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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

High-energy X-ray scattering and pair distribution function analysis (HEXS/PDF) is a powerful method to reveal the structure of materials lacking long-range order, but is underutilized for molecular complexes in solution. Here we demonstrate the application of HEXS/PDF with 0.26 Å resolution to uncover the solution structure of five bimetallic Cu I /Ru II /Os II complexes. HEXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metal...metal distances separated by over 12 Å. The metal…metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state. This work presents the first example of observing sub-Ångström conformational differences by direct comparison of solution phase and solid-state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.

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

Construction of Lattice Strain in Bimetallic Nanostructures and Its Effectiveness in Electrochemical Applications

Bimetallic nanocrystals (NCs), associated with various surface functions such as ligand effect, ensemble effect, and strain effect, exhibit superior electrocatalytic properties. The stress-induced surface strain effect can alter binding strength between the surface active sites and reactants as well as their intermediates, and the electrochemical performance of bimetallic NCs can be significantly facilitated by the lattice-strain modification via their morphologies, sizes, shell-thickness, surface defectiveness as well as compositions. Here in this review, an overview of fundamental principles, characterization techniques, and quantitative determination of the surface lattice strain is provided. Various strategies and synthesis efforts on creating lattice-strain-engineered bimetallic NCs, including the de-alloying process, atomic layer-by-layer deposition, thermal treatment evolution, one-pot synthesis, and other efforts are also discussed. It is further outlined how the lattice strain effect promotes electrochemical catalysis through the selected case studies. The reactions on oxygen reduction reaction, small molecular oxidation, water splitting reaction, and electrochemical carbon dioxide reduction reactions are focused. In particular, studies of lattice strain arisen from core–shell nanostructure and defectiveness are highlighted. Lastly, the potential challenges are summarized and the prospects of lattice-strain-based engineering on bimetallic nanocatalysts with suggestion and guidance of the future electrocatalyst design are envisioned.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Translating Fundamental Insights into Ag-Based Bimetallic Electrocatalysts to Anion-Exchange Membrane Fuel Cells

To address challenges of high costs and scalability for fuel cells, it is essential to develop af-fordable and earth-abundant materials that are Pt-group-metal (PGM)-free. Recent advance-ments in PGM-free electrocatalysis for the oxygen reduction reaction (ORR) in alkaline media show that high catalyst loadings are needed to achieve high reaction rates; however, there are associated mass transport limitations. To address this issue, we develop low-loading ionomer-less Ag-bimetallic thin films by alloying with 3d block elements or Sn. We bridge knowledge from fundamental rotating disk electrode (RDE) studies to gas-diffusion cathodes in high-temperature anion-exchange membrane fuel cells (HT-AEMFCs), resulting in high-activity ORR catalysis and peak power densities up to 1.2 W cm-² geo for the Ag-Sn and Ag-Co alloys. Here, experimental post-characterization and theoretical calculations reveal small Co or Sn oxide nano-islands on Ag as likely active sites enhancing ORR activity, ultimately offering these low-loading PGM-free ORR materials as a viable path towards sustainable energy conversion.

Catalysts↗
DOE OSTI2023

Highly Stable Fe/Co-TPY-MIL-88(NH 2 ) Metal–Organic Framework (MOF) in Enzymatic Cascade Reactions for Chemiluminescence-Based Detection of Extracellular Vesicles

Metal-Organic Frameworks (MOFs) can deliver many advantages when acting as enzyme mimics to assist with signal amplification in molecular detection: they have abundant active catalytic sites per unit volume of the material; their structures and elemental compositions are highly tunable, and their high specific surface area and porous property can assist with target separation and enrichment. In the present work, we have demonstrated that, by adding the pore partition agent, 2,4,6-tris(4-pyridyl)pyridine (TPY) during synthesis of the bimetallic Fe/Co-MIL-88(NH 2 ) MOF to block the open metal sites, a highly porous MOF of Fe/Co-TPY-MIL-88(NH 2 ) can be produced. This material also exhibits high stability in basic solutions and biofluids and possesses high peroxidase-mimicking activity, which can be utilized to produce long-lasting chemiluminescence (CL) from luminol and H 2 O 2 . Moreover, acting as the peroxidase-mimic, the Fe/Co-TPY-MIL-88(NH 2 ) MOF can form the enzymatic cascade with glucose oxidase (GOx) for biomarker detection. Further, when applied to detect extracellular vesicles (EVs), the MOF material and GOx are brought to the proximity on the EVs through two surface proteins, which triggers the enzyme cascade to produce high CL from glucose and luminol. EVs within the concentration range of 5 × 10 5 - 4 ×10 7 particles/mL can be detected, and the method can be used to analyze EV contents in human serum without sample preparation and EV purification. Overall, our work demonstrates that the high versatility and tunability of the MOF structures could bring in significant benefits to biosensing and enable ultrasensitive detection of biomarkers with judicious material designs.

