Thermal reactive hazards of HMX with contaminants.

PubMed

Peng, Deng-Jr; Chang, Cheng-Ming; Chiu, Miin

2004-10-18

In the past, many unexpected runaway accidents occurred in manufacturing processes, involving volatile chemical and explosive storage and transportation. Incompatible product reactions of high explosives must be carefully considered using loss prevention strategies for thermal hazards risk analysis. High explosive reactions vary via environmental changes, contact materials, or process situations, such as onset temperature and shifts in reaction type when high explosives are in contact with contaminants. Therefore, the manufacture and handling of high explosives require the utmost in safety and loss prevention. HMX (cyclotetramethyene tetranitramine) is one kind of high explosive widely used around the world which is stable with high detonation strength properties. In this study, the influences of contaminants on HMX are investigated. The studied contaminants include ferrous chloride tetrahydrate, ferric chloride hexahydrate, acetone solution, acetic acid, and nitric acid. DSC thermal curves and incompatible reaction kinetic evaluations were preformed using iron, chlorine and acid. Organic acetone solution has lesser effects on HMX. Hopefully, this study will lead to improved thermal hazards risk analysis and reduce accidents.

Thermal explosion violence of HMX-based explosives -- effect of composition, confinement and phase transition using the scaled thermal explosion experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maienschein, J L; Wardell, J F; Reaugh, J E

We developed the Scaled Thermal Explosion Experiment (STEX) to provide a database of reaction violence from thermal explosion of explosives of interest. A cylinder of explosive, 1, 2 or 4 inches in diameter, is confined in a steel cylinder with heavy end caps, and heated under controlled conditions until it explodes. Reaction violence is quantified by micropower radar measurement of the cylinder wall velocity, and by strain gauge data at reaction onset. Here we describe the test concept and design, show that the conditions are well understood, and present initial data with HMX-based explosives. The HMX results show that anmore » explosive with high binder content yields less-violent reactions that an explosive with low binder content, and that the HMX phase at the time of explosion plays a key role in reaction violence.« less

Toward a Role of Light Absorption in Initiation Chemistry of Shocked HMX single Crystals and Crystalline High Explosives

NASA Astrophysics Data System (ADS)

Plaksin, Igor; Rodrigues, L.

2013-06-01

Question which mechanism is driving radiation-induced reactions, thermal or athermal becomes a subject of conflicting discussions. Major challenge of this work is to identify at micro- (sub-granular), meso- (grain level) and macro-scale roles of these two mechanisms in triggering initiation chemistry in HMX-based HEs. Four acceptor-patterns were tested at 20 GPa input pressure: single HMX crystal-in-water, HMX/water-slurry, PBX(HMX/HTPB) & inert PBX-simulant (HMX-particles replaced by crystalline sucrose). Scenario of reaction onset-localizations-dissipation was spatially resolved using Multi-Channel Optical Analyzer MCOA-UC (96 channels, 100um-spatial accuracy, 0.2ns-timeresolution, 450-850 nm-spectral range) through real-time panoramic recording emitted reaction light and shock field in standard optic monitor. Experiments reveal a dual nature of initiation chemistry: athermal and thermal. Single-crystal tests disclose origination of photo-induced reactions downstream of emitting reaction spot due to intensified radiation absorption in surface micro-defects. Polycrystalline samples reveal cyclic reproducibility of radiation-induced thermal precursors in which radiation absorption causes thermal expansion/phase-changes of HMX-grains resulting in oscillating detonation. Work was supported by the Office of Naval Research under the ONR and ONR Global Grants N00014-12-1-0477 and N62909-12-1-7131 with Drs. Cliff Bedford and Shawn Thorne Program Managers.

Luminescence Properties of RDX and HMX

DTIC Science & Technology

1975-08-01

AD-AO15 538 LUMINESCENCE PROPERTIES OF RDX AND HMX Paul L. Marinkas Picatinny Arsenal Dover, New Jersey August 1975 DISTRIBUTED BY: National...Technical Information Service U. S. DEPARTMENT OF COMMERCE • i 289106. TECHNICAL REPORT 4840 LUMINESCENCE PROPERTIES, OF RDX AND HMX PAULL. MARINKAS -’-I...yields Charge transfer HMX Phosphorescence Reflectance spectra Circular dichroism Lifetimes Photodecomposition RDX Doping Luminescence Polynitramines

Initial decomposition of the condensed-phase β-HMX under shock waves: molecular dynamics simulations.

PubMed

Ge, Ni-Na; Wei, Yong-Kai; Ji, Guang-Fu; Chen, Xiang-Rong; Zhao, Feng; Wei, Dong-Qing

2012-11-26

We have performed quantum-based multiscale simulations to study the initial chemical processes of condensed-phase octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) under shock wave loading. A self-consistent charge density-functional tight-binding (SCC-DFTB) method was employed. The results show that the initial decomposition of shocked HMX is triggered by the N-NO(2) bond breaking under the low velocity impact (8 km/s). As the shock velocity increases (11 km/s), the homolytic cleavage of the N-NO(2) bond is suppressed under high pressure, the C-H bond dissociation becomes the primary pathway for HMX decomposition in its early stages. It is accompanied by a five-membered ring formation and hydrogen transfer from the CH(2) group to the -NO(2) group. Our simulations suggest that the initial chemical processes of shocked HMX are dependent on the impact velocity, which gain new insights into the initial decomposition mechanism of HMX upon shock loading at the atomistic level, and have important implications for understanding and development of energetic materials.

Charge transfer in TATB and HMX under extreme conditions.

PubMed

Zhang, Chaoyang; Ma, Yu; Jiang, Daojian

2012-11-01

Charge transfer is usually accompanied by structural changes in materials under different conditions. However, the charge transfer in energetic materials that are subjected to extreme conditions has seldom been explored by researchers. In the work described here, the charge transfer in single molecules and unit cells of the explosives TATB and HMX under high temperatures and high pressures was investigated by performing static and dynamic calculations using three DFT methods, including the PWC functional of LDA, and the BLYP and PBE functionals of GGA. The results showed that negative charge is transferred from the nitro groups of molecular or crystalline TATB and HMX when they are heated. All DFT calculations for the compressed TATB unit cell indicate that, generally, negative charge transfer occurs to its nitro groups as the compression increases. PWC and PBE calculations for crystalline HMX show that negative charge is first transferred to the nitro groups but, as the compression increases, the negative charge is transferred from the nitro groups. However, the BLYP calculations indicated that there was gradual negative charge transfer to the nitro groups of HMX, similar to the case for TATB. The unrelaxed state of the uniformly compressed TATB causes negative charge to be transferred from its nitro groups, in contrast to what is seen in the relaxed state. Charge transfer in TATB is predicted to occur much more easily than in HMX.

Live Decomposition Imaging of HMX/HTPB Based Formulations During Cook-Off in the Dual Window Test Vehicle

NASA Astrophysics Data System (ADS)

White, Nathan; Reeves, Tom; Cheese, Phil; Stennett, Christopher; Wood, Andrew; Cook, Malcolm; Syanco Ltd Team; Cranfield University Team; DE&S, MoD Abbey Wood Team

2017-06-01

Thin, cylindrical samples of HMX/HTPB formulations with solids loadings from 85-95% by mass have been heated at 1oC/minute until a reaction occurred in the new dual window cook-off test vehicle. The test vehicle has captured the response of these formulations, and shown the influence of variables such as confinement, heating rate and sample size. Live imaging of the heated samples revealed that as with pure nitramine samples, three distinct stages of change take place during heating; phase changes, melting and slow, flameless decomposition with production of gaseous intermediates and finally burning with a luminous flame of the gaseous intermediates. In addition, the binder appears to undergo decomposition before the HMX, darkening along the edge closest to the thermal input before the HMX melts. Prior to violent reaction, flame speeds were measured at approximately 30m/s for high confinement, which reduces by 2-3 orders of magnitude when confinement is lowered. The melting point of HMX has been observed below the widely reported value at 220oC, and requires further investigation.

Biotransformation of RDX and HMX by Anaerobic Granular Sludge with Enriched Sulfate and Nitrate.

PubMed

An, Chunjiang; Shi, Yarong; He, Yanling; Huang, Guohe; Liu, Yonghong; Yang, Shucheng

2017-05-01

  RDX and HMX are widely used energetic materials and they are recognized as environmental contaminants at numerous locations. The present study investigated the biotransformation of RDX and HMX by anaerobic granular sludge under sulfate- and nitrate-enriched conditions. The results showed that RDX and HMX could be transformed by anaerobic granular sludge when nitrate was present. However, the biotransformation of RDX and HMX was negatively influenced, especially with high nitrate concentrations. Sulfate-enriched conditions were more favorable for the removal of ammunition compounds by anaerobic granular sludge than nitrate-enriched conditions. The removal of RDX and HMX under both nitrate- and sulfate-enriched conditions was facilitated by the use of glucose as additional substrate. This knowledge may help identify factors required for rapid removal of RDX and HMX in high-rate bioreactors. These results can also be applied to devise an appropriate and practical biological treatment strategy for explosive contaminated wastewater.

Explosive performance of HMX/NTO co-crystal

NASA Astrophysics Data System (ADS)

Li, J. C.; Jiao, Q. J.; Gong, Y. G.; Wang, Y. Y.; Liang, T.; Sun, J.

2018-01-01

A new co-crystal explosive of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) and 3-nitro-1, 2, 4-triazol-5-one (NTO) in a molar ratio of 1:1 has been prepared by solvent/anti-solvent method. The SEM photographs show that HMX/NTO co-crystals are distinctly different from HMX and NTO crystals. The co-crystals are prisms with well formed crystal surfaces. Thermal analysis results indicate the melting point of the co-crystal is 29.3 °Chigher than that of NTO. Moreover, the co-crystal exhibits a modified mechanical sensitivity. The characteristic height (H50) of impact sensitivity increases 14.8cm, and the explosion percentage (P) of friction sensitivity decreases by 40% compared with HMX. The HMX/NTO co-crystals possess good thermal property and low sensitivity, which mean huge advantages in blasting engineering.

Synthesis and First Principles Investigation of HMX/NMP Cocrystal Explosive

NASA Astrophysics Data System (ADS)

Lin, He; Zhu, Shun-Guan; Zhang, Lin; Peng, Xin-Hua; LI, Hong-Zhen

2013-10-01

1,3,5,7-Tetranitro-l,3,5,7-tetrazocine (HMX)/N-methyl-2-pyrrolidone (NMP) cocrystal explosive was prepared by a solution evaporation method. This cocrystal explosive crystallized in the trigonal system (space group ? ), with cell parameters a = 16.605(8) Å and c = 31.496(4) Å. Theoretical investigations of the formation mechanism of HMX/NMP cocrystal were carried out in Cambridge serial total energy package (CASTEP) based on dispersion-corrected density functional theory (DFT-D) with a plane wave scheme. The exchange-correlation potential was treated with the Perdew-Burke-Ernzerhof function of generalized gradient approximation, and dispersion force was correlated using Grimme's method. The band structure, density of states, projected density of states, and Mulliken populations were calculated at the generalized gradient approximation level. The results showed that the main host-guest interactions in HMX/NMP cocrystal were hydrogen bonds and stacking interactions, which were the same as those analyzed using X-ray diffraction. Theoretical investigations of HMX/NMP cocrystal explosive may provide the basis for the preparation of cocrystal explosive composed of HMX and energetic materials.

Environmental Fate Studies of HMX Screening Studies. Phase 1

DTIC Science & Technology

1982-12-01

1,3,5,7-octahydro-l,3,5,7-tetranitrotetrazocirne, HMX, sorption and biosorption partition coefficients, photochemical rate constant, biotransformatLion...Holston River sediment was measured at 8.7. Based on an organic carbon con- tent of 1.3% in thc sediment, a K value of 670 was calculated. The biosorption ...27 Table 9 HMX Biosorption by Bacteria .............................. 39 ii -4 I: ’a LIST OF ILLUSTRATIONS

Synthesis, thermolysis, and sensitivities of HMX/NC energetic nanocomposites.

PubMed

Wang, Yi; Song, Xiaolan; Song, Dan; Liang, Li; An, Chongwei; Wang, Jingyu

2016-07-15

1,3,5,7-Tetranittro-1,3,5,7-tetrazocane/nitrocellulose (HMX/NC) nanocomposites were successfully synthesized by an improved sol-gel-supercritical method. NC nanoparticles with a size of ∼30nm were cross-linked to form a network structure, and HMX nanoparticles were imbedded in the nano-NC matrix. The key factors, i.e., the selection of catalyst and solvent, were probed. No phase transformation of the HMX occurred before or after fabrication, and the molecular structures of the HMX and NC did not change. Thermal analyses were performed, and the kinetic and thermodynamic parameters, such as activation energy (EK), per-exponent factor (lnAK), rate constant (k), activation heat (ΔH(≠)), activation free energy (ΔG(≠)), activation entropy (ΔS(≠)), critical temperature of thermal explosion (Tb), and critical heating rate of thermal explosion (dT/dt)Tb, were calculated. The results indicate that HMX/NC presented a much lower activation energy (165.03kJ/mol) than raw HMX (282.5kJ/mol) or raw NC (175.51kJ/mol). The chemical potential (ΔG(≠)) for the thermal decomposition of HMX/NC has a positive value, which means that the activation of the molecules would not proceed spontaneously. The significantly lower ΔH(≠) value of HMX/NC, which represents the heat needed to be absorbed by an explosive molecule to change it from its initial state to an activated state, implies that the molecules of HMX/NC are much easier to be activated than those of raw HMX. Similarly, the HMX/NC presented a much lower Tb (168.2°C) than raw HMX (283.2°C). From the results of the sensitivity tests, the impact and friction sensitivities of HMX/NC were significantly decreased compared with those of raw HMX, but the thermal sensitivity was distinctly higher. The activation of the particles under external stimulation was simulated, and the mechanism was found to be crucial. Combining the thermodynamic parameters, the mechanism as determined from the results of the sensitivity tests was

Modeling solid thermal explosion containment on reactor HNIW and HMX.

PubMed

Lin, Chun-Ping; Chang, Chang-Ping; Chou, Yu-Chuan; Chu, Yung-Chuan; Shu, Chi-Min

2010-04-15

2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (HNIW), also known as CL-20 and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are highly energetic materials which have been popular in national defense industries for years. This study established the models of thermal decomposition and thermal explosion hazard for HNIW and HMX. Differential scanning calorimetry (DSC) data were used for parameters determination of the thermokinetic models, and then these models were employed for simulation of thermal explosion in a 437L barrel reactor and a 24 kg cubic box package. Experimental results indicating the best storage conditions to avoid any violent runaway reaction of HNIW and HMX were also discovered. This study also developed an efficient procedure regarding creation of thermokinetics and assessment of thermal hazards of HNIW and HMX that could be applied to ensure safe storage conditions. 2009 Elsevier B.V. All rights reserved.

Sequential biodegradation of TNT, RDX and HMX in a mixture.

PubMed

Sagi-Ben Moshe, S; Ronen, Z; Dahan, O; Weisbrod, N; Groisman, L; Adar, E; Nativ, R

2009-01-01

We describe TNT's inhibition of RDX and HMX anaerobic degradation in contaminated soil containing indigenous microbial populations. Biodegradation of RDX or HMX alone was markedly faster than their degradation in a mixture with TNT, implying biodegradation inhibition by the latter. The delay caused by the presence of TNT continued even after its disappearance and was linked to the presence of its intermediate, tetranitroazoxytoluene. PCR-DGGE analysis of cultures derived from the soil indicated a clear reduction in microbial biomass and diversity with increasing TNT concentration. At high-TNT concentrations (30 and 90 mg/L), only a single band, related to Clostridium nitrophenolicum, was observed after 3 days of incubation. We propose that the mechanism of TNT inhibition involves a cytotoxic effect on the RDX- and HMX-degrading microbial population. TNT inhibition in the top active soil can therefore initiate rapid transport of RDX and HMX to the less active subsurface and groundwater.

Thermal Explosion Violence of HMX-Based and RDX-Based Explosives - Effects of Composition, Confinement, and Solid Phase Using the Scaled Thermal Explosion Experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maienschein, J L; Wardell, J F

The Scaled Thermal Explosion Experiment (STEX) has been developed to quantify the violence of thermal explosion under well defined and carefully controlled initial and boundary conditions. Here we present results with HMX-based explosives (LX-04 and PBX-9501) and with Composition B. Samples are 2 inches (50 mm) in diameter and 8 inches (200 mm) in length, under confinement of 7,500-30,000 psi (50-200 MPa), with heating rates of 1-3 C/hr. We quantify reaction violence by measuring the wall velocity in the ensuing thermal explosion, and relate the measured velocity to that expected from a detonation. Results with HMX-based explosives (LX-04 and PBX-9501)more » have shown the importance of confinement and HMX solid phase, with reaction violence ranging from mild pressure bursts to near detonations. By contrast, Composition B has shown very violent reactions over a wide range of conditions.« less

Ultrafast dynamic response of single crystal β-HMX

NASA Astrophysics Data System (ADS)

Zaug, Joseph M.; Armstrong, Michael R.; Crowhurst, Jonathan C.; Radousky, Harry B.; Ferranti, Louis; Swan, Raymond; Gross, Rick; Teslich, Nick E.; Wall, Mark A.; Austin, Ryan A.; Fried, Laurence E.

2017-01-01

We report results from ultrafast compression experiments conducted on β-HMX single crystals. Results consist of nominally 12 picosecond time-resolved wave profile data, (ultrafast time domain interferometry -TDI measurements), that were analyzed to determine high-velocity wave speeds as a function of piston velocity. TDI results are used to validate calculations of anisotropic stress-strain behavior of shocked loaded energetic materials. Our previous results derived using a 350 ps duration compression drive revealed anisotropic elastic wave response in single crystal β-HMX from (110) and (010) impact planes. Here we present results using a 1.05 ns duration compression drive with a 950 ps interferometry window to extend knowledge of the anisotropic dynamic response of β-HMX within eight microns of the initial impact plane. We observe two distinct wave profiles from (010) and three wave profiles from (010) impact planes. The (110) impact plane wave speeds typically exceed (010) impact plane wave speeds at the same piston velocities. The development of multiple hydrodynamic wave profiles begins at 20 GPa for the (110) impact plane and 28 GPa for the (10) impact plane. We compare our ultrafast TDI results with previous gun and plate impact results on β-HMX and PBX9501.

Deflagration-to-detonation transition in granular HMX

NASA Technical Reports Server (NTRS)

Campbell, A. W.

1980-01-01

Granular HMX of three degrees of fineness was packed into heavy-walled steel tubes closed at both ends. Ignition was obtained at one end using an intimate mixture of finely divided titanium and boron as an igniter that produced heat with little gas. The distance to detonation was determined by examination of the resulting tube fragments. By inserting tightly-fitted neoprene diaphragms periodically into the HMX column, it was shown that the role of convective combustion was limited to the initial stage of the deflagration to detonation (DDT) process. Experiments in which various combinations of two of the three types of HMX were loaded into the same tube showed that heating by adiabatic shear of explosive grains was an essential factor in the final buildup to detonation. A description of the DDT process is developed in which conductive burning is followed in turn by convective burning, bed collapse with plug formation, onset of accelerated burning at the front of the plug through heating by intercrystalline friction and adiabatic shear, and intense shock formation resulting in high-order detonation.

Development of inert density mock materials for HMX

DOE PAGES

Yeager, John D.; Higginbotham Duque, Amanda L.; Shorty, Marvin; ...

2017-09-22

Inert surrogates or mocks for high explosives are commonly used in place of the real material for complex experiments or in situations where safety is a concern. We tested several materials as potential mocks for HMX in terms of density, thermal stability, and processability. Selection criteria were developed and a literature search was conducted primarily using the Cambridge Structural Database. Moreover, out of over 200 potentially acceptable materials, six were chosen for crystallization experiments and a suite of analytical characterization. Of these six, 5-iodo-2'-deoxyuridine, N,N'-bis(2,3,4,5,6-pentafluorophenyl)oxamide, and 2,3,4,5,6-pentafluorobenzamide all were found to be thermally stable at 150°C, matched HMX density asmore » a pressed pellet, and could be crystallized to appropriate particle sizes. These three materials are considered suitable inert density mocks for HMX and will be the subject of future testing.« less

Burning rate for steel-cased, pressed binderless HMX

NASA Technical Reports Server (NTRS)

Fifer, R. A.; Cole, J. E.

1980-01-01

The burning behavior of pressed binderless HMX laterally confined in 6.4 mm i.d. steel cases was measured over the pressure range 1.45 to 338 MPa in a constant pressure strand burner. The measured regression rates are compared to those reported previously for unconfined samples. It is shown that lateral confinement results in a several-fold decrease in the regression rate for the coarse particle size HMX above the transition to super fast regression. For class E samples, confinement shifts the transition to super fast regression from low pressure to high pressure. These results are interpreted in terms of the previously proposed progressive deconsolidation mechanism. Preliminary holographic photography and closed bomb tests are also described. Theoretical one dimensional modeling calculations were carried out to predict the expected flame height (particle burn out distance) as a function of particle size and pressure for binderless HMX burning by a progressive deconsolidation mechanism.

Accumulation of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) in indigenous and agricultural plants grown in HMX-contaminated anti-tank firing-range soil.

PubMed

Groom, Carl A; Halasz, Annamaria; Paquet, Louise; Morris, Neil; Olivier, Lucie; Dubois, Charles; Hawari, Jalal

2002-01-01

To investigate their potential for phytoremediation, selected agricultural and indigenous terrestrial plants were examined fortheir capacity to accumulate and degrade the explosive octahydro-1 ,3,5,7-tetra nitro-1,3,5,7-tetrazocine (HMX). Plant tissue and soil extracts were analyzed for the presence of HMX and possible degradative metabolites using high-performance liquid chromatography with diode-array UV detection (HPLC-UV), micellar electrokinetic chromatography with diode-array UV detection (MEKC-UV), and HPLC with electrospray ionization mass spectrometry (LC-MS). The pattern of HMX accumulation for alfalfa (Medicago sativa), bush bean (Phaseolus vulgaris), canola (Brassica rapa), wheat (Triticum aestivum), and perennial ryegrass (Loliumperenne) grown in a controlled environment on contaminated soil from an anti-tank firing range was similar to that observed for plants (wild bergamot (Monarda fistulosa), western wheat grass (Agropyron smithii), brome grass (Bromus sitchensis), koeleria (Koeleria gracilis), goldenrod (Solidago sp.), blueberry (Vaccinium sp.), anemone (Anemone sp.), common thistle (Circium vulgare), wax-berry (Symphoricarpos albus), western sage (Artemisia gnaphalodes), and Drummond's milk vetch (Astragalus drummondii)) collected from the range. No direct evidence of plant-mediated HMX (bio)chemical transformation was provided by the available analytical methods. Traces of mononitroso-HMX were found in contaminated soil extracts and were also observed in leaf extracts. The dominant mechanism for HMX translocation and accumulation in foliar tissue was concluded to be aqueous transpirational flux and evaporation. The accumulation of HMX in the leaves of most of the selected species to levels significantly above soil concentration is relevant to the assessment of both phytoremediation potential and environmental risks.

Acid and alkali effects on the decomposition of HMX molecule: a computational study.

PubMed

Zhang, Chaoyang; Li, Yuzhen; Xiong, Ying; Wang, Xiaolin; Zhou, Mingfei

2011-11-03

The stored and wasted explosives are usually in an acid or alkali environment, leading to the importance of exploring the acid and alkali effects on the decomposition mechanism of explosives. The acid and alkali effects on the decomposition of HMX molecule in gaseous state and in aqueous solution at 298 K are studied using quantum chemistry and molecular force field calculations. The results show that both H(+) and OH(-) make the decomposition in gaseous state energetically favorable. However, the effect of H(+) is much different from that of OH(-) in aqueous solution: OH(-) can accelerate the decomposition but H(+) cannot. The difference is mainly caused by the large aqueous solvation energy difference between H(+) and OH(-). The results confirm that the dissociation of HMX is energetically favored only in the base solutions, in good agreement with previous HMX base hydrolysis experimental observations. The different acid and alkali effects on the HMX decomposition are dominated by the large aqueous solvation energy difference between H(+) and OH(-).

Effects of HMX-lead mixtures on reproduction of the earthworm Eisenia andrei.

PubMed

Savard, Kathleen; Berthelot, Yann; Auroy, Aurelie; Spear, Philip A; Trottier, Bertin; Robidoux, Pierre Yves

2007-10-01

High metal (e.g., Pb) concentrations are typically found in explosive-contaminated soil, and their presence may increase, decrease, or not influence toxicity predicted on the basis of one explosive alone (e.g., HMX). Nevertheless, few data are available in the scientific literature for this type of multiple exposure. Soil organisms, such as earthworms, are one of the first receptors affected by the contamination of soil. Therefore, a reproductive study was conducted using Eisenia andrei in a forest-type soil. Both HMX and Pb decreased reproduction parameters (number of total cocoons, hatched cocoons, and surviving juveniles) individually. Based on the total number of cocoons, HMX was more toxic in a forest soil than Pb, with EC(50) of 31 mg kg(-1), and 1068 mg kg(-1), respectively. The slope of the concentration-response curve was significantly greater in the case of Pb, which is consistent with the possibility that the two compounds do not act on the same target site. The response-addition model was used to predict the response of earthworms and to test for interaction between the two contaminants. The predicted toxicity was not significantly different than the observed toxicity, implying that Pb and HMX were considered noninteractive compounds. The combined action of Pb-HMX may be described, therefore, as dissimilar-noninteractive joint action in a forest soil. The results illustrate the relevance of considering the presence of metals in the risk assessment of explosive-contaminated sites because metals can add their toxicity to explosives. Extension of this study to other types of soil and other metals would improve the understanding of toxicity at these sites.

The great diversity of HMX conformers: probing the potential energy surface using CCSD(T).

PubMed

Molt, Robert W; Watson, Thomas; Bazanté, Alexandre P; Bartlett, Rodney J

2013-04-25

The octahydro-1,3,5,7-tetranitro-1,3,5,7-tetraazocine (HMX) molecule is a very commonly studied system, in all 3 phases, because of its importance as an explosive; however, no one has ever attempted a systematic study of what all the major gas-phase conformers are. This is critical to a mechanistic study of the kinetics involved, as well as the viability of various crystalline polymorphs based on the gas-phase conformers. We have used existing knowledge of basic cyclooctane chemistry to survey all possible HMX conformers based on its fundamental ring structure. After studying what geometries are possible after second-order many-body perturbation theory (MBPT(2)) geometry optimization, we calculated the energetics using coupled cluster singles, doubles, and perturbative triples (CCSD(T))/cc-pVTZ. These highly accurate energies allow us to better calculate starting points for future mechanistic studies. Additionally, the plethora of structures are compared to existing experimental data of crystals. It is found that the crystal field effect is sometimes large and sometimes small for HMX.

The Thermal and Microstructural Effect of Plasticizing HMX-Nitrocellulose Composites

DOE PAGES

Yeager, John David; Watkins, Erik Benjamin; Duque, Amanda Lynn; ...

2017-03-15

Thermal ignition via self-heating (cook-off) of cyclotetramethylene-tetranitramine (HMX)-containing plastic-bonded explosives (PBXs) is driven by the β → δ phase transition in the HMX, which is affected if not dominated by microstructure. Here, we studied the HMX-binder interface and phase transition for several variations of PBX 9404 (HMX with plasticized nitrocellulose [NC] binder). Neutron reflectometry was used to examine the interface under several conditions—pristine, after aging, and after thermal treatment. The initial interfacial structure depended on the plasticizer, but the interface homogenized over time. Thermal and optical analyses showed that all formulated materials had higher transition temperatures than neat HMX. Thismore » effect increased with NC content.« less

The Thermal and Microstructural Effect of Plasticizing HMX-Nitrocellulose Composites

NASA Astrophysics Data System (ADS)

Yeager, John D.; Watkins, Erik B.; Higginbotham Duque, Amanda L.; Majewski, Jaroslaw

2018-01-01

Thermal ignition via self-heating (cook-off) of cyclotetramethylene-tetranitramine (HMX)-containing plastic-bonded explosives (PBXs) is driven by the β → δ phase transition in the HMX, which is affected if not dominated by microstructure. Here, the HMX-binder interface and phase transition were studied for several variations of PBX 9404 (HMX with plasticized nitrocellulose [NC] binder). Neutron reflectometry was used to examine the interface under several conditions-pristine, after aging, and after thermal treatment. The initial interfacial structure depended on the plasticizer, but the interface homogenized over time. Thermal and optical analyses showed that all formulated materials had higher transition temperatures than neat HMX. This effect increased with NC content.

Dissolution of a new explosive formulation containing TNT and HMX: comparison with octol.

PubMed

Monteil-Rivera, Fanny; Deschamps, Stéphane; Ampleman, Guy; Thiboutot, Sonia; Hawari, Jalal

2010-02-15

GIM (Greener Insensitive Material) is a new explosive formulation made of HMX (51.5%), TNT (40.7%), and a binder, ETPE (7.8%), which is currently investigated by the Canadian Department of National Defense for a wider use by the Army. In the present study, dissolution of GIM in water was measured and compared to the dissolution of octol (HMX/TNT: 70/30). Although the presence of ETPE did not prevent completely TNT and HMX from dissolving, GIM appeared to dissolve more slowly than octol. The ETPE was shown to prevent the formulation particles from collapsing and to retard the dissolution of both TNT and HMX by limiting their exposure to water. In both octol and GIM, the dissolution rate of the particles was governed by the compound(s) that are slower to dissolve, i.e. HMX in octol, and HMX and ETPE in GIM. A model based on Fick's diffusion law allowed fitting well the dissolution data of octol but was less appropriate to fit the data of GIM likely due to a physical rearrangement of the solid upon dissolution. The present findings demonstrate that ETPE in GIM decreases the risks of explosives leakage from particles of the new formulation and should facilitate the collecting of non-exploded GIM particles in training sites.

Toxicity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in three vertebrate species.

PubMed

Johnson, Mark S; McFarland, Craig A; Bazar, Matthew A; Quinn, Michael J; LaFiandra, Emily May; Talent, Larry G

2010-04-01

The explosive, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine or high-melting explosive (HMX), has been found in soils in areas used for testing and training by the military. Many of these areas contain habitat for valued wildlife species. In an effort to better understand the environmental consequences from exposure, a reptilian (western fence lizard [Sceloporus occidentalis]), an amphibian (red-backed salamander [Plethodon cinereus]), and a mammalian species (rabbit [Oryctolagus cuniculus]) were exposed to HMX under controlled laboratory conditions. Lizards and rabbits were exposed to HMX by way of corn oil through gavage, and salamanders were exposed to HMX in soil. Two deaths occurred from acute oral exposures to lizards to 5000 mg HMX/kg BW. Histological and gross pathologic assessment suggested gut impaction as a possible cause of death. Salamanders exposed to concentrations of HMX in soil < or = 1970 mg HMX/kg soil for 10 days did not show adverse effects. Rabbits, however, showed neurologic effects manifested as hyperkinetic events with convulsions at > 24 h after oral exposures. An LD(50) for rabbits was calculated as 93 mg/kg (95% confidence interval 76-117). A subacute 14-day testing regime found a lowest observed effect level of 10 mg/kg-d and a no observed adverse effect level of 5 mg/kg-d based on hyperkinesia and seizure incidence, although changes suggesting functional hepatic alterations were also found. These data suggest that physiologic differences between species, particularly in gastrointestinal structure and function, can affect the absorption of HMX and hence lead to marked differences in toxicity from exposure to the same compound.

Frictional properties of single crystals HMX, RDX and PETN explosives.

PubMed

Wu, Y Q; Huang, F L

2010-11-15

The frictional properties of single crystals of cyclotetramethylene tetranitramine (HMX), cyclotrimethylene trinitramine (RDX) and pentaerythritol tetranitrate (PETN) secondary explosives are examined using a sensitive friction machine. The explosive crystals used for the measurements are at least 3.5 mm wide. The friction coefficients between crystals of the same explosive (i.e., HMX on HMX, etc.), crystals of different explosives (i.e., HMX on RDX, etc.), and each explosive and a well-polished gauge steel surface are determined. The frictional surfaces are also studied under an environmental scanning electron microscope (ESEM) to analyze surface microstructural changes under increasing loading forces. The friction coefficients vary considerably with increasing normal loading forces and are particularly sensitive to slider shapes, crystal roughness and the mechanical properties of both the slider and the sample. With increasing loading forces, most friction experiments show surface damage, consisting of grooves, debris, and nano-particles, on both the slider and sample. In some cases, a strong evidence of a localized molten state is found in the central region of the friction track. Possible mechanisms that affect the friction coefficient are discussed based on microscopic observations. Copyright © 2010 Elsevier B.V. All rights reserved.

Treatment of HMX-production wastewater in an aerobic granular reactor.

PubMed

Zhang, Jin-Hua; Wang, Min-Hui; Zhu, Xiao-Meng

2013-04-01

Aerobic granules were applied to the treatment of HMX-production wastewater using a gradual domestication method in a SBR. During the process, the granules showed a good settling ability, a high biomass retention rate, and high biological activity. After 40 days of stable operation, aerobic granular sludge performed very effectively in the removal of carbon and nitrogen compounds from HMX-production wastewater. Organic matter removal rates up to 97.57% and nitrogen removal efficiencies up to 80% were achieved during the process. Researchers conclude that using aerobic granules to treat explosive wastewater has good prospects for success.

Modeling Ignition of HMX with the Gibbs Formulation

NASA Astrophysics Data System (ADS)

Lee, Kibaek; Stewart, D. Scott

2017-06-01

We present a HMX model with the Gibbs formulation in which stress tensor and temperature are assumed to be in local equilibrium, but phase/chemical changes are not assumed to be in equilibrium. We assume multi-components for HMX including beta- and delta-phase, liquid, and gas phase of HMX and its gas products. Isotropic small strain solid model, modified Fried Howard liquid EOS, and ideal gas EOS are used for its relevant component. Phase/chemical changes are characterized as reactions and are in individual reaction rate. Maxwell-Stefan model is used for diffusion. Excited gas products in the local domain lead unreacted HMX solid to the ignition event. Density of the mixture, stress, strain, displacement, mass fractions, and temperature are considered in 1D domain with time histories. Office of Naval Research and Air Force Office of Scientific Research.

A contribution to the knowledge of HMX decomposition and application of results. [at atmospheric pressure

NASA Technical Reports Server (NTRS)

Kraeutle, K. J.

1980-01-01

The decomposition of cyclotramethylenetetranitramine (HMX) in the solid and liquid phase was studied by isothermal and nonisothermal heating at atmospheric pressure. Decomposition rates of solid HMX changed with sample size and gaseous environment. Kinetic parameters were obtained from weight loss measurements in the temperature range 229 C - 269 C. These tests also yielded highly porous solid residues. Qualitative aspects of solid and liquid phase decomposition of HMX with additives were also investigated in isothermal and nonisothermal tests.

Coupling crystal plasticity and phase-field damage to simulate β-HMX-based polymer-bonded explosive under shock load

NASA Astrophysics Data System (ADS)

Grilli, Nicolo; Dandekar, Akshay; Koslowski, Marisol

2017-06-01

The development of high explosive materials requires constitutive models that are able to predict the influence of microstructure and loading conditions on shock sensitivity. In this work a model at the continuum-scale for the polymer-bonded explosive constituted of β-HMX particles embedded in a Sylgard matrix is developed. It includes a Murnaghan equation of state, a crystal plasticity model, based on power-law slip rate and hardening, and a phase field damage model based on crack regularization. The temperature increase due to chemical reactions is introduced by a heat source term, which is validated using results from reactive molecular dynamics simulations. An initial damage field representing pre-existing voids and cracks is used in the simulations to understand the effect of these inhomogeneities on the damage propagation and shock sensitivity. We show the predictions of the crystal plasticity model and the effect of the HMX crystal orientation on the shock initiation and on the dissipated plastic work and damage propagation. The simulation results are validated with ultra-fast dynamic transmission electron microscopy experiments and x-ray experiments carried out at Purdue University. Membership Pending.

Shock Initiation Experiments with Ignition and Growth Modeling on the HMX-Based Explosive LX-14

NASA Astrophysics Data System (ADS)

Vandersall, Kevin S.; Dehaven, Martin R.; Strickland, Shawn L.; Tarver, Craig M.; Springer, H. Keo; Cowan, Matt R.

2017-06-01

Shock initiation experiments on the HMX-based explosive LX-14 were performed to obtain in-situ pressure gauge data, characterize the run-distance-to-detonation behavior, and provide a basis for Ignition and Growth reactive flow modeling. A 101 mm diameter gas gun was utilized to initiate the explosive charges with manganin piezoresistive pressure gauge packages placed between sample disks pressed to different densities ( 1.57 or 1.83 g/cm3 that corresponds to 85 or 99% of theoretical maximum density (TMD), respectively). The shock sensitivity was found to increase with decreasing density as expected. Ignition and Growth model parameters were derived that yielded reasonable agreement with the experimental data at both initial densities. The shock sensitivity at the tested densities will be compared to prior work published on other HMX-based formulations. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. This work was funded in part by the Joint DoD-DOE Munitions Program.

Synthesis, Characterization, Detonation Performance, and DFT Calculation of HMX/PNO Cocrystal Explosive

NASA Astrophysics Data System (ADS)

Lin, He; Chen, Jian-Fu; Zhu, Shun-Guan; Li, Hong-Zhen; Huang, Yong

2017-01-01

A novel 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX)/pyridine-N-oxide (PNO) cocrystal at 1:1 molar ratio was synthesized by a solvent evaporation method, and its crystal structure was determined using X-ray diffraction (XRD). It crystallizes in the orthorhombic system with the Pbcn space group and cell parameters a = 12.712(3)Å, b = 9.315(3)Å, c = 12.909(3)Å. In addition, detonation performance of this cocrystal was estimated. The predicted detonation velocity and detonation pressure of this cocrystal are 7.47 km/s and 23.20 GPa, respectively, suggesting that it is less powerful than β-HMX. Finally, density functional theory, involving binding energy, atoms in molecule (AIM) theory, natural bond orbital (NBO) analysis, band structure, and density of states, was adopted to characterize the driving forces for the formation of this cocrystal. The results show that driving forces are dominated by the interactions between O atoms of PNO and methylene groups of HMX. It is expected that this research provides some bases for further HMX cocrystal design and preparation.

Biodegradation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by Phanerochaete chrysosporium: new insight into the degradation pathway.

PubMed

Fournier, Diane; Halasz, Annamaria; Thiboutot, Sonia; Ampleman, Guy; Manno, Dominic; Hawari, Jalal

2004-08-01

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is a recalcitrant energetic chemical that tends to accumulate in soil, close to the surface. The present study describes the aerobic biodegradability of HMX using Phanerochaete chrysosporium. When added to 7 day old static P. chrysosporium liquid cultures, HMX (600 nmol) degraded within 25 days of incubation. The removal of HMX was concomitant with the formation of transient amounts of its mono-nitroso derivative (1-NO-HMX). The latter apparently degraded via two potential routes: the first involved N-denitration followed by hydrolytic ring cleavage, and the second involved alpha-hydroxylation prior to ring cleavage. The degradation of 1-NO-HMX gave the ring-cleavage product 4-nitro-2,4-diazabutanal (NDAB), nitrite (NO2 -), nitrous oxide (N2O), and formaldehyde (HCHO). Using [14C]-HMX, we obtained 14CO2 (70% in 50 days), representing three C atoms of HMX. Incubation of real soils, contaminated with either HMX (403 micromol kg(-1)) (military base soil) or HMX (3057 micromol kg(-1)), and RDX (342 micromol kg(-1)) (ammunition soil) with the fungus led to 75 and 19.8% mineralization of HMX (liberated 14CO2), respectively, also via the intermediary formation of 1-NO-HMX. Mineralization in the latter soil increased to 35% after the addition of glucose, indicating that a fungus-based remediation process for heavily contaminated soils is promising. The present findings improve our understanding about the degradation pathway of HMX and demonstrate the utility of using the robust and versatile fungus P. chrysosporium to develop effective remediation processes for the removal of HMX.

Modeling initiation trains based on HMX and TATB

NASA Astrophysics Data System (ADS)

Drake, R. C.; Maisey, M.

2017-01-01

There will always be a requirement to reduce the size of initiation trains. However, as the size is reduced the performance characteristics can be compromised. A detailed science-based understanding of the processes (ignition and growth to detonation) which determine the performance characteristics is required to enable compact and robust initiation trains to be designed. To assess the use of numerical models in the design of initiation trains a modeling study has been undertaken, with the aim of understanding the initiation of TATB and HMX charges by a confined, surface mounted detonator. The effect of detonator diameter and detonator confinement on the formation of dead zones in the acceptor explosives has been studied. The size of dead zones can be reduced by increasing the diameter of the detonator and by increasing the impedance of the confinement. The implications for the design of initiation trains are discussed.

Finite element code development for modeling detonation of HMX composites

NASA Astrophysics Data System (ADS)

Duran, Adam; Sundararaghavan, Veera

2015-06-01

In this talk, we present a hydrodynamics code for modeling shock and detonation waves in HMX. A stable efficient solution strategy based on a Taylor-Galerkin finite element (FE) discretization was developed to solve the reactive Euler equations. In our code, well calibrated equations of state for the solid unreacted material and gaseous reaction products have been implemented, along with a chemical reaction scheme and a mixing rule to define the properties of partially reacted states. A linear Gruneisen equation of state was employed for the unreacted HMX calibrated from experiments. The JWL form was used to model the EOS of gaseous reaction products. It is assumed that the unreacted explosive and reaction products are in both pressure and temperature equilibrium. The overall specific volume and internal energy was computed using the rule of mixtures. Arrhenius kinetics scheme was integrated to model the chemical reactions. A locally controlled dissipation was introduced that induces a non-oscillatory stabilized scheme for the shock front. The FE model was validated using analytical solutions for sod shock and ZND strong detonation models and then used to perform 2D and 3D shock simulations. We will present benchmark problems for geometries in which a single HMX crystal is subjected to a shock condition. Our current progress towards developing microstructural models of HMX/binder composite will also be discussed.

Synthesis, characterization, AIM and NBO analysis of HMX/DMI cocrystal explosive

NASA Astrophysics Data System (ADS)

Lin, He; Zhu, Shun-Guan; Li, Hong-Zhen; Peng, Xin-Hua

2013-09-01

1,3,5,7-Tetranitro-1,3,5,7-tetrazacyclooctane (HMX)/1,3-dimethyl-2-imidazolidinone (DMI) cocrystal explosive was synthesized and characterized by using X-ray single crystal diffraction. HMX/DMI cocrystal crystallizes in the monoclinic system (space group Cm), with cell parameters a = 7.231(2)Å, b = 14.739(2)Å, c = 7.552(1)Å, β = 96.66°. In addition, density functional theory, involving binding energy, natural bond orbital (NBO) analysis, atoms in molecule (AIM) analysis, band structure, and density of states, was adopted to investigate intermolecular interactions for the formation of HMX/DMI cocrystal. The results show that hydrogen bondings between methylene groups of HMX molecules and O atoms of DMI molecules are the main intermolecular interactions. This research provides the basis for further design of cocrystal explosives, which are composed of HMX and energetic materials.

