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At least 847 records · Page 47

Resolving Nanoscopic and Mesoscopic Heterogeneity of Fluorinated Species in Battery Solid-Electrolyte Interphases by Cryogenic Electron Microscopy

The stability of lithium batteries is tied to the physicochemical properties of the solid-electrolyte interphase (SEI). Owing to the difficulty in characterizing this sensitive interphase, the nanoscale distribution of SEI components is poorly understood. Here, we use cryogenic scanning transmission electron microscopy (cryo-STEM) to map the spatial distribution of SEI components across the metallic Li anode. We reveal that LiF, an SEI component widely believed to play an important role in battery passivation, is absent within the compact SEI film (~15 nm); instead, LiF particles (100–400 nm) precipitate across the electrode surface. We term this larger length scale as the indirect SEI regime. On the basis of these observations, we conclude that LiF cannot be a dominant contribution to anode passivation nor does it influence Li+ transport across the compact SEI film. We refine the traditional SEI structure derived from ensemble-averaged characterizations and nuance the role of SEI components on battery performance.

25 ENERGY STORAGE↗

Effect of Ice Number Concentration on the Evolution of Boundary Layer Clouds During Arctic Marine Cold‐Air Outbreaks

Abstract Marine cold‐air outbreaks (MCAOs) are crucial for Arctic Ocean heat loss, featuring convective cloud rolls that transition into convection cells downstream. Understanding factors controlling this transformation is the key for improving MCAO cloud representation in climate models. This study employs large‐eddy simulations to investigate how cloud ice number concentrations () affect cloud evolution using a case from the Cold‐Air Outbreaks in the Marine Boundary Layer Experiment (COMBLE) campaign. The simulations, performed in a Lagrangian framework following an air mass trajectory, are driven by ERA5 reanalysis data. Initially, all simulations produce similar cloud patterns, but higher leads to earlier breakup of cloud rolls. Between 4 and 10 hr, surface precipitation rates are similar across simulations, but precipitation initiates earlier, and the cloud‐base precipitation rates are higher when is higher. The stronger precipitation evaporation leads to increased stability of the boundary layer and reduced intensity of vertical mixing between the surface and cloud layer. An increased sink of cloud layer moisture via precipitation and decreased source through diminished vertical transport result in earlier cloud breakup in higher conditions. Simulations with different sea surface temperatures (SST) indicate that this cloud breakup mechanism remains valid for MCAOs of different strengths, although the cloud organization is more sensitive to SST changes in low environments. This work highlights the importance of accurate representations of ice processes in simulating MCAO clouds and suggests the need for observational constraints of ice nucleating particles and over the mixed‐phase cloud regimes.

54 ENVIRONMENTAL SCIENCES↗

Application of an Affine Nonlinear Galerkin Reduced-order Model to Compressible Fluid Flows

Galerkin reduced-order models (ROMs) often struggle to accurately capture multiscale fluid physics in challenging flow regimes such as flows experiencing compressibility effects. This in part stems from the global nature of both the basis construction problem and the spectral formulation itself. In this work, a multi-basis ROM is developed in an affine space based on proper orthogonal decomposition (POD) by projecting the full Navier-Stokes equations expressed in terms of the specific volume, velocity, and pressure primitive variables. The model is applied to high-fidelity numerical simulation datasets obtained for a canonical compressible flow configuration: the flow over a backward facing step at different subsonic Mach numbers. It is observed that application of an eigenvalue reassignment (ER) stabilization method is required to avoid early divergence of the ROM predictions for this configuration in the three Mach numbers tested. The sensitivity of the POD-ROM results to the choice of parameters in the stabilization algorithm is discussed.

reduced-order model↗

Application of an Affine Nonlinear Galerkin Reduced-order Model to Compressible Fluid Flows

