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At least 793 records · Page 44

Large off-diagonal magnetoelectricity in a triangular Co2+-based collinear antiferromagnet

Abstract Magnetic toroidicity is an uncommon type of magnetic structure in solid-state materials. Here, we experimentally demonstrate that collinear spins in a material with R -3 lattice symmetry can host a significant magnetic toroidicity, even parallel to the ordered spins. Taking advantage of a single crystal sample of CoTe 6 O 13 with an R -3 space group and a Co 2+ triangular sublattice, temperature-dependent magnetic, thermodynamic, and neutron diffraction results reveal A-type antiferromagnetic order below 19.5 K, with magnetic point group -3′ and k = (0,0,0). Our symmetry analysis suggests that the missing mirror symmetry in the lattice could lead to the local spin canting for a toroidal moment along the c axis. Experimentally, we observe a large off-diagonal magnetoelectric coefficient of 41.2 ps/m that evidences the magnetic toroidicity. In addition, the paramagnetic state exhibits a large effective moment per Co 2+ , indicating that the magnetic moment in CoTe 6 O 13 has a significant orbital contribution. CoTe 6 O 13 embodies an excellent opportunity for the study of next-generation functional magnetoelectric materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Finite element modeling of biomass hopper flow

Hoppers are widely used biomass handling devices that channel bulk biomass from storage to subsequent handling equipment. Jenike’s longstanding approach, based on the Mohr-Coulomb model, has been successfully used to design hoppers handling cohesionless granular materials such as grains and other agricultural produces. However, designing a hopper to ensure reliable biomass flow is found to be challenging due to cohesion, irregular particle shape, and bulk material elastoplasticity. This study aims to address the biomass handling engineering challenge with alternative constitutive material models concerning the flow behavior of bulk solids. Finite element modeling is an approach that allows for implementation of different material models, whose underlying constitutive theories assist in investigating the origin and manifestation of bulk mechanical behavior of granular materials. This study focuses on the incipient gravity hopper flow of two types of biomass feedstocks, i.e., ground corn stover and Douglas fir wood. Three widely used constitutive material models, i.e., Mohr-Coulomb model, modified Cam-Clay model, and Drucker-Prager/Cap model, are implemented. Using the flow pattern represented by the volume of biomass exhibiting more than 7% of axial strain (Kamath and Puri, 1999), the finite element model predicts that the bulk corn stover particulate material forms an arch, which represents a hampered transition from the static state to the dynamic flow-state out of the hopper, whereas bulk Douglas fir wood particulate material develops a reliable mass flow pattern. A laboratory scale hopper was used to experimentally determine the biomass flow conditions, which were subsequently compared with the predicted onset of flow by a finite element model (FEM). The developed FEM was found to correctly predict the initiation of mass flow for the milled Douglas fir wood, whereas corn stover was predicted to establish a strong core flow suggesting an unreliable handling characteristic. This observation aligns with the reported poor handling of milled corn stover.

09 BIOMASS FUELS↗

Phenomenological Model of Nonlinear Dynamics and Deterministic Chaotic Gas Migration in Bentonite: Experimental Evidence and Diagnostic Parameters

Understanding gas migration in compacted clay materials, e.g., bentonite and claystone, is important for the design and performance assessment of an engineered barrier system of a radioactive waste repository system, as well as many practical applications. Existing field and laboratory data on gas migration processes in low-permeability clay materials demonstrate the complexity of flow and transport processes, including various types of instabilities, caused by nonlinear dynamics of coupled processes of liquid–gas exchange, dilation, fracturing, fracture healing, etc., which cannot be described by classical models of fluid dynamics in porous media. We here show that the complexity of gas migration processes can be explained using a phenomenological concept of nonlinear dynamics and deterministic chaos theory. To do so, we analyzed gas pressure and gas influx (i.e., input) and outflux (i.e., output), recorded during the gas injection experiment in the compact Mx80-D bentonite sample, and calculated a set of the diagnostic parameters of nonlinear dynamics and chaos, such a global embedding dimension, a correlation dimension, an information dimension, and a spectrum of Lyapunov exponents, as well as plotted 2D and 3D pseudo-phase-space strange attractors, based on the univariate influx and outflux time series data. These results indicate the presence of phenomena of low-dimensional deterministic chaotic behavior of gas migration in bentonite. In particular, during the onset of gas influx in the bentonite core, before the breakthrough, the development of gas flow pathways is characterized by the process of chaotic gas diffusion. After the breakthrough, with inlet-to-outlet movement of gas, the prevailing process is chaotic advection. During the final phase of the experiment, with no influx to the sample, the relaxation pattern of gas outflux is resumed back to a process of chaotic diffusion. The types of data analysis and a proposed phenomenological model can be used to establish the basic principles of experimental data-gathering, modeling predictions, and a research design.

