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A METHODOLOGY FOR THE SYNTHESIS OF COMPUTATIONAL MODELING AND EXPERIMENTAL DESIGN
Personal Author(s): Laker, T S , Washburn, E B
Report Date: 08 Aug 2006
Descriptors: *COMPUTATIONS, *SYNTHESIS, *EXPERIMENTAL DESIGN, *HAZARDOUS MATERIALS, METHODOLOGY, HEAT FLUX, ENERGETIC PROPERTIES, CASE STUDIES, MODELS, SYMPOSIA
Identifiers: (U) COMPONENT REPORTS, PREPRINTS, WUAFRLHHLL052J
Abstract: (U) The development of new experiments focused on the analysis of different hazard characteristics of energetic materials can be expensive and time consuming. The progression of initial concepts into viable experiments that utilize available hardware can often be a tedious, trial and error process. However, coupling the experimental evolution with various available computational tools can lead to drastic savings in both time and money. The methodology for integrating computational modeling with experimental design is described in detail as a part of this paper. First, simple engineering analysis methods were used to determine the overall feasibility of initial concepts and designs. Once an initial concept is selected, an iterative process between the experimental design and high-fidelity computational models begins. The experimentalist establishes design boundaries, and modeling is used to identify a variety of optimal configurations. This exchange between experimentalist and modeler occurs constantly during this phase of the design process. Much of this exchange is motivated by new limitations and requirements that emerge as a result of this synthesis. Ultimately, the design process is concluded when an optimal experimental design is identified and fabricated. The recent development of the controllable heat flux device utilized this synergetic relationship.
Toxicity of a New Polynitramine Energetic Material, CL-20, to the Enchytraeid Worm, Enchytraeus Crypticus, in a Sandy Loam Soil
Personal Author(s): Kuperman, Roman G , Checkai, Ronald T ,Simini, Michael, Phillips, Carlton T ,Anthony, J S ,Kolakowski, Jan E ,Kurnas, Carl W Davis, Emily A
Report Date: Aug 2006
Descriptors: (U) *TOXICITY, *WORMS, *NITRAMINES, CONTAMINANTS, LOAMS, WEATHERING, ECOLOGY, ENERGETIC PROPERTIES
Identifiers: *CL-20(HEXANITROHEXAAZAISOWURTZITANE), *ENCHYTRAEUS CRYPTICUS, SOIL SCREENING, NATURAL SOIL, BIOAVAILABILITY
Abstract: (U) In this report, the toxicity of polynitramine energetic material, hexanitrohexaazaisowurtzitane (CL-20), to the soil invertebrate species, Enchytraeus crypticus, was investigated using the Enchytraeid Reproduction Test. The study was designed to develop eco-toxicological benchmark values for the ecological risk assessment of the potential impacts of the accidental release of this compound into the environment. Tests were conducted in Sassafras Sandy Loam soil, which supports the relatively high bio-availability of CL-20. Weathering and aging procedures for CL-20 amended into test soil were incorporated into the study design to produce toxicity data that better reflect soil exposure conditions in the field. Results showed that toxicities for E. crypticus adult survival and juvenile production were significantly increased in weathered and aged treatments compared with toxicity in freshly amended soil, based on 95% confidence intervals. These findings of increased toxicity to E. crypticus in weathered and aged CL-20 treatments show that future investigations should include a weathering and aging component to generate toxicity data that provide more complete information on the eco-toxicological effects of emerging energetic contaminants in soil.
THE NOMINAL/GENERIC SPECIFIC HEAT PER AVERAGE ATOM CONCEPT FOR CHNO ENERGETIC MATERIALS
Personal Author(s): Billingsley, James P
Report Date: Jul 2006
Descriptors: (U) *ATOMS, *ENERGETIC PROPERTIES, *SPECIFIC HEAT, REACTIVITIES, HMX, PLASTIC BONDED EXPLOSIVES, TNT, IMPACT SHOCK
Identifiers: (U) *CHNO ENERGETIC MATERIALS, REACTIVE TEMPERATURES, SHOCK LOADED EXPLOSIVES, SHOCK REACTION CRITERIA, PBX(PLASTIC BONDED EXPLOSIVES)
Abstract: (U) This document is a follow on to U.S. Army Micom TR-RD-SS-95-2, AMCOM-TR-RD-SS-98-2, and TR-RD-SS-06-09 that related plane impact shock sensitivity of CHNO energetic materials to specific heat per average atom magnitude and Reactive Temperature (T(r)) conditions. Observation of the C(p) per average atom versus absolute Temperature (T) plots revealed relatively little difference in magnitude for seven important explosive compounds. Thus, a universal nominal/generic C(p) per average atom is proposed for CHNO energetic materials. This report is devoted to substantiating this N/G C(p) per average atom concept and illustrating its practical utilization via examples for TNT, HMX, and PBX-9502.
THE MECHANISM AND DYNAMICS OF EXPLOSIVE COMBUSTION IN AEROSOL FUELS
Personal Author(s): Baer, Tomas , Miller, Roger E
Report Date: Jun 2006
Descriptors: (U) *AEROSOLS, *COMBUSTION, *CHEMICAL REACTIONS, ABLATION, IONIZATION, ION ION INTERACTIONS, IRRADIATION, FUELS, SPECTROMETRY, HIGH ENERGY
Identifiers: (U) LIQUID STATE COMBUSTION, CONDENSED PHASE COMBUSTION, ION EXTRACTION, COULOMB EXPLOSION, ENERGETIC MATERIALS, COMBUSTION REACTIONS, ION-ION RECOMBINATION, IONIC LIQUIDS
Abstract: (U) The research involves the production of high energy material particles with diameters between 1 and 5 microns and the study of its subsequent combustion by rapid laser heating or photolysis. Alternatively, the high-energy ionic liquids with no vapor pressure are placed on a plate inside the vacuum and irradiated with high intensity IR radiation. In either case, the reaction products are followed by single photon vacuum UV laser ionization in a time of flight (TOF) mass spectrometer. The purpose is the elucidation of reaction mechanisms in high density or condensed phases and the development of more efficient methods of combustion. The experimental set-up includes aerosol generation tools that inject the particles at atmospheric pressure into an aerodynamic lens, which focuses the particles onto the center of a 3 mm expansion nozzle, whereupon the particles are accelerated to velocities of 200 to 300 m/s depending upon their size.
PROGRESS TOWARDS A BENCHTOP ENERGETICS CAPABILITY (BRIEFING CHARTS)
Descriptive Note: AFOSR Meeting paper
Personal Author(s): Fajardo, Mario E, Lewis, William K
Report Date: Jun 2006
Descriptors: (U) *METALS, *MATERIALS, *ENERGETIC PROPERTIES, *OXIDIZERS, THERMAL PROPERTIES, THIN FILMS, TRANSPARENCE, WORKSHOPS, BENCH TESTS, MASS SPECTROMETRY, SHOCK TUBES, EXPANSION, TARGETS, LASERS, LASER BEAMS, FUELS, PARTICLES
Identifiers: (U) NANOMETRICS, COMPONENT REPORTS, PE61102F, PE62602F, WUAFRL23032502EM100215
Abstract: (U) The incorporation of nanometric (sub-micron size) metal fuel and oxidizer particles into energetic materials is a promising approach to increasing significantly the systems-level performance of munitions. We propose to exploit the phenomenon of laser driven shock initiation of energetic materials to enable bench-scale testing of initiation mechanisms and energy-release reaction kinetics of nanometric energetic materials using methods which utilize a minimum of often rare and expensive energetic materials, and which routinely yield rapid repetitive energetic events. Direct laser initiation of energetic materials involves a complicated combination of shock, electronic, and thermal effects which are very difficult to relate to real-world chemical-explosive-driven initiation processes. We will use laser driven flyer plates to decouple the laser photon flux from the energetic material, reducing interference from direct electronic and thermal initiation mechanisms, thus greatly simplifying matters. The technology for producing laser driven flyers is advancing rapidly, thanks to efforts in a number of laboratories around the world. We will exploit as much of the state-of-the-art as feasible, including the use of advanced numerical simulation techniques to model our benchtop experiments. We will adapt the "nanoshock target array" approach, pioneered by Dlott and coworkers, for generating repetitive energetic events. In this method thin films of energetic materials are prepared on a transparent substrate "target coupon" which is rastered mechanically through the fixed focus of a pulsed laser beam. Our novel adaptation will include the laser driven flyer plate intermediate and a target-in-vacuum capability. The expansion of reaction intermediates into vacuum will quench subsequent reactions and preserve these intermediates for spectroscopic and mass spectrometric interrogation.
STRUCTURE AND ENERGETICS OF MACROMOLECULAR SYSTEMS: POSS, METAL CLUSTERS AND OTHER OLIGOMERIC MOLECULES
Personal Author(s): Bowers, Michael T
Report Date: 31 Mar 2006
Descriptors: (U) *ELECTROOPTICS, *STRUCTURAL PROPERTIES, *MACROMOLECULES, *OLIGOMERS, *ENERGETIC PROPERTIES, IONS, METALS, CATIONS, OXYGEN, OXIDATION, BONDING, ALKENES, TITANIUM OXIDES, SILVER, ANIONS, FLUORIDES, GOLD, ORGANIC MATERIALS, LIGANDS, NUCLEAR BINDING ENERGY, X RAYS, MOLECULES, MOBILITY, DETECTION
Identifiers: (U) *POLYHEDRAL OLIGOMERIC SILSESQULOXANES, *MACROMOLECULAR SYSTEMS, *METAL CLUSTERS, *OLIGOMETRIC MOLECULES, POSS(POLYHEDRAL OLIGOMERIC SILSESQULOXANES), ION MOBILITY, POLYPHENYL VINYLENES, PARACYCLOPHANES
Abstract: (U) Work has been completed in three areas of research. The first is in characterization of polyhedral oligomeric silsesquioxanes (POSS) and their attachment to backbones of organic-based oligomers. Using ion mobility, we have structurally characterized a wide variety of POSS species attaining good agreement with x-ray structures when available. We have also characterized di- and tri-siloxanes, POSS cages covalently bound via oxygen bridges. Most recently we have been able to insert a fluoride ion into the cage which should make detection of larger POSS/oligomer systems feasible. The second area of research deals with organic oligomeric systems. We have focused on systems with potential for opto-electronic or organo-electronic device formation. Successful work has been completed on a series of polyphenyl vinylenes and several paracyclophanes. Finally, we have generated and characterized the structures and ligand binding energies of both anionic and cationic gold and silver clusters (n = 2 to 13). These systems have been shown to have size-dependent catalytic behavior for double bond oxidation in small alkenes when dispersed on titanium oxide surfaces. We have focused on C2H4 and CH3CHCH2 due to their industrial importance.
DEVELOPMENT OF A NOVEL CONTINUOUS PROCESSING TECHNOLOGY FOR FUNCTIONALLY GRADED COMPOSITE ENERGETIC MATERIALS USING AN INVERSE DESIGN PROCEDURE
Personal Author(s): Bruck, Hugh A, Gallant, Frederick M, Gowrisankaran, Swami
Report Date: Jan 2006
Descriptors: (U) *COMPOSITE MATERIALS, *ENERGETIC PROPERTIES, *SOLID ROCKET PROPELLANTS, ALGORITHMS, MICROSTRUCTURE, OPTIMIZATION, BURNING RATE, STRUCTURES, MODELS, PERFORMANCE(ENGINEERING)
Identifiers: (U) *FGM(FUNCTIONALLY GRADED MATERIALS), PEM(PETITE ENSEMBLE MODEL), DEGA(DIFFERENTIAL EVOLUTION GENETIC ALGORITHM)
Abstract: (U) For a variety of applications, the functional requirement of a material can vary with location within a structure. One way to address this has been to use different materials, joined together so as to take care of the functional requirements at different locations. This unfortunately gives rise to undesirably high stress concentrations at the interface, when the structure is loaded, which might lead to failure. Attempts at controlling these stresses have led to the concept of Functionally Graded Materials (FGMs). FGMs are structures that possess gradual variations in material behavior that enhance material and/or structural performance. For example, at one point the material may be hard and at another point it may be soft. The description of this functional variation is known as the FGM architecture. Typical architectural parameters include layer thickness, t, and composition gradient, p. In designing FGMs, it is desirable to determine the architectural parameters that optimize system performance for a given application by modeling the relationship between the processing of a FGM, the microstructures that develop, and their related properties. FGMs are being applied to a variety of structural and nonstructural applications. Recently, FGM concepts have become of interest to the U.S. Navy to improve large caliber gun propellant performance by replacing a 7-perf grain with a single perf grain that has the same performance, but burns more efficiently because it possesses a functionally graded architecture. In the case of composite energetic materials used as solid rocket propellants, referred to as a grain, the volume fraction of ingredients, such as 30 and 200 micron AP particles (VAP) can be varied along the length of the grain to produce a corresponding difference in burn rate. It can be noted that the burn rate is related not only the volume fraction of AP particles, but the particle size distribution as well.
EXTEND MANPADS M&S CAPABILITIES TO INCLUDE ENERGETIC MATERIALS, FRAGMENTATION EFFECTS, AND WING FLUTTER RESPONSE
Personal Author(s): Hinrichsen, Ronald L, Moshier, Monty A , Choules, Brian
Report Date: 31 Dec 2005
Descriptors: (U) *AIR DEFENSE, *SIMULATION, *WINGS, *MODELS, *MANPORTABLE EQUIPMENT, FRAGMENTATION, DETONATIONS, GRUNEISEN CONSTANT, BOUNDARY ELEMENT METHODS, EQUATIONS OF STATE, FLUTTER, PENETRATION, ENERGETIC PROPERTIES, INCOMPRESSIBLE FLOW, EULER EQUATIONS
Identifiers: ) *MANPADS(MAN-PORTABLE AIR DEFENSE SYSTEM), M&S(MODELING & SIMULATION), JWL(JONES-WILKINS-LEE) EQUATIONS
Abstract: (U) The purpose of this effort is to create an analytical physics based aircraft-MANPADS model capability that includes impact, detonation, penetration, and wing flutter response. This work extends an existing body-on-body missile model to include energetic materials, fragmentation effects and wing flutter response due to dynamic air loads. The detonation of the high explosive within the missile, as well as the expansion of the surrounding fluids, was modeled in the Eulerian domain. The Jones-Wilkins-Lee (JWL) equation of state was used to model the explosive and the Gruneisen equation of state was used for the surrounding fluids. Linear Boundary elements based on inviscid, incompressible flow theory were coupled with the wing structure model to simulate air loads. A modular approach was taken to separate the Eulerian domain and the JWL equation model, from the model including the target. Separating the models allows the complex physics to be mapped onto the missile including the target, preserving the physics without the added costs. Evaluation was done of various element failure criteria to increase model robustness. Lastly, the model was used to evaluate the dynamic air loads and response of wing flutter. A physics based MANPADS model has been created which includes impact penetration detonation and fragmentation with drag.
DESIGN METHODOLOGY FOR UNDERSTANDING THE SYMPATHETIC DETONATION CHARACTERISTICS OF INSENSITIVE HIGH EXPLOSIVES
Personal Author(s): Raghavan, Dinesh
Report Date: Dec 2005
Descriptors: (U) *INSENSITIVE EXPLOSIVES, *SYMPATHETIC DETONATIONS, REQUIREMENTS, SIMULATION, MATERIALS, THESES, SHELF LIFE, SHOCK, SAFETY, STORAGE, ENERGETIC PROPERTIES
Identifiers: (U) AUTODYN(COMPUTER PROGRAM)
Abstract: (U) The understanding of sympathetic detonation of energetic materials is important from the stand point of safety, shelf life, storage requirements and handling. The objective of this thesis is to introduce a methodology to assess performance and sensitivity levels of insensitive munitions to sympathetic detonations. AUTODYN code was utilized to validate the shock sensitivity results for Composition B explosives. Upon code validation, simulations were conducted to evaluate small scale sympathetic detonation via gap tests. Similarly, large scale simulations of sympathetic detonations, reflective of real life scenarios, were performed. The understanding of this analysis offers insights for the testing, design and storage orientation of future energetic materials.
ULTRAFAST VIBRATIONAL SPECTROSCOPY OF INHOMOGENEOUS ENERGETIC MATERIALS AND ENERGETIC INTERFACES
Personal Author(s): Dlott, Dana D
Report Date: Dec 2005
Descriptors: (U) *COMPOSITE MATERIALS, *LASERS, *ENERGETIC PROPERTIES, COMPRESSION, METHODOLOGY, OPTICS, MECHANICAL PROPERTIES, VIBRATION, VIBRATIONAL SPECTRA, DIAGNOSIS(GENERAL), SHOCK, HIGH RATE, SPECTROSCOPY, MOLECULAR STATES, INTERFACES, LIQUIDS
Identifiers: (U) VIBRATIONAL SPECTROCOPY, *NANOENERGETIC MATERIALS, *ENERGETIC INTERFACES
Abstract: (U) The goal of this project is the development of a fundamental understanding of nanocomposite energetic materials and fast mechanical processes at a molecular level. We are attacking these difficult problems using three parallel approaches. (1) Laser flash-heating of nanoenergetic materials combined with optical diagnostic techniques; (2) Ultrafast laser shock compression of solids combined with vibrational spectroscopy; (3) Multidimensional vibrational spectroscopy of liquids to study the flow of vibrational energy.
MICROSTRUCTURE OF CONVENTIONAL AND REDUCED SENSITIVITY RDX
Personal Author(s): Herrmann, Michael J, Ludwig, Bastian
Report Date: Dec 2005
Descriptors: (U) *MICROSTRUCTURE, *X RAY DIFFRACTION, *INSENSITIVE EXPLOSIVES, *RDX, CRYSTAL STRUCTURE, SENSITIVITY, GERMANY
Identifiers: (U) *INSENSITIVE MUNITIONS, *REDUCED SENSITIVITY, ENERGETIC MATERIALS, MICRO STRAIN, FOREIGN REPORTS
Abstract: (U) This report results from a contract tasking Fraunhofer Institute for Chemical Technology as follows: Reduced Sensitivity (RS) energetic materials are in the scope of interest, particularly, for the development and refinement of IM PBX as PBXN-109. Such improved versions of current explosive ingredients as RDX and HMX facilitate progress in times of limited funding, as an introduction of new ingredients as FOX-7 would give rise to considerably higher costs. However the mechanisms behind the sensitivity reduction are far from being clear. Particle size, shape, surface morphology, voids, inclusions and impurities, lattice dislocations and deformation twinning of ingredients as RDX and HMX have been discussed to influence the mechanical sensitivity. Within the last years X-ray diffraction methods have been elaborated and refined at ICT, particularly for investigating micro strain in energetic materials, These methods shall now be tested for characterizing and distinguishing reduced sensitivity from conventional RDX. A sample portfolio of different crystal qualities of RDX will be collected, including conventional and reduced sensitivity samples, and the samples will be investigated with advanced X-ray diffraction techniques.
ALKALINE HYDROLYSIS OF CL-20
Personal Author(s): Karakaya, P, Sidhourn, M, Christodoulatos, C Balas, Wendy, Nicolich, Steven
Report Date: Aug 2005
Descriptors: (U) *HYDROLYSIS, *ALKALINITY, TEMPERATURE, ENVIRONMENTS, MATERIALS, RATES, ACTIVATION ENERGY, HMX, RDX, ENERGETIC PROPERTIES, HIGH ENERGY, HIGH DENSITY, KINETICS
Abstract: (U) The Energetics and Warheads Division of the U.S. Army Armament Research, Development and Engineering Center has been involved in the development of CL-20. An alkaline hydrolysis study was performed to better understand the fate and transport of CL-2O through environmental systems. CL-20, also known as HN 1W (2,4,6,8,10,1 2-hexanitro-2,4,6,8, 10,1 2-hexaaziaisowurtzitane), is a high energy, high density material. Concerns regarding the envirnnmental fate and transport of CL-20 are arising due to its potential introduction into soil and water matrices. The aqueous hydrolysis of CL-20 was investigated as a possible remediation technique. Alkaline hydrolysis experiments were conducted at temperatures of 15, 20, 30, and 4000, with hydroxide concentrations ranging from 0.25 to 300 mM. Like RDX and HMX, alkaline hydrolysis of CL-20 follows second- order kinetics. CL-20 alkaline hydrolysis was found to proceed at a significantly faster rate than RDX. The temperature dependency of the second-order rate constants was evaluated using the Arrehnius model. The activation energy for CL-20 was found to be within close range of the activation energies reported for RDX and HMX.
ENERGETIC MATERIALS MODELING FOR ROCKET PROPULSION
Personal Author(s): Boatz, Jerry, Mills, Jeffrey
Report Date: Aug 2005
Descriptors: (U) *ENERGETIC PROPERTIES, *ROCKET PROPULSION, *ROCKET PROPELLANTS, MODELS, QUANTUM CHEMISTRY, SPECTRAL EMITTANCE, SOFTWARE TOOLS, IONIC STRENGTH, COMPUTATIONAL CHEMISTRY, CHEMICAL COMPOUNDS, MATERIALS, SYNTHESIS(CHEMISTRY), TARGETS
Identifiers: (U) HPC(HIGH PERFORMANCE COMPUTING), IONIC LIQUIDS, SPECTRAL THEORY, BRIEFING CHARTS, WUAFRL23030423
Abstract: (U) OUTLINE: 1. Introduction; 2. Technical challenges in propellant design; 3. Modeling and Simulation (M&S) techniques & tools: (a) Quantum chemistry; (b) High Performance Computing (HPC); 4. Examples: (a) Identification of suitable target compounds; (b) Determination of viable intermediates; (c) Confirmation of successful synthesis; 5. Challenges and Bottlenecks; 6. Summary and Conclusions.
AQUEOUS SOLUBILITY OF CL-20
Descriptive Note: Contractor rept.
Personal Author(s): Karakaya, P
Report Date: Aug 2005
Descriptors: (U) *SOLUBILITY, *AQUEOUS SOLUTIONS, TEMPERATURE, ENVIRONMENTS, MODELS, WATER, ENERGETIC PROPERTIES, MATERIALS, HIGH ENERGY, HIGH DENSITY, TRANSPORT
Identifiers: (U) CL-20
Abstract: (U) The Energetics and Warheads Division of the U.S. Army Armament Research, Development and Engineering Center has been involved in the development of CL-20. An aqueous solubility study was performed to better understand the fate and transport of CL-20 through environmental systems. CL-2O, also known as HN 1W (2,3,6,8,10,1 2-hexanitro-2,4,6,8, 10,1 2-hexaazaisowurtzitane), is a high energy, high density material. Concerns regarding the environmental fate and transport of CL-20 are arising due to its potential introduction into soil and water matrices. Work is currently being conducted to study the fate and transport of CL-20 in soil and water matrices. Determination of solubility characteristics of CL-20 in water is a preliminary task necessary to begin other fate and transport studies. The aqueous solubility of CL-20 was measured over a broad temperature range and the data were fitted to a generalized solubility model.
ENERGETIC IONIC LIQUIDS AS TNT REPLACEMENTS (BRIEFING CHARTS)
Personal Author(s): Hawkins, T W
Report Date: Jun 2005
Descriptors: (U) *LIQUID EXPLOSIVES, DENSITY, SYNTHESIS(CHEMISTRY), SALTS, TNT, DETONATIONS, HETEROCYCLIC COMPOUNDS, EUTECTICS, HEAT OF FORMATION
Identifiers: (U) *IONIC LIQUIDS, ENERGETIC MATERIALS, HETEROCYCLIC SALTS, TRIAZOLIUM SALTS, WUAFRL50260541
Abstract: (U) Presentation on the use of energetic ionic liquids as a substitute for TNT in melt-cast explosives.
IONIC LIQUIDS RESEARCH AND DEVELOPMENT - US AIR FORCE RESEARCH LABORATORY. MOLECULAR DYNAMICS CONTRACTORS MEETING
Personal Author(s): Hawkins, Tim, Schneider, Stefan, Alfano, Angelo, Vaghjiani, Gammy, Mills, Jeff, Hall, Leslie , Tzeng, Donald, Boatz, Jerry
Report Date: 24 May 2005
Descriptors: (U) *KINETIC ENERGY, *ENERGETIC PROPERTIES, *CRYSTALLOGRAPHY, SYMPOSIA, AIR FORCE RESEARCH, X RAYS, NITROGEN, COMBUSTION, REPLACEMENT, IGNITION, AIR FORCE FACILITIES, TNT, WORKSHOPS, MOLECULAR DYNAMICS
Identifiers: (U) *IONIC LIQUIDS, PRESENTATION SLIDES, ENERGETIC MATERIALS, HETEROCYCLES, ION LIQUID MOLECULES, SHOCK VELOCITY, TRIAZOLIUM
Abstract: (U) This documents reports on: 1) Recent Ionic Liquid Synthesis and Characterization; 2) Ionic Liquid Fuel for Biopropulsion; 3) Ionic Liquids in Munitions; 4) Energetic Ionic Liquids for TNT Replacements; and 5) Theoretical Performance.
MATERIALS MODELING FOR ROCKET PROPULSION
Descriptive Note: Briefing charts
Personal Author(s): Boatz, Jerry
Report Date: Apr 2005
Descriptors: (U) *SIMULATION, *MODELS, *MATERIALS, *ROCKET PROPULSION, *ROCKET PROPELLANTS, QUANTITATIVE ANALYSIS, QUANTUM CHEMISTRY, COMPUTER PROGRAMMING, SYNTHESIS(CHEMISTRY), ENERGETIC PROPERTIES, CHEMICAL COMPOUNDS, MOLECULAR DYNAMICS
Identifiers: (U) *M&S(MODELING AND SIMULATION), BRIEFING CHARTS, QSPR(QUANTITATIVE STRUCTURE-PROPERTY RELATIONSHIP), HPC(HIGH PERFORMANCE COMPUTING), WAFRL23030423
Abstract: (U) OUTLINE: 1. Introduction; 2. Technical challenges in propellant design; 3. Modeling and Simulation (M&S) techniques & tools: a) Quantum chemistry; b) Molecular dynamics; c) QSPR; d) High Performance Computing (HPC); 4. Examples: a) Identification of suitable target compounds; b) Determination of viable intermediates; c) Confirmation of successful synthesis; 5. Summary and Conclusions.
