Synchrotron Diffraction Research Articles

Centrosymmetry-Breaking Morphotropic Phase Boundary: A Pathway to Highly Sensitive and Strong Pressure-Responsive Nonlinear Optical Switches.

The quest for high-performance piezoelectric materials has been synonymous with the pursuit of the morphotropic phase boundary (MPB), yet the full potential of MPBs remains largely untapped outside of the realm of ferroelectrics. In this study, we reveal a new class of MPB by creating continuous molecular-based solid solutions between centro- and noncentrosymmetric compounds, exemplified by (tert-butylammonium)1-x(tert-amylammonium)xFeCl4 (0 ≤ x ≤ 1), where the MPB is formed due to disorder of molecular cations. Near the MPB, we discovered an exceptionally sensitive nonlinear optical material in the centrosymmetric phase, capable of activation at pressures as low as 0.12-0.27 GPa, and producing tunable second-harmonic generation (SHG) signals from zero to 18.8 times that of KH2PO4 (KDP). Meanwhile, synchrotron diffraction experiments have unveiled a third competing phase (P212121) appearing at low pressure, forming a triple-phase point near the MPB, thereby providing insight into the mechanism underpinning the nonlinear optical (NLO) switch behavior. These findings highlight the opportunity to harness exceptional physical properties in symmetry-breaking solid solution systems by strategically designing novel MPBs.

Determination of the onset of yielding and the Young’s modulus after a change in the loading direction

The onset of plastic deformation is an important parameter for an accurate description of the flow curve and the Young’s modulus. Determining the actual physical start of flow is already experimentally challenging for classic sheet metal materials. In addition to the experimental challenge, the onset of flow depends on numerous parameters such as strain rate, temperature and forming history. Non-proportional load paths in particular can significantly influence the onset of flow. Three different materials, a micro-alloyed steel HC340LA, a dual-phase steel CR330Y590-DP and an aluminium alloy AA6016-T4 are investigated in this publication. The physical onset of flow of the materials is determined at three different pre-strain levels as well as without and with a change in the load direction. Temperature-based approaches are used for this purpose. In-situ synchrotron diffraction is used to validate the results obtained. Those results can help to improve existing material models and springback prediction. Such models rely on material parameters that are as accurate as possible.

Rational Design of Multinary Metal Chalcogenide Bi0.4 Sb1.6 Te3 Nanocrystals for Efficient Potassium Storage.

Multinary metal chalcogenides hold considerable promise for high-energy potassium storage due to their numerous redox reactions. However, challenges arise from issues such as volume expansion and sluggish kinetics. Here, a design featuring a layered ternary Bi0.4 Sb1.6 Te3 anchored on graphene layers as a composite anode, where Bi atoms act as a lattice softening agent on Sb, is presented. Benefiting from the lattice arrangement in Bi0.4 Sb1.6 Te3 and structure, Bi0.4 Sb1.6 Te3 /graphene exhibits a mitigated expansion of 28% during the potassiation/depotassiation process and demonstrates facile K+ ion transfer kinetics, enabling long-term durability of 500 cycles at various high rates. Operando synchrotron diffraction patterns and spectroscopies including in situ Raman, ex situ adsorption, and X-ray photoelectron reveal multiple conversion and alloying/dealloying reactions for potassium storage at the atomic level. In addition, both theoretical calculations and electrochemical examinations elucidate the K+ migration pathways and indicate a reduction in energy barriers within Bi0.4 Sb1.6 Te3 /graphene, thereby suggesting enhanced diffusion kinetics for K+ . These findings provide insight in the design of durable high-energy multinary tellurides for potassium storage.

