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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 OSTI2024

Distinguishing Elements at the Sub‐Nanometer Scale on the Surface of a High Entropy Alloy

Materials in crystalline form possess translational symmetry (TS) when the unit cell is repeated in real space with long- and short-range orders. The periodic potential in the crystal regulates the electron wave function and results in unique band structures, which further define the physical properties of the materials. Amorphous materials lack TS due to the randomization of distances and arrangements between atoms, causing the electron wave function to lack a well-defined momentum. High entropy materials provide another way to break the TS by randomizing the potential strength at periodic atomic sites. The local elemental distribution has a great impact on physical properties in high entropy materials. It is critical to distinguish elements at the sub-nanometer scale to uncover the correlations between the elemental distribution and the material properties. Here, the use of synchrotron X-ray scanning tunneling microscopy (SX-STM) with sub-nm scale resolution in identifying elements on a high entropy alloy (HEA) surface is demonstrated. By examining the elementally sensitive X-ray absorption spectra with an STM tip to enhance the spatial resolution, the elemental distribution on an HEA's surface at a sub-nm scale is extracted. In conclusion, these results open a pathway towards quantitatively understanding high entropy materials and their material properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Engineering Active Sites of Metal/Metal Oxide Catalysts by Oxide Ligand Overlayers

Abstract Engineering sites of supported metal catalysts is essential to enhancing activity and selectivity. Such enhancement is typically achieved by particle size modification, surface alloying, or attaching molecular ligands. Yet, control strategies for complex, multifunctional molecules and catalysts, where selectivity is crucial, are lacking. Here, we demonstrate that submonolayer WO x with tunable coverage preferentially decorates well‐coordinated Pt terrace sites as a stable ligand. By combining experimental kinetics with probe molecules, in situ spectroscopies, and first‐principles modeling, we show that the WO x coverage on Pt modifies the metal‐to‐acid site balance while retaining the acid strength intact and results in optimal reactivity for metal‐acid catalyzed reactions at a specific metal, size, and support‐dependent WO x coverage. The oxide can also alter the reactant adsorption mode, reversing selectivity and pathways from terrace‐ to step‐dominated, as evidenced in furfural decarbonylation and hydrogenation. The insights open avenues for improving metal/metal oxide catalysts beyond the specific system.

Zhou, Jiahua↗
DOE OSTI2020

Au x Pd (300‐ x ) Alloy Nanoparticles for the Oxygen Reduction Reaction in Alkaline Media

Abstract Au x Pd (300‐ x ) nanoalloys were prepared using a dendrimer‐templating method and their electrocatalytic efficiencies towards the oxygen reduction reaction (ORR) were analyzed in alkaline media. The composition‐dependent PdO x reduction potentials of the Au x Pd (300‐ x ) nanoalloys were correlated to the oxygen‐binding (O‐binding) energy of the catalysts. Multiple PdO x reduction peaks were present for the Au 150 Pd 150 and Au 50 Pd 250 catalysts. These peaks were assigned to the alloyed and bulk‐like Pd active sites on the alloyed surface. The results described here are significant because modulation of the O‐binding energies improved the ORR activity on the nanoalloys. Specifically, a linear trend in O‐binding energies of Au x Pd (300‐ x ) dendrimers (DENs) as a function of Pd composition resulted in a volcano‐shaped trend in ORR activity. The optimal O‐binding energy of Au 50 Pd 250 resulted in an approximate 89 mV shift in PdO x reduction relative to Pd 300 and a shift of approximately 76 mV in ORR peak potential.

Trindell, Jamie A.↗
DOE OSTI2024

A data-driven multiscale model for reactive wetting simulations

Here, we describe a data-driven, multiscale technique to model reactive wetting of a silver–aluminum alloy on a Kovar™ (Fe-Ni-Co alloy) surface. We employ molecular dynamics simulations to elucidate the dependence of surface tension and wetting angle on the drop’s composition and temperature. A design of computational experiments is used to efficiently generate training data of surface tension and wetting angle from a limited number of molecular dynamics simulations. The simulation results are used to parameterize models of the material’s wetting properties and compute the uncertainty in the models due to limited data. The data-driven models are incorporated into an engineering-scale (continuum) model of a silver–aluminum sessile drop on a Kovar™ substrate. Model predictions of the wetting angle are compared with experiments of pure silver spreading on Kovar™ to quantify the model-form errors introduced by the limited training data versus the simplifications inherent in the molecular dynamics simulations. The paper presents innovations in the determination of “convergence” of noisy MD simulations before they are used to extract the wetting angle and surface tension, and the construction of their models which approximate physio-chemical processes that are left unresolved by the engineering-scale model. Together, these constitute a multiscale approach that integrates molecular-scale information into continuum scale models.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Effect of excess Mg to control corrosion in molten MgCl 2 and KCl eutectic salt mixture

Structural alloys may experience corrosion when exposed to molten chloride salts due to selective dissolution of active alloying elements. One way to prevent this is to make the molten salt reducing. For the KCl + MgCl 2 eutectic salt mixture, pure Mg can be added to achieve this. However, Mg can form intermetallic compounds with nickel at high temperatures, which may cause alloy embrittlement. This work shows that an optimum level of excess Mg could be added to the molten salt which will prevent corrosion of alloys like 316 H, while not forming any detectable Ni-Mg intermetallic phases on Ni-rich alloy surfaces.

