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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Surface structure studies in 2D and 3D Nb resonators using GI-XRD

Superconductor radio frequency (SRF) Nb-resonators are a key element in the development of new generations of particle accelerators as well as in the fabrication of 3D circuit QED architecture for quantum computing. Nevertheless, Niobium is extremally reactive to light elements such as C, N, O and H, and therefore to the impurities ordering under special conditions, e.g., cryogenic temperatures. Since these resonators are put through a series of metallurgical and chemical processes, the number of impurities in the solid increases in tens of ppm. Upon operational conditions ~1.6 K, Nb become vulnerable to H atoms ordering, which leads to the nucleation of secondary phases such as Nb-hydrides. Thereupon to the energy dissipation and eventually to the superconductivity breakdown known as Q-disease and potentially High-Field Q-slope. In this contribution, we present a detailed structural analysis by high-energy grazing-incidence X-ray diffraction of specimens extracted from 3D Nb resonators to shed light on the kinetic formation of the resulting secondary phases and their crystal phase identification upon cooling and heating cycles. To our knowledge, this is the first study carried out in resonators samples using a light source, shallow angles and temperatures near ~4 K. Consequently, this work opens new routes to understand the chemical and phase composition, crystal and electronic structure of the Nb surface at temperatures near the operating conditions as a strategy to improve the physical and functional properties of Nb superconducting resonators.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Computational and Experimental Investigation of Thermal-Mechanical- Chemical Mechanisms of High-burnup Spent Nuclear Fuel (SNF) Processes at Elevated Temperatures and Degradation Behavior in Geologic Repositories

The overarching goal of the combined computational and experimental R&D activities proposed in this project is to enhance understanding of the mechanisms and thermal-mechanical-chemical (TMC) parameters controlling the instant release fraction (IRF) and matrix dissolution of high-burnup (HB; burnup) spent nuclear fuels (SNFs) and the subsequent formation, stability, and phase transformations of SNF alteration products under long-term storage and geological disposal conditions. Uranium dioxide may undergo oxidative corrosion/alteration, and the IRF may be increased for HB SNF, both of which may affect environmental systems associated with SNF long-term storage and disposal. The oxidative matrix dissolution may form various complex uranyl-based phases, including a rich variety of oxides, silicates, carbonates and other secondary minerals in varied geological environments (e.g., studtite, metastudtite, amorphous uranyl peroxide, uranium trioxide, triuranium octoxide, schoepite, dehydrated schoepite, metaschoepite, becquerelite, soddyite, rutherfordine,...). These uranyl phases generally have higher mobility UO 2 +2 species than less soluble U 4+ phases. However, limited information on the thermodynamic properties and formation kinetics of these uranyl-bearing phases is available to predict explicitly paragenesis under the conditions relevant to long-term storage or disposal. The proposed project draws on complementary expertise and research backgrounds from the team members: (i) to apply a combined ab initio modeling (UNLV/UTEP and SNL) and experimental (UNLV) strategy investigating the high-temperature TMC mechanisms of alteration of SNF under α-radiolysis conditions; (ii) to investigate the mechanistic of phase transformations in UNF degradation products under various conditions expected in long-term storage systems (e.g. (UO 2 )O 2 (H 2 O) 4 → (UO 2 )O 2 (H 2 O) 2 → U 2 O 7 → UO 3 → U 3 O 8 ); (iii) to determine high-accuracy TMC parameters for complex uranyl-based phases formed in storage or geological disposal environments (e.g. UO 3 (H 2 O) 2 , Ca[(UO 2 ) 6 O 4 (OH) 8 ] 8 H 2 O, (UO 2 ) 2 (SiO 4 ) 3 2H 2 O,…). The unforeseen COVID-19 pandemic led to the laboratory/campus closure since March 2020, that resulted in a significant delay in reaching milestones in a satisfactory manner, due to (i) the statewide recommendation from stop-working to later limited work in the lab and work-from-home (WFH), (ii) no in-person interactions, and (iii) a hiring freeze at UNLV. Therefore, a no cost extension (10/01/2021- 9/30/2022) was requested to help make up the time we lost during the global pandemic in 2020-2021, leading to paradigm shifts in the focus of the project in the following three main tasks: Task 1 (Computational), Task 2 (Experimental), and Task 3 (Final report, due on 12/29/2022).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Diffraction Measurement of Reaction Products in Shock Compressed TATB on the NIF

