Neutron Diffraction Research Articles

Magnetic ordering in the frustrated pyrochlore Yb2Ru2O7

Yb2Ru2O7 was studied using neutron diffraction and muon spin relaxation measurements to investigate the effect of the Yb anisotropy and Yb-Ru exchange interaction on the magnetic ordering transitions in this material. The Ru moments order into a long range ordered state below 85 K, while the Yb moments start to freeze/order below 20 K, which is at a higher temperature as suggested by previous reported bulk measurements. No structural distortions are observed at the magnetic transitions. Representational analysis shows that the ordering of the Ru and Yb moments can be described by the same irreducible representation. The two magnetic sublattices are, however, antiferromagnetically coupled. Unlike what has been suggested by bulk measurements and has been observed in other members of this family of Ru pyrochlores, the Yb single ion planar anisotropy, surprisingly, does not influence the Ru moment ordering. The ordering of the Ru moments, on the other hand, does influence freezing/ordering of the Yb moments.

Order-disorder phase transitions in Fe81Ga19-RE ALLOYS (RE = Dy, Er, Tb, Yb) according to neutron diffraction data

New data on the phase compositions and structural transformations in a number of Fe81Ga19 alloys doped with trace amount (≤ 0.2 at.%) of rare earth elements are presented. The data are obtained in neutron diffraction experiments performed with high resolution and in continuous temperature scanning mode when heated to 900 °C and subsequent cooling. It has been established that structural rearrangements proceed in a generally identical manner both in the original Fe81Ga19 alloy and in its doped analogues. Slow heating and subsequent cooling of the alloys (rate ±2 °C/min) leads to the formation of clusters of the D03 phase with sizes in the range (200–300) Å in the matrix of the disordered A2 phase. The sizes and volume fraction of clusters (~0.3 of the sample volume) weakly depend on the specific composition. The degree of ordering of the clusters atomic structure changes with temperature according to a second-order phase transition and is close to unity at room temperature. The search for structural ordering corresponding to the modified D03 phase, discovered in a number of electron diffraction studies, did not lead to a positive result.

2D to 3D Magnetism in Synthetic Micas.

Fe-based mica minerals usually display two opposing magnetic ground states, either they behave as spin-glasses or as layered ferrimagnets. No definite reason has been proposed as an explanation for this duality. This conundrum is unraveled by comparing the synthetic micas KFe3[MGe3]O10X2 with M═Fe and Ga, X═OH- and F-. Neutron diffraction demonstrates a 2D to 3D magnetic transition in KFe3[FeGe3]O10(OH)2 while just hints or no order at all are observed for the fluorides with M═Fe and Ga respectively. The 3D transition is triggered by the presence of iron in the intralayer tetrahedra. DFT+U calculations show that the magnetic exchange couplings between the previously believed solely magnetic octahedral layers would otherwise be frustrated without this intralayer iron.

Potassium- and Lithium-Ammonia Intercalation into Excitonic Insulator Candidate Ta2NiSe5.

Two new reduced phases derived from the topical excitonic insulator candidate Ta2NiSe5 have been synthesized via the intercalation of lithium and potassium from solutions of the metals in liquid ammonia. Li(NH3)Ta2NiSe5 and KTa2NiSe5 both crystallize in orthorhombic space group Pmnb with the following lattice parameters: a = 3.5175(1) Å, b = 18.7828(7) Å, and c = 15.7520(3) Å and a = 3.50247(3) Å, b = 13.4053(4) Å, and c = 15.7396(2) Å, respectively. They have increased unit cell volumes of 48% and 31%, respectively, relative to that of Ta2NiSe5. Significant rearrangement of the transition metal selenide layers is observed in both intercalates compared to the parent phase. In Li(NH3)Ta2NiSe5, neutron diffraction experiments confirm the location of the light Li, N, and H atoms, and solid-state nuclear magnetic resonance (NMR) experiments show that H, N, and Li each occupy a single environment at ambient temperature on the NMR time scale. Magnetometry data show that both intercalates have increased magnetic susceptibilities relative to that of Ta2NiSe5, consistent with the injection of electrons during intercalation and an enhancement of the Pauli paramagnetism.

