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At least 73 records · Page 4

Additive Manufacture of Refractory Metals for Aerospace Applications

High temperature refractory metals are required for a number of high temperature propulsion applications. Refractory metals are expensive, difficult to manufacture with high buy-to-fly ratios, and few vendors. Additive manufacture (AM) is used to produce C103, Molybdenum (Mo), and Tungsten (W) reaction chamber and thrust stand-off as well as Iridium ultra-fine lattice catalysts for integration into 1 N green propulsion thrusters. Refractory AM is in development and like traditional AM alloys requires substantial post-processing to include powder heat treatment, surface finish enhancement, inspection, and machining before placed in service. The combination of limited feedstock sources, high temperature processing, oxygen sensitivity, fracture prone nature, and need for elevated temperature mechanical testing limit the number of qualified facilities capable of post-processing AM refractory materials, which add to cost and schedule constraints. However, properly implemented refractory metal AM can overcome existing manufacture limitations by greatly increasing design flexibility, new material options, reduced price, decreased lead-time, and leverage the ever growing AM commercial supply base.

Refractory metal additive manufacture↗

Additive Manufacture of Refractory Metals for Aerospace Applications

High temperature refractory metals are required for a number of high temperature propulsion applications. Refractory metals are expensive, difficult to manufacture with high buy-to-fly ratios, and few vendors. Additive manufacture (AM) is used to produce C103, Molybdenum (Mo), and Tungsten (W) reaction chamber and thrust stand-off as well as Iridium ultra-fine lattice catalysts for integration into 1 N green propulsion thrusters. Refractory AM is in development and like traditional AM alloys requires substantial post-processing to include powder heat treatment, surface finish enhancement, inspection, and machining before placed in service. The combination of limited feedstock sources, high temperature processing, oxygen sensitivity, fracture prone nature, and need for elevated temperature mechanical testing limit the number of qualified facilities capable of post-processing AM refractory materials, which add to cost and schedule constraints. However, properly implemented refractory metal AM can overcome existing manufacture limitations by greatly increasing design flexibility, new material options, reduced price, decreased lead-time, and leverage the ever growing AM commercial supply base.

Refractory metal additive manufacture↗

How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode–Electrolyte Interface when Addressing Oxygen Redox

Sensitivity to the `bulk' oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes, Li 2 MnO 3 , Li-rich NMC, and NMC 442, that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degassing fluxes in a temperate hydropower reservoir predictable by deep‐water dissolved oxygen but highly sensitive to discharge variability

Hydropower reservoirs contribute to methane (CH 4 ) and carbon dioxide (CO 2 ) emissions, like all aquatic ecosystems. Unique to hydropower reservoirs are degassing emissions that occur when deep-water intakes move water with high CH 4 and CO 2 concentrations through turbines, leading to the release of these gases. However, few studies from hydropower reservoirs have measured seasonal variability and drivers of degassing fluxes, especially in temperate systems. We measured monthly degassing emissions in temperate Douglas Reservoir (Tennessee, USA) from 2023 to 2024. We found that degassing fluxes were highest in the summertime, and deep-water CH 4 and CO 2 concentrations were predictable by deep-water dissolved oxygen (DO) concentrations. Degassing emissions accounted for 37–62% of annually estimated CH 4 emissions, outweighing ebullitive emissions during summer months. We highlight the value of using DO data to estimate deep-water CH 4 and CO 2 concentrations and degassing fluxes at higher temporal resolution to improve annualization and extrapolation of reservoir degassing emissions at broader scales.