36 MATERIALS SCIENCE↗

Thermal Neutron Scattering Law Evaluations for Zirconium Carbide and Critical Mass Calculations [Slides]

Zirconium Carbide (ZrC) is a refractory material currently being investigated for high temperature reactor applications. ZrC was studied as a base of (U,Zr)C solid solution and UC 2 composite fuels for NERVA-type cores during the Rover program. Testing of the material was performed at Nuclear Furnace 1 (NF-1) located at Los Alamos. Thermal Scattering Law (TSL) evaluations generated with FLASSH are a new contribution to ENDF/B-VIII.1.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Strain-Induced Shifts in Defective Graphite Phonon Modes Predicted by Density Functional Theory

Carbon fiber composites have gained attention as a structural material because of their high strength-to-weight ratio, and understanding the effect of defects on reactivity and mechanical properties is important for the longevity and safety of the composite. Although it is known that strain causes the underlying graphitic vibrational modes to redshift, it is not clear how strain may alter reactivity and defect-induced vibrational changes. To investigate the strain-induced phonon changes of defective carbon fiber composites, density functional theory calculations of graphite are used, including intercalated hydrogen and fluorine defects. By comparing changes in the bond lengths, formation energies, and phonon density of states for uniaxially and biaxially strained graphite, strain was found to generally make defect formation more favorable and the specific behavior changes are dependent on the strain direction and defect identity. Specifically, intercalated fluorine phonons are more sensitive to strain than hydrogen intercalation phonons, and strain applied along the zigzag direction alters the calculated properties more than strain along the armchair direction. Finally, these results highlight the importance of understanding the microstructural effect of deviations from the ideal material because small changes in strain or defect type can significantly alter the behavior of the carbon fiber composite core.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intersection-distribution-based remapping between arbitrary meshes for staggered multi-material arbitrary Lagrangian-Eulerian hydrodynamics

In this paper, we present a new intersection-distribution-based remapping method between arbitrary polygonal meshes for indirect staggered multi-material arbitrary Lagrangian-Eulerian hydrodynamics. All cell-centered material quantities are conservatively remapped using intersections between the Lagrangian (old, source) mesh and the rezoned (new, target) mesh. The new nodal masses are obtained by conservative distribution of all material masses in each new cell to the cell's corners and then collecting those corner masses at new nodes. This distribution is done using a local constrained optimization approach for each cell in the new mesh. In order to remap nodal momentum we first define cell-centered momentum for each cell in the old mesh, conservatively remap this to the new mesh and then conservatively distribute the new zonal momentum to each cell's bounding nodes, again using local constrained optimization. Our method also conserves total energy by applying a new nodal kinetic energy correction that relies on a process similar to that used for remapping nodal mass and momentum. Cell-centered kinetic energy is computed, conservatively remapped and then distributed to nodes. The discrepancy between this conservatively remapped and actual nodal kinetic energy is then conservatively distributed to the internal energies of the materials in the cells surrounding each node. Unlike conventional cell-based corrections of this type, this new nodal kinetic energy correction has not been observed to drive material internal energy negative in any of our testing. Unlike flux based remapping, our new intersection-distribution method can be applied to remapping between source and target meshes that are arbitrarily different, which provides superior flexibility in the rezoning strategy. Our method is accurate, essentially conservative and essentially bounds preserving.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

