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T d to 1 T' structural phase transition in the WTe 2 Weyl semimetal

Elastic neutron scattering on a single crystal combined with powder x-ray diffraction measurements were carried out to investigate how the crystal structure evolves as a function of temperature in the Weyl semimetal WTe 2 . Here, a sharp transition from the low-temperature orthorhombic phase T d to the high-temperature monoclinic phase 1T' was observed at ambient pressure in the single crystal near ~565 K. Unlike in MoTe 2 , the solid-solid transition from T d to 1T' occurs without the cell doubling of the intermediate T d * phase with AABB (or ABBA) layer stacking. In powders, however, the thermal transition from the Td to the 1T' phase was broadened and a two-phase coexistence was observed until 700 K, well above the structural transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-Energy X-ray Diffraction Microscopy for Nuclear Forensics FY2022 Project Report

Morphological information on nuclear material has been identified using visible light and scanning electron microscopy. These identify qualitative differences in particle morphology. Three-dimensional imaging of materials through alternating scanning electron microscopy imaging and focused ion beam milling has also been used. Unfortunately, these techniques are time- and labor-intensive, with significant sample preparation required and lengthy analysis times. Further, the resulting 3D images are qualitative, require manual identification, and do not capture statistically-representative populations. High energy X-ray 3D imaging using a direct-beam or diffracted-beam (High-Energy Diffraction Microscopy) have been developed at the Advanced Photon Source and can produce quantitative information on grains (phase, location, etc.) and pores (size distribution, sphericity) in a material. These techniques require only minutes to characterize a sample volume and are non-destructive, thus suitable for a wide range of existing samples and for confirmatory analyses to be carried out using conventional microscopy techniques. In this first year of the project, all uranium oxide samples were synthesized and characterized using conventional analyses by the analytical chemistry laboratory. Conventional analysis methods included powder x-ray diffraction, scanning electron microscopy, impurity analysis via inductively coupled plasma mass spectrometry, and infrared spectroscopy. Impurity analysis shows a drop in boron content from UO 3 to the lowest U 3 O 8 calcination temperature, but otherwise no appreciable difference in any sample. Analysis of diffraction data shows a flip of peaks from UO 3 dominated for the 600 °C calcined sample to U 3 O 8 dominated at 700 °C and 800 °C. Analysis of scanning electron microscopy images shows that with increased calcination temperature the size distribution of particles seems to increase and broaden. Both of these last findings are in line with previously published data, though this work used significantly fewer particles to simply show similar trends instead of getting truly quantitative particle analysis. Infrared analysis similarly shows ingrowth of U 3 O 8 as calcination temperature is increased, along with depression of peaks associated with UO 3 and water. Samples were prepared for analysis at the Advanced Photon Source at beamline 1-ID. It is anticipated that analysis will occur in November of 2022. AI/ML techniques to de-noise data coming out of 1-ID during the analyses was also developed during this time using previously gathered data. Preliminary results using a self-supervision technique called Noise2Selfshow good de-noising of data. Once the uranium oxide samples are analyzed, real data will be used to test the de-noising and other AI/ML techniques that may be developed in the second year of the project.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The crystal structures of Fe-bearing MgCO 3 sp 2 - and sp 3 -carbonates at 98 GPa from single-crystal X-ray diffraction using synchrotron radiation

The crystal structure of MgCO 3 -II has long been discussed in the literature where DFT-based model calculations predict a pressure-induced transition of the carbon atom from the sp 2 to the sp 3 type of bonding. We have now determined the crystal structure of iron-bearing MgCO 3 -II based on single-crystal X-ray diffraction measurements using synchrotron radiation. We laser-heated a synthetic (Mg 0.85 Fe 0.15 )CO 3 single crystal at 2500 K and 98 GPa and observed the formation of a monoclinic phase with composition (Mg 2.53 Fe 0.47 )C 3 O 9 in the space group C 2/ m that contains tetrahedrally coordinated carbon, where CO 4 4- tetrahedra are linked by corner-sharing oxygen atoms to form three-membered C 3 O 9 6- ring anions. The crystal structure of (Mg 0.85 Fe 0.15 )CO 3 (magnesium iron carbonate) at 98 GPa and 300 K is reported here as well. In comparison with previous structure-prediction calculations and powder X-ray diffraction data, our structural data provide reliable information from experiments regarding atomic positions, bond lengths, and bond angles.