A streamlined approach to structure elucidation using in cellulo crystallized recombinant proteins, InCellCryst

With the advent of serial X-ray crystallography on microfocus beamlines at free-electron laser and synchrotron facilities, the demand for protein microcrystals has significantly risen in recent years. However, by in vitro crystallization extensive efforts are usually required to purify proteins and produce sufficiently homogeneous microcrystals. Here, we present InCellCryst, an advanced pipeline for producing homogeneous microcrystals directly within living insect cells. Our baculovirus-based cloning system enables the production of crystals from completely native proteins as well as the screening of different cellular compartments to maximize chances for protein crystallization. By optimizing cloning procedures, recombinant virus production, crystallization and crystal detection, X-ray diffraction data can be collected 24 days after the start of target gene cloning. Furthermore, improved strategies for serial synchrotron diffraction data collection directly from crystals within living cells abolish the need to purify the recombinant protein or the associated microcrystals.

Synthesis and crystal structure of a silver(I) 6-methylmercaptopurine riboside complex.

Silver nitrate reacts with 6-methylmercaptopurine riboside (6-MMPR) in aqueous solution containing methanol and dimethyl sulfoxide at room temperature to give a colourless crystalline complex, namely, bis(6-methylmercaptopurine riboside-κN7)(nitrato-κ2O,O')silver(I) 2.32-hydrate, [Ag(NO3)(C11H14N4O4S)2]·2.32H2O. The crystal structure, determined from synchrotron diffraction data, shows a central AgI ion on a crystallographic twofold rotation axis, coordinated in an almost linear fashion by two 6-MMPR ligands via atom N7 (purine numbering), with the nitrate counter-ion loosely coordinated as a bidentate ligand, forming a discrete molecular complex as an approximate dihydrate. The complex and water molecules are connected in a three-dimensional network by hydrogen bonding.

Investigating the influence of medium range order defects on shear instability in Cu64Zr36 metallic glass

The occurrence of shear instability in metallic glasses is profoundly influenced by the spatial perturbation of material properties. Despite the considerable research on the origin of shear transformation zones (STZ), it remains a challenge to understand the behavior from a structural perspective. In this study, extensive molecular simulations (MD) and synchrotron diffraction were employed to characterize the structural features of medium-range order (MRO) defects in Cu64Zr36 metallic glass. These defects manifest as line-like interruptions in the connections between full icosahedral clusters. And it was also observed that the size and content of these defects are closely related to the history of the glass formation process. Moreover, we explored the contribution of these MRO defects, which are comparable in size to the STZ, in the genesis of shear instability. We uncovered that a large strain gradient exists in these regions under external loads, providing a convenient pathway for STZ activation. Notably, the generation of MRO defects are also going on as the STZ evolves. These insightful findings provide valuable insights and offer a promising avenue for the design and development of advanced metallic glass materials with enhanced structural integrity.

Effects of Trace Zn on the Deformation Mechanisms of Mg–Gd–Y–Zr Alloy Investigated by In Situ Synchrotron Diffraction

Addition of trace Zn can impose notable effect on the deformation behavior of Mg–Gd–Y–Zr alloy, while the underlying mechanisms have not been revealed. In the present work, Mg–8.5Gd–2.5Y–0.3Zr (wt%) (0Zn) and Mg–8.5Gd–2.5Y–0.5Zn–0.3Zr (wt%) (0.5Zn) alloys are fabricated by casting and extrusion, to obtain a bimodal microstructure containing fine dynamic recrystallized (DRXed) grains and coarse unDRXed grains. The as‐extruded 0Zn and 0.5Zn alloys are studied by in situ synchrotron diffraction under uniaxial tension and compression to clarify the effect of trace Zn on the deformation mechanisms. It is found that both alloys exhibit stress softening in the basal slip‐favored grains under both tension and compression, and adding trace Zn highly enhances the stress softening. Furthermore, the addition of Zn stimulates the occurrence of discontinuous yielding which is in connection with the stress softening, resulting from the interaction between basal dislocations and solute atmospheres. The tension–compression‐yielding symmetry of the alloy is improved by adding Zn, which is mainly attributed to the suppression effect of γ′ phases and Gd/Y–Zn dimers on tensile twinning. Finally, the addition of Zn can promote the tensile and compressive strength, owing to the strength enhancement of the relevant deformation modes and the increase of the fraction of unDRXed regions.

