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Ionic Liquids to Replace Hydrazine

A method for developing safe, easy-to-handle propellants has been developed based upon ionic liquids (ILs) or their eutectic mixtures. An IL is a binary combination of a typically organic cation and anion, which generally produces an ionic salt with a melting point below 100 deg C. Many ILs have melting points near, or even below, room temperature (room temperature ionic liquids, RTILs). More importantly, a number of ILs have a positive enthalpy of formation. This means the thermal energy released during decomposition reactions makes energetic ILs ideal for use as propellants. In this specific work, to date, a baseline set of energetic ILs has been identified, synthesized, and characterized. Many of the ILs in this set have excellent performance potential in their own right. In all, ten ILs were characterized for their enthalpy of formation, density, melting point, glass transition point (if applicable), and decomposition temperature. Enthalpy of formation was measured using a microcalorimeter designed specifically to test milligram amounts of energetic materials. Of the ten ILs characterized, five offer higher Isp performance than hydrazine, ranging between 10 and 113 seconds higher than the state-of-the-art propellant. To achieve this level of performance, the energetic cations 4- amino-l,2,4-triazolium and 3-amino-1,2,4-triazolium were paired with various anions in the nitrate, dicyanamide, chloride, and 3-nitro-l,2,4-triazole families. Protonation, alkylation, and butylation synthesis routes were used for creation of the different salts.

Koelfgen, Syri↗

Adiabatic Compression Sensitivity of Liquid Fuels and Monopropellants

Liquid rocket propellants can be sensitive to rapid compression. Such liquids may undergo decomposition and their handling may be accompanied with risk. Decomposition produces small gas bubbles in the liquid, which upon rapid compression may cause catastrophic explosions. The rapid compression can result from mechanical shocks applied on the tank containing the liquid or from rapid closure of the valves installed on the lines. It is desirable to determine the conditions that may promote explosive reactions. At Air Force Research Laboratory (AFRL), we constructed an apparatus and established a safe procedure for estimating the sensitivity of propellant materials towards mechanical shocks (Adiabatic Compression Tester). A sample is placed on a stainless steel U-tube, held isothermally at a temperature between 20 and 150 C then exposed to an abrupt mechanical shock of nitrogen gas at a pressure between 6.9 and 20.7 MPa (1000 to 3000 psi). The apparatus is computer interfaced and is driven with LABTECH NOTEBOOK-pro (registered) Software. In this presentation, the design of the apparatus is shown, the operating procedure is outlined, and the safety issues are addressed. The results obtained on different energetic materials are presented.

Ismail, Ismail M. K.↗

X-ray emission from the Carina Nebula and the associated early stars

New Einstein observations of the Carina Nebula show the extent of the diffuse X-ray nebula to be 1.1 deg E-W by 0.7 deg N-S. The diffuse X-ray emission is generally associated with optically bright regions, but the correlation is not exact. Emission is strongest from regions bordering the apparently overlying dust lane, indicating an interaction between the energetic material of the optical nebula and the region containing the dust. The diffuse X-rays are from hot gas with temperatures of about 10 million K, and electron densities of 0.1-1/cu cm. The energy to heat this gas probably comes from strong stellar winds of the early stars embedded in the nebula. X-rays from 15 O and W-R stars in the Carina OBI association have been detected. Data are consistent with the hypothesis that X-ray luminosity is equal to about 2.0 x 10 to the -7th of bolometric luminosity for all O stars in this region with remarkably little scatter. X-ray emission from the three W-R stars observed is significantly different. In particular, the WN6 star, HD 93162, has an X-ray luminosity equal to about 2.0 x 10 to the -6th of bolometer luminosity, a factor of 30 higher than for two other W-R stars in this nebula, and perhaps the highest X-ray luminosity/bolometric luminosity of any W-R star for which X-ray observations have been made.

Seward, F. D.↗

A summary of recent developments in transportation hazard classification activities for ammonium perchlorate

The transportation hazard classification of Ammonium Perchlorate is discussed. A test program was completed and data were forwarded to retain a Class 5.1 designation (oxidizer) for AP which is shipped internationally. As a follow-on to the initial team effort to conduct AP tests existing data were examined and a matrix which catalogs test parameters and findings was compiled. A collection of test protocols is developed to standardize test methods for energetic materials of all types. The actions to date are summarized; the participating organizations and their roles as presently understood; specific findings on AP (matrix); and issues, lessons learned, and potential actions of particular interest to the propulsion community which may evolve as a result of future U.N. propellant transportation classification activities.

