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At least 559 records · Page 31

Data-driven predictions of complex organic mixture permeation in polymer membranes

Membrane-based organic solvent separations are rapidly emerging as a promising class of technologies for enhancing the energy efficiency of existing separation and purification systems. Polymeric membranes have shown promise in the fractionation or splitting of complex mixtures of organic molecules such as crude oil. Determining the separation performance of a polymer membrane when challenged with a complex mixture has thus far occurred in an ad hoc manner, and methods to predict the performance based on mixture composition and polymer chemistry are unavailable. Here, we combine physics-informed machine learning algorithms (ML) and mass transport simulations to create an integrated predictive model for the separation of complex mixtures containing up to 400 components via any arbitrary linear polymer membrane. We experimentally demonstrate the effectiveness of the model by predicting the separation of two crude oils within 6-7% of the measurements. Integration of ML predictors of diffusion and sorption properties of molecules with transport simulators enables for the rapid screening of polymer membranes prior to physical experimentation for the separation of complex liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elemental zoning enhances mass transport in zeolite catalysts for methanol to hydrocarbons

Mass transport limitations in zeolite catalysts pose major hurdles for their optimal performance in diverse chemical reactions. Most approaches to reduce these restrictions focus on the synthesis of either hierarchical or nanosized zeolites. Here we demonstrate that the existence of a siliceous, catalytically inactive exterior rim on ZSM-5 particles dramatically reduces the diffusion limitations, which leads to an enhanced catalyst lifetime for the methanol-to-hydrocarbon reaction. In this study, our findings reveal that binary inorganic and organic structure-directing agents enable a one-pot synthesis of Si-zoned ZSM-5 catalysts with diffusion properties that are characteristic of particles with a much smaller size. Operando ultraviolet–visible light diffuse reflectance spectroscopy reveals a marked reduction in external coking among Si-zoned samples. Molecular dynamics simulations to assess the diffusion of methanol and benzene in siliceous pores and in those with Brønsted acids reveal substantially reduced transport limitations in zoned regions, consistent with the improved catalyst activity of Si-zoned zeolites relative to that of ZSM-5 with a homogeneous acid-site distribution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

511 keV excess and primordial black holes

An excess of 511 keV photons has been detected from the central region of the Milky Way. It has been suggested that the positrons responsible for this signal might be produced through the Hawking evaporation of primordial black holes. After evaluating the constraints from INTEGRAL, COMPTEL, and Voyager 1, we find that black holes in mass range of ~ ( 1 - 4 ) × 10 16 g could potentially produce this signal if they make up a small fraction of the total dark matter density. Proposed MeV-scale gamma-ray telescopes such as AMEGO or e-ASTROGAM should be able to test this class of scenarios by measuring the diffuse gamma ray emission from the Milky Way’s inner halo.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Characterization of n-Type Iodine-Doped and Indium-Doped CdTe/Cd-Se-Te Thin Films Fabricated by Close-Spaced Sublimation Epitaxy

In this study, n-type CdTe thin films, specifically iodine-doped CdTe (CdTe:I), indium-doped CdTe (CdTe:In), and indium-doped Cd-Se-Te (CST:In), were synthesized using close-spaced sublimation epitaxy (CSSE). Characterization techniques secondary ion mass spectrometry (SIMS), electron backscatter diffraction (EBSD), Hall-effect measurements, and time-resolved photoluminescence (TRPL) were employed to analyze the chemical, structural, and electronic properties of these materials. The results indicated epitaxial single crystal CSSE films grew on the single crystal substrates, with carrier density ranging from 10^14 - 10^16 cm -3 , and after post-annealing, the minority-carrier lifetimes reach near the radiative limit. Additionally, a preliminary exploration of homojunction structures with an n- type (CdTe:In /CST:In /CdTe:I) /CdTe:P /Cu /Mo configuration was performed. The best device performance was achieved with CdTe:I including CdS aiding in band alignment, resulting in a power conversion efficiency (..eta..) of 2.61% with open circuit voltage (Voc) of 850 mV, fill factor (FF) of 47.8%, and short-circuit current (Jsc) of 6.44 mA/cm 2 . The observed low Jsc and efficiency may be attributed to a buried junction and a poor interface, due to dopant interdiffusion. Consequently, further investigations focusing on interface optimization, diffusion blocking, and reduced recombination through passivation, are crucial to enhancing the efficiency of CSSE CdTe homojunction devices in the future.