Chariton, Stella (ORCID:0000000155220498)↗

Radiation-Induced Long-Lived Transients and Metal Particle Formation in Solid KCl–MgCl 2 Mixtures

Here, the electron paramagnetic resonance and diffuse reflectance-optical absorption spectra of room-temperature γ-irradiated KCl–MgCl 2 binary solid salt mixtures (98:2 mol % and 2:98 mol %) and the eutectic (68:32 mol %) are reported. Additionally, powder X-ray diffraction of the pristine salts and thermal annealing studies of the irradiated salts were performed to evaluate the radiolysis product stability, annihilation, and association in metallic particles. The main long-lived transient species detected in 98:2 mol % KCl–MgCl 2 salts were perturbed F-centers, that is, trapped electrons (e t – ) in the vicinity of Mg ions (λ max at 561 nm), and the radiolytic reduction of Mg 2+ to Mg + and Mg 0 . Thermal annealing promoted the diffusion of defects to yield polycations (Mg n + ). On the other hand, irradiation of 2:98 mol % KCl/MgCl 2 salts showed the formation of cationic and neutral Mg dimers (Mg 2 + and Mg 2 ) and trimers as well as centers with a rhombic powder pattern apparently consisting of an electron shared between three Mg 2+ nuclei associated with an anion vacancy (ν a + –Mg 3 5+ ). Trapped electrons (e t – ) (F-centers) were not observed in the irradiated eutectic mixture; instead, Mg 2 , Mg 0 , and Cl 3 – were observed. It was observed that the higher temperature for thermal ionization of radiation-reduced Mg species decreased the extent of electron recombination reactions and the disproportionation of Cl 3 – compared to the pure KCl but enhanced the aggregation of Mg into larger metallic microstructures (metallic particles).

36 MATERIALS SCIENCE↗

Solvent-Driven Transformation of Zn/Cd 2+ -Deoxycholate Assemblies

Deoxycholic acid (DOC) is a unique, biologically derived surfactant with facial amphiphilicity that has been exploited, albeit minimally, in supramolecular assembly of materials. Here, we present the synthesis and structural characterization of three hybrid metal (Zn 2+ and Cd 2+ )-DOC compounds. Analysis by single-crystal Xray diffraction reveals the many interactions that are possible between these facial surfactants and the influence of solvent molecules that drive the assembly of materials. These structures are the first metal- DOC complexes besides those obtained from alkali and alkaline earth metals. We isolated polymeric chains of both Cd and Zn (Zn poly -DOC and Cd poly -DOC) from water. Major interactions between DOC molecules in these phases are hydrophobic in nature. Cd poly -DOC exhibits unique P1 symmetry, with complete interdigitation of the amphiphiles between neighboring polymeric chains. Zn 4 -DOC, obtained from methanol dissolution of Zn poly -DOC, features the OZn 4 tetrahedron, widely known in basic zinc acetate and MOF-5 (metal organic framework). We document a solvent-driven, roomtemperature transition between Zn poly -DOC and Zn 4 -DOC (in both directions) by scanning and transmission electron microscopies in addition to small-angle X-ray scattering, powder X-ray diffraction, and infrared spectroscopy. These studies show the methanoldriven transition of Zn poly -DOC to Zn 4 -DOC occurs via an intermediate with no long-range order of the Zn 4 clusters, indicating the strongest interactions driving assembly are intramolecular. On the contrary, water-driven solid-to-solid transformation from Zn 4 -DOC to Zn poly -DOC exhibits crystal-to-crystal transformation. Zn poly -DOC is robust, easy to synthesize, and comprised of biologically benign components, so we demonstrate dye absorption as a proxy for water treatment applications. It favors absorption of positively charged dyes. These studies advance molecular level knowledge of the supramolecular assembly of facial surfactants that can be exploited in the design of organic-inorganic hybrid materials. This research also highlights the potential of solvent for tuning supramolecular assembly processes, leading to new hybrid materials featuring facial surfactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fatigue performance of laser powder bed fusion hydride-dehydride Ti-6Al-4V powder

