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At least 469 records · Page 26

Upcycling Polyethylene Waste Into Hybrid Graphitic Porous Carbon Materials Used in High-Performance Zinc-Ion Hybrid Capacitors

Polyethylene (PE) waste is a challenge to upcycle into useful materials because this plastic tends to decompose into volatile compounds when heated at relatively low temperatures. In this work, we report a chemical process that addresses this challenge by converting mixtures of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE) waste into a hybrid graphitic porous carbon (HGPC) that can be used as a zinc-ion hybrid capacitor cathode. The process uses a low temperature thermal oxidation pre-treatment step, with assistance of an inert solid additive (KCl) to increase the effective surface area of the PE melt, to functionalize, cross-link, and stabilize the PE waste followed by carbonization and catalytic graphitization steps at higher temperatures with a potassium carbonate (K2CO3) catalyst. The PE waste derived HPGC (PW-HPGC) has a hybrid structure composed of graphene-like carbon nanosheets grown on the surface of carbon particles, high porosity with the Brunauer–Emmett–Teller (BET) specific surface area up to 1,763 m2g-1, and good graphitic degree with average Raman I2D/IG ratios of 0.53. When used as a cathode material for zinc-ion hybrid capacitors, this PW-HGPC exhibits an excellent specific capacity up to 126.7 mAhg-1 at high mass loading of 10 mgcm-2. Moreover, PW-HGPC exhibits remarkable cycling stability with capacity retention of >94% after 10,000 cycles at a current density of 2.0 A g-1.

hybrid graphitic porous carbon↗

Rao-Blackwellization for Adaptive Gaussian Sum Nonlinear Model Propagation

When dealing with imperfect data and general models of dynamic systems, the best estimate is always sought in the presence of uncertainty or unknown parameters. In many cases, as the first attempt, the Extended Kalman filter (EKF) provides sufficient solutions to handling issues arising from nonlinear and non-Gaussian estimation problems. But these issues may lead unacceptable performance and even divergence. In order to accurately capture the nonlinearities of most real-world dynamic systems, advanced filtering methods have been created to reduce filter divergence while enhancing performance. Approaches, such as Gaussian sum filtering, grid based Bayesian methods and particle filters are well-known examples of advanced methods used to represent and recursively reproduce an approximation to the state probability density function (pdf). Some of these filtering methods were conceptually developed years before their widespread uses were realized. Advanced nonlinear filtering methods currently benefit from the computing advancements in computational speeds, memory, and parallel processing. Grid based methods, multiple-model approaches and Gaussian sum filtering are numerical solutions that take advantage of different state coordinates or multiple-model methods that reduced the amount of approximations used. Choosing an efficient grid is very difficult for multi-dimensional state spaces, and oftentimes expensive computations must be done at each point. For the original Gaussian sum filter, a weighted sum of Gaussian density functions approximates the pdf but suffers at the update step for the individual component weight selections. In order to improve upon the original Gaussian sum filter, Ref. [2] introduces a weight update approach at the filter propagation stage instead of the measurement update stage. This weight update is performed by minimizing the integral square difference between the true forecast pdf and its Gaussian sum approximation. By adaptively updating each component weight during the nonlinear propagation stage an approximation of the true pdf can be successfully reconstructed. Particle filtering (PF) methods have gained popularity recently for solving nonlinear estimation problems due to their straightforward approach and the processing capabilities mentioned above. The basic concept behind PF is to represent any pdf as a set of random samples. As the number of samples increases, they will theoretically converge to the exact, equivalent representation of the desired pdf. When the estimated qth moment is needed, the samples are used for its construction allowing further analysis of the pdf characteristics. However, filter performance deteriorates as the dimension of the state vector increases. To overcome this problem Ref. [5] applies a marginalization technique for PF methods, decreasing complexity of the system to one linear and another nonlinear state estimation problem. The marginalization theory was originally developed by Rao and Blackwell independently. According to Ref. [6] it improves any given estimator under every convex loss function. The improvement comes from calculating a conditional expected value, often involving integrating out a supportive statistic. In other words, Rao-Blackwellization allows for smaller but separate computations to be carried out while reaching the main objective of the estimator. In the case of improving an estimator's variance, any supporting statistic can be removed and its variance determined. Next, any other information that dependents on the supporting statistic is found along with its respective variance. A new approach is developed here by utilizing the strengths of the adaptive Gaussian sum propagation in Ref. [2] and a marginalization approach used for PF methods found in Ref. [7]. In the following sections a modified filtering approach is presented based on a special state-space model within nonlinear systems to reduce the dimensionality of the optimization problem in Ref. [2]. First, the adaptive Gaussian sum propagation is explained and then the new marginalized adaptive Gaussian sum propagation is derived. Finally, an example simulation is presented.

