High-energy X-ray Diffraction Research Articles

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.

Rapid detection of rare events from in situX-ray diffraction data using machine learning.

High-energy X-ray diffraction methods can non-destructively map the 3D microstructure and associated attributes of metallic polycrystalline engineering materials in their bulk form. These methods are often combined with external stimuli such as thermo-mechanical loading to take snapshots of the evolving microstructure and attributes over time. However, the extreme data volumes and the high costs of traditional data acquisition and reduction approaches pose a barrier to quickly extracting actionable insights and improving the temporal resolution of these snapshots. This article presents a fully automated technique capable of rapidly detecting the onset of plasticity in high-energy X-ray microscopy data. The technique is computationally faster by at least 50 times than the traditional approaches and works for data sets that are up to nine times sparser than a full data set. This new technique leverages self-supervised image representation learning and clustering to transform massive data sets into compact, semantic-rich representations of visually salient characteristics (e.g. peak shapes). These characteristics can rapidly indicate anomalous events, such as changes in diffraction peak shapes. It is anticipated that this technique will provide just-in-time actionable information to drive smarter experiments that effectively deploy multi-modal X-ray diffraction methods spanning many decades of length scales.

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.

Synchrotron X-ray diffraction studies of the internal load transfer in Ni–CrC metal matrix composites

Strengthening in metal matrix composites (MMCs) is primarily due to the load transfer from the compliant matrix to the stiff reinforcement. While internal load transfer has been studied for conventionally manufactured MMCs, the extent to which it may be affected by the preexisting defects in additively manufactured MMCs remain elusive. In this study, we performed uniaxial compression loading on cold sprayed Ni–CrC particulate-reinforced MMC. We observe significantly enhanced strength and ductility compared to the brittle behavior previously reported in tension for the same MMC. In contrast to the absence of load transfer in tension, the presence of initial defects did not preclude the internal load transfer in the composites under compressive loading. In-situ high-energy X-ray diffraction analysis revealed a relatively constant load partitioning in the elastic regime, which aligned well with predictions by the Eshelby's inclusion model. Furthermore, an internal load transfer was observed from the Ni matrix to the CrC reinforcement upon plastic deformation of the Ni matrix. Finite element modeling further confirmed this and demonstrated that localized tensile stress at the interface in the transverse direction resulted in the interfacial debonding and partial relaxation of the matrix. We also report reinforcing particle fracture upon further compression which in turn triggered the eventual failure of the MMC.

Unveiling the formation of nanotwin-mediated metastable ζ-hydrides in fatigued Zr-1Nb-0.01Cu cladding tube

The impact of internal pressure fatigue treatment on the α-Zr matrix and hydride precipitates in Zr-1Nb-0.01Cu cladding tube has been systematically investigated using synchrotron-based high-energy X-ray diffraction, electron backscatter diffraction and transmission electron microscopy techniques. The evolution in d-spacings of the basal plane (0002), the pyramidal plane {101¯1} and the prismatic plane {101¯0} at azimuths from 0° to 360° indicates that the internal pressure fatigue treatment has imparted a degree of plastic deformation upon the α-Zr phase, which is further confirmed by the presence of {101¯2} deformation twins within the α-Zr phase. Concurrently, the prior internal pressure fatigue treatment at 400 °C significantly increased nucleation sites for zirconium hydrides during the subsequent furnace cooling process. High-density dislocations can be seen in both the δ-hydride precipitate ({111}<110> type) and the α-Zr matrix ({101¯0}<a> type) near the hydride-matrix interface. Additionally, δ-hydride {111}<112¯> nanotwins were observed within the micro-sized δ-hydrides in the fatigued cladding tube, resulting from the nucleation and growth of intra-granular δ-hydrides at different regions of the same parent α-Zr grain. Furthermore, the HCP-structured ζ-hydride phase was detected at the δ-hydride nanotwin forefront along the growth direction and at the curved δ-hydride nanotwin boundaries, providing direct experimental evidence to the notion that the metastable ζ-hydride serves as the precursor to the stable δ-hydride phase during the precipitation process. The current experimental findings contribute to the fundamental understanding of microscopic mechanisms underlying the delayed hydride cracking and the stress-induced hydride reorientation in Zr alloys.

Effects of High Al Content on the Phase Constituents and Thermal Properties in NiCoCrAlY Alloys.