We report hydride-dehydride (HDH) Ti-6Al-4V alloy with particle size distribution of 50–120 µm is laser powder bed fusion (L-PBF) processed using optimum processing parameters and a near-fully dense structure with a density of 99.9 % is achieved. Microstructural observations and phase analyses indicate formation of columnar β grains with acicular α/α' phases in as-built condition. The roughness of the as-fabricated samples is significant with an average roughness of R a = 15.71 ± 3.96 µm and a root mean square roughness of R rms = 108.4 ± 24.9 µm, however, both values are reduced to R a = 0.19 ± 0.04 µm and R rms = 4.9 ± 0.6 µm after mechanical grinding. Mechanical tests are carried out on as-fabricated specimens followed by stress relief treatment. All samples are tested to failure in fatigue, under fully-reversed tension-compression conditions of R = –1. The as-built samples failed from the surface with crack initiation mainly at micro-notches, whereas after mechanically grinding, crack initiation changed to subsurface defects such as pores. Minimizing surface roughness by mechanically grinding eliminates surface micro-notches which improves fatigue strength in the high cycle fatigue region. Fatigue notch factor calculations showed that the effect of surface roughness was significantly lower when HDH powder is used compared to standard spherical powder. X-ray diffraction analysis revealed an in-plane compressive stress, micro-strain and grain refinement on the surface of the mechanically ground samples. Fractography observations (macroscale) revealed a fully brittle fracture in the first stage of crack growth with a transition to a dominantly ductile fracture in the third stage of crack growth. On the other hand, at the micro scale, even the brittle fracture regions showed evidence of ductile fracture within the α' martensite laths.

36 MATERIALS SCIENCE↗

Crystal structure and thermal expansion of Ta 2 ⁢O 5 from neutron diffraction

Tantalum pentoxide (Ta 2 ⁢O 5 ) is a component of technologies ranging from photographic lenses to medical implants. Despite more than six decades of interest, however, there is no consensus on the crystal structure of Ta 2 ⁢O 5 . Here, we report the results of neutron diffraction experiments on Ta 2⁢ O 5 powders at temperatures up to 1000⁢°⁢C. Because neutron diffraction is sensitive to the positions of O atoms in the presence of heavy elements, our results provide strong evidence that the orthorhombic L SR structure can account for experimental observations better than any other proposal in the literature. Here, we also determine the anisotropic crystallographic thermal expansion parameters of Ta 2 ⁢O 5 , which are important for modeling the performance of Ta 2⁢ O 5 -bearing technologies.

36 MATERIALS SCIENCE↗

Syntheses and crystal structures of four new d 0 transition metal tellurites

Four new d 0 transition metal tellurites, namely InVTeO 6 (1), β-InVTe 2 O 8 (2), FeVTe 2 O 8 (3), and Fe 2 MoTe 2 O 10 (4), were synthesized under hydrothermal conditions, and their crystal structures were determined using single-crystal X-ray diffraction. Compound 1 crystallizes in the noncentrosymmetric space group P2 1 2 1 2 1 (No. 19), with unit cell parameters of a = 5.0759(2) Å, b = 8.5030(3) Å, c = 11.6376(5) Å, V = 502.28(3) Å 3 , and Z = 4, while the other three compounds crystallize in centrosymmetric structures, with space group Cmca and unit cell parameters of a = 7.0633(7) Å, b = 8.962(1) Å, c = 20.162(2) Å, V = 1276.3(2) Å 3 , and Z = 8 for compound 2, space group P2 1 /n and unit cell parameters of a = 7.8901(2) Å, b = 4.9617(1) Å, c = 16.4290(3) Å, β = 93.6198(8)°, V = 641.88(2) Å 3 , and Z = 4 for compound 3, and space group Pnma and unit cell parameters of a = 8.7878(2) Å, b = 6.1327(2) Å, c = 15.2423(4) Å, V = 821.45(4) Å 3 , and Z = 4 for compound 4. Compound 3 adopts a two-dimensional (2D) sheet structure composed of FeO 6 octahedra, VO 4 tetrahedra, and TeO 4 polyhedra. The other three compounds exhibit three-dimensional (3D) framework structures: Compound 1 is built from InO 6 octahedra, VO 4 tetrahedra, TeO 4 polyhedra; Compound 2 consists of InO 6 octahedra, VO 5 square pyramids, and TeO 3 polyhedra; and Compound 4 is composed of FeO 6 octahedra, MoO 6 octahedra, and TeO 3 polyhedra. The band structures, density of states, and electron localization functions of all four compounds were calculated. The vibrational spectra were examined for compounds 1, 2, and 4. Furthermore, powder X-ray diffraction, element analysis, and thermogravimetric analysis were conducted for compound 4.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantification of solution annealing effects on microstructure and property in a laser powder bed fusion 316H stainless steel

