Neutron Diffraction Research Articles

Multicomponent intermetallic compound CoCrFeNiSi: Crystal structure and magnetic properties

A novel intermetallic compound with a cubic crystal structure was successfully synthesized within the quinary system of CoCrFeNiSi, boasting an almost equiatomic chemical composition. The crystal structures of the intermetallics and the minor impurity phase has been meticulously investigated using X-ray diffraction (XRD), time-of-flight neutron diffraction and transmission electron microscopy. Magnetic measurements of this high-entropy intermetallic compound revealed that CoCrFeNiSi exhibits ferrimagnetic properties at room temperature. The structural disorder was investigated through theoretical calculations and magnetic moment measurements.

Internal Strain Measurement by Neutron Diffraction Under Transverse Compressive Stress for Nb3Sn Wires With and Without Cu-Nb Reinforcement

Internal Strain Measurement by Neutron Diffraction Under Transverse Compressive Stress for Nb₃Sn Wires With and Without Cu-Nb Reinforcement

Mechanical and high-temperature characterization of additively manufactured Ni-superalloys at SALSA neutron strain diffractometer

Neutron diffraction is a well-established method for the measurement and characterization of internal stresses in metallic and ceramic materials at room temperature. Some cases have been reported in the literature in which the method has been extended to higher temperatures. In this paper we report both novel setups for in-situ heat treatments and for in-situ mechanical testing at high temperature at SALSA in the Institut Laue-Langevin (ILL). Characterization of internal stresses in Ni-superalloys demonstrated the feasibility, stability and exploitation of results achieved by a tailored induction heating system. Different coils are adapted to accommodate several sample geometries for accurate focusing of the magnetic heating induction field on the sample, to achieve high heating rates up to 50 °C/s and therefore limiting the microstructural evolution impact during ramping-up to the target temperature. In return, this enhances the choice of reference d0, by either measurements at room temperature and extrapolated values to high temperature, or by direct measurements also at high temperature. A detailed strategy of d0 stress-free reference approaches for such in-situ experiments at high temperature is discussed.

Magnetic structure and lattice properties of R2Cu2In intermetallics (R = Dy, Tm, Lu)

Magnetic and structural properties of tetragonal R2Cu2In intermetallics are presented for R = Dy, Tm, and Lu. The neutron diffraction experiment clarifies the nature of magnetic order in Dy2Cu2In and Tm2Cu2In. While Tm2Cu2In orders ferromagnetically below TC = 31 K with magnetic space group (MSG) P4/mb'm', Dy2Cu2In forms a non-collinear ferromagnetic state below 50 K (MSG P2'/m') with another k = (½, ½, ½) component of magnetic moment (MSG Ibam.1'c) appearing at 20 K. The ground-state magnetic structure is described by the MSG Im'm'a with a magnetic moment of 9.35 μB. This subsequent transition is accompanied by the changes in the T-dependence of anisotropy constants, however, no related anomaly is observed in specific heat dominated by the CF and exchange interaction effects. Magnetic properties are discussed in the context of lattice response to temperature and pressure variations. The experimental results are supported by the analysis of the non-magnetic Lu analogue and by the first-principles calculations (electronic structure and material properties) based on Density Functional Theory (DFT).

Hydrogen Bonding Analysis of Structural Transition-Induced Symmetry Breaking and Spin Splitting in a Hybrid Perovskite Employing a Synergistic Diffraction-DFT Approach.

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) offer an outstanding opportunity for spin-related technologies owing in part to their tunable structural symmetry breaking and distortions driven by organic-inorganic hydrogen (H) bonds. However, understanding how H-bonds tailor inorganic symmetry and distortions and therefore enhance spin splitting for more effective spin manipulation remains imprecise due to challenges in measuring H atom positions using X-ray diffraction. Here, we report a thermally induced structural transition (at ∼209 K) for a 2D HOIP, (2-BrPEA)2PbI4 [2-BrPEA = 2-(2-bromophenyl)ethylammonium], which induces inversion asymmetry and a strong spin splitting (ΔE > 30 meV). While X-ray diffraction generally establishes heavy atom coordinates, we utilize neutron diffraction for accurate H atom position determination, demonstrating that the structural transition-induced rearrangement of H-bonds with distinct bond strengths asymmetrically shifts associated iodine atom positions. Consequences of this shift include an increased structural asymmetry, an enhanced difference between adjacent interoctahedra distortions (i.e., Pb-I-Pb bond angles), and therefore significant spin splitting. We further show that H-only density-functional theory (DFT) relaxation of the X-ray structure shifts H atoms to positions that are consistent with the neutron experimental data, validating a convenient pathway to more generally improve upon HOIP H-bonding analyses derived from quicker/less-expensive X-ray data.

