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At least 163 records · Page 9

A Laboratory Study on the Phase Transition for Polar Stratospheric Cloud Particles

The nucleation and growth of different phases of simulated polar stratospheric cloud (PSC) particles were investigated in the laboratory. Solutions and mixtures of solutions at concentrations 1 to 5 m (molality) of ammonium sulfate, ammonium bisulfate, sodium chloride, sulfuric acid, and nitric acid were supercooled to prescribed temperatures below their equilibrium melting point. These solutions were contained in small diameter glass tubing of volumes ranging from 2.6 to 0.04 ml. Samples were nucleated by insertion of an ice crystal, or in some cases by a liquid nitrogen cooled wire. Crystallization velocities were determined by timing the crystal growth front passages along the glass tubing. Solution mixtures containing aircraft exhaust (soot) were also examined. Crystallization rates increased as deltaT2, where deltaT is the supercooling for weak solutions (2 m or less). The higher concentrated solutions (greater than 3 m) showed rates significantly less than deltaT2. This reduced rate suggested an onset of a glass phase. Results were applied to the nucleation of highly concentrated solutions at various stages of polar stratospheric cloud development within the polar stratosphere.

Teets, Edward H., Jr.↗

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

David, Dennis D.↗

Studies on the "Aerobic" Acetyl-Coenzyme A Synthetase of Saccharomyces Cerevisiae: Purification, Crystallization, and Physical Properties of the Enzyme

A procedure for the purification of a stable acetyl-coenzyme A synthetase (ACS) from aerobic cells of Saccharomyces cerevisiae is presented. The steps include differential centrifugation, solubilization of the bound enzyme from the crude mitochondrial fraction, ammonium sulfate fractionation, crystallization to constant specific activity from ammonium sulfate solutions followed by Bio-Gel A-1.5 m column chromatography. The resulting enzyme preparation is homogeneous as judged by chromatography on Bio-Gel columns, QAE-Sephadex A-50 anion exchange columns, analytical ultracentrifugal studies, and polyacrylamide gel electrophoresis. Sedimentation velocity runs revealed a single symmetric peak with an s(sub (20,w)) value of 10.6. The molecular weight of the native enzyme, as determined by gel filtration and analytical ultracentrifugation, is 250,000 +/- 500. In polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulfate, the molecular weight of the single polypeptide chain is 83,000 +/- 500. The purified enzyme is inhibited by palmityl-coenzyme A with a Hill interaction coefficient, n, of 2.88. These studies indicate that the ACS of aerobic Saccharomyces cerevisiae is composed of three subunits of identical or nearly identical size.

Satyanarayana, T.↗

Crystallization of Chicken Egg White Lysozyme from Assorted Sulfate Salts

Chicken egg white lysozyme has been found to crystallize from ammonium, sodium, potassium, rubidium, magnesium, and manganese sulfates at acidic and basic pH, with protein concentrations from 60 to 190 mg/ml. Crystals have also been grown at 4 C in the absence of any other added salts using isoionic lysozyme which was titrated to pH 4.6 with dilute sulfuric acid. Four different crystal forms have been obtained, depending upon the temperature, protein concentration, and precipitating salt employed. Crystals grown at 15 C were generally tetragonal, with space group P4(sub 3)2(sub 1)2. Crystallization at 20 C typically resulted in the formation of orthorhombic crystals, space group P2(sub 1)2(sub 1)2(sub 1). The tetragonal reversible reaction orthorhombic transition appeared to be a function of both the temperature and protein concentration, occurring between 15 and 20 C and between 100 and 125 mg/ml protein concentration. Crystallization from 1.2 M magnesium sulfate at pH 7.8 gave a trigonal crystal, space group P3(sub 1)2(sub 1), a = b = 87.4, c = 73.7, gamma = 120 deg, which diffracted to 2.8 A. Crystallization from ammonium sulfate at pH 4.6, generally at lower temperatures, was also found to result in a monoclinic form. space group C2, a = 65.6, b = 95.0, c = 41.2, beta = 119.2 deg. A crystal of approximately 0.2 x 0.2 x 0.5 mm grown from bulk solution diffracted to approximately 3.5 A.