Influence of hydrogen on deformation and embrittlement mechanisms in a high Mn austenitic steel: In-Situ neutron diffraction and diffraction line profile analysis

Austenitic steels have relatively high resistance to hydrogen embrittlement and play a critical role in hydrogen service applications. In particular, high Mn austenitic steels are considered economically viable alloy alternatives for these applications. The current study employed in-situ and ex-situ neutron diffraction techniques combined with diffraction line profile analysis (DLPA) to investigate the influence of hydrogen on deformation and embrittlement mechanisms in a high Mn (approximately 30 wt pct) austenitic steel. Investigation using both neutron diffraction and electron backscatter diffraction revealed the presence of extensive deformation twins and stacking faults within the steel microstructure after tensile deformation in the non-charged condition. These microstructural features suggest planar deformation behavior, which is expected from the relatively low stacking fault energy (SFE) of the alloy (approximately 29 mJ/m2). Hydrogen pre-charging resulted in apparent increases in both dislocations and stacking faults, contributing to macroscopic hardening and embrittlement mechanisms. Overall, numerical parameters obtained through neutron DLPA were used to elucidate the underlying mechanisms associated with hydrogen effects on the mechanical behavior, i.e. macroscopic strengthening, strain hardening rate, and embrittlement.

Synthesis and Electrochemical Performance of High‐Entropy Spinel‐Type Oxides Derived from Multimetallic Polymeric Precursors

High‐entropy spinel‐type oxides are synthesized by a modified Pechini process, wet chemistry approach, and solid‐state synthesis method and characterized as anode materials for Li‐ion batteries. The Pechini process that involves chelation and polyesterification reactions facilitates the formation of high‐entropy spinel‐type oxides without compositional segregation at ≈600 °C as confirmed by in situ and ex situ XRD. XAFS analysis and the Rietveld refinement of room‐temperature neutron diffraction data suggest the composition (Mn0.05Fe0.48Co0.47, tetrahedral)(Cr0.61Mn0.52Fe0.11Co0.09Ni0.68, octahedral)O4 for phase‐pure specimens. Compared to high‐entropy spinel‐type oxides synthesized by the solid‐state method, the precursor‐derived materials demonstrate higher specific capacity as anodes, in which the materials without citric acid addition exhibit low capacity fading at high current densities and maintained a capacity of ≈200 mAh g−1 after 1000 cycles. The generation of a rock‐salt‐type phase during cycling is confirmed for the first time by in situ charging–discharging XRD. The charging–discharging of this anode material is achieved mainly through the embedding–disembedding of lithium ions in the lattice of the generated rock‐salt‐type phase.

Analysis of magnetic structures in JANA2020.

JANA2020 is a program developed for the solution and refinement of regular, twinned, modulated, and composite crystal structures. In addition, JANA2020 also includes a magnetic option for solving magnetic structures from powder and single-crystal neutron diffraction data. This tool uses magnetic space and superspace symmetry to describe commensurate and incommensurate magnetic structures. The basics of the underlying formulation of magnetic structure factors and the use of magnetic symmetry for handling modulated and non-modulated magnetic structures are presented here, together with the general features of the magnetic tool. Examples of structures solved in the magnetic option of JANA2020 are given to illustrate the operation and capabilities of the program.

Unique magnetic structure of the vdW antiferromagnet VBr3

VBr3 is a van der Waals antiferromagnet below the Néel temperature of 26.5 K with a saturation moment of 1.2 µB/f.u. above the metamagnetic transitions detected in the in-plane and out-of-plane directions. To reveal the AFM structure of VBr3 experimentally, we performed a single-crystal neutron diffraction study on a large high-quality crystal. The collected data confirmed a slight monoclinic distortion of the high-temperature rhombohedral structure below 90 K. The magnetic structure was, nevertheless, investigated within the R-3 model. The antiferromagnetic structure propagation vector k = (1, 0, ½) was revealed. In an attempt to determine the magnetic structure, 72 non-equivalent magnetic reflections were recorded. The experimental data were confronted with the magnetic space groups dictated by the R-3 lattice symmetry and propagation vector. The best agreement between the experimental data and the magnetic structure model was obtained for the space group P-1.1′_c. The magnetic unit cell of the proposed unique antiferromagnetic structure with periodicity 6c is built from two identical triple layers antiferromagnetically coupled along the c axis. Each triple layer comprises a Néel antiferromagnetic monolayer sandwiched between two antiferromagnetically coupled ferromagnetic monolayers.

Low-dimensional metal-organic frameworks: a pathway to design, explore and tune magnetic structures.

