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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 163 records · Page 9

Effects of anode material on arcjet performance

Anodes fabricated from four different materials were tested in a modular arcjet thruster at 1 kW power level on nitrogen/hydrogen mixtures. A two-percent thoriated tungsten anode served as the control. Graphite was chosen for its ease in fabrication, but experienced severe erosion in the constrictor and diverging side. Hafnium carbide and lanthanum hexaboride were chosen for their low work functions but failed due to thermal stress and reacted with the propellant. When compared to the thoriated tungsten nozzle, thruster performance was significantly lower for the lanthanum hexaboride insert and the graphite nozzle, but was slightly higher for the hafnium carbide nozzle. Both the lanthanum hexaboride and hafnium carbide nozzle operated at higher voltages. An attempt was made to duplicate higher performance hafnium carbide results, but repeated attempts at machining a second anode insert were unsuccessful. Graphite, hafnium carbide, and lanthanum hexaboride do not appear viable anode materials for low power arcjet thrusters.

Sankovic, John M.↗

CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

Nagaraj, Bangalore A.↗

Experimental Observations of Nuclear Activity in Deuterated Materials Subjected to a Low-Energy Photon Beam

Exposure of highly deuterated materials to a low-energy (nom. 2 MeV) photon beam resulted in nuclear activity of both the parent metals of hafnium and erbium and a witness material (molybdenum) mixed with the reactants. Gamma spectral analysis of all deuterated materials, ErD2.8+C36D74+Mo and HfD2+C36D74+Mo, showed that nuclear processes had occurred as shown by unique gamma signatures. For the deuterated erbium specimens, posttest gamma spectra showed evidence of radioisotopes of erbium ((163)Er and (171)Er) and of molybdenum ((99)Mo and (101)Mo) and by beta decay, technetium (99mTc and 101Tc). For the deuterated hafnium specimens, posttest gamma spectra showed evidence of radioisotopes of hafnium (180mHf and 181Hf) and molybdenum ((99)Mo and (101)Mo), and by beta decay, technetium ((99m)Tc and (101)Tc). In contrast, when either the hydrogenated or non-gas-loaded erbium or hafnium materials were exposed to the gamma flux, the gamma spectra revealed no new isotopes. Neutron activation materials showed evidence of thermal and epithermal neutrons. CR-39 solid-state nuclear track detectors showed evidence of fast neutrons with energies between 1.4 and 2.5 MeV and several instances of triple tracks, indicating (is) greater than 10 MeV neutrons. Further study is required to determine the mechanism causing the nuclear activity.

Steinetz, Bruce M.↗

High and Ultra-High Temperature Reaction Kinetics by Single Nanoparticle Mass Spectrometry

Methodology is presented for non-destructive, optically-detected single nanoparticle (NP) mass spectrometry, with the goal of extracting surface reaction kinetics for single NPs at high temperatures. Methods for determining the NP charge, mass, and temperature as a function of time are discussed, and the data are used to extract both the absolute kinetics for mass change, as well as the efficiencies of the surface processes that cause them. Factors that contribute to the uncertainties in absolute and relative mass determination, and in the resulting kinetic parameters, are discussed. The method allows the NP-to-NP variations in initial reactivity to be measured directly, along with the time evolution of reactivity resulting from NP structural/compositional changes that occur under reaction conditions. The strengths and limitations of single nanoparticle mass spectrometry as a high temperature surface kinetics tool are discussed in the context of sublimation and O2 oxidation kinetics experiments for single hafnium (Hf) NPs at temperatures ranging above 2400 K. The Hf oxidation kinetics are compared to analogous oxidation experiments for silicon, graphite, and carbon black NPs. In all four cases, the oxidation chemistry was dominated by processes that result in net mass loss, and the distinct mechanisms responsible are discussed. All four NPs also eventually passivated, i.e., the efficiencies for oxidative etching decreased by at least two orders of magnitude, relative to the initial efficiencies. Furthermore, the passivation mechanisms, which are quite different for carbon, compared to silicon or hafnium, are discussed. Carbon NP passivation is attributed to structural isomerization leading to fully coordinated, fullerene-like NP surfaces, while for silicon and hafnium, passivation results from delayed formation of an oxide layer, triggered by accumulation of oxygen in the NP sub-surface region.