Koller, A. M., Jr.↗

X-ray inverse Compton emission from the radio halo of M87

A significant fraction of known galaxies contain an active galactic nucleus (AGN) at their cores, the site of violent activity and non-stellar radiation seen across the entire electromagnetic spectrum. This activity is thought to be due to the accretion of gas onto a massive black hole. A fraction of AGNs also eject collimated beams of energetic material, usually seen by virtue of its synchrotron emission in the radio band. Efforts to study these jets from AGNs in the X-ray band with the Einstein Observatory has led to several detections, most notably the jets in the nearby radio galaxies Centaurus A and Virgo A = M87. In their study of M87, Schreier, Gorenstein and Feigelson (1982) noted that, in addition to the synchrotron jet 10"-20" from the nucleus, X-rays appear to be generated in the diffuse radio halo 2'-5' from the nucleus. This finding may be particularly important as it may constitute the first known case of X-ray inverse Compton emission from AGN ejecta, allowing for the first time direct determination of the magnetic field strengths.

Feigelson, E. D.↗

29th JANNAF Combustion Subcommittee Meeting

This volume, the second of five volumes, is a collection of 38 unclassified/unlimited papers which were presented at the 29th Joint Army-Navy-NASA-Air Force (JANNAF) Combustion Subcommittee Meeting, 19-23 October 1992, at NASA Langley Research Center, Hampton, Virginia. Specific subjects discussed include combustion phenomena in air breathing, liquid and solid systems, energetic materials in solids, and combustion instability in solid rocket motors.

Gannaway, Mary T.↗

JANNAF 28th Propellant Development and Characterization Subcommittee and 17th Safety and Environmental Protection Subcommittee Joint Meeting

This volume contains 37 unclassified/unlimited-distribution technical papers that were presented at the JANNAF 28th Propellant Development & Characterization Subcommittee (PDCS) and 17th Safety & Environmental Protection Subcommittee (S&EPS) Joint Meeting, held 26-30 April 1999 at the Town & Country Hotel and the Naval Submarine Base, San Diego, California. Volume II contains 29 unclassified/limited-distribution papers that were presented at the 28th PDCS and 17th S&EPS Joint Meeting. Volume III contains a classified paper that was presented at the 28th PDCS Meeting on 27 April 1999. Topics covered in PDCS sessions include: solid propellant rheology; solid propellant surveillance and aging; propellant process engineering; new solid propellant ingredients and formulation development; reduced toxicity liquid propellants; characterization of hypergolic propellants; and solid propellant chemical analysis methods. Topics covered in S&EPS sessions include: space launch range safety; liquid propellant hazards; vapor detection methods for toxic propellant vapors and other hazardous gases; toxicity of propellants, ingredients, and propellant combustion products; personal protective equipment for toxic liquid propellants; and demilitarization/treatment of energetic material wastes.

Cocchiaro, James E.↗

Lead-Free Propellant for Propellant Actuated Devices

Naval Surface Warfare Center, Indian Head Division's CAD/PAD Department has been working to remove toxic compounds from our products for about a decade. In 1992, we embarked on an effort to develop a lead-free double base propellant to replace that of a foreign sole source. At the time there were availability concerns. In 1995, the department developed a strategic proposal to include a wider range of products. Efforts included such efforts as removing lead sheathing from linear explosives and replacing lead azide and lead styphnate compounds. This paper will discuss efforts specifically related to developing non-leaded double base propellant for use in various Propellant Actuated Devices (PADs) for aircrew escape systems. The propellants can replace their leaded counterparts, mitigating lead handling, processing, or toxic exposure to the environment and personnel. This work eliminates the use of leaded compounds, replacing them with a more environmentally benign metal-organic salt. Historically double-base propellants have held an advantage over other families of energetic materials through their relative insensitivity of the burning rate to changes in temperature and pressure. This desirable ballistic effect has been obtained with the use of a lead-organic salt alone or in a physical mixture with a copper-organic salt, or more recently with a lead-copper complex. These ballistic modifiers are typically added to the double-base 'paste' prior to gelatinization on heated calendars or one type or another. The effect of constant burning rate over a pressure range is called a 'plateau' while an even more beneficial effect of decreasing burning rate with increasing pressure is termed a 'mesa.' The latter effect results in very low temperature sensitivity of the propellant burning rate. Propellants with such effects are ideal tactical rocket motor propellants. The use of lead compounds poses a concern for the environment and personnel safety due to the metal's toxic nature when introduced into the atmosphere by propellant manufacturing, rocket firings, and disposal. Two separate programs are underway at Indian Head to replace the leaded ballistic modifiers in NOSIH-AA-2 and KU propellants. Although the system requirements were very different, the programs gained valuable information from one another throughout their course.

