High-energy X-ray Diffraction Research Articles

In-situ synchrotron high energy X-ray diffraction study on the compressive creep behavior of an extruded Ti-45Al-8Nb-0.2C alloy

Wrought high Nb containing (high Nb-TiAl) alloys are potential materials for low pressure turbine blades in aero-engines. The performance and microstructure evolution under high temperature creep condition is of importance to the service stability of these materials. In this study, the internal strain and FWHM evolution of an extruded TNB-based high Nb-TiAl alloy during compressive creep are characterized by in-situ high energy X-ray diffraction (HEXRD) technique for the first time. The compressive creep test was conducted under a constant load of 300 MPa at 900 °C for 10 h in vacuum. The final creep strain is approximately 1.72 %. The microstructure and phase constitution after creep shows little difference from that before creep. Lattice strain analysis shows that γ phase is plastically deformed while the α2 phase deforms elastically due to the low creep strain. The lattice strain of α2 grains is dependent upon the deformation of surrounding γ grains. Creep induces dynamic recovery, exerting a softening effect. A high number of dislocations are visible in the γ lamellae while almost no dislocations exist within the α2 lamellae. α2 lamellae are partially decomposed and refined via the α2→γ transformation.

The influence of substantial intragranular orientation gradients on the micromechanical response of heavily-worked material

In this study, we employ high-energy X-ray characterization to examine the role of relatively large amounts of intragranular lattice misorientation – present after many thermomechanical processes – on the micromechanical response of Al-7085 with a modified T7452 temper. We utilize near-field high energy X-ray diffraction microscopy (HEDM) to measure three-dimensional (3D) spatial orientation fields, facilitated by a novel method that utilizes grain orientation envelopes measured using far-field HEDM to enable reconstruction of grains with intragranular orientation spreads greater than 20°. We then assess the consequences of consideration of intragranular orientation fields on the predicted deformation response of the sample through 3D micromechanical simulations of the forged Al-7085. We construct two virtual polycrystalline specimens for use in simulations: the first a faithful representation of the HEDM reconstruction, the second a microstructure with no intragranular misorientation (i.e., grain-averaged orientations). We find significant differences in the predicted deformation mechanism activation, distribution of stress, and distribution of plastic strain between simulations containing intragranular misorientation and those with grain-averaged orientations, indicating the necessity for consideration of intragranular orientation fields for accurate predictions. Further, the influence of elastic anisotropy is discussed, along with the effects of intragranular misorientation on fatigue life through the calculation and analysis of fatigue indicator parameters.

Phase transformation kinetics in Ti 575 titanium alloy during heat treatment: role of the initial microstructure during ageing

Phase transformation kinetics were studied of Ti-575 titanium alloy during cooling from solution annealing and subsequent ageing using in-situ high energy X-ray diffraction. Cooling rates of 1.7, 10 and 30 °C·s-1 were applied from Tβ-60 °C therefore generating several microstructures with different size, morphologies or spatial distribution of α precipitates. Isothermal ageing at 500 °C for 1h on these three microstructures allowed the study of the influence of the initial microstructural state upon phase transformation during ageing. For this purpose, the combined analysis of mass fraction, aβ mean lattice parameter and full width at half maximum is carried out for both cooling and ageing segment and is presented in this study. Displacive and diffusion-controlled transformations were recorded and seem to be cooling rate dependent, particularly with the precipitation of the αʺ orthorhombic phase. The chemical and mechanical evolution of these transformation products will influence the phase transformation kinetics during cooling and following ageing hence conditioning the final microstructure and mechanical properties of this alloy.

