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At least 19 records

High Pressure X-ray Diffraction and Equation of State of Hydrazine

Synchrotron X-ray diffraction has been used to investigate the structure and equation of state (EOS) of hydrazine (N 2 H 4 ) up to 54.3 GPa at 298 K. The diffraction patterns could be fit to a monoclinic unit-cell structure and put strong constraints on previously reported phase transitions documented by vibrational spectroscopy over this pressure range. Pressure–volume ( P–V ) data were fit using a Vinet EOS, yielding parameters: V 0 = 45.2 Å 3 /molecule (fixed), K 0 = 11.8(7) GPa, and K 0 ′ = 6.5(2). Previously measured high-pressure vibrational frequency shifts were used to estimate the vibrational free energy and model P–V–T isotherms from 0 to 1200 K. The results of the P–V–T isotherms are compared to existing shock Hugoniot data on hydrazine and 298 K isotherms for assemblages of possible decomposition products. This comparison suggests dissociation at high density under shock loading. Good correspondence was found between the static lattice EOS as calculated by the model and the previously reported EOS as calculated by density functional theory. Finally, these results resolve existing uncertainties about the EOS and crystal symmetry of hydrazine at high pressure and provide valuable baseline information on this important energetic material.

diffraction

High temperature stabilization of ultrafine grain tungsten alloys through synergistic compositional complexities

Thermally-stabilized fine-grained microstructures in tungsten provide a pathway to harnessing enhanced properties such as a reduced ductile-to-brittle transition temperature and improved strength while mitigating the adverse effects of grain growth and recrystallization. Here, in this study, we employ a material design strategy that relies on grain boundary segregation in the nanocrystalline state driven by alloy thermodynamics balanced with impurity scavenging through in situ formation of kinetically-stabilizing metal carbides. A W-Ti-Cr alloy is designed through lattice Monte Carlo methods and subsequently synthesized in a single-phase nanocrystalline state, which upon annealing, evolves into an ultrafine grained microstructure containing chromium grain boundary segregation collectively with a dispersed TiX (X=C,O) phase through the reaction of titanium with carbon and oxygen impurities. In situ synchrotron X-ray diffraction experiments demonstrate that increased Ti promotes stabilization across a larger temperature range but with diminishing returns above 10 at.% Ti. Long-term stability was confirmed through the retention of the ultrafine grained microstructure for a total of 8 days (192 h) at 1300 °C without grain/carbide growth and/or recrystallization. Our results demonstrate that, through strategic tailoring of composition and microstructure, one can harness the benefits of both thermodynamic and kinetic stabilization mechanisms, opening pathways for future alloy formulations that expand the window of stability.

36 MATERIALS SCIENCE

Comparative neutron-irradiation effects on thermal conductivity degradation and dimensional stability of TiC, TiB 2 , and ZrB 2 at 200–1000 °C

Ultra-high-temperature ceramics (UHTCs), including TiC, Ti 11 B₂, and Zr 11 B₂, show great potential for plasma-facing components due to their excellent high-temperature properties prior to irradiation. However, their response to neutron irradiation remains insufficiently understood, limiting robust assessment of their viability for fusion energy applications. Here, this study examines the thermal conductivity, dimensional stability and microstructure of TiC, TiB₂, and ZrB₂ following neutron irradiation at temperatures of 200–1000 °C and fast neutron fluences of 2.0 × 10 25 to 1.1 × 10 26 n/m 2 (E > 0.1 MeV). Lattice swelling measured by synchrotron X-ray diffraction in all three UHTCs was maximized at 200 °C and decreased with increasing irradiation temperature, with no evidence of amorphization observed at 200 °C. Above 600 °C, significant macroscopic volume swelling was observed in irradiated Ti 11 B₂ and Zr 11 B₂, but not in TiC, likely due to cavity formation in the diborides. The post-irradiation thermal conductivity, measured at the irradiation temperature, ranged from 28 to 45 W/m·K, representing a 34–45% reduction relative to the unirradiated material. Notably, neutron-irradiated UHTCs exhibit recoverable thermal conductivity at elevated temperatures, comparable to ferritic–martensitic steels and potentially superior to W when transmutation effects are considered, highlighting promise for shielding or armor plasma-facing components. At 600 °C, both thermal conductivity degradation and lattice swelling saturated at doses exceeding 2–4 dpa.