Effects of HMX exposure upon metabolic rate of northern bobwhite quail (Colinus virginianus) in ovo.

PubMed

Liu, Jun; Cox, Stephen B; Beall, Blake; Brunjes, Kristina J; Pan, Xiaoping; Kendall, Ronald J; Anderson, Todd A; McMurry, Scott T; Cobb, George P; Smith, Philip N

2008-05-01

We evaluated the use of the gas exchange rate as an ecologically relevant indicator of chemical stress in avian embryos/eggs. Northern bobwhite quail (Colinus virginianus) were exposed to octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) via feed containing nominal concentrations of 0, 12.5, 50.0, and 125.0 mg kg(-1). Metabolic rates (oxygen consumption) of developing quail eggs were then measured via respirometry to examine potential effects of HMX exposure. Metabolic rates were examined on 5, 9, and 21 d of incubation. Next, concentrations of HMX in embryos/eggs were determined by liquid chromatography-mass spectrometry. Mean (+/-SE) concentrations of HMX in eggs were 21.0+/-5.9, 1113+/-79.0, 3864+/-154.0, and 7426+/-301.1 ng g(-1) in control, low, medium and high dose groups, respectively. There were significant differences in oxygen consumption among the three embryo ages, however differences among the ages were not consistent among dose groups (age x dose group interaction p<0.0001). Oxygen consumption rates did not vary as a function of HMX in embryos (p=0.18). No evidence was observed for alterations of in ovo metabolic rates associated with HMX exposure.

Degradation kinetics and mechanism of RDX and HMX in TiO2 photocatalysis.

PubMed

Choi, J K; Son, H S; Kim, T S; Stenstrom, M K; Zoh, K D

2006-02-01

This study was undertaken to examine the photocatalytic degradation of explosives hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) with a circular photocatalytic reactor, using a UV lamp as a light source and TiO2 as a photocatalyst. The effects of various parameters, such as the RDX or HMX concentration, the amount of TiO, and the initial pH, on the photocatalytic degradation rates of explosives were examined. In the presence of both UV light and TiO2 RDX and HMX were more effectively degraded than with either UV or TiO2 alone. The degradation rates were found to obey pseudo-first-order kinetics represented by the Langmuir-Hinshelwood model. Increases in the RDX and HMX degradation rates were obtained with decreasing initial concentrations of the explosives. The RDX and HMX degradation rates were higher at pH 7 than at either pH 3 or pH 11. A dose of approximately 0.7 g l(-1) of TiO2 degraded HMX more rapidly than did higher or lower TiO2 doses. RDX (20 mg l(-1)) photocatalysis resulted in an approximately 20% decrease in TOC, and HMX (5 mg l(-1)) photocatalysis resulted in a 60%, decrease in TOC within 150 minutes. A trace amount of formate was produced as an intermediate that was further mineralized by RDX or HMX photocatalysis. The nitrogen byproducts from the photocatalysis of RDX and HMX were mainly NO3- with NO2-, and NH4+. The total nitrogen recovery was about 60% from RDX (20 mg l(-1)), and 70% from HMX (5 mg l(-1)), respectively. Finally, a mechanism for RDX/HMX photocatalysis was proposed, along with supporting qualitative and quantitative evidence.

Ultrasonic approach to the synthesis of HMX@TATB core-shell microparticles with improved mechanical sensitivity.

PubMed

Huang, Bing; Hao, Xiaofei; Zhang, Haobin; Yang, Zhijian; Ma, Zhigang; Li, Hongzhen; Nie, Fude; Huang, Hui

2014-07-01

To improve the safety of sensitive explosive HMX while maintaining explosion performance, a moderately powerful but insensitive explosive TATB was used to coat HMX microparticles via a facile ultrasonic method. By using Estane as surface modifier and nano-sized TATB as the shell layer, the HMX@TATB core-shell microparticles with a monodisperse size and compact shell structure were successfully constructed. Both scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results confirmed the formation of perfect core-shell structured composites. Based on a systematic and comparative study of the effect of experimental conditions, a possible formation mechanism of core-shell structure was proposed in detail. Moreover, the perfect core-shell HMX@TATB microparticles exhibited a unique thermal behavior and significantly improved mechanical sensitivity compared with that of the physical mixture. Copyright © 2014 Elsevier B.V. All rights reserved.

Microstructural Effects on Initiation Behavior in HMX

NASA Astrophysics Data System (ADS)

Molek, Christopher; Welle, Eric; Hardin, Barrett; Vitarelli, Jim; Wixom, Ryan; Samuels, Philip

Understanding the role microstructure plays on ignition and growth behavior has been the subject of a significant body of research within the detonation physics community. The pursuit of this understanding is important because safety and performance characteristics have been shown to strongly correlate to particle morphology. Historical studies have often correlated bulk powder characteristics to the performance or safety characteristics of pressed materials. We believe that a clearer and more relevant correlation is made between the pressed microstructure and the observed detonation behavior. This type of assessment is possible, as techniques now exist for the quantification of the pressed microstructures. Our talk will report on experimental efforts that correlate directly measured microstructural characteristics to initiation threshold behavior of HMX based materials. The internal microstructures were revealed using an argon ion cross-sectioning technique. This technique enabled the quantification of density and interface area of the pores within the pressed bed using methods of stereology. These bed characteristics are compared to the initiation threshold behavior of three HMX based materials using an electric gun based test method. Finally, a comparison of experimental threshold data to supporting theoretical efforts will be made.

Preparation and Characterization of the Solid Spherical HMX/F2602 by the Suspension Spray-Drying Method

NASA Astrophysics Data System (ADS)

Ji, Wei; Li, Xiaodong; Wang, Jingyu; Ye, Baoyun; Wang, Cailing

2016-10-01

Solid spherical octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine/fluororubber2602 (HMX/F2602) was prepared by the suspension spray-drying method as follows: firstly, thinning octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was obtained by a solvent-anti-solvent method. Secondly, thinning HMX suspended in ethyl acetate solvent in a solution of a binder-F2602-was made into a suspension. Finally, the samples were prepared by spray drying. The samples were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectrometry (XPS), X-ray diffraction (XRD), and Fourier transform infrared (FTIR), and its thermal stability as well as mechanical and spark sensitivities were measured. The results of SEM showed that the grain of HMX/F2602 was solid spherical and the particle distribution was homogeneous. The results of XPS indicated that F2602 can be successfully coated on the surface of HMX crystals. Compared to raw HMX, th characteristic drop height was increased from 19.60 to 40.37 cm, an increase of 79.10%. The friction sensitivities of HMX reduced from 100 to 28% and the spark sensitivity of HMX/F2602 increased. The critical explosion temperatures of raw HMX and HMX/F2602 were 275.43 and 274.30°C, respectively. The amount of gas evolution of raw HMX and HMX/F2602 was 0.15 and 0.12 ml.(5 g)-1, respectively. The results of DSC and vacuum stability tests (VSTs) indicate that the thermal stability of HMX/F2602 was equal to that of raw HMX and HMX and F2602 had good compatibility.

Ultrasonically promoted nitrolysis of DAPT to HMX in ionic liquid.

PubMed

Hua, Qian; Zhiwen, Ye; Chunxu, Lv

2008-04-01

The present work aims at developing a new process to synthesize HMX from DAPT using ultrasound in ionic liquid. Reaction has been carried out in ultrasonic bath, effect of various parameters such as presence and absence of ultrasound, volume and type of solvent, temperature, concentration of nitrating agent has been investigated with an aim of obtaining the optimum conditions for the synthesis of HMX. It was observed that ultrasonically promoted nitroylsis of DAPT to HMX has exhibited significant enhancement in yield at ambient condition.

Effects of high shock pressures and pore morphology on hot spot mechanisms in HMX

NASA Astrophysics Data System (ADS)

Springer, H. K.; Tarver, C. M.; Bastea, S.

2017-01-01

The shock initiation and detonation behavior of heterogeneous solid explosives is governed by its microstructure and reactive properties. New additive manufacturing techniques offer unprecedented control of explosive microstructures previously impossible, enabling us to develop novel explosives with tailored shock sensitivity and detonation properties. Since microstructure-performance relationships are not well established for explosives, there is little material design guidance for these manufacturing techniques. In this study, we explore the effects of high shock pressures (15-38 GPa) with long shock durations and different pore morphologies on hot spot mechanisms in HMX. HMX is chosen as the model material because we have experimental data on many of the chemical-thermal-mechanical properties required for pore collapse simulations. Our simulations are performed using the multi-physics arbitrary Lagrangian Eulerian finite element hydrocode, ALE3D, with Cheetah-based models for the unreacted and the product equation-of-states. We use a temperature-dependent specific heat with the unreacted equation-of-state and a temperature-dependent viscosity model to ensure accurate shock temperatures for subsequent chemistry. The Lindemann Law model is used for shock melting in HMX. In contrast to previous pore collapse studies at lower shock pressures (≤10 GPa) in HMX and shorter post-collapse burning times, our calculations show that shock melting occurs above 15 GPa due to higher bulk heating and a prominent elongated ("jet-like") hot spot region forms at later times. The combination of the elongated, post-collapse hot spot region and the higher bulk heating with increasing pressure dramatically increases the growth rate of reaction. Our calculations show that the reaction rate, dF/dt, increases with increasing shock pressure. We decompose the reaction rate into ignition ((dF/dt)ig) and growth ((dF/dt)gr) phases to better analyze our results. We define the ignition phase

Performance of mesophilic anaerobic granules for removal of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from aqueous solution.

PubMed

An, Chun-jiang; He, Yan-ling; Huang, Guo-he; Liu, Yong-hong

2010-07-15

The performance of mesophilic anaerobic granules to degrade octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was investigated under various conditions. The results of batch experiments showed that anaerobic granules were capable of removing HMX from aqueous solution with high efficiency. Both biotic and abiotic mechanisms contributed to the removal of HMX by anaerobic granules under mesophilic conditions. Adsorption appeared to play a significant role in the abiotic process. Furthermore, HMX could be biodegraded by anaerobic granules as the sole substrate. After 16 days of incubation, 99.04% and 96.42% of total HMX could be removed by 1g VSS/L acclimated and unacclimated granules, respectively. Vancomycin, an inhibitor of acetogenic bacteria, caused a significant inhibition of HMX biotransformation, while 2-bromoethanesulfonic acid, an inhibitor of methanogenic bacteria, only resulted in a slight decrease of metabolic activity. The presence of the glucose, as a suitable electron donor and carbon source, was found to enhance the degradation of HMX by anaerobic granules. Our study showed that sulfate had little adverse effects on biotransformation of HMX by anaerobic granules. However, nitrate had significant inhibitory effect on the extent of HMX removal especially in the initial period. This study offered good prospects of using high-rate anaerobic technology in the treatment of munition wastewater. 2010 Elsevier B.V. All rights reserved.

Mesoscale evolution of voids and microstructural changes in HMX-based explosives during heating through the β-δ phase transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Willey, Trevor M., E-mail: willey1@llnl.gov; Lauderbach, Lisa; Gagliardi, Franco

HMX-based explosives LX-10 and PBX-9501 were heated through the β-δ phase transition. Ultra-small angle x-ray scattering (USAXS) and molecular diffraction were simultaneously recorded as the HMX was heated. Mesoscale voids and structure dramatically change promptly with the β-δ phase transition, rather than with other thermal effects. Also, x-ray induced damage, observed in the USAXS, occurs more readily at elevated temperatures; as such, the dose was reduced to mitigate this effect. Optical microscopy performed during a similar heating cycle gives an indication of changes on longer length scales, while x-ray microtomography, performed before and after heating, shows the character of extensivemore » microstructural damage resulting from the temperature cycle and solid-state phase transition.« less

Mesoscale evolution of voids and microstructural changes in HMX-based explosives during heating through the β-δ phase transition

DOE PAGES

Willey, Trevor M.; Lauderbach, Lisa; Gagliardi, Franco; ...

2015-08-07

HMX-based explosives LX-10 and PBX-9501 were heated through the β-δ phase transition. Ultra-small angle x-ray scattering (USAXS) and molecular diffraction were simultaneously recorded as the HMX was heated. Mesoscale voids and structure dramatically change promptly with the β-δ phase transition, rather than with other thermal effects. Also, x-ray induced damage, observed in the USAXS, occurs more readily at elevated temperatures; as such, the dose was reduced to mitigate this effect. Optical microscopy performed during a similar heating cycle gives an indication of changes on longer length scales, while x-ray microtomography, performed before and after heating, shows the character of extensivemore » microstructural damage resulting from the temperature cycle and solid-state phase transition.« less

Ignition and growth modeling of detonation reaction zone experiments on single crystals of PETN and HMX

NASA Astrophysics Data System (ADS)

White, Bradley W.; Tarver, Craig M.

2017-01-01

It has long been known that detonating single crystals of solid explosives have much larger failure diameters than those of heterogeneous charges of the same explosive pressed or cast to 98 - 99% theoretical maximum density (TMD). In 1957, Holland et al. demonstrated that PETN single crystals have failure diameters of about 8 mm, whereas heterogeneous PETN charges have failure diameters of less than 0.5 mm. Recently, Fedorov et al. quantitatively determined nanosecond time resolved detonation reaction zone profiles of single crystals of PETN and HMX by measuring the interface particle velocity histories of the detonating crystals and LiF windows using a PDV system. The measured reaction zone time durations for PETN and HMX single crystal detonations were approximately 100 and 260 nanoseconds, respectively. These experiments provided the necessary data to develop Ignition and Growth (I&G) reactive flow model parameters for the single crystal detonation reaction zones. Using these parameters, the calculated unconfined failure diameter of a PETN single crystal was 7.5 +/- 0.5 mm, close to the 8 mm experimental value. The calculated failure diameter of an unconfined HMX single crystal was 15 +/- 1 mm. The unconfined failure diameter of an HMX single crystal has not yet been determined precisely, but Fedorov et al. detonated 14 mm diameter crystals confined by detonating a HMX-based plastic bonded explosive (PBX) without initially overdriving the HMX crystals.

Finite element code development for modeling detonation of HMX composites

NASA Astrophysics Data System (ADS)

Duran, Adam V.; Sundararaghavan, Veera

2017-01-01

In this work, we present a hydrodynamics code for modeling shock and detonation waves in HMX. A stable efficient solution strategy based on a Taylor-Galerkin finite element (FE) discretization was developed to solve the reactive Euler equations. In our code, well calibrated equations of state for the solid unreacted material and gaseous reaction products have been implemented, along with a chemical reaction scheme and a mixing rule to define the properties of partially reacted states. A linear Gruneisen equation of state was employed for the unreacted HMX calibrated from experiments. The JWL form was used to model the EOS of gaseous reaction products. It is assumed that the unreacted explosive and reaction products are in both pressure and temperature equilibrium. The overall specific volume and internal energy was computed using the rule of mixtures. Arrhenius kinetics scheme was integrated to model the chemical reactions. A locally controlled dissipation was introduced that induces a non-oscillatory stabilized scheme for the shock front. The FE model was validated using analytical solutions for SOD shock and ZND strong detonation models. Benchmark problems are presented for geometries in which a single HMX crystal is subjected to a shock condition.

Growth and dislocation studies of β-HMX.

PubMed

Gallagher, Hugh G; Sherwood, John N; Vrcelj, Ranko M

2014-01-01

The defect structure of organic materials is important as it plays a major role in their crystal growth properties. It also can play a subcritical role in "hot-spot" detonation processes of energetics and one such energetic is cyclotetramethylene-tetranitramine, in the commonly used beta form (β-HMX). The as-grown crystals grown by evaporation from acetone show prismatic, tabular and columnar habits, all with {011}, {110}, (010) and (101) faces. Etching on (010) surfaces revealed three different types of etch pits, two of which could be identified with either pure screw or pure edge dislocations, the third is shown to be an artifact of the twinning process that this material undergoes. Examination of the {011} and {110} surfaces show only one type of etch pit on each surface; however their natural asymmetry precludes the easy identification of their Burgers vector or dislocation type. Etching of cleaved {011} surfaces demonstrates that the etch pits can be associated with line dislocations. All dislocations appear randomly on the crystal surfaces and do not form alignments characteristic of mechanical deformation by dislocation slip. Crystals of β-HMX grown from acetone show good morphological agreement with that predicted by modelling, with three distinct crystal habits observed depending upon the supersaturation of the growth solution. Prismatic habit was favoured at low supersaturation, while tabular and columnar crystals were predominant at higher super saturations. The twin plane in β-HMX was identified as a (101) reflection plane. The low plasticity of β-HMX is shown by the lack of etch pit alignments corresponding to mechanically induced dislocation arrays. On untwinned {010} faces, two types of dislocations exist, pure edge dislocations with b = [010] and pure screw dislocations with b = [010]. On twinned (010) faces, a third dislocation type exists and it is proposed that these pits are associated with pure screw dislocations with b = [010

Molecular dynamics simulations of AP/HMX composite with a modified force field.

PubMed

Zhu, Wei; Wang, Xijun; Xiao, Jijun; Zhu, Weihua; Sun, Huai; Xiao, Heming

2009-08-15

An all-atom force field for ammonium perchlorate (AP) is developed with the framework of pcff force field. The structural parameters of AP obtained with the modified force field are in good agreement with experimental values. Molecular dynamics (MD) simulations have been performed to investigate AP/HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) composite at different temperatures. The binding energies, thermal expansion coefficient, and the trigger bond lengths of HMX in the AP/HMX composite have been obtained. The binding energies of the system increase slightly with temperature increasing, peak at 245K, and then gradually decrease. The volume thermal expansion coefficient of the AP/HMX composite has been derived from the volume variation with temperature. As the temperature rises, the maximal lengths of the trigger bond N-NO(2) of HMX increase gradually. The simulated results indicate that the maximal length of trigger bond can be used as a criterion for judging the sensitivity of energetic composite.

Reaction of Shocked but Undetonated HMX-Based Explosive

NASA Astrophysics Data System (ADS)

Taylor, P.; Salisbury, D. A.; Markland, L. S.; Winter, R. E.; Andrew, M. I.

2002-07-01

Cylindrical samples of the pressed plastic bonded HMX based explosive EDC37, backed by metal discs, were shocked through a stainless steel attenuator by an explosive donor. Reaction of the EDC37 sample was diagnosed with embedded PVDF pressure gauges and a distance to detonation for the geometry was determined. Sample length was then reduced to less than the observed detonation distance and laser interferometry was used to record the free surface velocity of the metal backing disc. The results provide data on the metal driving energy liberated by explosive which is shocked and reacting but not detonated. The results are compared with 2-D Eulerian calculations incorporating a 3-term ignition and growth reactive burn model with desensitisation. It is found that a parameter set for the reaction model which replicates the PVDF pressure profiles before reflection also gives good agreement to the metal disc velocity history at early times. The results show that an appreciable fraction of the metal driving potential of an explosive can be released without detonation being established.

Mechanical properties of β-HMX.

PubMed

Gallagher, Hugh G; Miller, John C; Sheen, David B; Sherwood, John N; Vrcelj, Ranko M

2015-01-01

For a full understanding of the mechanical properties of a material, it is essential to understand the defect structures and associated properties and microhardness indentation is a technique that can aid this understanding. The Vickers hardness on (010), {011} and {110} faces lay in the range of 304-363 MPa. The Knoop Hardnesses on the same faces lay in the range 314-482 MPa. From etching of three indented surfaces, the preferred slip planes have been identified as (001) and (101). For a dislocation glide, the most likely configuration for dislocation movement on the (001) planes is (001) [100] (|b| = 0.65 nm) and for the (101) plane as (101) [Formula: see text] (|b| = 1.084 nm) although (101) [010] (|b| = 1.105 nm) is possible. Tensile testing showed that at a stress value of 2.3 MPa primary twinning occurred and grew with increasing stress. When the stress was relaxed, the twins decreased in size, but did not disappear. The twinning shear strain was calculated to be 0.353 for the (101) twin plane. HMX is considered to be brittle, compared to other secondary explosives. Comparing HMX with a range of organic solids, the values for hardness numbers are similar to those of other brittle systems. Under the conditions developed beneath a pyramidal indenter, dislocation slip plays a major part in accommodating the local deformation stresses. Graphical abstractHMX undergoing tensile testing.

Effects of defects on thermal decomposition of HMX via ReaxFF molecular dynamics simulations.

PubMed

Zhou, Ting-Ting; Huang, Feng-Lei

2011-01-20

Effects of molecular vacancies on the decomposition mechanisms and reaction dynamics of condensed-phase β-HMX at various temperatures were studied using ReaxFF molecular dynamics simulations. Results show that three primary initial decomposition mechanisms, namely, N-NO(2) bond dissociation, HONO elimination, and concerted ring fission, exist at both high and lower temperatures. The contribution of the three mechanisms to the initial decomposition of HMX is influenced by molecular vacancies, and the effects vary with temperature. At high temperature (2500 K), molecular vacancies remarkably promote N-N bond cleavage and concerted ring breaking but hinder HONO formation. N-N bond dissociation and HONO elimination are two primary competing reaction mechanisms, and the former is dominant in the initial decomposition. Concerted ring breaking of condensed-phase HMX is not favored at high temperature. At lower temperature (1500 K), the most preferential initial decomposition pathway is N-N bond dissociation followed by the formation of NO(3) (O migration), although all three mechanisms are promoted by molecular vacancies. The promotion effect on concerted ring breaking is considerable at lower temperature. Products resulting from concerted ring breaking appear in the defective system but not in the perfect crystal. The mechanism of HONO elimination is less important at lower temperature. We also estimated the reaction rate constant and activation barriers of initial decomposition with different vacancy concentrations. Molecular vacancies accelerate the decomposition of condensed-phase HMX by increasing the reaction rate constant and reducing activation barriers.

Remediation of RDX- and HMX-contaminated groundwater using organic mulch permeable reactive barriers.

PubMed

Ahmad, Farrukh; Schnitker, Stephen P; Newell, Charles J

2007-02-20

Organic mulch is a complex organic material that is typically populated with its own consortium of microorganisms. The organisms in mulch breakdown complex organics to soluble carbon, which can then be used by these and other microorganisms as an electron donor for treating RDX and HMX via reductive pathways. A bench-scale treatability study with organic mulch was conducted for the treatment of RDX- and HMX-contaminated groundwater obtained from a plume at the Pueblo Chemical Depot (PCD) in Pueblo, Colorado. The site-specific cleanup criteria of 0.55 ppb RDX and 602 ppb HMX were used as the logical goals of the study. Column flow-through tests were run to steady-state at the average site seepage velocity, using a 70%:30% (vol.:vol.) mulch:pea gravel packing to approach the formation's permeability. Significant results included: (1) Complete removal of 90 ppb influent RDX and 8 ppb influent HMX in steady-state mulch column effluent; (2) pseudo-first-order steady-state kinetic rate constant, k, of 0.20 to 0.27 h(-1) based on RDX data, using triplicate parallel column runs; (3) accumulation of reduced RDX intermediates in the steady-state column effluent at less than 2% of the influent RDX mass; (4) no binding of RDX to the column fill material; and (5) no leaching of RDX, HMX or reduction intermediates from the column fill material. The results of the bench-scale study will be used to design and implement a pilot-scale organic mulch/pea gravel permeable reactive barrier (PRB) at the site.

Hmx1 is required for the normal development of somatosensory neurons in the geniculate ganglion

PubMed Central

Quina, Lely A.; Tempest, Lynne; Hsu, Yun-Wei A.; Cox, Timothy C.; Turner, Eric E.

2012-01-01

Hmx1 is a variant homeodomain transcription factor expressed in the developing sensory nervous system, retina, and craniofacial mesenchyme. Recently, mutations at the Hmx1 locus have been linked to craniofacial defects in humans, rats, and mice, but its role in nervous system development is largely unknown. Here we show that Hmx1 is expressed in a subset of sensory neurons in the cranial and dorsal root ganglia which does not correspond to any specific sensory modality. Sensory neurons in the dorsal root and trigeminal ganglia of Hmx1dm/dm mouse embryos have no detectable Hmx1 protein, yet they undergo neurogenesis and express sensory subtype markers normally, demonstrating that Hmx1 is not globally required for the specification of sensory neurons from neural crest precursors. Loss of Hmx1 expression has no obvious effect on the early development of the trigeminal (V), superior (IX/X), or dorsal root ganglia neurons in which it is expressed, but results in marked defects in the geniculate (VII) ganglion. Hmx1dm/dm mouse embryos possess only a vestigial posterior auricular nerve, and general somatosensory neurons in the geniculate ganglion are greatly reduced by mid-gestation. Although Hmx1 is expressed in geniculate neurons prior to cell cycle exit, it does not appear to be required for neurogenesis, and the loss of geniculate neurons is likely to be the result of increased cell death. Fate mapping of neural crest-derived tissues indicates that Hmx1-expressing somatosensory neurons at different axial levels may be derived from either the neural crest or the neurogenic placodes. PMID:22586713

Numerical Parameter Optimization of the Ignition and Growth Model for HMX Based Plastic Bonded Explosives

NASA Astrophysics Data System (ADS)

Gambino, James; Tarver, Craig; Springer, H. Keo; White, Bradley; Fried, Laurence

2017-06-01

We present a novel method for optimizing parameters of the Ignition and Growth reactive flow (I&G) model for high explosives. The I&G model can yield accurate predictions of experimental observations. However, calibrating the model is a time-consuming task especially with multiple experiments. In this study, we couple the differential evolution global optimization algorithm to simulations of shock initiation experiments in the multi-physics code ALE3D. We develop parameter sets for HMX based explosives LX-07 and LX-10. The optimization finds the I&G model parameters that globally minimize the difference between calculated and experimental shock time of arrival at embedded pressure gauges. This work was performed under the auspices of the U.S. DOE by LLNL under contract DE-AC52-07NA27344. LLNS, LLC LLNL-ABS- 724898.

Surface properties of HMX crystal

NASA Technical Reports Server (NTRS)

Yee, R. Y.; Adicoff, A.; Dibble, E. J.

1980-01-01

The surface properties of Beta-HMX crystals were studied. The surface energies of three principal crystal faces were obtained by measuring contact angles with several reference liquids. The surface energies and polarity of the three crystal faces are found to be different.

Mouse H6 Homeobox 1 (Hmx1) mutations cause cranial abnormalities and reduced body mass

PubMed Central

Munroe, Robert J; Prabhu, Vinay; Acland, Greg M; Johnson, Kenneth R; Harris, Belinda S; O'Brien, Tim P; Welsh, Ian C; Noden, Drew M; Schimenti, John C

2009-01-01

Background The H6 homeobox genes Hmx1, Hmx2, and Hmx3 (also known as Nkx5-3; Nkx5-2 and Nkx5-1, respectively), compose a family within the NKL subclass of the ANTP class of homeobox genes. Hmx gene family expression is mostly limited to sensory organs, branchial (pharyngeal) arches, and the rostral part of the central nervous system. Targeted mutation of either Hmx2 or Hmx3 in mice disrupts the vestibular system. These tandemly duplicated genes have functional overlap as indicated by the loss of the entire vestibular system in double mutants. Mutants have not been described for Hmx1, the most divergent of the family. Results Dumbo (dmbo) is a semi-lethal mouse mutation that was recovered in a forward genetic mutagenesis screen. Mutants exhibit enlarged ear pinnae with a distinctive ventrolateral shift. Here, we report on the basis of this phenotype and other abnormalities in the mutant, and identify the causative mutation as being an allele of Hmx1. Examination of dumbo skulls revealed only subtle changes in cranial bone morphology, namely hyperplasia of the gonial bone and irregularities along the caudal border of the squamous temporal bone. Other nearby otic structures were unaffected. The semilethality of dmbo/dmbo mice was found to be ~40%, occured perinatally, and was associated with exencephaly. Surviving mutants of both sexes exhibited reduced body mass from ~3 days postpartum onwards. Most dumbo adults were microphthalmic. Recombinant animals and specific deletion-bearing mice were used to map the dumbo mutation to a 1.8 Mb region on Chromosome 5. DNA sequencing of genes in this region revealed a nonsense mutation in the first exon of H6 Homeobox 1 (Hmx1; also Nkx5-3). An independent spontaneous allele called misplaced ears (mpe) was also identified, confirming Hmx1 as the responsible mutant gene. Conclusion The divergence of Hmx1 from its paralogs is reflected by different and diverse developmental roles exclusive of vestibular involvement. Additionally

Driving Ability of HMX based Aluminized Explosive Affected by the Reaction Degree of Aluminum Powder

NASA Astrophysics Data System (ADS)

Duan, Yingliang

2017-06-01

Due to the time scale of aluminum reaction, the detonation process of the aluminized explosive becomes very complex, and there is less agreement on the reaction mechanism of aluminum powder. If the reaction of aluminum occurs in the reaction zone, the energy released will further strengthen the work ability of detonation wave. So it is very important for characterizing the detonation parameters and detonation driving ability to accurately understand the role of aluminum powder in the reaction zone. In this paper, detonation driving process of HMX based aluminized explosive was studied by cylinder test, obtaining the expansion track of cylinder wall. In order to further research the reaction degree (λ) of aluminum in the reaction zone, the thermodynamic program VHL was used to calculate the detonation process at different reaction degrees, obtaining the parameters of detonation products thermodynamic state. Using the dynamic software LS-DYNA and the JWL equation of state by fitting the pressure and relative volume relationship, the cylinder test was simulated. Compared with the experimental results, when the reaction degree is 20%, the driving ability is found to be in agreement with measured ones. It is concluded that the driving ability of HMX based aluminized explosive can be more accurately characterized by considering the reaction degree of aluminum powder in the reaction zone.

Quasi-dynamic pressure and temperature initiated β<-->δ solid phase transitions in HMX

NASA Astrophysics Data System (ADS)

Zaug, Joseph M.; Farber, Daniel L.; Craig, Ian M.; Blosch, Laura L.; Shuh, David K.; Hansen, Donald W.; Aracne-Ruddle, Chantel M.

2000-04-01

The phase transformation of β-HMX (>0.5% RDX) to δ phase has been studied for over twenty years and more recently with an high-contrast optical second harmonic generation technique. Shock studies of the plastic binder composites of HMX have indicated that the transition is perhaps irreversible, a result that concurs with the static pressure results published by F. Goetz et al. [1] in 1978. However, the stability field favors the β polymorph over δ as pressure is increased (up to 5.4 GPa) along any thermodynamically reasonable isotherm. In this experiment, strict control of pressure and temperature is maintained while x-ray and optical diagnostics are applied to monitor the conformational dynamics of HMX. Unlike the temperature induced β→δ transition, the pressure induced is heterogeneous in nature. The 1 bar 25 °C δ→β transition is not immediate, occuring over tens of hours. Transition points and kinetics are path dependent and consequently this paper describes our work in progress.

Dissociative electron attachment to the nitroamine HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine).

PubMed

Postler, Johannes; Goulart, Marcelo M; Matias, Carolina; Mauracher, Andreas; Ferreira da Silva, Filipe; Scheier, Paul; Limão-Vieira, Paulo; Denifl, Stephan

2013-05-01

In the present study, dissociative electron attachment (DEA) measurements with gas phase HMX, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, C4H8N8O8, have been performed by means of a crossed electron-molecular beam experiment. The most intense signals are observed at 46 and 176 u and assigned to NO2(-) and C3H6N5O4(-), respectively. Anion efficiency curves for 15 negatively charged fragments have been measured in the electron energy region from about 0-20 eV with an energy resolution of ~0.7 eV. Product anions are observed mainly in the low energy region, near 0 eV, arising from surprisingly complex reactions associated with multiple bond cleavages and structural and electronic rearrangement. The remarkable instability of HMX towards electron attachment with virtually zero kinetic energy reflects the highly explosive nature of this compound. Substantially different intensity ratios of resonances for common fragment anions allow distinguishing the nitroamines HMX and royal demolition explosive molecule (RDX) in negative ion mass spectrometry based on free electron capture.

Specific Heat of Octahydro - 1,3,5,7 - Tetranitro - 1,3,5,7 - Tetrazocine (HMX).

DTIC Science & Technology

1983-01-01

impurities probably consist of molecules of similar atomic weights as those present in the HMX molecule. Usually the major impurity in HMX is RDX (5...crystal and powdered blend HMX . Data beyond the normal transformation temperature (i.e. 0*6 transition ) were obtained from 472 to 486*K. Also, due to the...Cady, H.H.; Smith, L.C., "Studies on the Polymorphs of HMX ," Los Alamos Scientific Laboratory, Los Alamos, N.M., LAMS-2652, May 1962. (6) Brill, T.B

Theoretical Insight into the Influences of Molecular Ratios on Stabilities and Mechanical Properties, Solvent Effect of HMX/FOX-7 Cocrystal Explosive

NASA Astrophysics Data System (ADS)

Wei, Yan-Ju; Ren, Fu-De; Shi, Wen-Jing; Zhao, Qi

2016-10-01

A molecular dynamics method was employed to study the binding energies of the selected crystal planes of the 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane/1,1-diamino-2,2-dinitroethylene (HMX/FOX-7) cocrystal in different molecular molar ratios. Mechanical properties, densities, and detonation velocities of the cocrystals in different ratios were estimated. The intermolecular interactions and bond dissociation energies (BDEs) of the N-NO2 bond in the HMX:FOX-7 (1:1) complex were calculated using the B3LYP and MP2(full) methods at the 6-311++G (d,p) and 6-311++G(2df,2p) basis sets. Solvent effects on stability are discussed. The results indicate that HMX/FOX-7 cocrystals prefer cocrystalizing in a 1:1 molar ratio, which has good mechanical properties. The N-NO2 bond becomes strong upon the formation of a complex and the sensitivity of HMX might decrease in cocrystals. The sensitivity change of HMX/FOX-7 originates from not only the formation of intermolecular interaction but also the increment in the N-NO2 BDE. HMX/FOX-7 cocrystals exhibit good detonation performance and meet the requirements of high-density energetic materials. Solvents with low dielectric constants may be chosen to obtain stable HMX/FOX-7 cocrystals.

The response of the HMX-based material PBXN-9 to thermal insults: thermal decomposition kinetics and morphological changes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glascoe, E A; Hsu, P C; Springer, H K

PBXN-9, an HMX-formulation, is thermally damaged and thermally decomposed in order to determine the morphological changes and decomposition kinetics that occur in the material after mild to moderate heating. The material and its constituents were decomposed using standard thermal analysis techniques (DSC and TGA) and the decomposition kinetics are reported using different kinetic models. Pressed parts and prill were thermally damaged, i.e. heated to temperatures that resulted in material changes but did not result in significant decomposition or explosion, and analyzed. In general, the thermally damaged samples showed a significant increase in porosity and decrease in density and a smallmore » amount of weight loss. These PBXN-9 samples appear to sustain more thermal damage than similar HMX-Viton A formulations and the most likely reasons are the decomposition/evaporation of a volatile plasticizer and a polymorphic transition of the HMX from {beta} to {delta} phase.« less

Understanding the desensitizing mechanism of olefin in explosives: shear slide of mixed HMX-olefin systems.

PubMed

Zhang, Chaoyang; Cao, Xia; Xiang, Bin

2012-04-01

We simulated the shear slide behavior of typical mixed HMX-olefin systems and the effect of thickness of olefin layers (4-22 Å) on the behavior at a molecular level by considering two cases: bulk shear and interfacial shear. The results show that: (1) the addition of olefin into HMX can reduce greatly the shear sliding barriers relative to the pure HMX in the two cases, suggesting that the desensitizing mechanism of olefin is controlled dominantly by its good lubricating property; (2) the change of interaction energy in both systoles of shear slide is strongly dominated by van der Waals interaction; and (3) the thickness of olefin layers in the mixed explosives can influence its desensitizing efficiency. That is, the excessive thinness of olefin layers in the mixed explosive systems, for example, several angstroms, can lead to very high sliding barriers.

Deletion of a conserved regulatory element required for Hmx1 expression in craniofacial mesenchyme in the dumbo rat: a newly identified cause of congenital ear malformation

PubMed Central

Quina, Lely A.; Kuramoto, Takashi; Luquetti, Daniela V.; Cox, Timothy C.; Serikawa, Tadao; Turner, Eric E.

2012-01-01

SUMMARY Hmx1 is a homeodomain transcription factor expressed in the developing eye, peripheral ganglia, and branchial arches of avian and mammalian embryos. Recent studies have identified a loss-of-function allele at the HMX1 locus as the causative mutation in the oculo-auricular syndrome (OAS) in humans, characterized by ear and eye malformations. The mouse dumbo (dmbo) mutation, with similar effects on ear and eye development, also results from a loss-of-function mutation in the Hmx1 gene. A recessive dmbo mutation causing ear malformation in rats has been mapped to the chromosomal region containing the Hmx1 gene, but the nature of the causative allele is unknown. Here we show that dumbo rats and mice exhibit similar neonatal ear and eye phenotypes. In midgestation embryos, dumbo rats show a specific loss of Hmx1 expression in neural-crest-derived craniofacial mesenchyme (CM), whereas Hmx1 is expressed normally in retinal progenitors, sensory ganglia and in CM, which is derived from mesoderm. High-throughput resequencing of 1 Mb of rat chromosome 14 from dmbo/dmbo rats, encompassing the Hmx1 locus, reveals numerous divergences from the rat genomic reference sequence, but no coding changes in Hmx1. Fine genetic mapping narrows the dmbo critical region to an interval of ∼410 kb immediately downstream of the Hmx1 transcription unit. Further sequence analysis of this region reveals a 5777-bp deletion located ∼80 kb downstream in dmbo/dmbo rats that is not apparent in 137 other rat strains. The dmbo deletion region contains a highly conserved domain of ∼500 bp, which is a candidate distal enhancer and which exhibits a similar relationship to Hmx genes in all vertebrate species for which data are available. We conclude that the rat dumbo phenotype is likely to result from loss of function of an ultraconserved enhancer specifically regulating Hmx1 expression in neural-crest-derived CM. Dysregulation of Hmx1 expression is thus a candidate mechanism for congenital

Pressure-dependent decomposition kinetics of the energetic material HMX up to 3.6 GPa.

PubMed

Glascoe, Elizabeth A; Zaug, Joseph M; Burnham, Alan K

2009-12-03

The effect of pressure on the global thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Global decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low-to-moderate pressures (i.e., between ambient pressure and 0.1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure-enhanced autocatalysis, whereas the deceleration at high pressures is attributed to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the beta- and delta-polymorphs of HMX are sensitive to pressure in the thermally induced decomposition kinetics.

Understanding metastable phase transformation during crystallization of RDX, HMX and CL-20: experimental and DFT studies.

PubMed

Ghosh, Mrinal; Banerjee, Shaibal; Shafeeuulla Khan, Md Abdul; Sikder, Nirmala; Sikder, Arun Kanti

2016-09-14

Multiphase growth during crystallization severely affects deliverable output of explosive materials. Appearance and incomplete transformation of metastable phases are a major source of polymorphic impurities. This article presents a methodical and molecular level understanding of the metastable phase transformation mechanism during crystallization of cyclic nitramine explosives, viz. RDX, HMX and CL-20. Instantaneous reverse precipitation yielded metastable γ-HMX and β-CL-20 which undergo solution mediated transformation to the respective thermodynamic forms, β-HMX and ε-CL-20, following 'Ostwald's rule of stages'. However, no metastable phase, anticipated as β-RDX, was evidenced during precipitation of RDX, which rather directly yielded the thermodynamically stable α-phase. The γ→β-HMX and β→ε-CL-20 transformations took 20 and 60 minutes respectively, whereas formation of α-RDX was instantaneous. Density functional calculations were employed to identify the possible transition state conformations and to obtain activation barriers for transformations at wB97XD/6-311++G(d,p)(IEFPCM)//B3LYP/6-311G(d,p) level of theory. The computed activation barriers and lattice energies responsible for transformation of RDX, HMX and CL-20 metastable phases to thermodynamic ones conspicuously supported the experimentally observed order of phase stability. This precise result facilitated an understanding of the occurrence of a relatively more sensitive and less dense β-CL-20 phase in TNT based melt-cast explosive compositions, a persistent and critical problem unanswered in the literature. The crystalline material recovered from such compositions revealed a mixture of β- and ε-CL-20. However, similar compositions of RDX and HMX never showed any metastable phase. The relatively long stability with the highest activation barrier is believed to restrict complete β→ε-CL-20 transformation during processing. Therefore a method is suggested to overcome this issue.

Mechanism of xanthine oxidase catalyzed biotransformation of HMX under anaerobic conditions.

PubMed

Bhushan, Bharat; Paquet, Louise; Halasz, Annamaria; Spain, Jim C; Hawari, Jalal

2003-06-27

Enzyme catalyzed biotransformation of the energetic chemical octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is not known. The present study describes a xanthine oxidase (XO) catalyzed biotransformation of HMX to provide insight into the biodegradation pathway of this energetic chemical. The rates of biotransformation under aerobic and anaerobic conditions were 1.6+/-0.2 and 10.5+/-0.9 nmolh(-1)mgprotein(-1), respectively, indicating that anaerobic conditions favored the reaction. The biotransformation rate was about 6-fold higher using NADH as an electron-donor compared to xanthine. During the course of reaction, the products obtained were nitrite (NO(2)(-)), methylenedinitramine (MDNA), 4-nitro-2,4-diazabutanal (NDAB), formaldehyde (HCHO), nitrous oxide (N(2)O), formic acid (HCOOH), and ammonium (NH(4)(+)). The product distribution gave carbon and nitrogen mass-balances of 91% and 88%, respectively. A comparative study with native-, deflavo-, and desulfo-XO and the site-specific inhibition studies showed that HMX biotransformation occurred at the FAD-site of XO. Nitrite stoichiometry revealed that an initial single N-denitration step was sufficient for the spontaneous decomposition of HMX.

Effect of Long Term Low-Level Gamma Radiation on Thermal Sensitivity of RDX/HMX Mixtures

DTIC Science & Technology

1976-11-01

1.1x10 R. It was concluded that the slight exothermic reaction before the 3^6 HMX polymorphic transition could be caused by a radiation-induced...Radiation on Thermal Sensitivity of RDX / HMX Mixtures 5. TYPE OF REPORT 4 PERIOD COVERED Final Report 6. PERFORMING ORG. REPORT NUMBER 7...and Identity by block number) Gamma radiation Weight loss HMX Impact sensitivity test RDX Vacuum stability test DTA Infrared spectrometry TGA

Accumulation and effects of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) exposure in the green anole (Anolis carolinensis).