Forsythe, Elizabeth L.↗

Computational and Experimental Study of Energetic Material in a Counterflow Microgravity Environment

Ground based (normal gravity) combustion studies can provide important information on the processes by which monopropellants and composite systems burn. The effects of gravitational forces, however, can often complicate the interpretation of the models and the implementation of experiments designed to help elucidate complex issues. We propose to utilize a combined computational/experimental approach in a microgravity environment to understand the interaction of oxidizer-binder diffusion flames in composite propellants. By operating under microgravity conditions we will be able to increase the length scales and suppress the gravitational forces on melting binders such that increased resolution of both major and minor species will be possible thus reducing the demands placed on both the computational and diagnostic tools. Results of a detailed transport/finite rate chemistry model will be compared with nonintrusive optical diagnostic measurements of the structure and extinction of diffusion flames in which oxidizers such as ammonium perchlorate (AP) and ammonium dinitramide (ADN) are counterflowed against realistic binders such as hydroxyl-terminated polybutadiene (HTPB) and 3,3-bis(azidomethyl)oxetane (BAMO). The work proposed herein represents a collaborative effort among the research groups at Yale University, Princeton University and the Combustion Diagnostics Laboratory at the Naval Air Warfare Center in China Lake, CA.

Smooke, Mitchell D.↗

Crystallization of Chicken Egg White Lysozyme from Assorted Sulfate Salts

Chicken egg white lysozyme has been found to crystallize from ammonium, sodium, potassium, rubidium, magnesium, and manganese sulfates at acidic and basic pH, with protein concentrations from 60 to 190 mg/ml. Four different crystal morphologies have been obtained, depending upon the temperature, protein concentration, and precipitating salt employed, Crystals grown at 15 C were generally tetragonal, with space group P43212. Crystallization at 20 C typically resulted in the formation of orthorhombic crystals, space group P21212 1. The tetragonal much less than orthorhombic morphology transition appeared to be a function of both the temperature and protein concentration, occurring between 15 and 20 C and between 100 and 125 mg/ml protein concentration. Crystallization from 0.8 -1.2M magnesium sulfate at pH 7.6 - 8.0 gave a hexagonal (trigonal) crystal form, space group P3121, which diffracted to 2.8 A. Ammonium sulfate was also found to result in a monoclinic form, space group C2. Small twinned monoclinic crystals of approx. 0.2 mm on edge were grown by dialysis followed by seeded sitting drop crystallization.

