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NASA NTRS1986

Lower power dc arcjet operations with hydrogen hydrogen/nitrogen propellant mixtures

The arcjet assembly from a flight model system was modified with a new thoriated tungsten nozzle insert and has been tested with hydrogen-nitrogen mixtures simulating the decomposition products of ammonia and hydrazine. Arcjet power consumption ranged from 0.7 to 1.15 kW depending on low rate, input current, and mixture composition. At a nominal 1 kW power level the ammonia mixtures thrust efficiency was about 0.31 at specific impulse values ranging between 460 and 500 sec. Hydrazine mixtures gave similar thrust efficiencies at the same power level with specific impulse values between 395 and 430 sec. Large, spontaneous voltage mode changes were not observed once the thruster had passed a period of instability immediately following start up. This period of instability, and the startup at low pressure, were seen as major causes of constrictor damage during the tests.

Curran, F. M.↗

DOE OSTI2026

Autonomous Hydrogen Fueling Station

This project “Autonomous Hydrogen Fueling Station” covered the autonomous refueling with both gaseous hydrogen and liquid hydrogen. The part on gaseous hydrogen focused on the development of an autonomous robotic fueling arm that would couple to a fuel cell engine for hydrogen refueling without guidance from the forklift operator and budget period. Research was also covered for the robotic fueling with a commercial vehicle. The second phase of the project created the baseline for an autonomous liquid hydrogen transfer system that would minimize boil off losses by operating at thermodynamically efficient state points. For the development of the robotic fueling arm, testing was conducted to establish a baseline measurement of the accuracy and repeatability of a human operator positioning a lift truck in front of a dispenser. The goal was to establish the range of motion required for an autonomous fueling mechanism to mate a hydrogen nozzle with a receptacle on a fuel cell system installed in a forklift. The final design comprised a selective compliance articulated robot arm (SCARA)-type mechanism with two arms for horizontal motion and a ball screw for vertical movement and color and LIDAR cameras were used for marker identification and proximity awareness to guide the robotic arm to its target receptacle. Initial tests resulted in 199 out of 200 successful attempts at autonomous coupling of the dispensing coupler and a fuel cell engine, without hydrogen. The dispenser prototype was modified to include tubing for both hydrogen fuel and air purge lines, but subsequent tests were confounded by the shoulder motor over current errors which limited the robot from getting to the fully inserted position to achieve a positive latch. Robotic hydrogen refueling was successfully demonstrated over 1.5 hours of testing, Plug completed 29 successful latches with an average number of 4 sequential latches before failure. However, a robot capable of placing the nozzle with more force is required for higher reliability. For budget period two, a small scale (10 kg / transfer) automated control system was designed that would operate valves to control pressure and flow of liquid nitrogen between a source and receiving tank with an aim to minimize boil off losses by operating at the most thermodynamically efficient state points. Control system logic flow and a P&ID were developed prior to system safety characterization via HAZOP. A control narrative and system state points were defined. Delays in approval for a change of project objective and procurement issues precluded the construction and test of the final prototype system.

08 HYDROGEN↗

DOE OSTI2021

Insertion products in the reaction of carbonyl oxide Criegee intermediates with acids: Chloro(hydroperoxy)methane formation from reaction of CH 2 OO with HCl and DCl

The reactions of carbonyl oxides (“Criegee intermediates”) with organic and inorganic acids have been postulated to proceed predominantly by an insertion mechanism, and the hydroperoxy-substituted ester products from reactions with organic acids have been spectroscopically observed. Here this work characterizes the products from one of the simplest reactions of carbonyl oxides with inorganic acids, that of formaldehyde oxide, CH 2 OO, with hydrogen chloride, which occurs via a 1,2-insertion in the H–Cl bond. Reactions of both HCl and DCl isotopologues yield product signal at the mass of the insertion product chloro(hydroperoxy)methane and a dissociative ionisation peak at the mass of the protonated (or deuteronated) Criegee intermediate. The isotopic composition of the insertion product has been measured for reaction mixtures where both HCl isotopologues are present, and the H/D ratio of the product is consistently higher (by a factor of 1.6 ± 0.3) than that of the reactants. This isotope selectivity in the products has smaller uncertainty than the ratio of measured rate coefficients and suggests a normal (k H > k D ) kinetic isotope effect in the reaction. Theoretical kinetics calculations predict a small normal kinetic isotope effect for the overall reaction (k H / k D = 1.35 at 20 Torr N 2 and k H / k D = 1.2 for 1 atm N 2 ) but predict a substantial inverse kinetic isotope effect (k D > k H ) for the stabilisation fraction, in disagreement with the experimental observation.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2022

