High-resolution Synchrotron Diffraction Research Articles

Anisotropic thermal expansion in high-entropy multicomponent AlB2-type diboride solid solutions

High-entropy (HE) ultra-high temperature ceramics have the chance to pave the way for future applications propelling technology advantages in the fields of energy conversion and extreme environmental shielding. Among others, HE diborides stand out owing to their intrinsic anisotropic layered structure and ability to withstand ultra-high temperatures. Herein, we employed in-situ high-resolution synchrotron diffraction over a plethora of multicomponent compositions, with four to seven transition metals, with the intent of understanding the thermal lattice expansion following different composition or synthesis process. As a result, we were able to control the average thermal expansion (TE) from 1.3 × 10−6 to 6.9 × 10−6 K−1 depending on the combination of metals, with a variation of in-plane to out-of-plane TE ratio ranging from 1.5 to 2.8.

Magnetic, structural and magnetocaloric properties of Y0.9Gd0.1Fe2Hx hydrides

At 300 K, Y$_{0.9}$Gd$_{0.1}$Fe$_{2}$H$_{x}$ hydrides crystallize sequentially with increasing H concentration in various structures related to a lowering of the cubic MgCu$_{2}$ type structure of the parent alloy: cubic C1, monoclinic M1, cubic C2, monoclinic M2, cubic C3, orthorhombic O. Above 300 K, they undergo a first-order transition at a T$_{O-D}$ temperature driven by order-disorder of hydrogen atoms into interstitial sites. Their magnetic, structural and magnetocaloric properties have been investigated through magnetic measurements, and high-resolution synchrotron diffraction experiments. The magnetization at 5 K decreases slightly from 4 to 3.8 ${\mu}_{B}$ for x = 3 to 3.9 H f.u., then with a larger slope for higher H content. A discontinuous decrease of the magnetic transition temperature is observed: M1 and C2 hydrides are ferrimagnetic with T$_{C}$ near 300 K, M2 hydride displays a sharp ferromagnetic-antiferromagnetic transition at T$_{FM-AFM}$ =144 K, whereas C3 and O hydrides present only a sharp increase of the magnetization below 15 K and a weak magnetization up to RT. Negative magnetic entropy variations (${\Delta}$S$_{M}$) are measured near T$_{C}$ for the M1 and C2 phases, near T$_{FM-AFM}$ for the M2 phase, whereas positive ${\Delta}$S$_{M}$ peaks due to inverse MCE effect are found near T$_{O-D}$. A structural and magnetic phase diagram is proposed.

Structural phase transition in cobalt oxyfluoride Co3Sb4O6F6 observed by high-resolution synchrotron and neutron diffraction

A structural transition was observed in non-centrosymmetric oxyfluoride Co3Sb4O6F6 at TS ∼180 K from a cubic phase (I4‾3m) to a c > a tetragonal phase (I4‾), through high-resolution neutron and synchrotron powder diffraction. In addition, specific heat, magnetization, and dielectric measurements were performed to investigate this phase transition. Although the specific heat and dielectric constant showed anomalies at TS, no transition to a ferroelectric phase was observed in the polarization hysteresis loop down to 30 K. Moreover, a magnetic structure analysis using neutron powder diffraction data revealed a transition from a paramagnetic phase to a G-type antiferromagnetic phase at TN ∼67 K, at which a peak was also observed in the specific heat measurements. The magnetic moments of Co2+ were aligned along the tetragonal c-axis with a Co2+ moment of 2.80(1) μB at 13 K. The rotation and deformation of the CoO2F4 octahedron due to the large displacement of F atoms were observed at TS from the structural analysis, which play an important role in the structural phase transition in Co3Sb4O6F6.

Preparation of Bulk-Phase Nitride Perovskite LaReN3 and Topotactic Reduction to LaNiO2 -Type LaReN2.