Ascertaining the deformation accommodation of a novel Ti-652 alloy by tracking the evolution of slip traces and lattice strain

The exploration of slip modes in metallic materials during deformation has been long suffered from either insufficient statistical accuracy of slip trace analysis or limited spatial resolution by X-ray diffraction. In this work, a combination of slip trace analysis based on in-situ Electron Backscatter Diffraction (EBSD) and lattice strain analysis supported by in-situ Synchrotron Radiation High-Energy X-ray Diffraction (SR-HEXRD) was employed to determine the deformation accommodation mechanisms of a new developed Ti-6Al-5Mo-2Sn-0.3Si-0.5V (Ti-652) alloy. Different from conventional cases, it was surprisingly found that pyramidal (101̅1)α slip is easier to be initiated than prismatic (101̅0)α within α grains, resulting in the dominant slip modes evolving from prismatic <a> to pyramidal I <c+a>. In addition, in-situ EBSD results show that slip can transfer across grain boundary (GB) in counterintuitive situations with low geometric compatibility factor m′ of 0.5, or with GB misorientations in the range of θ≥24.5°, which are contractive to the slip transfer criterion in hcp structures. Further detailed crystallographic analysis revealed that specific slip transferred across GBs with 24.5°≤θ≤60° because of high Schmid Factor (SF) values, while with θ>60° slip transfer occurred by activating another slip systems. The accumulation of multi-mode slip dislocations induced by deformation accommodation with different phases was suggested to promote the formation of sub-GBs within the deformed parent grain. These findings provide insights of the slip behaviors and property tailoring in Ti alloys.

3D in situ observations of stress redistribution in Ti-6Al-4V within rogue grain neighborhoods during monotonic and cyclic loading

Grain-scale stress redistribution events are characterized within the Ti-6Al-4V (Ti64) hexagonal close-packed α phase using far-field high-energy X-ray diffraction microscopy. Specimens were deformed in monotonic uniaxial tension and under cyclic tensile loading with approximately 7000 grains probed in each specimen. Analyses focused on the evolution of the resolved shear stresses applied to the basal 〈a〉, prismatic 〈a〉, and pyramidal 〈c+a〉 slip systems, as well as normal stresses applied to basal planes, within individual grains. Slip system softening is observed in the basal 〈a〉 and prismatic 〈a〉 slip systems across the ensemble, while hardening is observed for the pyramidal 〈c+a〉 slip systems during both monotonic and cyclic loading. In addition, discrete stress redistribution events in which increases of normal stresses in grains not favorably oriented for slip that may lead to crack initiation are analyzed. It is observed that these increases in normal stresses are correlated to crystallographic slip in multiple neighboring grains favorably oriented for slip.

On the precipitation and transformation kinetics of precipitation-hardening steel X5CrNiCuNb16-4 in a wide range of heating and cooling rates

In this work, the transformation and dissolution/precipitation behaviour of the soft martensitic, precipitation-hardening steel X5CrNiCuNb16-4 (often referred to as 17-4 PH or AISI 630) has been investigated by various analytical in situ techniques. First, austenite formation during the heating stage of a solution treatment (or austenitization) is examined. Subsequently, a major part of this work evaluates precipitation during cooling from the solution treatment (i.e., the quench-induced precipitation of Cu-rich particles). The following analytical in situ techniques were utilised: synchrotron high-energy X-ray diffraction, synchrotron small-angle X-ray scattering, differential scanning calorimetry, and dilatometry. These were complemented by ex situ high-angle annular dark-field scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy on as-quenched samples after various cooling rates. The continuous heating transformation and continuous cooling transformation diagrams have been updated. Contrary to previous reports, X5CrNiCuNb16-4 is rather quench sensitive and the final properties after ageing degrade if cooling is done slower than a certain critical cooling rate. Quench-induced Cu-rich precipitation happens in two reactions: a larger, nearly pure Cu face-centred cubic phase forms at higher temperatures, while at medium temperatures, spherical Cu-rich nanoparticles form, which are found to be body-centred cubic at room temperature. The dimensions of the quench-induced particles range from several µm after cooling at 0.0001 K/s down to just a few nm after cooling at 1 K/s. The maximum age hardening potential of X5CrNiCuNb16-4 can be exploited if a fully supersaturated solid solution is reached at cooling rates above the critical cooling rate of about 10 K/s.

