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From Oxygen Generation to Metals Production: In Situ Resource Utilization by Molten Oxide Electrolysis

For the exploration of other bodies in the solar system, electrochemical processing is arguably the most versatile technology for conversion of local resources into usable commodities: by electrolysis one can, in principle, produce (1) breathable oxygen, (2) silicon for the fabrication of solar cells, (3) various reactive metals for use as electrodes in advanced storage batteries, and (4) structural metals such as steel and aluminum. Even so, to date there has been no sustained effort to develop such processes, in part due to the inadequacy of the database. The objective here is to identify chemistries capable of sustaining molten oxide electrolysis in the cited applications and to examine the behavior of laboratory-scale cells designed to generate oxygen and to produce metal. The basic research includes the study of the underlying high-temperature physical chemistry of oxide melts representative of lunar regolith and of Martian soil. To move beyond empirical approaches to process development, the thermodynamic and transport properties of oxide melts are being studied to help set the limits of composition and temperature for the processing trials conducted in laboratory-scale electrolysis cells. The goal of this investigation is to deliver a working prototype cell that can use lunar regolith and Martian soil to produce breathable oxygen along with metal by-product. Additionally, the process can be generalized to permit adaptation to accommodate different feedstock chemistries, such as those that will be encountered on other bodies in the solar system. The expected results of this research include: (1) the identification of appropriate electrolyte chemistries; (2) the selection of candidate anode and cathode materials compatible with electrolytes named above; and (3) performance data from a laboratory-scale cell producing oxygen and metal. On the strength of these results it should be possible to assess the technical viability of molten oxide electrolysis for in situ resource utilization on the Moon and Mars. In parallel, there may be commercial applications here on earth, such as new green technologies for metals extraction and for treatment of hazardous waste, e.g., fixing heavy metals.

Khetpal, Deepak↗

Light and Gravity Effects on Circadian Rhythms of Rhesus Macaques

Temporal integration of a biological organism's physiological, behavioral and biochemical systems depends upon its circadian timing system. The endogenous period of this timing system is typically synchronized to the 24- hour day by environmental cues. The daily alternation of light and dark has long been known as one of the most potent environmental synchronizers influencing the circadian timing system. Alterations in the lighting environment (length or intensity of light exposure) can also affect the homeostatic state of the organism. A series of experiments was performed using rhesus monkeys with the objective of defining the fundamental properties of the circadian rhythm of body temperature. Three major experiments were performed in addition to several preliminary studies. These experiments explored 1.) the response of the rhesus body temperature rhythm to varying day length and light intensity; 2.) the response of the body temperature rhythm to light exposure as a function of time of day; and 3.) the characteristics of the metabolic heat production rhythm which is responsible for the daily cycle in body temperature. Results of these three completed experiments will be reported here. In addition, preliminary experiments were also performed in social entrainment of rhesus circadian rhythms and the properties of rhesus body temperature rhythms in constant conditions, where no external time cues were provided. Four adult male rhesus monkeys served as subjects in all experiments. All experiments were performed at the California Regional Primate Research Center. Each animal was implanted with a biotelemetry unit that measured deep body temperature. All surgeries were performed by a board certified veterinary surgeon under sterile conditions. The biotelemetry implants also provided an index of activity level in each animal. For metabolic heat production measurements, oxygen consumption and carbon dioxide production were measured and the caloric equivalent of these was calculated. Specific methodologies are described in detail.

Fuller, Charles↗

Mars Atmospheric In Situ Resource Utilization Projects at the Kennedy Space Center

The atmosphere of Mars, which is 96 percent carbon dioxide (CO2), is a rich resource for the human exploration of the red planet, primarily by the production of rocket propellants and oxygen for life support. Three recent projects led by NASAs Kennedy Space Center have been investigating the processing of CO2. The first project successfully demonstrated the Mars Atmospheric Processing Module (APM), which freezes CO2 with cryocoolers and combines sublimated CO2 with hydrogen to make methane and water. The second project absorbs CO2 with Ionic Liquids and electrolyzes it with water to make methane and oxygen, but with limited success so far. A third project plans to recover up to 100 of the oxygen in spacecraft respiratory CO2. A combination of the Reverse Water Gas Shift reaction and the Boudouard reaction eventually fill the reactor up with carbon, stopping the process. A system to continuously remove and collect carbon has been tested with encouraging results.

