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At least 685 records · Page 38

Magnetic glassiness in noncentrosymmetric Sm 7 Pd 3 : Interplay of magnetic frustration, long-range order, and frozen domains

Here, we present a comprehensive investigation of the intricate spin dynamics in the noncentrosymmetric compound Sm 7 ⁢Pd 3 , revealing the coexistence of spin-glass, domain-glass, and ferromagnetic (FM) behaviors. Magnetic field-dependent measurements indicate large coercivity, suggesting ferromagnetic domain formation below the Curie temperature (𝑇 C ≈ 173 K), while temperature-dependent magnetization data point to antiferromagnetic (AFM) coupling, highlighting the competition between FM and AFM interactions. Detailed ac susceptibility, isothermal remanent magnetization, and aging effect measurements demonstrate the presence of two distinct types of glassiness in the sample, and their possible origins are discussed extensively. Magnetization measurements reveal the mixing of the 𝐽 = 5/2 ground state of Sm 3+ with the excited 𝐽 = 7/2 multiplet, lying 965 K above. The specific heat data show further crystalline electric field splitting of the 𝐽 = 5/2 state into a ground-state doublet and a fourfold-degenerate excited state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Climate-Relevant Gas Absorption Properties from AWARE and Other ARM Spectral Measurements (Final Report)

The objective of this project has been to use measurements from the Atmospheric Emitted Radiance Interferometer (AERI) deployed at ARM sites to improve our knowledge of uncertain infrared spectroscopic parameters of importance to climate, remote sensing, and data assimilation. A primary focus has been the water vapor continuum in the infrared atmospheric window. Radiation codes used to predict climate and weather base their representation of the water vapor continuum in this window on the MT_CKD model, but in this spectral region the MT_CKD water vapor continuum absorption coefficients were derived almost two decades ago by an analysis of AERI measurements for conditions with a limited range of precipitable water vapor (PWV) and temperature values, leading to uncertainty in the derived coefficients. This project has included a new, comprehensive analysis of all aspects of the water vapor continuum in the atmospheric window -- the self continuum, the foreign continuum, and the self continuum temperature dependence, all resolved spectrally. Having a wide range of PWV amounts and temperatures from deployments of the ARM Mobile Facility for GoAmazon as well as the more than a decade of AERI measurements at SGP has provided an appropriate foundation for such a comprehensive analysis.

54 ENVIRONMENTAL SCIENCES↗

Nuclear temperature and its dependence on the source neutron-proton asymmetry deduced using the Albergo thermometer

Albergo thermometers with double isotope, isotone and isobar yield ratio pairs with one proton or/and neutron difference are investigated. Without any extra sequential decay correction, a real temperature value of 4.9 ± 0.5 MeV is deduced from the yields of the experimentally reconstructed primary hot intermediate mass fragments (IMFs) from 64 Zn + 112 Sn collisions at 40 MeV/nucleon using the Albergo thermometer for the first time. An experimental sequential decay correction from the apparent temperatures to the real ones for twelve other reaction systems with different neutron-proton (N/Z) asymmetries in the same experiment, 70 Zn, 64 Ni on 112,124 Sn, 58,64 Ni, 197 Au, 232 Th at 40 MeV/nucleon, is performed using an empirical correction factor approach of Tsang et al. with the deduced 4.9 MeV temperature value. The dependence of nuclear temperature on the source N/Z asymmetry is further investigated using these deduced real source temperature values from the present thirteen systems. It is found that the deduced real source temperatures at the present source N/Z range show a rather weak dependence on the source N/Z asymmetry. In conclusion, by comparison between our previous results and those from other independent experiments, a consistent description for the N/Z asymmetry dependence of nuclear temperature is addressed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Electrically-driven IMT and volatile memristor behavior in NdNiO 3 films