Thermal stability of a newly developed Mn containing β-solidifying γ-TiAl intermetallic compound at 750 °C

A newly low-cost β-solidifying γ-TiAl alloy Ti-44Al-3Mn-0.4Mo-0.4W-0.1B-0.1C (in at. %, named as TMMW) was invented. The rolled bars with a diameter of 12 mm were successfully fabricated by conventional hot rolling process, directly carrying out from the ingot without the pre-forging or hot-packing. The heat-treated TMMW rolled bar, which had a fine-grained nearly lamellar (NL) microstructure, was then air-exposed at 750 °C for up to 3000 h. The changes of the microstructure during this exposure were characterized using electron probe X-ray micro-analyzer (EPMA), transmission electron microscope (TEM), electron backscattered diffraction (EBSD) and high-energy X-ray diffraction (HEXRD). The tensile properties of the samples before and after thermal exposure were also tested. The fine-grained NL microstructure is found to be thermodynamically stable during the exposure. Meanwhile, the combined addition of Mo and W shows a positive effect on the stabilization of βo phase at colony boundaries, with only slight precipitation of the nanometer βo phases with no other brittle phases, such as Laves, in the metastable α2 lamellae. It is found that the thickness of the α2 lamellae decreases after 500 h exposure, while remains basically unchanged from 500 h to 3000 h, which is contributed by the effective pinning effect of the precipitated βo phase in α2 lamellae. As a result, the exposure-induced embrittlement under room temperature and elevated temperature does not take place. Interestingly, the ductility tested at 800 °C improves significantly after exposure. As for the tensile strength, it is only reduced by less than 10 % after 500 h exposure, while it remains essentially unchanged when increasing the exposure time from 500 h to 3000 h. Finally, the mechanisms of the precipitation of βo phases in the α2 lamellae and the tensile properties evolution during the exposure were carefully discussed.

Revealing the role of B-site cations in the antiferroelectricity of NaNbO3-based perovskites

The promising prospects of antiferroelectric perovskite oxides in the realm of energy storage applications hinge on the unique field-induced phase transitions. Once the transition is triggered by the application of an electric field, characteristic double polarization loops appear. However, NaNbO3-based materials that exhibit a reversible phase transition are still rare, which hinders the practical applications of lead-free antiferroelectrics. Here, the impact of materials chemistry on the competition between antiferroelectric and ferroelectric states is demonstrated in a series of NaNbO3-based solid solutions with varying perovskite B-site cations, while the A-site is fixed as strontium. The crystal structure is analyzed on the basis of Rietveld refinement of high-energy X-ray diffraction data. The phase transition behavior as well as the antiferroelectric and ferroelectric properties are probed by a series of electrical measurements. The antiferroelectric phase is universally observed for all investigated materials in the virgin state. The SrTiO3-substituted system shows an irreversible phase transition similar to that of pure NaNbO3. In contrast, double polarization hysteresis loops are observed in the SrHfO3-, SrZrO3-, and SrSnO3-substituted systems. It is confirmed that compounds that can reduce the tolerance factor of the system contribute to the stabilization of the antiferroelectric order, while those that can reduce the electronegativity difference lead to more pronounced double loops. The competition between antiferroelectricity and ferroelectricity is linked to the competition between covalent and ionic bonding in perovskites.

Quantitative analysis of the micromechanical behavior and work hardening in Fe-0.1C–10Mn steel via in-situ high-energy X-ray diffraction

In the current work, the micromechanical behavior and work hardening behavior of Fe-0.1C–10Mn (in wt.%) steel deformed at 100, 63, 25 and −50 °C were investigated via in-situ high-energy X-ray diffraction (HE-XRD) technique. As the deformation temperature decreased, the yield strength (YS) and ultimate tensile strength (UTS) increased, while the total elongation (TE) reached a maximum value at 25 °C. The transformation kinetics of retained austenite (RA) was fitted by the Olson and Cohen (OC) model. The phase stress and flow stress contributed by the constituent phases were obtained based on the lattice strain and the volume fraction of the corresponding phase. The work hardening rate was decomposed into four contributors related to the TRIP effect and load partitioning, ie., the austenite phase stress, load partitioning between austenite and martensite, martensitic formation rate and load partitioning between ferrite and austenite. The influence of each contributor on the work hardening behavior was quantitatively evaluated and stacked, the stacked results agreed reasonably well with the experimental work hardening rate obtained from the true stress-strain curve. Finally, the volume fraction of austenite to martensite transformation promoted by the Lüders band (LB) and the stacking fault energy (SFE) of RA were found to be highly temperature-dependent. A linear relationship was revealed between the volume fraction of austenite to martensite transformation during the LB propagation and the SFE of RA. These findings offer insights into the TRIP effect and the LB propagation in medium-Mn steels.