oxygen production and recovery↗

Characterization of Spirulina biomass for CELSS diet potential

Cyanobacteria, Spirulina maxima as a biogenerative photosynthetic and an edible alga for the space craft crew in a CELSS, was evaluated in an effort to increase the growth rate, biomass, yield, and chemical analysis in continuous cultures. The cell characteristics were determined for cultures maintained at steady state with respect to the substrate concentration. The productivity increased in experiments exposed to low light (30 uE m(exp -2)s(exp -1). Oxygen evolved and protein production were higher in cultures exposed to low light intensity. There was a relationship between nitrate concentration and the yield of the culture. Increasing the concentration of nitrate in the growth medium up to 20 mM was enough to produce a culture having the same chemical composition as that of complete medium. High light was inhibiting the yield of the culture. Increasing the concentration of phosphate beyond 1 mM did not improve the yield of the culture. Increasing the concentration of sodium chloride in the growth medium did not affect the growth of the alga up to 0.1 M but beyond that the culture started to be stressed. The response to stress appeared in high production of total carbohydrate on the expense of protein production. The oxygen production was also higher in cultures stressed with sodium chloride.

Tadros, Mahasin G.↗

Plants for water recycling, oxygen regeneration and food production

During long-duration space missions that require recycling and regeneration of life support materials the major human wastes to be converted to usable forms are CO2, hygiene water, urine and feces. A Controlled Ecological Life Support System (CELSS) relies on the air revitalization, water purification and food production capabilities of higher plants to rejuvenate human wastes and replenish the life support materials. The key processes in such a system are photosynthesis, whereby green plants utilize light energy to produce food and oxygen while removing CO2 from the atmosphere, and transpiration, the evaporation of water from the plant. CELSS research has emphasized the food production capacity and efforts to minimize the area/volume of higher plants required to satisfy all human life support needs. Plants are a dynamic system capable of being manipulated to favour the supply of individual products as desired. The size and energy required for a CELSS that provides virtually all human needs are determined by the food production capacity. Growing conditions maximizing food production do not maximize transpiration of water; conditions favoring transpiration and scaling to recycle only water significantly reduces the area, volume, and energy inputs per person. Likewise, system size can be adjusted to satisfy the air regeneration needs. Requirements of a waste management system supplying inputs to maintain maximum plant productivity are clear. The ability of plants to play an active role in waste processing and the consequence in terms of degraded plant performance are not well characterized. Plant-based life support systems represent the only potential for self sufficiency and food production in an extra-terrestrial habitat.

NASA Discipline Life Support Systems↗

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these "oxygenated" compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing

Mansell, J. Matthew↗

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these oxygenated compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing.