Galerkin reduced-order models (ROMs) often struggle to accurately capture multiscale fluid physics in challenging flow regimes such as flows experiencing compressibility effects. This in part stems from the global nature of both the basis construction problem and the spectral formulation itself. In this work, a multi-basis ROM is developed in an affine space based on proper orthogonal decomposition (POD) by projecting the full Navier-Stokes equations expressed in terms of the specific volume, velocity, and pressure primitive variables. The model is applied to high-fidelity numerical simulation datasets obtained for a canonical compressible flow configuration: the flow over a backward facing step at different subsonic Mach numbers. It is observed that application of an eigenvalue reassignment (ER) stabilization method is required to avoid early divergence of the ROM predictions for this configuration in the three Mach numbers tested. The sensitivity of the POD-ROM results to the choice of parameters in the stabilization algorithm is discussed.

reduced-order model↗

Resistance to Rolling in the Adhesive Contact of Two Elastic Spheres

For the stability of agglomerates of micron sized particles it is of considerable importance to study the effects of tangential forces on the contact of two particles. If the particles can slide or roll easily over each other, fractal structures of these agglomerates will not be stable. We use the description of contact forces by Johnson, Kendall and Roberts, along with arguments based on the atomic structure of the surfaces in contact, in order to calculate the resistance to rolling in such a contact. It is shown that the contact reacts elastically to torque forces up to a critical bending angle. Beyond that, irreversible rolling occurs. In the elastic regime, the moment opposing the attempt to roll is proportional to the bending angle and to the pull-off force P(sub c). Young's modulus of the involved materials has hardly any influence on the results. We show that agglomerates of sub-micron sized particles will in general be quite rigid and even long chains of particles cannot be bent easily. For very small particles, the contact will rather break than allow for rolling. We further discuss dynamic properties such as the possibility of vibrations in this degree of freedom and the typical amount of rolling during a collision of two particles.

Dominik, C.↗

Resistance to Rolling in the Adhesive Contact of Two Elastic Spheres

For the stability of agglomerates of micron sized particles it is of considerable importance to study the effects of tangential forces on the contact of two particles. If the particles can slide or roll easily over each other, fractal structures of these agglomerates will not be stable. We use the description of contact forces by Johnson, Kendall and Roberts, along with arguments based on the atomic structure of the surfaces in contact, in order to calculate the resistance to rolling in such a contact. It is shown that the contact reacts elastically to torque forces up to a critical bending angle. Beyond that, irreversible rolling occurs. In the elastic regime, the moment opposing the attempt to roll is proportional to the bending angle and to the pull-off force P(sub c). Young's modulus of the involved materials has hardly any influence on the results. We show that agglomerates of sub-micron sized particles will in general be quite rigid and even long chains of particles cannot be bent easily. For very small particles, the contact will rather break than allow for rolling. We further discuss dynamic properties such as the possibility of vibrations in this degree of freedom and the typical amount of rolling during a collision of two particles.

Dominik, C.↗

"Dust Devils": Gardening Agents on the Surface of Mars, and Hidden Hazards to Human Exploration?

