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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Ethanol Conversion over La 0.7 Sr 0.3 MnO 3–x (100): Autocatalysis, Adjacent O-Vacancies, Disproportionation, and Dehydrogenation

The mechanism for catalytic conversion of ethanol over La 0.7 Sr 0.3 MnO 3– x (100) surface to acetaldehyde and ethene was investigated. Pre-exposure temperature-programmed reaction (PE-TPR) experiments were performed in which ethanol was introduced to oxidized or reduced surfaces followed by heating. In particular, sequential PE-TPR experiments were conducted to incrementally and gradually reduce the surface. The products and their ratios were investigated as a function of surface reduction. The data show that acetaldehyde and ethene production is catalyzed with hydrogen abstraction and oxygen abstraction reactions occurring by intermediates in vacancies at various temperatures >400 K. Adsorption of acetaldehyde followed by a temperature-programmed reaction does not produce ethene, indicating that acetaldehyde is not an intermediate to ethene and that the hydrogen and oxygen abstraction from ethanol to ethene are decoupled steps. Further evidence for this mechanistic nuance was obtained using isotopically labeled ethanol (CD 3 CH 2 OH), which produces CD 3 CHO and CD 2 CH 2 . Additionally, the ratio of aldehyde production to alkene production increases with reduction, suggesting that aldehyde is produced from a disproportionation reaction between ethoxy species in adjacent O-vacancies, while ethene is produced from a dehydrogenation reaction with ethoxy species in vacancies without requiring adjacent O-vacancies. Counterintuitively, this finding indicates that the more oxygenated product (aldehyde vs ethene) is favored with more vacancies and that the net alcohol conversion is autocatalytic. Density functional theory calculations were able to find the previously unknown disproportionation pathway between ethoxies in adjacent O-vacancies, and kinetic Monte Carlo simulations support this interpretation by reproducing experimental selectivities. The activation energies for these pathways are estimated as 132 ± 10 kJ/mol for the disproportionation reaction (when occurring between ethoxies in adjacent vacancies) and as 148 ± 11 kJ/mol for the direct dehydrogenation reaction of an ethoxy in a vacancy. Based on these results, a mechanism with operative pathways based on elementary steps in O-vacancies is reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Corrosion Prevention in Copper Combustion Chamber Liners of Liquid Oxygen/Methane Booster Engines

Prior research conducted by United Technologies Research Center and Rockwell International Rocketdyne Division encountered severe copper corrosion while flowing hydrocarbon fuels through copper cooling tubes. These experimental results have very important implications for the development of low-cost, regeneratively cooled, oxygen/hydrocarbon bipropellant booster engines. Aerojet TechSystems undertook a program sponsored by NASA/Lewis Research Center in 1986 with two objectives: (1) to define the corrosive interaction process that occurs between hydrocarbon fuels and copper combustion chamber liner materials, using both static and dynamic test methods, and (2) to identify and demonstrate protective measures against this corrosive process. The results of the first program task demonstrated that the most damaging corrosive process was caused by trace amounts of sulfur-containing impurities in the hydrocarbon fuel which react with the copper chamber liner material to form cuprous sulfide (Cu2S), as reported in Paper No. AlAA 88-3215. Experiments were conducted which demonstrated this corrosive process with Mil-Spec RP-1, propane, and methane fuels in contact with OFHC, NASA-Z, and ZrCu coppers. The preliminary results of the second program task demonstrated that electrodeposited gold and platinum coatings held promise of preventing corrosion of copper chamber liners by methane contaminated with sulfur-containing impurities, as reported in Paper No. AIAA 89-2738. Experiments were conducted which demonstrated greatly reduced corrosion of copper by hydrogen sulfide (H2S) and methyl mercaptan (CH3SH) as measured impurities in methane. This paper presents the concluding, confirmatory results from the second program task. The efficacy of a protective gold coating on NASA-Z copper cooling channel walls was conclusively demonstrated. Tests were conducted in the Aerojet Carbothermal Test Facility which provide realistic simulations of booster engine cooling channel conditions such as temperature, pressure, flow velocity, and heat flux. Dynamic test series were performed with methane containing 5 and 10 ppm (by volume) hydrogen sulfide. Gold-plated and unplated copper alloy specimens were evaluated. The tests demonstrated that gold coatings were effective in preventing corrosion of the copper. Posttest metallographic examinations of the unplated specimens showed severe corrosion as a result of reaction with the sulfur containing contaminant in the fuel. In contrast, posttest metallographic examination of the gold-coated specimens showed no corrosion under similar operating conditions. The findings from metallurgical and chemical analyses of the copper specimens, chemical analysis of the methane, and description of all test conditions are provided. Conclusions are reached as to the efficacy of the plating methods and the effectiveness of the metal coatings in the prevention of corrosion in hydrocarbon-fueled booster engine combustion chamber liners.