MCrAlY (M = Ni and/or Co) metallic coatings are essential for the protection of hot-end components against thermal and corrosion damage. Increasing the Al content is considered a feasible solution to improve the high-temperature performance of MCrAlY coatings. In this paper, the effects of high Al contents (12-20 wt.%) on the phase constituents and cast microstructures in MCrAlY alloys were studied by high-energy X-ray diffraction and electron microscopy techniques combined with phase equilibria calculations. High Al content improved the stability of β, σ, and α phases. Meanwhile, an evolution of the cast microstructure morphology from a dendrite structure to an equiaxed grain structure was observed. The thermal properties were analyzed, which were closely related to the phase constituents and solid-to-solid phase transitions at evaluated temperatures. This work is instructive for developing high-Al-content MCrAlY coatings for next-generation thermal barrier applications.

In situ HEXRD experimental study and prediction of microstructures and internal stresses during heat treatment of carburized and carbonitrided low-alloyed steels

Thermochemical surface treatments of steels, such as carburizing and carbonitriding are used to improve mechanical properties, especially resistance to fatigue. Carbonitriding can achieve excellent properties, but the origins remain to be understood, as it has been less studied than carburizing. Fundamental understanding has to be established regarding the formation of microstructures and internal stresses as well as their couplings, during the cooling which follows the enrichment treatment.For this purpose, an original experimental method is introduced to follow in situ by High-Energy X-Ray Diffraction the phase transformation kinetics as well as the evolutions of the internal stresses during cooling, inside laboratory scale, 3 mm-thick samples with C and/or N composition gradients. The usual trends are confirmed regarding carburizing: the carbon-enriched case is the last to transform and the surface ends up with compression residual stresses. Conversely, for carbonitriding, unusual evolutions of microstructure and internal stresses are observed. The presence of nitrogen reduces the hardenability in the enriched case. This modifies the chronology of the phase transformations and this leads to tensile residual stresses at the surface.A coupled thermal, mechanical and metallurgical model predicting the phase transformation kinetics and the evolutions of internal stresses is set up. It achieves quantitative predictions and it shows that, in the studied cases, the phase transformation plasticity strains are the main origin of the residual stresses.

Microstructure and Phase Transformation Behavior of NiTiCu Shape Memory Alloys Produced Using Twin-Wire Arc Additive Manufacturing

NiTiCu thin walls were produced by twin-wire arc additive manufacturing (T-WAAM) using commercial NiTi and Cu wires as the feedstock materials. This approach aims to solve the problems typically associated with large phase transformation hysteresis in NiTi shape memory alloys. The microstructure, mechanical properties, and phase transformation behavior of the as-deposited NiTiCu alloy were comprehensively examined. The results revealed that the as-deposited NiTiCu alloy was well-formed, with its microstructure showed columnar, equiaxed, and needle-like grains, depending on the location within the deposited walls. The microhardness gradually increased from the first to the third layer. The Cu content was 20.80 at%, and Cu-based precipitates were formed in the as-deposited NiTiCu. The volume fractions and lattice parameters of the matrix and precipitates in the as-deposited NiTiCu material were analyzed using high-energy synchrotron X-ray diffraction. The martensitic phase was identified as a B19 crystal structure, and the as-deposited NiTiCu underwent a one-step B2-B19 phase transformation. The tensile strength and fracture strain were approximately 232 MPa and 3.72%, respectively. In particular, the addition of Cu narrowed the phase transformation hysteresis of the as-deposited NiTiCu alloy from 24.4 to 7.1 ℃ compared with conventional binary NiTi alloys. This study expands the potential of T-WAAM in modifying the phase transformation behavior of NiTi-based ternary alloys.

Strains and Stresses in Multilayered Materials Determined Using High-Energy X-ray Diffraction

This work explores the advantages and disadvantages of a methodology using high-energy X-ray diffraction to determine residual stresses in multilayer structures produced by atmospheric plasma spraying. These structures comprise a titanium alloy substrate (Ti64), a bonding layer (Ni-Al), and an abrasive coating (Al2O3). This study focuses on analyzing the residual stress gradients within these layers. The presented method is used to determine stresses across the entire thickness of multilayer structures. Experiments were carried out using a high-energy rectangular beam, operating in transmission mode, on the cross-section of the sample. The results indicate variable stresses throughout the depth of the sample, particularly near the layer interfaces. The semi-automatic methodology presented here enables us to follow stress evolution within the different layers, providing indications of the load transfer between them and at their interfaces. The sin2ψ method was used to analyze the diffraction data and to determine the stresses in each phase along the sample depth. However, interpreting results near the interfaces is complex due to the geometric and chemical effects. We present a discussion of the main advantages and disadvantages of the methodology for this kind of industrial sample.

