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At least 991 records · Page 55

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

Abstract We report a supramolecular strategy for promoting the selective reduction of O 2 for direct electrosynthesis of H 2 O 2 . We utilized cobalt tetraphenylporphyrin (Co‐TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co‐PB‐1(6) bearing six Co‐TPP subunits connected through twenty‐four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co‐rPB‐1(6). Both Co‐PB‐1(6) and Co‐rPB‐1(6) cages produce 90–100 % H 2 O 2 from electrochemical ORR catalysis in neutral pH water, whereas the Co‐TPP monomer gives a 50 % mixture of H 2 O 2 and H 2 O. Bimolecular pathways have been implicated in facilitating H 2 O formation, therefore, we attribute this high H 2 O 2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.

Smith, Peter T.↗

Advanced solar-propelled cargo spacecraft for Mars missions

At the University of Washington, three concepts for an unmanned, solar powered, cargo spacecraft for Mars-support missions have been investigated. These spacecraft are designed to carry a 50,000 kg payload from a low Earth orbit to a low Mars orbit. Each design uses a distinctly different propulsion system: a solar radiation absorption (SRA) system, a solar-pumped laser (SPL) system, and a solar powered mangetoplasmadynamic (MPD) arc system. The SRA directly converts solar energy to thermal energy in the propellant through a novel process developed at the University of Washington. A solar concentrator focuses sunlight into an absorption chamber. A mixture of hydrogen and potassium vapor absorbs the incident radiation and is heated to approximately 3700 K. The hot propellant gas exhausts through a nozzle to produce thrust. The SRA has an I(sub sp) of approximately 1000 sec and produces a thrust of 2940 N using two thrust chambers. In the SPL system, a pair of solar-pumped, multi-megawatt, CO2 lasers in sun-synchronous Earth orbit converts solar energy to laser energy. The laser beams are transmitted to the spacecraft via laser relay satellites. The laser energy heats the hydrogen propellant through a plasma breakdown process in the center of an absorption chamber. Propellant flowing through the chamber, heated by the plasma core, expands through a nozzle to produce thrust. The SPL has an I(sub sp) of 1285 sec and produces a thrust of 1200 N using two thrust chambers. The MPD system uses indium phosphide solar cells to convert sunlight to electricity, which powers the propulsion system. In this system, the argon propellant is ionized and electromagnetically accelerated by a magnetoplasmadynamic arc to produce thrust. The MPD spacecraft has an I(sub sp) of 2490 sec and produces a thrust of 100 N. Various orbital transfer options are examined for these concepts. In the SRA system, the mother ship transfers the payload into a very high Earth orbit and a small auxiliary propulsion system boosts the payload into a Hohmann transfer to Mars. The SPL spacecraft releases the payload as the spacecraft passes by Mars. Both the SRA-powered spacecraft and the SPL-powered spacecraft return to Earth for subsequent missions. The MPD-propelled spacecraft, however, remains at Mars as an orbiting space station. A patched conic approximation was used to determine a heliocentric interplanetary transfer orbit for the MPD propelled spacecraft. All three solar-powered spacecraft use an aerobrake procedure to place the payload into a low Mars parking orbit. The payload delivery times range from 160 days to 873 days (2.39 years).