Pilla, Rachel M. [Oak Ridge National Laboratory (O↗

Sensitivity of Seawater Oxygen Isotopes to Climatic and Tectonic Boundary Conditions in an Early Paleogene Simulation with GISS ModelE-R

An isotope-enabled ocean-atmosphere general circulation model (GISS ModelE -R) is used to estimate the spatial gradients of the oxygen isotopic composition of seawater (delta O-18(sub sw), where delta is the deviation from a known reference material in per mil) during the early Paleogene (45.65 Ma). Understanding the response of delta O-18(sub sw) to changes in climatic and tectonic boundary conditions is important because records of carbonate delta O-18 document changes in hydrology, as well as changes in temperature and global ice -volume. We present results from an early Paleogene configuration of ModelE -R which indicate that spatial gradients of surface ocean delta O-18(sub sw) during this period could have been significantly different to those in the modern ocean. The differences inferred from ModelE -R are sufficient to change early Paleogene sea surface temperature estimates derived from primary carbonate delta O-18 signatures by more than +/-2 C in large areas of the ocean. In the North Atlantic, Indian, and Southern Oceans, the differences in d18Osw inferred from our simulation with ModelE -R are in direct contrast with those from another d18O ]tracing model study which used different, but equally plausible, early Paleogene boundary conditions. The large differences in delta O-18(sub sw) between preindustrial and early Paleogene simulations, and between models, emphasizes the sensitivity of d18Osw to climatic and tectonic boundary conditions. For this reason, absolute estimates of Eocene/ Paleocene temperature derived from carbonate delta O-18 alone are likely to have larger uncertainties than are usually assumed.

Roberts, Christopher D.↗

The effect of a non-Maxwellian electron distribution on oxygen and iron ionization balances in the solar corona

Analytic expressions are derived for ionization and recombination rates in a parameterized non-Maxwellian electron velocity distribution with an enhanced high-energy tail. These expressions are then used in investigating the effect of such an enhancement in the high-energy tail of the coronal electron velocity distribution on the oxygen and iron ionization balances, O(+6) - O(+7) and Fe(+11) - Fe(+12). Relative to a Maxwellian of the same mean electron energy, the degree of ionization allowed by such a distribution is found to be either unchanged or slightly decreased for iron but often substantially increased for oxygen. The greater sensitivity of oxygen ionization balance to the high-energy distribution tail derives from the higher oxygen ionization threshold energy. It is noted that the electron temperature inferred from a measurement of the oxygen ionization ratio, O(+6)/O(+7), could indeed overestimate the actual coronal electron temperature by nearly 10 to the 6th K if the coronal electron distribution is incorrectly assumed to be Maxwellian.

Owocki, S. P.↗

Evaluation of Oxygen Consumption as a Sensitive Measure of Electrical Cable Polymer Insulation Degradation

Polymers used as dielectric materials in nuclear grade electrical cables, such as cross-linked polyethylene (XLPE) and ethylene-propylene rubber (EPR), are long-lived and durable. Estimating the decades-long useful service life of polymers experimentally in a feasible timeframe of weeks or months requires greatly accelerated aging in the laboratory at elevated temperatures and/or gamma dose rates. Many limitations of accelerated aging, such as due to artefacts of the process including diffusion limited oxidation and dose rate effects, have been identified that can make accurate lifetime prediction at service conditions challenging. This can be due to differences in degradation mechanisms between rapid and extended aging or to the presence of induction periods during which early aging is undetectable using common metrics of polymer insulation characterization such as tensile elongation at break. Conceptually, an ideal measure of aging would track clearly and predictably with material changes throughout the lifecycle of the evolving material state from early aging through end of useful life. With such a metric accelerated aging could be performed at much milder conditions, conditions closer to those found in long term service, and end of life calculated from the early data. Oxygen consumption has previously been proposed as a sensitive measure of insulation polymer oxidation that might meet such desirable characteristics. In this work, nuclear cable insulation samples of the two most common types, XLPE and EPR, from two of the most sourced manufacturers, RSCC and The Okonite Company, were subjected to gamma irradiation at dose rates of 100, 200, and 300 Gy/hr for up to 42 days at 26°C. The aged samples were used to evaluate oxygen consumption as a sensitive measure of aging for these materials and these conditions. For comparison and validation, the aged samples were also characterized using the more conventional tests of mass change, density, carbonyl index, and yellowness index. For both materials, oxygen consumption during irradiation was found to track consistently with applied dose—oxygen consumption rate was linear with time. Mass change and carbonyl index were also clearly proportional to exposure dose. Yellowness index, a surface sensitive measure, was observed to increase linearly with dose at low exposure levels before plateauing. Sample density was not observed to change under the conditions explored. Oxygen consumption was found to be a particularly sensitive metric to measure the degradation of polymeric cable insulation exposed to radiation. Oxygen consumption was compared to Arrhenius and time-temperature-superposition methods for activation energy calculation using literature date and found to be a useful and viable alternative for lifetime prediction. The techniques developed in this work are anticipated to be valuable in the estimation of insulation aging rates under mild conditions approaching service conditions. Direction comparison of useful life prediction by oxygen consumption with prediction via Arrhenius methodology for thermal aging and existing methods for radiation and combined thermal/radiation aging would serve to further validate this promising approach and refine our understanding of material-specific aging rates.