History and State of the Art in Advanced Thermal Protection Systems

This report documents the current state of the art of thermal protection systems (TPS) relevant to missile application materials and MTCR control language. The information is intended to provide data on current TPS for determining the current state of development and identifying potential research directions. Various vehicle configurations and types of TPS are described, including the evolution of materials and systems. Vehicle configurations such as high drag rocket and capsule systems and low-drag air-breathers are discussed. TPS are complex, transitioning from often very low temperatures to temperatures exceeding 3000°C and heat fluxes of up to 30,000 W/cm 2 . They can take the form of blankets, sheets, tiles and fabricated rigid structures, and can be made from high temperature capable alloys, refractory metals, ceramics, ceramic matrix composites, ultra-high temperature ceramics, carbon-carbon composites or ablative carbonaceous materials. Current state of the art in TPS is based on materials any systems developed for the initial space program. TPS was upgraded to the point of the Space Shuttle development and has stagnated since them.

36 MATERIALS SCIENCE↗

Coherent-Precipitation-Stabilized Phase Formation in Over-Stoichiometric Rocksalt-Type Li Superionic Conductors

Rationalizing synthetic pathways is crucial for material design and property optimization, especially for polymorphic and metastable phases. Over-stoichiometric rocksalt (ORX) compounds, characterized by their face-sharing configurations, are a promising group of materials with unique properties; however, their development is significantly hindered by challenges in synthesizability. Here, taking the recently identified Li superionic conductor, over-stoichiometric rocksalt Li–In–Sn–O (o-LISO) material as a prototypical ORX compound, the mechanisms of phase formation are systematically investigated. It is revealed that the spinel-like phase with unconventional stoichiometry forms as coherent precipitate from the high-temperature-stabilized cation-disordered rocksalt phase upon fast cooling. This process prevents direct phase decomposition and kinetically locks the system in a metastable state with the desired face-sharing Li configurations. This insight enables us to enhance the ionic conductivity of o-LISO to be >1 mS cm -1 at room temperature through low-temperature post-annealing. This work offers insights into the synthesis of ORX materials and highlights important opportunities in this new class of materials.

36 MATERIALS SCIENCE↗

Atomistic Mechanisms of the Crystallographic Orientation‐Dependent Cu 1.8 S Conductive Channel Formation in Cu 2 S‐Based Memristors

Achieving multiple types of resistive switching in a single material with controlled ionic motion is a key challenge in neuromorphic computing, traditionally addressed by combining materials with distinct switching behaviors. Here, Cu 2-x S is identified as a promising candidate to overcome this limitation due to its hierarchical phase transitions. Using in situ biasing experiments, reversible and non-reversible phase transitions (and resistive switching) are demonstrated in γ-Cu 2 S by controlling the compliance current. The formation of parallel high-digenite Cu 1.8 S channels, orientated along the γ-Cu 2 S [201] crystallographic direction, drives the nonvolatile resistive switching. These channels emerge via an intermediate δ-Cu 2 S phase and are stabilized at room temperature by residual strains, alongside β-Cu 2 S phase. In conclusion, the work clarifies the complex, electrically triggered phase transformations in γ-Cu 2 S, and highlights the potential of Cu 2-x S as a versatile material for neuromorphic computing.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Crossbreeding Effect of Chalcogenation and Iodination on Benzene Additives Enables Optimized Morphology and 19.68% Efficiency of Organic Solar Cells

Volatile solid additives have attracted increasing attention in optimizing the morphology and improving the performance of currently dominated non-fullerene acceptor-based organic solar cells (OSCs). However, the underlying principles governing the rational design of volatile solid additives remain elusive. Herein, a series of efficient volatile solid additives are successfully developed by the crossbreeding effect of chalcogenation and iodination for optimizing the morphology and improving the photovoltaic performances of OSCs. Five benzene derivatives of 1,4-dimethoxybenzene (DOB), 1-iodo-4-methoxybenzene (OIB), 1-iodo-4-methylthiobenzene (SIB), 1,4-dimethylthiobenzene (DSB) and 1,4-diiodobenzene (DIB) are systematically studied, where the widely used DIB is used as the reference. The effect of chalcogenation and iodination on the overall property is comprehensively investigated, which indicates that the versatile functional groups provided various types of noncovalent interactions with the host materials for modulating the morphology. Among them, SIB with the combination of sulphuration and iodination enabled more appropriate interactions with the host blend, giving rise to a highly ordered molecular packing and more favorable morphology. As a result, the binary OSCs based on PM6:L8-BO and PBTz-F:L8-BO as well as the ternary OSCs based on PBTz-F:PM6:L8-BO achieved impressive high PCEs of 18.87%, 18.81% and 19.68%, respectively, which are among the highest values for OSCs.

