In-situ time-resolved small-angle neutron scattering (SANS) experiments were conducted on homogenised cold-rolled ternary Fe-Au-W alloys during aging for 12 h at temperatures of 650 to 700 °C in order to study the kinetics of the nanoscale precipitation. For comparison the precipitation kinetics in the binary counterparts Fe-Au and Fe-W alloys were also studied. In the ternary Fe-Au-W alloy nanoscale Au-rich precipitates were observed by both transmission electron microscopy (TEM) and SANS, while no significant W-rich precipitation was observed. The SANS pattern of the cold-rolled Fe-Au-W alloy clearly reveals a preferred orientation for the plate-shaped nanoscale Au-rich precipitates. As these Au-rich precipitates have a fixed orientation relation with the matrix lattice this preferred orientation originates from the texture of the bcc matrix grains, as confirmed by X-ray diffraction (XRD) pole figure measurements. The effect of texture on the nuclear and the magnetic SANS signal during the precipitation kinetics was included in the data analysis. This enables us to monitor the temperature dependence of the precipitation kinetics for the Au-rich precipitates in the Fe-Au-W alloy during aging at temperatures of 650, 675 and 700 °C. It is found that an increase in aging temperature results in a faster kinetics and a lower final precipitate fraction.

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Abstract: This work studies the effect of TiC and VC precipitate sizes on hydrogen trapping and embrittlement. Two experimental ferritic HSLA steels containing either TiC or VC carbides for precipitation strengthening are annealed in nitrogen and hydrogen gas. This results in a hydrogen uptake of up to 0.91 and 0.44 wppm in the TiC and VC steels, respectively. TEM and TDS analysis indicate that semi-coherent TiC particles trap hydrogen in misfit dislocations with an activation energy of 43 kJ/mol. Coherent VC particles are suggested to trap hydrogen in interface carbon vacancies, with an energy between 53 and 72 kJ/mol. Carbon vacancies are the likely trapping site in incoherent precipitates, where SIMS imaging confirms that incoherent TiC precipitates trap preferentially near the interface, whereas incoherent VC precipitates trap throughout their bulk. Neither alloy is embrittled in SSRT tests after hydrogen absorption, which shows that these precipitates can be used as both a hydrogen sink and a strengthening mechanism in steels. Graphical abstract: (Figure presented.)

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Since the oxidation reactions in the process of steel production occur in harsh conditions (i.e., high temperatures and gas atmospheres), it is practically impossible to observe in situ the compositional changes in the steel and the formed oxide scale. Hence, a coupled thermodynamic-kinetic numerical model is developed that predicts the formation of oxide phases and the composition profile of the steel alloy’s constituents in a short time due to external oxidation. The model is applied to high-temperature oxidation of Fe–Mn alloys under different conditions. Oxidizing experiments executed with a thermogravimetric analyzer (TGA) on Fe–Mn alloys with different Mn contents (below 10 wt %) are used to determine kinetic parameters that serve as an input for the model. The mass gain data as a function of time show both linear and parabolic regimes. The results of the numerical simulations are presented. The effect of different parameters, such as temperature, Mn content of the alloy, oxygen partial pressure, and oxidizing gas flow rate on the alloy composition and oxide phases formed, is determined. It is shown that increasing the temperature and decreasing the oxygen partial pressure both lead to a thicker depleted area.

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The parabolic growth rate constant (k_p) of high-temperature oxidation of steels is predicted via a data analytics approach. Four machine learning models including Artificial Neural Networks, Random Forest, k-Nearest Neighbors, and Support Vector Regression are trained to establish the relations between the input features (composition and temperature) and the target value (k_p). The models are evaluated by the indices: Mean Absolute Error, Mean Squared Error, Root Mean Squared Error and Coefficient of Determination. The steel composition regarding Cr and Ni content and the temperature were the most significant input features controlling the oxidation kinetics.

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Surface compositions play a predominant role in the efficiency and lifetime of membranes and catalysts. The surface composition can change during operation due to segregation, thus controlling and predicting the surface composition is essential. Computational modelling can aid in predicting alloy stability, along with designing surface alloys and near-surface alloys that can outperform existing materials. In this work, a computational model to predict surface segregation in ternary alloys is developed. The model, based on Miedema's semi-empirical model and Monte Carlo simulations, enables to predict long- and short-range ordering in the surface and subsurface layers. It is used to screen a vast range of alloy compositions to design a novel ternary Pd-based material for H₂ separation membranes. The addition of specific amounts of Cu and Zr to Pd is expected to reduce poisoning and enhance the permeability as compared to pure Pd.

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The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo₂C decorated carbon nanosheets, α-Mo₂C nanoparticles, θ-Fe₃C nanoparticles, and χ-Fe₅C₂ nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NO_x impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.