fusion materials

From Cation Order to Disorder: Unlocking Ion Transport Pathways in Li–Zn–Zr–Cl Halospinels

Lithium metal chloride halospinels of the general formula Li 2 MCl 4 are a promising class of earth-abundant ion conductors for all-solid-state batteries. However, poor roomtemperature ionic conductivity has historically limited their use in practical applications. Here, we substitute Zr 4+ into Li 2 ZnCl 4 along the series Li 2−2x/3 Zn 1−x Zr 2x/3 Cl 4 (x = 0, 0.1, 0.3, 0.4, 0.6, 0.9, and 1.0) to understand how cation disorder and vacancy tuning impact ion transport in “normal” halospinels. Aliovalent Zr 4+ substitution increases ionic conductivity by nearly 5 orders of magnitude, from 1.320(3) × 10 −9 S cm −1 in Li 2 ZnCl 4 to 6.74(1)× 10 −5 S cm −1 for x = 0.6. Average and local structure characterization through synchrotron X-ray diffraction (SXRD) and neutron pair distribution function (nPDF) analysis reveal that Zr 4+ redistributes the Zn 2+ and Li + sublattices into previously unoccupied interstitial sites, which form new low-energy hopping pathways that facilitate ion transport. We rationalize the dramatic rearrangement of the cation local structure by considering the coordination preferences of the cations and the potential electrostatic penalties incurred by the higher-valent Zr 4+ cations. This work delivers an atomistic understanding of substitution-induced cation disorder and ion transport properties in a new family of earth-abundant halospinels.

Cardoza, Abby M. [Colorado School of Mines, Golden

Amorphous ZrCl 4 -Based Superionic Conductor as a Cost-Effective Solid Electrolyte for Batteries

Developing highly conductive and cost-effective solid electrolytes is essential for the commercialization of all-solid-state batteries (ASSBs). Zr-based halide electrolytes hold great promise due to their low estimated cost and high oxidation stability. However, the ionic conductivities of most of them are not high enough to enable moderate- and high-rate cycling of ASSBs. Here, fast ion transport is achieved in a group of cost-effective ZrCl 4 -based electrolytes via a design strategy to create highly disordered amorphous structures. Amorphous Li 0.8 ZrCl 4 (SO 4 ) 0.4 , with a low estimated cost of $21 kg –1 , achieves an ionic conductivity of 1.86 mS cm –1 at 25 °C. It also shows a high oxidation limit of 4.5 V vs Li/Li + and good compatibility with high-voltage cathodes, as demonstrated by the stable cycling of ASSBs (73.7% capacity retention after 1000 cycles at 1 C). Synchrotron X-ray diffraction, pair distribution function analysis, and electrochemical impedance spectroscopy reveal that the outstanding conductivity of these amorphous electrolytes is closely related to their short-range and medium-range ordering, revealing new insights for designing high-performance, cost-effective solid electrolytes.

Zhang, Guangxing [Georgia Institute of Technology,

Coupled Interfacial Kinetics and Transport Resistances Govern High-Current Behavior in Bipolar Membranes

Bipolar membranes (BPMs) enable electrochemical systems that operate across large pH gradients; however, high-current operation is often limited by voltage losses whose origins remain difficult to resolve in membrane−electrode assemblies. Here, we combine electrochemical impedance spectroscopy with distribution of relaxation times (EIS–DRT) analysis and operando synchrotron X-ray diffraction to examine interfacial polarization, membrane hydration, and transport in commercial and synthesized BPMs. EIS–DRT isolates the BPM-associated interfacial contribution and shows that the commercial BPM exhibits larger water-dissociation-associated overpotentials than the synthesized BPM. Operando hydration mapping shows that both membranes retain water at the bipolar junction during high-current operation, while anode-adjacent hydration gradients are more pronounced in the commercial membrane. These results indicate that high-current voltage losses are not governed by junction water starvation alone but by coupled interfacial polarization and transport resistances.