Hydrogen Localization and Cluster Formation in α-Zr from First-Principles Investigations

We report alpha-zirconium (α-Zr) is a hydrogen atom host material used in nuclear energy and semiconducting applications due to Zr's excellent properties such as corrosion resistance, low thermal neutrons cross-section, and thermodynamically favorable interstitial sequestering of H atoms. Herein we use density functional theory simulations to systematically analyze the initial stages of H insertion in the Zr matrix, and determine optimal hydrogen localization, distribution, and clustering tendencies from a thermodynamics and kinetics perspective. Our results suggest that H occupation of tetrahedral sites is strongly favored, consistent with previous experimental and theoretical studies. Further, a cooperative effect in H localization is shown where H atoms favor clustering. The H pair is found to be the most stable by occupying tetrahedral sites with pairs at second nearest-neighbor positions (TTn2). Among the four H atom clusters, the most favorable configuration has two TTn2 pairs forming "box " or "zig-zag" shaped-cluster with the pairs separated by 3.03 or 3.25 Å, respectively. Nudged elastic band simulations suggest that the formation of TTn2 is facile and is limited by the small diffusion barrier of the monomer of less than 0.1 eV. Further, the formation routes for the 4H atom clusters are also presented. The current study can serve as a foundation to systematically model H atom clustering in metals and alloys.

36 MATERIALS SCIENCE↗

NASA NTRS1986

Low power dc arcjet operation with hydrogen/nitrogen propellant mixtures

The arcjet assembly from a flight model system was modified with a new thoriated tungsten nozzle insert and has been tested with hydrogen-nitrogen mixtures simulating the decomposition products of ammonia and hygrazine. Arcjet power consumption ranged from 0.7 to 1.15 kW depending on low rate, input current, and mixture composition. At a nominal 1 kW power level the ammonia mixtures thrust efficiency was about 0.31 at specific impulse values ranging between 460 and 500 sec. Hydrazine mixtures gave similar thrust efficiencies at the same power level with specific impulse values between 395 and 430 sec. Large, spontaneous voltage mode changes were not observed once the thruster had passed a period of instability immediately following start up. This period of instability, and the startup at low pressure, were seen as major causes of constrictor damage during the tests.

Curran, F. M.↗

DOE OSTI2024

Towards Net-Zero: Nuclear-Assisted Waste Biomass to Liquid Fuel in Eastern Idaho

A nuclear assisted carbon negative hybrid energy process that enables production of synthetic bio-crude oil and biochar from Eastern Idaho waste biomass is proposed. The process integrates nuclear powered electricity with high temperature steam electrolysis and biomass hydropyrolysis. The bio-crude oil is of sufficient composition and blended with traditional crude oil at a refinery. Hydrogen from the electrolyzer is pressurized and inserted into the pyrolyzer. Non condensable gases generated in the hydropyrolysis process are burned with oxygen from the electrolyzer to produce heat for the electrolyzer, biomass dryer, and pyrolyzer. The biochar is returned to the soil via fertilizer application and remains there for thousands of years. Since the total process uses nuclear generated electricity, the carbon in the biochar is ultimately sequestered from the atmosphere, thus making the process carbon negative. Using Eastern Idaho wheat or barley straw, this hybrid energy process has the potential to provide an alternative petroleum source. Two options exist for the system design: 1) send electricity from the nuclear plant and straw to a chemical processing plant to produce the bio-crude and biochar, 2) construct the biomass processing facility near the nuclear plant to allow use of nuclear-generated process heat to drive the chemical. Process model description and results are discussed. The process is sized to produce gasoline and diesel at the rate that the INL uses every day for fleet usage.

