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At least 289 records · Page 16

Bio-inspired redox mediated electrolyte for high performance flexible supercapacitor applications over broad temperature domain

For practical supercapacitors, recent advances in electrolytes have diminished long-standing problems such chemical stability, low ionic conductivity and limited electrochemical performance. Herewith, we communicate a facile method to produce anhydrous redox-active Bio-inspired electrolytes for flexible supercapacitors with application over a broad temperature range. The glycerol (Gly) gel electrolyte consists of various fractions of potassium hydroxide (KOH) and redox active unit, i.e., ammonium molybdate, (NH 4 ) 2 MoO 4 (abbreviated as Mo), in the anhydrous state. The doped glycerol matrix acts as a framework that provides a stable gel electrolyte, forming hierarchical pathway for ion diffusion. The developed gel network with Gly-KOH-MoX (X = 3, 5, 10, and 15%, w/w) provides an effective route to carry the ions onto the pores of the electrodes. The supercapacitor with Gly-KOH5-Mo10 gel provides a specific capacitance of 328 F g –1 , and the same device achieved an energy density of 45.6 Wh kg –1 at a power density of 497 W kg –1 . In addition, the supercapacitor maintained extraordinary cyclic robustness and wide temperature tolerance. Thus, the low cost and environmentally benign, cyclic durability of Gly-KOH-Mo makes these gel electrolytes a potential candidate for use in various energy storage devices.

25 ENERGY STORAGE↗

Quantifying the hydrodynamic contribution to electrical transport in non-Brownian suspensions

Electrical transport in semiconducting and metallic particle suspensions is an enabling feature of emerging grid-scale battery technologies. Although the physics of the transport process plays a key role in these technologies, no universal framework has yet emerged. Here, we examine the important contribution of shear flow to the electrical transport of non-Brownian suspensions. We find that these suspensions exhibit a strong dependence of the transport rate on the particle volume fraction and applied shear rate, which enables the conductivity to be dynamically changed by over 10 7 decades based on the applied shear rate. We combine experiments and simulations to conclude that the transport process relies on a combination of charge and particle diffusion with a rate that can be predicted using a quantitative physical model that incorporates the self-diffusion of the particles.

42 ENGINEERING↗

Thermoacoustic Soret separation

In a fluid mixture in a channel with an axial time-averaged temperature gradient, high-amplitude oscillating flow can greatly increase the axial flux of thermal diffusion (Soret) separation of the components of the mixture. The enhancement occurs when the oscillating lateral temperature gradient greatly exceeds the axial gradient, causing a large oscillating concentration that can be favorably time-phased with the oscillating flow. This process can occur even with a negligible pressure oscillation or with a negligible temperature response to pressure, as is the case in most liquid solutions. The thermal boundary condition imposed by realistic solids on thermoacoustic liquids is imperfect, adding mathematical complications that are absent for typical gases, for which the solid surface is temporally isothermal. Compared with gas mixtures, the high Lewis number in typical liquid solutions reduces the separation flux associated with the time-averaged temperature gradient, but it also reduces the remixing associated with the time-averaged mole-fraction gradient. For large enough channels, the second-law separation efficiency is only slightly reduced from that of steady liquid Soret separation.

36 MATERIALS SCIENCE↗

The TW Hya Rosetta Stone Project. I. Radial and Vertical Distributions of DCN and DCO{sup +}