Abstract Transition metal oxides with insulator-metal transitions (IMTs) are uniquely suited for volatile memristor devices that mimic the spiking of biological neurons. Unlike most non-volatile memristors, which often operate via ion migration into filaments, volatile devices utilize a reversible phase change that returns to a ground state in the absence of applied stimulus. In these devices, Joule heating triggers the IMT and changes the bulk resistivity rather than influencing conduction through defects, as in previous studies. This volatile resistive switching behavior has previous been leveraged in niobium and vanadium oxides, but not in rare-earth nickelates, despite their tunable transition temperatures. This study demonstrates an electrically driven IMT in the prototypical rare-earth nickelate, NdNiO 3 , in large area devices. While previous work examining the electrically-driven IMT in NdNiO 3 suggests defect-dominated conduction, this study shows clear s-type negative differential resistance (NDR) consistent with temperature-dependent resistivity measurements. The NDR peak-to-valley voltage scales linearly with temperature as expected for conductivity pathways dominated by bulk IMT behavior. Unlike other transition metal oxides, which are modeled using the insulator-metal phase fraction as the internal state variable, a thermoelectric model with temperature as the internal state variable is found to more accurately describe the current–voltage characteristic of NdNiO 3 volatile memristors. Overall, we report the synthesis, fabrication, and characterization of NdNiO 3 volatile memristors with resistivity dominated by bulk-like IMT behavior which is scalable and not dependent upon oxygen vacancy migration or defect mediated conduction pathways.

36 MATERIALS SCIENCE↗

High-pressure CO 2 permeation properties and stability of ceramic-carbonate dual-phase membranes

CO 2 permeation properties and stability of ceramic-carbonate dual-phase membranes at high pressures/temperatures are critical to their CO 2 separation and membrane reactor applications, but such data are not available in the literature. Here, this work aims to study the effect of high transmembrane pressure on CO 2 permeation flux and the stability of molten carbonate in the dual-phase samarium-doped ceria (SDC) and molten-carbonate (MC) membranes. Dead-end porous SDC tubular supports were made by a cold isostatic press (CIP)/sintering method with a low porosity (below 7%), and gas-tight SDC-MC membranes were prepared by direct infiltration of molten lithium and sodium carbonate mixture into SDC pores, with a MC volume fraction less than 7%. CO 2 permeation/separation tests were performed on the SDC-MC membranes using feed gas of equal molar CO 2 /N 2 mixture at feed pressures up to 15 atm and sweep gas of helium at 1 atm. CO 2 permeation flux for the SDC-MC membranes depends logarithmically on feed/permeate CO 2 pressure ratio in 660–810°C. The temperature dependence of CO 2 permeation shows activation energy of 30 kJ/mol. Due to the small MC volume fraction and hence low effective carbonate conductivity, CO 2 permeation of the SDC-MC membranes is dominated by the carbonate ionic conduction in the MC phase. The SDC-MC membranes remain in the same structure, morphology, and gas-tightness after CO 2 separation tests at high feed pressures and temperatures, showing high stability of SDC-MC membranes for high-temperature, high-pressure separation and chemical reaction applications.

36 MATERIALS SCIENCE↗

In Situ/Operando Probing of Dynamic Phase Structures of Alumina‐Supported Ultrasmall Copper‐Gold Alloy Nanoparticles Under Reaction Conditions

Abstract The ability to control phase structures and surface sites of ultrasmall alloy nanoparticles under reaction conditions is essential for preparing catalysts by design. This is, however, challenging due to limited understanding of the atomic‐scale phases and their correlation with the ensemble‐averaged structures and activities of catalysts during catalytic reactions. We reveal here a dynamic structural stability of alumina‐supported ultrasmall and equiatomic copper‐gold alloy nanoparticles under reaction conditions as a model system in the in situ/operando study. In situ atomic‐scale morphological tracking under oxygen reveals temperature‐dependent dynamic crystalline‐amorphous dual‐phase structures, showing dynamic stability over an elevated temperature range. This atomic‐scale dynamic phase stability coincides with a “conversion plateau” observed for carbon monoxide oxidation on the catalyst. It is substantiated by the stable lattice ordering/disordering structures and surface sites with oscillatory characteristics shown by operando ensemble‐average structural tracking of the catalyst during the oxidation reaction. The understanding of the atomic‐scale dynamic phase structures in correlation with the ensemble‐average dynamic ordering/disordering phase structures and surface sites provides fresh insights into the unique synergy of the supported alloy nanoparticles. This understanding has implications for the design and structural tuning of active and stable ultrasmall alloy catalysts under elevated temperatures.

