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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Surface Tension and Viscosity of SCN and SCN-acetone Alloys at Melting Points and Higher Temperatures Using Surface Light Scattering Spectrometer

Succinonitrile has been and is being used extensively in NASA's Microgravity Materials Science and Fluid Physics programs and as well as in several ground-based and microgravity studies including the Isothermal Dendritic Growth Experiment (IDGE). Succinonitrile (SCN) is useful as a model for the study of metal solidification, although it is an organic material, it has a BCC crystal structure and solidifies dendriticly like a metal. It is also transparent and has a low melting point (58.08 C). Previous measurements of succinonitrile (SCN) and alloys of succinonitrile and acetone surface tensions are extremely limited. Using the Surface Light Scattering technique we have determined non invasively, the surface tension and viscosity of SCN and SCN-Acetone Alloys at different temperatures. This relatively new and unique technique has several advantages over the classical methods such as, it is non invasive, has good accuracy and measures the surface tension and viscosity simultaneously. The accuracy of interfacial energy values obtained from this technique is better than 2% and viscosity about 10 %. Succinonitrile and succinonitrile-acetone alloys are well-established model materials with several essential physical properties accurately known - except the liquid/vapor surface tension at different elevated temperatures. We will be presenting the experimentally determined liquid/vapor surface energy and liquid viscosity of succinonitrile and succinonitrile-acetone alloys in the temperature range from their melting point to around 100 C using this non-invasive technique. We will also discuss about the measurement technique and new developments of the Surface Light Scattering Spectrometer.

Tin, Padetha↗
DOE OSTI2022

Oxidative Self-Assembly of Au/Ag/Pt Alloy Nanoparticles into High-Surface Area, Mesoporous, and Conductive Aerogels for Methanol Electro-oxidation

The ability to assemble nanoparticles (NPs) into functional nanostructures is critical for the advancement of nanoscience. However, common assembling techniques utilize organic ligands or biomolecules, which are detrimental for charge transport and interparticle coupling, which impede the efficient integration of low-dimensional properties. Herein, we report a methodology for the self-supported assembly of ultra-small (3-6 nm) Au/Ag/Pt alloy NPs into large, free-standing alloy superstructures (aerogels) that exhibit direct NP connectivity, high surface area (125 ± 0.43 to142 ± 0.93 m 2 /g) and mesoporosity (21.6 ± 2.2 nm), and superior electrocatalytic activity for methanol oxidation reaction (MOR). Precursor Au/Ag/Pt alloy NPs and hydrogels were synthesized via stepwise galvanic replacement reaction (GRR) of the glutathione (GSH)-coated Ag NPs, followed by oxidative removal of the surfactant ligands. The composition of alloy aerogels was tuned by varying the oxidant/GSH molar ratio, which governs the extent of Ag dealloying with in-situ generated HNO 3 and increases the exposure of Au and Pt on the aerogel surface. The alloy aerogels exhibit superior MOR mass activity, which is 21.4 and 2.5 times higher than those of the precursor NPs and commercial Pt (40 wt.%)/C electrocatalysts, respectively. The MOR surface-specific activity (MOR-SSA) of the aerogels was improved by >17% when the Pt content was increased from 22.4% to 31.2%. The aerogels exhibit improved electronic conductivity, enhanced tolerance for carbonaceous byproducts, and maintained ~94% of the initial MOR activity at -0.3 V for 24 h in an alkaline medium. In conclusion, the interconnected porous superstructure of the aerogel provides a facile conduit for molecules to reach the pristine active surface whereas the presence of oxophilic Au promotes the dissociative adsorption of methanol, enabling the Au/Ag/Pt alloy aerogel a high efficiency, durable electrocatalyst for next generation of energy conversion studies.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Heats of Segregation of BCC Metals Using Ab Initio and Quantum Approximate Methods