S D Rosenberg↗
NASA NTRS1999

Propellant Densification for Launch Vehicles: Simulation and Testing 1999

One of the many key technologies required to make single-stage to orbit an actuality, the technology of sub-cooling cryogenic propellants below their normal saturation temperatures and thereby making them more dense, is unquestionably on its way towards full and practical realization. The technology of Propellant Densification has been the subject of an extensive research and development program overseen by Lockheed Martin Michoud Space Systems and NASA Glenn Research Center over the past several years. This paper presents a status report of this research and development. Specifically examined within this paper is the status of the current and continuing efforts on the mathematical simulation of the in-tank propellant densification process currently baselined for the Lockheed Martin VentureStar Reusable Launch Vehicle (RLV). Keys to this modeling effort are an understanding and quantification of the effects of thermal stratification and the ability to capture the complex and unique multiple section tank geometries being proposed for future launch vehicles. A simulation that properly captures these phenomena has been developed by Lockheed Martin. Also discussed is the significant test program that has been undertaken in coordination with NASA Glenn Research Center. In this testing, the liquid hydrogen recirculation and densification process was simulated and the thermal stratification of the densified propellant was recorded throughout the tank. This testing marks the first time that such a process has been carried out within a multiple-lobe, flight-similar tank. The results from this testing have gone a long way towards grounding the mathematical models and towards demonstrating the readiness of the technology for near-term use. A further and even more ambitious test program examining the production and utilization of densified propellants is being planned for late-autumn 1999. An overview of these plans is presented.

Knowles, Timothy E.↗
NASA NTRS1998

Bipolar Nickel-Metal Hydride Battery Being Developed

The NASA Lewis Research Center has contracted with Electro Energy, Inc., to develop a bipolar nickel-metal hydride battery design for energy storage on low-Earth-orbit satellites. The objective of the bipolar nickel-metal hydride battery development program is to approach advanced battery development from a systems level while incorporating technology advances from the lightweight nickel electrode field, hydride development, and design developments from nickel-hydrogen systems. This will result in a low-volume, simplified, less-expensive battery system that is ideal for small spacecraft applications. The goals of the program are to develop a 1-kilowatt, 28-volt (V), bipolar nickel-metal hydride battery with a specific energy of 100 watt-hours per kilogram (W-hr/kg), an energy density of 250 W-hr/liter and a 5-year life in low Earth orbit at 40-percent depth-of-discharge.

