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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Cost‐Effective Layered Oxide – Olivine Blend Cathodes for High‐Rate Pulse Power Lithium‐Ion Batteries

Abstract Sustainability and supply‐chain concerns require lithium‐ion batteries (LIBs) free from critical minerals, such as nickel and cobalt. While recent advances provide encouraging signs that cobalt can be removed, the question remains how much Ni can be removed from Co‐free layered oxide cathodes before sacrificing critical performance metrics. This study highlights the effect of reducing Ni by benchmarking several Co‐free cathodes with decreasing Ni content. Keeping the energy density the same by increasing the charge voltage, cathodes below 80% Ni content exhibit worsened capacity fade due to increasing oxygen release and electrolyte decomposition. Charge transfer and diffusion kinetics are also hindered with increasing Mn content and exacerbated by resistive surface phases formed at high voltages, rendering lower‐Ni, Co‐free cathodes less competitive than high‐Ni cathodes for high energy and power applications. It is demonstrated blending layered oxide with olivine as an effective alternative to deliver energy density and cycling stability comparable to lower‐Ni cathodes with moderate charging voltages. Blending with 30 wt% olivine LiMn 0.5 Fe 0.5 PO 4 (LMFP) virtually eliminates the diffusion limitation of layered oxides at low state‐of‐charge, with enhanced pulse power characteristics rivaling the high‐Ni counterparts. Cathode blending can further reduce the overall Ni content and cost without the performance limitations of lower‐Ni, Co‐free cathodes.

Lee, Steven↗
DOE OSTI2020

Carbohydrate‐binding domains facilitate efficient oligosaccharides synthesis by enhancing mutant catalytic domain transglycosylation activity

Abstract Chemoenzymatic approaches using carbohydrate‐active enzymes (CAZymes) offer a promising avenue for the synthesis of glycans like oligosaccharides. Here, we report a novel chemoenzymatic route for cellodextrins synthesis employed by chimeric CAZymes, akin to native glycosyltransferases, involving the unprecedented participation of a “non‐catalytic” lectin‐like domain or carbohydrate‐binding modules (CBMs) in the catalytic step for glycosidic bond synthesis using β‐cellobiosyl donor sugars as activated substrates. CBMs are often thought to play a passive substrate targeting role in enzymatic glycosylation reactions mostly via overcoming substrate diffusion limitations for tethered catalytic domains (CDs) but are not known to participate directly in any nucleophilic substitution mechanisms that impact the actual glycosyl transfer step. This study provides evidence for the direct participation of CBMs in the catalytic reaction step for β‐glucan glycosidic bonds synthesis enhancing activity for CBM‐based CAZyme chimeras by >140‐fold over CDs alone. Dynamic intradomain interactions that facilitate this poorly understood reaction mechanism were further revealed by small‐angle X‐ray scattering structural analysis along with detailed mutagenesis studies to shed light on our current limited understanding of similar transglycosylation‐type reaction mechanisms. In summary, our study provides a novel strategy for engineering similar CBM‐based CAZyme chimeras for the synthesis of bespoke oligosaccharides using simple activated sugar monomers.

Bandi, Chandra Kanth↗
DOE OSTI2024

Carbon Nanospheres Loaded with Ir Single Atoms: Enhancing the Activity toward Formic Acid Oxidation by Increasing the Porosity

Theoretically, single-atom catalysts (SACs) offer 100 % atom utilization, making them strong candidates to replace expensive nanoparticles for catalysis. However, the structural supports used to anchor the SACs dramatically reduce the utilization efficiency of atoms ( i. e ., the percent of atoms actually accessible by reactants) by either encapsulating the SACs completely or creating severe diffusion limitation. Either of which leads to an overall low atom utilization and thus poor electrocatalytic activity similar to that of nanoparticles. In addressing this issue, we systematically investigated how the porous structure of carbon nanospheres affects the activity of Ir-SACs toward formic acid oxidation (FAO). Specifically, we utilized a kinetically-controlled growth strategy to produce uniform carbon nanospheres featuring yolk-shell, mesoporous, and hollow structures with Ir-SACs loaded throughout the structure. At a high specific surface area of 441 m 2 g -1 and exposed metal content of 1.82 wt %, the Ir-SACs based on mesoporous carbon nanospheres showed a remarkable FAO peak current density of 30.6 mA cm -2 , which was 283 and 46 times greater when benchmarked against the catalysts based on solid carbon nanospheres and 20 wt % Ir/C, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cobalt Carbonyl Clusters Enable Independent Control of Two Proton Transfer Rates in the Mechanism for Hydrogen Evolution