PubMed

McMurry, S T; Jones, L E; Smith, P N; Cobb, G P; Anderson, T A; Lovern, M B; Cox, S; Pan, X

2012-03-01

Environmental contamination by energetic compounds is an increasing international concern, although little is known of their accumulation in and affect on wildlife. Reptiles are often good models for contaminants studies due to natural history traits that increase their potential for exposure. We report a study to assess accumulation and effects of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, High Melting Explosive) in green anoles (Anolis carolinensis). Acute oral toxicity (LD(50)) was estimated to exceed 2000 mg/kg body weight in adult male and female anoles using a standard up-and-down method. Accumulation of HMX was assessed in adult females via dietary exposure and into eggs by two routes (directly from the soil and via maternal transfer). HMX readily accumulated into adult females in a dose-dependent manner and into eggs following both exposure pathways. However, total HMX in soil-exposed eggs was up to 40-times greater than those exposed via maternal transfer. Although there was a suggestion of an HMX-induced reduction in body weight in adult females, overall there were no effects observed over the 12 week exposure period. The only significant effect on eggs was a 50% reduction in hatching success for eggs exposed to 2000 mg/kg HMX in the soil during incubation. Growth and survival of hatchlings was not affected by HMX exposure. Our results demonstrate that HMX accumulates through the food chain and into eggs from the soil, but likely poses minimal threat to lizards except to hatching success in eggs incubated in soils with HMX levels near maximum environmental concentrations.

Ab Initio Calculations of the N-N Bond Dissociation for the Gas-phase RDX and HMX.

PubMed

Liu, Lin-Lin; Liu, Pei-Jin; Hu, Song-Qi; He, Guo-Qiang

2017-01-17

NO 2 fission is a vital factor for 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) decomposition. In this study, the geometry of the gas-phase RDX and HMX molecules was optimized, and the bond order and the bond dissociation energy of the N-N bonds were examined. Moreover, the rate constants of the gas-phase RDX and HMX conformers, concerning the N-N bond dissociation, were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that HMX is more stable than RDX in terms of the N-N bond dissociation, and the conformers stability parameters were as follows: RDXaaa < RDXaae < HMX I < HMX II. In addition, for the RDX conformers, the N-N bond of the pseudo-equatorial positioning of the nitro group was more stable than the N-N bond of the axial positioning of the nitro group, while the results were opposite in the case of the HMX conformers. Moreover, it has been shown that the dissociation rate constant of the N-N bond is influenced by the temperature significantly, thus the rate constants were much lower (<10 -10  s -1 ) when the temperature was less than 1000 K.

Ab Initio Calculations of the N-N Bond Dissociation for the Gas-phase RDX and HMX

PubMed Central

Liu, Lin-lin; Liu, Pei-jin; Hu, Song-qi; He, Guo-qiang

2017-01-01

NO2 fission is a vital factor for 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) decomposition. In this study, the geometry of the gas-phase RDX and HMX molecules was optimized, and the bond order and the bond dissociation energy of the N-N bonds were examined. Moreover, the rate constants of the gas-phase RDX and HMX conformers, concerning the N-N bond dissociation, were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that HMX is more stable than RDX in terms of the N-N bond dissociation, and the conformers stability parameters were as follows: RDXaaa < RDXaae < HMX I < HMX II. In addition, for the RDX conformers, the N-N bond of the pseudo-equatorial positioning of the nitro group was more stable than the N-N bond of the axial positioning of the nitro group, while the results were opposite in the case of the HMX conformers. Moreover, it has been shown that the dissociation rate constant of the N-N bond is influenced by the temperature significantly, thus the rate constants were much lower (<10−10 s−1) when the temperature was less than 1000 K. PMID:28094774

Ab Initio Calculations of the N-N Bond Dissociation for the Gas-phase RDX and HMX

NASA Astrophysics Data System (ADS)

Liu, Lin-Lin; Liu, Pei-Jin; Hu, Song-Qi; He, Guo-Qiang

2017-01-01

NO2 fission is a vital factor for 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) decomposition. In this study, the geometry of the gas-phase RDX and HMX molecules was optimized, and the bond order and the bond dissociation energy of the N-N bonds were examined. Moreover, the rate constants of the gas-phase RDX and HMX conformers, concerning the N-N bond dissociation, were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that HMX is more stable than RDX in terms of the N-N bond dissociation, and the conformers stability parameters were as follows: RDXaaa < RDXaae < HMX I < HMX II. In addition, for the RDX conformers, the N-N bond of the pseudo-equatorial positioning of the nitro group was more stable than the N-N bond of the axial positioning of the nitro group, while the results were opposite in the case of the HMX conformers. Moreover, it has been shown that the dissociation rate constant of the N-N bond is influenced by the temperature significantly, thus the rate constants were much lower (<10-10 s-1) when the temperature was less than 1000 K.

Trace Detection of RDX, HMX and PETN Explosives Using a Fluorescence Spot Sensor

PubMed Central

Wang, Chen; Huang, Helin; Bunes, Benjamin R.; Wu, Na; Xu, Miao; Yang, Xiaomei; Yu, Li; Zang, Ling

2016-01-01

1,3,5-trinitroperhydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and pentaerythritol tetranitrate (PETN), the major components in plastic explosives, pose a significant threat to public safety. A quick, sensitive, and low-cost detection method for these non-volatile explosives is eagerly demanded. Here we present a fluo-spot approach, which can be employed for in situ detection of trace amount of explosives. The sensor molecule is a charge-transfer fluorophore, DCM, which is strongly fluorescent in its pristine state, but non-fluorescent after the quick reaction with NO2· (or NO2+) generated from the UV photolysis of RDX, HMX (or PETN). When fabricated within silica gel TLC plate, the fluo-spot sensor features high sensitivity owing to the large surface area and porous structure of the substrate. The sensor reaction mechanism was verified by various experimental characterizations, including chromatography, UV-Vis absorption and fluorescence spectroscopy, MS and 1H NMR spectrometry. The fluo-spot also demonstrated high selectivity towards RDX, HMX and PETN, as no significant fluorescence quenching was observed for other chemical compounds including common nitro-aromatic explosives and inorganic oxidative compounds. The DCM sensor can also be used as an economical spray kit to directly spot the explosives by naked eyes, implying great potential for quick, low-cost trace explosives detection. PMID:27146290

Trace Detection of RDX, HMX and PETN Explosives Using a Fluorescence Spot Sensor.

PubMed

Wang, Chen; Huang, Helin; Bunes, Benjamin R; Wu, Na; Xu, Miao; Yang, Xiaomei; Yu, Li; Zang, Ling

2016-05-05

1,3,5-trinitroperhydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and pentaerythritol tetranitrate (PETN), the major components in plastic explosives, pose a significant threat to public safety. A quick, sensitive, and low-cost detection method for these non-volatile explosives is eagerly demanded. Here we present a fluo-spot approach, which can be employed for in situ detection of trace amount of explosives. The sensor molecule is a charge-transfer fluorophore, DCM, which is strongly fluorescent in its pristine state, but non-fluorescent after the quick reaction with NO2· (or NO2(+)) generated from the UV photolysis of RDX, HMX (or PETN). When fabricated within silica gel TLC plate, the fluo-spot sensor features high sensitivity owing to the large surface area and porous structure of the substrate. The sensor reaction mechanism was verified by various experimental characterizations, including chromatography, UV-Vis absorption and fluorescence spectroscopy, MS and (1)H NMR spectrometry. The fluo-spot also demonstrated high selectivity towards RDX, HMX and PETN, as no significant fluorescence quenching was observed for other chemical compounds including common nitro-aromatic explosives and inorganic oxidative compounds. The DCM sensor can also be used as an economical spray kit to directly spot the explosives by naked eyes, implying great potential for quick, low-cost trace explosives detection.

The fate and transport of RDX, HMX, TNT and DNT in the volcanic soils of Hawaii: a laboratory and modeling study.

PubMed

Alavi, Ghasem; Chung, Mel; Lichwa, Joseph; D'Alessio, Matteo; Ray, Chittaranjan

2011-01-30

The adsorption and degradation behavior of RDX, HMX, TNT and DNT and the impact of pH, ionic strength and dissolved organic matter on sorption were examined for two volcanic soils of a former military training area on Hawaii Island, Hawaii, USA. The transport of these chemicals in the soil was also studied in small packed columns and simulated using a water-flow and solute-transport model, HYDRUS_1D. The results show that HMX and RDX are both significantly more mobile than TNT and DNT. The adsorbability of the four chemicals was ranked as: RDX<HMXHMX>RDX>DNT>TNT. No significant trend was observed for the effect of ionic strength, pH and dissolved organic carbon (DOC) on the adsorption of explosive compounds within the concentrations and pH ranges evaluated. The simulation results show that TNT and DNT would not leach beyond a depth of 30cm soil profile whereas a significant amount of HMX and RDX would pass the 30cm depth. It seems that the risk for contamination of groundwater is much higher for both HMX and RDX than for DNT and TNT as the substratum in this area consists of highly permeable lavas. Copyright © 2010 Elsevier B.V. All rights reserved.

DDT Behavior of Waxed Mixtures of RDX, HMX, and Tetryl

DTIC Science & Technology

1977-10-18

HMX (689*; Class A, 6 ’ 200p), RDX (659; Class E, 6 P 15p), tetryl (812; 6 s 470p), carnauba wax (134; 6 r 125p). The mixing procedure was that used...NSWC/WOL TR 77-96 O DDT BEHAVIOR OF WAXED MIXTURES OF " RDX, HMX, AND TETRYL BY DONNA PRICE and RICHARD R. BERNECKER RESEARCH AND TECHNOLOGY...BEFORE COMPLETING FORM RY PORT NUM ER 2. GOVT ACCESSION No. 3. RECIPIENT’S CATALOG NUMBER S. TYPE OF REPORT & PERIOD COVERED PDT Behavior of Waxed Mixtures

Deflagration to Detonation Transition (DDT) Simulations of HMX Powder Using the HERMES Model

NASA Astrophysics Data System (ADS)

White, Bradley; Reaugh, John; Tringe, Joseph

2017-06-01

We performed computer simulations of DDT experiments with Class I HMX powder using the HERMES model (High Explosive Response to MEchanical Stimulus) in ALE3D. Parameters for the model were fitted to the limited available mechanical property data of the low-density powder, and to the Shock to Detonation Transition (SDT) test results. The DDT tests were carried out in steel-capped polycarbonate tubes. This arrangement permits direct observation of the event using both flash X-ray radiography and high speed camera imaging, and provides a stringent test of the model. We found the calculated detonation transition to be qualitatively similar to experiment. Through simulation we also explored the effects of confinement strength, the HMX particle size distribution and porosity on the computed detonation transition location. This work was performed under the auspices of the US DOE by LLNL under Contract DE-AC52-07NA27344.

Solid-state modeling of the terahertz spectrum of the high explosive HMX.

PubMed

Allis, Damian G; Prokhorova, Darya A; Korter, Timothy M

2006-02-09

The experimental solid-state terahertz (THz) spectrum (3-120 cm(-1)) of the beta-crystal form of the high explosive octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) has been analyzed using solid-state density functional theory calculations. Various density functionals (both generalized gradient approximation and local density approximation) are compared in terms of their abilities to reproduce the experimentally observed solid-state structure and low-frequency vibrational motions. Good-to-excellent agreement between solid-state theory and experiment can be achieved in the THz region where isolated-molecule calculations fail to reproduce the observed spectral features, demonstrating a clear limitation of using isolated-molecule calculations for the assignment of THz frequency motions in molecular solids. The deficiency of isolated-molecule calculations is traced to modification of the molecular structure in the solid state through crystal packing effects and the formation of weak C-H...O hydrogen bonds.

Temperature and Pressure from Collapsing Pores in HMX

NASA Astrophysics Data System (ADS)

Hardin, D. Barrett

2017-06-01

The thermal and mechanical response of collapsing voids in HMX is analyzed. In this work, the focus is simulating the temperature and pressure fields arising from isolated, idealized pores as they collapse in the presence of a shock. HMX slabs are numerically generated which contain a single pore, isolated from the boundaries to remove all wave reflections. In order to understand the primary pore characteristics leading to temperature rise, a series of 2D, plane strain simulations are conducted on HMX slabs containing both cylindrical and elliptical pores of constant size equal to the area of a circular pore with a 1 micron diameter. Each of these pore types is then subjected to shock pressures ranging from a weak shock that is unable to fully collapse the pore to a strong shock which overwhelms the tendency for localization. Results indicate that as shock strength increases, pore collapse phenomenology for a cylindrical pore transitions from a mode dominated by localized melt cracking to an idealized hydrodynamic pore collapse. For the case of elliptical pores, the orientation causing maximum temperature and pressure rise is found. The relative heating in elliptical pores is then quantified as a function of pore orientation and aspect ratio for a pore of a given area. Distribution A: Distribution unlimited. (96TW 2017-0036).

Pressure-induced metallization of condensed phase β-HMX under shock loadings via molecular dynamics simulations in conjunction with multi-scale shock technique.

PubMed

Ge, Ni-Na; Wei, Yong-Kai; Zhao, Feng; Chen, Xiang-Rong; Ji, Guang-Fu

2014-07-01

The electronic structure and initial decomposition in high explosive HMX under conditions of shock loading are examined. The simulation is performed using quantum molecular dynamics in conjunction with multi-scale shock technique (MSST). A self-consistent charge density-functional tight-binding (SCC-DFTB) method is adapted. The results show that the N-N-C angle has a drastic change under shock wave compression along lattice vector b at shock velocity 11 km/s, which is the main reason that leads to an insulator-to-metal transition for the HMX system. The metallization pressure (about 130 GPa) of condensed-phase HMX is predicted firstly. We also detect the formation of several key products of condensed-phase HMX decomposition, such as NO2, NO, N2, N2O, H2O, CO, and CO2, and all of them have been observed in previous experimental studies. Moreover, the initial decomposition products include H2 due to the C-H bond breaking as a primary reaction pathway at extreme condition, which presents a new insight into the initial decomposition mechanism of HMX under shock loading at the atomistic level.

Vibrational and thermodynamic properties of β-HMX: a first-principles investigation.

PubMed

Wu, Zhongqing; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya

2011-05-28

Thermodynamic properties of β-HMX crystal are investigated using the quasi-harmonic approximation and density functional theory within the local density approximation (LDA), generalized gradient approximation (GGA), and GGA + empirical van der Waals (vdW) correction. It is found that GGA well describes the thermal expansion coefficient and heat capacity but fails to produce correct bulk modulus and equilibrium volume. The vdW correction improves the bulk modulus and volume, but worsens the thermal expansion coefficient and heat capacity. In contrast, LDA describes all thermodynamic properties with reasonable accuracy, and overall is a good exchange-correlation functional for β-HMX molecular crystal. The results also demonstrate significant contributions of phonons to the equation of state. The static calculation of equilibrium volume for β-HMX differs from the room-temperature value incorporating lattice vibrations by over 5%. Therefore, for molecular crystals, it is essential to include phonon contributions when calculated equation of state is compared with experimental data at ambient condition. © 2011 American Institute of Physics

Analysis of compaction shock interactions during DDT of low density HMX

NASA Astrophysics Data System (ADS)

Rao, Pratap T.; Gonthier, Keith A.

2017-01-01

Deflagration-to-Detonation Transition (DDT) in confined, low density granular HMX occurs by a complex mechanism that involves compaction shock interactions within the material. Piston driven DDT experiments indicate that detonation is abruptly triggered by the interaction of a strong combustion-supported secondary shock and a piston-supported primary (input) shock, where the nature of the interaction depends on initial packing density and primary shock strength. These interactions influence transition by affecting dissipative heating within the microstructure during pore collapse. Inert meso-scale simulations of successive shock loading of low density HMX are performed to examine how dissipation and hot-spot formation are affected by the initial density, and the primary and secondary shock strengths. This information is used to formulate an ignition and burn model for low density HMX that accounts for the effect of shock densensitization on burn. Preliminary DDT predictions are presented that illustrate how primary shock strength affects the transition mechanism.

Theoretical Study on Effects of Hydrogen-Bonding and Molecule-Cation Interactions on the Sensitivity of HMX.

PubMed

Li, Yunlu; Wu, Junpeng; Cao, Duanlin; Wang, Jianlong

2016-10-04

To assess the effects of weak interactions on the sensitivity of HMX, eleven complexes of HMX (where six of them are hydrogen-bonding complexes, and the other five are molecular-cation complexes) have been studied via quantum chemical treatment. The geometric and electronic structures were determined using DFT-B3LYP and MP2(full) methods with the 6-311++G(2df, 2p) and aug-cc-pVTZ basis sets. The changes of the bond dissociation energy (BDE) of the trigger bond (N-NO2 in HMX) and nitro group charge have been computed on the detail consideration to access the sensitivity changes of HMX. The results indicate that upon complex forming, the BDE increases and the charge of nitro group turns more negative in complexes, suggesting that the strength of the N-NO2 trigger bond is enhanced then the sensitivity of HMX is reduced. Atom-in-molecules analysis have also been carried to understand the nature of intermolecular interactions and the strength of trigger bonds.

Ab initio calculations of the effects of H+ and NH4+ on the initial decomposition of HMX.

PubMed

Wang, Luoxin; Tuo, Xinlin; Yi, Changhai; Wang, Xiaogong

2008-10-01

In this work, the effects of H(+) and NH(4)(+) on the initial decomposition of HMX were investigated on the basis of the B3P86/6-31G** and B3LYP/6-31G* calculations. Three initial decomposition pathways including the N-NO(2) bond fission, HONO elimination and C-N bond dissociation were considered for the complexes formed by HMX with H(+) (PHMX1 and PHMX2) or with NH(4)(+) (AHMX). We found that H(+) and NH(4)(+) did not evidently induce the HMX to trigger the N-NO(2) heterolysis because the energy barrier of N-NO(2) heterolysis was found to be higher than the bond dissociation energy of N-NO(2) homolytic cleavage. Meanwhile, the transition state barriers of the HONO elimination from the complexes were found to be similar to that from the isolated HMX, which means that the HONO elimination reaction of HMX was not affected by the H(+) and NH(4)(+). As for the ring-opening reaction of HMX due to the C-N bond dissociation, the calculated potential energy profile showed that the energy of the complex (AHMX) went uphill along the C-N bond length and no transition state existed on the curve. However, the transition state energy barriers of C-N bond dissociation were calculated to be only 5.0 kcal/mol and 5.5 kcal/mol for the PHMX1 and PHMX2 complexes, respectively, which were much lower than the C-N bond dissociation energy of isolated HMX. Moreover, among the three initial decomposition reactions, the C-N bond dissociation was also the most energetically favorable pathway for the PHMX1 and PHMX2. Our calculation results showed that the H(+) can significantly promote the initial thermal decomposition of C-N bond of HMX, which, however, is influenced by NH(4)(+) slightly.

Observation and modeling of deflagration-to-detonation transition (DDT) in low-density HMX

NASA Astrophysics Data System (ADS)

Tringe, Joseph W.; Vandersall, Kevin S.; Reaugh, John E.; Levie, Harold W.; Henson, Bryan F.; Smilowitz, Laura B.; Parker, Gary R.

2017-01-01

We employ simultaneous flash x-ray radiography and streak imaging, together with a multi-phase finite element model, to understand deflagration-to-detonation transition (DDT) phenomena in low-density (˜1.2 gm/cm3) powder of the explosive cyclotetramethylene-tetranitramine (HMX). HMX powder was lightly hand-tamped in a 12.7 mm diameter column, relatively lightly-confined in an optically-transparent polycarbonate cylinder with wall thickness 25.4 mm. We observe apparent compaction of the powder in advance of the detonation transition by the motion of small steel spheres pre-emplaced throughout the length of explosive. High-speed imaging along the explosive cylinder length provides a more temporally continuous record of the transition that is correlated with the high-resolution x-ray image record. Preliminary simulation of these experiments with the HERMES model implemented in the ALE3D code enables improved understanding of the explosive particle burning, compaction and detonation phenomena which are implied by the observed reaction rate and transition location within the cylinder.

Critical Analysis of Nitramine Decomposition Data: Activation Energies and Frequency Factors for HMX and RDX Decomposition

DTIC Science & Technology

1985-09-01

larger than the net energies of reaction for the same transitions ) represent energy needed for "freeing-up" of HMX or RDX molecules 70E. R. Lee, R. H...FACTORS FOR HMX AND RDX DECOMPOSITION Michael A. Schroeder DT!C .AECTE September 1985 SEP 3 0 8 * APPROVED FOR PUBUC RELEASE; DISTIR!UTION UNLIMITED. US...Final Activation Energies and Frequency Factors for HMX and RDX Decomposition b PERFORMING ORG. REPORT N, %1ER 7. AUTHOR(@) 6 CONTRACT OR GRANT NuMP

Effect of local void morphology on the reaction initiation mechanism in the case of pressed HMX

NASA Astrophysics Data System (ADS)

Roy, Sidhartha; Rai, Nirmal; Udaykumar, H. S.

2017-06-01

The microstructural characteristics of pressed HMX has a significant effect on its sensitivity under shock loading. The microstructure of pressed HMX contains voids of various orientation and aspect ratio. Subject to shock loading, these voids can collapse forming hotspots and initiate chemical reaction. This work shows how the ignition and growth of chemical reaction is dependent on the local microstructural features of the voids. Morphological quantities like size, aspect ratio and orientations are extracted from the real microstructural images of Class III and Class V pressed HMX. These morphological quantities are correlated with the ignition and growth rates of the chemical reaction. The dependency of the sensitivity of a given HMX sample on the local morphological features shows that these local features can create a mocroscale physical response.

Theoretical insight into the solvent effect of H2O and formamide on the cooperativity effect in HMX complex.

PubMed

Meng, Rui-Hong; Cao, Xiong; Hu, Shuang-Qi; Hu, Li-Shuang

2017-08-01

The cooperativity effects of the H-bonding interactions in HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane)∙∙∙HMX∙∙∙FA (formamide), HMX∙∙∙HMX∙∙∙H 2 O and HMX∙∙∙HMX∙∙∙HMX complexes involving the chair and chair-chair HMX are investigated by using the ONIOM2 (CAM-B3LYP/6-31++G(d,p):PM3) and ONIOM2 (M06-2X/6-31++G(d,p):PM3) methods. The solvent effect of FA or H 2 O on the cooperativity effect in HMX∙∙∙HMX∙∙∙HMX are evaluated by the integral equation formalism polarized continuum model. The results show that the cooperativity and anti-cooperativity effects are not notable in all the systems. Although the effect of solvation on the binding energy of ternary system HMX∙∙∙HMX∙∙∙HMX is not large, that on the cooperativity of H-bonds is notable, which leads to the mutually strengthened H-bonding interaction in solution. This is perhaps the reason for the formation of different conformation of HMX in different solvent. Surface electrostatic potential and reduced density gradient are used to reveal the nature of the solvent effect on cooperativity effect in HMX∙∙∙HMX∙∙∙HMX. Graphical abstract RDG isosurface and electrostatic potential surface of HMX∙∙∙HMX∙∙∙HMX.

How does low temperature coupled with different pressures affect initiation mechanisms and subsequent decompositions in nitramine explosive HMX?

PubMed

Wu, Qiong; Xiong, Guolin; Zhu, Weihua; Xiao, Heming

2015-09-21

We have performed ab initio molecular dynamics simulations to study coupling effects of temperature (534-873 K) and pressure (1-20 GPa) on the initiation mechanisms and subsequent chemical decompositions of nitramine explosive 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). A new initiation decomposition mechanism of HMX was found to be the unimolecular C-H bond breaking, and this mechanism was independent of the coupling effects of different temperatures and pressures. The formed hydrogen radicals could promote subsequent decompositions of HMX. Subsequent decompositions were very sensitive to the pressure at low temperatures (534 and 608 K), while the temperature became the foremost factor that affected the decomposition at a high temperature (873 K) instead of the pressure. Our study may provide a new insight into understanding the coupling effects of the temperature and pressure on the initiation decomposition mechanisms of nitramine explosives.

Molecular dynamics simulations of void defects in the energetic material HMX.

PubMed

Duan, Xiao Hui; Li, Wen Peng; Pei, Chong Hua; Zhou, Xiao Qing

2013-09-01

A molecular dynamics (MD) simulation was carried out to characterize the dynamic evolution of void defects in crystalline octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine (HMX). Different models were constructed with the same concentration of vacancies (10 %) to discuss the size effects of void. Energetic ground state properties were determined by annealing simulations. The void formation energy per molecule removed was found to be 55-63 kcal/mol(-1), and the average binding energy per molecule was between 32 and 34 kcal/mol(-1) according to the change in void size. Voids with larger size had lower formation energy. Local binding energies for molecules directly on the void surface decreased greatly compared to those in defect-free lattice, and then gradually increased until the distance away from the void surface was around 10 Å. Analysis of 1 ns MD simulations revealed that the larger the void size, the easier is void collapse. Mean square displacements (MSDs) showed that HMX molecules that had collapsed into void present liquid structure characteristics. Four unique low-energy conformers were found for HMX molecules in void: two whose conformational geometries corresponded closely to those found in HMX polymorphs and two, additional, lower energy conformers that were not seen in the crystalline phases. The ratio of different conformers changed with the simulated temperature, in that the ratio of α conformer increased with the increase in temperature.

Anaerobic transformation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by ovine rumen microorganisms.

PubMed

Perumbakkam, Sudeep; Craig, A M

2012-01-01

Explosives such as octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) provide a challenge in terms of bioremediation. In the present study, sheep rumen was studied for its potential to detoxify HMX using analytical chemistry and molecular microbial ecology tools. Results indicated significant loss (p < 0.05) of HMX at 8 h post-incubation and complete disappearance of the parent molecule after 16 h. Qualitative LC-MS/MS analysis provided evidence for the formation of 1-NO-HMX and MEDINA metabolites. A total of 1006 16S rRNA-V3 clones were sequenced and the Classifier tool of the RDPII database was used to sort the sequences at their phylum level. Most sequences were associated with either the phylum Bacteroidetes or Firmicutes. Significant differences at the phylum level (p < 0.001) were found between 0 h and 8 h HMX treatments. Using LibCompare analysis, 8 h HMX treatment showed enrichment of clones (p < 0.01) belonging to the genus Prevotella. From these results, it could be concluded that members of the genus Prevotella are enriched in the rumen and are capable of detoxifying HMX. Copyright © 2012 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

TNT, RDX, and HMX decrease earthworm (Eisenia andrei) life-cycle responses in a spiked natural forest soil.

PubMed

Robidoux, P Y; Hawari, J; Bardai, G; Paquet, L; Ampleman, G; Thiboutot, S; Sunahara, G I

2002-11-01

Sublethal and chronic toxicities of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) on earthworm Eisenia andrei in a sandy forest soil were assessed. Various reproduction parameters of fecundity (total and hatched number of cocoons, number of juveniles, and their biomass) were significantly decreased by TNT (> or = 58.8 +/- 5.1 mg/kg dry soil), RDX (> or = 46.7 +/- 2.6 mg/kg), and HMX (> or = 15.6 +/- 4.6 mg/kg). These effects occurred at much lower concentrations than those reported earlier using artificial soil preparations. Growth of adults was significantly decreased in the TNT-spiked natural soils at 136.2 +/- 25.6 mg/kg dry soil, the highest concentration having no significant mortality. In contrast, survival and growth were not significantly reduced at relatively high measured concentrations of RDX (167.3 mg/kg) and HMX (711.0 mg/kg). Although TNT, RDX, and HMX share a common life-cycle response ( i.e., decreased juvenile counts), a number of differences related to other reproduction parameters (e.g., productivity of cocoons) was observed. These results indicate that the tested explosives do not support a common mechanism of toxicity, at least in the earthworm, probably due to differences in their physical-chemical properties as well as metabolites formed during exposure.

Predicting elastic properties of β-HMX from first-principles calculations.

PubMed

Peng, Qing; Rahul; Wang, Guangyu; Liu, Gui-Rong; Grimme, Stefan; De, Suvranu

2015-05-07

We investigate the performance of van der Waals (vdW) functions in predicting the elastic constants of β cyclotetramethylene tetranitramine (HMX) energetic molecular crystals using density functional theory (DFT) calculations. We confirm that the accuracy of the elastic constants is significantly improved using the vdW corrections with environment-dependent C6 together with PBE and revised PBE exchange-correlation functionals. The elastic constants obtained using PBE-D3(0) calculations yield the most accurate mechanical response of β-HMX when compared with experimental stress-strain data. Our results suggest that PBE-D3 calculations are reliable in predicting the elastic constants of this material.

Physico-chemical measurements of CL-20 for environmental applications. Comparison with RDX and HMX.

PubMed

Monteil-Rivera, Fanny; Paquet, Louise; Deschamps, Stéphane; Balakrishnan, Vimal K; Beaulieu, Chantale; Hawari, Jalal

2004-01-30

CL-20 is a polycyclic energetic nitramine, which may soon replace the monocyclic nitramines RDX and HMX, because of its superior explosive performance. Therefore, to predict its environmental fate, analytical and physico-chemical data must be made available. An HPLC technique was thus developed to measure CL-20 in soil samples based on the US Environmental Protection Agency method 8330. We found that the soil water content and aging (21 days) had no effect on the recoveries (>92%) of CL-20, provided that the extracts were kept acidic (pH 3). The aqueous solubility of CL-20 was poor (3.6 mg l(-1) at 25 degrees C) and increased with temperature to reach 18.5 mg l(-1) at 60 degrees C. The octanol-water partition coefficient of CL-20 (log KOW = 1.92) was higher than that of RDX (log KOW = 0.90) and HMX (log KOW = 0.16), indicating its higher affinity to organic matter. Finally, CL-20 was found to decompose in non-acidified water upon contact with glass containers to give NO2- (2 equiv.), N2O (2 equiv.), and HCOO- (2 equiv.). The experimental findings suggest that CL-20 should be less persistent in the environment than RDX and HMX.

Dissolution of explosive compounds TNT, RDX, and HMX under continuous flow conditions.

PubMed

Wang, Chao; Fuller, Mark E; Schaefer, Charles; Caplan, Jeffrey L; Jin, Yan

2012-05-30

2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are common contaminants around active military firing ranges. Dissolution of these compounds is usually the first step prior to their spreading in subsurface environments. Nevertheless, dissolution of individual TNT, RDX, and HMX under continuous flow conditions has not been well investigated. This study applied spectral confocal microscopy to observe and quantify the dissolution of TNT, RDX, and HMX (<100 μm crystals) in micromodel channels. Dissolution models were developed to describe the changes of their radii, surface areas, volumes, and specific surface areas as a function of time. Results indicated that a model incorporating a resistance term that accounts for the surface area in direct contact with the channel surfaces (and hence, was not exposed to the flowing water) described the dissolution processes well. The model without the resistance term, however, could not capture the observed data at the late stage of TNT dissolution. The model-fitted mass transfer coefficients were in agreement with the previous reports. The study highlights the importance of including the resistance term in the dissolution model and illustrates the utility of the newly developed spectral imaging method for quantification of mass transfer of TNT, RDX, and HMX. Copyright © 2012 Elsevier B.V. All rights reserved.

Food avoidance behavior to dietary octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) exposure in the northern bobwhite (Colinusvirginianus).

PubMed

Johnson, Mark S; Gogal, Robert M; Larsen, Calvert T

2005-08-13

High-melting explosive (HMX; octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) is a widely utilized explosive component of munitions used by the military. Consequently, production and use through testing and training at military installations has resulted in deposition of HMX in soil. Since these areas are often used by birds, the oral toxicity of HMX exposure to northern bobwhite (Colinus virginianus) was evaluated. Attempts to determine the acute lethal dose were unsuccessful. Initially, 8 birds (1 male/1 female per dose group) were orally dosed at levels ranging from 125 to 2125 mg HMX/kg body weight. A single death at the midrange resulted in subsequent trials of oral doses up to 10,760 mg/kg body weight. Only a single death occurred at 7173 mg/kg. A subsequent 28-d feeding study was then conducted to evaluate the potential for toxicity resulting from repetitive oral exposures. Northern bobwhite were exposed to concentrations of HMX in feed of either 10000, 1000, 100, or 0 mg/kg. These exposures resulted in a clear concentration-related reduction in feed consumption and body mass. Reductions in egg production in females were correlated with changes in body mass and feed consumption. Other physiological indicators were consistent with a considerable reduction in feed intake. These results suggest that HMX concentration is responsible for intense feed aversion behavior and thus not likely a factor that would appreciably contribute to risk for wild birds at military ranges.

THERMAL COOK-OFF EXPERIMENTS OF THE HMX BASED HIGH EXPLOSIVE LX-04 TO CHARACTERIZE VIOLENCE WITH VARYING CONFINEMENT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garcia, F; Vandersall, K S; Forbes, J W

Thermal cook-off experiments were carried out using LX-04 explosive (85% HMX and 15% Viton by weight) with different levels of confinement to characterize the effect of confinement on the reaction violence. These experiments involved heating a porous LX-04 sample in a stainless steel container with varying container end plate thickness and assembly bolt diameter to control overall confinement. As expected, detonation did not occur and reducing the overall confinement lowered the reaction violence. This is consistent with modeling results that predict that a lower confinement will act to lower the cook-off pressure and thus the overall burn rate which lowersmore » the overall violence. These results suggest that controlling the overall system confinement can modify the relative safety in a given scenario.« less

Leaching of contaminated leaves following uptake and phytoremediation of RDX, HMX, and TNT by poplar.

PubMed

Yoon, Jong Moon; Van Aken, Benoit; Schnoor, Jerald L

2006-01-01

The uptake and fate of 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by hybrid poplars in hydroponic systems were compared and exposed leaves were leached with water to simulate potential exposure pathways from groundwater in the field. TNT was removed from solution more quickly than nitramine explosives. Most of radioactivity remained in root tissues for 14C-TNT, but in leaves for 14C-RDX and 14C-HMX. Radiolabel recovery for TNT and HMX was over 94%, but that of RDX decreased over time, suggesting a loss of volatile products. A considerable fraction (45.5%) of radioactivity taken up by whole plants exposed to 14C-HMX was released into deionized water, mostly as parent compound after 5 d of leaching. About a quarter (24.0%) and 1.2% were leached for RDX and TNT, respectively, mostly as transformed products. Leached radioactivity from roots was insignificant in all cases (< 2%). This is the first report in which small amounts of transformation products of RDX leach from dried leaves following uptake by poplars. Such behavior for HMX was reported earlier and is reconfirmed here. All three compounds differ substantially in their fate and transport during the leaching process.

Effects of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) exposure on reproduction and hatchling development in Northern bobwhite quail.

PubMed

Brunjes, Kristina J; Severt, Scott A; Liu, Jun; Pan, Xiaoping; Brausch, John; Cox, Stephen A; Cobb, George P; McMurry, Scott T; Kendall, Ronald J; Smith, Philip N

2007-04-15

Adult Northern bobwhite quail (Colinus virginianus) were exposed via food to octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), an energetic compound found in soils at military training installations. Depuration of HMX into eggs was examined in an initial study, and effects on egg production, hatching, growth, development, and survival of chicks were examined in a follow-up study. HMX was readily and rapidly transferred from female quail into eggs. Marked weight loss was observed in quail exposed to 125 and 250 mg/kg HMX in food, likely due to reductions in food intake rather than a toxic mechanism. In the second study, significant alterations in body mass occurred among quail at concentrations >52.5 +/- 9.3 mg/kg but not at 12.3 +/- 1.1 mg/kg in food. Treatment-related reductions in food consumption and decreases in egg laying rates were observed. No HMX-related effects were found in chick growth or survival. Quail inhabiting HMX-contaminated sites could possibly be exposed to HMX and therefore deposition of HMX into eggs is also possible. However, results of these studies further suggest that the potential for reproductive toxicity of HMX to birds is low.

Theoretical insights into the stabilities, detonation performance, and electrostatic potentials of cocrystals containing α- or β-HMX and TATB, FOX-7, NTO, or DMF in various molar ratios.

PubMed

Song, Ken-Peng; Ren, Fu-de; Zhang, Shu-Hai; Shi, Wen-Jing

2016-10-01

A molecular dynamics method was employed to study the binding energies associated with the cocrystallization (at selected crystal planes) of either 1,3,5-triamino-2,4,6-trinitro-benzene (TATB), 1,1-diamino-2,2-dinitroethylene, 3-nitro-1,2,4-triazol-5-one (TATB, FOX-7, and NTO, respectively, all of which are explosives), or N,N-dimethylformamide (DMF, a nonenergetic solvent) in various molar ratios with 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane in its α and β conformations (α-HMX and β-HMX, respectively). The results showed that the cocrystals with low molar ratios (2:1, 1:1, 1:2, and 1:3) were the most stable. The binding energies of HMX/NTO and HMX/DMF were larger than those of HMX/TATB and HMX/FOX-7. According to the calculated stabilities, HMX prefers to adopt its α form in HMX/TATB and its β form in HMX/NTO, whereas the two forms coexist in HMX/FOX-7. For HMX/TATB, HMX/NTO, and α-HMX/FOX-7, increasing the proportion of the cocrystal component with the highest detonation heat (HMX in the first two cases, FOX-7 in the latter) increases the detonation heat, velocity, and pressure of the cocrystal. However, increasing the proportion of the component with the highest detonation heat in β-HMX/FOX-7 and γ-CL-20/FOX-7 increases the detonation heat of the cocrystal but decreases its detonation velocity. An investigation of the surface electrostatic potential revealed how the sensitivity changes upon cocrystal formation. Graphical Abstract Surface electrostatic potential of HMX/TATB.

Surface polarity of beta-HMX crystal and the related adhesive forces with Estane binder.

PubMed

Yang, Lu

2008-12-02

Here I present the results on the study of surface properties of beta-HMX crystal utilizing molecular dynamics simulations. The surface polarity of three principal crystal surfaces, (011), (010), and (110), is investigated by measuring the water contact angles. The calculated contact angles are in excellent agreement with the values measured by experiment and show that the surface polarity of three crystal surfaces are different. The free energies and forces of detaching an Estane chain (with and without surrounding nitroplasticizer molecules) from the three principal crystal surfaces are also calculated using the umbrella sampling method. I find that the force for Estane detachment increases with the increasing HMX surface polarity. In addition, my results show that the nitroplasticizer also plays an important role in the adhesion between Estane and HMX surfaces.

A molecular dynamics simulation of solvent effects on the crystal morphology of HMX.

PubMed

Duan, Xiaohui; Wei, Chunxue; Liu, Yonggang; Pei, Chonghua

2010-02-15

The solvent has a large effect on the crystal morphology of the organic explosive compound octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, C(4)H(8)N(8)O(8)). The attachment energy calculations predict a growth morphology in vacuum dominated by (020), (011), (102 ), (111 ) and (100) crystal forms. Molecular dynamics simulations are performed for these crystal faces of HMX in contact with acetone solvent. A corrected attachment energy model, accounting for the surface chemistry and the associated topography (step structure) of the habit crystal plane, is applied to predict the morphological importance of a crystal surface in solvent. From the solvent-effected attachment energy calculations it follows that the (100) face becomes morphologically more important compared with that in vacuum, while the (020) and (102 ) are not visible at all. This agrees well with the observed experimental HMX morphology grown from the acetone solution.

Nanoindentation of HMX and Idoxuridine to Determine Mechanical Similarity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burch, Alexandra; Yeager, John; Bahr, David

Assessing the mechanical behavior (elastic properties, plastic properties, and fracture phenomena) of molecular crystals is often complicated by the difficulty in preparing samples. Pharmaceuticals and energetic materials in particular are often used in composite structures or tablets, where the individual grains can strongly impact the solid behavior. Nanoindentation is a convenient method to experimentally assess these properties, and it is used here to demonstrate the similarity in the mechanical properties of two distinct systems: individual crystals of the explosive cyclotetramethylene tetranitramine (HMX) and the pharmaceutical idoxuridine were tested in their as-precipitated state, and the effective average modulus and hardness (whichmore » can be orientation dependent) were determined. Both exhibit a hardness of 1.0 GPa, with an effective reduced modulus of 25 and 23 GPa for the HMX and idoxuridine, respectively. They also exhibit similar yield point behavior. This indicates idoxuridine may be a suitable mechanical surrogate (or “mock”) for HMX. While the methodology to assess elastic and plastic properties was relatively insensitive to specific crystal orientation (i.e., a uniform distribution in properties was observed for all random crystals tested), the indentation-induced fracture properties appear to be much more sensitive to tip-crystal orientation, and an unloading slope analysis is used to demonstrate the need for further refinement in relating toughness to orientation in these materials with relatively complex slip systems and crystal structures. View Full-Text« less

Nanoindentation of HMX and Idoxuridine to Determine Mechanical Similarity

DOE PAGES

Burch, Alexandra; Yeager, John; Bahr, David

2017-11-01

Assessing the mechanical behavior (elastic properties, plastic properties, and fracture phenomena) of molecular crystals is often complicated by the difficulty in preparing samples. Pharmaceuticals and energetic materials in particular are often used in composite structures or tablets, where the individual grains can strongly impact the solid behavior. Nanoindentation is a convenient method to experimentally assess these properties, and it is used here to demonstrate the similarity in the mechanical properties of two distinct systems: individual crystals of the explosive cyclotetramethylene tetranitramine (HMX) and the pharmaceutical idoxuridine were tested in their as-precipitated state, and the effective average modulus and hardness (whichmore » can be orientation dependent) were determined. Both exhibit a hardness of 1.0 GPa, with an effective reduced modulus of 25 and 23 GPa for the HMX and idoxuridine, respectively. They also exhibit similar yield point behavior. This indicates idoxuridine may be a suitable mechanical surrogate (or “mock”) for HMX. While the methodology to assess elastic and plastic properties was relatively insensitive to specific crystal orientation (i.e., a uniform distribution in properties was observed for all random crystals tested), the indentation-induced fracture properties appear to be much more sensitive to tip-crystal orientation, and an unloading slope analysis is used to demonstrate the need for further refinement in relating toughness to orientation in these materials with relatively complex slip systems and crystal structures. View Full-Text« less

Ignition and growth reactive flow modeling of recent HMX/TATB detonation experiments

NASA Astrophysics Data System (ADS)

Tarver, Craig M.