The magnetic structure adopted by a material relies on symmetry, the hierarchy of exchange interactions between magnetic ions and local anisotropy. A direct pathway to control the magnetic interactions is to enforce dimensionality within the material, from zero-dimensional isolated magnetic ions, one-dimensional (1D) spin-chains, two-dimensional (2D) layers to three-dimensional (3D) order. Being able to design a material with a specific dimensionality for the phenomena of interest is non-trivial. While many advances have been made in the area of inorganic magnetic materials, organic compounds offer distinct and potentially more fertile ground for material design. In particular magnetic metal-organic frameworks (mMOFs) combine magnetism with non-magnetic property functionality on the organic linkers within the structural framework, which can further be tuned with mild perturbations of pressure and field to induce phase transitions. Here, it is examined how neutron scattering measurements on mMOFs can be used to directly determine the magnetic structure when the magnetic ions are in a 2D layered environment within the wider 3D crystalline framework. The hydrated formate, in deuterated form, Co(DCOO)2·2D2O, which was one of the first magnetic MOFs to be investigated with neutron diffraction, is reinvestigated as an exemplar case.

Understanding the High-Temperature Deformation Behaviors in Additively Manufactured Al6061+TiC Composites via In Situ Neutron Diffraction

Aluminum matrix composites (AMCs) are designed to enhance the performance of conventional aluminum alloys for engineering applications at both room and elevated temperatures. However, the dynamic phase-specific deformation behavior and load-sharing mechanisms of AMCs at elevated temperatures have not been extensively studied and remain unclear. Here, in situ neutron diffraction experiments are employed to reveal the phase-specific structure evolution of additively manufactured Al6061+TiC composites under compressive loading at 250 °C. It is found that the addition of a small amount of nano-size TiC significantly alters the deformation behavior and increases the strength at 250 °C in comparison to the as-printed Al6061. Unlike the two-stage behavior observed in Al6061, the Al6061+TiC composites exhibit three stages during compression triggered by changes in the interphase stress states. Further analysis of Bragg peak intensity and broadening reveals that the presence of TiC alters the dislocation activity during deformation at 250 °C by influencing dislocation slip planes and promoting dislocation accumulation. These findings provide direct experimental observations of the phase-specific dynamic process in AMCs under deformation at an elevated temperature. The revealed mechanisms provide insights for the future design and optimization of high-performance AMCs.

Secondary phase increases the elastic modulus of a cast aluminum-cerium alloy

Alloying in metal castings is one of the principal methods of strengthening an alloy for various structural and functional applications, but very rarely does it modify an alloy’s elastic modulus. We report a methodology of combining isostructural Laves phases to form a multi-component, high symmetry, isotropic phase that was discovered to enhance the elastic modulus of a cast aluminum alloy to 91.5 ± 7.4 GPa. Flux grown single crystals of the rhombicuboctahedron phase (RCO), so named for the observed morphology, were used to enhance understanding of the structure and mechanical properties of the phase. The pure RCO phase’s structure and site occupancies were co-refined using x-ray and neutron diffraction. Dynamic nanomechanical testing of the cast alloy shows the primary RCO phase has a high, relatively isotropic, elastic modulus. This RCO containing aluminum alloy is found to have a specific modulus that exceeds that of the leading Al, Mg, Steel, and Ti alloys.

Coexistence of multiple magnetic interactions in oxygen-deficient V2O5 nanoparticles

This paper reports on the spin glass-like coexistence of competing magnetic orders in oxygen-deficient V2O5 nanoparticles with a broad size distribution. X-ray photoelectron spectroscopy yields the surface chemical stoichiometry of nearly V2O4.65 due to significant defect density. Temperature-dependent electrical conductivity and thermopower measurements demonstrate a polaronic conduction mechanism with a hopping energy of about 0.112 eV. The V2O5-δ sample exhibits strong field as well as temperature-dependent magnetic behaviour when measured with a SQUID magnetometer, showing positive magnetic susceptibility across the temperature range of 2-350 K. Field-cooled and zero-field-cooled data indicate hysteresis, suggesting glassy behaviour. The formation of small polarons due to oxygen vacancy defects, compensated by V4+ charge defects, results in Magneto-Electronic Phase Separation (MEPS) and various magnetic exchanges, as predicted by first-principle calculations. This is evidenced by the strong hybridisation of V orbitals in the vicinity of vacant oxygen site. An increase in V4+ defects shows an antiferromagnetic (AFM) component. The magnetic diversity in undoped V2O4.9 originates from defect density and their random distribution, leading to MEPS. This involves localised spins in polarons and ferromagnetic (FM) clusters on a paramagnetic (PM) background, while V4+ dimers induce AFM interactions. Electron paramagnetic resonance spectra measured at different temperatures indicate a dominant paramagnetic signal at a g-value of 1.97 due to oxygen defects, with a broad FM resonance-like hump. Both signals diminish with increasing temperature. Neutron diffraction data rules out long-range magnetic ordering, reflecting the composition as V2O4.886. Despite the FM hysteresis, no long-range order is observed in neutron diffraction data, consistent with the polaron cluster-like FM with MEPS nature. This detailed study shall advance the understanding of the diverse magnetic behaviour observed in undoped non-magnetic systems.