Approved for public release
TOXICITY OF NITRO-HETEROCYCLIC AND NITROAROMATIC ENERGETIC MATERIALS TO TERRESTRIAL PLANTS IN A NATURAL SANDY LOAM SOIL
Personal Author(s): Rocheleau, Sylvie, Martel, Majorie, Bardai, Ghalib, Sarrazin, Manon, Dodard, Sabine, Paquet, Louise, Corriveau, Alain ,Kuperman, Roman G , Checkai, Ronald T, Simini, Michael
Report Date: Apr 2005
Descriptors: (U) *TOXICITY, *ENERGETIC PROPERTIES, *SOIL TESTS, *PLANTS(BOTANY), *LOAMS, AGING(MATERIALS), RDX, HMX, DNT, RISK ANALYSIS, BENZENE COMPOUNDS, NITROGEN HETEROCYCLIC COMPOUNDS, WEATHERING, ECOLOGY, CHEMICAL ANALYSIS, CONTAMINANTS, AROMATIC COMPOUNDS
Identifiers: (U) ECO-SSL(ECOLOGICAL SOIL SCREENING LEVEL), TNB(TRINITROBENZENE)
Abstract: (U) The United States Environmental Protection Agency is developing ecological soil screening level (Eco-SSL) values for ecological risk assessment of contaminants at Superfund sites. Insufficient information for RDX, HMX, 2,4-DNT, 2,6-DNT, and TNB to generate Eco-SSLs for terrestrial plants necessitated toxicity testing to fill the data gaps. Standardized toxicity tests were selected and used, on the basis of their ability to measure chemical toxicity to ecologically relevant test species, and their inclusion of growth component among the measurement endpoints. Tests were conducted in Sassafras sandy loam soil, which supports relatively high bioavailability of the energetic materials. Weathering/aging of amended treatment soil was incorporated in the study to better reflect the exposure conditions in the field soils. Definitive toxicity tests conducted with freshly amended and weathered/aged amended soils generated eco-toxicological benchmarks, including EC20 values for growth that can be used for Eco-SSL development. These study results will be provided to the Eco-SSL workgroup for review and for developing ecological soil screening levels (Eco-SSLs) for RDX, HMX, 2,4-DNT, 2,6-DNT, and TNB.
DYNAMIC DEFORMATION PROPERTIES OF ENERGETIC COMPOSITE MATERIALS
Personal Author(s): Field, J E, Proud, W G , Siviour, C R, Walley, S M
Grantham, S G , Williamson, D M, Czerski, H
Report Date: Apr 2005
Descriptors: (U) *COMPOSITE MATERIALS, *DEFORMATION, METHODOLOGY, OPTICS, PARTICLE SIZE, STRAIN RATE, INSTRUMENTATION, SOLID STATE ELECTRONICS, HMX, ENERGETIC PROPERTIES, PHYSICS, MECHANICAL PROPERTIES, HIGH RATE, DYNAMICS, PHASE TRANSFORMATIONS
Identifiers: (U) *ENERGETIC COMPOSITE MATERIALS
Abstract: (U) This final report consists of six chapters: (1) An introduction to the PCS Fracture and Shock Physics Group (PCS FSP) and some preliminary experiments on PBXs (pp. 3-46); (2) The effect of particle size and temperature on the high strain rate properties of an AP/HTPB PBX (pp. 47-55); (3) Developments in Hopkinson bar instrumentation (pp. 56-74); (4) Visits of Clive R. Siviour to Eglin Airforce Base and studies of impact-induced solid-state phase change in HMX (pp. 75-77); (5) High rate mechanical properties of PBXs (pp. 78-102); (6) Optical techniques (pp. 103-160). Also in Appendix 2 there is a list of the papers published by the PCS FSP Group (and one report from Eglin AFB) during the duration of this contract (2003-2005). Most of these documents are available in pdf format.
FEMTOSECOND REAL-TIME PROBING OF ENERGETIC REACTIONS: COMPLEX ORGANICS AND ADVANCED TECHNIQUES
Personal Author(s): Zewail, Ahmed H
Report Date: 24 Jan 2005
Descriptors: (U) *MOLECULAR STRUCTURE, *ENERGETIC PROPERTIES, EXPERIMENTAL DATA, DYNAMICS, MOLECULES, THEORY, PROTOTYPES, EXPLOSIVES, ORGANIC MATERIALS, MOLECULAR PROPERTIES
Abstract: (U) The research was focused on two major areas. The first area is the advancement of new techniques to elucidate elementary steps of reactions in complex molecular systems. In the second area, the effort was on the applications of these techniques to: (i) the studies of reactive intermediates of energetic reactions, and (ii) the dynamics of prototype molecular explosives. We have succeeded in advancing the new techniques for the studies of structure and dynamics of highly-excited and energetic molecules, and the progress in theoretical and experimental studies has been published in a series of papers.
ULTRAFAST SPECTROSCOPY OF ENERGETIC MATERIALS: TOWARD A MOLECULAR UNDERSTANDING OF IMPACT SENSITIVITY
Personal Author(s): Dlott, Dana D
Report Date: 12 Jan 2005
Descriptors: (U) *SPECTROSCOPY, *MATERIALS, *ENERGETIC PROPERTIES, VIBRATION, TECHNOLOGY TRANSFER, ENERGY TRANSFER, COMBUSTION, SHOCK, MOLECULAR STRUCTURE, IGNITION, NANOTECHNOLOGY, MOLECULAR DYNAMICS
Identifiers: (U) SHOCK INITIATION, ENERGETIC MATERIALS, NONENERGETIC MATERIALS
Abstract: (U) We have progress to report in three areas: (1) fast vibrational spectroscopy of nanoenergetic material ignition; (2) ultrafast surface spectroscopy; (3) 3D spectroscopy of ultrafast vibrational energy transfer. The original goals of this project have not changed, however we have extended our work to include nanotechnology energetic materials. We developed a fast laser-ignition technique for these materials and have successfully probed the time and space dependence of chemistry of Al+ oxidizer systems. Using vibrational sum-frequency generation (SFG) we have probed the structure of shock fronts with 1.5 Angstrom resolution. With 3D spectroscopy we have studied vibrational energy transfer in water and for the first time we have been able to watch vibrational energy flow across the interface between a molecular nanostructure and its surroundings.
MOLECULAR SIMULATIONS OF DYNAMIC PROCESSES OF SOLID EXPLOSIVES
Personal Author(s): Rice, Betsy M, Sorescu, Dan C, Kabadi, Vinayak, Agrawal, Paras M, Thompson, Donald L
Report Date: Dec 2004
Descriptors: (U) *EXPLOSIVES, *ENERGETIC PROPERTIES, *MOLECULAR DYNAMICS, SIMULATION, SYMPOSIA, STRUCTURAL PROPERTIES, MATERIALS, THERMODYNAMIC PROPERTIES, ATOMIC ENERGY LEVELS
Identifiers: (U) COMPONENT REPORTS
Abstract: (U) A variety of molecular dynamics simulations of energetic materials is presented, demonstrating the ability to predict structural and thermodynamic properties of these materials. The studies are also used to explore at an atomic level dynamic processes that might influence conversion of the material to products. These studies are presented to illustrate how information generated through molecular dynamics simulations can be used in the design, development and testing of energetic materials.
CHEMICAL EQUILIBRIUM MIXTURE COMPUTATIONS FOR ENERGETIC MATERIAL COMBUSTION IN CLOSED VESSELS
Personal Author(s): Wong, F C , Gottlieb, J J , Lussier, L -S
Report Date: Dec 2004
Descriptors: (U) *COMPUTATIONS, *PHASE TRANSFORMATIONS, *COMBUSTION, *PRESSURE VESSELS, *ENERGETIC PROPERTIES, *CHEMICAL EQUILIBRIUM, SYMPOSIA, CANADA, GASES, CODING, COMBUSTION CHAMBERS, EQUATIONS OF STATE, COMPLEX VARIABLES
Identifiers: (U) *CERV(COMPUTATIONAL CODE), FOREIGN REPORTS, COMPONENT REPORTS, REACTION VARIABLES
Abstract: (U) A major computational code called CERV was developed to determine complex equilibrium compositions of a non-ideal mixture of numerous imperfect gases and compressible liquid and solid species with phase transitions for closed-vessel applications. This code minimizes Gibbs energy using reaction variables, in contrast to other major codes like BRL-Blake, BRCBagheera and NASA-CEA that use composition variables such as mole numbers. The CERV code has significant advantages in handling compressible condensed species with phase transitions and computing non-ideal mixture compositions accurately and efficiently. Computations are done robustly, without convergence failures from matrix inversions or iterative procedures, for problems with reaction products consisting of hundreds of gaseous, liquid and solid species.
ENERGETIC MATERIAL SIMULATIONS: ADVANCING THE FUTURE FORCE
Descriptive Note: Conference paper
Personal Author(s): Mattson, William D , Rice, Betsy M
Report Date: Dec 2004
Descriptors: (U) *COMPUTER PROGRAMS, *ENERGETIC PROPERTIES, *SIMULATION LANGUAGES, *MOLECULAR DYNAMICS, SYMPOSIA, COMPUTATIONS, COMPUTER PROGRAMMING, EXPLOSIVES, VISUAL PERCEPTION, PACKING DENSITY, GRAPHICAL USER INTERFACE
Identifiers: (U) *EXTENSIBLE SOFTWARE, *XML(EXTENSIBLE MARKUP LANGUAGE), VISUALML(VISUAL MARKUP LANGUAGE), VSDE(VISUAL SIMULATOR DEVELOPMENT ENVIRONMENT), COMPONENT REPORTS
Abstract: (U) We describe a new extensible software system to perform molecular simulations of energetic materials. A new approach for extensible software development based on an XML description of a program structure and a set of components stored in shared object libraries is described first. A specific example of molecular dynamics simulations for energetic materials is given next and this is finally expanded with the capability to perform molecular packing calculations to show the extensibility and applicability of the system.
NOVEL SIMULATIONS OF ENERGETIC MATERIALS: CIRCUMVENTING LIMITATIONS IN EXISTING METHODOLOGIES
Personal Author(s): Brennan, John K , Rice, Betsy M , Byrd, Edward F
Report Date: Dec 2004
Descriptors: (U) *SIMULATION, *METHODOLOGY, *SHOCK, *ENERGETIC PROPERTIES, *HUGONIOT EQUATIONS, ALGORITHMS, SYMPOSIA, COMPUTATIONS, PARAMETERS, REACTIVITIES, MONTE CARLO METHOD, LIQUID NITROGEN, EQUATIONS OF STATE, MOLECULAR DYNAMICS
Identifiers: (U) COMPONENT REPORTS
Abstract: (U) We present a methodology for the efficient calculation of the shock Hugoniot using standard molecular simulation techniques. The method is an extension of an equation of state methodology proposed by J. J. Erpenbeck and is considered as an alternative to other methods that generate Hugoniot properties. We illustrate the methodology for shocked liquid N(sub2) using two different simulation methods: (a) the Reaction Ensemble Monte Carlo method for a reactive system; and (b) the molecular dynamics method for a non-reactive system. The method is shown to be accurate, stable and generally independent of the algorithm parameters. We find excellent agreement with results calculated by other previous simulation studies. The results show that the methodology provides a simulation tool capable of determining points on the shock Hugoniot from a single simulation in an efficient, straightforward manner.
Ab Initio Predictions of Structures and Densities of Energetic Solids
Personal Author(s): Rice, Betsy M , Sorescu, Dan C
Report Date: Dec 2004
Descriptors: (U) *CRYSTAL STRUCTURE, *ORGANIC NITROGEN COMPOUNDS, *ENERGETIC PROPERTIES, COMPUTERIZED SIMULATION, DENSITY, SYMPOSIA, ALIPHATIC COMPOUNDS, EXPLOSIVES, MATHEMATICAL PREDICTION, MOLECULE MOLECULE INTERACTIONS, AROMATIC COMPOUNDS, ESTERS, ALIPHATIC HYDROCARBONS, NITRAMINES, NITRATES
Identifiers: (U) *ENERGETIC MATERIALS, AB INITIO CALCULATIONS, NITROAROMATIC COMPOUNDS, NITRATE ESTERS, NITROALIPHATIC COMPOUNDS, COMPONENT REPORTS
Abstract: (U) We have applied a powerful simulation methodology known as ab initio crystal prediction to assess the ability of a generalized model of CHNO intermolecular interactions to predict accurately crystal structures and densities of various classes of explosives. 174 crystals whose molecules contain functional groups common to CHNO energetic materials were subjected to this methodology and include acyclic and cyclic nitramines, nitrate esters, nitroaromatics, and nitroaliphatic systems. The results of these investigations have shown that for 148 of the 174 systems studied the predicted crystal structures matched the experimental configurations; 75% of these corresponded to the global energy minimum on the potential energy surface. The success rate in predicting crystals with structural parameters and space group symmetries in agreement with experiment indicates that this method and interaction potential are suitable for use in crystal predictions of similar CHNO systems when the molecular configuration is known.
THE STRENGTHENING OF ENERGETIC MATERIALS UNDER PRESSURE
Personal Author(s): Wiegand, Donald A, Reddingius, Brett
Report Date: Dec 2004
Descriptors: (U) *ENERGETIC PROPERTIES, MECHANICAL PROPERTIES, COMPOSITE MATERIALS, HIGH PRESSURE, BAROMETRIC PRESSURE, PLASTIC BONDED EXPLOSIVES, PLASTIC FLOW, HYDROSTATIC PRESSURE
Abstract: (U) The mechanical properties of composite plastic bonded explosives are being studied as a function of hydrostatic confining pressure. The flow stress and the modulus obtained in simple compression are both found to increase with increasing confining pressure. Thus, these materials become stronger and stiffer with increasing pressure. The sensitivity to pressure, however, decreases with increasing pressure. The failure process also changes with pressure. At atmospheric pressure failure is primarily due to crack processes while at elevated pressures failure is due primarily to plastic flow. Several mechanisms which may account for the pressure dependencies of the flow stress, the modulus and the failure processes are discussed.
HPLC DETERMINATION OF HEXANITROHEXAAZAISOWURTZITANE (CL-20) IN SOIL AND AQUEOUS MATRICES
Personal Author(s): Anthony, J S , Davis, Emily A , Haley, Mark V , Kolakowski, Jan E , Kurnas, Carl W
Report Date: Nov 2004
Descriptors: (U) *SOILS, *CONCENTRATION(COMPOSITION), *FORMULATIONS(CHEMISTRY), TEST AND EVALUATION, QUANTITATIVE ANALYSIS, DETECTION, ACETONITRILE, WATER, MATERIALS, PROPELLANTS, REPLACEMENT, EXTRACTION, MEDIA, ENERGETIC PROPERTIES, CHEMICAL ANALYSIS
Identifiers: (U) HPLC(HIGH PERFORMANCE LIQUID CHROMATOGRAPHY), HEXANITROHEXAAZAISOWURTZITANE, CL-20
Abstract: (U) Hexanitrohexaazaisowurtzitane (CL-20) is a novel energetic material being investigated as a potential replacement for currently used explosive and propellant formulations. The principal objective of this study was to focus on the quantitative chemical analysis of freshly amended (0.01-100 mg/kg) and weathered/aged (0.01-10000 mg/kg) CL-20 in Sassafras Sandy Loam (SSL) soil extracts. Using modified U.S. Environmental Protection Agency (USEPA) Method 8330A, the instrumental limit of detection was 0.01 mg/L. In acetonitrile extracts, the limits of detection for fresh and weathered/aged CL-20 in soils were 0.08 mg/kg and 0.10 mg/kg, respectively, while in ATCLP (water) extracts, the limits of detection for fresh and weathered/aged CL-20 in soils were 0.1 mg/kg and 0.25 mg/kg, respectively. At all amended concentrations, paired t-tests were used to show that the recovery percentages for freshly amended and weathered/aged CL-20 in soil were statistically different. The water extract recoveries were lower due to CL-20's reduced solubility in water. Higher concentrations of CL-20 in soil (>or=1000 mg/kg) did not show a decrease in recovery. The CL-20 (1.5-100 mg/L) was also directly amended to aquatic test media, and the percentage of recoveries were determined. An interlaboratory study was used to validate the modified method and verify experimental results.
MODELING THERMAL IGNITION OF ENERGETIC MATERIALS
Personal Author(s): Gerri, Norman J , Berning, Ellen
Report Date: Nov 2004
Descriptors: (U) *THERMAL PROPERTIES, *ENERGETIC PROPERTIES, VELOCITY, ARMOR, TEMPERATURE, MODELS, MATERIALS, FIELD TESTS, PROPELLANTS, PENETRATION, IGNITION, STORAGE, MELTING POINT, ENVELOPE(SPACE)
Abstract: (U) This report documents an attempt to computationally simulate the mechanics and thermal regimes created when a threat perforates an armor envelope and comes in contact with stowed energetic material (M30 granular propellant). Fragment simulating penetrators (FSP) of 208 and 830 gr were fired into plates of AISI 4340 steel hardened to a Rockwell C + 40. The existing fragment were captured in a polymetric material with a melting point equivalent to the ignition temperature of the propellant. Paralleling the field experiment, a series of CTH 3D finite element runs were carried out using the same initial conditions as the experiments. The temperatures calculated by the CTH codes are compared to the experiment al value. Experimental shots fired into live propellant at velocities selected from the CTH runs gave ignition or no ignition as predicted within reasonable limits.
TOOLS FOR CONDENSED PHASE COMPUTATIONAL CHEMISTRY
Personal Author(s): Szalewicz, Krzysztof
Report Date: 01 Oct 2004
Descriptors: (U) *ENERGETIC PROPERTIES, *COMPUTATIONAL CHEMISTRY, COMPUTATIONS, MOLECULES, WORKSHOPS, CONDENSATION
Identifiers: (U) COMPUTATIONAL CHEMISTRY, CONDENSED PHASE OF ENERGETIC MATERIALS
Abstract: (U) The workshop developed recommendations for those computational chemistry tools best suited to attack research problems in properties of energetic molecules - individually and in condensed phases. A small, international group of experts presented their work and discussed current tools of computational chemistry in the context of the Army program of energetic material design. These experts, chosen for their specific skills, came from Europe and the US.
ACCURATE THEORETICAL PREDICTION OF THE PROPERTIES OF ENERGETIC MATERIALS
Personal Author(s): Thompson, Donald L
Report Date: 31 Aug 2004
Descriptors: (U) *MATERIALS, VALIDATION, MODEL THEORY, MONTE CARLO METHOD, PHASE, CHEMICAL REACTIONS, MELTING, SEPARATION, FLUIDS, SUPERCRITICAL FLOW, POTENTIAL ENERGY, SOLVATION, ENERGETIC PROPERTIES, DECOMPOSITION, COMPUTER BENCHMARKING, MOLECULAR DYNAMICS
Identifiers: (U) AB INITIO QUANTUM CHEMISTRY
Abstract: (U) This report describes the progress and accomplishments for the period June 1, 2002 to August 31, 2004 for the MURI grant "Accurate Theoretical Predictions of the Properties of Energetic Materials" (no. DAAD19-02-1-0176). This is a multi-university, comprehensive theoretical/computational research program to develop, validate, benchmark, and apply methods and models that will provide predictive capabilities for energetic materials. The thrust of the work is the development of atomic-level models and ab initio quantum chemistry methods that are generally applicable to the chemical decomposition of condensed-phase energetic materials under extreme conditions.
EFFECTIVENESS OF SMALL WARHEADS
Personal Author(s): Sparrow, David A
Report Date: Aug 2004
Descriptors: (U) *MOBILITY, *COMMUNICATIONS NETWORKS, *ENERGETIC PROPERTIES, *WARHEADS, *PYROPHORIC MATERIALS, *ANTIPERSONNEL MINES, MINEFIELDS, COMBAT VEHICLES, SELF ORGANIZING SYSTEMS, TETRAFLUOROETHYLENE RESINS, FREQUENCY AGILITY, LETHALITY, ZIRCONIUM, OPERATIONAL EFFECTIVENESS, ALUMINUM
Identifiers: (U) *SHM(SELF-HEALING MINEFIELDS), BRIEFING CHARTS
Abstract: (U) This study was commissioned by the DARPA Self-Healing Minefield (SHM) program. The goal of the SHM program was to increase minefield effectiveness by adding communication and mobility functions to individual mines. This would enable a deployed field to self-organize as a network and detect breaching. Once detected, breaches would be sealed by mines hopping into the breach using their mobility capacity. To produce such mines in the current mine form factor, a smaller warhead was needed to make space for the communications and mobility subsystems. The warhead under consideration used a pyrophoric material, Zr, in the liner. The specific task of this study was to determine whether using pyrophorics or energetic materials such as Al-Teflon would enhance lethality against lightly armored or thin-skinned vehicles. Given the very limited data, assessments were made based on the underlying science of the various lethality mechanisms.
NEW TRENDS IN RESEARCH OF ENERGETIC MATERIALS
Personal Author(s): Zeman, Zvatopluk
Report Date: 31 May 2004
Descriptors: (U) *EXPLOSIVES, *PROPELLANTS, *ENERGETIC PROPERTIES, SYMPOSIA, DISPERSING, EXPLOSIONS, BOMBS, EXPLOSIVE GASES
Identifiers: (U) *ENERGETIC MATERIALS
Abstract: (U) The seventh consecutive Seminar on new trends in research of energetic materia?s is intended to be a world meeting of young people and university teachers working in the field of teaching research development processing analyzing and application of all kinds of energetic materials Topics include explosions of gaseous dispersing and condensed systems.
SOURCE CHARACTERIZATION MODEL (SCM): A PREDICTIVE CAPABILITY FOR THE SOURCE TERMS OF RESIDUAL ENERGETIC MATERIALS FROM BURNING AND/OR DETONATION ACTIVITIES
Personal Author(s): Brown, Robert C, Kolb, Charles E , Conant, John A , Zhang, John , Dussault, David M , Rush, Tamera L, Conway, Brooke E, Morris, James W , Touma, Joe
Report Date: Apr 2004
Descriptors: (U) *GROUND WATER, *CONTAMINATION, *WATER QUALITY, *DETONATIONS, EMISSION, THERMODYNAMICS, SURFACE BURST, THERMOCHEMISTRY, VOLATILITY, MILITARY TRAINING, NITROGEN OXIDES, ENERGETIC PROPERTIES, WASTE DISPOSAL, CARBON MONOXIDE, PARTICULATES, ORGANIC COMPOUNDS, RESIDUALS, TEST METHODS, UNDERGROUND EXPLOSIONS
Identifiers: (U) *SOURCE CHARACTERIZATION MODEL, *AIR POLLUTANTS, SERDP COLLECTION, SERDP(STRATEGIC ENVIRONMENTAL RESEARCH AND DEVELOPMENT PROGRAM), SCM(SOURCE CHARACTERIZATION MODEL), ACID GASES, ATMOSPHERIC POLLUTION, DETONATION CHARGES, ENERGETIC MATERIALS, MUNITIONS, PARTICULATE EMISSIONS, VOLATILE ORGANIC COMPOUNDS
Abstract: (U) This is the final report for the Source Characterization Model (SCM) developed by Aerodyne Research, Inc. (ARI) in collaboration with the U.S. Army Environmental Center (USAEC). It describes work performed under contract DACA72-00-C-0001 from the Strategic Environmental Research and Development Program (SERDP) for the project CP-1159 entitled "A Predictive Capability for the Source Terms of Residual Energetic Materials from Burning and/or Detonation Activities". A portion of thisreport was previously released as a supplement to the 2002 Annual Report for that SERDP project. Detonation of energetic materials produces a wide range of air and surface pollutants, including carbon monoxide, nitrogen oxides, volatile organic compounds, acid gases, and particulate matter. These emissions, including undecomposed or partially decomposed energetic materials, may lead to atmospheric pollution or ground water contamination. The speciation and amounts of these emitted pollutants depend on the identity and amount of energetic material detonated, the detonation order, the detonation mode (air burst, surface detonation, buried detonation), and the munitions type (shell, mine, detonation charge, etc.). In order to determine whether U.S. military training or munitions disposal activities produce emissions that threaten air or ground water quality, reliable estimates of emission factors must be available for a representative fraction of the thousands of munitions types in the inventory. A variety of recent detonation experiments, including detonation chamber tests, and open-air field detonations have yielded increasingly rich data sets of measured gaseous and particulate emissions factors from a range of energetic materials deployed as both unconfined charges and standard munitions. These data have been used under CP-1159 to guide the development of a detonation source characterization model (SCM) to be used to predict emissions across munitions classes and detonation modes.
REPRESENTATIVE SAMPLING FOR ENERGETIC COMPOUNDS AT AN ANTITANK FIRING RANGE
Personal Author(s): Jenkins, Thomas F , Ranney, Thomas A , Hewitt, Alan D , Walsh, Marianne E , Bjella, Kevin L
Report Date: Apr 2004
Descriptors: (U) *COMPOSITE MATERIALS, *EXPLOSIVES, *ENERGETIC PROPERTIES, FIRING TESTS(ORDNANCE), GRIDS, FIELD TESTS, PROPELLANTS, SOILS, TOLERANCE, MEAN, SITE INVESTIGATIONS, RANGES(FACILITIES), ANTITANK WEAPONS, HMX, NORMALITY
Identifiers: (U) *ANTITANK FIRING RANGES, *REPRESENTATIVE SAMPLING, COMPOSITE SAMPLING, EXPLOSIVES RESIDUES, NG, SITE CHARACTERIATION
Abstract: (U) Field sampling experiments were conducted at the CFB-Valcartier Arnhem antitank rocket range to investigate various sampling schemes that would yield representative soil samples at firing points and impact areas of antitank ranges. Three sampling strategies were evaluated. Between the firing point and the target, 10-m x 10-m grids were established and 30-increment composite soil samples were collected. In two of these grids, one near the firing point and one at the target, other grids were divided into 100 1-m x 1-m minigrids. Within each minigrid a discrete and a 10-increment composite soil sample were collected and analyzed for energetic compounds. In the target area, an alternative strategy was also evaluated using concentric halos around the target. Each halo was subdivided into increasing numbers of segments at increasing distances from the targets. Multi-increment composite samples were collected within each halo segment. Behind the firing line, nine line (linear) composites were collected at various distances from 0 to 25 m from the firing line. Results from the 100 1-m x 1-m minigrids near the firing line and the target demonstrated that the distribution of analyte concentrations in the discrete samples was non-Gaussian and the range of concentrations varied over two orders of magnitude. The distributions of data for multi-increment composite samples with various numbers of increments were simulated by averaging the concentration estimates from randomly selected discrete samples. For the firing line area, the distribution of NG computed composites exhibits increased normality as the number of increments is increased and the resulting tolerance range declined substantially. This was also true for HMX in the target area. Recommendations are made for appropriate sampling strategies to collect representative surface soil sample for antitank rocket ranges.