Novel Fe-rich hypo-eutectic high entropy alloy developed for laser powder bed fusion in the Al-Co-Cr-Fe-Ni-Zr system

A novel heat resistant Fe-rich hypo-eutectic high entropy alloy (HEA) was manufactured using laser powder bed fusion (LPBF). The prealloyed Al1/4Co2Cr2Fe6Ni3/2Zr powder was characterized and processed using different preheating temperatures (650°C, 700°C and 800°C). The as-built microstructure showed dissimilar morphologies throughout the melt pool, with eutectic grains of ultra fine lamella spacing (λ≈25nm) inside the core regions, and coarser dendritic and globulitic growth patterns at the interlayer boundaries (ILBs). An annealing treatment at 1000°C for 6h yielded a homogenous composite microstructure of a Fe-rich matrix with ~40% of fine dispersed Zr-rich intermetallic (IM) phases of submicron size. Synchrotron high energy x-ray diffraction (HEXRD) revealed M2Zr Laves (M = Co, Fe, Ni) as the main IM for the as-built condition and the additional growth of M23Zr6 upon annealing. Further HEXRD in-situ high temperature tests examined the lattice parameter evolution and coefficient of thermal expansion (CTE) up to 1100°C. The mechanical performance of the as-built and annealed condition was evaluated through hardness and compression testing at room temperature (RT). Additional compression testing from RT to 1000°C were conducted on the annealed condition to assess the high temperature strength and give comparison to other high temperature materials like Ni-based superalloys.

Atomic scale investigation and cytocompatibility of copper and zinc-loaded Phosphate-Based Glasses Prepared by Coacervation

Phosphate-based glasses (PBGs) are bioresorbable materials that find application in the field of controlled drug delivery and tissue engineering. The structural arrangements of the phosphate units in PBGs, along with the knowledge of how therapeutic metallic ions are embedded in the phosphate network are important in understanding the degradation and targeted release properties of these materials. Using a combination of Raman spectroscopy, high-energy X-ray diffraction and 31P and 23Na solid-state magic angle spinning nuclear magnetic resonance, the atomic structure of coacervate PBGs in the system P2O5-CaO-Na2O-MOx (M = Cu or Zn) with loadings of 2, 10 and 15 mol % of M2+ have been studied as functions of composition and calcination temperature. After drying at room temperature, the structures of the phosphate network in PBG-Cu and PBG-Zn are quite similar, with that of PBG-Zn exhibiting slightly higher connectivity. Heating at 300°C causes degradation of the polyphosphate chains, even though Q2 species remain predominant. X-ray photoelectron spectroscopy demonstrates that Cu in calcined PBGs is present in both oxidation states +1 and +2, with a predominance of the +2 state. Cu and Zn ions release data after 24 h exposure of PBGs in deionized water and cell medium DMEM show that release is proportional to their loadings. Cytotoxicity MTT assays of dissolution products of PBG-Cu/ZnX calcined at 300 °C on human osteoblast cells (MG63) and on human skin cells (HaCaTs) showed good cellular response for all compositions, indicating that PBGs have great potential for both hard and soft tissue regeneration.