Chemistry↗

Vacancy diffusion barrier spectrum and diffusion correlation in multicomponent alloys

Vacancy diffusion serves a crucial role in many important kinetic behaviors and properties of multicomponent alloys. Essential questions, however, persist regarding how chemical complexity affects diffusion and what unique characteristics, if any, set these alloys apart from traditional metals. Using neural network kinetics model, we study vacancy diffusion in NbMoTa alloy across a broad temperature range (2600 to 800 K). Unlike pure metals, the two key diffusion parameters—diffusion correlation factor f and activation energy ΔG m —are not constant in alloys, but instead substantially decrease with decreasing temperature. This temperature dependence arises from a reduced number of active vacancy jump pathways at lower temperatures, leading to more correlated diffusion. Upon examining vacancy diffusion throughout the entire compositional space of the Nb-Mo-Ta system, we discover that the slowest vacancy diffusion surprisingly occurs in the non-equimolar region, rather than the equimolar concentration where the configurational entropy is highest. The diffusion barrier spectrum, characterizing the diffusion energy landscape, is an intrinsic material characteristic, which controls both f and ΔG m and, thereby, the diffusivity. Lastly, we find that the vacancy diffusion rate drops noticeably in the presence of local chemical order in the NbMoTa system, particularly for MoTa alloys with long-range B2 order.

Defects↗

Electronic structure and charge-density wave transition in monolayer $\mathrm{VS}_2$

Vanadium disulfide (VS 2 ) attracts elevated interests for its charge-density wave (CDW) phase transition, ferromagnetism, and catalytic reactivity, but the electronic structure of monolayer has not been well understood yet. Here we report synthesis of epitaxial 1T VS 2 monolayer on bilayer graphene grown by molecular-beam epitaxy (MBE). Angle-resolved photoemission spectroscopy (ARPES) measurements reveal that Fermi surface with six elliptical pockets centered at the M points shows gap opening at low temperature. Temperature-dependence of the gap size suggests existence of CDW phase transition above room temperature. Here, our observations provide important evidence to understand the strongly correlated electron physics and the related surface catalytic properties in two-dimensional transition-metal dichalcogenides (TMDCs).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Characterizing Defect Dynamics in Silicon Carbide Using Symmetry-Adapted Collective Variables and Machine Learning Interatomic Potentials

Silicon carbide (SiC) divacancies are attractive candidates for spin-defect qubits possessing long coherence times and optical addressability. The high activation barriers associated with SiC defect formation and motion pose challenges for their study by first-principles molecular dynamics. In this work, we develop and deploy machine learning interatomic potentials (MLIPs) to accelerate defect dynamics simulations while retaining ab initio accuracy. We employ an active learning strategy comprising symmetry-adapted collective variable discovery and enhanced sampling to compile configurationally diverse training data, calculation of energies and forces using density functional theory (DFT), and training of an E(3)-equivariant MLIP based on the Allegro model. Here, the trained MLIP reproduces DFT-level accuracy in defect transition activation free energy barriers, enables the efficient and stable simulation of multidefect 216-atom supercells, and permits an analysis of the temperature dependence of defect thermodynamic stability and formation/annihilation kinetics to propose an optimal annealing temperature to maximally stabilize VV divacancies.

Computer simulations↗

Temperature Effect on Photoelectrochemical Water Splitting: A Model Study Based on BiVO 4 Photoanodes

Photoelectrochemical (PEC) water splitting is typically studied at room temperature. In this work, the temperature effect on PEC water splitting is studied using crystalline BiVO4 thin film photoanode as a model system. Systematic temperature-dependent electrochemical study demonstrates that the PEC activity is boosted at elevated electrolyte temperatures and indicates that thermal energy plays a main role in improving charge carrier transport in the bulk of BiVO 4 . Irreversible surface reconstruction is observed after PEC reactions at elevated temperature in the presence of hole scavengers, with regularly spaced stripes emerging on BiVO4 grains. The surface-reconstructed photoanode exhibits up to 40% improvement in photocurrent densities and ~0.25 V shift of photocurrent onset to favorable direction. Detailed investigation shows the formation of amorphous layer without stoichiometric change at the reconstructed surface. Furthermore, this work provides insights of temperature effect on photoelectrode in solar water splitting and reveals the non-negligible effect of hole scavengers in photoelectrochemical measurement.