09 BIOMASS FUELS↗

DOE OSTI2026

Effects of heteroatom doping on hydrogen uptake in tungsten oxide

Redox-active transition metal oxides (TMOs) that can undergo proton-insertion coupled electron transfer (PICET) are promising candidates for catalyzing molecular conversion reactions which require the transfer of hydrogen atoms (or the thermochemical equivalent, H + , e − ). Herein, we studied the effects of isovalent (Mo 6+ ) and aliovalent (V 5+ and Nb 5+ ) heteroatom doping on the electrochemical PICET behavior of monoclinic tungsten oxide (WO 3 ). Cyclic voltammetry in aqueous acidic electrolytes shows that the addition of redox-active heteroatoms (Mo 6+ and V 5+ ) leads to systematic shifts in redox couple half-wave potentials (E 1/2 ), broadening, and an overall decrease in the current response. Conversely, the non-redox active heteroatom (Nb 5+ ) only reduces the current response with no observable peak-current broadening. This broadening is attributed to changes in the proton binding affinities of oxygen in different chemical environments, i.e., bridging different pairs of redox-active transition metal cations. We determined the hydrogen bond dissociation free energy (H BDFE) values to elucidate the thermodynamic effect of heteroatom substitution. Density functional theory calculations reveal a differentiation in the hydrogen binding and oxygen vacancy formation energies between heteroatom doped structures. The PICET-induced structural phase transitions of the pristine and doped samples were further probed with operando electrochemical X-ray diffraction (EC-XRD) and with ex situ chemical reduction. The broadening of the potential-dependent current response with increased heteroatom doping manifests in the operando EC-XRD results as prolonged structural regions where multiple hydrogen bronze phases exist and the appearance of cubic bronze phases at lower degrees of reduction compared to pristine WO 3 .

Holzapfel, Noah P. [North Carolina State Universit↗

DOE OSTI2026

Directed Gas-Phase Formation of The Propargyl Family of Resonance-Stabilized Radicals in The Reactions of Ground-State Carbon Atoms (C; 3 P j ) with Butene Isomers (C 4 H 8 ): Dimethylpropargyl and Ethylpropargyl

The propargyl radical (C 3 H 3 ) is the simplest resonance-stabilized free radical (RSFR), but how does stepwise methyl substitution in the alkene reactant affect its dynamics of their formation? We report a crossed molecular beam study of the reactions of atomic carbon (C, 3 P j ) with four butene isomers (C 4 H 8 ) under single collision conditions at a collision energy of 28 ± 2 kJ mol −1 . Barrierless addition of atomic carbon to the alkene C=C bond triggers ring opening to triplet substituted allenes—a de facto insertion mechanism—followed by unimolecular decomposition via atomic hydrogen (H), methyl (CH 3 ) or ethyl (C 2 H 5 ) loss, yielding a family of propargyl‑type RSFRs. RRKM calculations reveal that the branching ratios are highly sensitive to the alkene structure. While the methyl loss channel, affording 1‑methylpropargyl, dominates for 2 butenes (80–90%), the predicted hydrogen atom loss channel (≈10%) leading to 1,3 dimethylpropargyl is identified in the experiment by comparison with theoretical energetics. For isobutene, a near‑equal competition is seen, with the reaction producing 3‑methylpropargyl (≈50%) and 1,1‑dimethylpropargyl (≈40%), along with 2‑vinylallyl (≈5%), whose formation is supported by the experimental data. Most notably, the reaction with 1 butene uniquely favors an enthalpically driven hydrogen shift, eventually producing 1 vinylallyl (≈38%), which is assigned based on the excellent agreement between the measured and calculated reaction exothermicity. Rapid entropically favored fragmentation channels yield ≈40% of propargyl type species (propargyl, 1- and 3-ethylpropargyls), slightly outcompeting the allyl type product. Furthermore, these results establish a systematic progression from C 2 H 4 to C 4 H 8 , where the increasing alkyl substitution unlocks new fragmentation channels, providing a versatile gas phase route to alkylated RSFRs—key intermediates in the growth of methylated and ethylated PAHs and aliphatic chains in combustion and cold interstellar environments (molecular clouds).

