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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The atmospheric importance of methylamine additions to Criegee intermediates

We report that Criegee intermediates are important targets for study in atmospheric chemistry because of their capacity to oxidize airborne species. Among these species, ammonia has received critical attention for its presence in polluted agricultural or industrial areas and its role in forming particulate matter and condensation nuclei. Although methylamine has been given less attention than ammonia, both theoretical and experimental studies have demonstrated that the additional methyl substitution on the ammonia derivatives increases the rate constants for some systems. This suggests that the methylamine addition to Criegee intermediates could be more significant to atmospheric processes. In this work, geometries are optimized at the DF-CCSD(T)/ANO1 level for the methylamine addition reactions to the simplest Criegee intermediate and the anti- and syn-methylated Criegee intermediates. Energies for each stationary point were computed at the CCSD(T)/CBS level with corrections from the CCSDT(Q) method. Rate constants are obtained for each reaction using canonical transition state theory. Although methylamine addition proved to be a more favorable reaction relative to ammonia addition, the significantly lower concentration of atmospheric methylamine limits the prevalence of these reactions, even in the most optimal conditions. It is unlikely that the methylamine addition to Criegee intermediates will contribute significantly to the consumption of Criegee intermediates in the atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1976

Low fluxes of X-rays

Analytic and experimental investigations of the interactions of high-energy protons with spacecraft materials and light nucleus atoms were conducted. Irradiation of typical materials for scintillation detectors using accelerator-produced energetic protons and associated theoretical calculations indicate activity within detectors produced by this mechanism is significant to detection of low-level cosmic gamma radiation. Samples of several materials were flown aboard Skylab to obtain measures of the neutron and proton flux environment. Extremely weak activity was produced in the samples. Calculations of interactions of intermediate-energy protons with light nuclei were performed and a more complete theoretical model programmed for digital computation. Preliminary results appear promising for calculating products of such interactions.

Source record↗
DOE OSTI2023

Experiments to Measure the Effect of Tantalum on Critical Systems

Sandia National Laboratories (SNL) and Oak Ridge National Laboratory (ORNL) collaborated to develop a capability to test the epithermal/intermediate cross sections of materials at the SNL critical experiment facility using the Seven Percent Critical Experiment (7uPCX) fuel. As a result, a new set of critical experiments has been designed to target the epithermal cross sections of tantalum (Ta) and is scheduled to be performed at SNL in 2023. These critical experiments will be evaluated for inclusion in the 2024 edition of the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook. The focus of these critical experiments is to measure the effects of Ta on the critical array size. The critical array size will be determined by an approach-to-critical experiment with the number of fuel rods in the array as a free parameter. The core configurations are designed to optimize the reactivity worth of Ta and the overall percentage of Ta absorption rates in the epithermal/intermediate energy range (0.625 eV – 100 keV). The baseline core configuration includes 7uPCX fuel rods set at a triangular pitch of 1.016 cm and a central dry test region that utilizes a cadmium liner for filtering out thermal neutrons. The central test region has locations for 85 Ta rods set at a triangular pitch of 0.813 cm. The Ta reactivity worth for the case with 85 Ta rods is approximately 2.55%, with the percentage of Ta absorption rates within the intermediate energy range at nearly 90%.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

IER-517: Molybdenum Optimized Benchmark System Demonstrating Integral Correlations (MOBY DICK)

Nuclear criticality experiments are essential to the validation of nuclear data used in simulation software. The quality of nuclear data becomes paramount as simulation software becomes more relied upon for criticality safety studies and designs of nuclear systems. To improve the quality of nuclear data, experimenters can design critical experiments that are sensitive to isotope reaction pairs in materials of interest. The efforts conducted by the Organisation for Economic Co-operation and Development - Nuclear Energy Agency (OECD-NEA) Working Party on Nuclear Criticality Safety (WPNCS) Subgroup 8: Preservation of Expert Knowledge and Judgement Applied to Criticality Benchmarks (SG8) to categorize benchmarks according to their usefulness for nuclear data validation have been of great importance. Based on the OECD studies benchmark experiments included in the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook are concisely used by nuclear data evaluators, criticality safety engineers and others to validate nuclear data and simulation results. A lack of benchmarks sensitive to molybdenum in the (ICSBEP), particularly in the intermediate range, was noted by Los Alamos National Laboratory (LANL), the French Institut de Radioprotection et de Sûreté Nucléaire (IRSN), and Y-12 National Security Site prompting them to submit a joint integral experiment request to the Nuclear Criticality Safety Program (NCSP) in 2019. The request included both HEU and Plutonium systems in order to validate differential nuclear data focusing on the intermediate energy range but also includes thermal and fast configurations. This document represents the preliminary design work for a series of molybdenum integral experiments known as Molybdenum Optimized Benchmark System Demonstrating Integral Correlations (MOBY DICK).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS2003

