High-energy Synchrotron X-ray Research Articles

Domain switching and shear-mode piezoelectric response induced by cross-poling in polycrystalline ferroelectrics

The mechanisms contributing to the electromechanical response of piezoelectric ceramics in the shear mode have been investigated using high-energy synchrotron x-ray diffraction. Soft lead zirconate titanate ceramic specimens were subjected to an electric field in the range 0.2–3.0 MV m−1, perpendicular to that of the initial poling direction, while XRD patterns were recorded in transmission. At low electric field levels, the axial strains remained close to zero, but a significant shear strain occurred due to the reversible shear-mode piezoelectric coefficient. Both the axial and shear strains increased substantially at higher field levels due to irreversible ferroelectric domain switching. Eventually, the shear strain decreased again as the average remanent polarization became oriented toward the electric field direction. The lattice strain and domain orientation distributions follow the form of the total strain tensor, enabling the domain switching processes to be monitored by the rotation of the principal strain axis. Reorientation of this axis toward the electric field direction occurred progressively above 0.6 MV m−1, while the angle of rotation increased from 0° to approximately 80° at the maximum field of 3.0 MV m−1. A strong correlation was established between the effective strains associated with different crystallographic directions, which was attributed to the effects of elastic coupling between grains in the polycrystal.

Solid-State Phase Transformation Kinetics and Mechanisms in Additively Manufactured Ti–6Al–4V Studied Using In-Situ High-Energy Synchrotron X-ray Diffraction

Solid-State Phase Transformation Kinetics and Mechanisms in Additively Manufactured Ti–6Al–4V Studied Using In-Situ High-Energy Synchrotron X-ray Diffraction

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-1 down to just a few nm after cooling at 1 K s-1. 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-1.

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≈25 nm) inside the core regions, and coarser dendritic and globulitic growth patterns at the interlayer boundaries (ILBs). An annealing treatment at 1000°C for 6 h 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.

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.

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.

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.

The development of grain resolved stress fields around notch tips in soft-textured zirconium polycrystals: A three-dimensional synchrotron X-ray diffraction study

Texture, microstructure, and local grain neighbourhood contribute to the development of localized stresses in polycrystals. For hexagonal close-packed materials, crystal's elastic and plastic anisotropy can also be a major contributing factor, yet there is a paucity of experimental studies focusing on the extent of contribution of such parameters on the magnitude of localized stresses at microscales. This study focuses on addressing this knowledge gap by deforming double-edge-notched soft-textured α-zirconium specimens in-situ, while measuring grain scale tensorial stresses using high energy synchrotron X-ray diffraction. The specimens were subjected to cyclic loads to study the evolution of stresses in the vicinity of both shallow and deep notches. The soft-texture of the specimens is such that there are no c-axes of grains aligned along the macroscopic loading direction thereby inhibiting deformation twinning. The “as-measured” microstructures and notch geometries were imported into a crystal plasticity finite element model for further analysis. Results show that despite the absence of c-axes of grains aligned along loading direction, the developed stresses were substantially influenced by crystallographic orientations. Stress drop was observed near the onset of plasticity with further loading and the orientation and position effects were highlighted. A plastic deformation mechanism was revealed where, upon specimen loading, the mechanical constraints enforced during grain-grain interactions led to hardening. Accordingly, a parameter was devised to quantify the grain level hardening arising from this mechanism. It was shown that grain-scale stress concentration factors vary significantly before the onset of plasticity, but they settle in the plastic zone and with the progression of cycles.

Dissimilar laser welding of an as-rolled CoCrFeMnNi high entropy alloy to Inconel 718 superalloy

In this work, dissimilar laser welding between an as-rolled CoCrFeMnNi high entropy alloy (HEA) and Inconel 718 Ni-base superalloy was successfully performed. Defect-free joints with a tensile strength of 822 MPa and a fracture strain of 7.1 % were obtained. The microstructural analysis was conducted using scanning electron microscopy (SEM), electron backscattered diffraction (EBSD), energy-dispersive X-ray spectroscopy (EDS) and high energy synchrotron X-ray diffraction (SXRD), complemented by thermodynamic calculations using the CalPhaD methodology. Mechanical assessment of the joints was conducted via microhardness mapping and tensile testing, allowing to unveil processing-microstructure-properties relationships. Although the precipitation of the Laves phase was identified within the fusion zone, our results reveal the excellent dissimilar weldability between the two alloys, allowing the deployment of this dissimilar material pair for structural applications.

