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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

LANL Response to SRS Requirement G-ESR-G-00035 Item 11 Bed Temperature Requirements, For the Addition of Direct Metal Oxidation Unit 3, Revision 0

Los Alamos National Laboratory has identified a number of plutonium-bearing materials that will be placed in storage in 3013 containers per requirements of DOE-STD-3013-2004, or DOE-STD-3013-2012 when it is implemented in the LANL contract. Before these items can be considered for storage at Savannah River Site, 20 points of agreement, described in Savannah River Site (SRS) document G-ESR-G-00035, Revision 1, must be documented and provided to SRS for review. These agreements include documentation that the requirements of the 3013 Standard are met and the storage facility’s safety envelope is not compromised. Point 11 of the 20 points is the requirement that material be stabilized at 950°C for a minimum of two hours prior to packaging. This report addresses the Point 11 requirement, describing the controls used during stabilization to ensure that the material is properly stabilized using a continuous process (Advanced Recovery and Integrated Extraction System [ARIES] direct metal oxidation [DMO] and recycle oxide calcination). These controls include verification of the furnace controller thermocouple profile and verification of the profiles for the calciner tube hot zone. This report is specific to Direct Metal Oxidation Unit 3 (DMO-3). The point 11 requirements for DMO-2 and muffle furnace oxidation are covered in reference. This report does not replace reference. The process and methodology used in this report are similar to that used for Direct Metal Oxidation Unit 2, or DMO-2, as documented in reference. This report documents the performance for ARIES DMO-3. The temperature on the outside of the calciner tube must be at least 1,032°C. The auger rotation rate set point will be dependent on the pitch of the installed auger. For an auger pitch of 1.297 in/rev the auger set point will be 0.0777 rpm or less, which allows for at least 132 minutes calcination time based on worst case conditions (i.e., lowest possible powder density at the lowest initial powder temperature, and under the least favorable heat transfer conditions, and with the least favorable auger pitch of the currently installed auger.) A new auger design may be used in future modifications of DMO-3 that has an auger pitch of 1.400 ± 0.025 inches which would change the required auger set point to 0.0707 rpm or less.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Surface area and particle size distribution of plutonium oxides derived from the direct oxidation of Pu metal (LA-UR-18-22581)

The intent of this paper is to interrogate the physical characteristics of PuO 2 powders and aggregates produced by direct metal oxidation to examine possible relationships between process parameters and the physical characteristics of the product. The majority of the PuO 2 samples considered were generated during the pre-production and production phases of the Advanced Recovery and Integrated Extraction System (ARIES) program at Los Alamos National Laboratory (LANL). Oxide formed passively on Pu metal surfaces at ambient atmospheric conditions is also characterized. Plutonium oxide powders from the ARIES Direct Metal Oxidation (DMO) furnace and muffle furnace process lines are very consistent in terms of their bulk and tapped density, specific surface area (SSA) and particle size distribution (PSD). The SSAs of calcined PuO 2 generated in the ARIES DMO-2 and muffle furnaces are between 0.1 and 0.5 m2/g. Oxides from both the DMO-2 and muffle furnaces also had similar tri-modal PSDs with maxima at 0.73–3.16 μm, 10.9–18.5 μm, and 41.3–63.0 μm. The PSDs of the oxide formed passively on Pu metal surfaces at ambient conditions were unimodal, with near-Gaussian distributions and D50 close to 1 μm. In conclusion, the oxide formed passively at ambient conditions also had significantly higher SSAs (6–8 m 2 /g).

36 MATERIALS SCIENCE↗
DOE OSTI2020

Rational synthesis of atomically precise graphene nanoribbons directly on metal oxide surfaces

Atomically precise graphene nanoribbons (GNRs) attract great interest because of their highly tunable electronic, optical, and transport properties. However, on-surface synthesis of GNRs is typically based on metal surface–assisted chemical reactions, where metallic substrates strongly screen their designer electronic properties and limit further applications. In this work, we present an on-surface synthesis approach to forming atomically precise GNRs directly on semiconducting metal oxide surfaces. The thermally triggered multistep transformations preprogrammed in our precursors’ design rely on highly selective and sequential activations of carbon-bromine (C-Br) and carbon-fluorine (C-F) bonds and cyclodehydrogenation. The formation of planar armchair GNRs terminated by well-defined zigzag ends is confirmed by scanning tunneling microscopy and spectroscopy, which also reveal weak interaction between GNRs and the rutile titanium dioxide substrate.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Thermal and Physical Properties of Plutonium Dioxide Produced from the Oxidation of Metal: a Data Summary