Abstract Metal carbonyl clusters (MCC's) are atomically defined nanomaterials which can be characterized using the precise tools of molecular (electro)chemistry. HER mechanisms involve two proton transfer (PT) steps in the catalytic cycle. For HER catalyzed by [Co 11 C 2 (CO) 23 ] 3− ( 1 3− ), cyclic voltammetry measurements were used to determine the rate for PT1 as k PT1 =3×10 8 M −1 s −1 , whereas the rate for PT2 is k PT2 =3.7×10 3 M −1 s −1 . The fast, diffusion‐limited rate for PT1 is consistent with a previous report describing [Co 13 C 2 (CO) 24 ] 4− ( 2 4− ), with PT=2.9×10 9 M −1 s −1 . In both cases rate enhancement in PT1 is promoted by the many Co−Co bonds on the surface of the MCC that serve as PT sites: a statistical enhancement of rate akin to the effects of proton relays. In contrast, k PT2 varies and is five orders of magnitude slower for 1 2− compared with 2 4− . Thus, MCC's and nanomaterials offer an opportunity to enhance the rate for PT1 while maintaining thermochemical or kinetic control of PT2.

Pattanayak, Santanu↗
DOE OSTI2024

Direct Synthesis of Layer-Tunable and Transfer-Free Graphene on Device-Compatible Substrates Using Ion Implantation Toward Versatile Applications

Direct synthesis of layer-tunable and transfer-free graphene on technologically important substrates is highly valued for various electronics and device applications. State of the art in the field is currently a two-step process: a high-quality graphene layer synthesis on metal substrate through chemical vapor deposition (CVD) followed by delicate layer transfer onto device-relevant substrates. Here, we report a novel synthesis approach combining ion implantation for a precise graphene layer control and dual-metal smart Janus substrate for a diffusion-limiting graphene formation to directly synthesize large area, high quality, and layer-tunable graphene films on arbitrary substrates without the post-synthesis layer transfer process. Carbon (C) ion implantation was performed on Cu–Ni film deposited on a variety of device-relevant substrates. A well-controlled number of layers of graphene, primarily monolayer and bilayer, is precisely controlled by the equivalent fluence of the implanted C-atoms (1 monolayer ~4 × 10 15 C-atoms/cm 2 ). Upon thermal annealing to promote Cu-Ni alloying, the pre-implanted C-atoms in the Ni layer are pushed toward the Ni/substrate interface by the top Cu layer due to the poor C-solubility in Cu. As a result, the expelled C-atoms precipitate into a graphene structure at the interface facilitated by the Cu-like alloy catalysis. After removing the alloyed Cu-like surface layer, the layer-tunable graphene on the desired substrate is directly realized. The layer-selectivity, high quality, and uniformity of the graphene films are not only confirmed with detailed characterizations using a suite of surface analysis techniques but more importantly are successfully demonstrated by the excellent properties and performance of several devices directly fabricated from these graphene films. Molecular dynamics (MD) simulations using the reactive force field (ReaxFF) were performed to elucidate the graphene formation mechanisms in this novel synthesis approach. With the wide use of ion implantation technology in the microelectronics industry, this novel graphene synthesis approach with precise layer-tunability and transfer-free processing has the promise to advance efficient graphene-device manufacturing and expedite their versatile applications in many fields.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Mechanical behavior of polyamide-6 after combined photo-oxidative and hygrothermal aging