Computational thermodynamics-guided alloy design and phase stability in CoCrFeMnNi-based medium-and high-entropy alloys: An experimental-theoretical study

A computational thermodynamics approach has been employed to design CoCrFeMnNi-based medium- and high-entropy alloys (M/HEAs) with systematically varied compositions (Co((80-X)/2)Cr((80-X)/2)FeXMn10Ni10 with x = 30, 40, and 50 at.%) and phase stability. Since the formation of sigma phase, usually brittle and undesirable, is a common concern, when this class of alloys is subjected to elevated temperatures (600–1000 °C), predicting its formation becomes essential. Thus, its formation and the phase equilibria were studied using the CALPHAD method, and two empirical methods, namely, valence electron concentration (VEC) and paired sigma-forming element (PSFE). Isothermal aging treatments at 900–1100 °C for 20 h were performed, since CALPHAD and VEC/PSFE predictions diverged. Both prediction methods were compared with experimental characterization by a combination of scanning electron microscopy and high-energy synchrotron X-ray diffraction. The predictions from the VEC/PSFE and CALPHAD calculations (depending on the database used) were shown to be quite accurate.

Dynamics of pore formation and evolution during multi-layer directed energy deposition additive manufacturing via in-situ synchrotron X-ray imaging: A case study on high-entropy Cantor alloy

Blown-powder directed energy deposition (DED) additive manufacturing is impeded for novel alloys processing by perceivable and detrimental porosity. During multi-layer depositions, however, mechanisms of pore formation and evolution remain elusive for developing pore mitigation strategies. Here, conduction-mode multi-layer DED process of an exemplary high-entropy Cantor alloy have been investigated in-situ by high-energy high-speed synchrotron X-ray imaging. Three new pore formation mechanisms are unveiled when depositing first layer and successive layers: gas pore induced by high-velocity powder injection into melt pool, pore generated from swirl shear of turbulent melt flow, and pore trapped by surface wave. Three pore formation mechanisms are reconfirmed: pore inheritance from feedstock powder, pore generation when laser remelting defect-sensitive locations of existing pore from previous layer or unmelted powder attached on the melt pool surface, and pore formation as cooling of melt pool. A unique mechanism for pore elimination is proposed: a counter-Marangoni melt flow is experimentally found in the stable melt pool and contributes to the prolonged pore lifetime at tens of milliseconds scale; pores are prone to coalesce into larger sizes in laser interaction zone and the adjacent location with circulation zone; coalesced larger pores driven by combined effect of Marangoni and buoyant forces easily get eliminated from melt pool. The results of pore formation and evolution dynamics revealed in Cantor alloy provide quantified experimental data for high-fidelity computational modeling and in-depth insights of porosity control for high-entropy alloy printing down to melt pool scale.

Kinetics of the α → γ′ stress-induced martensitic transformation in a Fe–Mn–Al–Ni shape memory bicrystal

The Fe–Mn–Al–Ni pseudoelastic system has garnered interest for diverse engineering applications owing to its promising characteristics. The poor pseudoelasticity in polycrystals is generally attributed to activation of new martensite variants and the high density of dislocations close to austenite/martensite interface. High-energy synchrotron X-ray diffraction and microscopy studies on a Fe–Mn–Al–Ni bicrystal reveal the sequence of transformation, deformation mechanisms, and grain boundary effects on martensite nucleation, shedding light on its limited pseudoelasticity in polycrystalline configurations. The results highlight challenges in achieving pseudoelasticity in polycrystalline configurations due to disparities in deformation between grains and at grain boundaries.