Solution annealing (SA) is an effective way to mitigate microstructural heterogeneity and to optimize mechanical performance of alloys manufactured by laser powder bed fusion (LPBF). In this study, a comprehensive and quantitative understanding of the recovery and recrystallization processes in the SA temperature range of LPBF 316H stainless steel is provided using results from analytical electron microscopy and in-situ high-energy synchrotron x-ray scattering. The profound effect of dislocation structures and secondary phase particles on mechanical performance, particularly under tension and creep conditions, is rationalized using deformation models that incorporate microstructural inputs. This study, for the first time, quantifies the broad effect of nano oxide inclusions on dislocation recovery kinetics, on grain growth and recrystallization kinetics, and on tension strength and creep resistance. The fundamental differences between the LPBF and the conventional wrought materials are revealed. The findings address critical questions in post-build processing of AM materials and pave the way for their rapid qualification for high temperature applications.

In-situ X-ray diffraction↗

An assessment of spall failure modes in laser powder bed fusion fabricated stainless steel 316L with low-volume intentional porosity

Here, this paper reports on spall failure and damage modes in Laser Powder Bed Fusion fabricated Stainless Steel 316L (SS316L) with intentional levels of low-volume (1–5 vol. %) porosity and pore sizes of 200, 350, and 500 μm. The fabricated specimens were subjected to uniaxial-strain plate-impact loading at ~4.5 GPa, to initiate incipient spall failure. Analysis of velocimetry profiles measured using multi-probe photon-Doppler velocimetry coupled with post-mortem analysis of soft-recovered samples reveals local suppression of spall failure (termed as spall-dominated) as a function of porosity, as the failure mechanism transitions from spall-centered tensile stress dominated to a pore-centered microstructure-dominated damage mode involving void/crack nucleation and growth at pre-existing pores. The critical porosity level where the suppression of spall failure is first observed, as well as the spall location, is dependent on both the volume fraction and the size of the initially fabricated pores. In samples of 500 μm pore size, the suppression of spall failure is observed with as little as 1 vol. % porosity, while samples with smaller pores (200 μm) still experience spall-centered tensile stress dominated failure with higher levels (5 vol. %) of porosity. In the case of pore-centered microstructure-dominated failure, spall damage can occur but the spall plane is shifted toward the rear free surface, or more generally in areas further away from the region with pores. Highly heterogeneous deformation twinning, shear banding, grain rotation, and cracking are observed in the vicinity of pre-existing pores and expected spall failure sites.

36 MATERIALS SCIENCE↗

From ammonium Hexahalorhenates(IV) to nanocrystalline rhenium metal: A combined thermal, diffraction and microscopic analysis

Rhenium metal powder is a material of industrial importance. Several industrial and laboratory methods have been developed for the preparation of ultrafine Re metal powder and nanoparticles. The present study provides a better understanding of the characteristic and formation of Re metal powder from the decomposition of (NH4)2ReX6 salt (X = F, Cl, Br, I) at high temperature in inert atmosphere. Such analysis resulted in the formation of nanocrystalline Re metal as characterized by powder XRD. Williamson-Hall, Scherrer, and Williamson-Smallman methods were employed to study the effect of crystallize size, lattice strain, and dislocation density as analyzed from powder XRD peak broadening. Here, the morphology and composition of the metal were analyzed using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy.

