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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Insights into the Enhanced Oxidative Thermal Stability of Nanoparticle Organic Hybrid Materials Developed for Carbon Capture and Energy Storage

Due to the growing need for Direct Air Capture (DAC) and integrated carbon capture and conversion technologies, CO 2 capture materials that can withstand a wide range of environmental conditions, including fluctuating ambient temperatures and high concentrations of oxidizing agents (i.e., oxygen and moisture), are critically needed. Liquid-like Nanoparticle Organic Hybrid Materials (NOHMs) have been proposed as candidates for DAC and electrolyte additives enabling sustainable energy storage (i.e., integrated CO 2 capture and conversion and flow batteries). Liquid-like NOHMs functionalized with an ionic bond have been shown to display greatly enhanced oxidative thermal stability compared to the untethered polymer. However, these studies were limited in terms of reaction conditions and the detailed mechanisms of the oxidative thermal degradation were not reported. In this work, a kinetic thermal degradation analysis was performed on NOHM-I-HPE and the neat polymer, Jeffamine M2070 (HPE), in both non-oxidative and oxidative conditions. NOHM-I-HPE displayed similar thermal stability to the untethered polymer in a nitrogen environment, but interestingly, the thermal stability of the ionically tethered polymer was significantly enhanced in the presence of air. This observed enhancement of oxidative thermal stability is attributed to the orders of magnitude larger viscosity of the liquid-like NOHMs compared to untethered polymer and the bond stabilization of the ionically tethered polymer in the NOHMs canopy. Further, spectroscopic analyses of the liquid residue revealed that in the presence of oxygen, the degradation of HPE and NOHM-I-HPE occurs through the formation of trace amounts of carbonyls. This study illustrated that NOHMs can serve as functional materials for sustainable energy storage applications because of their excellent oxidative thermal stability.

25 ENERGY STORAGE↗
NASA NTRS2016

Analysis of Risks to Oxygen Systems from Particulate and Fiber Contaminants and Derivation of Cleanliness Requirements

It has been well documented in the literature that contamination within oxygen systems can create significant fire hazards. Cleanliness limits for nonvolatile residues, ranging from 10 to 500 milligrams per square meter, have been established for various industries and types of oxygen systems to reduce the risk of ignition of flammable organic films. Particulate cleanliness limits used for oxygen systems, however, vary considerably, notably within the aerospace industry. Maximum allowed particle size, quantity limits, and allocations for fibers or metallic particles are all variables seen in aerospace cleanliness limits. Particles are known to have the potential to ignite within oxygen systems and must be limited to prevent fires. Particulate contamination may also pose risks to the performance of oxygen systems that are unrelated to ignition hazards. An extensive literature search was performed to better understand the relative importance of particle ignition mechanisms versus other deleterious effects of particles on oxygen systems and to identify rationale for derivation of particulate cleanliness limits for specific systems. The identified risks of different types and sizes of particles and fibers were analyzed. This paper summarizes the risks identified and rationale that may be used to derive particulate cleanliness limits for specific oxygen systems.

Lowrey, Nikki M.↗
NASA NTRS1996

Advanced waste management technology evaluation

The purpose of this program is to evaluate the feasibility of steam reforming spacecraft wastes into simple recyclable inorganic salts, carbon dioxide and water. Model waste compounds included cellulose, urea, methionine, Igapon TC-42, and high density polyethylenes. These are compounds found in urine, feces, hygiene water, etc. The gasification and steam reforming process used the addition of heat and low quantities of oxygen to oxidize and reduce the model compounds.The studied reactions were aimed at recovery of inorganic residues that can be recycled into a closed biologic system. Results indicate that even at very low concentrations of oxygen (less than 3%) the formation of a carbonaceous residue was suppressed. The use of a nickel/cobalt reforming catalyst at reaction temperature of 1600 degrees yielded an efficient destruction of the organic effluents, including methane and ammonia. Additionally, the reforming process with nickel/cobalt catalyst diminished the noxious odors associated with butyric acid, methionine and plastics.

