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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Kinetic and Thermodynamic Characterization of the Cobalt and Manganese Oxyhydroxide Cores Formed in Horse Spleen Ferritin

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05+/-0.10 e/M forming a stable M(OH)2 mineral core. At pH 9.0, ascorbic acid (AH2), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH2 shifted the reaction to completion with a M(3+)/AH2 stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(0)OH and excess AH2 was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74/M/min, respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH2 concentration, equilibrium constants at pH 9.0 of 5.0+/-1.9 for Co-HoSF and 2.9+/-0.9 for Mn-HoSF were calculated for 2M(O)OH + AH2 = 2M(OH)2 f D, where AH2 and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH2. Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.

Zhang, Bo↗
DOE OSTI2023

Combustion synthesis of Eu 2 O 3 nanomaterials with tunable phase composition and morphology

Combustion reactions in europium nitrate – acetylacetone – 2-methoxyethanol solutions and gels were investigated to produce europium (III) oxide (Eu 2 O 3 ) nanocrystalline materials and thin films. Thermal analyses of solutions indicated that the 2-methoxyethanol solvent also acts as a fuel in the absence of acetylacetone. Adding acetylacetone increases the overall heat of the reaction. Thermal analysis results revealed that the slow oxidation of unburned hydrocarbon residues follows the primary combustion reaction. Time-temperature profile measurements of the bulk combustion synthesis process in air and nitrogen atmospheres enabled the extraction of the maximum reaction temperature and the heating and cooling rates in the combustion zone. Several direct correlations exist between measured combustion parameters and the phase composition of the products. Combustion in air results in mixed-phase cubic and monoclinic nanocrystalline Eu 2 O 3 . Increasing the acetylacetone concentration in solutions increases the synthesis temperature and decreases the quantity of cubic Eu 2 O 3 . Here, the reaction of solutions in a nitrogen atmosphere or diluted with Eu 2 O 3 provides control of the product phase composition and reduces the quantity of the monoclinic phase. Transmission electron microscopy imaging shows that the Eu 2 O 3 end products are highly porous aggregates of nanocrystalline particles. Electrospraying of reactive solutions onto different substrates followed by short annealing makes the preparation of Eu 2 O 3 materials with diverse morphologies possible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Rate Equations for Reversible Disproportionation Reactions and Fitting to Time-Course Data

Integrated rate equations are straightforward to fit to experimental data to verify a proposed mechanism and to extract kinetic parameters. Such equations are derived for reversible disproportionation/comproportionation reactions with any set of initial concentrations. Extraction of forward and reverse rate constants from experimental data by fitting the rate law to the data is demonstrated for the disproportionation of 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO) under acidic conditions where the approach to equilibrium is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effects of stereoisomeric structure and bond location on the ignition and reaction pathways of hexenes

The current work presents new experimental autoignition and speciation data on the two cis-hexene isomers: cis-2-hexene and cis-3-hexene. The new data provide insights on the effects of carbon-carbon double bond location and stereoisomeric structures on ignition delay times and reaction pathways for linear hexene isomers. Experiments were performed using the University of Michigan rapid compression facility to determine ignition delay times from pressure-time histories. Stoichiometric (Φ = 1.0) mixtures at dilution levels of inert gas to O 2 = 7.5:1 (mole basis) were investigated at an average pressure of 11 atm and temperatures from 809 to 1052 K. Speciation experiments were conducted at T = 900 K for the two cis-hexene isomers, where fast-gas sampling and gas chromatography were used to identify and quantify the two cis-hexene isomers and stable intermediate species. The ignition delay time data showed negligible sensitivity to the location of the carbon-carbon double bond and the stereoisomeric structure (cis-trans), and the species data showed no correlation with the stereoisomeric structure, but there was a strong correlation of some of the measured species with the location of the double bond in the hexene isomer. In particular, 2-hexene showed strong selectivity to propene, acetaldehyde, and 1,3-butadiene, and 3-hexene showed selectivity to propanal. Model predictions of ignition delay times were in excellent agreement with the experimental data. Furthermore, there was generally good agreement for the model predictions of the species data for 2-hexene; however, the mechanism overpredicted some of the small aldehyde (C 2 -C 4 ) species for 3-hexene. Reaction pathway analysis indicates the hexenes are almost exclusively consumed by H-atom abstraction reactions at the conditions studied (P = 11 atm, T > 900 K), and not by C 3 -C 4 scission as observed in high-temperature (>1300 K) hexene ignition studies. Improved estimates for 3-hexene + OH reactions may improve model predictions for the species measured in this work.