Dust devils are familiar sites in the and regions of the world: they can produce quite spectacular displays of dust lofting when the vortices scavenge very loose dust from a dry lake bed or from recently disturbed agricultural fields. If one were to arrive at the center of an arid region, take one photograph, or even a series of photographs over a period of several days, then return the images for laboratory analysis, it would be most likely concluded that the region was inactive from an aeolian perspective. No images of general dust movement were obtained, nor were any dust devils "caught on camera" owing to their ephemeral and unpredictable appearance, and the fact that there was deceptively little residue of their actions. If, however, a camera were to take a 360 degree continuous recording over a period of a year, and the film were then to be shown at high speed over a period a several minutes, the impression might be that of a region ravaged by air vorticity and dust movement. Extrapolate this over geological time, and it is possible to visualize dust devils as prime aeolian agents, rather than insignificant vagaries of nature, On Mars, the thin atmosphere permits the surface of the planet to be heated but it does not itself retain heat with the capacity of the earth's atmosphere. This gives rise to greater thermal instability near the surface of Mars as "warm" air pockets diapiritically inject themselves into higher atmospheric layers. Resulting boundary-layer vorticity on Mars might therefore be expected to produce dust devils in abundance, if only seasonally. The spectacular images of dust devils obtained by Pathfinder within its brief functional period on the planet testify to the probability of highly frequent surface vorticity in light of the above reasoning about observational probability. Notably, the Pathfinder devils appeared to be at least a kilometer in height. There are several consequences for the geology of Mars, and for human exploration, if dust devils are to be expected in reasonable abundance. First, from a geological perspective, the vortices will act as "gardening" agents for the top few centimeters of entrainable material. Over time (hundreds of millions, or billions of years being available), they will cover the surface with scouring paths, and the grain sizes that can be lofted by a vortex probably extends over the whole sand to dust range. The depositional paths are, of course, much larger, so that vortex-induced deposition is more widespread than vortex-induced erosion, and will without doubt, affect the whole region in which the dust devils occur (this might explain why rocks at the Viking site seemed oddly capped with dust in a region apparently subject to general aeolian scouring). On Mars, the lift forces in dust devils might be less than on earth owing to the much thinner atmosphere, but this may be counterbalanced by lower gravity and greater vortex velocities. Certainly, when active, other aeolian phenomena on Mars --sand motion and dust storms, seem no less energetic and no less capable of lofting sediments than equivalent terrestrial aeolian phenomena. Every several years, within the current climatic regime, the surface of Mars is subject to light dust fall from global dust storms. Over time, this should develop a very uniform surface layer, with commensurate uniformity in grain size, mineralogy, albedo, color, and general spectroscopic properties. Dust devils will disturb this situation by continually mixing the surface dust with underlying layers, perhaps composed of silt and sand. This size mixing will also involve compositional mixing. After some years, the thin layer of dust that may be difficult to entrain alone, becomes progressively mixed with coarser materials that could reduce the general aeolian threshold of the soil. Certainly the continual disturbance by vorticity will prevent surface stabilization that may bind or indurate grains (caused by slow cementation or ice welding at grain boundaries). If dust devils continually loft dust to kilometer heights, and the dust is sprayed into many cubic kilometers of atmosphere each time, could the devils produce a continual background of atmospheric dust that might be mistaken for the fallout of a distant large-scale dust storm? From a human exploration perspective, dust devils are unlikely to pose any, life- threatening situation for an astronaut unfortunate enough to encounter a momentary swirling cloud of loose soil. However, it is noted that pervasive dust is probably one of the greatest long-term hazards for a human encampment. The fineness and penetration capabilities of the dust, its electrostatic adhesive properties, and its complete ubiquity, render the material a persistent nuisance at best, but at worst, over a period of many months it is possible that space suits, machinery, habitat interiors, air filters, and so forth, could become jeopardized. Owing to dust penetration, the space suits used in the Apollo landings were rendered unusable after a few EVA activities. There will be a definite attempt to situate a human colony on Mars in an area that is far removed from the regions of the planet known for being the centers of major dust storms. At the heart of these storm systems, the dust lofting mechanics are unknown, but they are energetic and perhaps potentially life-threatening for an astronaut. Locating a colony in a region that appears from space to be meteorologically benign may lead to colony placement in a region prone to dust devils, but dust devils are not (or have not been) detectable from orbital observations: the region surveyed for placement will appear like the apparently inactive and area referred to earlier. The region may be spared from highly energetic weather systems, but it may not be necessarily immune from continual dust disturbance. Additional information is contained in the original.

Marshall, J.↗

Titanium Nitride as an Intermetallic Diffusion Barrier for Hydrogen Permeation in Palladium–Vanadium Composite Membranes

Hydrogen purification is a critical industrial process, and there are ongoing efforts to develop low-cost alternatives to palladium foil membranes. Titanium nitride (TiN) is studied as an interdiffusion barrier to enable hydrogen permeation in composite palladium–vanadium membranes. TiN was deposited via reactive sputtering, and films with the desired (200) orientation were obtained in the metallic regime at 400 °C under a 200 V bias to the substrate. The permeability of thin-film TiN was determined with palladium-based sandwich structures. TiN layers up to 10 nm resulted in a minimal decrease in flux (~20%) relative to a freestanding PdCu foil, which was attributed to the interfacial resistance. At greater thicknesses, the TiN layer was rate-limiting, and it was found that the effective permeability of the sputtered TiN thin films was ~6 × 10−12 mol s−1 m−1 Pa−0.5. Composite Pd|TiN|V|TiN|Pd membranes exhibited permeability values up to three times greater than pure palladium, exhibiting stability at 450 °C for over 100 h, with the lack of intermetallic diffusion and alloy formation being confirmed with XRD. The membranes were unstable at 500 °C, which was attributed to the instability of the thin Pd layer and loss of catalytic activity.

