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At least 271 records · Page 15

Tungsten-dioxo single-site heterogeneous catalyst on carbon: synthesis, structure, and catalysis

This study investigates the application of a novel third-row metal, tungsten, to carbon-supported single-site metal-oxo heterogeneous catalysis. Tungsten is a green and earth-abundant metal, but an unexplored candidate in this role. The carbon (AC = activated carbon)-supported tungsten dioxo complex, AC/WO 2 was prepared via grafting of (DME)WO 2 Cl 2 (DME = 1,2-dimethoxyethane) onto high-surface-area activated carbon. AC/WO 2 was fully characterized by ICP-OES, XPS, EXAFS, XANES, SMART-EM, and DFT. W 4d 7/2 XPS and W L III -Edge XANES assign the oxidation state as W(VI), while EXAFS reveals two W=O double and two W–O single bonds at distances of 1.73 and 1.92 Å, respectively. These data align well with DFT computational results, supporting the structure as Carbon(–μ-O–) 2 M(=O) 2 . SMART-EM verifies that single W(VI) catalytic sites are bonded in an out-of-plane manner. The catalytic performance of air- and water-stable AC/WO 2 is compared to that of AC/MoO 2 . AC/WO 2 is more active and selective than the molybdenum analog in mediating alcohol dehydration of various substrates, and is recyclable. Notably, AC/WO 2 is an effective and recyclable catalyst for primary aliphatic alcohol dehydration and forms no dehydrogenation side products in contrast to AC/MoO 2 . However, AC/WO 2 is less effective in epoxidation and PET depolymerization. Overall, this work demonstrates the potential of carbon-supported third row metals for future studies.

02 PETROLEUM↗

Tungsten fiber reinforced FeCralY: A first generation composite turbine blade material

Tungsten-fiber/FeCrAlY (W/FeCrAlY) was identified as a promising aircraft engine, first generation, turbine blade composite material. Based on available data, W/FeCrAlY should have the stress-rupture, creep, tensile, fatigue, and impact strengths required for turbine blades operating from 1250 to 1370 K. It should also have adequate oxidation, hot corrosion, and thermal cycling damage resistance as well as high thermal conductivity. Concepts for potentially low cost blade fabrication were developed. These concepts were used to design a first stage JT9D convection cooled turbine blade having a calculated 50 K use-temperature advantage over the directionally solidified superalloy blade.

Petrasek, D. W.↗

Protective coating for ceramic materials

A protective coating for ceramic materials such as those made of silicon carbide, aluminum oxide, zirconium oxide, aluminoborosilicate and silicon dioxide, and a thermal control structure comprising a ceramic material having coated thereon the protective coating. The protective coating contains, in admixture, silicon dioxide powder, colloidal silicon dioxide, water, and one or more emittance agents selected from silicon tetraboride, silicon hexaboride, silicon carbide, molybdenum disilicide, tungsten disilicide and zirconium diboride. In another aspect, the protective coating is coated on a flexible ceramic fabric which is the outer cover of a composite insulation. In yet another aspect, a metallic foil is bonded to the outer surface of a ceramic fabric outer cover of a composite insulation via the protective coating. A primary application of this invention is as a protective coating for ceramic materials used in a heat shield for space vehicles subjected to very high aero-convective heating environments.

Kourtides, Demetrius A.↗

Probing the Framework Metal Dependent Properties of Actinide-Centered Polyoxoalkoxide Sandwich-Type Complexes

Development of a simple and scalable synthesis of (TBA) 3 [W 5 O 18 MoNO] provides for the formation of the mixed-metal lacunary polyoxoalkoxide, (TBA) 2 [W 4 O 13 (OMe) 4 MoNO][Na(MeOH)]. This complex was used to synthesize a series of polyoxoalkoxide sandwich-type complexes with the general formula (TBA) 2 [M{W 4 O 13 (OMe) 4 MoNO} 2 ], where M = Zr(IV), Hf(IV), Th(IV), U(IV), and Np(IV). Compared to the analogous all-molybdenum complexes, the series have drastically different optical and redox properties. The results indicate that framework metal substitution acts as a tool for “orbital engineering”, with Density Functional Theory (DFT) calculations revealing that the major consequence of incorporation of tungsten into the complexes is localization of LUMO and LUMO+1 on the molybdenum centers remaining in the molecule. The change in the distribution of the frontier orbitals translates to discrepancies in the electronic properties of the series. Given the rarity of polyoxometalate complexes featuring a U(V) ion, one electron oxidation of (TBA) 2 [U(IV){W 4 O 13 (OMe) 4 MoNO} 2 ] was pursued. Isolation of the corresponding U(V) centered sandwich-type complex is reported, only the second example of U(V)-polyoxometalate complex described to date.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermogravimetric study of reduction of oxides present in oxidized nickel-base alloy powders