42 ENGINEERING↗
NASA NTRS1993

Time-resolved tryptophan fluorescence in photosynthetic reaction centers from Rhodobacter sphaeroides

Tryptophan fluorescence of reaction centers isolated from Rhodobacter sphaeroides, both stationary and time-resolved, was studied. Fluorescence kinetics were found to fit best a sum of four discrete exponential components. Half of the initial amplitude was due to a component with a lifetime of congruent to 60 ps, belonging to Trp residues, capable of efficient transfer of excitation energy to bacteriochlorophyll molecules of the reaction center. The three other components seem to be emitted by Trp ground-state conformers, unable to participate in such a transfer. Under the influence of intense actinic light, photooxidizing the reaction centers, the yield of stationary fluorescence diminished by congruent to 1.5 times, while the number of the kinetic components and their life times remained practically unchanged. Possible implications of the observed effects for the primary photosynthesis events are considered.

NASA Program Exobiology↗
DOE OSTI2024

Adaptive tau-leaping methods for microscopic-lattice kinetic Monte Carlo simulations

Traditional Kinetic Monte Carlo (KMC) approaches, rooted in Gillespie’s stochastic simulation algorithm, become computationally demanding in systems with a large range of timescales. The goal of this work is to propose and study new adaptive lattice-KMC time integration strategies for spatially non-uniform systems. To that end, two novel adaptive tau-leaping methods and their corresponding time integration strategies are developed based on the idea of the “n-fold” direct KMC method. These strategies allow for the simultaneous execution of multiple reactions, advancing time by adaptively selected coarse increments. We present numerical experiments comparing the proposed methods with existing approaches in a catalytic surface kinetics application involving ammonia decomposition.

Bimolecular reactions↗
DOE OSTI2016

Characterisation of weld zone reactions in dissimilar glass-to-aluminium pulsed picosecond laser welds