Design and Performance Tests of Ultra-Compact Calorimeters for High Energy Astrophysics

This R&D project had two goals: a) the study of general-application ultra-compact calorimetry technologies for use in High Energy Astrophysics and, b) contribute to the design of an efficient calorimeter for the ACCESS mission. The direct measurement of galactic cosmic ray fluxes is performed from space or from balloon-borne detectors. Detectors used in those studies are limited in size and, specially, in weight. Since galactic cosmic ray fluxes are very small, detectors with high geometrical acceptances and long exposures are usually required for collecting enough statistics. We have studied calorimeter techniques that could produce large geometrical acceptance per unit of mass (G/w) and that may be used to study galactic cosmic rays at intermediate energies (knee energies).-The most important asset for detection of primary cosmic rays at and about the knee is large acceptance. To construct a large acceptance calorimeter (this term is used here in its most general accepted meaning of calorimeter as a device to measure particle energies ) the detector needs to be verv liaht or verv shallow . We studied two possible technologies to built compact calorimeters: the use of lead-tungstate crystals (PWO) and the use of sampling calorimetry using scintillating fibers embedded in a matrix of powder tungsten. For a very light detector, we considered the possibility of using Optical Transition Radiation (OTR) to measure the energy (and perhaps also direction and identity) of VHE cosmic rays.

Salgado, Carlos W.↗
NASA NTRSDate not supplied

Lithium Nucleation of Anode-Free Solid-State Batteries with a Dry Compressible Interlayer

Anode-free lithium batteries offer promising advantages, including increased energy density and the ability to address common mechanistic failures within the cell, thus increasing safety. One way that can make this possible is to control lithium nucleation. This could be achieved by reducing the overpotential required and implanting lithophilic nucleation sites in an anodic interlayer to aid in lithium ion transport and plating. The concept has been utilized in solid-state battery systems where electrolytes are solids with further improved safety and structural longevity. In this presentation, we discuss the use of a silver-holey graphene-based anodic interlayer that can be fabricated via direct dry compression without the use of solvent or binder. The addition of silver to the holey graphene matrix creates a route to lithium plating via a lower-energy intermediate. This idea is supported by the presence of a lithium-silver alloy that forms during the activation step. It is understood that the embedded silver acts as a nucleation site for lithium ions, thereby assisting in even plating. This control, combined with the added cushion of the holey graphene itself, can help reduce dendrite formation, ultimately increasing the safety and lifetime of the solid-state batteries.

Solid state batteries↗
DOE OSTI2020

Validation of Recent Changes in Actinide Evaluations U-235, U-233, Pu-239 [Slides]

This presentation discusses U-235 updates, including fluctuations in the fission cross section in the URR range that were refined to represent measured data following the Paradela et al. evaluation. There were small changes to the low-energy resonances to improve the fit to measured capture data from RPI (capture reduced by 5% from 0.06-7.8 eV, by 7.7% from 7.8-11 eV) and there was a very small change to the thermal nu-bar within uncertainties. Discrete level data are stored in MF=6 (format requirement, no impact on calculations) and issues leading to negative eigenvalues in cross-covariances in the RR have been sorted out. In conclusion, many improvements were made to evaluated nuclear data of actinides in the resonance region and above, such as minor changes to U-235 including assessment of changes that depend on the finalization of the O-16 evaluation. U-233 improvements show significant progress in performance and some further improvement might be needed at intermediate energies. Pu-239 ORNL/IAEA evaluation is promising; however, more work is needed.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2023

