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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 199 records · Page 11

Characteristics of a gelled liquid hyprogen polyphenylene oxide (PPO) foam open-cell insulation system, phase 1

A large scale gel production and storage facility and a small scale facility, the latter used for detailed visual examination of the gel/PPO foam interface, were developed. A subcontract was given to investigate techniques for the production of gelled liquid hydrogen, develop a process design for scale-up to a 1.89 cu m (500 gallon) gel production and storage facility, determine gel transfer characteristics, determine the solubility rate of gaseous helium in the gel, and investigate the gross gel/PPO foam interfacial phenomena. An inside-tank process for scaled-up production of gelled liquid hydrogen was selected. No detectable gel structure degradation occurred during repeated shearing. The viscosity of gelled liquid hydrogen at shear rates of 300/sec and higher is 2 to 5-fold greater than that of neat liquid hydrogen. No clogging problems were encountered during the transfer of gelled liquid hydrogen through warmed transfer lines. The solubility rate of helium in liquid hydrogen was significantly reduced by the presence of gel structure. The boil-off rates from gelled liquid hydrogen were reduced from 25 to 50 percent compared to those observed for the neat liquid hydrogen under compatible conditions. The polyphenylene oxide (PPO) foam insulation was found to be compatible with liquid ethane.

Source record↗

Oxidative degradation in polyethylene: the microscopic properties responsible for macroscopic weathering

Radiation-initiated crosslinking of polyethylene has proven to be an effective method of reducing creep and wear. This has allowed polyethylene to find widespread use in engineering and medical sectors where extreme conditions would otherwise cause it to degrade. However, despite their resilience, irradiated polyethylene products are still vulnerable to oxidative degradation in some long-term applications. A good deal of literature exists to discuss the effects that irradiation and oxidative degradation have on polyethylene’s mechanical properties, but not much literature exists to describe the microscopic properties that make irradiated polyethylene susceptible to this process. This review presents a micro-scale look at polyethylene’s morphology and chemistry, with the intention of describing which characteristics make the material more or less favorable for oxidation. By describing the factors that make irradiated polyethylene vulnerable to oxidation in the first place, the hope is to provide insight on how to mitigate oxidation in future applications.

36 MATERIALS SCIENCE↗

Biological methane production and accumulation under sulfate-rich conditions at Cape Lookout Bight, NC

Introduction: Anaerobic oxidation of methane (AOM) is hypothesized to occur through reverse hydrogenotrophic methanogenesis in marine sediments because sulfate reducers pull hydrogen concentrations so low that reverse hydrogenotrophic methanogenesis is exergonic. If true, hydrogenotrophic methanogenesis can theoretically co-occur with sulfate reduction if the organic matter is so labile that fermenters produce more hydrogen than sulfate reducers can consume, causing hydrogen concentrations to rise. Finding accumulation of biologically-produced methane in sulfate-containing organic-rich sediments would therefore support the theory that AOM occurs through reverse hydrogenotrophic methanogenesis since it would signal the absence of net AOM in the presence of sulfate. Methods: 16S rRNA gene libraries were compared to geochemistry and incubations in high depth-resolution sediment cores collected from organic-rich Cape Lookout Bight, North Carolina. Results: We found that methane began to accumulate while sulfate is still abundant (6–8 mM). Methane-cycling archaea ANME-1, Methanosarciniales, and Methanomicrobiales also increased at these depths. Incubations showed that methane production in the upper 16 cm in sulfate-rich sediments was biotic since it could be inhibited by 2-bromoethanosulfonoic acid (BES). Discussion: We conclude that methanogens mediate biological methane production in these organic-rich sediments at sulfate concentrations that inhibit methanogenesis in sediments with less labile organic matter, and that methane accumulation and growth of methanogens can occur under these conditions as well. Our data supports the theory that H2 concentrations, rather than the cooccurrence of sulfate and methane, control whether methanogenesis or AOM via reverse hydrogenotrophic methanogenesis occurs. We hypothesize that the high amount of labile organic matter at this site prevents AOM, allowing methane accumulation when sulfate is low but still present in mM concentrations

59 BASIC BIOLOGICAL SCIENCES↗

Damage Characterization of EBC-SiCSiC Ceramic Matrix Composites Under Imposed Thermal Gradient Testing