Alkyls↗

NASA NTRS2017

Exploring the Evolutionary Accident Hypothesis: Are Extant Protein Folds the Fittest or the Luckiest?

Considering the range of functions proteins perform, it is surprising they fold into a relatively small set of structures or "folds" that facilitate such function. One explanation is that only a minority were fit enough to emerge from Darwinian selection during the early evolution of life. Alternatively, perhaps only a fraction of all possible folds were trialed. Understanding proto-catalyst selection will aid understanding of the origins and early evolution of life. To investigate which explanation is correct, we study a protein evolved in vitro to bind ATP by Jack Szostak (Fig. 1). This protein adopts a fold which is absent from nature. We are testing whether this fold would have possessed the capability to evolve that would have been essential to survive natural selection on early Earth. Folds that couldn't improve their fitness and evolve to perform new functions would have been replaced by rivals that could. To determine whether the fold is evolvable, we are attempting to change the function of the protein by rationally redesigning to bind GTP. Two design strategies in the region of the nucleobase have been implemented to provide hydrogen bonding partners for the ligand i) an insertion ii) a MET to ASN mutation. Redesigns are being studied computationally at Ames Research Center including free energy of binding calculations. Binding affinities of promising redesigns are to be validated by experimental collaborators at ForteBio using Super Streptavidin Biosensors. If the fold is found to be non-evolvable, this may suggest that many structures were trialed, but the majority were pruned on the basis of their evolvability. Alternatively, if the fold is demonstrated to be evolvable, it would be difficult to explain its absence from nature without considering the possibility that the fold simply wasn't sampled on early Earth. This would not only further our understanding of the origins of life on Earth but also suggest a common phe-nomenon of proto-catalyst evolution.

Shannon, G.↗

NASA NTRS1994

Using Si Diodes To Detect H2 Liquid/Vapor Interfaces

Commercially available silicon-diode temperature sensors used to detect interfaces between hydrogen liquid and hydrogen vapor at steady-state saturation conditions. Sensors mounted at short intervals along rod to form rake-like array. Array inserted in tank with rod oriented vertically, where it senses level of liquid hydrogen to resolution equal to interval between sensors. Basic idea to measure voltage across sensor while supplying small electric current that heats sensor. Because vapor cools sensor less effectively than liquid does, sensor's steady-state temperature greater when sensor surrounded by vapor than when immersed in liquid. Voltage output decreases as temperature increases for silicon diodes. Thus, temperature (voltage) reading used to determine whether liquid level above or below sensor.

Dempsey, Paula Jean↗

DOE OSTI2025

Capsule Design and Preparation for YH x Specimen Irradiation in the High Flux Isotope Reactor

Advanced nuclear systems for terrestrial microreactors and space applications require moderator materials with high thermal stability, hydrogen retention, and efficient neutron moderation. Yttrium hydride (YH x ) is a promising candidate, but its irradiation performance and hydrogen stability remain insufficiently understood. To address this, Oak Ridge National Laboratory (ORNL) and Los Alamos National Laboratory, supported by the US Department of Energy’s Nuclear Science User Facilities program, have initiated an irradiation campaign in ORNL’s High Flux Isotope Reactor. The experiment employs six irradiation capsules containing YH x specimens (H/Y ≈ 1.9) designed for three target temperatures (300°C, 400°C, and 500°C) and two distinct neutron fast fluence levels. This report documents the irradiation test matrix, capsule design, specimen precharacterization, and experiment readiness for insertion. Planned postirradiation examinations will provide new insights into hydrogen retention and microstructural stability, advancing the understanding of YH x as a moderator for compact reactor applications.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Capsule Design and Preparation for YH x Specimen Irradiation in the High Flux Isotope Reactor

36 MATERIALS SCIENCE↗

DOE OSTI2025

Trigonal Planar Bis (carbene)Cu(I) Complexes Enable Divergent H 2 Activation with H 2 O for Accelerated Olefin Hydrogenation