Martensitic transformation-governed Lüders deformation enables large ductility and late-stage strain hardening in ultrafine-grained austenitic stainless steel at low temperatures

Deformation-induced martensitic transformation that rapidly occurs generally leads to a significant reduction in elongation of metastable austenitic steels, particularly at low temperatures. However, we proved that the ultrafine-grained 304 stainless steel is an exception. Using a hybrid method of in situ neutron diffraction and digital image correlation, we found that this material exhibits Lüders deformation after yielding, in which the deformation behavior changes from a cooperation mechanism involving dislocation slip and martensitic transformation to one primarily governed by martensitic transformation, as the temperature decreases from 295 K to 77 K. Such martensitic transformation-governed Lüders deformation delays the activation of plastic deformation in both the austenite parent and martensite product, resulting in delayed strain hardening. This preserves the strain-hardening capability for the later stage of deformation, thereby maintaining a remarkable elongation of 29 % while achieving a high tensile strength of 1.87 GPa at 77 K. Insights from this study point to a feasible pathway to achieve both high strength and high ductility by rearranging the deformation modes of ultrafine-grained materials.

Chemical pressure induced spin reorientation in the magnetic structure of Ca3Mn2−xSnxO7 ( x=0,0.03,0.05 )

The effect of partially substituting Tin (Sn) at the Manganese (Mn) site of Ca3Mn2O7 , viz. Ca3Mn2−xSnxO7 with x=0.03,0.05 , on its structural and magnetic properties have been investigated using synchrotron diffraction, neutron diffraction, and bulk magnetization measurements. It is observed that with a substitution of x=0.03 , the minor (≈8%) tetragonal ( I4/mmm ) structural phase that is present in the predominantly orthorhombic ( Cmc21 ) undoped Ca3Mn2O7 , completely disappears. The compounds order antiferromagnetically, the ordering temperature decreases with increasing Sn-content, indicating a weakening of the antiferromagnetic exchange interactions. Interestingly, in the ordered state, the spin magnetic moments which were aligned along the a-axis of the unit cell in the undoped compound, are observed to have reoriented with their major components lying in the b − c plane in the Sn-doped compounds. The above influence of Sn-doping is seen to be stemming from a significant modification of the octahedral rotation and tilt mode geometry in the unit cell, that is known to be responsible for driving ferroelectricity in these compounds.

Stress-tunable abilities of glass forming and mechanical amorphization

Mechanical amorphization, a widely observed phenomenon, has been utilized to synthesize novel phases by inducing disorder through external loading, thereby expanding the realm of glass-forming systems. Empirically, it has been plausible that mechanical amorphization ability consistently correlates with glass-forming ability. However, through a comprehensive investigation in binary, ternary, and quaternary systems combining neutron diffraction, calorimetric experimental approaches and molecular dynamics simulation, we demonstrate that this impression is only partly true and we reveal that the mechanical amorphization ability can be inversely correlated with the glass forming ability in certain cases To provide insights into these intriguing findings, we present a stress-dependent nucleation theory that offers a coherent explanation for both experimental and simulation results. Our study identifies the intensity of mechanical work, contributed by external stress, as the key control parameter for mechanical amorphization, rendering the ability to tune this process. This discovery not only unravels the underlying correlation between mechanical amorphization and glass-forming ability but also provides a pathway for the design and discovery of new amorphous phases with tailored properties.

Advances in the Parameter Space Concept towards Picometer Precise Crystal Structure Refinement—A Resolution Study

The Parameter Space Concept (PSC) is an alternative approach to solving and refining (partial) crystal structures from very few pre-chosen X-ray or neutron diffraction amplitudes without the use of Fourier inversion. PSC interprets those amplitudes as piecewise analytic hyper-surfaces, so-called isosurfaces, in the Parameter Space, which is spanned by the spatial coordinates of all atoms of interest. The intersections of all isosurfaces constitute the (possibly degenerate) structure solution. The present feasibility study investigates the La and Sr split position of the potential high-temperature super-conductor (La0.5Sr1.5)MnO4, I4/mmm, with a postulated total displacement between La and Sr of a few pm by theoretical amplitudes of pre-selected 00l reflections (l=2,4,…,20). The revision of 15-year-old results with state-of-the-art computing equipment enhances the former simplified model by varying the scattering power ratio fLa/fSr, as exploitable by means of resonant scattering contrast at synchrotron facilities, and irrevocably reveals one of the two originally proposed solutions as being a “blurred” pseudo-solution. Finally, studying the resolution limits of PSC as a function of intensity errors by means of Monte-Carlo simulations shows both that the split can only be resolved for sufficiently low errors and, particularly for the resonant scattering contrast, a theoretical precision down to ±0.19 pm can be achieved for this specific structural problem.

