High-energy X-ray Diffraction Measurements Research Articles

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

In situ high-pressure pair distribution function measurement of liquid and glass by using 100keV pink beam.

Understanding the pressure-induced structural changes in liquids and amorphous materials is fundamental in a wide range of scientific fields. However, experimental investigation of the structure of liquid and amorphous material under in situ high-pressure conditions is still limited due to the experimental difficulties. In particular, the range of the momentum transfer (Q) in the structure factor [S(Q)] measurement under high-pressure conditions has been limited at relatively low Q, which makes it difficult to conduct detailed structural analysis of liquid and amorphous material. Here, we show the in situ high-pressure pair distribution function measurement of liquid and glass by using the 100keV pink beam. Structures of liquids and glasses are measured under in situ high-pressure conditions in the Paris-Edinburgh press by high-energy x-ray diffraction measurement using a double-slit collimation setup with a point detector. The experiment enables us to measure S(Q) of GeO2 and SiO2 glasses and liquid Ge at a wide range of Q up to 20-29 Å-1 under in situ high-pressure and high-temperature conditions, which is almost two times larger than that of the conventional high-pressure angle-dispersive x-ray diffraction measurement. The high-pressure experimental S(Q) precisely determined at a wide range of Q opens the way to investigate detailed structural features of liquids and amorphous materials under in situ high-pressure and high-temperature conditions, as well as ambient pressure study.

Behavior of TRIP-aided medium Mn steels investigated by in situ synchrotron X-ray diffraction experiments and microstructure-based micromechanical modelling

Medium Mn steels belong to a new generation of advanced high-strength steels whose superior mechanical properties are explained by their ultrafine-grained ferrite/austenite/martensite microstructures and a possible transformation induced plasticity (TRIP) related to the stability of retained austenite. The mechanical behaviour of a set of model medium Mn steels is investigated during tensile testing using a combination of high-energy X-ray diffraction (HEXRD) and digital image correlation (DIC) measurements. HEXRD allows for the time-resolved determination of transformation kinetics and in situ stress partitioning among the different constituting phases. DIC provides precise spatiotemporal information on the strain evolution along the gauge length, particularly at the position of the diffracting volume. These experiments served to calibrate an innovative mean field micromechanical model which accounts for the local behaviour of each phase, as well as the strain-induced martensitic transformation (SIMT) of retained austenite. The work-hardening of both austenite and ferrite is modeled using a dislocation-based size-sensitive approach which includes kinematic hardening contributions. The behaviours of fresh and strain-induced martensite are predicted using a genuine model derived from the continuous composite approach. The model for SIMT is based on a thermodynamic assessment of the stability of retained austenite. The overall model is thus sensitive to the size of the microstructure components, their local chemistry, and their respective stability.

Pressure driven polymorphic transitions in nanocrystalline Lu2O3, Tm2O3 and Eu2O3

The crystallite size of the materials considerably influences the material properties, including their compressibility and resistance to external forces and the stability of the crystalline structure; a corresponding study for which, so far, has been limited for the important class of nanocrystalline Rare Earth Sesquioxides (REOs). In the present study, we report the crystallographic structural transitions in nanocrystalline Rare Earth Oxides (REOs) under the influence of pressure, investigated via high-energy X-Ray Diffraction (XRD) measurements. The study has been carried out on three of the REOs, namely Lutetium oxide (Lu2O3), Thulium oxide (Tm2O3) and Europium oxide (Eu2O3) up to the pressures of 33, 22 and 11 GPa, respectively. The diffraction data of Lu2O3 and Tm2O3 suggests the occurrence of irreversible structural transitions from cubic to monoclinic phase, while Eu2O3 showed a transition from the cubic to hexagonal phase. The transitions were found to be accompanied by a collapse in the volume and the resulting Pressure–Volume (P–V) graphs are fitted with the 3rd order Birch-Murnaghan (BM) equation of state (EOS) to estimate the bulk moduli and their pressure derivatives. Our study establishes a qualitative relationship between the crystallite size and various material properties such as the lattice parameters, transition pressure, bulk modulus etc., and strengthens the knowledge regarding the behaviour of this technologically important class of materials.