SIMULATION OF REACTION DYNAMICS FOR SYNTHESIS OF ENERGETIC MATERIALS AND RESISTANT COATINGS
Personal Author(s): Hammes-Schiffer, Sharon
Report Date: 10 Mar 2004
Descriptors: (U) *COMPOSITE MATERIALS, *MOLECULAR DYNAMICS, COMPUTATIONS, GRIDS, EXPLOSION EFFECTS, COATINGS, HIGH DENSITY, CHARGE TRANSFER, ENERGETIC PROPERTIES, ABRASION
Identifiers: (U) HEDM(HIGH ENERGY DENSITY MATTER), POSS(POLYHEDRAL OLIGOMERIC SILSESQUIOXANES), REACTION DYNAMICS
Abstract: (U) The objective of this research was the development of theoretical and computational methods to guide the efficient synthesis of HEDM (High Energy Density Matter) for use in advanced propellants and POSS (polyhedral oligomeric silsesquioxanes) for use in coatings resistant to extreme conditions such as heat and abrasion. The research centered on the design of new methodology for the simulation of hydrogen transfer reactions. The projects included the development of the following three types of approaches: grid methods for the calculation of hydrogen vibrational wave functions, nonadiabatic molecular dynamics methods for the simulation of proton transfer in liquids, and the nuclear-electronic orbital method for the incorporation of nuclear quantum effects in electronic molecular orbital calculations. The application of these approaches to hydrogen transfer reactions required for the synthesis of HEDM and POSS will provide insight into the detailed mechanisms, as well as the influence of solvent and substituents on the rates and yields. Such mechanistic information will aid in the efficient synthesis of HEDM and POSS and the design of new materials.
EFFECTIVENESS OF POCKET-WAVE ABSORBERS IN VERTICAL-WALL, COASTAL ENTRANCE STRUCTURES
Personal Author(s): Thompson, Edward F , Bottin, Jr , Robert R , Selegean, James P ,
Report Date: Mar 2004
Descriptors: (U) *ABSORBERS(EQUIPMENT), *CHANNELS(WATERWAYS), *BREAKWATERS, STEEL, WALLS, ENERGETIC PROPERTIES, POROUS MATERIALS, GREAT LAKES, PILE STRUCTURES, HARBORS, REHABILITATION, ARMY CORPS OF ENGINEERS, CLIMATE
Identifiers: (U) POCKET WAVE ABSORBERS
Abstract: (U) This Coastal and Hydraulics Engineering Technical Note (CHETN) provides preliminary information on the effectiveness of pocket wave absorbers (relative to wave conditions) in vertical steel sheet-pile coastal entrance structures. The U.S. Army Corps of Engineers is responsible for dozens of harbor entrances in the Great Lakes constructed with parallel jetties. These jetties, many in operation for more than 100 years, were typically constructed of rock-filled timber cribs. Over time, the wood cribbing has experienced significant deterioration, thus causing the jetty to be rather porous. Many of these structures have been rehabilitated. The typical rehabilitation approach has been to drive steel sheet pile around the existing structure and place a concrete cap on top, thereby encasing the original structure. After completion of the rehabilitation projects, the wave climate between the jetties appears to increase significantly causing navigational difficulties and damage to moored vessels within the harbor. This is apparently due to the fact that the timber crib jetties were rough, porous structures, especially in their deteriorated state, and were much more effective at dampening wave energy than the rehabilitated, sheet-pile encased jetties. The steel sheet-pile structures, being considerably more reflective than the deteriorating timber structures, are largely responsible for the increasingly energetic wave climate. To mitigate for the more energetic wave climate, the Corps has removed short sections of steel sheet piling at selected harbors and replaced them with pocket wave absorbers.
TOXICITY OF NITRO-HETEROCYCLIC AND NITROAROMATIC ENERGETIC MATERIALS TO ENCHYTRAEID WORM.ENCHYTRAEUS CRYPTICUS IN A NATURAL SANDY LOAM SOIL
Personal Author(s): Kuperman, Roman G, Checkai, Ronald T , Simini, Michael , Phillips, Carlton T , Kolakowski, Jan E
Report Date: Mar 2004
Descriptors: (U) *TOXICITY, *SOIL POLLUTION, TEST AND EVALUATION, AGING(MATERIALS), EXPOSURE(GENERAL), TEST METHODS, SAND, SURVIVAL(GENERAL), SOILS, ELECTROMAGNETIC RADIATION, STANDARDIZATION, AROMATIC COMPOUNDS, ENERGETIC PROPERTIES, RDX, SOIL TESTS, ADULTS, ECOLOGY, WEATHERING, NITROGEN COMPOUNDS, HMX, DNT, LOAMS, RISK ANALYSIS
Identifiers: (U) AQ F04-12-1397, TNB
Abstract: (U) U.S. Environmental Protection Agency is developing Ecological Soil Screening Level (Eco-SSL) values for ecological risk assessment of contaminants at Superfind sites. Insufficient information for RDX, HMX, 2,4-DNT, 2,6-DNT, and TNB to generate Eco-SSLs necessitated standardized toxicity testing to fill the data gaps. The Enchytraeid Reproduction Test (ISO/16387:2001) was adapted using Enchytraeus crypticus in these studies. Tests were conducted in Sassafras sandy loam soil, which supports relatively high bioavailability of energetic materials. Weathering/aging procedures for amended soil were incorporated in the study to better reflect the exposure conditions in the field soils. Definitive toxicity tests conducted with both freshly amended and weathered/aged amended soils showed that EM toxicity order based on EC(sub 20) values for juvenile production in tests with E. crypticus was TNB > 2,4-DNT > 2,6-DNT > RDX with EC(sub 20) values of 45, 116, 194, and 585 mg kg(exp -1), respectively. The octahydro-1, 3, 5, 7 - tetranitrol, 3, 5, 7 - tetrazocine (HMX) did not adversely affect adult survival or juvenile production up to 21750 mg kg(exp -1) treatment. These study results will be provided to the Eco-SSL workgroup for review and inclusion in the Eco-SSL database, and for developing Eco-SSLs for RDX, HMX, 2,4-DNT, 2,6-DNT, and TNB.
BIOSYNTHESIS OF ENERGETIC MATERIALS
Personal Author(s): Cramer, Randall J
Report Date: 31 Dec 2003
Descriptors: (U) *ORDNANCE, COMBAT SUPPORT, EXPLOSIVES, ENERGETIC PROPERTIES, TNT, BIOSYNTHESIS, NITROCELLULOSE, TRIAZINES, TETRAZOLES
Abstract: (U) The goal of this project was to transition the discoveries made from the basic research in ONR's Biomimetics Program into applications that support and improve the development, manufacture, and operational use of energetic materials in military ordnance that better support the warfighter. The objective of this work was to write and submit proposals for the biosynthesis of the energetic ingredients such as, nitrocellulose, TNT, TATB, triaminoguanidine, tetrazoles, triazenes, etc., and establish and coordinate research teams to transition the new products into real applications. Technical support was provided to the Biotechnology 6.1 Program Officer of the Office of Naval Research (ONR), Molecular Biomimetics Program, Code 342, by serving as point of contact the area or energetic materials synthesis, formulation and processing and other ordnance related issues. The necessary written proposals, milestone charts, marketing strategies, customers/sponsors for transitioning biosynthesis technology into advanced development and ordnance applications were provided.
CHARACTERIZATION OF THE MICROSTRUCTURE OF FINE ENERGETIC MATERIALS
Personal Author(s): Herrmann, Michael J
Report Date: Nov 2003
Descriptors: (U) *MICROSTRUCTURE, *ENERGETIC PROPERTIES, MECHANICAL PROPERTIES, HALL EFFECT, DEFORMATION, X RAY DIFFRACTION, PROPELLANTS, DISLOCATIONS, GERMANY, RDX, TWINNING(CRYSTALLOGRAPHY), HMX
Identifiers: (U) FOREIGN REPORTS, *ENERGETIC MATERIALS, LETTICE DEFECTS, MICRO STRAIN
Abstract: (U) This report results from a contract tasking Fraunhofer Institut fur Chemische Technologie as follows: Lattice defects in energetic materials will be measured using X-ray diffraction. The method shall be tested for its ability to characterize lattice defects in RDX and HMX, where dislocations gliding and deformation twinning are believed to dominate mechanical behavior. X-ray diffraction patterns will be evaluated relating to phase, residual strain, crystallite size and micro strain. The occurring phases and the lattice parameters of the samples will be determined by Rietveld-method using literature data. Micro strain and crystallite size will be determined with the Williamson Hall method by plotting reciprocal peak widths versus reciprocal lattice distances. New routines for size/strain evaluation, implemented in Rietveld programs will be tested and compared with the Williamson Hall method.
JOINT DEMILITARIZATION TECHNOLOGY PROGRAM A REPORT TO CONGRESS
Report Date: Oct 2003
Descriptors: U) *DEMILITARIZATION, GUIDED MISSILES, RECYCLED MATERIALS, CONVENTIONAL WARFARE, JOINT MILITARY ACTIVITIES, AMMUNITION, ENERGETIC PROPERTIES, TACTICAL WEAPONS, ROCKET ENGINES
Abstract: (U) The Department of Defense (DoD) established the Joint Demilitarization Technology Program (JDTP) to develop safe, efficient, environmentally acceptable demilitarization processes for the resource recovery and recycling (R3) or other disposition of conventional ammunition, tactical missiles, rocket motors, and energetics. Strategic, tactical, and conventional weapons systems, whether excess, obsolete or unserviceable, currently fielded, or under development for future applications, require disposition planning and capabilit
TOPICAL LIME TREATMENT FOR CONTAINMENT OF SOURCE ZONE ENERGETICS CONTAMINATION
Personal Author(s): Brooks, Michael C , Davis, Jeffrey L , Larson, Steven L , Felt, Deborah R , Nestler, Catherine C
Report Date: Sep 2003
Descriptors: (U) *SOILS, *CONTAMINATION, *ENERGETIC PROPERTIES, *CALCIUM OXIDES, TEST AND EVALUATION, IONS, SOURCES, MILITARY FACILITIES, DEFENSE SYSTEMS, DEGRADATION, WATER, MATERIALS, RESISTANCE, EXPLOSIVES, FLY ASH, RESPONSE, SCALE, ORGANIC MATERIALS, TRANSPORT, AMMUNITION, CONTAMINANTS, LABORATORIES, MIXING, AROMATIC COMPOUNDS, HYDROLYSIS, RANGES(FACILITIES), RDX, TNT, PH FACTOR, HYDROXIDES, NITRAMINES, ALKALINITY, NITRO RADICALS, ALKALI METAL COMPOUNDS, HMX
Abstract: (U) Energetic compounds, such as 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and their degradation products can act as a source of contamination for soil on Department of Defense testing and training ranges. Base hydrolysis degrades nitroaromatics and nitramines, and the potential effectiveness of lime to induce this reaction has been demonstrated at the laboratory scale. The objective of this research was to further examine both basic and applied aspects of alkaline application as an inexpensive and effective means of reducing source-zone contamination on military ranges. Bench-scale microcosms were used to examine basic conditions that could affect the alkaline hydrolysis reaction, such as soil organic matter content, lime concentration, soil type, and contamination type. Results from experiments using soil from a variety of ammunition production facilities and training ranges, in general, support the use of explosive contaminant treatment by alkaline material in well-mixed systems. RDX in crystalline form was more resistant to treatment, possibly due to limitations associated with the dissolution of the RDX from the crystal to the aqueous phase. Larger-scale experiments, conducted in vessels packed with approximately 55 kg of soil, were used to investigate topical versus well-mixed applications of three alkaline materials (hydrated lime, quicklime, and Class C fly ash). TNT, RDX, and HMX in the mixed system were removed quickly from both the leachate and soil. However, results from experiments with topical applications of alkali material indicated that the aqueous transport of hydroxide ion was not sufficient to overcome the buffering capacity of the soil. Consequently, the soil pH was not raised to the extent necessary for alkaline treatment of explosive compounds. This result is fundamentally related to the CEC properties of the soil and is consequently considered a soil specific (and therefore site specific) result.
USE OF PYROLYSIS GC/MS FOR PREDICTING EMISSION BYPRODUCTS FROM THE INCINERATION OF DOUBLE-BASE PROPELLANT
Personal Author(s): Cropek, Donald M , Kemme, Patricia A , Day, Jean M , Cochran, Jack
Report Date: Sep 2003
Descriptors: (U) *GAS CHROMATOGRAPHY, *PYROLYSIS, *MASS SPECTROMETRY, *COMBUSTION PRODUCTS, *DOUBLE BASE PROPELLANTS, EMISSION, DEGRADATION, MOLECULAR WEIGHT, ADDITIVES, DEMILITARIZATION, WASTE DISPOSAL, HAZARDOUS WASTES, EFFLUENTS, INCINERATORS, ENERGETIC PROPERTIES, WATER SOLUBLE MATERIALS, NITROCELLULOSE, BENCH TESTS, NITROGLYCERIN
Identifiers: (U) AA2 PROPELLANT, MUNITIONS WASTE, PE62272A, EP UCS
Abstract: (U) Gas chromatography/mass spectrometry was used to analyze the pyrolytic byproducts from an Army-unique propellant compound (AA2) that is composed of predominantly nitrocellulose and nitroglycerin. Compounds produced by AA2 pyrolysis were compared to compounds detected in the gaseous effluent from AA2 incineration. The light permanent gases and most of the higher molecular weight byproducts produced by AA2 incineration are replicated by laboratory pyrolysis on AA2. The reverse case also holds whereby 18 out of 24 high molecular weight AA2 pyrolytic byproducts are found in the incinerator emissions. Poor matching, however, was obtained between the two processes for the volatile, water-soluble species. None of these low molecular weight compounds produced under pyrolytic conditions were detected in the AA2 incinerator samples, likely indicating inefficient capture of these compounds from the effluent stream. Separate pyrolytic degradation of the individual components of AA2 provides evidence that nearly all of the incomplete combustion products detected during incineration originate not from the prevalent energetic ingredients but rather from the minor and trace additives in AA2. In addition, pyrolysis successfully identified the AA2 components capable of surviving the incineration process intact. This work illustrates the potential of bench-scale pyrolysis for predicting incineration behavior.
DISTRIBUTION AND FATE OF ENERGETICS ON DOD TEST AND TRAINING RANGES: INTERIM REPORT 3
Personal Author(s): Pennington, Judith C, Jenkins, Thomas F , Ampleman, Guy , Thiboutot, Sonia , Brannon, James M
Report Date: Sep 2003
Descriptors: (U) *EXPLOSIVES, *ENVIRONMENTAL IMPACT, *GROUND WATER, *WATER POLLUTION, MILITARY FACILITIES, DEGRADATION, MILITARY FORCES(FOREIGN), ARMY PERSONNEL, ADSORPTION, FIRING TESTS(ORDNANCE), PROJECTILES, CANADA, AQUIFERS, YIELD, HETEROGENEITY, MILITARY TRAINING, CONTAMINATION, PUBLIC HEALTH, ENERGETIC PROPERTIES, TNT, SOIL TESTS, DETONATIONS, RESIDUES, ARTILLERY AMMUNITION, TETRYL
Identifiers: (U) PETN(PENTAERYTHRITOL TETRANITRATE), ENERGETIC MATERIALS, DETONATION RESIDUES
Abstract: (U) Sustainment of training to maintain the readiness of our armed forces requires stewardship of human health and the environment. The objective of this project, initiated in FYOO and planned for completion in FYO5, was to determine the potential for environmental contamination from residues of energetic materials on ranges. This report describes accomplishments for FYO2. A U.S. and a Canadian site were characterized for explosives residues resulting from live-fire soldier training: Fort Bliss, Texas, and Canadian Forces Base (CFB), Shilo, Manitoba. Results are also reported on tests to determine residues associated with open detonations and low-order detonations and tests to define environmental fate and transport process descriptors. Results of intensive sampling at Fort Bliss indicated that judgmental sampling targeting low-order residues and firing points is superior to grid sampling for identifying potential point sources of contamination over the typically large training range areas. Furthermore, composite sampling offers the best opportunity of capturing a realistic concentration under the conditions of extreme heterogeneity. Results of open detonations tests confirmed that the use of C4 generates significant explosives residuals. In low-order detonation tests, controlling the percent energy yield of artillery projectiles proved difficult. Adjustments in the variables from these results will improve control of future detonation tests. At CFB Shilo, energetic materials found in soils were associated with targets, and propellants were associated with firing points. The Shilo ranges exhibited relatively low levels of contamination not requiring immediate corrective action. Results of soil partitioning tests demonstrated that pentaerythritol tetranitrate (PETN) and tetryl are degraded in surface and aquifer soils. While adsorption is relatively limited and will not impede transport, degradation may be sufficient to reduce transport of these explosives.
Descriptive Note: Final rept. Oct 2000-Aug 2003
Personal Author(s): Armstrong, Ronald W
Report Date: Sep 2003
Descriptors: (U) *NANOTECHNOLOGY, METALS, AIR FORCE RESEARCH, MODELS, STRUCTURAL PROPERTIES, MATERIALS, DEFORMATION, CRACKS, ENERGY TRANSFER, EXPLOSIVES, MECHANICS, DISLOCATIONS, LABORATORIES, AIR FORCE FACILITIES, BEHAVIOR, ENERGETIC PROPERTIES, DETONATIONS, SCIENTISTS, CLOUD SEEDING, TORNADOES
Identifiers: (U) PE61102F, WUAFRL2306AM01
Abstract: (U) This technical report is a compilation of unclassified articles, presentations, briefings, etc., produced by R.W. Armstrong, Senior Scientist, AFRL/MNME, mostly in collaboration with Air Force Research Laboratory, Munitions Directorate, Energetic Materials Branch and external national and international colleagues, during the three year period: October 2000 through August 2003. The topical items are mostly centered on dislocation mechanics model descriptions of the total deformation and cracking behaviors of energetic materials and/or structural metals, in the latter case, subjected to high rate loading conditions as experienced in explosive detonations. Additional items referenced are: (1) the forthcoming textbook in print "Deformable Bodies and Their Material Behaviors", co-authored with Henry W. Haslach, Jr.; and, (2) an article on "The Seeds of Tornado Prevention", co-authored with Joseph G. Glenn, and associated with the listed patent disclosure "Tornadic Disruption Through Nanometric Sized Cloud Seeding". The latter items represent a "spin-off" connection of Eglin Air Force Base research interest in the strength and energy release rate properties of energetic/reactive nanomaterials, as shown here to relate to an appreciable number of the described items.
NEW MATERIALS DESIGN
Personal Author(s): Boatz, Jerry , Gordon, Mark S , Voth, Gregory , Hammes-Schiffer, Sharon , Pachter, Ruth
Report Date: 28 May 2003
Descriptors: (U) *COMPOSITE MATERIALS, COMPUTER PROGRAMS, ALGORITHMS, SOFTWARE ENGINEERING, QUANTUM CHEMISTRY, OPTICAL MATERIALS, NONLINEAR OPTICS, LIQUID CRYSTALS, SCALING FACTOR, PROTECTIVE COATINGS, NUMERICAL METHODS AND PROCEDURES, DESIGN CRITERIA, ENERGETIC PROPERTIES, ROCKET ENGINES, ROCKET PROPULSION, COMPUTATIONAL CHEMISTRY, MOLECULAR DYNAMICS
Identifiers: (U) *HIGH ENERGY DENSITY MATERIALS, POSS(POLYHEDRAL OLIGOMERIC SILSESQUIOXANE), GAMESS(GENERAL ATOMIC AND MOLECULAR ELECTRONIC STRUCTURE SYSTEM), HEDM(HIGH ENERGY DENSITY MATERIALS), POLYNITROGEN
Abstract: (U) In this paper we report our recent results on the design of materials with controlled properties by the application of computational chemistry methods, new algorithms and scalable software.
THEORETICAL STUDIES OF THE SENSITIVITY OF ENERGETIC MATERIALS
Personal Author(s): Thompson, Donald L
Report Date: Apr 2003
Descriptors: (U) *ENERGETIC PROPERTIES, PROTONS, EXPLOSIVES, NITRIDES, PROPELLANTS, OXIDATION, CHEMICAL REACTIONS, CHARGE TRANSFER, SALTS, HYDROXYL RADICALS, AMMONIUM NITRATE
Identifiers: (U) HEDM(HIGH ENERGY DENSITY MATERIALS), IONIC ENERGETIC MATERIALS, ENERGETIC SALTS
Abstract: (U) The research supported by AFOSR grant F49620-00-1-0273 for the period 15 April 2000 to 14 April 2003 is described. The purpose of this research program is to develop atomic-level models for high energy density materials (HEDM), and to study their fundamental properties and behaviors that determine their suitability as practical propellants and explosives. The central focus of our research during this grant period was ionic energetic materials, although some studies of the interactions and reactions of energetic molecules with solid Al and Al(2)O(3), and of the hydrogen-bonded energetic solid 1,1 -diamino-2,2- dinitroethylene (FOX-7) were performed. The primary purpose of the work was to develop accurate models for describing the physical properties of strong oxidizing salts. We have successfully modeled crystal structures, melting, and liquid properties of ammonium dinitramide as a test case for our approaches, and we have partially developed models for ammonium nitrate and hydroxylammonium nitrate. A long-term goal of this work is to model the chemistry of ionic liquids and thus we have performed several quantum chemistry studies to determine the pathways for proton transfer and chemical decomposition of these three prototypical salts.
CHARACTERISATION AND BINDER STUDIES OF THE ENERGETIC PLASTICISER - GLYN OLIGOMER
Personal Author(s): Provatas, Arthur
Report Date: Apr 2003
Descriptors: (U) *INSENSITIVE EXPLOSIVES, *PLASTIC BONDED EXPLOSIVES, MIGRATION, INERT MATERIALS, BINDERS, AUSTRALIA, ENERGETIC PROPERTIES, TACTICAL WEAPONS
Identifiers: (U) FOREIGN REPORTS, AQ F03-11-2453
Abstract: (U) In an effort to comply with Insensitive Munitions (IM) criteria while minimising any reduction in performance, two part energetic binder systems which comprise an energetic polymer and an energetic plasticiser, are being developed for future use in PBX (polymer bonded explosive) fills in tactical missiles. Energetic binder systems confer energy output increases over conventional inert binder systems and are thus of interest to the ADF. Under a collaborative agreement with the UK, the ADF has received a new energetic plasticiser, GLYN oligomer, which promises to provide improvements such as higher energy output, good mechanical properties and low plasticiser exudation. This report serves to characterise the GLYN oligomer and examine its plasticising properties. Furthermore, comparison of migration data of the oligomer and other plasticiser(s) show that the GLYN oligomer is less likely to exude from PBX than other conventional plasticisers, thereby increasing the in- service life.
STABILITY OF CL-20, TNAZ, HMX, RDX, NG, AND PETN IN MOIST, UNSATURATED SOIL
Personal Author(s): Jenkins, Thomas F , Bartolini, Claudia , Ranney, Thomas A
Report Date: Apr 2003
Descriptors: (U) *CHEMICAL COMPOSITION, *SOILS, *ENERGETIC PROPERTIES, TEST AND EVALUATION, MILITARY FACILITIES, CHEMICALS, MATERIALS, SURFACES, MOISTURE, RANGES(FACILITIES), RDX, HMX, PETN, NITROGLYCERIN
Abstract: (U) The stability of a number of the chemical components of energetic materials was evaluated in three moist, unsaturated soils. This study was conducted to evaluate the stability of several components of currently used energetic materials and two chemicals that may be used in future energetic material compositions in unsaturated, moist surface soils from three military training ranges. The compounds studied were nitroglycerin (NG), pentaerythritol tetranitrate (PETN), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7- tetrazocine (HMX), hexanitrohexaazaisowurtzitane (CL-20), and 1,3,3-trinitroazetidine (TNAZ). Three soils from military training ranges were fortified using an aqueous spiking solution and the residual concentrations were measured after 0, 1, 4, 8, 14, and 29 days at 228C in the dark. The results indicate that the half-life of TNAZ and NG in all three test soils was less than one day, the half-life for PETN varied from 0.45 to 2.4 days, the half-life for RDX ranged from 94 to 154 days, the half-life for HMX varied from 133 to 2,310 days, and the halflife for CL-20 varied from 144 to 686 days.
STRUCTURAL EFFECTS ON THE PHYSICAL PROPERTIES OF IONIC LIQUIDS
Personal Author(s): Drake, Greg , Hawkins, Tom , Wilkes, John
Report Date: 31 Mar 2003
Descriptors: (U) *CATIONS, *PHYSICAL PROPERTIES, *SALTS, *ANIONS, HYDROGEN BONDS, SYMPOSIA, STRUCTURAL PROPERTIES, ELECTROCHEMISTRY, CHEMICAL BONDS, ORGANIC MATERIALS, ENERGETIC PROPERTIES, VISCOSITY, CRYOGENICS, MELTING POINT, ALKYL RADICALS, PHOSPHATES, MATRIX THEORY
Identifiers: (U) *IONIC LIQUIDS, WUAFRL2303M2C8
Abstract: (U) Recently work using ionic liquids has risen exponentially in both academic research efforts as well as by industrial large-scale organic synthesis. Much of these efforts have centered around the use of di-alkyl substituted imidazolium salts with an array of anions, many of which are commercially available. The pioneering work carried out by the USAF in the last several decades has shed some light upon some of the physical property effect relationships of increasing the alkyl side chain length of these imidazolium cations with viscosities, melting points, hygroscopicity/ hydrophobicity, and densities. However, most researchers in the field today are forging efforts in using ionic liquids in various aspects of synthesis and separations, as part of the environmentally driven "green chemistry" efforts. In our efforts we are coming to terms with what really drives the physical properties of ionic liquids and how we are beginning to understand the cation anion interactions. Discussions will focus on factors including size and shape of both the cation and anion, hydrogen bonding, charge delocalization on either/both cation and/or anion, in our quest to design, synthesize and characterize new ionic liquids of interest.