In-situ scattering and calorimetric studies of crystallization pathway and kinetics in a Cu-Zr-Al bulk metallic glass

The crystallization route and kinetics of a Cu-Zr-Al bulk metallic glass (BMG), based on Cu50Zr50, were investigated using in-situ synchrotron small- and wide-angle X-ray scattering (SAXS/WAXS), in-situ high-energy X-ray diffraction (HEXRD), and differential scanning calorimetry (DSC). The acquisition of kinetic diagrams of SAXS/WAXS enables the direct construction of the overall phase transformation route from room temperature to the onset temperature of solid state phase transformation upon heating. It is revealed that the studied alloy undergoes multiple steps (at least five steps) before reaching the high-temperature thermodynamic equilibrium. This is distinct from the commonly believed simple path of glass → Cu10Zr7 + CuZr2 → B2-CuZr predicted by the Cu-Zr equilibrium phase diagram. In addition to thermodynamics, we emphasize that kinetic factors play a prominent role in the phase transformation process of Cu-Zr-Al BMGs. Furthermore, isothermal crystallization kinetics analyses conducted by in-situ HEXRD and DSC indicate that the formation of the initial crystalline phase, specifically the Cu10Zr7, follows an interface-controlled quasi-polymorphic process with an increasing nucleation rate. The findings of this study may provide novel insights into the crystallization mechanism of glass-forming supercooled liquids from a thermophysical perspective.

Phase stability and microstructure of neutron-irradiated substoichiometric yttrium dihydrides

The impact of the neutron-displacement damage on phase stability and microstructure of substoichiometric yttrium dihydrides (YHx, x <2) were investigated to assess their use as solid moderator in high-temperature nuclear reactors. YHx specimens were, thus, subjected to neutron irradiations in the range of 0.1–2 displacements per yttrium atom (dpa-Y) in the temperature range of 536–878°C at the Oak Ridge National Laboratory's (ORNL's) High Flux Isotope Reactor (HFIR). YHx specimens were initially prepared at stoichiometry (H/Y) ratios of 1.69 and 1.83. HFIR-irradiated specimens were characterized by variety of techniques to investigate H retention characteristics including dimensional analysis, optical microscopy, scanning electron microscopy electron back scatter diffraction (EBSD), transmission electron microscopy, thermal desorption spectroscopy (TDS), and high-energy x-ray diffraction (HE-XRD) characterizations. Overall, YHx exhibited notable structural and phase stability under short-term neutron-irradiation, except for the samples with significant silicon carbide (SiC) interaction at high doses and temperatures. Basic dimensional and mass measurements were misleading for accurate assessment of H retention, as confirmed by EBSD phase maps, XRD line profiles, and TDS signals. Thus, it was discussed that a robust H retention metric is needed to assess irradiated hydrides. Nanoscale cavities were observed as a result of the neutron irradiation in all samples. Although no clear impact of dose and irradiation temperature was determined, the initial H/Y ratio had an impact on the cavity number density where low H/Y specimens had high-resistance to cavity formation. The Y-vacancy cluster formation at the collision stage of the displacement cascade and their stabilization by H were considered to be the likely underlying mechanisms for the observed cavity microstructure.

Effect of Coherent Nanoprecipitate on Strain Hardening of Al Alloys: Breaking through the Strength-Ductility Trade-Off.

So-called strength-ductility trade-off is usually an inevitable scenario in precipitation-strengthened alloys. To address this challenge, high-density coherent nanoprecipitates (CNPs) as a microstructure effectively promote ductility though multiple interactions between CNPs and dislocations (i.e., coherency, order, or Orowan mechanism). Although some strain hardening theories have been reported for individual strengthening, how to increase, artificially and quantitatively, the ductility arising from cooperative strengthening due to the multiple interactions has not been realized. Accordingly, a dislocation-based theoretical framework for strain hardening is constructed in terms of irreversible thermodynamics, where nucleation, gliding, and annihilation arising from dislocations have been integrated, so that the cooperative strengthening can be treated through thermodynamic driving force ∆G and the kinetic energy barrier. Further combined with synchrotron high-energy X-ray diffraction, the current model is verified. Following the modeling, the yield stress σy is proved to be correlated with the modified strengthening mechanism, whereas the necking strain εn is shown to depend on the evolving dislocation density and, essentially, the enhanced activation volume. A criterion of high ∆G-high generalized stability is proposed to guarantee the volume fraction of CNPs improving σy and the radius of CNPs accelerating εn. This strategy of breaking the strength-ductility trade-off phenomena by controlling the cooperative strengthening can be generalized to designing metallic structured materials.