Auziasdeturenne, J.↗

Separation and Conditioning of Mars Atmospheric Gases via TSA

Space and planetary exploration almost always presents interesting and unusual engineering challenges. Separations engineering for chemical processes that are critical to humans working in space is no exception. The challenges are becoming clearer as we make the transition from concepts and planning to hardware development, and as we understand better the constraints and environments in which the processes must perform. The coming decade will see a robotic Mars exploration program that has recovered from recent setbacks and is building a knowledge and technology base for human exploration. One of the missions will carry a small chemical pilot plant for demonstrating the manufacture of rocket propellants and life support consumables from the low-pressure (0.01 atm) Martian atmosphere. By manufacturing and storing the fuel and consumables needed for human-return missions in situ, launch mass and landed mass are reduced by tons and missions become far less expensive. The front-end to the pilot plant is a solid-state atmosphere acquisition and separation unit based on temperature-swing adsorption (TSA). The unit produces purified and pressurized (to 1.0 atm) carbon dioxide to downstream reactors that will make methane and oxygen. The unit also produces a nitrogen-argon mixture as a valuable by-product for life support, inflatable structures, and propellant pressurization. With nighttime temperatures falling to -100 degrees C, power availability restricted to a few watts, and flawless operation critical to success, the dusty Martian surface is a difficult place to operate a remote plant. This talk will focus on how this TSA separation process is designed and implemented for this application, and how it might be used in the more distant future for human exploration.

Finn, John E.↗

Combustion Module 1: Spacelab Racks Integrated at the Lewis Research Center for the First Time

The Combustion Module-1 (CM-1), NASA's largest (over 1800 lb) and one of the most sophisticated combustion experiments ever to fly on the Spacelab, will be carried on the first Microgravity Science Laboratory (MSL-1) mission aboard the space shuttle flight STS-84 in April 1997. The CM-1 project is a stepping stone to the space station era, because the hardware can support multiple investigators on the same mission and can be integrated at user locations and shipped to the launch site. CM-1 is being developed to accommodate microgravity combustion experiments that are designed to help explain and predict the behavior of combustion processes. Although the two principal investigators for CM-1 are both studying combustion processes, their investigations are quite different. Professor Paul D. Ronney of the University of Southern California will examine the Structures of Flame Balls at Low Lewis Numbers (SOFBALL), in which a variety of fuel-lean gaseous mixtures fill the combustion chamber and are ignited. Professor Gerard M. Faeth of the University of Michigan will investigate Laminar Soot Processes (LSP) by studying the key properties of burning gas jets of fuel, employing different fuels and nozzle sizes.

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Airborne Lightning Observatory for FEGS and TGFs (ALOFT)

The ALOFT campaign is a unique suborbital campaign to advance the science of highenergy radiation emissions from thunderstorms, validate existing spaceborne lightning mappers and evaluate design concepts for next-generation mappers, and study convection from a suborbital platform. ALOFT is a collaboration between NASA, the University of Bergen, and other institutions that will fly the ER-2 aircraft over tropical thunderstorms around the Gulf of Mexico, Central America, and the Caribbean. The payload will consist of lightning detectors, gamma-ray scintillators, and a mixture of passive and/or active microwave sensors. Supporting the flights will be a diverse groundbased network of lightning instruments spread across the region of interest.

Nikolai Ostgaard↗

ECAR-2322 As-Run Thermal Analysis Of The AGC-2 Experiment

The second Advanced Graphite Creep (AGC-2) experiment was designed to irradiate various types of graphite specimens at a temperature of 600°C. The specimens were irradiated in an instrumented leadout capsule experiment in the south flux trap of the ATR during cycles 149A, 1498, 1508, 151A, and 1518. Temperature was monitored using twelve thermocouples located at various elevations in the reactor core, and a helium-argon gas mixture was used for gas gap temperature control of the specimens. The purpose of this analysis is to calculate specimen temperature using measured data on reactor power and helium-argon gas flows, and as-run calculations of heating rates and displacement per atom (DPA) in graphite. The accuracy of the model is assessed by comparing measured and calculated thermocouple temperatures. Uncertainty in gas gaps may preclude an accurate temperature calculation. In these cases, adjustments are made to the thermal model in order to reconcile the measured and calculated thermocouple temperature and to ensure the accuracy of the calculated specimen temperature.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Iodine Sorption on AgZ-PAN