state estimation↗

A direct method for the solution of unsteady two-dimensional incompressible Navier-Stokes equations

The unsteady incompressible Navier-Stokes equations are formulated in terms of vorticity and stream function in generalized curvilinear orthogonal coordinates to facilitiate analysis of flow configurations with general geometries. The numerical method developed solves the conservative form of the transport equation using the alternating-direction implicit method, whereas the stream-function equation is solved by direct block Gaussian elimination. The method is applied to a model problem of flow over a back-step in a doubly infinite channel, using clustered conformal coordinates. One-dimensional stretching functions, dependent on the Reynolds number and the asymptotic behavior of the flow, are used to provide suitable grid distribution in the separation and reattachment regions, as well as in the inflow and outflow regions. The optimum grid distribution selected attempts to honor the multiple length scales of the separated-flow model problem. The asymptotic behavior of the finite-differenced transport equation near infinity is examined and the numerical method is carefully developed so as to lead to spatially second-order accurate wiggle-free solutions, i.e., with minimum dispersive error. Results have been obtained in the entire laminar range for the backstep channel and are in good agreement with the available experimental data for this flow problem.

Ghia, K. N.↗

Insights Into the Hydrology of the Congo Peatlands Through Land Surface Modeling and Data Assimilation

The 16.8 million ha of peatlands in the Cuvette Centrale wetland complex in the Congo Basin is one of the largest peatland regions on Earth but still highly understudied. Understanding the hydrological functioning of these peatlands and the effects of external disturbances thereon remains a major challenge. Recent research suggested fundamental hydrological differences between the Congo peatlands and the well-studied Southeast Asian peatlands. The Congo peatlands have a doming gradient that is up to ten times smaller, and they are influenced by river hydrology to some extent. In this study, we explore the Congo peatland hydrology through land surface modeling and data assimilation. We build upon our recently developed tropical PEATCLSM module (Apers et al., 2022) that was parameterized based on data from Southeast Asian peatlands due to the lack of field data from other tropical peatland regions. In a first step, we derive Congo-specific peat hydraulic and discharge function parameters from a scalar parametrization of water level dynamics in the Congo peatlands, using observed water level data at two locations. These Congo-specific parameters differ considerably from the original literature-based parameters from Southeast Asian peatlands. In a second step, we apply our original and Congo-specific parameters in an assimilation scheme for L-band brightness temperature (Tb) data from the Soil Moisture and Ocean Salinity (SMOS) mission. The data assimilation results are used in two ways. First, the effect of these parameters on the simulated peatland hydrology and the observation-minus-forecast Tb residuals is evaluated. It is hypothesized that the new parameters reduce the previously reported modeling errors over the Congo peatlands and reduce the residuals in Tb as well. Second, we analyze the data assimilation diagnostics to learn about other model improvement possibilities. In preliminary results, we found long periods of temporally autocorrelated total water storage increments (difference of pre- and post-update) that coincided with anomalies in river stages measured upstream of the peatlands. Since PEATLCSM neglects possible river influence, this concurrence suggests that the typically used grid-based approach of land surface models should be combined with a river routing scheme over the Congo peatlands.

