High-energy X-ray Diffraction Research Articles

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.

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.

An approach to surface electron density-sensing property correlation in non-stoichiometric boron carbide

The key to most surface phenomena lies in the surface electron density. Particularly, it is the electron density distribution over the surface that primarily controls the overall interaction of the material with the external environment, say in processes like heterogeneous catalysis. Hence, a precise understanding of surface electron density is essential to understand and design improved surface active materials for catalysis and sensing. Surface structure has been determined primarily using surface sensitive techniques like high-energy surface x-ray diffraction (XRD), the crystal truncation rod scattering method, low-energy electron diffraction, scanning transmission electron microscopy, and grazing incidence small angle x-ray scattering. In this work, using aspherical electron density models of crystal structures in different molecular and extended solids, we show a convenient and complementary way of determining high-resolution experimental surface electron density distribution from conventional bulk x-ray diffraction data. The usefulness of our method has been validated by the surface functionality of boron carbide. While certain surfaces in boron carbide show the presence of substantial electron deficient centers, they are absent in others. Based on that, a new surface property of boron carbide has been inferred and has also been validated by chemiresistive gas sensing experiments.

In-situ synchrotron X-ray diffraction investigation of martensite decomposition in Laser Powder Bed Fusion (L-PBF) processed Ti–6Al–4V

Laser powder bed fusion (L-PBF) processed Ti–6Al–4V components present two substantial challenges: the presence of tensile residual stress and brittleness of the as-fabricated component due to the formation of the martensite (α′) phase. Industrially, post-heat treatment is performed to improve the quasi-static mechanical properties of the Ti–6Al–4V component through martensite (α′) decomposition and residual stress relaxation. However, detailed insights into the martensite decomposition and stress relaxation mechanisms are still lacking. To address this, in-situ high-energy synchrotron x-ray diffraction (HEXRD) was employed to simultaneously track: (I) martensite (α′) decomposition into a mixture of hexagonal α and body-centered cubic β phases, (II) residual stress relaxation process during heating. Rietveld refinement of 2D diffraction patterns recorded over a temperature range spanning from 25 to 1000°C revealed a three-stage evolution in the α′ unit cell parameters. Unit cell parameter analysis combined with the phase fraction analysis based on the diffraction patterns and the chemical composition profiles predicted by Thermocalc simulation gave detailed insight into the martensite (α′) decomposition process. In Stage 1 (until 375°C), the α′ phase unit cell exhibited linear expansion without indications of any phase transformation or stress relaxation. Upon commencement of stage II at 375°C, an increased expansion rate of the martensite (α′) unit cell was observed, attributed to the enhanced outward diffusion of vanadium (V), succeeded by β phase nucleation at 575°C. Simultaneously, during stage II, residual stress relaxation was observed at both macro and micro scale, culminating in a stress-free state achieved at approximately 750–800°C. Lastly, α-to-β phase transformation was observed in stage 3. The thermal evolution of the hexagonal unit cell dimensions was compared between martensitic and mill-annealed α+β microstructures. This comparison unraveled the link between the initial microstructure and the thermal expansion behavior of the hexagonal α′ and α phase.

Pressure-Induced Changes in the Crystal Structure and Electrical Conductivity of GeV4S8.

Lacunar spinels, represented by AM4X8 compounds (A = Ga or Ge; M = V, Mo, Nb, or Ta; X = S or Se), form a unique group of ternary chalcogenide compounds. Among them, GeV4S8 has garnered significant attention due to its distinctive electrical and magnetic properties. While previous research efforts have primarily focused on studying how this material behaves under cooling conditions, pressure is another factor that determines the state and characteristics of solid matter. In this study, we employed a diamond anvil cell in conjunction with high-energy synchrotron X-ray diffraction, Raman spectroscopy, four-point probes, and theoretical computation to thoroughly investigate this material. We found that the structural transformation from cubic to orthorhombic was initiated at 34 GPa and completed at 54 GPa. Through data fitting of volume vs pressure, we determined the bulk moduli to be 105 ± 4 GPa for the cubic phase and 111 ± 12 GPa for the orthorhombic phase. Concurrently, electrical resistance measurements indicated a semiconductor-to-nonmetallic conductor transition at ∼15 GPa. Moreover, we experimentally assessed the band gaps at different pressures to validate the occurrence of the electrical phase transition. We infer that the electrical phase transition correlates with the valence electrons in the V4 cluster rather than the crystal structure transformation. Furthermore, the computational results, electronic density of states, and band structure verified the experimental observation and facilitated the understanding of the mechanism governing the electrical phase transition in GeV4S8.

Gallium Trichloride Fluid: Dimer Dissociation Mechanism, Local Structure, and Atomic Dynamics.

Molten gallium trichloride emerges as a promising solvent for oxidative metal recycling. The use of supercritical fluid enhances the performance and kinetics of metal dissolution due to significantly lower viscosity in the reaction media. Additionally, the dual molecular nature of gallium trichloride, existing as edge-sharing ES-Ga2Cl6 dimers at low temperatures and high pressure, or flat trigonal GaCl3 monomers in the vicinity of the critical point and low pressures, creates the possibility to tailor the chemical geometry to a particular metallic species. Nevertheless, the mechanism of dimer dissociation, local structure, and atomic dynamics in supercritical gallium trichloride fluids are not known. Using first-principles molecular dynamics, validated by comparison with our high-energy X-ray diffraction results, we illustrate the elementary steps in dimer dissociation. These include the formation of intermediate corner-sharing CS-Ga2Cl6 dimers, the partial disproportionation of GaCl3 monomers at high temperatures and low pressures, changes in the local environment of molecular entities, and unusual atomic dynamics in supercritical fluids.

Coupled study on in-situ synchrotron high-energy X-ray diffraction and in-situ EBSD on the interfacial stress gradient in layered metals

As one of the heterostructures, the layered structure has attracted extensive research interest as it achieves superior properties to individual components. The layer interface is considered a critical factor in determining the mechanical properties of layered metals, where heterogeneity across the interface results in the strengthening of the soft layer and forming an interfacial stress gradient in the hard layer. However, there is still limited research associated with the formation of interfacial stress gradients in the hard layer, as stress measurement at high spatial resolution remains technically challenging. In the present study, we experimentally quantified the formation of interfacial stress gradients in the Ti layer of Ti/Al layered metal upon tension using in-situ high-energy X-ray diffraction (XRD). The analysis coupling in-situ high-energy XRD and in-situ electron back-scattered diffraction (EBSD) suggested that the interfacial stress gradient in the Ti layer rapidly rose as the Al layer was insufficient to accommodate the deformation of Ti. During the later deformation stage, collective effects of dislocation motion and geometrically necessary dislocation (GND) accumulation in the Al layer determined the evolution of interfacial stress gradients. The maximum interfacial stress gradient is below 0.4 MPa/μm in Ti layers, with a constant range width of 35 μm independent of the macroscopic strain. The present study therefore opens a new window to local stress modification using incompatible component deformation, which is instructive for the design and fabrication of high-performance layered metals.