Magnetic structure of the noncentrosymmetric magnet Sr2MnSi2O7 through irreducible representation and magnetic space group analyses.

Magnetic structures of the noncentrosymmetric magnet Sr2MnSi2O7 were examined through neutron diffraction for powder and single-crystalline samples, as well as magnetometry measurements. All allowed magnetic structures for space group P421m with the magnetic wavevector qm = (0, 0, ½) were refined via irreducible representation and magnetic space group analyses. The compound was refined to have in-plane magnetic moments within the magnetic space group Cmc21.1'c (No. 36.177) under zero field, which can be altered to P212121.1'c (No.19.28) above μ0H = 0.067 (5) T to align induced weak-ferromagnetic components within one layer on the ab plane. All refined parameters are provided following the recent framework based upon the magnetic space group, which better conveys when exchanging crystallographic information for commensurate magnetic structures.

Ferrimagnetic structure in the high-pressure phase of α−Mn

The α−Mn phase exhibits a large anomalous Hall effect (AHE) in its pressure-induced weak ferromagnetic (WFM) state, despite its relatively small spontaneous magnetization of ∼0.02μB/Mn. To understand the underlying mechanism behind this AHE, we performed single crystal neutron diffraction measurements at 2.0 GPa to determine the magnetic structure of the WFM phase. Our investigation reveals a ferrimagnetic structure characterized by nearly collinear magnetic moments aligned along the [001] direction at sites I, II, III-1, and IV-1. In contrast, the small moments at sites III-2 and IV-2 lie within the (001) plane. The calculated net magnetization of this magnetic structure, (−0.08±0.10)μB/Mn atom, is in agreement with the experimentally determined spontaneous magnetization. The observation of a magnetic reflection at q=(0,0,0) satisfies a key condition for the emergence of the AHE. Published by the American Physical Society 2024

On the magnetic and crystal structures of NiO and MnO.

The magnetic and crystal structures of manganese and nickel monoxides have been studied using high-resolution neutron diffraction. The known 1k-structures based on the single propagation vector [½ ½ ½] for the parent paramagnetic space group Fm3m are forced to have monoclinic magnetic symmetry and are not possible in rhombohedral symmetry. However, the monoclinic distortions from the rhombohedral crystal metric allowed by symmetry are very small, and the explicit monoclinic splittings of the diffraction peaks have not been experimentally observed. We analyse the magnetic crystallographic models metrically compatible with our experimental data in full detail by using isotropy subgroup representation approach, including rhombohedral solutions based on the propagation vector star {[½ ½ ½], [-½ ½ ½], [½-½ ½], [½ ½ -½]}. Although the full star rhombohedral RI3c structure can equally well fit our diffraction data for NiO, we conclude that the best solution for the crystal and magnetic structures for NiO and MnO is the 1k monoclinic model with the magnetic space group Cc2/c (Belov-Neronova-Smirnova No. 15.90, UNI symbol C2/c.1'c[C2/m]).

Texture of Hot-Compressed Metastable β-Titanium Alloy Ti5321 Studied by Neutron Diffraction.

The textures of the β- and α-phases of the metastable β-titanium alloy Ti5321 after hot deformation were investigated by neutron diffraction. A hot-rolled bar was solutionized in the β-phase field and then hot compressed above and below the β-transus temperature. The initial texture after full recrystallization and grain growth in the β-phase field exhibits a weak cube component {001}<100> and minor {112}<110> and {111}<110> components. After hot compression, a <100> fiber texture is observed, increasing in intensity with compression temperature. Below the β-transus temperature, dynamic recrystallization of the β-phase and dynamic spheroidization of the α-phase interact strongly. The texture of the α-phase is a <11-20> fiber texture, increasing in intensity with decreasing compression temperature. The mechanisms of texture formation during hot compression are discussed.