36 MATERIALS SCIENCE

Laser-heated diamond anvil cell synthesis and recovery of metastable MnSb 2 and YbZn 2 for post-synthesis transport studies

The creation and exploration of new materials under extreme pressure–temperature conditions has become increasingly reliant on laser-heated diamond anvil cell (LHDAC) techniques, which provide direct access to previously unexplored regions of multinary phase diagrams. Whereas numerous high-pressure phases have been identified in situ, systematic recovery and post-synthesis physical property characterization of these materials remain significant challenges. In this work, we describe the setup and implementation of an LHDAC-based synthesis and recovery workflow and demonstrate its application to metastable MnSb 2 and YbZn 2 phases. Synchrotron x-ray diffraction and spatial mapping confirm dominant formation of the targeted phases, whereas laboratory-based refinement quantifies phase fractions despite intrinsic microstrain and minor secondary phases. High-pressure transport measurements on recovered samples reveal pressure-tunable electronic instabilities in both systems. In MnSb 2 , pressure suppresses two high-temperature magnetic ordering anomalies, observed in transport, by ∼5 GPa and, for higher pressures, induces a new low-temperature feature that increases with further pressure increase. In hexagonal high-pressure YbZn 2 , an electronic reconstruction emerges at ∼11 GPa, characterized by semiconducting-like behavior from ∼30 to 300 K and a broad low-temperature coherence crossover near 30 K. Our results establish LHDAC synthesis not only as a structural discovery tool but also as an experimental platform for investigating correlated quantum states stabilized far from equilibrium thermodynamic conditions.

Huyan, S. [Iowa State University, Ames, IA (United

Taking three-dimensional x-ray diffraction (3DXRD) from the synchrotron to the laboratory scale

Three-dimensional x-ray diffraction (3DXRD), a rotating x-ray diffraction technique, is a powerful tool for studying the micromechanical behavior of polycrystalline materials, capable of measuring the volume, position, orientation, and strain of thousands of grains simultaneously. However, its application has been historically limited to synchrotron facilities. Here, we present the first demonstration of laboratory-scale 3DXRD (Lab-3DXRD) using a liquid-metal-jet source. Lab-3DXRD achieves accuracy comparable to synchrotron-based 3DXRD, as validated against laboratory diffraction contrast tomography (LabDCT) and synchrotron-3DXRD. Over 96% of the grains detected with Lab-3DXRD are cross-validated, particularly for coarse grains (> ~60 μm), while the results suggest that finer grains should be accessible by taking advantage of high-efficiency detectors. We further demonstrate that its sensitivity to finer grains is enhanced by incorporating pre-characterization into the analysis. This study establishes Lab-3DXRD as a practical alternative to synchrotron techniques, making 3DXRD accessible to a wider range of academic and industrial researchers.

characterization and analytical techniques

Ca Metal Batteries and Sn Anode Alloying: Resolving Misconceptions in Ca–Sn Alloy Formation

Ca metal anode suffers from surface passivation and struggles to effectively plate and strip in conventional Ca electrolytes, making the development of alloy anode for calcium metal battery essential. This work systematically and carefully evaluates the electrochemical formation and feasibility of the Sn anode and its possibility of alloying with Ca using a combination of cyclic voltammetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD), and synchrotron transmission X-ray microscopy (TXM). Electrochemical measurements and SEM/EDS analyses indicate apparent Ca alloy formation. However, detailed XRD and TXM characterization reveal substantial lithium-ion involvement when lithium metal is employed as the reference electrode, even in electrolytes with high Ca salt concentrations. These findings highlight a significant risk of misinterpretation: Although limited Ca–Sn alloying may occur, the faster kinetics of Li + can dominate the alloying process, leading to a Li-driven reactions at the Sn anode. In contrast, cells constructed with Ca metal as both reference and counter electrodes exhibit distinct redox features only during the initial cycles, followed by rapid cell failure. The high oxidation currents induce severe Ca passivation, occurring nearly concurrently with Sn dealloying. Overall, this study provides critical insight into the practical limitations and common experimental artifacts associated with Ca metal battery systems and underscores the necessity for rigorous cell design and cautious interpretation when evaluating alloy chemistry in multivalent Ca-based batteries.