Many multicomponent alloys exhibit surface segregation, in which the composition at or near a surface may be substantially different from that of the bulk. A number of phenomenological explanations for this tendency have been suggested, involving, among other things, differences among the components' surface energies, molar volumes, and heats of solution. From a theoretical standpoint, the complexity of the problem has precluded a simple, unified explanation, thus preventing the development of computational tools that would enable the identification of the driving mechanisms for segregation. In that context, we investigate the problem of surface segregation in a variety of bcc metal alloys by computing dilute-limit heats of segregation using both the quantum-approximate energy method of Bozzolo, Ferrante and Smith (BFS), and all-electron density functional theory. In addition, the composition dependence of the heats of segregation is investigated using a BFS-based Monte Carlo procedure, and, for selected cases of interest, density functional calculations. Results are discussed in the context of a simple picture that describes segregation behavior as the result of a competition between size mismatch and alloying effects

Good, Brian↗
DOE OSTI2024

Surface Segregation Studies in Ternary Noble Metal Alloys: Comparing DFT and Machine Learning with Experimental Data

Abstract Surface segregation, whereby the surface composition of an alloy differs systematically from the bulk, has historically been hard to study, because it requires experimental and modeling methods that span alloy composition space. In this work, we study surface segregation in catalytically relevant noble and platinum‐group metal alloys with a focus on three ternary systems: AgAuCu, AuCuPd, and CuPdPt. We develop a data set of 2478 fcc slabs with those compositions including all three low‐index crystallographic orientations relaxed with Density Functional Theory using the PBEsol functional with D3 dispersion corrections. We fine‐tune a machine learning model on this data and use the model in a series of 1800 Monte Carlo simulations spanning ternary composition space for each surface orientation and ternary chemical system. The results of these simulations are validated against prior experimental surface segregation data collected using composition spread alloy films for AgAuCu and AuCuPd. Our findings reveal that simulations conducted using the (110) orientation most closely match experimentally observed surface segregation trends, and while predicted trends qualitatively match observation, biases in the PBEsol functional limit numeric accuracy. This study advances understanding of surface segregation and the utility of computational studies and highlights the need for further improvements in simulation accuracy.

Chemistry↗
DOE OSTI2024

Atomic-Scale Visualization of Surface Segregation and Ordering of Pt in a Dilute Cu(Pt) Alloy under a Hydrogen Atmosphere

Surface segregation is a common phenomenon in alloys exposed to reactive atmospheres, yet the atomic mechanisms underlying surface structure and composition dynamics remain largely unexplored. Using a combination of environmental transmission electron microscopy observations and atomistic modeling, here we report the surface segregation process of Pt atoms in a dilute Pt(Cu) alloy and determine the distribution of Pt atoms at both atomically flat and stepped surfaces of the Pt(Cu) alloy at elevated temperatures and in a hydrogen gas atmosphere. Through directly probing Pt segregation, we find that Pt atoms segregated on the (100) surface exhibit a p(2 × 2) ordering, with ~25% Pt occupancy. In contrast, on the stepped (410) surface, hydrogen adsorption induces Pt segregation, initially occurring at the step edges, which then expands to the terrace sites upon increased hydrogen coverage, resulting in an ordered distribution of segregated Pt atoms with ~22% occupancy. Finally, these observations offer mechanistic insights into the structure and composition dynamics of the topmost atomic layer of the alloy in response to environmental stimuli and hold practical implications for the design and optimization of catalysts based on Pt group metals.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Laser-interference pulse number dependence of surface chemistry and sub-surface microstructure of AA2024-T3 alloy

The laser-based treatment of a metal surface is an intrinsically non-chemical technique that can alter both the topology and chemistry of surfaces. A laser-based treatment for coating and joining applications can offer alternative surface preparations to the chemically-based surface preparation techniques, which are subject to severe environmental protection and hazardous-waste management considerations. In this study, the surface chemistry and sub-surface microstructural changes are investigated for a novel surface processing method using laser interferometry produced by two beams of a pulsed Nd:YAG laser. The two-beam laser-interference allowed the structuring of the surface at length scales much less than that of the laser beam spot. Surface chemistry changes in the oxide layer of AA 2024-T3 aluminum alloy rolled sheet due to laser processing were investigated using x-ray photoelectron spectroscopy (XPS). Near surface microstructural changes have been investigated with scanning electron microscopy and energy dispersive x-ray spectroscopy (SEM/EDS), and scanning transmission electron microscopy (STEM) as a function of number of interfering laser shots. SEM microstructure pictures of the top surface shows the minimization of surface defects, as all of the sharp features from a rolled sheet surface were smoothed by laser-structuring. STEM images indicate that the laser-interference processing reduced the formation of CuMn-rich precipitates over a 500–800 nm depth from the top surface. XPS data indicated that the Al oxide layer is modified compared to that of the baseline specimen and that the oxide thickness increases with the number of shots per spot. Finally, the additional thicker oxide on Al alloys is expected to increase the corrosion resistance of the coated Al 2024.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Theoretical investigation of surface chemical reactivity of compositionally disordered multi-metallic alloys