Molecular D/H ratios are frequently used to probe the chemical past of solar system volatiles. Yet it is unclear which parts of the solar nebula hosted an active deuterium fractionation chemistry. To address this question, we present 0."2–0."4 Atacama Large Millimeter/submillimeter Array (ALMA) observations of DCO{sup +} and DCN 2–1, 3–2, and 4–3 toward the nearby protoplanetary disk around TW Hya, taken as part of the TW Hya Rosetta Stone project, augmented with archival data. DCO{sup +} is characterized by an excitation temperature of ~40 K across the 70 au radius pebble disk, indicative of emission from a warm, elevated molecular layer. Tentatively, DCN is present at even higher temperatures. Both DCO{sup +} and DCN present substantial emission cavities in the inner disk, while in the outer disk the DCO{sup +} and DCN morphologies diverge: most DCN emission originates from a narrow ring peaking around 30 au, with some additional diffuse DCN emission present at larger radii, while DCO{sup +} is present in a broad structured ring that extends past the pebble disk. Based on a set of simple parametric disk abundance models, these emission patterns can be explained by a near-constant DCN abundance exterior to the cavity, and an increasing DCO{sup +} abundance with radius. In conclusion, the ALMA observations reveal an active deuterium fractionation chemistry in multiple disk regions around TW Hya, but not in the cold planetesimal-forming midplane and in the inner disk. More observations are needed to explore whether deuterium fractionation is actually absent in these latter regions, and if its absence is a common feature or something peculiar to the old TW Hya disk.

36 MATERIALS SCIENCE↗

Reduction of Porosity in Cementitious Waste Forms to Reduce Effective Diffusivity

Although current practices meet regulations for grout waste forms, development of sequestration materials and techniques for contaminants of concern could expand the use of grout waste forms and reduce risk to established processes from future compositional changes. There are contaminants in waste streams that are not permanently and completely sequestered in current grout waste forms under certain conditions. These contaminants include methyl mercury, 129 I, 99 Tc, and nitrate. Each of these species have minor fractions that are not permanently and completely isolated from the environment and therefore potentially contribute to long-term environmental impacts. An approach of interest includes the technique of reducing porosity to result in reduced leachability of all contaminants simultaneously. The current Savannah River Site (SRS) saltstone formulation was used to evaluate the relationship between leachability and porosity reduced waste forms by altering the water-to-binder ratio. Results indicated decreasing the water-to-binder directly reduced porosity and resulted in the waste form’s ability to more effectively immobilize nitrate. This work was funded by the Department of Energy Office of Environmental Management (DOE-EM) Technology Operations Office (TOO) Project # HQ221818.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Superior CO 2 /N 2 separation performance of highly branched Poly(1,3 dioxolane) plasticized by polyethylene glycol

With its high content of CO 2 -philic ether oxygen groups, poly(1,3-dioxolane) (PDXLA) has emerged as an attractive platform to achieve excellent CO 2 /N 2 separation properties for post-combustion carbon capture. Herein we demonstrate that the separation properties of PDXLA can be further enhanced by plasticizing with miscible polyethylene glycol (PEG)-based additives using an integrated experimentation and modeling approach. The effects of the chain end groups and loading level of the additives on the physical properties of the blends are thoroughly investigated, including glass transition temperature (T g ), fractional free volume, and gas transport properties, and the effects can be satisfactorily described using models available for homogeneous blends. Notably, a T g -integrated free volume model is adapted to successfully interpret the unified effect of the blend composition and temperature on gas diffusivity and permeability. A sample containing 45 mass% PEG dimethyl ether (PEGDME with a molecular mass of 240 g/mol) displays stable mixed-gas CO 2 permeability of 1540 Barrer and CO 2 /N 2 selectivity of 40 when challenged with a model flue gas at 60 °C, outperforming Robeson's 2008 upper bound. Elucidating how small plasticizers impact gas transport in homogeneous blends may unravel a facile way to design high-performance membranes for gas separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure–property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg 2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg 2+ (with time scales ranging from 0.5 μs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg 2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. In conclusion, this observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

25 ENERGY STORAGE↗

Diffusion characteristics of water molecules in a lamellar structure formed by triblock copolymers