36 MATERIALS SCIENCE

New perspectives on materials and device dynamics using time-resolved full-field diffraction X-ray imaging

Understanding how materials evolve during synthesis, processing, or device operation requires experimental access to structural dynamics across wide ranges of length and time scales, often in bulk samples or even within packaged devices. Time-resolved full-field diffraction X-ray microscopy has recently emerged as a powerful way to meet this need by combining the penetration and structural sensitivity of X-ray diffraction with objective-lens-based magnification, sensitive high-resolution X-ray imaging detectors, and pump-probe and real-time imaging strategies. Advances in full-field X-ray diffraction microscopy, often termed dark-field X-ray microscopy (DFXM), enable simultaneous imaging of extended fields of view while retaining crystallographic selectivity. Time-resolved DFXM promises to enable advances in materials processing and dynamics, electrochemical and photochemical processes, and the design of electronic devices. This Perspective summarizes the key instrumental concepts that define the performance of these methods, including the choice of imaging optics, detector considerations, and the impact of source time structure at synchrotron light sources and X-ray free-electron lasers (XFELs). We discuss the simultaneous use of complementary imaging modes that are increasingly used in practice. The early demonstrations of the potential of time-resolved DFXM include real-time defect and grain-boundary dynamics during metal annealing, stroboscopic imaging of functional devices with high strain sensitivity, and ultrafast pump-probe implementations at XFELs that directly visualize acoustic-wave propagation and energy dissipation in bulk crystals.

Dark-field X-ray microscopy

Synchrotron resolved microscale mineralogy and elemental composition of individual plinthic and manganiferous nodules from agricultural soils

Iron and manganese oxides are strong sorbents and elemental scavengers in the environment that can form macroscopic nodules in soils. Despite their importance in the geochemical cycling of nutrients and contaminants, nodules are rarely characterized. When analyzed, they are often combined into bulk samples, obscuring individual characteristics. This study investigates the composition and mineralogy of individual plinthic and manganiferous nodules in soil from cropping systems in the Farming Systems Project in Beltsville, Maryland. Elemental composition indicates the accumulation of contaminants and nutrients, including copper in all nodules and high levels of phosphorus in select nodules. Sequential extractions determine that highly crystalline minerals comprise the nodules, locking away these nutrients and contaminants. Bulk X-ray diffraction (XRD) demonstrated distinct mineralogies in the plinthic and manganiferous nodules, with the former comprised of quartz, goethite, and kaolinite, and the latter consisting of quartz, Mn 2 O 3 , and hematite. Synchrotron and laboratory-based X-ray fluorescence (XRF) mapping gives critical insight into the elemental distribution within the nodules and elucidates spatial elemental associations, including the coupling of manganese and iron in the manganiferous nodules. XRF maps paired with µXRD provide microscale spatial resolution in mineralogy, which resolved several phases not apparent in bulk XRD, manganese’s association with goethite, and minerals indicative of redox transformations, including magnetite and maghemite. These novel results provide critical insight into the microscale mineralogy and individual elemental composition of plinthic and manganiferous nodules, as well as how they alter bulk soil geochemistry in ways largely unaccounted for in research on soil systems.

36 MATERIALS SCIENCE

In-Situ Visualization of a Growing Brittle Crack in Aluminum Oxynitride Using Synchrotron X-Rays and the Double-Cleavage Drilled Compression Geometry

Brittle fracture is difficult to study in situ due to the speed of a growing crack and the often-catastrophic nature of failure in brittle materials. As a result, the influence of microstructural considerations, such as orientation, grain boundary locations, and strain field, on the crack path remains poorly understood. Presented in this study is a method addressing this knowledge gap, which utilizes the double-cleavage drilled compression geometry to achieve quasi-stable fracture in aluminum oxynitride (AlON). Synchrotron X-ray micro-computed tomography is used to characterize the crack shape and length, while high-energy diffraction microscopy provides information on the strains, orientations, and shapes of grains in the microstructure surrounding the crack tip. During testing, the crack grew in discrete and irregular jumps while the fracture toughness falls within reported ranges. The crack in AlON is found to have no greater tendency to crack intergranularly as compared to transgranularly, and grains which are cracked transgranularly do not display a trend in orientation or stress when compared to those around which the crack followed a grain boundary. The high resolution of the crack path and microstructural data provides a path forward for modeling and understanding 3D brittle fracture.

Gorske, Sara F.