The Department of Energy (DOE) Nuclear Fuel Cycle and Supply Chain Program Material Recovery and Waste Form Development (MRWFD) Campaign Off-gas Sigma Team has performed research and development on iodine control and iodine waste forms for the past several years. This research and development has included iodine adsorption tests using a laboratory-scale test system containing multiple-segmented fixed beds of iodine adsorbents. Iodine capture performance has been tested using (a) non-radioactive synthetic gas mixtures blended from air, nitrogen, NO, NO 2 , water, to simulate dissolver off-gas (DOG) and vessel off-gas (VOG) streams from used nuclear fuel aqueous reprocessing, (b) inorganic and organic iodine species, and (c) different sorbents. An initial test of silver-functionalized mordenite in polyacrylonitrile matrix (AgZ-PAN) was conducted to assess if this sorbent, initially designed for selective sorption of Xe that evolves into used fuel reprocessing off-gas streams, could also be a candidate for iodine sorption. This test was conducted using the same deep-bed test system and methodologies used in many prior iodine sorption tests using other sorbents. Diatomic iodine (I2) was used as the target iodide in a gas stream containing air, NO, NO 2 , and moisture designed to simulate an aqueous reprocessing dissolver off-gas (DOG) stream.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cassette bacteria detection system

The design, fabrication, and testing of an automatic bacteria detection system, with a zero-g capability, based on the filter-capable approach, and intended for monitoring the sterility of regenerated water in spacecraft is discussed. The principle of detection is based on measuring the increase in chemiluminescence produced by the action of bacterial porphyrins on a luminol-hydrogen peroxide mixture. Viable organisms are detected by comparing the signal of an incubated water sample with an unincubated control. High signals for the incubated water sample indicate the presence of viable organisms.

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Solar heating and hot water system installed at Saint Louis, Missouri

The solar heating and hot water system installed at the William Tao & Associates, Inc., office building in St. Louis, Missouri is described, including maintenance and construction problems, final drawings, system requirements, and manufacturer's component data. The solar system was designed to provide 50 percent of the hot water requirements and 45 percent of the space heating needs for a 900 sq ft office space and drafting room. The solar facility has 252 sq ft of glass tube concentrator collectors and a 1000 gallon steel storage tank buried below a concrete slab floor. Freeze protection is provided by a propylene glycol/water mixture in the collector loop. The collectors are roof mounted on a variable tilt array which is adjusted seasonally and is connected to the solar thermal storage tank by a tube-in-shell heat exchanger. Incoming city water is preheated through the solar energy thermal storage tank.

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Methods used to investigate and resolve the Space Shuttle helium pressure regulator instability

The Space Shuttle main propulsion system (MPS) has seven 750-psia regulators used to purge the Space Shuttle main engines to prevent mixture between oxygen and hydrogen and to pneumatically actuate the propellant valves. Methods used to investigate the instability of the MPS regulators which caused a failure of the 750-psia regulator during a test in 1986 are discussed, with special attention given to the analytical tools and the facilities. As a result of this investigation, a well-understood regulator was designed, with excellent stability over a wide range of inlet pressures from 900 to 4500 psia, flow rates from 1 to 2000 scfm, very fast response, minimal overshoot and undershoot, and durable cycle life. Diagrams of the MPS helium system and of a new -0006 fail-safe improved-stability regulator are presented.

Hurlbert, Eric A.↗

Control of Propellant Lead/Lag to the LAE in the AXAF Propulsion System

Control of the rate at which hypergolic propellants are supplied to a rocket engine prior to ignition is critically important. Potentially damaging explosions may result from excessive lead of either propellant into the combustion chamber. Because the injector fill process is governed by the engine as well as the propellant feed system design, proper management of this issue must take both into consideration. This was recognized early in the development of TRW's Advanced Columbium-Liquid Apogee Engine (LAE), which was flight-qualified in 1996 to maneuver the Advanced X-Ray Astrophysics Facility (AXAF) spacecraft into orbit. The LAE runs on hydrazine and nitrogen tetroxide (MON-3) at a nominal mixture ratio of 1.0. This paper describes the comprehensive test program conducted to ensure reliable startup operation of the LAE in the AYAF propulsion system. The most significant factors affecting chamber fuel lead were found to be: (1) engine location, (2) propellant saturation level, (3) amount of undissolved gas in the lines, and (4) off- nominal tank pressures. Hot-fire tests at a chamber fuel lead range over and above that expected for the LAEs in AXAF demonstrated extremely tolerant behavior of the engine. AY-AF is scheduled for launch on NASA's STS-93 in December 1998.