The distribution and diffusion of water molecules are playing important roles in determining self-assembly and transport properties of polymeric systems. Small-angle neutron scattering (SANS) experiments and molecular dynamics (MD) simulation have been applied to understand the distribution of water molecules and their dynamics in the lamellar membrane formed by Pluronic L62 block copolymers. Penetration of water molecules into the polyethylene oxide (PEO) layers of the membranes has been estimated using scattering length density (SLD) profiles obtained from SANS measurements, which agree well with the molecular distribution observed from MD simulations. The water diffusion coefficient at different regions of the lamellar membrane was further investigated using MD simulation. The diffusion characteristic shows a transition from normal to anomalous diffusion as the position of the water molecule changes from the bulk to PEO and to the polypropylene oxide (PPO) layer. Here we find that water molecules within the PEO or PPO layers follow subdiffusive dynamics, which can be interpreted by the model of fractional Brownian motion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phase stability of a eutectic high entropy alloy under extremes of pressures and temperatures

Additively manufactured high-entropy alloys are of interest because of their unique combination of high yield strength and large ductility achieved with far-from-equilibrium crystalline phases and micro/nanostructure morphology. We report on the phase transformation and thermal equation of state of the eutectic high-entropy alloy (EHEA) Al 18 Co 20 Cr 10 Fe 10 Ni 40 W 2 , produced by laser powder-bed fusion (L-PBF). The EHEA was studied in a large-volume Paris–Edinburgh cell using energy-dispersive x-ray diffraction to a pressure of 5.5 GPa and a temperature of 1723 K. Static compression studies in diamond anvil cells using angle-dispersive x-ray diffraction extended the high-pressure structural data to 317 GPa at ambient temperature. The initial dual-phase nanolamellar face-centered cubic (FCC) and body-centered cubic (BCC) structure of Al 18 Co 20 Cr 10 Fe 10 Ni 40 W 2 transforms into a single FCC phase under high pressure, with the BCC-to-FCC phase transformation completing at 9 ± 2 GPa. The FCC phase remained stable up to the highest pressure of 317 GPa. The measured thermal equation of state for the FCC phase of Al 18 Co 20 Cr 10 Fe 10 Ni 40 W 2 is presented up to 5.5 GPa and 1473 K. We observed melting of the EHEA at 1698 ± 25 K at a pressure of 5.5 GPa, and the recrystallized sample shows an increased fraction of the CsCl-type (B2) phase at ambient conditions following release from the high-pressure high-temperature state. The BCC-to-FCC phase transition completion pressure is correlated with the nanolamellae thickness of the BCC layer in this diffusion-less transformation at ambient temperature.

36 MATERIALS SCIENCE↗

Quantitative local state of charge mapping by operando electrochemical fluorescence microscopy in porous electrodes

We introduce operando quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. Here, we observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.

42 ENGINEERING↗

Room temperature corrosion behaviour of plastically deformed AISI 304 stainless steel by friction stir welding in neutral and acidified chloride solutions

Severe plastic deformation of 304L stainless steel plate was carried out by friction stirring under an isothermal tool temperature at 825°C. The friction stirred zone showed extensive grain refinement, high fraction of low angle grain boundaries due to dislocation rearrangement, Σ3 and Σ9 special grain boundaries and discrete Fe–Cr–Mn-rich particles. Electrochemical polarisation measurements were done on the base metal (BM) and friction stir welded (FSW) specimens in the neutral and acidified 3.5% NaCl solutions. The BM showed marginally better pitting resistance in the neutral chloride solution than the FSW because of a larger fraction of special grain boundaries, and larger grain size. Whereas in acidified 3.5% NaCl solution, the FSW showed better corrosion resistance than the BM. Furthermore, the surface film of the FSW had a lower impedance and a lower defect concentration than the BM indicating higher diffusivity of point defects in the FSW.

36 MATERIALS SCIENCE↗

Tusqh

SAND2025-00675O Tusqh is a software tool that generates cubical meshes in 2D and 3D and computes the homology of these meshes using persistent homology. It includes a grid cell in the output if its volume-fraction is above a selectable threshold, estimated by sampling points within the cell. Tusqh incorporates anti-aliasing algorithms to mitigate grid orientation and scale effects. It is designed for creating finite element meshes for simulations and can be used in various applications such as heat diffusion, mechanical simulations, and computer graphics rendering. The software outputs meshes in an open format compatible with downstream software. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

