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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 253 records · Page 14

Influence of Silane Coupling Agents on Filler Network Structure and Stress-Induced Particle Rearrangement in Elastomer Nanocomposites

Filled rubber materials are key in many technologies having broad impact on the economy and sustainability, the most obvious being tire technology. Adding filler dramatically improves the strength of rubber by reinforcement and tailoring the type of filler and the chemistry of the interface between filler and rubber matrix is important for optimizing performance metrics such as fuel efficiency. In a highly loaded, silica-filled, crosslinked model rubber closely mimicking commercial materials, both the filler network structure and the dynamics of the silica filler particles change when the silica surface is modified with silane coupling agents. Reduction in size scales characteristic of the structure are quantified using ultra-small-angle X-ray scattering (USAXS) measurements and the particle dynamics probed with X-ray photon correlation spectroscopy (XPCS). While the structure averaged over the scattering volume changes little with aging after step strain, the dynamics slow appreciably in a manner that varies with the treatment of the silica filler. The evolution of filler particle dynamics depends on the chemical functionality at the silica surface and observing these differences suggests a way of thinking about the origins of hysteresis in nanoparticle-reinforced rubbers. These microscopic filler dynamics are correlated with the macroscopic stress relaxation of the filled materials. The combination of static and dynamic X-ray scattering techniques with rheological measurements is a powerful approach for elucidating the microscopic mechanisms of rubber reinforcement.

36 MATERIALS SCIENCE↗

Development of Emergency Vehicle Preemption Strategies on Smart Corridors in a Digital Twin Environment

Emergency Response Vehicles (ERVs), such as firetrucks, ambulances, etc. operate with the purpose of saving lives and mitigating property damage. As such, ERV travel-time reductions may result in significant benefits to the community. A common strategy to improve travel times is Emergency Vehicle Preemption (EVP). EVP seeks to reduce ERV delays by providing the right-of-way to ERVs as they approach an intersection. This study proposes a new Dynamic Preemption strategy that determines the need for preemption prior to the ERV reaching the vicinity of the intersection, utilizing real-time data streams. This paper evaluates the effectiveness of some existing and proposed preempt control strategies using a digital twin testbed consisting of a series of signalized intersections on an urban arterial in Georgia. The best EVP strategy maximizes the improvement in ERV travel time while minimizing the adverse effect of preemption on the traffic in conflicting directions. Therefore, this study evaluates both the positive impact of EVP on the ERV as well as the adverse impact on the cross-street traffic. The study found that the potential exists for significant improvements in ERV travel time with the proposed Dynamic Preemption strategy, with minimal impact to the conflicting traffic. For the simulation corridor there was a 20% reduction in the ERV travel times with the implementation of the Dynamic Preemption strategy, compared to traditional EVP practices.

Roy, Somdut [Georgia Institute of Technology]↗

Modeling oxygen reduction activity loss mechanisms in atomically dispersed Fe–N–C electrocatalysts

Materials degradation is a major factor that limits the wider adoption of renewable and clean energy technologies. This is particularly true for the Pt group metal-free (PGM-free) atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts. Here, while many experimental studies have investigated and reported the phenomenological aspects of M-N-C degradation, only a few modeling studies have considered degradation mechanisms at the atomic level. Understanding the mechanisms responsible for activity loss occurring in atomically dispersed M-N-C’s is crucial towards rationally designing active, durable, and less expensive Earth-abundant catalysts. Towards this end, we have surveyed recent literature concerning the modeling of corrosion mechanisms that impact M-N-C catalysts (Fe–N–C, in particular) and offer our own perspectives on the future direction of this field.

36 MATERIALS SCIENCE↗

Pd-promoted reduction and restructuring of an In 2 O 3 -based catalyst for CO 2 hydrogenation at room temperature

