Search NASA⌕ Search

SEARCH · Search NASA

Results for “Mixed Oxides”

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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

DFT-guided flux synthesis of a family of layered titanates crystallizing in the lepidocrocite structure type

K 0.72 Fe 0.72 Ti 1.28 O 4 , a layered mixed-metal oxide belonging to the lepidocrocite structure type, was grown out of a molten KCl-KF mixture at 800 °C. The compound crystallizes in orthorhombic space group Cmcm and exhibits two-dimensional layers, composed of mixed Fe/Ti octahedra, separated by K ions that occupy the interlayer layer space and maintain charge balance. The targeted flux synthesis of the Ni, Cu, and Zn analogs was carried out after density functional theory (DFT) calculations predicted their formation to be energetically favorable, yielding K 0.77 Ni 0.38 Ti 1.62 O 4 , K 0.77 Cu 0.38 Ti 1.62 O 4 , and K 0.73 Zn 0.36 Ti 1.64 O 4 . Finally, all four compositions can be prepared via conventional solid-state technique by mixing and heating stoichiometric amounts of KNO 3 , appropriate transition metal oxide precursors, and TiO 2 .

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

Computational Screening of Supported Metal Oxide Nanoclusters for Methane Activation: Insights into Homolytic versus Heterolytic C–H Bond Dissociation

Since its discovery in zeolites, the [CuOCu] 2+ motif has played an important role in our understanding of selective methane activation over supported metal oxide nanoclusters. Although there are two known C-H bond dissoci-ation mechanisms, namely homolytic and heterolytic cleavage, most computational studies on optimizing metal oxide nanoclusters for improved methane activation reactivity have focused only on the homolytic mechanism. In this work, both mechanisms were examined for a set of 21 mixed metal oxide complexes of the form of [M 1 OM 2 ] 2+ (M 1 , M 2 = Mn, Fe, Co, Ni, Cu, Zn). Except for pure copper, heterolytic cleavage was found to be the dominant C-H bond activation pathway for all systems. Furthermore, mixed systems including [CuOMn] 2+ , [CuONi] 2+ , and [CuOZn] 2+ are predicted to possess similar methane activation activity as pure [CuOCu] 2+ . Furthermore, these results suggest that both homolytic and heterolytic mechanisms should be considered in computing methane activation energies on supported metal oxide nanoclusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Sterilizable Binder Is Stable at 135 degrees C

Polyurethane binder for solid propellants endures heat sterilization without decomposition based on an ester diol. Binder resists oxidation under prolonged exposure to 135 degrees C temperature, low enough in viscosity to be handled easily during processing, and readily mixed with oxidizers, such as ammonium perchlorate. Polyurethane is also suitable material for encapsulants, potting compounds, and coatings that must be sterilized.

Kalfayan, S. H.↗
DOE OSTI2024

Metallic Coating of Cerium Oxide Microspheres

The ability to remove heat is paramount to nuclear fuel performance and longevity. Retaining fission product and separating fuel from reactor coolant and the environment is also necessary to prevent radiological contamination. Conventional nuclear fuel for commercial light water reactors and radioisotope power systems (RPS) is composed of oxide powders pressed into a pellet (cm-scale) and then sealed into a metal cladding to confine the fuel. What typical fuels lack is a method to surround each particle of nuclear fuel in metal, thus providing a more intimate protection layer for accident tolerance and boosting the thermal extraction from the fuel element. In such a way, metal-coated fuel particles increase heat extraction efficiency over clad-pellet designs while increasing the accident tolerance of the fuel. Metal oxide microspheres have wide-ranging applications, including the realm of fuels for nuclear reactors and RPS. Microspheres of uranium oxide/uranium carbide, mixed uranium/plutonium oxides, transuranics, and thorium fuels have been extensively studied. Pacific Northwest National Laboratory has also demonstrated the production of 238 PuO 2 microspheres for RPS applications. Metal-coated oxide microsphere fuels may also be attractive for other applications such as nuclear thermal rockets, future nuclear reactor designs, and catalysts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1991

Oxidation-chlorination of binary Ni-Cr alloys in flowing Ar-O2-Cl2 gas mixtures at 1200 K

Nickel-chromium alloys are resistant to oxidation because of the selective oxidation of chromium to form a protective Cr2O3 scale. In chlorine-containing environments, volatile corrosion products can also be formed. The mixed oxidation-chlorination of Ni-4.5Cr, Ni-13.8Cr, and Ni-26.5Cr (by weight) alloys in Ar-O2-Cl2 gas mixtures is investigated using thermogravimetric analysis and atmospheric-pressure-sampling mass spectrometry, followed by examination of the corrosion products using scanning electron microscopy and X-ray diffraction analysis. The overall kinetics of the corrosion are affected by the relative amounts of oxides and chlorides formed and the composition of the oxide corrosion products.