Manzo, Michelle A.↗
DOE OSTI2019

Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors

During ex situ catalytic fast pyrolysis (CFP) of biomass, the separation of reactive char and alkali/alkaline particulates from biomass pyrolysis vapors by hot-gas filtration (HGF) leads to improved vapor stability and quality. HGF in tandem with chemical tailoring (e.g., partial deoxygenation) of the clean pyrolysis vapors, denoted as catalytic hot-gas filtration (CHGF), has the potential to further improve vapor composition by removing reactive oxygen moieties and protect downstream upgrading catalysts from fouling. Downstream upgrading refers to both vapor phase upgrading (e.g., ex situ CFP) and condensed phase upgrading (e.g., hydrotreating). Consequently, CHGF (as a single unit operation) was evaluated for preconditioning pyrolysis vapors for downstream upgrading processes. In order to understand the effective operating conditions that successfully filter and partially deoxygenate pyrolysis vapors, a titania-supported molybdenum heteropolyacid (Mo-HPA/TiO 2 ) catalyst was studied for use in CHGF. Here, pine pyrolysis vapors were generated in a small pilot-scale pyrolyzer and transferred to a CHGF unit via a continuous-flow slipstream. In the CHGF unit, the pyrolysis vapors were filtered and upgraded over a packed Mo-HPA/TiO 2 catalyst bed. Real-time monitoring and identification of the products formed were achieved by molecular beam mass spectrometry. The results showed that under a hydrogen-rich environment, the pine vapors were partially deoxygenated and alkylated over the Mo-HPA/TiO 2 catalyst. Reactivity studies revealed that an increase in hydrogen concentration and a reduction in weight-hourly space velocity enhanced deoxygenation and alkylation. Time-on-stream (TOS) studies showed stable product formation up to 1 h with little change in catalyst activity. Additionally, the liquid product was collected using a custom fractional condensation unit (built in-house) and analyzed by gas chromatography mass spectrometry to confirm that the product was partially deoxygenated and alkylated. The combination of CHGF and fractional condensation allowed for chemical and physical removal of both foulant and value-added compounds (e.g., phenols, alkylphenols, methoxyphenols, cyclopentenones) for additional enhancement of downstream upgrading processes. The pre- and postreaction catalysts were characterized using temperature-programmed desorption, N 2 physisorption, and elemental analysis with results indicating some catalyst coking. A hydrogen-based catalyst regeneration procedure restored the reacted catalyst activity to that of fresh Mo-HPA/TiO 2 .

09 BIOMASS FUELS↗
DOE OSTI2020

Design and out-of-pile testing of a novel irradiation experiment vehicle to support qualification of nuclear thermal propulsion components

Fission power systems have demonstrated higher thermal energy density per unit mass than chemical systems. High mass specific energy density offers advantages in space thermal propulsion applications. In the 1960s, nuclear thermal propulsion (NTP) development included the ROVER/NERVA program, in which full-scale prototype reactors were tested on the ground using hydrogen as the reactor coolant and propellant. NTP systems are being revisited, with expectations of improved performance resulting from improved fuel materials, allowing propellant temperatures near 2,800 K and over 20 thermal propulsion cycles. An apparatus has been developed to test NTP fuel materials in a research reactor at temperature and in a radiation environment typical of the NTP application. Here, this paper presents the design constraints, preliminary scoping thermal analysis, and basic thermal qualification testing for the out-of-pile experiment set apparatus, or OUTSET.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2019

Rational Design of Metalorganic Complexes for the Deposition of Solid Films: Growth of Metallic Copper with Amidinate Precursors

A fourth-generation copper metalorganic compound, Cu(I)-2-(tert-butylimino)-5,5,-dimethylpyrrolidinate, was designed, and its chemistry on nickel surfaces characterized, for use as a precursor for the atomic layer deposition (ALD) of thin solid metal films. On the basis of surface-science studies with similar acetamidinate, guanidinate, and iminopyrrolidinate complexes, it was concluded that the high (and undesirable) reactivity of those when adsorbed on metal surfaces is due to the lability of their C–N bonds, which can be triggered by β-hydrogen elimination steps. Accordingly, a ligand was designed without any available hydrogen atoms at those positions. The result is a much more stable reactant. Temperature programed desorption (TPD) experiments indicated that dehydrogenation from the new compound on Ni(110) starts only at 450 K, an increase of about 200 K in comparison with any of the earlier-generations ALD precursors. TPD and X-ray photoelectron spectroscopy (XPS) data were used to establish the details of the decomposition mechanism of the ligands, which appears to be initiated by the scission of the imino-pyrrolidine C–N bond. Many byproducts are produced, including HCN, N 2 , iso-butene, and possibly pyrroline and other olefins such as pentenes. However, all of that occurs at relatively high temperatures, leaving an acceptable temperature window for the use of this complex for the deposition of copper films. An increased stability of the new ligands in our new copper ALD precursor was also observed on SiO 2 thin films, attesting to the generality of our conclusions. We suggest that our methodology for the rational design of this ALD precursor, based on studies of its surface chemistry, can be easily extended to other cases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Caustic Precipitation of Plutonium and Uranium with Gadolinium as a Neutron Poison