Alloys are widely used in both academic and industrial research as heterogeneous catalysts for accelerating technologically important reactions ranging from hydrocarbon reforming, selective hydrogenation, to electrochemical reactions involving hydrogen and oxygen that are fundamental and indispensable to a sustainable future energy infrastructure. Most basic catalysis research has been limited to combinations of two elements that are usually ordered in some manner at the nanoscale because doing so allows observable results to be easily rationalized. It however leaves a huge material space consisting of multi metallic, compositionally disordered alloys unexplored. This research demonstrates a viable theoretical approach combining different types of first principles calculations (including Green’s function-based Korringa–Kohn–Rostoker coherent potential approximation (KKR–CPA) and planewave-based density functional theory) to enable the surface chemical reactivity of compositionally complex alloy surfaces to be investigated. We demonstrate the approach by investigating hydrogen adsorption and evolution on two types of compositionally disordered alloys: a quaternary CoCrFeNi high-entropy alloy, and binary Pt-3d base metal alloys.

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

Aeroheating model advancements featuring electroless metallic plating

Discussed are advancements in wind tunnel model construction methods and hypersonic test data demonstrating the methods. The general objective was to develop model fabrication methods for improved heat transfer measuring capability at less model cost. A plated slab model approach was evaluated with cast models containing constantan wires that formed single-wire-to-plate surface thermocouple junctions with a seamless skin of electroless nickel alloy. The surface of a space shuttle orbiter model was selectively plated with scaled tiles to simulate, with high fidelity, the probable misalignments of the heatshield tiles on a flight vehicle. Initial, Mach 8 heating results indicated a minor effect of tile misalignment roughness on boundary layer transition, implying a possible relaxation of heatshield manufacturing tolerances. Some loss of the plated tiles was experienced when the model was tested at high heating rates.

Stalmach, C. J., Jr.↗
DOE OSTI2025

Alloying of Mn with Bi‐Rich Surfaces of Bi 2 Te 3 by Topotactic Reaction

Interfacing topological insulators (TI) with magnetic materials enables accessing quantum effects for advanced devices. The synthesis of such heterostructures faces challenges due to interlaying mixing and the often-complex multicomponent materials required to combine the desired properties. An alternative synthesis to direct growth is the modification of 2D materials by topotactic reactions to introduce new functionalities into pre-formed single or few-component 2D sheets. Here, the self-formation of bismuthene (a bilayer of Bi; Bi 2 ) is utilized by thermal decomposition of Bi 2 Te 3 as a platform to create novel 2D overlayers on the TI- substrate. Specifically, the Bi 2 layer is modified by reacting it with vapor deposited Mn in an attempt to induce magnetic properties. Scanning tunneling microscopy indicates that the Mn modified surface remains in a planar 2D layer, indicating the formation of an ordered Mn-rich surface layer. Density functional theory (DFT) is used to develop models of both the Bi-rich Bi 2 Te 3 surface as well as their subsequent Mn-modified structure. The DFT models indicate the possibility of magnetic ordering of the high spin Mn 2+ ions. The successful synthesis of planar MnBi alloys on a van der Waals material illustrates topotactic reactions as an alternative for creating novel layered heterostructures.

2D materials↗
DOE OSTI2023

Surface Film Formation on Al-V Alloys with Far-From-Equilibrium Microstructure

Nanocrystalline supersaturated Al-V alloys produced by high-energy ball milling have been reported to exhibit enhanced corrosion resistance and mechanical properties compared to commercial Al alloys. Corrosion of passive alloys such as Al-V alloy relies on the characteristics of the surface film, which is studied using scanning/transmission electron microscopy and time-of-flight secondary ion mass spectrometry. The effect of microstructure and composition on the surface film has been investigated after different immersion periods (30 min, 2 h, and 1 day) in 0.1 M NaCl. The surface film was complex and composed of oxidized Al and V. The heterogeneous surface film was observed due to the presence of secondary phases and initiation of localized corrosion. The void formation was observed beneath the surface film that would potentially cause pitting corrosion. The generation of nano-sized voids was dependent on grain orientation. Compared to pure Al, the chloride penetration is suppressed in Al-V alloys. The effect of composition and microstructure on surface film formation and attendant corrosion behavior is discussed herein.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Compositionally-driven surface nanostructuring on refractory compositionally complex alloys under low energy helium bombardment

