Neutron Diffraction Research Articles

Identification of degree of ordering in spinel LiNi0.5Mn1.5O4 through NMR and Raman spectroscopies supported by theoretical calculations

The performance of the high voltage spinel LiNi0.5Mn1.5O4 (LNMO) in Li-ion batteries strongly depends on its synthesis conditions, actual Ni/Mn stoichiometry, and degree of ordering of Ni and Mn. Depending on the extent of this ordering, the spinel structure can be described in the conventional space group Fd3¯m as the non-substituted LiMn2O4 or, for the highly ordered phase, in the space group P4332. As previously reported in the literature, using neutron and electron diffraction, a qualitative description of the extent of ordering can be achieved and roughly related to the electrochemical performance of LNMO. To deeper characterize and understand this complex system, in this paper, we will show that Raman spectroscopy, and especially the characteristics of the band located at 160 cm−1 attributed for the first time to a twisting motion of octahedral entities, allow to estimate the degree of ordering in LNMO, whereas NMR spectroscopy allows to give a clear description of the local environments of Li, in relationship with the Ni/Mn stoichiometry and extent of ordering. Theoretical calculations were used to support the analysis and attribution of the Raman and NMR signals/spectra. These spectroscopic characterizations enabled in-depth insights into the complexity of LNMO in stoichiometry, degree of ordering, and purity versus the presence of rock-salt or layered oxides as defects or crystalline domains.

In situ neutron diffraction study and electron microscopy analysis of microstructure and texture evolution during annealing of rolled CoCrFeNi alloy doped with 1 at.%C

In situ neutron diffraction studies of changes in the dislocation density, volume fraction of carbides, and crystallographic texture have been performed during annealing of a cold-rolled multi-principal element CoCrFeNi alloy doped with 1 at.%C. In addition, microstructures of the as-rolled and several annealed samples of this alloy have been investigated using electron microscopy-based techniques. It is found that cold rolling to a thickness reduction of 74% results in a brass-type rolling texture with a spread of orientations between the Goss and brass components and with a pronounced 〈111〉//ND fiber. The deformed microstructure is characterized by a high density of dislocations and shows large variations in deformation structures in regions of different crystallographic orientations. In particular, bundles of deformation twins and high frequencies of shear bands are observed in regions having orientations along the 〈111〉//ND fiber. Annealing at 700 °C–1000 °C leads to recovery and recrystallization, during which shear bands and regions of mixed orientations act as preferential nucleation sites for recrystallized grains. Precipitation of M23C6 particles also takes place during annealing. The particles retard boundary migration, thus slowing down recrystallization and restricting grain growth. The average size of recrystallized grains does not exceed 5 μm even after annealing at 1000 °C for 60 min. While rolling textures are retained in some annealed samples, other samples demonstrate distinct recrystallization textures with new texture components. The results obtained in this work are compared with the literature data for several carbon-doped face-centered cubic multi-principal element alloys and for a carbon-free CoCrFeNi alloy.

Features of the crystal structure and surface of superprotonic conductor caesium hydrogen sulfate phosphate.

The crystal structure of superprotonic conductor caesium hydrogen sulfate phosphate [Cs4(HSO4)3(H2PO4)] have been analyzed using neutron diffraction methods. Additionally, its structure and surface layers have been investigated using atomic force microscopy. From the diffraction data obtained, Fourier syntheses of neutron scattering densities were calculated, and the localization of hydrogen atoms and the parameters of three types of hydrogen bonds in the crystal structure were accurately determined. Correlation of surface characteristics of samples obtained by atomic force microscopy with their crystal structure is shown.

Direct observation of the atomic density fluctuation originating from the first sharp diffraction peak in SiO2 glass

The intermediate-range order of covalently bonded glasses has been extensively studied in terms of their diffraction peaks observed at low scattering angles; these peaks are called the first sharp diffraction peaks (FSDPs). Although the atomic density fluctuations originating from the quasilattice planes are a critical scientific target, direct experimental observations of these fluctuations are still lacking. Here, we report the direct observation of the atomic density fluctuations in silica glass by energy-filtered angstrom-beam electron diffraction. The correspondence between the local electron diffraction patterns of FSDPs and the atomic configurations constructed based on the X-ray and neutron diffraction results revealed that the local atomic density fluctuations originated from the quasi-periodic alternating arrangements of the columnar chain-like atomic configurations and interstitial tubular voids, as in crystals. We also discovered longer-range fluctuations associated with the shoulder of the FSDP on the low-Q side. The hierarchical fluctuations inherent in materials could aid in the elucidation of their properties and performance.