Here, the caustic precipitation of plutonium (Pu) and uranium (U) from Pu and U containing waste solutions has been investigated to determine whether gadolinium (Gd) could be used as a neutron poison for precipitation with greater than a fissile mass containing both Pu and enriched U. Precipitation experiments were performed using both actual samples and simulant solutions with a range of 2.6-5.16 g/L U and 0-4.3 to 1 U to Pu. Analyses were performed on solutions at intermediate pH to determine the partitioning of elements for accident scenarios. When both Pu and U were present in the solution, precipitation began at pH 4.5 and by pH 7, 99% of Pu and U had precipitated. When complete neutralization was achieved at pH greater than 14 with 1.2 M excess OH - , greater than 99% of Pu, U, and Gd had precipitated. At pH greater than 14, the particles sizes were larger and the distribution was a single mode. The ratio of hydrogen to fissile atoms in the precipitate was determined after both settling and centrifuging and indicates that sufficient water was associated with the precipitates to provide the needed neutron moderation for Gd to prevent a criticality in solutions containing up to 4.3 to 1 U to Pu and up to 5.16 g/L U.

08 HYDROGEN↗
DOE OSTI2011

Program Accomplishments

The U.S. Department of Energy's (DOE's) efforts have greatly advanced the state of the art of hydrogen and fuel cell technologies—making significant progress toward overcoming many of the key challenges to widespread commercialization. DOE has also made major advances by demonstrating and validating the technologies under real-world conditions, supporting early markets through Recovery Act deployments, and leveraging domestic and international partnerships to advance the pace of commercialization.

accomplishments↗
DOE OSTI2024

Reduction of Iron (III) Oxide in Microwaves Toward Gasification Studies

The purpose of this study is to reduce hematite (Fe2O3) using hydrogen (H2), carbon monoxide (CO), and methane (CH4) gases using microwave irradiation. Conventional temperature programmed reduction of iron phase transformation under H2, CO, and CH4 agree with the literature. Furthermore, the activation energy for the iron phase transformation in a conventional reactor was in the order of H2>CO>CH4, suggesting that CH4 was the best reductant to initiate the reduction at a much lower temperature than CO, and CO was significantly better than H2 atmosphere. Due to the uneven temperature distribution, the apparent activation energy of microwave reduction under H2 was approximately 1/4th when compared to the conventional reduction in H2. X-ray diffraction (XRD) analysis showed a mixed oxide phase in microwave reduction as opposed to the clear phase transformation in conventional studies. To combat the temperature measurement issues in microwave studies, fiber optic sensors and Forward Looking InfraRed (FLIR) sensors were used to acquire the actual temperature distribution in the catalyst bed. Therefore, a reasonably accurate activation energy estimation was achieved in the catalyst bed. Combining these with the characterization and quantification of the different iron phases in microwave reduction will provide a blueprint for future microwave-assisted gasification studies.

Aireddy, Divakar Reddy↗
NASA NTRS1971

The cryogenics analysis program for Apollo mission planning and analysis

The cryogenics analysis program was developed as a simplified tool for use in premission planning operations for the Apollo command service module. Through a dynamic development effort, the program has been extended to include real time and postflight analysis capabilities with nominal and contingency planning features. The technical aspects of the program and a comparison of ground test and mission data with data generated by using the cryogenics analysis program are presented. The results of the program capability to predict flight requirements also are presented. Comparisons of data from the program with data from flight results, from a tank qualifications program, and from various system anomalies that have been encountered are discussed. Future plans and additional considerations for the program also are included. Among these plans are a three tank management scheme for hydrogen, venting profile generation for Skylab, and a capability for handling two gas atmospheres. The plan for two gas atmospheres will involve the addition of the capability to handle nitrogen as well as oxygen and hydrogen.