Operando-XRD of Electrochemical Reactors for Selective Li+ Extraction from Brines and Seawater

In times of rising demand of Li for use in Li-ion batteries (LIBs), and ensuring its supply for aluminum electrolysis, ultralight alloys, optics, synthesis, nuclear research, and pharmaceuticals, it is essential to simplify the processing of Li sources in a sustainable manner. Current extraction from ores is complex and requires large energy input while generating high amounts of waste. This causes the danger of making Li a limited resource and even more expensive.[1] A new promising way is the electrochemical extraction of Li by desalination batteries (DBs) from brines or seawater[2]. Thereby, selective extraction of ions can be promoted by the chemistry of the electrode material, e.g., by using FePO4. To further enhance the selectivity, potentiostatic application proved to be useful[3]. DBs are superior to other extraction methods in terms of energy efficiency, and waste generation. Still, varying Li+ concentrations in brines[1b], competitive intercalation of other cations with similar size - especially Na+ [2] -, and degradative effects of anions[4], H2O, and O2 [5] are major challenges to overcome for DBs with FePO4.In this contribution, we focus on the selective extraction of Li+ using FePO4 electrodes by specifically-designed multi-step potentiostatic application. Results are shown for salt solutions containing a mixture of Na+/Li+, and artificial seawater. It is vital to understand the atomic-scale processes so that the electrodes, and electrochemical parameters can be optimized. Therefore, we used operando high-energy X-ray diffraction (HEXRD) microscopy to investigate the crystal structure of FePO4 during the electrochemical process. The experiments showed that the energy barrier for Na+ (de)intercalation was higher than that of Li+ during galvanostatic cycling, i.e., FePO4 is selective for Li+. Using a multi-step potentiostatic procedure, the (de)intercalation process could be enhanced, as evident from our HEXRD results and simultaneous conductivity measurements. Our tentative interpretation is that Li+ is highly selectively (de)intercalated, although electrochemical signatures hinted on a two-step process during deintercalation, which may indicate the intercalation of Na+. To selectively deintercalate the remaining Na+ over Li+, we further optimized the applied potentials. During galvanostatic cycling in artificial seawater, the (de)intercalation potentials were at more positive and more negative potentials, respectively, likely caused by the variety of cations. We expect that our results contribute to the design of high-performance DBs and inspire the exploration of further systems based on our proposed multi-step process.

Investigating Cathode Dynamics in Realistic Desalination Reactors Using Operando High-Energy Synchrotron X-Ray Microscopy

Four billion people suffer from lack of clean water at least one month of the year.[1] This critical water shortage applies not only to the supply of potable water, but also to water for use in industrial, agricultural, and energy applications. While water resources like seawater are abundant, hardly any water resource is clean enough for direct use. Desalination provides a methodology to render unusable waters from such water resources fit for use. An innovative and particularly energy-efficient electrochemistry-based approach is the Desalination Battery (DB), which stores the energy input during desalination in chemical bonds between ions and faradaic electrode, allowing for its recovery during the salination process. DBs are at the forefront of the water-energy nexus[2]. While they are promising for seawater desalination (e.g., for seawater to brackish water conversion), practical implementation and their full potential still need to be unlocked. To this end, foundational understanding of the atomic- to electrode-scale physics/chemistry underlying functionality and degradation must be unraveled.Towards this end, we utilized our unique flow-by reactor setup to combine electrochemistry, conductivity, and temperature measurements with high-energy (75 keV) operando synchrotron X-ray diffraction (HEXRD) microscopy. Our investigation encompasses both the atomic and electrode levels, using a 3-electrodes setup with LiMn2O4 and Na0.44MnO2 as electrode active materials. As such, we were able to simulate a realistic electrode environment for operando measurements, as well as observe spatially resolved structural changes by scanning the beam across the electrodes surface. These phenomena are manifested through changes in unit cell parameters and the emergence of new phases during desalination cycles. Specifically, we tracked the changes in XRD patterns over the course of several desalination cycles in LiCl and NaCl solutions, as well as synthetic seawater and mixed solutions of LiCl/MgCl2. We were able to observe high selectivity of LiMn2O4 towards Li+, even in the highly concentrated synthetic seawater solutions, and could not observe the emergence of a new Mg+ rich phase down to potentials of 0 V vs. AgCl. Na0.44MnO2 exhibited good cycling behavior in synthetic seawater akin to pure NaCl solutions, and apart from the Na+ rich phase showed no signs of additional new phases, suggesting a highly selective nature towards Na+. Furthermore, we compared constant current and constant potential protocols and observed distinct differences in peak shift behavior. Ongoing analysis of the unit cell parameters and atomic positions allows us to allocate specific intercalation sites to specific potentials, providing foundational insight into the chemistry and physics underlying the selectivity of these materials.Literature:[1] M. M. Mekonnen, et al., Sci Adv 2016, 2, e1500323.[2] Q. Li, et al., Adv Sci (Weinh) 2020, 7, 2002213.