Precision welded joints, produced between fused silica glass and aluminium by a newly-developed picosecond-pulse laser technique, have been analysed for the first time using a full range of electron microscopy methods. The welds were produced as lap joints by focusing a 1.2 μm diameter laser beam through the transparent glass top sheet, slightly below the surface of the metal bottom sheet. Despite the extremely short interaction time, extensive reaction was observed in the weld zone, which involved the formation of nanocrystalline silicon and at least two transitional alumina phases, γ- and δ-Al{sub 2}O{sub 3}. The weld formation process was found to be complex and involved: the formation of a constrained plasma cavity at the joint interface, non-linear absorption in the glass, and the creation of multiple secondary keyholes in the metal substrate by beam scattering. The joint area was found to expand outside of the main interaction volume, as the energy absorbed into the low conductivity and higher melting point silica glass sheet melted the aluminium surface across a wider contact area. The reasons for the appearance of nanocrystalline Si and transitional alumina reaction products within the welds are discussed. - Highlights: •Pulsed laser welding of dissimilar materials causes extensive chemical reactivity. •Metastable Al{sub 2}O{sub 3} phases form due to laser-induced highly-transient thermal regime. •Fused silica is reduced by Al to form nanocrystalline Si. •Mechanism of joint formation is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Molecular Mass Growth Processes to Polycyclic Aromatic Hydrocarbons through Radical–Radical Reactions Exploiting Photoionization Reflectron Time-of-Flight Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) represent critical building blocks in molecular mass growth processes to carbonaceous nanoparticles, referred to as interstellar and circumstellar grains along with soot particles in astrophysical environments and combustion systems, respectively. Recent advancements on elucidating elementary steps to PAHs have utilized reactions of aromatic radicals, resonantly stabilized free radicals, and aliphatic radicals with closed shell hydrocarbons. However, the role of radical–radical reactions (RRRs) leading to PAHs has remained largely unexplored on the molecular level due to preceding experimental challenges in producing sufficiently high number densities of radical reactants for isomer-selective detection of products from bimolecular and termolecular reactions. This Account offers the latest developments in our knowledge on the mechanisms and pathways to PAHs via RRRs probed in a chemical microreactor at temperatures as high as 1600 K. Product preservation in a molecular beam coupled with synchrotron vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and photoelectron photoion coincidence spectroscopy enabled isomer-selective detection of PAHs of up to three rings by their photoionization efficiency curves, which were fit with a linear combination of reference curves for identification. Experiments were combined with computational fluid dynamics modeling of the physicochemical processes in the microreactor, as well as high-level electronic structure calculations to reveal the reaction pathways of each system. Six distinct reaction mechanisms were discovered in this work: propargyl addition─benzannulation (PABA), methyl addition─ring expansion (MARE), cyclopentadienyl addition─naphthylization (CPAN), fulvenallenyl addition─cyclization─aromatization (FACA), benzyl addition─aromatization (BAA), and phenyl addition─pentacyclization (PAP). By systematically varying the number of carbon atoms in the radical reactants, molecular mass growth processes involving reactions between radicals with odd numbers of carbon atoms access aromatics carrying one, two, or three six-membered rings, whereas reactions between even- and odd-carbon-numbered radicals produce aromatics combining five- and six-membered rings. Our investigations reveal unconventional cycloadditions on excited state triplet surfaces, additions of radicals to low spin density carbon-centered radicals, spiroaromatic and fulvene-type intermediates, and highly strained bicyclic reaction intermediates, challenging current perceptions of PAH molecular mass growth processes. All of the listed mechanisms, except for FACA, feature endoergic reactions or barriers which lie above the separated reactants and therefore might be central to circumstellar environments of carbon-rich stars and planetary nebulae as their descendants, but they play no role in the gas phase of cold molecular clouds where temperatures as low as 10 K dominate. Altogether, this work provides detailed reaction mechanisms of PAH growth processes, advancing our knowledge of the chemistry of carbonaceous matter in the universe.

Addition reactions↗
DOE OSTI2025

A Review of Tank 48H Treatment of Tetraphenylborate with Permanganate

Tank 48H contains roughly 270,000 gallons of radioactive waste material. The waste stored in this tank was to be processed in multiple stages utilizing facilities at the Savannah River Site (SRS) almost 30 years ago. The In-Tank Precipitation Process (ITP) was initiated in Tank 48H, which precipitated highly radioactive cesium-137 using sodium tetraphenylborate (NaTPB). While the process succeeded in precipitating the Cs, Sr, and other actinides, it also generated an unexpectedly large amount of benzene. The evolved benzene created a safety concern and made the waste incompatible with further downstream processing. This halted the ITP, and a new method of treatment was required to continue processing the legacy waste contained in Tank 48H. A myriad of treatment options have been proposed with multiple teams of researchers assembled to work on this highly complex issue over the last few decades. This review investigated one potentially viable treatment option, in-tank oxidation with sodium permanganate. Permanganate has been well known in literature as a strong oxidizing agent for organic compounds, as well as being utilized at the Savannah River Site (SRS) in other processes. A small number of studies have been conducted utilizing waste simulants to evaluate the use of permanganate as an oxidant for tetraphenylborate (TPB). A search of the literature and data from these studies indicates that permanganate could be a viable treatment for destruction of TPB in Tank 48H. While the scoping studies had a small number of individual experiments and nonideal conditions, the permanganate decomposed up to 90% of the TPB. A free hydroxide concentration above 1.0 M is required for tank corrosion control. Simulant studies indicate no decrease in TPB decomposition by permanganate until pH 14. The simulant studies show an increase in TPB decomposition as the temperature of the solution is increased to 40 °C. The post-reaction analysis of previous simulant tests did not look at all of the organic degradation products. Investigations into what these organic products are and in what quantity will help guide determinations as to whether the downstream processing facilities are able to handle the material that will be generated. Study on the time frame for the reaction between permanganate and TPB should be investigated as the literature reports only extend out to two weeks reaction time. The permanganate treatment conditions indicate no corrosion control concerns and a longer timescale reaction may be needed for in-tank treatment. In addition, further study would be useful to identify a lower boundary condition for the ratio of TPB and oxidant. The simulant tests applied large excesses of permanganate, and this may be unnecessary. The size constraint of the tank means that there will be practical limitations on the amount of sodium permanganate that can be added to the tank. The amount of permanganate should be minimized as much as possible while still ensuring decomposition of the TPB to minimize the amount of manganese dioxide solids generated.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Atomistic Explanation of the Dramatically Improved Oxygen Reduction Reaction of Jagged Platinum Nanowires, 50 Times Better than Pt