Due to their high temperature capabilities, Ceramic Matrix Composite (CMC) components are being developed for use in hot-section aerospace engine applications. Harsh engine environments have led to the development of Environmental Barrier Coatings (EBCs) for silicon-based CMCs to further increase thermal and environmental capabilities. This study aims at understanding the damage mechanisms associated with these materials under simulated operating conditions. A high heat-flux laser testing rig capable of imposing large through-thickness thermal gradients by means of controlled laser beam heating and back-side air cooling is used. Tests are performed on uncoated composites, as well as CMC substrates that have been coated with state-of-the-art ceramic EBC systems. Results show that the use of the EBCs may help increase temperature capability and creep resistance by reducing the effects of stressed oxidation and environmental degradation. Also, the ability of electrical resistance (ER) and acoustic emission (AE) measurements to monitor material condition and damage state during high temperature testing is shown; suggesting their usefulness as a valuable health monitoring technique. Micromechanics models are used to describe the localized stress state of the composite system, which is utilized along with ER modeling concepts to develop an electromechanical model capable of characterizing material behavior.

protective coatings (nonmetallic)↗

Potentially Habitable Ancient Environments in Gusev Crater, Mars

Habitable environments must sustain liquid water at least intermittently and also provide both chemical building blocks and useful sources of energy for life. Observations by Spirit rover indicate that conditions have probably been too dry to sustain life, at least since the emplacement of the extensive basalts that underlie the plains around the Columbia Memorial Station landing site. Local evidence of relatively minor aqueous alteration [1] probably occurred under conditions where the activity of water was too low to sustain biological processes as we know them. In contrast, multiple bedrock units in West Spur and Husband Hill in the Columbia Hills have been extensively altered. Patterns of elemental abundances are consistent with aqueous processes involving migrating fluids [2]. Fe in several of these units has been extensively oxidized [3]. Conceivably any microbiota present during the aqueous alteration of these rocks might have obtained energy from Fe oxidation. Spirit discovered olivine-rich ultramafic rocks during her descent from Husband Hill southward into Inner Basin. Alteration of similar ultramafic rocks on Earth can yield H2 that can provide both energy and reducing power for microorganisms. Spirit's discovery of deposits rich in ferric sulfate is consistent with the aqueous dissolution and/or alteration of olivine under acidic conditions [2] such as those associated with hydrothermal activity. The oxidation of iron and sulfur that can accompany such activity can be an energy source for life. Hydrothermal systems on Earth that sustain either acidic [4] or neutral to alkaline fluids [5] have been shown to provide this energy. Collectively the observations by Spirit rover are consistent with the possibility that habitable environments existed in Gusev crater at least intermittently in the distant geologic past.

Fe oxidation↗

A general strategy and a consolidated mechanism for low-methane hydrogenolysis of polyethylene over ruthenium

Polyethylene (PE) is one of the most environment-threatening plastic waste. Its Ru-catalyzed hydrogenolysis is rapid but produces too much methane. Here, in this study, low-density PE hydrogenolysis is performed at mild conditions and short times over Ru-doped zirconia catalysts (Ru-XZr, X = Ti, Nb, Ce, W, V, Mo, Fe) to determine low-methane catalysts. Methane is produced via direct terminal C-C scission and surface cascade of consecutive C-C scissions, with the latter sensitive to hydrogen availability and dominant in hydrogen-lean conditions. Reactivity studies, characterization and theory reveal that the most effective dopant oxides (W, V, and Mo) are intermediately reducible, as they store and supply extra hydrogen to Ru via reverse hydrogen spillover. This hydrogen readily hydrogenates and desorbs long alkyl surface intermediates that would otherwise produce cascade methane. Our proposed mechanism reconciles the low methane production achieved by increasing the hydrogen pressure or reducing the particle size and exposes the key selectivity descriptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transient kinetic insights into selective propene oxidation over industrial bismuth molybdate catalysts

