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NASA NTRSDate not supplied

Novel Aprotic Heterocyclic Anion-based Ionic Liquids for Carbon Dioxide Capture

Ionic liquids (ILs), or organic salts with melting points at or below room temperature are an incredibly versatile class of materials with many possible applications for NASA’s exploration needs. In particular, appropriately designed ILs can have a high affinity for absorbing carbon dioxide, making them excellent candidates for use as liquid sorbents in cabin air revitalization systems. Unfortunately, many of these ILs have high viscosity, which is only exacerbated by carbon dioxide uptake. High viscosity limits the rate of carbon dioxide uptake. A new class of IL sorbent containing aprotic heterocyclic anions (AHA) has been shown to offer excellent carbon dioxide uptake without a corresponding increase in viscosity. However, there is a paucity of sorption data for these AHA ILs at low partial pressures of carbon dioxide. This paper reports on the characterization of sorption behavior for AHA ILs previously reported in the literature at low concentrations of carbon dioxide and the synthesis and characterization of new, water miscible AHA ILs. Characterization of the new ILs includes measurement of density, viscosity, thermal stability, carbon dioxide capacity, carbon dioxide absorption kinetics, and water-IL vapor liquid equilibrium. Overall, these news ILs are promising alternatives to many of the commonly used IL sorbents.

Eric Townsend Fox↗

NASA NTRS1999

Peroxide-modified titanium dioxide: a chemical analog of putative Martian soil oxidants

Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

Review↗

NASA NTRS1966

Stabilization of Tungsten-Uranium Dioxide Composites Under Thermal Cycling Conditions

Uranium losses during thermal cycling of tungsten - uranium dioxide composites to 2500° C in flowing purified hydrogen for specimens initially containing 35 volume percent uranium dioxide were reduced by the use of thorium dioxide, calcium oxide, or yttrium oxide as additives in solid solution with the uranium dioxide. The effectiveness of the additives decreased in the order yttrium oxide, calcium oxide, and thorium dioxide. Stabilization of uranium dioxide by calcium oxide or yttrium oxide can be explained in part on the basis of the introduction of oxygen vacancies into the fluorite lattice and the associated lowered partial molar free energy of oxygen. The difference in the effectiveness of calcium oxide and yttrium oxide is discussed, and a possible explanation of the observed behavior is proposed. Of the concentrations of yttrium oxide tested (i.e., 2. 5, 5, and 10 mole percent), 10 mole percent of yttrium oxide was the most effective in pre venting loss of uranium from composities.

Gluyas, Richard E.↗

NASA NTRS1974

Method and apparatus for stable silicon dioxide layers on silicon grown in silicon nitride ambient

A method and apparatus for thermally growing stable silicon dioxide layers on silicon is disclosed. A previously etched and baked silicon nitride tube placed in a furnace is used to grow the silicon dioxide. First, pure oxygen is allowed to flow through the tube to initially coat the inside surface of the tube with a thin layer of silicon dioxide. After the tube is coated with the thin layer of silicon dioxide, the silicon is oxidized thermally in a normal fashion. If the tube becomes contaminated, the silicon dioxide is etched off thereby exposing clean silicon nitride and then the inside of the tube is recoated with silicon dioxide. As is disclosed, the silicon nitride tube can also be used as the ambient for the pyrolytic decomposition of silane and ammonia to form thin layers of clean silicon nitride.

Cohen, R. A.↗

NASA NTRS2009

Carbon Dioxide - Our Common "Enemy"