Pt is the best catalyst for the oxygen reduction reactions (ORRs), but it is far too slow. Huang and co-workers showed that dealloying 5 nm Ni 7 Pt 3 nanowires (NW) led to 2 nm pure Pt jagged NW (J-PtNW) with ORRs 50 times faster than Pt/C. They suggested that the undercoordinated surface Pt atoms, mechanical strain, and high electrochemically active surface area (ECSA) are the main contributors. We report here multiscale atomic simulations that further explain this remarkably accelerated ORR activity from an atomistic perspective. We used the ReaxFF reactive force field to convert the 5 nm Ni 7 Pt 3 NW to the jagged 2 nm NW. We applied quantum mechanics to find that 14.4% of the surface sites are barrierless for O ads + H 2 O ads → 2OH ads , the rate-determining step (RDS). The reason is that the concave nature of many surface sites pushes the OH bond of the H 2 O ads close to the O ads , leading to a dramatically reduced barrier. We used this observation to predict the performance improvement of the J-PtNW relative to Pt (111). Assuming every surface site reacts independently with this predicted rate leads to a 212-fold enhancement at 298.15 K, compared to 50 times experimentally. The atomic structures of the active sites provide insights for designing high-performance electrocatalysts for ORR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Kinetic Study of Methyl Acetate Oxidation in a Pt/Al2O3 Fixed-Bed Reactor

To support technology development for future long-term missions, a metabolic simulator will be used in a closed chamber to test the functions of a Controlled Ecological Life Support System (CELSS). Methyl acetate (MA) was selected as the fuel because its metabolic respiratory quotient is near that of humans. A kinetic study of the catalytic oxidation of MA over Pt/Al203 was then conducted to support the design and operation of the simulator. Kinetic data were obtained as a conversion percentage of MA versus retention time. The reaction was studied at one atmosphere and temperatures from 220 to 340 deg. C. The inlet MA concentration was varied from 100 to 2000 ppm with retention times from 0.01 to 10 sec. A first-order rate law and a Langmuir-Hinshelwood rate equation were tested by nonlinear regression of the kinetic data to estimate rate constants in the rate law. Regression results of the L-H equation explain the kinetic data better than the results of the first-order rate law. A Taguchi experimental design was used to study the effects of temperature, retention time, and concentrations of MA, CO2, and O2 on the conversion of MA. Results indicate that temperature has greatest effect, followed by retention time, and finally MA concentration. It was further determined that the effects of CO2 and O2 concentrations, and the cross effects, are negligible.

Hoy, Michael↗
NASA NTRS2001

Switching between simple cognitive tasks: the interaction of top-down and bottom-up factors

How do top-down factors (e.g., task expectancy) and bottom-up factors (e.g., task recency) interact to produce an overall level of task readiness? This question was addressed by factorially manipulating task expectancy and task repetition in a task-switching paradigm. The effects of expectancy and repetition on response time tended to interact underadditively, but only because the traditional binary task-repetition variable lumps together all switch trials, ignoring variation in task lag. When the task-recency variable was scaled continuously, all 4 experiments instead showed additivity between expectancy and recency. The results indicated that expectancy and recency influence different stages of mental processing. One specific possibility (the configuration-execution model) is that task expectancy affects the time required to configure upcoming central operations, whereas task recency affects the time required to actually execute those central operations.