Mcnallan, M. J.↗
NASA NTRS1990

Hybrid propulsion technology program

Technology was identified which will enable application of hybrid propulsion to manned and unmanned space launch vehicles. Two design concepts are proposed. The first is a hybrid propulsion system using the classical method of regression (classical hybrid) resulting from the flow of oxidizer across a fuel grain surface. The second system uses a self-sustaining gas generator (gas generator hybrid) to produce a fuel rich exhaust that was mixed with oxidizer in a separate combustor. Both systems offer cost and reliability improvement over the existing solid rocket booster and proposed liquid boosters. The designs were evaluated using life cycle cost and reliability. The program consisted of: (1) identification and evaluation of candidate oxidizers and fuels; (2) preliminary evaluation of booster design concepts; (3) preparation of a detailed point design including life cycle costs and reliability analyses; (4) identification of those hybrid specific technologies needing improvement; and (5) preperation of a technology acquisition plan and large scale demonstration plan.

Source record↗
NASA NTRS1991

Progress of simulations for reacting shear layers

An attempt was made to develop a high speed, chemically reactive shear layer test rig. The purpose of the experiment was to study the mixing of oxidizer and fuel streams in reacting shear layers for various density, velocity, and Mach number. The primary goal was to understand the effects of the compressibility upon mixing and combustion in a fundamental way. Therefore, a two-dimensional shear layer is highly desirable for its simplicity to quantify the compressibility effects. The RPLUS 2D code is used to calculate the flow fields of different sections of the test rig. The emphasis was on the supersonic nozzle design, the vitiation process for the hot air stream and the overall thermodynamic conditions of the test matrix. The k-epsilon turbulence model with wall function was successfully implemented in the RPLUS code. The k and epsilon equations are solved simultaneously and the LU scheme is used to make it compatible with the flow solver.

Yu, Sheng-Tao↗
DOE OSTI2020

Evidence of Inverse Hall-Petch Behavior and Low Friction and Wear in High Entropy Alloys

We present evidence of inverse Hall-Petch behavior for a single-phase high entropy alloy (CoCrFeMnNi) in ultra-high vacuum and show that it is associated with low friction coefficients (~0.3). Grain size measurements by STEM validate a recently proposed dynamic amorphization model that accurately predicts grain size-dependent shear strength in the inverse Hall-Petch regime. Wear rates in the initially soft (coarse grained) material were shown to be remarkably low (~10 –6 mm 3 /N-m), the lowest for any HEA tested in an inert environment where oxidation and the formation of mixed metal-oxide films is mitigated. The combined high wear resistance and low friction are linked to the formation of an ultra-nanocrystalline near-surface layer. The dynamic amorphization model was also used to predict an average high angle grain boundary energy (0.87 J/m 2 ). This value was used to explain cavitation-induced nanoporosity found in the highly deformed surface layer, a phenomenon that has been linked to superplasticity.

36 MATERIALS SCIENCE↗
NASA NTRS2009

Crystallographic Oxide Phase Identification of Char Deposits Obtained from Space Shuttle Columbia Window Debris

Analyzing the remains of Space Shuttle Columbia has proven technically beneficial years after the vehicle breakup. This investigation focused on charred deposits on fragments of Columbia overhead windowpanes. Results were unexpected relative to the engineering understanding of material performance in a reentry environment. The TEM analysis demonstrated that the oxides of aluminum and titanium mixed with silicon oxides to preserve a history of thermal conditions to which portions of the vehicle were exposed. The presence of Ti during the beginning of the deposition process, along with the thermodynamic phase precipitation upon cool down, indicate that temperatures well above the Ti melt point were experienced. The stratified observations implied that additional exothermic reaction, expectedly metal combustion of a Ti structure, had to be present for oxide formation. Results are significant for aerospace vehicles where thermal protection system (TPS) breaches cause substructures to be in direct path with the reentry plasma. 1

Olivas, J. D.↗
DOE OSTI2022

Analysis of inconel 600 oxidized under loss-of-coolant accident conditions: A multi-modal approach