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For Pd thin films, microstructural changes involved during hydrogen cycling provide the information needed to predict and optimize the film's mechanical strength. In this paper, a systematic study of the morphology, microstructure, texture, and stress has been performed on Pd thin films during hydrogen loading and deloading cycles at room temperature. Pd thin films of similar morphology were prepared by magnetron sputtering on substrates of different compliances, i.e., Si-oxide, Titanium (Ti) and Polyimide (PI). The evolution of the morphology, grain-orientation distribution (texture), state of stress, and dislocation densities are analyzed for each of the film substrate types for 20 hydrogen loading/deloading cycles. The lattice expansion and contraction caused by the transition from Pd to Pd-hydride and back result in a strong stress increase. This stress increase stabilizes after a few cycles by grain boundary motion that leads to a gradual enhancement of the (111) texture and changes in the dislocation density for Pd films that are strongly clamped on to an oxidized Si(100) wafer substrate with an intermediate layer (Ti or PI). For Pd on PI, the stress is also partly released by a crack-based (crack widening/growth/propagation) pathway. Pd films on Ti and PI do not buckle or blister after 20 hydrogen cycles. By providing a sufficiently compliant substrate the traditional problems of buckle-delamination of a film on a stiff substrate are mitigated.

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High-temperature oxidation of steels can be relatively fast when exposed to air. Consequently, elucidating the effect of different parameters on the oxidation mechanism and kinetics is challenging. In this study, short-time oxidation was investigated to determine the oxidation mechanism, the affecting parameters, and the linear-to-parabolic growth transition of different Fe–Mn alloys in various oxygen partial pressures (10–30 kPa) and gas flow rates (26.6 and 53.3 sccm) in a temperature range of 950–1150 °C. Oxidation kinetics was investigated using a thermogravimetric analyzer (TGA) under controlled atmosphere. Linear oxide growth was observed within the first 20 minutes of oxidation. The linear rate constant was significantly increased by increasing the oxygen partial pressure or the flow rate of the oxidizing gas. The morphology of the oxide layer was determined by scanning electron microscopy (SEM). The crystal structure of the oxides formed was followed by in-situ X-ray diffraction (XRD), confirming that the growing layer consists of wustite mainly, which upon slow cooling to room temperature, transformed into magnetite. Energy-dispersive X-ray spectroscopy (EDS) showed that the atomic ratio of Fe+Mn to O was ~ 1.03:1 in the oxide scale, corresponding to Fe(Mn)O formation. Based on the characterization and a model for linear growth kinetics, it is concluded that the oxidation rate is controlled by the diffusion of oxidizing molecules through the gas layer to the sample’s surface. The findings led to a better understanding of initial oxidation behavior and provided a pathway for improved insight into the high-temperature oxidation behavior for more complex alloys.

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In this work, we studied the mechanical and thermal stability of ~100 nm Pd thin films magnetron sputter deposited on a bare oxidized Si(100) wafer, a sputtered Titanium (Ti) intermediate layer, and a spin-coated Polyimide (PI) intermediate layer. The dependence of the film stability on the film morphology and the film-substrate interaction was investigated. It was shown that a columnar morphology with elongated voids at part of the grain boundaries is resistant to embrittlement induced by the hydride formation (α↔β phase transitions). For compact film morphology, depending on the rigidity of the intermediate layer and the adherence to the substrate, complete transformation (Pd-PI-SiO₂/Si) or partly suppression (Pd-Ti-SiO₂/Si) of the α to β-phase was observed. In the case of Pd without intermediate layer (Pd-SiO₂/Si), buckling delamination occurred. The damage and deformation mechanisms could be understood by the analysis of the stresses and dislocation (defects) behavior near grain boundaries and the film-substrate interface. From diffraction line-broadening combined with microscopy analysis, we showed that in Pd thin films, stresses relax at critical stress values via different relaxation pathways depending on film-microstructure and film-substrate interaction. On the basis of the in-situ hydriding experiments, it was concluded that a Pd film on a flexible PI intermediate layer exhibits free-standing film-like behavior besides being strongly clamped on a stiff SiO₂/Si substrate.

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An attachment has been developed for x-ray diffractometer systems equipped with a domed stage when using a 2D or 1D detector. It consists of a single screen in front of the detector positioned such that it blocks diffraction from the dome. This results in measured data free of disturbing spurious peaks and background, thereby greatly facilitating further data analysis. Its working principle is universally applicable and allows for all specimen orientation movements needed for x-ray diffraction measurements, including texture, stress, and mapping.

