Search NASA⌕ Search

SEARCH · Search NASA

Results for “elimination reactions”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Examination of Ac-225 production from Ra-226 using fast reactor JOYO

In this study, the authors investigated the method of producing the radionuclide Ac{sup 225} used for targeted alpha therapy (TAT). Currently, Ac{sup 225} is mainly generated from ORNL's Th{sup 229} generator, and the annual production amount is limited to about 63 GBq, and methods for generating it using accelerators are under development in each country. The method using an accelerator has the advantage of being able to generate Ac{sup 225} from a small amount of target nuclides with high efficiency but has the disadvantage of not being able to irradiate a large amount of target nuclides at once due to the small irradiation area. Therefore, the authors investigated a method to generate Ac{sup 225} by neutron irradiation of Ra{sup 226} as a target nuclide using the experimental fast reactor JOYO, which has abundant neutrons and a large loading region. Irradiation of Ra{sup 226} with fast neutrons causes a (n, 2n) reaction to generate Ra{sup 225}, and then decay to produce Ac{sup 225}. In addition, although harmful Ac{sup 227} is also produced at the same time by the (n,γ) reaction, first of all the actinium isotope is chemically separated and eliminated. Since the remaining Ra{sup 225} collapses and Ac{sup 225} is produced, pure Ac{sup 225} can be extracted by performing chemical separation again. As a result of the analysis, 1 g of Ra{sup 226} is irradiated with JOYO for 60 days, and milking is performed 4 times every 17.5 days. By doing these three times a year, it was found that about 50 GBq of Ac{sup 225} was generated. (authors)

07 ISOTOPE AND RADIATION SOURCES↗
NASA NTRS1987

Use of control umbilicals as a deployment mode for free flying telerobotic work systems

Work to date on telerobotic work systems for use in space generally consider two deployment modes, free flying, or fixed within a limited work envelope. Control tethers may be employed to obtain a number of operational advantages and added flexibility in the basing and deployment of telerobotic work systems. Use of a tether allows the work system to be separated into two major modules, the remote work package and the control module. The Remote Work Package (RWP) comprises the free flying portion of the work system while the Control Module (CM) remains at the work system base. The chief advantage of this configuration is that only the components required for completion of the work task must be located at the work site. Reaction mass used in free flight is stored at the Control module and supplied to the RWP through the tether, eliminating the need for the RWP to carry it. The RWP can be made less massive than a self contained free flying work system. As a result, reaction mass required for free flight is lower than for a self contained free flyer.

Kuehn, J. S.↗
DOE OSTI2024

Rubisco supplies pyruvate for the 2- C -methyl-D-erythritol-4-phosphate pathway

RIBULOSE-1,5-BISPHOSPHATE CARBOXYLASE/OXYGENASE (Rubisco) produces pyruvate in the chloroplast through β-elimination of the aci-carbanion intermediate. Here we show that this side reaction supplies pyruvate for isoprenoid, fatty acid and branched-chain amino acid biosynthesis in photosynthetically active tissue. 13 C labelling studies of intact Arabidopsis plants demonstrate that the total carbon commitment to pyruvate is too large for phosphoenolpyruvate to serve as a precursor. Low oxygen stimulates Rubisco carboxylase activity and increases pyruvate production and flux through the 2-C-methyl-d-erythritol-4-phosphate (MEP) pathway, which supplies the precursors for plastidic isoprenoid biosynthesis. Metabolome analysis of mutants defective in phosphoenolpyruvate or pyruvate import and biochemical characterization of isolated chloroplasts further support Rubisco as the main source of pyruvate in chloroplasts. Seedlings incorporated exogenous, 13 C-labelled pyruvate into MEP pathway intermediates, while adult plants did not, underscoring the developmental transition in pyruvate sourcing. Rubisco β-elimination leading to pyruvate constituted 0.7% of the product profile in in vitro assays, which translates to 2% of the total carbon leaving the Calvin–Benson–Bassham cycle. These insights solve the “pyruvate paradox”, improve the fit of metabolic models for central metabolism and connect the MEP pathway directly to carbon assimilation.