Carbon, hydrogen, and hydrogen plus carbon reduction of three oxidized nickel-base alloy powders (a solid solution strengthened alloy both with and without the gamma prime formers aluminum and titanium and the solid solution strengthened alloy NiCrAlY) were evaluated by thermogravimetry. Hydrogen and hydrogen plus carbon were completely effective in reducing an alloy containing chromium, columbium, tantalum, molybdenum, and tungsten. However, with aluminum and titanium present the reduction was limited to a weight loss of about 81 percent. Carbon alone was not effective in reducing any of the alloys, and none of the reducing conditions were effective for use with NiCrAlY.

Herbell, T. P.↗

Low-Power Nuclear Heating Tests of UN Fuel Particles in Hydrogen Environment for Nuclear Thermal Propulsion

Recently, there has been a reemergence of interest within the space-exploration community regarding nuclear thermal propulsion (NTP) for interplanetary travel. NTP, as conceptualized, is a compact propulsion source, is relatively light because there is no need for an oxidizing agent and has a very high specific impulse compared to traditional forms of propulsion. These factors would reduce first-leg orbital-rocketry costs (by the source’s low weight and volume) and decrease overall travel time for astronauts with higher transit speeds. Idaho National Laboratory was provided bare, uncoated, and tungsten-coated uranium nitride fuel particles as part of a preliminary investigation. The fuel was fabricated by BWX Technologies and irradiated at the Massachusetts Institute of Technology research reactor. X-ray computed tomography and scanning electron microscopy and associated chemical analysis techniques were performed on these particles at Idaho National Laboratory. Both coated and uncoated forms were examined in the as-fabricated and as-irradiated conditions. The tungsten coating was found to be intact following the irradiation, indicating positive attributes for performance under these low-power-irradiation conditions. The irradiation of uncoated particles resulted in nitrogen enrichment at the edge of the particle.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Development of a fused slurry silicide coating for the protection of tantalum alloys

Results are reported of a research program to develop a reliable high-performance, fused slurry silicide protective coating for a tantalum-10 tungsten alloy for use at 1427 to 1538 C at 0.1 to 10 torr air pressure under cyclic temperature conditions. A review of silicide coating performance under these conditions indicated that the primary wear-out mode is associated with widening of hairline fissures in the coating. Consideration has been given to modifying the oxidation products that form on the coating surface to provide a seal for these fissures and to minimize their widening. On the basis of an analysis of the phase relationships between silica and various other oxides, a coating having the slurry composition 2.5Mn-33Ti-64.5Si was developed that is effective in the pressure range from 1 to 10 torr.

Packer, C. M.↗

Bismuth Passivation Technique for High-Resolution X-Ray Detectors

The Athena-plus team requires X-ray sensors with energy resolution of better than one part in 3,000 at 6 keV X-rays. While bismuth is an excellent material for high X-ray stopping power and low heat capacity (for large signal when an X-ray is stopped by the absorber), oxidation of the bismuth surface can lead to electron traps and other effects that degrade the energy resolution. Bismuth oxide reduction and nitride passivation techniques analogous to those used in indium passivation are being applied in a new technique. The technique will enable improved energy resolution and resistance to aging in bismuth-absorber-coupled X-ray sensors. Elemental bismuth is lithographically integrated into X-ray detector circuits. It encounters several steps where the Bi oxidizes. The technology discussed here will remove oxide from the surface of the Bi and replace it with nitridized surface. Removal of the native oxide and passivating to prevent the growth of the oxide will improve detector performance and insulate the detector against future degradation from oxide growth. Placing the Bi coated sensor in a vacuum system, a reduction chemistry in a plasma (nitrogen/hydrogen (N2/H2) + argon) is used to remove the oxide and promote nitridization of the cleaned Bi surface. Once passivated, the Bi will perform as a better X-ray thermalizer since energy will not be trapped in the bismuth oxides on the surface. A simple additional step, which can be added at various stages of the current fabrication process, can then be applied to encapsulate the Bi film. After plasma passivation, the Bi can be capped with a non-diffusive layer of metal or dielectric. A non-superconducting layer is required such as tungsten or tungsten nitride (WNx).