Scott, W.↗
NASA NTRS1975

Studies of the use of high-temperature nuclear heat from an HTGR for hydrogen production

The results of a study which surveyed various methods of hydrogen production using nuclear and fossil energy are presented. A description of these methods is provided, and efficiencies are calculated for each case. The process designs of systems that utilize the heat from a general atomic high temperature gas cooled reactor with a steam methane reformer and feed the reformer with substitute natural gas manufactured from coal, using reforming temperatures, are presented. The capital costs for these systems and the resultant hydrogen production price for these cases are discussed along with a research and development program.

Peterman, D. D.↗
NASA NTRS1978

Detection of hydrogen chloride gas in air

Launch vehicle effluent (LVE) monitoring is part of NASA's overall tropospheric and stratospheric environmental program. Following nine techniques are evaluated and developed in report: bubbler method, pH measurements, indicator tubes, microcoulometers, modified condensation nuclei counter, dual-isotope absorption, gas-filter correlation, chemiluminescent nitric oxide detection, chemiluminescent luminol-oxidation detection.

Gregory, G. L.↗
NASA NTRS1984

Separator development and testing of nickel-hydrogen cells

The components, design, and operating characteristics of Ni-H2 cells and batteries were improved. A separator development program was designed to develop a separator that is resistant to penetration by oxygen and loose active material from the nickel electrode, while retaining the required chemical and thermal stability, reservoir capability, and high ionic conductivity. The performance of the separators in terms of cell operating voltage was to at least match that of state-of-the-art separators while eliminating the separator problems. The separators were submitted to initial screening tests and those which successfully completed the tests were built into Ni-H2 cells for short term testing. The separators with the best performance are tested for long term performance and life.

Gonzalez-Sanabria, O. D.↗
NASA NTRS1988

Integrated control and health management. Orbit transfer rocket engine technology program

To insure controllability of the baseline design for a 7500 pound thrust, 10:1 throttleable, dual expanded cycle, Hydrogen-Oxygen, orbit transfer rocket engine, an Integrated Controls and Health Monitoring concept was developed. This included: (1) Dynamic engine simulations using a TUTSIM derived computer code; (2) analysis of various control methods; (3) Failure Modes Analysis to identify critical sensors; (4) Survey of applicable sensors technology; and, (5) Study of Health Monitoring philosophies. The engine design was found to be controllable over the full throttling range by using 13 valves, including an oxygen turbine bypass valve to control mixture ratio, and a hydrogen turbine bypass valve, used in conjunction with the oxygen bypass to control thrust. Classic feedback control methods are proposed along with specific requirements for valves, sensors, and the controller. Expanding on the control system, a Health Monitoring system is proposed including suggested computing methods and the following recommended sensors: (1) Fiber optic and silicon bearing deflectometers; (2) Capacitive shaft displacement sensors; and (3) Hot spot thermocouple arrays. Further work is needed to refine and verify the dynamic simulations and control algorithms, to advance sensor capabilities, and to develop the Health Monitoring computational methods.

Holzmann, Wilfried A.↗
NASA NTRS1993

CFD analyses of combustor and nozzle flowfields

The objectives of the research are to improve design capabilities for low thrust rocket engines through understanding of the detailed mixing and combustion processes. A Computational Fluid Dynamic (CFD) technique is employed to model the flowfields within the combustor, nozzle, and near plume field. The computational modeling of the rocket engine flowfields requires the application of the complete Navier-Stokes equations, coupled with species diffusion equations. Of particular interest is a small gaseous hydrogen-oxygen thruster which is considered as a coordinated part of an ongoing experimental program at NASA LeRC. The numerical procedure is performed on both time-marching and time-accurate algorithms, using an LU approximate factorization in time, flux split upwinding differencing in space. The integrity of fuel film cooling along the wall, its effectiveness in the mixing with the core flow including unsteady large scale effects, the resultant impact on performance and the assessment of the near plume flow expansion to finite pressure altitude chamber are addressed.