The Interplay of Electronic Configuration and Anion Ordering on the Magnetic Behavior of Hydroxyfluoride Diaspores.

We report a new nickel hydroxyfluoride diaspore Ni(OH)F prepared using hydrothermal synthesis from NiCl2·6H2O and NaF. Magnetic characterization reveals that, contrary to other reported transition-metal hydroxyfluoride diaspores, Ni(OH)F displays weak ferromagnetism below the magnetic ordering temperature. To understand this difference, neutron diffraction is used to determine the long-range magnetic structure. The magnetic structure is found to be distinct from those reported for other hydroxyfluoride diaspores and shows an antiferromagnetic spin ordering in which ferromagnetic canting is allowed by symmetry. Furthermore, neutron powder diffraction on a deuterated sample, Ni(OD)F, reveals partial anion ordering that is distinctive to what has previously been reported for Co(OH)F and Fe(OH)F. Density functional theory calculations show that OH/F ordering can have a directing influence on the lowest energy magnetic ground state. Our results point toward a subtle interplay between the sign of magnetic exchange interactions, the electronic configuration, and anion disordering.

Dynamical and structural properties of undercooled Cu-Ti melts investigated by neutron and x-ray diffraction

Dynamical and structural properties of undercooled Cu-Ti melts investigated by neutron and x-ray diffraction

Magnetic order in holmium and erbium formate: Parent frameworks for a potential random spin chain paramagnet

This work uses a combination of neutron diffraction and bulk property measurements to establish the low temperature magnetic states in the dense metal-organic frameworks Ho(HCO2)3 and Er(HCO2)3; whose structures feature chains of face-sharing LnO9 polyhedra packed into a triangular lattice. Below 0.7 K Ho(HCO2)3 is found to adopt a state in which the magnetic moment on its ferromagnetic chains vary from neighbouring chains but the sum around each triangle is constant. Er(HCO2)3 is found to be the first lanthanide formate to adopt an ordered magnetic state with antiferromagnetic coupling within its chains near 50 mK. The potential to combine the ferromagnetic and antiferromagnetic coupling within chains associated with Ho and Er cations, respectively, in the same compound has also been explored via the series Ho1-xErx(HCO2)3. Ho0.5Er0.5(HCO2)3 remains paramagnetic to 0.4 K, suggesting it may be a starting point to search for a random spin chain paramagnet.

Structural origins of dielectric anomalies in the filled tetragonal tungsten bronze Sr2NaNb5O15

The tetragonal tungsten bronze, Sr2NaNb5O15, shows promise for application in high-temperature high-efficiency capacitors vital for the sustainable energy revolution. Previously, the structural complexity of this and related materials has obscured the mechanisms underpinning two large anomalies in relative permittivity (εr) which give rise to their exceptionally broad dielectric response. Here, we comprehensively investigate the structural evolution from −173 to 627 °C, combining electron, X-ray and neutron diffraction, electron microscopy, and first principles electronic structure calculations to unambiguously identify the structural origins of both anomalies. The peak in εr at 305 °C is associated with a polar-nonpolar phase transition, wherein cations displace along the c axis. Guided by DFT, we identify a further transition upon cooling, associated with the second peak at −14 °C, linked to the softening of an in-plane polar distortion with a correlation length limited by ferroelastic nano-domains arising from rigid-unit-like tilting of NbO6 octahedra at high temperature, imparting relaxor-like behaviour. Thus, the two dielectric anomalies in Sr2NaNb5O15 are associated with two distinct crystallographic phase transitions and their interplay with a microstructure that arises from a third, non-polar structural distortion. Chemical control of these will enable development of tuneable materials with dielectric properties suitable for high-temperature energy storage applications.

Residual stress relief strategy in thick steel weldments via local induction heat treatment: Simulation and neutron diffraction experiment

This study investigated the effect of local induction post-weld heat treatment (PWHT) on residual stress relief in thick submerged arc welded steel plates. A combination of numerical and neutron diffraction methods was used to examine the effect of various PWHT parameters, such as annealing temperature and holding time, on the relief of residual stress in welded plates with various thicknesses. A sequentially coupled thermal–mechanical finite element model was used to calculate the residual stress distribution in welded AH36 steel plates before and after PWHT. The model was validated by comparing its predictions with the experimental measurements, and the results showed good agreement. The residual stress of the thick welded plates was effectively reduced via PWHT with local induction. The primary mechanism for this stress release was identified as stress relaxation caused by creep strain. Furthermore, a process map was established considering the PWHT conditions and plate geometry. This map provides a means of determining the optimal PWHT conditions to achieve desired stress reduction levels.

