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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 541 records · Page 30

Capture of Iodine from Nuclear-Fuel-Reprocessing Off-Gas: Influence of Aging on a Reduced Silver Mordenite Adsorbent after Exposure to NO/NO 2

Iodine radioisotopes released during nuclear fuel reprocessing must be removed from the off-gas stream before discharge. One promising material for iodine capture is reduced silver mordenite (Ag 0 Z). Nevertheless, the adsorbent’s capacity will degrade, or age, over time when the material is exposed to other off-gas constituents. Though the overall impact of aging is known, the underlying physical and chemical processes are not. To examine these processes, Ag 0 Z samples were prepared and aged in 2% NO 2 in dry air and in 1% NO in N 2 gas streams at 150 °C for up to six months. Aged samples were then characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray absorption spectroscopy. These techniques show that aging involves two overarching processes: (i) oxidation of the silver nanoparticles present in Ag 0 Z and (ii) migration of oxidized silver into the mordenite’s inner network. Silver on the nanoparticle’s surface is oxidized through adsorption of O 2 , NO, and NO 2 . Additionally, Raman spectroscopy and X-ray absorption spectroscopy indicate that nitrates are the primary products of this adsorption. Most of these nitrates migrate into the interior of the mordenite and exchange at framework binding sites, returning silver to its unreduced state (AgZ). The remaining nitrates exist at a persistent concentration without aggregating into bulk-phase AgNO 3 . X-ray absorption spectroscopy results further indicate that iodine adsorption occurs on not just Ag 0 Z but also on AgZ and a portion of the nitrates in the system. AgZ adsorbs a sizable quantity of iodine early in the aging process, but its capacity drops rapidly over time. For well-aged samples, nitrates are responsible for up to 95% of mordenite’s iodine capacity. Overall, these results have enhanced our understanding of the aging process in silver mordenite and are expected to guide the development of superior adsorbents for the capture of radioactive iodine from reprocessing off-gas.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Flexible atomic layer deposition system for coating porous materials

In this paper, we describe an atomic layer deposition (ALD) system that is optimized for the growth of thin films on high-surface-area, porous materials. The system incorporates a moveable dual-zone furnace allowing for rapid transfer of a powder substrate between heating zones whose temperatures are optimized for precursor adsorption and oxidative removal of the precursor ligands. The reactor can both be evacuated, eliminating the need for a carrier gas during precursor exposure, and rotated, to enhance contact between a powder support and the gas phase, both of which help us to minimize mass transfer limitations in the pores during film growth. The capabilities of the ALD system were demonstrated by growing La 2 O 3 , Fe 2 O 3 , and LaFeO 3 films on a 120 m 2 g -1 MgAl 2 O 4 powder. Analysis of these films using scanning transmission electron microscopy and temperature-programmed desorption of 2-propanol confirmed the conformal nature of the oxide films.

36 MATERIALS SCIENCE↗

Self-contamination and environment of an orbiting spacecraft

The flux of molecules emitted by a spacecraft and subsequently reflected to its surface was investigated. The reflection occurs upon collision of the outgassed molecules with ambient molecules. Evaluation of the flux was based on a knowledge of the spacecraft outgassing rate, the spacecraft dimensions, and the orbit parameters. Condensation rates and adsorption layers on critical surfaces were calculated from the knowledge of this flux and the nature and temperature of the gas and the surface. Based on estimated and measured emission rates, calculation of these parameters was performed for a number of spacecraft. The relationships and graphs developed allow an estimate of several important parameters for an orbiting spacecraft to be made. The pressures and densities at various distances from the spacecraft, as produced by the surrounding ambient molecules and by the spacecraft's own outgassing, are presented. The pressure and density produced by the outgassing can be obtained as a function of time if the behavior of the outgassing with time is known. The number of desorbed molecules ionized by impact with ambient charged particles and the effect of the spacecraft's electric field on polarized desorbed molecules were considered.