Plant physiology↗
DOE OSTI2024

Initiation and Carbene Induced Radical Chain Reactions in CH 2 F 2 Pyrolysis

High temperature dissociations of organic molecules typically involve a competition between radical and molecular processes. In this work, we use a modeling, experiment, theory (MET) framework to characterize the high temperature thermal dissociation of CH 2 F 2 , a flammable hydrofluorocarbon (HFC) that finds widespread use as a refrigerant. Initiation in CH 2 F 2 proceeds via a molecular elimination channel; CH 2 F 2 →CHF+HF. Here we show that the subsequent self-reactions of the singlet carbene, CHF, are fast multichannel processes and a facile source of radicals that initiate rapid chain propagation reactions. These have a marked influence on the decomposition kinetics of CH 2 F 2 . The inclusion of these reactions brings the simulations into better agreement with the present and literature experiments. Additionally, flame simulations indicate that inclusion of the CHF+CHF multichannel reaction leads to a noticeable enhancement in predictions of laminar flame speeds, a key parameter that is used to determine the flammability of a refrigerant.

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

Mechanism and kinetics of light alkane dehydrogenation and cracking over isolated Ga species in Ga/H-MFI

The objective of this study is to examine the mechanisms and kinetics of C2H6 dehydrogenation and n-C4H10 dehydrogenation and cracking over isolated Ga species in Ga/HMFI and to compare these results to those reported previously for C3H8 dehydrogenation and cracking. C2H6 dehydrogenation is found to be catalyzed by both [GaH]2+ and [GaH2]+ cations at similar turnover frequencies. Rate measurements over Ga/H-MFI containing predominantly [GaH2]+ cations reveal that C2H6 dehydrogenation rates exhibit a Langmuir.Hinshelwood dependence on C2H6 partial pressure at elevated temperatures (>730 K), consistent with the involvement of chemisorbed [C2H5.GaH]+ species. The reaction kinetics suggest that C2H6 dehydrogenation proceeds via heterolytic C-H cleavage of adsorbed C2H6 by [GaH2]+ cations to form H2 and [C2H5-GaH]+ species, which further decompose via β-hydride elimination to form C2H4. By contrast, C4H10 dehydrogenation and both terminal and central cracking are catalyzed exclusively by [GaH]2+ cations. All three reactions exhibit a Langmuir-Hinshelwood dependence on C4H10 partial pressure and are inhibited by H2. Ratios of dehydrogenation to cracking (total) and terminal to central cracking are approximately independent of C4H10 partial pressure consistent with the involvement of a common C4H10-derived surface intermediate. The observed reaction kinetics are consistent with an alkyl-mediated mechanism occurring over [GaH]2+, analogous to that reported previously for C3H8 dehydrogenation/cracking over Ga/H-MFI (Phadke, N. M.; et al. J. Am. Chem. Soc. 2019, 141, 1614-1627). The mechanism proceeds via facile, heterolytic dissociation of adsorbed C4H10 to form [C4H9-GaH]+-H+ cation pairs via methyl C-H-activated pathways. Dehydrogenation then proceeds via β-hydride elimination, respectively, forming butene, while terminal and central cracking proceed via C-H-activated H+ attack. Methylene activation was also considered but found to occur at a significantly lower rate. Theoretical analysis of the proposed reaction pathways leads to apparent activation enthalpies in good agreement with values extracted from the measured kinetics, thereby supporting the proposed pathways and the roles of [GaH]2+ and [GaH2]+ cations in the dehydrogenation and cracking of light alkanes on Ga/H-MFI.

Phadke, NM↗
DOE OSTI2025

Chemical timescale effects on detonation convergence

Numerical simulations of detonation-containing flows have emerged as crucial tools for designing next- generation power and propulsion devices. As these tools mature, it is important for the combustion community to properly understand and isolate grid resolution effects when simulating detonations. To this end, the objective of this work is to provide a comprehensive analysis of the numerical convergence of unsteady detonation simulations, with focus on isolating the impacts of chemical timescale modifications on convergence characteristics in the context of operator splitting. With the aid of an AMReX-based adaptive mesh refinement flow solver-which enables resolutions up to ($\mathcal{O}$ (1000) cells-per-induction length-the convergence analysis is conducted using two kinetics configurations: (1) the simplified three-step Arrhenius-based model mechanism of Short and Quirk (1997), where chemical timescales in the detonation are modified by adjusting activation energies in the initiation and branching reactions, and (2) a detailed hydrogen- air mechanism, where the chemical timescales are adjusted by varying the ambient pressure. The convergence of unsteady self-sustained detonations in one-dimensional channels is then analyzed with reference to steady-state theoretical baseline solutions using these mechanisms. The goal of the analysis is to provide a detailed comparison of the effects of grid resolution on both macroscopic (peak pressures and wave speeds) and microscopic (wave structure) quantities of interest, drawing connections between the deviations from steady-state baselines and minimum chemical timescales. In particular, chemical timescale reductions were found to have minimal impact on the convergence of macroscopic properties. Furthermore, analyses of microscopic convergence trends, particularly in the reaction front location, revealed a key insight: maintaining the induction time while eliminating prohibitive chemical timescales through mechanism simplifications and combustion modeling can significantly enhance detonation convergence properties. Ultimately, this work uncovers resolution-dependent unsteady detonation convergence regimes and highlights the important role played by not only the chemical timescales, but also the ratio between the chemical timescale and induction time on the numerical convergence of the detonation wave structure.