Relative population of states in 21 Mg from few-nucleon removal reactions

Nuclear reactions with intermediate-energy beams in which three, four, and five nucleons are removed are expected to proceed through a combination of nondissipative and statistical processes. In an experiment at the National Superconducting Cyclotron Laboratory, in-beam γ-ray spectroscopy was utilized to study few-nucleon removal reactions from incoming beams of 24 Mg, 25 Al, and 26 Si projectiles to the same reaction product, 21 Mg. Here, new γ-ray transitions and γ-γ coincidences in 21 Mg were established using the CsI(Na) array CAESAR and the inclusive cross section for three-neutron removal from 24 Mg was measured. Significant differences in the relative population of states in 21 Mg from 25 Al compared to 26 Si were observed and found to be correlated with the spins of the 21 Mg states. As a result, this intermediate regime between direct and statistical nucleon removal may have potential as a tool to deliver unique patterns of level populations in fast-beam experiments and alter isomer to ground state ratios in the production of exotic beams.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Perform Design Support with MCNP for New Measurements

This report incorporates our work carried out during our 5-month internship at LANL under an internship agreement with EAMEA (École des Applications Militaires de l’Énergie Atomique). After outlining the context in which we worked, we present our work as aid to modeling and predicting the neutronic behavior of nuclear systems, with a view to carrying out criticality experiments qualifying the MCNP code as part of innovative projects. Fourth generation reactors will enable to tackle a lot of issues such as environmental crisis, affordable energy access, and nuclear waste management. They seem to be one of the keys for a sustainable future. Most of the projects that emerge nowadays include the use of HALEU (high assay low enriched uranium) or MOX recycled fuels. Our projects are part of this dynamic and addresses concrete scientific research issues in the nuclear field. Studies of HALEU package are essential to anticipate the need, therefore the Optimus L (OPTImal Modular Universal Shipping cask technology) designed by NAC (Nuclear Assurance Corporation) international but filled with 20 % enriched uranium dioxide (UO 2 ) will be studied to support safe transportation. However, it seems there is no benchmark with a high correlation with the combination of this fuel and this package to validate MCNP simulations. As such, the study will focus on the development of new criticality safety benchmarks for this case. On the other hand, there is a great need for critical benchmarks in the intermediate energy range with MOX fuel. An IER (Integral Experiment Request) has then be requested to answer it through a partnership between French institution IRSN and U.S. Department of Energy's Nuclear Criticality Safety Program (NCSP). This experience planned for 2025 requires to gather calculated data through a MCNP model to be realized safely. Finally, a presentation of our one-week experience at the DAF as part of our discovery of criticality experiments will be introduced in Appendix 1: Week at the DAF (Device Assembly Facility)

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

The Technical and Economic Potential of Hydrogen within the United States

Hydrogen markets have an opportunity to grow as its value as an energy intermediate increases. Hydrogen’s estimated serviceable consumption potential in the United States is 106 MMT/yr which is a ten-fold increase over the current market size. That opportunity is driven primarily by increased demands for metals refining, biofuel and hydrocarbon production, supplementing the natural gas system, seasonal storage for the electricity grid, and fuel cell electric vehicles. The U.S. has many renewable, nuclear, and fossil resources that each could meet that demand itself. The economic potential, which considers both costs to produce hydrogen and willingness of applications to pay for it, is 22 to 41 MMT/yr. The range is impacted by factors that impact the cost to produce including the price of natural gas and the cost of electrolyzers. It is also impacted by competition to provide the same services as hydrogen including electrification.

electrolysis↗
DOE OSTI2020

Developing Scaling Relationships for Molecular Electrocatalysis through Studies of Fe-Porphyrin-Catalyzed O 2 Reduction