Magnetic structure of Tb[formula omitted]NbO[formula omitted] determined using neutron diffraction experiments and magnetic anisotropy calculations

We determined the magnetic structure of Tb3NbO7 based on powder neutron diffraction experiments and magnetic anisotropy calculations. We calculated the energy levels split by crystalline electric fields, and the magnetic moments using McPhase. The c axis is the easy axis for Tb1 moments, and magnetic anisotropy is small for Tb2 moments. Magnetic reflections were observed at low temperatures. The propagation vector is k1=(0,0,0) at 1.8 K and k2=(1/2,1/2,0) at 2.5 K between transition temperatures TN1=2.0 K and TN2=3.2 K. We selected candidates for an irreducible representation (IR) of the magnetic structures using magnetic anisotropy. From Rietveld refinements, we determined the following: The IRs are mΓ4 and mS2 at 1.8 K and 2.5 K, respectively. The main component of Tb1 ordered moments is w at 1.8 K. The order of the main components in each chain along the c axis is antiferromagnetic. Tb1 moments are disordered at 2.5 K. Tb2 moments form noncollinear magnetic structures in the ab plane perpendicular to Tb1 chains with a small w component at both the 1.8 K and 2.5 K. The magnetic structure at 1.8 K is consistent with the magnetic anisotropies obtained using McPhase calculations. Only Tb2 moments are ordered at 2.5 K, indicating the appearance of a partially disordered state. We also considered the origin of the two magnetic transitions.

Long-range magnetic order in CePdAl3 enabled by orthorhombic deformation

We investigate the effect of structural deformation on the magnetic properties of orthorhombic CePdAl3 in relation to its tetragonal polymorph. Utilizing x-ray and neutron diffraction, we establish that the crystal structure has the Cmcm space-group symmetry and exhibits pseudotetragonal twinning. According to density functional calculations, the tetragonal-orthorhombic deformation mechanism has its grounds in the relatively small free enthalpy difference between the polymorphs, allowing either phase to be quenched, and fully accounts for the twinned microstructure of the orthorhombic phase. Neutron diffraction measurements show that orthorhombic CePdAl3 establishes long-range magnetic order below TN=5.29(5) K characterized by a collinear, antiferromagnetic arrangement of magnetic moments. Magnetic anisotropies of orthorhombic CePdAl3 arise from strong spin-orbit coupling as evidenced by the crystal-field splitting of the 4f multiplet, fully characterised with neutron spectroscopy. We discuss the potential mechanism of frustration posed by antiferromagnetic interactions between nearest neighbors in the tetragonal phase, which hinders the formation of long-range magnetic order in tetragonal CePdAl3. We propose that orthorhombic deformation releases the frustration and allows for long-range magnetic order. Published by the American Physical Society 2024

Stroboscopic time-of-flight neutron diffraction in long pulsed magnetic fields

We present proof-of-principle experiments of stroboscopic time-of-flight (TOF) neutron diffraction in long pulsed magnetic fields. By utilizing electric double-layer capacitors, we developed a long pulsed magnet for neutron diffraction measurements, which generates pulsed magnetic fields with the full widths at half maximum of >102 ms. The field variation is slow enough to be approximated as a steady field within the time scale of a polychromatic neutron pulse passing through a sample placed in a distance of the order of 101 m from the neutron source. This enables us to efficiently explore the reciprocal space using a wide range of neutron wavelength in high magnetic fields. We applied this technique to investigate field-induced magnetic phases in the triangular lattice antiferromagnets CuFe1−xGaxO2 (x=0,0.035). Published by the American Physical Society 2024

Bulk Nanostructure of Mixtures of Choline Arginate, Choline Lysinate, and Water.

Neutron diffraction with empirical potential structure refinement was used to investigate the bulk liquid nanostructure of mixtures of choline arginate (Ch[Arg]), choline lysinate (Ch[Lys]), and water at mole ratios of 1Ch[Arg]:1Ch[Lys]:6H2O (balanced), 1Ch[Arg]:1Ch[Lys]:20H2O (balanced dilute), 3Ch[Arg]:1Ch[Lys]:12H2O (Arg- rich), and 1Ch[Arg]:3Ch[Lys]:12H2O (Lys- rich). The Arg- and Lys- anions tend not to associate due to electrostatic repulsion between charge groups and weak anion-anion attractions. This means that the local ion structures around the anions in these mixtures resemble the parent single-component systems. The bulk liquid nanostructure varies with the Arg-:Lys- ratio. In the Lys--rich mixture (1Ch[Arg]:3Ch[Lys]:12H2O), Lys- side chains cluster into a continuous apolar domain separated from a charged domain of polar groups. In the balanced mixture (1Ch[Arg]:1Ch[Lys]:6H2O), Lys- side chains form discrete apolar aggregates within a continuous polar domain of Arg-, Ch+, and water, and in the Arg--rich mixture (3Ch[Arg]:1Ch[Lys]:12H2O), the distribution of Lys- and Arg- is nearly homogeneous. Finally, in the balance dilute system (1Ch[Arg]:1Ch[Lys]:20H2O), a percolating water domain forms.