While halide and oxide perovskites are numerous and many display outstanding properties, ABN3 perovskite nitrides are extremely rare due to synthetic challenges arising from the low chemical potential of nitrogen and a tendency to form low-coordination nitridometallate anions. We report the preparation of a perovskite nitride LaReN3 through azide-mediated oxidation at high pressure. High-resolution synchrotron diffraction shows that LaReN3 has a low-symmetry, triclinic, perovskite superstructure resulting from orbital ordering with strong spin-orbit coupling distortions. Topotactic reduction of LaReN3 above 500 °C leads to layered tetragonal LaReN2 via a probable LaReN2.5 intermediate, which is the first reported example of nitride defect perovskites. Magnetisation and conductivity measurements indicate that LaReN3 and LaReN2 are both metallic solids. The two chemical approaches presented are expected to lead to new classes of ABN3 and defect ABN3-x nitride perovskite materials.

Phase coexistence and negative thermal expansion in the triple perovskite iridate Ba3CoIr2O9

The anomalous thermal expansion in a layered $3d\text{\ensuremath{-}}5d$ based triple perovskite iridate ${\mathrm{Ba}}_{3}{\mathrm{CoIr}}_{2}{\mathrm{O}}_{9}$ is investigated using high resolution synchrotron diffraction. Below the magnetostructural transition at 107 K, the onset of antiferromagnetic order is associated with a monoclinic distortion of the hexagonal structure. Deeper within the magnetically ordered state, a part of the monoclinic phase distorts even further, and both these structural phases co-exist down to the lowest measured temperatures. We observe negative thermal expansion in this phase co-existence regime, which appears to be intimately connected to the temperature driven relative fractions of these monoclinic phases. The significant NTE observed in this system could be driven by magnetic exchange striction and is of relevance to a number of systems with pronounced spin orbit interactions.

Characterisation of White Etching Layers formed on rails subjected to different traffic conditions

Brittle White Etching Layers on rail initiate surface cracking and further progress to cause squats. The nature of WELs and their formation mechanism are not fully understood. In current study, ex-service damaged rails containing both WELs and squats, obtained from distinct rail track regions associated with different traffic contact conditions, were investigated in details. The particular interested sites of WELs, including topmost, middle and transition regions, were characterised by advanced material characterisation technologies, such as high resolution Synchrotron diffraction, Focus Ion Beam milling, transmission electron microscopy and selected area electron diffraction. In heavy braking rail regions, WEL containing martensite and retained austenite was observed, alongside undeformed pearlite at the interface between the WEL and the parent rail matrix. It was concluded that this type of WEL, referred as TP-WEL, is induced by temperature and pressure changes. In contrast, in low braking utilisation regions where the traffic speed is steady, WEL caused by rolling contact fatigue deformation contained nanocrystalline martensite and a region of severe plastic deformation immediately below the WEL. This type of WEL is termed as SD-WEL. Microstructural observations suggest that both WELs types play significant roles in crack initiation and squat formation.

On the measurement of dislocations and dislocation substructures using EBSD and HRSD techniques

The accumulation of the dislocations and development of dislocation structures in plastically deformed Ni201 is examined using dedicated analyses of Electron Back-Scatter Diffraction (EBSD) acquired orientation maps, and High-Resolution Synchrotron Diffraction (HRSD) acquired patterns. The results show that the minimum detectable microstructure-averaged (bulk) total dislocation density (ρT) measured via HRSD is approximately 1E13 m−2, while the minimum GND density (ρG) measured via EBSD is approximately 2E12 m−2 – the EBSD technique being more sensitive at low plastic strain. This highlights complementarity of the two techniques when attempting to quantify amount of plastic deformation (damage) in a material via a measurement of present dislocations and their structures. Furthermore, a relationship between EBSD-measured ρG and the size of HRSD-measured Coherently Scattering Domains (CSDs) has been mathematically derived – this allows for an estimation of the size of CSDs from EBSD-acquired orientation maps, and conversely an estimation of ρG from HRSD-measured size of CSDs. The measured evolution of ρT, and ρG is compared with plasticity theory models – the current results suggest that Ashby's single-slip model underestimates the amount of GNDs (ρG), while Taylor's model is correctly predicting the total amount of dislocation (ρT) present in the material as a function of imparted plastic strain.