Health effects of brief and prolonged exposure to carbon dioxide continue to be a concern for those of us who manage this pollutant in closed volumes, such as in spacecraft and submarines. In both examples, considerable resources are required to scrub the atmosphere to levels that are considered totally safe for maintenance of crew health and performance. Defining safe levels is not a simple task because of many confounding factors, including: lack of a robust database on human exposures, suspected significant variations in individual susceptibility, variations in the endpoints used to assess potentially adverse effects, the added effects of stress, and the fluid shifts associated with micro-gravity (astronauts only). In 2007 the National Research Council proposed revised Continuous Exposure Guidelines (CEGLs) and Emergency Exposure Guidelines (EEGLs) to the U.S. Navy. Similarly, in 2008 the NASA Toxicology Group, in cooperation with another subcommittee of the National Research Council, revised Spacecraft Maximum Allowable Concentrations (SMACs). In addition, a 1000-day exposure limit was set for long-duration spaceflights to celestial bodies. Herein we examine the rationale for the levels proposed to the U.S. Navy and compare this rationale with the one used by NASA to set its limits. We include a critical review of previous studies on the effects of exposure to carbon dioxide and attempt to dissect out the challenges associated with setting fully-defensible limits. We also describe recent experiences with management of carbon dioxide aboard the International Space Station with 13 persons aboard. This includes the tandem operations of the Russian Vozduk and the U.S. Carbon Dioxide Removal System. A third removal system is present while the station is docked to the Shuttle spacecraft, so our experience includes the lithium hydroxide system aboard Shuttle for the removal of carbon dioxide. We discuss strategies for highly-efficient, regenerable removal of carbon dioxide that could meet the 1000-day SMAC of 0.5%, which would apply to long-duration voyages to Mars.

James, John T.↗

NASA NTRS2017

Triple-Pulse Integrated Path Differential Absorption Lidar for Carbon Dioxide Measurement - Novel Lidar Technologies and Techniques with Path to Space

The societal benefits of understanding climate change through identification of global carbon dioxide sources and sinks led to the desired NASA's active sensing of carbon dioxide emissions over nights, days, and seasons (ASCENDS) space-based missions of global carbon dioxide measurements. For more than 15 years, NASA Langley Research Center (LaRC) have developed several carbon dioxide active remote sensors using the differential absorption lidar (DIAL) technique operating at the two-micron wavelength. Currently, an airborne two-micron triple-pulse integrated path differential absorption (IPDA) lidar is under development. This IPDA lidar measures carbon dioxide as well as water vapor, the dominant interfering molecule on carbon dioxide remote sensing. Advancement of this triple-pulse IPDA lidar development is presented.

Singh, Upendra N.↗

NASA NTRSDate not supplied

Comparison of Alternative Configurations of an Integrated Open-Loop Carbon Dioxide Removal System using Liquid Amine

Several carbon dioxide removal systems are being investigated for applications in microgravity. The liquid amine wedge system utilizes the capillary action of liquids to prevent the mixing of the air and liquid while still allowing for carbon dioxide capture at their interface. A one crew mission requires approximately 1 kg per day of carbon dioxide removal to prevent adverse health effects. A proposed design of a wedge tray system can be improved from the initial testing parameters to achieve the required carbon dioxide capture for one crew. The wedge trays in the contactor can be organized in either a parallel configuration to accumulate less CO2 in the liquid but at a higher flow rate or a series configuration to yield a higher weight percentage of CO2 in the liquid but at a lower flow rate. The gas flow rate and composition were held constant at 26scfm and 2600ppm, respectively, due to constraints of other proposed systems but the liquid flow rate was adjusted between 0.1mL/min and 10mL/min. The flow rate that yielded the best carbon dioxide capture was X mL/min and Y mL/min for the parallel and series configurations, respectively. The degasser temperature and pressure were varied from 80 to 100°C and 0 and -3 inHg. The largest carbon dioxide flux of Z kg/day/m2 was observed at a contactor liquid flow rate of X mL/min and a degasser temperature and pressure of T°C and P inHg.

Adrian Cortez↗

NASA NTRS2016

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Oxygen recovery↗

NASA NTRS2016

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon, is capable of recovering all the oxygen from carbon dioxide, and it is a promising alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon, and the resulting carbon buildup eventually fouls the catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

ECLSS↗

NASA NTRS2016

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50 because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Oxygen Recovery↗

NASA NTRS1964

Fuel Retention Improvement at High Temperatures in Tungsten-Uranium Dioxide Dispersion Fuel Elements by Plasma-Spray Cladding

An investigation was undertaken to determine the feasibility of depositing integrally bonded plasma-sprayed tungsten coatings onto 80-volume-percent tungsten - 20-volume-percent uranium dioxide composites. These composites were face clad with thin tungsten foil to inhibit uranium dioxide loss at elevated temperatures, but loss at the unclad edges was still significant. By preheating the composite substrates to approximately 3700 degrees F in a nitrogen environment, metallurgically bonded tungsten coatings could be obtained directly by plasma spraying. Furthermore, even though these coatings were thin and somewhat porous, they greatly inhibited the loss of uranium dioxide. For example, a specimen that was face clad but had no edge cladding lost 5.8 percent uranium dioxide after 2 hours at 4750 dgrees F in flowing hydrogen. A similar specimen with plasma-spray-coated edges, however, lost only 0.75 percent uranium dioxide under the same testing conditions.