The use of diffraction techniques for understanding structure–property relationships in Heusler alloys

Heusler compounds are intermetallic alloys that are capable of a wide range of unique properties such as magnetocaloric, thermoelectric, and magnetic-shape-memory effects, antiferromagnetism, superconductivity, and they can even act as topological insulators. These multifunctional behaviors make Heusler alloys prime candidates for numerous smart device applications. However, their specific properties critically depend on their crystalline structures, chemical order, structural phase transformations, and crystallographic texture. Thus, as compositions and processing parameters are varied it becomes essential to be able to accurately characterize the structure of these materials at various scales. This paper provides a brief review of diffraction-based characterization techniques ideally suited for the characterization of Heusler alloys with examples from our previous works including use of synchrotron, neutron, and electron diffraction, especially as a function of temperature and/or magnetic field to explain important phenomena demonstrated by Heusler alloys.

LiOH Decomposition by NiO/ZrO2 in Li-Air Battery: Chemical Imaging with Operando Synchrotron Diffraction and Correlative Neutron/X-Ray Computed-Tomography Analysis.

Li-air batteries attract significant attention due to their highest theoretical energy density among all existing energy storage technologies. Currently, challenges related to extending lifetime and long-term stability limit their practical application. To overcome these issues and enhance the total capacity of Li-air batteries, this study introduces an innovative approach with NiO/ZrO2 catalysts. Operando advanced chemical imaging with micrometer spatial resolution unveils that NiO/ZrO2 catalysts substantially change the kinetics of crystalline lithium hydroxide (LiOH) formation and facilitate its rapid decomposition with heterogeneous distribution. Moreover, ex situ combined neutron and X-ray computed tomography (CT) analysis, provide evidence of distinct lithium phases homogeneously distributed in the presence of NiO/ZrO2. These findings underscore the material's superior physico-chemical and electronic properties, with more efficient oxygen diffusion and indications of lower obstruction to its active sites, avoiding clogging in the active electrode, a common cause of capacity loss. Electrochemical tests conducted at high current density demonstrated a significant kinetic enhancement of the oxygen reduction and evolution reactions, resulting in improved charge and discharge processes with low overpotential. This pioneering approach using NiO/ZrO2 catalysts represents a step toward on developing the full potential of Li-air batteries as high-energy-density energy storage systems.

High deformation and delamination mechanisms explained through mesoscale and nanoscale phenomena in pearlitic steel wires

Pearlitic steel wires subjected to severe cold drawing deformation exhibit a unique combination of high strength and excellent ductility, making them suitable for critical applications such as hanging bridge cables, crane cables and tire cord. Torsion tests up to rupture are commonly used in the industry for quality control purposes. A flat fracture surface is indicative of wire aptitude, while a delaminated surface suggests degradation of mechanical properties. This paper aims to expand the understanding of the structural evolution and deformation mechanisms that occur during wire drawing, as well as the origin of delamination problems. Different deformation and strengthening mechanisms are identified and discussed, applying different microscopy techniques (optical microscopy, scanning electron microscopy, electron backscatter diffraction), synchrotron diffraction and atom probe tomography. The information is correlated with the cementite stability on the structure studied at meso, nano, and atomic scale, reaching an understanding of the compositional evolution of cementite and ferrite even at the very lowest level. All the obtained information, including thermal analysis and thermodynamic simulation results, allow to identify the deformation mechanisms present during cold drawing and at the delamination process. In addition, the compositional evolution of cementite and ferrite is also clarified by atom probe tomography.

Aluminothermic reduction of CeO2: mechanism of an economical route to aluminum-cerium alloys.

Cerium oxide is a low-value byproduct of rare-earth mining yet constitutes the largest fraction of the rare earth elements. The reduction of cerium oxide by liquid aluminum is proposed as an energy- and cost-efficient route to produce high-strength Al-Ce alloys. This work investigated the mechanism of a multi-step reduction reaction to facilitate the industrial adaptation of the process. Differential scanning calorimetry in combination with time-resolved synchrotron diffraction data uncovered the rate-limiting reaction step as the origin of the reported temperature dependence of reduction efficiency. This is the first in situ study of a metallothermic reaction mechanism and will serve as guidance for cost- and energy efficient industrial process control.