Chervenak, James↗

Robust Dissimilar Metal Friction Welded Spool for Enhanced Capability for Steam Power Components (Final Program Report)

This project successfully demonstrated the feasibility and advantages of producing durable, friction-welded dissimilar-metal spools, both with and without transition pieces, as well as the use of advanced oxidation-protective coatings for steam power applications. The work encompassed the optimization and full-scale production of NFA tubing, overcoming manufacturing and processing challenges to achieve enhanced strength, creep, and fatigue properties validated by extensive microstructural characterization. Optimized welding techniques were developed and refined for joining dissimilar materials, resulting in defect-free welds optimized for both low- and high-pressure boiler circuits. Systematic evaluation of welding parameters, coupled with heat treatments, ensured reliable performance and minimized weld defects such as banding and cracking. Comprehensive mechanical and non-destructive testing, including tensile, bend, fatigue, and CT scanning, confirmed the superior integrity and durability of the friction-welded joints under representative service conditions. To address oxidation-related degradation, a range of protective alloy coatings—such as IN625, APMT, Duplex 2507, and FeCrAlY—were selected and evaluated for their ability to counteract oxide notch formation at dissimilar metal interfaces. These coatings demonstrated improved oxidation resistance and long-term stability under thermal cycling, thereby extending weld service life. Thermal cyclic testing and long-term studies captured the phase stability and diffusion behavior of coated and uncoated configurations. Validated models for low-cycle fatigue (LCF), creep, and thermal mechanical fatigue (TMF) were developed to predict component life and failure modes. These models confirmed that friction-welded configurations exhibited significantly enhanced performance compared to conventional gas-tungsten arc welding (GTAW), with up to 7× improvement in creep resistance and at least 2× enhancement in fatigue properties. The introduction of a tailored transition piece further reduced thermally induced strains, enhancing fatigue life. The results demonstrate a robust pathway for retrofitting existing steam fleet components and upgrading future equipment to deliver substantially improved cold-start cycling behavior and reduction of unplanned outages due to premature weld failures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Ni/NiO Reference Electrode Potential Measurements in Molten CaCl 2 –CaO

A direct oxide reduction (DOR) process is used to reduce PuO 2 to Pu metal via Ca metal. Molten CaCl 2 is commonly used as the electrolyte for this reaction. As the DOR reaction proceeds, CaO accumulates in the salt and must be measured in real-time to know when the reaction has gone to completion. Open circuit potential (OCP) was measured in this report between a reference electrode consisting of Ni/NiO contained in a MgO tube and a tungsten working electrode. Two methods of CaO additions were performed over several experiments, and both methods correlated to a 0.11 to 0.23 V decrease in OCP up to 14.4 wt% CaO. CaO concentrations were separately measured via sampling and acid-base titration. A plot of OCP versus concentration of CaO fits the Nernst equation with the CaO powder additions up to 5.2 wt% and also at the higher end of the CaO pellet concentration range. While the MgO tubes were observed to be structurally stable in the molten salt, scanning electron microscopy and energy dispersive X-ray spectroscopy showed that Mg in the tubes had been partially replaced with Ca.

36 MATERIALS SCIENCE↗

Rolling Behavior of Surface Tagged Aluminum 6061 using Photoluminescent Oxides

Physical tagging of nuclear fuel is potentially one way of tracking throughout the fuel lifecycle. The process of tagging can take many forms, but one promising method is to embed a small amount of photoluminescent particles in the surface of a material which are not detectable under normal illumination but are readily visible under excitation by ultraviolet light. The goal of this project was to explore the potential to tag simulated nuclear fuel cladding with small ceramic particles, via laser beam welding or gas tungsten arc welding, and measure the photoluminescent response. Surface tagging using this method has demonstrated viability and detectability throughout this project; work in FY24 focused on the survivability of these tags through subsequent deformation processing similar to what taggants in a fuel manufacturing environment would be subjected to. This work demonstrated that particles are readily visible in the as-welded state (i.e., before subsequent rolling treatment to represent mechanical processing of a fuel material), but visibility is reduced as the deformation is induced. Despite the reduction in photoluminescence, the taggants are still visible after rolling processes are performed, making this surface tagging technique a promising candidate for nuclear fuel cladding tagging. This work demonstrated, though, that targeted optimization work would be necessary to develop a robust taggant depending on the fidelity and luminescent properties required.

