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At least 325 records · Page 18

Progression of creep deformation from grain boundaries to grain interior in Al-Cu-Mn-Zr alloys

Creep mechanisms are studied in θ'-Al 2 Cu-strengthened Al-Cu-Mn-Zr alloys at 300 and 350°C for (i) ACMZ, a base alloy without further alloying elements and (ii) RR350, a commercial alloy with additions of Ni and Co forming distinct grain-boundary precipitates. At high stresses, creep is dominated by dislocations bypassing θ' precipitates within grains via the Orowan mechanism, as evidenced by (i) very high stress exponent (n~20-25) and (ii) α-Al and θ' lattice strains (measured via in-situ neutron diffraction) evolving during creep in a manner consistent with load transfer from the plastically-deforming α-Al matrix to elastically-deforming θ' precipitates. At intermediate stresses, both alloys exhibit a n~3 regime, where α-Al and θ' lattice strains scale near-linearly with applied stress while remaining largely unaffected by strain accumulation, indicating that Orowan looping or dislocation pile-up around θ' is now inactive within the grains. Rather, dislocation motion occurs solely in θ'-precipitate-free zones (θ'-PFZ) where high dislocation densities are observed via TEM after creep deformation. Plastic flow at θ'-PFZ and/or localized pipe diffusion are expected to enable grain-boundary sliding (GBS), which is proposed as the rate-limiting mechanism in the n~3 regime. Ni/Co-rich precipitates at RR350 grain-boundaries, with negligible θ'-PFZ around them, share load (as determined via neutron diffraction) with the α-Al matrix more effectively than θ-Al 2 Cu precipitates at ACMZ grain-boundaries, with wide surrounding θ'-PFZ. So, high creep resistance in the n~3 GBS regime of RR350 is enabled by coarsening-resistant grain-boundary precipitates, forming without concomitant development of weak θ'-PFZ, which effectively share load with the grains.

36 MATERIALS SCIENCE↗

Evaluation of residual stresses in isothermal friction stir welded 304L stainless steel plates

Friction stir welding was performed on 304L SS plates in order to heal simulated cracks created by electrical discharge machining. Two different tool temperatures (825 and 725 °C) were chosen for this study. Both neutron diffraction and X-ray diffraction techniques were employed to evaluate the residual stresses along two orthogonal reference directions, longitudinal (syy) and transverse (sxx). The former technique was also used to measure residual stresses at various depths. It was found that, at 1 mm depth from the top surface inside the stir zone (SZ), the longitudinal component was tensile in nature while the transverse component was compressive. The nature and magnitude of the residual stress fields, and the position of the peak residual stresses were found to vary with the weld depth. The SZ of the 725 °C weld exhibited higher peak stress than 825 °C weld mainly due to a lack of stress relief at the lower temperature.

Friction stir welding, Steel↗

The hydrogen-containing bronzes H 0.23 WO 3 and H 0.10 ReO 3 synthesized via a polymer route

We report the synthesis of two hydrogen-containing perovskite-type bronzes H 0.23 WO 3 and H 0.10 ReO 3 utilizing an unconventional solid-state synthetic approach, involving the use of the polymer Poly(vinylidene fluoride) (CH 2 CF 2 ) n. Powder neutron diffraction at ambient temperature shows that H 0.23 WO 3 crystallizes in a tetragonal symmetry distortion of the simple perovskite structure (space group P4/nmm), with lattice parameters a = 5.2279(2) Å, and c =3.8763(1) Å. H 0.10 ReO 3 , in contrast, crystallizes in a monoclinic distortion of a simple cubic perovskite (space group P2/m), with lattice parameters a = 5.3125(1) Å, b = 5.3155(3) Å, c = 3.7045(3) Å, and γ = 90.43(1)°. Both H 0.23 WO 3 and H 0.10 ReO 3 exhibit intrinsically diamagnetic behavior, with low temperature paramagnetic upturns and no signs of bulk superconductivity down to 0.35 K.

