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NASA NTRS2013

Method of Separating Oxygen From Spacecraft Cabin Air to Enable Extravehicular Activities

Extravehicular activities (EVAs) require high-pressure, high-purity oxygen. Shuttle EVAs use oxygen that is stored and transported as a cryogenic fluid. EVAs on the International Space Station (ISS) presently use the Shuttle cryo O2, which is transported to the ISS using a transfer hose. The fluid is compressed to elevated pressures and stored as a high-pressure gas. With the retirement of the shuttle, NASA has been searching for ways to deliver oxygen to fill the highpressure oxygen tanks on the ISS. A method was developed using low-pressure oxygen generated onboard the ISS and released into ISS cabin air, filtering the oxygen from ISS cabin air using a pressure swing absorber to generate a low-pressure (high-purity) oxygen stream, compressing the oxygen with a mechanical compressor, and transferring the high-pressure, high-purity oxygen to ISS storage tanks. The pressure swing absorber (PSA) can be either a two-stage device, or a single-stage device, depending on the type of sorbent used. The key is to produce a stream with oxygen purity greater than 99.5 percent. The separator can be a PSA device, or a VPSA device (that uses both vacuum and pressure for the gas separation). The compressor is a multi-stage mechanical compressor. If the gas flow rates are on the order of 5 to 10 lb (.2.3 to 4.6 kg) per day, the compressor can be relatively small [3 ~16 ~16 in. (.8 ~41 ~41 cm)]. Any spacecraft system, or other remote location that has a supply of lowpressure oxygen, a method of separating oxygen from cabin air, and a method of compressing the enriched oxygen stream, has the possibility of having a regenerable supply of highpressure, high-purity oxygen that is compact, simple, and safe. If cabin air is modified so there is very little argon, the separator can be smaller, simpler, and use less power.

Graf, John C.↗

DOE OSTI2022

Influence of microorganisms on uranium release from mining-impacted lake sediments under various oxygenation conditions

Microbial processes can be involved in the remobilization of uranium (U) from reduced sediments under O 2 reoxidation events such as water table fluctuations. Such reactions could be typically encountered after U-bearing sediment dredging operations. Solid U(IV) species may thus reoxidize into U(VI) that can be released in pore waters in the form of aqueous complexes with organic and inorganic ligands. Non-uraninite U(IV) species may be especially sensitive to reoxidation and remobilization processes. Nevertheless, little is known regarding the effect of microbially mediated processes on the behaviour of U under these conditions.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1994

A detailed evaluation of heating processes in the middle atmosphere

A fundamental problem in the study of the terrestrial middle atmosphere is to calculate accurately the local heating due to the absorption of solar radiation. Knowledge of the heat budget is essential to understanding the atmospheric thermal structure, atmospheric motions, atmospheric chemistry, and their coupling. The evaluation of heating rates is complicated (especially above the stratopause) by the fact that the heating is not a simple one-step process. That is, the absorbed solar energy does not all immediately appear as heat. Rather, substantial portions of the incident energy may appear as internal energy of excited photolysis products (e.g., O(1D) or O2(1 delta)) or as chemical potential energy of product species such as atomic oxygen. The ultimate disposition of the internal and chemical energy possessed by the photolysis products determines the efficiency and thus the rate at which the middle atmosphere is heated. In studies of the heat budget, it is also vitally important to consider transport of long lived chemical species such as atomic oxygen above approximately 80 km. In such cases, the chemical potential energy may be transported great distances (horizontally or vertically) before undergoing a reaction to release the heat. Atomic oxygen influences the heating not only by reactions with itself and with O2 but also by reactions with odd-hydrogen species, especially those involving OH (Mlynczak and Solomon, 1991a). Consequently, absorbed solar energy may finally by converted to heat a long time after and at a location far from the original deposition. The purpose of this paper is to examine the solar and chemical heating processes and to present parameterizations for the heating efficiencies readily applicable for use in numerical models and heat budget studies. In the next two sections the processes relevant to the heating efficiencies for ozone and molecular oxygen will be reviewed. In section 4 the processes for the exothermic reactions will be reviewed and parameterizations for the heating efficiencies for both the solar and chemical processes will be presented in Section 5.