Casillas, A. R.↗

Experimental Study on Flow Condensation of Low Global Warming Potential Refrigerants in a Micro-fin Aluminum Tube

This study investigates the dynamic shifts in refrigerant technologies driven by environmental regulations, particularly emphasizing low global warming potential (GWP). Moreover, there is a rising trend in the adoption of aluminum tubes with internal axial micro-fin structures in heat exchangers to reduce costs. The research focuses on the condensation process within an expanded axial micro-fin aluminum tube with a 5.96 mm fin-tip diameter. Various refrigerants are analyzed, including both single compounds (R-32, R-1234yf, R-1234ze(E)) and zeotropic mixtures (R-454B, R-454C, R-455A). Experimental procedures cover a range of condensation temperatures (35~45 °C), reduced pressures (0.21~0.55), and mass fluxes (150~350 kg/(m² s)), providing crucial data on heat transfer coefficients (HTC) and frictional pressure gradient (FPG). This data is particularly significant for high-glide refrigerants and is instrumental in the design of advanced air conditioning and refrigeration systems aimed at mitigating global warming.

Hu, Yifeng↗

Utilizing Commercial Submersible Mixer Pumps for Sludge Removal in Savannah River Site's Tank 26 - 20289

The Savannah River Site (SRS) Liquid Waste System (LWS) safely manages, stores, treats, and dispositions liquid radioactive waste. The LWS consists of 51 underground waste storage tanks (eight of which are operationally closed and filled with grout), waste evaporators, treatment facilities, and solidification facilities, known as the Defense Waste Processing Facility (DWPF) and Saltstone Production Facility (SPF). One of the waste storage tanks, Tank 26, was placed into service in 1980 as an F Tank Farm (FTF) Evaporator Feed Tank. From 1980 to 2013, Tank 26 received F Canyon receipts and dilute supernate that was then transferred to the 242-16F FTF Evaporator for volume reduction. In 2013, the steam tube bundle failed in the FTF Evaporator, and the decision was made not to repair/resume evaporator operation. During operation of Tank 26, solids built up to a level of 2.03 m in the tank with a volume of 1062.9 kL. Due to the evaporator failure and subsequent shutdown, the solids in Tank 26 were selected to feed Sludge Batch 10, which is collected and prepped prior to being sent to DWPF for final disposition. To accomplish solids removal, Commercial Submersible Mixer Pumps (CSMPs) were selected to slurry the solids in preparation to be sent to Tank 51. Four CSMPs were installed in Tank 26 with each one installed in a separate quadrant of Tank 26. This work would mark the first deployment of CSMPs in an SRS waste tank. The CSMPs were developed in response to operational issues from previous mixing pumps and budgetary constraints. The CSMPs use the concept of modifying commercially available equipment for nuclear waste applications. The CSMPs consist of a 230-horsepower submersible mixing pump (manufactured by GPM, Inc.) joined to a mast fabricated at SRS. For this application, Savannah River Remediation (SRR) design services was challenged to provide a mast design that required no steel superstructure support system on top of Tank 26. Also, SRR design services provided a simplified Tank 26 riser interface that did not require extensive machine parts to adjust height of the suction screen of the CSMP within the tank. Other design improvements include no requirements for tank top radiation monitors and no requirements for flushing of the CSMPs during startup/shutdown operations. The CSMPs were operated at an initial height of 2.29 m above the Tank 26 bottom for 10 days. After sludge sounding, the CSMPs were lowered to a height of 1.52 m with no issues due to proper work planning and the simplified riser interface. With the CSMPs lowered to a level of 1.52 meters above the tank bottom, the CSMPs were operated for 12 days and another sounding was performed. The sounding level came back matching the disturbance depth results of the first pump run. Chemistry samples were analyzed while the tank was left to settle. The analysis revealed enough weight percent solids to provide good feed to Sludge Batch 10. Also, the results revealed the supernate within the mixture would provide good salt solution feed to Salt Waste Processing Facility (SWPF) Salt Batch 3. So, the plan was modified to let the disturbed solids settle and decant the salt solution for addition to SWPF Salt Batch 3. Then water will be added back to Tank 26, and the CSMPs run in order to wash the solids to decrease settling time prior to being sent to Tank 51 for Sludge Batch 10. Utilizing CSMPs for waste removal in an SRS Tank has provided a cost-effective means for further waste removal efforts. In addition, the CSMPs are easier to operate by utilizing a robust and simplified design. The CSMPs performed quite well with no process shutdown or delays during operation. As a result, CSMPs are integral to the future of removing radioactive waste from storage tanks at SRS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Porous Organic Cage Membranes for Molecular Gas Separations (Final Technical Report for DE-SC0021357)