Intermolecular Correlations in Liquid Lactic Acid Based on ab initio Molecular Dynamics Simulations Combined with High-Energy X-ray Diffraction Measurements

Intermolecular Correlations in Liquid Lactic Acid Based on ab initio Molecular Dynamics Simulations Combined with High-Energy X-ray Diffraction Measurements

The effect of double intercritical annealing on micromechanical behavior of a medium Mn transformation induced plasticity steel investigated by in situ high energy X-ray diffraction

The micromechanical behavior of a medium Mn transformation induced plasticity (TRIP) steel processed by intercritical annealing (IA) and double intercritical annealing (DIA) has been investigated by using in situ high energy X-ray diffraction during uniaxial tensile deformation. The results show that the ultimate tensile strength (UTS) and total elongation are 777.1 MPa and 39.6 % for IA and 953.6 MPa and 59.1 % for DIA, and that the product of UTS and total elongation is 30.8 GPa·% for IA and 56.4 GPa·% for DIA, respectively. Discontinuous phase transformation from austenite to martensite leads to Portevin-Le Châtelier (PLC) band propagation for both IA and DIA. The pronounced TRIP effect takes place in DIA step by step during deformation and contributes to higher strain hardening, which results in almost doubling the product of UTS and total elongation. The stepwise phase transformation highly corresponds to the lattice strain evolution of ferrite and austenite, indicating that load partitioning occurs during the deformation. The change of grain structure generated by different heat-treatments correlate with the load partitioning, thereby inducing large discrepancy in micromechanical behavior. The present investigation provides a deeper fundamental understanding of the effect of double inter-critical annealing on micromechanical behavior and effective engineering strategies for improving the product of UTS and total elongation for the medium Mn TRIP steels.

Structure of TeO2 Glass and Melt by Reverse Monte Carlo Simulations of High-Energy X-Ray Diffraction Data Sets.

The short-range and medium-range structures of TeO2 glass and melt are elucidated by Reverse Monte Carlo (RMC) simulations of High-Energy X-ray Diffraction data sets published in an earlier study by Alderman et al. (J. Phys. Chem. Lett.11(1) (2020)427-431). The RMC analysis reveals that there exists a wide range of Te-O bond lengths in both TeO2 glass and melt short-range structures. The Te-O pair distribution function (PDF) of the melt has peaks centered at 1.87, 2.06, 2.35, 2.65, and 3.00 (±0.01) Å, whereas the corresponding peaks in the glass are at 1.91, 2.07, 2.28, 2.54, 2.77, and 3.00 (±0.01) Å. The Te-O partial PDF of the melt shows a peak at 2.35 Å, which is not present in the glass structure; therefore, the same co-ordination sphere radius of 2.36 Å cannot be used for calculating the Te-O co-ordination numbers in the TeO2 melt and glass, as done in the earlier study by Alderman et al. Using a more appropriate radius of 2.41 Å for glass and 2.22 Å for the melt, the corresponding Te-O co-ordination numbers are found to be 3.99 and 3.33, respectively. The RMC analysis successfully determined the O-O pair distributions, which show the first peaks at 2.31-2.33 (±0.01) Å. Finally, Te-Te pair distributions show peaks at slightly longer distances in the melt compared to those in glass, and the melt is found to have greater medium-range disorder.

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.

Influence of Zr element on the atomic structure of Al-Cu alloy liquid

The relationship among chemical composition, structure and glass-forming ability in multicomponent alloys is a long-standing puzzle due to the complexity of compositions. In this work, Al77.8Cu22.2 and Al70Cu20Zr10 amorphous alloy liquids were investigated by combining high-energy X-ray diffraction at a synchrotron facility, ab-initio molecular dynamics and reverse Monte Carlo simulations. The analysis of short- and medium-range order structures of two liquid alloys show that the addition of Zr element increases the number of cluster types and makes the distribution of cluster content more uniform, and enhances the structural heterogeneity and correlation of clusters with high five-fold symmetry. These findings reveal the influence of Zr element on the atomic structure of the Al-Cu liquid alloy and deepen the understanding of Al-based metallic glasses formation.