36 MATERIALS SCIENCE↗

Micromechanical and microstructure analysis of strain-induced phenomena in ultrasonic additively-manufactured Al-6061 alloy

This work investigates the anisotropic mechanical behavior (both macro and micro) of Al6061 alloy samples manufactured using ultrasonic additive manufacturing. Samples from both sonotrode travel and vibration directions (TD and VD, respectively) were investigated in the as-built and aged (8 h at 180 °C under Argon gas) conditions. The aged VD-specimens showed appearance and propagation of Luders-like band, which did not exist in the TD-specimens, deformed at the same strain rate. X-ray diffraction, x-ray computed tomography, scanning electron microscopy, laser flash technique and in-situ loading with neutron diffraction were used to characterize the material and its hardening behavior during straining. Furthermore, aging was mainly found to lead to relaxation of stresses, induced by the build process, some decrease in yield stress, and potential secondary phase reprecipitation. Stress partitioning, revealed via in situ neutron diffraction, showed that one of grain families, (110) || tensile axis, revealed strain softening at small strain range. This texture component, (110) || tensile axis, dominated the structure of VD-specimens, and was one of key factors stimulating band appearance and propagation.

36 MATERIALS SCIENCE↗

Record High Hydrogen Storage Capacity in the Metal–Organic Framework Ni 2 ( m -dobdc) at Near-Ambient Temperatures

Hydrogen holds promise as a clean alternative automobile fuel, but its on-board storage presents significant challenges due to the low temperatures and/or high pressures required to achieve a sufficient energy density. The opportunity to significantly reduce the required pressure for high density H 2 storage persists for metal-organic frameworks due to their modular structures and large internal surface areas. The measurement of H 2 adsorption in such materials under conditions most relevant to on-board storage is crucial to understanding how these materials would perform in actual applications, although such data have to date been lacking. In the present work, the metal-organic frameworks M 2 (m-dobdc) (M = Co, Ni; m-dobdc 4- = 4,6-dioxido-1,3-benzenedicarboxylate) and the isomeric frameworks M 2 (dobdc) (M = Co, Ni; dobdc 4- = 1,4-dioxido-1,3-benzenedicarboxylate), which are known to have open metal cation sites that strongly interact with H 2 , were evaluated for their usable volumetric H 2 storage capacities over a range of near-ambient temperatures relevant to on-board storage. Based upon adsorption isotherm data, Ni 2 (m-dobdc) was found to be the top-performing physisorptive storage material with a usable volumetric capacity between 100 and 5 bar of 11.0 g/L at 25 °C and 23.0 g/L with a temperature swing between -75 and 25 °C. Additional neutron diffraction and infrared spectroscopy experiments performed with in situ dosing of D 2 or H 2 were used to probe the hydrogen storage properties of these materials under the relevant conditions. Finally, the results provide benchmark characteristics for comparison with future attempts to achieve improved adsorbents for mobile hydrogen storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-Situ Grain Resolved Stress Characterization During Damage Initiation in Cu-10%W Alloy

The evolution of stress during damage initiation and accumulation in a two-phase alloy consisting of a ductile copper (Cu) matrix with a randomly dispersed brittle tungsten (W) phase was studied using multiple non-destructive experimental probes. Neutron diffraction measurements were performed to examine the macroscopic strain partitioning between the two phases during a uniaxial tension test. The same material was then examined with high-energy x-ray diffraction microscopy (HEDM) and micro-computed tomography (μ-CT) measurements to monitor micromechanical field evolution. The neutron diffraction data indicated a redistribution of load between the Cu and W phases as deformation proceeds. Therefore, using HEDM to monitor individual grain micromechanical behavior, an increase followed by decrease in hydrostatic stress and a similar stress triaxiality behavior were found to occur in a subset of W grains. These same W grains were found to be in close proximity to voids observed via tomography at later stages of deformation. From these observations, we conclude that high stress triaxiality development in the W particles leads to decohesion of the interface between the Cu and W phases. The debonded regions eventually grew and coalesced with neighboring voids leading to material failure.