36 MATERIALS SCIENCE↗

Topography and canopy cover influence soil organic carbon composition and distribution across a forested hillslope in the discontinuous permafrost zone

Abstract Topography and canopy cover influence ground temperature in warming permafrost landscapes, yet soil temperature heterogeneity introduced by mesotopographic slope positions, microtopographic differences in vegetation cover, and the subsequent impact of contrasting temperature conditions on soil organic carbon (SOC) dynamics are understudied. Buffering of permafrost‐affected soils against warming air temperatures in boreal forests can reflect surface soil characteristics (e.g., thickness of organic material) as well as the degree and type of canopy cover (e.g., open cover vs. closed cover). Both landscape and soil properties interact to determine meso‐ and microscale heterogeneity of ground warming. We sampled a hillslope catena transect in a discontinuous permafrost zone near Fairbanks, Alaska, to test the small‐scale (1 to 3 m) impacts of slope position and cover type on soil organic matter composition. Mineral active layer samples were collected from backslope, low backslope, and footslope positions at depths spanning 19 to 60 cm. We examined soil mineralogical composition, soil moisture, total carbon and nitrogen content, and organic mat thickness in conjunction with an assessment of SOC composition using Fourier‐transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS). Soils in the footslope position had a higher relative contribution of lignin‐like compounds, whereas backslope soils had more aliphatic and condensed aromatic compounds as determined using FT‐ICR‐MS. The effect of open versus closed tree canopy cover varied with the slope position. On the backslope, we found higher oxidation of molecules under open cover than closed cover, indicating an effect of warmer soil temperature on decomposition. Little to no effect of the canopy was observed in soils at the footslope position, which we attributed, in part, to the strong impact of soil moisture content in SOC dynamics in the water‐gathering footslope position. The thin organic mat under open cover on the backslope position may have contributed to differences in soil temperature and thus SOC oxidation under open and closed canopies. Here, the thinner organic mat did not appear to buffer the underlying soil against warm season air temperatures and thus increased SOC decomposition as indicated by the higher oxidation of SOC molecules and a lower contribution of simple molecules under open cover than the closed canopy sites. Our findings suggest that the role of canopy cover in SOC dynamics varies as a function of landscape position and soil properties, namely, organic mat thickness and soil moisture. Condition‐specific heterogeneity of SOC composition under open and closed canopy cover highlights the protective effect of canopy cover for soils on backslope positions.

54 ENVIRONMENTAL SCIENCES↗

Analysis of anion exchange membrane water electrolyzer performance and its evolution over time

Understanding water, evolved gas, and ionic transport in membrane-electrode-assemblies (MEAs) is essential for the development of high performance and durable anion exchange membrane water electrolyzers (AEMWEs). This study evaluates the MEA conditioning process, operating conditions, and short-term stability in a 1 M potassium hydroxide (KOH) electrolyte, focusing on the underlying transport phenomena. We observe a significant initial voltage loss in continuous cell operation, which could be associated with gas bubble accumulation, transport layer or flow field passivation, and changes in the catalyst oxidation state. Further, we investigate the effects of materials and operational configurations, including the membrane type and thickness, and the electrolyte flow rate, including KOH being fed to both electrodes as well as to the anode only. Furthermore, the effect of membrane drying temperature on ex situ as well as in situ electrochemical performance is evaluated. Finally, we discuss 700 h of AEMWE operation at 1 A/cm 2 , highlighting the underlying degradation phenomena.