36 MATERIALS SCIENCE↗

High Temperature Mechanical Behavior of Refractory Alloys with Digital Image Correlation

Gas turbine efficiency is typically limited by the maximum allowable temperature for components at the inlet side and in the hot gas flow. Refractory alloys and SiC/SiC ceramic-matrix composites (CMCs) are promising candidates for advancing operating temperatures beyond those of Ni-based alloys (>1200 °C). Refractory alloys are more suitable than SiC/SiC CMCs for dynamic components, due to the latter's low toughness and ductility. However, it is well known that refractory alloys suffer from poor oxidation behavior under service lifetimes and conditions, leading to embrittlement concerns. The ARPA-E ULTIMATE program has set out to combine new alloys with advanced coatings to mitigate oxidation/embrittlement effects, while increasing the mechanical performance benefits of refractory materials. Low oxygen (inert gas) or vacuum systems are needed to assess high temperature mechanical performance of developed alloys. To investigate the environmental sensitivity of candidate alloys and develop high temperature testing capabilities, four argon tensile frames were upgraded as well as a single vacuum system at Oak Ridge National Laboratory. Digital image correlation was incorporated into the vacuum frame allowing for surface strain determination and refined insight into thermomechanical response. Creep testing was performed at 1300 °C on two alloys, C-103 and MHC in vacuum and high purity argon environments. The Mo-based alloy showed less sensitivity to oxygen, indicating that testing in well-controlled argon environments may be suitable. The C-103 alloy demonstrated a stronger sensitivity to oxygen in the well-controlled argon environment, illustrating the need for the developed vacuum testing capabilities. “Small” 25 mm and “large” 76 mm MHC specimens showed comparable results in terms of strain rate during creep testing and ultimate tensile strength during tensile testing, suggesting the viability of smaller geometries that use less material of advanced developmental alloys.

Bell, Sam↗

Rhenium-Selenido Corroles: Reflections on 5d Metalloporphyrins and Metallocorroles as Triplet Emitters and Photosensitizers

Following the successful synthesis of rhenium-oxido, rhenium-imido, and rhenium-sulfido corroles, a series of para-X-substituted rhenium-selenido triarylcorroles (X = OCH 3 , CH 3 , H, F, CF 3 ) have been prepared in 70–76% yields. A one-pot, two-step procedure was used, analogous to that used for ReS corroles, involving rhenium insertion via high-temperature reaction of Re 2 (CO) 10 and free-base corroles in refluxing decalin, followed by exposure to PCl 3 (which is thought to deoxygenate ReO corroles formed under the reaction) and elemental selenium. An analogous procedure, however, failed to yield rhenium-tellurido corroles, presumably reflecting, according to DFT calculations, the limited stability of these species. Unlike ReO corroles, ReS and ReSe corroles were found not to exhibit phosphorescence in the NIR-I regime (600–1000 nm); nor did they sensitize singlet oxygen formation. In the hope of obtaining a broader perspective of this negative result, we also examined ReN porphyrins and found them not to phosphoresce or to sensitize singlet oxygen formation. These results were explained by DFT and TDDFT calculations in terms of low-energy triplet states, which are not energetic enough to excite molecular oxygen to its lowest singlet state. Whether some of the new Re corroles exhibit phosphorescence in the NIR-II regime remains an interesting question for future investigation.