The shock-induced reaction of high explosives to gaseous and solid reaction products is a rapid, complex process. Understanding solid reaction product structure and formation kinetics is essential in determining the high-pressure equation of state of these multicomponent systems. We use the National Ignition Facility (NIF) to shock compress ~500-µm thick pressed powder high-explosive TATB samples to 70-135 GPa and collect in situ structural data on detonation byproducts using the TARDIS X-ray diffraction diagnostic. Velocimetry is used to record the transmitted compression wave profile, which is well described by Cheetah hydrocode simulations coupled with a reactive flow model, providing strong evidence of reaction in the TATB sample. While an unambiguous determination of the product phases was not possible owing to the low signal-to-noise quality of the diffraction signal, X-ray diffraction data of the product phases formed within the first 50 ns of the reaction is most consistent with a mixture of amorphous products and crystalline hexagonal diamond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Investigating Kinetic Mechanisms of Soot Formation in Plasma Pyrolysis of Methane via Active Learning (Final Technical Report)

Plasma pyrolysis of methane is an effective route for zero-carbon hydrogen production. Yet, soot generated from pyrolysis of hydrocarbons is detrimental to the climate and human health. There is ample experimental and theoretical evidence that suggests polycyclic aromatic hydrocarbons (PAHs) are the molecular precursors to soot particles. The reaction pathways of PAH formation are intricately dependent on a multitude of process parameters, whose kinetic mechanisms are not well-understood in plasma pyrolysis. This project aims to leverage advances in the kinetic modeling of soot formation in combustion, as well as in surrogate modeling and active learning, to systematically investigate the effects of process parameter on the kinetics of PAH formation in plasma pyrolysis of methane. To this end, we propose to use the PAH formation kinetics model developed by the PPPL/PU group based on the well-established ABF and HACA mechanisms, coupled with low-temperature plasma models. We will develop an active learning (AL) framework based on Bayesian optimization to systematically and data-efficiently explore the complex and multivariable parameter space of plasma pyrolysis in order to quantify the effects of plasma and feed parameters on the ABF and HACA kinetic pathways. AL is the branch of machine learning concerned with systematically querying samples from a system (experimental or computational) to train a data-driven model that maps design parameters to a performance criterion. We will use the data generated via AL to perform global sensitivity analysis, combined with uncertainty quantification, to elucidate the impact of different reaction pathways on minimizing formation of soot precursors. This study will result in an improved understanding of kinetics of PAH formation in plasma pyrolysis and can pave the way for more advanced mechanistic studies (e.g., soot nucleation mechanisms). Additionally, the findings will be useful for establishing practical strategies for increasing the pyrolysis efficiency and producing high-grade carbon for synthesis of nanomaterials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Surface Crust Formation Controls Evaporation Kinetics of Secondary Organic Aerosols

Gas-particle partitioning is critical for the evolution of secondary organic aerosols (SOA) in the atmosphere. SOA particles evaporate more slowly than expected at nearly size-independent rates, but the underlying mechanism remains controversial. Here, in this study, we apply kinetic multilayer modeling to simulate evaporation of α-pinene SOA, demonstrating that surface crust formation, emerging from accumulation of low-volatility compounds at the particle surface, leads to slow evaporation and reduced size dependence of the evaporation rate. While evaporation induced by decomposition of oligomers would naturally lead to size-independent evaporation rates, we observe and simulate nearly size-independent slow evaporation of polyethylene glycol mixture particles containing polymeric species that do not decompose, confirming the relevance of composition-dependent diffusivity for size-independent, slow evaporation. Slow evaporation of limonene SOA was also observed in environmental chamber experiments, and model simulations demonstrate strong surface crust formation with bulk diffusivity being depressed by up to 5 orders of magnitude compared to the inner bulk. We present experimental evidence using a surface-based mass spectrometry technique that shows that the particle surface becomes enriched in high molecular weight compounds upon evaporation of monomers. Our findings imply that viscous surface crusts may also limit the growth and chemical transformation of SOA particles, influencing their impacts on air quality and climate.