Scialdone, J. J.↗

Development of a compact dilution refrigerator for zero gravity operation

A compact dilution refrigerator design based on internal charcoal adsorption is being tested for operation in zero gravity. This refrigerator is self-contained with no external pumps or gas handling system and provides reliable operation since it has no moving parts. All operations are performed with heaters and are completely computer controlled. The refrigerator is capable of providing many hours of operation at very low temperature before the charcoal pumps must be recycled.

Roach, Pat R.↗

Evaluation of spacecraft toxic gas removal agents

A study of the decomposition of various compounds adsorbed on charcoal was made, with a view toward providing a critical appraisal of previous data from charcoal adsorption studies. It was found that thermal decomposition occurs at temperature lower than previously suspected during the charcoal stripping process. A discussion is presented dealing with the various types of reactions found. A rough, quantitative scheme for correcting previous analytical results is developed and presented.

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Adsorption separation of heavier isotope gases in subnanometer carbon pores

Isotopes of heavier gases including carbon ( 13 C/ 14 C), nitrogen ( 13 N), and oxygen ( 18 O) are highly important because they can be substituted for naturally occurring atoms without significantly perturbing the biochemical properties of the radiolabelled parent molecules. These labelled molecules are employed in clinical radiopharmaceuticals, in studies of brain disease and as imaging probes for advanced medical imaging techniques such as positron-emission tomography (PET). Established distillation-based isotope gas separation methods have a separation factor ( S ) below 1.05 and incur very high operating costs due to high energy consumption and long processing times, highlighting the need for new separation technologies. Here, we show a rapid and highly selective adsorption-based separation of 18 O 2 from 16 O 2 with S above 60 using nanoporous adsorbents operating near the boiling point of methane (112 K), which is accessible through cryogenic liquefied-natural-gas technology. A collective-nuclear-quantum effect difference between the ordered 18 O 2 and 16 O 2 molecular assemblies confined in subnanometer pores can explain the observed equilibrium separation and is applicable to other isotopic gases.

36 MATERIALS SCIENCE↗

Classification and generation of terrestrial rare gases

A Kr-84/Xe-130 versus Ne-20/Ar-36 diagram is a very useful format with which to study the elemental ratios of rare gases from terrestrial materials. It can separate not only the three types of rare gases which Ozima and Alexander (1976) classified but also the 'planetary' type rare gases from the other three types of rare gases. When all the available terrestrial rare gas data are plotted in a Kr-84/Xe-130 versus Ne-20/Ar-36 diagram, several observations can be made. First, most of the analyses of rare gases from shales yield Kr-84/Xe-130 ratios between the 'planetary' and atmospheric values. If, however, the atmosphere's high Kr-84/Xe-130 ratio was produced by the selective adsorption of xenon onto shales from an initially 'planetary' atmosphere, as is widely accepted, then the Kr-84/Xe-130 ratio in shales should be even lower than the 'planetary' value. Second, the rare gas pattern in the quenched rims of submarine basalts may be explained as fractionated samples of the rare gases in sea water.

Saito, K.↗

CO Adsorption on a Single‐Atom Catalyst Stably Embedded in Graphene

Abstract Confined single metal atoms in graphene‐based materials have proven to be excellent catalysts for several reactions and promising gas sensing systems. However, whether the chemical activity arises from the specific type of metal atom or is a direct consequence of the confinement itself remains unclear.

Chemistry↗

Toluene Adsorption and TPD

Raw data for toluene adsorption and TPD experiments on two different adsorbents using a custom flow-through, bench-top reactor capable of controlling gas compositions and temperature.

36 MATERIALS SCIENCE↗

Self-contamination and environment of an orbiting satellite.

The flux of molecules emitted by the satellite and subsequently returning to its surface is investigated. The reflection occurs upon collision of these with ambient molecules. The evaluation of this flux is carried out from a knowledge of the outgassing rate of the satellite, its dimensions, and the orbit parameters. Condensation rates and adsorption layers on critical surfaces are calculated from the knowledge of this flux, and from the natures and temperatures of the gas and the surface. The calculation of these parameters, based on estimated and in some cases measured emission rates, has been carried out for a number of satellites. These developed relationships and graphs allow the estimation of several important parameters for an orbiting satellite. This report presents the pressures and densities at various distances from the satellite as produced by the surrounding ambient molecules and by the outgassing of the satellite.