Sebastian Apers↗

Shapiro steps and stability of skyrmions interacting with alternating anisotropy under the influence of ac and dc drives

Here we use atomistic simulations to examine the sliding dynamics of a skyrmion in a two-dimensional system containing a periodic one-dimensional stripe pattern of variations between low and high values of the perpendicular magnetic anisotropy. The skyrmion changes in size as it crosses the interface between two anisotropy regions. On applying combined dc and ac driving in either parallel or perpendicular directions, we observe a wide variety of Shapiro steps, Shapiro spikes, and phase-locking phenomena. The phase-locked orbits have two-dimensional dynamics due to the gyrotropic or Magnus dynamics of the skyrmions and are distinct from the phase-locked orbits found for strictly overdamped systems. Along a given Shapiro step when the ac drive is perpendicular to the dc drive, the velocity parallel to the ac drive is locked while the velocity in the perpendicular direction increases with increasing drive to form Shapiro spikes. At the transition between adjacent Shapiro steps, the parallel velocity jumps up to the next step value, and the perpendicular velocity drops. The skyrmion Hall angle shows a series of spikes as a function of increasing dc drive, where the jumps correspond to the transition between different phase-locked steps. At high drives, the Shapiro steps and Shapiro spikes are lost. When both the ac and dc drives are parallel to the stripe periodicity direction, Shapiro steps appear, while if the dc drive is parallel to the stripe periodicity direction and the ac drive is perpendicular to the stripe periodicity, then there are only two locked phases, and the skyrmion motion consists of a combination of sliding along the interfaces between the two anisotropy values and jumping across the interfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Sequential Infiltration Synthesis of Multinary Metal Oxides: The Role of Precursor Diffusion and Reactivity

Understanding volatile metal–organic precursor transport in polymer matrices during sequential infiltration synthesis (SIS) is critical to the design of hybrid materials of tailored composition and uniform structure. Here, we investigate the diffusion and reaction behavior of diethylzinc (DEZ) in poly(methyl methacrylate) (PMMA) matrices with variable indium and zinc incorporation. Unlike conventional SIS where precursors adduct or react directly with the polymer backbone, DEZ shows minimal interaction with PMMA. However, DEZ may interact strongly with In–OH or Zn–OH moieties that are previously incorporated into a PMMA thick film. Using spectroscopic ellipsometry, X-ray photoelectron spectroscopy depth profiling, and EDX line scans, we quantify Zn incorporation as a function of exposure time, polymer thickness, and previous infiltration steps. The Zn distribution evolves from surface-localized to deep within the ∼1 μm thick film with increasing DEZ exposures up to 30 min. A reaction-diffusion model incorporating a hindering factor to capture diffusivity decay due to product accumulation reproduces the Zn depth profile and yields physically meaningful parameters to guide future growth. Furthermore, this study provides a framework for interpreting metal–organic precursor infiltration behavior and highlights the utility of model-guided SIS process design.

diethylzinc↗

High-Temperature Water Adsorption Isotherms and Ambient Temperature Water Diffusion Rates on Water Harvesting Metal–Organic Frameworks

Water adsorption isotherms from 25 to 125 °C were measured for three metal−organic frameworks (MOFs), MOF-303, MOF-LA2-1, and MIL-100(Fe), which are frequently studied for water harvesting applications. The results show how the step in the water adsorption isotherm varies as a function of temperature and detail the combination of pressure and temperature necessary to remove adsorbed water. Furthermore, isobaric−isothermal Gibbs ensemble Monte Carlo simulations performed for MOF-303 shed light on the change in occupation numbers of the different known water adsorption sites with increasing temperature. Additionally, the diffusion rates of water through these materials were measured using concentration swing frequency response, and micropore diffusion was identified as the controlling mechanism. The Darken relation was used to show the dependence of the diffusion rate on the concentration and the impact of the adsorption isotherm slope. The adsorption of water on MOF-LA2-1 is faster than that on MIL-100(Fe). These data show that MOF-LA2-1 with its high-water adsorption capacity, quick adsorption rate, and favorable desorption energetics is a leading candidate for atmospheric water harvesting.