Selective oxidation of propene to acrolein over industrial multicomponent bismuth molybdate (BMO) catalysts significantly depends on reaction conditions that include operating parameters and catalyst state. Here, this work investigates selective propene oxidation in the intrinsic kinetic paradigm of Temporal Analysis of Products (TAP) reactor by systematically varying catalyst redox state, temperature, and oxygen-to-propene feed ratio. A 93 % propene conversion with an acrolein yield of 80 % is achieved at elevated temperatures (450 °C) on oxidized catalysts under oxygen-rich conditions (O 2 :C 3 H 6 = 10). However, these conditions diminish acrolein-to-CO 2 selectivity due to enhanced total oxidation to CO 2 . In contrast, a reduced catalyst state, moderate temperature (350 °C), and lower oxygen feed (O 2 :C 3 H 6 = 1) nearly doubles the acrolein to-CO 2 selectivity, albeit at a lower acrolein yield (33 %). Transient kinetic studies together with a kinetic model that simplify the major product formation pathways in lumped non-elementary forms reveal that the availability of surface oxygen species plays a pivotal role in governing reaction pathways. Additionally, density functional theory (DFT) calculations on pure BMO catalysts inform the role of surface redox states on propene and oxygen activation barriers. Lattice oxygen at acrolein-selective sites drives both acrolein and CO 2 formation, while adsorbed oxygen at activation sites favors unselective CO 2 generation. This work establishes a critical relationship between transient product selectivity and surface oxygen availability, which is strongly influenced by catalyst redox state, feed ratio, and reaction temperature. These insights underscore the importance of dynamic reactor operation strategies and offer a foundation for designing next-generation propene oxidation processes with tunable acrolein selectivity.

42 - ENGINEERING↗

Rapid, Sensitive, Label-Free Electrical Detection of SARS-CoV-2 in Nasal Swab Samples

Rapid diagnosis of coronavirus disease 2019 (COVID-19) is key for the long-term control of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) amid renewed threats of mutated SARS-CoV-2 around the world. Here, we report on an electrical label-free detection of SARS-CoV-2 in nasopharyngeal swab samples directly collected from outpatients or in saliva-relevant conditions by using a remote floating-gate field-effect transistor (RFGFET) with a 2-dimensional reduced graphene oxide (rGO) sensing membrane. RFGFET sensors demonstrate rapid detection (<5 min), a 90.6% accuracy from 8 nasal swab samples measured by 4 different devices for each sample, and a coefficient of variation (CV) < 6%. Also, RFGFET sensors display a limit of detection (LOD) of pseudo-SARS-CoV-2 that is 10 000-fold lower than enzyme-linked immunosorbent assays, with a comparable LOD to that of reverse transcriptionpolymerase chain reaction (RT-PCR) for patient samples. To achieve this, comprehensive systematic studies were performed regarding interactions between SARS-CoV-2 and spike proteins, neutralizing antibodies, and angiotensin-converting enzyme 2, as either a biomarker (detection target) or a sensing probe (receptor) functionalized on the rGO sensing membrane. Finally, taken together, this work may have an immense effect on positioning FET bioelectronics for rapid SARS-CoV-2 diagnostics.

60 APPLIED LIFE SCIENCES↗

Controlling Oxidation of Nb in Oxygen Abundant Environments

Modern particle accelerators depend on Superconducting Radio Frequency (SRF) cavities made from high-purity niobium (Nb) to achieve optimal performance, including high quality factors and strong accelerating gradients. However, when exposed to air, niobium naturally forms a complex oxide layer that can introduce surface imperfections and carbon contamination. This work examines an alternative oxidation strategy under oxygen-rich conditions to better regulate the oxide formation process. The ultimate objective is to improve surface uniformity and cleanliness, thereby reducing defect density and enhancing performance. We used Confocal Microscopy, Scanning Electron Microscopy (SEM), and X-Ray Photoelectron Spectroscopy (XPS) to analyze surface changes. We used standard metrics, like Arithmetic Average Roughness (Ra) and Root Mean Square (Rq). Three oxidation methods were applied: short, extended, and a repeated HF and H₂O₂ oxidation process. Preliminary results show promising reductions in carbon contamination and surface defects.

Romero, Juan [Fermilab]↗

The Rise of Oxygen and the Hydrogen Hourglass

Oxygenic photosynthesis appears to be necessary for an oxygen-rich atmosphere like Earth's. But available geological and geochemical evidence suggest that at least 200 Myr, and possibly more than 700 Myr, elapsed between the advent of oxygenic photosynthesis and the establishment of an oxygen atmosphere. The interregnum implies that at least one other necessary condition for O2 needed to be met. Here we argue that the second condition was the oxidation of the surface and crust to the point where O2 became more stable than competing reduced gases such as CH4. The cause of Earth's surface oxidation would be the same cause as it is for other planets with oxidized surfaces: hydrogen escape to space. The duration of the interregnum would have been determined by the rate of hydrogen escape and by the size of the reduced reservoir that needed to be oxidized before O2 became favored. We suggest that continental growth has been influenced by hydrogen escape, and we speculate that, if there must be an external bias to biological evolution, hydrogen escape can be that bias.