Mechanical properties and thermal stability of ZrCuAlx thin film metallic glasses: Experiments and first-principle calculations

In this work, we provide a holistic picture about the relationship between atomic structure, mechanical properties, and thermal stability of ZrCuAlx thin film metallic glasses (TFMGs) varying the Al content from 0 to 12 at.%, carrying out a broad characterization involving experiments and ab initio molecular dynamic simulations (AIMD). We show that the addition of Al resulted in a change of average interatomic distances by ∼10 pm with the formation of shorter bonds (Al-Zr and Al-Cu), influencing the mechanical response (shear/elastic moduli and hardness) which increases by ∼15% for 12 at.% Al. Moreover, tensile tests on polymer substrate revealed a maximum value for the crack initiation strain of 2.1% for ZrCuAl9, while the strain-to-failure rapidly decreases at higher Al contents. The observed reduction in damage tolerance is correlated to a transition in atomic configuration. Specifically, a maximum in density of full and defective icosahedral cluster population is observed at 9 at.% Al, inducing a more shear-resistant behavior to the material. Thermal stability is investigated by high-energy and conventional x-ray diffraction and electrical resistivity measurements as a function of the temperature. Glass transition (Tg) and crystallization (Tx) temperature increase by Al addition reaching 450 and 500 °C, respectively for ZrCuAl12. The increase in thermal stability is related to the reduction in atomic mobility due to the formation of shorter chemical bonds, inhibiting atomic reconfiguration during crystallization. In conclusion, we provide guidelines to the design of compositional-tailored ZrCuAlx TFMGs with tuned mechanical properties and thermal stability with potential impact on industrial applications.

Atomic Structure of Mn-Doped CoFe2O4 Nanoparticles for Metal–Air Battery Applications

We discuss the atomic structure of cobalt ferrite nanoparticles doped with Mn via an analysis based on combining atomic pair distribution functions with high energy X-ray diffraction and high-resolution transmission electron microscopy measurements. Cobalt ferrite nanoparticles are promising materials for metal–air battery applications. Cobalt ferrites, however, generally show poor electronic conductivity at ambient temperatures, which limits their bifunctional catalytic performance in oxygen electrocatalysis. Our study reveals how the introduction of Mn ions promotes the conductivity of the cobalt ferrite electrode.

Driving Force of the Initial Step in Electrochemical Pt(111) Oxidation

The first step of electrochemical surface oxidation is extraction of a metal atom from its lattice site to a location in a growing oxide. Here we show by fast simultaneous electrochemical and in situ high-energy surface X-ray diffraction measurements that the initial extraction of Pt atoms from Pt(111) is a fast, potential-driven process, whereas charge transfer for the related formation of adsorbed oxygen-containing species occurs on a much slower time scale and is evidently uncoupled from the extraction process. It is concluded that potential plays a key independent role in electrochemical surface oxidation.

Structure and Physical Properties of Mg93-xZnxCa7 Metallic Glasses.

The Mg-Zn-Ca system has previously been proposed as the most suitable biodegradable candidate for biomedical applications. In this work, a series of ribbon specimens was fabricated using a melt-spinning technique to explore the glass-forming ability of the Mg-Zn-Ca system along the concentration line of 7 at.% of calcium. A glassy state is confirmed for Mg50Zn43Ca7, Mg60Zn33Ca7, and Mg70Zn23Ca7. Those samples were characterised by standard methods to determine their mass density, hardness, elastic modulus, and crystallisation temperatures during devitrification. Their amorphous structure is described by means of pair distribution functions obtained by high-energy X-ray and neutron diffraction (HEXRD and ND) measurements performed at large-scale facilities. The contributions of pairs Mg-Mg, Mg-Zn, and Zn-Zn were identified. In addition, a transformation process from an amorphous to crystalline structure is followed in situ by HEXRD for Mg60Zn33Ca7 and Mg50Zn43Ca7. Intermetallic compounds IM1 and IM3 and hcp-Mg phase are proposed to be formed in multiple crystallisation eventss.