Melting temperature of bismuth to 55 GPa using synchrotron X-ray phase contrast imaging

The melting temperature of elemental bismuth under high pressure has been measured to 55 GPa using synchrotron X-ray phase-contrast imaging in the laser-heated diamond anvil cell. Imaging of solid-liquid interface formation, combined with radiometric temperature and X-ray diffraction measurements, reveals a pronounced reduction in melting boundary slope in Bi-V with pressure. The unusually steep initial slope is attributed to low configurational entropy of melting, arising from structural ordering and coordination matching in the cool liquid, while slope reduction is driven by entropy increase correlated with significant liquid structure changes with rising pressure and temperature. Finally, the data rule out kinetic effects on melting in shock compression experiments and demonstrate the need for improved theoretical phase diagrams.

Materials science

Polarized Resonant Soft X-ray Scattering (P-RSoXS) as a New Technique for Characterizing Amorphous Astromaterials

In the coming years, samples will be returned from several asteroids, the lunar surface, and the first material returned directly from the Martian surface. Previous in-situ and remote studies indicate these samples will contain abundant amorphous or weakly crystalline materials. However, detailed characterization and quantification of these amorphous materials remains challenging. Conventional techniques, including electron microscopy and X-ray diffraction, provide important information on material structure, but are generally limited to crystalline materials. Polarized resonant soft X-ray scattering (P-RSoXS) is a synchrotron-based X-ray scattering technique that has been used to characterize and quantify weakly crystalline systems, including soft materials. This research aims to translate this technique to geologic and extraterrestrial materials, building off the knowledge of using P-RSoXS to interrogate soft materials. P-RSoXS is well-suited to interrogate geologic materials, which are often multiphase, heterogeneous systems with crystalline and amorphous components, and domain sizes on the order of tens of nanometers. It is anticipated that future work will help reveal new chemical and structural information in geologic materials. Maturation of this preliminary work to develop P-RSoXS to characterize astromaterial-relevant samples will provide new understanding of the secondary processes responsible for the development of amorphous astromaterials and further elucidate our knowledge of the geologic history and past alteration processes.

Joshua H Litofsky

Fast and bright scintillators for ultrafast materials dynamics using 4th generation synchrotron

We present recent advances in fast and bright scintillators for ultrafast X-ray phase contrast imaging of dynamic materials experiments at the upgraded Advanced Photon Source (APS-U), a fourth generation synchrotron. APS-U enables hard X-ray imaging at frame rates of at least 13 MHz (corresponding to 77 ns or shorter interframe intervals), creating a new need for scintillators with faster response and higher light output than lutetium yttrium oxyorthosilicate (LYSO). For indirect imaging and diffraction with ultrafast cameras, commercial lanthanum bromide (LaBr3) and cerium bromide (CeBr3) are promising candidates. These materials exhibit decay times approximately a factor of two shorter than LYSO (around 40 ns) and lutetium oxyorthosilicate (LSO), while maintaining comparable light yield per incident X-ray photon. However, their implementation at APS-U requires addressing several challenges, including material limitations due to hygroscopicity, efficient optical coupling to imaging systems, and high quantum efficiency for conversion of scintillation light, predominantly at wavelengths below 400 nm, into detectable electronic signals. We report results from material characterization, detector integration and packaging, and beamline experiments of materials with impact. In addition, emerging scintillator classes, including perovskites and high-entropy materials, are discussed as potential alternatives for next-generation ultrafast X-ray diagnostics.

Wang, Zhehui [Los Alamos] (ORCID:0000000178264063)

FY26 Progress Report on the Operation of the Activated Materials Laboratory at the Advanced Photon Source as a Nuclear Science User Facilities Partner Facility