cadmium compounds↗

MASCOT: molecular gas depletion times and metallicity gradients – evidence for feedback in quenching active galaxies

ABSTRACT We present results from the first public data release of the MaNGA-ARO Survey of CO Targets (MASCOT), focusing our study on galaxies whose star formation rates and stellar masses place them below the ridge of the star-forming main sequence. In optically selected type 2 AGN/low-ionization nuclear emission regions (LINERs)/Composites, we find an empirical relation between gas-phase metallicity gradients ∇Z and global molecular gas depletion times $t_{\rm dep} = M_{\rm H_2} /{\rm SFR}$ with ‘more quenched’ systems showing flatter/positive gradients. Our results are based on the O3N2 metallicity diagnostic (applied to star-forming regions within a given galaxy), which was recently suggested to also be robust against emission by diffuse ionized gas (DIG) and LINERs. We conduct a systematic investigation into possible drivers of the observed ∇Z − tdep relation (ouflows, gas accretion, in situ star formation, mergers, and morphology). We find a strong relation between ∇Z or tdep and centralized outflow strength traced by the [O iii] velocity broadening. We also find signatures of suppressed star formation in the outskirts in AGN-like galaxies with long depletion times and an enhancement of metals in the outer regions. We find no evidence of inflows impacting the metallicity gradients, and none of our results are found to be significantly affected by merger activity or morphology. We thus conclude that the observed ∇Z–tdep relation may stem from a combination of metal redistribution via weak feedback, and a connection to in situ star formation via a resolved mass-metallicity–SFR relation.

Astronomy & Astrophysics↗

Degradation of Adsorbed Bisphenol A by Soluble Mn(III)

Bisphenol A (BPA), a high production volume chemical and potential endocrine disruptor, is found to be associated with sediments and soils due to its hydrophobicity (log K OW of 3.42). Here, we used superfine powdered activated carbon (SPAC) with a particle size of 1.38 ± 0.03 μm as a BPA sorbent and assessed degradation of BPA by oxidized manganese (Mn) species. SPAC strongly sorbed BPA, and desorption required organic solvents. No degradation of adsorbed BPA (278.7 ± 0.6 mg BPA g –1 SPAC) was observed with synthetic, solid α-MnO 2 with a particle size of 15.41 ± 1.35 μm; however, 89% mass reduction occurred following the addition of 0.5 mM soluble Mn(III). Small-angle neutron scattering data suggested that both adsorption and degradation of BPA occurred in SPAC pores. The findings demonstrate that Mn(III) mediates oxidative transformation of dissolved and adsorbed BPA, the latter observation challenging the paradigm that contaminant desorption and diffusion out of pore structures are required steps for degradation. Soluble Mn(III) is abundant near oxic-anoxic interfaces, and the observation that adsorbed BPA is susceptible to degradation has implications for predicting, and possibly managing, the fate and longevity of BPA in environmental systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A higher-order finite element reactive transport model for unstructured and fractured grids

Abstract This work presents a new reactive transport framework that combines a powerful geochemistry engine with advanced numerical methods for flow and transport in subsurface fractured porous media. Specifically, the PhreeqcRM interface (developed by the USGS) is used to take advantage of a large library of equilibrium and kinetic aqueous and fluid-rock reactions, which has been validated by numerous experiments and benchmark studies. Fluid flow is modeled by the Mixed Hybrid Finite Element (FE) method, which provides smooth velocity fields even in highly heterogenous formations with discrete fractures. A multilinear Discontinuous Galerkin FE method is used to solve the multicomponent transport problem. This method is locally mass conserving and its second order convergence significantly reduces numerical dispersion. In terms of thermodynamics, the aqueous phase is considered as a compressible fluid and its properties are derived from a Cubic Plus Association (CPA) equation of state. The new simulator is validated against several benchmark problems (involving, e.g., Fickian and Nernst-Planck diffusion, isotope fractionation, advection-dispersion transport, and rock-fluid reactions) before demonstrating the expanded capabilities offered by the underlying FE foundation, such as high computational efficiency, parallelizability, low numerical dispersion, unstructured 3D gridding, and discrete fraction modeling.