Goodwin, John L.↗

Uncertainty Analysis of Decomposing Polyurethane Foam

Sensitivity/uncertainty analyses are necessary to determine where to allocate resources for improved predictions in support of our nation's nuclear safety mission. Yet, sensitivity/uncertainty analyses are not commonly performed on complex combustion models because the calculations are time consuming, CPU intensive, nontrivial exercises that can lead to deceptive results. To illustrate these ideas, a variety of sensitivity/uncertainty analyses were used to determine the uncertainty associated with thermal decomposition of polyurethane foam exposed to high radiative flux boundary conditions. The polyurethane used in this study is a rigid closed-cell foam used as an encapsulant. Related polyurethane binders such as Estane are used in many energetic materials of interest to the JANNAF community. The complex, finite element foam decomposition model used in this study has 25 input parameters that include chemistry, polymer structure, and thermophysical properties. The response variable was selected as the steady-state decomposition front velocity calculated as the derivative of the decomposition front location versus time. An analytical mean value sensitivity/uncertainty (MV) analysis was used to determine the standard deviation by taking numerical derivatives of the response variable with respect to each of the 25 input parameters. Since the response variable is also a derivative, the standard deviation was essentially determined from a second derivative that was extremely sensitive to numerical noise. To minimize the numerical noise, 50-micrometer element dimensions and approximately 1-msec time steps were required to obtain stable uncertainty results. As an alternative method to determine the uncertainty and sensitivity in the decomposition front velocity, surrogate response surfaces were generated for use with a constrained Latin Hypercube Sampling (LHS) technique. Two surrogate response surfaces were investigated: 1) a linear surrogate response surface (LIN) and 2) a quadratic response surface (QUAD). The LHS techniques do not require derivatives of the response variable and are subsequently relatively insensitive to numerical noise. To compare the LIN and QUAD methods to the MV method, a direct LHS analysis (DLHS) was performed using the full grid and timestep resolved finite element model. The surrogate response models (LIN and QUAD) are shown to give acceptable values of the mean and standard deviation when compared to the fully converged DLHS model.

Hobbs, Michael L.↗

JANNAF 30th Propellant Development and Characterization Subcommittee Meeting

This volume, the first of three volumes, is a compilation of 22 unclassified/unlimited technical papers presented at the Joint Army-Navy-NASA-Air Force (JANNAF) 30th Propellant Development & Characterization Subcommittee Meeting, held on 18-21 March 2002 at the Sheraton Colorado Springs Hotel, Colorado Springs, Colorado. The papers presented herein reflect work performed in the areas of green energetic materials (GEM) development; liquid and gel propellant development; propellant surveillance and aging; and propellant chemistry test methods.

Moore, T. L.↗

Advanced-to-Revolutionary Space Technology Options - The Responsibly Imaginable

Paper summarizes a spectrum of low TRL, high risk technologies and systems approaches which could massively change the cost and safety of space exploration/exploitation/industrialization. These technologies and approaches could be studied in a triage fashion, the method of evaluation wherein several prospective solutions are investigated in parallel to address the innate risk of each, with resources concentrated on the more successful as more is learned. Technology areas addressed include Fabrication, Materials, Energetics, Communications, Propulsion, Radiation Protection, ISRU and LEO access. Overall and conceptually it should be possible with serious research to enable human space exploration beyond LEO both safe and affordable with a design process having sizable positive margins. Revolutionary goals require, generally, revolutionary technologies. By far, Revolutionary Energetics is the most important, has the most leverage, of any advanced technology for space exploration applications.