atmospheric evolution↗

Charge Yield at Low Electric Fields: Considerations for Bipolar Integrated Circuits

A significant reduction in total dose damage is observed when bipolar integrated circuits are irradiated at low temperature. This can be partially explained by the Onsager theory of recombination, which predicts a strong temperature dependence for charge yield under low-field conditions. Reduced damage occurs for biased as well as unbiased devices because the weak fringing field in thick bipolar oxides only affects charge yield near the Si/SiO2 interface, a relatively small fraction of the total oxide thickness. Lowering the temperature of bipolar ICs - either continuously, or for time periods when they are exposed to high radiation levels - provides an additional degree of freedom to improve total dose performance of bipolar circuits, particularly in space applications.

ionizing radiation↗

Reply to: How much does corrosion of nuclear waste matrices matter

We thank Mallants and Chapman for their comments on our recent work and are mostly in agreement. However, while the applicability of the results to different environmental conditions requires more attention, we maintain that this study could be relevant even to repositories in saturated reduced environments. Oxidants other than oxygen might be present in anoxic groundwater repository environments and could also trigger the corrosion mechanism we described. .

Guo, Xiaolei↗

Visible and Near-IR Reflectance Spectra of Smectite Acquired Under Dry Conditions for Interpretation of Martian Surface Mineralogy

Visible and near-IR (VNIR) spectra from the MEx OMEGA and the MRO CRISM hyper-spectral imaging instruments have spectral features associated with the H2O molecule and M OH functional groups (M = Mg, Fe, Al, and Si). Mineralogical assignments of martian spectral features are made on the basis of laboratory VNIR spectra, which were often acquired under ambient (humid) conditions. Smectites like nontronite, saponite, and montmorillionite have interlayer H2O that is exchangeable with their environment, and we have acquired smectite reflectance spectra under dry environmental conditions for interpretation of martian surface mineralogy. We also obtained chemical, Moessbauer (MB), powder X-ray diffraction (XRD), and thermogravimetric (TG) data to understand variations in spectral properties. VNIR spectra were recorded in humid lab air at 25-35C, in a dynamic dry N2 atmosphere (50-150 ppmv H2O) after exposing the smectite samples (5 nontronites, 3 montmorillionites, and 1 saponite) to that atmosphere for up to approximately l000 hr each at 25-35C, approximately 105C, and approximately 215C, and after re-exposure to humid lab air. Heating at 105C and 215C for approximately 1000 hr is taken as a surrogate for geologic time scales at lower temperatures. Upon exposure to dry N2, the position and intensity of spectral features associated with M-OH were relatively insensitive to the dry environment, and the spectral features associated with H2O (e.g., approximately 1.90 micrometers) decreased in intensity and are sometimes not detectable by the end of the 215C heating step. The position and intensity of H2O spectral features recovered upon re-exposure to lab air. XRD data show interlayer collapse for the nontronites and Namontmorillionites, with the interlayer remaining collapsed for the latter after re-exposure to lab air. The interlayer did not collapse for the saponite and Ca-montmorillionite. TG data show that the concentration of H2O derived from structural OH was invariant to the dry N2 treatment for saponite and the montmorillionites, but the nontronites had additional structural OH after treatment. Upon exposure to dry N2, the VNIR spectra also acquired a red slope with decreasing albedo between approximately 0.4 and approximately 2.0 micrometers. The magnitude of the effects covaries with exposure time to dry N2 and heating temperature. Upon re-exposure to lab air, the slope and albedo do not completely recover to pre-exposure values. MB data show that these effects do not result from partial reduction of ferric to ferrous iron, and TG data show they do not result from loss of structural OH. Possible explanations include formation of small clusters of (superparamagnetic) ferric oxide and reduced smectite crystallinity. The difference in spectral properties between spectra acquired in humid lab air and under dry conditions are consequential for interpretation of CRISM and OMEGA spectra. For example, nontronite by itself and not nontronite plus ferrihydrite can account for the red spectral slope in martian spectra where nontronite is indicated by the Fe-OH spectral features.