36 MATERIALS SCIENCE↗

Real-space observation of ergodicity transitions in artificial spin ice

Abstract Ever since its introduction by Ludwig Boltzmann, the ergodic hypothesis became a cornerstone analytical concept of equilibrium thermodynamics and complex dynamic processes. Examples of its relevance range from modeling decision-making processes in brain science to economic predictions. In condensed matter physics, ergodicity remains a concept largely investigated via theoretical and computational models. Here, we demonstrate the direct real-space observation of ergodicity transitions in a vertex-frustrated artificial spin ice. Using synchrotron-based photoemission electron microscopy we record thermally-driven moment fluctuations as a function of temperature, allowing us to directly observe transitions between ergodicity-breaking dynamics to system freezing, standing in contrast to simple trends observed for the temperature-dependent vertex populations, all while the entropy features arise as a function of temperature. These results highlight how a geometrically frustrated system, with thermodynamics strictly adhering to local ice-rule constraints, runs back-and-forth through periods of ergodicity-breaking dynamics. Ergodicity breaking and the emergence of memory is important for emergent computation, particularly in physical reservoir computing. Our work serves as further evidence of how fundamental laws of thermodynamics can be experimentally explored via real-space imaging.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Unprecedented non-hysteretic superelasticity of [001]-oriented NiCoFeGa single crystals

Superelasticity associated with the martensitic transformation has found a broad range of engineering applications. However, the intrinsic hysteresis and temperature sensitivity of the first-order phase transformation significantly hinder the usage of smart metallic components in many critical areas. In this paper, we report a large superelasticity up to 15.2% strain in [001]-oriented NiCoFeGa single crystals, exhibiting non-hysteretic mechanical responses, a small temperature dependence and high-energy-storage capability and cyclic stability over a wide temperature and composition range. In situ synchrotron X-ray diffraction measurements show that the superelasticity is correlated with a stress-induced continuous variation of lattice parameter accompanied by structural fluctuation. Neutron diffraction and electron microscopy observations reveal an unprecedented microstructure consisting of atomic-level entanglement of ordered and disordered crystal structures, which can be manipulated to tune the superelasticity. The discovery of the large elasticity related to the entangled structure paves the way for exploiting elastic strain engineering and development of related functional materials. NiCoFeGa single crystals exhibit large non-hysteretic superelasticity over broad temperature and composition ranges. It is attributed to the continuous phase transition with applied stress, which is related to the fluctuation of entangled ordered and disordered crystal structures.

36 MATERIALS SCIENCE↗

Extended spin relaxation times of optically addressed vanadium defects in silicon carbide at telecommunication frequencies

Optically interfaced solid-state defects are promising candidates for quantum communication technologies. The ideal defect system would feature bright telecom emission, long-lived spin states, and a scalable material platform, simultaneously. Here, in this study, we use one such system, vanadium (V 4+ ) in silicon carbide, to establish a potential telecom spin-photon interface within a mature semiconductor host. This demonstration of efficient optical spin polarization and readout facilitates all-optical measurements of temperature-dependent spin relaxation times (T 1 ). By using this technique, and lowering the temperature from approximately 2 K to approximately 100 mK, we observe a remarkable 4-orders-of-magnitude increase in spin T 1 across all measured sites, with site-specific values ranging from 57.1 ms to 27.9 s. Furthermore, we identify the underlying relaxation mechanisms, which involve a two-phonon Orbach process, indicating the opportunity for strain tuning to enable qubit operation at higher temperatures. These results position V 4+ in SiC as a prime candidate for scalable quantum nodes in future quantum networks.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Complex fermiology and electronic structure of antiferromagnet EuSnP