Crystal structure of LaSr3Fe3O9 and its phase relation with LaSr3Fe3O10

The Ruddlesden-Popper phase LaSr3Fe3O10 and its reduced derivatives with nominal composition LaSr3Fe3O10–x, with 0 < x < 1.21, are described in detail with respect to crystal structure, magnetic order, thermal stability and likely vacancy mechanisms. The crystal structure of the LaSr3Fe3O9 (x = 1) phase is described. The LaSr3Fe3O10-δ phase prevails for x < 0.51, whereas LaSr3Fe3O9±ε prevails for x > 0.85. The phases are separated by a two-phase region 0.51 < x < 0.85. By combined Rietveld refinements of high-resolution powder synchrotron and neutron diffraction, the crystallographic and magnetic structure of LaSr3Fe3O9 is described. LaSr3Fe3O9 takes a layer like RP3 type structure with features of the brownmillerite structure in the triple perovskite type slabs; unit cell dimensions a = 28.7562(13) Å, b = 5.5280(2) Å, c = 5.4583(2) Å, space group Cmcm. LaSr3Fe3O9 is an antiferromagnet with TN > 350 K and with a G-type magnetic structure, magnetic space group PCbcm. Based on unit cell volume considerations, local oxygen vacancy ordering schemes are suggested.

Measurement of Electric Fields Experienced by Urea Guest Molecules in the 18-Crown-6/Urea (1:5) Host-Guest Complex: An Experimental Reference Point for Electric-Field-Assisted Catalysis.

High-resolution synchrotron and neutron single-crystal diffraction data of 18-crown-6/(pentakis)urea measured at 30 K are combined, with the aim of better appreciating the electrostatics associated with intermolecular interactions in condensed matter. With two 18-crown-6 molecules and five different urea molecules in the crystal, this represents the most ambitious combined X-ray/synchrotron and neutron experimental charge density analysis to date on a cocrystal or host-guest system incorporating such a large number of unique molecules. The dipole moments of the five urea guest molecules in the crystal are enhanced considerably compared to values determined for isolated molecules, and 2D maps of the electrostatic potential and electric field show clearly how the urea molecules are oriented with dipole moments aligned along the electric field exerted by their molecular neighbors. Experimental electric fields in the range of 10-19 GV m-1, obtained for the five different urea environments, corroborate independent measurements of electric fields in the active sites of enzymes and provide an important experimental reference point for recent discussions focused on electric-field-assisted catalysis.

Comprehensive Study of Oxygen Storage in YbFe2O4+x (x ≤ 0.5): Unprecedented Coexistence of FeOn Polyhedra in One Single Phase.

The multiferroic LuFe2.5+2O4 was recently proposed as a promising material for oxygen storage due to its easy reversible oxidation into LuFe3+2O4.5. We have investigated the similar scenario in YbFe2O4+x, leading to a slightly greater oxygen storage (OSC) capacity of 1434 μmol O/g. For the first time, the structural model of LnFe2O4.5 was fully understood by high-resolution microscopy images, and synchrotron and neutron diffraction experiments, as well as maximum entropy method. The oxygen uptake promotes a reconstructive shearing of the [YbO2] sub-units controlled by the adaptive Ln/Fe oxygen coordination and the Fe2/3+ redox. After oxidation, the rearrangement of the Fe coordination polyhedra is unique such that all available FeOn units (n = 6, 5, 4 in octahedra, square pyramids, trigonal bipyramids, tetrahedra) were identified in modulated rows growing in plane. This complex pseudo-ordering gives rise to short-range antiferromagnetic correlation within an insulating state.