Morris, Richard V.↗

Continuous Wet Air Oxidation of the Hydrothermal Liquefaction Aqueous Product from Various Wet Wastes

Wet air oxidation (WAO) offers an effective method for treating waste streams, converting pollutants into benign substances, and holds significant potential for processing the aqueous product from the hydrothermal liquefaction (HTL-AP) of wet wastes, a promising renewable fuel technology. Here, we conducted a comprehensive study of the WAO of HTL-AP from four different wet wastes. Through continuous testing under various conditions, we produced samples with different chemical oxygen demand (COD) levels, enhancing understanding of reaction parameters necessary for substantial COD reduction (>95%). Chemical analysis revealed that alcohols and ketones in the HTL-AP rapidly oxidized to acetic acid through aldehyde intermediates, while acetic acid, other carboxylic acids, and phenols oxidized relatively slowly. The light N-containing compounds were found to exhibit a change in concentration only after the whole sample reaches an 80% COD reduction, indicating their refractory nature under applied conditions. Energy released in the WAO reaction was calculated, and anaerobic toxicity assay demonstrated that WAO treatment enhanced methane production kinetics due to reduced inhibitory effects, suggesting partial oxidative transformation of inhibitory compounds into less toxic derivatives. These findings provide insights into designing effective WAO processes for valorizing HTL aqueous products, addressing key barriers to HTL process commercialization.

anaerobic digestion↗

Safety Testing and Destructive Examination of AGR-2 UO 2 Compact 3-1-1

Post-irradiation examination and elevated-temperature safety testing are being performed on compacts from the Advanced Gas Reactor (AGR) Fuel Development and Qualification Program’s second irradiation experiment (AGR-2). The compacts in the AGR-2 irradiation experiment held either tristructural isotropic (TRISO)-coated particles containing uranium oxide fuel kernels (UO 2 ) or TRISO-coated particles containing fuel kernels with both uranium carbide and uranium oxide phases (UCO). In UO 2 TRISO particles, oxygen released by uranium fission can react with the surrounding carbon in the buffer layer to form carbon monoxide (CO). Excess CO can lead to various irradiation performance issues under certain operating conditions, such as pressure-induced fracture, kernel migration, and silicon carbide (SiC) corrosion. In UCO TRISO particles, CO formation is reduced because the chemical potential for oxidation of uranium carbide is lower than for oxidation of carbon.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effect of sucrose on the oxidation-reduction conditions and retention of rhenium during vitrification of low-activity waste

Technetium speciation and solubility during nuclear waste vitrification are affected by oxygen partial pressure in the melt. Thus, reducing agents such as sucrose, which are routinely added to nuclear waste feeds to repress foaming, can significantly affect the volatilization of Tc and increase its retention in glass. Using Re as a surrogate for Tc, we measured the effect of sucrose addition to two low-activity waste melter feeds on the Re retention, oxygen partial pressure, and iron redox as functions of temperature. As expected, Re retention in glass increased as the sucrose content increased. Furthermore, this is attributed to sucrose reaction with nitrates and nitrites in the feed. Destruction of nitrates and nitrites reduces the salt phase fraction and thus likely promotes Re diffusion into the glass-forming melt. In agreement with available literature, we discuss that a modest increase in the sucrose content (compared to current practice) can significantly improve the Tc retention without reducing Fe 2+ to metal.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Exploring Atomic-Scale Interactions at the Interface of Reducible Oxide and Ruthenium Nanocatalyst for Ammonia Decomposition

Restructuring atomic-scale interfaces between noble metal nanoparticles and metal oxides provides a promising approach to enhancing catalytic properties. In this study, Ru nanoparticles were supported on CeO 2 , ZrO 2 , and HfO 2 via pyrolysis of MOFs under oxygen-suppressed high-temperature conditions. Despite its nearly ideal particle size (∼2.3 nm), the Ru–CeO 2 /C catalyst exhibited the lowest ammonia decomposition activity. X-ray absorption spectroscopy and DFT calculations revealed that electron transfer from Ru to CeO 2 formed positively charged Ru and partially reduced Ce 4+ , weakening the catalytic performance. In contrast, oxygen-deficient ZrO 2 and HfO 2 support donated electrons to Ru, preserving its metallic state. These findings demonstrate that the reducibility of oxide supports governs the direction and magnitude of interfacial charge transfer, directly tuning catalytic behavior. This study provides insights into the design of oxide-supported Ru catalysts for ammonia decomposition.

Catalysts↗