The effect of moisture on the photo-oxidative degradation of polyamide-6 (PA-6) was studied by analyzing the mechanical response after two different accelerated aging procedures. In the first aging procedure, the PA-6 was only exposed to ultra-violet (UV) radiation at 60 °C. In the second procedure, the same duration of UV radiation was periodically interrupted while the relative humidity was raised to 100%. Diffusion-limited and nominally homogeneous degradation conditions were investigated using bulk and film specimens, respectively. Accelerated UV aging reduced the ductility of PA-6, but the additional hygrothermal exposure had no effect on the ductility or strength, indicating that humidity did not influence the photo-oxidation of PA-6. In conclusion, this finding contrasts with previous studies that found thermo-oxidation of PA-6 was accelerated by moisture.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Corrosion Response of Ni-19Cr-5Fe in Molten NaCl-MgCl 2 Salt

Ni-based alloys are strong candidates for use in high-temperature molten salt reactors due to their superior corrosion resistance and mechanical stability compared to stainless steels. In this study, the static corrosion behavior of a Ni-19Cr-5Fe model alloy was systematically evaluated in a purified molten NaCl-MgCl 2 salt at 700°C for 30, 240, and 500 h. Post-exposure analyses were conducted to assess microstructural evolution, corrosion depth, and elemental depletion profiles. Corrosion rates, quantified by chromium depletion depth, followed an inverse power-law trend with increasing exposure time, indicating diffusion-limited kinetics. This trend is attributed to limitations in mass transport in the static salt and to the progressive local depletion of reactive chromium species. Coupled electron backscatter diffraction and energy dispersive X-ray spectroscopy analysis further revealed that the grain boundary character significantly influences corrosion susceptibility: high-angle grain boundaries exhibited pronounced Cr depletion and pitting, while low-angle and Σ3 boundaries remained comparatively resistant. These results offer valuable insight into the role of microstructure in corrosion processes and reinforce the importance of time-dependent material evaluation in molten salt environments relevant to advanced reactor designs.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Mass transport in nanoarray monolithic catalysts: An experimental-theory study

Reducing the mass transfer resistance globally of a catalyst is a key to enhancing the catalytic reaction kinetics and fully utilizing the catalyst activity. Despite the success in tailoring the external mass transfer in the widely studied washcoat monoliths, the internal mass transfer resistance is difficult to be reduced due to the requirement of increasing macroporosity while maintaining high specific surface area and mechanical stability. Therefore, nanostructured array-based monolithic catalysts (nanoarray catalysts) have been developed in the past decade as a promising class of structured catalysts that may complement or substitute washcoat catalysts. This work fundamentally elucidates the enhanced mass transport properties of the nanoarray monolithic catalysts by a combination of experimental measurements and theoretical modeling. Using a low-dimensional model, the relative contributions of resistances were quantified in terms of chemical kinetics, internal and external mass transfers based on a probe model of C2H4 oxidation over the TiO2 supported Pt-based monolithic catalysts. The nanoarray catalysts displayed a lower internal mass transfer resistance than the washcoat counterparts as a result of the high macroporosity and small thickness of nanoarray layers. Finally, the nanoarray configuration provides a new pathway towards designing high-performance monolithic reactors and catalysts with low internal diffusion limitations for various gas phase reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A simulation-based model studying monoethanolamine and aprotic heterocyclic anion ionic liquid (AHA-IL) mixtures for carbon capture