FORMULATION AND PERFORMANCE STUDIES OF POLYMER BONDED EXPLOSIVES (PBX) CONTAINING ENERGETIC BINDER SYSTEMS. PART 1
Personal Author(s): Provatas, Arthur
Report Date: Mar 2003
Descriptors: (U) *GUIDED MISSILE WARHEADS, *POLYMERS, *PLASTIC BONDED EXPLOSIVES, *FILLERS, *PLASTICIZERS, FORMULATIONS, INERT MATERIALS, AIR TO AIR MISSILES, BINDERS, AUSTRALIA, ENERGETIC PROPERTIES, INSENSITIVE EXPLOSIVES
Identifiers: (U) PBX(POLYMER BONDED EXPLOSIVES), AQ F03-09-2216, FOREIGN REPORTS
Abstract: (U) In an effort to comply with Insensitive Munitions (IM) criteria together with the expectation of increasing warhead performance against specified targets, two-part energetic binder systems comprising an energetic polymer and plasticizer that offer promise for future use in PBX (polymer bonded explosive) fills in high-performance, tactical missiles were investigated. Warhead fills within modern missiles such as ASRAAM (Advanced Short Range Air-to-Air Missiles) typically contain cast-cured PBXs comprising high-energetic loadings in an inert binder matrix. The use of the inert binder, which constitutes around 20% of the final formulation, dilutes the final energy output of the PBX. To this end, several energetic binder formulations were developed that may offer potential use in ASRAAM-type missiles. By use of energetic binder systems comprising polyGLYN and K10 or GLYN oligomer plasticizer, increases in performance parameters were observed. This technical report details the formulation of several PBXs developed to maximize casting density and processibility for potential use in ASRAAM warheads that may offer improved IM properties.
A MICROSTRUCTURE DEPENDANT REACTIVE FLOW MODEL FOR HETEROGENEOUS ENERGETIC MATERIALS
Personal Author(s): Doolan, C J
Report Date: Feb 2003
Descriptors: (U) *ENERGETIC PROPERTIES, *INSENSITIVE EXPLOSIVES, THERMOMECHANICS, MATHEMATICAL MODELS, REACTION KINETICS, SHOCK WAVES, POROSITY, IGNITION, FLOW, AUSTRALIA, HMX
Identifiers: (U) AQ F03-08-1883, FOREIGN REPORTS, REACTIVE FLOW MODEL, ENERGETIC MATERIALS
Abstract: (U) A new reactive flow model for heterogeneous energetic materials has been developed based the physical and chemical parameters of the material as much as possible rather than solely relying on empirical constants to determine the reaction rates behind the shock wave Firstly this report presents an extended viscoplastic pore collapse (hot spot) model based on previous models presented in the literature. Results from this hot spot model are then used to develop a reactive flow model embedded into the multi-material hydrocode, MULTI, using an Induction-Parameter- Model to describe the thermomechanical processes of pore collapse in a computationally efficient manner. One and two-dimensional hydrocode results are presented for the energetic material HMX undergoing bare and cased projectile impact. The results show- the importance of microstructure in determining the shock ignition and subsequent growth behavior in energetic materials. Thus, a new capability- is described for determining the effects of varying porosity (due to manufacture aging damage, etc) on shock sensitivity and can be used to help evaluate the Insensitive Munitions (IM) qualities of weapon systems.
ANALYTICAL MODELLING OF IGNITION OF CONDENSED ENERGETIC MATERIALS, PULSED DETONATION ENGINES AND MINIATURIZATION OF EXPLOSIVE SYSTEMS: FINAL REPORT
Personal Author(s): Short, Mark , Stewart, Scott
Report Date: 14 Jan 2003
Descriptors: (U) *MINIATURIZATION, *DETONATIONS, AIR BREATHING ENGINES, PROPULSION SYSTEMS, PULSES, ENGINES, ENERGETIC PROPERTIES, EXPLOSIVES INITIATORS
Identifiers: (U) ARRHNIUS KINETICS, EOS(EQUATION OF STATE), LINEAR STABILITY OF DETONATION
Abstract: (U) Over the duration of the grant, several papers were written by Short, his collaborators and students on AFOSR issues related to the proposal outline. Those that list whole or partial support of the AFOR (F49620-00-1-0005) are given below. Copies of the publications listed are also included. Some highlights of the most recent work are also included.
DYNAMIC DEFORMATION PROPERTIES OF ENERGETIC COMPOSITE MATERIALS
Personal Author(s): Field, John E , Walley, S M , Sivior, C R , Proud, W G
Report Date: Dec 2002
Descriptors: (U) *COMPOSITE MATERIALS, *DEFORMATION, *STRAIN RATE, *ENERGETIC PROPERTIES, STRESS STRAIN RELATIONS, METHODOLOGY, OPTICS, PARTICLE SIZE, HIGH RATE, DYNAMICS, SOLIDS, MICROSCOPY, PHYSICS, SHOCK, ULTRAFINES, PETN
Identifiers: (U) AQ F03-05-1021, POS(PHYSICS AND CHEMISTRY OF SOLIDS), ENERGETIC MATERIALS, DYNAMIC PROPERTIES, HOPKINSON BAR, PBX
Abstract: (U) This report outlines the mechanical, optical and microscopic techniques available in the Physics and Chemistry of Solids (POS) Fracture and Shock Physics group, Cavendish Laboratory, Cambridge, for studying the impact and high strain rate properties of materials. Results are presented for high strain rate stress-strain response of PBX, with effect of particle size and temperature. Results are presented on studies of ultrafines and conventional PETN and RDX.
DESTRUCTION OF ENERGETIC MATERIALS IN SUPERCRITICAL WATER
Personal Author(s): Buelow, S J , Allen, D , Anderson, G K , Archuleta, F L , Atencio, J H
Report Date: 25 Jun 2002
Descriptors: (U) *HYDRAZINES, *DESTRUCTION, *SUPERCRITICAL FLOW, MATHEMATICAL MODELS, STABILITY, DETECTION, WATER, TEST METHODS, EXPLOSIVES, CRITICAL TEMPERATURE, PROPELLANTS, SCALING FACTOR, KINETICS, WASTES, CARBON DIOXIDE, ORGANIC SOLVENTS, HYDROLYSIS, ENERGETIC PROPERTIES, DECOMPOSITION, DETERMINATION, NITROMETHANE, ALKALI METAL COMPOUNDS
Identifiers: (U) *SUPERCRITICAL WATER, *ENERGETIC MATERIALS, NITROALIPHATIC, NITROAROMATIC, DRE(DESTRUCTION AND REMOVAL EFFICIENCY), PE62206F
Abstract: (U) This effort was a survey of the compatibility of a broad series of representative energetic materials (EM) commonly used in propellants, munitions and explosives with a proposed process of controlled decomposition in water near or above the critical temperature (approximately 373 CC), Central issues, in order of consideration, are safety, environmental compatibility of decomposition products, destruction efficiency, extrapolation to compounded formulations of EM, and engineering considerations for scale-up to full-scale operation. The sequence followed in these investigations was: (1) initial safety evaluation and small-scale stability tests on each of 13 individual energetic ingredients commonly used in rocket propellants, munitions, or explosives (all passed this stage); (2) determination of global kinetics and Destruction and Removal Efficiencies (DREs) (destruction was complete - all DREs are limited by sensitivity of detection); (3) identification of products and byproducts of the process to verify environmental compatibility (all tested passed this criterion); and (4) detailed reaction kinetics determinations and development of computational models (qualitatively successful application to nitromethane). An important result was the development of safe and practical means to deliver water-insoluble energetic materials (EM) into the supercritical region These methods included: 1) slurried particles, 2) dissolution in an organic solvent or supercritical carbon dioxide, and 3) digestion in aqueous alkali. A pilot-scale continuous pipe reactor suitable for handling slurried, dissolved, or hydrolyzed explosives was built and tested. Results show that supercritical water is a favorable medium for decomposition of waste and off-spec EM. The process appears to be controllable, and the decomposition products are contained until they are consciously released.
INITIAL STEPS IN THE DECOMPOSITION OF ENERGETIC MATERIALS: PATHWAYS INVOLVING THEIR EXCITED ELECTRONIC STATES
Personal Author(s): Bernstein, Elliot R
Report Date: 01 Jun 2002
Descriptors: (U) *ENERGETIC PROPERTIES, *HIGH EXPLOSIVES, TUNABLE LASERS, FRAGMENTATION, QUANTUM CHEMISTRY, PHOTOLYSIS, EXCITATION, MASS SPECTROSCOPY, VAPOR PHASES, ELECTRONIC STATES, ORGANIC NITROGEN COMPOUNDS, VALENCE, AMMONIUM COMPOUNDS, IGNITION, SUPERSONIC CHARACTERISTICS, DISSOCIATION, DECOMPOSITION, RDX, TNT, NITRAMINES, QUANTUM STATISTICS, LASER MATERIALS, HMX
Identifiers: (U) RYDBERG STATES, DMNA(DIMETHYL NITRAMINE), ADN(AMMONIUM DINITRAMIDE), LASER ABLATION, COVARIANCE MAPPING, NITRAMIDE, TIME OF FLIGHT MASS SPECTROSCOPY, FLUORESCENCE SPECTROSCOPY, PATHWAYS, AB INITIO CALCULATIONS
Abstract: (U) The study of dissociation pathways, mechanism, and products for the energetic materials RDX C3H6N3(NO2)3 and ADN NH4N(NO2)2 in excited electronic valence and Rydberg states is undertaken. These spectroscopic and dissociation studies will be carried out on gas phase species that have been cooled and isolated in a supersonic expansion. A number of recent advances in experimental and theoretical techniques and capabilities have been incorporated into our laboratory so that these studies become feasible. The experiments are carried out on laser ablated materials that are cooled in a supersonic expansion and accessed with tunable photolysis lasers. Time-of-flight mass spectroscopy and fluorescence spectroscopy are employed to analyze the fragments. Covariance mapping of spectral data will aid in identifying the fragmentation pathways. Experiments will be supported by a theoretical effort of ab initio quantum chemistry calculations. These studies are important to the functioning of energetic materials in real applications because the ignition process can create excited electronic states of RDX and ADN and each state can have a different decomposition mechanism and set of products (e.g., CH2NNO2, CO2, NO, NO2, OH, etc.). System and material performance, as fuels and explosives, can be adjusted and tuned to maximize overall effectiveness and efficiency if RDX and ADN decomposition chemistry can be elucidated and understood as a function of electronic state.
COMBUSTION OF SOLID PROPELLANTS
Personal Author(s): Lengelle, G , Duterque, J , Trubert, J F
Report Date: May 2002
Descriptors: (U) *SOLID PROPELLANTS, NATO, POLYMERS, GASES, COMBUSTION, FRANCE, FLAMES, INERT MATERIALS, ENERGETIC PROPERTIES, RDX, NITRAMINES, NITROCELLULOSE, HMX, NITROGLYCERIN, DOUBLE BASE PROPELLANTS
Identifiers: (U) NATO FURNISHED, FOREIGN REPORTS
Abstract: (U) A review of the understanding of the combustion mechanisms of solid propellants that the authors have built from their work and from the literature is presented. Such an understanding is an important part of the process carried out to master the behavior of solid propellants and to obtain desired characteristics (with respect to energetic level, burning rate level, sensitivity to pressure and initial temperature, nature of emitted combustion products, vulnerability to various aggressions...). The propellants and propellant components considered are: double-base propellants, based on nitrocellulose and nitroglycerin, " active binder, based on an inert polymer (or energetic such as PAG) and a liquid nitrate ester, inert binders, such as polybutadiene, ammonium perchlorate, nitramines, such as HMX, RDX and CL20 (HNIW), composite ammonium perchlorate-inert binder propellants, composite propellants based on a nitramine and an active binder, aluminum, with respect to the two previous types of propellants, additives, when appropriate. The features of the combustion zone described are: In the condensed phase, the thickness of the temperature profile and of the decomposition zone, the kinetics of the decomposition, the energy released, the nature of the gases evolved, the surface temperature; In the gas phase, the type of flame structure (diffusion or kinetically controlled), the possibility of staging (such as in double-base propellants), the kinetics of the reaction(s), the energy released, the flame temperature (primary and final, when applicable).
INVESTIGATIONS OF NOVEL ENERGETIC MATERIALS TO STABILIZE ROCKET MOTORS
Personal Author(s): Beckstead, Merrill W , Culick, Fred E , Brill, Thomas B , Litzinger, Thomas A , Yang, Vigor , Flandro, Gary A , Frederick, Robert A , Lin, M C , Price, E W , Sigman, R , Seitzman, J
Report Date: 30 Apr 2002
Descriptors: (U) *STABILITY, *ENERGETIC PROPERTIES, *SOLID PROPELLANT ROCKET ENGINES, MAGNETIC FIELDS, DYNAMICS, GAS DYNAMICS, SOLID PROPELLANTS, COLLABORATIVE TECHNIQUES, ROCKET PROPELLANTS, COMBUSTION, COMBUSTION CHAMBERS, ACOUSTICS, BEHAVIOR
Identifiers: (U) MURI(MULTIDISCIPLINARY UNIVERSITY RESEARCH INITIATIVE), ROCKET MOTORS, UNSTEADY BEHAVIOR, DISTRIBUTED COMBUSTION
Abstract: (U) This document is the final report of the Caltech Multidisciplinary University Research Initiative (MURI), "Investigations of Novel Energetic Materials to Stabilize Rocket Motors," ONR Contract No. N00014-95-1-1338. With a one-year no-cost extension, the program covered the period 1 October 1995 to 30 September 2001 and involved Principal Investigators at nine Universities. In addition, for three years, funds from another source supported research by seven Russian research groups. Participants in the Caltech MURI provided technical oversight of that work. A second MURI devoted to the same general subject was carried out at the University of Illinois at Urbana- Champaign (UIUC). The two programs were largely complementary. Some of the sections in this report have been co-authored by representatives of both MURIs. Similarly, the final report of the UIUC MURI will contain some duplication of material covered in this document. The Caltech MURI was a multidisciplinary program devoted to research on fundamental problems of the chemistry, combustion and gas dynamics of novel energetic propellants and their unsteady behavior in rocket motors. This program achieved significant progress towards the ultimate overall objective of research in this field, to identify and quantify the influences of propellant composition on the stability of motions in a solid propellant rocket motor. To attain that objective it is essential to support cross-disciplinary effort between propellant chemists and researchers; combustion researchers; and researchers concentrating on the dynamics of solid rocket combustors. This MURI program was the first sustained effort to accomplish the necessary collaborations among faculty and students in universities, with participation by representatives of government laboratories and industry; in the many respects described in this report the program has been highly successful.
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SIMULATIONS OF ENERGETIC MATERIALS FOR ROCKET PROPULSION: OBTAINING MORE "BANG FOR THE BUCK
Personal Author(s): Sorescu, Dan C , Thompson, Donald L , Boatz, Jerry
Report Date: 29 Apr 2002
Descriptors: (U) *SIMULATION, *ENERGETIC PROPERTIES, *ROCKET PROPELLANTS, *HMX, COATINGS, COMBUSTION, PARTICLES, ALUMINUM, BURNING RATE, ROCKET PROPULSION, NITROMETHANE, ULTRAFINES
Identifiers: (U) *OXIDE OVERCOAT, CYCLIC NITRAMINES, WUAFRL2303M2C8345709
Abstract: (U) Powderized aluminum has long been used as an energetic ingredient in rocket propellant formulations, comprising approximately 15-20% of some conventional ammonium perchlorate solid propellant formulations. However, the performance of aluminum is reduced by the rapid formation of an aluminum oxide overcoat on aluminum particles prior to combustion, which also inhibits efficient burning. Furthermore, formation of the oxide overcoat severely reduces the potential advantages of using high surface-to-volume-ratio ultrafine aluminum particles, which would otherwise have highly desirable properties such as enhanced burn rates. In order to inhibit the rapid formation of an oxide overcoat on the ultrafine aluminum particles without simultaneously degrading performance, it has been proposed to coat the aluminum particles with an energetic material such as HMX.
NEW TRENDS IN RESEARCH OF ENERGETIC MATERIALS (5TH SEMINAR) HELD IN PARDUBICE, CZECH REPUBLIC ON 24-25 APR 2002
Personal Author(s): Zeman, Svatopluk
Report Date: Apr 2002
Descriptors: (U) *EXPLOSIVES, *ENERGETIC PROPERTIES, SYMPOSIA, PROPELLANTS
Identifiers: (U) AQ F02-08-1613, ENERGETIC DEVICES, ENERGETIC MATERIALS
Abstract: (U) The Final Proceedings for New Trends in Research of Energetic Materials, 5th Seminar, 24 April 2002 - 25 April 2002. The fifth consecutive Seminar on new trends in research of energetic materials is intended to be a worlds meeting of young people and university teachers working in the field of teaching, research, development, processing, analysing and application of all kinds of energetic materials. A subject of interest for this Seminar includes also explosions of the gaseous, dispersing and condensed systems. It will not be aimed only at the exchange of professional information but also to create pleasant meeting where young specialists from different countries will have the opportunity to meet and gain personal contacts.
INITIATION OF CHEMICAL REACTIONS IN ENERGETIC MATERIALS USING PLASMAS AND ARC CHANNELS
Personal Author(s): Bourham, Mohamed A
Report Date: 29 Mar 2002
Descriptors: (U) *PLASMAS(PHYSICS), *CHEMICAL REACTIONS, *SOLID PROPELLANTS, DENSITY, TEMPERATURE, RADIATIVE TRANSFER, HIGH ENERGY, SPECTRA, FLOW FIELDS, LOW ENERGY, EMISSION SPECTROSCOPY, BURNING RATE, HEAT FLUX, ENERGETIC PROPERTIES, BEDS(PROCESS ENGINEERING), CAPILLARITY, PERFORATION, RADIANT HEATING, THERMOELECTRICITY, ELECTROTHERMAL CHEMICAL GUNS
Identifiers: (U) *ARC CHANNELS, DIFFUSIVE TRANSPORT, JA-2 PROPELLANTS, ELECTROTHERMAL SOURCES, PLASMA IGNITION, PROPELLANT TEMPERATURE SENSITIVITY
Abstract: (U) Experiments were conducted to determine the spatial and temporal distribution of the plasma temperature, pressure, number density, and velocity in the plasma-flow-field of an electrothermal source. The experiments revealed a decreasing plasma pressure, plasma temperature and plasma number density as plasma is leaving the capillary source and expands in air. The plasma jet velocity 2 inches from the source exit was found to be about 1300 m/s. Following plasma flow-field characterization, a set of experiment were conducted on the plasma-propellant interaction with increased propellant bed temperature. Experiments were conducted on JA-2 solid propellant with controlled bed temperature. Obtained results were used to develop a semi-empirical model that includes the bed temperature. Increased burn rates were observed with increased bed temperature, which appears to follow a power BR = A P(sup a) (T/T ambient)(sup b). Further investigation on plasma parameters, through optical emission spectroscopy measurements, allowed modifying the model to include plasma radiative heat flux and plasma number density in the proposed model. Arc channels were initiated in the central perforation of the propellant sample using two arc energy regimes, low and medium energies. The low energy, milli-joule range, has shown weight change of +/- 0.03 mg. Medium energy range between 260 and 1050 joules has shown an increased weight loss (increased burn rate) with increased arc energy. Experimental data has a linear fit Am = 2 x 10(exp -4) (E + 282), where delta m is the mass loss in mg and E is the arc energy in joules. The linear fit has R(sup 2) ^ 0.91. Arc modeling using approximated modified Coulomb logarithm has shown over-prediction of arc plasma parameters, as seen from arc temperature calculated by the model when compared to spectral results.
CHARACTERIZATION OF SCRAP MATERIALS FOR MASS DETONATING ENERGETIC MATERIALS
Personal Author(s): Phelan, James M , Barnett, James L , Fisher, Mark
Report Date: Feb 2002
Descriptors: (U) *DEBRIS, *ENERGETIC PROPERTIES, *RESIDUES, LABORATORY TESTS, RECYCLED MATERIALS, DETECTION, DETECTORS, HAZARDS, FIELD TESTS, ORDNANCE, TNT, HAND HELD, DETONATIONS, DEMOLITION CHARGES, GRANULES, DNT, CONVEYORS
Identifiers: (U) *SCRAP METALS, *ENERGETIC MATERIAL RESIDUES, SERDP COLLECTION, SERDP(STRATEGIC ENVIRONMENTAL RESEARCH AND DEVELOPMENT PROGRAM), FIELD SCREENING, UNEXPLODED ORDANCE
Abstract: (U) Military test and training ranges generate scrap materials from targets and ordinance debris. These materials are routinely removed from the range for recycling; however, energetic material residues in the range scrap has presented a significant safety hazard to operations personnel and damaged recycling equipment. The Strategic Environmental Research and Development Program (SERDP) sought proof of concept evaluations for monitoring technologies to identify energetic residues among range scrap. Sandia National Laboratories teamed with Nomadics, Inc. to evaluate the Nomadics FIDO vapor sensor for application to this problem. Laboratory tests were conducted to determine that the vapor-sensing threshold to be 10 to 20 ppt for TNT and 150 to 200 ppt for DNT. Field tests with the FIDO demonstrated the proof of concept that energetic material residues can be identified with vapor sensing in enclosed scrap bins. Items such as low order detonation debris, demolition block granules, and unused 8 1-nun mortars were detected quickly and with minimum effort. Conceptual designs for field-screening scrap for energetic material residues include handheld vapor sensing systems, batch scrap sensing systems, continuous conveyor sensing systems and a hot gas decontamination verification system.
GUIDE FOR CHARACTERIZATION OF SITES CONTAMINATED WITH ENERGETIC MATERIALS
Personal Author(s): Thiboutot, Sonia , Ampleman, Guy , Hewitt, Alan D
Report Date: Feb 2002
Descriptors: (U) *CONTAMINATION, *ENERGETIC PROPERTIES, *UNEXPLODED AMMUNITION, MILITARY FACILITIES, MILITARY REQUIREMENTS, POLICIES, HAZARDS, HEALTH, DEMOLITION, EXPLOSIVES, ENVIRONMENTAL IMPACT, PROPELLANTS, GROUND WATER, SOILS, WATER POLLUTION, SAMPLING, ADVERSE CONDITIONS, AMMUNITION, SOIL POLLUTION, DEMILITARIZATION, SITE INVESTIGATIONS, TEST FACILITIES, BASE CLOSURES, HIGH EXPLOSIVES, TOXICOLOGY, PYROTECHNICS
Identifiers: (U) *ENERGETIC MATERIALS, SITE CHARACTERIZATION
Abstract: (U) One consequence of the development, testing, and firing of ammunition is the potential contamination of test sites by high explosives, propellants, and pyrotechnics. These energetic compounds pose particular environmental concerns because of their unusual chemical, physical, and toxicological properties. For this reason there is a need to scrutinize past and current defense activities to ensure that they have had no adverse effect upon the surrounding environment. The need for environmentally sound policies, especially within the context of base closures and demilitarization, makes studies of the environmental impact of munitions an increasingly important issue. Moreover, in the future the implementation of environmentally benign defense activities should be encouraged. All aspects of the life cycle of munitions can affect the environment or human health. Production and firing of munitions, demolition procedures, and destruction of outdated ammunition can all cause dispersion of energetic compounds into the environment. These various scenarios lead to different patterns of contamination, thereby creating a need for a general protocol that is applicable in all circumstances. The goal of this guidance document is to collate information relevant to the characterization of sites contaminated by energetic materials. This guide will serve as a reference for future sampling campaigns on sites potentially contaminated with explosives. The characterization of training and firing ranges, demolition, and open burning/open detonation ranges will allow assessment of the environmental impacts of these various operational activities. In addition, it will provide information critical to the establishment of future operational requirements and procedures that minimize environmental damage.
ULTRAFAST VIBRATIONAL SPECTROMETER FOR ENGINEERED NANOMETRIC ENERGETIC MATERIALS
Personal Author(s): Dlott, Dana D
Report Date: 03 Jan 2002
Descriptors: (U) *MOLECULAR VIBRATION, LASER PUMPING, METALS, REAL TIME, SPECTROSCOPY, OXIDATION, ALUMINUM, THERMOCHEMISTRY, OXIDIZERS, ENERGETIC PROPERTIES, CARBON DIOXIDE LASERS, NANOTECHNOLOGY
Identifiers: (U) SFG(SUM FREQUENCY GENERATION)
Abstract: (U) The proposer requested funding for laser equipment that would be used to study engineered nanometric energetic materials consisting of nanometer metal particles, passivation layers and oxidizing binders. The laser equipment is set up for vibrational sum-frequency generation spectroscopy, which looks at the vibrational transitions of molecules at interfaces between metal particles, their passivation layer and the surrounding oxidizer, in real time while the material is being combusted by a carbon dioxide laser. Interface spectroscopy is crucial because almost all of the relevant chemistry in nanoenergetic materials occurs at interfaces. The needed equipment was ordered and installed, and assembled into a working SFG set up that has been tested on a model system consisting of a self assembled monolayer of alkane on gold. The next step will be to finish integrating the carbon dioxide laser system and to begin looking at aluminum based energetic materials.