36 MATERIALS SCIENCE↗

Canted antiferromagnetism in the quasi-one-dimensional iron chalcogenide BaFe 2 Se 4

We report the synthesis and physical properties studies of quasi-one-dimensional (quais-1D) iron chalcogenide BaFe 2 Se 4 which shares the FeSe 4 tetrahedra building motif commonly seen in the iron chalcogenide superconductors. A high-quality polycrystalline sample was achieved by solid-state reaction method and characterized by x-ray diffraction, electrical resistivity, magnetic susceptibility, and neutron diffraction measurements. BaFe 2 Se 4 is a narrow gap semiconductor that magnetically orders at ~310 K. Therefore, both neutron powder diffraction results and isothermal M-H loops suggest a canted antiferromagnetic structure where Fe sublattices are antiferromagnetically ordered along the c-axis quasi-1D chain direction, resulting in a net ferromagnetic moment in the perpendicular direction along the a axis with tilted angle of 18.7° towards the b axis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Disorder and hydrogenation in graphene nanopowder revealed by complementary X-ray and neutron scattering

Functionalization of graphene's two-dimensional sheets can be used to modify the physical properties of graphene, such as changing its conductivity or inducing ferromagnetism, which is of broad interest for a myriad of applications. However, functionalized graphene can possess significant structural disorder that is often overlooked and is difficult to characterize quantitatively. Here we investigate hydrogenated graphene nanopowder (H-Gr) produced by Birch reduction of graphene oxide. By combining complementary x-ray and neutron diffraction, we show how to quantitatively characterize the H-Gr nanostructure, including the hydrogen content. Further, we show that the majority of the H-Gr consists of highly disordered molecular-scale carbon while a small portion of the sample contains few-layered graphene having an expanded interlayer spacing. Modeling the coherent diffuse scattering for both x-ray and neutron diffraction, and comparing it with the incoherent neutron scattering, the hydrogen to carbon ratio was measured and it was determined that most of the hydrogen resides within the disordered carbon rather than in the graphene. Evidence is presented for hydrogen clustering as well as for hydrogen bonded perpendicular to the plane of molecular-carbon bonds. Our quantitative approach to characterizing carbon nanopowders has broad relevance to understanding disorder and bonding of hydrogen in graphitic carbons and other nanomaterials.

36 MATERIALS SCIENCE↗

Tuning the magnetic ground state of Ce 1 - x Yb x RhIn 5 by Yb valence fluctuations

We characterize the properties of Ce 1–x Yb x RhIn 5 single crystals with 0 ≤ x ≤ 1 using measurements of powder x-ray diffraction, energy dispersive x-ray spectroscopy, electrical resistivity, magnetic susceptibility, specific heat, x-ray absorption near edge structure (XANES), and neutron diffraction. Here, the Yb valence v Yb , calculated from the magnetic susceptibility and measured using XANES, decreases from 3+ at x = 0 to ~2.1+ at x act = 0.2 , where x act is the measured Yb concentration. A transition from incommensurate to commensurate antiferromagnetism is observed in neutron diffraction measurements along Q = (0.5, 0.5, l) between 0.2 ≤ x act ≤ 0.27; this narrative is supported by specific-heat measurements in which a second robust feature appears at a temperature T I (T I < T N ) for the same concentration range. Magnetic susceptibility measurements also reveal features which provide additional evidence of magneticordering. The results of this study suggest that the evolution of the Yb valence plays a critical role in tuning the magnetic ground state of Ce 1–x Yb x RhIn 5 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Steam-Assisted Ammonolysis of MoO2 as a Synthetic Pathway to Oxygenated δ-MoN