Cognition↗
NASA NTRS2003

Quantum Dynamics Scattering Study of AB+CDE Reactions: A Seven Dimensional Treatment for the H2+C2H Reaction

A time-dependent wave-packet approach is presented for the quantum dynamics study of the AB+CDE reaction system for zero total angular momentum. A seven-degree-of-freedom calculation is employed to study the chemical reaction of H2+C2H yields H + C2H2 by treating C2H as a linear molecule. Initial state selected reaction probabilities are presented for various initial ro-vibrational states. This study shows that vibrational excitation of H2 enhances the reaction probability, whereas the excitation of C2H has only a small effect on the reactivity. An integral cross section is also reported for the initial ground states of H2 and C2H. The theoretical and experimental results agree with each other very well when the calculated seven dimensional results are adjusted to account for the lower transition state barrier heights found in recent ab initio calculations.

Wang, Dunyou↗
DOE OSTI2015

Farnesoid-X-receptor expression in monocrotaline-induced pulmonary arterial hypertension and right heart failure

Objective: The farnesoid-X-receptor (FXR) is a metabolic nuclear receptor superfamily member that is highly expressed in enterohepatic tissue and is also expressed in the cardiovascular system. Multiple nuclear receptors, including FXR, play a pivotal role in cardiovascular disease (CVD). Pulmonary arterial hypertension (PAH) is an untreatable cardiovascular system disease that leads to right heart failure (RHF). However, the potential physiological/pathological roles of FXR in PAH and RHF are unknown. We therefore compared FXR expression in the cardiovascular system in PAH, RHF and a control. Methods and results: Hemodynamic parameters and morphology were assessed in blank solution-exposed control, monocrotaline (MCT)-exposed PAH (4 weeks) and RHF (7 weeks) Sprague–Dawley rats. Real-time reverse transcription polymerase chain reaction (real-time RT-PCR), Western blot (WB), immunohistochemistry (IHC) analysis and immunofluorescence (IF) analysis were performed to assess FXR levels in the lung and heart tissues of MCT-induced PAH and RHF rats. In normal rats, low FXR levels were detected in the heart, and nearly no FXR was expressed in rat lungs. However, FXR expression was significantly elevated in PAH and RHF rat lungs but reduced in PAH and RHF rat right ventricular (RV) tissues. FXR expression was reduced only in RHF rat left ventricular (LV) tissues. Conclusions: The differential expression of FXR in MCT-induced PAH lungs and heart tissues in parallel with PAH pathophysiological processes suggests that FXR contributes to PAH. - Highlights: • FXR was expressed in rat lung and heart tissues. • FXR expression increased sharply in the lung tissues of PAH and RHF rats. • FXR expression was reduced in PAH and RHF rat RV tissue. • FXR expression was unaltered in PAH LV but reduced in RHF rat LV tissue. • FXR expression was prominent in the neovascularization region.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Five Rules for Measuring Biomass Pyrolysis Rates: Pulse-Heated Analysis of Solid Reaction Kinetics of Lignocellulosic Biomass

Pyrolytic conversion of lignocellulosic biomass utilizes high temperatures to thermally fragment biopolymers to volatile organic compounds. The complexity of the degradation process includes thousands of reactions through multiple phases occurring in less than a second. In this work, the requirements are established for measuring the reaction kinetics of high temperature (>400 °C) biomass pyrolysis in the absence of heat and mass transfer limitations. Additionally, experimental techniques must heat and cool biomass samples sufficiently fast to elucidate the evolution of reaction products with time while also eliminating a substantial reaction during the heating and cooling phases, preferably by measuring the temperature of the reacting biomass sample directly. Furthermore, these requirements are described with the PHASR (pulse-heated analysis of solid reactions) technique and demonstrated by measuring the time-resolved evolution of six major chemical products from loblolly pine pyrolysis over a temperature range of 400 to 500 °C. Differential kinetics of loblolly pine pyrolysis are measured to determine the apparent activation energy for the formation of six major product compounds including levoglucosan, furfural, and 2-methoxyphenol.

08 HYDROGEN↗