INTERNATIONAL CONFERENCE ON SOLID STATE CRYSTALS 2000: GROWTH, CHARACTERIZATION, AND APPLICATIONS OF SINGLE CRYSTALS HELD IN ZAKOPANE, POLAND ON 9-12 OCTOBER 2000
Descriptive Note: Conference proceedings
Personal Author(s): Rogalski, Antoni , Madejczyk, Pawet , Adamiec, Krzysztof
Report Date: 24 Oct 2001
Descriptors: (U) *SINGLE CRYSTALS, *RARE EARTH COMPOUNDS, STRESSES, THERMAL PROPERTIES, OPTICAL PROPERTIES, ANNEALING, MECHANICAL PROPERTIES, SYMPOSIA, OPTIMIZATION, ELECTROOPTICS, PHASE TRANSFORMATIONS, SILICON DIOXIDE, CRYSTAL LATTICES, ENERGY TRANSFER, POINT DEFECTS, ELECTRICAL PROPERTIES, ION IMPLANTATION, HYDROGEN, HOLOGRAPHY, ZINC OXIDES, HALIDES, GAMMA RAYS, IONIZATION, ELECTRON DONORS, DIFFUSION, DOPING, PHONONS, SUPERSATURATION, HIGH TEMPERATURE SUPERCONDUCTORS, PRASEODYMIUM, ENERGETIC PROPERTIES, FLUORIDES, LITHIUM NIOBATES, CRYSTAL GROWTH, STOICHIOMETRY, SOLID STATE PHYSICS, POLAND, BORATES, MAGNETIC MATERIALS, OXIDATION REDUCTION REACTIONS, CHROMIUM COMPOUNDS, GADOLINIUM COMPOUNDS, HYDROSTATIC PRESSURE, ZINC SELENIDES, GALLIUM ANTIMONIDES, CZOCHRALSKI CRYSTALS, ALKALI METAL COMPOUNDS, DYSPROSIUM, YTTERBIUM COMPOUNDS, SILICON ON INSULATOR, WIDE GAP SEMICONDUCTORS, YTTRIUM BARIUM COPPER OXIDES
Identifiers: (U) COMPILATION REPORT, AQ F02-02-0480, MULTIOXIDES, POTASSIUM GADOLINIUM TNNGSTATES, ORDERING PROCESSES, DEBYE-SMOLUCHOWSKI EQUATION, QUANTUM CRYSTALS, CHARGE TRAPS, ANHARMONIC APPROXIMATION, MANGANITES, MAGNETIC RESONANCE SPECTROSCOPY, POTASSIUM ERBIUM TUNGSTATES, GROUP I-V COMPOUNDS, GROUP II-V COMPOUNDS, JAHN-TELLER, MAGNETOPHONON SPECTROSCOPY, YTTRIUM ALUMINUM OXIDES, ZINC CADMIUM MERCURY TELLURIDES, FOREIGN REPORTS
Abstract: (U) Partial Contents: Scope of ZnO growth; Influence of mechanical stress on the growth of crystals; Crystal growth of new functional materials for electro-optical applications; Possibilities and limitations of multioxide crystals growth; Single-domain HTC superconducting materials synthesis: BaZrO3 substrates as a tool for optimized systems; Very high quality crystals of wide-gap II-V semiconductors: What for?; Annealing of GaSb single crystals in ionized hydrogen atmosphere; Growth and structure of strontium-doped LaGaO3; Al-Cu-Co single quasi-crystals obtained by the method of inclined front crystallization; Correlation of Cu and V sub Zn concentration within the diffusion region of ZnSe monocrystals; Chromium recharging processes in the Y3Al5O12:Mg,Cr single crystal under the reducing and oxidizing annealing influence.
PYROLYTIC DECOMPOSITION STUDIES OF AA2, A DOUBLE-BASE PROPELLENT
Personal Author(s): Cropek, Donald M , Kemme, Patricia A , Day, Jean M
Report Date: Oct 2001
Descriptors: (U) *DECOMPOSITION, *THERMAL DEGRADATION, *PYROLYSIS, CHEMICALS, COMPOSITE MATERIALS, OXYGEN, COMBUSTION, SAMPLING, STANDARDS, DISPOSAL, GAS CHROMATOGRAPHY, MASS SPECTROMETRY
Identifiers: (U) AA2, HAZARDOUS WASTE DISPOSAL, EM(ENERGETIC MATERIALS), MUNITIONS WASTE
Abstract: (U) Pyrolysis is the thermal decomposition of a substance into a variety of by-products, usually in the absence of oxygen. Pyrolysis experiments comparing the behavior of AA2 with the behavior of individual constituents of AA2 provide an excellent example of the additive property that sometimes exists during thermal degradation of composites. The origin of each pyrolytic by-product from AA2 can be deduced by examining set of pyrolysis products from each constituent. Good matching between pyrolytic and incineration data can support using laboratory pyrolysis to predict incineration behavior. Samples of original AA2 from an Army installation were collected for analysis. In addition, chemical standards were obtained for the major components of AA2. All samples and standards were subjected to pyrolysis and the by-products were analyzed by gas chromatography/mass spectrometry.
DISTRIBUTION AND FATE OF ENERGETICS ON DOD TEST AND TRAINING RANGES
Personal Author(s): Pennington, Judith C , Jenkins, Thomas F , Ranney, Thomas A , Walsh, Marianne E , Hewitt, Alan D
Report Date: Sep 2001
Descriptors: (U) *EXPLOSIVES, *ENVIRONMENTAL IMPACT, *WATER POLLUTION, *CONTAMINATION, *ENERGETIC PROPERTIES, *RANGES(FACILITIES), TEST AND EVALUATION, SOOT, DEGRADATION, DISTRIBUTION, CHEMICAL PROPERTIES, PARAMETERS, PHYSICAL PROPERTIES, WATER, MATERIALS, RATES, TEST METHODS, SURFACES, GROUND WATER, SOILS, SNOW, RESIDUALS, COEFFICIENTS, SURFACE WATERS, SAMPLING, TRANSPORT, AMMUNITION, MILITARY APPLICATIONS, BLAST, GRENADES, DETONATIONS, ARTILLERY AMMUNITION, TRANSFORMATIONS, CRATERS
Identifiers: (U) DINITROTOLUENE, *EXPLOSIVE CONTAMINATION
Abstract: (U) The current state of knowledge concerning the nature and extent of residual explosives contamination on military testing and firing ranges is inadequate to ensure management of these facilities as sustainable resources. The objective of this project is to develop techniques for assessing the potential for enviromnental impacts from energetic materials on testing and training ranges; methods for defining the physical and chemical properties, concentration, and distribution of energetics and residuals of energetics in soils; and the potential for transport of these materials to groundwater. The approach includes characterization of posthiast residues from various heavy artillery munitions and from hand grenades by sampling surface soils in craters from both high- and low-order detonations. Residues from specific munitions will also be determined by sampling soot deposited on snow by the blast. Where possible, groundwater and surface water associated with the ranges will also be sampled. In addition to range characterization, the study will also generate soil transport parameters for explosives and explosives breakdown products for which such data are lacking. Transport parameters of interest include dissolution kinetics, soil/water partitioning coefficients, and transformation/degradation rates.
MODELING AND ANALYSIS OF REACTIVE COMPACTION FOR GRANULAR ENERGETIC SOLIDS
Descriptive Note: Final rept May-Aug 2001
Personal Author(s): Gonthier, Keith A
Report Date: Sep 2001
Descriptors: (U) *SOLIDS, *ENERGETIC PROPERTIES, *GRANULAR MATERIALS, VELOCITY, COUPLING(INTERACTION), PISTONS, TEMPERATURE, PARAMETRIC ANALYSIS, IMPACT, PREDICTIONS, MODELS, DYNAMICS, QUANTITY, ENERGY, REACTIVITIES, SENSITIVITY, VARIATIONS, MECHANICS, COMBUSTION, HEATING, EVOLUTION(GENERAL), HETEROGENEITY, HOT SPOTS, IGNITION, MECHANICAL ENERGY, COMPACTING, DDT
Identifiers: (U) *GRANULAR ENERGETIC SOLIDS, *REACTIVE COMPACTION, PE62602F, WUAFRL25020693
Abstract: (U) A technique is described for modeling mechanically induced localized heating and ignition at the grain scale (meso-scale) of granular reactive solids that maintains proper consistency with the experimentally characterized bulk (macro-scale) material behavior. The technique is illustrated for the dynamic compaction, localized heating, and ignition of granular HMX due to mild impact of a constant speed piston (^86 m/s). Guided by basic principles of contact mechanics, bulk dissipated mechanical energy is thermalized at localization sites (hot-spots) within the material meso-structure which are centered at intergranular contact points (surfaces). The evolution of bulk quantities is tracked at the macro-scale and the evolution of hot-spot temperature, mass fraction, and reaction progress are tracked at the meso-scale. Model predictions indicate that the onset of sustained combustion occurs for a piston speed that agrees well with confined Defiagration-to-Detonation Transition (DDT) experiments. This result suggests that the coupling technique may provide a rational framework for the development of improved energy localization, and ignition models for heterogeneous reactive solids. Results of a parametric sensitivity analysis show that the model is reasonably insensitive to variation in key energy localization parameters.
INCINERATION BY-PRODUCTS OF AA2, NC FINES, AND NG SLUMS
Personal Author(s): Cropek, Donald M , Day, Jean M , Kemme, Patricia A
Report Date: Sep 2001
Descriptors: (U) *WASTE DISPOSAL, DECONTAMINATION, HEAT TREATMENT, PROPELLANTS, WASTE MANAGEMENT, RADIOACTIVE WASTES, HAZARDOUS WASTES, POLLUTION ABATEMENT, INCINERATORS, ENERGETIC PROPERTIES, EXPLOSIVE ORDNANCE DISPOSAL
Identifiers: (U) EW(ENERGETIC WASTES), EM(ENERGETIC MATERIALS), PE62720D, WUUC5
Abstract: (U) Incineration is one technology used for thermal treatment of energetic materials (EM) and associated energetic wastes (EW). Knowledge of the by-products from incineration is invaluable for the proper design of emission control systems and selection of operating parameters to ensure maximum destruction efficiency. This project focuses on uncovering the by-products resulting from the incineration of EM and EW. The sampling and analysis of by-products from a hazardous waste incinerator were performed at an Army installation during the burning of several Army waste streams. The three EW burned at this rotary kiln incinerator are nitrocellulose (NC) fines, nitroglycerin (NO) slums, and AA2, a solventless double base propellant. Combustion by-products were collected from a sampling port located between the rotary kiln and incinerator afterburner, upstream of all pollution control devices. Several different sample collection trains were used for characterization of the by-products including volatile and semi-volatile organic compounds, hydrogen cyanide, carbon monoxide, nitrogen oxides, and total hydrocarbons. The collection plan, the instrumental set-up, and the analytical results are presented for the incineration of all three EW listed above. The challenges and problems encountered during sample collection at the incinerator kiln port are discussed as well as solutions used to overcome these problems.
INTERNATIONAL CONFERENCE OF ICT HELD IN KARLSRUHE, FEDERAL REPUBLIC OF GERMANY ON JULY 3-6, 2001. ENERGETIC MATERIALS: IGNITION, COMBUSTION AND DETONATION
Report Date: 06 Jul 2001
Descriptors: (U) *COMBUSTION, SYMPOSIA, CHEMISTRY, GERMAN LANGUAGE, DETONATIONS
Identifiers: (U) FOREIGN REPORTS, AQ F02-02-0262
Abstract: (U) These are presentation and poster session papers presented at the 32nd International Annual Conference of ICT held in Karlsruhe, Germany, on July 3-6, 2001. The main topic concerning energetic materials is the formulation and synthesis of new components. Their characterization is based on experimental research of ignition, combustion and detonation phenomena. Conference objectives include experimental and theoretical activities on: initiation and ignition processes; investigation of combustion and detonation phenomena, plume signature, and improved diagnostics and measurement techniques.
NUCLEOPHILIC NITRATION OF SELECTED AZA-AROMATICS: EXPERIMENTS AND MODELLING
Personal Author(s): Lochert, Ian J , Dorsett, Helen E
Report Date: Jul 2001
Descriptors: (U) *QUINOLINES, *NITRATION, SITES, SUBSTRATES, YIELD, AUSTRALIA, REACTANTS(CHEMISTRY), ACIDS, QUINOXALINES
Identifiers: (U) ENERGETIC MATERIALS, COMPUTATIONAL CHEMISTRY, MOLECULAR MODELLING, QUANTUM THEORY, ISOQUINOLINE, FOREIGN REPORTS
Abstract: (U) Nitration of isoquinoline and phthalazine has been successfully demonstrated using a novel process which does not require strong acids. In this study, nitration of isoquinoline was repeated and the method applied to 1-nitroisoquinoline and the aza-aromatics quinoline, quinazoline, quinoxaline and pyridine. Nitration of only quinoline was observed, with a product yield lower than that reported for nitration of isoquinoline. For 1-nitroisoquinoline and quinoxaline, the substrates were recovered essentially unchanged. For quinazoline and pyridine, neither the substrates nor any reaction products were isolated. In no case was multiple nitration detected. Thus, while the scope of the reaction is broader than initially reported, it is clearly not a universal method for nitrating aza-aromatics. Molecular modelling calculations have identified a correlation between the acidity of the intended nitration site and the observed yield, which might be used to screen potential substrates for this nitration technique.
ENERGETIC ELECTRON GENERATION BY FORWARD STIMULATED RAMAN SCATTERING USING -.35 AND 0.53 MICRON LASER LIGHT IN A PLASMA
Descriptive Note: Master's thesis
Personal Author(s): Ortelli, Michael A
Report Date: Jun 2001
Descriptors: (U) *COMPUTERIZED SIMULATION, *LASER BEAMS, *ENERGETIC PROPERTIES, *PLASMA WAVES, *RAMAN SCATTERING, HIGH POWER, NUCLEAR WEAPONS, SIMULATION, IONS, SOURCES, STIMULATION(GENERAL), TWO DIMENSIONAL, MATERIALS, HIGH VELOCITY, INTENSITY, X RAYS, NUCLEAR EXPLOSION TESTING, VARIATIONS, HIGH ENERGY, ELECTRONS, HIGH DENSITY, WEAPONS EFFECTS, HEAT, INSTABILITY, DRIVES(ELECTRONICS), STOCKPILES, NEODYMIUM LASERS, FORWARD SCATTERING, PHASE VELOCITY
Abstract: (U) This research investigates the use of high-powered lasers to produce 50-100 keV x-ray sources for applications for programs such as Stockpile Stewardship and nuclear weapons effects testing (NWET). To produce these x-ray sources requires irradiating targets with intense laser light to efficiently generate high-energy electrons. Stimulated Raman scattering (SRS) of intense laser light produces electron plasma waves, which in turn generate high-energy electrons. To make a high-energy x-ray source, the maximization of this laser-driven instability is desired. Using computer simulations, we show that SRS can be driven by using a combination of frequency-tripled and a 'seed' beam of frequency doubled Neodymium laser light in a plasma of the appropriate density. Electron plasma waves with a high phase velocity are produced, which trap electrons and accelerate them to high energy. These energetic electrons will in turn generate high energy x-rays via collisions with nearby dense material. By adjusting the angle between the 0.35 micrometers and 0.53 micrometers laser beams, the characteristic temperature of the heated electrons (and the x-rays) can be varied. We show one and two-dimensional simulations and illustrate the important role that laser-driven ion fluctuations play.
INITIATION OF CHEMICAL REACTIONS IN ENERGETIC MATERIALS USING PLASMAS AND ARC CHANNELS
Personal Author(s): Bourham, Mohamed A
Report Date: 24 May 2001
Descriptors: (U) *PLASMAS(PHYSICS), *CHEMICAL REACTIONS, *SOLID PROPELLANTS, SOURCES, TEMPERATURE, MATERIALS, RADIATIVE TRANSFER, HIGH ENERGY, COMBUSTION, FLOW FIELDS, PRESSURE, IGNITION, BURNING RATE, ENERGETIC PROPERTIES, BEDS(PROCESS ENGINEERING), CAPILLARITY, THERMOELECTRICITY
Identifiers: (U) *ARC CHANNELS, ELECTROTHERMAL CHEMICAL GUNS, DIFFUSIVE TRANSPORT, JA-2 PROPELLANTS
Abstract: (U) Development of arc channels in propellant beds will lead to initiation of chemical reactions and possible ignition. Same initiation can take place with high-energy density plasmas generated by electrothermal plasma sources. Arc channels can be simulated via arc generators from as low as few milli-joules to several joules of energy. For electrothermal plasmas, the energy is in the range of few kilo-joules. When using electrothermal plasmas, the performance of the propellant is more governed by radiation transport and the plasma-flow-field parameters. The temperature of the propellant's bed may also play a role in the burn rates under plasma injection. In this report, a set of experiments were first conducted on the plasma-flow-field to determine the spatial and temporal distribution of the plasma temperature, pressure, number density, and velocity. The experiments revealed a decreasing plasma pressure, plasma temperature and plasma number density as plasma is leaving the capillary source and expands in air. The plasma jet velocity 2 inches from the source exit was found to be about 1300 m/s. Following characterization of the plasma-flow-field, a set of experiments were conducted on JA-2 solid propellant with controlled bed temperature. Increased burn rates were observed with increased bed. A model for the burn rate is proposed, which includes the bed temperature and has the BR = A P(sup a) (T/T(sub ambient))(sup b).
STUDIES OF THE MECHANICS AND COMBUSTION OF ENERGETIC MATERIALS FOR THE DESIGN OF EXPLOSIVE SYSTEMS
Personal Author(s): Stewart, D S
Report Date: May 2001
Descriptors: (U) *EXPLOSIVES, *MECHANICS, *COMBUSTION, *ENERGETIC PROPERTIES, COMPUTERIZED SIMULATION, PROPAGATION, REACTION KINETICS, CURVATURE, IGNITION, DETONATIONS
Identifiers: (U) REACTIVE FLOW, DSD(DETONATION SHOCK DYNAMICS), PE62602F, WUAFRL25020693
Abstract: (U) This is the final report that summarizes the research activities carried out under the grant F08630-95-1-0004 (for 5 year, period 01/30/95 to 01/29/00), awarded to the University of Illinois (D. Scott Stewart, Principle Investigator) and the Air Force Research Laboratory, Munition Directorate, Eglin AFB. The major research findings are summarized in the Discussion of Research Accomplishments and they describe (1) development of new models for reactive flow and ignition of energetic materials, (2) improved computational ability for reactive flow and ignition problems, (3) the transfer of detonation propagation algorithms to explosive design codes. A bibliography of all the main archival research papers and technical reports are included with their abstracts.
DYNAMIC CRACKING AND ENERGY ABSORPTION IN LAMINATES CONTAINING THROUGH-THICKNESS REINFORCEMENT
Personal Author(s): Cox, B N , Narayanaswamy, S
Report Date: 18 Apr 2001
Descriptors: (U) *LAMINATES, *CRACKING(FRACTURING), *REINFORCEMENT(STRUCTURES), STEADY STATE, PROBES, THICKNESS, FIBERS, INERTIA, MODELS, DYNAMICS, RESISTANCE, LOADS(FORCES), DYNAMIC RESPONSE, CRACKS, FIBER REINFORCED COMPOSITES, TOUGHNESS, FRACTURE(MECHANICS), CRACK PROPAGATION, DYNAMIC LOADS, MULTIMODE, BEHAVIOR, ENERGETIC PROPERTIES, MICROMECHANICS, DELAMINATION, REINFORCING MATERIALS, BRIDGES, ENERGY ABSORBERS
Identifiers: (U) *ENERGY ABSORPTION, THROUGH THICKNESS REINFORCEMENT
Abstract: (U) We report several fundamental results in the delamination resistance of through-thickness reinforced structures under dynamic load conditions. The main results are: (1) An elaborate micromechanical model shows how a bridging tow should behave if it is initially inclined to the fracture plane and subject to mixed mode quasistatic loading (2) A bridging law for fiber reinforced composites under dynamic crack propagation conditions has been derived. INertial effects in the mechanism of fiber pullout during dynamic propagation of a bridged crack are critically examined for the first time. (3) The dynamic delamination cracking behavior and the energetics of crack growth in through thickness double cantilever beam specimens has been analyzed. Steady state crack growth is attainable provided certain conditions are satisfied. Guidelines for design of experiments to probe the efficacy of bridging on improving the dynamic fracture toughness of through thickness reinforced structures are established. In summary, these results form a sound fundamental basis for design and life prediction of through thickness reinforced structures.
HIGH-TEMPERATURE EXPLOSIVES FOR INSENSITIVE-MUNITIONS APPLICATIONS
Personal Author(s): Chapman, R D , Fronabarger, J W , Gilardi, R D
Report Date: Apr 2001
Descriptors: (U) *INSENSITIVE EXPLOSIVES, *NITROGEN HETEROCYCLIC COMPOUNDS, HIGH TEMPERATURE, THERMAL STABILITY, SENSITIVITY, HIGH DENSITY, POLYCYCLIC COMPOUNDS, HIGH EXPLOSIVES, YIELD, AROMATIC COMPOUNDS, ENERGETIC PROPERTIES, MELTING POINT
Identifiers: (U) CHEMICAL STRUCTURE, ENERGETIC MATERIALS, EXPLOSIVE YIELDS, INSENSITIVITY CHARACTERISTICS, SHOCK SENSITIVITY
Abstract: (U) We are developing new energetic structures expected to have superior insensitivity characteristics and superior performance characteristics relative to currently used insensitive high explosives. The chemical structures proposed herein are a series of zero- to low-hydrogen-content, polynitro, polycyclic heteroaromatic compounds based on novel nitrogenous heterocycles. By analogy to other nitrated nitrogenous heterocycles, which have been discovered to exhibit superior insensitivity properties, the proposed derivatives are predicted to have similarly attractive stability characteristics. The new compounds are expected to be high-density materials with explosive yields comparable to or better than hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) but with high melting points, comparable or better shock sensitivity, and significantly better thermal stabilities. This project is being conducted as a collaboration, via a Cooperative Research and Development Agreement (CRADA), with Pacific Scientific Energetic Materials Co., Chandler, AZ, which provides independent funding for its comparable contribution to this effort.
TTCP INGREDIENTS FOR ENERGETIC MATERIALS: AIR FORCE RESEARCH LABORATORY, EDWARDS AFB, CA
Personal Author(s): Drake, Greg
Report Date: 16 Mar 2001
Descriptors: (U) *MATERIALS, *SALTS, *ENERGETIC PROPERTIES, *NITROGEN COMPOUNDS, CATIONS, CRYSTAL STRUCTURE, OXIDIZERS, FLUORIDES, ANTIMONY, ANIONS, INORGANIC CHEMISTRY, MONOPROPELLANTS
Identifiers: (U) TTCP(THE TECHNICAL COOPERATION PROGRAM), COUNTERIONS, *POLYNITROGEN, N5SBF6, WUAFRL2303345709
Abstract: (U) Fundamental Chemistry in oxidizers: Work on novel polynitrogen continues at the Edwards Air Force Base in Karl Christe's group. The N5(+)SbF6(-) salt was fully characterized and its crystal structure determined. The salt is thermally surprisingly stable (70 deg C) and exhibits very little impact sensitivity, Safer methods for the synthesis of N5(+)SbF6(-) have been developed and the salt is routinely prepared on a 5 g scale. Ongoing and future work is aimed at the syntheses of combinations of N5(+) with energetic counterions and novel large polynitrogen anions.
THEORETICAL STUDIES OF ELEMENTARY REACTIONS IN ENERGETIC MATERIALS
Descriptive Note: Final rept. 16 Feb 1998-15 Feb 2001
Personal Author(s): Thompson, Donald L
Report Date: Mar 2001
Descriptors: (U) *POLYATOMIC MOLECULES, *EXPLOSIVES, *CHEMICAL REACTIONS, *ENERGETIC PROPERTIES, COMPUTERIZED SIMULATION, CRYSTAL STRUCTURE, REACTION KINETICS, QUANTUM THEORY, SINGLE CRYSTALS, SOLIDS, MONTE CARLO METHOD, MOLECULAR STRUCTURE, DIFFUSION, POTENTIAL ENERGY, ELECTRON TRANSITIONS, DECOMPOSITION, RDX, MOLECULAR DYNAMICS
Identifiers: (U) AB INITIO CALCULATIONS, GAS SURFACE REACTIONS
Abstract: (U) Research performed over the three-year period February 16, 1998 - February 15.2001 supported by the U.S. Army Research Office (Grant number: DAAG55-98-1-0089) is described. This research program is concerned with the development of methods and simulations to study the reaction dynamics of polyatomic molecules and molecular crystals of interest as energetic materials. The work during this grant focused on the following: (1) The development and demonstration of methods for treating unimolecular reactions in IVR-limited regime with applications to molecules and reactions pathways relevant to the decomposition of energetic materials. (2) Studies of the decomposition of energetic molecules in liquids (3) The development and testing of condensed-phase (solids and liquids) models for energetic materials. (4) The development of semiclassical methods that can be used to incorporate quantum effects in multidimensional MD simulations. (5) Studies of the products of decomposition reactions of energetic materials with metals.
ULTRAFAST SPECTROSCOPY OF ENERGETIC MATERIALS AND ENERGETIC MECHANICAL PROCESSES
Personal Author(s): , Dana D
Report Date: 26 Feb 2001
Descriptors: (U) *SHOCK WAVES, *COMBUSTION, *ENERGETIC PROPERTIES, *MOLECULAR PROPERTIES, *MECHANICAL ENERGY, *NANOSTRUCTURES, LASER PUMPING, POLYMERS, RAMAN SPECTROSCOPY, CRACKING(FRACTURING), LASER BEAMS, OXIDATION, FAILURE(MECHANICS), LUBRICATION, SHORT PULSES, INTERMEDIATE INFRARED RADIATION, COMPRESSIVE PROPERTIES, SPALLATION, VIBRATIONAL SPECTRA
Identifiers: (U) *ENERGETIC MATERIALS, *ENERGETIC MECHANICAL PROCESSES, SHOCK COMPRESSION, ENERGETIC CHEMISTRY, MATERIAL DYNAMICS, DEBONDING, FEMTOSECOND LASERS, CARS(COHERENT ANTI STOKES RAMAN PROBING), CARS PROBING, VIBRATIONAL SPECTROSCOPY
Abstract: (U) The goal of this project is to develop a fundamental understanding of fast mechanical processes at a molecular level. It is believed that this fundamental research will lead to a clearer understanding of energetic mechanical processes relevant to the AFOSR mission and in the broader world as well. These include the following: (1) impact initiation of energetic materials; (2) mechanical failure by debonding, cracking, or spallation; (3) lubrication dynamics of high speed parts; and (4) fast combustion of metal particle/oxidizer composites. These processes are induced by laser-generated shock waves, laser heating, or specific vibrational pumping with tunable femtosecond mid-infrared pulses. These perturbations are followed by fast infrared or Raman probing to study the vibrational transitions of mechanically perturbed molecules or materials. Mid-infrared absorption creates a highly nonequilibrium vibrational population whose relaxation is relevant to all highly energetic chemical processes. Shock waves create high pressure, large amplitude structural perturbations, high temperatures, and large strain rates. Using ultrafast shock compression, the authors could initiate energetic chemistry, cracking, debonding and spallation, and produce stress on liquids at solid interfaces that mimics the stress felt in high speed engines. Laser flash heating is used to heat metal nanoparticles embedded in oxidizing matrices. The hot metal particles can then undergo fast energetic oxidization chemistries.