36 MATERIALS SCIENCE↗

Hot Hydrogen Testing of W-Coated UN Kernels in a Mo30W Matrix

Ceramic uranium mononitride (UN) is being considered as a reactor fuel for nuclear thermal propulsion. To avoid or reduce the dissociation of UN at the high temperatures needed, embedding it in a metallic matrix (cermet) has been proposed. To assess the viability of this concept, hot hydrogen testing of tungsten-coated UN kernels embedded in a Mo-30 wt% W (Mo30W) alloy matrix has been performed at temperatures from 1800°C to 2300°C. Both the isolated kernels and kernels consolidated by spark plasma sintering in the Mo30W matrix were tested. In addition to direct observations and mass loss measurements, the samples were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM)/energy dispersive X-ray spectroscopy (EDS) after each run. The decomposition of UN started at 1800°C despite the coating and matrix, and increased at 2000°C. Uranium seeped through the tungsten grain boundaries of the coating at all temperatures. The consolidated sample expanded irregularly at 2000°C through the formation of voids, and SEM/EDS analysis showed uranium-containing veins in the matrix consisting of U 2 Mo according to the XRD data. The observed pore generation at 2000°C was explained by the formation of water vapor from residual oxides and diffused hydrogen. At 2200°C and above, both the kernels and the consolidated samples melted through the formation of uranium or low–melting point uranium-molybdenum alloys.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of aircraft brake materials

The requirements of brake materials were outlined and a survey made to select materials to meet the needs of high temperature brakes. A number of metals and ceramic materials were selected and evaluated in sliding tests which simulated aircraft braking. Nickel, molybdenum tungsten, Zr02, high temperature cements and carbons were tested. Additives were then incorporated into these materials to optimize their wear or strength behavior with particular emphasis on nickel and molybdenum base materials and a high temperature potassium silicate cement. Optimum materials were developed which improved wear behavior over conventional brake materials in the simulated test. The best materials are a nickel, aluminum oxide, lead tungstate composition containing graphite or molybdenum disulphite; a molybdenum base material containing LPA100 (an intermetallic compound of cobalt, molybdenum, and silicon); and a carbon material (P5).

Ho, T. L.↗

Factors Influencing Residual Stresses in Yttria Stabilized Zirconia Thermal Barrier Coatings

To improve gas turbine and diesel engine performance using thermal barrier coatings (TBC's) requires an understanding of the factors that influence the in-service behavior of thermal barrier coatings. One of the many factors related to coating performance is the state of stress in the coating. The total stress state is composed of the stresses due to the in-service loading history and the residual stresses. Residual stresses have been shown to affect TBC life, the bond strength of thermal spray coatings, and the fatigue life of tungsten carbide coatings. Residual stresses are first introduced in TBC's by the spraying process due to elevated temperatures during processing and the difference in coefficients of thermal expansion of the top coat, bond coat, and substrate. Later, the residual stresses can be changed by the in-service temperature history due to a number of time and temperature dependent mechanisms, such as oxidation, creep, and sintering. Silica content has also been shown to affect sintering and the cyclic life of thermal barrier coatings. Thus, it is important to understand how the spraying process, the in-service thermal cycles, and the silica content can create and alter residual stresses in thermal barrier coatings.

McGrann, Roy T. R.↗

Origin of tungsten and geochemical controls on its occurrence and mobilization in shallow sediments from Fallon, Nevada, USA

In this study, tungsten (W) occurrence and speciation was investigated in sediments collected from Fallon, Nevada where previous studies have linked elevated W levels in human body fluids to an unusual cluster of childhood leukemia cases. The speciation of sedimentary W was determined by μ-XRF mapping and μ-XANES. The W content of the analyzed surface sediments ranged between 81 and 25,908 mg/kg, which is significantly higher than the W content in deeper sediments which ranged from 37 to 373 mg/kg at 30 cm depth. The μ-XANES findings reveal that approximately 20–50% of the total W in the shallow sediment occurs in the metallic form (W 0 ); the rest occurs in the oxide form (W VI O 3 ). Because W 0 does not occur naturally, its elevated concentrations in surface sediments point toward a possible local anthropogenic origin. The oxidation of metallic W 0 with meteoric waters likely leads to the formation of W VI O 3 . The chief water-soluble W species was identified as WO 4 2– by chromatographic separation and speciation modeling. These results led us to postulate that W 0 particles from a currently unknown but local source(s) is (are) deposited onto the soils and/or surface sediments. The W 0 in interaction with meteoric water is oxidized to W VI O 3 , and as these sediment-water interactions progress, WO 4 2– is formed in the water at pH ~7. Under pH < 7, and sufficient W concentrations, tungstate tends to polymerize, and polymerized species are less likely to adsorb onto sediments. Polymerized species have lower affinity than monomers, which leads to enhanced mobility of W.