Forsythe, Elizabeth L.↗

Development of a Reference Dose for Perchlorate: Current Issues and Status

The perchlorate anion (ClO4) is typically manufactured as the ammonium salt. The most common use of ammonium perchlorate is in the aerospace program as a component of solid rocket fuel. The perchlorate anion is exceedingly stable under environmental conditions and has been found in ground and surface waters in CA, NV, UT, AZ, TX, AK, NY, MD, WV and FL. The National Center for Environmental Assessment (NCEA) of the U.S. Environmental Protection Agency (US EPA) is in the process of developing an oral reference dose (RfD) for perchlorate. An oral RfD is a body-weight-adjusted dose that can be consumed daily over an entire lifetime with the expectation of no adverse health effects. Once developed, the new RfD will be used by US EPA as the basis of a safe-drinking-water level (SDWL) guideline. US EPA and regional regulatory agencies will then jointly or separately propose clean-up action levels for ground and surface waters at contaminated sites. The toxicological database on CIO4- as of March 1997 was determined by an expert peer-review panel to be inadequate for the purpose of deriving an oral RfD. For example, little or no experimental data existed on the subchronic, reproductive, or developmental toxicity of perchlorate. To fill gaps in the toxicological database, eight animal studies were designed by a government-industry consortium that included US EPA and AFRL. These studies were performed in 1997-1998. It has been known for many years that in the thyroid, high doses of perchlorate block the function of iodide by competing for iodide binding sites. Perchlorate was used in the 1950s-60s as a treatment for Graves' disease (a hyperthyroid condition). Because of what was already known about the pharmacological mode of action of perchlorate, specific concerns addressed in the design of the recent animal studies included the potential for developmental toxicity, notably neurological development. Upon review of complete study reports from four of the studies and incomplete data from the other two, US EPA/NCEA issued a document in December 1998 stating that the critical effects were hormone and histology data from the neurodevelopmental/behavioral toxicity study that had been performed in rats; an RfD was proposed based upon the observation of thyroid-follicular-cell hypertrophy in the 5-day-old pups (PND) of dams given perchlorate in drinking water at 0.1 mg/kg-day (the lowest dose tested) in this study. US EPA/NCEA also focused attention on a nonsignificant increase in motor activity observed in 14-day-old male pups in the same study at the same dose. In February 1999, a public workshop was convened at which an external peer-review panel determined that there was still insufficient data to support the development of a RfD. Additional studies were recommended. Since that time a clinical study revealed significant depression of thyroidal uptake of iodide in volunteers receiving potassium perchlorate at 10 mg/day for 14 days. Follow-up studies currently underway include a pathology working-group review of histology slides from the all of the previous studies, a motor activity study similar to the first behavioral study, an additional immunotoxicity study, male and female rat kinetic studies, a hormone interlaboratory study, and an effects study for thyroid and brain in developing rats. These studies are expected to be complete by mid-2000. A clinical study is planned to determine inhibition of iodide uptake and kinetic parameters in humans following 14-day perchlorate ingestion. The kinetics studies will provide data for developing physiologically based pharmacokinetic (PBPK) models for rats and humans needed to establish the RfD.

Pleus, R. C.↗

Detection of Soluble and Fixed NH4+ in Clay Minerals by DTA and IR Reflectance Spectroscopy : A Potential Tool for Planetary Surface Exploration

Nitrogen is an essential element for life. It is the only element among the six major biogenic elements, C, O, S, O, P, H, whose presence in the Martian soil has not been positively and directly established. We describe here a study assessing the ability to detect NH4 in soils by two methods: differential thermal analysis (DTA) and infrared (IR) reflectance spectroscopy. Four standard clay minerals (kaolinite, montmorillonite, illite and attapulgite) and an altered tephra sample from Mauna Kea were treated with NH4 in this study. Samples of the NH4-treated and leached clays were analyzed by DTA and infrared (IR) reflectance spectroscopy to quantify the delectability of soluble and sorbed/fixed NH4. An exotherm at 270-280 C was clearly detected in the DTA curves of NH4-treated (non-leached) samples. This feature is assigned to the thermal decomposition reaction of NH4. Spectral bands observed at 1.56, 2.05, 2.12, 3.06, 3.3, 3.5, 5.7 and 7.0 microns in the reflectance spectra of NH4-treated and leached samples are assigned to the sorbed/fixed ammonium in the clays. The montmorillonite has shown the most intense absorbance due to fixed ammonium among the leached samples in this study, as a result of its high cation sorption capacity. It is concluded that the presence of sorbed or fixed NH4 in clays may be detected by infrared (IR) reflectance or emission spectroscopy. Distinction between soluble and sorbed NH4 may be achieved through the presence or absence of several spectral features assigned to the sorbed NH4 moietyi and, specifically, by use of the 4.2 micrometer feature assigned to solution NH4. Thermal analyses furnish supporting evidence of ammonia in our study through detection of N released at temperatures of 270-330 C. Based on these results it is estimated that IR spectra measured from a rover should be able to detect ammonia if present above 20 mg NH4/g sample in the surface layers. Orbital IR spectra and thermal analyses measured on a rover may be able to detect ammonia in soils as well but at higher abundances. The spectral features at 3.06 and 7.0 microns due to bound NH4 in clays and altered Hawaiian tephra appear to be the most promising for detection by orbital spectrometers. If N species are present on Mars the sedimentary deposits may be the best regions to look for them.