LATTICE IMPERFECTIONS OF ENERGETIC MATERIALS MEASURED BY X-RAY DIFFRACTION
Descriptive Note: Final technical rept. Aug 1999-Aug 2000
Personal Author(s): Engel, Walter, Herrmann, Michael
Report Date: 20 Feb 2001
Descriptors: (U) *EXPLOSIVES, *CRYSTAL DEFECTS, X RAY DIFFRACTION, CRYSTALLIZATION, SENSITIVITY, GERMANY, LATTICE DYNAMICS, ENERGETIC PROPERTIES, HMX
Identifiers: (U) FOREIGN REPORTS, *LATTICE DEFECTS
Abstract: (U) The mechanical sensitivity is an important issue for energetic materials and explosives, which has been discussed as a function of lattice defects originated during crystallization. However, hitherto a conclusive correlation was not achieved, because the quantitative measurement of defects is difficult. An approach is made to quantify defects in energetic materials with X-ray diffraction. Samples of HMX were crystallized under varying conditions yielding different defect concentrations. The samples are investigated with X-ray diffraction, SEM, and the densities and the mechanical sensitivities were measured. The SEM delivered information for the characterization of surface defects. Quantitative results were obtained by measurements of the density and the mechanical sensitivity. Both delivered significant deviations of the different HMX samples. X-ray diffraction patterns of the samples were measured with different diffraction geometries, and the widths of diffraction peaks were determined. The data were evaluated with Williamson Hall plots revealing the micro strain for each sample. The seed project shows that X-ray diffraction is capable for detecting qualities of coarse crystals, when suited systems are applied. Moreover, the correlation of micro strain and mechanical sensitivities gives an idea, how far lattice imperfections influence macroscopic properties of energetic materials. The encouraging results give rise for further, refined investigations with an extended variety of crystallization conditions.
A CHEMICALLY SPECIFIC BURNING RATE PREDICTOR MODEL FOR ENERGETIC MATERIALS
Personal Author(s): Miller, Martin S , Anderson, William R
Report Date: Feb 2001
Descriptors: (U) *BURNING RATE, *ENERGETIC PROPERTIES, MATHEMATICAL MODELS, COMPUTATIONS, INTERFACES, RATES, VAPOR PHASES, FREEZING, CHEMICAL REACTIONS, ADDITIVES, OZONE, RDX, PYROLYSIS, NITROGLYCERIN
Abstract: (U) The application of complex networks of elementary chemical reactions to the gas phase of burning energetic materials has increased markedly over the last decade. The exquisite complexity of these gas-phase reaction networks, coupled with available high-rigor treatments of transport, is not matched by an equivalent level of sophistication in descriptions of the condensed-phase and interfacial phenomena. Owing to the vastly more complicated, many-body nature of the condensed phase, this condition is not likely to be relieved soon. In response to these difficulties, a new semi-empirical approach to burning-rate calculation has been developed and applied to frozen ozone, cyclotrimethylenetrinitramine (RDX), and nitroglycerine. The new approach hypothesizes a single overall reaction linking the unreacted material to the net products of condensed-phase decomposition and characterizes their rate of formation according to an empirically derived pyrolysis law. These condensed-phase products become the reactants for the gas phase, which are treated in full elementary-reaction detail. Using this new semi-empirical model, a methodology for computing the relative effects of several additives on the burning rate of nitroglycerine is developed and demonstrated. Hopefully this approach will enable more rapid progress in modeling multi-ingredient propellants than did previous approaches attempting to model the condensed-phase processes in detail.
PREDICTING HEATS OF FORMATION OF ENERGETIC MATERIALS USING QUANTUM MECHANICAL CALCULATIONS
Personal Author(s): Rice, Betsy M , Pai, Sharmila V , Hare, Jennifer
Report Date: Feb 2001
Descriptors: (U) *QUANTUM CHEMISTRY, *QUANTUM THEORY, *POTENTIAL ENERGY, *ENERGETIC PROPERTIES, *ELECTROSTATIC CHARGE, THERMAL PROPERTIES, MOLECULES, MATERIALS, ISOLATION, SUBLIMATION, MEAN, VAPORIZATION, QUANTUM STATISTICS, MECHANICAL ENERGY
Abstract: (U) Quantum mechanical calculations are used to predict gas, liquid, and solid heats of formation of energetic molecules. A simple atom-equivalent method converts quantum mechanical energies of molecules and their atomic constituents to gas-phase heats of formation of energetic materials. Functional relationships between heats of vaporization and sublimation and properties associated with quantum, mechanically determined electrostatic potentials of isolated molecules are established. These are used with the gas-phase heats of formation to predict condensed-phase heats of formation. The calculated gas-phase heats of formation have a root mean square (rms) deviation of 3.1 kca1/mol and a maximum deviation of 7.3 kca1/mol from 35 experimental values. The rms and maximum deviation of predicted heats of vaporization from 27 experimental values are 1.7 and 6.1 kca1/mol, respectively. The rms and maximum deviations of predicted heats of sublimation from 36 experimental values are 3.6 and 12.4 kca1/mol, respectively. The rms and maximum deviations of predictions of liquid heats of formation from 41 measured values (corresponding to 24 molecules) are 3.3 and 9.3 kca1/mol, respectively. Similarly, the rms and maximum deviations of predictions of solid heats of formation from 75 measured values (corresponding to 44 molecules) are 9.0 and 35.4 kca1/mol, respectively.
DETECTION OF ENERGETIC MATERIALS BY LASER PHOTOFRAGMENTATION/FRAGMENT DETECTION AND PYROLYSIS/LASER-INDUCED FLUORESCENCE
Personal Author(s): Sausa, Rosario C , Swayambunathan, Vaidhianat , Singh, Gurbax
Report Date: Feb 2001
Descriptors: (U) *DETECTION, *FRAGMENTATION, *PHOTOCHEMICAL REACTIONS, *LASER INDUCED FLUORESCENCE, *LASER APPLICATIONS, *ENERGETIC PROPERTIES, *PHOTOFRAGMENT SPECTROSCOPY, AIR, MOLECULES, MATERIALS, SAND, LASERS, SENSITIVITY, ELECTRODES, SAMPLING, PRESSURE, VISIBLE SPECTRA, SPACE(ROOM), PHOTODETECTORS, RDX, TNT, MINIATURIZATION, PYROLYSIS, TRACER STUDIES, PETN
Identifiers: (U) PHOTOFRAGMENTATION, ENERGETIC MATERIAL DETECTION, PE61102A, ASH43
Abstract: (U) Trace concentrations of energetic materials such as 2,4,6-trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), and hexahydro-l,3,5-tinnitro-s-triazine (RDX) are detected by laser photofragmentationlfragment detection (PF/FD) spectrometry. In this technique, a single laser operating near 227 nm photofragments the parent molecule and facilitates the detection of the characteristic NO fragment by means of its A2lr-X2 II (0,0) transitions near 227 nm. Fragment detection is accomplished by resonance-enhanced multiphoton ionization (REMPI) with miniature electrodes and by laser-induced fluorescence (LIF) with a photodetector. Experiments are also conducted in the visible region using 453.85-nm radiation for photofragmentation and fragment detection. Sand samples contaminated with PETN and RDX are analyzed by a pyrolysis/LIF technique, which involves pyrolysis of the energetic material with subsequent detection of the pyrolysis products NO and NO2 by LIF and PF/LlF, respectively, near 227 nm. Applying these techniques to the trace analysis of TNT, PETN, and RDX at ambient pressure in room air is demonstrated with limits of detection (S/N = 3) in the range of low parts-per-billion to parts-per-million for a 20-s integration time with l0-l20 micronj of laser energy at 226.8 nm and 5 mJ at 453.85 mm An increase in detection sensitivity is projected with an increase in laser energy and an improved system design. The analytical merits of these techniques are discussed and compared to other laser-based techniques.
SIMULATION OF REACTION DYNAMICS: NONADIABATIC AND SOLVATION EFFECTS
Personal Author(s): Hammes-Schiffer, Sharon
Report Date: 09 Jan 2001
Descriptors: (U) *COMPUTATIONS, *PHOTOCHEMICAL REACTIONS, *POLYATOMIC MOLECULES, *SYNTHESIS, *SOLVATION, *ENERGETIC PROPERTIES, SIMULATION, ELECTRONICS, VIBRATION, REAL TIME, DYNAMICS, MATERIALS, QUANTUM THEORY, THEORY, GRIDS, PATHS, EFFICIENCY, HYDROGEN, COATINGS, SOLVENTS, MIXING, TRANSFER, WAVE FUNCTIONS, DIABETES, FOURIER ANALYSIS, HAMILTONIAN FUNCTIONS, ABRASION
Identifiers: (U) PE61102F
Abstract: (U) This research involved four projects centered on the design of theoretical and computational approaches to predict promising energetic materials and to guide the efficient synthesis of these materials. First, mixed quantum/classical methodology was developed for the simulation of photochemical reactions, which could play an important role in the design and synthesis of energetic materials. Second, the time-dependent self-consistent-field reaction path Hamiltonian method was developed for the calculation of the real-time quantum dynamics of polyatomic reactions. Third, a new approach for investigating the solvent effects of fundamental organic reactions was developed in order to aid in the efficient synthesis of energetic materials. This approach combined electronic structure calculations with reactive flux molecular dynamics calculations based on a reaction path Hamiltonian. Application of this approach to two fundamental organic reactions provided insight into the dynamical role of solvent and elucidated possible reaction mechanisms. Fourth, the Fourier grid Hamiltonian multi configurational self-consistent-field and partial multidimensional grid generation methods were developed for the efficient calculation of multidimensional hydrogen vibrational wavefunctions. These two methods enable the simulation of hydrogen transfer reactions required for the synthesis of polyhedral oligomeric silsesquioxanes, which are used in coatings that are resistant to extreme conditions such as heat and abrasion.
NAVAL RESEARCH LAB REVIEW 2001
Personal Author(s): Bultman, John D
Report Date: Jan 2001
Descriptors: (U) *NAVAL RESEARCH LABORATORIES, *INFORMATION PROCESSING, MATHEMATICAL MODELS, COMPUTERIZED SIMULATION, AEROSOLS, PHASE TRANSFORMATIONS, COMPOSITE MATERIALS, NUMERICAL ANALYSIS, ELECTRONIC EQUIPMENT, BOUNDARY LAYER, SINGLE CRYSTALS, ELECTRON SPIN RESONANCE, ELECTRON BEAMS, TOMOGRAPHY, ACOUSTIC SCATTERING, IONOSPHERIC MODELS, OPTICAL DETECTORS, MILITARY PUBLICATIONS, ENERGETIC PROPERTIES, FIRE SUPPRESSION, UNDERWATER ACOUSTICS, PLASMA DEVICES, ELECTROMAGNETISM, OZONE LAYER, INTERNET, MILITARY SATELLITES, REMOTE SYSTEMS, LIGHT EMITTING DIODES, STRATOSPHERE, OCEANOGRAPHY, ACOUSTIC COMMUNICATIONS, UNEXPLODED AMMUNITION, SPACE DEFENSE, RADIOTELEPHONES, FOREST FIRES, NANOTECHNOLOGY
Identifiers: (U) NORTHWEST PROVIDENCE CHANNEL, OCEAN ACOUSTIC SOLITON MODELING, POAM(POLAR OZONE AND AEROSOL MEASUREMENT) III, BIOSENSORS, SPIN INJECTION, PULSED DETONATION ENGINES
MOLECULAR MODELING OF ENERGETIC MATERIALS: THE PARAMETERIZATION AND VALIDATION OF NITRATE ESTERS IN THE COMPASS FORCE FIELD
Personal Author(s): Bunte, Steven W , Sun, Huai
Report Date: Nov 2000
Descriptors: (U) *COMPUTERIZED SIMULATION, *ENERGETIC PROPERTIES, *MOLECULAR PROPERTIES, *COMPUTATIONAL CHEMISTRY, ESTERS, NITRATES
Identifiers: (U) MOLECULAR MODELING, NITRATE ESTERS, COMPASS(CONDENSED PHASE OPTIMIZED MOLECULAR POTENTIALS), ATOMISTIC SIMULATION, FORCE FIELDS
Abstract: (U) To investigate the mechanical and other condensed phase properties of energetic materials using atomistic simulation techniques, the COMPASS force field has been expanded to include high-energy nitro functional groups. This report presents the parameterization and validation of COMPASS for nitrate esters (-ONO2). The functional forms of this force field are of the consistent force field type. The parameters were derived with an emphasis on the nonbonded parameters, which include a Lennard-Jones 9-6 function for the van der Waals (vdW) term and a Coulombic term for an electrostatic interaction. To validate the force field, molecular mechanics calculations and molecular dynamics simulations have been made on a variety of molecules containing the nitrate ester functionality. Using this force field, excellent agreement has been obtained between the calculated and experimental values for molecular structures, vibrational frequencies, liquid densities, heats of vaporization, crystal structure, mechanical properties and lattice energy.
ANALYSIS OF ENERGETIC MATERIAL DETECTION TECHNOLOGIES FOR USE AT ARMY ENERGETIC MATERIAL PRODUCTION FACILITIES
Personal Author(s): Hanson, Michelle J , Gizzi, Leo R , Schneider, Roger L
Report Date: Nov 2000
Descriptors: (U) *ARMY FACILITIES, *EXPLOSIVES, MILITARY EQUIPMENT, SUBSTRATES, PROPELLANTS, ELECTROMAGNETIC RADIATION, AMMUNITION, ORDNANCE, CONTAMINATION, DISPOSAL, ASBESTOS, ENVIRONMENTAL PROTECTION, ENERGETIC PROPERTIES, PYROTECHNICS
Identifiers: (U) *ENERGETIC MATERIAL DETECTION, PE62272A, U10
Abstract: (U) The U.S. Army has numerous excess ordnance production facilities slated for destruction. These buildings may have considerable quantities of residual energetic materials (EMs) and asbestos, and may also be structurally unsound. The EMs in these facilities include finished military explosives, propellants, and pyrotechnics as well as precursors to these materials. The Construction Engineering Research Laboratory (CERL) is developing alternatives for safe, economic, and environmentally benign assessment, decontamination, and disposal of excess ordnance production facilities. For this study, CERL selected four EM detection technologies and tested them at the Radford Army Ammunition Plant (RAAP) in Virginia. Facilities selected as test sites reflected as much variation in EM usage, construction, building materials, and other conditions as possible. All of the instruments evaluated in this study are capable of detecting EMs. They are designed and were demonstrated to be very sensitive to small levels of contamination. Instrument performance was not hindered by either the conditions at RAAP or the building material substrate. Each instrument had superior qualities, as well as features less suited for use in field work like that experienced at RAAP.
SYNTHESIS AND SCREENING OF ADVANCED HYDROCARBON FUELS
Personal Author(s): Suri, Suresh C , Tinnirello, Michael, Marcischak, Jacob
Report Date: 24 Oct 2000
Descriptors: (U) *FUELS, *HYDROCARBONS, REQUIREMENTS, SYNTHESIS, PHYSICAL PROPERTIES, STRUCTURAL PROPERTIES, TARGETS, PROPELLANTS, PRESSURE, ENERGETIC PROPERTIES, SELECTION, CHAMBERS, HAZARDOUS MATERIALS, BENCH TESTS
Identifiers: (U) VIEWGRAPHS ONLY
Abstract: (U) These viewgraphs discuss these various goals: the HEDM program, NASA program, IHPRPT program (propellant perspective), criteria for fuel selection, approach, results and accomplishments during fiscal year 2000. The HEDM goal is to develop fuels with increased lsp over LOX/RP-1 (determined at sea level and 1000 psi chamber pressure). The IHPRPT goal (propellant contribution) is to meet IHPRPT Phase II and Phase III objectives. The NASA goal is to deliver three advanced hydrocarbon fuel in 8-10 lb. quantity and screen four hydrocarbons for their physical and hazardous properties. The criteria for fuel selection is that it predicts better performance (lsp) over LOX/RP-1 system. The most desirable physical properties are listed. The approach is thus: structural requirements, survey of energetic hydrocarbons, selection of hydrocarbons based on improved theoretical performance, synthesis of target hydrocarbons at bench scale, translate bench-scale synthesis to pilot scale.
OVERVIEW OF MOLECULAR MODELLING AND AB INITIO MOLECULAR ORBITAL METHODS SUITABLE FOR USE WITH ENERGETIC MATERIALS
Personal Author(s): Dorsett, H , White, A
Report Date: Sep 2000
Descriptors: (U) *ENERGETIC PROPERTIES, *COMPUTATIONAL CHEMISTRY, QUANTUM CHEMISTRY, AUSTRALIA, MOLECULAR ORBITALS, MOLECULAR DYNAMICS
Identifiers: (U) *MOLECULAR MODELING, FOREIGN REPORTS, FIRST PRINCIPLE CALCULATIONS
Abstract: (U) This is a review of molecular modelling techniques which may be applied to studies of energetic materials. It focuses on ab initio (first-principles') molecular orbital calculations, since these methods offer the greatest accuracy. Since ab initio calculations are very computer-intensive, approximate MO methods are also discussed, which offer reasonably accurate predictions with reduced calculation times. These approximate methods include density functional theory and layered' techniques which combine different levels of theoretical sophistication into one calculation.
INTERMOLECULAR POTENTIALS OF MIXED SYSTEMS: TESTING THE LORENTZ-BERTHELOT MIXING RULES WITH AB INITIO CALCULATIONS
Personal Author(s): White, A
Report Date: Aug 2000
Descriptors: (U) *PHYSICOCHEMICAL PROPERTIES, EXPLOSIVES, GASES, HIGH ENERGY, COMBUSTION, MOLECULE MOLECULE INTERACTIONS, AUSTRALIA, ENERGETIC PROPERTIES, GROUPS(MATHEMATICS), LORENTZ FORCE, MOLECULAR DYNAMICS
Identifiers: (U) AB INITIO CALCULATIONS, FOREIGN REPORTS, LORENTZ-BERTHELOT MIXING RULES, INTERMOLECULAR POTENTIAL, ENERGETIC MATERIALS
Abstract: (U) The Lorentz-Berthelot mixing rules are extensively used for estimating intermolecular potential parameters between pairs of non-identical molecules (ij) from those between pairs of identical molecules (ii and jj). Ab initio molecular calculations allow direct estimation of intermolecular potentials in all three systems and hence afford a method of testing the Lorentz-Berthelot mixing rules.
AB INITIO CALCULATION OF INTERMOLECULAR POTENTIAL PARAMETERS FOR GASEOUS DECOMPOSITION PRODUCTS OF ENERGETIC MATERIALS
Personal Author(s): White, A , Zerilli, F J , Jones, H D
Report Date: Aug 2000
Descriptors: (U) *EXPLOSIVES, MONTE CARLO METHOD, GASES, MOLECULE MOLECULE INTERACTIONS, POTENTIAL ENERGY, AUSTRALIA, ENERGETIC PROPERTIES, DECOMPOSITION, COMBUSTION PRODUCTS
Identifiers: (U) FOREIGN REPORTS, *AB INITLO CALCULATIONS, *INTERMOLECULAR FORCES
Abstract: (U) This document describes the results obtained using two methods for ab initlo calculation of intermolecular potential parameters for gaseous decomposition products of energetic materials: a Multipole Expansion method, suitable for axially symmetric molecules, and a Monte Carlo method, which can be used to obtain temperature dependent average potential energy parameters for any molecule.
INTERNATIONAL SYMPOSIUM ON SPECIAL TOPICS IN CHEMICAL PROPULSION (5TH); COMBUSTION OF ENERGETIC MATERIALS HELD IN STRESA (LAKE MAGGIORE), ITALY ON 18-22 JUNE 2000
Report Date: 06 Jul 2000
Descriptors: (U) *MATERIALS, *COMBUSTION, *ENERGETIC PROPERTIES, RECYCLED MATERIALS, SYMPOSIA, REACTION KINETICS, EXPLOSIVES, PROPULSION SYSTEMS, DATA REDUCTION, ITALY, BALLISTICS, SOLID PROPELLANT ROCKET ENGINES, PYROLYSIS, ROCKET PROPULSION, GUN PROPELLANTS, SOLID ROCKET PROPELLANTS, SOLID PHASES, HYBRID ROCKET ENGINES
Identifiers: (U) FOREIGN REPORTS, AQ F01-07-1428
Abstract: (U) The Final Proceedings for 5th-ISICP Combustion of Energetic Materials, 19 June 2000-22 June 2000. This is an interdisciplinary conference. Topics include: Measurement techniques of thermophysical and ballistic properties of energetic materials (in particular, solid rocket propellant explosives); how to handle data especially in the presence of sensible errors and noise; and to which extent the obtained data depend on the specific data reduction technique implemented.
INTERNATIONAL ANNUAL CONFERENCE (31ST) OF ICT HELD IN KARISRUHE, FEDERAL REPUBLIC OF GERMANY ON JULY 3-JULY 6, 2001. ENERGETIC MATERIALS: ANALYSIS, DIAGNOSTICS AND TESTING
Report Date: 27 Jun 2000
Descriptors: (U) *EXPLOSIVES, *ENERGETIC PROPERTIES, TEST AND EVALUATION, INFRARED SPECTROSCOPY, SYMPOSIA, POLYMERS, RAMAN SPECTROSCOPY, THERMAL STABILITY, COMBUSTION, AMINES, GERMANY, IGNITION, UNDERWATER EXPLOSIONS, GERMAN LANGUAGE, RDX, INSENSITIVE EXPLOSIVES, ANALYTICAL CHEMISTRY, PLASTIC BONDED EXPLOSIVES, GUN PROPELLANTS, NITRAMINES, FOURIER SPECTROSCOPY, SOLID PROPELLANTS, NITRATES, CALORIMETRY, NITROGEN COMPOUNDS, PETN, CRYOGENIC PROPELLANTS, HEAT TRANSMISSION, HYDROXY TERMINATED POLYBUTADIENE, DIPOLAR IONS
Identifiers: (U) AQ F02-02-0284, FOREIGN REPORTS, STANAG(STANDARDIZATION AGREEMENT), FORMATES/NITRO HYDRAZINIUM, GEM DINITROALIFATIC COMPOUNDS, CYCLODEXTRINS, HEXANITROHEXAAZAISOWURTZITANE, TNAZ(1-3-3-TRINITROAZETIDINE), DINITROALIPHATIC COMPOUNDS
Abstract: (U) These are presentation and poster session papers presented at the 31st International Annual Conference of CT held in Karlsruhe, Germany, on June 27-30, 2000. In recent years the technical progress in synthesis, processing and application of energetic materials was positively influenced by advanced analytical methods, diagnostics and measuring techniques. Efficient screening methods, new sensoring techniques and combinatorical approaches are examples for analytical strategies making accurate data available and allowing their fast evaluation. The conference objectives include the investigation and characterization of energetic materials by analytical methods, the improvement of existing measuring techniques and the development of new analytical methods and strategies.
CHEMICAL MECHANISMS AT THE BURNING SURFACE
Personal Author(s): Brill, Thomas B
Report Date: 31 May 2000
Descriptors: (U) *COMBUSTION, *CHEMICAL REACTIONS, *NITROGEN COMPOUNDS, *TETRAZOLES, INFRARED SPECTROSCOPY, SYNTHESIS, X RAYS, EXPLOSIVES, BURNING RATE, ENERGETIC PROPERTIES, PYROLYSIS, CRYSTALLOGRAPHY, GAS GENERATING SYSTEMS, SOLID PROPELLANTS, VIBRATIONAL SPECTRA
Identifiers: (U) *BURNING SURFACE, FURAZAN RING COMPOUNDS, DENSITY FUNCTIONAL THEORY, ENERGETIC MATERIALS, 5-ATZ(AMINOTETRAZOLE), 5-NATZ(NITRAMINOTETRAZOLE)
Abstract: (U) This research program was devoted to the study of high-nitrogen compounds that have been of worldwide interest as gas generators, explosives, and propellants. The focus was specifically on substituted tetrazole and furazan ring compounds. The Russian FLAME database reveals that many of these compounds have high burning rates. In the United States these compounds are of interest to AFRL, Los Alamos National Laboratory, and the Thiokol Corporation as highly energetic materials. The research program required synthesis of most of the compounds, flash pyrolysis studies to identify and quantify the gaseous products, vibrational spectroscopy and X-ray crystallography to determine the structural details, and density functional theory computations. All of this work was aimed at fundamental understanding the energetic behavior of these compounds. The research program has resulted in the awarding of two M.S. degrees in chemistry, the submission of five manuscripts, and presentation of the work at several conferences.
INTERNATIONAL CONFERENCE ON ENERGETIC MATERIALS
Report Date: 23 Feb 2000
Pagination Code: 0
Descriptors: (U) *MATERIALS, *EXPLOSIVES, *ENERGETIC PROPERTIES, SYMPOSIA, PRODUCTION, SYNTHESIS, PROPELLANTS, PARTICLES, SAFETY, GERMANY, QUALITY ASSURANCE, ENVIRONMENTAL MANAGEMENT, GERMAN LANGUAGE
Identifiers: (U) *ENERGETIC MATERIALS, AQ F00-12-3869, FOREIGN REPORTS
Abstract: (U) The Final Proceedings for International Conference on Energetic Materials, 29 June 1999 - 2 July 1999. This is an interdisciplinary conference. Topics include Components; Particle Technology; Synthesis, Production and Processing; Characterization of Energetic Materials; Safety Technology; Quality Assurance and Environmental Aspects.