25 ENERGY STORAGE↗

CO 2 adsorption mechanisms at the ZIF-8 interface in a Type 3 porous liquid

Porous liquids (PLs) are an attractive material for gas separation and carbon sequestration due to their permanent internal porosity and high adsorption capacity. PLs that contain zeolitic imidazole frameworks (ZIFs), such as ZIF-8, form PLs through exclusion of aqueous solvents from the framework pore due to its hydrophobicity. The gas adsorption sites in ZIF-8 based PLs are historically unknown; gas molecules could be captured in the ZIF-8 pore or adsorb at the ZIF-8 interface. To address this question, ab initio molecular dynamics was used to predict CO 2 binding sites in a PL composed of a ZIF-8 particle solvated in a water, ethylene glycol, and 2-methylimidazole solvent system. Further, the results show that CO 2 energetically prefers to reside inside the ZIF-8 pore aperture due to strong van der Waals interactions with the terminal imidazoles. However, the CO 2 binding site can be blocked by larger solvent molecules that have greater adsorption interactions. CO 2 molecules were unable to diffuse into the ZIF-8 pore, with CO 2 adsorption occurring due to binding with the ZIF-8 surface. Therefore, future design of ZIF-based PLs for enhanced CO 2 adsorption should be based on the strength of gas binding at the solvated particle surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The influence of thermomechanical treatment pathways on texture and mechanical properties in ARB Cu/Nb nanolaminates

Accumulative roll-bonded Cu/Nb nanolaminates (ARB Cu/Nb) possess high strength, thermal stability, and radiation tolerance arising from a high content of heterophase interfaces at fine layer thicknesses. These properties can be tailored by processing parameters used in the ARB Cu/Nb fabrication process, in which layer thickness, thermal history, and strain pathway determine the interface types and resultant properties found in the material. In this work, we subject ARB Cu/Nb to annealing, and then two different rolling pathways – one where rolling direction is held constant (longitudinal rolling, or LR), and one where rolling direction is rotated by 90º and held constant thereafter (cross rolling, or CR). Rolling is performed on ARB Cu/Nb over a targeted range of layer thicknesses from 193 to 25 nm and resultant bulk textures measured by neutron diffraction are correlated with mechanical properties measured by miniaturized tensile tests. The annealing procedure sharpens texture in both phases. We find that Cu mostly develops the same texture in LR and CR. In contrast, Nb develops a distinct texture along the CR pathway that is distinct from the LR texture. The composite texture of Cu/Nb is thus distinct between LR and CR pathways. This difference in texture development between Cu and Nb as a function of strain after change in rolling direction demonstrates the viability for deliberate pairing of Cu LR and Nb CR textures at a desired layer thickness. For mechanical properties, we find that differences in texture do not result in yield or flow stress differences above a layer thickness of 25 nm. Below a layer thickness of 25 nm, despite similar Taylor factors, yield and flow stress and are significantly different. In conclusion, this indicates texture only influences mechanical behavior at low layer thickness, where interface structure dominates mechanical properties.

36 MATERIALS SCIENCE↗

Extended use of face masks during the COVID-19 pandemic - Thermal conditioning and spray-on surface disinfection

The current COVID-19 pandemic has resulted in globally constrained supplies for face masks and personal protective equipment (PPE). Production capacity is limited in many countries and the future course of the pandemic will likely continue with shortages for high quality masks and PPE in the foreseeable future. Therefore, expectations are that mask reuse, extended wear and similar approaches will enhance the availability of personal protective measures. Repeated thermal disinfection could be an important option and likely easier implemented in some situations, at least on the small scale, than UV illumination, irradiation or hydrogen peroxide vapor exposure. In this paper, an overview on thermal responses and ongoing filtration performance of multiple face mask types is provided. Most masks have adequate material properties to survive a few cycles (i.e. 30 min disinfection steps) of thermal exposure in the 75°C regime. Some are more easily affected, as seen by the fusing of plastic liner or warping, given that preferred conditioning temperatures are near the softening point for some of the plastics and fibers used in these masks. Hence adequate temperature control is equally important. As guidance, disinfectants sprayed via dilute solutions maintain a surface presence over extended time at 25 and 37°C. Some spray-on alcohol-based solutions containing disinfectants were gently applied to the top surface of masks. Neither moderate thermal aging (less than 24 h at 80 and 95°C) nor gentle application of surface disinfectant sprays resulted in measurable loss of mask filter performance. Subject to bio-medical concurrence (additional checks for virus kill efficiency) and the use of low risk non-toxic disinfectants, such strategies, either individually or combined, by offering additional anti-viral properties or short term refreshing, may complement reuse options of professional masks or the now ubiquitous custom-made face masks with their often unknown filtration effectiveness.