2017-01-01

Two experimental studies in which faster HMX detonation waves produced oblique detonation waves in adjoining slower detonating TATB charges were modeled using the Ignition and Growth (I&G) reactive flow detonation model parameters for PBX 9501 (95% HMX / 2.5% Estane / 2.5% BDNPA/F) and PBX 9502 (95% TATB / 5% Kel-F binder). Matignon et al. used X1 explosive (96% HMX / 4% binder) to drive an oblique detonation wave into an attached charge of T2 explosive (97% TATB / 3% binder). The flow angles were measured in the T2 shock initiation region and in steady T2 detonation. Anderson et al. used detonating PBX 9501 slabs of various thicknesses ranging from 0.56 mm to 2.5 mm to create oblique detonation waves in 8 mm thick slabs of PBX 9502. Several diagnostics were employed to: photograph the waves; measure detonation velocities and flow angles; and determine the output of the PBX 9501 slabs, the PBX 9502 slabs, and the "initiation regions" using LiF windows and PDV probes.

Hot Spots from Generated Defects in HMX Crystals

NASA Astrophysics Data System (ADS)

Sorensen, Christian; Cummock, Nicholas; O'Grady, Caitlin; Gunduz, I. Emre; Son, Steven

2017-06-01

There are several hot spot initiation mechanisms that have been proposed. However, direct observation of shock or impact compression of these mechanisms at macroscopic scale in explosives is difficult. Phase contrast imaging (PCI) may be applied to these systems. Here, high-speed video was used to record optical spectrum and for x-ray Phase Contrast Imaging (PCI) of shockwave interaction with low defect HMX crystals and crystals with engineered defects. Additionally, multiple crystals were arranged and observed under shock loading with PCI and optical high-speed video. Sample preparation techniques for generating voids and other engineered defects will be discussed. These methods include drilled holes and laser machined samples. Insight into hot spot mechanisms was obtained. Funding from ONR's PC@Xtreme MURI.

Investigation of the kinetics and microscopic mechanism of solid-solid phase transitions in HMX

NASA Astrophysics Data System (ADS)

Bowlan, Pamela; Suvorova, Natalya; Oschwald, Dave; Bowlan, John; Rector, Kirk; Henson, Bryan; Smilowitz, Laura

2017-06-01

Although studied intensely in the 2000's, a number of important questions about solid-solid phase transitions in the energetic organic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) remain. The mechanism by which one of the four isomorphs, known as δ, γ, α and β, transforms into another, and the conditions (i.e. temperature and pressure) and rates at which these transitions take place are still not fully known, yet important for predicting and controlling energy release phenomena in HMX such as detonation. The theory of virtual melting, by which a liquid forms at the interface of a nucleation site, is necessary to explain transformations between certain of the four different phases of HMX, such as the β to δ transition. However the existence of this disordered intermediate state has never been directly proven due to the need for both spatial (<µm), temporal (the lifetime of the transient melt state is unknown) and structural information. Also, while the β to δ transition was more thoroughly studied, less is known about the other 10 possible phase transitions. We will report on our study of phase transitions in HMX using X-ray diffraction and confocal Raman and near-field infrared microscopy.

Ignition Prediction of Pressed HMX based on Hotspot Analysis Under Shock Pulse Loading

NASA Astrophysics Data System (ADS)

Kim, Seokpum; Miller, Christopher; Horie, Yasuyuki; Molek, Christopher; Welle, Eric; Zhou, Min

The ignition behavior of pressed HMX under shock pulse loading with a flyer is analyzed using a cohesive finite element method (CFEM) which accounts for large deformation, microcracking, frictional heating, and thermal conduction. The simulations account for the controlled loading of thin-flyer shock experiments with flyer velocities between 1.7 and 4.0 km/s. The study focuses on the computational prediction of ignition threshold using James criterion which involves loading intensity and energy imparted to the material. The predicted thresholds are in good agreement with measurements from shock experiments. In particular, it is found that grain size significantly affects the ignition sensitivity of the materials, with smaller sizes leading to lower energy thresholds required for ignition. In addition, significant stress attenuation is observed in high intensity pulse loading as compared to low intensity pulse loading, which affects density of hotspot distribution. The microstructure-performance relations obtained can be used to design explosives with tailored attributes and safety envelopes.

Evaluation of Aluminum Participation in the Development of Reactive Waves in Shock Compressed HMX

NASA Astrophysics Data System (ADS)

Pahl, R. J.; Trott, W. M.; Snedigar, S.; Castañeda, J. N.

2006-07-01

A series of gas gun tests has been performed to examine contributions to energy release from micron-sized and nanometric aluminum powder added to sieved (212-300μm) HMX. In the absence of added metal, 4-mm-thick, low-density (64-68% of theoretical maximum density) pressings of the sieved HMX respond to modest shock loading by developing distinctive reactive waves that exhibit both temporal and mesoscale spatial fluctuations. Parallel tests have been performed on samples containing 10% (by mass) aluminum in two particle sizes: 2-μm and 123-nm mean particle diameter, respectively. The finely dispersed aluminum initially suppresses wave growth from HMX reactions; however, after a visible induction period, the added metal drives rapid increases in the transmitted wave particle velocity. Wave profile variations as a function of the aluminum particle diameter are discussed.

Phytoremediation of explosives (TNT, RDX, HMX) by wild-type and transgenic plants.

PubMed

Panz, Katarzyna; Miksch, Korneliusz

2012-12-30

The large-scale production and processing of munitions has led to vast environmental pollution by the compounds TNT(2,4,6-trinitrotoluene), RDX(hexahydro-1,3,5-trinitro-1,3,5-triazine) and HMX(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine). Explosives contain these toxic and mutagenic xenobiotics, which are stable in the environment and recalcitrant to remediation. Certain technologies used thus far (incineration, adsorption, advanced oxidations processes, chemical reduction etc.) have not only been very expensive but also caused additional environmental problems. During recent decades, the most popular technologies have been biotechnological methods, such as phytoremediation, which is relatively cheap, environmentally friendly, and a highly accepted solution by society. The most promising of these technologies is the usage of genetically modified plants, which combines the ability of bacterial genes to detoxify compounds with the phytoremediation benefits of plants. This paper is a review related to the latest and most important achievements in the field of phytoremediation of water and soil contaminated with TNT, RDX and HMX. Copyright © 2012 Elsevier Ltd. All rights reserved.

Peierls–Nabarro stresses of dislocations in monoclinic cyclotetramethylene tetranitramine (β-HMX)

NASA Astrophysics Data System (ADS)

Pal, Anirban; Picu, Catalin R.

2018-06-01

HMX (cyclotetramethylene tetranitramine) is an energetic material which releases substantial amounts of energy upon decomposition. The role of defects and deformation in causing reaction initiation was discussed in the literature but remains insufficiently understood. In this work, we identify, using computational methods, the slip systems which are potentially active in β-HMX and rank them in terms of their propensity for slip. To this end, we develop first a tentative ranking based on the degree of steric hindrance associated with slip. This is quantified using a geometric analog of the γ-surface. Further, we use atomistic models to compute the Peierls–Nabarro (PN) stress for the motion of dislocations in the slip systems with smallest degree of steric hindrance. A complex mechanical behavior is observed, including strong slip asymmetry, twinning and cleavage. The five systems with the lowest PN stress are (011)[01\\bar{1}], (011)[100], (101)[010], (101)[10\\bar{1}] and (021)[100]. We conclude that the material has enough slip systems available for supporting a generalized state of plastic strain provided the twinning system (101)[10\\bar{1}] is taken into consideration and that the resolved shear stress is at least 260 MPa.

Contribution of hydrolysis in the abiotic attenuation of RDX and HMX in coastal waters.

PubMed

Monteil-Rivera, Fanny; Paquet, Louise; Giroux, Romain; Hawari, Jalal

2008-01-01

Sinking of military ships, dumping of munitions during the two World Wars, and military training have resulted in the undersea deposition of numerous unexploded ordnances (UXOs). Leaching of energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from these UXOs may cause adverse ecological effects so that the long-term fate of these chemicals in the sea should be known. The present study assesses the contribution of alkaline hydrolysis into the natural attenuation of RDX and HMX in coastal waters. Alkaline hydrolysis rates were shown to be unaffected by the presence of sodium chloride, the most common component in marine waters. Kinetic parameters (E(a), ln A, k(2)) quantified for the alkaline hydrolysis of RDX and HMX in deionized water (30-50 degrees C, pH 10-12) agreed relatively well with abiotic degradation rates determined in sterilized natural coastal waters (50 and 60 degrees C, variable salinity) even if the latter were generally slightly faster than the former. Furthermore, similar products (HCHO, NO(2)(-), O(2)NNHCH(2)NHCHO) were obtained on alkaline hydrolysis in deionized water and abiotic degradation in coastal waters. These two findings suggested that degradation of nitramines in sterilized natural coastal waters, away from light, was mainly governed by alkaline hydrolysis. Kinetic calculations using the present parameters showed that alkaline hydrolysis of RDX and HMX in marine waters at 10 degrees C would respectively take 112 +/- 10 and 2408 +/- 217 yr to be completed (99.0%). We concluded that under natural conditions hydrolysis should not contribute significantly to the natural attenuation of HMX in coastal waters whereas it could play an active role in the natural attenuation of RDX.

Observation and modeling of deflagration-to-detonation (DDT) transition in low-density HMX

NASA Astrophysics Data System (ADS)

Tringe, Joseph; Vandersall, Kevin; Reaugh, Jack; Levie, Harold; Henson, Bryan; Smilowitz, Laura; Parker, Gary

2015-06-01

We employ simultaneous flash x-ray radiography and streak imaging, together with a multi-phase finite element model, to understand deflagration-to-detonation transition (DDT) phenomena in low-density (~ 1.2 gm/cm3) powder of the explosive cyclotetramethylene-tetranitramine (HMX). HMX powder was lightly hand-tamped in a 12.7 mm diameter column, relatively lightly-confined in an optically-transparent polycarbonate cylinder with wall thickness 25.4 mm. We observe apparent compaction of the powder in advance of the detonation transition, both by x-ray contrast and by the motion of small steel spheres pre-emplaced throughout the length of explosive. High-speed imaging along the explosive cylinder length provides a temporally continuous record of the transition that is correlated with the high-resolution x-ray image record. Preliminary simulation of these experiments with the HERMES model implemented in the ALE3D code enables improved understanding of the explosive particle burning, compaction and detonation phenomena which are implied by the observed reaction rate and transition location within the cylinder. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Method for synthesizing HMX

DOEpatents

McGuire, Raymond R.; Coon, Clifford L.; Harrar, Jackson E.; Pearson, Richard K.

1984-01-01

A method and apparatus for electrochemically synthesizing N.sub.2 O.sub.5 cludes oxidizing a solution of N.sub.2 O.sub.4 /HNO.sub.3 at an anode, while maintaining a controlled potential between the N.sub.2 O.sub.4 /HNO.sub.3 solution and the anode. A potential of about 1.35 to 2.0 V vs. SCE is preferred, while a potential of about 1.80 V vs. SCE is most preferred. Thereafter, the N.sub.2 O.sub.5 is reacted with either 1.5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) or 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclooctane (TAT) to form cyclotetramethylenetetraamine (HMX).

Structures, mechanical properties, equations of state, and electronic properties of β-HMX under hydrostatic pressures: a DFT-D2 study.

PubMed

Peng, Qing; Rahul; Wang, Guangyu; Liu, Gui-Rong; De, Suvranu

2014-10-07

We report the hydrostatic compression studies of the β-polymorph of a cyclotetramethylene tetranitramine (HMX) energetic molecular crystal using DFT-D2, a first-principles calculation based on density functional theory (DFT) with van der Waals (vdW) corrections. The molecular structure, mechanical properties, electronic properties, and equations of state of β-HMX are investigated. For the first time, we predict the elastic constants of β-HMX using DFT-D2 studies. The equations of state under hydrostatic compression are studied for pressures up to 100 GPa. We found that the N-N bonds along the minor axis are responsible for the sensitivity of β-HMX. The analysis of the charge distribution shows that the electronic charge is transferred from hydrogen atoms to nitro groups with the amount of 0.131 and 0.064e for the nitro groups along the minor axis and major axis, respectively, when pressure changes from 0 GPa to 100 GPa. The electronic energy band gap changes from direct at a pressure of 0 GPa to indirect at a pressure of 50 GPa and higher. The band gap decreases with respect to an increase in pressure, implying that the impact sensitivity increases with compression. Our study suggests that the van der Waals interactions are critically important in modeling the mechanical properties of this molecular crystal.

Studying multiply shocked states in HMX and TATB based explosives with a gas gun ring up geometry

NASA Astrophysics Data System (ADS)

Ferguson, James; Finnegan, Simon; Millett, Jeremy; Goff, Michael

2017-06-01

A series of ring up shots investigating partially reacted and multiply shocked states in both HMX and TATB based explosives are reported on. Results of experiments using PCTFE and LiF in place of the explosives are also described. The experiments were performed using 50 mm diameter bore and 70 mm diameter bore single stage gas guns. By locating the target between a high impedance copper flyer and sapphire window, shocks of increasing magnitude are reflected into the target at each interface. The particle velocity at the target-window interface was measured using multiple points of HetV reflected from an 800 nm layer of gold sputtered onto the sapphire. The stress state at the target-flyer interface were observed using manganin gauges. A range of different input pressures were investigated, these were picked to either allow a comparison to double shock and particle velocity work, or to provide the maximum number of rings within the one dimensional time. For the inert shots input pressures matched the explosive shots.

Abundance and diversity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)-metabolizing bacteria in UXO-contaminated marine sediments.

PubMed

Zhao, Jian-Shen; Manno, Dominic; Hawari, Jalal

2007-03-01

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is a toxic explosive known to be resistant to biodegradation. In this study, we found that sediment collected from two unexploded ordnance (UXO) disposal sites (UXO-3, UXO-5) and one nearby reference site (midref) in Hawaii contained anaerobic bacteria capable of removing HMX. Two groups of HMX-removing bacteria were found in UXO-5: group I contained aerotolerant anaerobes and microaerophiles, and group II contained facultative anaerobes. In UXO-3 and midref sediments, HMX-metabolizing bacteria were strictly anaerobic (group III and group IV). Using 16S rRNA sequencing, group I was assigned to a novel phylogenetic cluster of Clostridiales, and groups II and III were related to Paenibacillus and Tepidibacter of Firmicutes, respectively. Group IV bacteria were identified as Desulfovibrio of Deltaproteobacteria. Using [UL-(14)C]-HMX, group IV isolates were found to mineralize HMX (26.8% in 308 d) as determined by liberated (14)CO(2), but negligible mineralization was observed in groups I-III. Resting cells of isolates metabolized HMX to N(2)O and HCHO via the intermediary formation of 1-nitroso-octahydro-3,5,7-trinitro-1,3,5,7-tetrazocine together with methylenedinitramine. These experimental findings suggest that HMX biotransformation occurred either via initial denitration followed by ring cleavage or via reduction of one or more of the N-NO(2) group(s) to the corresponding N-NO bond(s) prior to ring cleavage.

A distal 594 bp ECR specifies Hmx1 expression in pinna and lateral facial morphogenesis and is regulated by the Hox-Pbx-Meis complex

DOE PAGES

Rosin, Jessica M.; Li, Wenjie; Cox, Liza L.; ...

2016-07-19

Hmx1 encodes a homeodomain transcription factor expressed in the developing lateral craniofacial mesenchyme, retina and sensory ganglia. Mutation or mis-regulation of Hmx1 underlies malformations of the eye and external ear in multiple species. Deletion or insertional duplication of an evolutionarily conserved region (ECR) downstream of Hmx1 has recently been described in rat and cow, respectively. Here, we demonstrate that the impact of Hmx1 loss is greater than previously appreciated, with a variety of lateral cranioskeletal defects, auriculofacial nerve deficits, and duplication of the caudal region of the external ear. Using a transgenic approach, we demonstrate that a 594 bp sequencemore » encompassing the ECR recapitulates specific aspects of the endogenous Hmx1 lateral facial expression pattern. Moreover, we show that Hoxa2, Meis and Pbx proteins act cooperatively on the ECR, via a core 32 bp sequence, to regulate Hmx1 expression. In conclusion, these studies highlight the conserved role for Hmx1 in BA2-derived tissues and provide an entry point for improved understanding of the causes of the frequent lateral facial birth defects in humans.« less

A distal 594 bp ECR specifies Hmx1 expression in pinna and lateral facial morphogenesis and is regulated by the Hox-Pbx-Meis complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosin, Jessica M.; Li, Wenjie; Cox, Liza L.

Hmx1 encodes a homeodomain transcription factor expressed in the developing lateral craniofacial mesenchyme, retina and sensory ganglia. Mutation or mis-regulation of Hmx1 underlies malformations of the eye and external ear in multiple species. Deletion or insertional duplication of an evolutionarily conserved region (ECR) downstream of Hmx1 has recently been described in rat and cow, respectively. Here, we demonstrate that the impact of Hmx1 loss is greater than previously appreciated, with a variety of lateral cranioskeletal defects, auriculofacial nerve deficits, and duplication of the caudal region of the external ear. Using a transgenic approach, we demonstrate that a 594 bp sequencemore » encompassing the ECR recapitulates specific aspects of the endogenous Hmx1 lateral facial expression pattern. Moreover, we show that Hoxa2, Meis and Pbx proteins act cooperatively on the ECR, via a core 32 bp sequence, to regulate Hmx1 expression. In conclusion, these studies highlight the conserved role for Hmx1 in BA2-derived tissues and provide an entry point for improved understanding of the causes of the frequent lateral facial birth defects in humans.« less

Role of soil organic carbon and colloids in sorption and transport of TNT, RDX and HMX in training range soils.

PubMed

Sharma, Prasesh; Mayes, Melanie A; Tang, Guoping

2013-08-01

Contamination of soils and groundwater by munitions compounds (MCs) is of significant concern at many U.S. Department of Defense sites. Soils were collected from operational training ranges in Maryland (APG), Massachusetts (MMR-B and MMR-E) and Washington (JBLM) and sorption and transport studies were conducted to investigate the effects of soil organic carbon (OC) and textural clay content on fate of dissolved MCs (TNT, RDX, HMX). Sorption experiments showed higher distribution coefficients [TNT:42-68 L kg(-1), RDX:6.9-8.7 L kg(-1) and HMX:2.6-3.1 L kg(-1)] in OC rich soils (JBLM, MMR-E) compared to clay rich soils (MMR-B and APG) [TNT:19-21 L kg(-1), RDX:2.5-3.4 L kg(-1), HMX:0.9-1.2 L kg(-1)]. In column experiments, breakthrough of MCs was faster in MMR-B and APG compared to MMR-E and JBLM soils. Among TNT, RDX and HMX, breakthrough was fastest for RDX followed by HMX and TNT for all columns. Defining the colloidal fraction as the difference between unfiltered samples and samples filtered with a 3 kDa filter, ~36%, ~15% and ~9% of TNT, RDX and HMX were found in the colloidal fraction in the solutions from sorption experiments, and around 20% of TNT in the effluent from the transport experiments. Results demonstrate that OC rich soils may enhance sorption and delay transport of TNT, RDX and HMX compared to clay-rich soils. Further, transport of TNT may be associated with soil colloid mobilization. Copyright © 2013 Elsevier Ltd. All rights reserved.

Common explosives (TNT, RDX, HMX) and their fate in the environment: Emphasizing bioremediation.

PubMed

Chatterjee, Soumya; Deb, Utsab; Datta, Sibnarayan; Walther, Clemens; Gupta, Dharmendra K

2017-10-01

Explosive materials are energetic substances, when released into the environment, contaminate by posing toxic hazards to environment and biota. Throughout the world, soils are contaminated by such contaminants either due to manufacturing operations, military activities, conflicts of different levels, open burning/open detonation (OB/OD), dumping of munitions etc. Among different forms of chemical explosives, 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX) are most common. These explosives are highly toxic as USEPA has recommended restrictions for lifetime contact through drinking water. Although, there are several utilitarian aspects in anthropogenic activities, however, effective remediation of explosives is very important. This review article emphasizes the details of appropriate practices to ameliorate the contamination. Critical evaluation has also been made to encompass the recent knowledge and advancement about bioremediation and phytoremediation of explosives (especially TNT, RDX and HMX) along with the molecular mechanisms of biodegradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Combustion modeling of RDX, HMX and GAP with detailed kinetics

NASA Astrophysics Data System (ADS)

Davidson, Jeffrey Edward

A one-dimensional, steady-state numerical model of the combustion of homogeneous solid propellant has been developed. The combustion processes is modeled in three regions: solid, two-phase (liquid and gas) and gas. Conservation of energy and mass equations are solved in the two-phase and gas regions and the eigenvalue of the system (the mass burning rate) is converged by matching the heat flux at the interface of these two regions. The chemical reactions of the system are modeled using a global kinetic mechanism in the two-phase region and an elementary kinetic mechanism in the gas region. The model has been applied to RDX, HMX and GAP. There is very reasonable agreement between experimental data and model predictions for burning rate, temperature sensitivity, surface temperature, adiabatic flame temperature, species concentration profiles and melt-layer thickness. Many of the similarities and differences in the combustion of RDX and HMX are explained from sensitivity analysis results. The combustion characteristics of RDX and HMX are similar because of their similar chemistry. Differences in combustion characteristics arise due to differences in melting temperature, vapor pressure and initial decomposition steps. A reduced mechanism consisting of 18 species and 39 reactions was developed from the Melius-Yetter RDX mechanism (45 species, 232 reactions). This reduced mechanism reproduces most of the predictions of the full mechanism but is 7.5 times faster. Because of lack of concrete thermophysical property data for GAP, the modeling results are preliminary but indicate what type of experimental data is necessary before GAP can be modeled with more certainty.

Direct numerical simulation of shear localization and decomposition reactions in shock-loaded HMX crystal

DOE PAGES

Austin, Ryan A.; Barton, Nathan R.; Reaugh, John E.; ...

2015-05-14

A numerical model is developed to study the shock wave ignition of HMX crystal. The model accounts for the coupling between crystal thermal/mechanical responses and chemical reactions that are driven by the temperature field. This allows for the direct numerical simulation of decomposition reactions in the hot spots formed by shock/impact loading. The model is used to simulate intragranular pore collapse under shock wave loading. In a reference case: (i) shear-enabled micro-jetting is responsible for a modest extent of reaction in the pore collapse region, and (ii) shear banding is found to be an important mode of localization. The shearmore » bands, which are filled with molten HMX, grow out of the pore collapse region and serve as potential ignition sites. The model predictions of shear banding and reactivity are found to be quite sensitive to the respective flow strengths of the solid and liquid phases. In this regard, it is shown that reasonable assumptions of liquid-HMX viscosity can lead to chemical reactions within the shear bands on a nanosecond time scale.« less

Live Imaging and Heating of Confined RDX and HMX Crystals Until Reaction Using the Dual Windowed Test Vehicle

NASA Astrophysics Data System (ADS)

Stennett, Chris; Cook, Malcolm; Cheese, Philip; Wood, Andrew; White, Nathan; Reeves, Tom

2017-06-01

A high fidelity live camera feed recording RDX and HMX crystals, measuring 1 mm thick and 15 mm in diameter, decomposing while heavily confined and subjected to various heating rates until a reaction occurs has been analysed. Video records reveal unexpected behaviour in both RDX and HMX crystals prior to ignition. Three distinct stages can be observed: phase changes and melting; slow, flameless decomposition with production of gaseous intermediates; and finally burning with a luminous flame of the gaseous intermediates. Tests with pure RDX and HMX crystals reveal pockets of gaseous materials forming above the molten and bubbling nitramine, before a flame appears at one side then burns inwards in an apparent conductive manner at a few metres per second. This causes the remaining bubbling nitramine to be compressed. Violent reaction appears to occur via a bubble collapse mechanism. The violence of this event is dependent on the loss of confinement; if it fails in the first or second phase the reaction is less violent than if the third phase is reached. The third phase burning reaction has associated pressure waves, which is presumed oscillation of the flame front, leading to wave interactions, pressure spikes and ultimately a violent reaction.

The Nkx5/HMX homeodomain protein MLS-2 is required for proper tube cell shape in the C.elegans excretory system

PubMed Central

Abdus-Saboor, Ishmail; Stone, Craig E.; Murray, John I.; Sundaram, Meera V.

2012-01-01

Cells perform wide varieties of functions that are facilitated, in part, by adopting unique shapes. Many of the genes and pathways that promote cell fate specification have been elucidated. However, relatively few transcription factors have been identified that promote shape acquisition after fate specification. Here we show that the Nkx5/HMX homeodomain protein MLS-2 is required for cellular elongation and shape maintenance of two tubular epithelial cells in the C.elegans excretory system, the duct and pore cells. The Nkx5/HMX family is highly conserved from sea urchins to humans, with known roles in neuronal and glial development. MLS-2 is expressed in the duct and pore, and defects in mls-2 mutants first arise when the duct and pore normally adopt unique shapes. MLS-2 cooperates with the EGF-Ras-ERK pathway to turn on the LIN-48/Ovo transcription factor in the duct cell during morphogenesis. These results reveal a novel interaction between the Nkx5/HMX family and the EGF-Ras pathway and implicate a transcription factor, MLS-2, as a regulator of cell shape. PMID:22537498

Face-Dependent Solvent Adsorption: A Comparative Study on the Interfaces of HMX Crystal with Three Solvents.

PubMed

Liu, Yingzhe; Lai, Weipeng; Ma, Yiding; Yu, Tao; Kang, Ying; Ge, Zhongxue

2017-07-27

To understand the crystal-solvent interfacial interactions on the molecular scale, the interfaces between three solvents, that is, acetone, γ-butyrolactone, and cyclohexanone, and three growth faces of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) crystal have been investigated with the aid of theoretical chemistry. The results show that the structural features of crystal faces play a critical role in the energetic, structural, and dynamic properties at the interfaces. For each solvent, the same change trend of some properties among the three faces of HMX crystal is observed, including adsorption affinity, local mass density, and solvent diffusion. For example, the rate of solvent diffusion at the three faces ranks as (011) > (110) > (020) regardless of solvent species. This can be attributed to the similar adsorption sites for solvent incorporation at the same face, which are concentrated at the cavities formed by surficial HMX molecules.

Fate and transport of TNT, RDX, and HMX in streambed sediments: Implications for riverbank filtration.

PubMed

Zheng, Weixi; Lichwa, Joseph; D'Alessio, Matteo; Ray, Chittaranjan

2009-08-01

Riverbank filtration (RBF) refers to the process of capturing surface water passing through the river-sediment-aquifer system by using a collection technique such as a well or an infiltration gallery. RBF removes nearly all suspended and a large number of dissolved contaminants from the surface water. Therefore, it can function as an effective pretreatment process in drinking-water production. TNT (2,4,6-trinitrotoluene), RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), and HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) are three military explosive chemicals that are considered of concern to human health when present in source waters. This study is to evaluate the ability of the filtration media in RBF systems to remove these chemicals. The results from an anoxic batch test showed that all three chemicals will degrade while passing through streambed sediments. The pseudo first-order degradation-rate constants for TNT, RDX, and HMX were measured to be 0.33, 0.055, and 0.033d(-1), respectively. Under aerobic conditions only TNT showed significant degradation. Results from a model RBF system showed that the mobility of the three chemical contaminants in streambed sediments was in the order: HMX>RDX>TNT. The results suggest that RBF is capable of removing TNT and RDX but HMX levels may continue to be of concern-especially when collector wells use laterals running directly beneath the stream or riverbed.

Solid phase microextraction-high performance liquid chromatographic determination of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in the presence of sodium dodecyl sulfate surfactant.

PubMed

Malik, Ashok Kumar; Rai, Parmod Kumar

2008-07-01

A simple and sensitive method has been developed using preconcentration technique solid phase microextraction (SPME) and analytical technique HPLC-UV for the determination of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from the environmental samples. Aqueous solution of anionic surfactant SDS was used for the extraction of both nitramine high explosives, viz., HMX and RDX from soil samples which were subsequently sorbed on SPME fiber. The static desorption was carried out in the desorption chamber of the SPME-HPLC interface in the presence of mobile phase ACN/methanol/water (30:35:35) and the subsequent chromatographic analysis at a flow rate of 0.5 mL/min and detection at 230 nm. For this purpose, a C(18), 5 microm RP analytical column was used as a separation medium in this method. Several parameters relating to SPME, e.g., adsorption/desorption time, concentration of salt, stirring rate, etc., were optimized. The method was linear over the range of 20-400 ng/mL for HMX and RDX standards in the presence of surfactant in aqueous phase, respectively. The correlation coefficient (R(2)) for HMX and RDX are 0.9998 and 0.9982, respectively. With SPME, the detection limits (S/N = 3) in ng/mL are 0.05 and 0.1 for HMX and RDX, respectively in the presence of the SDS surfactant. The developed method has been applied successfully to the analysis of real environmental samples like bore well water, river water, and ground alluvial soil.

Liquid chromatography/electrospray ionization tandem mass spectrometry analysis of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

PubMed

Pan, Xiaoping; Zhang, Baohong; Tian, Kang; Jones, Lindsey E; Liu, Jun; Anderson, Todd A; Wang, Jia-Sheng; Cobb, George P

2006-01-01

A quantitative liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method was developed for the analysis of the explosive, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). In negative ionization mode, HMX forms an acetate adduct ion [M + CH(3)COO](-), m/z 355, in the presence of a small amount of acetic acid in the mobile phase. The ESI collision-induced dissociation (CID) spectrum of m/z 355 was acquired and the transitions m/z 355 --> 147 and m/z 355 --> 174 were chosen for the determination of HMX in samples. Using this quantification technique, the method detection limit was 1.57 microg/L and good linearity was achieved in the range 5-500 microg/L. This method will help to unambiguously analyze environmentally relevant concentrations of HMX. Copyright (c) 2006 John Wiley & Sons, Ltd.

Effect of HMX on the combustion response function

NASA Technical Reports Server (NTRS)

Strand, L. D.; Cohen, N. S.

1980-01-01

Over a pressure range of 3.5-7 MPa and a frequency range of 500-2000 Hz and compared to propellants having equivalent energy and burn rate, HMX produces less pressure-coupled acoustic driving than AP and is equivalent to NC/TMETN. Formation of carbonaceous combustion products indicates that binder decomposition does not follow equilibrium thermochemistry, and that this is aggravated by fuel richness or the absence of AP.

Theoretical insight into the binding energy and detonation performance of ε-, γ-, β-CL-20 cocrystals with β-HMX, FOX-7, and DMF in different molar ratios, as well as electrostatic potential.

PubMed

Feng, Rui-Zhi; Zhang, Shu-Hai; Ren, Fu-de; Gou, Rui-Jun; Gao, Li

2016-06-01

Molecular dynamics method was employed to study the binding energies on the selected crystal planes of the ε-, γ-, β-conformation 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (ε-, γ-, β-CL-20) cocrystal explosives with 1,1-diamino-2,2-dinitroethylene (FOX-7), 1,3,5,7-tetranitro- 1,3,5,7-tetrazacyclooctane with β-conformation (β-HMX) and N,N-dimethylformamide (DMF) in different molar ratios. The oxygen balance, density, detonation velocity, detonation pressure, and surface electrostatic potential were analyzed. The results indicate that the binding energies E b (*) and stabilities are in the order of 1:1 > 2:1 > 3:1 > 5:1 > 8:1 (CL-20:FOX-7/β-HMX/DMF). The values of E b (*) and stabilities of the energetic-nonenergetic CL-20/DMF cocrystals are far larger than those of the energetic-energetic CL-20/FOX-7 and CL-20/β-HMX, and those of CL-20/β-HMX are the smallest. For CL-20/FOX-7 and CL-20/β-HMX, the largest E b (*) appears in the cocrystals with the 1:1, 1:2 or 1:3 molar ratio, and the stabilities of the cocrystals with the excess ratio of CL-20 are weaker than those in the cocrystals with the excess ratio of FOX-7 or β-HMX. In CL-20/FOX-7, CL-20 prefers adopting the γ-form, and ε-CL-20 is the preference in CL-20/β-HMX, and ε-CL-20 and β-CL-20 can be found in CL-20/DMF. The CL-20/FOX-7 and CL-20/β-HMX cocrystals with low molar ratios can meet the requirements of low sensitive high energetic materials. Surface electrostatic potential reveals the nature of the sensitivity change upon the cocrystal formation. Graphical Abstract MD method was employed to study the binding energies on the selected crystal planes in the ε-, γ-, β-CL-20 cocrystals with FOX-7, β-HMX and DMF in different molar ratios. Surface electrostatic potential reveals the nature of the sensitivity change in cocrystals.

Understanding and Predicting the Thermal Explosion Violence of HMX-Based and RDX-Based Explosives - Experimental Measurements of Material Properties and Reaction Violence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maienschein, J L; Wardell, J F; Weese, R K

The violence of thermal explosions with energetic materials is affected by many material properties, including mechanical and thermal properties, thermal ignition kinetics, and deflagration behavior. These properties must be characterized for heated samples as well as pristine materials. We present available data for these properties for two HMX-based formulations--LX-04 and PBX-9501, and two RDX-based formulations--Composition B and PBXN-109. We draw upon separately published data on the thermal explosion violence with these materials to compare the material properties with the observed violence. We have the most extensive data on deflagration behavior of these four formulations, and we discuss the correlation ofmore » the deflagration data with the violence results. The data reported here may also be used to develop models for application in simulation codes such as ALE3D to calculate and Dredict thermal explosion violence.« less

Oblique impact and friction of HMX and/or TATB-based PBXs

NASA Astrophysics Data System (ADS)

Picart, Didier; Junqua-Moullet, Alexandra

2017-06-01

Transportation, handling, vibrations can lead to moderate compressive but dynamic loadings requiring the characterization of the safety of PBXs submitted to such scenarios. Knowing that ignition can occur at a lower critical height during a fall on an inclined surface than a normal impact, the attention is focused in this paper on the heating due to the friction between PBXs and surfaces. A lot of experiments have been made using free-falling samples in vertical drop configurations on inclined targets or pendulum (skid) drop configurations (Green et al. 1971; Randolph et al. 1976). Data obtained on our HMX and/or TATB-based plastic-bonded explosives using pendulum drop configurations will be detailed. Evaluation of the heating due to friction requires the determination of the tangential projectile/target relative displacement and the contact pressure. The pressure is related to the normal force during the impact and the evolving contact surface, the latter being evaluated using a series of normal impacts. The aim of our paper is to compare the experimental diameter of the contact zones to (i) the classical Hertz's theory of contacting elastic solids and (ii) a spring-mass description of the impact. Data and models are then used to evaluate the increase of the temperature at the projectile/target interface for our explosives. We highlight the experimental bias which has already been attributed to the grits used to mimic the roughness of the surfaces.

Investigating Deformation and Mesoscale Void Creation in HMX Based Composites using Tomography Based Grain Scale Finite Element Modeling

NASA Astrophysics Data System (ADS)

Walters, David J.; Luscher, Darby J.; Manner, Virginia; Yeager, John D.; Patterson, Brian M.

2017-06-01

The microstructure of plastic bonded explosives (PBXs) significantly affects their macroscale mechanical characteristics. Imaging and modeling of the mesoscale constituents allows for a detailed examination of the deformation of mechanically loaded PBXs. In this study, explosive composites, formulated with HMX crystals and various HTPB based polymer binders have been imaged using micro Computed Tomography (μCT). Cohesive parameters for simulation of the crystal/binder interface are determined by comparing numerical and experimental results of the delamination of a polymer bound bi-crystal system. Similarly, polycrystalline samples are discretized into a finite element mesh using the mesoscale geometry captured by in-situ μCT imaging. Experimentally, increasing the stiffness of the HTPB binder in the polycrystalline system resulted in a transition from ductile flow with little crystal/binder delamination to brittle behavior with increased void creation along the interfaces. Simulating the macroscale compression of these samples demonstrates the effects that the mesoscale geometry, cohesive properties, and binder stiffness have on the creation and distribution of interfacial voids. Understanding void nucleation is critical for modeling damage in these complex materials.

The Nkx5/HMX homeodomain protein MLS-2 is required for proper tube cell shape in the C. elegans excretory system.

PubMed

Abdus-Saboor, Ishmail; Stone, Craig E; Murray, John I; Sundaram, Meera V

2012-06-15

Cells perform wide varieties of functions that are facilitated, in part, by adopting unique shapes. Many of the genes and pathways that promote cell fate specification have been elucidated. However, relatively few transcription factors have been identified that promote shape acquisition after fate specification. Here we show that the Nkx5/HMX homeodomain protein MLS-2 is required for cellular elongation and shape maintenance of two tubular epithelial cells in the C. elegans excretory system, the duct and pore cells. The Nkx5/HMX family is highly conserved from sea urchins to humans, with known roles in neuronal and glial development. MLS-2 is expressed in the duct and pore, and defects in mls-2 mutants first arise when the duct and pore normally adopt unique shapes. MLS-2 cooperates with the EGF-Ras-ERK pathway to turn on the LIN-48/Ovo transcription factor in the duct cell during morphogenesis. These results reveal a novel interaction between the Nkx5/HMX family and the EGF-Ras pathway and implicate a transcription factor, MLS-2, as a regulator of cell shape. Copyright © 2012 Elsevier Inc. All rights reserved.

Critical analysis of nitramine decomposition data: Activation energies and frequency factors for HMX and RDX decomposition

NASA Technical Reports Server (NTRS)

Schroeder, M. A.

1980-01-01

A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.

Theoretical insights into the structures and mechanical properties of HMX/NQ cocrystal explosives and their complexes, and the influence of molecular ratios on their bonding energies.

PubMed

Li, Yong-Xiang; Chen, Shu-Sen; Ren, Fu-de

2015-09-01

Molecular dynamics (MD) methods were employed to study the binding energies and mechanical properties of selected crystal planes of 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX)/nitroguanidine (NQ) cocrystals at different molecular molar ratios. The densities and detonation velocities of the cocrystals at different molar ratios were estimated. The intermolecular interaction and bond dissociation energy (BDE) of the N-NO2 bond in the HMX:NQ (1:1) complex were calculated using the B3LYP, MP2(full) and M06-2X methods with the 6-311++G(d,p) and 6-311++G(2df,2p) basis sets. The results indicated that the HMX/NQ cocrystal prefers cocrystalizing in a 1:1 molar ratio, and the cocrystallization is dominated by the (0 2 0) and (1 0 0) facets. The K, G, and E values of the ratio of 1:1 are smaller than those of the other ratios, and the 1:1 cocrystal has the best ductility. The N-NO2 bond becomes stronger upon the formation of the intermolecular H-bonding interaction and the sensitivity of HMX decreases in the cocrystal. This sensitivity change in the HMX/NQ cocrystal originates not only from the formation of the intermolecular interaction but also from the increment of the BDE of N-NO2 bond in comparison with isolated HMX. The HMX/NQ (1:1) cocrystal exhibits good detonation performance. Reduced density gradient (RDG) reveals the nature of cocrystallization. Analysis of the surface electrostatic potential further confirmed that the sensitivity decreases in complex (or cocrystal) in comparison with that in isolated HMX.

Toxicity and bioconcentration evaluation of RDX and HMX using sheepshead minnows in water exposures.

PubMed

Lotufo, Guilherme R; Gibson, Alfreda B; Yoo, J Leslie

2010-10-01

Lethal effects of the explosives RDX and HMX were assessed using ten-day water exposures to juvenile sheepshead minnows (Cyprinodon variegatus). For RDX, maximum mortality occurred during the first two days of exposure with a 10-d median lethal concentration (LC50) of 9.9 mg L(-1). The RDX 10-d median lethal residue (LR50) was 9.6 mg kg(-1) (34.9 μmol kg(-1)) wet weight (ww), the first RDX critical body residue reported for fish. Previous investigations reported that RDX body residues in marine amphipods up to 96 μmol kg(-1) ww and in marine mussels up to 86 μmol kg(-1) ww failed to result in significant mortality. The highest HMX concentration tested, corresponding to its apparent solubility limit in seawater (2.0 mg L(-1)), and the associated mean body residue (3 mg kg(-1) or 14 μmol kg(-1) ww) resulted in no significant mortality for exposed minnows. The mean 10-d bioconcentration factors for RDX (0.6-0.9 L kg(-1)) and HMX (0.3-1.6 L kg(-1)) were typically lower than 1, reflecting the low bioaccumulative potential for these compounds. Published by Elsevier Inc.

Preparation and catalytic activities of LaFeO3 and Fe2O3 for HMX thermal decomposition.

PubMed

Wei, Zhi-Xian; Xu, Yan-Qing; Liu, Hai-Yan; Hu, Chang-Wen

2009-06-15

Perovskite-type LaFeO(3) and alpha-Fe(2)O(3) with high specific surface areas were directly prepared with appropriate stearic acid-nitrates ratios by a novel stearic acid solution combustion method. The obtained powders were characterized by XRD, FT-IR and XPS techniques. The catalytic activities of perovskite-type LaFeO(3) and alpha-Fe(2)O(3) for the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were investigated by TG and TG-EGA techniques. The experimental results show that the catalytic activity of perovskite-type LaFeO(3) was much higher than that of alpha-Fe(2)O(3) because of higher concentration of surface-adsorbed oxygen (O(ad)) and hydroxyl of LaFeO(3). The study points out a potential way to develop new and more active perovskite-type catalysts for the HMX thermal decomposition.

Removal of RDX, TNB, TNT, and HMX from Cornhusker Army Ammunition Plant waters using adsorption technologies. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fleming, E.C.; Cerar, R.; Christenson, K.

1996-04-01

The Cornhusker Army Ammunition Plant (CAAP) is located in Grand Island, NE, and occupies 11,936 acres (4,832.38 ha) in Hall County. The CAAP is classified as a load, assembly, and pack facility and was constructed in 1942 for the purpose of manufacturing bombs for World War II. Environmental impacts of explosives manufacturing were evaluated in an Installation Assessment Study that identified 58 sources of contamination by explosive compounds. The plant is currently in standby status until completion of environmental studies required for real estate transactions. The U.S. Army Engineer Waterways Experiment Station (WES) performed evaluations of adsorption and ultraviolet chemicalmore » oxidation for remediation of explosives contamination in CAAP waters. Average initial concentrations of 33.5 micrograms/l RDX, 110.8 micrograms/l TNB, 246.1 micrograms/l TNT, and 33.9 micrograms/l HMX were analyzed in the samples collected for the WES studies. Adsorption studies included evaluation of carbons, carbonaceous resins, one polymeric resin, and organophilic clays for removal of RDX, TNB, TNT, and HMX. Preliminary tests indicated that RDX, TNB, TNT, and HMX could be reduced to less than 0.2 micrograms/l most cost effectively by carbons, i.e., Calgon Filtrasorb 400 (F-400), Westates CC-601, and American Norit ROW 0.8. Isotherm evaluations verified results of the preliminary tests and indicated RDX, TNB, TNT, and HMX could be reduced below the current analytical detection limit of 0.2 micrograms/l. Regeneration tests indicated regenerated Westates CC-601 and regenerated American Norit ROW 0.8 could remove RDX, TNB, TNT, and HMX to less than 0.2 micrograms/l. Regenerated Calgon F-400 was not as effective as regenerated Westates CC-601 and regenerated American Norit ROW 0.8.« less

Electronic excitations and chemistry in Nitromethane and HMX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, E J; Manaa, M R; Joannopoulos, J D

2001-06-19

The nature of electronic excitations in crystalline solid nitromethane under conditions of shock loading and static compression are examined. Density functional theory calculations are used to determine the crystal bandgap under hydrostatic stress, uniaxial strain, and shear strain. Bandgap lowering under uniaxial strain due to molecular defects and vacancies is considered. In all cases, the bandgap is not lowered enough to produce a significant population of excited states in the crystal. Preliminary simulations on the formation of detonation product molecules from HMX are discussed.