The oxygen reduction reaction (ORR) is a multiproton/multielectron transformation in which dioxygen (O 2 ) is reduced to water or hydrogen peroxide and serves as the cathode reaction in most fuel cells. The ORR (O 2 + 4e – + 4H + → 2H 2 O) involves up to nine substrates and thus requires navigating a complicated reaction landscape, typically with several high-energy intermediates. Many catalysts can perform this reaction, though few operate with fast rates and at low overpotentials (close to the thermodynamic potential). Attempts to optimize these parameters, both in homogeneous and heterogeneous electrocatalytic systems, have focused on modifying catalyst design and understanding kinetic/thermodynamic relationships between catalytic intermediates. One such method for analyzing and predicting catalyst reactivity and efficiency has been the development of “molecular scaling relationships”. In this work, we share our experience deriving and utilizing molecular scaling relationships for soluble, iron-porphyrin-catalyzed O 2 reduction in organic solvents. These relationships correlate turnover frequencies (TOF max ) and effective overpotentials (η eff ), properties uniquely defined for homogeneous catalysts. Following a general introduction of scaling relationships for both homogeneous and heterogeneous electrocatalysis, we describe the components of such scaling relationships: (i) the overall thermochemistry of the reaction and (ii) the rate and rate law of the catalyzed reaction. We then show how connecting these thermodynamic and kinetic parameters reveals multiple molecular scaling relationships for iron-porphyrin-catalyzed O 2 reduction. For example, the log(TOF max ) responds steeply to changes in ηeff that result from different catalyst reduction potentials (18.5 decades in TOF max /V in η eff ) but much less dramatically to changes in η eff that arise from varying the pKa of the acid buffer (5.1 decades in TOF max /V in η eff ). Thus, a single scaling relationship is not always sufficient for describing molecular electrocatalysis. This is particularly evident when the catalyst identity and reaction conditions are coupled. Using these multiple scaling relationships, we demonstrate that the metrics of turnover frequency and effective overpotential can be predictably tuned to achieve faster rates at lowered overpotentials. This Account uses a collection of related stories describing our research on soluble iron-porphyrin-catalyzed ORR to show how molecular scaling relationships can be derived and used for any electrocatalytic reaction. Such scaling relationships are powerful tools that connect the thermochemistry, mechanism, and rate law for a catalytic system. We hope that this collection shows the utility and simplicity of the molecular scaling approach for understanding catalysis, for enabling direct comparisons between catalyst systems, and for optimizing catalytic processes.

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

Regioselective Arene C−H Alkylation Enabled by Organic Photoredox Catalysis

Abstract Expanding the toolbox of C−H functionalization reactions applicable to the late‐stage modification of complex molecules is of interest in medicinal chemistry, wherein the preparation of structural variants of known pharmacophores is a key strategy for drug development. One manifold for the functionalization of aromatic molecules utilizes diazo compounds and a transition‐metal catalyst to generate a metallocarbene species, which is capable of direct insertion into an aromatic C−H bond. However, these high‐energy intermediates can often require directing groups or a large excess of substrate to achieve efficient and selective reactivity. Herein, we report that arene cation radicals generated by organic photoredox catalysis engage in formal C−H functionalization reactions with diazoacetate derivatives, furnishing sp 2 –sp 3 coupled products with moderate‐to‐good regioselectivity. In contrast to previous methods utilizing metallocarbene intermediates, this transformation does not proceed via a carbene intermediate, nor does it require the presence of a transition‐metal catalyst.

Holmberg‐Douglas, Natalie↗
DOE OSTI2020

Regioselective Arene C−H Alkylation Enabled by Organic Photoredox Catalysis

Abstract Expanding the toolbox of C−H functionalization reactions applicable to the late‐stage modification of complex molecules is of interest in medicinal chemistry, wherein the preparation of structural variants of known pharmacophores is a key strategy for drug development. One manifold for the functionalization of aromatic molecules utilizes diazo compounds and a transition‐metal catalyst to generate a metallocarbene species, which is capable of direct insertion into an aromatic C−H bond. However, these high‐energy intermediates can often require directing groups or a large excess of substrate to achieve efficient and selective reactivity. Herein, we report that arene cation radicals generated by organic photoredox catalysis engage in formal C−H functionalization reactions with diazoacetate derivatives, furnishing sp 2 –sp 3 coupled products with moderate‐to‐good regioselectivity. In contrast to previous methods utilizing metallocarbene intermediates, this transformation does not proceed via a carbene intermediate, nor does it require the presence of a transition‐metal catalyst.

Holmberg‐Douglas, Natalie↗
DOE OSTI2021

Higher-rank tensor field theory of non-abelian fracton and embeddon

We formulate a new class of tensor gauge field theories in any dimension that is a hybrid class between symmetric higher-rank tensor gauge theory (i.e., higher-spin gauge theory) and anti-symmetric tensor topological field theory. Our theory describes a mixed unitary phase interplaying between gapless and gapped topological order phases (which can live with or without Euclidean, Poincaré, or anisotropic symmetry, at least in ultraviolet high or intermediate energy field theory, but not yet to a lattice cutoff scale). The “gauge structure” can be compact, continuous, abelian or non-abelian. Our theory sits outside the paradigm of Maxwell electromagnetic theory in 1865 and Yang–Mills isospin/color theory in 1954. We discuss its local gauge transformation in terms of the ungauged vector-like or tensor-like higher-moment global symmetry. The non-abelian gauge structure is caused by gauging the non-commutative symmetries: a higher-moment symmetry and a charge conjugation (particle–hole) symmetry. Vector global symmetries along time direction may exhibit time crystals. We explore the relation of these long-range entangled matters to a non-abelian generalization of Fracton order in condensed matter, a field theory formulation of foliation, the spacetime embedding and Embeddon that we newly introduce, and possible fundamental physics applications to dark matter or dark energy.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Simulations and analysis tools for charge-exchange (d, 2 He) reactions in inverse kinematics with the AT-TPC