The ARIES Program at the Los Alamos National Laboratory removes plutonium metal from decommissioned nuclear weapons, and converts it to plutonium dioxide in a specially-designed Direct Metal Oxidation furnace. The plutonium dioxide is analyzed for specific surface area, particle size distribution, and moisture content. The purpose of these analyses is to certify that the plutonium dioxide powder meets or exceeds the specifications of the end-user, and the specifications for the packaging and transport of nuclear materials. Analytical results from plutonium dioxide from ARIES development activities, from ARIES production activities, from muffle furnace oxidation of metal, and from metal that was oxidized over a lengthy time interval in air at room temperature, are presented. The processes studied produce plutonium dioxide powder with distinct differences in measured properties, indicating the significant influence of oxidation conditions on physical properties.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Theoretical Perspective of Promoting Direct Methane-to-Methanol Conversion at Complex Metal Oxide–Metal Interfaces

Direct methane conversion to methanol has been considered as an effective and economic way to release greenhouse effects and current high demand on methanol in industry. However, the process has long been challenging due to lack of viable catalysts to compromise the activation of methane that typically occurs high temperatures and retaining of produced methanol that requires mild conditions. Here, this perspective demonstrates an effective strategy to promote direct methane to methanol conversion by engineering the active sites and chemical environments at complex metal oxide - copper oxide - copper interfaces. Such effort strongly depends on the extensive theoretical studies by combining density functional theory (DFT) calculations and kinetic Monte Carlo (KMC) simulations to provide in-depth understanding of reaction mechanism and active sites, which built the strong basis to enable the identification of design principles and advance the catalyst optimization for selective CH 4 -to-CH 3 OH conversion.

03 NATURAL GAS↗
DOE OSTI2021

Prompt Gamma Analysis of ARIES Materials and Updates to the 2015 Calibration Equations

Prompt gamma (PG) analysis is a nondestructive, nuclear, elemental analysis technique that uses charged particle reactions to interrogate a sample, and elements present in the sample matrix are identified through the characteristic gamma-rays emitted from the product nuclei in alpha-p and alpha-n nuclear reactions. This technique has been applied to plutonium oxide packaged in over 4,000 individual 3013 containers, and the concentrations of certain light elements were determined from the integrated peak areas based on a calibration that was published previously. This report provides the results for a new population of 3013 containers packaged with oxide materials produced by the conversion of metal by Advanced Recovery and Integrated Extraction System (ARIES) project using the direct metal oxidation (DMO) process and muffle furnaces. New PG and analytical chemistry data collected since 2015 were added to the existing calibration data sets to refine the calibration parameters. Calibration equations were also developed for determining beryllium and fluorine at low concentrations in high-purity ARIES product oxides. The new fluorine calibration provides an order of magnitude greater sensitivity and results in an additional 1,408 containers in the original population identified as having fluorine as an impurity. Additionally, equations for calculating the lower limits of detection (LLDs) as a function of the actual counting time (live time) were obtained using WLS regression technique for samples in the calibration data set. This resulted in changes to the LLDs published previously.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

LANL Response to SRS Requirement G-ESR-G-00035 Item 11 Bed Temperature, Revision 4