Understanding the performance of cladding materials during a loss-of-coolant accident scenario is crucial for developing next-generation accident tolerant nuclear fuel rod claddings. We describe a multi-modal approach combining synchrotron-based diffraction, and Raman spectroscopy with nano-scale electron microscopy techniques for investigating oxidation of Inconel 600 (A600) in steam and air environments at 1200 °C for 2 h. We report that A600 exposed to steam develops a Cr 2 O 3 -enriched surface layer while a mixed phase oxide layer containing NiFe 2 O 4 , Cr 2 O 3 , Fe 3 O 4 and Fe (3–x) CrxO 4 is formed in air. Mechanism of oxidation for A600 in air and steam environments is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synthesis of Hf 6 Ta 2 O 17 superstructure via spark plasma sintering for improved oxidation resistance of multi-component ultra-high temperature ceramics

Ultra-high temperature ceramics (UHTCs) have shown aspiration to overcome challenges in the thermal protection system (TPS) by designing new materials referred to as multi-component UHTCs (MC-UHTCs) in the compositional space. MC-UHTCs have shown remarkable improvement in oxidation resistance due to the formation of the Hf6Ta2O17 superstructure during plasma exposure. Herein, the Hf 6 Ta 2 O 17 superstructure is synthesized via a solid-state reaction between HfO 2 and Ta 2 O 5 powder mixtures during spark plasma sintering (SPS). The compositions chosen are 50 vol% of HfO 2 -50 vol% of Ta 2 O 5 (50HO-50TO) and 70 vol% of HfO 2 -30 vol% of Ta 2 O 5 (70HO-30TO). The phase quantification via Rietveld analysis showed Hf 6 Ta 2 O 17 as a principal phase with some residual Ta 2 O 5 phase in both the samples. The high-temperature thermal stability of the samples was evaluated using high-velocity plasma jet exposure for up to 3 min. 50HO-50TO was able to withstand the intense plasma condition, which is attributed to the higher content of the Hf 6 Ta 2 O 17 phase (~84%) and lower strain in the Ta 2 O 5 phase. The augmentation in the Hf 6 Ta 2 O 17 phase to 94.7% (in 50HO-50TO) post plasma exposure has been attributed to the invariant transformation from a liquid state to Hf 6 Ta 2 O 17 at temperatures >2500 °C during testing. The mechanical integrity is elucidated from the insignificant change in the hardness ~13.3 GPa before and 11.2 GPa after plasma exposure of the 50HO-50TO sample. As a result, the Hf 6 Ta 2 O 17 superstructure's thermo-mechanical stability suggests developing novel oxidation-resistant MC-UHTCs in compositional space for reusable space vehicle applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

SCALE 6.2.4 Validation: Nuclear Criticality Safety

The computational bias of criticality safety computer codes must be established through the validation of the codes to critical experiments. A large collection of suitable experiments has been vetted by the International Criticality Safety Benchmark Evaluation Project (ICSBEP) and made available in the International Handbook of Evaluated Criticality Safety Benchmark Experiments (ICSBEP Handbook). More than 600 cases from this handbook have been prepared and reviewed within the Verified, Archived Library of Inputs and Data (VALID), which is maintained by the Reactor and Nuclear Systems Division at Oak Ridge National Laboratory. The performance of the KENO V.a and KENO-VI Monte Carlo codes within the SCALE 6.2.4 code system is assessed using the VALID models of benchmark experiments. A range of nuclear cross section libraries based on Evaluated Nuclear Data File (ENDF)/B-VII.1 in both multigroup (MG) and continuous energy (CE) formats is considered. The critical experiments available to validate the KENO V.a code cover 15 broad categories of systems. These systems use a range of fissile materials, including a range of uranium enrichments, various plutonium isotopic vectors, and some mixed uranium/plutonium oxides. The physical forms of the fissile material also vary and are represented as metal, solutions, or arrays of rods or plates in a water moderator. The neutron energy spectra of the systems also vary and cover fast, intermediate, mixed, and thermal spectra. Over 550 of the total cases use the KENO V.a code for the four nuclear data libraries considered in this report.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Highly selective cross ketonization of renewable acids over magnesium oxide

The rising demand for linear alkylbenzene surfactants (LAS) poses an environmental threat as LAS are industrially produced from petroleum using corrosive acid catalysts. Cross ketonization is a promising route of converting furans and fatty acids to oleo-furansulfonates, precursors for renewable, performance-enhanced LAS replacements. Here, we explore various alkaline earth metals and mixed metal oxides for the cross-ketonization reaction and find that MgO achieves ~90% yield by minimizing the decarboxylation side reaction. Here, we illustrate the role of molecular structure on the cross-ketonization reaction and the role of complex formation over alkaline-earth metal oxides in minimizing side reactions. We overcome catalyst deactivation by regeneration over multiple runs. This research demonstrates the effectiveness of heterogeneous catalysts for cross ketonization toward developing renewable surfactants.