Grisaffe, Salvatore J.↗

NASA NTRS1973

The control of carbon dioxide cryodeposits

An experimental study has been conducted to investigate the parameters affecting the cryodeposition of carbon dioxide frost. In the investigation carbon dioxide frost was cryodeposited from a helium-carbon dioxide mixture into a layer of fibrous insulation surrounding a cylindrical cryogenic tank. Results of the study indicated that not only did deposition occur on the frost surface but also within the frost layer. Over the range of variables investigated both the frost density and the mass of frost deposited were most sensitive to the time of deposition, the percent of carbon dioxide in the purge-gas mixture, and the thickness of the insulation. Frost density and mass of frost deposition were found to increase with time and percent carbon dioxide, and to decrease with increasing insulation thickness.

Sharpe, E. L.↗

NASA NTRS2000

Separation of Carbon Monoxide and Carbon Dioxide for Mars ISRU-Concepts

Solid oxide electrolyzers, such as electrolysis cells utilizing yttria-stabilized zirconia, can produce oxygen from Mars atmospheric carbon dioxide and reject carbon monoxide and unreacted carbon dioxide in a separate stream. The oxygen-production process has been shown to be far more efficient if the high-pressure, unreacted carbon dioxide can be separated and recycled back into the feed stream. Additionally, the mass of the adsorption compressor can be reduced. Also, the carbon monoxide by-product is a valuable fuel for space exploration and habitation, with applications from fuel cells to production of hydrocarbons and plastics. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU. Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, respectively. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU, Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, Research needs for the design shown are as follows: (1) The best adsorbent for the process must be determined. (2) Adsorption isotherms must be measured, both for pure components and mixtures. (3) Mathematical modeling must be performed to provide a solid framework for design. (4) The separation system must be constructed and tested. (5) System integration must be studied.

LeVan, M. Douglas↗

NASA NTRSDate not supplied

Design for an Integrated Open-Loop System for Carbon Dioxide Removal using Liquid Amine

Manned Space missions require maintaining a safe environment for the crew that can both sustain a breathable atmosphere and remove pollutants. Carbon dioxide, while not toxic in low concentrations, accumulates as crew members work and breath and can eventually affect the crew’s health. Therefore, a constant, passive system to remove the carbon dioxide build up is necessary for long-term missions. Currently, the prevailing liquid sorbent used in submarines and industrial flue gas utilizes the primary amine, monoethanolamine (MEA), to capture, transfer, and remove carbon dioxide from air. Diglycolamine (DGA) is an alternate primary amine that has similar performance and less volatility. It is currently being studied at Ames Research Center (ARC) and is the primary candidate for the operation of the sub-scale liquid amine test stand. The test stand is used to investigate liquid flow and liquid gas interfaces to assist in a system design for microgravity applications. The test stand includes a wedge design utilizes capillary action to hold the liquid while allowing gas-liquid interaction for carbon dioxide transfer. These wedge trays are placed in a contactor unit to remove carbon dioxide from the air stream, a degasser unit to replenish the liquid amine, and a capillary condensing heat exchanger (CCHX) to recapture water lost in the degasser unit. Nominal operating conditions for the contactor are a gas flow rate of 26scfm enriched with pure CO2 to 2600ppm and a liquid mixture of 65/35 vol% DGA/H2O at 0.65mL/min while the degasser was operated at 100°C and 1 atm. This paper discusses the challenges and limitations of a fully integrated system which will influence the design of a new subscale test stand.