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In-situ resource utilization (ISRU) is increasingly acknowledged as an essential requirement for the construction of sustainable extra-terrestrial colonies. Even with decreasing launch costs, the ultimate goal of establishing colonies must be the usage of resources found at the destination of interest. Typical approaches towards ISRU are often constrained by the mass and energy requirements of transporting processing machineries, such as rovers and massive reactors, and the vast amount of consumables needed. Application of self-reproducing bacteria for the extraction of resources is a promising approach to reduce these pitfalls. In this work, the bacterium Shewanella oneidensis was used to reduce three different types of Lunar and Martian regolith simulants, allowing for the magnetic extraction of iron-rich materials. The combination of bacterial treatment and magnetic extraction resulted in a 5.8-times higher quantity of iron and 43.6% higher iron concentration compared to solely magnetic extraction. The materials were 3D printed into cylinders and the mechanical properties were tested, resulting in a 400% improvement in compressive strength in the bacterially treated samples. This work demonstrates a proof of concept for the on-demand production of construction and replacement parts in space exploration.

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Alkaline water electrolysis becomes increasingly important for the supply of renewable energy, and of raw material for the chemical industry. An attractive choice for the encapsulation of the electrolyte cell is an (advanced) engineering polymer. The objective of this paper is to find a suitable one that can withstand for many years: 30 wt% KOH solution and pure oxygen at a high pressure of 50 bar and at an elevated temperature of 90°C. Using CES EduPack, 12 possible thermoplastic polymers were selected, of which polyphenylene sulfide (PPS) and polysulfone (PSU) were further investigated using accelerated testing. The polymers have been exposed to three KOH concentrations (15, 30 and 45 wt%), two oxygen pressures (pure O2 at 5 bar and air with pO2 = 20%), and three temperatures (90°C, 120°C, and 170°C). Extensive characterization of the exposed samples has been carried out using various techniques, including weight, tensile, DMA, and creep-recovery measurements, as well as DSC, FTIR, XRD and SEM. After 12 weeks of aging, glass fiber reinforced PPS failed in a strong alkaline solution at high temperatures, due to the dissolution of the glass fibers. The PPS matrix itself and PSU turned out to be resistant to thermo-oxidative and chemical degradation under the conditions tested. Only marginal changes in mechanical, visco-elastic and thermal behavior were observed, which can be ascribed to physical rather than chemical aging. In view of the brittle nature of PPS, it could be concluded that PSU is the most promising candidate for the long-term application in alkaline electrolysis. Extrapolating the data using time-temperature superposition, it is predicted that PSU will retain its integrity and mechanical properties for a period of 20 years of operation.@en

Pd–Cu alloys have been investigated as promising candidates for hydrogen separation membranes. Surface segregation influences the long-term performance of these membranes since their catalytic effect is mainly controlled by the surface composition. In the present research, surface segregation of Pd-40 at.% Cu alloy in vacuum and various gas atmospheres (H₂, CO and CO₂) was investigated with both XPS and LEISS probing different depths below the surface. Adsorption of H₂ and CO on the surface has a significant impact and the surface segregation trend can be reversed as compared to segregation in vacuum, however, CO₂ has almost no influence on the segregation behaviour. A thermodynamic model is also presented to explain these phenomena and to understand surface segregation behaviour of binary alloys in various gas atmospheres. The results can be considered as basic guidelines to design novel alloys for hydrogen separation membranes and predict their long-term performance under actual working conditions.

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Single-crystal copper films on sapphire have recently been reported upon in relation to graphene growth on these films. In the present paper the kinetics of the formation of single crystal copper films is investigated. We demonstrate the importance of heating the sapphire substrate in 1000 hPa oxygen, followed by a fast cooling prior to depositing the copper film. The importance of this treatment is tentatively explained by the dissolution of oxygen in sapphire and subsequent out-diffusion during recrystallization of the copper film to form a copper-oxide interface layer. Also, the importance of avoiding oxygen incorporation in the sputter deposited film is demonstrated.

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Ternary alloys have been developed for a wide range of applications and surface segregation of ternary alloys has a decisive impact on their performance. Different from binary alloys, in which surface energy is usually the dominant factor, the interaction between solute elements has a noticeable effect on the surface segregation behavior of ternary alloys. As a practical example, Pd-based ternary alloys have been proposed as promising candidates for hydrogen separation membranes due to their excellent permeability and selectivity. In the present work, surface segregation of Pd-Cu-Ag and Pd-Cu-Mo ternary alloys in both vacuum and hydrogen atmosphere is investigated. X-ray photoelectron spectroscopy and low energy ion scattering spectroscopy analyses reveal that the segregation trend of the outermost atomic layer is not always the same as that of the near-surface region. A thermodynamic model is developed to describe the surface segregation of ternary alloys. The results of the model are in good qualitative agreement with experimental results. Furthermore, calculations for other ternary alloy systems confirm that the model provides a simple but universal method for surface segregation in ternary alloys. The results can also be considered as basic guidelines to design novel ternary alloys for various applications.