Adsorption↗

Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here, in this work, we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

Choi, Chungseok [Yale Univ., New Haven, CT (United↗

The ionomer as an oxygen evolution reaction promoter: piperidinium’s impact on mechanistic pathways on NiO, IrO 2 , and Fe–NiO

The commercial viability of anion exchange membrane (AEM) electrolysis requires optimization of various stack components, with specific catalyst-ionomer combinations often yielding higher current densities, lowered Tafel slopes, and improved mass activity. In this joint theoretical-experimental study, theoretical calculations detail the impact of Versogen’s piperidinium functional group on the complex, kinetically limiting oxygen evolution reaction, finding that the functional group can act as a promoter of specific steps (O*/O 2 * formation; H 2 O/O 2 desorption with reaction enthalpies ranging between 0.2–0.6 eV at higher coverages of O x H y intermediates) on NiO and NiFeO x catalysts. In particular, Fe sites on the NiFeO x catalyst facilitate concerted mechanisms of O*/O 2 * formation and H 2 O desorption with a low enthalpy of 0.5 eV; O 2 desorption alone requires only 0.3 eV. In contrast, Versogen-IrO 2 results in stronger Ir–O bonds, where the enthalpies for bond breaking (Ir–OH 2 and Ir–O 2 ) are considerably higher (1.4 eV and 1.6 eV, respectively). Rotating disk electrode studies utilized commercially available NiO and IrO 2 and synthesized 7.5 wt % Fe in NiFeO x catalysts in combination with Versogen, a common AEM ionomer, and Nafion, an alternative binder. Electrochemical testing validated the impact of these mechanistic changes on ionomer-catalyst combinations, finding that Versogen particularly activates NiO and NiFeO x compared to IrO 2 . Following a 13.5 h hold at 1.8 V, mass activities and Tafel slopes improved to 34 ± 13 A g −1 and 79 ± 2 mV dec −1 (NiO) and 82 ± 4.9 A g −1 and 72 ± 2 mV dec −1 (NiFeO x ). In contrast, Versogen-IrO 2 only reached 17 ± 2.9 A g −1 and 81 ± 3 mV dec −1 . Optimization of the ionomer-catalyst can yield significant increases in performance from initial activity and after an electrochemical conditioning procedure: this enhancement to the mass activity resulted in a 200.9 ± 106.1% improvement for Versogen-NiFeO x and 1284.2 ± 260.5% for Versogen-NiO. In contrast, Nafion-NiFeO x and -NiO offered moderate improvements of 39.1 ± 30.5% and 120.9 ± 59.1%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Masked Particle Modeling on Sets: Towards Self-Supervised High Energy Physics Foundation Models

Abstract We propose masked particle modeling (MPM) as a self-supervised method for learning generic, transferable, and reusable representations on unordered sets of inputs for use in high energy physics (HEP) scientific data. This work provides a novel scheme to perform masked modeling based pre-training to learn permutation invariant functions on sets. More generally, this work provides a step towards building large foundation models for HEP that can be generically pre-trained with self-supervised learning and later fine-tuned for a variety of down-stream tasks. In MPM, particles in a set are masked and the training objective is to recover their identity, as defined by a discretized token representation of a pre-trained vector quantized variational autoencoder. We study the efficacy of the method in samples of high energy jets at collider physics experiments, including studies on the impact of discretization, permutation invariance, and ordering. We also study the fine-tuning capability of the model, showing that it can be adapted to tasks such as supervised and weakly supervised jet classification, and that the model can transfer efficiently with small fine-tuning data sets to new classes and new data domains.