Ligand solid-solution tuning of magnetic and mechanical properties of the van der Waals metal-organic magnet NiCl2(btd)1-x(bod)x.

Van der Waals (vdW) magnets offer unique opportunities for exploring magnetism in the 2D limit. Metal-organic magnets (MOM) are of particular interest as the functionalisation of organic ligands can control their physical properties. Here, we demonstrate tuning of mechanical and magnetic function of a noncollinear vdW ferromagnet, NiCl2(btd) (btd = 2,1,3-benzothiadiazole), through creating solid-solutions with the oxygen-substituted analogue ligand 2,1,3-benzoxadiazole (bod). We synthesise NiCl2(btd)1-x(bod)x up to x = 0.33, above which we find mixtures primarily composed of 1D NiCl2(bod)2. Magnetometry reveals bod incorporation reduces the coercivity significantly (up to 60%), without altering the ordering temperatures. High pressure synchrotron diffraction measurements up to 0.4 GPa demonstrate that the stiffest axis is the b axis, through the Ni-N-(O/S)-N-Ni bonds, and the softest is the interlayer direction. Doping with bod fine-tunes this compressibility, softening the layers, but stiffening the interlayer axis. This demonstrates that substitution of organic ligands in vdW MOMs can be used to realise targeted magnetic and mechanical properties.

Synthesis and Structural Characterization of Layered Ni+1/+2 Oxides Obtained by Topotactic Oxygen Release on Nd2−xSrxNiO4−δ Single Crystals

Layered nickelate oxides containing Ni1+/Ni2+ are isoelectronic to Cu2+/Cu3+ compounds and of present interest with respect to recent findings of superconductivity in a series of different compositions. It is thereby questionable why superconductivity is still rare to find in nickelates, compared to the much larger amount of superconducting cuprates. Anisotropic dz2 vs. dx2−y2 orbital occupation as well as interface-induced superconductivity are two of the main advanced arguments. We are here interested in investigating the feasibility of synthesizing layered nickelate-type oxides, where the Ni1+/Ni2+ ratio can be tuned by oxygen and/or cation doping. Our strategy is to synthesize Sr-doped n = 1 Ruddlesden–Popper type Nd2−xSrxNiO4+δ single crystals, which are then reduced by H2 gas, forming Nd2−xSrxNiO4−δ via a topotactic oxygen release at moderate temperatures. We report here on structural studies carried out on single crystals by laboratory and synchrotron diffraction using pixel detectors. We evidence the general possibility to obtain reduced single crystals despite their increased orthorhombicity. This must be regarded as a milestone to obtain single crystalline nickelate oxides, which further on contain charge-ordering of Ni1+/Ni2+, opening the access towards anisotropic properties.

Magnetic structures and properties of new 1:1 MoB-type RCo0.6Ni0.4 and RCo0.5Ni0.5 (R = Tb, Dy, Ho): Structural transition induced by magnetic ordering

The magnetic properties, the crystal and the magnetic structures of the new 1: 1 RCo1−xNix phase formed by R = Tb, Dy and Ho, have been studied for x = 0.4 and 0.5 by means of physical property measurements, neutron and X-ray (from both laboratory and synchrotron) diffraction methods. These compounds crystallize in the tetragonal MoB structure type (tI16, I41/amd) at room temperature, with no ordered arrangement of Co/Ni atoms on the 8e Wyckoff site available for the transition element. Both the lattice parameters a and c (and unit cell volume, Vobs) decrease from Tb to Ho, with a and c following a linear and a quadratic trend, respectively. A magnetic phase transition is detected by heat capacity and magnetization data for TbCo0.6Ni0.4 at about 85 K. Similar transitions appear in DyCo0.6Ni0.4 and HoCo0.6Ni0.4 at 49 K and 27 K, respectively. These TC well follow the de Gennes factor along the lanthanide series. Neutron diffraction shows for the Tb- and Ho-compounds that strongly ferromagnetic structures characterized by a k = 0 magnetic propagation vector are formed on two different rare earth sublattices which are canted to each other. Only in the Tb-containing phases the magnetic transition leads to a symmetry reduction from tetragonal I41/amd to at least monoclinic I2/a. Magnetic symmetry analysis is used to argue that the presence of a magnetic moment component along the original tetragonal axis should be at the origin of this magneto-structural transition in the Tb-compounds with a possible further symmetry lowering.