Aromatic compounds↗

Diffusivities of Redox-Sensitive Elements in Basalt vs. Oxygen Fugacity Determined by LA-ICP-MS

Several diffusion experiments were conducted in a piston cylinder device across a range of oxygen fugacities (FMQ-3 FMQ-1.2, FMQ+6) at 1 GPa and 1300 C. This was done to explore the effects of oxygen fugacity (fO2) on diffusivity of redox sensitive trace elements. This allows investigation of how these elements diffuse across the fO2 range encountered in different reservoirs on planets and moons in our solar system. The University of Rochester LA-ICP-MS system was used for analysis of samples. Analyses were conducted using an Agilent 7900 quadrupole mass spectrometer connected to a Photon Machines 193 nm G2 laser ablation (LA) system equipped with a HelEx 2-volume sample chamber. Spots used were 35 micrometers circles spaced at 65 micrometers intervals. Laser fluence was 7.81 J/cm^2 with a rep rate of 10 Hz. The iolite software package was used to reduce data collected from laser ablation analysis of experiments with Si-29 used as the internal standard isotope. Iolite's global fit module was used to simultaneously fit elements' diffusivities in each experiment while keeping the Matano interface constant. Elements analysed include V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Figures

Szumila, Ian↗

Synthesis and magnetic performance of gadolinium powder produced with rotating disk atomization

Spherical powder is key for achieving good heat transfer and maintaining low pressure drop for heat transfer fluid in magnetocaloric regenerator. Obtaining relatively large spherical powder of rare earth metals that are extremely sensitive to oxygen is challenging. Comparing to gas atomization and plasma rotating electrode methods, rotating disk atomization (RDA) method is more robust for obtaining a small amount of powder with a short turn-around time, thereby, more suitable for research and development of new magnetocaloric materials. In this work, commercially bulk gadolinium was successfully atomized to produce spherical powder in the targeted 150–250 μm range. The obtained powder exhibited the expected magnetocaloric performance with a maximum change of magnetic entropy of 12.1 J/kg K and a maximum adiabatic temperature change of 12.8 K with an applied magnetic field of 7 T.

36 MATERIALS SCIENCE↗

Notch sensitivity of hydrogenated oxygen-strengthened titanium

While earlier studies have shown that the tensile properties and fracture test intensity factors of oxygen-strengthened Ti remain nearly unaffected by the presence of about 70 ppm (weight) hydrogen, the Charpy V-notch test-determined impact properties of oxygen-bearing Ti are strongly affected by the presence of hydrogen. The present study establishes that, concurrently with the strengthening effect of oxygen, there is a substantial lowering of ductility. The presence of hydrogen has virtually no effect on the notch strength of Ti alloys of either low or high oxygen content, where hydrogen contents lie in the 25-80 range.

Wasz, M. L.↗

Sensitive Probing of Exoplanetary Oxygen via Mid-Infrared Collisional Absorption

The collision-induced fundamental vibration–rotation band at 6.4 μm is the strongest absorption feature from O2 in the infrared, yet it has not been previously incorporated into exoplanet spectral analyses for several reasons. Either collision-induced absorptions (CIAs) were not included or incomplete/obsolete CIA databases were used. Also, the current version of HITRAN does not include CIAs at 6.4 μm with other collision partners (O2–X). We include O2–X CIA features in our transmission spectroscopy simulations by parameterizing the 6.4-μm O2–N2 CIA based on ref. 3 and the O2–CO2 CIA based on ref. 4. Here we report that the O2–X CIA may be the most detectable O2 feature for transit observations. For a potential TRAPPIST-1 e analogue system within 5 pc of the Sun, it could be the only O2 signature detectable with the James Webb Space Telescope (JWST) (using MIRI LRS (Mid-Infrared Instrument low-resolution spectrometer)) for a modern Earth-like cloudy atmosphere with biological quantities of O2. Also, we show that the 6.4-μm O2–X CIA would be prominent for O2-rich desiccated atmospheres and could be detectable with JWST in just a few transits. For systems beyond 5 pc, this feature could therefore be a powerful discriminator of uninhabited planets with non-biological ‘false-positive’ O2 in their atmospheres, as they would only be detectable at these higher O2 pressures.