Capturing of waste CO 2 , particularly from large industrial point sources, is necessary for either permanent storage or CO 2 utilization. Amine solvents used for carbon capture have certain drawbacks, particularly the high energy required by the reboiler for solvent regeneration and degradation of the amine with absorption/regeneration cycling. These challenges may be overcome using ionic liquids (ILs) that can be tailored for operating under typical flue gas stream conditions (8–10% CO 2 , 18–20% H 2 O, 2–3% O 2 , and 67–72% N 2 ). ILs, however, oftentimes suffer from high viscosities, leading to diffusion limitations when compared to amine solvents. This work models the combinations of aprotic heterocyclic anion ILs (AHA-IL) with monoethanolamine (MEA) and studies the carbon capture effectiveness of these mixtures. Furthermore, this study found that all AHA-IL/MEA mixtures exhibited 32 % lower enthalpy of reaction (compared to MEA) and 64 % lower viscosity (compared to AHA-IL), which are desirable characteristics for CO 2 capture solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A window into atmospheric escape on early Mars provided by argon isotopes in a Martian meteorite

Novel analytical approaches to determining the trapped 38 Ar/ 36 Ar ratio of gases contained within Martian meteorites are presented and applied to the Martian regolith breccia Northwest Africa (NWA) 7034 and paired stone NWA 11220. The resulting data indicate that extensive mass-dependent fractionation of atmospheric Ar may have occurred within 150 million years of planetary formation, ostensibly as a result of diffusion-limited hydrodynamic escape. The inferred fractional loss of Ar and lighter atmospheric constituents exceeds 50%. In conclusion, these data suggest that volatiles derived from planetary outgassing and/or impactors may dominate the present abundance of atmospheric Ar.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2021

Microbubble dynamics and heat transfer in boiling droplets

Dissipating large heat fluxes from a surface is critically important in numerous industrial and natural applications. Boiling based spray cooling and surface texturing are two of the most promising methods being investigated to address this problem. Although our understanding on these topics has significantly improved over past decades, critical gaps remain in the knowledgebase stymieing the realization of their full potential. As an example, while bubble growth in pool boiling have been investigated in detail, comparatively little is known about how the bubbles evolve inside boiling drops. In the present work, we have investigated for the first time, the microbubble dynamics inside water droplets boiling on superhydrophilic textured substrates using high-speed X-ray phase contrast imaging (XRPCI). Our observations show that the transient bubble density variation follows similar characteristics irrespective of the texture spacing at a given surface temperature. For an example microstructure, we found that the number of discrete bubbles on the surface decreases as temperature is increased although their growth rate increases. Here, we observe that bubble growth is highly non-uniform during the lifetime of a drop on the surface. Initially, bubbles grow under diffusion-limited regime, but at later times they grow as ~t 1.45 due to combined effects of coalescence and evaporation. In some conditions, we found that bubbles shrink dramatically af- ter the initial growth spurt presumably due to severe quenching of the surface, and migration of bubbles on the surface. Using the bubble sizes, for the first time we analyzed the heat flux removed by a single bubble and also by all the bubbles at a given time. We find that the highest dissipation through latent- heat component (~600 W/cm 2 ) occurs just in the beginning and thereafter it decreases. We expect that our findings and the analysis would guide further work on the topic and will aid in the overarching goal of engineering surfaces that are more efficient in boiling heat transfer.

42 ENGINEERING↗
DOE OSTI2026

Theoretical model of dielectrophoretic water vapor condensation during multiphase flow of electrically charged water droplets in air

Water droplet growth in air, influenced by vapor diffusion and electrical charging, has significant implications for indoor air quality, cloud formation, and aerosol dynamics. Here, this study presents a comprehensive theoretical model that describes the growth dynamics of electrically charged water droplets under external electric fields, incorporating diffusion, electrostatic, and dielectrophoretic forces to enhance understanding and practical applications in air dehumidification and environmental control. A theoretical model was established to analyze the growth dynamics of the charged water droplets. The approach extended the thermodynamic framework of the Modified Kelvin-Thomson equation by integrating electrostatic and dielectrophoretic effects, enabling a comprehensive evaluation of vapor concentration near the surface of charged droplets. A sensitivity analysis was performed to assess the roles of droplet size, electric field intensity, surface charge, and vapor concentration on condensation rates. The study progressed beyond the classical diffusion-limited growth of neutral droplets, addressing the behavior of charged droplets in electrohydrodynamic environments. The model highlighted the significance of dielectrophoretic drift flux for dipolar vapor molecules, especially in micron-sized droplets ranging from 10 to 100 µm. Findings demonstrated that, for smaller droplets subjected to elevated electrical charge, average growth rates varied from 0.3 to 1.6 µm/s if the air relative humidity increased from 50 to 100 %. Analytical results are corroborated by numerical simulations, which exhibited strong concordance, thereby validating the proposed theoretical approach. This research introduced an innovative and scalable analytical methodology for electric field-enhanced droplet growth, offering valuable insights into the advancement of energy-efficient air dehumidification, water desalination, and atmospheric water harvesting technologies.