High Resolution Synchrotron Diffraction Study on Charge Density Distribution of Ampicillin Trihydrate

Charge density distribution in ampicillin trihydrate was investigated experimentally. Results were compared with the quantum calculations using density functional theory. The charge derived properties including Mulliken atomic charges, dipole moment, and molecular electrostatic potential were calculated. The multipole analysis was done for the refinement of experimental population parameters. The structure factors obtained from multipole treatment were used for the construction of Fourier maps. Topological properties of the charge distribution were discussed and the characteristics of (3, −1) critical points were analyzed.

Oxidation under Air of Tavorite LiVPO4F: Influence of Vanadyl-Type Defects on Its Electrochemical Properties

Tavorite-type compositions offer a very rich crystal chemistry, among which LiVIIIPO4F has the highest theoretical energy density (i.e., 655 Wh/kg). In this article, an in-depth study of vanadyl-type defects generated by temperature-controlled oxidation of LiVIIIPO4F under air is proposed, and the influence of the defects on the electrochemical properties is demonstrated. A combination of high resolution synchrotron diffraction, infrared spectroscopy, and magic angle spinning nuclear magnetic resonance was used to fully characterize the materials thus generated, from their average long-range structure to their local structure with the presence of defects. The increase of the annealing temperature tends to substitute oxygen for fluorine with the formation of a series of LiVPO4F1–xOx compositions. The miscibility domains appear to be narrow at the two ends of the solid solution (i.e., in the composition ranges LiVPO4F[1-0.9]O[0-0.1] and LiVPO4F[0-0.1]O[1-0.9]). The presence of vanadyl-type defects obtained ...

Magnetic anisotropy in the frustrated spin-chain compoundβ−TeVO4

Isotropic and anisotropic magnetic behavior of the frustrated spin chain compound $\beta$-TeVO$_4$ is reported. Three magnetic transitions observed in zero magnetic field are tracked in fields applied along different crystallographic directions using magnetization, heat capacity, and magnetostriction measurements. Qualitatively different temperature-field diagrams are obtained below 10 T for the field applied along $a$ or $b$ and along $c$, respectively. In contrast, a nearly isotropic high-field phase emerges above 18 T and persists up to the saturation that occurs around 22.5 T. Upon cooling in low fields, the transitions at $T_{\rm N1}$ and $T_{\rm N2}$ toward the spin-density-wave and stripe phases are of the second order, whereas the transition at $T_{\rm N3}$ toward the helical state is of the first order and entails a lattice component. Our microscopic analysis identifies frustrated $J_1-J_2$ spin chains with a sizable antiferromagnetic interchain coupling in the $bc$ plane and ferromagnetic couplings along the $a$ direction. The competition between these ferromagnetic interchain couplings and the helical order within the chain underlies the incommensurate order along the $a$-direction, as observed experimentally. Although a helical state is triggered by the competition between $J_1$ and $J_2$ within the chain, the plane of the helix is not uniquely defined because of competing magnetic anisotropies. Using high-resolution synchrotron diffraction and $^{125}$Te nuclear magnetic resonance, we also demonstrate that the crystal structure of $\beta$-TeVO$_4$ does not change down to 10 K, and the orbital state of V$^{4+}$ is preserved.

High Spatial Resolution Evaluation of Residual Stresses in Shot Peened Specimens Containing Sharp and Blunt Notches by Micro-hole Drilling, Micro-slot Cutting and Micro-X-ray Diffraction Methods