Scialdone, J. J.↗

Reactive Carbon from Life Support Wastes for Incinerator Flue Gas Cleanup

This paper presents the results from a joint research initiative between NASA Ames Research Center and Lawrence Berkeley National lab. The objective of the research is to produce activated carbon from life support wastes and to use the activated carbon to adsorb and chemically reduce the NO(sub x) and SO(sub 2) contained in incinerator flue gas. Inedible biomass waste from food production is the primary waste considered for conversion to activated carbon. Results to date show adsorption of both NO(sub x) and SO(sub 2) in activated carbon made from biomass. Conversion of adsorbed NO(sub x) to nitrogen has also been observed.

Fisher, J. W.↗

Mass accommodation and gas–particle partitioning in secondary organic aerosols: dependence on diffusivity, volatility, particle-phase reactions, and penetration depth

Abstract. Mass accommodation is an essential process for gas–particle partitioning of organic compounds in secondary organic aerosols (SOA). The mass accommodation coefficient is commonly described as the probability of a gas molecule colliding with the surface to enter the particle phase. It is often applied, however, without specifying if and how deep a molecule has to penetrate beneath the surface to be regarded as being incorporated into the condensed phase (adsorption vs. absorption). While this aspect is usually not critical for liquid particles with rapid surface–bulk exchange, it can be important for viscous semi-solid or glassy solid particles to distinguish and resolve the kinetics of accommodation at the surface, transfer across the gas–particle interface, and further transport into the particle bulk. For this purpose, we introduce a novel parameter: an effective mass accommodation coefficient αeff that depends on penetration depth and is a function of surface accommodation coefficient, volatility, bulk diffusivity, and particle-phase reaction rate coefficient. Application of αeff in the traditional Fuchs–Sutugin approximation of mass-transport kinetics at the gas–particle interface yields SOA partitioning results that are consistent with a detailed kinetic multilayer model (kinetic multilayer model of gas–particle interactions in aerosols and clouds, KM-GAP; Shiraiwa et al., 2012) and two-film model solutions (Model for Simulating Aerosol Interactions and Chemistry, MOSAIC; Zaveri et al., 2014) but deviate substantially from earlier modeling approaches not considering the influence of penetration depth and related parameters. For highly viscous or semi-solid particles, we show that the effective mass accommodation coefficient remains similar to the surface accommodation coefficient in the case of low-volatility compounds, whereas it can decrease by several orders of magnitude in the case of semi-volatile compounds. Such effects can explain apparent inconsistencies between earlier studies deriving mass accommodation coefficients from experimental data or from molecular dynamics simulations. Our findings challenge the approach of traditional SOA models using the Fuchs–Sutugin approximation of mass transfer kinetics with a fixed mass accommodation coefficient, regardless of particle phase state and penetration depth. The effective mass accommodation coefficient introduced in this study provides an efficient new way of accounting for the influence of volatility, diffusivity, and particle-phase reactions on SOA partitioning in process models as well as in regional and global air quality models. While kinetic limitations may not be critical for partitioning into liquid SOA particles in the planetary boundary layer (PBL), the effects are likely important for amorphous semi-solid or glassy SOA in the free and upper troposphere (FT–UT) as well as in the PBL at low relative humidity and low temperature.

54 ENVIRONMENTAL SCIENCES↗

Solid phase characterization and transformation of illite mineral with gas-phase ammonia treatment

In situ remediation applications of ammonia (NH 3 ) gas have potential for sequestration of subsurface contamination. Ammonia gas injections initially increase the pore water pH leading to mineral dissolution followed by formation of secondary precipitates as the pH is neutralized. However, there is a lack of understanding of fundamental alteration processes due to NH 3 treatment. In these batch studies, phyllosilicate minerals (illite and montmorillonite) were exposed to NH 3 gas with subsequent aeration to simulate in situ remediation. Following treatments, solids were characterized using a variety of techniques, including X-ray diffraction, N 2 adsorption-desorption analysis for surface area, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and microscopy methods to investigate physicochemical transformations. The results of this study indicate that, at high pH, the clays are altered as observed by differences in morphology and particle size via microscopy. However, the two clays interact differently with NH 3 . While montmorillonite interlayers collapsed due to intercalation, illite layers were unaffected as confirmed by FTIR analysis. Further, structural changes in silicate ([SiO 4 ] n- ) and aluminol (Al-OH) groups were identified by NMR and FTIR. This research showed that mineral alteration processes occur during and after NH 3 gas treatment which may be used to remove radionuclides from the aqueous phase through sorption, co-precipitation, and coating with secondary phyllosilicate alteration products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adsorptive denitrogenation of model aviation fuel using mesoporous silica in a packed bed adsorption system