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

H 2 O-assisted O 2 reduction by H 2 on Pt and PtAu bimetallic nanoparticles: Influences of composition and reactant coverages on kinetic regimes, rates, and selectivities

Hydrogen peroxide (H 2 O 2 ) can replace hazardous oxidants in industrial processes but is currently too expensive for many such applications. While direct synthesis of H 2 O 2 (H 2 + O 2 → H 2 O 2 ) may reduce costs in comparison to incumbent technology, current catalysts lack the requisite stability and selectivity. Here, we examine the direct synthesis of H 2 O 2 on bimetallic Pt 1 Au x (0 ≤ x ≤ 230) and Pt catalysts at steady-state in pure water and relate kinetic parameters for H 2 O 2 and H 2 O formation to possible active site structures informed by complementary characterization methods. X-ray photoelectron spectra show significant Pt surface enrichment compared to the bulk composition. Analysis of infrared spectra of mixed monolayers of 12 CO* and 13 CO* indicate that Pt and Au form substitutional surface alloys. The Pt 1 Au x nanoparticles with the greatest mole fractions of Au predominantly expose Pt monomers (i.e., isolated Pt atoms), yet Pt atoms exposed upon all these nanoparticles possess electronic structures distinct from bulk Pt. Despite these differences, rate measurements are consistent with product formation through proton-electron transfer pathways for all Pt 1 Au x catalysts. In situ XAS indicate that Pt remains metallic during H 2 O 2 synthesis. Under the most oxidizing conditions, selectivities toward H 2 O 2 increase strongly with the Au to Pt ratio from 2% for monometallic Pt to 85% for Pt 1 Au 170 . However, selectivities are similar among all catalysts within reducing conditions. Comparisons of apparent activation enthalpies for the formation of H 2 O 2 and H 2 O across these catalysts and the range of conditions suggest that Pt monomers within Au provide the greatest selectivities for H 2 O 2 formation, because these active sites present high barriers for O-O bond rupture. Further, selectivities decrease with increasing ratios of H 2 to O 2 pressures, because Pt atoms aggregate and form oligomers that readily dissociate dioxygen intermediates. The combined use of spectroscopy, kinetics, and concepts employed in reaching these conclusions take inspiration from the legacy of Prof. Michel Boudart, and specifically his elegant methods for interrogating bimetallic catalysts.

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

Carburization of metals by a chemical mechanism of carbon transport through molten fluoride salts

Carburization of structural alloys used in Fluoride Cooled High Temperature Reactors (FHR) can result from the interaction between the metal and graphite components and cause changes in alloy properties. However, carburization requires transport of carbon from graphite to alloy surfaces through the molten fluoride coolant. This work introduces an alternative to previously proposed carbon transport mechanisms. The new mechanism is based on the generation of carbonate ions (CO 3 2- ) by oxide impurities in the salt reacting with graphite. CO 3 2- is then reduced on metal surfaces to deposit carbon. This work demonstrates the reduction of dissolved CO 3 2- on pure Fe, Ni, Cr, Mo, and W surfaces without an applied potential in molten FLiNaK at 700 °C. Finally, we also demonstrate that the interaction between oxide and graphite in molten FLiNaK media produces CO 3 2- .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Periodic Trends in Adsorption Energies around Single-Atom Alloy Active Sites

Single-atom alloys (SAAs) make up a special class of alloy surface catalysts that offer well-defined, isolated active sites in a more inert metal host. The dopant sites are generally assumed to have little or no influence on the properties of the host metal, and transport of chemical reactants and products to and from the dopant sites is generally assumed to be facile. Here, by performing density functional theory calculations and surface science experiments, we identify a new physical effect on SAA surfaces, whereby adsorption is destabilized by ≤300 meV on host sites within the perimeter of the reactive dopant site. We identify periodic trends for this behavior and demonstrate a zone of exclusion around the reactive sites for a range of adsorbates and combinations of host and dopant metals. Experiments confirm an increased barrier for diffusion of CO toward the dopant on a RhCu SAA. Furthermore, this effect offers new possibilities for understanding and designing active sites with tunable energetic landscapes surrounding them.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Elementally Resolved Dissolution Kinetics of a Ni-Fe-Cr-Mn-Co Multi-Principal Element Alloy in Sulfuric Acid Using AESEC-EIS

Atomic emission spectroelectrochemistry (AESEC) combined with linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) provided insights on both active and passive dissolution of Ni-Fe-Cr-Mn-Co multi-principal element alloy. Elemental dissolution rates measured by AESEC during open circuit experiment were in agreement with those extrapolated from AESEC-LSV and indicated element-specific dissolution tendencies. AESEC-EIS at open circuit potential showed nearly in-phase elemental dissolution during potential modulation which suggests direct dissolution from the alloy surface to the electrolyte. In the passive potential domain, no oscillation of the elemental dissolution rate was detected by AESEC-EIS, suggesting non-oxidative chemical dissolution of the outer layer of the passive film. In this case, dissolution at the passive film/electrolyte interface was equal to the metal oxidation rate (passive current density) at the metal/passive film interface and the passive current density was independent of potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1969