Modification of structural, mechanical, corrosion and biocompatibility properties of Ti40Zr10Cu36Pd14 metallic glass by minor Ga and Sn additions

Ti40Zr10Cu32Pd14Ga4 and Ti40Zr10Cu32Pd14Sn4 (in at%) bulk metallic glasses (BMGs) with different geometries (wedges, rods, ribbons and discs) were prepared by suction casting, melt spinning and splat quenching, respectively. For comparison, the reference Ti40Zr10Cu36Pd14 BMG was cast as a rod with 2 mm diameter and in wedge-shaped form. High-energy X-ray diffraction measurements yielded a critical casting thickness of 2.4, 2.1 and at least 4 mm for the reference, Ga-containing, and Sn-containing BMGs, respectively. The extension of the supercooled liquid region of about 50 K, measured for the glassy rods and ribbons by differential scanning calorimetry, is larger than that of only 20 K found for the splat-quenched discs. As to the alloys’ mechanical properties, the Ti40Zr10Cu36Pd14 glassy rods deform plastically in compression up to a strain of 3.8% and possess a Young’s modulus of 78 GPa. The Sn- and Ga- containing BMG rods reach respectively a plastic strain of 6.1% and 4.7%, and a Young’s modulus of 72 and 63 GPa. Corrosion tests were performed by electrochemical experiments, and the highest pitting resistance was observed for Ti40Zr10Cu32Pd14Sn4 (pitting overpotential ηpit = 446 mV) compared to Ti40Zr10Cu32Pd14Ga4 (379 mV) and Ti40Zr10Cu36Pd14 (183 mV). The results of live/dead assay and cell viability revealed excellent biocompatibility for the Ga-containing BMGs.

Extrinsic and intrinsic contributions to the electrostrain in precipitation-hardened barium calcium titanate

Deconvoluting the extrinsic and intrinsic contributions to electrostrain is of great importance to understand the hardening mechanism of piezoceramics. Here, in situ electric-field high-energy x-ray diffraction measurements are performed to investigate the polycrystalline barium calcium titanate hardened by precipitation, a recently developed hardening technique that pins domain walls with fine intragranular precipitates. The effect of precipitates on extrinsic and intrinsic mechanisms is examined. Under a low-frequency and large-signal field, the precipitates suppress non-180° wall motion, which is the major source of loss, by 40%. Anisotropy is observed in the field-induced lattice strain, which is dominantly contributed by an intergranular effect instead of pure piezoelectricity. At small fields, the lattice strain is barely affected by precipitates, while both lattice strain and strain from non-180° domain wall motion are suppressed and are coupled with each other at large fields, leading to an unchanged relative percentage of the extrinsic contribution.

Reverse Monte Carlo Modeling for Catalyst Nanoparticles in Polymer Electrolyte Fuel Cells By High-Energy X-Ray Diffraction Measurement

Polymer electrolyte fuel cells (PEFCs) consist of a gas diffusion layer (GDL) and an electrode on each side, and a polymer electrolyte membrane (MEA) between the electrodes. The main components of the MEA are catalysts, electrolyte membranes and electrodes. In this study, the local atomic structures of catalytic nanoparticles in MEA were investigated by high-energy X-ray diffraction measurement and reverse Monte Carlo (RMC) modeling. The purpose of this study is to show guidelines for improving the performance of the PEFCs that contribute to industry by clarifying the differences in each catalyst structure and linking them with catalyst performance such as catalytic activity and catalyst durability.In this conference, we report the structural work on the platinum nanoparticles-supported carbon catalyst TEC10V30E (manufactured by TANAKA KIKINZOKU KOGYO K.K.). Although this sample is a commercial product, it is important to investigate its structure because it can be used as a standard sample for evaluating various catalyst samples in the future.RMC modeling based on the structure factor S(Q) obtained from high-energy X-ray diffraction measurement is suitable to determine the 3-dimensional (3D) atomic structures of nanoparticles. High-energy X-ray diffraction measurements were performed using a two-axis diffractometer at the beamline BL04B2 in SPring-8; the energy was used 61.4 keV corresponding to 0.202 Å in wavelength. RMC simulations were performed to obtain structure information from RMC-generated 3D configuration models using RMC_POT software in the case of non-periodic boundary conditions for experimental structure factor data. Figure 1 shows the experimental structure factor of the Pt nanoparticles in TEC10V30E and the RMC-simulated structure factor. For the Pt nanoparticle studied here, the initial configuration of the RMC simulations is a spherical shape with 3.8 nm in diameter based on the fcc bulk crystal structure. The agreement between the experiment and the RMC-simulated S(Q) is satisfactory. The 3D structure model of the Pt nanoparticle obtained by RMC simulations is shown in Fig. 1. It was found that the deviation from the lattice position was larger on the surface than on the inside in the obtained structure model.This research approach is expected to accelerate the creation of new catalysts for fuel cells by providing local atomic-scale structural information. It is also important to create the database of atomic arrangement structure data that is the basis of material design and material research.In the meeting, data recorded from actual catalyst samples will also be presented, including those from the MIRAI fuel cell (manufactured by Toyota Motor Corp.).This work was performed under the NEDO FC-Platform project. Figure 1