The Activated Materials Laboratory (AML), located in the Long Beamline Building of the Advanced Photon Source (APS) at Argonne National Laboratory (ANL), provides a centralized radiological capability for preparing, handling, and supporting synchrotron experiments on activated materials. As a Nuclear Science User Facilities (NSUF) partner facility, the AML enables the receipt of radioactive shipments, open-form sample handling, encapsulation, transport of specimens to and from APS beamlines, and experimentation with dedicated equipment. The partnership includes the APS 1-ID and 20-ID beamlines, which provide high-energy x-ray scattering, tomography, and diffraction microscopy techniques for ex-situ, in-situ, and grainresolved three-dimensional (3D) characterization. All samples supported through the AML and partner beamlines must meet radiological limits of less than 100 mrem/h at 30 cm. This FY26 progress report summarizes the first full year of AML operations as an NSUF partner facility and highlights progress in both user support and capability development. By the end of FY26, the AML had received a total of 10 NSUF-awarded projects, including 2 Consolidated Innovative Nuclear Research (CINR), 7 Rapid Turnaround Experiment (RTE), and 1 Super RTE projects. Beamtime was fully delivered for 3 RTE projects and partially delivered for 1 CINR project, demonstrating successful workflows for receipt, encapsulation, beamline transfer, and radiological experiment execution. These efforts demonstrated safe radiological experiments at APS beamlines for samples with dose rates above the historical 5 mrem/h threshold and now up to 100 mrem/h at 30 cm, marking an important milestone for neutron-irradiated materials research. During FY26, the AML also expanded its experimental capabilities. A Psylotech xTS load frame with in-grip rotation was deployed for room-temperature mechanical testing with threedimensional x-ray characterization during interrupted loading. A Linkam TS1500V vacuum heater was commissioned for thermally driven studies, and temperature calibration experiments were performed to establish specimen-relevant thermal profiles. In parallel, a customized split-tube furnace for high-temperature mechanical testing entered commissioning, and initial work began on robotic sample handling to reduce worker dose and improve operational efficiency. Data workflow and beamline operations continued to mature. Together, these developments demonstrate that the AML is becoming a unique national resource for safe, efficient, and scientifically advanced characterization of activated materials at the APS.

Zhang, Xuan

Metal oxide-promoted calcium cuprate catalysts for diol oxidative dehydrocyclization to lactones

Here, this work investigates structure-function relationships in electronically tunable, redox-active, basic Cu-Ca mixed metal oxide catalysts for oxidative dehydrocyclization of liquid diols to lactones. Compositional screening identified Ni 2+ and Zn 2+ as effective promoters that increase the surface Cu 2+ population by ∼1.7× and Cu-normalized activity for liquid 1,4-butanediol conversion to γ-butyrolactone by ∼3–4×. In situ Raman spectroscopy, in situ X-ray absorption spectroscopy (XAS), in situ diffuse-reflectance Fourier transform infrared spectroscopy (DRIFTS), ex situ X-ray diffraction (XRD), and H 2 -temperature-programmed reduction (H 2 -TPR) show that Ni 2+ or Zn 2+ incorporation promotes the formation of Ca 0.82 Cu 1.00 O 2 nanoparticles under mild calcination conditions. This cuprate phase features stronger and shorter Cu–O bonds (1.90 Å) than inactive bulk CuO (1.95 Å) and square-planar Cu 2+ O 4 sites with enhanced d z2 electrophilicity, strengthening alkoxy adsorption. Pyridine-DRIFTS confirms the purely basic nature of the catalyst surface, while methanol-DRIFTS indicates Cu 2+ surface enrichment with Ni or Zn promotion, where Cu–O(Ca)–Cu sites can exist as amorphous domains or a truncation layer on crystalline nanoparticles.

09 BIOMASS FUELS

High Pressure Synthesis of Ultrasmall Nanodiamonds with Nitrogen Vacancy Centers

C–H terminated nanometer scale diamonds ( d = 1 to 15 nm) are synthesized from 1-fluoroadamantane at high pressure (6–8 GPa) and high temperature (500–1500 °C) in a multianvil press. High resolution transmission electron microscopy, X-ray diffraction, Raman, diffuse reflectance Fourier transform infrared, and X-ray absorption spectroscopies demonstrate the excellent crystallinity and atomically flat C–H terminated surfaces of nanodiamonds with (111) and (110) facets. The importance of hydrogen to the synthesis of nanodiamond and its faceting is discussed. Following vacancy generation, annealing and oxidation of the nanodiamonds, optically detected magnetic resonance and electron spin resonance coherence times ( T 2 = 0.9 and 2.1 μs) of nitrogen vacancy (NV) centers are measured. Finally, the obtained T 2 values are equivalent to the shallow NV centers (depth <10 nm) in bulk diamond crystals and larger nanocrystals prepared by mechanical milling.

36 MATERIALS SCIENCE