Throughout this work, we studied the electronic structure of a layered antiferromagnetic metal, EuSnP, in the paramagnetic and in the antiferromagnetic phase using angle-resolved photoemission spectroscopy (ARPES) alongside density-functional theory (DFT)-based first-principles calculations. The temperature dependence of the magnetic susceptibility measurements exhibits an antiferromagnetic transition at a Néel temperature of 21 K. Employing high-resolution ARPES, the valence-band structure was measured at several temperatures above and below the Néel temperature, which produced identical spectra independent of temperature. Through analysis of the ARPES results presented here, we attribute the temperature-independent spectra to the weak coupling of the Sn and P conduction electrons with Eu 4⁢ƒ states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evaluation of Thermolytic Hydrogen Generation Rate Models at High-Temperature/High-Hydroxide Regimes

This report describes the results of testing performed to extend the applicable ranges of temperature and hydroxide concentration for use within the Glycolate and Global Total Organic Carbon (TOC) Hydrogen Generation Rate (HGR) expressions. Seven experimental conditions (six simulants of the 242-25H Evaporator system chosen as a D-optimal set of experiments and a single test conducted at an elevated boiling point of 170 °C) were investigated in the presence of sodium glycolate and Xiameter TM AFE-1010. Glycolate was employed to study the extension of the Glycolate Thermolytic HGR expression while Xiameter TM AFE-1010 was employed to study the extension of the Global TOC Thermolytic HGR expression. The following conclusions were derived from this testing: The Glycolate Thermolytic HGR expression may be confidently used to predict thermolytic HGRs from glycolate at temperatures as high as 170 °C and hydroxide concentrations as high as 23 M.; The hydroxide and temperature-dependence predicted by the Global TOC Thermolytic HGR expression has been confirmed at temperatures as high as 170 °C and hydroxide concentrations as high as 23 M, suggesting that the Global TOC Thermolytic HGR expression may be used at these ranges.; Methane was observed from tests with Xiameter TM AFE-1010 at production rates higher than those observed for hydrogen. These rates were observed at temperatures higher than 100 °C.; Preliminary models suggest that increasing hydroxide/temperature causes an increase in Methane Generation Rate (MGR) from Xiameter TM AFE-1010. The following recommendations are based on this testing: The existing equations for thermolytic HGR from glycolate and non-glycolate organics should be used at Concentration, Storage, and Transfer Facilities (CSTF) storage and evaporation conditions, including temperatures and hydroxide concentrations exhibited in the 242-25H Evaporator.; Further investigation should be made into the influence of methylsilanes on CSTF flammability. This investigation should include: determination of the types of methylsilanes historically added to the CSTF, determination of methane formation rates from each type of methylsilane, and determination of the extent of degradation of methylsilanes in CSTF waste.; Characterization techniques should be developed by Savannah River National Laboratory (SRNL) to assist in the speciation of methylsilane-containing waste in the CSTF.; Additional testing with radioactive waste should be performed to determine the MGRs possible in radioactive waste and better inform model predictions made from testing with simulants.

08 HYDROGEN↗

Sensor Development for Liquid Water Detection in Dry Storage Casks: FY 2023 Status