Mlynczak, Martin↗

DOE OSTI2020

Oxygen Affinity: The Missing Link Enabling Prediction of Proton Conductivities in Doped Barium Zirconates

Proton-conducting oxides, specifically doped barium zirconates, have garnered much attention as electrolytes for solid-state electrochemical devices operable at intermediate temperatures (400–600 °C). In chemical terms, hydration energy, E hyd , and proton–dopant association energy, E as , are two key parameters that determine whether an oxide exhibits fast proton conduction, but to date ab initio studies have for the most part studied each parameter separately, with no clear correlation with proton conductivity identified in either case. Here, we demonstrate that the oxygen affinity, E O.dopant , defined as the energy released when an oxide ion enters an oxygen vacancy close to a dopant atom, is the missing link between these two parameters and correlates well with experimental proton conductivities in doped barium zirconates. Ab initio calculations of point defects and their complexes in Sc-, In-, Lu-, Er-, Y-, Gd-, and Eu-doped barium zirconates are used to determine E hyd , E as , E O.dopant , and the hydrogen affinity, E H.host , of each system. These four energy terms are related by E hyd = E O.dopant + 2E H.host + 2E as . Complementary impedance spectroscopy measurements reveal that the stronger the calculated oxygen affinity of a system, the higher the proton conductivity at 350 °C. Although the proton trapping site is also an important factor, the results show that oxygen affinity is an excellent predictor of proton conductivity in these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2015

Results from On-Board CSA-CP and CDM Sensor Readings During the Burning and Suppression of Solids II (BASS-II) Experiment in the Microgravity Science Glovebox (MSG)

For the first time on ISS, BASS-II utilized MSG working volume dilution with gaseous nitrogen (N2). We developed a perfectly stirred reactor model to determine the N2 flow time and flow rate to obtain the desired reduced oxygen concentration in the working volume for each test. We calibrated the model with CSA-CP oxygen readings offset using the Mass Constituents Analyzer reading of the ISS ambient atmosphere data for that day. This worked out extremely well for operations, and added a new vital variable, ambient oxygen level, to our test matrices. The main variables tested in BASS-II were ambient oxygen concentration, ventilation flow velocity, and fuel type, thickness, and geometry. BASS-II also utilized the on-board CSA-CP for oxygen and carbon monoxide readings, and the CDM for carbon dioxide readings before and after each test. Readings from these sensors allow us to evaluate the completeness of the combustion. The oxygen and carbon dioxide readings before and after each test were analyzed and compared very well to stoichiometric ratios for a one step gas-phase reaction. The CO versus CO2 followed a linear trend for some datasets, but not for all the different geometries of fuel and flow tested. Lastly, we calculated the heat release rates during each test from the oxygen consumption and burn times, using the constant 13.1 kJ of heat released per gram of oxygen consumed. The results showed that the majority of the tests had heat release rates well below 100 Watts.

combustion products↗

DOE OSTI2023

Effects of Water Table Fluctuation on Greenhouse Gas Emissions from Wetland Soils in the Peruvian Amazon

Amazonian swamp forests remove large amounts of carbon dioxide (CO 2 ) but produce methane (CH 4 ). Both are important greenhouse gases (GHG). Drought and cultivation cut the CH 4 emissions but may release CO 2 . Varying oxygen content in nitrogen-rich soil produces nitrous oxide (N 2 O), which is the third most important GHG. Despite the potentially tremendous changes, GHG emissions from wetland soils under different land uses and environmental conditions have rarely been compared in the Amazon. We measured environmental characteristics, and CO 2 , CH 4 and N 2 O emissions from the soil surface with manual opaque chambers in three sites near Iquitos, Peru from September 2019 to March 2020: a pristine peat swamp forest, a young forest and a slash-and-burn manioc field. The manioc field showed moderate soil respiration and N 2 O emission. The peat swamp forests under slight water table drawdown emitted large amounts of CO 2 and CH 4 . A heavy post-drought shower created a hot moment of N 2 O in the pristine swamp forest, likely produced by nitrifiers. All in all, even small changes in soil moisture can create hot moments of GHG emissions from Amazonian wetland soils, and should therefore be carefully monitored.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Key problems of the four-dimensional Earth system

Compelling evidence indicates that the solid Earth consists of two physicochemically distinct zones separated radially in the middle of the lower mantle at ~1800 km depth. The inner zone is governed by pressure-induced physics and chemistry dramatically different from the conventional behavior in the outer zone. These differences generate large physical and chemical potentials between the two zones that provide fundamental driving forces for triggering major events in Earth’s history. One of the main chemical carriers between the two zones is H 2 O in hydrous minerals that subducts into the inner zone, releases hydrogen, and leaves oxygen to create superoxides and form oxygen-rich piles at the core–mantle boundary, resulting in localized net oxygen gain in the inner zone. Accumulation of oxygen-rich piles at the base of the mantle could eventually reach a supercritical level that triggers eruptions, injecting materials that cause chemical mantle convection, superplumes, large igneous provinces, extreme climate changes, atmospheric oxygen fluctuations, and mass extinctions. Interdisciplinary research will be the key for advancing a unified theory of the four-dimensional Earth system.