36 MATERIALS SCIENCE↗

Mechanism of Vapor-Phase Infiltration of Organometallic Hf in Poly(Methyl Methacrylate) for Hybrid Resist Applications

Inorganic–organic hybrid thin films synthesized by vapor-phase infiltration (VPI) of metal oxides into organic photoresists, such as poly(methyl methacrylate) (PMMA), have recently demonstrated their utility in extreme ultraviolet lithography, critical for angstrom-era semiconductor device miniaturization. Hafnium oxide infiltration has been reported recently for this purpose, but its detailed VPI mechanism has remained largely unexplored. In this study, we investigated the VPI characteristics and mechanisms of tetrakis(dimethylamido)hafnium (TDMAHf)─the hafnium precursor predominantly used for VPI in the field─into PMMA and examined its impact on electron-beam lithography (EBL) exposure behavior. VPI was performed at temperatures ranging from 85 to 150 °C, with chemical interactions characterized using infrared reflection-absorption spectroscopy, and resist patterning performance was evaluated through EBL dose-sensitivity assessments. The results indicate that TDMAHf forms a reversible adduct with PMMA at temperatures up to 120 °C, whereas at 150 °C, covalent bond formation occurs, most likely via dealkylation that leads to acetate formation. EBL studies reveal that resist sensitivity is influenced by both infiltration temperature and developer selection, with aqueous isopropyl alcohol development demonstrating enhanced sensitivity compared to organic solvent-based development. The optimized infiltration protocol at 120 °C ensures a uniform inorganic distribution without compromising resist dissolution. These findings not only help refine hybrid resist patterning performance but also offer insights potentially applicable to the VPI of other homoleptic metal-amide organometallic VPI precursors that include TDMA ligands.

36 MATERIALS SCIENCE↗

Study of gas tungsten arc welding procedures for tantalum alloy T-111 (Ta-8 W-2Hf) plate

Methods of eliminating or reducing underbread cracking in multipass GTA welds in thick T-111 plate were studied. Single V butt welds prepared using experimental filler metal compositions and standard weld procedures resulted in only moderate success in reducing underbread cracking. Subsequent procedural changes incorporating manual welding, slower weld speeds, and three or fewer fill passes resulted in crack-free single V welds only when the filler metal was free of hafnium. The double V joint design with successive fill passes on opposite sides of the joint produced excellent welds. The quality of each weld was determined metallographically since the cracking, when present, was very slight and undetectable using standard NDT techniques. Tensile and bend tests were performed on selected weldments. The inherent filler metal strength and the joint geometry determined the strength of the weldment. Hardness and electron beam microprobe traverses were made on selected specimens with the result that significant filler metal-base metal dilution as well as hafnium segregation was detected. A tentative explanation of T-111 plate underbread cracking is presented based on the intrinsic effects of hafnium in the weldment.

Gold, R. E.↗

Effects of alloy composition in alleviating embrittlement problems associated with the tantalum alloy T-111

The causes of aging embrittlement in T-111 (Ta-8W-2Hf) and the effect of alloy modification were investigated. Results show that T-111 possesses a critical combination of tungsten and hafnium that leads to loss in ductility at -196 C after aging near 1040 C. It was found that this occurs because tungsten enhances hafnium segregation to grain boundaries, which also leads to increased susceptibility to hydrogen embrittlement. Aging embrittlement was not observed in tantalum alloys with reduced tungsten or hafnium contents; most of the alloys studied have lower strengths than T-111 and exhibit susceptibility to hydrogen embrittlement.

Stephens, J. R.↗

Evaluation of T-111 forced-convection loop tested with lithium at 1370 C

A T-111 alloy (Ta-8% W-2% Hf) forced-convection loop containing molten lithium was operated 3000 hr at a maximum temperature of 1370 C. Flow velocities up to 6.3 m/sec were used, and the results of this forced-convection loop are very similar to those observed in lower velocity thermal-convection loops of T-111 containing lithium. Weight changes were determined at 93 positions around the loop. The maximum dissolution rate occurred at the maximum wall temperature of the loop and was less than 1.3 microns/year. Mass transfer of hafnium, nitrogen, and, to a lesser extent, carbon occurred from the hotter to cooler regions. Exposed surfaces in the highest temperature region were found to be depleted in hafnium to a depth of 60 microns with no detectable change in tungsten content. There was some loss in room-temperature tensile strength for specimens exposed to lithium at 1370 C, attributable to depletion of hafnium and nitrogen and to attendant grain growth.