Carbon and nitrogen isotope ratios of factory-produced RDX and HMX.

PubMed

Howa, John D; Lott, Michael J; Chesson, Lesley A; Ehleringer, James R

2014-07-01

RDX and HMX are explosive compounds commonly used by the military and also occasionally associated with acts of terrorism. The isotopic characterization of an explosive can be a powerful approach to link evidence to an event or an explosives cache. We sampled explosive products and their reactants from commercial RDX manufacturers that used the direct nitration and/or the Bachmann synthesis process, and then analyzed these materials for carbon and nitrogen isotope ratios. For manufacturers using the Bachmann process, RDX (13)C enrichment relative to the hexamine substrate was small (+0.9‰) compared to RDX produced using the direct nitration process (+8.2‰ to +12.0‰). RDX (15)N depletion relative to the nitrogen-containing substrates (-3.6‰) was smaller in the Bachmann process than in the direct nitration process (-12.6‰ to -10.6‰). The sign and scale of these differences agree with theorized mechanisms of mass-dependent fractionation. We also examined the isotopic relationship between RDX and HMX isolated from explosive samples. The δ(13)C and δ(15)N values of RDX generally matched those of the HMX with few exceptions, most notably from a manufacturer known to make RDX using two different synthesis processes. The range in δ(13)C values of RDX in a survey of 100 samples from 12 manufacturers spanned 33‰ while the range spanned by δ(15)N values was 26‰; these ranges were much greater than any previously published observations. Understanding the relationship between products and reactants further explains the observed variation in industrially manufactured RDX and can be used as a diagnostic tool to analyze explosives found at a crime scene. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)

Integrated Risk Information System (IRIS)

Octahydro - 1,3,5,7 - tetranitro - 1,3,5,7 - tetr . . . ( HMX ) ; CASRN 2691 - 41 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I

A LC-MS method allowing the analysis of HMX and RDX present at the picogram level in natural aqueous samples without a concentration step.

PubMed

Vigneau, Olivier; Machuron-Mandard, Xavier

2009-03-15

The introduction of chloroform into the nebulising gas of a LC/MS electrospray interface (ESI), in a perfectly controlled way, leads to the formation of intense adducts ([M+Cl](-)) when a mobile phase containing HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane or octogen) and RDX (1,3,5-trintro-1,3,5-triazacyclohexane or hexogen) is eluted. This LC/MS method allows the direct analysis of aqueous samples containing HMX and RDX at the pictogram level without a concentration step. The method is used to determine HMX and RDX concentrations in ground water samples from a military site.

The growth and perfection of β-cyclotetramethylene-tetranitramine (HMX) studied by laboratory and synchrotron X-ray topography

NASA Astrophysics Data System (ADS)

Gallagher, H. G.; Sherwood, J. N.; Vrcelj, R. M.

2017-10-01

An examination has been made of the defect structure of crystals of the energetic material β-cyclotetramethylene-tetranitramine (HMX) using both Laboratory (Lang method) and Synchrotron (Bragg Reflection and Laue method) techniques. The results of the three methods are compared with particular attention to the influence of potential radiation damage caused to the samples by the latter, more energetic, technique. The comparison shows that both techniques can be confidently used to evaluate the defect structures yielding closely similar results. The results show that, even under the relatively casual preparative methods used (slow evaporation of unstirred solutions at constant temperature), HMX crystals of high perfection can be produced. The crystals show well defined bulk defect structures characteristic of organic materials in general: growth dislocations, twins, growth sector boundaries, growth banding and solvent inclusions. The distribution of the defects in specific samples is correlated with the morphological variation of the grown crystals. The results show promise for the further evaluation and characterisation of the structure and properties of dislocations and other defects and their involvement in mechanical and energetic processes in this material.

Shock-to-detonation transition of RDX and NTO based composite high explosives: experiments and modeling

NASA Astrophysics Data System (ADS)

Baudin, Gerard; Roudot, Marie; Genetier, Marc

2013-06-01

Composite HMX and NTO based high explosives (HE) are widely used in ammunitions. Designing modern warheads needs robust and reliable models to compute shock ignition and detonation propagation inside HE. Comparing to a pressed HE, a composite HE is not porous and the hot-spots are mainly located at the grain - binder interface leading to a different behavior during shock-to-detonation transition. An investigation of how shock-to-detonation transition occurs inside composite HE containing RDX and NTO is proposed in this lecture. Two composite HE have been studied. The first one is HMX - HTPB 82:18. The second one is HMX - NTO - HTPB 12:72:16. These HE have been submitted to plane sustained shock waves at different pressure levels using a laboratory powder gun. Pressure signals are measured using manganin gauges inserted at several distances inside HE. The corresponding run-distances to detonation are determined using wedge test experiments where the plate impact is performed using a powder gun. Both HE exhibit a single detonation buildup curve in the distance - time diagram of shock-to-detonation transition. This feature seems a common shock-to-detonation behavior for composite HE without porosity. This behavior is also confirmed for a RDX - HTPB 85:15 based composite HE. Such a behavior is exploited to determine the heterogeneous reaction rate versus the shock pressure using a method based on the Cauchy-Riemann problem inversion. The reaction rate laws obtained allow to compute both run-distance to detonation and pressure signals.

Response of explosive HMX to low-velocity impact: modeling by the crystal plasticity finite element method

NASA Astrophysics Data System (ADS)

Ilnitsky, Denis; Inogamov, Nail; Zhakhovsky, Vasily

2017-12-01

Crystal plasticity finite element method (CPFEM) is a powerful tool for modeling the various deformation problems, which takes into account the different plasticity mechanisms at microscale of grain sizes and contribution of anisotropic behavior of each grain to macroscopic deformation pattern. Using this method we simulated deformation and plasticity of high explosive HMX produced by relatively low velocity impact. It was found that such plastic deformations of grains cause local heating which is sufficient to induce chemical reactions.

DMSO/base hydrolysis method for the disposal of high explosives and related energetic materials

DOEpatents

Desmare, Gabriel W.; Cates, Dillard M.

2002-05-14

High explosives and related energetic materials are treated via a DMSO/base hydrolysis method which renders them non-explosive and/or non-energetic. For example, high explosives such as 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane (HMX), 1,3,5-triaza-1,3,5-trinitrocyclohexane (RDX), 2,4,6-trinitrotoluene (TNT), or mixtures thereof, may be dissolved in a polar, aprotic solvent and subsequently hydrolyzed by adding the explosive-containing solution to concentrated aqueous base. Major hydrolysis products typically include nitrite, formate, and nitrous oxide.

Dynamic Responses and Initial Decomposition under Shock Loading: A DFTB Calculation Combined with MSST Method for β-HMX with Molecular Vacancy.

PubMed

He, Zheng-Hua; Chen, Jun; Ji, Guang-Fu; Liu, Li-Min; Zhu, Wen-Jun; Wu, Qiang

2015-08-20

Despite extensive efforts on studying the decomposition mechanism of HMX under extreme condition, an intrinsic understanding of mechanical and chemical response processes, inducing the initial chemical reaction, is not yet achieved. In this work, the microscopic dynamic response and initial decomposition of β-HMX with (1 0 0) surface and molecular vacancy under shock condition, were explored by means of the self-consistent-charge density-functional tight-binding method (SCC-DFTB) in conjunction with multiscale shock technique (MSST). The evolutions of various bond lengths and charge transfers were analyzed to explore and understand the initial reaction mechanism of HMX. Our results discovered that the C-N bond close to major axes had less compression sensitivity and higher stretch activity. The charge was transferred mainly from the N-NO2 group along the minor axes and H atom to C atom during the early compression process. The first reaction of HMX primarily initiated with the fission of the molecular ring at the site of the C-N bond close to major axes. Further breaking of the molecular ring enhanced intermolecular interactions and promoted the cleavage of C-H and N-NO2 bonds. More significantly, the dynamic response behavior clearly depended on the angle between chemical bond and shock direction.

Theoretical insights into the effects of molar ratios on stabilities, mechanical properties, and detonation performance of CL-20/HMX cocrystal explosives by molecular dynamics simulation.

PubMed

Hang, Gui-Yun; Yu, Wen-Li; Wang, Tao; Wang, Jin-Tao; Li, Zhen

2017-01-01

To research and estimate the effects of molar ratios on structures, stabilities, mechanical properties, and detonation properties of CL-20/HMX cocrystal explosive, the CL-20/HMX cocrystal explosive models with different molar ratios were established in Materials Studio (MS). The crystal parameters, structures, stabilities, mechanical properties, and some detonation parameters of different cocrystal explosives were obtained and compared. The molecular dynamics (MD) simulation results illustrate that the molar ratios of CL-20/HMX have a direct influence on the comprehensive performance of cocrystal explosive. The hardness and rigidity of the 1:1 cocrystal explosive was the poorest, while the plastic property and ductibility were the best, thus implying that the explosive has the best mechanical properties. Besides, it has the highest binding energy, so the stability and compatibility is the best. The cocrystal explosive has better detonation performance than HMX. In a word, the 1:1 cocrystal explosive is worth more attention and further research. This paper could offer some theoretical instructions and technological support, which could help in the design of the CL-20 cocrystal explosive.

Adsorption behavior of acetone solvent at the HMX crystal faces: A molecular dynamics study.

PubMed

Liu, Yingzhe; Yu, Tao; Lai, Weipeng; Ma, Yiding; Kang, Ying; Ge, Zhongxue

2017-06-01

Molecular dynamics simulations have been performed to understand the adsorption behavior of acetone (AC) solvent at the three surfaces of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctan (HMX) crystal, i.e. (011), (110), and (020) faces. The simulation results show that the structural features and electrostatic potentials of crystal faces are determined by the HMX molecular packing, inducing distinct mass density distribution, dipole orientation, and diffusion of solvent molecules in the interfacial regions. The solvent adsorption is mainly governed by the van der Waals forces, and the crystal-solvent interaction energies among three systems are ranked as (020)≈(110)>(011). The adsorption sites for solvent incorporation at the crystal surface were found and visualized with the aid of occupancy analysis. A uniform arrangement of adsorption sites is observed at the rough (020) surface as a result of ordered adsorption motif. Copyright © 2017 Elsevier Inc. All rights reserved.

Application of global kinetic models to HMX beta-delta transition and cookoff processes.

PubMed

Wemhoff, Aaron P; Burnham, Alan K; Nichols, Albert L

2007-03-08

The reduction of the number of reactions in kinetic models for both the HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) beta-delta phase transition and thermal cookoff provides an attractive alternative to traditional multi-stage kinetic models due to reduced calibration effort requirements. In this study, we use the LLNL code ALE3D to provide calibrated kinetic parameters for a two-reaction bidirectional beta-delta HMX phase transition model based on Sandia instrumented thermal ignition (SITI) and scaled thermal explosion (STEX) temperature history curves, and a Prout-Tompkins cookoff model based on one-dimensional time to explosion (ODTX) data. Results show that the two-reaction bidirectional beta-delta transition model presented here agrees as well with STEX and SITI temperature history curves as a reversible four-reaction Arrhenius model yet requires an order of magnitude less computational effort. In addition, a single-reaction Prout-Tompkins model calibrated to ODTX data provides better agreement with ODTX data than a traditional multistep Arrhenius model and can contain up to 90% fewer chemistry-limited time steps for low-temperature ODTX simulations. Manual calibration methods for the Prout-Tompkins kinetics provide much better agreement with ODTX experimental data than parameters derived from differential scanning calorimetry (DSC) measurements at atmospheric pressure. The predicted surface temperature at explosion for STEX cookoff simulations is a weak function of the cookoff model used, and a reduction of up to 15% of chemistry-limited time steps can be achieved by neglecting the beta-delta transition for this type of simulation. Finally, the inclusion of the beta-delta transition model in the overall kinetics model can affect the predicted time to explosion by 1% for the traditional multistep Arrhenius approach, and up to 11% using a Prout-Tompkins cookoff model.

Growth morphology of CL-20/HMX cocrystal explosive: insights from solvent behavior under different temperatures.

PubMed

Han, Gang; Li, Qi-Fa; Gou, Rui-Jun; Zhang, Shu-Hai; Ren, Fu-de; Wang, Li; Guan, Rong

2017-11-28

A 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) /1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX)-isopropanol (IPA) interfacial model was constructed to investigate the effect of temperature on cocrystal morphology. A constant volume and temperature molecular dynamics (NVT-MD) simulation was performed on the interfacial model at various temperatures (295-355 K, 20 K intervals). The surface electrostatic potential (ESP) of the CL-20/HMX cocrystal structure and IPA molecule were studied by the B3LYP method at 6-311++G (d, p) level. The surface energies, polarities, adsorption energy, mass density distribution, radial distribution function (RDF), mean square displacement (MSD) and relative changes of attachment energy were analyzed. The results show that polarities of (1 0 0) and (0 1 1) cocrystal surfaces may be more negative and affected by IPA solvent. The adsorption energy per area indicates that growth of the (1 0-2) face in IPA conditions may be more limited, while the (1 0 0) face tends to grow more freely. MSD and diffusion coefficient (D) analyses demonstrated that IPA molecules gather more easily on the cocrystal surface at lower temperatures, and hence have a larger effect on the growth of cocrystal faces. RDF analysis shows that, with the increasing of temperature, the strength of hydrogen bond interactions between cocrystal and solvent becomes stronger, being highest at 335 K for the (1 0 0) and (0 1 1) interfacial models. Results of relative changes of modified attachment energy show that (1 0 0) and (0 1 1) faces tends to be larger than other faces. Moreover, the predicted morphologies at 295 and 355 K are consistent with experimental values, proving that the CL-20/HMX-IPA interfacial model is a reasonable one for this study. Graphical Abstract Construction of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) /1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX)-isopropanol (IPA) interfacial model, analysis

Structure and bonding in beta-HMX-characterization of a trans-annular N...N interaction.

PubMed

Zhurova, Elizabeth A; Zhurov, Vladimir V; Pinkerton, A Alan

2007-11-14

Chemical bonding in the beta-phase of the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) crystal based on the experimental electron density obtained from X-ray diffraction data at 20 K, and solid state theoretical calculations, has been analyzed in terms of the quantum theory of atoms in molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. An unusual N...N bonding interaction across the 8-membered ring has been discovered and characterized. Hydrogen bonding, O...O and O...C intermolecular interactions are reported. Atomic charges and features of the electrostatic potential are discussed.

Template-Directed Crystallization of High Energy Materials

DTIC Science & Technology

2014-04-01

objectives of this grant were to (a) examine the solution crystallization of RDX , HMX and CL-20 from a variety of solvents, withdetailed analysis of...crystal nucleation templates and (c) to assess the growth of RDX , HMX and CL-20 on these templates. High explosives, crystallization, RDX , CL-20...crystallization of RDX , HMX and CL-20 from a variety of solvents, with detailed analysis of their phase, size, and morphological properties; (b) to

Chemotaxis-mediated biodegradation of cyclic nitramine explosives RDX, HMX, and CL-20 by Clostridium sp. EDB2.

PubMed

Bhushan, Bharat; Halasz, Annamaria; Thiboutot, Sonia; Ampleman, Guy; Hawari, Jalal

2004-04-09

Cyclic nitramine explosives, RDX, HMX, and CL-20 are hydrophobic pollutants with very little aqueous solubility. In sediment and soil environments, they are often attached to solid surfaces and/or trapped in pores and distribute heterogeneously in aqueous environments. For efficient bioremediation of these explosives, the microorganism(s) must access them by chemotaxis ability. In the present study, we isolated an obligate anaerobic bacterium Clostridium sp. strain EDB2 from a marine sediment. Strain EDB2, motile with numerous peritrichous flagella, demonstrated chemotactic response towards RDX, HMX, CL-20, and NO(2)(-). The three explosives were biotransformed by strain EDB2 via N-denitration with concomitant release of NO(2)(-). Biotransformation rates of RDX, HMX, and CL-20 by the resting cells of strain EDB2 were 1.8+/-0.2, 1.1+/-0.1, and 2.6+/-0.2nmol h(-1)mgwet biomass(-1) (mean+/-SD; n=3), respectively. We found that commonly seen RDX metabolites such as TNX, methylenedinitramine, and 4-nitro-2,4-diazabutanal neither produced NO(2)(-) during reaction with strain EDB2 nor they elicited chemotaxis response in strain EDB2. The above data suggested that NO(2)(-) released from explosives during their biotransformation might have elicited chemotaxis response in the bacterium. Biodegradation and chemotactic ability of strain EDB2 renders it useful in accelerating the bioremediation of explosives under in situ conditions.

Small Scale Characterization of the Presence of the Explosive Octahydro-1,3,5,7-tetranitro- 1,3,5,7 tetrazocine (HMX) Near Former Naval Sites on Vieques Island, Puerto Rico

NASA Astrophysics Data System (ADS)

Simmons, C. C.; Carvalho-Knighton, K. M.; Pyrtle, A. J.

2007-12-01

Octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazocine (HMX) is a synthetic energetic compounds that has been commonly used in military munitions. The presence and movement of HMX through the environment is of growing concern because of potential civilian exposure and impacts on human health. HMX remains in the environment unreactive with little degradation. It can be transported great distances in water thus having the possibility for migrating into groundwater. The former naval sites in Vieques were used for weapons training and housed several disposal sites. Previous studies around these sites indicate the presence of radioactive materials produced through thermal fission, such as Cs-137. Since HMX was primarily used to implode fissionable materials in nuclear devices, evaluating the release of HMX and consequent movement through the environment at these sites is essential. Surface water and soil samples as well as core and pore water samples were collected from two sites in Vieques; Kiani Lagoon and Mosquito Bay. All samples were extracted using EPA method 8330 and analyzed using RP-HPLC analysis with a C-18 column. HMX was undetected in samples collected from both Kiani Lagoon and Mosquito Bay. The development of a model that studies the flow rates and fate of water runoff in these areas of interest, coupled with data on groundwater testing inside the actual former naval facilities, is being explored for further sample collection and analysis.

Thermal Decomposition Behaviors and Burning Characteristics of AN/Nitramine-Based Composite Propellant

NASA Astrophysics Data System (ADS)

Naya, Tomoki; Kohga, Makoto

2015-04-01

Ammonium nitrate (AN) has attracted much attention due to its clean burning nature as an oxidizer. However, an AN-based composite propellant has the disadvantages of low burning rate and poor ignitability. In this study, we added nitramine of cyclotrimethylene trinitramine (RDX) or cyclotetramethylene tetranitramine (HMX) as a high-energy material to AN propellants to overcome these disadvantages. The thermal decomposition and burning rate characteristics of the prepared propellants were examined as the ratio of AN and nitramine was varied. In the thermal decomposition process, AN/RDX propellants showed unique mass loss peaks in the lower temperature range that were not observed for AN or RDX propellants alone. AN and RDX decomposed continuously as an almost single oxidizer in the AN/RDX propellant. In contrast, AN/HMX propellants exhibited thermal decomposition characteristics similar to those of AN and HMX, which decomposed almost separately in the thermal decomposition of the AN/HMX propellant. The ignitability was improved and the burning rate increased by the addition of nitramine for both AN/RDX and AN/HMX propellants. The increased burning rates of AN/RDX propellants were greater than those of AN/HMX. The difference in the thermal decomposition and burning characteristics was caused by the interaction between AN and RDX.

(Bio)degradation of RDX and HMX in Marine/Estuarine Water and Sediments

DTIC Science & Technology

2006-09-01

and capability to metabolize organic acids and sugar. Both strains HAW-EB2 and HAW-EB5T utilize malate , valerate, peptone and yeast extract as sole...MEDINA) confirming that the nitramines were metabolized by sediment indigenous microorganisms. Both nitramines were also removed in microcosms prepared...Thus far all enzymes or crude enzyme extract examined were found to metabolize RDX or HMX via a le transfer process leading to denitration although 2e

Measurement and reactive burn modeling of the shock to detonation transition for the HMX based explosive LX-14

NASA Astrophysics Data System (ADS)

Jones, J. D.; Ma, Xia; Clements, B. E.; Gibson, L. L.; Gustavsen, R. L.

2017-06-01

Gas-gun driven plate-impact techniques were used to study the shock to detonation transition in LX-14 (95.5 weight % HMX, 4.5 weight % estane binder). The transition was recorded using embedded electromagnetic particle velocity gauges. Initial shock pressures, P, ranged from 2.5 to 8 GPa and the resulting distances to detonation, xD, were in the range 1.9 to 14 mm. Numerical simulations using the SURF reactive burn scheme coupled with a linear US -up / Mie-Grueneisen equation of state for the reactant and a JWL equation of state for the products, match the experimental data well. Comparison of simulation with experiment as well as the ``best fit'' parameter set for the simulations is presented.

Mechanical and chemical responses of low-velocity impacted RDX and HMX explosive powders

NASA Astrophysics Data System (ADS)

Wu, Yanqing; Guo, Hongfu; Huang, Fenglei; Bao, Xiaowei; Explosion; damage Team

2017-06-01

The experimental analyses of mechanical and chemical responses of RDX and HMX particles were performed based on the optimized drop-weight experimental system equipped with the High-Speed Camera (HSC). It has been found that Jetting phenomenon observed by HSC is the result of the energy released by gaseous products, which push the pulverized or melted explosives to splash radially. Jetting is the only and the most obvious difference between reactive and inert particles prior to combustion so that jetting can be regarded as the sign of ignition. Area expansion velocity, jetting velocity, and flame propagation velocity have been estimated via image processing, making it possible to characterize mechanical deformation and violence of reaction of each stage. Hot-spots coalescence promotes flame propagation whose velocity reflects the violence of deflagration reaction. Jetting appearance time can be used to determine time-to-ignition more accurately than other ways. For RDX, molten phase plays an important role to the formation of the hot-spots. Multiple particles experienced more severe burning reactions than an individual particle. China National Nature Science Foundation (11572045), ``Science Challenging Program'' (JCKY2016212A501),opening fund from Safety ammunition research and Development Center (RMC2015B03).

Electronic properties of RDX and HMX: Compton scattering experiment and first-principles calculation.

PubMed

Ahuja, B L; Jain, Pradeep; Sahariya, Jagrati; Heda, N L; Soni, Pramod

2013-07-11

The first-ever electron momentum density (EMD) measurements of explosive materials, namely, RDX (1,3,5-trinitro-1,3,5-triazacyclohexane, (CH2-N-NO2)3) and HMX (1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, (CH2-N-NO2)4), have been reported using a 740 GBq (137)Cs Compton spectrometer. Experimental Compton profiles (CPs) are compared with the EMDs derived from linear combination of atomic orbitals with density functional theory. It is found that the CPs deduced from generalized gradient approximation (GGA) with Wu-Cohen exchange energies give a better agreement with the corresponding experimental profiles than those from local density approximation and other schemes of GGA. Further, Mulliken population, energy bands, partial and total density of states, and band gap have also been reported using GGA calculations. Present ground state calculations unambiguously show large band gap semiconductor nature of both RDX and HMX. A similar type of bonding in these materials is uniquely established using Compton data and density of states. It is also outstandingly consistent with the Mulliken population, which predicts almost equal amount of charge transfer (0.84 and 0.83 e(-)) from H1 + H2 + N2 to C1 + N1 + O1 + O2 in both the explosives.

An Analytic Tool to Investigate the Effect of Binder on the Sensitivity of HMX-Based Plastic Bonded Explosives in the Skid Test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayden, D. W.

This project will develop an analytical tool to calculate performance of HMX based PBXs in the skid test. The skid-test is used as a means to measure sensitivity for large charges in handling situations. Each series of skid tests requires dozens of drops of large billets. It is proposed that the reaction (or lack of one) of PBXs in the skid test is governed by the mechanical properties of the binder. If true, one might be able to develop an analytical tool to estimate skid test behavior for new PBX formulations. Others over the past 50 years have tried tomore » develop similar models. This project will research and summarize the works of others and couple the work of 3 into an analytical tool that can be run on a PC to calculate drop height of HMX based PBXs. Detonation due to dropping a billet is argued to be a dynamic thermal event. To avoid detonation, the heat created due to friction at impact, must be conducted into the charge or the target faster than the chemical kinetics can create additional energy. The methodology will involve numerically solving the Frank-Kamenetskii equation in one dimension. The analytical problem needs to be bounded in terms of how much heat is introduced to the billet and for how long. Assuming an inelastic collision with no rebound, the billet will be in contact with the target for a short duration determined by the equations of motion. For the purposes of the calculations, it will be assumed that if a detonation is to occur, it will transpire within that time. The surface temperature will be raised according to the friction created using the equations of motion of dropping the billet on a rigid surface. The study will connect the works of Charles Anderson, Alan Randolph, Larry Hatler, Alfonse Popolato, and Charles Mader into a single PC based analytic tool. Anderson's equations of motion will be used to calculate the temperature rise upon impact, the time this temperature is maintained (contact time) will be obtained from the

Ignition and Growth Modeling of Detonating LX-04 (85% HMX / 15% VITON) Using New and Previously Obtained Experimental Data

NASA Astrophysics Data System (ADS)

Tarver, Craig

2017-06-01

An Ignition and Growth reactive flow model for detonating LX-04 (85% HMX / 15% Viton) was developed using new and previously obtained experimental data on: cylinder test expansion; wave curvature; failure diameter; and laser interferometric copper and tantalum foil free surface velocities and LiF interface particle velocity histories. A reaction product JWL EOS generated by the CHEETAH code compared favorably with the existing, well normalized LX-04 product JWL when both were used with the Ignition and Growth model. Good agreement with all existing experimental data was obtained. Keywords: LX-04, HMX, detonation, Ignition and Growth PACS:82.33.Vx, 82.40.Fp This work was performed under the auspices of the U. S. Department of Energy by the Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344.

Determination of the band parameters of bulk 2H-MX2 (M = Mo, W; X = S, Se) by angle-resolved photoemission spectroscopy

PubMed Central

Kim, Beom Seo; Rhim, Jun-Won; Kim, Beomyoung; Kim, Changyoung; Park, Seung Ryong

2016-01-01

Monolayer MX2 (M = Mo, W; X = S, Se) has recently been drawn much attention due to their application possibility as well as the novel valley physics. On the other hand, it is also important to understand the electronic structures of bulk MX2 for material applications since it is very challenging to grow large size uniform and sustainable monolayer MX2. We performed angle-resolved photoemission spectroscopy and tight binding calculations to investigate the electronic structures of bulk 2H-MX2. We could extract all the important electronic band parameters for bulk 2H-MX2, including the band gap, direct band gap size at K (-K) point and spin splitting size. Upon comparing the parameters for bulk 2H-MX2 (our work) with mono- and multi-layer MX2 (published), we found that stacked layers, substrates for thin films, and carrier concentration significantly affect the parameters, especially the band gap size. The origin of such effect is discussed in terms of the screening effect. PMID:27805019

Pilot-scale in situ bioremediation of HMX and RDX in soil pore water in Hawaii.

PubMed

Payne, Zachary M; Lamichhane, Krishna M; Babcock, Roger W; Turnbull, Stephen J

2013-10-01

A nine-month in situ bioremediation study was conducted in Makua Military Reservation (MMR) in Oahu, Hawaii (USA) to evaluate the potential of molasses to enhance biodegradation of royal demolition explosive (RDX) and high-melting explosive (HMX) contaminated soil below the root zone. MMR has been in operation since the 1940's resulting in subsurface contamination that in some locations exceeds USEPA preliminary remediation goals for these chemicals. A molasses-water mixture (1 : 40 dilution) was applied to a treatment plot and clean water was applied to a control plot via seven flood irrigation events. Pore water samples were collected from 12 lysimeters installed at different depths in 3 boreholes in each test plot. The difference in mean concentrations of RDX in pore water samples from the two test plots was very highly significant (p < 0.001). The concentrations differences with depth were also very highly significant (p < 0.001) and degradation was greatly enhanced at depths from 5 to 13.5 ft. biodegradation was modeled as first order and the rate constant was 0.063 per day at 5 ft and decreased to 0.023 per day at 11 ft to 13.5 ft depth. Enhanced biodegradation of HMX was also observed in molasses treated plot samples but only at a depth of 5 ft. The difference in mean TOC concentration (surrogate for molasses) was highly significant with depth (p = 0.003) and very highly significant with treatment (p < 0.001). Mean total nitrogen concentrations also differed significantly with treatment (p < 0.001) and depth (p = 0.059). The molasses water mixture had a similar infiltration rate to that of plain water (average 4.12 ft per day) and reached the deepest sensor (31 ft) within 5 days of application. Most of the molasses was consumed by soil microorganisms by about 13.5 feet below ground surface and treatment of deeper depths may require greater molasses concentrations and/or more frequent flood irrigation. Use of the bioremediation method described herein

Systematic study of the reaction kinetics for HMX.

PubMed

Long, Yao; Chen, Jun

2015-05-07

The reaction process of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in wide temperature and pressure ranges is simulated by molecular dynamics. A set of postprocessing programs is written to evaluate the intermediate molecules and chemical reactions. On the basis of these evaluations, the reaction rates, reactive Hugoniot curves, and detonation wave profile are calculated. The detonation velocity and detonation pressure are determined as 9984 m/s and 38.3349 GPa, in agreement with the experimental results, 9110 m/s and 39.5 GPa. The width of the reaction zone is 10 μm, and the main products are N2, H2O, and CO2. We find some molecules play an important role in intermediate reactions but are not exhibited in final products, such as N2O2, N2O5, and C3H3N3.

Microstructural characterization of pressed HMX material sets at differing densities

NASA Astrophysics Data System (ADS)

Molek, C. D.; Welle, E. J.; Wixom, R. R.; Ritchey, M. B.; Samuels, P.; Horie, Y.

2017-01-01

The detonation physics community has embraced the idea that initiation of high explosives (HE) proceeds from an ignition event through subsequent growth to steady detonation. A weakness of all the commonly used ignition and growth models is the microstructural characteristics of the HE are not explicitly incorporated in their ignition and growth terms. This is the case in spite of a demonstrated, but not well-understood, empirical link between particle morphology and initiation of HE. Morphological effects have been parametrically studied in many ways, the majority of efforts focus on establishing a tie between bulk powder metrics and initiation of the pressed beds. More recently, there has been a shift toward characterizing the microstructure of pressed beds in order to understand the underlying mechanisms governing initiation behavior. In this work, we have characterized the microstructures of two HMX classes pressed at three densities using ion bombardment techniques. We find more significant compaction associated with the larger crystalline material - Class 3 - than the smaller fluid energy milled material. The Class 3 material exhibits evidence of crystal cracking. Finally, we discuss this evidence and our attempt to correlate microstructural features to observed changes in continuum level initiation behavior.

Shock initiation studies of low density HMX using electromagnetic particle velocity and PVDF stress gauges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheffield, S.A.; Gustavsen, R.L.; Alcon, R.R.

1993-09-01

Magnetic particle velocity and PVDF stress rate gauges have been used to measure the shock response of low density octotetramethylene tetranitramine (HMX) (1.24 &/cm{sup 3}). In experiments done at LANL, magnetic particle velocity gauges were located on both sides of the explosive. In nearly identical experiments done at SNL, PVDF stress rate gauges were located at the same positions so both particle velocity and stress histories were obtained for a particular experimental condition. Unreacted Hugoniot data were obtained and an EOS was developed by combining methods used by Hayes, Sheffield and Mitchell (for describing the Hugoniot of HNS at variousmore » densities) with Hermann`s P-{alpha} model. Using this technique, it is only necessary to know some thermodynamic constants or the Hugoniot of the initially solid material and the porous material sound speed to obtain accurate unreacted Hugoniots for the porous explosive. Loading and reaction paths were established in the stress-particle velocity plane for some experimental conditions. This information was used to determine a global reaction rate of {approx} 0.13 {mu}s{sup {minus}1} for porous HMX shocked to 0.8 GPa. At low input stresses the transmitted wave profiles had long rise times (up to 1 {mu}s) due to the compaction processes.« less

Simulation of hot spots formation and evolution in HMX

NASA Astrophysics Data System (ADS)

Wang, Cheng; Yang, Tonghui

2017-06-01

In order to study the formation and evolution of hot spots under shock loading, HMX explosives were selected as the object of study for the two-dimensional finite difference numerical simulation. A fifth order finite difference weighted essentially non-oscillatory (WENO) scheme and a third order TVD Runge-Kutta method are utilized for the spatial discretization and the time advance, respectively. The governing equations are based on the fluid elasto-plastic control equations. The Mie-Gruneisen equation of state and the ideal gas equation of state are selected to use in the state equation of the solid explosives and gas material. In order to simplify the calculation of the model, the reaction can be considered to complete in one step. The calculated area is [ 3.0 ×10-5 m ] × [ 3.0 ×10-5 m ] . The radius is 0.6 ×10-5 m, and the internal gas is not involved in the reaction. The calculation area is divided into 300×300 grids and 10 grids are selected from the bottom of each column to give the particle velocity u as the initial condition. In the selected grid, different initial velocity 100m/s and 200m/s are loaded respectively to study the influence of hot spot formation and evolution in different impact intensity.

Cohesive finite element modeling of the delamination of HTPB binder and HMX crystals under tensile loading

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walters, David J.; Luscher, Darby J.; Yeager, John D.

Accurately modeling the mechanical behavior of the polymer binders and the degradation of interfaces between binder and crystal is important to science-based understanding of the macro-scale response of polymer bonded explosives. The paper presents a description of relatively a simple bi-crystal HMX-HTPB specimen and associated tensile loading experiment including computed tomography imaging, the pertinent constitutive theory, and details of numerical simulations used to infer the behavior of the material during the delamination process. Within this work, mechanical testing and direct numerical simulation of this relatively simple bi-crystal system enabled reasonable isolation of binder-crystal interface delamination, in which the effects ofmore » the complicated thermomechanical response of explosive crystals were minimized. Cohesive finite element modeling of the degradation and delamination of the interface between a modified HTPB binder and HMX crystals was used to reproduce observed results from tensile loading experiments on bi-crystal specimens. Several comparisons are made with experimental measurements in order to identify appropriate constitutive behavior of the binder and appropriate parameters for the cohesive traction-separation behavior of the crystal-binder interface. This research demonstrates the utility of directly modeling the delamination between binder and crystal within crystal-binder-crystal tensile specimen towards characterizing the behavior of these interfaces in a manner amenable to larger scale simulation of polycrystalline PBX materials. One critical aspect of this approach is micro computed tomography imaging conducted during the experiments, which enabled comparison of delamination patterns between the direct numerical simulation and actual specimen. In addition to optimizing the cohesive interface parameters, one important finding from this investigation is that understanding and representing the strain-hardening plasticity of HTPB

Cohesive finite element modeling of the delamination of HTPB binder and HMX crystals under tensile loading

DOE PAGES

Walters, David J.; Luscher, Darby J.; Yeager, John D.; ...

2018-02-27

Accurately modeling the mechanical behavior of the polymer binders and the degradation of interfaces between binder and crystal is important to science-based understanding of the macro-scale response of polymer bonded explosives. The paper presents a description of relatively a simple bi-crystal HMX-HTPB specimen and associated tensile loading experiment including computed tomography imaging, the pertinent constitutive theory, and details of numerical simulations used to infer the behavior of the material during the delamination process. Within this work, mechanical testing and direct numerical simulation of this relatively simple bi-crystal system enabled reasonable isolation of binder-crystal interface delamination, in which the effects ofmore » the complicated thermomechanical response of explosive crystals were minimized. Cohesive finite element modeling of the degradation and delamination of the interface between a modified HTPB binder and HMX crystals was used to reproduce observed results from tensile loading experiments on bi-crystal specimens. Several comparisons are made with experimental measurements in order to identify appropriate constitutive behavior of the binder and appropriate parameters for the cohesive traction-separation behavior of the crystal-binder interface. This research demonstrates the utility of directly modeling the delamination between binder and crystal within crystal-binder-crystal tensile specimen towards characterizing the behavior of these interfaces in a manner amenable to larger scale simulation of polycrystalline PBX materials. One critical aspect of this approach is micro computed tomography imaging conducted during the experiments, which enabled comparison of delamination patterns between the direct numerical simulation and actual specimen. In addition to optimizing the cohesive interface parameters, one important finding from this investigation is that understanding and representing the strain-hardening plasticity of HTPB

Identification of Metabolic Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro-Substituted Explosives TNT, RDX, and HMX

DTIC Science & Technology

2006-07-31

Identification of Metabolic Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro- Substituted Explosives TNT, RDX...Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro-Substituted Explosives TNT, RDX, and HMX Final Technical Report 5a. CONTRACT NUMBER... Phytoremediation has been shown to provide a cost-effective alternative to classical technologies for cleaning up nitro-substituted explosive

4-Aminothiophenol functionalized gold nanoparticle-based colorimetric sensor for the determination of nitramine energetic materials.

PubMed

Üzer, Ayşem; Can, Ziya; Akın, Ilknur; Erçağ, Erol; Apak, Reşat

2014-01-07

The heterocyclic nitramine compounds, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are two most important military-purpose high explosives. Differentiation of RDX and HMX with colorimetric methods of determination has not yet been made because of their similar chemical structures. In this study, a sensitive colorimetric method for the determination of RDX and HMX was proposed on the basis of differential kinetics in the hydrolysis of the two compounds (yielding nitrite as a product) followed by their colorimetric determination using 4-aminothiophenol (4-ATP) modified gold nanoparticles (AuNPs) and naphthylethylene diamine (NED) as coupling agent for azo-dye formation, abbreviated as "4-ATP-AuNP+NED" colorimetric method. After alkaline hydrolysis in a 1 M Na2CO3 + 0.04 M NaOH mixture solution at room temperature, only RDX (but not HMX) was hydrolyzed to give a sufficient colorimetric response in neutralized solution, the molar absorptivity (ε) at 565 nm and the limit of detection (LOD) for RDX being (17.6 ± 1.3) × 10(3) L mol(-1) cm(-1) and 0.55 μg mL(-1), respectively. On the other hand, hot water bath (at 60 °C) hydrolysis enabled both nitramines, RDX and HMX, to give substantial colorimetric responses; i.e., ε and LOD for RDX were (32.8 ± 0.5) × 10(3) L mol(-1)cm(-1) and 0.20 μg mL(-1) and for HMX were (37.1 ± 2.8) × 10(3) L mol(-1)cm(-1) and 0.24 μg mL(-1), respectively. Unlike other AuNP-based nitrite sensors in the literature showing absorbance quenching within a relatively narrow concentration range, the developed sensor operated with an absorbance increase over a wide range of nitrite. Synthetic mixtures of (RDX + HMX) gave additive responses, and the proposed method was statistically validated against HPLC using nitramine mixtures.

Theoretical Design on a Series of Novel Bicyclic and Cage Nitramines as High Energy Density Compounds.

PubMed

Pan, Yong; Zhu, Weihua

2017-11-30

We designed four bicyclic nitramines and three cage nitramines by incorporating -N(NO 2 )-CH 2 -N(NO 2 )-, -N(NO 2 )-, and -O- linkages based on the HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) framework. Then, their electronic structure, heats of formation, energetic properties, strain energy, thermal stability, and impact sensitivity were systematically studied using density functional theory (DFT). Compared to the parent compound HMX, all the title compounds have much higher density, better detonation properties, and better oxygen balance. Among them, four compounds have extraordinary high detonation properties (D > 9.70 km/s and P > 44.30 GPa). Moreover, most of the title compounds exhibit better thermal stability and lower impact sensitivity than CL-20 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) or HNHAA (hexanitrohexaazaadamantane). Thus, all of the seven new nitramine compounds are promising candidates for high energy density compounds. In particular, five compounds exhibit a best combination of better oxygen balance, good thermal stability, excellent detonation properties superior to or comparable to CL-20 or HNHAA, and lower impact sensitivity than CL-20 or HNHAA. The results indicate that our unusual design strategy that constructing bicyclic or cage nitramines based on the HMX framework by incorporating the intramolecular linkages is very useful for developing novel energetic compounds with excellent detonation performance and low sensitivity.

Ab initio studies of 1,3,5,7-tetranitro-1,3,5,7-tetrazocine/1,3-dimethyl-2-imidazolidinone cocrystal under high pressure using dispersion corrected density functional theory

NASA Astrophysics Data System (ADS)

Gu, Bang-Ming; Lin, He; Zhu, Shun-Guan

2014-04-01

A detailed study of structural, electronic, and thermodynamic properties of 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)/1,3-dimethyl-2-imidazolidinone (DMI) cocrystal under the hydrostatic pressure of 0-100 GPa was performed by using dispersion-corrected density functional theory (DFT-D) method. The calculated crystal structure is in reasonable agreement with the experimental data at the ambient pressure. Based on the analysis of lattice constants, bond lengths, bond angles, and dihedral angles under compression, it is found that HMX molecules in HMX/DMI cocrystal are seriously distorted. In addition, as the pressure increases, the band gap decreases gradually, which suggests that HMX/DMI cocrystal is becoming more metallic. Some important intermolecular interactions between HMX and DMI are also observed in the density of states spectrum. Finally, its thermodynamic properties were characterized, and the results show that HMX/DMI cocrystal is more easily formed in the low pressure.