SciDAC↗

Mechanisms of energetic-particle transport in magnetically confined plasmas

Super-thermal ions and electrons occur in both space and fusion plasmas. Because these energetic particles (EP) have large velocities, EP orbits necessarily deviate substantially from magnetic surfaces. Orbits are described by conserved constants of motion that define topological boundaries for different orbit types. Electric and magnetic field perturbations produced by instabilities can disrupt particle orbits, causing the constants of motion to change. The statistics of the “kicks” associated with these perturbations determines the resulting cross field transport. A unifying theme of this tutorial is the importance of the perturbation’s phase at the particle’s position Θ = k • r – ωt, where k and ω are the wavevector and frequency of the perturbation, r is the EP position, and t is the time. A distinction is made between field perturbations that resonate with an aspect of the orbital motion and those that do not. Resonance occurs when the wave phase returns to its initial value in an integer multiple of an orbital period. Convective transport occurs when resonant particles experience an unvarying wave phase. Alternatively, multiple wave-particle resonances usually decorrelate the phase, resulting in diffusive transport. Large orbits increase the number of important resonances and can cause chaotic orbits even for relatively small amplitude waves. In contrast, in the case of non-resonant perturbations, orbital phase averaging reduces transport. Here, large field perturbations introduce additional effects, including nonlinear resonances at fractional values of the orbital motion. In summary, large orbits are a blessing and a curse: For non-resonant modes, orbit-averaging reduces transport but, for resonant transport, large orbits facilitate jumps across topological boundaries and enhance the number of important resonances.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Volatility Basis Set Distributions and Viscosity of Organic Aerosol Mixtures: Insights from Chemical Characterization Using Temperature-Programmed Desorption–Direct Analysis in Real-Time High-Resolution Mass Spectrometry

Quantitative assessment of gas-particle partitioning of individual components within complex atmospheric organic aerosols (OA) mixtures is critical for predicting and comprehending the formation and evolution of OA particles in the atmosphere. This investigation leverages previously documented data obtained through a temperature programmed desorption - direct analysis in real time – high resolution mass spectrometry (TPD-DART-HRMS) platform. This methodology facilitates the bottom-up construction of volatility basis set (VBS) distributions for constituents found in three biogenic secondary organic aerosol (SOA) mixtures produced through the ozonolysis of a-pinene, limonene, and ocimene. The apparent enthalpies (ΔH*, kJ mol -1 ) and saturated vapor mass concentrations (C T *, µg∙m -3 ) of individual SOA components, determined as a function of temperature (T, K), facilitated an assessment of changes in VBS distributions and gas-particle partitioning with respect to T and atmospheric total organic mass loadings (tOM, µg∙m -3 ). Further, the VBS distributions reveal distinct differences in volatilities among monomers, dimers, and trimers, enabling their categorization into separate volatility bins. At the ambient temperature of T = 298 K, only monomers efficiently partition between gas and particle phases across a broad range of atmospherically relevant total organic mass loadings (tOM) values of 1–100 µg∙m -3 . Partitioning of dimers and trimers becomes notable only at T > 360 K and T > 420 K, respectively. The viscosity of SOA mixtures is assessed using a bottom-up calculation approach, incorporating the input of elemental formulas, ΔH*, C T *, and particle-phase mass fractions of the SOA components. Through this approach, we are able to accurately estimate the variations in SOA viscosity that result from the evaporation of its components. These variations are, in turn, influenced by atmospherically relevant changes in tOM and T. Comparison of the calculated SOA viscosity and diffusivity values with literature reported experimental results shows close agreement, thereby validating the employed calculation approach. These findings underscore the significant potential for TPD-DART-HRMS measurements in enabling the untargeted analysis of organic molecules within OA mixtures. This approach facilitates quantitative assessment of their gas-particle partitioning and allows for the estimation of their viscosity and condensed-phase diffusion, thereby contributing valuable insights to atmospheric models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SDSS-IV MaNGA: The MaNGA Dwarf Galaxy Sample Presentation