Janice, Bishop↗

Preparation and Characterization of Polyimide/Organoclay Nanocomposites

Organically modified montmorrrillonite clay, containing a long chain aliphatic quarternary ammonium cation, was used to prepare polyimide/organoclay hybrids. Several approaches were examined in an attempt to achieve fully exfoliated nanocomposites. These included simple mixing of the clay in a pre-made high molecular weight poly(amide acid) solution; simple mixing followed by sonication of the organoclay/poly(amide acid) solutions; and the preparation of high molecular weight poly(amide acid)s in the presence of the organoclay dispersed in N-methyl-2-pyrrolidinone (NMP). The best results were obtained using the in-situ polymerization approach. The resulting nanocomposite films (both amide acid and imide), containing 3-8% by weight of organoclay, were characterized by differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction (XRD), and thin film tensile properties. A significant degree of dispersion was observed in the nanocomposite films of the amide acid and the imide. After thermal treatment of amide acid films to effect imidization, in both air and nitrogen, the films were visually darker than control films without clay and the level of clay dispersion appeared to have decreased. In the latter case, the separation between the layers of the clay decreased to a spacing less than that present in the original organoclay. These observations suggest that thermal degradation of the aliphatic quarternary ammonium cation occurred likely during thermal treatment to effect imidization and solvent removal. These thermal degradation effects were less pronounced when thermal treatment was performed under nitrogen. The polyimide/organoclay hybrid films exhibited higher room temperature tensile moduli and lower strength and elongation to break than the control films.

Delozier, D. M.↗

Boundary Layer Aerosol Composition over Sierra Nevada Mountains using 9.11- and 10.59-micron CW Lidars and Modeled Backscatter from Size Distribution Data

An inversion technique has been developed to determine volume fractions of an atmospheric aerosol composed primarily of ammonium sulfate and ammonium nitrate and water combined with fixed concentration of elemental and organic carbon. It is based on measured aerosol backscatter obtained with 9.11 - and 10.59-micron wavelength continuous wave CO2 lidars and modeled backscatter from aerosol size distribution data. The technique is demonstrated during a flight of the NASA DC-8 aircraft over the Sierra Nevada Mountain Range, California on 19 September, 1995. Volume fraction of each component and effective complex refractive index of the composite particle were determined assuming an internally mixed composite aerosol model. The volume fractions were also used to re-compute aerosol backscatter, providing good agreement with the lidar-measured data. The robustness of the technique for determining volume fractions was extended with a comparison of calculated 2.1,-micron backscatter from size distribution data with the measured lidar data converted to 2.1,-micron backscatter using an earlier derived algorithm, verifying the algorithm as well as the backscatter calculations.

Cutten, D. R.↗

Efficient, environmentally acceptable method for waterproofing insulation material