A common route for the synthesis of molybdenum nitrides is through the temperature-programmed reaction of molybdenum oxides with NH3, or ammonolysis. In this work, the role of precursor phase, gas phase chemistry (impact of H2O), and temperature profile on the reaction outcome (700 °C) was examined, which resulted in varying amounts of MoO2, H2MoO5, and the nitride phases—cubic γ (nominally Mo2N) and hexagonal δ (nominally MoN). The phase fraction of the δ phase increased with precursor in the sequence MoO2 > MoO3 > H2MoO5. Steam in the reaction gas also favored the production of δ over γ, but with too much steam, MoO2 was obtained in the product. Synthesis conditions for obtaining nearly phase-pure δ were identified: MoO2 as the precursor, 2% H2O in the gas stream, and a moderate heating rate (3 °C/min). In situ X-ray diffraction provided insights into the reaction pathway. Extensive physico-chemical analysis of the δ phase, including synchrotron X-ray and neutron diffraction, electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and prompt gamma activation analysis, revealed its stoichiometry to be MoO0.108(8)N0.892(8)H0.012(5), indicating non-trivial oxygen incorporation. The presence of N/O ordering and an impurity phase Mo5N6 were also revealed, detectable only by neutron diffraction. Notably, a computationally predicted MoON phase (doi: 10.1103/PhysRevLett.123.236402), of interest due to its potential to display a metal-insulator transition, did not appear under any reaction condition examined.

Pandey, Shobhit↗

3⁢𝑄 magnetic order with spatially alternating spin scalar chirality in overdoped C⁢o 0.336⁢ Ta⁢S 2

C⁢o 𝑥 ⁢Ta⁢S 2 (𝑥≈1/3) exhibits a spontaneous Hall effect from spin texture in antiferromagnets, with a tetrahedral triple-Q (3Q) order and uniform spin scalar chirality. Upon Co overdoping (𝑥>1/3), it undergoes a shift in magnetic ordering vectors from 𝐐 m =(1/2, 0, 0) to (1/3, 0, 0). Interestingly, the spontaneous Hall effect disappeared in the overdoped regime, which was originally attributed to the loss of 3Q order. However, a question remains whether a new type of 3Q order can exist with alternating chirality in the overdoped regime. To address this, we investigated C⁢o 0.336⁢ Ta⁢S 2 using inelastic neutron scattering (INS), neutron diffraction, and optical dichroism, and found that INS data and spin-wave simulations support a 3Q order with alternating chirality. Moreover, neutron diffraction data show field-independent Bragg peaks, while linear dichroism detects no in-plane anisotropy, consistent with threefold rotation symmetry. Our data support the scenario of an alternating-chirality 3Q order in C⁢o 0.336 ⁢Ta⁢S 2 , canceling the spontaneous Hall effect. Furthermore, this study highlights a combined neutron-optical approach to identify complex spin textures.

Landau-Lifschitz-Gilbert equation↗

To grind or not to grind? The influence of mechanical and thermal treatments on the $\mathrm{Cu/Zn}$ disorder in $\mathrm{Cu}$ 2 $\mathrm{ZnSn}$($\mathrm{S}$ x $\mathrm{Se}$ 1-x ) 4 monograins

We report that Kesterite-type based thin film solar cell technologies are mainly based on polycrystalline absorber layers. A promising low cost alternative technology uses Cu 2 ZnSn(S x Se 1-x ) 4 (CZTSSe) monograins (single crystals of 20–100 μm size) which are fixed in a polymer matrix to form a flexible solar cell. The Cu/Zn disorder is discussed as a possible reason for band tailing causing voltage losses limiting the efficiency of CZTSSe-based devices. The experimental determination of the order parameter Q which is a quantitative measure of Cu/Zn disorder, requires a differentiation between the isoelectronic cations Cu + and Zn 2+ . An in-depth analysis of neutron diffraction data allows the determination of type and concentration of intrinsic point defects including a distinction between Cu and Zn. Neutron diffraction requires large sample volumes, thus monograins offer the unique possibility to correlate structural disorder in CZTSSe with device performance parameters. In this study we tackle the influence of grinding the monograins on stoichiometry deviations, the Cu/Zn disorder as well as intrinsic point defects and optoelectronic properties of CZTSSe monograins. Moreover, an easy methodology based on Raman scattering spectroscopy is proposed for the assessment of Cu/Zn disorder in the CZTSSe compounds.