heterogeneous chemistry↗
DOE OSTI2024

Phase transformation mechanism in irradiation-induced superlattice formation

Atomic kinetic Monte Carlo simulations were used to model void superlattice formation under irradiation in molybdenum, driven by anisotropic diffusion of self-interstitial atoms. A change in the phase transformation mechanism from nucleation and growth to spinodal decomposition occurred with increasing dose rate, with both mechanisms leading to superlattice formation. Analysis of a rate-theory based analytical model showed that an observed change in the kinetics of vacancy accumulation, the appearance of a region of positive second derivative in the plot of average vacancy concentration versus time, was caused by the onset of spinodal instability. Further, the analytical model showed that for molybdenum and several other metals where void superlattice formation is commonly observed, the phase transformation likely occurs by nucleation and growth. However, nickel may offer the possibility of experimental observation of the transition between phase transformation mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Kinetics of Aragonite Formation from Solution via Amorphous Calcium Carbonate

Magnesium doped Amorphous Calcium Carbonate was synthesised from precursor solutions containing varying amounts of calcium, magnesium, H2O and D2O. The Mg/Ca ratio in the resultant Amorphous Calcium Carbonate was found to vary linearly with the Mg/Ca ratio in the precursor solution. All samples crystallised as aragonite. No Mg was found in the final aragonite crystals. Changes in the Mg to Ca ratio were found to only marginally effect nucleation rates but strongly effect crystal growth rates. These results are consistent with a dissolution-reprecipitation model for aragonite formation via an Amorphous Calcium Carbonate intermediate.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO 2 regimes

Abstract. The atmospheric oxidation of dimethyl sulfide (DMS) represents a major natural source of atmospheric sulfate aerosols. However, there remain large uncertainties in our understanding of the underlying chemistry that governs the product distribution and sulfate yield from DMS oxidation. Here, chamber experiments were conducted to simulate gas-phase OH-initiated oxidation of DMS under a range of reaction conditions. Most importantly, the bimolecular lifetime (τbi) of the peroxy radical CH3SCH2OO was varied over several orders of magnitude, enabling the examination of the role of peroxy radical isomerization reactions on product formation. An array of analytical instruments was used to measure nearly all sulfur-containing species in the reaction mixture, and results were compared with a near-explicit chemical mechanism. When relative humidity was low, “sulfur closure” was achieved under both high-NO (τbi<0.1 s) and low-NO (τbi>10 s) conditions, though product distributions were substantially different in the two cases. Under high-NO conditions, approximately half the product sulfur was in the particle phase, as methane sulfonic acid (MSA) and sulfate, with most of the remainder as SO2 (which in the atmosphere would eventually oxidize to sulfate or be lost to deposition). Under low-NO conditions, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), formed from CH3SCH2OO isomerization, dominates the sulfur budget over the course of the experiment, suppressing or delaying the formation of SO2 and particulate matter. The isomerization rate constant of CH3SCH2OO at 295 K is found to be 0.13±0.03 s−1, in broad agreement with other recent laboratory measurements. The rate constants for the OH oxidation of key first-generation oxidation products (HPMTF and methyl thioformate, MTF) were also determined (kOH+HPMTF=2.1×10-11 cm3 molec.−1 s−1, kOH+MTF=1.35×10-11 cm3 molec.−1 s−1). Product measurements agree reasonably well with mechanistic predictions in terms of total sulfur distribution and concentrations of most individual species, though the mechanism overpredicts sulfate and underpredicts MSA under high-NO conditions. Lastly, results from high-relative-humidity conditions suggest efficient heterogenous loss of at least some gas-phase products.