A process of waterproofing alumina-rich or silica-rich fibrous thermal insulation material, the process including the steps of: (a) providing an alumina-rich or a silica-rich fibrous material; (b) providing a waterproofing solution including: (1) a carrier solvent selected from the group consisting of aliphatic alcohols having from 1C to 6C, water, and mixtures thereof; and (2) an alkoxysilane defined by the formula R.sub.4-x -Si-(O-R').sub.x where x is 1-3 and R is selected from the group consisting of alkyl groups having from 1C to 10C, hydrogen, or fluorocarbon groups having from 1F to 15F; and where O-R' is an alkoxy group having from 1C to 5C, or a mixture of alkoxysilanes defined by the above formula R.sub.4-x -Si-(O-R').sub.x ; and optionally (3) modifiers including acids, such as acetic acid or nitric acid, or bases, such as ammonium hydroxide, RNH.sub.2, R.sub.2 NH, or R.sub.3 N, or MOH, where R is selected from the group consisting of alkyl groups having from 1C to 10C or hydrogen, and where M=Na, Li, or K; (c) contacting the fibrous material with the waterproofing solution for a sufficient amount of time to waterproof the fibrous material; and (d) curing the coated fibrous material to render it sufficiently waterproof. A chemical solution for waterproofing alumina-rich or silica-rich fibrous thermal insulation materials, the solution including: (a) a carrier solvent selected from the group consisting of aliphatic alcohols having from 1C to 6C, water, and mixtures thereof; and (b) an alkoxysilane defined by the formula R.sub.4-x -Si-(O-R').sub.x where x is 1-3 and R is selected from the group consisting of alkyl groups having from 1C to 10C, hydrogen, or fluorocarbon groups having from 1F to 15F; and where O-R' is an alkoxy group having from 1C to 5C, or a mixture of alkoxysilanes defined by the above formula R.sub.4-x -Si-(O-R').sub.x ; and optionally (c) modifiers including acids, such as acetic acid or nitric acid, or bases, such as ammonium hydroxide, RNH.sub.2, R.sub.2 NH, or R.sub.3 N, or MOH, where R is selected from the group consisting of alkyl groups having from 1C to 10C or hydrogen, and where M=Na, Li, or K.

Blohowiak, Kay Y.↗

Carbonaceous Meteorites Contain a Wide Range of Extraterrestrial Nucleobases

All terrestrial organisms depend on nucleic acids (RNA and DNA), which use pyrimidine and purine nucleobases to encode genetic information. Carbon-rich meteorites may have been important sources of organic compounds required for the emergence of life on the early Earth; however, the origin and formation of nuc1eobases in meteorites has been debated for over 50 y. So far, the few nuc1eobases reported in meteorites are biologically common and lacked the structural diversity typical of other indigenous meteoritic organics. Here, we investigated the abundance and distribution of nucleobases and nucleobase analogs in formic acid extracts of 12 different meteorites by liquid chromatography-mass spectrometry. The Murchison and Lonewolf Nunataks 94102 meteorites contained a diverse suite of nucleobases, which included three unusual and terrestrially rare nucleobase analogs; purine, 2,6-diminopurine, and 6,8-diaminopurine. In a parallel experiment, we found an identical suite of nucleobases and nucleobase analogs generated in reactions of ammonium cyanide. Additionally, these nucleobase analoge were not detected above our parts-per-billion detection limits in any of the procedural blanks, control samples, a terrestrial soil sample, and an Antarctic ice sample. Our results demonstrate that the purines detected in meteorites are consistent with products of ammonium cyanide chemistry, which provides a plausible mechanism for their synthesis in the asteroid parent bodies, and strongly supports an extraterrestrial origin. The discovery of new nucleobase analogs in meteorites also expands the prebiotic molecular inventory available for constructing the first genetic molecules.

Callahan, Michael P.↗

Friction modifier using adherent metallic multilayered or mixed element layer conversion coatings

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, silicon, and one or more non-alkaline metals. The process comprises forming a first aqueous solution of silicate, potassium hydroxide, and ammonium hydroxide; forming a second aqueous solution of water, phosphoric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals, and then combining the first solution with the second solution to form a final solution. This final solution forms an anti-friction multi-layer conversion coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly or as an additive in lubricating fluids.

Schramm, Harry F.↗

Hydrocarbon-Seeded Ignition System for Small Spacecraft Thrusters Using Ionic Liquid Propellants