Couch, H.↗
NASA NTRS1978

Radiometer system to map the cosmic background radiation

A 33-GHz airborne radiometer system has been developed to map large angular scale variations in the temperature of the 3 K cosmic background radiation. A ferrite circulator switches a room-temperature mixer between two antennas pointing 60 deg apart in the sky. In 40 min of observing, the radiometer can measure the anisotropy of the microwave background with an accuracy of plus or minus 1 mK rms, or about 1 part in 3000 of 3 K. The apparatus is flown in a U-2 jet to 20 km altitude where 33-GHz thermal microwave emission from the atmosphere is at a low level. A second radiometer, tuned to 54 GHz near oxygen emission lines, monitors spurious signals from residual atmospheric radiation. The antennas, which have an extremely low side-lobe response of less than -65 dB past 60 deg, reject anisotropic radiation from the earth's surface. Periodic interchange of the antenna positions and reversal of the aircraft's flight direction cancel equipment-based imbalances. The system has been operated successfully in U-2 aircraft flown from NASA-Ames at Moffett Field, Calif.

Gorenstein, M. V.↗
NASA NTRS1992

Scanning electron microscope/energy dispersive x ray analysis of impact residues on LDEF tray clamps

To better understand the nature of particulates in low-Earth orbit (LEO), and their effects on spacecraft hardware, we are analyzing residues found in impacts on the Long Duration Exposure Facility (LDEF) tray clamps. LDEF experiment trays were held in place by 6 to 8 chromic-anodized aluminum (6061-T6) clamps that were fastened to the spacecraft frame using three stainless steel hex bolts. Each clamp exposed an area of approximately 58 sq cm (4.8 cm x 12.7 cm x .45 cm, minus the bolt coverage). Some 337 out of 774 LDEF tray clamps were archived at JSC and are available through the Meteoroid & Debris Special Investigation Group (M&D SIG). Optical scanning of clamps, starting with Bay/Row A01 and working toward H25, is being conducted at JSC to locate and document impacts as small as 40 microns. These impacts are then inspected by Scanning Electron Microscopy/Energy Dispersive X-ray Analysis (SEM/EDXA) to select those features which contain appreciable impact residue material. Based upon the composition of projectile remnants, and using criteria developed at JSC, we have made a preliminary discrimination between micrometeoroid and space debris residue-containing impact features. Presently, 13 impacts containing significant amounts of unmelted and semi-melted micrometeoritic residues were forwarded to Centre National d'Etudes Spatiales (CNES) in France. At the CNES facilities, the upgraded impacts were analyzed using a JEOL T330A SEM equipped with a NORAN Instruments, Voyager X-ray Analyzer. All residues were quantitatively characterized by composition (including oxygen and carbon) to help understand interplanetary dust as possibly being derived from comets and asteroids.

Bernhard, Ronald P.↗
NASA NTRS2009

In Situ Resource Utilization (ISRU) on the Moon: Moessbauer Spectroscopy as a Process Monitor for Oxygen Production