Adaptive mesh refinement↗
DOE OSTI2021

A low-cost sulfate-based all iron redox flow battery

Redox flow batteries (RFBs) are promising choices for stationary electric energy storage. Nevertheless, commercialization is impeded by high-cost electrolyte and membrane materials. Here, we report a low-cost all-iron RFB that features inexpensive FeSO 4 electrolytes, microporous membrane along with a glass fiber separator. The addition of 0.1 м 1-ethyl-3-methylimidazolium chloride (EMIC) overcomes the low solubility of FeSO 4 in water which is raised to 2.2 м. DFT calculations demonstrate that EMI + can strengthen the interaction between sulfate anions and water molecules. This electrolyte composition also allows both anode and cathode reactions to operate without actively maintaining a pH gradient between them, thus eliminating the need for expensive ion exchange membranes. The all-iron RFB demonstrates stable operation at a current density of 20 mA cm –2 for more than 800 cycles via a simple, periodic regeneration process. Furthermore, the system cost of FeSO 4 /EMIC RFBs is projected to be $ 50 per kWh due to its low-cost active materials and the inexpensive microporous membrane. Finally, this low-cost, high-concentration all-iron RFB is a promising stationary energy–storage system for storing renewable energy.

25 ENERGY STORAGE↗
NASA NTRS1972

Cryogenic liquid O2/H2 reaction control systems for Space Shuttle.

A Space Shuttle liquid oxygen/hydrogen reaction control system design analysis has been performed. The system concept considered eliminates propellant conditioning equipment and delivers the propellants to the engines in a liquid rather than a gaseous state. This paper provides system design analyses results and compares various means of implementing the concept on the basis of weight, technology requirements, and operational considerations. Additionally, weight comparisons are made between cryogenic oxygen/hydrogen system requirements. These comparisons show that the liquid oxygen/hydrogen system concept could effect marked weight reductions in the Space Shuttle orbiter total impulse range.

Kelly, P. J.↗
NASA NTRS1987

Polyphase alloys as rechargeable electrodes in advanced battery systems

The rechargeability of electrochemical cells is often limited by negative electrode problems. These may include loss of capacity, increased impedance, macroscopic shape change, dendrite growth, or a tendency for filamentary or whisker growth. In principle, these problems can be reduced or eliminated by the use of alloys that undergo either displacement or insertion reactions at reactant species activities less than unity, rather than pure elements. The fundamental reasons for some of these problems with elemental electrodes, as well as the basic principles involved in the different behavior of alloys, are briefly discussed. More information is now available concerning the thermodynamic and kinetic properties of a number of alloys of potential interest for use as electrodes in elevated temperature lithium battery systems. Recent results have extended these results down to ambient temperatures, indicating that some such materials may be of interest for use with new low temperature molten salt electrolytes, or with organic solvent electrolytes. The all solid mixed conductor matrix concept is also reviewed.

Huggins, Robert A.↗
NASA NTRS1999

Friction Stir Welding of SiC/Aluminum Metal Matrix Composites

Friction Stir Welding (FSW) is a new solid state process for joining metals by plasticizing and consolidating materials around the bond line using thermal energy producing from frictional forces. A feasibility study for FSW of Metal Matrix Composites (MMC) was investigated using aluminum 6092 alloy reinforced with 17% SiC particulates. FSW process consists of a special rotating pin tool that is positioned to plunge into the MMC surface at the bond line. As the tool rotates and move forward along the bond line, the material at the bond line is heated up and forced to flow around the rotating tip to consolidate on the tip's backside to form a solid state joint. FSW has the potential for producing sound welds with MMC because the processing temperature occurs well below the melting point of the metal matrix; thereby eliminating the reinforcement-to-matrix solidification defects, reducing the undesirable chemical reactions and porosity problems.