Comprehensive Investigation of the Crystal Structure of Cation-Disordered Li3VO4 as a High-Rate Anode Material: Unveiling the Dichotomy between Order and Disorder.

This study investigates mechanochemical synthesis and cation-disordering mechanism of wurtzite-type Li3VO4 (LVO), highlighting its promise as a high-performance anode material for lithium-ion batteries and hybrid supercapacitors. Mechanochemical treatment of pristine LVO using a high-energy ball mill results in a "pure cation-disordered" LVO phase, allowing for meticulous analysis of cation arrangement. The X-ray and neutron diffraction study demonstrates progressive loss of order in LVO crystal with increasing milling duration. High-resolution transmission electron microscopy reveals disrupted lattice fringes, indicating cationic misalignment. Pair-distribution function analysis confirms loss of cation arrangements and the presence of short-range order. Combination of these multiple analytical techniques achieves a comprehensive understanding of cation regularity and clearly demonstrates order/disorder dichotomy in cation-disordered materials, ranging from short (<8 Å) to middle-long range (8-30 Å), using an integrated superstructure model of the cation-disordered LVO crystals. Electrochemical testing reveals that mechanochemically treated LVO exhibits superior rate capability, with a 70% capacity retention at a high current density of 50C-rate. Lithium diffusion coefficient measurements demonstrate enhanced lithium-ion mobility in the mechanochemically treated LVO, attributed to cation-disordering effect. These findings provide valuable insights into mechanochemical cation-disordering in LVO, presenting its potential as an efficient anode material for lithium-ion-based electrochemical energy storage.

Dynamic Evolution of Antisite Defect and Coupling Anionic Redox in High-Voltage Ultrahigh-Ni Cathode.

High-voltage ultrahigh-Ni cathodes (LiNixCoyMn1-x-yO2, x ≥ 0.9) can significantly enhance the energy density and cost-effectiveness of Li-ion batteries beyond current levels. However, severe Li-Ni antisite defects and their undetermined dynamic evolutions during high-voltage cycling limit the further development of these ultrahigh-Ni cathodes. In this study, we quantify the dynamic evolutions of the Li-Ni antisite defect using operando neutron diffraction and reveal its coupling relationship with anionic redox, another critical challenge restricting ultrahigh-Ni cathodes. We detect a clear Ni migration coupled with an unstable oxygen lattice, which accompanies the oxidation of oxygen anions at high voltages. Based on these findings, we propose that minimized Li-Ni antisite defects and controlled Ni migrations are essential for achieving stable high-voltage cycling structures in ultrahigh-Ni cathodes. This is further demonstrated by the optimized ultrahigh-Ni cathode, where reduced dynamic evolutions of the Li-Ni antisite defect effectively inhibit the anionic redox, enhancing the 4.5 V cycling stability.

Impact of scan strategy on principal stresses in laser powder bed fusion

Additive manufacturing techniques, such as laser powder bed fusion (PBF-LB), are well known for their exceptional freedom in part design. However, these techniques are also characterized by the development of large thermal gradients during production and thus residual stress (RS) formation in produced parts. In this context, neutron diffraction enables the non-destructive characterization of the bulk RS distribution. By control of the thermal gradients in the powder-bed plane by scan strategy variation we study the impact of in-process scan strategy variations on the microstructure and the three-dimensional distribution of RS. Microstructural analysis by means of electron backscatter diffraction reveals sharp microstructure transitions at the interfaces ranging from 100-200 µm. The components of the RS tensor are determined by means of neutron diffraction and the principal stress directions and magnitudes are determined by eigenvalue decomposition. We find that the distribution of RS in the powder-bed plane corresponds to the underlying scan strategy. When the alternating scan vectors align with the x- and y sample coordinate axes, the principal stress directions co-align. In the present geometry, nearly transverse isotropic stress states develop when the scan vectors are either aligned 45° between x and y or continuously rotated by 67° between each layer.