Additive manufacturing enables user-defined control of the compositional complexity, opening new design spaces for complex concentrated alloys (CCAs). Refractory CCAs may offer enhanced performance in the divertor region of a fusion reactor environment where plasma-facing materials will be subject to high temperatures, low energy He and D particles, and 14 MeV neutrons. In this work, specimens with the nominal composition of NbTaMoTi, NbTaMo, NbTaTi, and NbTa were fabricated via directed energy deposition (DED) then bombarded with 40 eV He ions to a fluence of 2x10 26 m −2 at ∼ 1000 K. Post irradiation, the surface morphology and composition were examined with electron microscopy and x-ray photoelectron spectroscopy to offer information on the spatial distribution of surface nano-structuring. Sub-surface He bubbles driving the nano-structuring were examined with electron microscopy techniques. Analysis indicates the local composition directly influences the He bubble and tendril size, while the region with the highest complexity showed the shortest nano-structuring. Molecular Dynamics simulations complement the experimental results, showing comparable helium bubble growth and migration as a function of compositional complexity. This work demonstrates the compositional dependence of surface nanostructure formation of compositionally complex alloys, important for future design of complex plasma facing materials in fusion reactors.

Complex concentrated alloys↗
DOE OSTI2023

Bimetallic-Derived Catalytic Structures for CO 2 -Assisted Ethane Activation

In recent years, the simultaneous upgrading of CO 2 and ethane has emerged as a promising approach for generating valuable gaseous (CO, H 2 , and ethylene) and liquid (aromatics and C 3 oxygenates) chemicals from the greenhouse gas CO 2 and large-reserved shale gas. The key challenges for controlling product selectivity lie in the selective C-H and C-C bond cleavage of ethane with the assistance of CO 2 . Bimetallic-derived catalysts likely undergo alloying or oxygen-induced segregation under reaction conditions, thus providing diverse types of interfacial sites, e.g., metal/support (M/M'O x ) interface and metal oxide/metal (M'O x /M) inverse interface, that are beneficial for selective CO 2 -assisted ethane upgrading. The alloying extent can be initially predicted by cohesive energy and atomic radius (or Wigner-Seitz radius), while the preference for segregation to form the on-top suboxide can be approximated using the work function, electronegativity, and binding strength of adsorbed oxygen. Furthermore, bimetallic-derived catalysts are typically supported on high surface area oxides. Modifying the reducibility and acidity/basicity of the oxide supports and introducing surface defects facilitate CO 2 activation and oxygen supplies for ethane activation. Using in situ synchrotron characterization and density functional theory (DFT) calculations, we found that the electronic properties of oxygen species influence the selective cleavage of C-H/C-C bonds in ethane, with electron-deficient oxygen over the metal (or alloy) surface promoting nonselective bond scission to produce syngas and electron-enriched oxygen over the metal oxide/metal interface enhancing selective C-H scission to yield ethylene. Here, we further demonstrate that the preferred structures of the catalyst surfaces, either alloy surfaces or metal oxide/metal inverse interfaces, can be controlled through the appropriate choice of metal combinations and their atomic ratios. Through a comprehensive comparison of experimental results and DFT calculations, the selectivity of C-C/C-H bond scission is correlated with the thermodynamically favorable bimetallic-derived structures (i.e., alloy surfaces or metal oxide/metal inverse interfaces) under reaction conditions over a wide range of bimetallic catalysts. These findings not only offer structural and mechanistic insights into bimetallic-derived catalysts but also provide design principles for selective catalysts for CO 2 -assisted activation of ethane and other light alkanes. This Account concludes by discussing challenges and opportunities in designing advanced bimetallic-derived catalysts, incorporating new reaction chemistries for other products, employing precise synthesis strategies for well-defined structures with optimized site densities, and leveraging time/spatial/energy-resolved in situ spectroscopy/scattering/microscopy techniques for comprehensive structural analysis. The research methodologies established here are helpful for the investigation of dynamic alloy and interfacial structures and should inspire more efforts toward the simultaneous upgrading of CO 2 and shale gas.