Effect of a novel controlled thermomechanical treatment on the microstructure and mechanical properties of a high-carbon nanobainitic steel

The effect of the novel controlled thermomechanical treatment, including torsion components in the elastic strain range during the isothermal holding on the microstructure and mechanical properties of the high-carbon nanobainitic steel, was investigated. TEM observations of the thermo-mechanically treated steel revealed bainitic ferrite laths with an average size of 68 ± 40 nm and films of retained austenite with an average size of 34 ± 17 nm, along with the blocky morphology of retained austenite in sub-micron scale. The XRD synchrotron diffraction allows estimating the amount of retained austenite at 43.1 ± 1.2% volume fraction with a carbon concentration of 1.17 ± 0.09 wt.%. Furthermore, the deconvolution of (200) Fe-γ reflections corresponding to two different low-carbon and high-carbon retained austenite peaks and, simultaneously, the blocky and film-like retained austenite was performed. In addition, the Nishiyama–Wassermann (N–W) crystallographic orientation relationship between bainitic ferrite and retained austenite was described as dominant using the misorientation distribution function (MDF). The crystallographic texture results indicated that the main growth of bainitic ferrite plates occurred after removing external stress during isothermal holding. The tensile tests and hardness measurements showed a high tensile strength achieved mainly by nano-metric bainitic ferrite plates and a high dislocation density. The high level of elongation is most likely attained due to a high amount of retained austenite in steel and both TRIP and TWIP effects during tensile deformation.

Fe Site Order and Magnetic Properties of Fe1/4NbS2.

Transition-metal dichalcogenides (TMDs) have long been attractive to researchers for their diverse properties and high degree of tunability. Most recently, interest in magnetically intercalated TMDs has resurged due to their potential applications in spintronic devices. While certain compositions featuring the absence of inversion symmetry such as Fe1/3NbS2 and Cr1/3NbS2 have garnered the most attention, the diverse compositional space afforded through the host matrix composition as well as intercalant identity and concentration is large and remains relatively underexplored. Here, we report the magnetic ground state of Fe1/4NbS2 that was determined from low-temperature neutron powder diffraction as an A-type antiferromagnet. Despite the presence of overall inversion symmetry, the pristine compound manifests spin polarization induced by the antiferromagnetic order at generic k points, based on density functional theory band-structure calculations. Furthermore, by combining synchrotron diffraction, pair distribution function, and magnetic susceptibility measurements, we find that the magnetic properties of Fe1/4NbS2 are sensitive to the Fe site order, which can be tuned via electrochemical lithiation and thermal history.

Exploring the effects of high pressure on hydrogen bonding in pharmaceutical cocrystals: A systematic study of pyridine dicarboxylic acid systems using synchrotron and neutron diffraction

Pharmaceutical cocrystals use common robust hydrogen bonding synthons to create novel materials with different physicochemical properties. In this systematic study of a series of cocrystals, we explore the effect of high pressure on one of these commonly used motifs, the acid-pyridine motif, to assess the commonality of behaviour under extreme conditions. We have surveyed five pyridine dicarboxylic acid systems using both synchrotron and neutron diffraction methods to elucidate the changes in structure. We observe that the hydrogen bonding in these systems compress at a similar rate despite the changes to the molecular make-up of the solids and that on compression the changes in structure are indicative that the layers move along the major slip planes in the structure. We have observed two phase transitions to new forms of the pyrazine:malonic acid system, one for each stoichiometric ratio. This study demonstrates that the combination of two complementary diffraction approaches is key to understanding polymorphic behaviour at high pressure.

Defect-Promoted Ni-Based Layer Double Hydroxides with Enhanced Deprotonation Capability for Efficient Biomass Electrooxidation.