Bushnell, Dennis M.↗

Energetic oxygen atom material degradation studies

As part of a study designed to test potential Shuttle surface materials for the extents of degradation and mass loss expected to be suffered in space from the velocity impacts of ambient oxygen atoms, a novel technique was developed for generation of a high flux of energetic oxygen atoms. The generation technique involves laser-induced breakdown of molecular oxygen followed by a rapid expansion of energetic oxygen atoms. The high-velocity streams developed in an evacuated hypersonic nozzle have average O-atom velocities of about 5 to 13 km/s, with an estimated total production of 10 to the 18th atoms per pulse over pulse durations of several microseconds. Results on preliminary material degradation tests conducted with this test facility have been reported by Caledonia et al. (1987). Diagrams of the experimental setup are included.

Caledonia, George E.↗

Development of a high flow source of energetic oxygen atoms for material degradation studies

A technique for the generation, in the laboratory, of thermally 'cold', high flux of energetic oxygen atoms is presented. The flux of nearly mono-energetic oxygen atoms is obtained after a laser-induced breakdown of oxygen molecules followed by a rapid expansion of the recombining plasma. The experimental apparatus, the optical and spectral measurements, the O-atom source characterization, and the material degradation studies are discussed. Average oxygen atom velocities of about 5 to 13 km/s are measured with an estimated flux of 10 to the 18th per pulse, over pulse durations of several microseconds. The flow of the O2 gas for about 200 microseconds before applying the laser pulse is found to give best results. It is also found that the energetic O-atom irradiation of sample targets such as Al, Fe, and polyethylene, induces mass removal. In addition, spectral scans of the radiation reveals the existence of two main spectral subsets.

Caledonia, G. E.↗

Innovative techniques for the production of energetic radicals for lunar materials processing including photogeneration via concentrated solar energy

The Department of Materials Science and Engineering (MSE) is investigating the use of monatomic chlorine produced in a cold plasma to recover oxygen and metallurgically significant metals from lunar materials. Development of techniques for the production of the chlorine radical (and other energetic radicals for these processes) using local planetary resources is a key step for a successful approach. It was demonstrated terrestrially that the use of UV light to energize the photogeneration of OH radicals from ozone or hydrogen peroxide in aqueous solutions can lead to rapid reaction rates for the breakdown of toxic organic compounds in water. A key question is how to use the expanded solar resource at the lunar surface to generate process-useful radicals. This project is aimed at investigating that question.

Osborn, D. E.↗

Isotope abundances of solar coronal material derived from solar energetic particle measurements

Coronal isotopic abundances for the elements He, C, N, O, Ne, and Mg are derived from previously published measurements of the isotopic composition of solar energetic particles by first measuring, and then correcting for, the charge-to-mass-dependent fractionation due to solar flare acceleration and propagation processes. The resulting coronal composition generally agrees with that of other samples of solar system material, but the previously noted difference between the solar flare and solar wind Ne-22/Ne-20 ratios remains unresolved.

Mewaldt, R. A.↗

Innovative techniques for the production of energetic radicals for lunar materials processing including photogeneration via concentrated solar energy

A technique for photo generation of radicals is discussed that can be used in the recovery of oxygen and metals from extraterrestrial resources. The concept behind this work was to examine methods whereby radicals can be generated and used in the processing of refractory materials. In that regard, the focus is on the use of sunlight. Sunlight provides useful energy for processing in the forms of both thermal and quantum energy. A number of experiments were conducted in the chlorination of metals with and without the aid of UV and near UV light. The results of some of those experiments are discussed.

Osborn, D. E.↗

Electron Radiation Effects on Candidate Solar Sail Material

Solar sailing is a unique form of propulsion where a spacecraft gains momentum from incident photons. Solar sails are not limited by reaction mass and provide continual acceleration, reduced only by the lifetime of the lightweight film in the space environment and the distance to the Sun. Once thought to be difficult or impossible, solar sailing has come out of science fiction and into the realm of possibility. Any spacecraft using this propulsion method would need to deploy a thin sail that could be as large as many kilometers in extent. The availability of strong, ultra lightweight, and radiation resistant materials will determine the future of solar sailing. The National Aeronautics and Space Administration's (NASA) Marshall Space Flight Center (MSFC) is concentrating research into the utilization of ultra lightweight materials for spacecraft propulsion. The Space Environmental Effects Team at MSFC is actively characterizing candidate solar sail material to evaluate the thermo-optical and mechanical properties after exposure to space environmental effects. This paper will describe the irradiation of candidate solar sail materials to energetic electrons, in vacuum, to determine the hardness of several candidate sail materials.

Edwards, David L.↗