An unconventional reaction mechanism in an In 2 O 3 /Pd(1 1 1) inverse model catalyst for the CO 2 hydrogenation reaction has been uncovered: In 2 O 3 is partially reduced at room temperature in a reaction atmosphere as a result of its direct contact with Pd(1 1 1), which is an efficient H 2 splitter. The reduction induces changes in surface free energy, leading to a dynamical restructuring at the In 2 O 3 /Pd(1 1 1) interface via formation of InO x and outward diffusion of Pd, as revealed by ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and density functional theory simulations. This dynamical restructuring eventually promotes the growth of 2D InPd y O x nanodomains as the catalytically active phase and the exclusive formation of methanol upon hydrogenation of CO 2 at room temperature. A comparable high selectivity toward CH 3 OH was found in more realistic bulk catalytic systems (2 wt% Pd/In 2 O 3 catalyst and commercial CZA catalyst). Scanning tunneling microscopy under ultrahigh vacuum and ambient pressure reaction atmospheres further reveals the structural dynamics at the InO x /Pd(1 1 1) interface, where we follow in situ the evolution of the InO x particles on Pd(1 1 1) and the mobility of the InPd y O x nanodomains in a CO 2 + H 2 environment. The present findings of the formation of a mixed oxide phase in a dynamically restructuring metal/reducible-oxide interface indicate further implications for other heterogeneous catalytic systems beyond the present CO 2 hydrogenation example and highlight the importance of in situ investigations.

36 MATERIALS SCIENCE↗

Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries

Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si–R or Si–O–R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g –1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. In conclusion, the effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.

25 ENERGY STORAGE↗

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↗

Molecular-level design of alternative media for energy-saving pilot-scale fibrillation of nanocellulose

The outstanding mechanical properties, light weight, and biodegradability of cellulose nanofibrils (CNFs) make them promising components of renewable and sustainable next-generation reinforced composite biomaterials and bioplastics. Manufacturing CNFs at a pilot scale requires disc-refining fibrillation of dilute cellulose fibers in aqueous pulp suspensions to shear the fibers apart into their nanodimensional forms, which is, however, an energy-intensive process. Here, in this study, we used atomistic molecular dynamics (MD) simulation to examine media that might facilitate the reduction of interactions between cellulose fibers, thereby reducing energy consumption in fibrillation. The most suitable medium found by the simulations was an aqueous solution with 0.007:0.012 wt.% NaOH:urea, and indeed this was found in pilot-scale experiments to reduce the fibrillation energy by ~21% on average relative to water alone. The NaOH:urea-mediated CNFs have similar crystallinity, morphology, and mechanical strength to those formed in water. The NaOH and urea act synergistically on CNFs to aid fibrillation but at different length scales. NaOH deprotonates hydroxyl groups leading to mesoscale electrostatic repulsion between fibrils, whereas urea forms hydrogen bonds with protonated hydroxyl groups thus disrupting interfibril hydrogen bonds. This suggests a general mechanism in which an aqueous medium that contains a strong base and a small organic molecule acting as a hydrogen-bond acceptor and/or donor may be effectively employed in materials processes where dispersion of deprotonable polymers is required. The study demonstrates how atomic-detail computer simulation can be integrated with pilot-scale experiments in the rational design of materials processes for the circular bioeconomy.

36 MATERIALS SCIENCE↗

Role of isospin composition in low-energy nuclear fusion

We employ a microscopic approach that examines the impact of isospin dynamics on the process of low- energy nuclear fusion along an isotope chain and dependence on deformation. Our method utilizes the density constrained time-dependent Hartree-Fock theory (DC-TDHF), where isoscalar and isovector characteristics of the energy density functional (EDF) are examined in turn. This approach is applied to a series of fusion interactions of 176 Yb with increasingly neutron rich isotopes of calcium. By evaluating the contributions from the isoscalar and isovector components of the EDF, we look to quantify the influence of isospin composition on the conditions under which fusion is most likely to take place. Furthermore, our findings reveal that, in nonsymmetric systems, the isovector dynamics plays a significant role. Its typical effect is a reduction in the potential barrier, which turns into enhancement for neutron-rich systems.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Characterization and Optimization of the Fitting of Quantum Correlation Functions

This case study presents a characterization and optimization of an application code for extracting parton distribution functions from high energy electron-proton scattering data. Profiling this application code reveals that the phase-space density computation accounts for 93% of the overall execution time for a single iteration on a single core. When executing multiple iterations in parallel on a multicore system, the application spends 78% of its overall execution time idling due to load imbalance. We address these issues by first transforming the application code from Python to C++ and then tackling the application load imbalance via a hybrid scheduling strategy that combines dynamic and static scheduling. These techniques result in a 62% reduction in CPU idle time and a 2.46x speedup in overall execution time per node. In addition, the typically enabled power-management mechanisms in supercomputers (e.g., AMD Turbo Core, Intel Turbo Boost, and RAPL) can significantly impact intra-node scalability when more than 50% of the CPU cores are used. This finding underscores the importance of understanding system interactions with power management, as they can adversely impact application performance, and highlights the necessity of intra-node scaling tests to identify performance degradation that inter-node scaling tests might otherwise overlook.