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

Property-structure-process relationships in dissimilar material repair with directed energy deposition: Repairing gray cast iron using stainless steel 316L

Directed energy deposition (DED) based remanufacturing leverages the flexibility of additive manufacturing to add value to broken or worn components. DED offers the ability to repair cast iron, a material difficult to repair with traditional welding techniques. Despite this, development of appropriate DED process conditions for bimetallic cast iron structures lags low- and medium-carbon steel repair. Thermal stresses and porosity generated by high-temperature deposition on cast iron often lower mechanical properties and hinder the qualification process. In this report scanning speed, powder mass flow rate, and stepover width are studied in multiple-track structures deposited on gray cast iron. Dilution and residual stresses are found to be highly dependent on the selected process parameters. Samples with a higher volumetric energy input, e.g., slower scanning speeds and higher powder feed rates, showed improved density and lower residual stresses but suffered lower dilution into the substrate. The presented conditions further the development of additive manufacturing technologies for automotive repair.

42 ENGINEERING↗
NASA NTRS1977

Bimetallic junctions

The formation of voids through interdiffusion in bimetallic welded structures exposed to high operating temperatures is inhibited by utilizing an alloy of the parent materials in the junction of the parent materials or by preannealing the junction at an ultrahigh temperature. These methods are also used to reduce the concentration gradient of a hardening agent.

Arcella, F. G.↗
DOE OSTI2021

Identification of earth-abundant materials for selective dehydrogenation of light alkanes to olefins

Catalytic alkane dehydrogenation is of considerable importance in the synthesis of olefins industrially. However, discovery of highly active, selective, and stable heterogeneous catalysts to replace noble metal Pt remains challenging. By combining descriptor-based microkinetic modeling, high-throughput computations, machine-learning concepts, and experiments, we efficiently evaluated 1,998 bimetallic alloys and successfully identified Ni 3 Mo as one of the most promising catalysts in selective ethane dehydrogenation. This work will open new possibilities of using earth-abundant materials as catalysts for essential heterogeneous catalytic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Bimetallic Channel Wall Nozzle Development and Hot-Fire Testing Using Additively Manufactured Laser Wire Direct Closeout Technology

NASA has been developing and advancing regeneratively-cooled channel wall nozzle technology for liquid rocket engines to reduce cost and schedules associated with fabrication. One of the primary methods being advanced is Laser Wire Direct Closeout (LWDC). LWDC was developed to provide an additively manufactured laser deposited closeout of the coolant channels that also forms the structural jacket in-situ. This technique has been previously demonstrated through process development and hot-fire testing on a series of subscale nozzles at NASA Marshall Space Flight Center. The hot-fire test articles were fabricated using monolithic alloys to simplify the fabrication process. Ongoing research is being conducted to further expand use of this process for increased scale and bimetallic or multi-alloy options. The use of multi-alloys is desired to fully optimize the combination of materials in the radial and axial directions to reduce overall weight of the nozzle and allow for higher thermal and structural margins on the channel wall nozzle. NASA recently completed process development and hot-fire testing of a series of channel wall nozzles that incorporate a copper-alloy as the hotwall liner material and a superalloy and combination thereof for the structural jacket using the LWDC technique. The fabrication process was further advanced by using a multi-alloy axial joint using explosive bonding integrating a copper-alloy at the forward end of the nozzle hotwall and a stainless-alloy for the remaining length. A third alloy was then used for the channel closeout using the LWDC process. This paper will describe the process development using the LWDC process for channel closeout utilizing the multi-alloys, hardware design and results from hot-fire testing on subscale multi-alloy LWDC channel cooled nozzles.