CuH-catalyzed olefin hydrogenation is rare compared to those of carbonyl-derived substrates. Olefin insertion into Cu–H to form Cu-alkyl is ubiquitous; however, subsequent H 2 activation remains unknown to our knowledge. Herein, we investigated the transformations of β-H elimination, H 2 cleavage, and catalytic olefin hydrogenation in a series of linear and trigonal planar Cu(I)-alkyl complexes supported by monodentate N-heterocyclic carbene and bidentate naphthyridine- bis (carbene) ligands, respectively. Contrary to unreactive linear species, trigonal planar variants promote β-H elimination, hydrogenolysis, and catalytic hydrogenation of unactivated alkenes at mild temperatures and H 2 pressure. The rare isolation of a naphthyridine- bis (carbene)CuH monomer further affirms two predominant competing pathways for H 2 cleavage of metal–ligand cooperativity at Cu(I)-alkyl or internal electrophilic substitution at Cu(I)-OH. Employing either isolated or in situ generated Cu(I)-OH complex, via protonolysis of alkyl precatalyst by adventitious water, significantly accelerated catalysis compared to that operating primarily by the metal–ligand cooperativity pathway. DFT calculations and energy decomposition analysis on the disparate β-H elimination reactivity between linear and trigonal planar tert-butyl complexes and the mechanism of H 2 activation at a hydroxide complex, indicate that coordination geometry at Cu(I) and properties of the naphthyridine- bis (carbene) ligand are integral to the transformations reported here.

ALMO-EDA↗

NASA NTRS1967

Hand-operated plug insertion valve

Hand-operated plug insertion valve seals an evacuated insulation system for upper stage liquid hydrogen tanks on the launch pad. It is light in weight, demountable, and permits evacuation of the system plus sealing after evacuation.

Jones, R. G.↗

DOE OSTI2022

Pellet cladding mechanical interaction as a potential failure mechanism during a control rod drop accident in a boiling water reactor

Boiling water reactors (BWRs) represent approximately one-third of the operating fleet in the United States, contributing significantly towards the global effort in reducing carbon emissions. Even though most of the operating fleet has been in operation for quite some time, continued advancements in new nuclear fuel (such as accident tolerant fuel) or operating regimes (such as power up-rates and higher burnup operation) necessitates similar advancements in modeling and simulation capabilities. Bison, a component of the Virtual Environment for Reactor Applications (VERA), is a high-fidelity fuel performance code able to explore the fuel performance of a wide variety of fuel types in one-, two-, and three-dimensions. Until recently, the code had not been used for analyses of BWRs. Modeling capabilities have been added for Gd-bearing UO{sub 2} and pure zirconium liners. New models have been added based upon the U.S. Nuclear Regulatory Commission (NRC) guide-lines for hydrogen pickup in Zircaloy-2 claddings and pellet-clad mechanical interaction (PCMI) failure during a reactivity insertion accident (RIA), known as a rod drop accident (CRDA) in BWRs. Implementing and/or improving Bison modeling capabilities extended its analytical reach to areas beyond its original intended purpose. This paper demonstrates one of these capabilities as a proof of concept. Recently developed models enable Bison to provide an alternate approach for cladding integrity determination in CRDA evaluations, which currently use bounding conservative estimates. As part of this demonstration, NRC guidance on hydrogen-pickup and PCMI failure models were utilized in this research. Even though more research is needed in establishing right inputs and process in this area, this paper demonstrates Bison's ability to determine cladding integrity in a CRDA evaluation. This first of a kind demonstration is a proof of concept in this area, which could potentially be extended to a number of other areas where a more accurate cladding integrity determination would be needed. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2025