58 GEOSCIENCES↗

DOE OSTI2022

Tritium Fires: Simulation and Safety Assessment

This is the Sandia report from a joint NSRD project between Sandia National Labs and Savannah River National Labs. The project involved development of simulation tools and data intended to be useful for tritium operations safety assessment. Tritium is a synthetic isotope of hydrogen that has a limited lifetime, and it is found at many tritium facilities in the form of elemental gas (T 2 ). The most serious risk of reasonable probability in an accident scenario is when the tritium is released and reacts with oxygen to form a water molecule, which is subsequently absorbed into the human body. This tritium oxide is more readily absorbed by the body and therefore represents a limiting factor for safety analysis. The abnormal condition of a fire may result in conversion of the safer T 2 inventory to the more hazardous oxidized form. It is this risk that tends to govern the safety protocols. Tritium fire datasets do not exist, so prescriptive safety guidance is largely conservative and reliant on means other than testing to formulate guidelines. This can have a consequence in terms of expensive and/or unnecessary mitigation design, handling protocols, and operational activities. This issue can be addressed through added studies on the behavior of tritium under representative conditions. Due to the hazards associated with the tests, this is being approached mainly from a modeling and simulation standpoint and surrogate testing. This study largely establishes the capability to generate simulation predictions with sufficiently credible characteristics to be accepted for safety guidelines as a surrogate for actual data through a variety of testing and modeling activities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS2016

In-Space Production of Storable Propellants

Our exploration of the feasibility of in-space production of storable propellants from resourcesavailable on asteroids, and also on Mars and the Moon, has considered the process of sampleacquisition; the energy requirements for heating and volatile release; the thermodynamic behaviorof gas release from minerals and organic polymers containing hydrogen, oxygen, carbon, sulfur,and nitrogen; purification of the released water and carbon dioxide; the storage and transportation of these materials in the condensed state; synthesis of fuels including methanol and dimethyl ether(DME); and the co-production, concentration, stability, and storage of the complementary oxidizer high-test hydrogen peroxide (HTP). We call attention to the ability of the storable propellant/oxidizer combination of DME and HTP to carry out deep-space missions and to perform retrieval and relocation of any and all space-derived resources, such as retrieving asteroidal metal to high Earth orbit. This study's analyses are based on returning resources to a storage/processing/dispensing facility in a Highly Eccentric Earth Orbit (HEEO) with a perigee above geosynchronous orbit and an apogee approach or beyond the Moon's orbit.The methane/LOX option, notable for good engine performance, has not been included in this study because our scope includes only fully storable propellants.

Lewis, John S.↗

NASA NTRSDate not supplied

Asymptotic Analysis of Premixed N-alkane Cool Flame Propagation

A simplified chemical-kinetic cool-flame mechanism for n-alkanes developed recently is applied to premixed laminar cool-flame deflagrations. The present contribution derives the structure of the associated freely propagating cool premixed flame controlled by the low-temperature chemistry and develops formulas for calculating the corresponding laminar burning velocity. Application of activation-energy asymptotics reveals finite-rate chemistry without heat release occurring throughout the preheat zone and leakage of both fuel and oxygen through the thin heat-release zone, there being zones of consumption of an intermediate species on each side of the heat-release zone, thicker than that zone but still thin compared with the preheat-zone thickness. Predicted laminar burning velocities are compared with recently reported measurements for n-dodecane, performed in a newly deigned high-pressure ignition apparatus, resulting in reasonable agreement.