Adrian Cortez↗

NASA NTRS1999

A tenuous carbon dioxide atmosphere on Jupiter's moon Callisto

An off-limb scan of Callisto was conducted by the Galileo near-infrared mapping spectrometer to search for a carbon dioxide atmosphere. Airglow in the carbon dioxide nu3 band was observed up to 100 kilometers above the surface and indicates the presence of a tenuous carbon dioxide atmosphere with surface pressure of 7.5 x 10(-12) bar and a temperature of about 150 kelvin, close to the surface temperature. A lifetime on the order of 4 years is suggested, based on photoionization and magnetospheric sweeping. Either the atmosphere is transient and was formed recently or some process is currently supplying carbon dioxide to the atmosphere.

unmanned↗

NASA NTRS2016

Game Changing Development Program - Next Generation Life Support Project: Oxygen Recovery From Carbon Dioxide Using Ion Exchange Membrane Electrolysis Technology

This report summarizes the Phase I research and development work performed during the March 13, 2015 to July 13, 2016 period. The proposal for this work was submitted in response to NASA Research Announcement NNH14ZOA001N, "Space Technology Research, Development, Demonstration, and Infusion 2014 (SpaceTech-REDDI-2014)," Appendix 14GCD-C2 "Game Changing Development Program, Advanced Oxygen Recovery for Spacecraft Life Support Systems Appendix" The Task Agreement for this Phase I work is Document Control Number: GCDP-02-TA-15015. The objective of the Phase I project was to demonstrate in laboratories two Engineering Development Units (EDU) that perform critical functions of the low temperature carbon dioxide electrolysis and the catalytic conversion of carbon monoxide into carbon and carbon dioxide. The low temperature carbon dioxide electrolysis EDU was built by the University of Delaware with Dr. Feng Jiao as the principal investigator in charge of this EDU development (under NASA Contract NNC15CA04C). The carbon monoxide catalytic conversion EDU was built by the NASA Glenn Research Center with Kenneth Burke as the principal investigator and overall project leader for the development of both EDUs. Both EDUs were successfully developed and demonstrated the critical functions for each process. The carbon dioxide electrolysis EDU was delivered to the NASA Johnson Space Center and the carbon monoxide catalytic conversion EDU was delivered to the NASA Marshall Spaceflight Center.

Oxygen Recovery↗

NASA NTRSDate not supplied

Improving the Recovery of Oxygen from Carbon Dioxide

Long duration human exploration missions far from Earth will need to recycle life support consumables for missions to be affordable. The state-of-the-art for atmosphere revitalization is not closed. Although the Sabatier Carbon Dioxide Reduction Assembly (CRA) on the International Space Station has the capability for full closure, there is insufficient metabolic hydrogen available from the Oxygen Generation System to recover more than about 47% of oxygen from carbon dioxide. Methane is produced as a byproduct, which consumes hydrogen that would otherwise be available to reduce additional carbon dioxide. Several strategies are available to increase the fraction of oxygen recovered. One is to pyrolyze methane to recover the lost hydrogen. Others are to replace the Sabatier with a new processor that is more efficient. Candidates include Bosch, Carbon Dioxide Electrolysis and Co-Electrolysis, and electrochemical reactors. The National Aeronautics and Space Administration (NASA) has recently made investments in several of these technologies which will be described in this presentation.

Carbon dioxide reduction↗

NASA NTRSDate not supplied

Nonlinear Plant Responses to Carbon Dioxide and Climate Diminish Water Availability

Water availability for people and its future with global warming is intimately tied to uncertain interactions between the biogeophysical and biogeochemical land responses to enhanced atmospheric carbon dioxide. In particular, research has centered on the question of whether (and by how much) plants will mediate projections of enhanced aridity and drought expected with atmospheric warming. Using an idealized set of Earth System Model (ESM) experiments that decouple the radiative and biogeochemical responses to increased carbon dioxide, we show that ecosystem water use nonlinearly increases across most of the globe under forcing, in spite of increased water use efficiencies attributable to physiological responses to plants. Enhanced ecosystem water consumption is associated with decreased runoff efficiency and soil moisture declines and emerges from nonlinear interactions between the radiative and biogeochemical response of the land surface to increased atmospheric carbon dioxide concentrations, which preferences the partitioning of precipitation to plants, irrespective of precipitation changes. Increased partitioning to runoff is associated with precipitation changes that outpace canopy interception changes. Crucially, our results suggest that within the models, warming and carbon dioxide nonlinearly interact to make plants consume more water rather than save it, with implications for responsible interpretation of drought risks under forcing.

water availability↗