Effects of micro-alloying with lead for battery grid material

Pb-alloys are used as grid material for lead-acid batteries and have been implemented for years, and studying these Pb-alloys is critical to understanding the effects minor alloying additions on material characteristics. The current objective of this research is to evaluate the effects of minor alloying additions of Sb, As, Ca, Sn, Al, In, and Bi in Pb-alloy grid material during thermal cycling. In this study, Pb-grid material alloyed with a combination of elements mentioned above are examined using high-energy Synchrotron radiation X-ray diffraction measurements during in situ thermal cycling from RT to 75 °C to analyze grain inhibition and potential phase evolution. In addition, sulfation studies are performed in a solution of approximately 0.5 M H2SO4 and the Pb-alloys are added to an electrochemical cell to undergo cyclic voltammetry. Results show In mitigates grain growth, and, during electrochemical testing, increases passivation of Pb-alloys. Bi causes increased grain growth during thermal cycling and promotes sulfate formation. Ca refines and stabilizes grains during thermal cycling and increases corrosion resistance during cyclic voltammetry testing. Sn and Al attribute to texturing in the material and increase corrosion rates.

Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics.

Understanding and mitigating filament formation, short-circuit and solid electrolyte fracture is necessary for advanced all-solid-state batteries. Here, we employ a coupled far-field high-energy diffraction microscopy and tomography approach for assessing the chemo-mechanical behaviour for dense, polycrystalline garnet (Li7La3Zr2O12) solid electrolytes with grain-level resolution. In situ monitoring of grain-level stress responses reveals that the failure mechanism is stochastic and affected by local microstructural heterogeneity. Coupling high-energy X-ray diffraction and far-field high-energy diffraction microscopy measurements reveals the presence of phase heterogeneity that can alter local chemo-mechanics within the bulk solid electrolyte. These local regions are proposed to be regions with the presence of a cubic polymorph of LLZO, potentially arising from local dopant concentration variation. The coupled tomography and FF-HEDM experiments are combined with transport and mechanics modelling to illustrate the degradation of polycrystalline garnet solid electrolytes. The results showcase the pathways for processing high-performing solid-state batteries.

Superior high-temperature piezoelectric performances in BF-PT-BT ceramics via electric field constructed phase boundary

Owing to the mutual restriction between piezoelectric coefficient (d33) and Curie temperature (Tc), the discovery of high-temperature piezoceramics with large d33 is highly desirable but challenging. Here, BiFeO3-BaTiO3-PbTiO3 (BF-BT-PT) ternary system is redesigned by combining the low lattice distortion of BF-BT perovskites and rhombohedral-tetragonal coexistence of BF-PT phase boundary. As a result, excellent comprehensive piezoelectric properties with a large d33 of ∼380 pC/N and a high Tc of ∼483 °C are obtained in a tetragonal composition close to the triple point. Interestingly, even though a c/a ratio as large as 1.04 can be detected in the virgin sample, hierarchical domains that macrodomains composed of nanosized stripe domains can be found. The tetragonal phase could partly transform into a monoclinic phase under electric field according to in-situ high-energy synchrotron X-ray diffraction measurement, constructing a field-induced morphotropic phase boundary. The large lattice distortion and unstable phase structure simultaneously contribute to the high Tc, and large d33 for the studied BF-BT-PT ceramics, respectively, showing great potential for high-temperature sensors and transducers.

Microstructural Constituents and Mechanical Properties of Low-Density Fe-Cr-Ni-Mn-Al-C Stainless Steels.

Metallic material concepts associated with the sustainable and efficient use of resources are currently the subject of intensive research. Al addition to steel offers advantages in view of lightweight, durability, and efficient use of high-Fe scrap from the Al industry. In the present work, Al was added to Fe-12Cr-(9,12)Ni-3Mn-0.3C-xAl (x = 0.1–6) (wt.%) stainless steels to assess its influence on microstructure and mechanical properties. According to density measurements based on Archimedes’ principle, densities were between 7.70 and 7.08 g/cm3. High-energy X-ray diffraction estimations of the lattice parameter indicated that nearly 31% of density reduction was caused by the lattice expansion associated with Al addition. Depending on Al concentration, austenitic and duplex matrix microstructures were obtained at room temperature. In the presence of up to 3 wt.% Al, the microstructure remained austenitic. At the same time, strength and hardness were slightly enhanced. Al addition in higher quantities resulted in the formation of duplex matrix microstructures with enhanced yield strength but reduced ductility compared to the austenitic alloys. Due to the ready formation of B2-(Ni,Fe)Al intermetallics in the ferrite phase of the present alloy system, the increase in strength due to the presence of ferrite was more pronounced compared to standard duplex stainless steels. The occurrence of B2 intermetallics was implied by dilatometry measurements and confirmed by electron microscopy examinations and high-energy X-ray diffraction measurements.