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

Imaging and speciation of intracellular metallic implant debris using synchrotron-based X-ray fluorescence micro-spectroscopy: a study of two cases

Debris generated from total hip arthroplasty (THA) components made from metal alloys can cause, in some cases, inflammatory cell (e.g., macrophages) responses that lead to adverse local tissue reactions (ALTR) and implant failure. The lack of information on intracellular chemical alterations of metal debris has hindered the understanding of the pathogenesis of ALTR. The goal of this study was to characterize intracellular debris within macrophages using Synchrotron imaging and spectroscopy. We studied periprosthetic tissues of two retrieved THAs with (1) a metal-on-metal (MoM) articulation and (2) a metal-on-polyethylene (MoP) articulation exhibiting corrosion of the metal femoral head. The MoM-THA exhibited different valence states of chromium- and cobalt-containing debris, suggesting three different moieties: Cr 2 O 3 , CrPO 4 , and an alloy-oxide mixture. The findings further suggest that Cr 2 O 3 formed in the tribological interfaces of the implant, while CrPO 4 is a by-product of the phagocytosis process of cobalt alloy-containing debris. Titanium debris appeared to occur in a mixed crystalline/amorphous oxide state. It remains unclear if this chemical state results from the tribochemical processes at the implant surface or intracellular alterations. The MoP-THA specimen exhibited no intracellular particulate debris associated with macrohpages, indicating that the ALTR may be entirely triggered by metal ionic species in this case. A better understanding of in vivo chemical alteration of implant debris will aid in assessing the risk for ALTR during implant design and material choice. However, various techniques are needed to accurately determine the interaction between metal particles and the inta- and extra-cellular environment.

60 APPLIED LIFE SCIENCES↗
NASA NTRS2026

Thermodynamic Properties of Uranium-Zirconium Carbide Solid Solutions with Oxygen

Uranium-zirconium carbide solid solutions are potential candidates for fuel in space nuclear reactors. To support development of advanced robust fuels for space applications, (U y Zr 1-y )C x O z solid solutions were synthesized via carbothermic reduction with uranium, carbon, and oxygen contents raging from y=0.05 – 0.3, x=0.95 – 0.98, and z = 0.02 – 0.07. These solid solutions were subsequently characterized by X-ray diffraction and elemental combustion analysis. High-temperature oxidative drop solution calorimetry in molten sodium molybdate solvent at 1073 K was employed to determine the formation, oxidation, and mixing enthalpies of (U y Zr 1-y )C x O z solid solutions, and thereby for evaluating their thermodynamic stability. The solid solutions are enthalpically less stable than the UC and ZrC end members. They also become less stable and more reactive towards oxidation with increasing uranium content. Incorporation of oxygen into solid solutions increases their solid solution-stability and improves their oxidation resistance.

Calorimetry↗
DOE OSTI2020

Acidic Oxygen Evolution Reaction Activity–Stability Relationships in Ru-Based Pyrochlores

Ru-based oxygen evolution reaction (OER) catalysts show significant promise for efficient water electrolysis, but rapid degradation poses a major challenge for commercial applications. In this work, we explore several Ru-based pyrochlores (A 2 Ru 2 O 7 , A = Y, Nd, Gd, Bi) as OER catalysts and demonstrate improved activity and stability of catalytic Ru sites relative to RuO 2 . Furthermore, we combine complementary experimental and theoretical analysis to understand how the A-site element impacts activity and stability under acidic OER conditions. Among the A 2 Ru 2 O 7 studied herein, we find that a longer Ru–O bond and a weaker interaction of the Ru 4d and O 2p orbitals compared with RuO 2 results in enhanced initial activity. We observe that the OER activity of the catalysts changes over time and is accompanied by both A-site and Ru dissolution at different relative rates depending on the identity of the A-site. Pourbaix diagrams constructed using density functional theory (DFT) calculations reveal a driving force for this experimentally observed dissolution, indicating that all compositions studied herein are thermodynamically unstable in acidic OER conditions. Theoretical activity predictions show consistent trends between A-site cation leaching and OER activity. These trends coupled with Bader charge analysis suggest that dissolution exposes highly oxidized Ru sites that exhibit enhanced activity. Overall, using the stability number (molO2 evolved/molRu dissolved) as a comparative metric, the A 2 Ru 2 O 7 materials studied in this work show substantially greater stability than a standard RuO2 and commensurate stability to some Ir mixed metal oxides. Finally, the insights described herein provide a pathway to enhanced Ru catalyst activity and durability, ultimately improving the efficiency of water electrolyzers.