EFFECT OF CONFINEMENT ON THE MECHANICAL RESPONSE OF COMPOSITE PLASTIC BONDED EXPLOSIVES
Personal Author(s): Wiegand, Donald A
Report Date: Feb 2000
Descriptors: (U) *CONFINEMENT(GENERAL), *PLASTIC BONDED EXPLOSIVES, COMPRESSION, MECHANICAL PROPERTIES, POLYMERS, COMPOSITE MATERIALS, ELASTIC PROPERTIES, FAILURE, HIGH PRESSURE, STRAIN(MECHANICS), STEEL, CRACK PROPAGATION, YIELD STRENGTH, WAFERS, BINDERS, ENERGETIC PROPERTIES, FRICTION, TNT, PLASTIC FLOW, AXIAL FLOW, POLYCRYSTALLINE, RADIAL STRESS
Identifiers: (U) OIL IMMERSION, STEEL CYLINDER, CONFINING PRESSURE, COMPOSITION B
Abstract: (U) The mechanical properties of composite explosives are being studied as a function of mechanical confinement and three techniques for confinement were used. These are: (a) a constant confining pressure obtained by oil immersion, (b) radial confinement of a cylindrical sample by a thick walled steel cylinder that surrounds the sample (negligible radial strain), and (c) radial confinement of thin wafers by the platen-sample friction. while many energetic materials fail by crack growth when unconfined (significant surface area free of stress), with all of these forms of confinement, they appear to fail by yield and plastic flow. For crystalline explosives (e.g., TNT and Composition B), the yield strength and the modulus are independent of confining pressure so that useful results can be easily obtained by use of the steel cylinder technique. However, for materials containing polymer binders, such as plastic bonded explosives, a constant confining pressure is used because these properties are found to significantly increase with this pressure. These results indicate the very significant role of the polymer binders in determining the mechanical properties of these energetic materials.
SIMULATION OF ENERGETIC MATERIALS COMBUSTION
Personal Author(s): Zarko, V E , Gusachenko, L K
Report Date: 31 Jan 2000
Descriptors: (U) *MATHEMATICAL MODELS, *EXPLOSIVES, *SOLID PROPELLANTS, COMBUSTION, RUSSIA, ENERGETIC PROPERTIES, PYROTECHNICS
Identifiers: (U) FOREIGN REPORTS, AQ F00-09-2885
Abstract: (U) This report results from a contract tasking Institute of Chemical Kinetics and Combustion as follows: The contractor will investigate mathematical modeling of self-sustaining and transient combustion of energetic materials (e.g. solid propellants, explosives, pyrotechnics). He will perform a critical survey of original materials of authors and papers published in open literature. He will present various approaches for combustion models; and investigate the problems of intrinsic stability of energetic materials combustion in unconfined volume.
FEMTOSECOND SHOCK WAVE DYNAMICS OF INSENSITIVE ENERGETIC MATERIALS
Personal Author(s): Dlott, Dana D
Report Date: Jan 2000
Descriptors: (U) *SHOCK WAVES, *ENERGETIC PROPERTIES, *INSENSITIVE EXPLOSIVES, MOLECULAR STATES, CHEMICAL PROPERTIES, TEST METHODS, CRACK PROPAGATION, IMPACT SHOCK, FAILURE(MECHANICS)
Identifiers: (U) *FEMTOSECONDS
Abstract: (U) The goal of this project is to develop a fundamental understanding, at the molecular level, of the initial events occurring during the first picoseconds of impact initiation of energetic materials. It is believed this fundamental research will lead to a clearer picture of the factors which determine the sensitivity of energetic materials to shock impact initiation. Understanding and perhaps controlling sensitivity will result in safer explosives. In a larger sense, the problem of molecular level understanding of chemical and physical phenomena involved in impact processes has much wider and more general implications for such relevant processes as mechanical failure, crack propagation, lubrication and wear, etc. At the present time experimental techniques to study these problems are lacking. By developing such techniques with the goal of understanding impact initiation of energetic materials, these other areas may be addressed as well.
THEORETICAL STUDIES OF ENERGETIC MATERIALS
Personal Author(s): Thompson, Donald L
Report Date: 06 Dec 1999
Descriptors: (U) *ENERGETIC PROPERTIES, *INSENSITIVE EXPLOSIVES, VIBRATION, COMPOSITE MATERIALS, REACTION TIME, FORMULATIONS, SOLIDS, ORGANIC NITROGEN COMPOUNDS, MOLECULE MOLECULE INTERACTIONS, DIFFUSION THEORY
Identifiers: (U) AASERT(AUGMENTATION AWARDS FOR SCIENCE AND ENGINEERING RESEARCH TRAINING), ENERGETIC MATERIALS, INTRAMOLECULAR FORCE FIELDS, NTO( 5-NITRO-2-4-DIHYDRO-3H-1-2-3-TRIAZOL-3-ONE), TRIAZOLE/5-AMINO-3-NITRO-1H-1, 2, 4, ANTA, IDDT(INTRAMOLECULAR DYNAMICS DIFFUSION THEORY)
Abstract: (U) The research supported by AFOSR-AASERT grant F49620-95-L-0411 (parent grant F49620-95-L-0310) for the period 1 June 1995 to 31 May 1999 is described. The purpose of the research is the formulation of methods and realistic models for studying the fundamental properties and behavior of insensitive energetic materials. The work performed during this grant focused on the development of intramolecular potentials to describe the vibrational dynamics of the "insensitive" energetic materials NTO (5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one) and ANTA (5-amino-3-nitro-1H-1,2,4-triazole). In addition, the applicability of intramolecular dynamics diffusion theory (IDDT) for computing reaction rates in large, complex systems such as energetic molecules and solids was demonstrated.
ENERGETIC MATERIALS PYROMETRY
Personal Author(s): Hopkins, Mark F , Derniak, Eustace L , Garcia, John P
Report Date: Oct 1999
Descriptors: (U) *HIGH TEMPERATURE, *ENERGETIC PROPERTIES, *EMISSIVITY, COMPUTER PROGRAMS, INFRARED DETECTION, FOURIER TRANSFORMATION, RADIATION, HIGH RESOLUTION, EXPLOSIVES, INFRARED IMAGES, ORDNANCE, REMOTE DETECTION, RADIOMETRY, FOURIER SPECTROMETERS, MULTISPECTRAL, PYROMETERS, HIGH SPEED CAMERAS, INFRARED CAMERAS
Identifiers: (U) *ENERGETIC MATERIALS, HIGH SPEED, *PYROMETRY, PE62602F, WUAFRL25022849
Abstract: (U) In this research, a remotely located, high-speed, infrared (IR) camera is used to obtain detailed measurements of the passive radiation from an object in an energetic environment. This radiation information is used to determine both the emissivity and the temperature of the surface of an object. However, before the temperature or emissivity was determined, the functional form of the emissivity was assumed to be an Mth degree polynomial with respect to wavelength dependence. Using a commercial Fourier transform spectrometer, this functional form was verified to accuracy's on the order of 0.1%, to be a polynomial of the second degree. With the advent of large (greater than 128 X 128 pixels), high-speed, IR detector arrays, it has now become possible to realize IR imaging spectrometers that have very high spatial resolution. The IR spectrometer system developed in this research utilized a large detector array to allow multiple spectral images to be formed simultaneously on the image plane, with the information from each spectral image being concurrently collected. In conjunction with the correct emissivity model, this imaging IR spectrometer can determine the temperature of the surface of an object within an energetic environment to within +/- 5 degrees Celsius. These experimentally verified temperature/emissivity maps can then be integrated into the newly developed computer models. This additional information will result in more accurate computer codes for modeling the energetic environment. In turn, this will allow the weapon designer to optimize weapon performance with respect to different materials, geometries and kinetics.
CHEMICAL ANALYSIS OF FLOOR SWEEPINGS FROM ABERDEEN PROVING GROUND BUILDING 1107
Personal Author(s): Pesce-Rodriguez, Rose A
Report Date: Oct 1999
Descriptors: (U) *SAMPLING, *ENERGETIC PROPERTIES, *GAS CHROMATOGRAPHY, SCANNING, MATERIALS, MASS SPECTROSCOPY, DESORPTION, CHEMICAL ANALYSIS, PYROLYSIS, CALORIMETRY
Abstract: (U) A sampling of floor sweepings taken from Building 1107 of the Aberdeen Proving Ground (APG) was provided for analysis with the request that it be examined for the presence of energetic materials. An analysis was performed using a desorption/pyrolysis-gas chromatography-mass spectroscopy (GC-MS) and differential scanning calorimetry (DSC). No evidence of the presence of energetic materials in the sample was found.
SYNTHETIC DIRECTIONS IN NEW ENERGETIC MATERIALS FOR ADVANCED SOLID ROCKET PROPELLANTS
Personal Author(s): Velarde, S P , Cannizzo, L F , Highsmith, T K , Hamilton, R S , Edwards, W W
Report Date: 09 Sep 1999
Descriptors: (U) *ENERGETIC PROPERTIES, *SOLID ROCKET PROPELLANTS, OXIDIZERS, FORMULATIONS(CHEMISTRY), SOLID ROCKET FUELS, HYBRID PROPELLANTS, SOLID ROCKET OXIDIZERS
Identifiers: (U) IHPRPT(INTEGRATED HIGH PERFORMANCE ROCKET PROPULSION TECHNOLOGY), THREAT(TACTICAL HYBRID ROCKET ENGINE APPLIED TECHNOLOGY)
Abstract: (U) Several programs are currently underway at Thiokol Propulsion which strive to meet or exceed the goals of the Integrated High Performance Rocket Propulsion Technology (IHPRPT) Program. The three major program efforts are: the completed Advanced Oxidizers and Fuels Program, in which was synthesized and evaluated a series of new ingredients for solid rocket propellants; the current Hybrid Fuel Program, which will produce fuels that complement the Tactical Hybrid Rocket Engine Applied Technology (THREAT) Program design and proposed advanced oxidizer; and the current Phase III Ingredient Program, which strives to identify novel, high performance, solid propellant ingredients for boost and orbit transfer applications. All three programs have already undergone down-selection from myriad of possible compounds to a much more workable number of candidates for synthetic consideration.
Personal Author(s): Bowers, Michael T
Report Date: 31 Aug 1999
Descriptors: (U) *IONS, *CLUSTERING, MATHEMATICAL MODELS, BENZENE, TRANSITION METALS, PHOTODISSOCIATION, POLYMERS, COMPOSITE MATERIALS, PROTEINS, VAPOR PHASES, INSTRUMENTATION, ENERGETIC PROPERTIES
Identifiers: (U) *CLUSTER IONS, BIOPOLYMERS
Abstract: (U) Progress has been made on the objectives listed below. The structures and energetics of a number of important synthetis polymers have been successfully investigated. A successful model for the gas phase HID exchange mechanism for proteins has been developed. Progress has been made on determining the basis for gas phase salt bridge formation in biopolymers. Finally, promising results have been obtained on the reactivity, energetics and structures of transition metal/benzene clusters. At present, we are developing theoretical models to help us interpret the data. Finally, the design of a new instrument has been completed and construction initiated.
A MICROFORCE-BASED THEORY FOR ENERGETIC MATERIALS
Personal Author(s): Ruderman, Gregory A , Stewart, D S , Fried, Eliot
Report Date: 08 Jun 1999
Descriptors: (U) *THERMOMECHANICS, *SOLID ROCKET PROPELLANTS, ABSTRACTS, HIGH ENERGY PROPELLANTS
Identifiers: (U) WUAFRL1011100NF
Abstract: (U) Employing advanced tools of continuum thermomechanics, we have developed a fully three-dimensional framework, which in its most general form is able to model all the mentioned behaviors of energetic materials. The concept of microforces, forces that drive changes in material microstructure, is employed to generate consistent equations of evolution for combustion and phase transitions. The method of generating equations for thermomechanical behavior using microforces begins with the generation of a free-energy function that encompasses all the material changes. The Clausius-Duhem inequality, a statement of the second law of thermodynamics, is then applied, restricting the material behavior to be thermodynamically correct a prori. Appropriate forms of coupling behavior and dissipation functions are derived.
PROCEEDINGS OF THE WORKSHOP ON THE MICROCALORIMETRY OF ENERGETIC MATERIALS HELD IN LEEDS, UNITED KINGDOM ON 17-19TH MAY 1999
Personal Author(s): Griffiths, Trevor
Report Date: 19 May 1999
Descriptors: (U) *COMPOSITE MATERIALS, *ENERGETIC PROPERTIES, *PYROTECHNICS, *MICROCALORIMETRY, THERMAL PROPERTIES, MEASUREMENT, SYMPOSIA, AGING(MATERIALS), CORROSION, LIFE EXPECTANCY(SERVICE LIFE), COMPATIBILITY, ABSORBERS(MATERIALS), HEAT, DECOMPOSITION, PYROLYSIS, GUN PROPELLANTS, PLASTICIZERS, UNITED KINGDOM
Identifiers: (U) FOREIGN REPORTS
Abstract: (U) Eighteen papers were presented at the workshop about uses of microcalorimetry as a tool to study service life of gun propellants, aging, stability, heat generation, thermal decomposition of energetic plastisizers, modelling, absorbant surfaces, absolute calibration, corrosion rate, DSC studies, compatibility of energetic materials, sample preparations and measuring conditions.
INITIATION OF ENERGETIC SOLIDS: THE FIRST NANOSECOND
Personal Author(s): Dlott, Dana D
Report Date: 31 Mar 1999
Descriptors: (U) *SOLIDS, *LASER APPLICATIONS, *ENERGETIC PROPERTIES, IMAGE PROCESSING, VIBRATION, TECHNOLOGY TRANSFER, MOLECULAR VIBRATION, COMPOSITE MATERIALS, EXPERIMENTAL DESIGN, SHOCK WAVES, ENERGY TRANSFER, ATOMS, ELECTRONS, INFRARED RADIATION, RDX, MOLECULAR PROPERTIES, RAMAN SPECTRA, NITROMETHANE, ANTHRACENES, VIBRATIONAL SPECTRA, GRAPHIC ARTS, PHOTOTHERMAL ENERGY, NANOTECHNOLOGY
Identifiers: (U) NANOSECONDS, NANOSHOCK TECHNIQUE, *ULTRAFAST VIBRATIONAL SPECTROSCOPY, SHOCK INITIATION, MOLECULAR SOLIDS, NTO(NITROGEN TETROXIDE)
Abstract: (U) The goal is to understand what occurs at the molecular level during shock initiation of energetic materials. We have developed the nanoshock technique, which lets us shock any solid material and study its molecules using ultrafast vibrational spectroscopy with 25 ps time resolution. Test experiments were conducted with anthracene to verify the performance of this technique, which was subsequently extended to energetic materials including RDX and NTO. A related theoretical effort looked at orientation effects in initiation. A related project is understanding the role of molecular vibrational energy transfer processes in initiation. Since we know little about energy transfer, we are concentrating on simple model systems under non shock conditions. We have used a new experimental apparatus which uses a infrared-Raman technique with 1 ps resolution to study nitromethane and other simpler liquids. A minor effort relates to technology transfer from our ARO-funded shock wave program to industry. in particular we have used ultrafast microscopy and shock wave generation techniques to improve laser photothermal imaging processes used in graphic arts by incorporating energetic materials into the imaging media.
INT'L WORKSHOP ON ERRORS AND NOISE IN ENERGETIC MATERIAL COMBUSTION EXPERIMENTS
Report Date: 24 Mar 1999
Descriptors: (U) *COMBUSTION, ABSTRACTS, EXPLOSIVES, ERRORS, ENERGETIC PROPERTIES, BALLISTICS, ROCKET ENGINES, WORKSHOPS, NOISE(SOUND), SOLID ROCKET PROPELLANTS, SOLID FUELS
Identifiers: (U) AQ F00-12-3868
Abstract: (U) The Final Proceedings for International Workshop on Errors and Noise in Energetic Material Combustion Experiment, 14 March 1999 - 18 March 1999 This is an interdisciplinary conference. Topics include: Measurement techniques of thermophysical and ballistic properties of energetic materials (in particular, solid rocket propellant explosives); how to handle data especially in the presence of sensible errors and noise; and to which extent the obtained data depend on the specific data reduction technique implemented.
A FORENSIC WORKSHOP REPORT CONCERNING (1) THE MEASUREMENT AND ANALYSIS OF ENERGETIC MATERIALS AND (2) DATABASING
Personal Author(s): Heimerl, Joseph M
Report Date: Jan 1999
Descriptors: (U) *RAMAN SPECTROSCOPY, *TRACE ELEMENTS, *EXPLOSIVES DETECTION, DATA BASES, ENERGETIC PROPERTIES, SMOKELESS PROPELLANTS
Identifiers: (U) SMOKELESS GUNPOWDERS, EXPLOSIVE REFERENCE STANDARDS, TRACE ENERGETIC MATERIALS, PE61102A
Abstract: (U) On Thursday, 20 June 1996, this workshop was convened at BRL Hall (Bldg. 330), located at the U.S. Army Research Laboratory (ARL), Aberdeen Proving Ground (APG), MD. The purposes of this workshop were: (1) to define the critical problems that cut across forensic agencies; (2) to provide an open, multidisciplinary forum in which these problems could be addressed and better defined; and (3) to lay the foundation for practical, timely, and cost-effective solutions. The technical focus of the workshop pivoted on two questions: (1) What is required for a sample to be traceable to a unique compound (or unique class of compounds)? (2) How can the present databases be made into user-friendly, complete, and current databases, accessible by all forensic laboratories? This report documents the background leading up to the calling for a workshop, the manuscripts of the talks given, and the discussion held.
ENZYMES FOR DEGRADATION OF ENERGETIC MATERIALS AND DEMILITARIZATION OF EXPLOSIVES STOCKPILES
Personal Author(s): Shah, M M
Report Date: Jan 1999
Descriptors: (U) *DEGRADATION, *ENZYMES, *EXPLOSIVES, *ENERGETIC PROPERTIES, *STOCKPILES, ENVIRONMENTS, CHEMICALS, WATER, HIGH TEMPERATURE, ROOM TEMPERATURE, SOLUTIONS(GENERAL), VALUE, DEMILITARIZATION, BAROMETRIC PRESSURE, DISPOSAL
Identifiers: (U) SERDP COLLECTION
Abstract: (U) The current stockpile of energetic materials requiring disposal contains about half a million tons. Through 2001, over 2.1 million tons are expected to pass through the stockpile for disposal. Safe and environmentally acceptable methods for disposing of these materials are needed. This project is developing safe, economical, and environmentally sound processes using biocatalysts (enzymes) to degrade energetic materials and to convert them into economically valuable products. Alternative methods for destroying these materials are hazardous, environmentally unacceptable, and expensive. These methods include burning, detonation, land and sea burial, treatment at high temperature and pressure, and treatment with harsh chemicals. Enzyme treatment operates at room temperature and atmospheric pressure in a water solution.
ELIMINATION OF TOXIC MATERIALS AND SOLVENTS FROM SOLID PROPELLANT COMPONENTS (PP1058)
Personal Author(s): Stanley, Robert , Hagler, Diane
Report Date: 17 Dec 1998
Descriptors: (U) *SOLVENTS, *ELIMINATION, *SOLID PROPELLANT ROCKET ENGINES, *HAZARDOUS MATERIALS, TOXIC HAZARDS, STRATEGIC WEAPONS, ORGANIC COMPOUNDS, SIGNATURES, CATALYSTS, GUIDED MISSILE DEFENSE SYSTEMS, ENVIRONMENTAL PROTECTION, ENERGETIC PROPERTIES, LEAD(METAL), HYDROGEN CHLORIDE, COMBUSTION PRODUCTS, SOLID ROCKET OXIDIZERS, OZONE DEPLETION
Identifiers: (U) SERDP(STRATEGIC ENVIRONMENTAL RESEARCH AND DEVELOPMENT PROGRAM), SERDP COLLECTION, SRM(SOLID ROCKET MOTOR), VOLATILE ORGANIC COMPOUNDS
Abstract: (U) Solid rocket motor (srm) propellant used in military tactical and strategic missile weapon systems contain hazardous and toxic materials. Lead is used as a ballistic catalyst in minimum signature propellants. It's use results in approximately 161,000 pounds of lead compound usage per year. In some "smoky" propellant formulations, hydrogen chloride (HCl) is a combustion product which contributes to stratospheric ozone depletion. It is estimated that seven million pounds of HCL is emitted from military rocket motors per year. Lastly, processing of energetic oxidizer materials used in SRMs requires the use of solvents which are toxic, considered ozone depleting substances and also release volatile organic compounds (VOCs). Approximately four million pounds of oxidizer solvents are utilized in propellant production per year. Due to the human health hazards associated with these toxic compounds, several regulations have been and are being promulgated to curtail or eliminate the use of these substances and their associated emissions. Therefore, alternatives are required to permit future propellant production and maintain weapon system readiness.
STRUCTURE OF PARTIALLY PREMIXED FLAMES AND ADVANCED SOLID PROPELLANTS
Personal Author(s): Branch, Melvyn C
Dreyer, Christopher B
Report Date: 30 Nov 1998
Descriptors: (U) *GASES, *MIXING, *FLAMES, *SOLID ROCKET PROPELLANTS, VELOCITY, EXTINCTION, RATIOS, EXPERIMENTAL DATA, MATERIALS, VARIATIONS, SURFACES, PROPELLANTS, COMBUSTION, RESPONSE, COMBUSTION CHAMBERS, DIFFUSION, NITROGEN OXIDES, ENERGETIC PROPERTIES, DECOMPOSITION, INSTABILITY
Identifiers: (U) PE61102F, WUAFOSR2308AX
Abstract: (U) The combustion of solid rocket propellants of advanced energetic materials involves a complex process of decomposition and condensed phase reactions in the solid propellant, gaseous flame reactions above the propellant surface, and subsequent mixing and flow through the combustion chamber. The response to combustion instabilities is influenced by the structure of the premixed and partially premixed diffusion flames and triple flames at the propellant surface. This research provided experimental data and modeling of partially premixed diffusion flames supported by nitrogen oxides that are common with advanced solid propellants. Of particular interest was the stability and possible extinction of the flames in the presence of velocity fluctuations across the propellant. It was shown that premix flames of highly disparate equivalence ratio can be supported in opposed-flow geometry and will form a triple flame structure. Evidence was presented which indicates that a diffusion flame forms between the premix flames and is due to the conversion of H2, O2, and CO originating from the premix flame zones to H20 and CO2.
CHEMICAL DYNAMICS STUDIES OF REACTIONS IN SOLIDS
Personal Author(s): Thompson, Donald L
Report Date: Sep 1998
Descriptors: (U) *DYNAMICS, *SOLIDS, *CHEMICAL REACTIONS, *ENERGETIC PROPERTIES, *MOLECULAR PROPERTIES, SIMULATION, METHODOLOGY, CRYSTAL STRUCTURE, AIR FORCE RESEARCH, MODELS, QUANTUM CHEMISTRY, MOLECULES, MATERIALS, COMPOSITE MATERIALS, QUANTUM THEORY, ATOMS, MONTE CARLO METHOD, HIGH ENERGY, HIGH DENSITY, NUMERICAL METHODS AND PROCEDURES, TUNNELING, TRAJECTORIES, ISOMERIZATION, ATOMIC STRUCTURE, NITROGEN COMPOUNDS, RARE GASES, COMPUTATIONAL CHEMISTRY
Identifiers: (U) HEDM(HIGH ENERGY DENSITY MATERIALS), *MOLECULAR DYNAMICS, NTO(NITRODIHYDRO-H-TRIAZOLONE), 5-NITRO-2, 4-DIHYDRO-3H-1, 2, 4-TRIAZOL-3-ONE, ADN(AMMONIUM DINITRAMIDE), HONO, CLASSICAL MECHANICS, ZERO POINT ENERGY, MASS MIGRATION, MANY ATOM SYSTEMS, TRANSITION STATE, AB INITIO, POTENTIAL ENERGY SURFACES, PE61102F
Abstract: (U) The research performed with support by AFOSR grant F49620-95-1-0310 for the period April 1, 1995 to September 30, 1998 is described. Theoretical methods and atomic-level models were developed for studies of fundamental processes and properties of potential HEDM materials. The long-term goal of this research is to perform molecular dynamics and Monte Carlo simulations of the various kinds of processes, including chemical reactions, for systems that display the properties inherent in high-energy high-density materials. This research lays the groundwork for that by providing the theoretical and computational methods as well as accurate molecular and crystal models for important types of energetic systems; for example, molecules such as NTO (5-Nitro-2,4-dihydro-3H-1,2,4-triazol-3-one) and ADN (ammonium dinitramide). Classical dynamics simulations of molecular isomerization in a solid (Ar matrix) were performed for a prototypical energy material (HONO). A significant part of this project was the refinement of chemical dynamics methods for multidimensional problems. A new method was introduced in this work that can be used for accurate treatment of quantum effects such as tunneling in many-atom systems. A fundamental analysis of the failure in some cases of classical mechanics to accurately account for the behavior of zero-point energy was also presented. A method based on simple transtion-state theory was developed for computing the rates of mass migration in solids; it was demonstrated for various kinds of atoms in rare gas matrices, and the results are in good agreement with experiment.
SYNTHESIS OF HIGH ENERGY DENSITY MATERIALS BASED ON STRAINED RING CHEMISTRY
Personal Author(s): Dailey, William P
Report Date: Sep 1998
Descriptors: (U) *SYNTHESIS, *COMPOSITE MATERIALS, *HIGH ENERGY, *CHEMISTRY, *HYDROCARBONS, *ORGANIC MATERIALS, *HIGH DENSITY, *RINGS, *CYCLIC COMPOUNDS, CRYSTAL STRUCTURE, AIR FORCE RESEARCH, ISOLATION, X RAYS, FUELS, PROPENES, INERT MATERIALS, ENERGETIC PROPERTIES, CRYSTALLOGRAPHY, ALKENES, PENTANES
Identifiers: (U) *CYCLOPROPENES, HEDM(HIGH ENERGY DENSITY MATERIAL), PROPELLANE, BICYCLO-1.1.-PENTANES, PENTYLCARBENES, PRISMANE DERIVATIVES, *STRAINED RING CHEMISTRY, MATRIX ISOLATION, HIGH ENERGY FUELS, PE62601F, WUAFRL3058RFEU
Abstract: (U) Several new cyclopropenes were synthesized and evaluated as new High Energy Density Material (HEDM) candidates. An optimized synthetic route to 1.1.1 propellane was developed and several bicyclo1.1.1pentanes were prepared and evaluated as HEDM materials. Preliminary work toward the preparation and study of bicyclo1.1.1pentyl carbenes under inert gas matrix isolation conditions was undertaken. Several new prismane derivatives were prepared and their stuctures determined by X-ray crystallography.