Modeling efforts were undertaken in fiscal year (FY) 2023 to evaluate the feasibility and capability for sensing of liquid water inside canister-based dry cask storage systems (DCSSs). The focus was on the development of full-scale finite element models (FEMs) of ultrasound propagation through DCSS canister components. For these initial investigations, simulation of the baseplate component was targeted, envisioning water collection at the bottom of a vertically oriented canister. The effects of internal canister components (i.e., fuel basket, fuel assemblies) on ultrasound propagation in the baseplate component were evaluated in these efforts. The environment inside a DCSS confinement is intended to be inert and free of water to prevent potential corrosion of used fuel cladding or other internal hardware. Spent fuel assemblies are dried, after storage in water pools, to make sure water has been removed from assembly cavities. However, there is some uncertainty about the amount of residual water potentially left behind in a DCSS after drying processes, because water can become trapped in cavities or other small crevices in the surfaces formed by the fuel cladding, fuel assemblies, and other internal hardware components. Considering the complex space- and time-dependent temperature profiles in DCSSs, water may be in a liquid or gas phase depending on its location in the cask and how long the cask has been in storage. Evacuating most water and oxidizing agents contained within a canister is recommended by NUREG-1536 (NRC 2010), which covers DCSSs. As summarized by Salazar et al. (2020), existing guidance typically relies on achievable vacuum pumping pressures sustained over a hold period as a signal of dryness and water removal. However, time series data about water removal from full-scale commercial drying procedures are lacking (Hanson and Alsaed 2019). A review of drying specifications from several vendors led to the conclusion that if the specifications are followed correctly, the residual moisture in DCSSs should present an insignificant risk of cladding degradation (Knoll and Gilbert 1987). A more recent analysis concluded that much larger quantities of residual water could remain in DCSSs, but the amount would still not be expected to lead to significant corrosion of fuel cladding or other internal components (Jung et al. 2013). Industry drying procedures are mostly prescriptive in nature, and operational issues arising during the process could result in incomplete drying. A summary of operational issues and potential negative effects of residual water is provided by Salazar et al. (2019). Experimental efforts are ongoing to validate the extent of water removal in a DCSS based on drying procedures used at nuclear power plants through well-designed investigations of drying process efficacy and water retention (Durbin et al. 2021; Pulido et al. 2022a, Pulido et al. 2022b). This has been approached by simulating limited portions of a DCSS internal volume and fuel assemblies. So far, these efforts have focused on the effects of potential water trapping in the dashpot region of control rod guide tubes but are expected to be expanded to include the effects of other internal hardware features and failed fuel rod cladding. A method for detection and measurement of liquid water (Meyer et al. 2022; Meyer et al. 2021), in tandem with the drying information gained through experimental investigations, provides comprehensive bases for understanding the internal conditions of DCSSs and provides technical information to support licensing decisions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Implementation of Johnson Noise Thermometry into Radiation Hardened Electronics

The random motion of charge carriers in an electrical conductor is a function of its temperature. This phenomenon generates an electrical signal, referred to as Johnson noise, that is present in all analog signals. Conversely, the temperature dependence of the Johnson noise spectrum also enables a direct measurement of absolute temperature, which can provide a secondary measurement of temperature when quantified using sensors such as resistive temperature devices (RTDs) in a process called Johnson noise thermometry (JNT). For nuclear environments, this is of particular interest in correcting for RTDs signal drift caused by accumulation, transmutation, and displacement damage caused by neutron and gamma irradiation.

42 ENGINEERING↗

Thermodynamic Modeling of Complex Solid Solutions in the Lu-H-N System via Graph Neural Network Accelerated Monte Carlo Simulations

Metal hydrides are important across diverse applications, such as hydrogen storage, batteries, gas sensors, nuclear reactions, and high-temperature superconductivity. Previous computational studies of metal hydrides under extreme pressures, e.g., 𝑂⁡(10 2 ) ⁢GPa, usually treat them as stoichiometric compounds without considering interstitial lattice disorder. As pressures become more moderate in the 𝑂⁡(10 0 ) ⁢GPa and below range, hydrogen disorder at interstitial lattice sites becomes prominent, e.g., in the N-doped Lu hydride that was recently claimed superconducting near 1 GPa. Further adding compositional complexity from alloying and/or multielement interstitial occupation makes elucidating pressure- and temperature-dependent observables intractable by first-principles calculations alone. We therefore propose a lattice graph neural-network surrogate modeling approach to predict configuration- and pressure-dependent equation-of-state properties. Their efficiency permits Monte Carlo simulations to calculate Gibbs energies and pressure-dependent phase diagrams, thereby revealing insights into the synthesis conditions required for achieving desired phase equilibria. We demonstrate this concept for the compositionally complex cubic Lu(H,N,Va) 3 system where three constituents (hydrogen, nitrogen and vacancy) have disordered multielement interstitial occupancies and insights into pressure-dependent phase equilibria are critically needed, e.g., N-doping levels can significantly lower dehydrogenation temperatures and provide a new strategy to optimize hydrogen-storage alloys. This work can improve the thermodynamic understanding of the Lu-H-N system and help rational synthesis of N-doped Lu hydrides, but more generally demonstrates an efficient approach to model pressure-dependent thermodynamics of multicomponent solid solutions.

Monte Carlo methods↗