(Invited) Structural Transformations of OER Catalysts during Activation and Operation

Electrocatalysis of the oxygen evolution reaction (OER) plays a pivotal role in the hydrogen economy. Optimizing materials for this reaction presents a significant challenge, as many highly active materials exhibit low stability during activation and/or operation. Therefore, operando methods capable of probing catalyst structure and morphology become key tools for monitoring transformations during operation. These transformations not only determine activity but also influence long-term stability. In this context, high-energy X-rays provide a valuable probe, easily penetrating electrolytes and cell walls, offering unprecedented insight into material behavior. This contribution presents several classes of OER catalysts operating in alkaline and acidic environments, with their structural transformations studied using high-energy synchrotron scattering techniques.Layered double hydroxides (LDH) represent an important class of catalysts functioning in alkaline environments. Notably, NiFe and CoFe serve as exemplary materials due to their high activity and stability. However, in many cases, the structure during the OER reaction differs from the as-prepared materials, undergoing an α-phase to γ-phase transition, where the latter is the active phase. This transition, at times reversible with potential, is challenging to observe without high-energy wide-angle X-ray scattering (WAXS) techniques [1,2]. Another interesting example involves the origin of high activity in spinel-type Co3O4 thin film catalysts, elucidated by high-energy surface X-ray diffraction (HE-SXRD). Here, the superior performance is attributed to the formation of a 3D CoOx(OH)y active phase skin layer during activation, and its thickness defines the final activity [3].In the case of catalysts operating in an acidic environment, RuOx and IrOx are acknowledged as promising materials. While RuOx exhibits high activity, it is prone to instability, whereas IrOx, although stable, demonstrates lower activity and have significantly higher price. A prevailing trend is to create solid solution alloys of Ir and Ru to capitalize on the strengths of both materials [4]. This contribution details structural investigations of a series of IrRu alloys with varying compositions prepared through DC magnetron sputtering. The study investigates the unusual stability of these materials at high current densities using operando WAXS and a custom-built electrolyzer cell [5]. The findings reveal that these alloys undergo Ru dissolution upon activation, forming a thin amorphous IrOx layer that protects the alloy underneath. The stability is defined by this layer, while the activity is mainly determined by the electronic structure of the IrRu alloy core.The examples presented are a reminder that without operando characterization of the materials it is very difficult to ascribe origins of activity and stability, as the ex-situ characterization might be misleading regarding the structure and electronic structure of the active phase.[1] Dionigi, F. et al. In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution. Nature Communications, 2020, 11. https://doi.org/10.1038/s41467-020-16237-1[2] Dresp, S. et al., Molecular Understanding of the Impact of Saline Contaminants and Alkaline pH on NiFe Layered Double Hydroxide Oxygen Evolution Catalysts. ACS Catalysis, 2021, 11, 6800–6809. https://doi.org/10.1021/acscatal.1c00773.[3] Wiegmann, T. et al., OperandoIdentification of the Reversible Skin Layer on Co3O4 as a Three-Dimensional Reaction Zone for Oxygen Evolution. ACS Catalysis, 2022, 12, 3256–3268. https://doi.org/10.1021/acscatal.1c05169.[4] Galyamin, D. et al, Unraveling the Most Relevant Features for the Design of Iridium Mixed Oxides with High Activity and Durability for the Oxygen Evolution Reaction in Acidic Media. JACS Au, 2023, 3, 2336–2355. https://doi.org/10.1021/jacsau.3c00247.[5] Moss, A. B. et al., Versatile High Energy X-Ray Transparent Electrolysis Cell for Operando Measurements. Journal of Power Sources, 2023, 562, 232754. https://doi.org/10.1016/j.jpowsour.2023.232754.