Lee, Jonathan A.↗
DOE OSTI2023

The Crucial Role of Sb 2 F 10 in the Chemical Synthesis of F 2

The purely chemical synthesis of fluorine is a spectacular reaction which for more than a century had been believed to be impossible. In 1986, it was finally experimentally achieved, but since then this important reaction has not been further studied and its detailed mechanism had been a mystery. The known thermal stability of MnF 4 casts serious doubts on the originally proposed hypothesis that MnF 4 is thermodynamically unstable and decomposes spontaneously to a lower manganese fluoride and F 2 . This apparent discrepancy has now been resolved experimentally and by electronic structure calculations. It is shown that the reductive elimination of F 2 requires a large excess of SbF 5 and occurs in the last reaction step when in the intermediate [SbF 6 ][MnF 2 ][Sb 2 F 11 ] the addition of one more SbF 5 molecule to the [SbF 6 ] - anion generates a second tridentate [Sb 2 F 11 ] - anion. The two tridentate [Sb 2 F 11 ] - anions then provide six fluorine bridges to the Mn atom thereby facilitating the reductive elimination of the two fluorine ligands as F 2 .

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

Implementing hydrogen oxidation reaction on Pt for controlling counter electrode processes

The search for active, stable, and durable materials for electrochemical energy technologies requires increasing levels of precision to establish true structure-function relationships and guide materials design from atomic and molecular scale. This increases the level of control required over the experimental system for proper materials evaluation. The choice of counter electrode material become crucial, as Pt dissolution at high voltages may cause contamination to the working electrode, especially when studying reductive processes in reactions such as oxygen reduction reaction (ORR), H 2 evolution reaction (HER), and the CO 2 reduction reaction. The learnings from “old school” electrochemistry groups lead us to leverage H 2 reactions over Pt to construct a counter electrode system with controlled potential that eliminates Pt ion contamination concerns. In here we discuss the construction of such Pt|H 2 counter electrode where key experimental aspects such as the H 2 flow rate and effective distribution determines the maximum current this counter electrode can accommodate before switching to high voltage and triggering Pt dissolution. Lastly, we demonstrate the use of the Pt|H 2 counter electrode in aqueous electrolytes during HER occurring on the working electrode at varying currents, showing that the Pt content in the cell remains below parts per trillion (ppt) up to 10 mA, and below 50 ppt at 100 mA up to 1 h of constant current hold. This work provides a guide to the implementation of Pt|H 2 counter electrodes to improve the precision of electrochemical experiments in search of highly active, selective, and durable materials for energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Combustion of Metals in Reduced-Gravity and Extra Terrestrial Environments

The combustion of metals is a field with important practical applications in rocket propellants, high-temperature flames, and material synthesis. Also, the safe operation of metal containers in high-pressure oxygen systems and with cryogenic fuels and oxidizers remains an important concern in industry. The increasing use of metallic components in spacecraft and space structures has also raised concerns about their flammability properties and fire suppression mechanisms. In addition, recent efforts to embark on unmanned and manned planetary exploration, such as on Mars, have also renewed the interest in metal/carbon-dioxide combustion as an effective in situ resource utilization technology. In spite of these practical applications, the understanding of the combustion properties of metals remains far behind that of the most commonly used fuels such as hydrocarbons. The lack of understanding is due to the many problems unique to metal- oxidizer reactions such as: low-temperature surface oxidation prior to ignition, heterogeneous reactions, very high combustion temperatures, product condensation, high emissivity of products, and multi-phase interactions. Very few analytical models (all neglecting the influence of gravity) have been developed to predict the burning characteristics and the flame structure details. Several experimental studies attempting to validate these models have used small metal particles to recreate gravity-free conditions. The high emissivity of the flames, rapid reaction, and intermittent explosions experienced by these particles have made the gathering of any useful information on burning rates and flame structure very difficult. The use of a reduced gravity environment is needed to clarify some of the complex interactions among the phenomena described above. First, the elimination of the intrusive buoyant flows that plague all combustion phenomena is of paramount importance in metal reactions due to the much higher temperatures reached during combustion. Second, a low-gravity environment is absolutely essential to remove the destructive effect of gravity on the shape of a molten metal droplet in order to study a spherically symmetric condition with large bulk samples. The larger size of the spherical metal droplet and the longer burning times available in reduced gravity extend the spatial and temporal dimensions to permit careful probing of the flame structure and dynamics. Third, the influence of the radiative heat transfer from the solid oxides can be studied more carefully by generating a stagnant spherical shell of condensed products undisturbed by buoyancy.