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We report the design, fabrication and experimental investigation of a MEMS micro-hotplate (MHP) for fast time-resolved X-ray diffraction (TRXRD) study of Cu nanoparticle paste (nanoCu paste) sintering process. The device and its system are designed to have a 60 ms minimum time interval, uniform temperature distribution and variant gas environments. A TRXRD study of nanoCu paste sintering at 200 °C in H₂-N₂ gas mixture was done using this device. With 1 sec interval, Cu₈O reduction and Cu crystallization in sintering is observed. Results can be combined with other studies to optimize material design and process development.

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In this work, the effect of the deposition parameters of a magnetron sputtered Ti adhesive intermediate layer on the morphology and hydrogen absorption properties of thin Pd films of about 100 nm was investigated. The insertion of an adhesive layer between a Pd film and a rigid substrate usually suppresses or reduces hydrogen absorption. In this study, it is shown that by tuning the surface topography of the intermediate layer the morphology, crystallographic texture and hydrogen absorption properties of the Pd film can be controlled. The surface topography of the Ti layer was characterized using atomic force microscopy. The surface topography strongly depends on the Ti deposition conditions and can vary from widely spread large islands to densely packed small-grained islands depending on thickness (between 1 and 6 nm) and sputter pressure (0.4 and 3 Pa). TEM and XRD analysis led to the conclusion that rough Ti intermediate layers result in Pd films with an open columnar structure with small voids, and a weak and broad (111) texture. Smooth Ti intermediate layers promote the formation of Pd films with a dense columnar structure with fewer voids, and a strong and sharp (111) texture. Changes in the Pd adatom surface diffusion and shadowing effects are the main cause of the observed differences. Pd films with an open columnar morphology and weaker texture show better hydrogen absorption properties with respect to absorption capacity and kinetics of the films with dense columnar morphology. By tuning the surface topography of the Ti adhesive layer, Pd films with controlled morphology and texture can be prepared such that no delamination from the substrate occurs without compromising on absorption properties.

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Surface segregation of a series of forty Palladium-based binary alloys has been investigated using a thermodynamic model based on an atom exchange approach. Their surface segregation behaviour, both in vacuum and in gas environments, were comprehensively estimated. The calculated results are in good agreement with the available experimental and computational data reported in literatures. Effects of mixing enthalpy, temperature, crystal orientation on the surface, elastic strain energy, adsorption and absorption of gases like H₂, O₂, CO have been discussed in detail. These results can be considered as basic guidelines to design novel Pd alloys for hydrogen separation membranes, sensors or catalysts. The model itself also offers a convenient and accurate routine to predict the surface segregation of other than Pd-based binary alloys in different gas atmospheres.

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As a powder-bed-based additive manufacturing technology, selective laser melting (SLM) offers high-level flexibility and enables efficient fabrication of complex parts. In connection with complex thermal events occurring during dynamic sequential layer-by-layer deposition, the as-built material is usually hierarchical at different length scales and possesses anisotropy at each level. As a result of a moderate heating temperature of the baseplate and high cooling rates involved in the process, the as-built Ti-6Al-4V alloy has an α′ martensite microstructure. Microstructure evolution occurring during post-SLM heat treatment is strongly affected by the stability of the initial acicular martensite. The present study was aimed at developing an optimum post-SLM heat treatment scheme at a temperature below the β transus temperature, based on the understanding of microstructure evolution occurring during subtransus treatment and the resultant mechanical properties of the alloy. It was observed that the growth of the α and β phases during the heat treatment was inhibited by the initial α′ phase. A higher heating temperature could effectively improve microstructure homogeneity on a micrometer-scale to some extent. Heating temperature affected the strength and fracture strain of the alloy far more than cooling rate. A post-SLM heat treatment at a temperature of 850 °C or higher could lead to an improvement of fracture strain to the level of the forged counterpart, accompanied by the losses in yield strength and ultimate compressive strength from the as-built values. Full annealing (i.e., subtransus treatment at a high temperature) was thus recommended to be an appropriate post-SLM heat treatment for Ti-6Al-4V.

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Unencapsulated CIGS solar cells were simultaneously exposed to damp heat and illumination. In-situ monitoring of their electrical parameters demonstrated a rapid decrease of the efficiency, mainly driven by changes in the series and shunt resistances. The non-degraded and degraded solar cells were studied by SIMS and XRD to investigate the material changes leading to efficiency loss. SIMS showed the migration of sodium and potassium, likely leading to changes in the shunt resistance and output voltage. Extensive XRD measurements showed that molybdenum oxide was formed and that the in-plane stress in the ZnO:Al film increased. The stress increase is most likely due to the incorporation of species like hydroxide in the grain boundaries. These phenomena could lead to the observed increased series resistance in the solar cells.

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