This proposal aims at demonstrating the development of a novel family of membranes, composed of porous organic cages (POC) which offer the possibility of displaying high separation performance for challenging molecular gas separations relevant to natural gas purification, and olefin/paraffin separation. The proposed POCs synthesized in membrane form will display the most desirable properties of polymers (facile processability and flexibility) and inorganic materials (hierarchically ordered pores with molecular sieving properties) leading to highly selective and permeable membranes. POCs should display distinctive structural, compositional, adsorption and transport properties than those of conventional porous materials, opening the doors for a new research direction in membrane science, and gas separations. Our preliminary results demonstrate the feasibility of preparing POC crystals with controlled size, and continuous POC membranes with remarkable high permeances, and separation ability for CO 2 /CH 4 , N 2 /CH 4 and C 3 H 6 /C 3 H 8 separations serving as a solid foundation for our proposed work. Fundamentally, this proposal aims at elucidating separation mechanisms of different gas mixtures related to natural gas composition, and olefin/paraffin separation over porous organic cage membranes. The proposed research will result in fundamental understanding of adsorption and transport properties of industrially relevant gas molecules through novel microporous membranes, and may lead to the development of a cost effective membrane technology for natural gas purification, and olefin/paraffin separation surpassing the conventional benchmark technology distillation. Furthermore, we aim at demonstrating selective water transport through POC membranes, which can be positively impactful in numerous industrial applications in which water is present. The ability to fabricate thin, chemically and mechanically stable POC membranes for societal relevant gas separations constitute a new and distinctive direction in membrane science. Our proposed work aims at addressing some of the challenges recognized in the Research Agenda for Transforming Separation Science . Specifically: (a) advancing understanding of complex mixtures on separation performance; (b) exploring thermodynamic and kinetic mechanisms through the elucidation of separation mechanisms, and (c) study potential stability issues of the membranes to be assessed by evaluating the long term membrane stability and performance at various temperatures and pressures. The team is uniquely qualified to execute the proposed work. The PI has solid expertise in the rational molecular engineering design of porous crystalline membranes for molecular gas separations. The PNNL collaborator has extensive experience in the synthesis, characterization, and functional applications of microporous crystals, with particular emphasis on gas adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluations of lunar samples for the presence of viable organisms

Samples from the six successful Apollo lunar exploration missions were examined for the presence of biological formed elements and were used to inoculate a variety of culture media designed to promote growth of a broad spectrum of microorganisms. No evidence of viable organisms was obtained from any of these analyses. Following incubation of the lunar material-culture medium complexes, microbial growth dynamics studies were conducted with known test species to evaluate the possible presence of toxic factors. Only extracts of culture media which had been in contact with a mixture of lunar material from both Apollo 11 core tubes proved to be toxic to all species tested. Attempts to reproduce this toxic effect with individual Apollo 11 core samples obtained at other parts of the core and analyzed under somewhat different conditions were unsuccessful. In all, 48 different lunar samples were examined. These samples were collected at the lunar surface, in trenches, and in core samples to a depth of 297 cm.