Enabling BWR fuel rod analysis in the BISON fuel performance code

Nuclear fuel vendors around the world are pursuing approaches to sustain the existing nuclear reactor fleet consisting primarily of pressurized-water reactors (PWRs) and boiling-water reactors (BWRs). To support the industry's efforts, advanced modeling and simulation tools need to be capable of analyzing both legacy reactor concepts. BWR fuel rods are significantly different than those used in PWRs, which can affect fuel performance analysis. BWR fuel rods include: (1) an extensive use of gadolinia dopant as a burnable absorber, (2) an axial variation in fuel enrichment and gadolinia content, (3) the inclusion of a liner on the inner cladding surface to mitigate the impact of pellet-clad mechanical interaction (which impacts hydrogen and hydride distribution), (4) a lower initial fill gas pressure, (5) bottom-entry control rods, and (6) a lower coolant pressure that results in the two-phase flow boiling phenomenon. Although the primary focus of BISON has been in the area of PWR and advanced reactor fuel analyses, this paper presents the developments in BISON to support BWR fuel performance analysis. An overview of the models that account for the effects of gadolinia is highlighted. Internal mesh generation capabilities to include a liner is presented. Normal operating and transient (reactivity insertion accident) demonstration problems are presented to illustrate the impact of gadolinia, the hydrogen and hydride evolution due to the presence of the liner, and BISON's ability to simulate axially varying enrichments and dopant concentration. Bottom-entry control effects are captured by the axial power peaking factors present in the demonstration cases. Comparisons to integral experiments from the Halden IFA-681 experiments are discussed as initial validation. Reasonable comparisons are obtained for fuel centerline temperature and rod internal pressure as a function of time. In conclusion, simulations of additional experiments containing Gd 2 O 3 -bearing fuel are necessary to completely validate the code for BWR applications.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2022

Revitalizing Iron Redox by Anion-Insertion-Assisted Ferro- and Ferri-Hydroxides Conversion at Low Alkalinity

Iron hydroxides are desirable alkaline battery electrodes for low cost and environmental beneficence. However, hydrogen evolution on charging and Fe 3 O 4 formation on discharging cause low storage capacity and poor cycling life. Here, we report that green rust (GR) (Fe 2+ 4 Fe 3+ 2 (HO – ) 12 SO 4 ), formed via sulfate insertion, promotes Fe(OH) 2 /FeOOH conversion and shows a discharge capacity of ~211 mAh g –1 in half-cells and Coulombic efficiency of 93% after 300 cycles in full-cells. Theoretical calculations show that Fe(OH) 2 /FeOOH conversion is facilitated by intercalated sulfate anions. Classical molecular dynamics simulations reveal that electrolyte alkalinity strongly impacts the energetics of sulfate solvation, and low alkalinity ensures fast transport of sulfate ions. Anion-insertion-assisted Fe(OH) 2 /FeOOH conversion, also achieved with Cl – ion, paves a pathway toward efficient utilization of Fe-based electrodes for sustainable applications.

25 ENERGY STORAGE↗

DOE OSTI2022

Hydrogen bonds and dispersion forces serving as molecular locks for tailored Group 11 bis(amidine) complexes

A flexible polydentate bis(amidine) ligand LH 2 , LH 2 = {CH 2 NH( t Bu)C=N-2-(6-MePy)} 2 , operates as a molecular lock for various coinage metal fragments and forms the dinuclear complexes [LH 2 (MCl) 2 ], M = Cu (1), Au (2), the coordination polymer [{(LH 2 ) 2 (py) 2 (AgCl) 3 }(py) 3 ] n (3), and the dimesityl-digold complex [LH 2 (AuMes) 2 ] (4) by formal insertion of MR fragments (M = Cu, Ag, Au; R = Cl, Mes) into the N–H∙∙∙N hydrogen bonds of LH 2 in yields of 43–95%. Complexes 1, 2, and 4 adopt C 2 -symmetrical structures in the solid state featuring two interconnected 11-membered rings that are locked by two intramolecular N–H∙∙∙R–M hydrogen bonds. QTAIM analyses of the computational geometry-optimized structures 1a, 2a, and 4a reveal 13, 11, and 22 additional bond critical points, respectively, all of which are related to weak intramolecular attractive interactions, predominantly representing dispersion forces, contributing to the conformational stabilization of the C2-symmetrical stereoisomers in the solid state. Variable-temperature 1 H NMR spectroscopy in combination with DFT calculations indicate a dynamic conformational interconversion between two C 2 -symmetrical ground state structures in solution (ΔG ‡ c = 11.1–13.8 kcal mol –1 ), which is accompanied by the formation of an intermediate possessing C i symmetry that retains the hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