The moderately high lateral RS gradients (on the order of tens of MPa/μm) near shot peened notches in conjunction with the shallow treatment depth (some hundreds of microns) limit the application of far-field and/or high resolution synchrotron diffraction residual stress measurement techniques. Recently proposed Focused Ion Beam – Scanning Elecron Microscope – Digital Image Correlation (FIB-SEM-DIC) based micro mechanical stress relaxation methods for the measurement of residual stress at the micron scale became suitable techniques for local evaluation of residual stresses and stress gradients in shot peened specimens. In this paper ultra-high resolution (~0.5–0.8 μm depth and 5–10 μm lateral resolution) mechanical relaxation stress measurements were used to evaluate the stress variation local to individual peening dimples in ceramic (60–120 μm diameter beads) shot peened Al-7075-T651 double notched samples having 0.15, 0.5 and 2.0 mm radii using Micro-Hole Drilling (μHD), Micro-Slot Cutting (μSC) and micro X-ray Diffraction (μXRD) methods. The micron-sized sampling volumes enabled the stress to be evaluated in individual impact craters (dimples) showing significant point-to-point variation (~ +/−150 MPa) (with certain dimples even recording tensile stresses). After around 30 μm of layer removal the heavily deformed region had largely been removed and the stress profile became much more homogeneous. At this depth the μHD and μSC results were in good accord with those from μXRD measurements which sample over a much larger volume (~40 μm depth × 50 μm laterally) showing an in-plane compressive stress of around 150 MPa far from the notches with the residual stress rising to about 200 MPa at a blunt (2 mm) notch and 500 MPa for a sharp (0.15 mm) one. Further, these recorded variations of residual stresses were correlated with microstructural features, e.g. grains, networks of sub-surface cracks, intermetallics and highly deformed sub-surface regions, revealed by large volume Serial Sectioning Tomography using Plasma Xe+ Focus Ion Beam – Scanning Electron Microscope (PFIB-SEM), EDS and EBSD maps. This allowed for the first time characterize large volume (100 × 66 × 30 μm3) of shot peened regions with resolution of dozens of nanometers and correlate residual stress depth profiles with 3D microstructural features. Finally, in (Benedetti et al. 2016, Int. J. Fatigue) these RS measurements are used to reconstruct the RS field through finite element (FE) analyses.

高角度分解能放射光X線回折によるスピネル型酸化物CoV 2 O 4 の微小格子歪み

高角度分解能放射光X線回折によるスピネル型酸化物CoV 2 O 4 の微小格子歪み

Structure and chemical bonding in MgNi2H3 from combined high resolution synchrotron and neutron diffraction studies and ab initio electronic structure calculations

Our earlier study Yartys et al. (2015) showed that at high hydrogen pressures, hexagonal MgNi2 undergoes a hydrogen assisted phase transition into the orthorhombic MoSi2-type structure. Here we report on a combined high resolution synchrotron and neutron diffraction investigation of the crystal structure of MgNi2D3, and ab initio calculation of its electronic structure that revealed the nature of the metal–hydrogen bonding. The diffraction data (293 and 1.8K) are well described with a Cmca unit cell with H atoms filling the deformed octahedra Mg4Ni2 and the positions within the buckled nets –Ni–H–Ni–H– penetrating through the structure. DFT and phonon calculations showed that the Cmca structure of MgNi2D3 is the most stable, both from the electronic structure and the lattice dynamical arguments. The Bader charge analysis indicates an electronic transfer from Mg (−1.59e−) to Ni (+0.21e−), H1 (+0.55e−) and H2 (+0.31e−). The phonon dispersion curves of MgNi2H3 show positive frequencies, indicating that the structure is mechanically stable. The calculated gross heat of formation for the Cmca phase of MgNi2H3 is −37.3kJ/mol-H2, which makes it more stable by 3kJ/mol-H2 than the prototype structures tested in Yartys et al. (2015). The stability of the Cmca crystal structure of MgNi2H3 is enhanced by the formation of the directional Ni–H covalent bonds supplemented by the electron transfer from Mg to both Ni and H. The heat capacity as a function of temperature is obtained by phonon calculation in the quasi-harmonic approximation.

Low Temperature Synthesis and Characterization of AlScMo₃O12.