58 GEOSCIENCES↗

Isotope effects on transport in LHD

Abstract Isotope effects are one of the most important issues for predicting future reactor operations. Large helical device (LHD) is the presently working largest stellarator/helical device using super conducting helical coils. In LHD, deuterium experiments started in 2017. Extensive studies regarding isotope effects on transport have been carried out. In this paper, the results of isotope effect studies in LHD are reported. The systematic studies were performed adjusting operational parameters and nondimensional parameters. In L mode like normal confinement plasma, where internal and edge transport barriers are not formed, the scaling of global energy confinement time ( τ E ) with operational parameters shows positive mass dependence ( M 0.27 ; where M is effective ion mass) in electron cyclotron heating plasma and no mass dependence ( M 0.0 ) in neutral beam injection heating plasma. The non-negative ion mass dependence is anti-gyro-Bohm scaling. The role of the turbulence in isotope effects was also found by turbulence measurements and gyrokinetic simulation. Better accessibility to electron and ion internal transport barrier (ITB) plasma is found in deuterium (D) plasma than in hydrogen (H). Gyro kinetic non-linear simulation shows reduced ion heat flux due to the larger generation of zonal flow in deuterium plasma. Peaked carbon density profile plays a prominent role in reducing ion energy transport in ITB plasma. This is evident only in plasma with deuterium ions. New findings on the mixing and non-mixing states of D and H particle transports are reported. In the mixing state, ion particle diffusivities are higher than electron particle diffusivities and D and H ion density profiles are almost identical. In the non-mixing state, ion particle diffusivity is much lower than electron diffusivity. Deuterium and hydrogen ion profiles are clearly different. Different turbulence structures were found in the mixing and non-mixing states suggesting different turbulence modes play a role.

Physics↗

Intrinsic kinetics of water-inhibited ultra-lean methane oxidation over PtPd-Mg/ θ -Al 2 O 3 catalyst

Here, this study develops intrinsic methane oxidation kinetics for ultra-lean methane conditions in the presence of water over a highly active and stable PtPd–Mg/θ-Al 2 O 3 catalyst. Comprehensive laboratory experiments were conducted over a wide range of methane concentrations (150–1200 ppm CH 4 ), water contents (1–5% H 2 O), and industrially relevant space velocities (80,000 ≤ GHSV ≤ 160,000 h -1 ). These systematic experiments informed a two-dimensional, axisymmetric, multiscale reactor model that was used to develop and validate methane oxidation kinetics under practically relevant conditions, including non-isothermal operation and high conversion regimes. Combined experimental and modeling results revealed significant intraparticle diffusion resistance and transport-induced reaction exotherm at elevated temperatures, which limited catalyst utilization despite high intrinsic activity. These transport effects were explicitly incorporated into the reactor model, enabling accurate estimation of intrinsic kinetic parameters without reliance on conventional effectiveness-factor corrections. The resulting kinetic model successfully captured both kinetically controlled and mass-transfer-limited regimes and reliably predicted CH 4 conversion across broad ranges of temperature, methane concentration, and water content

Heat and mass transfer limitations↗

Analysis of furnace contamination on superconducting radio frequency niobium using secondary-ion mass spectrometry