Biochemistry & Molecular Biology↗

Predicting the Slowing of Stellar Differential Rotation by Instability-driven Turbulence

Abstract Differentially rotating stars and planets transport angular momentum (AM) internally due to turbulence at rates that have long been a challenge to predict reliably. We develop a self-consistent saturation theory, using a statistical closure approximation, for hydrodynamic turbulence driven by the axisymmetric Goldreich–Schubert–Fricke instability at the stellar equator with radial differential rotation. This instability arises when fast thermal diffusion eliminates the stabilizing effects of buoyancy forces in a system where a stabilizing entropy gradient dominates over the destabilizing AM gradient. Our turbulence closure invokes a dominant three-wave coupling between pairs of linearly unstable eigenmodes and a near-zero frequency, viscously damped eigenmode that features latitudinal jets. We derive turbulent transport rates of momentum and heat and provide them in analytic forms. Such formulae, free of tunable model parameters, are tested against direct numerical simulations; the comparison shows good agreement. They improve upon prior quasi-linear or “parasitic saturation” models containing a free parameter. Given model correspondences, we also extend this theory to heat and compositional transport for axisymmetric thermohaline-instability-driven turbulence in certain regimes.

Astronomy & Astrophysics↗

Intelligent Control for the BEES Flyer

This paper describes the effort to provide a preliminary capability analysis and a neural network based adaptive flight control system for the JPL-led BEES aircraft project. The BEES flyer was envisioned to be a small, autonomous platform with sensing and control systems mimicking those of biological systems for the purpose of scientific exploration on the surface of Mars. The platform is physically tightly constrained by the necessity of efficient packing within rockets for the trip to Mars. Given the physical constraints, the system is not an ideal configuration for aerodynamics or stability and control. The objectives of this effort are to evaluate the aerodynamics characteristics of the existing design, to make recommendaaons as to potential improvements and to provide a control system that stabilizes the existing aircraft for nominal flight and damaged conditions. Towards this several questions are raised and analyses are presented to arrive at answers to some of the questions raised. CART3D, a high-fidelity inviscid analysis package for conceptual and preliminary aerodynamic design, was used to compute a parametric set of solutions over the expected flight domain. Stability and control derivatives were extracted from the database and integrated with the neural flight control system. The Integrated Vehicle Modeling Environment (IVME) was also used for estimating aircraft geometric, inertial, and aerodynamic characteristics. A generic neural flight control system is used to provide adaptive control without the requirement for extensive gain scheduling or explicit system identification. The neural flight control system uses reference models to specify desired handling qualities in the roll, pitch, and yaw axes, and incorporates both pre-trained and on-line learning neural networks in the inverse model portion of the controller. Results are presented for the BEES aircraft in the subsonic regime for terrestrial and Martian environments.

Krishnakumar, K.↗

Equation of state for Hf, Ta, W, Re, Os, Ir, Pt, and Au to multi-terapascal pressures from density-functional theory

We present the zero-temperature equation of state (pressure dependence of compression) and phase stability predictions for the 5d-transition metals obtained from all-electron density-functional theory (DFT) calculations. The results compare favorably with experiments but extend beyond current experimental capabilities to 10 TPa. Our study reveals phase changes that are explained from the calculated electronic structure. The cubic face-centered and body-centered structures (fcc and bcc), together with two-, three-, and four-layered hexagonal structures, play major roles under compression. The results’ dependence on the electron exchange and correlation in the DFT approach is investigated, and it is shown that the impact of the choice, while significant at lower pressures, diminishes in the terapascal regime. We further illustrate that the normal parabolic trends in atomic volume and bulk modulus with atomic number, due to the occupation of bonding and anti-bonding 5d states, break down at TPa pressures, suggesting drastically different chemical bonding at these extreme conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Battery performance of the SKYNET 4A spacecraft during the first six years of on station operation