Heinrich, Lukas (ORCID:0000000240487584)↗

UDP-glucuronic acid decarboxylase in alfalfa: a target to improve ruminal digestibility of stems

Alfalfa (Medicago sativa) has a high nutritional value, but poor digestibility of the stems limits its value as an energy source in ruminant diets. Xylan and lignin negatively affect cell wall digestibility, whereas pectins have high digestibility in the rumen. In plants, UDP-xylose synthase (UXS) catalyses the decarboxylation of UDP-glucuronic acid to form UDP-xylose in an irreversible step that is key for xylan synthesis. Here, we functionally characterized two UXS genes in alfalfa, namely MsaUXS2 and MsaUXS4, and investigated their impact on ruminal digestibility. Both genes are more highly expressed in stems than leaves, and the enzymes have UDP-glucuronic acid decarboxylase activity in vitro. Silencing of MsaUXS2 and MsaUXS4 via RNAi altered plant growth and resulted in a 40% decrease in xylose, a 115% increase in arabinose, and a 60% increase in galacturonic acid in the polysaccharide matrix as well as a 20% decrease in lignin in the cell wall. Together, our results show a major role for UXS2 and UXS4 in xylan synthesis and secondary cell wall deposition in alfalfa. Additionally, in vitro rumen digestibility assays for the silenced lines had on average 30% increased gas production at 24 h, demonstrating the potential of targeting UXS genes to increase stem digestibility.

UDP-xylose synthase↗

Dynamic Temporal Graph Sequence Data for Resilience-Oriented Distribution Network Reconfiguration

This dataset comprises temporal dynamic graph sequences generated from power grid simulations focused on grid reconfiguration to enhance resilience. The simulations model failure propagation under varying conditions, with nodes assigned distinct failure probabilities. For each time step, the dataset captures the evolution of node states (functional or failed) and features critical to grid operations, such as pv_output, load_profile, load_dispatch, dg_output, loss, and voltage. Node types include sources, normal loads, and nodes with specific equipment like PVs, micro turbines, or shunt capacitors. The dataset is structured to support the training of dynamic graph neural networks, facilitating research on node feature prediction and edge dynamics under failure scenarios. Three distinct configurations are included, providing a robust foundation for modeling power grid resilience.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Non-contact Real-time Target Health Monitor

Targets are an essential part of many accelerator-based experiments, yet their constant radiation exposure eventually affects their internal structure and, consequently, their properties. Current methods typically involve either direct contact with the target or complete removal of the system, which may not be the most efficient for assessing radiation damage. For this reason, a system has been proposed that will monitor a target s radiation damage without the need for direct contact or removal. This sensor will achieve this by measuring the reflectivity of S- and P-polarized waves, which are expected to change measurably due to radiation-induced alterations. As is commonly done, smaller-scale tests were performed to ensure that the necessary equipment was functioning correctly. Once all equipment is tested, the next step will be to perform reflectivity measurements using a tungsten sample, a material often used in targets. Longer-term work will involve scaling up the system and implementing higher-energy beams. This sensor will enable a more comprehensive study of radiation damage in materials and is being considered for projects such as Mu2e, Mu2e-II, LBNF, AMF, and muon colliders.

Agosto Reyes, Alanice↗

Aerospace technology development of three types of solid state remote power controllers for 120VDC with current ratings of five, and thirty amperes, one type having current limiting

The first generation of remote power controllers (RPC) developed included: a 5-ampere design (Type 1), capable of limiting maximum overload current to 15 amperes for .1 sec; and 5-ampere noncurrent (Type 2) and 30-ampere noncurrent (Type 3) limiting designs, both with selectable instant trip levels for high-current overload. Each design provides overcurrent protection through an inverse I squared T trip-out function with an automatic reset option and demonstrates step-applied fault capability with a 4000-ampere surge, fast-risetime (low-inductance) power source. They also meet MIL - STD - 461A specification for electromagnetic interference. The second generation RPCs traded off specification compliance for reduction in cost and complexity for the Type 1 and 2 designs and give comparable or improved performance in most areas. The noncurrent limiting RPC proved to be a more economical and feasible method of overload protection for certain load types.