"Green" propellants based on Ionic-liquids (ILs) like Ammonium DiNitramide and Hydroxyl Ammonium Nitrate have recently been developed as reduced-hazard replacements for hydrazine. Compared to hydrazine, ILs offer up to a 50% improvement in available density-specific impulse. These materials present minimal vapor hazard at room temperature, and this property makes IL's potentially advantageous for "ride-share" launch opportunities where hazards introduced by hydrazine servicing are cost-prohibitive. Even though ILs present a reduced hazard compared to hydrazine, in crystalline form they are potentially explosive and are mixed in aqueous solutions to buffer against explosion. Unfortunately, the high water content makes IL-propellants difficult to ignite and currently a reliable "coldstart" capability does not exist. For reliable ignition, IL-propellants catalyst beds must be pre-heated to greater than 350 C before firing. The required preheat power source is substantial and presents a significant disadvantage for SmallSats where power budgets are extremely limited. Design and development of a "micro-hybrid" igniter designed to act as a "drop-in" replacement for existing IL catalyst beds is presented. The design requires significantly lower input energy and offers a smaller overall form factor. Unlike single-use "squib" pyrotechnic igniters, the system allows the gas generation cycle to be terminated and reinitiated on demand.

Whitmore, Stephen A.↗

Familiarization and Detection of Green Monopropellants Project

Ammonium dinitramide (ADN) and hydroxyl ammonium nitrate (HAN) are green monopropellants which will be appearing at Kennedy Space Center (KSC) for processing in the next few years. These are relatively safe replacements for hydrazine as a monopropellant; however, little is known about methods of leak detection, vapor scrubbing, air emissions, or cleanup that will be required for safe and environmentally benign operations at KSC. The goal of this work is to develop leak detection and related technologies for the two new green monopropellants.

Technology Portfolio System↗

Green Propulsion Auxiliary Power Unit Demonstration at MSFC

In 2012, the National Aeronautics & Space Administration (NASA) Space Technology Mission Directorate (STMD) began the process of building an integrated technology roadmap, including both technology pull and technology push strategies. Technology Area 1 (TA-01) for Launch Propulsion Systems is one of fourteen TA's that provide recommendations for the overall technology investment strategy and prioritization of NASA's space technology activities. Identified within TA-01 was the need for a green propulsion auxiliary power unit (APU) for hydraulic power by 2015. Engineers led by the author at the Marshall Space Flight Center (MSFC) have been evaluating green propellant alternatives and have begun the development of an APU testbed to demonstrate the feasibility of use. NASA has residual APU assets remaining from the retired Space Shuttle Program. Likewise, the F-16 Falcon fighter jet also uses an Emergency Power Unit (EPU) that has similar characteristics to the NASA hardware. Both EPU's and APU components have been acquired for testing at MSFC. In concert with this effort, ATK has been developing green propellant technology based on the Swedish Space Corp ECAPS LMP-103S propellant. Propellant blending and test facilities have been established at ATK's Elkton MD facility with the intent to provide suitable propellant blends for application to green APU systems as well as thrusters. This paper will summarize the status of the testing efforts with ATK for use of the green propellant LMP-103S based on ammonium dinitramide and use of the Air Force Research Laboratory (AFRL) propellant AF-M315E based on hydroxyl ammonium nitrate with these test assets.

Robinson, Joel W.↗

Green Mono Propulsion Activities at MSFC

In 2012, the National Aeronautics & Space Administration (NASA) Space Technology Mission Directorate (STMD) began the process of building an integrated technology roadmap, including both technology pull and technology push strategies. Technology Area 1 (TA-01) for Launch Propulsion Systems and TA-02 In-Space Propulsion are two of the fourteen TA's that provide recommendations for the overall technology investment strategy and prioritization of NASA's space technology activities. Identified within these documents are future needs of green propellant use. Green ionic liquid monopropellants and propulsion systems are beginning to be demonstrated in space flight environments. Starting in 2010 with the flight of PRISMA, a one Newton thruster system began on-orbit demonstrations operating on ammonium dinitramide based propellant. The NASA Green Propellant Infusion Mission (GPIM) plans to demonstrate both 1 N, and 22 N hydroxyl ammonium nitrate based thrusters in a 2015 flight demonstration. In addition, engineers at MSFC have been evaluating green propellant alternatives for both thrusters and auxiliary power units. This paper summarizes the status of these development/demonstration activities and investigates the potential for evolution of green propellants from small spacecraft and satellites to larger spacecraft systems, human exploration, and launch system auxiliary propulsion applications.

Robinson, Joel W.↗