Chuang, Pi-Yueh [Virginia Tech,Dept. of Computer S↗

Heliostat Consortium: Gap Analysis on State of the Art in Wind Load Design

Wind loads are a major driver of heliostat cost. Standardized methods and tools are needed for a more detailed understanding of the static and dynamic loads of a heliostat design. This will enable cost reduction of wind-dependent heliostats to avoid unnecessarily conservative heliostat designs and increase field efficiency and reliability to reduce the risk of component failures due to high-wind events. Gaps related to wind load include lack of site characterization for wind measurements, insufficient critical load cases for heliostat design, insufficient understanding of turbulence impacts on heliostat tracking error, lack of knowledge on wind load under various heliostat array configurations, and underexplored heliostat field wind-load reduction and operating strategies. Recommended pathway forward is to develop wind load and site characterization guidelines for heliostat design and develop heliostat field wind-load models with optical performance impacts.

aerodynamics↗

Parameterized Neural Ordinary Differential Equations: Applications to Computational Physics Problems

This work proposes an extension of neural ordinary differential equations (NODEs) by introducing an additional set of ODE input parameters to NODEs. This extension allows NODEs to learn multiple dynamics specified by the input parameter instances. Our extension is inspired by the concept of parameterized ordinary differential equations, which are widely investigated in computational science and engineering contexts, where characteristics of the governing equations vary over the input parameters. We apply the proposed parameterized NODEs (PNODEs) for learning latent dynamics of complex dynamical processes that arise in computational physics, which is an essential component for enabling rapid numerical simulations for time-critical physics applications. For this, we propose an encoder-decoder-type framework, which models latent dynamics as PNODEs. We demonstrate the effectiveness of PNODEs with important benchmark problems from computational physics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Effect of mammalian mesopredator exclusion on vertebrate scavenging communities

Carrion is a valuable resource used by facultative scavengers across the globe. Due to conficts with humans, many vertebrate scavengers have experienced population declines due to direct persecution or indirect efects of human activities. However, little is known about the implications of altered scavenger community composition on the fate and efciency of carrion removal within ecosystems. In particular, mammalian mesopredators are efcient scavengers that are often subjected to control, thus, it is important to understand how the reduction of this scavenger guild infuences the fate of carrion resources and efciency of carrion removal within ecosystems. We evaluated the infuence of the absence of mammalian mesopredators on vertebrate scavenging dynamics by comparing the efciency of carrion removal and species composition at carrion between sites where we experimentally manipulated mesopredator abundance and paired control sites. Overall scavenging rates were high, even within our mesopredator exclusion sites (79% of carcasses). Despite the exclusion of an entire guild of dominant scavengers, we saw little efect on scavenging dynamics due to the extensive acquisition of carrion by avian scavengers. However, we observed a slight reduction in vertebrate scavenging efciency in sites where mesopredators were excluded. Our results suggest vertebrate communities are highly efcient at carrion removal, as we saw a functional response by avian scavengers to increased carrion availability. These data provide insights into the impact of mesopredator control on food web dynamics, and build upon the growing body of knowledge investigating the role of vertebrate scavengers on ecosystem services provided through carrion removal.

54 ENVIRONMENTAL SCIENCES↗

Biogeochemical dynamics and microbial community development under sulfate- and iron-reducing conditions based on electron shuttle amendment