Identification of Metabolic Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro- Substituted Explosives TNT, RDX, and HMX

DTIC Science & Technology

2006-07-31

Identification of Metabolic Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro- Substituted Explosives TNT, RDX...Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro- Substituted Explosives TNT, RDX, and HMX 5a. CONTRACT NUMBER 5b. GRANT NUMBER...and groundwater in the United States and across Europe. The compounds have been shown to be toxic and are considered pollutants. Phytoremediation has

Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

PubMed

Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

2016-07-14

We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

Theoretical Prediction of the Heats of Formation, Densities and Relative Sensitivities, and/or Synthetic Approaches Toward the Synthesis of High Energy Dense Materials (HEDMs): 3,5-Dinitro-1,3,5-Oxadiazinane, Bis-Adjacent RDX, Bis-Adjacent HMX, 4,4’,6,6’-Tetranitro-1,1’-Bis(N-oxide)-5,5’,6,6’-4H,4’H-5,5’-Bisimidazo Oxadiazole, and the Open-Cage Derivative of CL-20

DTIC Science & Technology

2015-09-01

HMX , 4,4’,6,6’- Tetranitro-1,1’-Bis(N-oxide)-5,5’,6,6’-4H,4’H- 5,5’-Bisimidazo Oxadiazole, and the Open- Cage Derivative of CL-20...HEDMs): 3,5-Dinitro-1,3,5-Oxadiazinane, Bis-Adjacent RDX, Bis-Adjacent HMX , 4,4’,6,6’- Tetranitro-1,1’-Bis(N-oxide)-5,5’,6,6’-4H,4’H- 5,5’-Bisimidazo...Materials (HEDMs): 3,5-Dinitro-1,3,5-Oxadiazinane, Bis-Adjacent RDX, Bis-Adjacent HMX , 4,4’,6,6’-Tetranitro-1,1’-Bis(N-oxide)-

Dynamic evolutions of electron properties: A theoretical study for condensed-phase β-HMX under shock loading

NASA Astrophysics Data System (ADS)

He, Zheng-Hua; Chen, Jun; Wu, Qiang; Ji, Guang-Fu

2017-11-01

We present the density functional theory (DFT) calculations for microscopic electron properties of β-HMX under shock loading. The metallization pressure is determined to be within 30-55 GPa. The frontier molecular orbitals mainly localize on N-NO2 groups initially and disperse with pressure increase, while HOMO and LUMO orbitals trend to aggregate with each other. The deformation of N-NO2 groups and enhanced hydrogen-bonding interactions cause the electron delocalization and lower the band gap, inducing the reaction initiation finally. Our results show that using the electron properties can reliably predict the initial decomposition of energetic materials under shock loading.

Alkaline hydrolysis of the cyclic nitramine explosives RDX, HMX, and CL-20: new insights into degradation pathways obtained by the observation of novel intermediates.

PubMed

Balakrishnan, Vimal K; Halasz, Annamaria; Hawari, Jalal

2003-05-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, I) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) hydrolyze at pH > 10 to form end products including NO2-, HCHO, HCOOH, NH3, and N2O, but little information is available on intermediates, apart from the tentatively identified pentahydro-3,5-dinitro-1,3,5-triazacyclohex-1-ene (II). Despite suggestions that RDX and HMX contaminated groundwater could be economically treated via alkaline hydrolysis, the optimization of such a process requires more detailed knowledge of intermediates and degradation pathways. In this study, we hydrolyzed the monocyclic nitramines RDX, MNX (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine), and HMX in aqueous solution (pH 10-12.3) and found that nitramine removal was accompanied by formation of 1 molar equiv of nitrite and the accumulation of the key ring cleavage product 4-nitro-2,4-diazabutanal (4-NDAB, O2NNHCH2NHCHO). Most of the remaining C and N content of RDX, MNX, and HMX was found in HCHO, N2O, HCOOH, and NH3. Consequently, we selected RDX as a model compound and hydrolyzed it in aqueous acetonitrile solutions (pH 12.3) in the presence and absence of hydroxypropyl-beta-cyclodextrin (HP-beta-CD) to explore other early intermediates in more detail. We observed a transient LC-MS peak with a [M-H] at 192 Da that was tentatively identified as 4,6-dinitro-2,4,6-triaza-hexanal (O2NNHCH2NNO2CH2NHCHO, III) considered as the hydrolyzed product of II. In addition, we detected another novel intermediate with a [M-H] at 148 Da that was tentatively identified as a hydrolyzed product of III, namely, 5-hydroxy-4-nitro-2,4-diaza-pentanal (HOCH2NNO2CH2NHCHO, IV). Both III and IV can act as precursors to 4-NDAB. In the case of the polycyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), denitration (two NO2-) also led to the formation of HCOOH, NH3, and N2O, but neither HCHO nor 4-NDAB were detected. The results provide strong evidence that initial denitration

Ab initio studies of 1,3,5,7-tetranitro-1,3,5,7-tetrazocine/1,3-dimethyl-2-imidazolidinone cocrystal under high pressure using dispersion corrected density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Bang-Ming; Lin, He; Zhu, Shun-Guan, E-mail: zhusguan@yahoo.com

A detailed study of structural, electronic, and thermodynamic properties of 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)/1,3-dimethyl-2-imidazolidinone (DMI) cocrystal under the hydrostatic pressure of 0–100 GPa was performed by using dispersion-corrected density functional theory (DFT-D) method. The calculated crystal structure is in reasonable agreement with the experimental data at the ambient pressure. Based on the analysis of lattice constants, bond lengths, bond angles, and dihedral angles under compression, it is found that HMX molecules in HMX/DMI cocrystal are seriously distorted. In addition, as the pressure increases, the band gap decreases gradually, which suggests that HMX/DMI cocrystal is becoming more metallic. Some important intermolecular interactions between HMXmore » and DMI are also observed in the density of states spectrum. Finally, its thermodynamic properties were characterized, and the results show that HMX/DMI cocrystal is more easily formed in the low pressure.« less

A thermodynamically based definition of fast verses slow heating in secondary explosives

NASA Astrophysics Data System (ADS)

Henson, Bryan; Smilowitz, Laura

2013-06-01

The thermal response of energetic materials is often categorized according to the rate of heating as either fast or slow, e.g. slow cook-off. Such categorizations have most often followed some operational rationale, without a material based definition. We have spent several years demonstrating that for the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) a single mechanism of thermal response reproduces times to ignition independent of rate or means of heating over the entire range of thermal response. HMX is unique in that bulk melting is rarely observed in either thermal ignition or combustion. We have recently discovered a means of expressing this mechanism for HMX in a reduced form applicable to many secondary explosives. We will show that with this mechanism a natural definition of fast versus slow rates of heating emerges, related to the rate of melting, and we use this to illustrate why HMX does not exhibit melting, and why a number of other secondary explosives do, and require the two separate categories.

Compressible Heating in the Condense Phase due to Pore Collapse in HMX

NASA Astrophysics Data System (ADS)

Zhang, Ju; Jackson, Thomas

Axisymmetric pore collapse in HMX is studied numerically by solving multi-phase reactive Euler equations. The generation of hot spots in the condense phase due to compressible heating is examined. The motivation is to improve the understanding of the role of embedded cavities in the initiation of reaction in explosives, and to investigate the effect of hot spots in the condense phase due to compressible heating alone, complementing previous study on hot spots due to the reaction in the gas phase and at the interface. It is found that the shock-cavity interaction results in pressures and thus temperatures that are substantially higher than the post-shock values in the condense phase. However, these hot spots in the condense phase due to compressible heating alone do not seem to be sufficiently hot to lead to ignition at shock pressures of 1-3 GPa. Thus, compressible heating in the condense phase may be excluded as a mechanism for initiation of explosives. It should be pointed out that the ignition threshold for the temperature, the so-called ``switch-on'' temperature, of hot spots depend on chemistry kinetics parameters. Switch-on temperature is lower for faster reaction rate. The current chemistry kinetics parameters are based on previous experimental work. This work was supported in part by the Defense Threat Reduction Agency and by the U.S. Department of Energy.

Cluster evolution during the early stages of heating explosives and its relationship to sensitivity: a comparative study of TATB, β-HMX and PETN by molecular reactive force field simulations.

PubMed

Wen, Yushi; Zhang, Chaoyang; Xue, Xianggui; Long, Xinping

2015-05-14

Clustering is experimentally and theoretically verified during the complicated processes involved in heating high explosives, and has been thought to influence their detonation properties. However, a detailed description of the clustering that occurs has not been fully elucidated. We used molecular dynamic simulations with an improved reactive force field, ReaxFF_lg, to carry out a comparative study of cluster evolution during the early stages of heating for three representative explosives: 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), β-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and pentaerythritol tetranitrate (PETN). These representatives vary greatly in their oxygen balance (OB), molecular structure, stability and experimental sensitivity. We found that when heated, TATB, HMX and PETN differ in the size, amount, proportion and lifetime of their clusters. We also found that the clustering tendency of explosives decreases as their OB becomes less negative. We propose that the relationship between OB and clustering can be attributed to the role of clustering in detonation. That is, clusters can form more readily in a high explosive with a more negative OB, which retard its energy release, secondary decomposition, further decomposition to final small molecule products and widen its detonation reaction zone. Moreover, we found that the carbon content of the clusters increases during clustering, in accordance with the observed soot, which is mainly composed of carbon as the final product of detonation or deflagration.

Vibrational and thermal properties of β-HMX and TATB from dispersion corrected density functional theory

NASA Astrophysics Data System (ADS)

Landerville, Aaron C.; Oleynik, Ivan I.

2017-01-01

Dispersion Corrected Density Functional Theory (DFT+vdW) calculations are performed to predict vibrational and thermal properties of the bulk energetic materials (EMs) β-octahydrocyclotetramethylene-tetranitramine (β-HMX) and triaminotrinitrobenzene (TATB). DFT+vdW calculations of pressure-dependent crystal structure and the hydrostatic equation of state are followed by frozen-phonon calculations of their respective vibration spectra at each pressure. These are then used under the quasi-harmonic approximation to obtain zero-point and thermal free energy contributions to the pressure, resulting in pressure-volume-temperature (PVT) EOS for each material that are in excellent agreement with experiment. Heat capacities, and coefficients of thermal expansion as functions of temperature are also calculated and compared with experiment.

Degradation of high energetic and insensitive munitions compounds by Fe/Cu bimetal reduction.

PubMed

Koutsospyros, Agamemnon; Pavlov, Julius; Fawcett, Jacqueline; Strickland, David; Smolinski, Benjamin; Braida, Washington

2012-06-15

A reductive technology based on a completely mixed two-phase reactor (bimetallic particles and aqueous stream) was developed for the treatment of aqueous effluents contaminated with nitramines and nitro-substituted energetic materials. Experimental degradation studies were performed using solutions of three high energetics (RDX, HMX, TNT) and three insensitive-munitions components (NTO, NQ, DNAN). The study shows that, on laboratory scale, these energetic compounds are easily degraded in solution by suspensions of bimetallic particles (Fe/Ni and Fe/Cu) prepared by electro-less deposition. The type of bimetal pair (Fe/Cu or Fe/Ni) does not appear to affect the degradation kinetics of RDX, HMX, and TNT. The degradation of all components followed apparent first-order kinetics. The half-lives of all compounds except NTO were under 10 min. Additional parameters affecting the degradation processes were solids loading and initial pH. Copyright © 2012 Elsevier B.V. All rights reserved.

Anisotropic responses and initial decomposition of condensed-phase β-HMX under shock loadings via molecular dynamics simulations in conjunction with multiscale shock technique.

PubMed

Ge, Ni-Na; Wei, Yong-Kai; Song, Zhen-Fei; Chen, Xiang-Rong; Ji, Guang-Fu; Zhao, Feng; Wei, Dong-Qing

2014-07-24

Molecular dynamics simulations in conjunction with multiscale shock technique (MSST) are performed to study the initial chemical processes and the anisotropy of shock sensitivity of the condensed-phase HMX under shock loadings applied along the a, b, and c lattice vectors. A self-consistent charge density-functional tight-binding (SCC-DFTB) method was employed. Our results show that there is a difference between lattice vector a (or c) and lattice vector b in the response to a shock wave velocity of 11 km/s, which is investigated through reaction temperature and relative sliding rate between adjacent slipping planes. The response along lattice vectors a and c are similar to each other, whose reaction temperature is up to 7000 K, but quite different along lattice vector b, whose reaction temperature is only up to 4000 K. When compared with shock wave propagation along the lattice vectors a (18 Å/ps) and c (21 Å/ps), the relative sliding rate between adjacent slipping planes along lattice vector b is only 0.2 Å/ps. Thus, the small relative sliding rate between adjacent slipping planes results in the temperature and energy under shock loading increasing at a slower rate, which is the main reason leading to less sensitivity under shock wave compression along lattice vector b. In addition, the C-H bond dissociation is the primary pathway for HMX decomposition in early stages under high shock loading from various directions. Compared with the observation for shock velocities V(imp) = 10 and 11 km/s, the homolytic cleavage of N-NO2 bond was obviously suppressed with increasing pressure.

New Outlook on the High-Pressure Behavior of Pentaerythritol Tetranitrate

DTIC Science & Technology

2007-09-01

energetic materials, such as Octahydro-1, 3, 5, 7-tetranitro- 1, 3, 5, 7-tetrazocine ( HMX ) and RDX , and this phenomenon is most likely caused by...H.; Smith, L. C. Studies on the Polymorphs of HMX . Los Alamos Technical Report No. LAMS-2652, 1962. 2. Halleck, P. M.; Wackerle, J. Dynamic...429, 827. 10. Sorescu, D. C.; Rice, B. M.; Thompson, D. L. Theoretical Studies of the Hydrostatic Compression of RDX , HMX , HNIW, and PETN Crystals

Method and apparatus for synthesizing HMX and N/sub 2/O/sub 5/. [Patent application; cyclotetramethylenetetraamine

DOEpatents

McGuire, R.R.; Coon, C.L.; Harrar, J.E.; Pearson, R.K.

1982-07-20

A method and apparatus for electrochemically synthesizing N/sub 2/O/sub 5/ includes oxidizing a solution of N/sub 2/O/sub 4//HNO/sub 3/ at an anode, while maintaining a controlled potential between the N/sub 2/O/sub 4//HNO/sub 3/ solution and the anode. A potential of about 1.35 to 2.0V vs. SCE is preferred, while a potential of about 1.80V vs. SCE is most preferred. Thereafter, the N/sub 2/O/sub 5/ is reacted with either 1.5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) or 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclooctane (TAT) to form cyclotetramethylenetetraamine (HMX).

Comparative theoretical studies of differently bridged nitramino-substituted ditetrazole 2-N-oxides with high detonation performance and an oxygen balance of around zero.

PubMed

Wu, Qiong; Kou, Bo; Hang, Zusheng; Zhu, Weihua

2017-06-01

In this work, six (A-F) nitramino (-NHNO 2 )-substituted ditetrazole 2-N-oxides with different bridging groups (-CH 2 -, -CH 2 -CH 2 -, -NH-, -N=N-, and -NH-NH-) were designed. The six compounds were based on the parent compound tetrazole 2-N-oxide, which possesses a high oxygen balance and high density. The structure, heat of formation, density, detonation properties (detonation velocity D and detonation pressure P), and the sensitivity of each compound was investigated systematically via density functional theory, by studying the electrostatic potential, and using molecular mechanics. The results showed that compounds A-F all have outstanding energetic properties (D: 9.1-10.0 km/s; P: 38.0-46.7 GPa) and acceptable sensitivities (h 50 : 28-37 cm). The bridging group present was found to greatly affect the detonation performance of each ditetrazole 2-N-oxide, and the compound with the -NH-NH- bridging group yielded the best results. Indeed, this compound (F) was calculated to have comparable sensitivity to the famous and widely used high explosive 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), but with values of D and P that were about 8.7% and 19.4% higher than those for HMX, respectively. The present study shows that tetrazole 2-N-oxide is a useful parent compound which could potentially be used in the design of new and improved high-energy compounds to replace existing energetic compounds such as HMX.

Gas gun experiments and numerical simulations on the HMX-based explosive PBX 9501 in the overdriven 30 to 120 GPa pressure regime

NASA Astrophysics Data System (ADS)

Pittman, E. R.; Gustavsen, R. L.; Hagelberg, C. R.; Schmidt, J. H.

2017-06-01

The focus of this set of experiments is the development of data on the Hugoniot for the overdriven products equation of state (EOS) of PBX 9501 (95 weight % HMX, 5 weight % plastic binder) and to extend data from which current computational EOS models draw. This series of shots was conducted using the two-stage gas-guns at Los Alamos and aimed to gather data in the 30 to 120 GPa pressure regime. Experiments were simulated using FLAG, a Langrangian multiphysics code, using a one-dimensional setup which employs the Wescott Stewart Davis (WSD) reactive burn model. Prior to this study, data did not extend above 90 GPa, so the new data allowed the model to be re-evaluated. A comparison of the simulations with the experimental data shows that the model fits well below 80 GPa. However, the model did not fall within the error bars of the data for higher pressures. This is an indication that the PBX 9501 overdriven EOS products model could be modified to better match the data.

Examining the effects of microstructure and loading on the shock initiation of HMX with mesoscale simulations

NASA Astrophysics Data System (ADS)

Springer, H. Keo; Tarver, Craig; Bastea, Sorin

2015-06-01

We perform reactive mesoscale simulations to study shock initiation in HMX over a range of pore morphologies and sizes, porosities, and loading conditions in order to improve our understanding of structure-performance relationships. These relationships are important because they guide the development of advanced macroscale models incorporating hot spot mechanisms and the optimization of novel energetic material microstructures. Mesoscale simulations are performed using the multiphysics hydrocode, ALE3D. Spherical, elliptical, polygonal, and crack-like pore geometries 0.1, 1, 10, and 100 microns in size and 2, 5, 10, and 14% porosity are explored. Loading conditions are realized with shock pressures of 6, 10, 20, 38, and 50 GPa. A Cheetah-based tabular model, including temperature-dependent heat capacity, is used for the unreacted and the product equation-of-state. Also, in-line Cheetah is used to probe chemical species evolution. The influence of microstructure and shock loading on shock-to-detonation-transition run distance, reaction rate and product gas species evolution are discussed. This work performed under the auspices of the U.S. DOE by LLNL under Contract DE-AC52-07NA27344. This work is funded by the Joint DoD-DOE Munitions Program.

Investigating the fate of nitroaromatic (TNT) and nitramine (RDX and HMX) explosives in fractured and pristine soils.

PubMed

Douglas, Thomas A; Walsh, Marianne E; McGrath, Christian J; Weiss, Charles A

2009-01-01

Explosives compounds, known toxins, are loaded to soils on military training ranges predominantly during explosives detonation events that likely fracture soil particles. This study was conducted to investigate the fate of explosives compounds in aqueous slurries containing fractured and pristine soil particles. Three soils were crushed with a piston to emulate detonation-induced fracturing. X-ray diffraction, energy-dispersive X-ray spectrometry, gas adsorption surface area measurements, and scanning electron microscopy were used to quantify and image pristine and fractured soil particles. Aqueous batches were prepared by spiking soils with solutions containing 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4-dinitrotoluene (2,4-DNT). Samples were collected over 92 d and the concentrations of the spiked explosives compounds and TNT transformation products 2-amino-4,6-dinitrotoluene (2ADNT) and 4-amino-2,6-dinitrotoluene (4ADNT) were measured. Our results suggest soil mineralogical and geochemical compositions were not changed during piston-induced fracturing but morphological differences were evident with fractured soils exhibiting more angular surfaces, more fine grained particles, and some microfracturing that is not visible in the pristine samples. TNT, 2,4-DNT, RDX, and HMX exhibited greater analyte loss over time in batch solutions containing fractured soil particles compared to their pristine counterparts. 2ADNT and 4ADNT exhibited greater concentrations in slurries containing pristine soils than in slurries containing fractured soils. Explosives compound transformation is greater in the presence of fractured soil particles than in the presence of pristine soil particles. Our results imply fractured soil particles promote explosive compound transformation and/or explosives compounds have a greater affinity for adsorption to fractured soil particle surfaces.

Multichannel emission spectrometer for high dynamic range optical pyrometry of shock-driven materials

NASA Astrophysics Data System (ADS)

Bassett, Will P.; Dlott, Dana D.

2016-10-01

An emission spectrometer (450-850 nm) using a high-throughput, high numerical aperture (N.A. = 0.3) prism spectrograph with stepped fiberoptic coupling, 32 fast photomultipliers and thirty-two 1.25 GHz digitizers is described. The spectrometer can capture single-shot events with a high dynamic range in amplitude and time (nanoseconds to milliseconds or longer). Methods to calibrate the spectrometer and verify its performance and accuracy are described. When a reference thermal source is used for calibration, the spectrometer can function as a fast optical pyrometer. Applications of the spectrometer are illustrated by using it to capture single-shot emission transients from energetic materials or reactive materials initiated by kmṡs-1 impacts with laser-driven flyer plates. A log (time) data analysis method is used to visualize multiple kinetic processes resulting from impact initiation of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) or a Zr/CuO nanolaminate thermite. Using a gray body algorithm to interpret the spectral radiance from shocked HMX, a time history of temperature and emissivity was obtained, which could be used to investigate HMX hot spot dynamics. Finally, two examples are presented showing how the spectrometer can avoid temperature determination errors in systems where thermal emission is accompanied by atomic or molecular emission lines.

Multichannel emission spectrometer for high dynamic range optical pyrometry of shock-driven materials.

PubMed

Bassett, Will P; Dlott, Dana D

2016-10-01

An emission spectrometer (450-850 nm) using a high-throughput, high numerical aperture (N.A. = 0.3) prism spectrograph with stepped fiberoptic coupling, 32 fast photomultipliers and thirty-two 1.25 GHz digitizers is described. The spectrometer can capture single-shot events with a high dynamic range in amplitude and time (nanoseconds to milliseconds or longer). Methods to calibrate the spectrometer and verify its performance and accuracy are described. When a reference thermal source is used for calibration, the spectrometer can function as a fast optical pyrometer. Applications of the spectrometer are illustrated by using it to capture single-shot emission transients from energetic materials or reactive materials initiated by km⋅s -1 impacts with laser-driven flyer plates. A log (time) data analysis method is used to visualize multiple kinetic processes resulting from impact initiation of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) or a Zr/CuO nanolaminate thermite. Using a gray body algorithm to interpret the spectral radiance from shocked HMX, a time history of temperature and emissivity was obtained, which could be used to investigate HMX hot spot dynamics. Finally, two examples are presented showing how the spectrometer can avoid temperature determination errors in systems where thermal emission is accompanied by atomic or molecular emission lines.

A Computationally Based Study of Polycyclic Nitramines and Their Precursors: Comparisons between Known and Notional Compounds

DTIC Science & Technology

2015-02-01

bicyclo- HMX (22) ..................................................................................29 4.4.2 2,6,7-Trinitro-2,6,7-triaza[2.2.2]octane... HMX , and CL-20 ................................................................2 Fig. 2 Molecular structures of 1, 2, and 3...4 Fig. 4 Molecular structures of the precursor (HMTA) for the industrial-scale production of RDX and HMX

Accurately predicting the structure, density, and hydrostatic compression of crystalline β-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane based on its wave-function-based potential

NASA Astrophysics Data System (ADS)

Song, H.-J.; Huang, F.

2011-09-01

A wave-function-based intermolecular potential of the β phase 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) molecule has been constructed from first principles using the Williams-Stone-Misquitta method and the symmetry-adapted perturbation theory. Using the potential and its derivatives, we have accurately predicted not only the structure and lattice energy of the crystalline β-HMX at 0 K, but also its densities at temperatures of 0-403 K within an accuracy of 1% of density. The calculated densities at pressures within 0-6 GPa excellently agree with the results from the experiments on hydrostatic compression.

Low-mass ions observed in plasma desorption mass spectrometry of high explosives

PubMed

Hakansson; Coorey; Zubarev; Talrose; Hakansson

2000-03-01

The low-mass ions observed in both positive and negative plasma desorption mass spectrometry (PDMS) of the high explosives HMX, RDX, CL-20, NC, PETN and TNT are reported. Possible identities of the most abundant ions are suggested and their presence or absence in the different spectra is related to the properties of the explosives as matrices in PDMS. The detection of abundant NO+ and NO2- ions for HMX, RDX and CL-20, which are efficient matrices, indicates that explosive decomposition takes place in PDMS of these three substances and that a contribution from the corresponding chemical energy release is possible. The observation of abundant C2H4N+ and CH2N+ ions, which have high protonation properties, might also explain the higher protein charge states observed with these matrices. Also, the observation of NO2-, possibly formed by electron scavenging which increases the survival probability of positively charged protein molecular ions, completes the pattern. TNT does not give any of these ions and it is thereby possible to explain why it does not work as a PDMS matrix. For NC and PETN, decomposition does not seem to be as pronounced as for HMX, RDX and CL-20, and also no particularly abundant ions with high protonation properties are observed. The fact that NC works well as a matrix might be related to other properties of this compound, such as its high adsorption ability.

Remediating munitions-contaminated soil with zerovalent iron and cationic surfactants.

PubMed

Park, J; Comfort, S D; Shea, P J; Machacek, T A

2004-01-01

Soils contaminated from military operations often contain mixtures of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and TNT (2,4,6-trinitrotoluene) rather than a single explosive. Differences among explosives in solubility and reactivity make developing a single remediation treatment difficult. When Fe(0) was used to treat a munitions-contaminated soil, we observed high rates of destruction for RDX and TNT (98%) but not HMX. Our objective was to determine if HMX destruction by Fe(0) could be enhanced by increasing HMX solubility by physical (temperature) or chemical (surfactants) means. To determine electron acceptor preference, we treated RDX and HMX with Fe(0) in homogeneous solutions and binary mixtures. Increasing aqueous temperature (20 to 55 degrees C) increased HMX solubility (2 to 22 mg L(-1)) but did not increase destruction by Fe(0) in a contaminated soil slurry that also contained RDX and TNT. Batch experiments using equal molar concentrations of RDX and HMX demonstrated that RDX was preferentially reduced over HMX by Fe(0). By testing various surfactants, we found that the cationic surfactants (HDTMA [hexadecyltrimethylammonium bromide], didecyl, and didodecyl) were most effective in increasing HMX concentration in solution. Didecyl and HDTMA were also found to be highly effective in facilitating the transformation of HMX by Fe(0). Using HDTMA or didecyl solutions (3%, w/v) containing solid-phase HMX, we observed that 100% of the added HMX was transformed by Fe(0) in the didecyl matrix and 60% in the HDTMA matrix. These results indicate that cationic surfactants can increase HMX solubility and facilitate Fe(0)-mediated transformation kinetics but HMX destruction rates will be slowed when RDX is present.

Impact of glycerin and lignosulfonate on biodegradation of high explosives in soil.

PubMed

Won, Jongho; Borden, Robert C

2016-11-01

Soil microcosms were constructed and monitored to evaluate the impact of substrate addition and transient aerobic and anaerobic conditions on TNT, RDX and HMX biodegradation in grenade range soils. While TNT was rapidly biodegraded under both aerobic and anaerobic conditions with and without organic substrate, substantial biodegradation of RDX, HMX, and RDX daughter products was not observed under aerobic conditions. However, RDX and HMX were significantly biodegraded under anaerobic conditions, without accumulation of TNT or RDX daughter products (2-ADNT, 4-ADNT, MNX, DNX, and TNX). In separate microcosms containing grenade range soil, glycerin and lignosulfonate addition enhanced oxygen consumption, increasing the consumption rate >200% compared to untreated soils. Mathematical model simulations indicate that oxygen consumption rates of 5 to 20g/m 3 /d can be achieved with reasonable amendment loading rates. These results indicate that glycerin and lignosulfonate can be potentially used to stimulate RDX and HMX biodegradation by increasing oxygen consumption rates in soil. Copyright © 2016 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vandersall, K S; Tarver, C M; Garcia, F

Shock initiation experiments on the HMX based explosives LX-10 (95% HMX, 5% Viton by weight) and LX-07 (90% HMX, 10% Viton by weight) were performed to obtain in-situ pressure gauge data, run-distance-to-detonation thresholds, and Ignition and Growth modeling parameters. A 101 mm diameter propellant driven gas gun was utilized to initiate the explosive samples with manganin piezoresistive pressure gauge packages placed between sample slices. The run-distance-to-detonation points on the Pop-plot for these experiments and prior experiments on another HMX based explosive LX LX-04 (85% HMX, 15% Viton by weight) will be shown, discussed, and compared as a function of themore » binder content. This parameter set will provide additional information to ensure accurate code predictions for safety scenarios involving HMX explosives with different percent binder content additions.« less

Ultrafast dynamic response of single-crystal β-HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)

NASA Astrophysics Data System (ADS)

Zaug, Joseph M.; Austin, Ryan A.; Armstrong, Michael R.; Crowhurst, Jonathan C.; Goldman, Nir; Ferranti, Louis; Saw, Cheng K.; Swan, Raymond A.; Gross, Richard; Fried, Laurence E.

2018-05-01

We report experimental and computational studies of shock wave dynamics in single-crystal β-HMX on an ultrafast time scale. Here, a laser-based compression drive (˜1 ns in duration; stresses of up to ˜40 GPa) is used to propagate shock waves normal to the (110) and (010) lattice planes. Ultrafast time-domain interferometry measurements reveal distinct, time-dependent relationships between the shock wave velocity and particle velocity for each crystal orientation, which suggest evolving physical processes on a sub-nanosecond time scale. To help interpret the experimental data, elastic shock wave response was simulated using a finite-strain model of crystal thermoelasticity. At early propagation times (<500 ps), the model is in agreement with the data, which indicates that the mechanical response is dominated by thermoelastic deformation. The model agreement depends on the inclusion of nonlinear elastic effects in both the spherical and deviatoric stress-strain responses. This is achieved by employing an equation-of-state and a pressure-dependent stiffness tensor, which was computed via atomistic simulation. At later times (>500 ps), the crystal samples exhibit signatures of inelastic deformation, structural phase transformation, or chemical reaction, depending on the direction of wave propagation.

Carbon cluster formation during thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine and 1,3,5-triamino-2,4,6-trinitrobenzene high explosives from ReaxFF reactive molecular dynamics simulations.

PubMed

Zhang, Luzheng; Zybin, Sergey V; van Duin, Adri C T; Dasgupta, Siddharth; Goddard, William A; Kober, Edward M

2009-10-08

We report molecular dynamics (MD) simulations using the first-principles-based ReaxFF reactive force field to study the thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) at various densities and temperatures. TATB is known to produce a large amount (15-30%) of high-molecular-weight carbon clusters, whereas detonation of nitramines such as HMX and RDX (1,3,5-trinitroperhydro-1,3,5-triazine) generate predominantly low-molecular-weight products. In agreement with experimental observation, these simulations predict that TATB decomposition quickly (by 30 ps) initiates the formation of large carbonaceous clusters (more than 4000 amu, or approximately 15-30% of the total system mass), and HMX decomposition leads almost exclusively to small-molecule products. We find that HMX decomposes readily on this time scale at lower temperatures, for which the decomposition rate of TATB is about an order of magnitude slower. Analyzing the ReaxFF MD results leads to the detailed atomistic structure of this carbon-rich phase of TATB and allows characterization of the kinetics and chemistry related to this phase and their dependence on system density and temperature. The carbon-rich phase formed from TATB contains mainly polyaromatic rings with large oxygen content, leading to graphitic regions. We use these results to describe the initial reaction steps of thermal decomposition of HMX and TATB in terms of the rates for forming primary and secondary products, allowing comparison to experimentally derived models. These studies show that MD using the ReaxFF reactive force field provides detailed atomistic information that explains such macroscopic observations as the dramatic difference in carbon cluster formation between TATB and HMX. This shows that ReaxFF MD captures the fundamental differences in the mechanisms of such systems and illustrates how the ReaxFF may be applied to model complex chemical phenomena

Combustion mechanism of double-base propellant containing nitrogen heterocyclic nitroamines (II): The temperature distribution of the flame and its chemical structure

NASA Astrophysics Data System (ADS)

Yan, Qi-Long; Song, Zhen-Wei; Shi, Xiao-Bing; Yang, Zhi-Yuan; Zhang, Xiao-Hong

2009-03-01

In order to evaluate the actual pros and cons in the use of new nitroamines for solid rocket applications, the combustion properties of double-base propellants containing nitrogen heterocyclic nitroamines such as RDX, TNAD, HMX and DNP are investigated by means of high-speed photography technique, Non-contact wavelet-based measurement of flame temperature distribution. The chemical reactions in different combustion zone which control the burning characteristics of the double-base propellant containing nitrogen heterocyclic nitroamines were systematically investigated and descriptions of the detailed thermal decomposition mechanisms from solid phase to liquid phase or to gas phase are also included. It was indicated that the thermodynamic phase transition consisting of both evaporation and condensation of NC+NG, HMX, TNAD, RDX and DNP, are considered to provide a complete description of the mass transfer process in the combustion of these double-base propellants, and the combustion mechanisms of them are mainly involved with the oxidation mechanism of the NO 2, formaldehyde (CH 2O) and hydrogen cyanide (HCN). The entire oxidation reaction rate might be dependent on the pressure of the combustion chamber and temperature of the gas phase.

A Fast Liquid Chromatography Tandem Mass Spectrometric Analysis of PETN (Pentaerythritol Tetranitrate), RDX (3,5-Trinitro-1,3,5-triazacyclohexane) and HMX (Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) in Soil, Utilizing a Simple Ultrasonic-Assisted Extraction with Minimum Solvent.

PubMed

Anilanmert, Beril; Aydin, Muhammet; Apak, Resat; Avci, Gülfidan Yenel; Cengiz, Salih

2016-01-01

Direct analyses of explosives in soil using liquid chromatography tandem mass spectrometry (LC-MS/MS) methods are very limited in the literature and require complex procedures or relatively high amount of solvent. A simple and rapid method was developed for the determination of pentaerythritol tetranitrate (PETN), 3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), which are among the explosives used in terrorist attacks. A one-step extraction method for 1.00 g soil with 2.00 mL acetonitrile, and a 8-min LC-MS/MS method was developed. The detection limits for PETN, RDX and HMX were 5.2, 8.5 and 3.4 ng/g and quantitation limits were 10.0, 24.5, 6.0 ng/g. The intermediate precisions and Horwitz Ratio's were between 4.10 - 13.26% and 0.24 - 0.98, in order. This method was applied to a model post-blast debris collected from an artificial explosion and real samples collected after a terrorist attack in Istanbul. The method is easy and fast and requires less solvent use than other methods.

Electrochemical Determination of TNT, DNT, RDX, and HMX with Gold Nanoparticles/Poly(Carbazole-Aniline) Film-Modified Glassy Carbon Sensor Electrodes Imprinted for Molecular Recognition of Nitroaromatics and Nitramines.

PubMed

Sağlam, Şener; Üzer, Ayşem; Erçağ, Erol; Apak, Reşat

2018-06-19

Since nitroaromatic- and nitramine-type energetic materials, mostly arising from military activities, are persistent pollutants in soil and groundwater, on-site sensing of these hazardous chemicals has gained importance. A novel electrochemical sensor was designed for detecting nitroaromatic- and nitramine-type energetic materials, relying on gold nanoparticles (Au nano ), modified glassy carbon (GC) electrode coated with nitro-energetic memory-poly(carbazole-aniline) copolymer (Cz- co-ANI) film (e.g., TNT memory-GC/P(Cz- co-ANI)-Au nano modified electrode). Current was recorded against concentration to build the calibration curves that were found to be linear within the range of 100-1000 μg L -1 for 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT): 50-1000 μg L -1 for 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The corresponding limits of detection were 25 μg L -1 for TNT, 30 μg L -1 for DNT, and 10 μg L -1 for both RDX and HMX, using nitro-energetic memory-GC/P(Cz- co-ANI)-Au nano electrodes. These electrodes were used separately, and specific determinations were made in various mixtures of nitro-energetic materials. The developed method could be efficiently used in electroanalyzing nitroaromatics and nitramines in military explosives (i.e., comp B, octol, and comp A5). The sensor electrodes were specific for the tested nitro-energetic compounds and did not respond to paracetamol-caffeine-based analgesic drug, acetylsalicylic acid (aspirin), sweetener, and sugar that can be used as camouflage materials in passenger belongings. The developed method was statistically validated against the standard LC-MS reference method in contaminated clay soil samples containing TNT and RDX explosives.

Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous Fe¹¹ solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boparai, Hardiljeet K.; Comfort, Steve; Satapanajaru, Tunlawit

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated FeII phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron FeII/FeIII minerals. This was accomplished by quantifying the effects of initial FeII concentration, pH, and the presence of aquifermore » solids (FeIII phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing FeII concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous FeII during HE treatment under anaerobic conditions. Geochemical modeling also predicted FeII activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated FeII/FeIII minerals in aqueous FeII solutions play in the transformation of high explosives.« less

Insensitive High Energy Propellants for Advanced Gun Concepts

DTIC Science & Technology

2001-10-01

tetranitrate pentaerythritol), RDX , HMX , r3- and 6- polymorphs of CL20, HNS (2,2’,4,4’,6,6’-hexanitrostilbene), methyl picrate, styphnic acid, NTO (3...cyclic nitramines RDX (hexahydro-l,3,5-trinitro-l,3,5-7-triazine) and HMX (1,3,5,7-tetranitro-l,3,5,7- tetraazacyclooctane) to address these goals...inclusion of energetic fillers, such as RDX and 3 CL20, while maintaining good physical properties and providing the option for reprocessing. TPEs

Phase Transition in Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) under Static Compression: An Application of the First-Principles Method Specialized for CHNO Solid Explosives.

PubMed

Zhang, Lei; Jiang, Sheng-Li; Yu, Yi; Long, Yao; Zhao, Han-Yue; Peng, Li-Juan; Chen, Jun

2016-11-10

The first-principles method is challenged by accurate prediction of van der Waals interactions, which are ubiquitous in nature and crucial for determining the structure of molecules and condensed matter. We have contributed to this by constructing a set of pseudopotentials and pseudoatomic orbital basis specialized for molecular systems consisting of C/H/N/O elements. The reliability of the present method is verified from the interaction energies of 45 kinds of complexes (comparing with CCSD(T)) and the crystalline structures of 23 kinds of typical explosive solids (comparing with experiments). Using this method, we have studied the phase transition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) under static compression up to 50 GPa. Kinetically, intramolecular deformation has priority in the competition with intermolecular packing deformation by ∼87%. A possible γ → β phase transition is found at around 2.10 GPa, and the migration of H 2 O has an effect of kinetically pushing this process. We make it clear that no β → δ/ε → δ phase transition occurs at 27 GPa, which has long been a hot debate in experiments. In addition, the P-V relation, bulk modulus, and acoustic velocity are also predicted for α-, δ-, and γ-HMX, which are experimentally unavailable.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Myint, Philip C.; Nichols, Albert L.

In this paper, we present thermodynamic models for the five most commonly studied phases of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX): liquid HMX and four solid polymorphs (α-, β-, γ-, and δ-HMX). We show results for the density, heat capacity, bulk modulus, and sound speed, as well as a phase diagram that illustrates the temperature and pressure regions over which the various HMX phases are most thermodynamically stable. The models are based on the same equation of state presented in our recently published paper [Myint et al., Ind. Eng. Chem. Res., 2016, 55, 2252] on another energetic material, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Wemore » combine our HMX and RDX models together so that the equation of state can also be applied to liquid and solid mixtures of HMX/RDX. This allows us to generate an HMX/RDX phase diagram and calculate the enthalpy change associated with a few different kinds of phase transitions that these mixtures may undergo. Our paper is the first to present a single equation of state that is capable of modeling both pure HMX and HMX/RDX mixtures. A distinct feature of HMX is the strongly metastable nature of its polymorphs. This has caused some ambiguity in the literature regarding the thermodynamic stability of α-HMX. Finally, by examining possible arrangements for the relative order of the six different solid-solid transition (α–β, α–γ, α–δ, β–γ, β–δ, and γ–δ) temperatures, we conclude that α-HMX must be thermodynamically stable so that the HMX phase diagram must have an α phase region.« less

Molecular design and property prediction of high density polynitro[3.3.3]-propellane-derivatized frameworks as potential high explosives.

PubMed

Zhang, Qinghua; Zhang, Jiaheng; Qi, Xiujuan; Shreeve, Jean'ne M

2014-11-13

Research in energetic materials is now heavily focused on the design and synthesis of novel insensitive high explosives (IHEs) for specialized applications. As an effective and time-saving tool for screening potential explosive structures, computer simulation has been widely used for the prediction of detonation properties of energetic molecules with relatively high precision. In this work, a series of new polynitrotetraoxopentaaza[3.3.3]-propellane molecules with tricyclic structures were designed. Their properties as potential high explosives including density, heats of formation, detonation properties, impact sensitivity, etc., have been extensively evaluated using volume-based thermodynamic calculations and density functional theory (DFT).These new energetic molecules exhibit high densities of >1.82 g cm(-3), in which 1 gives the highest density of 2.04 g cm(-3). Moreover, most new materials show good detonation properties and acceptable impact sensitivities, in which 5 displays much higher detonation velocity (9482 m s(-1)) and pressure (43.9 GPa) than HMX and has a h50 value of 11 cm. These results are expected to facilitate the experimental synthesis of new-generation nitramine-based high explosives.

In Silico Alkaline Hydrolysis of Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine: Density Functional Theory Investigation.

PubMed

Sviatenko, Liudmyla K; Gorb, Leonid; Hill, Frances C; Leszczynska, Danuta; Shukla, Manoj K; Okovytyy, Sergiy I; Hovorun, Dmytro; Leszczynski, Jerzy

2016-09-20

HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), an energetic material used in military applications, may be released to the environment during manufacturing, transportation, storage, training, and disposal. A detailed investigation of a possible mechanism of alkaline hydrolysis, as one of the most promising methods for HMX remediation, was performed by computational study at PCM(Pauling)/M06-2X/6-311++G(d,p) level. Obtained results suggest that HMX hydrolysis at pH 10 represents a highly exothermic multistep process involving initial deprotonation and nitrite elimination, hydroxide attachment accompanied by cycle cleavage, and further decomposition of cycle-opened intermediate to the products caused by a series of C-N bond ruptures, hydroxide attachments, and proton transfers. Computationally predicted products of HMX hydrolysis such as nitrite, 4-nitro-2,4-diazabutanal, formaldehyde, nitrous oxide, formate, and ammonia correspond to experimentally observed species. Based on computed reaction pathways for HMX decomposition by alkaline hydrolysis, the kinetics of the entire process was modeled. Very low efficiency of this reaction at pH 10 was observed. Computations predict significant increases (orders of magnitude) of the hydrolysis rate for hydrolysis reactions undertaken at pH 11, 12, and 13.

Large Area and Short-Pulse Shock Initiation of a Tatb/hmx Mixed Explosive

NASA Astrophysics Data System (ADS)

Guiji, Wang; Chengwei, Sun; Jun, Chen; Cangli, Liu; Jianheng, Zhao; Fuli, Tan; Ning, Zhang

2007-12-01

The large area and short-pulse shock initiation experiments on the plastic bonded mixed explosive of TATB(80%) and HMX(15%) have been performed with an electric gun where a Mylar flyer of 10-19 mm in diameter and 0.05˜0.30 mm in thickness was launched by an electrically exploding metallic bridge foil. The cylindrical explosive specimens (Φ16 mm×8 mm in size) were initiated by the Mylar flyers in thickness of 0.07˜0.20 mm, which induced shock pressure in specimen was of duration ranging from 0.029 to 0.109 μs. The experimental data were treated with the DRM(Delayed Robbins-Monro) procedure and to provide the initiation threshold of flyer velocities at 50% probability are 3.398˜1.713 km/s and that of shock pressure P 13.73˜5.23 GPa, respectively for different pulse durations. The shock initiation criteria of the explosive specimen at 50% and 100% probabilities are yielded. In addition, the 30° wedged sample was tested and the shock to detonation transition (SDT) process emerging on its inclined surface was diagnosed with a device consisting of multiple optical fiber probe, optoelectronic transducer and digital oscilloscope. The POP plot of the explosive has been gained from above SDT data.