Environmental cell for USANS/SANS studies with aggressive fluids at high pressures and temperatures

The new (Ultra) Small Angle Neutron (USANS/SANS) cell provides in-situ monitoring capability of the evolving microstructure and physical properties of a wide range of natural and artificial materials. This modular, portable compact environmental cell is designed for thermal, mechanical and chemical loading measurements compatible with all neutron and X-ray-based research facilities worldwide that is fine-tuned to a specific beamline. A seamless integration of time-lapse structural information, on scales ranging from the sub-nano to the micrometre has been demonstrated in a series of USANS/SANS experiments performed on rock samples subjected to hydrostatic and uniaxial load, reactive fluid flow and elevated temperatures. The modular design of the cell allows optimisation for specific applications, ranging from cryogenic to temperatures over 500 °C, with plans for further extensions of this range in the future. Uniaxial mechanical stress up to 1000 bar, and sample surrounding fluid/gas pressure of up to 1000 bar in the constant pressure or constant flow rate mode can be applied independently to the sample during data acquisition. Due to the modular design, components such as windows, seals and pistons can be interchanged optimising the cell for use with chemically aggressive (including ultra-supercritical) fluids. This development supports research initiatives in geology, energy and minerals, resource engineering, civil engineering, material sciences, biotechnology, and medical sciences. The cell is also extendable for use in neutron diffraction and tomographic experiments.

Origins of multi-sublattice magnetism and superexchange interactions in double–double perovskite CaMnCrSbO6

The multi-sublattice magnetism and electronic structure in double–double perovskite compound CaMnCrSbO6 is explored using density functional theory. The bulk magnetization and neutron diffraction suggest a ferrimagnetic order ( TC∼ 49 K) between between Mn2+ and Cr3+ spins. Due to the non-equivalent Mn atoms (labelled as Mn(1) and Mn(2) which have tetrahedral and planar oxygen coordinations, respectively) and the Cr atom in the centre of distorted oxygen octahedron in the unit cell, the exchange interactions are more complex than that expected from a two sublattice magnetic system. The separations between the on-site energies of the d-orbitals of Mn(1), Mn(2) and Cr obtained from Wannier function analysis are in agreement with their expected crystal field splitting. While the DOS obtained from non spin-polarized calculations show a metallic character, starting from Hubbard U = 0 eV the spin-polarized electronic structure calculations yield a ferrimagnetic insulating ground state. The band gap increases with Ueff (U − J), thereby showing a Mott–Hubbard nature of the system. The inclusion of anti-site disorder in the calculations show decrease in band-gap and also reduction in the total magnetic moment. Due to the ∼90∘ superexchange, nearest neighbour exchange constants obtained from DFT are an order of magnitude smaller than those reported for various magnetic perovskite and double-perovskite compounds. The Mn(1)–O–Mn(2) (out of plane and in-plane), Mn(1)–O–Cr and Mn(2)–O–Cr superexchange interactions are found to be anti-ferromagnetic, while the Cr–O–O–Cr super-superexchange is found to be ferromagnetic. The Mn(2)–O–Cr superexchange is weaker than the Mn(1)–O–Cr super-exchange, thus effectively resulting in ferrimagnetism. From a simple 3-site Hubbard model, we derived expressions for the antiferromagnetic superexchange strength JAFM and also for the weaker ferromagnetic JFM . The relative strengths of JAFM for the various superexchange interactions are in agreement with those obtained from DFT. The expression for Cr–O–O–Cr super-superexchange strength ( J~SS ), which has been derived considering a 4-site Hubbard model, predicts a ferromagnetic exchange in agreement with DFT. Finally, our mean field calculations reveal that assuming a set of four magnetic sub-lattices for Mn2+ spins and a single magnetic sublattice for Cr3+ spins yields a much improved T C , while a simple two magnetic sublattice model yields a much higher T C .