Iron reduction and sulfate reduction are two of the major biogeochemical processes that occur in anoxic sediments. Microbes that catalyze these reactions are therefore some of the most abundant organisms in the subsurface, and some of the most important. Due to the variety of mechanisms that microbes employ to derive energy from these reactions, including the use of soluble electron shuttles, the dynamics between iron- and sulfate-reducing populations under changing biogeochemical conditions still elude complete characterization. Here, we amended experimental bioreactors comprised of freshwater aquifer sediment with ferric iron, sulfate, acetate, and the model electron shuttle AQDS (9,10-anthraquinone-2,6-disulfonate) and monitored both the changing redox conditions as well as changes in the microbial community over time. The addition of the electron shuttle AQDS did increase the initial rate of Fe III reduction; however, it had little effect on the composition of the microbial community. Our results show that in both AQDS- and AQDS+ systems there was an initial dominance of organisms classified as Geobacter (a genus of dissimilatory Fe III -reducing bacteria), after which sequences classified as Desulfosporosinus (a genus of dissimilatory sulfate-reducing bacteria) came to dominate both experimental systems. Furthermore, most of the ferric iron reduction occurred under this later, ostensibly “sulfate-reducing” phase of the experiment. This calls into question the usefulness of classifying subsurface sediments by the dominant microbial process alone because of their interrelated biogeochemical consequences. To better inform models of microbially-catalyzed subsurface processes, such interactions must be more thoroughly understood under a broad range of conditions.

59 BASIC BIOLOGICAL SCIENCES↗

Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes

Multivalent counterion-induced bridging interactions have been identified as the key mechanism of drastic collapse of the height of polyelectrolyte (PE) brushes. In this article, we employ all-atom molecular dynamics (MD) simulations to quantify the bridging interactions in PE brushes for counterions of different sizes and valences. We identify that unlike the current notion, bridging interactions are not the sole function of the counterion valence. Rather the bridging interactions depend on the fraction of counterions (of a given type) that get physically condensed on the PE backbone as well as the size of the counterion solvation shell. These mechanisms ensure that certain monovalent counterions demonstrate much stronger bridging interactions than that witnessed for certain divalent and trivalent counterions, while certain counterions of identical valences show drastically different bridging. Here, we argue that these counterion-specific bridging interactions eventually enable not only the significant reduction of the PE brush height in presence of certain multivalent screening counterions, but may also give rise to scenarios where the brush height reduction for certain monovalent counterions is larger than certain divalent and trivalent counterions. This latter observation contradicts the experimental findings where the multivalent counterions invariably led to a larger decrease in the height of the PE brushes: we argue that this discrepancy stems from the fact that in our simulations we only consider densely grafted and short (and hence less flexible) PE brushes that hinder the formation of different laterally inhomogeneous structures (like pinned micelles and cylindrical bundles) that would have led to a larger brush height reduction (in experiments, which invariably consider longer and less densely grafted brushes, the formation of such inhomogeneous structures are primarily responsible for larger brush height reduction in presence of multivalent counterions). Finally, we also probe the dynamic properties of the counterions (i.e., their time-dependent displacements) and their bridging interactions (i.e., lifetime of bridging interactions).

42 ENGINEERING↗

Reduced‐Order Probabilistic Emulation of Physics‐Based Ring Current Models: Application to RAM‐SCB Particle Flux

Abstract In this work, we address the computational challenge of large‐scale physics‐based simulation models for the ring current. Reduced computational cost allows for significantly faster than real‐time forecasting, enhancing our ability to predict and respond to dynamic changes in the ring current, valuable for space weather monitoring and mitigation efforts. Additionally, it can also be used for a comprehensive investigation of the system. Thus, we aim to create an emulator for the Ring current‐Atmosphere interactions Model with Self‐Consistent magnetic field (RAM‐SCB) particle flux that not only improves efficiency but also facilitates forecasting with reliable estimates of prediction uncertainties. The probabilistic emulator is built upon the methodology developed by Licata and Mehta (2023), https://doi.org/10.1029/2022sw003345 . A novel discrete sampling is used to identify 30 simulation periods over 20 years of solar and geomagnetic activity. Focusing on a subset of particle flux, we use Principal Component Analysis for dimensionality reduction and Long Short‐Term Memory (LSTM) neural networks to perform dynamic modeling. Hyperparameter space was explored extensively resulting in about 5% median symmetric accuracy across all data sets for one‐step dynamic prediction. Using a hierarchical ensemble of LSTMs, we have developed a reduced‐order probabilistic emulator (ROPE) tailored for time‐series forecasting of particle flux in the ring current. This ROPE offers accurate predictions of omnidirectional flux at a single energy with no pitch angle information, providing robust predictions on the test set with an error score below 11% and calibration scores under 8% with bias under 2% providing a significant speed up as compared to the full RAM‐SCB run.