Charge-exchange (d, 2 He) reactions in inverse kinematics at intermediate energies are a very promising method to investigate the Gamow–Teller transition strength in unstable nuclei. A simulation and analysis software based on the attpcroot package was developed to study this type of reactions with the active-target time projection chamber (AT-TPC). The simulation routines provide a realistic detector response that can be used to understand and benchmark experimental data. Analysis tools and correction routines can be developed and tested from simulations in ATTPCROOT , because they are processed in the same way as the real data. In particular, we study the feasibility of using coincidences with beam-like particles to unambiguously identify the (d, 2 He) reaction channel, and to develop a kinematic fitting routine for future applications. More technically, the impact of space-charge effects in the track reconstruction, and a possible correction method are investigated in detail. Finally, this analysis and simulation package constitutes an essential part of the software development for the fast-beams program with the AT-TPC.

(d,2He)↗
DOE OSTI2023

Bayesian inference of in-medium baryon-baryon scattering cross sections from HADES proton flow data

Within a Bayesian statistical framework using a Gaussian Process emulator for an isospin-dependent Boltzmann-Uehling-Uhlenbeck (IBUU) transport model simulator of heavy-ion reactions at intermediate energies, we infer from the HADES proton flow data the posterior probability distribution functions of in-medium baryon-baryon scattering cross section modification factor X with respect to free-space and the corresponding incompressibility K of nuclear matter as well as their correlation function. In conclusion, the mean value of X is found to be $X$ = $1.32_ {+0.28} ^ {-0.40} $ at 68% confidence level assuming the nuclear incompressibility K will not exceed 400 MeV, providing circumstantial evidence for enhanced baryon-braryon scattering cross sections in hot and dense nuclear matter.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

An alternative viewpoint on the nuclear structure towards 100 Sn: Lifetime measurements in 105 Sn

This work aims at presenting an alternative approach to the long standing problem of the B(E2) values in Sn isotopes in the vicinity of the N=Z double-magic nucleus 100 Sn, until now predominantly measured with relativistic and intermediate-energy Coulomb excitation reactions. The direct measurement of the lifetime of low-lying excited states in odd-even Sn isotopes provides a new and precise guidance for the theoretical description of the nuclear structure in this region. Lifetime measurements have been performed in 105 Sn for the first time with the coincidence Recoil Distance Doppler Shift technique. The lifetime results for the $7/2^+_1$ first excited state and the $11/2^+_1$ state, $2^+ (^{104}$Sn) Ⓧ $v1g_{7/2}$ multiplet member, are discussed in comparison with state-of-the-art shell model and mean field calculations, highlighting the crucial contribution of proton excitation across the core of 100 Sn. The reduced transition probability B(E2) of the $11/2^+_1$ core-coupled state points out an enhanced staggering with respect to the B(E2; $2^+_1$ → $0^+_1$) in the even-mass 104 Sn and 106 Sn isotopes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Proton-Coupled Group Transfer Enables Concerted Protonation Pathways Relevant to Small-Molecule Activation

The mechanistic identification of Nature's use of concerted reactions, in which all bond-breaking and bond-making occurs in a single step, has inspired rational designs for artificial synthetic transformations via pathways that bypass high energy intermediates that would otherwise be thermodynamically and kinetically inaccessible. Here, we electrochemically activate an organometallic Ruthenium(II) complex to show that, in acetonitrile solutions, the movement of protons from weak Brønsted acids, such as water and methanol, is coupled with the transfer of its negatively charged counterpart to carbon dioxide (CO 2 ) - a process termed proton-coupled group transfer - to stoichiometrically produce a metal-hydride complex and a carbonate species. These previously unidentified pathways have played key roles in CO 2 and proton reduction catalysis by enabling the generation of key intermediates such as hydrides and metallocarboxylic acids, while its applicability to carbon acids may provide alternative approaches in the electrosynthesis of chemical commodities via alkylation and carboxylation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