Los Alamos National Laboratory has identified a number of plutonium-bearing materials that will be placed in interim storage in 3013 containers per requirements of DOE-STD-3013- 2004, or DOE-STD-3013-2012. Before these items can be considered for storage at Savannah River Site, 20 points of agreement, described in Savannah River Site (SRS) document G-ESR-G-00035, Revision 1, must be documented and provided to SRS for review. These agreements include documentation that the requirements of the 3013 Standard are met and the storage facility’s safety envelope is not compromised. Point 11 of the 20 points is the requirement that material be stabilized at 950°C for a minimum of two hours prior to packaging. This report addresses the Point 11 requirement, describing the controls used during stabilization to ensure that the material is properly stabilized using either a batch (calciner boat) or continuous process (Advanced Recovery and Integrated Extraction System [ARIES] direct metal oxidation unit 2 [DMO-2] and recycle oxide calcination). These controls include verification of the furnace controller thermocouple profile and verification of the profiles for the two thermocouples located in the bed and/or calciner tube hot zone. Revision 4 to this document only modifies the ARIES DMO-2 process controls. Batch processing requirements are unchanged. Changes to the DMO-2 process include use of alternate augers with differing pitch values and reduction of the minimum powder bulk density value. The new DMO-3 unit requirements are covered in a separate document.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1992

Flight-vehicle materials, structures, and dynamics - Assessment and future directions. Vol. 3 - Ceramics and ceramic-matrix composites

The present volume discusses ceramics and ceramic-matrix composites in prospective aerospace systems, monolithic ceramics, transformation-toughened and whisker-reinforced ceramic composites, glass-ceramic matrix composites, reaction-bonded Si3N4 and SiC composites, and chemical vapor-infiltrated composites. Also discussed are the sol-gel-processing of ceramic composites, the fabrication and properties of fiber-reinforced ceramic composites with directed metal oxidation, the fracture behavior of ceramic-matrix composites (CMCs), the fatigue of fiber-reinforced CMCs, creep and rupture of CMCs, structural design methodologies for ceramic-based materials systems, the joining of ceramics and CMCs, and carbon-carbon composites.

Levine, Stanley R.↗
NASA NTRS1992

Reaction-bonded Si3N4 and SiC matrix composites

A development status evaluation is presented for the reaction-bonded SiC- and Si3N4-matrix types of fiber-reinforced ceramic-matrix composite (FRCMC). A variety of reaction-bonding methods are being pursued for FRCMC fabrication: CVI, CVD, directed metal oxidation, and self-propagating high-temperature synthesis. Due to their high specific modulus and strength, toughness, and fabricability, reaction-bonded FRCMC are important candidate materials for such heat-engine components as combustor liners, nozzles, and turbine and stator blading. The improvement of long-term oxidative stability in these composites is a major goal of current research.

Bhatt, Ramakrishna T.↗
DOE OSTI2020

Directional Gateway to Metal Oxidation: 3D Chemical Mapping Unfolds Oxygen Diffusional Pathways in Rhodium Nanoparticles

The interaction of oxygen with a reactive metal is ubiquitous, yet the precise atomic-level mechanisms and pathways leading to the formation of a surface oxide are not well-understood. We report oxygen atom distributions inside Rh single nanoparticles using atom probe microscopy (APM) and demonstrate that mainly facets of the ?022¯? crystallographic directions act as oxygen-permeable gateways. The highly anisotropic spatial distribution of incorporated oxygen atoms is in agreement with video-field emission analyses according to which {113} facets of the ?022¯? zones act as portals for subsurface diffusion. In addition to providing a more fundamental understanding of the precursor states to metal corrosion, in particular for the case of nanosized metal particles, our studies are also relevant for heterogeneous catalysis where catalytic activity and selectivity conform to reaction-induced structural changes of metal nanoparticles.

Lambeets, Sten V M.↗
DOE OSTI2024

High-resolution chemical patterns from negative tone resists for the integration of extreme ultraviolet patterns of metal-oxide resists with directed self-assembly of block copolymers

Extreme ultraviolet (EUV) lithography faces significant challenges in designing suitable resist materials that can provide adequate precision, while maintaining economically viable throughput. These challenges in resist materials have led to printing failures and high roughness in EUV patterns, compromising the performance of semiconductor devices. Integrating directed self-assembly (DSA) of block copolymers (BCPs) with EUV lithography offers a promising solution because, while the BCPs register to the EUV-defined chemical guiding pattern, the thermodynamically determined structures of the BCPs automatically rectify defects and roughness in the EUV pattern. Despite the superior resolution of metal-oxide EUV resists (MORs), their application to DSA is limited by the difficulty in converting them into chemical patterns that allow effective transfer of the rectified patterns of DSA films into inorganic materials. To address this challenge, this study introduces a novel strategy for fabricating chemical patterns using hydrogen silsesquioxane (HSQ), a high-resolution negative tone inorganic resist, as a model system for MORs. Initially, a sacrificial Cr pattern is generated from HSQ patterns via reactive ion etching. The sacrificial Cr pattern is converted into a chemical pattern by first grafting a water-soluble polyethylene oxide brush onto the substrate, then wet etching the Cr, and finally grafting nonpolar polystyrene brushes. Assembling polystyrene-block-poly(methyl methacrylate) on these patterns results in structures oriented and registered with the underlying pattern, achieving 24 nm full-pitch resolutions. In conclusion, this approach has the potential to integrate MOR patterns into the DSA process, thereby enabling the generation of high-quality sub-10 nm patterns with high-χ BCPs.