Detection of surface contamination on niobium materials used in superconducting radio frequency (SRF) applications is difficult due to quantitative sensitivity and near-atomic depth resolution needed. Inspection of samples known to have experienced surface contamination was found to have inconsistent nitride coverage after high-temperature nitrogen gas exposure (“doping”). Here we compare contaminating species found on samples treated in several different vacuum furnaces, both “exposed” directly in the chamber and “protected” by containment shielding from evaporative sources with “furnace caps.” Typically, furnace caps are used to impede contamination from reaching the interior surface of cavities during the high-temperature vacuum bake that immediately precedes exposure to nitrogen gas. Although, to date, little is known about the effectiveness of these caps, SIMS results showed that they were effective in limiting contamination arising from the furnace environment. Inspection of sample surfaces by SEM showed a lack of nitrides present on contaminated specimens. TEM with energy dispersive spectroscopy performed on these samples revealed that a carbon-rich layer now existed, indicating that a relatively high contaminant load prevents the nucleation and growth of surface nitrides, while thus inhibiting interstitial nitrogen uptake. Except in extreme cases, subsequent removal of the top several micrometers of the surface via electropolishing appears to effectively eliminate any strong influence on the subsequent SRF cavity performance. With the absence of furnace cleaning, carbon contamination was found to be nearly 10× higher for protected nitrogen-doped and electropolished samples, with minimal metallic contamination detected for both processes. SIMS analysis was also performed to compare the cleanliness of samples fully prepared by such nitrogen “doping” with those prepared by a related process, involving the dissolution of niobium surface oxide and diffusion of oxygen into the surface. This oxygen doping or alloying process offers attractive advantages.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ductility evaluation of nitrided Zircaloy-4 cladding by ring compression testing

Here, this study evaluated the embrittlement of Zircaloy-4 cladding by dry air and dry nitrogen environments as a function of process temperature and duration of exposure. A Netzsch thermogravimetric analyzer was used to measure the mass gain of cladding sections over time with specified temperature and gas flow programs. Oxidation of Zircaloy in dry air produced a brittle ZrO 2 layer with ductile unreacted metal. In contrast, nitridation of Zircaloy had a slower reaction rate but produced a brittle cladding that was more easily breached during ring compression tests. The ring compression tests demonstrated that ductility of Zircaloy cladding decreases as nitrogen pickup increases; a ductile-to-brittle transition occurs near a mass gain of 2.1 wt %. Nitridation showed minimal temperature dependency in ductility degradation, whereas oxidation showed significant temperature dependency in ductility degradation, with severe embrittlement occurring at 1200 °C. Optical micrographs confirmed the formation of uniform ZrN layers (approximately 12 µm thick) on the cladding surface, indicating that cladding embrittlement is primarily the result of nitrogen diffusion rather than metal layer thinning.

36 MATERIALS SCIENCE↗

The Role of the Toroidal Vortex in Cumulus Clouds' Entrainment and Mixing

Abstract Shallow convective clouds play a crucial role in Earth's energy budget, as they modulate the radiative transfer in the atmosphere and participate in the vertical transport of aerosols, energy, and humidity. The parameterizations representing these complex, vital players in weather and climate models are mostly based on a description of steady‐state plumes and are a source of major uncertainty. Recently, several studies have shown that buoyant thermals are inherent in atmospheric convection and contain a toroidal (ring) vortex. This work studies those vortices in growing shallow cumulus (Cu) clouds using high‐resolution (10 m) Large Eddy Simulations that resolve these vortices in much detail. Recent analysis of such data showed that small‐scale turbulent diffusion is unable to explain the large diluted portion of the cloud. Here we advocate for the important role of the Cu toroidal vortex (TV) in cloud dilution and present the complex dynamics and structure of a Cu TV. Nevertheless, since the vortex dominates the cloud's dilution, simplicity emerges when considering the cloud's lateral mass flux profile. The cloud mixing is quantified using direct flux calculations and Eulerian tracers. In addition, Lagrangian tracers are used to identify the origin of the entrained air and its thermodynamic properties. It shows that most of the air entrained by the vortex is not recycled by the vortex, yet is significantly more humid than the environment. We suggest that the development of new models describing thermals, together with their toroidal vortices, might improve cloud parameterizations in weather and climate models.