Branch, M.C.↗
NASA NTRS1997

Modulated FT- Raman Fiber-Optic Spectroscopy: A technique for Remotely Monitoring High-Temperature Reactions in Real-Time

A modification to a commercial FT-Raman spectrometer is presented for the elimination of thermal backgrounds in FT-Raman spectra. The modification involves the use of a mechanical chopper to modulate the CW laser, remote collection of the signal via fiber optics, and connection of a dual-phase digital signal processor lock-in amplifier between the detector and the spectrometer's collection electronics to demodulate and filter the optical signals. The resulting modulated FT-Raman fiber-optic spectrometer is capable of completely eliminating thermal backgrounds at temperatures exceeding 370 C. In addition, the signal/noise of generated Raman spectra is greater than for spectra collected with the conventional FT-Raman under identical conditions and incident laser power. This is true for both room-temperature and hot samples. The method allows collection of data using preexisting spectrometer software. The total cost of the modification (excluding fiber optics) is approximately $3000 and requires less than 2 h to implement. This is the first report of Fr-Raman spectra collected at temperatures in excess of 300 C in the absence of thermal backgrounds.

Cooper, John B.↗
DOE OSTI2026

A Short-Lived Isotope Counting System (SLICS) to measure reaction cross sections producing light, beta-decaying nuclei on OMEGA

A new activation detector optimized for short-lived isotopes was designed, installed, and tested on OMEGA. The Short-Lived Isotope Counting System (SLICS) can be positioned as close as 35 cm from the OMEGA target chamber center in a ten-inch-manipulator. Stable target samples can be mounted on the front end of the detector assembly to undergo triton-, deuteron-, or neutron-induced reactions that produce short-lived reaction products that beta decay. The emitted betas are detected in a phoswich configuration to eliminate the gamma background. The detector is optimized for isotopes with half-lives from 150 ms to 20 s, filling a gap in OMEGA’s current activation detectors for isotopes with half-lives >5 min. In a pilot study, SLICS achieved an efficiency of 24.5% ± 2.0% for counting 8Li, with a total of 505.8 ± 4.4 qualifying events. Using the existing triton laser-ion acceleration platform on OMEGA, this detector can be used to measure rarely studied tritium-induced reactions on light nuclei with an estimated uncertainty of 12%. As a result, the design of the detector and its performance during a first experiment employing deuterium as a surrogate will be discussed.

Beta spectrometry↗
DOE OSTI2026

Kinetics Modeling and Reactor Design Study of Glucose-to-Terpenes Cell-Free Conversion

Cell-free systems offer many advantages over traditional biological conversion by eliminating biological growth constraints. It also offers easy manipulation and finetuning of the reaction conditions for each individual enzyme. The conversion of cellulosic glucose to Limonene, a terpene, is a promising pathway for producing fuels and chemicals. Recent advances in developing cell-free systems focuses on bench scale optimization of terpene yield and to demonstrate its feasibility towards commercialization [1,2]. There is significant knowledge gap regarding reaction kinetics of these cell-free systems to further study how it will perform at larger scale. We present here, our studies on reaction kinetics and reactor design implications of cell-free glucose to Limonene conversion to facilitate the further development and commercialization of this process. We developed a novel kinetic model based on the metabolic-network structure of the cell-free system with multi-substrate reversible Michaelis-Menten rate law. To estimate kinetic parameters for this system of rate equations, we employed Bayesian optimization to perform global search with the assistance of gaussian processes to balance exploration and exploitation. The model parameters estimated showed good results compared with experimental data. The estimated parameters were used to perform sensitivity analysis. We found that Hexokinase is one of the most critical enzymes that affect the conversion of the glucose. We also observed that abundance of co-factors is also critical to the conversion of glucose to limonene. We investigated packed bed reactors with enzymes immobilized on the surface of particles to convert glucose stream into Limonene for larger scale production. The reactor design such as particle size, enzyme loading, and flow rate are found to be critical for improving yields. [1] Dudley, Q.M., Nash, C.J. and Jewett, M.C., 2019. Synthetic Biology, 4(1), p.ysz003. [2] Korman, T.P., Opgenorth, P.H. and Bowie, J.U., 2017. Nature communications, 8(1), p.15526.

09 BIOMASS FUELS↗