Ye, Qing (ORCID:0000000337978988)↗
DOE OSTI2022

Multiscale Interaction of Turbulence, Temperature, and Soot Formation: Measurements for Critical Assessments of Chemical Kinetics and Mechanisms

This program targeted an improved understanding of how turbulence affects soot formation chemistry (directly and indirectly) with a particular focus on detailing the multiscale coupling between flow turbulence, mixing, thermal transport, and soot formation kinetics in gas-phase reacting systems. In this project, simultaneous, quantitative multi-dimensional velocity, soot volume fraction, and gas-phase temperature measurements in turbulent non-premixed sooting flames were developed. These new diagnostics tools can be used to elucidate the relative effects of fluid kinematics, mixing, thermal processes, and turbulence/scalar time/length scales on soot formation chemistry and topology. Simultaneous multi-parameter measurements were acquired within a series of flames with different Reynolds numbers and spatial locations to investigate the inter-dependence of soot, temperature, and turbulence within the soot inception, growth, and oxidation region. Preliminary assessment of the results has been completed at the project end and detailed analysis is planned following the completed program.

02 PETROLEUM↗
DOE OSTI2024

Exploring CO 2 reduction and crossover in membrane electrode assemblies

Electrochemical CO 2 reduction (CO 2 R) using renewable electricity is a key pathway toward synthesizing fuels and chemicals. In this study, multi-physics modeling is used to interpret experimental data obtained for CO 2 R to CO using Ag catalysts in a membrane electrode assembly. The one-dimensional model is validated using measured CO 2 crossover and product formation rates. The kinetics of CO formation are described by Marcus–Hush–Chidsey kinetics, which enables accurate prediction of the experimental data by accounting for the reorganization of the solvent during CO 2 R. Further, the results show how the performance is dictated by competing phenomena including ion formation and transport, CO 2 solubility, and water management. The model shows that increasing the ion-exchange capacity of the membrane and surface area of the catalyst increases CO formation rates by >100 mA cm –2 without negatively impacting CO 2 utilization. Here we provide insights into how to manage the trade-off between productivity and CO 2 utilization in CO 2 electrolyzers.

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

1D kinetic study of pinch formation in a dense plasma focus: Transition from collisional to collisionless regimes

Here, the pinch-formation stage of a deuterium dense plasma focus, and associated “shock-flash” neutron yield, is studied using 1D kinetic simulations considering a plasma column with initial pressure P, initial radius R, and the compression to be driven by a constant current I. The relative behavior of the compression is shown to be similar for fixed ratios of the characteristic ion mean free path to the radius of the plasma column at stagnation, $λ_{st}/R_{st}$. This dimensionless parameter is shown to scale like $I^4/(P^3R^5)$. The compression ratio, $R/R_{st}$, is found to be a minimum when $λ_{st}/R_{st} ≈$ 1 and is the largest in the collisionless limit where $λ_{st} \gg R_{st}$. This behavior is in contrast to the analogous planar pinch where R/Rst decreases from one constant for λst/Rst$\ll$1 to a smaller constant for $λ_{st}/R_{st} \gg$ 1. The yield in the collisionless regime is shown to fall between the two well-known $I^4$ scaling laws. Furthermore, this regime exhibits qualities that potentially make it appealing for radiography applications, such as increased localization in time and space of the neutron formation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Application of soot carbonization kinetics to deduce meaningful soot formation rates in premixed flat flames