High energy X-ray diffraction and small-angle scattering measurements of hydrogen fatigue damage in AISI 4130 steel

Accurate lifetime predictions are critical for repurposing existing pipelines for hydrogen transmission as well as for developing novel steels which are minimally susceptible to lifetime degradation by hydrogen. Ultimately, lifetime prediction models assess the amount of damage a material undergoes during a typical service cycle and the cumulative damage a material can withstand prior to failure. However, not all damage processes are equal, and neither is the manner in which mechanical loading translates to damage the same when materials are in inert environments compared to in hydrogen environments. For example, in the three leading proposed mechanisms of hydrogen embrittlement (Hydrogen-Enhanced Decohesion (HEDE), the Hydrogen-Enhanced Localized Plasticity (HELP), and the Nano-Void Coalescence (NVC)), hydrogen is proposed to enhance the manifestation of grain separation, dislocation generation/movement, and void coalescence, respectively. A full understanding of the damage modes requires a measurement capable of probing all three mechanisms at once. Here we present simultaneous High Energy X-ray Diffraction (HEXRD) and Small-Angle X-ray Scattering (SAXS) during fatiguing of steel in hydrogen. HEXRD measurements probe strain and dislocation density; SAXS measurements probe nano-pore generation and coalescence. We will discuss the differences in damage modes between steels fatigued in air and in hydrogen and the role these difference play in lifetime predictions.

Understanding Disordered Structures by Accurate High-Energy X-ray Diffraction Measurement

Understanding Disordered Structures by Accurate High-Energy X-ray Diffraction Measurement

Novel characterization of lead-based micro-alloys for battery applications

Although Pb-alloy acid batteries have been incorporated in vehicles for decades, a significant gap exists in the scientific understanding of minor alloying elements in the complex Pb-alloy grid materials. The aim of this research is to close this gap by using modern analytical techniques to examine the effects associated with adding minor alloying elements, less than 100 ppm, in Pb-alloy grid materials during isothermal holds and thermal cycling at relatively high temperatures. In this study, pure Pb, Pb-Bi, and Pb-Ba foils are examined using high-energy synchrotron radiation X-ray diffraction measurements during in situ isothermal holding at 85 °C and thermal cycling from RT to 85°C to analyze the grain inhibition and phase evolution. It is observed that Ba inhibits grain growth while Bi does not, when compared to pure Pb. Furthermore, no obvious phase evolution in any of the three cases is observed. After the synchrotron radiation X-ray diffraction measurements, the three materials are examined ex situ using scanning electron microscopy to verify the results. Additionally, baseline sulfation studies were performed in a solution of approximately 5 M H2SO4 and Pb-Bi and Pb-Ba were added to the electrochemical cell to undergo cyclic voltammetry.

Shape memory effect in metallic glasses

Shape memory effect in metallic glasses

The boson peak and the first sharp diffraction peak in (As2S3)x(GeS2)1–x glasses

The parameters of the boson peak (BP) and the first sharp diffraction peak (FSDP) in (As2S3)x(GeS2)1x glasses measured using high-resolution Raman spectroscopy and high-energy synchrotron X-ray diffraction measurements are examined as a function of x. It has been found that there is no correlation between the positions of BP and FSDP. The BP position shows a nonlinear composition behavior with a maximum at about x = 0.4, whereas the FSDP position changes virtually linearly with x. The intensities of both BP and FSDP show nonlinear composition dependences with the slope changes at x = 0.4, although there is no direct proportionality. Analysis of the partial structure factors for the glasses with x = 0.2, 0.4 and 0.6 obtained in another study has shown that the cation-cation atomic pairs of Ge–Ge, Ge–As and As–As make the largest contribution to FSDP, where the Ge–Ge and Ge–As pairs are dominant.