Baker, D. E.↗

A finite difference solution for the propagation of sound in near sonic flows

An explicit time/space finite difference procedure is used to model the propagation of sound in a quasi one-dimensional duct containing high Mach number subsonic flow. Nonlinear acoustic equations are derived by perturbing the time-dependent Euler equations about a steady, compressible mean flow. The governing difference relations are based on a fourth-order, two-step (predictor-corrector) MacCormack scheme. The solution algorithm functions by switching on a time harmonic source and allowing the difference equations to iterate to a steady state. The principal effect of the non-linearities was to shift acoustical energy to higher harmonics. With increased source strengths, wave steepening was observed. This phenomenon suggests that the acoustical response may approach a shock behavior at at higher sound pressure level as the throat Mach number aproaches unity. On a peak level basis, good agreement between the nonlinear finite difference and linear finite element solutions was observed, even through a peak sound pressure level of about 150 dB occurred in the throat region. Nonlinear steady state waveform solutions are shown to be in excellent agreement with a nonlinear asymptotic theory.

Hariharan, S. I.↗

A finite difference solution for the propagation of sound in near sonic flows

An explicit time/space finite difference procedure is used to model the propagation of sound in a quasi one-dimensional duct containing high Mach number subsonic flow. Nonlinear acoustic equations are derived by perturbing the time-dependent Euler equations about a steady, compressible mean flow. The governing difference relations are based on a fourth-order, two-step (predictor-corrector) MacCormack scheme. The solution algorithm functions by switching on a time harmonic source and allowing the difference equations to iterate to a steady state. The principal effect of the non-linearities was to shift aocustical energy to higher harmonics. With increased source strength, wave steepening was observed. This phenomenon suggests that the acoustical response may approach a shock behavior at higher sound pressure level as the throat Mach number approaches unity. On a peak level basis, good agreement between the nonlinear finite difference and linear finite element solutions was observed, even through a peak sound pressure level of about 150 dB occurred in the throat region. Nonlinear steady state waveform solutions are shown to be in excellent agreement with a nonlinear asymptotic theory. Previously announced in STAR as N83-30167

Hariharan, S. I.↗

Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

Dissimilatory sulfur metabolism in phototrophic sulfur bacteria provides the bacteria with electrons for photosynthetic electron transport chain and, with energy. Assimilatory sulfate reduction is necessary for the biosynthesis of sulfur-containing cell components. Sulfide, thiosulfate, and elemental sulfur are the sulfur compounds most commonly used by phototrophic bacteria as electron donors for anoxygenic photosynthesis. Cytochromes or other electron transfer proteins, like high-potential-iron-sulfur protein (HIPIP) function as electron acceptors or donors for most enzymatic steps during the oxidation pathways of sulfide or thiosulfate. Yet, heme- or siroheme-containing proteins themselves undergo enzymatic activities in sulfur metabolism. Sirohemes comprise a porphyrin-like prosthetic group of sulfate reductase. eenzymatic reactions involve electron transfer. Electron donors or acceptors are necessary for each reaction. Cytochromes and iron sulfur problems, are able to transfer electrons.

Fischer, U.↗

Precise solution for a finite set of spherical coefficients from equiangular gridded data

An important goal of geodesy is to determine the anomalous potential and its derivatives outside of the earth. Representing the surface anomalies by a series of spherical harmonics is useful since it is then possible to do a term by term solution of Laplace's equation and upward continuation. The problem of finding such a spherical harmonic series for anomaly values given on an equiangular surface grid is addressed. (This is a first step toward the more complicated problem of finding a function such that locally averaged values fit a grid of mean anomalies.) Three approaches to this fitting problem are discussed and compared: the discrete Fourier technique, the discrete integral technique, and a new approach. The peculiar nature of the equiangular grid, with its increasing density of (noisy) data toward the poles, causes each method to exhibit a different type of difficulty. The new method is shown to be practical as well as precise since the numerical conditioning problems which appear can be successfully handled by such well-known techniques as a (simple) Kalman filter.

Zucker, Paul A.↗