The SKYNET 4A spacecraft is a three-axis stabilized geostationary earth-orbiting military communications satellite which was launched on 1 Jan. 1990 aboard a Titan 3 launch vehicle. The power subsystem is a twin bus, twin battery semi-regulated system and is equipped with one 28-cell, 35 Ampere-hour battery per bus. The cells were manufactured by Gates Aerospace Batteries of Gainesville, FL, and the batteries were built, tested and integrated by British Aerospace Space Systems Ltd. This paper presents a brief survey of the first six years of on-station operation and the operational battery management strategy that has been adopted. Thermal management constraints have led to an unconventional battery operational regime. However, no sign of degradation is evident and the observed spacecraft battery performance remains nominal.

Johnson, P. J.↗

EXPERIMENTAL STUDIES OF NONLINEAR INTEGRABLE OPTICS

State-of-the-art accelerators at energy and intensity frontiers require increasingly bright and powerful particle beams. In conventional linear lattices, intense beams suffer from collective instabilities, resulting in beam losses and maximum beam intensity limits. This thesis presents experimental studies of a novel lattice design concept, the nonlinear integrable optics (NIO), aimed at enhancing beam stability limits with little to no beam dynamics degradation. Single-particle beam dynamics measurements of two NIO devices, the quasi-integrable octupole system and the fully integrable Danilov-Nagaitsev system, were carried out at the purpose-built Integrable Optics Test Accelerator (IOTA) at Fermilab. Their simulation, hardware design, and commissioning process are presented. Extensive model and analysis algorithm development and benchmarking is described. Electron beam data from two scientific runs is analyzed, yielding frequency and phase space dynamics consisten t with m odels. These results demonstrate viability and advantages of the NIO design, providing the groundwork for proton studies in the strong space-charge regime and future integrable accelerators.

Kuklev, Nikita↗

Strain induced electronic structure, and magnetic and structural properties in quaternary Heusler alloys ZrRhTiZ (Z = Al, In)

In this work, electronic structure, and magnetic and structural properties of quaternary Heusler alloys ZrRhTiZ (Z = Al, In) have been analyzed from first principles calculations. The ferromagnetic ground state and thermodynamical stability of these compounds are supported by relative total energies, and by derived formation and cohesive energies, respectively. The investigated Curie temperatures of the compounds exceed room temperature indicating that these compounds are promising candidates for beyond room temperature spintronics and magneto-electronics applications. Both compounds follow the Slater-Pauling 18 electron rule and exhibit half-metallic ferromagnetic behavior with magnetic moments of 2 μB with 100% spin polarization in one spin channel at the Fermi-level. The effect of uniform strain on half-metallicity of these compounds inverts the band gap from one spin channel to another spin channel with a mixed spin (magnetic moment) regime that can be mapped to an exchange bias like effect observed in some of the magnetic Heusler compounds. The half metallic ferromagnetic behavior is retained within –2 to 2% strain contrasting with the anomalous spin flip in –1% and 1% strain in ZrRhTiZ (Z = Al, In).

36 MATERIALS SCIENCE↗

Heterobimetallic Iridium-Niobia Catalyst for Efficient and Selective Methane Ammonia Reforming