Devan, J. H.↗

Effects of alloy composition in alleviating embrittlement problems associated with the tantalum alloy T-111

The causes of aging embrittlement in T-111 (Ta-8W-2Hf) and the effects of alloy modification were investigated. Results showed that T-111 contains a critical combination of tungsten and hafnium that leads to loss of ductility at -196 C after aging near 1040 C. This appears to occur because tungsten enhances hafnium segregation to grain boundaries and this also leads to increased susceptibility to hydrogen embrittlement. Aging embrittlement was not observed in tantalum alloys with reduced tungsten or hafnium contents; however, most of the alloys studied have lower strengths than T-111 and exhibit susceptibility to hydrogen embrittlement.

Stephens, J. R.↗

Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium diboride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Riedell, James A.↗

Methods of repairing a substrate

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium boride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Riedell, James A.↗

Ammonia decomposition catalyst systems

Disclosed are ruthenium-based catalyst systems, hafnium-based catalyst systems, and yttrium-based catalyst systems for use in ammonia decomposition. Catalyst systems include ruthenium, hafnium, and/or yttrium optionally in combination with one or more additional metals that can be catalytic or catalyst promoters. Hafnium-based and yttrium-based catalyst systems can be free of ruthenium. The catalyst systems also include a support material. Disclosed catalyst systems can decompose ammonia at relatively low temperatures and can provide an efficient and cost-effective route to utilization of ammonia as a carbon-free hydrogen storage and generation material.

McCullough, Katherine↗

Design of Sodium Chalcohalide Solid Electrolytes with Mixed Anions for All‐Solid‐State Sodium‐Ion Batteries

Solid-state sodium-ion batteries (SSNIBs) have emerged as a promising alternative to lithium-ion systems for grid-scale energy storage, owing to sodium's abundance and the improved safety of solid-state designs. Among various solid-state electrolytes (SSEs), halide-based Na + SSEs offer high electrochemical stability but are limited by low ionic conductivity and poor thermal stability. Herein, a novel class of sodium hafnium chalcohalide SSEs is reported with a dual-anion (S 2− /Cl − ) framework, with a high ionic conductivity of 4.5 × 10 −4 S cm −1 . The incorporation of sulfur enhances Na⁺ mobility by reducing the migration barrier through increased anion polarizability and expanded diffusion pathways. Additionally, S 2− contributes to stronger interatomic bonding, leading to higher cohesive energy density, improved thermal stability, and mechanical robustness. These SSEs exhibit minimal sulfur oxidation and excellent chemical/electrochemical interface stability with different cathode materials, such as O3-layered NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 , and Na 3 V 2 (PO 4 ) 3 cathodes. As a result, SSNIBs with P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 employing the sodium hafnium chalcohalide SSEs demonstrate outstanding cycling performance, achieving a capacity retention of 88.5% after 200 cycles at 0.1 C. This study establishes a new design strategy for high-performance SSEs, demonstrating that mixed-anion frameworks offer a viable route to overcome the intrinsic limitations of single-anion electrolytes in next-generation SSNIBs.

DFT calculation↗

Mid- to Far-Infrared Anisotropic Dielectric Function of HfS 2 and HfSe 2

The far-infrared (far-IR) remains a relatively underexplored region of the electromagnetic spectrum extending roughly from 20 to 100 µm in free-space wavelength. Research within this range has been restricted due to a lack of optical materials that can be optimized to reduce losses and increase sensitivity, as well as by the long free-space wavelengths associated with this spectral region. Here the exceptionally broad Reststrahlen bands of two Hf-based transition metal dichalcogenides (TMDs) that can support surface phonon polaritons (SPhPs) within the mid-infrared (mid-IR) into the terahertz (THz) are reported. In this vein, the IR transmission and reflectance spectra of hafnium disulfide (HfS 2 ) and hafnium diselenide (HfSe 2 ) flakes are measured and their corresponding dielectric functions are extracted. These exceptionally broad Reststrahlen bands (HfS 2 : 165 cm -1 ; HfSe 2 : 95 cm -1 ) dramatically exceed that of the more commonly explored molybdenum- (Mo) and tungsten- (W) based TMDs (≈5–10 cm -1 ), which results from the over sevenfold increase in the Born effective charge of the Hf-containing compounds. Further, this work therefore identifies a class of materials for nanophotonic and sensing applications in the mid- to far-IR, such as deeply sub-diffractional hyperbolic and polaritonic optical antennas, as is predicted via electromagnetic simulations using the extracted dielectric function.

36 MATERIALS SCIENCE↗