14 SOLAR ENERGY↗

Coexisting spin resonance and long-range magnetic order of Eu in EuRbFe 4 As 4

Here, magnetic excitations and magnetic structure of EuRbFe 4 As 4 were investigated by inelastic neutron scattering (INS), neutron diffraction, and random phase approximation (RPA) calculations. Below the superconducting transition temperature T c =36.5 K, the INS spectra exhibit the neutron spin resonances at Q res =1.27(2) and 1.79(3)Å –1 . They correspond to the Q=(0.5,0.5,1) and (0.5,0.5,3) nesting wave vectors, showing three-dimensional nature of the band structure. The characteristic energy of the neutron spin resonance is E res =17.7(3) meV corresponding to 5.7(1)k B T c . Observation of the neutron spin resonance mode and our RPA calculations in conjunction with the recent optical conductivity measurements are indicative of the s± superconducting pairing symmetry in EuRbFe 4 As 4 . In addition to the neutron spin resonance mode, upon decreasing temperature below the magnetic transition temperature T N =15 K, the spin wave excitation originating in the long-range magnetic order of the Eu sublattice was observed in the low-energy inelastic channel. Single-crystal neutron diffraction measurements demonstrate that the magnetic propagation vector of the Eu sublattice is k=(0,0,0.25), representing the three-dimensional antiferromagnetic order. Linear spin wave calculations assuming the obtained magnetic structure with the intra- and interplane nearest neighbor exchange couplings of J 1 /k B =–1.31 K and J c /k B =0.08 K can reproduce quantitatively the observed spin wave excitation. Our findings show that superconductivity and long-range magnetic order of Eu coexist in EuRbFe 4 As 4 , whereas the coupling between them is rather weak.

36 MATERIALS SCIENCE↗

Pressure-Stabilized MnSb2 with Complex Incommensurate Magnetic Order

Marcasite-type compounds have been proposed as promising hosts of exotic magnetic quantum states, yet experimental realizations in stoichiometric, disorder-free systems remain limited. Here, we report the high-pressure stabilization and magnetic characterization of MnSb2, a marcasite-type compound that is thermodynamically metastable under ambient pressure. Single crystals were synthesized using a cubic multianvil press at 3.3 GPa and 490 °C for 24 h, and powder and single-crystal X-ray diffraction confirm the orthorhombic Pnnm structure. These crystals are stable at ambient pressure for a long time up to between 450 and 500 K. Heat-capacity measurements reveal phase transitions at approximately T0 ∼ 118 K and T1 ∼ 220 K. Neutron diffraction uncovers an unconventional magnetic state below T1 ∼ 220 K. Magnetic powder neutron diffraction refinements reveal possible multiple magnetic configurations that provide comparably acceptable fits to the experimental data. While most solutions are consistent with a spin-density-wave (SDW) description, helical models systematically yield inferior agreement factors. Across a broad range of models, the Mn ordered moment reaches a maximum value of approximately 2 μB and remains predominantly collinear, with minimal canting along the c-axis. At 200 K, the magnetic propagation vector is q = (0, 0.3975, 0.3783); upon cooling, the b component increases toward 0.5, reflecting a temperature-dependent evolution of the modulation. The need for modification of the magnetic model between high and low temperatures further highlights the complex and strongly temperature-dependent nature of the magnetic order in this system. These results establish MnSb2 as a pressure-stabilized marcasite magnet with a tunable, complex magnetic state and a compelling stoichiometric platform for exploring unconventional magnetic behavior, including potential altermagnetism.