Atomic force microscopy↗
DOE OSTI2022

Cation-Dependent Multielectron Kinetics of Metal Oxide Splitting

We report direct electrolytic extraction of metals from metal oxides is a promising process for the sustainable production of metals. In this work, we elucidate the inherent thermodynamic driving forces behind the reduction of metal oxides to metals (M-OER). It is shown that the thermodynamics of M-OER can be systematically tuned via the interactions of oxygen with the participating metal cations as a function of metal–oxygen covalency, oxygen–oxygen covalency, and metal–oxygen ionicity. We screen both group 1 elements and metals that are able to exist in the +2 oxidation state for M-OER thermodynamics. Li, Fe, and Co are identified as having low thermodynamic overpotentials for electrolytic extraction from their metal oxides due to interactions between oxygen and these metals being neither too strong (covalent) nor too weak (ionic). We further show that the bulk formation energies are predictive of M-OER reaction energetics on surfaces by developing unified design principles for tuning the thermodynamics of these reduction reactions both in bulk oxides and on surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Multiphase Nanostructure of a Quinary Metal Oxide Electrocatalyst Reveals a New Direction for OER Electrocatalyst Design

Ce-rich mixed metal oxides comprise a recently discovered class of ­electrocatalysts for the oxygen evolution reaction (OER). In particular, at current densities below 10 mA cm -2 , Ni 0.3 Fe 0.07 Co 0.2 Ce 0.43 O x exhibits ­superior activity compared to the corresponding transition metal oxides, despite the relative inactivity of ceria. To elucidate the enhanced activity and underlying catalytic mechanism, detailed structural characterization of this quinary oxide electrocatalyst is reported in this paper. Transmission electron microscopy imaging of cross-section films as-prepared and after electrochemical testing reveals a stable two-phase nanostructure composed of 3–5 nm diameter crystallites of fluorite CeO 2 intimately mixed with 3–5 nm crystallites of transition metal oxides alloyed in the rock salt NiO structure. Dosing experiments demonstrate that an electron flux greater than ≈1000 e Å -2 s -1 causes the inherently crystalline material to become amorphous. A very low dose rate of 130 e Å -2 s -1 is employed for atomic resolution imaging using inline holography techniques to reveal a nanostructure in which the transition metal oxide nanocrystals form atomically sharp boundaries with the ceria nanocrystals, and these results are corroborated with extensive synchrotron X-ray absorption spectroscopy measurements. Finally, ceria is a well-studied cocatalyst for other heterogeneous and electrochemical reactions, and our discovery introduces biphasic cocatalysis as a design concept for improved OER electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Microbial-mediated method for metal oxide nanoparticle formation

The invention is directed to a method for producing metal oxide nanoparticles, the method comprising: (i) subjecting a combination of reaction components to conditions conducive to microbial-mediated formation of metal oxide nanoparticles, wherein said combination of reaction components comprise: metal-reducing microbes, a culture medium suitable for sustaining said metal-reducing microbes, an effective concentration of one or more surfactants, a reducible metal oxide component containing one or more reducible metal species, and one or more electron donors that provide donatable electrons to said metal-reducing microbes during consumption of the electron donor by said metal-reducing microbes; and (ii) isolating said metal oxide nanoparticles, which contain a reduced form of said reducible metal oxide component. The invention is also directed to metal oxide nanoparticle compositions produced by the inventive method.

36 MATERIALS SCIENCE↗