42 ENGINEERING↗
DOE OSTI2023

A family of independent Variable Eddington Factor methods with efficient preconditioned iterative solvers

We present a family of discretizations for the Variable Eddington Factor (VEF) equations that have high-order accuracy on curved meshes and efficient preconditioned iterative solvers. The VEF discretizations are combined with the Discontinuous Galerkin transport discretization from to form effective high-order, linear transport methods. The VEF discretizations are derived by extending the unified analysis of Discontinuous Galerkin methods for elliptic problems presented by Arnold et al. to the VEF equations. This framework is used to define analogs of the interior penalty, second method of Bassi and Rebay, minimal dissipation local Discontinuous Galerkin, and continuous finite element methods. The analysis of subspace correction preconditioners, which use a continuous operator to iteratively precondition the discontinuous discretization, is extended to the case of the non-symmetric VEF system. Numerical results demonstrate that the VEF discretizations have arbitrary-order accuracy on curved meshes, preserve the thick diffusion limit, and are effective on a proxy problem from thermal radiative transfer in both outer transport iterations and inner preconditioned linear solver iterations. We demonstrate that the VEF solution converges to the S N transport solution as the mesh is refined on both problems with smooth and non-smooth behavior in angle. Parallel performance studies show that the interior penalty VEF discretization's linear solve weak scales out to 1024 processors and strong scales well on a single node. Particular attention is paid to the parallel performance of the VEF algorithm when used in combination with a parallel block Jacobi transport sweep.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

Moment-based adaptive time integration for thermal radiation transport

Here, in this paper we develop a framework for moment-based adaptive time integration of deterministic multifrequency thermal radiation transpot (TRT). We generalize our recent semi-implicit-explicit (IMEX) integration framework for gray TRT to multifrequency TRT, and also introduce a semi-implicit variation that facilitates higher-order integration of TRT, where each stage is implicit in all components except opacities. To appeal to the broad literature on adaptivity with Runge–Kutta methods, we derive new embedded methods for four asymptotic preserving IMEX Runge–Kutta schemes we have found to be robust in our previous work on TRT and radiation hydrodynamics. We then use a moment-based high-order-low-order representation of the transport equations. Due to the high dimensionality, memory is always a concern in simulating TRT. We form error estimates and adaptivity in time purely based on temperature and radiation energy, for a trivial overhead in computational cost and memory usage compared with the base second order integrators. We then test the adaptivity in time on the tophat and Larsen problem, demonstrating the ability of the adaptive algorithm to naturally vary the timestep across 4–5 orders of magnitude, ranging from the dynamical timescales of the streaming regime to the thick diffusion limit.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

A channel flow cell with double disk electrodes for oxygen electroreduction study at elevated temperatures and pressures: Theory

We report a new double-disk-electrode channel flow cell has been designed, constructed and tested. A theoretical treatment and implicit finite difference numerical simulations are presented, which permit the computation of the hydrodynamic behavior of this cell under steady state conditions, i.e., the diffusion limited current at the working electrode and the collection efficiency of the detector. The simulated results are consistent with those measured experimentally, indicating that our simulations appropriately describe the hydrodynamic behavior of this cell. The oxygen reduction reaction (ORR) on a carbon-supported nanoparticle Pt catalyst at both room temperature and 110 °C were preliminarily studied with this cell.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