carbon substrates. The method produces various nanostructures such as WC nanoparticles, WC supported films and others. Nevertheless, we focus on the gradual graphitization and gasification of the C substrate as it interacts with the material expelled from the WO2.9 microparticles. The progressive gasification transforms the substrate from amorphous C down to hybrid graphitic nanoribbons incorporating W nanoparticles. We think these observations open interesting possibilities for the synthesis of 2D nanomaterials in the TEM.
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.
A systematic study on a face‐centered cubic‐based compositionally complex alloy system Al–Co–Cr–Cu–Fe–Ni in its single‐phase state is carried out, where a mother senary compound Al₈Co₁₇Cr₁₇Cu₈Fe₁₇Ni₃₃ and five of its suballoys, obtained by removing one element at a time, are investigated and exhaustively analyzed determining the contribution of each alloying element in the solid solution. The senary and the quinaries are compared using experimental techniques including X‐ray absorption spectroscopy, X‐ray diffraction, transmission electron microscopy, and first principles hybrid Monte Carlo/molecular dynamics simulations. Chemical short‐range order and bond length distances have been determined both at the experimental and computational level. Electronic structure and local atomic distortions up to 5.2 Å have been correlated to the microhardness values. A linear regression model connecting hardness with local lattice distortions is presented.
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.
Surface degradation phenomena of two model equiatomic alloys from the CrMnFeCoNi alloy system were investigated in 2% O2 and 10% H2O (pO2 = 0.02 and 10−7 atm, respectively) at 800 °C for times up to 96 h. The crystallographic structures, morphologies, and chemical compositions of the corrosion layers developing on CrMnFeCoNi and CrCoNi were comparatively analyzed by mass gain analysis, X-ray diffraction, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. The oxidation resistance of CrMnFeCoNi is relatively poor due to the fast growth of porous Mnoxide(s). CrCoNi forms an external chromia layer that is dense and continuous in a dry 2% O2 atmosphere. This layer buckles and spalls off after exposure to 10% H2O atmosphere. Beneath the chromia layer, a Cr-depleted zone forms in the CrCoNi alloy in both environments. As the oxide scale spalls off in the H2O-containing
atmosphere, a secondary chromia layer was observed and correspondingly enlarges the Cr-depleted zone. In contrast, as the chromia layer remains without significant spallation when CrCoNi is exposed to a dry oxidizing atmosphere, the region depleted in Cr is narrower.
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.
Hierarchical microstructures are created when additional γ particles form in γ’ precipitates and they are linked to improved strength and creep properties in high-temperature alloys. Here, we follow the formation and evolution of a hierarchical microstructure in Ni86.1Al8.5Ti5.4 by in situ synchrotron X-ray diffraction at 1023 K up to 48 h to derive the lattice parameters of the γ matrix, γ’ precipitates and γ particles and misfits between phases. Finite element method-based computer simulations of hierarchical microstructures allow obtaining each phase's lattice parameter, thereby aiding peak identification in the in situ X-ray diffraction data. The simulations further give insight into the heterogeneous strain distribution between γ’ precipitates and γ particles, which gives rise to an anisotropic diffusion potential that drives the directional growth of γ particles. We rationalize a schematic model for the growth of γ particles, based on the Gibbs-Thomson effect of capillary and strain-induced anisotropic diffusion potentials. Our results highlight the importance of elastic properties, elastic anisotropy, lattice parameters, and diffusion potentials in controlling the behavior and stability of hierarchical microstructures.
Technically relevant P92 steel (9% Cr) was coated with a micron-thick porous alumina layer prepared by sol-gel technique and treated with flue gas (60 CO2-30 H2O-2 O2-1 SO2-7 N2 (mole fraction in %)) at 650 ° to mimic an oxyfuelcombustion process. Local defects in the coating were marked using focused ion beam (FIB) technique and were inspected after exposition to hot flue gas atmosphere at 300, 800, and 1300 h, respectively. Local defects like agglomerated alumina sol particles tend to spall off from the coating uncovering the underlying dense chromia scale. Re-coating was found to restore the protection ability from oxidation when repeatedly treated with hot flue gas. Cracks and voids did not promote the local oxidation due to the formation of crystalline Mn/S/O species within and on top of the coating. The protective character of the steel-coating system is a result of (i) the fast formation of a dense chromia scale at the surface of sol-gel alumina-coated P92 steel bars in combination with (ii) the porous alumina coating acting as diffusion barrier, but also as diffusion partner in addition with (iii) fast Mn outward diffusion capturing the S species from flue gas.
The temperature dependences of the periods of the crystal lattices of the γ and γ' phases, their dimensional mismatch (misfit), and volume fraction of the γ' phase of an experimental single-crystal hightemperature nickel-based alloy have been determined by X-ray diffraction analysis in the temperature range of 18–1150°C. The temperature ranges in which intense changes in the structural and phase characteristics of the alloy under study take place have been determined.
The damage mechanisms of metallic components produced by process laser powder bed fusion differ significantly from those typically observed in conventionally manufactured variants of the same alloy. This is due to the unique microstructures of additively manufactured materials. Herein, the focus is on the study of the evolution of creep damage in stainless steel 316L specimens produced by laser powder bed fusion. X-ray computed tomography is used to unravel the influence of the process-specific microstructure from the influence of the initial void distribution on creep damage mechanisms. The void distribution of two specimens tested at 600 °C and 650 °C is analyzed before a creep test, after an interruption, and after fracture. The results indicate that the formation of damage is not connected to the initial void distribution. Instead, damage accumulation at grain boundaries resulting from intergranular cracking is observed.