36 MATERIALS SCIENCE↗

Pressure-Induced Superconductivity in the Wide-Band-Gap Semiconductor Cu 2 Br 2 Se 6 with a Robust Framework

We report pressure-induced superconductivity in a ternary and nonmagnetic Cu-containing semiconductor, Cu 2 Br 2 Se 6 , with a wide band gap of 1.89 eV, in which the Cu and Br atoms generate infinite 2, helical chains along the c-axis and are linked by the cyclohexane-like Se 6 rings to form a three-dimensional framework. We find that this framework is remarkably robust under compression, and the ambient-pressure phase survives at least to our experimental limit of 32.1 GPa. Concurrent semiconductor-to-metal transition and superconductivity are observed above 21.0 GPa. The superconducting temperature monotonically increases from 4.0 to 6.7 K at 40.0 GPa. Furthermore, first-principles calculations show that the emergence of superconductivity is associated with the formation of weak multicentered bonds that involve the increase in coordination of the Cu atoms and a subset of the Se atoms. The observation of superconductivity in this type of nonmagnetic transition-metal-based material will inspire the exploration of related new superconductors under pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electrochemically induced amorphous-to-rock-salt phase transformation in niobium oxide electrode for Li-ion batteries

Intercalation-type metal oxides are promising negative electrode materials for safe rechargeable lithium-ion batteries due to the reduced risk of Li plating at low voltages. Nevertheless, their lower energy and power density along with cycling instability remain bottlenecks for their implementation, especially for fast-charging applications. Here, we report a nanostructured rock-salt Nb 2 O 5 electrode formed through an amorphous-to-crystalline transformation during repeated electrochemical cycling with Li + . This electrode can reversibly cycle three lithiums per Nb 2 O 5 , corresponding to a capacity of 269 mAh g –1 at 20 mA g –1 , and retains a capacity of 191 mAh g –1 at a high rate of 1 A g –1 . Further, it exhibits superb cycling stability with a capacity of 225 mAh g –1 at 200 mA g –1 for 400 cycles, and a Coulombic efficiency of 99.93%. We attribute the enhanced performance to the cubic rock-salt framework, which promotes low-energy migration paths. Our work suggests that inducing crystallization of amorphous nanomaterials through electrochemical cycling is a promising avenue for creating unconventional high-performance metal oxide electrode materials.

25 ENERGY STORAGE↗

Evaluation of the interfacial bonding strength between hafnia and silica layers deposited by electron-beam evaporation

Factors contributing to the mechanical strength of multilayer optical coatings involving alternating layers of electron-beam evaporated hafnia and silica is investigated. It is observed that upon rupture resulting from nanosecond laser damage, fragments consisting of layer pairs are produced. These pairs are formed as a result of a strong asymmetry in adhesion strength between interfaces, leading to preferential delamination at interfaces where silica is deposited on hafnia, and not the reverse, despite the fact that both interface types consist of the same pair of materials. The observed disparity in adhesion strength was further studied using nanomechanical scratch tests, revealing loads at which fracture occurs, and fracture morphology, both of which are highly dependent on deposition order. Based on these measurements, along with the morphological analysis of the nanostructure of the coatings, we conclude that the surface microstructure in each coating layer affects its adhesion strength with the succeeding layer. The findings outlined here are particularly relevant to the production of large aperture, high-performance optics designed for use in next-generation lasers.

adhesion strength↗