03 NATURAL GAS↗
DOE OSTI2023

Mechanistic origins of corrosion protection of aluminum alloys by graphene/polyetherimide nanocomposite coatings

Light-weighting vehicular components through adoption of light-metal structural alloys holds promise for reducing the fuel consumption of internal combustion engine vehicles and increasing the range of battery electric vehicles. However, the alloyed microstructure and surface precipitates of aluminum alloys render these materials susceptible to corrosion under modest excursions from neutral pH. Traditional chromium-based anodic passivation layers are subject to increasingly stringent environmental regulations, whereas options for sacrificial cathodic films are sparse for electropositive metals. While hybrid nanocomposite coatings have shown initial promise, mechanistic underpinnings remain poorly understood. Here, a fully imidized polyetherimide (PEI) resin is utilized as the continuous phase with inclusion of unfunctionalized exfoliated graphite (UFG). A comprehensive investigation of the mechanisms of corrosion protection reveals key fundamental design principles underpinning corrosion inhibition. First, strong interfacial adhesion, which for PEI is facilitated by binding of imide carbonyl moieties to Lewis acidic sites on Al surfaces. Second, the miscibility of ion-impervious nanoscopic UFG fillers and stabilization of a substantial interphase region at UFG/PEI boundaries that result in minimizing the free volume at the filler/polymer interface. Finally, extended tortuosity of ion diffusion pathways imbued by the below-percolation-threshold 2D fillers. These three design principles help govern and modulate ion transport from electrolyte/coating interfaces to the coating/metal interface and are crucial for the extended preservation of barrier properties. The results suggest an approach to systematically activate multiple modes of corrosion inhibition through rational design of hybrid nanocomposite coatings across hard-to-abate sectors where light metal alloys are likely to play an increasingly prominent role.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Hydrogen permeation in iron-chromium-aluminum (FeCrAl) alloys and the effects of microstructure and surface oxide

Iron–chromium–aluminum (FeCrAl) class alloys are candidates for use as cladding for accident-tolerant fuels and moderators. In this context, hydrogen isotope permeation in FeCrAl alloys is an important material property. Here, in the present work, the apparent permeability, effective diffusivity, and apparent solubility of hydrogen in the FeCrAl alloys C26M and Kanthal D (KD) were measured with gas-driven hydrogen permeation. Permeation measurements were conducted at temperatures of 400 to 700 °C and at gas-driven pressures from 1 to 100 kPa. In particular, the effect of grain size on hydrogen transport was studied with KD samples with three different microstructures: nanocrystalline (NC), ultra-fine grained (UFG), and coarse-grained (CG). The UFG and NC specimens had higher apparent activation energies (73.4 kJ mol -1 and 65.2 kJ mol -1 , respectively) for hydrogen permeability than the CG sample (46.9 kJ mol -1 ). An aluminum oxide layer formed on the primary- and secondary-side surfaces of all samples subjected to permeation experiments which demonstrated the propensity of FeCrAl alloys to form these innate oxide permeation barriers.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1982

Plasma Spray for Difficult-To-Braze Alloys

Nickel plating on surfaces makes brazing easier for some alloys. Sometimes nickel plating may not be feasible because of manufacturing sequence, size of hardware, or lack of suitable source for nickel plating. Alternative surface preparation in such cases is to grit-blast surface lightly and then plasma-spray 1 1/2 to 2 mils of fine nickel powder or braze-alloy material directly on surface. Powder is sprayed from plasma gun, using argon as carrier gas to prevent oxidation of nickel or braze alloy.

Brennan, A.↗
NASA NTRS1993

Surface Segregation in Cu-Ni Alloys

Monte Carlo simulation is used to calculate the composition profiles of surface segregation of Cu-Ni alloys. The method of Bozzolo, Ferrante, and Smith is used to compute the energetics of these systems as a function of temperature, crystal face, and bulk concentration. The predictions are compared with other theoretical and experimental results.

Good, Brian↗