Epitaxial growth and magnetic properties of Mn5(SixGe1-x)3 thin films

Structural and magnetic properties of Mn5(SixGe1-x)3 thin films were investigated. Ferromagnetic Mn5Ge3 and anti-ferromagnetic Mn5Si3 thin films have been synthesized and characterized as these compounds exhibit interesting features for the development of spintronics. Here, Mn5(SixGe1-x)3 thin films were grown on Ge(111) substrates by co-deposition using molecular beam epitaxy. Crystalline thin films can be produced with controlled Si concentrations ranging from 0 to 1. The thin films were relaxed by dislocations at the interface with the substrate. A lattice parameter variation was observed as the Si content increased, which is comparable to previous works done in bulk. Reflection high-energy electron diffraction diagrams and X-ray diffraction profiles showed that lattice parameters a and c are shrinking and that the surface roughness and crystallinity degrade as the Si amount increases. Magnetometric measurements revealed a ferromagnetic behavior for all Si concentrations. The measured average ferromagnetic moment per manganese atom decreased from 2.33 to 0.05 μB/Mn atom. No ferro to anti-ferromagnetic transition was observed contrary to the bulk Mn5(SixGe1-x)3 compound.

Supercritical Gallium Trichloride in Oxidative Metal Recycling: Ga2Cl6 Dimers vs GaCl3 Monomers and Rheological Behavior.

Oxidative recycling of metals is crucial for a circular economy, encompassing the preservation of natural resources, the reduction of energy consumption, and the mitigation of environmental impacts and greenhouse gas emissions associated with traditional mining and processing. Low-melting gallium trichloride appears to be a promising oxidative solvent for rare-earth metals, transuranium elements, platinum, pnictogens, and chalcogens. Typically, oxidative dissolution with GaCl3 occurs at relatively low temperatures over a few days, assuming the presence of tetrahedral Ga-Cl entities. While supercritical gallium trichloride holds the potential for advanced recycling, little is known about its structure and viscosity. Using high-energy X-ray diffraction and multiscale modeling, which includes first-principles simulations, we have revealed a dual molecular nature of supercritical gallium trichloride, consisting of tetrahedral dimers and flat trigonal monomers. The molecular geometry can be precisely tuned by adjusting the temperature and pressure, optimizing the recycling process for specific metals. The derived viscosity, consistent with the reported results in the vicinity of melting, decreases by a factor of 100 above the critical temperature, enabling fast molecular diffusion, and efficient recycling kinetics.

In-situ synchrotron X-ray diffraction study of the effects of grain orientation on the martensitic phase transformations during tensile loading at different strain rates in metastable austenitic stainless steel

In this work, in-situ high-energy X-ray diffraction was used to analyze the effects of strain rate and austenite (γ) grain orientation on the strain-induced martensitic transformation in metastable austenitic stainless steel 301LN. The diffraction measurements were carried out at strain rates ranging from 10−3 s−1 to 1 s−1 continuously without interrupting the experiment and thus creating nearly adiabatic conditions at the highest studied strain rate. The results indicate that <100>γ fiber-oriented grains preferentially transform at the strain rate of 10−3 s−1 when the true strain is above 0.10, whereas the <111>γ fiber-oriented grains transform only at later stages of plastic deformation. The phase transformation rate of the <111>γ and <100>γ fiber-oriented grains decreases with increase in strain rate. A theoretical model based on stacking fault width as a function of external stress and temperature (stacking fault energy) was used to predict lower-bound estimates for the critical tensile stress needed to start ε-martensite and α’-martensite phase transformations. The model can predict the experimentally observed phase transformation behavior of the <111>γ fiber orientations at all strain rates but is unable to predict the decrease of phase transformation rate of <100> fiber-oriented γ grains with increase in strain rate, which could be related to change in dislocation structure.

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.

Austenite formation in a medium-Mn steel during intercritical annealing via in situ high-energy X-ray diffraction

The microstructural evolution of a prototype Fe-0.15C-5.56Mn-1.1Si-1.89Al medium-Mn third-generation advanced high strength steel (3G AHSS) with a martensite-ferrite (MF) starting microstructure during intercritical annealing was determined in situ using high energy X-ray diffraction (HEXRD). Intercritical annealing was carried out at 665 °C and 710 °C for 120 s and 240 s, followed by cooling to room temperature. HEXRD data were analyzed to monitor the austenite fraction and lattice parameters throughout the thermal cycle. During isothermal holding, the austenite fraction increased, up to 31% and 45% for the samples annealed for 120 s, and up to 33% and 46% for the samples annealed for 240 s at 665 °C and 710 °C, respectively. Observed changes in lattice parameters during isothermal holding were attributed to composition changes due to the partitioning of C between austenite and ferrite. Diffusion simulations using DICTRA were used to calculate solute partitioning during intercritical annealing, providing further insights into both austenite growth and the distribution of alloying elements within the austenite.