Essential consumables like oxygen must to be produced from materials on the lunar surface to enable a sustained, long-term presence of humans on the Moon. The Outpost Precursor for ISRU and Modular Architecture (OPTIMA) field test on Mauna Kea, Hawaii, facilitated by the Pacific International Space Center for Exploration Systems (PISCES) of the University of Hawaii at Hilo, was designed to test the implementation of three hardware concepts to extract oxygen from the lunar regolith: Precursor ISRU Lunar Oxygen Testbed (PILOT) developed by Lockheed Martin in Littleton, CO; Regolith & Environmental Science and Oxygen & Lunar Volatiles Extraction (RESOLVE) developed at the NASA Kennedy Space Center in Cape Canaveral, FL; and ROxygen developed at the NASA Johnson Space Center in Houston, TX. The three concepts differ in design, but all rely on the same general principle: hydrogen reduction of metal cations (primarily Fe2+) bonded to oxygen to metal (e.g., Fe0) with the production of water. The hydrogen source is residual hydrogen in the fuel tanks of lunar landers. Electrolysis of the water produces oxygen and hydrogen (which is recycled). We used the miniaturized M ssbauer spectrometer MIMOS II to quantify the yield of this process on the basis of the quantity of Fe0 produced. Iron M ssbauer spectroscopy identifies iron-bearing phases, determines iron oxidation states, and quantifies the distribution of iron between mineral phases and oxidation states. The oxygen yield can be calculated by quantitative measurements of the distribution of Fe among oxidation states in the regolith before and after hydrogen reduction. A M ssbauer spectrometer can also be used as a prospecting tool to select the optimum feedstock for the oxygen production plants (e.g., high total Fe content and easily reduced phases). As a demonstration, a MIMOS II backscatter spectrometer (SPESI, Germany) was mounted on the Cratos rover (NASA Glenn Research Center in Cleveland, OH), which is one of several rover concepts designed to excavate and transfer regolith to the stationary hydrogen reduction plants. Spaceflight versions of the MIMOS II are part of the instrument payloads of NASA s Mars Exploration Rovers and still operating five years after landing on the surface of the planet. MIMOS II was also selected for Phobos-Grunt, a Russian sample return mission to the martian moon Phobos scheduled to launch in 2009, and ESA s ExoMars rover, an exobiology mission scheduled to launch in 2013. An advanced version of the instrument is currently under development. A new detector system with a higher energy resolution will not only reduce the necessary measurement time considerably, but also allow the simultaneous acquisition of an X-ray fluorescence spectrum to determine the elemental composition of samples.

Morris, R.V.↗
NASA NTRS1989

Structural materials for space applications

The long-term performance of structural materials in the space environment is a key research activity within NASA. The primary concerns for materials in low Earth orbit (LEO) are atomic oxygen erosion and space debris impact. Atomic oxygen studies have included both laboratory exposures in atomic oxygen facilities and flight exposures using the Shuttle. Characterization of atomic oxygen interaction with materials has included surface recession rates, residual mechanical properties, optical property measurements, and surface analyses to establish chemical changes. The Long Duration Exposure Facility (LDEF) is scheduled to be retrieved in 1989 and is expected to provide a wealth of data on atomic oxygen erosion in space. Hypervelocity impact studies have been conducted to establish damage mechanisms and changes in mechanical properties. Samples from LDEF will be analyzed to determine the severity of space debris impact on coatings, films, and composites. Spacecraft placed in geosynchronous Earth orbit (GEO) will be subjected to high doses of ionizing radiation which for long term exposures will exceed the damage threshold of many polymeric materials. Radiation interaction with polymers can result in chain scission and/or cross-linking. The formation of low molecular weight products in the epoxy plasticize the matrix at elevated temperatures and embrittle the matrix at low temperatures. This affects both the matrix-dominated mechanical properties and the dimensional stability of the composite. Embrittlement of the matrix at low temperatures results in enhanced matrix microcracking during thermal cycling. Matrix microcracking changes the coefficient of thermal expansion (CTE) of composite laminates and produces permanent length changes. Residual stress calculations were performed to estimate the conditions necessary for microcrack development in unirradiated and irradiated composites. The effects of UV and electron exposure on the optical properties of transparent polymer films were also examined to establish the optimum chemical structure for good radiation resistance. Thoughts on approaches to establishing accelerated testing procedures are discussed.

Tenney, Darrel R.↗
DOE OSTI2020

Effect and measurement of residual water in CaCl 2 intended for use as electrolyte in molten salt electrochemical processing

We report CaCl 2 has applications for electrochemical processing of nuclear materials. Thermal dehydration leads to formation of oxide ions, which are shown to react and cause precipitation of dissolved CeCl 3 that was selected as a surrogate for actinide chlorides. Thus, measurement of residual water in CaCl 2 is an essential capability. Thermogravimetric analysis (TGA) was shown to underestimate starting water concentration. Subsequent analysis of solid samples via acid–base titration and cyclic voltammetry (CV) of the molten salt yielded consistent values within 5% for residual water. Hydroxides were shown to be unstable, thus oxygen is retained as oxide ions. Thus, total water in a sample of CaCl 2 can be quantified by combining TGA with with either CV of molten salt or titration of salt samples. The importance of quantifying residual water in the salt was demonstrated by showing that cerium chloride (surrogate for actinide chlorides) will react with oxide ions in CaCl 2 to form insoluble oxides and oxychlorides.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