A Surface OrganoMetallic Chemistry (SOMC) approach, leveraging a molecularly defined heterobimetallic niobium–iridium complex, was used to prepare a mesoporous SBA-15 silica-supported Ir-NbOx catalyst. The resulting Ir-NbOx/SiO2 catalyst exhibited excellent catalytic performance in selective methane/ammonia reforming. Specifically, the Ir-NbOx/SiO2 catalyst showed significantly higher activity (turnover frequency 8.5 s–1), selectivity (75%), and stability than the Ir/SiO2 analog, whereas the NbOx/SiO2 counterpart was almost inactive. This contrasts with ethane/ammonia reforming via C–C cleavage, for which the bimetallic Ir-NbOx/SiO2 was less active than Ir/SiO2, demonstrating tuned selectivity toward C–H activation rather than C–C cleavage due to the Ir/NbOx synergy. Importantly, an Ir-NbOx/SiO2 reference catalyst, prepared by conventional impregnation/calcination/reduction steps, was found to be inactive, highlighting the value of the SOMC catalyst preparation approach using well-defined heterobimetallic precursors. These results represent a significant advance over existing catalysts due to the atomic-scale synergy between Ir and NbOx sites, enabling access to activity and selectivity regimes inaccessible to monometallic analogs.

Wu, Jiachun↗

Bilayer Wigner crystals in a transition metal dichalcogenide heterostructure

One of the first theoretically predicted manifestations of strong interactions in many-electron systems was the Wigner crystal, in which electrons crystallize into a regular lattice. The crystal can melt via either thermal or quantum fluctuations. Quantum melting of the Wigner crystal is predicted to produce exotic intermediate phases and quantum magnetism because of the intricate interplay of Coulomb interactions and kinetic energy. However, studying two-dimensional Wigner crystals in the quantum regime has often required a strong magnetic field or a moiré superlattice potential, thus limiting access to the full phase diagram of the interacting electron liquid. Here we report the observation of bilayer Wigner crystals without magnetic fields or moiré potentials in an atomically thin transition metal dichalcogenide heterostructure, which consists of two MoSe 2 monolayers separated by hexagonal boron nitride. We observe optical signatures of robust correlated insulating states at symmetric (1:1) and asymmetric (3:1, 4:1 and 7:1) electron doping of the two MoSe 2 layers at cryogenic temperatures. Here, we attribute these features to bilayer Wigner crystals composed of two interlocked commensurate triangular electron lattices, stabilized by inter-layer interaction. The Wigner crystal phases are remarkably stable, and undergo quantum and thermal melting transitions at electron densities of up to 6 × 10 12 per square centimetre and at temperatures of up to about 40 kelvin. Our results demonstrate that an atomically thin heterostructure is a highly tunable platform for realizing many-body electronic states and probing their liquid–solid and magnetic quantum phase transitions.

36 MATERIALS SCIENCE↗

On the instability of a 3-dimensional attachment line boundary layer: Weakly nonlinear theory and a numerical approach

The instability of a three dimensional attachment line boundary layer is considered in the nonlinear regime. Using weakly nonlinear theory, it is found that, apart from a small interval near the (linear) critical Reynolds number, finite amplitude solutions bifurcate subcritically from the upper branch of the neutral curve. The time dependent Navier-Stokes equations for the attachment line flow have been solved using a Fourier-Chebyshev spectral method and the subcritical instability is found at wavenumbers that correspond to the upper branch. Both the theory and the numerical calculations show the existence of supercritical finite amplitude (equilibrium) states near the lower branch which explains why the observed flow exhibits a preference for the lower branch modes. The effect of blowing and suction on nonlinear stability of the attachment line boundary layer is also investigated.

Hall, P.↗

Stability analysis of the accretion line

The stability of the flow along the accretion line in the Bondi-Hoyle-Lyttleton-type accretion flow is studied. The WKB approximation is used to analyze short wavelength linear perturbations of the axisymmetric steady state flow. The viscosity terms in the gasdynamical equations are included in the analysis. The radial modes are studied both in two- and three-dimensional accretion flow. Since a displaced accretion line cannot be defined in three-dimensional flow, the tangential modes are only analyzed in the two-dimensional flow. The analysis of the perturbed gasdynamical equations are made simpler as a result of the radial and tangential modes being decoupled in the linear regime. As was shown before, the three-dimensional accretion flow is unstable against radial modes. The two-dimensional accretion flow is found to be unstable against tangential modes, as well as against radial modes. Using typical numerical parameters which are in common use, the wavelength which gives the maximum growth rate of a small perturbation is found to be about 0.5 r(a), where r(a) is the accretion radius.

Soker, Noam↗