Recent interest in low and negative thermal expansion materials has led to significant research on compounds that exhibit this property, much of which has targeted the A2M3O12 family (A = trivalent cation, M = Mo, W). The expansion and phase transition behavior in this family can be tuned through the choice of the metals incorporated into the structure. An undesired phase transition to a monoclinic structure with large positive expansion can be suppressed in some solid solutions by substituting the A-site by a mixture of two cations. One such material, AlScMo3O12, was successfully synthesized using non-hydrolytic sol-gel chemistry. Depending on the reaction conditions, phase separation into Al2Mo3O12 and Sc2Mo3O12 or single-phase AlScMo3O12 could be obtained. Optimized conditions for the reproducible synthesis of stoichiometric, homogeneous AlScMo3O12 were established. High resolution synchrotron diffraction experiments were carried out to confirm whether samples were homogeneous and to estimate the Al:Sc ratio through Rietveld refinement and Vegard’s law. Single-phase samples were found to adopt the orthorhombic Sc2W3O12 structure at 100 to 460 K. In contrast to all previously-reported A2M3O12 compositions, AlScMo3O12 exhibited positive thermal expansion along all unit cell axes instead of contraction along one or two axes, with expansion coefficients (200–460 K) of αa = 1.7 × 10−6 K−1, αb = 6.2 × 10−6 K−1, αc = 2.9 × 10−6 K−1 and αV = 10.8 × 10−6 K−1, respectively.

High-resolution synchrotron diffraction study of porous buffer InP(001) layers

X-ray reciprocal space mapping was used for quantitative investigation of porous layers in indium phosphide. A new theoretical model in the frame of the statistical dynamical theory for cylindrical pores was developed and applied for numerical data evaluation. The analysis of reciprocal space maps provided comprehensive information on a wide range of the porous layer parameters, for example, layer thickness and porosity, orientation, and correlation length of segmented pore structures. The results are in a good agreement with scanning electron microscopy data.

Triclinic–Cubic Phase Transition and Negative Expansion in the Actinide IV (Th, U, Np, Pu) Diphosphates

The AnP(2)O(7) diphosphates (An = Th, U, Np, Pu) have been synthesized by various routes depending on the stability of the An(IV) cation and its suitability for the unusual octahedral environment. Synchrotron and X-ray diffraction, thermal analysis, Raman spectroscopy, and (31)P nuclear magnetic resonance reveal them as a new family of diphosphates which probably includes the recently studied CeP(2)O(7). Although they adopt at high temperature the same cubic archetypal cell as the other known MP(2)O(7) diphosphates, they differ by a very faint triclinic distortion at room temperature that results from an ordering of the P(2)O(7) units, as shown using high-resolution synchrotron diffraction for UP(2)O(7). The uncommon triclinic-cubic phase transition is first order, and its temperature is very sensitive to the ionic radius of An(IV). The conflicting effects which control the thermal variations of the P-O-P angle are responsible for a strong expansion of the cell followed by a contraction at higher temperature. This inversion of expansion occurs at a temperature significantly higher than the phase transition, at variance with the parent compounds with smaller M(IV) cations in which the two phenomena coincide. As shown by various approaches, the P-O(b)-P linkage remains bent in the cubic form.

Nb3Sn nucleation and growth in multifilament superconducting strands monitored by high resolution synchrotron diffraction during in situ reaction

The Nb3Sn volume, crystallite size, and Sn content evolution during the reaction of a recent high critical current density Nb3Sn/Cu composite wire has been monitored by high energy, high resolution synchrotron x-ray diffraction. Thanks to the high flux of high energy x-rays at the ID15A beamline of the European Synchrotron Radiation Facility. It was possible to monitor the Nb3Sn crystallite growth in situ from the early stages of Nb3Sn nucleation at 540 °C up to nearly complete transformation of the Nb precursor into Nb3Sn. Simultaneously, the uptake of Sn in the A15 phase could be monitored by Nb3Sn lattice parameter measurements.