36 MATERIALS SCIENCE↗

AFRL Additive Manufacturing Modeling Series: Challenge 1, Characterization of Residual Strain Distribution in Additively-Manufactured Metal Parts Using Energy-Dispersive Diffraction

A machine component fabricated by additive manufacturing (AM) of metal powders often possesses steep residual stress gradients with significant magnitudes due to large temperature gradients that transpire within a localized area during fabrication. These processing-induced residual stresses can cause distortion of the part, and if they are of significant magnitude, they could induce cracking of the component, degrade printability, and/or diminish subsequent mechanical performance. The ability to predict these residual stresses imparted by AM is an important step in permeating AM technology for advanced manufacturing. Calibration and validation of AM process models used for prediction are, therefore, a critical step in understanding the origin and mitigating the challenges associated with residual stresses inherent to the AM process. In the present work, the residual strain distributions in components with simple geometries fabricated by a laser powder bed fusion (LBPF) process were characterized non-destructively using energy-dispersive X-ray diffraction in support of the US Air Force Research Laboratory Additive Manufacturing Modeling Challenge Series Groeber et al. (JOM 70:441-448, 2018). The measurement setup and approach are described in detail so that the data can be used as a benchmark to calibrate and validate models for the prediction of macro-scale residual stresses due to the LPBF process.

36 MATERIALS SCIENCE↗

Giant and Reversible Barocaloric Effect in Trinuclear Spin–Crossover Complex Fe 3 (bntrz) 6 (tcnset) 6

A giant barocaloric effect (BCE) in a molecular material Fe 3 (bntrz) 6 (tcnset) 6 (FBT) is reported, where bntrz = 4-(benzyl)-1,2,4-triazole and tcnset = 1,1,3,3-tetracyano-2-thioethylepropenide. The crystal structure of FBT contains a trinuclear transition metal complex that undergoes an abrupt spin-state switching between the state in which all three FeII centers are in the high-spin (S = 2) electronic configuration and the state in which all of them are in the low-spin (S = 0) configuration. Despite the strongly cooperative nature of the spin transition, it proceeds with a negligible hysteresis and a large volumetric change, suggesting that FBT should be a good candidate for producing a large BCE. Powder X-ray diffraction and calorimetry reveal that the material is highly susceptible to applied pressure, as the transition temperature spans the range from 318 at ambient pressure to 383 K at 2.6 kbar. Despite the large shift in the spin-transition temperature, its nonhysteretic character is maintained under applied pressure. Such behavior leads to a remarkably large and reversible BCE, characterized by an isothermal entropy change of 120 J kg –1 K –1 and an adiabatic temperature change of 35 K, which are among the highest reversible values reported for any caloric material thus far.

36 MATERIALS SCIENCE↗

Enhancing Chiroptoelectronic Activity in Chiral 2D Perovskites via Chiral–Achiral Cation Mixing

Rational design of chiral two-dimensional hybrid organic–inorganic perovskites is crucial to achieve chiroptoelecronic, spintronic, and ferroelectric applications. Here, in this study, an efficient way to manipulate the chiroptoelectronic activity of 2D lead iodide perovskites is reported by forming mixed chiral (R- or S-methylbenzylammonium (R-MBA + or S-MBA + )) and achiral (n-butylammonium (nBA + )) cations in the organic layer. The strongest and flipped circular dichroism signals are observed in (R/S-MBA 0.5 nBA 0.5 ) 2 PbI 4 films compared to (R/S-MBA) 2 PbI 4 . Moreover, the (R/S-MBA 0.5 nBA 0.5 ) 2 PbI 4 films exhibit pseudo-symmetric, unchanged circularly polarized photoluminescence peak as temperature increases. First-principles calculations reveal that mixed chiral–achiral cations enhance the asymmetric hydrogen-bonding interaction between the organic and inorganic layers, causing more structural distortion, thus, larger spin-polarized band-splitting than pure chiral cations. Temperature-dependent powder X-ray diffraction and pair distribution function structure studies show the compressed intralayer lattice with enlarged interlayer spacing and increased local ordering. Overall, this work demonstrates a new method to tune chiral and chiroptoelectronic properties and reveals their atomic scale structural origins.