This study aims to understand the effects of system process parameters such as flow rate, adsorbent particle size, and use of recycled adsorbent on denitrogenation performance of a model fuel using mesoporous silica gel. The goal is to reduce the nitrogen content of the model fuel from 1500 parts per million to single-digit ppm to meet ASTM specifications for drop-in fuels. This work was done with the intent of applying adsorptive denitrogenation to sustainable aviation fuel (SAF) product fractions produced via hydrothermal liquefaction (HTL). The adsorption performance of the silica is evaluated via packed column breakthrough data, with data generated from collecting from the column outlet and quantifying nitrogen content via gas chromatography. Select experiments use a significantly larger (2.5x column diameter and length) column to demonstrate linear scalability of the process. Thermogravimetric analysis data is collected to evaluate the effects of thermal calcination as a sorbent regeneration method. Effects of a more complex feed are also investigated using a known reference fuel with additional added nitrogen containing compounds. The results presented in this work successfully demonstrate up to 99.8 % removal of NCCs from a model fuel fraction at an original NCC concentration of approximately 1500 ppm to single-digit parts per million after treatment. We also examine calcination of sorbent materials to remove the adsorbed species to enable sorbent reuse and minimize waste generation and show that the calcined material can be reused up to 5 cycles with reduced adsorption capacity. Overall, this work indicates that adsorptive denitrogenation using silica gel is a viable solution to enable the integration of HTL-derived aviation fuels into existing fuel infrastructure.

Adsorption techniques↗

Area G FTWC Venting Operations, Transportation, and Moving to the WETF Facility [Slides]

What is a FTWC? Flanged Tritium Waste Containers (FTWC) are designed to hold tritium contaminated waste. The tritium contaminated waste is in secondary containers such as plastic bags and paint cans. Tritium is a gas that is lighter than air. Hydrogen gas is lighter-than-air. Hydrogen gas forms explosive mixtures with air from 4% concentration to 75% concentration. Tritium gas has a Biological ½ life = 10 – 12 days. It is a beta particle emitter. Exposure can occur by inhalation or by skin adsorption.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Theoretical analysis of the density within an orbiting molecular shield

An analytical model based on the kinetic theory of a drifting Maxwellian gas is used to determine the nonequilibrium molecular density distribution within a hemispherical shell open aft with its axis parallel to its velocity. Separate numerical results are presented for the primary and secondary density distribution components due to the drifting Maxwellian gas for speed ratios between 2.5 and 10. An analysis is also made of the density component due to gas desorbed from the wall of the hemisphere, and numerical results are presented for the density distribution. It is shown that the adsorption process may be completely ignored. The results are applicable to orbital trajectories in any planet-atmosphere system and interplanetary transfer trajectories. Application to the earth's atmosphere is mentioned briefly.

Hueser, J. E.↗

Evaluation of analytical methodology for hydrocarbons in high pressure air and nitrogen systems

Samples of liquid oxygen, high pressure nitrogen, low pressure nitrogen, and missile grade air were studied to determine the hydrocarbon concentrations. Concentration of the samples was achieved by adsorption on a molecular sieve and activated charcoal. The trapped hydrocarbons were then desorbed and transferred to an analytical column in a gas chromatograph. The sensitivity of the method depends on the volume of gas passed through the adsorbent tubes. The value of the method was verified through recoverability and reproducibility studies. The use of this method enables LOX, GN2, and missile grade air systems to be routinely monitored to determine low level increases in specific hydrocarbon concentration that could lead to potentially hazardous conditions.

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