A Post-translational Histidine–Histidine Cross-Link Enhances Enzymatic Oxygen Reduction Activity with Greater pH Adaptability

Cross-linked protein residues exist as enzyme cofactors to enable or enhance catalytic activities. Despite their importance in nature, the chemical identity of the cross-links is limited to certain amino acid combinations, whose function and the formation mechanism remain insufficiently understood due to the difficulty in isolating native enzymes without the cross-links. Herein, we report the formation and characterization of both His-Tyr and His-His cross-links under oxidative enzymatic turnover conditions in L29H/F33Y/F43H Mb, a structural and functional model of heme-copper oxidase (HCO). The connectivity of the cross-link was characterized as Ne ε2 (His29)-Cd δ2 (His43) by mass spectrometry (LC-MS/MS) and nuclear magnetic resonance (NMR). Interestingly, formation of the cross-link significantly enhances the oxygen reduction activity of the enzyme at neutral or basic pH with higher product specificity. X-ray crystallography has identified a novel Tyr-His cross-link through a Tyr-O-His linkage. Our mechanistic studies indicate the involvement of high-valent heme-iron and the neighboring tyrosine in an oxidative self-processing pathway to generate the cross-link. In conclusion, this work serves as a new example while providing insights into the enzyme cross-link formation, allowing the design of artificial biocatalysts containing these novel cross-links with higher activity and pH adaptability.

Liu, Yiwei [Univ. of Texas, Austin, TX (United Sta↗
NASA NTRS2005

Highly Siderophile Elements and Osmium Isotope Systematics in Ureilites: Are the Carbonaceous Veins Primary Components?

Ureilites are an enigmatic group of primitive carbon-bearing achondrites of ultramafic composition. The majority of the ~143 ureilite meteorites consist primarily of olivine and pyroxene (and occasionally chromite) [1]. They are coarse-grained, slowly cooled, and depleted in incompatible lithophile elements. Minor amounts of dark interstitial material consisting of carbon, metal, sulfides, and fine-grained silicates occur primarily along silicate grain boundaries, but also intrude the silicates along fractures and cleavage planes. Variable degrees of impact shock features have also been imparted on ureilites. The prevailing two origins proposed for these rocks are either as melting residues of carbonaceous chondritic material [2], [3], or alternatively, derivation as mineral cumulates from such melts [4], [5], [6]. It has recently been proposed that ureilites are the residues of a smelting event, i.e. residues of a partial melting event under highly reducing conditions, where a solid Fe-bearing phase reacts with a melt and carbon to form Fe metal and carbon monoxide [7]. Rapid, localized extraction and loss of the basaltic component into space resulting from high eruption velocities could preserve unequilibrated oxygen isotopes and produce the observed olivine-pyroxene residues via 25-30% partial melting of chondritic-like precursor material.

Rankenburg, K.↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS2001

Carbon Dioxide Collection and Purification System for Mars

One of the most abundant resources available on Mars is the atmosphere. The primary constituent, carbon dioxide, can be used to produce a wide variety of consumables including propellants and breathing air. The residual gases can be used for additional pressurization tasks including supplementing the oxygen partial pressure in human habitats. A system is presented that supplies pure, high-pressure carbon dioxide and a separate stream of residual gases ready for further processing. This power-efficient method freezes the carbon dioxide directly from the atmosphere using a pulse-tube cryocooler. The resulting CO2 mass is later thawed in a closed pressure vessel, resulting in a compact source of liquefied gas at the vapor pressure of the bulk fluid. Results from a demonstration system are presented along with analysis and system scaling factors for implementation at larger scales. Trace gases in the Martian atmosphere challenge the system designer for all carbon dioxide acquisitions concepts. The approximately five percent of other gases build up as local concentrations of CO2 are removed, resulting in diminished performance of the collection process. The presented system takes advantage of this fact and draws the concentrated residual gases away as a useful byproduct. The presented system represents an excelient volume and mass solution for collecting and compressing this valuable Martian resource. Recent advances in pulse-tube cryocooler technology have enabled this concept to be realized in a reliable, low power implementation.