Soot formation rates measured in fuel-rich premixed flat flames are frequently used to calibrate or validate chemical kinetic models of soot formation. Unfortunately, these flames feature an extended region of soot precursor particle inception and carbonization that complicates interpretation of soot measurements and leads to a fundamental inconsistency in the nature of the soot material that is modeled versus what is being measured when using non-intrusive, optical techniques. In the work presented here, previously reported data on two canonical sooting ethylene-air premixed flames at 1 atm pressure are interpreted via a new analysis approach that combines soot optical dispersion coefficient measurements with soot carbonization kinetics. This analytical approach explicitly accounts for the production of poorly ordered soot precursor particle mass and its carbonization over time in the flames, providing a clear distinction between the formation rate of precursor particles and their transformation into ordered, solid soot particulate mass. In particular, the results of the analysis show that the precursor particles form much earlier in the flame than the majority of the carbonized soot and their formation rate is two to three times faster than that of ordered soot. The results also show that particle agglomeration begins when the particles are at an intermediate state of carbonization. In conclusion, these results offer a valuable new interpretation of these important datasets and should lead to substantial improvements in the development and calibration of quantitative soot models.

Soot formation↗
DOE OSTI2023

HP1-driven phase separation recapitulates the thermodynamics and kinetics of heterochromatin condensate formation

The spatial segregation of pericentromeric heterochromatin (PCH) into distinct, membrane-less nuclear compartments involves the binding of Heterochromatin Protein 1 (HP1) to H3K9me2/3-rich genomic regions. While HP1 exhibits liquid–liquid phase separation properties in vitro, its mechanistic impact on the structure and dynamics of PCH condensate formation in vivo remains largely unresolved. Here, using a minimal theoretical framework, we systematically investigate the mutual coupling between self-interacting HP1-like molecules and the chromatin polymer. We reveal that the specific affinity of HP1 for H3K9me2/3 loci facilitates coacervation in nucleo and promotes the formation of stable PCH condensates at HP1 levels far below the concentration required to observe phase separation in purified protein assays in vitro. These heterotypic HP1–chromatin interactions give rise to a strong dependence of the nucleoplasmic HP1 density on HP1-H3K9me2/3 stoichiometry, consistent with the thermodynamics of multicomponent phase separation. The dynamical cross talk between HP1 and the viscoelastic chromatin scaffold also leads to anomalously slow equilibration kinetics, which strongly depend on the genomic distribution of H3K9me2/3 domains and result in the coexistence of multiple long-lived, microphase-separated PCH compartments. The morphology of these complex coacervates is further found to be governed by the dynamic establishment of the underlying H3K9me2/3 landscape, which may drive their increasingly abnormal, aspherical shapes during cell development. These findings compare favorably to 4D microscopy measurements of HP1 condensate formation in live Drosophila embryos and suggest a general quantitative model of PCH formation based on the interplay between HP1-based phase separation and chromatin polymer mechanics.

3D genomics↗
DOE OSTI2024

Formation of the oxyl’s potential energy surface by the spectral kinetics of a vibrational mode

One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti–O●−) created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode is derived from its spectral shape, which exhibited a Fano resonance—a coupling of a sharp normal mode to continuum excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode’s cross-section). All three perspectives yield logistic function growth with a half-rise of 2.3 ± 0.3 ps and a time constant of 0.48 ± 0.09 ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t ∼ 0) to have an exponential growth rate that quickly decreases toward zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for oxyl radical coverage.

Chemistry↗
DOE OSTI2024

Kinetic study of shock formation and particle acceleration in laser-driven quasi-parallel magnetized collisionless shocks

Quasi-parallel magnetized collisionless shocks are believed to be one of the most efficient accelerators in the universe. Compared to quasi-perpendicular shocks, quasi-parallel shocks are more difficult to form in the laboratory and to simulate because of their large spatial scales and long formation times. Our two-dimensional particle-in-cell simulations show that the early stages of quasi-parallel shock formation are achievable in experiments planned for the National Ignition Facility and that particles accelerated by diffusive shock acceleration (DSA) are expected to be observable in the experiment. Repetitive ion acceleration by crossings of the shock front, a key feature of DSA, is seen in the simulations. Other characteristic features of quasi-parallel shocks such as upstream wave excitation by energetic ions are also observed, and energy partition between the ions and the electrons in the downstream of the shock is briefly discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