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

Evaluation of Tritium Behavior in Forest Vegetation for the Purpose of Determining Appropriate Non-Zero Deposition Velocities for Tritium Oxide

Modeling and field measurements have been conducted between 2019 and 2021 to assess the practicality of using a non-zero deposition velocity for safety basis estimates of tritium oxide fate and transport modeling. A model was developed which used a complex deposition algorithm designed to assess how tritium oxide would mix based on the turbulent motions and wind speed effects that the forest canopy has on the atmosphere. The model was driven based on measurements of wind and turbulence taken from the Aiken AmeriFlux Tower which measures these properties at five levels located within and just above the forest. The model was then validated against a series of field experiments which were designed to test the model predictions and estimate the deposition velocity occurring over the forest environment at the Savannah River Site. The field releases used deuterium oxide as a surrogate for tritium oxide and was released as a fine mist which rapidly evaporated, creating a gaseous tracer in the atmosphere. Using air samplers, the elevations in deuterium concentration in the air relative to background measurements was assessed and then modeled. Generally, the numerical model tended to underpredict the amount of deuterium being mixed from above the canopy to the forest floor, indicating that the predictions it provides are still conservative relative to what was measured during the field experiments. Across a suite of modeling runs, the 95 th and 99 th percentile deposition velocities were estimated to be 1.2 and 0.7 cm s -1 , respectively. Estimated deposition velocities in the 2021 field experiments, which specifically assessed a release above the forest canopy and its mixing to the surface, predicted deposition velocities ranging from 1.75 to 6.61 cm s -1 . While these field releases do not cover all possible meteorological conditions, it seems appropriate to use a non-zero deposition velocity when performing safety-basis modeling of tritium oxide. The recommendation presented in this report is to use 1.0 cm s -1 . This is between the 95 th and 99 th percentile value estimated from the modeling study, suggesting it should be appropriate for the majority of release scenarios given the model’s apparent conservatism relative to field measurements.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

LDRD poster - Identifying the speciation of salt-based actinides in the presence of contaminants

Molten salt reactors (MSRs) are among the most promising Generation IV nuclear reactors. The salts used in these reactors exhibit a high affinity for moisture and oxygen, and heating does not eliminate the oxides that are formed. Additionally, due to the high operating temperatures, reactor parts experience pronounced corrosion, and the resulting corrosion products integrate into the fuel salt system. It is hypothesized that the speciation of f-elements in molten salts would change in the presence of oxides and corrosion products. These changes in local structure can alter the rheological properties, which are critical to the operational and safety parameters of the reactors. Therefore, an in-depth understanding of how corrosion products influence lanthanide/actinide speciation is crucial. To test this hypothesis, lanthanides (as surrogates for actinides) and actinide chlorides were mixed with oxides (such as nickel oxide and lithium oxide) and/or corrosion products (e.g., nickel chloride) and reacted in molten salts. The resulting phases were analyzed using techniques such as powder X-ray diffraction, Raman spectroscopy, UV-Visible spectroscopy, and nuclear magnetic resonance spectroscopy. In the presence of oxides, due to the high oxophilicity of f-elements, these elements capture oxygen from the oxides, forming lanthanide/actinide oxide or oxychloride phases. Specifically, with cerium chloride, the introduction of lithium oxide to the formation of various final products depending on the oxide concentration. At lower oxide concentrations, cerium oxychloride (CeOCl) in the +3 oxidation state was observed, while an increase in the oxide concentration led to the formation of cerium dioxide (CeO2), where cerium is in the +4 oxidation state. In contrast, with nickel oxide, CeOCl formation was consistently observed, regardless of the oxide concentration. This project successfully determined that the speciation of f-elements change in the presence of oxides and different oxides in molten salts result in different final products. When the influence of nickel chloride was examined, changes in f-element speciation were not observed. However, it reacted with lithium chloride to generate a lithium-nickel-chloride (Li6NiCl8) phase, which was also observed when nickel oxide was reacted. Computational models were developed to simulate the phases anticipated under experimental conditions.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