A modern reappraisal of the U-Zr phase diagram

By integrating published experimental data on the uranium-zirconium (U-Zr) system into a machine learning framework, insight into the two differing views on the thermochemical equilibrium, particularly on the U-rich portion of the phase diagram (PD) was developed, ultimately resulting in a new U-Zr PD. Phase diagram sensitivity to model parameters, tolerances, physical preconceptions and experimental biases, are considered to establish the validity of the generated PDs. A systematic assessment of the most reliable and most recent thermochemical data was made, and the traditional modeling bias to search the space of free energy parameters was removed by using recently developed machine learning strategies. The readily validated methodology enables a thermodynamically consistent search of free energy parameters by leveraging modern experimental work from an array of sources including phase transformations, phase transition temperatures, and enthalpy changes between 723-1173 K (450-900°C). These changes include the truncation of β-U stability at 6 at.% Zr, prominent isotherms at 884 K (611°C) and 961 K (688°C), and δ-U-Zr phase boundaries ranging from 66.5 to 80.2 at.% Zr at 823 K (550°C). The newly proposed PD captures fundamental constants measured experimentally and improves the agreement with phase transformation studies such as neutron diffraction with in situ heating. As such, it is proposed that the new U-Zr PD developed in this work be used to resolve the historically opposing views.

The Non-Centrosymmetric Borate Hydride Sr4Ba3(BO3)3.83H2.5.

Sr4Ba3(BO3)3.83H2.5, as the second compound to combine borate and hydride ions, has been synthesized by a mechanochemical synthesis route. The structure has been elucidated by synchrotron X-ray and neutron diffraction and determined to crystallize in the non-centrosymmetric space group P63mc (186) with the cell parameters a=10.87762(15) Å and c=6.98061(11) Å. A detailed investigation of the compound by vibrational spectroscopy in combination with Density Functional Theory calculations reveals the disordered nature of the structure and proves the presence of both borate and hydride ions. Electronic band structure calculations predict a large band gap of 7.1 eV. Hydride states are predicted at the topmost valence band, which agrees well with earlier reported heteroanionic hydrides. We hereby were able to successfully apply previously synthetic and analytical schemes to introduce another member of the rare compounds that contain complex oxoanions simultaneously with hydride ions.

Brightening triplet excitons enable high-performance white-light emission in organic small molecules via integrating n–π*/π–π* transitions

Luminescent materials that simultaneously embody bright singlet and triplet excitons hold great potential in optoelectronics, signage, and information encryption. However, achieving high-performance white-light emission is severely hampered by their inherent unbalanced contribution of fluorescence and phosphorescence. Herein, we address this challenge by pressure treatment engineering via the hydrogen bonding cooperativity effect to realize the mixture of n–π*/π–π* transitions, where the triplet state emission was boosted from 7% to 40% in isophthalic acid (IPA). A superior white-light emission based on hybrid fluorescence and phosphorescence was harvested in pressure-treated IPA, and the photoluminescence quantum yield was increased to 75% from the initial 19% (blue-light emission). In-situ high-pressure IR spectra, X-ray diffraction, and neutron diffraction reveal continuous strengthening of the hydrogen bonds with the increase of pressure. Furthermore, this enhanced hydrogen bond is retained down to the ambient conditions after pressure treatment, awarding the targeted IPA efficient intersystem crossing for balanced singlet/triplet excitons population and resulting in efficient white-light emission. This work not only proposes a route for brightening triplet states in organic small molecules, but also regulates the ratio of singlet and triplet excitons to construct high-performance white-light emission.

Origin of zero thermal expansion in an average cubic structure in Pb-free relaxor ferroelectrics

This study presents “K0.5Na0.5NbO3-based” Pb-free smart material 0.80(K0.5Na0.5NbO3)–0.20(Ba0.9Sr0.1TiO3) (KBST20) as exhibiting zero thermal expansion (ZTE) at low temperatures (T≤ 100 K) with long-range cubic symmetry stable over a wide temperature range (9 K ≤T≤ 500 K). The linear coefficient of the thermal expansion (αl) obtained from temperature-dependent neutron diffraction data is in the range of 0.255–5.75 × 10−6 K–1 (9–500 K), which is rarely observed for Pb-free materials possessing long-range cubic symmetry. The temperature-dependent dielectric data of KBST20 exhibits a strong relaxational behavior with high frequency dispersion (ΔT≈ 27 K), suggesting the presence of polar phased regions known as polar nano regions. The ZTE has been attributed to enhanced correlations among PNRs exhibiting ferroelectrostriction. Furthermore, temperature-dependent Raman scattering data reveal polar monoclinic distortion at short ranges rather than cubic symmetry at long ranges. In addition, the intensity of Raman modes increases with the decrease in temperature, suggesting enhancement of the polar phase at low temperatures, which consequently leads to zero thermal expansion in KBST20.