Meteorology & Atmospheric Sciences↗

Unveiling the Role of Critical Impurities in Spent LiFePO 4 Cathodes for Scalable Direct Regeneration

Direct regeneration offers a promising alternative to recycling End-of-Life (EoL) batteries by restoring metal elements and preserving the material structure, yet scaling these technologies to handle practical cathode black mass (CBM) with impurities remains challenging. Here, this study investigates the evolution of impurities, including aluminum (Al), polyvinylidene difluoride (PVDF) binder, and residual carbon (C), during direct recycling of spent LiFePO 4 (LFP) cathodes and their impact on electrochemical performance. Using various ex situ and in situ analyses, it is shown that the formation of lithium fluoride (LiF) during the traditional direct recycling process hinders lithium diffusion and deteriorates the reversible capacity. To address this major challenge, the combination of pH-controlled hydrothermal purification and the two-step sintering process is proposed effectively to regenerate spent LFP cathodes, eliminating the negative effect of Al and fluorine (F) impurities while mitigating any potential impacts of carbon residuals. The regenerated LFP from spent CBM achieves superior performance, retaining 152.5 mAh g −1 at 0.1 C and 133 mAh g −1 at 1 C with 98.7% capacity retention after 200 cycles. This approach is further validated using three distinct waste feedstocks from battery modules, enhancing impurity management and scalability in direct recycling. These findings present a sustainable and economically viable solution for large-scale LFP regeneration.

25 ENERGY STORAGE↗

Drought-induced changes in groundwater-surface water exchange at Lake Mead area

This study focuses on the Lake Mead region in the southwestern United States, a key water reservoir serving over 25 million people and agricultural lands across several states. The area has experienced recurring anthropogenic droughts since the early 2000s. We investigate the hydrological response of the coupled surface-groundwater system to the 2020–2022 drought, one of the most severe on record. To this end, we use Sentinel-1 Interferometric Synthetic Aperture Radar (InSAR) data to quantify vertical land motion caused by the elastic response of the crust to water-mass loss in the lake vicinity. Next, we apply an inverse elastic load modeling framework to quantify water loss. We further assess possible hydraulic connectivity between Lake Mead and adjacent groundwater reservoirs. We detect ground uplift of up to 8 mm/yr near the lake center, likely due to crustal rebound from reduced water-mass loading. We estimated the total water storage loss at 3.03 ± 0.25 km 3 /yr across a 3150 km 2 area surrounding Lake Mead. Groundwater accounts for approximately a third of that, being 0.94 ± 0.32 km 3 /yr. In addition, observed time lags of 6–98 days between lake and groundwater level responses, corresponding to a lateral diffusivity of 3.2–86 m 2 /s, suggest spatially variable connectivity between the lake and aquifers. These findings highlight that drought impacts propagate through the subsurface within interconnected systems, resulting in reduced buffering capacity of groundwater resources following droughts, and emphasizing the need for more integrated surface and groundwater management strategies to enhance resilience under climate and anthropogenic stressors.

58 GEOSCIENCES↗

Resonant interactions involving local vibrational modes in crystals

When an impurity with a light mass is inserted into a crystal, it can undergo a high-frequency oscillation referred to as a local vibrational mode (LVM). A Fermi resonance may occur between the LVM and lower-frequency modes of the defect. The LVM may also interact with phonons or the electromagnetic field. Understanding these interactions can help model and control diffusion, defect reactions, and thermal conductivity. LVMs have been probed in semiconductors using pressure and alloying as experimental parameters, resulting in anticrossing between localized and extended vibrational modes. Furthermore, these types of vibrational interactions could play an important role in the stability and thermal properties of organic–inorganic hybrid semiconductors. The coupling between an LVM and electromagnetic wave yields an “LVM polariton,” an excitation that has significant vibrational and electric-field amplitudes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Theoretical estimates of flammability bounds for thin condensed fuel diffusion flames in microgravity using detailed models of chemistry and radiation

Recently, U-shape flammability maps have been constructed showing minimal oxygen vs. flame strain for opposed flame spread in micro-gravity by Olson and Ferkul. The U-shape defines the limiting flammability bounds from radiative extinction and flame blow-off. Here, the minimum of the U corresponds to the minimum possible oxidizer concentration where burning can occur, and is an important quantity of interest for fire safety. While high strain extinction bounds have been well analyzed, low strain radiative extinction has not. To estimate low strain extinction, in this study an analytical theory is developed based on thin flame theory coupled with a heat and mass transfer model for solid fuels. A reaction progress variable based on the Damköhler number is adapted in the theory to account for incomplete combustion at high strain rates and enable the capturing of the full flammability map. The analytical model is compared to a one dimensional numerical model w/ detailed chemical kinetics and coupled radiation heat transfer in planar and spherical geometries. The flammability maps are then qualitatively compared to experimental extinguishment data compiled by Olson and Ferkul for cylindrical rods of PMMA showing similar trends. The results show the newly developed analytics capture the radiative extinction bound compared to the numerical model and qualitatively agrees with microgravity data.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Soot and PAH formation in high pressure spray pyrolysis of gasoline and diesel fuels