Structure of ZnxFe3−xO4 nanoparticles studied by neutron diffraction and its relation with their response in magnetic hyperthermia experiments

The mixed zinc-ferrite spinel magnetic nanoparticles (MNPs) with the general formula ZnxFe3−xO4 are among the most extensively studied families of Fe oxides due to their interesting and diverse chemical, electronic, and magnetic properties. These systems offer the possibility of surface functionalization and possess high biocompatibility, making them highly attractive for applications in biomedicine, such as magnetic fluid hyperthermia (MFH). The efficiency of the MFH process relies on the magnetic, structural and morphological properties of the MNPs. The substitution with the Zn ion and the cationic distribution, as well as the synthesis process employed, have a direct impact on the final properties of these oxides. Therefore, it is essential to have tools that enable a comprehensive characterization of the system to assess its performance in MFH. In this study, we have synthesized four ZnxFe3−xO4 MNP systems using three different methods: two by thermal decomposition at high temperatures, one by co-precipitation, and another by co-precipitation followed by ball milling. We analyze the effect of these various synthesis processes on the magnetic and crystallographic properties, aiming to correlate them with the response of each system in MFH. Neutron diffraction data are employed to determine the cation site occupation and to investigate the correlation with the synthesis method. MFH measurements were conducted in media of diverse viscosities, revealing different values of specific loss power, thus demonstrating a clear dependence on the synthesis process and Zn content.

Mechanical Behavior Analysis on SiC/Al Composites via In-Situ Neutron Diffraction combined with Finite Element Methods

In this study, in-situ neutron diffraction and finite element (FE) analysis were employed to analyze the mechanical behavior of SiC/Al composites with 9 (M9) and 25 (M25) vol.% SiC during tensile tests. The analysis of stress concentration factors in SiC/Al composites during the tensile process revealed that load-redistribution between the matrix and the reinforcement was accompanied by local and overall plastic deformation. The strength analysis shows that the load transfer and the dislocation strengthening were the main reasons for the strength increase. The dislocation strengthening and load transfer strengthening of M25 were 4 and 3 times higher than that of M9, respectively. In addition, during the tensile process, the load-redistribution occurred simultaneously with micro-yielding. The comparison between the external loading-macro elastic strain and stress-strain curves could reflect the micro-yielding beginning. It was found that the micro-yielding of M25 was more obvious, because more stress concentration around reinforcement and a large number of movable thermal mismatch dislocations were induced at high content reinforcement.

Temperature calibration of sample rods for neutron diffraction apparatus in the range of 6–473 K

Abstract Internal stresses play a crucial part in determining a material’s properties, which emphasizes the significance of accurate stress measurement and analysis. Neutron diffraction technology is a very promising approach to studying the complex microstructural properties of many materials, especially with the growing demand for cryogenic studies. This new device has a robust load capacity of 50 kN and works smoothly in a wide temperature range of 6 K–473 K. Furthermore, the diffraction angle is 47 degrees broader. Regardless of the samples, we observed that a thermal balance point existed close to 180 K. Importantly, thermal resistance was eliminated by the use of an analytical method, which has an extraordinarily small error of 2%. Using this exact calibration methodology ensures that the sample temperature is accurate during the experiments. This work presents a crucial apparatus for investigating the complexity of internal stresses in materials and offers an effective method for estimating and managing sample temperatures while doing research.

Revealing the atomic and electronic mechanism of human manganese superoxide dismutase product inhibition

Human manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting superoxide (O2●−) to molecular oxygen (O2) and hydrogen peroxide (H2O2) with proton-coupled electron transfers (PCETs). Human MnSOD has evolved to be highly product inhibited to limit the formation of H2O2, a freely diffusible oxidant and signaling molecule. The product-inhibited complex is thought to be composed of a peroxide (O22−) or hydroperoxide (HO2−) species bound to Mn ion and formed from an unknown PCET mechanism. PCET mechanisms of proteins are typically not known due to difficulties in detecting the protonation states of specific residues that coincide with the electronic state of the redox center. To shed light on the mechanism, we combine neutron diffraction and X-ray absorption spectroscopy of the product-bound, trivalent, and divalent states of the enzyme to reveal the positions of all the atoms, including hydrogen, and the electronic configuration of the metal ion. The data identifies the product-inhibited complex, and a PCET mechanism of inhibition is constructed.