Xu, Mingyu [Michigan State University , , , ,; Iow↗

Magnetization distribution in Cu 0.6 Mn 2.4 Ge 2 ferromagnet from polarized and non-polarized neutron powder diffraction aided by density-functional theory calculations

The crystal structure and magnetic properties of Cu 0.6 Mn 2.4 Ge 2 have been re-investigated by a combination of extensive magnetic measurements and neutron scattering experiments, aided by electronic structure calculations. The material is found to be a soft ferromagnet with the ordering temperature T C = 316 K. The magnetocaloric effect evaluated from field-dependent magnetization isotherms is equal to 1.2 J/(kg·K) and 2.5 J/(kg·K) under the maximum applied magnetic field of 2 T and 5 T, respectively. The compound crystallizes in the hexagonal space group P6 3 /mmc. A complex structural disorder necessitated testing of several disorder models against the results of non-polarized and polarized neutron scattering experiments and magnetization measurements. Simulations at the density-functional theory level were also performed to identify the most robust solution that properly described the data observed. The final magnetic structure model reveals non-equal magnetic moments on the Mn1 and Mn2 atoms (2.29(9) µ B and 2.7(1) µ B , respectively) and the presence of vacancies and minor Cu substitution defects in both Mn sites. The work demonstrates how the non-polarized and polarized neutron scattering methods can be combined with electronic structure calculations to establish the microscopic structure of magnetic materials with complex crystallographic disorder.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantitative texture analysis using the NOMAD time-of-flight neutron diffractometer

Strategies for efficient and reliable texture measurements have been explored using the Nanoscale Ordered Materials Diffractometer (NOMAD) at the Spallation Neutron Source located at Oak Ridge National Laboratory (ORNL). To test these strategies, the texture of an Al alloy was also investigated using another neutron diffraction instrument, a constant-wavelength neutron diffractometer (NRSF2) located at the High Flux Isotope Reactor, also at ORNL. Reasonable agreement was found across the two experimental methods, but differences in overall texture strength and the symmetry of some components were noted, depending on the data reduction and analysis method selected. Finally, on the basis of these results, potential improvements are identified which would enhance the texture measurement capability on NOMAD.

47 OTHER INSTRUMENTATION↗

Structural Competition and Reactivity of Rare-Earth Oxide Phases in Y x Pr 2– x O 3 (0.05 ≤ x ≤ 0.80)

We report, for the first time, members of the Y x Pr 2–x O 3 system with non-bixbyite or defect fluorite structures. The synthesis, structure, phase transitions, and high temperature reactivity of the trigonal A-type and monoclinic B-type structures are reported along with those of the cubic C-type phase (bixbyite). Combined powder X-ray and neutron diffraction Rietveld refinements are used to report structural details of all three reported phases. Phase transitions are investigated, showing a clear dependence on average cation size. Using neutron diffraction, phase transitions are followed in situ, revealing that all high temperature phases are quenchable. In-situ powder X-ray diffraction experiments in flowing oxygen allow insights into mechanistic details of redox processes in the reported phases. In contrast to the C-type cubic bixbyite, the trigonal A-type and monoclinic B-type structures do not allow for topotactic oxygen uptake, displaying instead a phase transition to either the bixbyite C-type capable of accommodating additional oxide anions or the direct oxidation to the cubic defect fluorite structure. The findings reported here agree with the accepted lanthanide sesquioxide phase diagrams and provide exceptional control of phases. The work is important for the prediction of structures, and the synthetic control needed for rational design of functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and properties of NdCuGa 3 single crystals

Here this manuscript reports on the structural and magnetic properties of NdCuGa 3 using powder and single crystal X-ray diffraction (XRD), zero-field single crystal neutron diffraction, magnetization, and specific heat measurements. Our XRD on a single crystal specimen of NdCuGa3 confirmed that it crystallizes in the tetragonal BaNiSi 3 -type structure. A magnetic phase transition at T N = 3.3 K is assessed using specific heat and ac magnetic susceptibility measurements. No additional anomaly below T N down to 50 mK was detected by performing specific heat measurements. Neutron single crystal diffraction data collected at T = 300 mK confirm the antiferromagnetic phase below T N = 3.3 K with the propagation vector $\vec{\tau}$ = (0.2, 0, 0). Possible magnetic structure solutions of NdCuGa 3 are discussed

36 MATERIALS SCIENCE↗