Clark, D. Larry↗
DOE OSTI2024

Oxygen Limit for Flammability of a Gas Mixture of Helium – Hydrogen – Oxygen in the U.S. Department of Energy Standard Canister

The radiolytic breakdown of residual free, physisorbed, and chemisorbed waters is anticipated in the sealed dry storage of spent nuclear fuel (SNF), releasing H 2 gas into the initial cover gas of helium. For aluminum-clad SNF (ASNF) in particular, the expected total hydrogen in the canister is enough to dominate the cover gas mixture if fully released, and based on experimental rates of H 2 generation, H 2 percentages exceeding the lower flammability limit appear likely. However, no evidence of radiolytic generation of O 2 has been observed to date, so the potential for flammability is averted due to the lack O 2 . Lack of oxygen has been credited for avoiding flammability in some existing storage and transportation approaches for SNF and other waste. This report reviews literature on flammability limits with a focus on the limiting oxygen concentration to provide technical underpinnings to refine a flammability criterion for gas mixtures of helium, hydrogen, and oxygen where the oxygen is expected to be the limiting species. While there is general consensus on H 2 flammability limits at standard temperature and pressure, the decay heat and gas generation within ASNF sealed dry storage canisters could push them to elevated temperatures and pressures, so the goal is to identify an oxygen threshold that will bound the behavior over the temperature and pressure range of the U.S. Department of Energy (DOE) Standard Canister. The information reviewed in this document supports the criterion that the oxygen concentration in a He-H 2 -O 2 mixture should be less than 1.5% to avoid flammability at temperatures and pressures relevant to sealed dry storage of ASNF in the DOE Standard Canister, i.e., up to 343°C (650°F) and 500 psig, respectively. Note that while data covering the full range of temperature at atmospheric pressure and nearly the full range of pressure at room temperature were available, data for the combined effects was available only at moderate temperatures and pressures; the recommended 1.5% O 2 threshold is based on the breadth of available data reported here and apparent trends therein.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2004

Improved Method of Purifying Carbon Nanotubes

An improved method of removing the residues of fabrication from carbon nanotubes has been invented. These residues comprise amorphous carbon and metal particles that are produced during the growth process. Prior methods of removing the residues include a variety of processes that involved the use of halogens, oxygen, or air in both thermal and plasma processes. Each of the prior methods entails one or more disadvantages, including non-selectivity (removal or damage of nanotubes in addition to removal of the residues), the need to dispose of toxic wastes, and/or processing times as long as 24 hours or more. In contrast, the process described here does not include the use of toxic chemicals, the generation of toxic wastes, causes little or no damage to the carbon nanotubes, and involves processing times of less than 1 hour. In the improved method, purification is accomplished by flowing water vapor through the reaction chamber at elevated temperatures and ambient pressures. The impurities are converted to gaseous waste products by the selective hydrogenation and hydroxylation by the water in a reaction chamber. This process could be performed either immediately after growth or in a post-growth purification process. The water used needs to be substantially free of oxygen and can be obtained by a repeated freeze-pump-thaw process. The presence of oxygen will non-selectively attach the carbon nanotubes in addition to the amorphous carbon.

Delzeit, Lance D.↗
DOE OSTI2023

Base excision repair of the N -(2-deoxy- d - erythro -pentofuranosyl)-urea lesion by the hNEIL1 glycosylase