In-situ microstructural evolution during tensile loading of CoCrFeMnNi high entropy alloy welded joint probed by high energy synchrotron X-ray diffraction

The research regarding high entropy alloys (HEAs) has proved them to be suitable for engineering applications. Nevertheless, assessing their processability is key for industrial deployment. Of special relevance in terms of processing techniques arised welding. In this work, Gas Tungsten Arc Welding (GTAW) was chosen as a processing method to attest for the suitability of the equiatomic CoCrFeMnNi HEA for one of the most common real-world mechanical solicitations, tensile loading. We delve into an in-situ synchrotron X-ray diffraction analysis of the mechanical behavior of a high-performing GTAW CoCrFeMnNi HEA joint. Local analysis of the microstructure evolution, considering the base material, heat affected zone and fusion zone, was performed by tracking changes in the diffracted intensity and lattice strain. Orientation-dependent evolution is highlighted by considering partial azimuthal integration detailing texture impact across the joint. Evidence of strain concentration at specific locations is correlated with the microstructure and overall macroscopic mechanical behavior.

In-situ X-ray Fluorescence Analysis of In-plane Cerium-ion Distribution Under Humidity Gradients in Proton Exchange Membrane

Cerium ions are incorporated into proton exchange membranes (PEMs) of fuel cells to mitigate its chemical degradation caused by radical species. However, under fuel cell operating conditions, cerium ions move in in-plane direction in the cell by humidity gradient. This cerium ion transport results in cerium ion depletion leading to accelerated chemical degradation. This study developed an in-situ and operando measurement technique utilizing synchrotron high-energy X-ray fluorescence spectroscopy to monitor the cerium ion transport across the membrane under the in-plane humidity gradient. This method effectively tracks the dynamic behavior of cerium ions under fuel cell operating conditions.

Behavior of Microstrain in Nd3+-Sensitized Near-Infrared Upconverting Core-Shell Nanocrystals for Defect-Induced Tailoring of Luminescence Intensity.

In an attempt to optimize the upconversion luminescence (UCL) output of a Nd3+-sensitized near-infrared (808 nm) upconverting core-shell (CS) nanocrystal through deliberate incorporation of lattice defects, a comprehensive analysis of microstrain both at the CS interface and within the core layer was performed using integral breadth calculation of high-energy synchrotron X-ray (λ = 0.568551 Å) diffraction. An atomic level interpretation of such microstrain was performed using pair distribution function analysis of the high-energy total scattering. The core NC developed compressive microstrain, which gradually transformed into tensile microstrain with the growth of the epitaxial shell. Such a reversal was rationalized in terms of a consistent negative lattice mismatch. Upon introduction of lattice defects into the CS systems upon incorporation of Li+, the corresponding UCL intensity was maximized at some specific Li+ incorporation, where the tensile microstrain of CS, compressive microstrain of the core, and atomic level disorders exhibited their respective extreme values irrespective of the activator ions.

High throughput automated characterization of enamel microstructure using synchrotron tomography and optical flow imaging

The remarkable damage-tolerance of enamel has been attributed to its hierarchical microstructure and the organized bands of decussated rods. A thorough characterization of the microscale rod evolution within the enamel is needed to elucidate this complex structure. While prior efforts in this area have made use of single particle tracking to track a single rod evolution to various degrees of success, such a process can be both computationally and labor intensive, limited to the evolution path of a single rod, and is therefore prone to error from potentially tracking outliers. Particle image velocimetry (PIV) is a well-established algorithm to derive field information from image sequences for processes that are time-dependent, such as fluid flows and structural deformation. In this work, we demonstrate the use of PIV in extracting the full-field microstructural distribution of rods within the enamel. Enamel samples from a wild African lion were analyzed using high-energy synchrotron X-ray micro-tomography. Results from the PIV analysis provide sufficient full-field information to reconstruct the growth of individual rods that can potentially enable rapid analysis of complex microstructures from high resolution synchrotron datasets. Such information can serve as a template for designing damage-tolerant bioinspired structures for advanced manufacturing. Statement of significanceThorough characterization and analysis of biological microstructures (viz. dental enamel) allows us to understand the basis of their excellent mechanical properties. Prior efforts have successfully replicated these microstructures via single particle tracking, but the process is computationally and labor intensive. In this work, optical flow imaging algorithms were used to extract full-field microstructural distribution of enamel rods from synchrotron X-ray computed tomography datasets, and a field method was used to reconstruct the growth of individual rods. Such high throughput information allows for the rapid production/prototyping and advanced manufacturing of damage-tolerant bioinspired structures for specific engineering applications. Furthermore, the algorithms used herein are freely available and open source to broaden the availability of the proposed workflow to the general scientific community.