Burning mechanism and regression rate of RX-35-AU and RX-35-AV as a function of HMX particle size measured by the hybrid closed bomb-strand burner

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, W.C.; Costantino, M.S.; Ornellas, D.L.

1990-04-01

In this study, the average surface regression rate of two HMX-based cast explosives, RX-35-AU and RX-35-AV, is measured to pressures above 750 MPa using a hybrid closed bomb-strand burner. The hybrid design allows the simultaneous measurement of pressure and regression rate over a large range of pressures in each experiment. Nitroglycerin/Triacetin (75/25) and polyethylene glycol (PEG) are used as the energetic plasticizer and polymeric binder, respectively, in both formulations. The HMX solids loading in each formulation is 50 wt %, consisting of a narrow particle size distribution of 6--8 {mu}m for RX-35-AU and 150--177 {mu}m for RX-35-AV. Of special interestmore » are the regression rate and burning mechanism as a function of the initial particle size distribution and the mechanical properties fo the cast explosives. In general, the regression rate for the larger particle size formulation, RX-35-AV, is two to three times faster compared to that for RX-35-AU. Up to 750 MPa and independent of the initial confinement pressure, RX-35-AU exhibits a planar burning mechanism with the regression rate obeying the classical aP{sup n} formalism. For RX-35-AV, however, the burning behavior is erratic for samples ignited at 200 MPa confinement pressure. At confinement pressures above 400 MPa, the regression exhibits more of a planar burning mechanism. The unstable combustion behavior for RX-35-AV at lower confinement pressures is related to several mechanisms: (1) an abrupt increase in surface area due to particle fracture and subsequent translation and rotation, resulting in debonding and creating porosity, (2) thixotropic'' separation of the binder and nitramine, causing the significantly greater fracture damage to the nitramine during the loading cycle, (3) microscopic damage to the nitramine crystals that increase its intrinsic burning rate. 12 refs., 8 figs., 2 tabs.« less

The effect of explosive percentage on underwater explosion energy release of hexanitrohexaazaisowurtzitane and octogen based aluminized explosives

NASA Astrophysics Data System (ADS)

Jiao, Qingjie; Wang, Qiushi; Nie, Jianxin; Guo, Xueyong; Zhang, Wei; Fan, Wenqi

2018-03-01

To control the explosion energy output by optimizing explosive components is a key requirement in a number of different application areas. The effect of different Al/O Ratio on underwater explosion of aluminized explosives has been studied detailedly. However, the effect of explosive percentage in the same Al/O Ratio is rarely researched, especially for Hexanitrohexaazaisowurtzitane (CL-20) based aluminized explosives. In this study, we performed the underwater explosion experiments with 1.2-kilogram explosives in order to investigate the explosion energy released from CL-20 and Octogen (HMX) based aluminized explosives. The percentage of the explosive varied from 5% to 30% and it is shown that: the shockwave peak pressure (pm) grows gradually; shock wave energy (Es) continues increasing, bubble energy (Eb) increases then decreases peaking at 15% for both formulas, and the total energy (E) and energy release rate (η) peak at 20% for CL-20 and 15% for HMX. This paper outlines the physical mechanism of Eb change under the influence of an aluminium initial reaction temperature and reaction active detonation product percentage coupling. The result shows that CL-20 is superior as a new high explosive and has promising application prospects in the regulation of explosive energy output for underwater explosives.

Exploring the High-Pressure Behavior of PETN: A Combined Quantum Mechanical and Experimental Study

DTIC Science & Technology

2006-11-01

calculations to explore the hypothesized compression-induced polymorphic phase transition [Gruzdkov 2004]. The initial crystal in these Figure 4...Scuseria, G.E., and Chabalowski, C.F. 2004: An ab Initio Study of Solid Nitromethane, HMX , RDX , and CL20: Successes and Failures of DFT. J. Phys. Chem... RDX , HMX , HNIW, and PETN Crystals. J. Phys. Chem. B, 103, 6783. Trotter, J., 1963: Bond lengths and angles in Pentaerythritol Tetranitrate. Acta

Analysis of nitrogen-based explosives with desorption atmospheric pressure photoionization mass spectrometry.

PubMed

Kauppila, T J; Flink, A; Pukkila, J; Ketola, R A

2016-02-28

Fast methods that allow the in situ analysis of explosives from a variety of surfaces are needed in crime scene investigations and home-land security. Here, the feasibility of the ambient mass spectrometry technique desorption atmospheric pressure photoionization (DAPPI) in the analysis of the most common nitrogen-based explosives is studied. DAPPI and desorption electrospray ionization (DESI) were compared in the direct analysis of trinitrotoluene (TNT), trinitrophenol (picric acid), octogen (HMX), cyclonite (RDX), pentaerythritol tetranitrate (PETN), and nitroglycerin (NG). The effect of different additives in DAPPI dopant and in DESI spray solvent on the ionization efficiency was tested, as well as the suitability of DAPPI to detect explosives from a variety of surfaces. The analytes showed ions only in negative ion mode. With negative DAPPI, TNT and picric acid formed deprotonated molecules with all dopant systems, while RDX, HMX, PETN and NG were ionized by adduct formation. The formation of adducts was enhanced by addition of chloroform, formic acid, acetic acid or nitric acid to the DAPPI dopant. DAPPI was more sensitive than DESI for TNT, while DESI was more sensitive for HMX and picric acid. DAPPI could become an important method for the direct analysis of nitroaromatics from a variety of surfaces. For compounds that are thermally labile, or that have very low vapor pressure, however, DESI is better suited. Copyright © 2016 John Wiley & Sons, Ltd.

Workshop Report: Fundamental Reactions in Solid Propellant Combustion

DTIC Science & Technology

1979-05-01

combustion conditions. 6. What effect might a pressure-induced phase transition to a polymorph other than 6- HMX have on the pressure slope break during...pure HMX as well. Nevertheless, it is recommended that the high pressure polymorphs of HMX and RDX be determined. It was also felt that there...plateau burning phenomena E. Solid phase, surface, gas phase reactions F. Phase transitions : melting, vaporization, polymorphs G. Flame

Shock initiated thermal and chemical responses of HMX crystal from ReaxFF molecular dynamics simulation.

PubMed

Zhou, Tingting; Song, Huajie; Liu, Yi; Huang, Fenglei

2014-07-21

To gain an atomistic-level understanding of the thermal and chemical responses of condensed energetic materials under thermal shock, we developed a thermal shock reactive dynamics (TS-RD) computational protocol using molecular dynamics simulation coupled with ReaxFF force field. β-Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) was selected as a a target explosive due to its wide usage in the military and industry. The results show that a thermal shock initiated by a large temperature gradient between the "hot" region and the "cold" region results in thermal expansion of the particles and induces a thermal-mechanical wave propagating back and forth in the system with an averaged velocity of 3.32 km s(-1). Heat propagating along the direction of thermal shock leads to a temperature increment of the system and thus chemical reaction initiation. Applying a continuum reactive heat conduction model combined with the temperature distribution obtained from the RD simulation, a heat conduction coefficient is derived as 0.80 W m(-1) K(-1). The chemical reaction mechanisms during thermal shock were analyzed, showing that the reaction is triggered by N-NO2 bond breaking followed by HONO elimination and ring fission. The propagation rates of the reaction front and reaction center are obtained to be 0.069 and 0.038 km s(-1), based on the time and spatial distribution of NO2. The pressure effect on the thermal shock was also investigated by employing uniaxial compression before the thermal shock. We find that compression significantly accelerates thermal-mechanical wave propagation and heat conduction, resulting in higher temperature and more excited molecules and thus earlier initiation and faster propagation of chemical reactions.

Aqueous solubility and alkaline hydrolysis of the novel high explosive hexanitrohexaazaisowurtzitane (CL-20).

PubMed

Karakaya, Pelin; Sidhoum, Mohammed; Christodoulatos, Christos; Nicolich, Steve; Balas, Wendy

2005-04-11

The recently developed polycyclic nitramine CL-20 is considered as a possible replacement for the monocyclic nitramines RDX and HMX. The present study reports aqueous solubility data for CL-20, as well as the kinetic parameters for its alkaline hydrolysis with sodium hydroxide below and above its solubility limits. Aqueous solubility of CL-20 was measured in the temperature range of 4-69 degrees C and the data were fitted to a generalized solubility model. Alkaline hydrolysis experiments were conducted at 15, 20, 30 and 40 degrees C, 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 Arrhenius model. The activation energy for CL-20 was found to be within close range of the activation energies reported for RDX and HMX.

Experimental and TD-DFT study of optical absorption of six explosive molecules: RDX, HMX, PETN, TNT, TATP, and HMTD.

PubMed

Cooper, Jason K; Grant, Christian D; Zhang, Jin Z

2013-07-25

Time dependent density function theory (TD-DFT) has been utilized to calculate the excitation energies and oscillator strengths of six common explosives: RDX (1,3,5-trinitroperhydro-1,3,5-triazine), β-HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), TATP (triacetone triperoxide), HMTD (hexamethylene triperoxide diamine), TNT (2,4,6-trinitrotoluene), and PETN (pentaerythritol tetranitrate). The results were compared to experimental UV-vis absorption spectra collected in acetonitrile. Four computational methods were tested including: B3LYP, CAM-B3LYP, ωB97XD, and PBE0. PBE0 outperforms the other methods tested. Basis set effects on the electronic energies and oscillator strengths were evaluated with 6-31G(d), 6-31+G(d), 6-31+G(d,p), and 6-311+G(d,p). The minimal basis set required was 6-31+G(d); however, additional calculations were performed with 6-311+G(d,p). For each molecule studied, the natural transition orbitals (NTOs) were reported for the most prominent singlet excitations. The TD-DFT results have been combined with the IPv calculated by CBS-QB3 to construct energy level diagrams for the six compounds. The results suggest optimization approaches for fluorescence based detection methods for these explosives by guiding materials selections for optimal band alignment between fluorescent probe and explosive analyte. Also, the role of the TNT Meisenheimer complex formation and the resulting electronic structure thereof on of the quenching mechanism of II-VI semiconductors is discussed.

Saturation Transfer Difference NMR as an Analytical Tool for Detection and Differentiation of Plastic Explosives on the Basis of Minor Plasticizer Composition

DTIC Science & Technology

2015-05-01

HMX ); ethylene glycol dinitrate (EGDN); ammonium nitrate (AN); and nitrocellulose (NC).1–4 Alternatively, in one recent study,5 fluorescence-based...saturation transfer difference AN ammonium nitrate BSA bovine serum albumin EGDN ethylene glycol dinitrate HDO partially deuterated water HMX

Investigating the Deflagration to Detonation Transition in LLM-105 and RX-55-DQ Using High Confinement as a Function of Density

NASA Astrophysics Data System (ADS)

Strickland, Shawn L.; Vandersall, Kevin S.; Dehaven, Martin R.

2017-06-01

The potential for deflagration-to-detonation transition (DDT) in LLM-105 and RX-55-DQ (94/6 LLM-105/Viton) has been investigated as a function of loading density using high confinement tubes. The high confinement arrangement uses a 76 mm outer diameter by 25 mm inner diameter mild steel tube 320 mm in length with 25 mm thick mild steel end caps ignited using a thermite igniter and was loaded with samples of varying densities. None of the experiments showed a transition to detonation over the entire length with non-violent burning or extinguishing of the burning observed. The hand packed RX-55-DQ molding powder or neat LLM-105 ( 1.1 g/cm3) burned nearly completely and vented non-violently by deforming or splitting the end caps. The RX-55-DQ was tested at higher densities with 1.35 g/cm3 resulting in a burning reaction on the 2nd attempt that fractured the end cap while the 1.85 g/cm3 resulted in the burning reaction extinguishing in the first 15 mm on the 2nd attempt. This work will outline the testing details, present the results, and compare them to the relatively high binder content HMX-based LX-04 (85% HMX and 15% Viton) and ultra-fine TATB results tested under similar confinement. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Accuracy and Calibration of High Explosive Thermodynamic Equations of State

DTIC Science & Technology

2010-08-01

physics descriptions, but can also mean increased calibration complexity. A generalized extent of aluminum reaction, the Jones-Wilkins-Lee ( JWL ) based...predictions compared to experiments 3 3 PAX-30 JWL and JWLB cylinder test predictions compared to experiments 4 4 PAX-29 JWL and JWLB cylinder test...predictions compared to experiments 5 5 Experiment and modeling comparisons for HMX/AI 85/15 7 TABLES 1 LX-14 JWL and JWLB cylinder test velocity

Burning Rate Studies of HMX Propellants at High Pressures

DTIC Science & Technology

1975-03-01

slopes of propellants containing amonium perch- lorate and anmonium nitrate oxidizers. Same of these compounds were eval- uated with IMX to detereine their...Branch/Cuns, Rockets Man RV 75 anid Explos-’ives Division/Armamnent Deavelopment an~ d Test Center/E&lin Air Force Base Florida 32542 21____6...NAME & CiESI( d ~’, ntfc, ContrVIIIA9 OjicN) I URIT t SS. (oft his repor’) UCLASSIFIED D ~ ECIASSI F1ICATION/ DOWN GRADING 1SCHEDULE Distribuition limited

CHNO Energetic Polymer Specific Heat Prediction From The Proposed Nominal/Generic (N/G) CP Concept

DTIC Science & Technology

2007-02-01

HMX can exist in different solid polymorphic forms. At a certain temperature, TT, one form may change to another form if the heat energy of...more than 100 °K for TNT, HNS and HMX and over 200 °K for TETRYL, PETN, and RDX ). So based on the above remarks and similar remarks in References...are very close to (or equal to) the RDX CP values and TNT CP values near absolute zero. In Reference 7, two examples (TNT and HMX ) were selected for

An Overview of Combustion Mechanisms and Flame Structures for Advanced Solid Propellants

NASA Technical Reports Server (NTRS)

Beckstead, M. W.

2000-01-01

Ammonium perchlorate (AP) and cyclotretamethylenetetranitramine (HMX) are two solid ingredients often used in modern solid propellants. Although these two ingredients have very similar burning rates as monopropellants, they lead to significantly different characteristics when combined with binders to form propellants. Part of the purpose of this paper is to relate the observed combustion characteristics to the postulated flame structures and mechanisms for AP and HMX propellants that apparently lead to these similarities and differences. For AP composite, the primary diffusion flame is more energetic than the monopropellant flame, leading to an increase in burning rate over the monopropellant rate. In contrast the HMX primary diffusion flame is less energetic than the HMX monopropellant flame and ultimately leads to a propellant rate significantly less than the monopropellant rate in composite propellants. During the past decade the search for more energetic propellants and more environmentally acceptable propellants is leading to the development of propellants based on ingredients other than AP and HMX. The objective of this paper is to utilize the more familiar combustion characteristics of AP and HMX containing propellants to project the combustion characteristics of propellants made up of more advanced ingredients. The principal conclusion reached is that most advanced ingredients appear to burn by combustion mechanisms similar to HMX containing propellants rather than AP propellants.

Effects of void anisotropy on the ignition and growth rates of energetic materials

NASA Astrophysics Data System (ADS)

Rai, Nirmal Kumar; Sen, Oishik; Udaykumar, H. S.

2017-06-01

Initiation of heterogeneous energetic materials is thought to occur at hot spots; reaction fronts propagate from sites of such hot spots into the surrounding material resulting in complete consumption of the material. Heterogeneous materials, such as plastic bonded explosives (PBXs) and pressed materials contain numerous voids, defects and interfaces at which hot spots can occur. Amongst the various mechanisms of hot spot formation, void collapse is considered to be the predominant one in the high strain rate loading conditions. It is established in the past the shape of the voids has a significant effect on the initiation behavior of energetic materials. In particular, void aspect ratio and orientations play an important role in this regard. This work aims to quantify the effects of void aspect ratio and orientation on the ignition and growth rates of chemical reaction from the hot spot. A wide range of aspect ratio and orientations is considered to establish a correlation between the ignition and growth rates and the void morphology. The ignition and growth rates are obtained from high fidelity reactive meso-scale simulations. The energetic material considered in this work is HMX and Tarver McGuire HMX decomposition model is considered to capture the reaction mechanism of HMX. The meso-scale simulations are performed using a Cartesian grid based Eulerian solver SCIMITAR3D. The void morphology is shown to have a significant effect on the ignition and growth rates of HMX.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, G.D.; Bharadwaj, R.K.

The molecular geometries and conformational energies of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 1,3-dimethyl-1,3-dinitro methyldiamine (DDMD) and have been determined from high-level quantum chemistry calculations and have been used in parametrizing a classical potential function for simulations of HMX. Geometry optimizations for HMX and DDMD and rotational energy barrier searches for DDMD were performed at the B3LYP/6-311G** level, with subsequent single-point energy calculations at the MP2/6-311G** level. Four unique low-energy conformers were found for HMX, two whose conformational geometries correspond closely to those found in HMX polymorphs from crystallographic studies and two additional, lower energy conformers that are not seen in the crystallinemore » phases. For DDMD, three unique low-energy conformers, and the rotational energy barriers between them, were located. In parametrizing the classical potential function for HMX, nonbonded repulsion/dispersion parameters, valence parameters, and parameters describing nitro group rotation and out-of-plane distortion at the amine nitrogen were taken from the previous studies of dimethylnitramine. Polar effects in HMX and DDMD were represented by sets of partial atomic charges that reproduce the electrostatic potential and dipole moments for the low-energy conformers of these molecules as determined from the quantum chemistry wave functions. Parameters describing conformational energetics for the C-N-C-N dihedrals were determined by fitting the classical potential function to reproduce relative conformational energies in HMX as found from quantum chemistry. The resulting potential was found to give a good representation of the conformer geometries and relative conformer energies in HMX and a reasonable description of the low-energy conformers and rotational energy barriers in DDMD.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, Brian M.; Cordes, Nikolaus Lynn; Tappan, Bryce C.

HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) is a powerful high explosive that is routinely used in formulations such as PBX 9501. Much remains to be learned about the performance and mechanical properties of HMX formulations such as these, particularly after dynamic damage has occurred. We have prepared formulations with HMX using hydroxyl terminated polybutadiene (HTPB) binder in order to form an explosive that is relatively insensitive to mild stimuli, analogous to PBXB-110 (different only is substitution of dioctyladipate (DO) for isodecyl pelargonate).

Experimental investigations of mechanical and reaction responses for drop-weight impacted energetic particles

NASA Astrophysics Data System (ADS)

Bao, Xiao-Wei; Wu, Yan-Qing; Wang, Ming-Yang; Huang, Feng-Lei

2017-02-01

Low-velocity drop-weight impact experiments on individual and multiple Cyclotetramethylene tetranitramine (HMX) energetic particles were performed using a modified drop-weight machine equipped with high-speed photography components. Multiple particles experienced more severe burning reactions than an individual particle. Comparisons between impacted salt and HMX particle show that jetting in HMX is mainly due to the motion of fragmented particles driven by gaseous reaction products. Velocity of jetting, flame propagation, and area expansion were measured via image processing, making it possible to quantify the chemical reaction or mechanical deformation violence at different stages.

DOE Office of Scientific and Technical Information (OSTI.GOV)

K., S C; M., T C

Plastic bonded explosives (PBX) generally consist of 85 - 95 % by weight energetic material, such as HMX, and 5 - 15 % polymeric binder. Understanding of the structure and morphology at elevated temperatures and pressures is important for predicting of PBX behavior in accident scenarios. The crystallographic behavior of pure HMX has been measured as functions of temperature and grain size. The investigation is extended to the high temperature behavior of PBX 9501 (95% HMX, 2.5 % Estane, 2.5 % BDNPA/F). The results show that the HMX {beta}-phase to {delta}-phase transition in PBX 9501 is similar to that inmore » neat HMX. However, in the presence of the PBX 9501 binder, {delta}-phase HMX readily converts back to {beta}-phase during cooling. Using the same temperature profile, the conversion rate decreases for each subsequent heating and cooling cycle. As observed in earlier experiments, no reverse conversion is observed without the polymer binder. It is proposed that the reversion of {delta}-phase to {beta}-phase is due to changes in the surface molecular potential caused by the influence of the polymer binder on the surface molecules of the {delta}-phase. Upon thermal cycling, the polymer binder segregates from the HMX particles and thus reduces the influence of the binder on the surface molecules. This segregation increases the resistance for the {delta}-phase to {beta}-phase transition, as demonstrated in an aged PBX 9501 material for which the reversion is not observed.« less

Low-Cost Production of Nano-Pyrotechnics

DTIC Science & Technology

2010-07-01

possibly flawed. Two well-known materials. HMX and picric acid , with known impact sensitivities were tested and the results were compared with...However, the HMX used could not be confirmed to be a high level of purity. As a result, lab grade picric acid was tested and EMPl’s numbers agreed

The Effect of Propellant Composition on Secondary Muzzle Blast Overpressure

DTIC Science & Technology

1983-04-01

LOVA propellants evaluated included PU/HMX, CTBN /HMX, HTPB/HMX, CAB/RDX, CA/RDX, Kraton/RDX, and EC/NC/RDX. Details of the propellant compositions...RDX tests. Secondary flash was observed for all the firings of all the other candidates, even CTBN /HMX, which had some suppressant. All of these...Propellant Flame Temp (K) Intensity (Mcd) Observations of Flash Kraton/RDX 2283 18.2 ± 1 . 2 11 11 CTBN /HMX 2379 13.8 ± • 72 8 8 HTPB/HMX 2363 10.5

Spectral signatures for RDX-based explosives in the 3 micron region

NASA Astrophysics Data System (ADS)

Osborn, Tabetha; Kaimal, Sindhu; Reeve, Scott W.; Burns, William

2008-04-01

Explosive compounds such as RDX, and HMX present significant challenges to optically based sensors. This difficulty is due in part to the low vapor pressures these compounds possess. One approach for sensing explosives that circumvents the low explosive vapor pressure problem, involves focusing on the trace amounts of relatively high vapor pressure impurities that will be present in the vapor signature. In order to effectively detect these volatile impurities, the spectral signature databases must be readily available. One of our goals therefore, is the generation of a database of high resolution spectral signatures for these volatile organic impurities. Some rather formidable spectroscopic measurement challenges have been encountered while working to extend the spectral signature effort to the 3 micron region. Here we will outline progress to date, with a focus on the volatile organic compounds formaldehyde, acetaldehyde, nitromethane, acetone, isobutene, and cyclohexanone.

Toward Improved Fidelity of Thermal Explosion Simulations

NASA Astrophysics Data System (ADS)

Nichols, Albert; Becker, Richard; Burnham, Alan; Howard, W. Michael; Knap, Jarek; Wemhoff, Aaron

2009-06-01

We present results of an improved thermal/chemical/mechanical model of HMX based explosives like LX04 and LX10 for thermal cook-off. The original HMX model and analysis scheme were developed by Yoh et.al. for use in the ALE3D modeling framework. The improvements were concentrated in four areas. First, we added porosity to the chemical material model framework in ALE3D used to model HMX explosive formulations to handle the roughly 2% porosity in solid explosives. Second, we improved the HMX reaction network, which included the addition of a reactive phase change model base on work by Henson et.al. Third, we added early decomposition gas species to the CHEETAH material database to improve equations of state for gaseous intermediates and products. Finally, we improved the implicit mechanics module in ALE3D to more naturally handle the long time scales associated with thermal cookoff. The application of the resulting framework to the analysis of the Scaled Thermal Explosion (STEX) experiments will be discussed.

Changes in Blow-Off Velocity Observed in Two Explosives at the Threshold for Sustained Ignition Using the Modified Gap Test

NASA Astrophysics Data System (ADS)

Lee, R. J.; Forbes, J. W.; Tasker, D. G.; Orme, R. S.

2009-12-01

The Modified Gap Test was used to quantify different levels of partial reaction for various input stresses. This test configuration has been historically useful in highlighting thresholds for first reaction, sustained ignition, and detonation. Two different HMX based compositions were studied; a cast-cured composition with 87% HMX and a pressed composition with 92% HMX. Each explosive was prepared from large industrially produced batches consisting of different unreactive polymeric binder systems. Short samples (50.8 mm in diameter and 12.7 mm thick) were shock loaded using the standard large-scale gap test donor system. Product-cloud blow-off velocities at the opposite end of the sample were measured using a high-speed digital-camera. Velocity versus input pres sure plots provided changes in reactivity that had developed by the 12.7 mm run distance. Results appear consistent for the lower input stresses. In contrast, the results varied widely in a range of input stresses around the transition to detonation in both explosives. These results indicate that both explosives are subject to large variation in blow-off velocity in a range of input stresses near the threshold for prompt detonation. This is explained by localized variations of HMX particle size and density in industrially prepared samples. Approved for public release, Distribution unlimited, IHDIV Log No. 09-108.

Temperature Dependent Characterization of Terahertz Vibrations of Explosives and Related Threat Materials

DTIC Science & Technology

2010-12-10

absorption spectra of 1,3,5,7- tetranitro-1,3,5,7-tetrazocane ( HMX ) polymorphs ,” Chem. Phys. Lett. 489(1-3), 48–53 (2010). 23. P. Main, R. E...The β polymorph is the most stable form of the four polymorphs (α,β,γ,δ) of HMX and the room temperature THz spectrum of β- HMX has been measured by...EXPRESS 27248 polymorph to be formed. The α- HMX and δ- HMX forms are described as stable above room temperature: α- HMX is stable from 377 K to 429 K [24

Kinetic Deuterium Isotope Effects in the Combustion of Nitramine Propellants

DTIC Science & Technology

1988-07-01

Transition state 33 7. Possible Isotope Effects in HMX -d., and RDX -d. 38 8. HMX synthesis 48 9. a- HMX 52 10. V- HMX 53 11. RDX Synthesis 55 12 Pellet...configuration of the transition state in HMX decomposition could be rade. KDIE in RDX Decomposition The KDIE values obtained for RDX decomposition -ire...0.13 HMX -d 8 60.3 35.7 8.6 0.10 RDX 61.2 36.7 11.8 0.10 RDX -de 53.7 22.8 8.3 0.11 DSC EXPERIMENTS The 13 -+ 8 phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saw, C K

To date a global kinetic rate law has not been written to accurately describe solid-solid phase transformations of HMX and TATB where contributions from grain size effects, binder contents, and impurity levels are explicitly defined. Our recent work presented at the 2001 SCCM topical APS meeting, Atlanta, GA, demonstrated one can not confidently use the second harmonic generation (SHG) diagnostic to study energetic material phase transitions where non-uniform grain size distributions are present. For example, in HMX, the early arrival of SHG before the XRD in the SHG/XRD simultaneous high temperature experiment clearly indicates the partial molecular conversion from centrosymmetricmore » to non-centrosymmetric without any structural changes as exhibit by the XRD pattern. This conversion is attributed to the changes of the surface molecules due to the differences in potential between the surface and the bulk. The present paper reports on accurate XRD measurements following changes of {beta}-HMX to {delta}-HMX at elevated temperature. The results are compared for sample with 2 different grain sizes for HMX. We report accurate temperature dependent lattice parameters and hence volume and linear thermal expansion coefficients along each crystallographic axis. We have also conducted kinetic studies of the behavior of 2 grain-sizes of HMX and concluded that their kinetics, are drastically different.« less

Mesodermal expression of the C. elegans HMX homolog mls-2 requires the PBC homolog CEH-20

PubMed Central

Jiang, Yuan; Shi, Herong; Amin, Nirav M.; Sultan, Ibrahim; Liu, Jun

2008-01-01

Metazoan development proceeds primarily through the regulated expression of genes encoding transcription factors and components of cell signaling pathways. One way to decipher the complex developmental programs is to assemble the underlying gene regulatory networks by dissecting the cis-regulatory modules that direct temporal-spatial expression of developmental genes and identify corresponding trans-regulatory factors. Here, we focus on the regulation of a HMX homoebox gene called mls-2, which functions at the intersection of a network that regulates cleavage orientation, cell proliferation and fate specification in the C. elegans postembryonic mesoderm. In addition to its transient expression in the postembryonic mesodermal lineage, the M lineage, mls-2 expression is detected in a subset of embryonic cells, in three pairs of head neurons and transiently in the somatic gonad. Through mutational analysis of the mls-2 promoter, we identified two elements (E1 and E2) involved in regulating the temporal-spatial expression of mls-2. In particular, we showed that one of the elements (E1) required for mls-2 expression in the M lineage contains two critical putative PBC-Hox binding sites that are evolutionarily conserved in C. briggsae and C. remanei. Furthermore, the C. elegans PBC homolog CEH-20 is required for mls-2 expression in the M lineage. Our data suggests that mls-2 might be a direct target of CEH-20 in the M lineage and that the regulation of CEH-20 on mls-2 is likely Hox-independent. PMID:18316179

On the low pressure shock initiation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine based plastic bonded explosives

NASA Astrophysics Data System (ADS)

Vandersall, Kevin S.; Tarver, Craig M.; Garcia, Frank; Chidester, Steven K.

2010-05-01

In large explosive and propellant charges, relatively low shock pressures on the order of 1-2 GPa impacting large volumes and lasting tens of microseconds can cause shock initiation of detonation. The pressure buildup process requires several centimeters of shock propagation before shock to detonation transition occurs. In this paper, experimentally measured run distances to detonation for lower input shock pressures are shown to be much longer than predicted by extrapolation of high shock pressure data. Run distance to detonation and embedded manganin gauge pressure histories are measured using large diameter charges of six octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) based plastic bonded explosives (PBX's): PBX 9404; LX-04; LX-07; LX-10; PBX 9501; and EDC37. The embedded gauge records show that the lower shock pressures create fewer and less energetic "hot spot" reaction sites, which consume the surrounding explosive particles at reduced reaction rates and cause longer distances to detonation. The experimental data is analyzed using the ignition and growth reactive flow model of shock initiation in solid explosives. Using minimum values of the degrees of compression required to ignite hot spot reactions, the previously determined high shock pressure ignition and growth model parameters for the six explosives accurately simulate the much longer run distances to detonation and much slower growths of pressure behind the shock fronts measured during the shock initiation of HMX PBX's at several low shock pressures.

β-δ phase transition during dropweight impact on cyclotetramethylene-tetranitroamine

NASA Astrophysics Data System (ADS)

Czerski, H.; Greenaway, M. W.; Proud, W. G.; Field, J. E.

2004-10-01

The secondary explosive cyclotetramethylene-tetranitroamine (HMX) exists in a variety of crystal structures; the most widely used being the β-phase which is stable at room temperature and pressure. On heating, a more impact sensitive form (δ phase) is produced. The nonlinear optical technique of second harmonic generation (SHG) can be used as a probe of phase since δ-phase HMX generates a second harmonic at 532nm when 1064nm laser light is incident upon it. We present high-speed photography of SHG in HMX samples during dropweight impact and show that this technique can provide good spatial information and time resolution. We find evidence for small areas of δ-phase HMX appearing in the period from 13μs before ignition to 10μs afterwards, demonstrating that the heating on impact is sufficient to overcome the loading conditions and cause the phase change.

Detonation Characteristics of Plastic Explosives Based on Attractive Nitramines with Polyisobutylene and Poly(methyl methacrylate) Binders

NASA Astrophysics Data System (ADS)

Elbeih, Ahmed; Pachman, Jiri; Zeman, Svatopluk; Vávra, Pavel; Trzciński, Waldemar A.; Akštein, zbyněk

2012-10-01

Four highly brisant nitramines, RDX (1,3,5-trinitro-1,3,5-triazinane), HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), BCHMX (cis-1,3,4,6-tetranitro-octahydroimidazo-[4,5-d]imidazole), and ɛ-HNIW (ɛ-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), were studied as extruded plastic explosives bonded by two plastic matrices based on polyisobutylene (C4 matrix) and poly-methylmethacrylate (plasticized by dioctyl-adipate) binders. The detonation velocities, D, were measured experimentally. Detonation parameters were also calculated by means of the Kamlet and Jacobs method and CHEETAH and EXPLO5 codes. These detonation parameters showed that plastic-bonded explosives (PBXs) based on BCHMX are more powerful explosives than those based on RDX. The Urizar coefficient for poly(methyl methacrylate) binder was also calculated.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tarver, C M

Recent laser ignition experiments on octahydro-1,3,5,7-tetranitro-1,3,5,7-terrazocine (HMX) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) subjected to laser fluxes ranging from 10 to 800 W/cm{sup 2} produced ignition times from seconds to milliseconds. Global chemical kinetic thermal decomposition models for HMX and TATB have been developed to calculate times to thermal explosion for experiments in the seconds to days time frame. These models are applied to the laser ignition experimental data in this paper. Excellent agreement was obtained for TATB, while the calculated ignition times were longer than experiment for HMX at lower laser fluxes. At the temperatures produced in the laser experiments, HMX melts.more » Melting generally increases condensed phase reaction rates so faster rates were used for three of the HMX reaction rates. This improved agreement with experiments at the lower laser fluxes but yielded very fast ignition at high fluxes. The calculated times to ignition are in reasonable agreement with the laser ignition experiments, and this justifies the use of these models for estimating reaction times at impact and shock ''hot spot'' temperatures.« less

LX-04 VIOLENCE MEASUREMENTS- STEVEN TESTS IMPACTED BY PROJECTILES SHOT FROM A HOWITZER GUN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chidester, S K; Vandersall, K S; Switzer, L L

Characterization of the reaction violence of LX-04 explosive (85% HMX and 15% Viton A by weight) was obtained from Steven Impact Tests performed above the reaction initiation threshold. A 155 mm Howitzer propellant driven gas gun was used to accelerate the Steven Test projectiles in the range of approximately 170-300 m/s to react (ignite) the LX-04 explosive. Blast overpressure gauges, acoustic microphones, and high-speed photography characterized the level of high explosive reaction violence. A detonation in this velocity range was not observed and when comparing these results (and the Susan test results) with that of other HMX based explosives, LX-04more » has a more gradual reaction violence slope as the impact velocity increases. The high binder content (15%) of the LX-04 explosive is believed to be the key factor to the lower level of violence.« less

Isolation of three hexahydro-1,3,5-trinitro-1,3,5-triazine-degrading species of the family Enterobacteriaceae from nitramine explosive-contaminated soil.

PubMed Central

Kitts, C L; Cunningham, D P; Unkefer, P J

1994-01-01

Three species of the family Enterobacteriaceae that biochemically reduced hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were isolated from nitramine explosive-contaminated soil. Two isolates, identified as Morganella morganii and Providencia rettgeri, completely transformed both RDX and the nitroso-RDX reduction intermediates. The third isolate, identified as Citrobacter freundii, partially transformed RDX and generated high concentrations of nitroso-RDX intermediates. All three isolates produced 14CO2 from labeled RDX under O2-depleted culture conditions. While all three isolates transformed HMX, only M. morganii transformed HMX in the presence of RDX. PMID:7811097

Relaxed structure of typical nitro explosives in the excited state: Observation, implication and application

NASA Astrophysics Data System (ADS)

Chu, Genbai; Yang, Zuhua; Xi, Tao; Xin, Jianting; Zhao, Yongqiang; He, Weihua; Shui, Min; Gu, Yuqiu; Xiong, Ying; Xu, Tao

2018-04-01

Understanding the structural, geometrical, and chemical changes that occur after an electronic excitation is essential to elucidate the inherent mechanism of nitro explosives. Herein, relaxed structures of typical nitro explosives in the lowest singlet excited state are investigated using time-dependent density functional theory. During the excitation process, the nitro group is activated and relaxes via geometrical change. The five explosives RDX, HMX, CL-20, PETN, and LLM-105 exhibit similar relaxed structures, and the impact sensitivity is related to their excitation energy. High-sensitivity δ-HMX has a lower excitation energy for relaxed structure than β-HMX. This study offers novel insight into energetic materials.

Bis(4-nitraminofurazanyl-3-azoxy)azofurazan and Derivatives: 1,2,5-Oxadiazole Structures and High-Performance Energetic Materials.

PubMed

Liu, Yuji; Zhang, Jiaheng; Wang, Kangcai; Li, Jinshan; Zhang, Qinghua; Shreeve, Jean'ne M

2016-09-12

Bis(4-nitraminofurazanyl-3-azoxy)azofurazan (1) and ten of its energetic salts were prepared and fully characterized. Computational analysis based on isochemical shielding surface and trigger bond dissociation enthalpy provide a better understanding of the thermal stabilities for nitramine-furazans. These energetic compounds exhibit good densities, high heats of formation, and excellent detonation velocity and pressure. Some representative compounds, for example, 1 (vD : 9541 m s(-1) ; P: 40.5 GPa), and 4 (vD : 9256 m s(-1) ; P: 38.0 GPa) exhibit excellent detonation performances, which are comparable with current high explosives such as RDX (vD : 8724 m s(-1) ; P: 35.2 GPa) and HMX (vD : 9059 m s(-1) ; P: 39.2 GPa). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmentally Responsible Microbiological Production of Energetic Ingredients

DTIC Science & Technology

2007-11-01

effort was to develop an environmentally benign and economical microbial process for nitro-energetics production . The specific targets of this method...microbial production of nitro-based EM. As the processes and compounds of choice, RDX/HMX (nitramine) generation was selected. Microorganisms capable of...Current synthetic methods for the production of RDX and HMX utilize hexamine as the precursor. Hexamine is an industrial chemical available on a large

Short communication: Estimation of yield stress/viscosity of molten octol

DOE PAGES

Davis, S. M.; Zerkle, D. K.

2018-05-04

Explosive HMX particles are similar in morphology and chemistry to RDX particles, the main constituent of Composition B-3 (Comp B-3). This suggests molten HMX-TNT formulations may show Bingham plasticity, much like recent studies have shown for Comp B-3. Here a Bingham plastic viscosity model, including yield stress and shear thinning, is presented for octol (70/30wt% HMX/TNT) as a function of HMX particle volume fraction. The effect of HMX dissolution into molten TNT is included in this analysis.

Short communication: Estimation of yield stress/viscosity of molten octol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, S. M.; Zerkle, D. K.

Explosive HMX particles are similar in morphology and chemistry to RDX particles, the main constituent of Composition B-3 (Comp B-3). This suggests molten HMX-TNT formulations may show Bingham plasticity, much like recent studies have shown for Comp B-3. Here a Bingham plastic viscosity model, including yield stress and shear thinning, is presented for octol (70/30wt% HMX/TNT) as a function of HMX particle volume fraction. The effect of HMX dissolution into molten TNT is included in this analysis.

Short communication: Estimation of yield stress/viscosity of molten octol

NASA Astrophysics Data System (ADS)

Davis, S. M.; Zerkle, D. K.

2018-05-01

Explosive HMX particles are similar in morphology and chemistry to RDX particles, the main constituent of Composition B-3 (Comp B-3). This suggests molten HMX-TNT formulations may show Bingham plasticity, much like recent studies have shown for Comp B-3. Here a Bingham plastic viscosity model, including yield stress and shear thinning, is presented for octol (70/30wt% HMX/TNT) as a function of HMX particle volume fraction. The effect of HMX dissolution into molten TNT is included in this analysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Seong-Wook; Tian, Chao; Martini, Rainer, E-mail: rmartini@stevens.edu

We demonstrated highly sensitive detection of explosive dissolved in solvent with a portable spectroscopy system (Q-MACS) by tracing the explosive byproduct, N{sub 2}O, in combination with a pulsed electric discharge system for safe explosive decomposition. Using Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), the gas was monitored and analyzed by Q-MACS and the presence of the dissolved explosive clearly detected. While HMX presence could be identified directly in the air above the solutions even without plasma, much better results were achieved under the decomposition. The experiment results give an estimated detection limit of 10 ppb, which corresponds to a 15 pg of HMX.

Influence of Small Change of Porosity on Shock Initiation of an HMX/TATB/Viton Explosive and Ignition and Growth Modeling

NASA Astrophysics Data System (ADS)

Liu, Yan; Hussain, Tariq; Huang, Fenglei; Duan, Zhuoping

2016-07-01

All solid explosives in practical use are more or less porous. Although it is known that the change in porosity affects the shock sensitivity of solid explosives, the effect of small changes in porosity on the sensitivity needs to be determined for safe and efficient use of explosive materials. In this study, the influence of a small change in porosity on shock initiation and the subsequent detonation growth process of a plastic-bonded explosive PBXC03, composed of 87% cyclotetramethylene-tetranitramine (HMX), 7% triaminotrinitrobenzene (TATB), and 6% Viton by weight, are investigated by shock to detonation transition experiments. Two explosive formulations of PBXC03 having the same initial grain sizes pressed to 98 and 99% of theoretical mass density (1.873 g/cm3) respectively are tested using the in situ manganin piezoresistive pressure gauge technique. Numerical modeling of the experiments is performed using an ignition and growth reactive flow model. Reasonable agreement with the experimental results is obtained by increasing the growth term coefficient in the Lee-Tarver ignition and growth model with porosity. Combining the experimental and simulation results shows that the shock sensitivity increases with porosity for PBXC03 having the same explosive initial grain sizes for the pressures (about 3.1 GPa) applied in the experiments.

High speed X-ray phase contrast imaging of energetic composites under dynamic compression

NASA Astrophysics Data System (ADS)

Parab, Niranjan D.; Roberts, Zane A.; Harr, Michael H.; Mares, Jesus O.; Casey, Alex D.; Gunduz, I. Emre; Hudspeth, Matthew; Claus, Benjamin; Sun, Tao; Fezzaa, Kamel; Son, Steven F.; Chen, Weinong W.

2016-09-01

Fracture of crystals and frictional heating are associated with the formation of "hot spots" (localized heating) in energetic composites such as polymer bonded explosives (PBXs). Traditional high speed optical imaging methods cannot be used to study the dynamic sub-surface deformation and the fracture behavior of such materials due to their opaque nature. In this study, high speed synchrotron X-ray experiments are conducted to visualize the in situ deformation and the fracture mechanisms in PBXs composed of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and hydroxyl-terminated polybutadiene binder doped with iron (III) oxide. A modified Kolsky bar apparatus was used to apply controlled dynamic compression on the PBX specimens, and a high speed synchrotron X-ray phase contrast imaging (PCI) setup was used to record the in situ deformation and failure in the specimens. The experiments show that synchrotron X-ray PCI provides a sufficient contrast between the HMX crystals and the doped binder, even at ultrafast recording rates. Under dynamic compression, most of the cracking in the crystals was observed to be due to the tensile stress generated by the diametral compression applied from the contacts between the crystals. Tensile stress driven cracking was also observed for some of the crystals due to the transverse deformation of the binder and superior bonding between the crystal and the binder. The obtained results are vital to develop improved understanding and to validate the macroscopic and mesoscopic numerical models for energetic composites so that eventually hot spot formation can be predicted.