We present the MaNGA Dwarf galaxy (MaNDala) Value Added Catalog (VAC), from the final release of the Sloan Digital Sky Survey-IV program. MaNDala consists of 136 randomly selected bright dwarf galaxies with M * < 10 9.1 M ⊙ and M g > -18.5, making it the largest integral field spectroscopy homogeneous sample of dwarf galaxies. We release a photometric analysis of the g, r, and z broadband imaging based on the DESI Legacy Imaging Surveys, as well as a spectroscopic analysis based on the Pipe3D SDSS-IV VAC. Our release includes the surface brightness (SB), geometric parameters, and color profiles, Sérsic fits as well as stellar population properties (such as stellar ages, metallicities, and star formation histories), and emission lines' fluxes within the FOV and the effective radii of the galaxies. We find that the majority of the MaNDala galaxies are star-forming late-type galaxies with $\langle$n Sersic,r $\rangle$ ~ 1.6 that are centrals (central/satellite dichotomy). MaNDala covers a large range of SB values (we find 11 candidate ultra-diffuse galaxies and three compact ones), filling the gap between classical dwarfs and low-mass galaxies in the Kormendy Diagram and in the size–mass/luminosity relation, which seems to flatten at 10 8 < M * /M ⊙ < 10 9 with $\langle$R e,r $\rangle$ ~ 2.7 kpc. A large fraction of MaNDala galaxies formed from an early low-metallicity burst of SF, but also from late SF events from more metal-enriched gas: half of the MaNDala galaxies assembled 50% of their mass at $\langle$z$\rangle$ > 2, while the last 20% was at $\langle$z$\rangle$ < 0.3. Finally, a bending of the sSFR-M * relation at M * ~ 10 9 M ⊙ for the main-sequence galaxies seems to be supported by MaNDala.

79 ASTRONOMY AND ASTROPHYSICS↗

Constraints on the origin of the radio synchrotron background via angular correlations

ABSTRACT The origin of the radio synchrotron background (RSB) is currently unknown. Its understanding might have profound implications in fundamental physics or might reveal a new class of radio emitters. In this work, we consider the scenario in which the RSB is due to extragalactic radio sources and measure the angular cross-correlation of Low-Frequency Array (LOFAR) images of the diffuse radio sky with matter tracers at different redshifts, provided by galaxy catalogues and cosmic microwave background lensing. We compare these measured cross-correlations to those expected for models of RSB sources. We find that low-redshift populations of discrete sources are excluded by the data, while higher redshift explanations are compatible with available observations. We also conclude that at least 20 per cent of the RSB surface brightness level must originate from populations tracing the large-scale distribution of matter in the Universe, indicating that at least this fraction of the RSB is of extragalactic origin. Future measurements of the correlation between the RSB and tracers of high-redshift sources will be crucial to constraining the source population of the RSB.

79 ASTRONOMY AND ASTROPHYSICS↗

A consistent and conservative model and its scheme for N -phase- M -component incompressible flows

Here, we propose a consistent and conservative model for multiphase and multicomponent incompressible flows, where there can be arbitrary numbers of phases and components. Each phase has a background fluid called the pure phase, each pair of phases is immiscible, and components are dissolvable in some specific phases. The model is developed based on the multiphase Phase-Field model including the contact angle boundary condition, the diffuse domain approach, and the analyses on the proposed consistency conditions for multiphase and multicomponent flows. The model conserves the mass of individual pure phases, the amount of each component in its dissolvable region, and thus the mass of the fluid mixture, and the momentum of the flow. It ensures that no fictitious phases or components can be generated and that the summation of the volume fractions from the Phase-Field model is unity everywhere so that there is no local void or overfilling. It satisfies a physical energy law and it is Galilean invariant. A corresponding numerical scheme is developed for the proposed model, whose formal accuracy is 2nd-order in both time and space. It is shown to be consistent and conservative and its solution is demonstrated to preserve the Galilean invariance and energy law. Numerical tests indicate that the proposed model and scheme are effective and robust to study various challenging multiphase and multicomponent flows.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