In Situ Measurements of NiAl Precipitation During Aging of Dual Hardening Hybrid Steels

The performance of modern dual hardening steels strongly relies on a well-controlled precipitation processes during manufacturing and heat treatment. Here, the precipitation of intermetallic β-NiAl in recently developed dual hardening steels has been investigated during aging using combined high-energy synchrotron X-ray diffraction and small-angle scattering. The effects of heating rate and aging temperature on the precipitation kinetics and lattice mismatch in two alloys (Hybrid 55 and Hybrid 60) were studied. Precipitation starts already during heating, typically in the temperature range 450 °C to 500 °C. The precipitation process is significantly faster at 570 °C compared to 545 °C for both steel grades, and the number density reaches its maximum already within 1 hours during aging at 545 °C and within 15 minutes during aging at 570 °C. The effect of heating rate is limited, but the precipitation during heating increases in Hybrid 60 when slower heating rate is used. This led to slightly higher volume fractions during subsequent aging, but did not affect the particle size. The lattice mismatch between β-NiAl and the matrix initially develops rapidly with time during aging, presumably due to a developing chemistry of the β phase, until a particle size of around 1.5 nm is reached, whereafter it saturates. After saturation, the lattice mismatch is small, but positive, and independent of temperature during cooling.

Unravelling dynamic recrystallisation in a microalloyed steel during rapid high temperature deformation using synchrotron X-rays

Microstructure evolution during high-strain rate and high-temperature thermo-mechanical processing of a 44MnSiV6 microalloyed steel is investigated using in situ synchrotron high-energy powder X-ray diffraction. The conditions selected replicate a newly developed near solidus high-strain rate process designed for reducing raw material use during the hot processing of steels. High temperatures (exceeding 1300 °C) and high strain rate ε˙ = 9 s-1 processing regimes are explored. The lattice strains and dislocation activity estimated from diffraction observations reveal that the microstructure evolution is primarily driven by dynamic recrystallisation. A steady-state stress regime is observed during deformation, which develops due to intermittent and competing work hardening and recovery processes. The texture evolution during the heating, tension, shear deformation and cooling stages is systematically investigated. The direct observation of phase evolution at high-temperature and high-strain rate deformation enables a comprehensive understanding of new manufacturing processes and provides deep insights for the development of constitutive models for face-centred cubic alloys.

Hydrogen Bonding in Amorphous Indomethacin.

Amorphous Indomethacin has enhanced bioavailability over its crystalline forms, yet amorphous forms can still possess a wide variety of structures. Here, Empirical Potential Structure Refinement (EPSR) has been used to provide accurate molecular models on the structure of five different amorphous Indomethacin samples, that are consistent with their high-energy X-ray diffraction patterns. It is found that the majority of molecules in amorphous Indomethacin are non-bonded or bonded to one neighboring molecule via a single hydrogen bond, in contrast to the doubly bonded dimers found in the crystalline state. The EPSR models further indicate a substantial variation in hydrogen bonding between different amorphous forms, leading to a diversity of chain structures not found in any known crystal structures. The majority of hydrogen bonds are associated with the carboxylic acid group, although a significant number of amide hydrogen bonding interactions are also found in the models. Evidence of some dipole-dipole interactions are also observed in the more structurally ordered models. The results are consistent with a distribution of Z-isomer intramolecular type conformations in the more disordered structures, that distort when stronger intermolecular hydrogen bonding occurs. The findings are supported by 1H and 2H NMR studies of the hydrogen bond dynamics in amorphous Indomethacin.