Cool flames↗

NASA NTRSDate not supplied

Asymptotic Analysis of Premixed N-alkane Cool Flame Propagation

cool flames↗

NASA NTRSDate not supplied

Cryogenic Modules for Synergistic O2 Generation and CO2 Retention in Closed-Circuit Escape Respirators

Since 2018, NASA and the National Institute for Occupational Safety and Health (NIOSH) have been developing a liquid oxygen storage module (LOXSM) based on the NASA patent-pending Cryogenic Flux Capacitor (CFC) technology. LOXSM’s could potentially replace the gaseous or chemical-based oxygen supply in current closed-circuit escape respirators (CCER), with reducing CCER size being a primary goal. By virtue of the CFC functionality, cryogenic oxygen stored within the LOXSM is released in response to heat input, ideally from the breathing loop. Prior efforts focused on the oxygen storage potential of silica aerogel materials that the CFC utilizes, and were previously reported. Current work explored the LOXSM’s potential to remove and retain CO 2 produced by the CCER user, in conjunction with oxygen generation, creating a synergy that may be exploited to reduce or eliminate the chemical CO 2 absorber used in current CCERs. A test program for determining CO 2 retention is presented, as well as the evolution of LOXSM prototypes. Testing showed that it is possible to completely remove CO 2 out of an effluent stream at the flowrate required for the capacity of the CCER for an appreciable time, and that the LOXSM prototype design progression had a positive effect on that duration.

A.M. Swanger↗

NASA NTRS1999

Fe(VI) as a Possible Oxidant on the Martian Surface

The essential findings of the three biological experiments (Gas Exchange, Labeled Released, and Pyrolitic Release) aboard the Viking Mars landers were the discovery of the presence of one or more strong oxidants on the Martian surface. The Gas Exchange experiments showed that wetting Martian soil leads to the evolution of oxygen, while in the Labeled Release experiment addition of a nutrient solution containing C-14-labeled formate, glycine, lactate, alanine, and glycolic acid induced CO2 evolution. A general consensus was reached that all data taken together pointed to the presence on Martian surface of a strong oxidant, or most probably several different types of oxidants. Several candidates have been proposed as oxidants, including superoxides, hydrogen peroxide, and iron oxides (possibly gamma-Fe2O3). Additional information is contained in the original extended abstract.

Tsapin, A. I.↗

DOE OSTI2021

Thermally Aged Li–Mn–O Cathode with Stabilized Hybrid Cation and Anion Redox

Though low-cost and environmentally friendly, Li–Mn–O cathodes suffer from low energy density. Although synthesized Li 4 Mn 5 O 12 -like overlithiated spinel cathode with reversible hybrid anion- and cation-redox (HACR) activities has a high initial capacity, it degrades rapidly due to oxygen loss and side-reaction-induced electrolyte decomposition. In this study, we develop a two-step heat treatment to promote local decomposition as Li 4 Mn 5 O 12 → 2LiMn 2 O 4 + Li 2 MnO 3 + 1/2 O 2 ↑, which releases near-surface reactive oxygen that is harmful to cycling stability. The produced nanocomposite delivers a high discharge capacity of 225 mAh/g and energy density of over 700 Wh/kg at active-material level at a current density of 100 mA/g between 1.8 to 4.7 V. Benefiting from suppressed oxygen loss and side reactions, 80% capacity retention is achieved after 214 cycles in half cells. With industrially acceptable electrolyte amount (6 g/Ah), full cells paired with Li 4 Ti 5 O 12 anode have a good retention over 100 cycles.

25 ENERGY STORAGE↗

DOE OSTI2023

Effects of the surface termination and the oxygen vacancy position on LaNiO 3 ultra-thin films: First-principles study

In this study, while ultra-thin layers of the LaNiO 3 film exhibit a remarkable metal-insulator transition as the film thickness becomes smaller than a few unit cell (u.c.), the formation of possible oxygen vacancies and their effects on the correlated electronic structure have been rarely studied using first principles. Here, we investigate the effects of the surface termination and the oxygen vacancy position on the electronic properties and vacancy energetics of LaNiO 3 ultra-thin films under the compressive strain using density functional theory plus U (DFT + U). We find that oxygen vacancies can be easily formed in the Ni layers with the NiO 2 terminated surface (0.5 u.c. and 1.5 u.c. thickness) compared to the structures with the LaO terminated surface and the in-plane vacancy is energetically favored than the out-of-plane vacancy. When two vacancy sites are allowed, the Ni square plane geometry is energetically more stable in most cases as two oxygen vacancies tend to stay near a Ni ion. Strong anisotropy between the in-plane and out-of-plane vacancy formation as well as the layer and orbital dependent electronic structure occur due to strain, surface termination, charge reconstruction, and quantum confinement effects. The in-plane vacancy of the NiO 2 terminated structure is favored since the released charge due to the oxygen vacancy can be easily accommodated in the d x 2 -y 2 orbital, which is less occupied than the d z 2 orbital. Remarkably, the oxygen vacancy structure containing the Ni square-plane geometry becomes an insulating state in DFT + U with a sizable band gap of 1.2 eV because the large crystal field splitting between d z 2 and d x 2 -y 2 orbitals in the square-plane favors an insulating state and the Mott insulating state is induced in other Ni sites due to strong electronic correlations. In the thin-film structure without oxygen vacancies, the strong correlation effect in DFT + U drives a pseudogap ground state at the Fermi energy, similarly as the experimental photo-emission spectra; however, the variation of the DFT + U electronic structure depending on the surface termination becomes weaker compared to those obtained in DFT.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS2013