Ni-based hydroxides are promising electrocatalysts for biomass oxidation reactions, supplanting the oxygen evolution reaction (OER) due to lower overpotentials while producing value-added chemicals. The identification and subsequent engineering of their catalytically active sites are essential to facilitate these anodic reactions. Herein, the proportional relationship between catalysts' deprotonation propensity and Faradic efficiency of 5-hydroxymethylfurfural (5-HMF)-to-2,5 furandicarboxylic acid (FDCA,FEFDCA ) is revealed by thorough density functional theory (DFT) simulations and atomic-scale characterizations, including in situ synchrotron diffraction and spectroscopy methods. The deprotonation capability of ultrathin layer-double hydroxides (UT-LDHs) is regulated by tuning the covalency of metal (M)-oxygen (O) motifs through defect site engineering and selection of M3+ co-chemistry. NiMn UT-LDHs show an ultrahigh FEFDCA of 99% at 1.37V versus reversible hydrogen electrode (RHE) and retain a high FEFDCA of 92.7% in the OER-operating window at 1.52V, about 2× that of NiFe UT-LDHs (49.5%) at 1.52V. Ni-O and Mn-O motifs function as dual active sites for HMF electrooxidation, where the continuous deprotonation of Mn-OH sites plays a dominant role in achieving high selectivity while suppressing OER at high potentials. The results showcase a universal concept of modulating competing anodic reactions in aqueous biomass electrolysis by electronically engineering the deprotonation behavior of metal hydroxides, anticipated to be translatable across various biomass substrates.

Structure Evolution of Ge-Doped CaTiO3 (CTG) at High Pressure: Search for the First 2:4 Locked-Tilt Perovskite by Synchrotron X-ray Diffraction and DFT Calculations.

This research investigates the high-pressure behavior of the Ca(Ti0.95Ge0.05)O3 perovskite, a candidate of the locked-tilt perovskite family (orthorhombic compounds characterized by the absence of changes in the octahedral tilt and volume reduction under pressure controlled solely by isotropic compression). The study combines experimental high-pressure synchrotron diffraction data with density functional theory (DFT) calculations, complemented by the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), to understand the structural evolution of the perovskite under pressure. The results show that CTG undergoes nearly isotropic compression with the same compressibility along all three unit-cell axes (i.e., Ka0 = Kb0 = Kc0, giving a normalized cell distortion factor with pressure dnorm(P) = 1). However, a modest increase in octahedral tilting with pressure is revealed by DFT calculations, qualifying CTG as a new type of GdFeO3-type perovskite that exhibits both isotropic compression and nonlocked tilting. This finding complements two existing types: perovskites with anisotropic compression and tilting changes and those with isotropic compression and locked tilting. The multimethod approach provides valuable insights into the structural evolution of locked-tilt perovskites under high pressure and establishes a protocol for the efficient study of complex high-pressure systems. The results have implications for the design of new functional materials with desirable properties.

Phase evolution and electrical resistance properties in vanadium dioxide nanobeams with mechanical deformation-induced strain gradients

Understanding the effect of strain on the physical properties of vanadium dioxide (VO2) is crucial for its effective use in flexible devices exposed to various strains. Stress (or strain) applied to VO2 plays a critical role in modulating its electrical and optical properties. Herein, we investigate the structural and electronic responses of VO2 nanobeams to bending deformation using interfacial adhesion between the VO2 and substrate, which can provide a route for understanding the correlation between the structural inhomogeneity and electrical properties associated with the strain gradient. The temperature-dependent phase evolution associated with the strain gradient in the bent nanobeam is resolved by characteristic Raman shifts and synchrotron diffraction, combined with stress analyses using a finite element method. The electrical resistance change and electro-thermal simulations reveal that the strain gradient-induced multiple phases in the bent nanobeam result in a higher resistance in the insulating state region, a higher transition temperature, a much broader transition range, and a smaller Joule heating effect, compared to the straight nanobeam. Our results may provide insight into the impact of the strain gradient in correlated materials, and can enable the deliberate control of physical properties using the strain gradient in nanostructures for flexible device applications.