Gradl, Paul↗
DOE OSTI2026

Si–Cl Bond Activations at Ni(0) to Give Bimetallic Ni(I) μ 1,2 -Cl–SiR 1 R 2 Complexes that Undergo Selective Hydrogenolyses to R 1 R 2 SiH 2 Dihydrosilanes

Chlorosilanes are cheap and abundant raw materials as crucial building blocks in silicon chemistry, yet the metal-mediated activation and functionalization of Si–Cl bonds typically require precious metal sources due to their thermodynamic inertness. Herein, we report the stoichiometric, facile activation, and hydrogenolysis of chlorosilanes mediated by a series of low-valent NHC–Ni (NHC = N-heterocyclic carbene) complexes. Treatment of a Ni(0) complex (IPr)Ni(η 6 -toluene) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene) with chlorosilanes (R 1 R 2 SiCl 2 , R 1 = Cl, R 2 = Cl, Me, Ph, or R 1 = R 2 = Me, Et, Ph, 4-MePh) rapidly afforded di-Ni(I) complexes with a bridging silyl ligand ([(IPr)Ni] 2 (μ-SiR 1 R 2 Cl)(μ-Cl), 1 R1,R2 ) in high yields. Use of a bulkier chlorosilane, Ph 2 SiCl 2 , allowed the isolation of the mono-Ni(II) silyl complex (IPr)Ni(SiPh 2 Cl)Cl (2 Ph ) as an intermediate generated via Si–Cl oxidative addition, which underwent comproportionation with (IPr)Ni(η 6 -toluene) to form 1 Ph,Ph in nearly quantitative yield. Interestingly, 1 R1,R2 was found to react with H 2 at room temperature to form mono- or di-hydrosilanes in moderate to high yields, and the product selectivity was found to be highly dependent on the identity of substituents on Si. In conclusion, these results demonstrate a novel example of facile Si–Cl activation and hydrogenolysis mediated by low-valent mono- and dinuclear NHC–Ni complexes under mild conditions.

Liu, Tianchang [University of California, Berkeley↗
DOE OSTI2024

Medium-Entropy Engineering of Magnetism in Layered Antiferromagnet Cu x Ni 2(1- x ) Cr x P 2 S 6

Antiferromagnetic van der Waals-type M 2 P 2 X 6 compounds provide a versatile material platform for studying 2D magnetism and relevant phenomena. Establishing ferromagnetism in 2D materials is technologically valuable. Though magnetism is generally tunable via a chemical way, it is challenging to induce ferromagnetism with isovalent chalcogen and bimetallic substitutions in M 2 P 2 X 6 . Here, we report co-substitution of Cu 1+ and Cr 3+ for Ni 2+ in Ni 2 P 2 S 6 , creating Cu x Ni 2(1-x) Cr x P 2 S 6 medium-entropy alloys spanning a full substitution range (x = 0 to 1). Such substitution strategy leads to a unique evolution in crystal structure and magnetic phases that are distinct from traditional isovalent bimetallic doping, with Cu and Cr co-substitution enhancing ferromagnetic correlations and generating a weak ferromagnetic phase in intermediate compositions. This aliovalent substitution strategy offers a universal approach for tuning layered magnetism in antiferromagnetic systems, which along with the potential for light-matter interaction and high-temperature ferroelectricity, can enable multifunctional device applications.

2D magnetism↗
NASA NTRS2019

Progress in Additively Manufactured Copper-Alloy GRCop-84, GRCop-42, and Bimetallic Combustion Chambers for Liquid Rocket Engines