Mansell, J. Matthew↗

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Narayan, Sri↗

An Overview of Recent Cryogenic Fluid Management Developments

Long-term storage, supply, and transfer of cryogenic fluids are critical capabilities needed to advance the human exploration of space. Technologies and advanced development programs have been pursued to address issues likely to confront the designers and developers of future cryogenic fluid management (CFM) subsystems and propulsion systems. NASA and aerospace industries have continued to conduct research and development for the propulsion applications of cryogenic fluids. From the well known in-space applications, to new applications involving superconducting motors within multiple different aircraft, and a renewed interest in production of oxygen on Mars, NASA continues to probe cryogenic applications within propulsion. This article presents brief reviews of several of the current CFM efforts to support future space missions. NASA GRC is currently focusing on understanding some of the finer points in the application of multilayer insulation. GRC recently finished the activation of a new calorimeter that operates at 20 K with a warm boundary that can operate either around 90 K or at 300 K. Current testing is focused on investigating multiple different seam concepts, initially between temperatures of 300 K and 20 K, and between 20 K and 90 K. One of the larger recent NASA investments has been on the Structural Heat Intercept, Insulation, and Vibration Experiment Rig (SHIIVER). SHIIVER is a 4 m diameter tank that is approximately 1/2 scale of the planned upper stage of the new Space Launch System (SLS) rocket. SHIIVER is focused on demonstrating the thermal benefits of multilayer insulation on the tank domes and boil-off vapor cooling on structural cylinders that hold the tank in-line on the rocket. It will also quantify any damage that may incur during the acoustic environment of over 160 decibels that SLS will experience on its trip to Earth orbit. In support of the possible production of oxygen out of the Mars' atmosphere, a team comprised of four NASA centers (GRC, MSFC, JSC, and KSC) collaborated to investigate multiple different hardware combinations, refrigeration cycles, and integration techniques to minimize power and mass of the storage and liquefaction system. Moreover, high efficiency, high capacity cryocoolers are an element of CFM which is essential for achieving NASA's future long duration missions. Currently in development is a 20W at 20K unit for use with liquid hydrogen. It is scheduled for delivery to NASA in the summer of 2017. Two Phase I SBIRS have recently concluded resulting in the preliminary design of two different 90K units, each having a refrigeration capacity of approximately 150W. Once the development efforts are complete, these high capacity 90K units will be integrated into the design of NASA's Liquid Oxygen (LOX)/Methane applications such as the Lander and Ascent Vehicles, or possibly an in-space stage. CFM technology is critical to the success of missions to Mars, Planetary Exploration, and In-Situ Resource Utilization (ISRU) for cryogenic propellant production. NASA is focusing on the development of CFM technologies needed to provide necessary data and relevant experience to support informed decisions on implementation of design of cryogenic systems for long term space missions. Lessons learned from the described CFM developments would lead to enhanced safety and reliability and enabling technologies which could allow NASA to meet future space exploration goals.

Hedayat, A.↗

Carbon monoxide production in low energy oxygen ion bombardment of pyrolytic graphite and Kapton surfaces

The results of an investigtion of the interaction of low energy oxygen ions with pyrolytic graphite and Kapton surface are reported. CO molecules emitted from the surface as a result of the ion bombardment were detected by a mass spectrometer. Because the ion-induced signals were small compared to that arising from the CO background pressure in the vacuum system, the ion beam was modulated and the modulated component of the CO signal measured with a lock-in amplifier. The quantum yield (CO molecules emitted per incident oxygen ion) for graphite rose from 1.9 at 4.5 eV ion energy to 6.6 at 465 eV. Comparable yields were obtained for Kapton. The large size of the yields suggests contributions to the reaction process from the background O2 molecules in the vacuum system.

Horton, C. C.↗

Production of pulsed atomic oxygen beams via laser vaporization methods

Energetic pulsed atomic oxygen beams were generated by laser-driven evaporation of cryogenically frozen ozone/oxygen films and thin films of indium-tin oxide (ITO). Mass and energy characterization of beams from the ozone/oxygen films were carried out by mass spectrometry. The peak flux, found to occur at 10 eV, is estimated from this data to be 3 x 10(20) m(-2) s(-1). Analysis of the time-of-flight data indicates a number of processes contribute to the formation of the atomic oxygen beam. The absence of metastable states such as the 2p(3) 3s(1) (5S) level of atomic oxygen blown off from ITO films is supported by the failure to observe emission at 777.3 nm from the 2p(3) 3p(1) (5P sub J) levels. Reactive scattering experiments with polymer film targets for atomic oxygen bombardment are planned using a universal crossed molecular beam apparatus.

Brinza, David E.↗

Production of pulsed atomic oxygen beams via laser vaporization methods

The generation of energetic pulsed atomic oxygen beams by laser-driven evaporation of cryogenically frozen ozone/oxygen films and thin indium-tin oxide (ITO) films is reported. Mass spectroscopy is used in the mass and energy characterization of beams from the ozone/oxygen films, and a peak flux of 3 x 10 to the 20th/sq m per sec at 10 eV is found. Analysis of the time-of-flight data suggests that several processes contribute to the formation of the oxygen beam. Results show the absence of metastable states such as the 2p(3)3s(1)(5S) level of atomic oxygen blown-off from the ITO films. The present process has application to the study of the oxygen degradation problem of LEO materials.

Brinza, David E.↗

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate-solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Hung, Ching-Cheh↗

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a percursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Hung, Ching-Chen↗

Process for Producing Metal Compounds from Graphite Oxide

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Hung, Ching-Cheh↗

Process for Producing Metal Compounds From Graphite Oxide

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be fiber processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Ching-Cheh Hung↗