Some topics in electrocatalysis

Liquid metal alloys surface composition and electronic structure roles in electrocatalysis evaluated by studying hydrogen-ion discharge reaction and electrical double layer

Butler, J. N.↗
NASA NTRS1981

Design and fabrication of a stringer stiffened discrete-tube actively cooled panel for a hypersonic aircraft

A 0.61 x 1.22 m (2 x 4 ft) test panel was fabricated and delivered to the Langley Research Center for assessment of the thermal and structural features of the optimized panel design. The panel concept incorporated an aluminum alloy surface panel actively cooled by a network of discrete, parallel, redundant, counterflow passage interconnected with appropriate manifolding, and assembled by adhesive bonding. The cooled skin was stiffened with a mechanically fastened conventional substructure of stringers and frames. A 40 water/60 glycol solution was the coolant. Low pressure leak testing, radiography, holography and infrared scanning were applied at various stages of fabrication to assess integrity and uniformity. By nondestructively inspecting selected specimens which were subsequently tested to destruction, it was possible to refine inspection standards as applied to this cooled panel design.

Anthony, F. M.↗
NASA NTRS1985

Molecular orbital studies in oxidation: Sulfate formation and metal-metal oxide adhesion

The chemical mechanisms for sulfate formation from sodium chloride and sulfur trioxide, which is a product of jet fuel combustion was determined. Molten sodium sulfate leads to hot corrosion of the protective oxide layers on turbine blades. How yttrium dopants in nidkel-aluminum alloys used in turbine blades reduce the spalling rate of protective alumina films and enhance their adhesion was also determined. Two other fulfate mechanisms were deduced and structure of carbon monoxide on a clean chronium and clean platinum-titanium alloys surfaces was determined. All studies were by use of the atom superposition and electron delocalization molecular orbital (ASED-MO) theory. Seven studies were completed. Their titles and abstracts are given.

Anderson, A. B.↗
NASA NTRS1986

Outgassing measurement of the aluminum alloy UHV chamber

A large vacuum chamber (580 mm diameter) was fabricated from an aluminum alloy surface treated by a special process normally used on small chambers. The chamber was tested unbaked and baked at various temperatures, pressures, and holding periods. The chamber was filled with N2 gas, and the outgassing rate was measured after one hour. Then the ultimate pressure was measured. Outgassing rates for baked and unbaked groups were compared. It is concluded that the same surface treatment technique can be used on both large and small chambers produced by the same special extrusion process.

Miyamoto, M.↗
NASA NTRS2005

Deposition and Characterization of Thin Films on Metallic Substrates

A CVD method was successfully developed to produce conversion coatings on aluminum alloys surfaces with reproducible results with a variety of precursors. A well defined protocol to prepare the precursor solutions formulated in a previous research was extended to other additives. It was demonstrated that solutions prepared following such a protocol could be used to systematically generate protective coatings onto aluminum surfaces. Experiments with a variety of formulations revealed that a refined deposition protocol yields reproducible conversion coatings of controlled composition. A preliminary correlation between solution formulations and successful precursors was derived. Coatings were tested for adhesion properties enhancement for commercial paints. A standard testing method was followed and clear trends were identified. Only one precursors was tested systematically. Anticipated work on other precursors should allow a better characterization of the effect of intermetallics on the production of conversion/protective coatings on metals and ceramics. The significance of this work was the practical demonstration that chemical vapor deposition (CVD) techniques can be used to systematically generate protective/conversion coating on non-ferrous surfaces. In order to become an effective approach to replace chromate-based pre- treatment processes, namely in the aerospace or automobile industry, the process parameters must be defined more precisely. Moreover, the feasibility of scale-up designs necessitates a more comprehensive characterization of the fluid flow, transport phenomena, and chemical kinetics interacting in the process. Kinetic characterization showed a significantly different effect of magnesium-based precursors when compared to iron-based precursors. Future work will concentrate on refining the process through computer simulations and further experimental studies on the effect of other transition metals to induce deposition of conversion/protective films on aluminum and other metallic substrates.

Gatica, Jorge E.↗
NASA NTRS2003

Surface Tension and Viscosity of Quasicrystal-Forming Ti-Zr-Ni Alloys

The surface tension and viscosity of quasicrystal-forming Ti-Zr-Ni alloys were measured over a range of temperature, including both stable and undercooled liquids by an Electrostatic Levitation (ESL) technique. ESL is a containerless technique which allows processing of samples without contact, greatly reducing contamination and increasing access to the metastable undercooled liquid. The measured viscosity is typical of glass-forming alloys of similar composition to the quasicrystal-forming alloys studied here, while the surface tension shows an anomaly at deep undercoolings.

Hyers, R. W.↗