Taylor, G. R.↗

Combustion characteristics of hydrogen. Carbon monoxide based gaseous fuels

An experimental rig program was conducted with the objective of evaluating the combuston performance of a family of fuel gases based on a mixture of hydrogen and carbon monoxide. These gases, in addition to being members of a family, were also representative of those secondary fuels that could be produced from coal by various gasification schemes. In particular, simulated Winkler, Lurgi, and Blue-water low and medium energy content gases were used as fuels in the experimental combustor rig. The combustor used was originally designed as a low NOx rich-lean system for burning liquid fuels with high bound nitrogen levels. When used with the above gaseous fuels this combustor was operated in a lean-lean mode with ultra long residence times. The Blue-water gas was also operated in a rich-lean mode. The results of these tests indicate the possibility of the existence of an 'optimum' gas turbine hydrogen - carbon monoxide based secondary fuel. Such a fuel would exhibit NOx and high efficiency over the entire engine operating range. It would also have sufficient stability range to allow normal light-off and engine acceleration. Solar Turbines Incorporated would like to emphasize that the results presented here have been obtained with experimental rig combustors. The technologies generated could, however, be utilized in future commercial gas turbines.

Notardonato, J. J.↗

The relative performance obtained with several methods of control of an overcompressed engine using gasoline

This report presents some results obtained during an investigation to determine the relative characteristics for several methods of control of an overcompressed engine using gasoline and operating under sea-level conditions. For this work, a special single cylinder test engine, 5-inch bore by 7-inch stroke, and designed for ready adjustment of compression ratio, valve timing and valve lift while running, was used. This engine has been fully described in NACA-TR-250. Tests were made at an engine speed of 1,400 R. P. M. for compression ratios ranging from 4.0 to 7.6. The air-fuel ratios were on the rich side of the chemically correct mixture and were approximately those giving maximum power. When using plain domestic gasoline, detonation was controlled to a constant, predetermined amount (audible), such as would be permissible for continuous operation, by (a) throttling the carburetor, (b) maintaining full throttle but greatly retarding the ignition, and (c) varying the timing of the inlet valve to reduce the effective compression ratio. From the results of the tests, it may be concluded that method (b) gives the best all-round performance and, being easily employed in service, appears to be the most practicable method for controlling an overcompressed engine using gasoline at low altitudes.

Gardiner, Arthur W↗

Demonstration Testing for Ground Servicing of the Commercial Crew Vehicle Emergency Breathing Air Assembly

The new Commercial crew vehicle (CCV) Breathing Air Assembly (CEBAA) is a Composite Overwrapped Pressure Vessel (COPV) filled with high-pressure air, which is designed to provide portable emergency breathing air for up to five crew in the event of an ammonia leak aboard the International Space Station (ISS). Industrially, several common methods of delivering breathing air exist; however, ground processing constraints and flight requirements necessitate the more unusual approach of servicing a COPV with high purity gaseous nitrogen and oxygen serially to achieve a specific mixture of breathing air at approximately 4000 PSIA. A dwell period allows the gases to mix before sampling for composition verification. The novelty of this approach led to concerns about acceptable gas mixing and the ability to deliver accurate gas compositions. Tests examining mixing rate over a series of post-servicing dwell periods were conducted to determine the optimal time for achieving a homogeneous mixture. Further testing was conducted to examine process accuracy using temperature-pressure load criteria to target a specific concentration of oxygen and nitrogen. Test results show that while some stratification of nitrogen and oxygen was observed, a seven-day dwell is adequate time to achieve an acceptable level of mixing, and that existing ground support equipment can accurately service CEBAA COPVs to the required temperature, pressure and composition for flight.

Active Thermal↗