79 ASTRONOMY AND ASTROPHYSICS↗

Dynamic modeling of near isothermal compressor for Transcritical carbon dioxide cycle to support efficiency improvement

Compressors are the primary components of energy consumption in vapor compression systems, drawing considerable research effort to reduce carbon emissions and improve energy efficiency. This work presents an isothermal compressor that integrates the compression chamber with the gas cooler to achieve near-isothermal compression, resulting in up to 30% energy reduction compared to traditional isentropic compression, according to the experiment results. A detailed dynamic model for the isothermal compression cycle of carbon dioxide (CO 2 ) is first presented, coupled with a liquid-piston model for chamber design. The model is experimentally validated on a 3.5 kW prototype, yielding a 6.2% relative error in chamber pressure and a 0.5 K deviation in chamber temperature. The liquid piston exhibits reduced frictional heating and geometric adaptability relative to the mechanical piston. Leveraging these attributes, the study further evaluates approaches that enhance the heat transfer to achieve isothermal compression by increasing the effective heat transfer area during compression. As a result, simulations demonstrated up to a 5% improvement in the coefficient of performance over the baseline case through chamber design, providing guidelines for design of isothermal compression cycle.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Catalytic Bias in Enzymatic Metal Cofactor-Based Oxidation-Reduction Catalysis

Catalytic bias refers to the relative rate preference of a catalyst for either the forward or reverse direction. In enzymatic metal cofactor-based oxidation-reduction catalysis, the tuning of catalytic bias plays an underlying role in controlling rates of reactivity. For this, enzymes have evolved complex active sites that can exist in multiple oxidation states with differing reduction potentials in order to achieve challenging multi-step, oxidation-reduction reactions. Conceivably, the relative stability of the intermediates that contribute to determining the rate-limiting step of the catalytic cycle could impose catalytic bias, although mechanisms for this concept are just beginning to be realized. As one example, recent work on Clostridium pasteurianum [FeFe]-hydrogenases which catalyze reversible hydrogen oxidation have shown that the differential stabilization/destabilization of active site oxidation states through either static or dynamic protein interactions can preferentially promote either the hydrogen oxidation or proton reduction direction of the reaction. This revealed how an enzymatic cofactor can impose bias in oxidation-reduction catalysis through various tuning mechanisms by protein scaffold interactions. The hypothesis based on achieving catalytic bias through the modulation of cofactor oxidation states critical for the reaction cycle can be extended more generally to other cofactor-based oxidation-reductions catalysts. The current understanding of catalytic bias has significant implications for the design of synthetic catalysts used in industrial settings, as well as providing a greater fundamental understanding of the factors that control metabolic processes in all life.

catalysis↗

N and OH-Immobilized Cu 3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO 2 Electromethanation in Bicontinuous Mesochannels

Cu-based catalysts hold promise for electrifying CO 2 to produce methane, an extensively used fuel. However, the activity and selectivity remain insufficient due to the lack of catalyst design principles to steer complex CO 2 reduction pathways. Herein, we develop a concept to design carbon-supported Cu catalysts by regulating Cu active sites’ atomic-scale structures and engineering the carbon support’s mesoscale architecture. This aims to provide a favorable local reaction microenvironment for a selective CO 2 reduction pathway to methane. In situ X-ray absorption and Raman spectroscopy analyses reveal the dynamic reconstruction of nitrogen and hydroxyl-immobilized Cu 3 (N,OH-Cu 3 ) clusters derived from atomically dispersed Cu–N 3 sites under realistic CO 2 reduction conditions. The N,OH-Cu 3 sites possess moderate *CO adsorption affinity and a low barrier for *CO hydrogenation, enabling intrinsically selective CO 2 -to-CH 4 reduction compared to the C–C coupling with a high energy barrier. Importantly, a block copolymer-derived carbon fiber support with interconnected mesopores is constructed. The unique long-range mesochannels offer an H 2 O-deficient microenvironment and prolong the transport path for the CO intermediate, which could suppress the hydrogen evolution reaction and favor deep CO 2 reduction toward methane formation. Thus, the newly developed catalyst consisting of in situ constructed N,OH-Cu 3 active sites embedded into bicontinuous carbon mesochannels achieved an unprecedented Faradaic efficiency of 74.2% for the CO 2 reduction to methane at an industry-level current density of 300 mA cm –2 . In conclusion, this work explores effective concepts for steering desirable reaction pathways in complex interfacial catalytic systems via modulating active site structures at the atomic level and engineering pore architectures of supports on the mesoscale to create favorable microenvironments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