Additive Manufacturing (AM) has significantly evolved over the last decade for use in the aerospace industry, particularly for liquid rocket engines. AM offers a considerable departure from traditional manufacturing to rapidly fabricate components with complex internal features. High performance liquid rocket engine combustion chambers that operate in a high heat flux environment are fabricated using a copper-alloy liner with a series of integral coolant channels. Copper-alloys provide the necessary conductivity and material strength for adequate design margins offering high performance without the need for film coolant. Copper-alloys present unique challenges to properly melt the powder in laser-based AM processes due to their high reflectivity and conductivity. Starting in 2014, NASA’s Marshall Space Flight Center (MSFC) and Glenn Research Center (GRC) have developed a process for AM of GRCop (Copper- Chrome-Niobium) alloys using Selective Laser Melting (SLM). GRCop, originally developed at GRC, is a high conductivity, high-strength, dispersion strengthened copper-alloy for use in high-temperature, high heat flux applications. NASA has completed significant material characterization and testing, along with hot-fire testing, to demonstrate that GRCop-42 and GRCop-84 alloys are suitable for use in combustion chambers. Additional development and testing has been completed on AM bimetallic chambers using GRCop-84 liners and superalloy jackets, fabricated using two Directed Energy Deposition (DED) processes: Electron Beam Freeform Fabrication (EBF³) and Blown Powder DED. NASA completed hot-fire testing on various AM chambers using GRCop-84, GRCop-42, and bimetallic chambers in Liquid Oxygen (LOX)/Hydrogen, LOX/Methane, and LOX/Kerosene propellants.

Gradl, Paul R.↗
NASA NTRS2012

The Evolution of Friction Stir Welding Theory at Marshall Space Flight Center

From 1995 to the present the friction stir welding (FSW) process has been under study at Marshall Space Flight Center (MSFC). This is an account of the progressive emergence of a set of conceptual tools beginning with the discovery of the shear surface, wiping metal transfer, and the invention of a kinematic model and making possible a treatment of both metallurgical structure formation and process dynamics in friction stir welding from a unified point of view. It is generally observed that the bulk of the deformation of weld metal around the FSW pin takes place in a very narrow, almost discontinuous zone with high deformation rates characteristic of metal cutting. By 1999 it was realized that this zone could be treated as a shear surface like that in simple metal cutting models. At the shear surface the seam is drawn out and compressed and pressure and flow conditions determine whether or not a sound weld is produced. The discovery of the shear surface was followed by the synthesis of a simple 3- flow kinematic model of the FSW process. Relative to the tool the flow components are: (1) an approaching translational flow at weld speed V, (2) a rotating cylindrical plug flow with the angular velocity of the tool , and (3) a relatively slow ring vortex flow (like a smoke ring) encircling the tool and driven by shoulder scrolls and pin threads. The rotating plug flow picks up an element of weld metal, rotates it around with the tool, and deposits it behind the tool ( wiping metal transfer ); it forms plan section loops in tracers cut through by the tool. Radially inward flow from the ring vortex component retains metal longer in the rotating plug and outward flow expels metal earlier; this interaction forms the looping weld seam trace and the tongue and groove bimetallic weld contour. The radial components of the translational and ring vortex flows introduce parent metal intrusions into the small grained nugget material close to the tool shoulder; if this feature is pronounced, nugget collapse may result. Certain weld features, in particular internal banding seen in transverse section as onion rings and associated surface ridges called tool marks , have long implied an oscillation flow component, but have only recently been attributed in the literature to tool eccentricity. Rotating plug shape, typically a hollow cylinder flared at the end where it sticks to the shoulder, varies as pressure distribution on the tool determines where sticking occurs. Simplified power input estimates balanced against heat loss estimates give reasonable temperature estimates, explain why the power requirement changes hardly at all over a wide range of RPM s, and yield isotherms that seem to fall along boundaries of parameter windows of operation.

Nunes, Arthur C.↗
DOE OSTI2025

Multimetallic Metal-Organic Frameworks as Heterogeneous Catalysts for Gas Phase Hydroformylation and Hydrogenation Reactions