Endowing low fatigue for elastocaloric effect by refined hierarchical microcomposite in additive manufactured NiTiCuCo alloy

NiTiCu-based shape memory alloys have been considered as ideal materials for solid-state refrigeration due to their superb cycling stability for elastocaloric effect. However, the embrittlement and deterioration caused by secondary phase and coarse grains restrict their applications, and it is still challenging since the geometric components are required. Here, bulk NiTiCuCo parts with excellent forming quality were fabricated by laser powder bed fusion (LPBF) technique. The as-fabricated alloy exhibits refined three-phases hierarchical microcomposite formed based on the rapid cooling mode of LPBF, composed of intricate dendritic Ti2Ni–NiTi composite and nano Ti2Cu embedded inside the NiTi-matrix. This configuration endows far superior elastocaloric stability compared to the as-cast counterpart. The low fatigue stems from the strong elastic coupling between the interphases with reversible martensite transformation, revealed by in-situ synchrotron high-energy x-ray diffraction. The fabrication of NiTiCuCo alloy via LPBF fills the bill of complex geometric structures for elastocaloric NiTiCu alloys. The understanding of interphase micro-coupling could provide the guide for designing LPBF fabricated shape memory-based composites, enabling their applications for special demands on other functionalities.

In-Situ synchrotron investigation of elastic and tensile properties of oxide dispersion strengthened EUROFER97 steel for advanced fusion reactors

The augmentation of mechanical properties of reduced activation ferritic martensitic steels through the introduction of creep resistant nano-oxide particles produces a class of oxide dispersion strengthened steels, which have attracted significant interest as candidates for first wall supporting structural materials in future nuclear fusion reactors. In the present work, the effect of temperature on the elastic properties and micro-mechanics of 0.3 wt% Y2O3 oxide dispersion strengthened steel EUROFER97 is investigated using synchrotron high energy X-ray diffraction in-situ tensile testing at elevated temperatures, alongside the non-oxide strengthened base steel as a point of comparison. The single crystal elastic constants of both steels are experimentally determined through analysis of the diffraction peaks corresponding to specific grain families in the polycrystalline samples investigated. The effect of temperature on the evolving dislocation density and character in both materials is interrogated, providing insight into deformation mechanisms. Finally, a constitutive flow stress model is used to evaluate the factors affecting yield strength, allowing the strengthening contribution of the oxide particles to be assessed, and correlation between the thermally driven microstructural behaviour and macroscopic mechanical response to be determined.

Unveiling the correlation between anomalous hardening and grain boundary diffusional transformation in ω single-phase nano-grained Ti-Fe alloy

A metastable ω single-phase nanograined (NG) Ti-Fe alloy was synthesized using laser inert-gas condensation (IGC). Upon being annealed at 360 °C, the NG Ti-Fe alloy exhibited a remarkable ultra-hardening, increasing the hardness from 4.7 to 8.6 GPa. Subsequent findings revealed an unexpected hardness enhancement, rising from 6.6 GPa at 420 °C to 7.6 GPa at 460 °C, despite the occurrence of grain growth. In-depth investigations into the strengthening mechanisms of the NG Ti-Fe alloy were conducted using in-situ synchrotron high-energy X-ray diffraction (XRD) and transmission electron microscopy (TEM). The comprehensive analysis unveiled that the diffusion-controlled structure evolution during annealing played a pivotal role in enhancing the alloy’s mechanical properties. This study not only presents the synthesis of a novel metastable alloy but also provides valuable insights into the intricate relationship between diffusion-controlled structure evolution and the resulting superior mechanical properties.