Abstract The N-(2-deoxy-d-erythro-pentofuranosyl)-urea DNA lesion forms following hydrolytic fragmentation of cis-5R,6S- and trans-5R,6R-dihydroxy-5,6-dihydrothymidine (thymine glycol, Tg) or from oxidation of 7,8-dihydro-8-oxo-deoxyguanosine (8-oxodG) and subsequent hydrolysis. It interconverts between α and β deoxyribose anomers. Synthetic oligodeoxynucleotides containing this adduct are efficiently incised by unedited (K242) and edited (R242) forms of the hNEIL1 glycosylase. The structure of a complex between the active site unedited mutant CΔ100 P2G hNEIL1 (K242) glycosylase and double-stranded (ds) DNA containing a urea lesion reveals a pre-cleavage intermediate, in which the Gly2 N-terminal amine forms a conjugate with the deoxyribose C1′ of the lesion, with the urea moiety remaining intact. This structure supports a proposed catalytic mechanism in which Glu3-mediated protonation of O4′ facilitates attack at deoxyribose C1′. The deoxyribose is in the ring-opened configuration with the O4′ oxygen protonated. The electron density of Lys242 suggests the ‘residue 242-in conformation’ associated with catalysis. This complex likely arises because the proton transfer steps involving Glu6 and Lys242 are hindered due to Glu6-mediated H-bonding with the Gly2 and the urea lesion. Consistent with crystallographic data, biochemical analyses show that the CΔ100 P2G hNEIL1 (K242) glycosylase exhibits a residual activity against urea-containing dsDNA.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1977

Noble gases in separated meteoritic minerals - Murchison /C2/, Ornans /C3/, Karoonda /C5/, and Abee /E4/

The distribution of all five noble gases was measured in four meteorites of different classes by mass spectrometry and stepwise heating of HCl-HF-insoluble residues and of samples treated with HNO3 and atomic oxygen. The distribution of the gases among the three main phases, chromite, polymer, and the ill-defined Q-phase, was determined, and also the isotopic distribution of the gases in the phases was obtained.

Srinivasan, S.↗
NASA NTRS1983

Apollo 14 very low titanium glasses - Melting experiments in iron-platinum alloy capsules

This paper describes two techniques that have been developed to produce Fe-Pt alloy capsules for hgh-pressure experiments, and reports liquidus-phase relations of the Apollo 14 very low titanium glasses determined using Fe-rich capsules (a/Fe/ approximately 0.6). The liquid is multiply saturated with olivine and clinopyroxene at equal to or greater than 22 kbar. The multiple saturation is at least 3 kbar higher than that determined using pure Fe capsules and corresponds to a source region at least 60 km deeper if olivine and clinopyroxene were the residual phases. However, independent data on iron activity or oxygen fugacity of the glasses are still needed in order to choose a container of optimum composition. Preliminary experiments in Fe-poor alloy capsules suggest that the valence state of iron and the crystallization sequence in the melt have changed, possibly as a result of oxidizing materials entrapped during the iron-plating processes. The FeO content of the charge decreases linearly with increasing run duration in experiments using pure Fe capsules. The observation that iron-rich globules grow with time suggests that the equilibrium Fe (bleb) + Fe2O3 (liq) = 3 FeO (liq) might be established in the liquid at high pressure. If this explanation is correct, an appreciable amount of 'FeO' in the liquid could actually be Fe2O3, and some natural lunar volcanic glasses may contain ferric iron as well.

Chen, H.-K.↗
NASA NTRS1995

Hardware cleanliness methodology and certification

Inadequacy of mass loss cleanliness criteria for selection of materials for contamination sensitive uses, and processing of flight hardware for contamination sensitive instruments is discussed. Materials selection for flight hardware is usually based on mass loss (ASTM E-595). However, flight hardware cleanliness (MIL 1246A) is a surface cleanliness assessment. It is possible for materials (e.g. Sil-Pad 2000) to pass ASTM E-595 and fail MIL 1246A class A by orders of magnitude. Conversely, it is possible for small amounts of nonconforming material (Huma-Seal conformal coating) to not present significant cleanliness problems to an optical flight instrument. Effective cleaning (precleaning, precision cleaning, and ultra cleaning) and cleanliness verification are essential for contamination sensitive flight instruments. Polish cleaning of hardware, e.g. vacuum baking for vacuum applications, and storage of clean hardware, e.g. laser optics, is discussed. Silicone materials present special concerns for use in space because of the rapid conversion of the outgassed residues to glass by solar ultraviolet radiation and/or atomic oxygen. Non ozone depleting solvent cleaning and institutional support for cleaning and certification are also discussed.

Harvey, Gale A.↗