ALTERNATIVES TO OPEN BURNING/OPEN DETONATION OF ENERGETIC MATERIALS
Personal Author(s): Adrian, Neal R , Strata, James, Schneider, Roger , Weber, Robert A , Donahue, Bernard A
Report Date: Aug 1998
Descriptors: (U) *COMBUSTION, *ENERGETIC PROPERTIES, *DETONATIONS, *EXPLOSIVE ORDNANCE DISPOSAL, EMISSION, MILITARY FACILITIES, RISK, PRODUCTION, AIR, WATER, HEALTH, ARMY FACILITIES, ELECTROCHEMISTRY, ENVIRONMENTAL IMPACT, PROPELLANTS, SOILS, OXIDATION, SURVEYS, AMMUNITION, WASTE DISPOSAL, CONTAMINATION, HAZARDOUS WASTES, MOISTURE, ARMY OPERATIONS, BIODEGRADATION, CRYOGENICS, WASTE TREATMENT, PYROTECHNICS, WASTES(INDUSTRIAL)
Identifiers: (U) EMCW(ENERGETIC MATERIAL CONTAMINATED WASTE), EOD(EXPLOSIVE ORDNANCE DISPOSAL), OB/OD(OPEN BURNING/OPEN DETONATION), LAP(LOAD ASSEMBLE AND PACK), PEP(PYROTECHNIC EXPLOSIVE AND PROPELLANT), EM(ENERGETIC MATERIAL), CRYOGENIC CUTTING, SUPERCRITICAL CARBON DIOXIDE EXTRACTION, HYDROTHERMAL OXIDATION, HYDROMILLING, WET AIR OXIDATION, *OPEN BURNING/OPEN DETONATION, PE62720A
Abstract: (U) U.S. Army Ammunition Plants (AAPs) and load, assemble, and pack (LAP) facilities generate diverse pyrotechnic, explosive, and propellant (PEP) production wastes as part of munitions production activities. These energetic material (EM) wastes and EM contaminated wastes (EMCW) continue to be destroyed by open burning and open detonation (OB/OD), the most common ("first generation") method of EM disposal. Incineration is a currently used, feasible "second generation" treatment option, but has enjoyed poor regulator and public acceptance. Concerns for potential human health risk created by OB/OD at Army installations as well as environmental impacts on the air, soil, and water are forcing the Army to identify and develop alternatives to OB/OD treatment. This document summarizes research initiatives by the U.S. Army Construction Engineering Research Laboratories (CERL) into several "third generation" pretreatment and treatment technologies for EM and EMCW, including: cryogenic cutting, supercritical CO2 extraction and hydrothermal oxidation, hydromilling, wet air oxidation, hydrothermal oxidation, biodegradation, and electrochemical treatment. Results are also given from a waste generation survey of nine Army Materiel Command (AMC) facilities, and of a study that characterizes the emissions from burning propellants under experimental conditions.
CHARACTERIZATION OF RAMAN SPECTRAL CHANGES IN ENERGETIC MATERIALS AND PROPELLANTS DURING HEATING
Personal Author(s): Fell, Nicholas F , Vanderhoff, John A , Rodriquez, Rose A , McNesby, Kevin L
Report Date: Aug 1998
Descriptors: (U) *MATERIALS, *EXPLOSIVES, *PROPELLANTS, *COMBUSTION, *HEATING, *ENERGETIC PROPERTIES, *RAMAN SPECTRA, MEASUREMENT, ARMY RESEARCH, RAMAN SPECTROSCOPY, CRYSTALS, LASERS, SAMPLING, FORMULATIONS(CHEMISTRY), VIBRATIONAL SPECTRA
Identifiers: (U) PE61102A
Abstract: (U) Raman spectroscopy has been shown to be a useful tool for characterizing neat crystalline explosive samples and for identifying principle components in many propellant and explosive formulations. Herein, we report recent measurements of Raman spectra of explosives and propellant formulations during bulk heating and recent measurements of laser heating of the samples during measurement of Raman spectra. The results of these measurements are important to investigators using Raman spectroscopy to measure vibrational spectra of burning propellant samples.
NUMERICAL SIMULATION OF DETONATION IN CONDENSED PHASE EXPLOSIVES
Personal Author(s): Jones, D A, Kemister, G , Borg, R A
Report Date: Aug 1998
Descriptors: (U) *COMPUTERIZED SIMULATION, *NUMERICAL ANALYSIS, *SYMPATHETIC DETONATIONS, *DETONATIONS, *EXPLOSIVE WARHEADS, TEST AND EVALUATION, COMPUTER PROGRAMS, MATHEMATICAL MODELS, ALGORITHMS, COUPLING(INTERACTION), COMPUTATIONS, INTERFACES, TWO DIMENSIONAL, COMPOSITE MATERIALS, REACTION TIME, ONE DIMENSIONAL, MILITARY APPLICATIONS, HYDRODYNAMIC CODES, IGNITION, EULER EQUATIONS, AUSTRALIA, ENERGETIC PROPERTIES, MOMENTUM, EQUATIONS OF STATE, COMPRESSIVE PROPERTIES
Identifiers: (U) *EULERIAN HYDROCODE, *CONDENSED PHASE EXPLOSIVES, FOREIGN REPORTS, CONSERVATION OF MASS, FCT(FLUX CORRECTED TRANSPORT), MIE-GRUNEISEN, TAIT EQUATION OF STATE, FOREST FIRE REACTION RATE MODEL, IGNITION AND GROWTH REACTION RATE MODEL, GAP TEST, BKW EQUATION OF STATE, JWL EQUATION OF STATE, OPERATOR SPLITTING, BULLET IMPACT SIMULATION, UNDERWATER SENSITIVITY TEST SIMULATION
Abstract: (U) This report describes the development of a two-dimensional multi-material Eulerian hydrocode to model the effects of detonating condensed phase explosives on surrounding materials. The code solves the Euler equations for the conservation of mass, momentum, and energy for an inviscid, compressible fluid. Operator splitting is used to reduce the two-dimensional calculation into coupled one-dimensional equations which are then solved using the Flux-Corrected Transport (FCT) algorithm of Boris and Book. Non-reacting materials are described using either a perfect gas, Mie-Gruneisen, or Tait equation of state, while the energetic materials are described using either a BKW equation of state and Forest Fire reaction rate model, or the JWL equation of state and the Ignition and Growth reaction rate model. A modified Young's algorithm is used to maintain a sharp interface between different materials on the computational mesh. A brief description of the major components of the coding is provided and then several applications of the code are described, including the simulation of bullet impact experimental the underwater sympathetic detonation test, and the modified gap test.
RYDBERG STATES OF ENERGETIC MATERIALS
Personal Author(s): Bernstein, Elliot R
Report Date: 01 Jul 1998
Descriptors:(U) *MATERIALS, *ENERGETIC PROPERTIES, *ATOMIC PROPERTIES, ABLATION, ARMY RESEARCH, MODELS, SPECTROSCOPY, FRAGMENTATION, METHYL RADICALS, EXCITATION, REACTIVITIES, LASERS, EXPLOSIVES, AMINES, ELECTRONS, CLUSTERING, ELECTRONIC STATES, COVARIANCE, DISSOCIATION, RDX, ETHYL RADICALS, ALKYL RADICALS, NITRAMINES, NITRO RADICALS, CHEMICAL RADICALS, NITROGEN COMPOUNDS
Identifiers: (U) ENERGETIC MATERIALS, *RYDBERG STATES, COVARIANCE MAPPING, LASER ABLATION
Abstract: (U) Energetic materials are modeled experimentally and theoretically with regard to possible excited electronic Rydberg state reactivity and dissociation. The systems of methyl and ethyl alkyl amines have been studied. We show that these Rydberg states can be both highly reactive and dissociative. Thus, excited Rydberg states are a possible route to radicals and other reactive species for these model systems. We are presently expanding our experimental capabilities to allow study of broad spectra of model energetic materials such as nitramines and nitro compounds in general. Studies employing covariance spectroscopy of clusters are used to demonstrate the importance of this technique for finding parent/daughter relations in fragmentation studies. Radical behavior is investigated as it relates to fragments of energetic materials.
IGNITION, COMBUSTION AND KINETICS OF ENERGETIC MATERIALS
Personal Author(s): Kuo, K K , Thynell, S T , Brill, T B , Yang, V , Litzinger, T A
Report Date: 30 Jun 1998
Descriptors: (U) *REACTION KINETICS, *IGNITION, *MONOPROPELLANTS, *COMPOSITE PROPELLANTS, FLAMES, RDX, LIQUID ROCKET PROPELLANTS, NITROMETHANE, NITRAMINES, NITROCELLULOSE, CELLULOSE ACETATES, BUTYRATES
Abstract: (U) To develop a comprehensive model of nitramine propellant ignition and combustion, the appropriate numerical analysis was developed to solve both transient and steady state combustion, including detailed finite rate chemical kinetics, thermodynamic phase transition, and sub-surface reactions. The model was advanced to predict ignition phenomena. Modeling work was complemented by conducting various experiments. Using fast thermolysis, significant accomplishments were made in studies of the decomposition behavior of propellant ingredients, such as RDX, cellulose acetate butyrate, nitrocellulose, and mixtures of RDX and binders. Intrusive mass spectroscopic techniques were utilized to acquire gas phase species profiles under laser assisted burning of monopropellants and composite propellants. Nonintrusive diagnostic techniques were developed and used to determine temperature and species profiles within propellant flames at elevated pressures, which are needed for model validation. Temperature sensitivities were deduced for RDX and nitramine propellants, and ignition delays were deduced for RDX, HMX and RDX/CAB pseudo propellants. In situ observation of burning surfaces revealed the formation of complex, sooty like structures and intermittent flame attachment. A liquid strand burner was established and successfully demonstrated to have the capability of maintaining a steady liquid propellant (LP) burning surface at the tip of the feeding tube using nitromethane. The burning behavior of nitromethane was also characterized.
INTERNATIONAL ANNUAL CONFERENCE (29TH) OF ICT HELD IN KARLSRUHE, FEDERAL REPUBLIC OF GERMANY ON JUNE 30-JULY 3, 1998. ENERGETIC MATERIALS; PRODUCTION, PROCESSING AND CHARACTERIZATION
Report Date: 26 Jun 1998
Descriptors: (U) *MATERIALS, *EXPLOSIVES, *ENERGETIC PROPERTIES, SYMPOSIA, PRODUCTION, SYNTHESIS, ELASTOMERS, COPOLYMERS, PROPELLANTS, PARTICLES, SAFETY, QUALITY ASSURANCE, ENVIRONMENTAL MANAGEMENT, WEST GERMANY, NITROGEN COMPOUNDS, PLASTICIZERS
Identifiers: (U) AQ F00-30693, FOREIGN REPORTS, CL-20 EXPLOSIVE, CYCLODEXTRIN NITRATE, COPOLYURETHANE THERMOPLASTIC ELASTOMERS, GLYCIDYL AZIDE POLYMER
Abstract: (U) The Final Proceedings for 29th International Annual Conference of ICT, 30 June 1998 - 3 July 1998. This is an interdisciplinary conference. Topics include: (1) Components; (2) Particle Technology; (3) Synthesis, Production and Processing; (4) Characterization of Energetic Materials; (5) Safety Technology; and (6) Quality Assurance and Environmental Aspects.
HYDROTHERMOLYSIS OF ENERGETIC MATERIALS: SAFETY AND CONTINUOUS PROCESS PARAMETERS
Descriptive Note: Final rept. 16 Oct 94-16 Jun 96
Personal Author(s): Jayaweera, Indira S , Ross, David S , Mill, Theodore , Penwell, Paul
Report Date: Jun 1998
Descriptors: (U) *SOLUBILITY, *EXPLOSIVE ORDNANCE DISPOSAL, BENZENE, ENERGETIC PROPERTIES, TNT, PETN, AMMONIUM PICRATE
Identifiers: (U) *HYDROTHERMOLYSIS
Abstract: (U) SRI conducted a study on the hydrothermolytic disposal of energetic materials (EMs) using a continuous flow reactor which was designed, assembled and tested in studies of the hydrothermolysis of ammonium picrate at 360 deg C. The dissolution study showed that the TNT solubility in water increased by a factor of about 200 from 25 deg C to 200 deg C. The literature shows that the solubility of benzene in water increases by a factor of about 50 over the same interval and benzene becomes completely soluble at about 300 deg C. Therefore, the complete dissolution of TNT in water at temperatures no greater than 300 deg C. Calculations of the critical radii for explosion were made for TNT, HMS, and PETN at 200-350 deg C based on relations for kinetics of self heating. TNT has a critical radius of 0.019 cm at 350 deg C, meaning that spherical particles exceeding this radius will self heat to explosion at 350 deg C.
SOME CHEMICAL AND STRUCTURAL FACTORS RELATED TO THE METASTABILITIES OF ENERGETIC COMPOUNDS
Personal Author(s): Politzer, Peter , Murray, Jane S
Report Date: 27 Apr 1998
Descriptors: (U) *IMPACT, *CHEMICAL PROPERTIES, *STRUCTURAL PROPERTIES, *SHOCK, *ENERGETIC PROPERTIES, *CHEMICAL COMPOUNDS, MATERIALS, FORMULATIONS, SENSITIVITY, EXPLOSIVES, SURFACES, PROPELLANTS, MOLECULAR STRUCTURE, ELECTROSTATICS
Identifiers: (U) *METASTABILITY, IMPACT SENSITIVITY, SHOCK SENSITIVITY
Abstract: (U) We have presented an overview of various attempts to relate the impact and shock sensitivities of energetic materials to their molecular structures. The objectives of such efforts are to better understand the chemical and structural determinants of these sensitivities, and to develop a predictive capability to facilitate the evaluation of new and proposed energetic compounds. Our particular emphasis in this discussion has been upon the relationship of impact sensitivities to the electrostatic potential patterns on the molecular surfaces. The current status of our analyses is represented by eqs. (7) - (9). While the success of these expressions is pleasing, we certainly do not claim that they are in final form. They reflect small data bases and measurements with a relatively high level of uncertainty. As more compounds are included, it may well be that the specific formulations given in eqs. (7) - (9) will be modified; i.e. other functions of V-bar s(-) and V-bar s(+) sigma 2 - and sigma 2 + may turn out to be more effective. What is important at present, however, is the unifying concept that we have found to apply to all three of these classes of compounds, namely that their impact sensitivities can be related to the degree of imbalance between their typically stronger positive surface electrostatic potentials and weaker negative ones.
PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY OF ENERGETIC MATERIALS
Personal Author(s): Cropek, Donald M , Kemme, Patricia A , Day, Jean M
Report Date: Apr 1998
Descriptors: (U) *DISPOSAL, *HAZARDOUS WASTES, *ENERGETIC PROPERTIES, WEAPONS, EMISSION, INDUSTRIES, ENVIRONMENTS, IMPACT, OPERATIONAL READINESS, MATERIALS, EXPLOSIVES, REDUCTION, OXYGEN, PROPELLANTS, COMBUSTION, MISSIONS, RDX, TNT, PYROLYSIS, DETONATIONS, BACKUP SYSTEMS, PETN
Abstract: (U) The armaments industry generates approximately 1600 tons per year of hazardous waste containing explosives and propellants. By far, the most common disposal method for this hazardous waste is open burning/open detonation (OB/OD). Unfortunately, OB/OD has the potential to create environmental problems due to uncontrolled emission of by-products. Incineration is currently the most mature and well-characterized alternative disposal technology. In the event that OB/OD is curtailed or even eliminated, studies examining incineration as a back-up treatment technology could have an immediate impact on mission readiness, especially if the focus of the work is on characterization and reduction of emissions. The objective of this work was to examine the pyrolysis of energetic materials and to study the by-products produced during thermal decomposition in the absence of oxygen. Pyrolytic by-products from RDX, TNT, and PETN were examined. Samples were prepared and analyzed, results were studied and compared with work done in previous studies, and recommendations for further research were made.
THERMAL DECOMPOSITION OF ENERGETIC MATERIALS: TNCHP, TNAZ, 24DNI, ANTA, DNBT AND HMX
Personal Author(s): Behrens, Richard
Report Date: 31 Mar 1998
Descriptors: (U) *EXPLOSIVES, *THERMAL ANALYSIS, *ENERGETIC PROPERTIES, *DECOMPOSITION, POLYMERS, PROPELLANTS, CHEMICAL REACTIONS, ORGANIC NITROGEN COMPOUNDS, KINETICS, TNT, INSENSITIVE EXPLOSIVES, NITRAMINES, SOLID PHASES, HMX, THERMOGRAVIMETRIC ANALYSIS
Identifiers: (U) TNCHP, TNAZ(1-3-3-TRINITROAZETIDINE), 24DNI(2-4-DINITROIMIDAZOLE), ANTA(3-AMINO-5-NITRO-1-2-4-TRIAZOLE), DNBT(5-5-DINITRO-3--BI-1-2-4-TRIAZOLE), STMBMS(SIMULTANEOUS THERMOGRAVIMETRIC MODULATED BEAM MASS SPECTROMETER)
Abstract: (U) The physical and chemical processes that control the thermal decomposition of several different types of energetic materials have been determined from measurements with a simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS). The compounds studied include HMX, hexahydro-1-nitroso-3,5-dinitro-s-triazine (ONDNTA), 2,4-dinitroimidazole (24DNI), TNAZ, 1-nitro-3,3-dinitroazetidine (NDNAZ), 3-amino-5-nitro-1,2,4-triazole (ANTA), 5,5'-dinitro-3,3'-bi-1,2,4-triazole (DNBT), and a complex of DNBT.2ANTA. The results on HMX provide new insights on the solid-phase decomposition processes that take place within individual particles. The results on ONDNTA provide new insight to the reaction mechanisms that control the decomposition of this important cyclic nitramine reaction intermediate. The results on 24DNI, TNAZ, and NDNAZ provide sufficient data to construct a model of the underlying chemical and physical processes. A model has been formulated to represent the decomposition of 24DNI and the parameters for the model have been determined from the STMBMS results. The model consists of seven different physical processes, which include the nucleation and growth of a polymeric residue that acts as an "autocatalyst". Global chemical reactions are used in each step. A qualitative model of the thermal decomposition of TNAZ and NDNAZ is presented. Sufficient data has been collected to formulate mathematical models of their decomposition.
PREPARATION OF MAGNESIUM-FLUOROPOLYMER PYROTECHNIC MATERIAL
Descriptive Note: Patent Application, Filed 25 Feb 98
Personal Author(s): Nauflett, George W , Farncomb, Robert E , Chordia, Lalit
Report Date: 25 Feb 1998
Descriptors: (U) *MAGNESIUM, *PATENT APPLICATIONS, *FLUOROPOLYMERS, *PYROTECHNICS, METALS, METHYL RADICALS, MATERIALS, COPOLYMERS, REACTIVITIES, ALLOYS, SLURRIES, PARTICLES, ALUMINUM, CARBON DIOXIDE, ENERGETIC PROPERTIES, ACETONES, ETHYL RADICALS, KETONES, TETRAFLUOROETHYLENE RESINS
Identifiers: (U) VINYLIDENEFLUORIDE, HEXAFLUOROPROPYLENE, POLYTETRAFLUOROETHYLENE, *ENERGETIC MATERIALS
Abstract: (U) A process for preparing energetic materials by: (1) dissolving a vinylidene fluoride-hexafluoropropylene copolymer in a ketone that is acetone, methyl ethyl ketone, or mixtures thereof, (2) adding polytetrafluoroethylene particles and reactive metal (magnesium, aluminum, or their alloys) particles to form a slurry, (3) adding CO2 to the slurry to precipitate out the copolymer which then coats the polytetrafluoroethylene and reactive metal particles, and (4) separating the copolymer-coated particles from the ketone and CO2.
RECOVERY OF PYROTECHNIC INGREDIENTS USING SUPERCRITICAL FLUIDS
Personal Author(s): Hong, Glenn T
Report Date: 21 Jan 1998
Descriptors: (U) *RECOVERY, *RECYCLED MATERIALS, *SMOKE MUNITIONS, *SUPERCRITICAL FLOW, *PYROTECHNICS, METALS, MAGNESIUM, LIQUIDS, COPPER, ALUMINUM, OXIDIZERS, RESOURCES, FLUIDS, DYES, SALTS, CARBON DIOXIDE, BINDERS, ENERGETIC PROPERTIES, ACETONES, BARIUM, STRONTIUM, FLARES, POTASSIUM COMPOUNDS, PERCHLORATES, SODIUM NITRATES
Identifiers: (U) MTV(MAGNESIUM TEFLON VITON)
Abstract: (U) Many pyrotechnics contain valuable resources which could be used in commercial applications, for example metals (e.g. magnesium, aluminum); metallic salts of copper, strontium, and barium; oxidizer (e.g. sodium nitrate, potassium perchlorate); binders such as viton, and dyes which have reclaimed value. The Navy is seeking technology that can recover the valuable ingredients from pyrotechnic flares and smoke munitions in an environmentally acceptable manner. This Phase I program studied the recovery of constituents from a Magnesium-Teflon-Viton (MTV) pyrotechnic material. The use of near critical liquid and supercritical carbon dioxide with acetone cosolvent to dissolve the Viton-A binder component was investigated. Viton-A was readily dissolved by carbon dioxide with acetone cosolvent. This key finding may form the basis for an environmentally friendly process for the recycling of pyrotechnic and other energetic materials.
75 YEARS, NAVAL RESEARCH LABORATORY 1998 NRL REVIEW
Report Date: Jan 1998
Descriptors: (U) *MILITARY HISTORY, *NAVAL RESEARCH LABORATORIES, ELECTRONICS, OPTICS, INFORMATION SYSTEMS, BIOLOGY, COMPOSITE MATERIALS, PLASMAS(PHYSICS), COMMUNICATION EQUIPMENT, CHEMISTRY, SPACE SCIENCES, COMPUTER APPLICATIONS, ACOUSTICS, OCEANS, ENERGETIC PROPERTIES, MARINE ENGINEERING, ELECTROMAGNETISM, REMOTE SYSTEMS, PARTICLE BEAMS, ATMOSPHERICS
Abstract: (U) The mission is to conduct a broadly based multidisciplinary program of scientific research and advanced technological development directed toward maritime applications of new and improved materials, techniques, equipment, systems, and ocean, atmospheric, and space sciences and related technologies.
EXPERIMENTAL CHARGE DENSITIES AND ELECTROSTATIC POTENTIALS IN ENERGETIC MATERIALS AND INFRASTRUCTURE UPGRADE FOR AN X-RAY CRYSTALLOGRAPHY LABORATORY
Personal Author(s): Miller, R , Goldwasser, J
Report Date: Jan 1998
Descriptors: (U) *X RAY DIFFRACTION, *CHARGE DENSITY, *ELECTROSTATIC CHARGE, *CRYSTALLOGRAPHY, *DIFFRACTOMETERS, THERMAL PROPERTIES, CATIONS, LOW TEMPERATURE, CRYSTAL STRUCTURE, DETECTORS, STATE OF THE ART, ELECTRON DENSITY, THERMAL EXPANSION, ANISOTROPY, DATA REDUCTION, DATA ACQUISITION, GRAPHICS, COOLING AND VENTILATING EQUIPMENT, LABORATORIES, HELIUM, SALTS, ENERGETIC PROPERTIES, COMPRESSIVE PROPERTIES, AREA SCANNING
Abstract: (U) To install a state-of-the-art X-ray crystallography laboratory with a new diffractometer using CCD area detector technology and develop data collection and data reduction protocols for charge density studies. To compare charge density results from a CCD detector to those obtained by conventional diffractometers. To fully evaluate the suitability of CCD detectors for the experimental study of electron density distributions and the derived electrostatic potentials. To develop, optimize and calibrate a new helium cooling system for X-ray diffraction for ultra low temperature measurements. To experimentally map the electron density distribution and derived electrostatic potentials in series of related solid energetic materials of differing shock sensitivities from high angle, low temperature X-ray diffraction data. To develop methods of graphical representation of charge densities and electrostatic potentials. To measure the anisotropy of thermal expansion parameters for energetic materials. To relate the thermal expansion to molecular thermal motion. To develop the necessary protocols for compressibilities studies on a CCD diffractometer. To measure the compressibility of energetic materials. To investigate possible cations compatible with the dinitramide anion to form high density salts. To provide crystal structures of energetic materials to others in the field.
NRL REVIEW 1998
Personal Author(s): Bultman, John D, Buckley, Bruce W, Coffey, Timothy
Report Date: Jan 1998
Descriptors: (U) *NAVAL RESEARCH LABORATORIES, OPTICS, INFORMATION SYSTEMS, COMPOSITE MATERIALS, REMOTE DETECTORS, SPACE SCIENCES, RADAR EQUIPMENT, ACOUSTICS, OCEANS, BIOLOGICAL WARFARE AGENTS, MILITARY PUBLICATIONS, ENERGETIC PROPERTIES, ELECTROMAGNETISM, PERIODICALS, AMPLIFIERS, CHEMICAL WARFARE AGENTS, VOLCANOES, KLYSTRONS, W BAND, SCIENTIFIC RESEARCH
Identifiers: (U) NRL REVIEW, LINK 22/NILE TESTBED, GYROKLYSTRON, EL NINO
Abstract: (U) The mission is to conduct a broadly based multidisciplinary program of scientific research and advanced technological development directed toward maritime applications of new and improved materials, techniques, equipment, systems, and ocean, atmospheric, and space sciences and related technologies.
SHOCK WAVES IN CONDENSED MATTER, INTERNATIONAL CONFERENCE, SAINT-PETERSBURG, RUSSIA, 12-17 JULY 1998
Personal Author(s): Krivchenko, Aleksei L , Dolgoborodov, Alexander Yu, Klimenko, Igor Yu
Report Date: Jan 1998
Descriptors: (U) *SYMPOSIA, *SHOCK WAVES, *ENERGETIC PROPERTIES, *DETONATIONS, MATHEMATICAL MODELS, METALS, PHASE TRANSFORMATIONS, COMPOSITE MATERIALS, CERAMIC MATERIALS, RUSSIA, MOLECULAR PROPERTIES, EQUATIONS OF STATE
Identifiers: (U) FOREIGN REPORTS, MOLECULAR DYNAMICS
Abstract: (U) The report documents information presented at the International Conference on Shock Waves in Condensed Matter held 12-17 July 1998 at Saint-Petersburg, Russia. The report primarily focuses on detonation physics of energetic materials and mathematical modeling of detonation processes, and also covers important issues related to shock wave processes in metals, ceramics and composites. In addition, Molecular dynamics in study of shock wave processes were greatly discussed in detail along with the equations of state and phase transitions.