Time-resolved soot and PAH formation from gasoline and diesel spray pyrolysis are visualized and quantified using diffuse back illumination (DBI) and laser induced fluorescence (LIF) at 355 nm, respectively, in a constant-volume vessel at 60 bar from 1400 to 1700 K for up to 30 ms. The delay, maximum formation rate, and yield of soot and PAHs are compared across fuels and temperatures and correlated with the yield sooting indices on either the mass or mole basis. The delays generally decrease with increasing temperature, and the formation rates of both PAHs and soot generally increase with temperature. The apparent PAH-LIF yield may decrease with temperature due to PAH growth and conversion into larger species, signal trapping, and thermal quneching. Soot yield generally increases with temperature. The mass-based YSI correlates reasonably well with soot delay, but YSI does not correlate well with soot yield. Here, the mass-based YSI is a more appropriate predictor of sooting propensity than the mole-based YSI.

42 ENGINEERING↗

Evaluation of methods for characterizing the fine particulate matter emissions from aircraft and other diffusion flame combustion aerosol sources

The U. S. Environmental Protection Agency in collaboration with the U. S. Air Force Arnold Engineering Development Complex conducted the VAriable Response In Aircraft nvPM Testing (VARIAnT) 3 and 4 test campaigns to compare nvPM emissions measurements from a variety of diffusion flame combustion aerosol sources (DFCASs), including a Cummins diesel engine, a diesel powered generator, two gas turbine start carts, a J85-GE-5 turbojet engine burning multiple fuels, and a Mini-CAST soot generator. The VARIAnT research program has conducted four test campaigns to date with the VARIAnT 3 and 4 test campaigns focusing on BC mass instrument performance, use of gas turbine engine sources for BC mass instrument calibration, and the characterization of the aerosols produced from the combustion sources. Results from both campaigns revealed agreement of about 20% between the AVL Micro-Soot Sensor, the Cavity Attenuated Phase Shift (CAPS PMSSA) monitor and the thermal-optical reference method for elemental carbon (EC), independent of the calibration source used. For the Artium LII-300, the measured mass concentrations in VARIAnT3 fall within 18% and in VARIAnT4 fall within 32% of the reference EC mass concentration when calibrated on a combustor rig in VARIAnT3 and on a LGT-60 start cart in VARIAnT4, respectively. It was also found that the three mass instrument types (MSS, CAPS PMSSA, and LII-300) can exhibit different BC to reference EC ratios depending on the emission source that appear to correlate to particle geometric mean mobility diameter, morphology, or some other parameter associated with particle geometric mean diameter (GMD) with the LII-300 showing a slightly stronger apparent trend with GMD. Systematic differences in LII-300 measured mass concentrations have been reduced by calibrating with a turbine combustion source (combustor or turbine engine). With respect to the particle size measurements made, the sizing instruments (TSI SMPS, TSI EEPS, and Cambustion DMS 500) were found to be in general agreement in terms of size distributions and concentrations with some exceptions. Teflon filter measurements of the total aerosol mass produced by the various DFCASs differed from the reference EC, BC, and integrated particle sized distribution measured aerosol masses. The Teflon filter measured mass was 30 to 40% greater than the reference EC and 50 to 60% greater than the BC mass for the J85 in both test campaigns. The measurements of particle size distributions and single particle analysis by miniSPLAT indicated the presence of large particles (>100 nm) having more compact morphologies, higher effective density, and a composition dominated by OC and ash. This increased large particle fraction is also associated with higher values of single scattering albedo measured by the CAPS PMSSA instrument and higher OC/EC measurements. These measurements indicate gas turbine engine emissions can be a more heterogeneous mix of particle types beyond the original E31 assumption that it is mainly composed of black carbon.

33 ADVANCED PROPULSION SYSTEMS↗