2D perovskites↗

Pressure‐Induced Structural and Optoelectronic Modulations in 2D Dion‐Jacobson Hybrid Lead Iodide Perovskites With a Rigid Spacer

2D hybrid organic-inorganic perovskites (HOIPs) are known for their superior chemical and thermal stability over 3D variants, positioning them as promising materials for advanced optoelectronic applications. Applying external high pressure is an effective strategy to modify their structures and tune their optoelectronic properties. This study examines the high-pressure behavior of a Dion-Jacobson type 2D HOIP, DPDAPbI 4 , which incorporates the rigid organic spacer N,N-dimethylphenylene-p-diammonium (DPDA). Utilizing photoluminescence, UV–visible absorption, vibrational spectroscopy, and in situ synchrotron powder X-ray diffraction, an isostructural phase transition is identified near 1.5 GPa, marked by a notable shift in photoluminescence intensity linked to free exciton emission. Synchrotron X-ray diffraction reveals significant anisotropic compression along the c-axis, while structural analysis indicates the rare phenomenon of reduced lead-iodide octahedral distortion below 2 GPa, contrasting with the increased octahedral distortion reported in most previous studies on lead-based 2D HOIPs. Density functional theory calculations elucidate the structural origins and mechanisms driving the pressure-induced phase transition and optoelectronic tuning. These findings underscore the critical interplay between rigid organic spacers and inorganic octahedra in modulating high-pressure optoelectronic properties, offering valuable insights for designing future 2D HOIPs with tailored functionalities.

14 SOLAR ENERGY↗

Overcoming Fundamental Limitations in Adsorbent Design: Alkene Adsorption by Non-porous Copper(I) Complexes

Purifying alkenes from alkanes requires cryogenic distillation. This consumes energy equivalent to countries of ca. 5 million people. Replacing distillation with adsorption processes would significantly increase energy efficiency. Trade-offs between kinetics, selectivity, capacity, and heat of adsorption have prevented production of an optimal adsorbent. Here, we report adsorbents that overcome these trade-offs. [Cu-Br] 3 and [Cu-H] 3 are air-stable trinuclear complexes that undergo reversible solid-state inter-molecular rearrangements to produce dinuclear [Cu-Br∙(alkene)] 2 and [Cu-H∙(alkene)] 2 . The reversible solid-state rearrangement, confirmed in situ using powder X-ray diffraction, allows adsorbent design trade-offs to be overcome, coupling low heat of adsorption (-10 to -17 kJ mol -1 alkene ), high alkene:alkane selectivity (47; 29), and uptake capacity (>2.5 molalkene mol -1 Cu3 ). Most remarkably, [Cu-H] 3 displays fast uptake and regenerates capacity within 10 minutes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deinterpenetration of IRMOF‐9.

One of the iconic characteristics of metal-organic frameworks (MOFs) is the possesssion of guest-accessible pores. Increasing pore size has a direct and often beneficial impact on a MOF's adsorption and separation properties. However, as pore size increases, the resulting void spaces are often filled by interpenetrated frameworks, where one or more networks crystallize within the pore system of another identical network, reducing the MOF's free volume and pore size. Furthermore, due to the thermodynamic favorability of interpenetration during solvothermal synthesis, techniques to synthetically differentiate interpenetrated from non-interpenetrated MOFs are paramount. This study reports the synthesis of deinterpenetrated IRMOF-9 via halide mediated deinterpenetrative conversion of Zn 4 O-derived IRMOF-9. IRMOF-9, when treated with ethylammonium bromide, is quasi-selectively etched, revealing the non-interpenetrated analogue, IRMOF-10 (deinterpenetrated IRMOF-9), which can be isolated prior to complete dissolution by the bromide solution. Dye adsorption, surface area and pore size distribution analysis, and powder X-ray diffraction are consistent with successful deinterpenetration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