This project focused on the development bimetallic metal-organic frameworks (MOFs) as gas phase heterogeneous catalysts for hydrogenation and hydroformylation reactions. MOFs are a new class of hybrid inorganic/organic materials that are highly crystalline, with structures consisting of metal nodes of specific geometries connected by organic linkers. Although there have been a number of studies of catalysis at MOF nodes in solution, there is little experimental data in the literature for gas phase reactions despite the fact that industrial heterogeneous catalysis on MOFs is more economically viable than homogeneous catalysis. The use of MOFs as heterogeneous catalysts presents the unique opportunity to carefully control the composition, geometry and ensemble sizes of the active sites, which are all critical factors for the rational design of new catalysts. Specific objectives of the project are as follows: (1) to tailor the geometry, composition and ensemble size of the active sites; (2) to understand how the adsorption of molecules at metal sites can be modified by interactions with a neighboring metal site; (3) to determine how oxidation states of the metal change during reaction and how these states can be modified by metal-metal electronic interactions; and (4) to elucidate reaction mechanisms and intermediates. For these studies, we have chosen to investigate selective hydrogenation of hydrocarbons and hydroformylation, which are industrially relevant reactions. Our interdisciplinary team of Chen, Shustova and Vogiatzis/Henkelman provides critical expertise in novel MOF synthesis (Shustova), atomic-scale surface science and catalysis (Chen) and computational studies of reaction mechanisms (Vogiatzis/Henkelman) that are necessary for the development of these catalysts. We believe that this work will lead directly to the rational design of new catalysts that are versatile, highly active/selective and suitable for industrial processes.

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

Stability Criteria for Self-Propagating Reaction Waves in Co/Al Multilayers

The propagation of self-sustained formation reactions in sputter-deposited Co/Al multilayers is known to exhibit a design-dependent instability. Multilayers having thin bilayers (<55 nm period) exhibit stable propagating waves, whereas those with a larger period react unstably. The specific two-dimensional (2D) instability observed involves the transverse propagation of a band in front of a stalled front commonly referred to as a “spin band.” Previous finite-element studies have shown that these instabilities are thermodynamically driven by the forward conduction of heat away from the flame front. However, the magnitude of that loss is inherently tied to the bilayer design in traditional bimetallic multilayers, which couples any proposed stability criteria to a varying critical diffusion distance. Here, this work utilizes a recently developed class of materials known as “inert-mediated reactive multilayers” to decouple the thermodynamic and kinetic contributions to propagating wave stability by reducing the stored chemical energy density in normally stable bilayer designs. By depositing an inert product phase (B2-CoAl) within the mid-plane of Co and Al reactant layers, spin instabilities arise as a function of both diluted volume and critical diffusion distance. From there, a stability criterion is determined for Co/Al multilayers based on enthalpy loss from the reaction zone, and its physical significance is explored.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Mechanistic Investigations of Gas-Phase Catalytic Hydrogenation in Metal–Organic Frameworks: Cooperative Activity of the Metal and Linker Sites in Cu x Rh 3– x (BTC) 2

We report the Cu x Rh 3–x (BTC) 2 catalyst (abbreviated CuRhBTC, BTC 3– = benzene tricarboxylate) provides excellent dispersion of active metal sites coupled with well-defined, robust structures for propylene hydrogenation reactions. This material therefore serves as a unique prototype for understanding catalytic activity in metal organic frameworks (MOFs). The mechanism of gas-phase hydrogenation at the bimetallic metal nodes of a MOF has been investigated in detail for the first time using in situ spectroscopy and diffraction experiments combined with density functional theory (DFT) calculations. The reaction occurs via a cooperative process in which the metal and linker sites play complementary roles; specifically, H 2 is dissociated at a Rh 2+ site with a missing Rh–O bond, while protonation of the decoordinated carboxylate linker stabilizes the active sites and promotes H 2 dissociation. In situ X-ray diffraction experiments show that the crystalline structure of the MOF is retained under reaction conditions at 20–100 °C. In situ Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments demonstrate that propylene adsorbs at both Rh 2+ and Cu 2+ sites via π bonding. Cu 2+ is catalytically inactive, but at Rh 2+ sites, a propyl intermediate is observed when H 2 is introduced into the propylene feed. Furthermore, the appearance of the O–H stretch of COOH at ~3690 cm –1 in the DRIFT spectra is characteristic of defects consisting of missing Rh–O bonds. These experimental results are in general agreement with a reaction mechanism proposed by DFT, in which the decoordinated carboxylate linker is protonated, and the active Rh 2+ site remains available for readsorption of reactants in the subsequent catalytic cycle.

36 MATERIALS SCIENCE↗