RESOLVE OVEN Field Demonstration Unit for Lunar Resource Extraction

The Oxygen and Volatile Extraction Node (OVEN) is a subsystem within the Regolith & Environment Science and Oxygen & Lunar Volatile Extraction (RESOLVE) project. The purpose of the OVEN subsystem is to release volatiles from lunar regolith and extract oxygen by means of a hydrogen reduction reaction. The complete process includes receiving, weighing, sealing, heating, and disposing of core sample segments while transferring all gaseous contents to the Lunar Advanced Volatile Analysis (LAVA) subsystem. This document will discuss the design and performance of the OVEN Field Demonstration Unit (FDU), which participated in the 2012 RESOLVE field demonstration.

Paz, Aaron↗

DOE OSTI2024

Assessing root–soil interactions in wetland plants: root exudation and radial oxygen loss

Abstract. Plant rhizosphere processes, such as root exudation and root oxygen loss (ROL), could have significant impacts on the dynamics and magnitude of wetland methane fluxes and other biogeochemical processes but are rarely measured directly. Here, we measure root exudation and ROL from Schoenoplectus americanus and Spartina patens, two plants that have had opposite relationships between biomass and methane flux in field experiments (positive in S. patens, negative in S. americanus). We found contrasting rates of ROL in the two species, with S. americanus releasing orders of magnitude more oxygen (O2) to the soil than S. patens. At the same time, S. patens exuded high amounts of carbon to the soil, and much of the rhizosphere carbon pool was reduced compared to exudates from other wetland species. This work suggests that the relative inputs of O2 and carbon to the rhizosphere vary significantly between wetland plant species, potentially with major consequences on biogeochemical cycling, and highlights the importance of understanding how plant rhizosphere processes mediate soil biogeochemistry at a community level. As global change drivers continue to affect wetlands, future research should consider how feedbacks from plant rhizosphere processes may exacerbate or mitigate coastal wetland methane emissions.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1995

Internal and surface phenomena in metal combustion

Combustion of metals has been widely studied in the past, primarily because of their high oxidation enthalpies. A general understanding of metal combustion has been developed based on the recognition of the existence of both vapor-phase and surface reactions and involvement of the reaction products in the ensuing heterogeneous combustion. However, distinct features often observed in metal particle combustion, such as brightness oscillations and jumps (spearpoints), disruptive burning, and non-symmetric flames are not currently understood. Recent metal combustion experiments using uniform high-temperature metal droplets produced by a novel micro-arc technique have indicated that oxygen dissolves in the interior of burning particles of certain metals and that the subsequent transformations of the metal-oxygen solutions into stoichiometric oxides are accompanied with sufficient heat release to cause observed brightness and temperature jumps. Similar oxygen dissolution has been observed in recent experiments on bulk iron combustion but has not been associated with such dramatic effects. This research addresses heterogeneous metal droplet combustion, specifically focusing on oxygen penetration into the burning metal droplets, and its influence on the metal combustion rate, temperature history, and disruptive burning. A unique feature of the experimental approach is the combination of the microgravity environment with a novel micro-arc Generator of Monodispersed Metal Droplets (GEMMED), ensuring repeatable formation and ignition of uniform metal droplets with controllable initial temperature and velocity. The droplet initial temperatures can be adjusted within a wide range from just above the metal melting point, which provides means to ignite droplets instantly upon entering an oxygen containing environment. Initial droplet velocity will be set equal to zero allowing one to organize metal combustion microgravity experiments in a fashion similar to usual microgravity liquid fuel droplet combustion studies. In addition, the internal compositions of rapidly quenched metal particles will be analyzed using SEM technique. Such compositions are similar to those existing during the combustion and provide new insight on metal combustion processes. The results of this experimental work will be used to model the fundamental mechanisms of metal combustion. Preliminary experimental results on Al and Zr particle combustion at normal gravity are discussed here.

Dreizin, Edward L.↗