Neutron diffraction: a primer

Abstract Because of the neutron’s special properties, neutron diffraction may be considered one of the most powerful techniques for structure determination of crystalline and related matter. Neutrons can be released from nuclear fission, from spallation processes, and also from low-energy nuclear reactions, and they can then be used in powder, time-of-flight, texture, single crystal, and other techniques, all of which are perfectly suited to clarify crystal and magnetic structures. With high neutron flux and sufficient brilliance, neutron diffraction also excels for diffuse scattering, for in situ and operando studies as well as for high-pressure experiments of today’s materials. For these, the wave-like neutron’s infinite advantage (isotope specific, magnetic) is crucial to answering important scientific questions, for example, on the structure and dynamics of light atoms in energy conversion and storage materials, magnetic matter, or protein structures. In this primer, we summarize the current state of neutron diffraction (and how it came to be), but also look at recent advances and new ideas, e.g., the design of new instruments, and what follows from that.

Morphology and kinetics of nanoheterogeneities in Fe81Ga19–Tb alloy: A small-angle neutron scattering study

The formation of nanoprecipitates in the Fe81Ga19 alloy doped with Tb (∼0.1 at. %) was studied by small-angle neutron scattering (SANS). Measurements at room temperature for several samples pre-aged at a fixed temperature in the range of (300–700)°C revealed a dilute system of precipitates with a characteristic size at nanoscale (<1000 Å) growing with an increase in ageing temperature. In situ measurements during isothermal ageing at 300 °C for 3 h revealed fast (order of 10 min) formation of precipitates. SANS analysis is consistent with the results of neutron diffraction experiments, which suggest the microstructure of this alloy as a matrix of disordered atomic structure (A2 phase) with embedded precipitates of the structurally and magnetically ordered D03 phase.

Exploring Reversible Redox Behavior in the 6H-BaFeO3-δ (0 < δ < 0.4) System: Impact of Fe3+/Fe4+ Ratio on CO Oxidation.

This work is devoted to evaluating the relationship between the oxygen content and catalytic activity in the CO oxidation process of the 6H-type BaFeO3-δ system. Strong evidence is provided about the improvement of catalytic performance with increasing Fe average oxidation state, thus suggesting the involvement of lattice oxygen in the catalytic process. The compositional and structural changes taking place in both the anionic and cationic sublattices of the catalysts during redox cycles have been determined by temperature-resolved neutron diffraction. The obtained results evidence a structural transition from hexagonal (P63/mmc) to orthorhombic (Cmcm) symmetry. This transition is linked to octahedra distortion when the Fe3+ concentration exceeds 40% (δ values higher than 0.2). The topotactical character of the redox process is maintained in the δ range 0 < δ < 0.4. This suggests that the cationic framework is only subjected to slight structural modifications during the oxygen exchange process occurring during the catalytic cycle.

Thermochemical and structural study of sodium, iron, and niobium phosphate NASICON solid solutions

Solid solutions NaxFe0.5+0.5xNb1.5-0.5x(PO4)3 (0 ≤ x ≤ 1; x = 2) of NASICON structure (sp.gr. R3-c) and NbOPO4 were prepared via solid-state reaction and characterized by electron microprobe analysis, powder X-ray and neutron diffraction, and differential thermal analysis. The decrease of the a- and b-unit cell parameter prevails over the increase in c-parameters, resulting in nonlinear decrease of the unit cell volume with Na content. Enthalpies of drop solution in molten sodium molybdate solvent at 700 °C were measured by high temperature oxide melt solution calorimetry and were used to derive the enthalpies of formation. Strongly negative enthalpies of formation from elements and from constituent oxides indicate high thermodynamic stability. The mixing enthalpies of solid solutions show negative deviation from the ideality. Negative mixing enthalpies and negative mixing volumes indicate short-range ordering of cations in the structure.

Investigation of structural phase stability, modified magnetic spin order and low temperature spin glass-like phase transitions in Sc-doped M-type BaFe12O19 hexaferrite

This work used two approaches of mechanical alloying before high temperature solid state reaction to synthesize BaFe12-xScxO19 (x = 0.5 to 6.0) system. Rietveld refinement of X-ray diffraction patterns showed the formation of extra phases at higher Sc doping, along with the main magnetoplumbite structure. Raman spectroscopy suggested random distribution of Sc ions at the Fe-sites of hexaferrite structure. X-ray photoelectron spectroscopy (XPS) confirmed the +3 charge state at the Fe/Sc-sites. The Fe 3s band suggested dilution of ferromagnetic 3s-3d spin exchange interactions. The neutron diffraction study re-confirmed random occupancy of the non-magnetic Sc3+ ions at Fe3+ sites of the Sc doped Ba hexaferrite system. The transformation of magnetic spin order from collinear to non-collinear state has shown spin glass-like features at low temperature regime in the dc magnetization curves. This is an effect of dilution of Fe–O–Fe ferrimagnetic super exchange interactions and spin frustration in Sc-doped samples.