58 GEOSCIENCES↗

Materials and processes for space shuttle's engines

It is pointed out that over 50 different alloys are used in construction of the space shuttle main engines (SSME). Primary construction of the SSME is by welding or brazing of wrought and cast components. Welding processes involve both gas tungsten-arc welds and electron-beam welds. Electroforming has been developed as a process to fabricate and bond structural members for the SSME. Important aspects in the selection of materials and processes are related to weight saving considerations and the high-pressure hydrogen environment. Special problems and their solution in the case of various engine components are discussed, giving attention to the oxidizer preburner, the high pressure oxidizer turbopump, and the heat exchanger.

J. R. Lewis↗

Experimental Shock Decomposition of Siderite and the Origin of Magnetite in Martian Meteorite ALH84001

Shock recovery experiments to determine whether magnetite could be produced by the decomposition of iron-carbonate were initiated. Naturally occurring siderite was first characterized by electron microprobe (EMP), transmission electron microscopy (TEM), Mossbauer spectroscopy, and magnetic susceptibility measurements to be sure that the starting material did not contain detectable magnetite. Samples were shocked in tungsten-alloy holders (W=90%, Ni=6%, Cu=4%) to further insure that any iron phases in the shock products were contributed by the siderite rather than the sample holder. Each sample was shocked to a specific pressure between 30 to 49 GPa. Previously reported results of TEM analyses on 49 GPa experiments indicated the presence of nano-phase spinel-structured iron oxide. Transformation of siderite to magnetite as characterized by TEM was found in the 49 GPa shock experiment. Compositions of most magnetites are greater than 50% Fe sup(+2) in the octahedral site of the inverse spinel structure. Magnetites produced in shock experiments display the same range of single-domain, superparamagnetic sizes (approx. 50 100 nm), compositions (100% magnetite to 80% magnetite-20% magnesioferrite), and morphologies (equant, elongated, euhedral to subhedral) as magnetites synthesized by Golden et al. (2001) or magnetites grown naturally by MV1 magnetotactic bacteria, and as the magnetites in Martian meteorite ALH84001. Fritz et al. (2005) previously concluded that ALH84001 experienced approx. 32 GPa pressure and a resultant thermal pulse of approx. 100 - 110 C. However, ALH84001 contains evidence of local temperature excursions high enough to 1 melt feldspar, pyroxene, and a silica-rich phase. This 49 GPa experiment demonstrates that magnetite can be produced by the shock decomposition of siderite as a result of local heating to greater than 470 C. Therefore, magnetite in the rims of carbonates in Martian meteorite ALH84001 could be a product of shock devolatilization of siderite as well.

Bell, Mary Sue↗

Solar Thermal Propulsion Improvements at Marshall Space Flight Center

Solar Thermal Propulsion (STP) is a concept which operates by transferring solar energy to a propellant, which thermally expands through a nozzle. The specific impulse performance is about twice that of chemical combustions engines, since there is no need for an oxidizer. In orbit, an inflatable concentrator mirror captures sunlight and focuses it inside an engine absorber cavity/heat exchanger, which then heats the propellant. The primary application of STP is with upperstages taking payloads from low earth orbit to geosynchronous earth orbit or earth escape velocities. STP engines are made of high temperature materials since heat exchanger operation requires temperatures greater than 2500K. Refractory metals such as tungsten and rhenium have been examined. The materials must also be compatible with hot hydrogen propellant. MSFC has three different engine designs, made of different refractory metal materials ready to test. Future engines will be made of high temperature carbide materials, which can withstand temperatures greater than 3000K, hot hydrogen, and provide higher performance. A specific impulse greater than 1000 seconds greatly reduces the amount of required propellant. A special 1 OkW solar ground test facility was made at MSFC to test various STP engine designs. The heliostat mirror, with dual-axis gear drive, tracks and reflects sunlight to the 18 ft. diameter concentrator mirror. The concentrator then focuses sunlight through a vacuum chamber window to a small focal point inside the STP engine. The facility closely simulates how the STP engine would function in orbit. The flux intensity at the focal point is equivalent to the intensity at a distance of 7 solar radii from the sun.

Gerrish, Harold P.↗