Thomas J Fauchez↗

Sensitive Probing of Exoplanetary Oxygen via Mid-Infrared Collisional Absorption

The collision-induced fundamental vibration–rotation band at 6.4 μm is the strongest absorption feature from O2 in the infrared1,2,3, yet it has not been previously incorporated into exoplanet spectral analyses for several reasons. Either collision-induced absorptions (CIAs) were not included or incomplete/obsolete CIA databases were used. Also, the current version of HITRAN does not include CIAs at 6.4 μm with other collision partners (O2–X). We include O2–X CIA features in our transmission spectroscopy simulations by parameterizing the 6.4-μm O2–N2 CIA based on ref. 3 and the O2–CO2 CIA based on ref. 4. Here we report that the O2–X CIA may be the most detectable O2 feature for transit observations. For a potential TRAPPIST-1 e analogue system within 5 pc of the Sun, it could be the only O2 signature detectable with the James Webb Space Telescope (JWST) (using MIRI LRS (Mid-Infrared Instrument low-resolution spectrometer)) for a modern Earth-like cloudy atmosphere with biological quantities of O2. Also, we show that the 6.4-μm O2–X CIA would be prominent for O2-rich desiccated atmospheres5 and could be detectable with JWST in just a few transits. For systems beyond 5 pc, this feature could therefore be a powerful discriminator of uninhabited planets with non-biological ‘false-positive’ O2 in their atmospheres, as they would only be detectable at these higher O2 pressures.

Thomas Fauchez↗

Influence of Oxygen Flow and Stoichiometry on Optical Properties and Damage Resistance of Hafnium Oxide Thin Films

Hafnium oxide (HfO 2 ) is predominantly used as a high-index material in multi-layer dielectric coatings for high-peak- and high-average-power lasers, but laser damage often initiates within the HfO 2 layers despite their wide bandgap. Oxygen deficiency during deposition can introduce vacancy-related sub-bandgap states and absorptive defects, lowering damage resistance. This study investigates how oxygen flow during HfO 2 deposition with ion beam sputtering (IBS) affects its stoichiometry, defect formation, and nanosecond laser-induced damage threshold (LIDT) and whether single-layer trends predict multilayer performance. Single layers were deposited at varying oxygen flows, characterized for optical and structural properties, and tested for the LIDT at 1064 nm and 355 nm. Increasing oxygen flow drove the layer toward near-stoichiometric HfO 2 , reduced the refractive index, and altered the density of surface pinhole-like features. The single-layer LIDT at 355 nm increased with oxygen, whereas the 1064 nm LIDT was comparatively less sensitive to oxygen flow, consistent with the wavelength-dependent roles of absorptive precursors and microstructural defects. In contrast, a HfO 2 -based high-reflector (HR) showed a higher LIDT at lower oxygen flow, indicating that the family of damage precursors changes between single layers and multilayers; in stacks, structural properties such as stress, gas entrapment and thermal dissipation may outweigh the isolated absorptive defects found in single layers. These results demonstrate that the optimal oxygen flow condition depends on both LIDT wavelength and film architecture. We identified, for single layers, a 15–35 sccm window for maximizing the 1064 nm LIDT and a high-flow optimum (45 sccm) for the 355 nm LIDT and, for 355 nm HR stacks, a distinct lower-flow regime (~10 sccm).

Optics and optical instruments↗