Effects of Fe substitution for Mn on structural, magnetic and magnetocaloric properties of TbMn2-xFexSi2

The structural and magnetic properties of TbMn2-xFexSi2 compounds (x = 0.0–0.4) have been investigated in details by high-resolution synchrotron x-ray and neutron powder diffraction, specific heat, and dc magnetization measurements. The replacement of Fe for Mn in TbMn2-xFexSi2 does not change the crystal structure but leads to a significant contraction of the unit cell (dV/dx ∼ - 6 Å3) and modification of three magnetic phase transition temperatures – the Curie temperatures Tc1, Tc2 and the Néel temperature TN. For example, the Tc1, Tc2 and TN values of TbMn2Si2 decrease from Tc1 = 50 K, Tc2 = 64 K and TN = 500 K to Tc1 = 27 K, Tc2 = 37 K and TN = 440 K for TbMn1.6Fe0.4Si2. Detailed neutron diffraction investigations have allowed us to determine the magnetic structures and construct the magnetic phase diagram as well as confirm the presence of magnetoelastic coupling effects. The significantly different responses of Tc1 and Tc2 to applied magnetic fields (e.g. dTc1/dB = 0.52 K/T and dTc2/dB = 4.7 K/T for TbMn1.6Fe0.4Si2), leads to expansion of the temperature region (ΔT = Tc2- Tc1) for the canted ferromagnetic state Fmc-ii between Tc1 and Tc2. In the case of TbMn1.6Fe0.4Si2, ΔT increases from ΔT = 9 K for applied magnetic field B = 0.2 T to ΔT = 36 K for B = 6 T, resulting in plateau-like behaviour of magnetic entropy change and enhances the relative cooling power (RCP) in this system. Under a change of magnetic field of 0 T – 5 T, the maximum value of the magnetic entropy changes -ΔSmax and adiabatic temperature change, ΔTad are derived to be -ΔSmax = 13.1 J/kg K and ΔTad = 8.4 K with the RCP = 411 J/kg for x=0.4 sample. The plateau-like magnetocaloric effect and relatively large RCP make these materials potentially suitable for application in cryogenic magnetic refrigeration.

Giant Room-Temperature Topological Hall Effect in a Square-Net Ferromagnet LaMn2Ge2.

A topological magnetic material showcases a multitude of intriguing properties resulting from the compelling interplay between topology and magnetism. These include notable phenomena such as a large anomalous Nernst effect (ANE), an anomalous Hall effect (AHE), and a topological Hall effect (THE). In most cases, topological transport phenomena are prevalent at temperatures considerably lower than room temperature, presenting a challenge for practical applications. However, the noncollinear ferromagnetic (FM) LaMn2Ge2, characterized by a Mn square-net lattice and a notably high Curie temperature (TC) of approximately 325 K, defies this trend as a topological semimetal. This work observes a giant topological Hall resistivity, , of ≈4.5 µΩ cm at room temperature when the angle between the applied field and the c-axis is 75°, which is significantly higher than state-of-the-art materials with noncoplanar spin structures. The single crystal neutron diffraction measurements agree with an incommensurate conical magnetic structure as the ground state. This observation suggests the enhanced spin chirality resulting from the noncoplanar spin configuration when the applied field is away from the magnetic easy axis as the origin of a large contribution to the observed THE. The findings unequivocally demonstrate that the FM LaMn2Ge2 holds great promise as a potential topological semimetal for spintronic applications even at room temperature.

In-situ tensile deformation of austenitic stainless steels with various grain sizes during synchrotron and neutron diffraction

In-situ tensile deformation of austenitic stainless steels with various grain sizes during synchrotron and neutron diffraction

Evolution of Material Properties and Residual Stress with Increasing Number of Passes in Aluminium Structure Printed via Additive Friction Stir Deposition.

Additive friction stir deposition (AFSD) is an emerging solid-state additive manufacturing process with a high deposition rate. Being a non-fusion additive manufacturing (AM) process, it significantly eliminates problems related to melting such as cracking or high residual stresses. Therefore, it is possible to process reactive materials or high-strength alloys with high susceptibility to cracking. Although the residual stresses are lower in this process than with the other AM processes, depending on the deposition path, geometry, and boundary conditions, residual stresses may lead to undesired deformations and deteriorate the dimensional accuracy. Thermal cycling during layer deposition, which also depends on the geometry of the manufactured component, is expected to affect mechanical properties. To this day, the influence of the deposit geometry on the residual stresses and mechanical properties is not well understood, which presents a barrier for industry uptake of this process for large-scale part manufacturing. In this study, a stepped structure with 4, 7, and 10 passes manufactured via AFSD is used to investigate changes in microstructure, residual stress, and mechanical property as a function of the number of passes. The microstructure and defects are assessed using scanning electron microscopy and electron backscatter diffraction. Hardness maps for each step are created. The residual stress distributions at the centreline of each step are acquired via non-destructive neutron diffraction. The valuable insights presented here are essential for the successful utilisation of AFSD in industrial applications.