Tsuei, Hsin-Hua↗
NASA NTRS2003

X-43C Flight Demonstrator Project Overview

The X-43C Flight Demonstrator Project is a joint NASA-USAF hypersonic propulsion technology flight demonstration project that will expand the hypersonic flight envelope for air-breathing engines. The Project will demonstrate sustained accelerating flight through three flights of expendable X-43C Demonstrator Vehicles (DVs). The approximately 16-foot long X-43C DV will be boosted to the starting test conditions, separate from the booster, and accelerate from Mach 5 to Mach 7 under its own power and autonomous control. The DVs will be powered by a liquid hydrocarbon-fueled, fuel-cooled, dual-mode, airframe integrated scramjet engine system developed under the USAF HyTech Program. The Project is managed by NASA Langley Research Center as part of NASA's Next Generation Launch Technology Program. Flight tests will be conducted by NASA Dryden Flight Research Center off the coast of California over water in the Pacific Test Range. The NASA/USAF/industry project is a natural extension of the Hyper-X Program (X-43A), which will demonstrate short duration (approximately 10 seconds) gaseous hydrogen-fueled scramjet powered flight at Mach 7 and Mach 10 using a heavy-weight, largely heat sink construction, experimental engine. The X-43C Project will demonstrate sustained accelerating flight from Mach 5 to Mach 7 (approximately 4 minutes) using a flight-weight, fuel-cooled, scramjet engine powered by much denser liquid hydrocarbon fuel. The X-43C DV design flows from integrating USAF HyTech developed engine technologies with a NASA Air-Breathing Launch Vehicle accelerator-class configuration and Hyper-X heritage vehicle systems designs. This paper describes the X-43C Project and provides the background for NASA's current hypersonic flight demonstration efforts.

Moses, Paul L.↗
NASA NTRS1997

Enhancement of Mixing and Reaction in High-speed Combustor Flowfields

Research has been underway for a number of years, both in the United States and abroad, to develop advanced aerospace propulsion systems for use late in this century and beyond. One program is now underway at the NASA Langley Research Research has been underway for a number of years, both in the United States and abroad, to develop advanced aerospace propulsion systems for use late in this century and beyond. One program is now underway at the NASA Langley Research Center to develop a hydrogen-fueled supersonic combustion ramjet (scramjet) that is capable of propelling a vehicle at hypersonic speeds in the atmosphere. A part of that research has been directed toward the optimization of the scramjet combustor and, in particular, the efficiency of fuel-air mixing and reaction taking place in the engine. In the high-speed vehicle configurations currently being considered, achieving a high combustor efficiency becomes particularly difficult. With increasing combustor Mach number, the degree of fuel-air mixing that can be achieved through natural convective and diffusive processes is reduced leading to an overall decrease in combustion efficiency and thrust. Compressible shear layers and jets provide a good model for studying the physical processes occurring in high speed mixing and combustion in a scramjet. Mixing layers are characterized by large scale eddies that form due to the high shear that is present between the fuel and the air streams. These eddies entrain the fuel and air into the mixing region between the fluids leading to increased surface area and locally steep concentration gradients. Molecular diffusion then occurs across the strained interfaces. In an early study of high-speed mixing, Brown and Roshko show that the spreading rate of a supersonic mixing layer decreases with increasing Mach number, exhibiting a factor of three decrease in spread rate as compared with an incompressible mixing layer with the same density ratio. They conclude that the reduced spread rate is primarily due to compressibility. Papamoschou and Roshko also observe that the spreading rate of compressible mixing layers is significantly reduced over that of incompressible layers. To characterize the structure of the flow quantitatively, they define a convective Mach number. The reduction in mixing layer spreading rate is shown in these experiments to correlate well with increasing convective Mach number.

Drummond, J. Philip↗