High speed X-ray phase contrast imaging of energetic composites under dynamic compression

DOE PAGES

Parab, Niranjan D.; Roberts, Zane A.; Harr, Michael H.; ...

2016-09-26

Fracture of crystals and subsequent frictional heating are associated with formation of hot spots in energetic composites such as polymer bonded explosives (PBXs). Traditional high speed optical imaging methods cannot be used to study the dynamic sub-surface deformation and fracture behavior of such materials due to their opaque nature. In this study, high speed synchrotron X-ray experiments are conducted to visualize the in situ deformation and fracture mechanisms in PBXs manufactured using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and hydroxyl-terminated polybutadiene (HTPB) binder. A modified Kolsky bar apparatus was used to apply controlled dynamic compression on the PBX specimens, and a high speedmore » synchrotron X-ray phase contrast imaging (PCI) setup was used to record the in situ deformation and failure in the specimens. The experiments show that synchrotron X-ray PCI provides a sufficient contrast between the HMX crystals and the doped binder, even at ultrafast recording rates. Under dynamic compression, most of the cracking in the crystals was observed to be due to the tensile stress generated by the diametral compression applied from the contacts between the crystals. Tensile stress driven cracking was also observed for some of the crystals due to the transverse deformation of the binder and superior bonding between the crystal and the binder. In conclusion, the obtained results are vital to develop improved understanding and to validate the macroscopic and mesoscopic numerical models for energetic composites so that eventually hot spot formation can be predicted.« less

Formation of double front detonations of a condensed-phase explosive with powdered aluminium

NASA Astrophysics Data System (ADS)

Kim, Wuhyun; Gwak, Min-cheol; Yoh, Jack J.

2018-03-01

The performance characteristics of aluminised high explosive are considered by varying the aluminium (Al) mass fraction in a hybrid non-ideal detonation model. Since the time scales of the characteristic induction and combustion of high explosives and Al particles differ, the process of energy release behind the leading detonation wave front occurs over an extended period of time. Two cardinal observations are reported: a decrease in detonation velocity with an increase in Al mass fraction and a double front detonation (DFD) feature when anaerobic Al reaction occurs behind the front. In order to simulate the performance characteristics due to the varying Al mass fraction, the tetrahexamine tetranitramine (HMX) is considered as a base high explosive when formulating the multiphase conservation laws of mass, momentum, and energy exchanges between particles and HMX product gases. While experimental studies have been reported on the effect of Al mass fraction on both gas-phase and solid-phase detonations, the numerical investigations have been limited to only gas-phase detonation for the varying Al particles in the mixture. In the current study, a two-phase model is utilised for understanding the volumetric effects of Al mass fraction in condensed phase detonations. A series of unconfined and confined rate sticks are considered for characterising the performance of aluminised HMX with a maximum Al mass fraction of 50%. The simulated results are compared with the experimental data for 5-25% mass fractions, and the higher mass fraction behaviours are consistent with the experimental observations.

Toward Improved Fidelity of Thermal Explosion Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nichols, A L; Becker, R; Howard, W M

2009-07-17

We will present results of an effort to improve the thermal/chemical/mechanical modeling of HMX based explosive like LX04 and LX10 for thermal cook-off. The original HMX model and analysis scheme were developed by Yoh et.al. for use in the ALE3D modeling framework. The current results were built to remedy the deficiencies of that original model. We concentrated our efforts in four areas. The first area was addition of porosity to the chemical material model framework in ALE3D that is used to model the HMX explosive formulation. This is needed to handle the roughly 2% porosity in solid explosives. The secondmore » area was the improvement of the HMX reaction network, which included the inclusion of a reactive phase change model base on work by Henson et.al. The third area required adding early decomposition gas species to the CHEETAH material database to develop more accurate equations of state for gaseous intermediates and products. Finally, it was necessary to improve the implicit mechanics module in ALE3D to more naturally handle the long time scales associated with thermal cook-off. The application of the resulting framework to the analysis of the Scaled Thermal Explosion (STEX) experiments will be discussed.« less

Toward Improved Fidelity of Thermal Explosion Simulations

NASA Astrophysics Data System (ADS)

Nichols, A. L.; Becker, R.; Howard, W. M.; Wemhoff, A.

2009-12-01

We will present results of an effort to improve the thermal/chemical/mechanical modeling of HMX based explosives like LX04 and LX10 for thermal cook-off The original HMX model and analysis scheme were developed by Yoh et al. for use in the ALE3D modeling framework. The current results were built to remedy the deficiencies of that original model. We concentrated our efforts in four areas. The first area was addition of porosity to the chemical material model framework in ALE3D that is used to model the HMX explosive formulation. This is needed to handle the roughly 2% porosity in solid explosives. The second area was the improvement of the HMX reaction network, which included a reactive phase change model base on work by Henson et al. The third area required adding early decomposition gas species to the CHEETAH material database to develop more accurate equations of state for gaseous intermediates and products. Finally, it was necessary to improve the implicit mechanics module in ALE3D to more naturally handle the long time scales associated with thermal cook-off The application of the resulting framework to the analysis of the Scaled Thermal Explosion (STEX) experiments will be discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Urtiew, P A; Forbes, J W; Tarver, C M

LX-04 is a widely used HMX-based plastic bonded explosive, which contains 85 weight % HMX and 15 weight % Viton binder. The sensitivity of LX-04 to a single stimulus such as heat, impact, and shock has been previously studied. However, hazard scenarios can involve multiple stimuli, such as heating to temperatures close to thermal explosion conditions followed by fragment impact, producing a shock in the hot explosive. The sensitivity of HMX at elevated temperatures is further complicated by the beta to delta solid-state phase transition, which occurs at approximately 165 C. This paper presents the results of shock initiation experimentsmore » conducted with LX-04 preheated to 190 C, as well as density measurements and small scale safety test results of the {delta} phase HMX at room temperature. This work shows that LX-04 at 190 C is more shock sensitive than LX-04 at 150 C or 170 C due to the volume increase during the {beta} to {delta} solid phase transition, which creates more hot spots, and the faster growth of reaction during shock compression.« less

Self-assembly of silver(i)-based high-energy metal-organic frameworks (HE-MOFs) at ambient temperature and pressure: synthesis, structure and superior explosive performance.

PubMed

Shen, Cheng; Liu, Yang; Zhu, Zhong-Qin; Xu, Yuan-Gang; Lu, Ming

2017-07-04

Two new high-energy metal-organic frameworks (HE-MOFs), {Ag 2 (DNMAF)(H 2 O) 2 } n (1) and {Ag 2 (DNMAF)} n (2) were prepared using potassium 4,4'-bis(dinitromethyl)-3,3'-azofurazanate (K 2 DNMAF) in a self-assembly strategy. Compound 1 exhibits a 3D HE-MOF structure with coordinated water molecules. Compound 2 exhibits compact solvent-free 3D HE-MOFs. Both compounds show good thermostability (decomposition temperature (T d ) of 211 and 218 °C) and superior detonation velocities (D) of 9673 m s -1 and 10 242 m s -1 , detonation pressures (P) of 50.01 GPa and 58.30 GPa, and heat of detonation (Q) of 1.95 kcal g -1 and 2.19 kcal g -1 , respectively, which are even higher than those of RDX and HMX.

Thermally stable, plastic-bonded explosives

DOEpatents

Benziger, Theodore M.

1979-01-01

By use of an appropriate thermoplastic rubber as the binder, the thermal stability and thermal stress characteristics of plastic-bonded explosives may be greatly improved. In particular, an HMX-based explosive composition using an oil-extended styrene-ethylenebutylene-styrene block copolymer as the binder exhibits high explosive energy and thermal stability and good handling safety and physical properties.

The ARO Working Group Meeting on Ignition Processes, June 1978.

DTIC Science & Technology

1980-03-01

great variety of products are formed from HMX and RDX , including several which cannot be readily explained by the propellant molecules simply breaking...nascent product from HMX is N20, which indicates that some chemistry has taken place somewhere (Figure I shows the HMX and RDX molecules for reference...who described his research into the gas phase unimolecular decomposition of molecules used as explosives (TNT, HMX , RDX ). The purpose of this research

Thermal Decomposition of Energetic Materials. 2. Deuterium Isotope Effects and Isotopic Scrambling in Condensed-Phase Decomposition of Octahydro-1, 3,5,7-Tetranitro-1,3,5,7-Tetrazocine

DTIC Science & Technology

1993-02-01

HMX , 1) and hexahydro- 1,3,5-trinitro-s-triazine decomposition of H MX show that the identity and rates of release ( RDX , 11) are energetic ingredients...quadruple scission pathway Reviews$ of the literature on RDX and HMX have discussed HMX -- 4H2C=N-NO2 (R2) the roles of unimolecular decomposition and...N-NO2 -- CH 2O + NO (R3) lavior otCyclotrimethylene-trinitraminr ( RDX ) and Cycloteiramethylene- tctranitramine ( HMX ). In Fundamentals of Solid

Ignition and Combustion Studies of Hazard Division 1.1 and 1.3 Substances

DTIC Science & Technology

2010-07-01

Effect of Time at Temperature on Burning Rate. The burning rate of the HD1.1 explosive PBXN -5 is compared to that of neat cyclotetramethylene...tetranitramine (HMX) in Figure 14. The explosive, PBXN -5, is composed of 95 weight percent HMX and 5 percent Viton A as binder. The HMX burning rate...the closed bomb technique (Reference 18). The PBXN -5 was composed of small agglomerates of HMX coated with the binder (Reference 19). The PBXN -5

Shock Initiation Behavior of PBXN-9 Determined by Gas Gun Experiments

NASA Astrophysics Data System (ADS)

Sanchez, N. J.; Gustavsen, R. L.; Hooks, D. E.

2009-12-01

The shock to detonation transition was evaluated in the HMX based explosive PBXN-9 by a series of light-gas gun experiments. PBXN-9 consists of 92 wt% HMX, 2wt% Hycar 4054 & 6 wt&percent; dioctyl adipate with a density of 1.75 g/cm3 and 0.8&% voids. The experiments were designed to understand the specifics of wave evolution and the run distance to detonation as a function of input shock pressure. These experiments were conducted on gas guns in order to vary the input shock pressure accurately. The primary diagnostics were embedded magnetic gauges, which are based on Faraday's law of induction, and Photon Doppler Velocimetry (PDV). The run distance to detonation vs. shock pressure, or "Pop plot," was redefined as log(X) = 2.14-1.82 log (P), which is substantially different than previous data. The Hugoniot was refined as Us = 2.32+2.211 Up. This data will be useful for the development of predictive models for the safety and performance of PBXN-9 along with providing increased understanding of HMX based explosives in varying formulations.

Energetic Salts Based on 3,5-Bis(dinitromethyl)-1,2,4-triazole Monoanion and Dianion: Controllable Preparation, Characterization, and High Performance.

PubMed

Zhang, Jiaheng; Dharavath, Srinivas; Mitchell, Lauren A; Parrish, Damon A; Shreeve, Jean'ne M

2016-06-22

Molecular modification of known explosives is considered to be an efficient route to design new energetic materials. A new family of energetic salts based on the 3,5-bis(dinitromethyl)-1,2,4-triazole monoanion and dianion were controllably synthesized by using 1-diamino-2,2-dinitroethene as a precursor. X-ray structure determination of monohydrazinium 3,5-bis(dinitromethyl)-1,2,4-triazolate (5) and monoammonium (6) and diammonium 3,5-bis(dinitromethyl)-1,2,4-triazolate hydrate (8·H2O) further confirmed the structures of these anions. In addition, as supported by X-ray data, in the monoanion system, the roving proton on the ring nitrogen rather than on the gem-dinitro carbon results in extensive hydrogen-bonding interactions and higher packing coefficients. Interestingly, 5 and 6 possess the highest calculated crystal densities, 1.965 and 1.957 g cm(-3) at 150 K, for hydrazinium and ammonium energetic salts, respectively. Energetic evaluation indicates that 5 (detonation velocity vD = 9086 m s(-1); detonation pressure P = 38.7 GPa) and 6 (vD, 9271 m s(-1); P = 41.0 GPa) exhibit great detonation properties, superior to those of current highly explosive benchmarks, such as 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeager, John David; Watkins, Erik Benjamin; Duque, Amanda Lynn

Thermal ignition via self-heating (cook-off) of cyclotetramethylene-tetranitramine (HMX)-containing plastic-bonded explosives (PBXs) is driven by the β → δ phase transition in the HMX, which is affected if not dominated by microstructure. Here, we studied the HMX-binder interface and phase transition for several variations of PBX 9404 (HMX with plasticized nitrocellulose [NC] binder). Neutron reflectometry was used to examine the interface under several conditions—pristine, after aging, and after thermal treatment. The initial interfacial structure depended on the plasticizer, but the interface homogenized over time. Thermal and optical analyses showed that all formulated materials had higher transition temperatures than neat HMX. Thismore » effect increased with NC content.« less

1982 AFOSR/AFRPL Rocket Propulsion Research Meeting Held at Lancaster, California on 2-4 March 1982.

DTIC Science & Technology

1982-02-01

OF DELAWARE P.I.: THOMAS B. BRILL I I THE L*6 HMX SOLID PHASE DIAGRAM 00 •6- HMX is the stable polymorph 0 3 iM above 248*C regardless of 500 the...MX trans forma- <ia is orders of maqnitude faster miian p-piezllant combustion rates. ’- HMX is therefore the polymorph that initiates decomposition...rapidly accelerating Osage of HMX / RDX for minimu smoke solid propellants has been hampered by a lack of ballistic tailoring flexability which limits

Hydrolytic Stability Study of Tetranitroglycoluri (TNGU) Produced via the US Army Research Laboratory’s Synthetic Method

DTIC Science & Technology

2015-03-01

Molecular structures of TNGU and HMX ................................................1 Fig. 2 Potential mechanism of hydrolytic decomposition of TNGU...tetranitro-1,3,5,7-tetrazocine ( HMX or 2) (see Fig. 1), but unfortunately suffers from hydrolytic instability and until recently was often...N N N NN N N N O O O2N NO2 O2N NO2 O2N NO2 NO2 O2N 1 TNGU 2 HMX Fig. 1 Molecular structures of TNGU and HMX The origin of the hydrolytic

Measurement of the flow properties within a copper tube containing a deflagrating explosive

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hill, Larry G; Morris, John S; Jackson, Scott I

2009-01-01

We report on the propagation of deflagration waves in the high explosive (HE) PBX 9501 (95 wt % HMX, 5 wt% binder). Our test configuration, which we call the def1agration cylinder test (DFCT), is fashioned after the detonation cylinder test (DTCT) that is used to calibrate the JWL detonation product equation of state (EOS). In the DFCT, the HE is heated to a uniform slightly subcritical temperature, and is ignited at one end by a hot wire. For some configurations and initial conditions, we observe a quasi-steady wave that flares the tube into a funnel shape, stretching it to themore » point of rupture. This behavior is qualitatively like the DTCT, such that, by invoking certain additional approximations that we discuss, its behavior can be analyzed by the same methods. We employ an analysis proposed by G.I. Taylor to infer the pressure-volume curve for the burning, expanding flow. By comparing this result to the EOS of HMX product gas alone. we infer that only {approx}20 wt% of the HMX has burned at tube rupture. This result confirms pre-existing observations about the role of convective burning in HMX cookoff explosions.« less

Shock initiation behavior of PBXN-9 determined by gas gun experiments

NASA Astrophysics Data System (ADS)

Sanchez, Nathaniel; Gustavsen, Richard; Hooks, Daniel

2009-06-01

The shock to detonation transition was evaluated in the HMX based explosive PBXN-9 by a series of light-gas gun experiments. PBXN-9 consists of 92 wt% HMX, 2wt% Hycar 4054 & 6 wt% dioctyl adipate with a density of 1.75 g/cm^3 and 0.8% voids. The experiments were designed to understand the specifics of wave evolution and the run distance to detonation as a function of input shock pressure. These experiments were conducted on gas guns in order to vary the input shock pressure accurately. The primary diagnostics are embedded magnetic gauges which are based on Faraday's law of induction along with photon Doppler velocimetry (PDV). The run distance to detonation vs. shock pressure, or ``Pop plot,'' was redefined as log (X*) = 2.14 -- 1.82 log (P), which is substantially different than previous data. The Hugoniot was refined as Us = 2.32 + 2.21 Up. This data will be useful for the development of predictive models for the safety and performance of PBXN-9 in addition to providing an increased understanding of HMX based explosives in varying formulations.

The Nominal/Generic Specific Heat per Average Atom Concept for CHNO Energetic Materials

DTIC Science & Technology

2006-07-01

Heat Per Average Atom for TATB. RDX . TNT. HMX . and HNS... HMX can exist in different solid polymorphic forms. At a certain temperature, TT, one form may change to another form if the heat energy of...densities ( p. ) up to, and including, crystals at TMD for TNT, RDX , HMX , and TATB. The presently proposed N/G CP magnitude, in certain temperature

Correlation Between Hot Spots and 3-d Defect Structure in Single and Polycrystalline High-explosive Materials

NASA Astrophysics Data System (ADS)

Hawkins, Cameron; Tschuaner, Oliver; Fussell, Zachary; Smith, Jesse

2017-06-01

A novel approach that spatially identifies inhomogeneities from microscale (defects, con-formational disorder) to mesoscale (voids, inclusions) is developed using synchrotron x-ray methods: tomography, Lang topography, and micro-diffraction mapping. These techniques pro-vide a non-destructive method for characterization of mm-sized samples prior to shock experiments. These characterization maps can be used to correlate continuum level measurements in shock compression experiments to the mesoscale and microscale structure. Specifically examined is a sample of C4. We show extensive conformational disorder in gamma-RDX, which is the main component. Further, we observe that the minor HMX-component in C4 contains at least two different phases: alpha- and beta-HMX. This work supported by National Security Technologies, LLC, under Contract No. DE-AC52-06NA25946 with the U.S. Department of Energy and by the Site-Directed Research and Development Program. DOE/NV/25946-3071.

Isolation of three hexahydro-1,3,5-trinitro-1,3,5-triazine-degrading species of the family Enterobacteriaceae from nitramine explosive-contaminated soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kitts, C.L.; Cunningham, D.P.; Unkefer, P.J.

1994-12-01

Nitramine explosives, RDX and HMX, are used by the military in high-yield munitions. Manufacture and testing have resulted in contaminated soils and bioremediate has been proposed as a safe and cost-effective means of cleanup. Biodegradation under aerobic conditions has not been successful. However, biodegradation of both RDX and HMX has been reported under anaerobic conditions. In this report, the authors describe the isolation and identification of three individual members of the family Enterobacteriaceae, each of which degrades RDX in pure culture. 20 refs., 1 fig., 2 tabs.

Creation of a Data Base on Energetic Materials

DTIC Science & Technology

1987-08-10

Examples of booster explosives are Tetryl, RDX , and HMX . Examples of bursting explosives are Amatols, TNT, Compositions A, B, & C, and Picatrol. Within...Test Thermal Shock Resistance Glass Transition Temperature Toxicity Grain Size Viscosity Hardness Volatility Heat Capacity Water Resistance Heat of...Tensile Strength Flammability Thermal Conductivity Flexural Strength Thermal Expansion Coefficient Gap Test Thermal Shock Resistance Glass Transition

Thermophysical Property Testing Using Transient Techniques.

DTIC Science & Technology

1984-06-29

WORDS (Continue on reverse side if necessary and identify by block number) Specific heat HMX carbon/carbon Diffusivity RDX solid propellants Conductivity...energetic materials (AP, " HMX , RDX and HTPB) used in solid rocket fuel to carbon/carbon materials used as rocket nozzles. Studies on AP included single...32 4.1b HMX and RDX ............................35 a 4.2 Carbon/Carbon Materials ...................... 36 5.0 SUMMARY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Renlund, Anita Mariana; Tappan, Alexander Smith; Miller, Jill C.

The HMX {beta}-{delta} solid-solid phase transition, which occurs as HMX is heated near 170 C, is linked to increased reactivity and sensitivity to initiation. Thermally damaged energetic materials (EMs) containing HMX therefore may present a safety concern. Information about the phase transition is vital to predictive safety models for HMX and HMX-containing EMs. We report work on monitoring the phase transition with real-time Raman spectroscopy aimed towards obtaining a better understanding of physical properties of HMX through the phase transition. HMX samples were confined in a cell of minimal free volume in a displacement-controlled or load-controlled arrangement. The cell wasmore » heated and then cooled at controlled rates while real-time Raman spectroscopic measurements were performed. Raman spectroscopy provides a clear distinction between the phases of HMX because the vibrational transitions of the molecule change with conformational changes associated with the phase transition. Temperature of phase transition versus load data are presented for both the heating and cooling cycles in the load-controlled apparatus, and general trends are discussed. A weak dependence of the temperature of phase transition on load was discovered during the heating cycle, with higher loads causing the phase transition to occur at a higher temperature. This was especially true in the temperature of completion of phase transition data as opposed to the temperature of onset of phase transition data. A stronger dependence on load was observed in the cooling cycle, with higher loads causing the reverse phase transitions to occur at a higher cooling temperature. Also, higher loads tended to cause the phase transition to occur over a longer period of time in the heating cycle and over a shorter period of time in the cooling cycle. All three of the pure HMX phases ({alpha}, {beta} and {delta}) were detected on cooling of the heated samples, either in pure form or as a mixture.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Prasesh; Mayes, Melanie; Tang, Guoping

Contamination of soils/groundwater by munition compounds (TNT, RDX, HMX) is of significant concern at many U.S. Department of Defense sites. We collected soils from operational ranges in Maryland (APG), Massachusetts (MMR-B and MMR-E) and Washington (JBLM) and conducted sorption/transport studies to investigate effects of soil organic carbon (OC) and clay content on fate of dissolved munition compounds (MCs). Sorption experiments showed higher sorption coefficients [TNT:42-68 kg/L, RDX:6.9-8.7 Kg/L and HMX:2.6-3.1 Kg/L] in OC rich soils (JBLM, MMR-E) compared to clay rich soils MMR-B and APG [TNT:19-21 Kg/L, RDX:2.5-3.4 Kg/L, HMX:0.9-1.2 Kg/L]. In column experiments, breakthrough of MCs was mostly quickermore » in MMR-B and APG soil filled columns compared to MMR-E and JBLM. Between TNT, RDX and HMX, breakthrough was fastest for RDX followed by HMX and TNT for all soil columns. Separation of effluents into dissolved (<3 kDa) vs unfiltered (total) fractions in effluents showed 30-50% of TNT in the fraction >3kDa (colloidal fraction). HMX and RDX were completely associated with dissolved fraction. Results demonstrate that OC rich soils may enhance sorption and delay transport of TNT, RDX and HMX. Furthermore, colloids could contribute to transport of dissolved TNT to a significant amount.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weese, Randall K.

In order to calculate the kinetic parameters from DSC data, we have used the generally accepted methods of Bershtein [13]. We have calculated the rate constants for 4 temperatures and the activation energy based on the shift in the transition temperature, β→δ for HMX. The values of E a from this work is 402 kJ/mol compared to previous results by Brill [9] of 204 kJ/mol. Brill and associates measured the phase transition of HMX using FTIR, sodium chloride plates and silicon oil. Given the differences in technique between FTIR and DSC the results found in this work are reasonable. Inmore » this investigation a large sample set (16) proved to be statistically valid for the determinations of k. Linear regressions were performed, observed and good fits were obtained, for each temperature. The enthalpy determination of ΔH o, for the β→δ phase transition was reproducible with in 3 parts in 100 over the range of this experiment. Thus, the data derived from this experiment k, E a, and ΔH o are valid parameters for the solid-solid phase transition. Obtaining pure β phase HMX was very important for this investigation. Related to the phase change is the particle size distribution and is presented in Figure 3. Compared to previous work on HMX, this study utilized very pure β phase material. In addition, the particle size was controlled more rigorously at about 160 μm, giving a more consistent result for α. Thus, these kinetic results should have less scatter than results with less control of HMX purity and particle size. The kinetic basis of the polymorphic conversion is due to the cohesive forces in the HMX crystal lattice [21]. The energy required to bring about change from chair to chair-chair conformation has been reported by Brill [21] as ring torsion and is essentially a normal mode of the molecule that requires about 4 kJ mol -1. For the purpose of this investigation the energy of activation found in this work relates to the disruption of the

Modeling the measured effect of a nitroplasticizer (BDNPA/F) on cookoff of a plastic bonded explosive (PBX 9501)

DOE PAGES

Hobbs, Michael L.; Kaneshige, Michael J.; Erikson, William W.

2016-09-12

Here, we have used a modified version of the Sandia Instrumented Thermal Ignition (SITI) experiment to develop a pressure-dependent, five-step ignition model for a plastic bonded explosive (PBX 9501) consisting of 95 wt% octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazoncine (HMX), 2.5 wt% Estane® 5703 (a polyurethane thermoplastic), and 2.5 wt% of a nitroplasticizer (NP): BDNPA/F, a 50/50 wt% eutectic mixture bis(2,2-dinitropropyl)-acetal (BDNPA) and bis(2,2-dinitropropyl)-formal (BDNPF). The five steps include desorption of water, decomposition of the NP to form NO2, reaction of the NO2 with Estane® and HMX, and decomposition of HMX. The model was fit using our experiments and successfully validated with experiments from fivemore » other laboratories with scales ranging from about 2 g to more than 2.5 kg of PBX. Our experimental variables included density, confinement, free gas volume, and temperature. We measured internal temperatures, confinement pressure, and ignition time. In some of our experiments, we used a borescope to visually observe the decomposing PBX. Our observations included the endothermic β–δ phase change of the HMX, a small exothermic temperature excursion in low-density unconfined experiments, and runaway ignition. We hypothesize that the temperature excursion in these low density experiments was associated with the NP decomposing exothermically within the PBX sample. This reactant-limited temperature excursion was not observed with our thermocouples in the high-density experiments. For these experiments, we believe the binder diffused to the edges of our high density samples and decomposed next to the highly conductive wall as confirmed by our borescope images.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hobbs, Michael L.; Kaneshige, Michael J.; Erikson, William W.

Here, we have used a modified version of the Sandia Instrumented Thermal Ignition (SITI) experiment to develop a pressure-dependent, five-step ignition model for a plastic bonded explosive (PBX 9501) consisting of 95 wt% octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazoncine (HMX), 2.5 wt% Estane® 5703 (a polyurethane thermoplastic), and 2.5 wt% of a nitroplasticizer (NP): BDNPA/F, a 50/50 wt% eutectic mixture bis(2,2-dinitropropyl)-acetal (BDNPA) and bis(2,2-dinitropropyl)-formal (BDNPF). The five steps include desorption of water, decomposition of the NP to form NO2, reaction of the NO2 with Estane® and HMX, and decomposition of HMX. The model was fit using our experiments and successfully validated with experiments from fivemore » other laboratories with scales ranging from about 2 g to more than 2.5 kg of PBX. Our experimental variables included density, confinement, free gas volume, and temperature. We measured internal temperatures, confinement pressure, and ignition time. In some of our experiments, we used a borescope to visually observe the decomposing PBX. Our observations included the endothermic β–δ phase change of the HMX, a small exothermic temperature excursion in low-density unconfined experiments, and runaway ignition. We hypothesize that the temperature excursion in these low density experiments was associated with the NP decomposing exothermically within the PBX sample. This reactant-limited temperature excursion was not observed with our thermocouples in the high-density experiments. For these experiments, we believe the binder diffused to the edges of our high density samples and decomposed next to the highly conductive wall as confirmed by our borescope images.« less

Quantum Mechanical Predictions Of Energetic Materials: When Good Theories Go Bad

DTIC Science & Technology

2008-12-01

pressures. The systems studied were nitromethane, 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane ( HMX ), cyclotrimethylenetrinitramine ( RDX ...degrees of compression. The systems are RDX , HMX , CL-20, nitromethane, PETN, and TATB. The GGA DFT Perdew-Burke-Ernzerhof (PBE) [Perdew et al., 1996...nitromethane, HMX , RDX and CL-20). At higher degrees of compression, planewave kinetic energy cut- offs (Ecut) were restricted to either 396 eV and/or

Molecular Simulations of Dynamic Processes of Solid Explosives

DTIC Science & Technology

2004-12-01

compression. Therefore, we analyzed the dynamics of the energetic crystals RDX , HMX , HNIW and PETN under hydrostatic compression conditions using...for the RDX , HMX and HNIW crystals were found in good agreement with experimental values over the entire range of pressures investigated...Theoretical studies of the hydrostatic compression of RDX , HMX , HNIW, and PETN crystals, J. Phys. Chem. B 103, 6783. scu, D. C.; Rice, B. M. and

On the Explicit Determination of the Chapman-Jouguet Parameters for an Explosive Compound

DTIC Science & Technology

2014-11-19

relations were tested for the very well characterise explosives PETN, HMX , RDX, TATB, TNT and the calculated values obtained for the C-J parameters...Cyclotrimethylenetrinitramine (RDX), Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine ( HMX ), Pentaerythritol tetranitrate (PETN) and Triamino...the Chapman-Jouguet parameters of PETN, HMX , RDX and TATB Table 1 below provides a summary of the relations in order of requirement to obtain the C

Behavior of energetic materials in ground water at an anti-tank range.

PubMed

Martel, Richard; Mailloux, Michel; Gabriel, Uta; Lefebvre, René; Thiboutot, Sonia; Ampleman, Guy

2009-01-01

An environmental issue has arisen with M-72 malfunction on anti-tank ranges because many of these rockets break into pieces without exploding on impact, dispersing their energetic materials content on the ground surface and exposing them to transport by infiltration of rainfall and snowmelt. A case study (1998--2005) at Arnhem Anti-Tank Range (Garrison Valcartier, Canada, in operation since the 1970s) revealed octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) contamination and traces of 1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) in ground water at varying concentrations, with all detected HMX concentrations below the USEPA guideline for drinking water of 400 microg L(-1). An HMX mass balance on a transect perpendicular to ground water flow, about 300 m downgradient of the impact area, indicated an HMX flux of about 3 g d(-1) (0.7-1 kg yr(-1), 2005). The HMX mass in the impact area on the sand terrace was estimated at 7 to 10 kg (in 2005). The annual dissolved HMX flux represents about 10% of the source. The dissolved HMX plume in ground water consisted of a series of slugs, generated at each significant infiltration event. HMX is weakly retarded by sorption and is neither biotransformed nor mineralized under the aerobic conditions of the aquifer. TNT and RDX exceeded the USEPA guideline (2 microg L(-1) RDX and 1 microg L(-1) TNT) in three and two samples, respectively. The TNT plume was discontinuous because this compound was not always present at the ground surface. TNT is biotransformed, weakly sorbed, and not mineralized. In two wells, perchlorate associated with the propellant was found at concentrations above the Health Canada preliminary guideline of 6 microg L(-1) near the firing position.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeager, John D.; Higginbotham Duque, Amanda L.; Shorty, Marvin

Inert surrogates or mocks for high explosives are commonly used in place of the real material for complex experiments or in situations where safety is a concern. We tested several materials as potential mocks for HMX in terms of density, thermal stability, and processability. Selection criteria were developed and a literature search was conducted primarily using the Cambridge Structural Database. Moreover, out of over 200 potentially acceptable materials, six were chosen for crystallization experiments and a suite of analytical characterization. Of these six, 5-iodo-2'-deoxyuridine, N,N'-bis(2,3,4,5,6-pentafluorophenyl)oxamide, and 2,3,4,5,6-pentafluorobenzamide all were found to be thermally stable at 150°C, matched HMX density asmore » a pressed pellet, and could be crystallized to appropriate particle sizes. These three materials are considered suitable inert density mocks for HMX and will be the subject of future testing.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glascoe, E A; Zaug, J M; Burnham, A K

The effect of pressure on the thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low to moderate pressures (i.e. between ambient pressure and 1 GPa) and decelerates the decomposition at higher pressures.more » The decomposition acceleration is attributed to pressure enhanced autocatalysis whereas the deceleration at high pressures is attributed pressure inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both {beta} and {delta} phase HMX are sensitive to pressure in the thermally induced decomposition kinetics.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

M Pravica; M Galley; E Kim

We report two separate synchrotron FTIR measurements of the high explosive HMX at ambient temperature and static high pressure in the far- (100-500 wavenumbers) and mid- (500-3200 wavenumbers) infrared (IR) regions up to 30 GPa. The sample for the far-IR experiment was loaded with no pressure-transmitting medium and the sample for the mid-IR study utilized a KBr pressurizing medium. Two possible phase transitions from beta-HMX at ambient conditions were observed near 5 and 12 GPa (likely into the epsilon phase). A phase transition was observed near 25 GPa probably into the delta phase. Pressure cycling in both experiments found nomore » irreversible damage within this pressure range.« less

Numerical study on tailoring the shock sensitivity of TATB-based explosives using mesostructural features

NASA Astrophysics Data System (ADS)

Springer, H. Keo

2017-06-01

Advanced manufacturing techniques offer control of explosive mesostructures necessary to tailor its shock sensitivity. However, structure-property relationships are not well established for explosives so there is little material design guidance for these techniques. The objective of this numerical study is to demonstrate how TATB-based explosives can be sensitized to shocks using mesostructural features. For this study, we use LX-17 (92.5%wt TATB, 7.5%wt Kel-F 800) as the prototypical TATB-based explosive. We employ features with different geometries and materials. HMX-based explosive features, high shock impedance features, and pores are used to sensitive the LX-17. Simulations are performed in the multi-physics hydrocode, ALE3D. A reactive flow model is used to simulate the shock initiation response of the explosives. Our metric for shock sensitivity in this study is run distance to detonation as a function of applied pressure. These numerical studies are important because they guide the design of novel energetic materials. This work was performed under the auspices of the United States Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL-ABS-724986.

Application of Van Der Waals Density Functional Theory to Study Physical Properties of Energetic Materials

NASA Astrophysics Data System (ADS)

Conroy, M. W.; Budzevich, M. M.; Lin, Y.; Oleynik, I. I.; White, C. T.

2009-12-01

An empirical correction to account for van der Waals interactions based on the work of Neumann and Perrin [J. Phys. Chem. B 109, 15531 (2005)] was applied to density functional theory calculations of energetic molecular crystals. The calculated equilibrium unit-cell volumes of FOX-7, β-HMX, solid nitromethane, PETN-I, α-RDX, and TATB show a significant improvement in the agreement with experimental results. Hydrostatic-compression simulations of β-HMX, PETN-I, and α-RDX were also performed. The isothermal equations of state calculated from the results show increased agreement with experiment in the pressure intervals studied.

New Approach to Predict Hugoniot Properties of Explosives Materials

DTIC Science & Technology

2015-03-12

Cyclotrimethylenetrinitramine (RDX), Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine ( HMX ), Pentaerythritol tetranitrate (PETN) and Triamino-trinitrobenzene...experimental values. The four materials chosen are RDX, HMX , PETN and TATB. The detonation velocity is one of the key performance characteristics of energetic...were used and the gas products of reaction were assumed as an ideal gas. The four materials to be characterised are RDX, HMX , PETN and TATB and their

The HMX/NKX homeodomain protein MLS-2 specifies the identity of the AWC sensory neuron type via regulation of the ceh-36 Otx gene in C. elegans

PubMed Central

Kim, Kyuhyung; Kim, Rinho; Sengupta, Piali

2010-01-01

The differentiated features of postmitotic neurons are dictated by the expression of specific transcription factors. The mechanisms by which the precise spatiotemporal expression patterns of these factors are regulated are poorly understood. In C. elegans, the ceh-36 Otx homeobox gene is expressed in the AWC sensory neurons throughout postembryonic development, and regulates terminal differentiation of this neuronal subtype. Here, we show that the HMX/NKX homeodomain protein MLS-2 regulates ceh-36 expression specifically in the AWC neurons. Consequently, the AWC neurons fail to express neuron type-specific characteristics in mls-2 mutants. mls-2 is expressed transiently in postmitotic AWC neurons, and directly initiates ceh-36 expression. CEH-36 subsequently interacts with a distinct site in its cis-regulatory sequences to maintain its own expression, and also directly regulates the expression of AWC-specific terminal differentiation genes. We also show that MLS-2 acts in additional neuron types to regulate their development and differentiation. Our analysis describes a transcription factor cascade that defines the unique postmitotic characteristics of a sensory neuron subtype, and provides insights into the spatiotemporal regulatory mechanisms that generate functional diversity in the sensory nervous system. PMID:20150279

Self-deflagration rates of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). [burning tate, thermal stability

NASA Technical Reports Server (NTRS)

Boggs, T. L.; Price, C. F.; Zurn, D. E.; Atwood, A. I.; Eisel, J. L.

1980-01-01

The thermal stability and resistance to impact was investigated for the ingredient TABA. Particular attention was given to determining the use of TABA as a possible alternative ingredient or substitute for HMX in explosives and high energy propellants. The burn rate of TABA was investigated as a function of pressure. It was concluded that the self deflagration rate of TABA is an order of magnitude lower than HMX over the range 2000-15000 psi; TABA will not sustain self deflagration at low pressures (less than or equal to 1500 psi) in the sample configuration and apparatus used.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hobbs, Michael L.

We have previously developed a PBX 9501 cookoff model for the plastic bonded explosive PBX 9501 consisting of 95 wt% octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazoncine (HMX), 2.5 wt% Estane® 5703 (a polyurethane thermoplastic), and 2.5 wt% of a nitroplasticizer (NP): BDNPA/F, a 50/50 wt% eutectic mixture bis(2,2-dinitropropyl)-acetal (BDNPA) and bis(2,2-dinitropropyl)-formal (BDNPF). This fivestep model includes desorption of water, decomposition of the NP to form NO 2, reaction of the NO 2 with Estane and HMX, and decomposition of HMX [1]. This model has been successfully validated with data from six laboratories with scales ranging from 2 g to more than 2.5 kg of explosive.more » We have determined, that the PBX 9501 model can be used to predict cookoff of other plastic bonded explosives containing HMX and an inert binder, such as LX-04 consisting of 85 wt% HMX and 15 wt% Viton A (vinylidine fluoride/hexafluoropropylene copolymer), LX-07 (90 wt% HMX and 10 wt% Viton A), LX- 10-0 (95 wt% HMX and 5 wt% Viton A), and LX-14 consisting of 95.5 wt % HMX and 4.5 wt% Estane® 5702-F1 (a polyurethane thermoplastic). Normally our cookoff models are verified using Sandia’s Instrumented Thermal Initiation (SITI) experiment. However, SITI data for LX-04, LX-07, LX-10-0, and LX-14 are not available at pressed density; although, some molding powder SITI data on LX-10-0 and LX-14 exists. Tarver and Tran [2] provide some one-dimensional time-to-explosion (ODTX) data for these explosives. The applicability of the PBX 9501 model to LX-04, LX-07, LX-10-0, AND LX-14 was made using this ODTX data [2]. The PBX 9501 model is applied to these other explosives by accounting for the correct amount of HMX in the explosive and limiting the NP reaction. We have found the PBX 9501 model to be useful for predicting the response of these PBXs to abnormal thermal environments such as fire.« less

Ab initio Quantum Chemical Reaction Kinetics: Recent Applications in Combustion Chemistry (Briefing Charts)

DTIC Science & Technology

2015-06-28

HMX RDX  Recent Works  See Geith et al...Propellants, Explosives, Pyrotechnics, 29, 3 (2004)  ∆Hcomb(DNB) = (5195 ± 300) kJ kg-1 (bomb calorimetry and MP2/cc-pVTZ ∆Hf) cf HMX 9435 & RDX 9560 kJ...kg-1  Vd = 8660 ms-1, cf HMX 9100 & RDX 8750 ms-1  See Geith et al., Combust and Flame, 139, 358 (2004)  Recent synthesis (known since 1898 by

76 FR 1402 - Notice of allocation of Tariff Rate Quotas (TRQ) on the Import of Certain Worsted Wool Fabrics...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-10

... Receiving Allocation Adrian Jules LTD--Rochester, NY, HMX, LLC-- New York, NY, Hugo Boss Cleveland, Inc... York, NY, HMX, LLC--New York, NY, Hugo Boss Cleveland, Inc.--Brooklyn, OH, JA Apparel Corp.--New York...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leonard, Philip; Francois, Elizabeth Green

During this project we investigated a number of energetic materials both old and new and determined that most of them were unsuitable due to safety or sensitivity reasons. Unsuccessful coformulants include TNAZ and BNFF for volatility reasons, and DAAF due to thermal compatibility issues. The powerful explosive HMX became a focus of the work in later stages as it conferred excellent power while being commonly available in well-regulated particle size lots and is chemically compatible in the melt with many coformulants. Ultimately three preferred formulations emerged from this work: a formulation tested on large scale by ARDEC involving PrNQ andmore » HMX; a formulation tested at ARDEC and LANL using a nitrate salt eutectic and HMX; a formulation tested at LANL using LLM-201 and HMX.« less

Molecular Dynamics in Nitramines and Modified Nitramines

DTIC Science & Technology

1983-11-01

34melts"? Uhat is the structure of RDX and HMX molecules in the "melt", solution, and ,gas phases? What is the structure of the O- RDX polymorph ? These... RDX molecule has 4sentially 3v oeulrsrutr L~j -in all environments except the stable solid"V- RDX ph&*e. The RDX and HMX --~J meslts were found to be...otion and phase transition characteristics of HMX . These studies involve approaches not previously used in this field such as 14 N nuclear quadrupole

Detonation performance measurements of cyclotol 80/20

NASA Astrophysics Data System (ADS)

Kuiper, T. A.; Anderson, E. K.; Short, M.; Jackson, S. I.

2017-01-01

Cyclotol is a melt-castable high explosive composed of RDX and TNT, and typically a small amount of HMX. The term Cyclotol may apply to other mixtures of these components, but for the present work, experiments were conducted using Cyclotol containing 80 wt% RDX and HMX and 20 wt% TNT (we will refer to mixtures of RDX and TNT using the notation RDX%/TNT%). In the current effort, we report detonation velocity measurements at several diameters for unconfined rate sticks. The results are compared to prior diameter-effect data for Cyclotol 77/23, and a density-corrected Eyring-form fit for all available rate-stick data is reported.

Novel CE-MS technique for detection of high explosives using perfluorooctanoic acid as a MEKC and mass spectrometric complexation reagent.

PubMed

Brensinger, Karen; Rollman, Christopher; Copper, Christine; Genzman, Ashton; Rine, Jacqueline; Lurie, Ira; Moini, Mehdi

2016-01-01

To address the need for the forensic analysis of high explosives, a novel capillary electrophoresis mass spectrometry (CE-MS) technique has been developed for high resolution, sensitivity, and mass accuracy detection of these compounds. The technique uses perfluorooctanoic acid (PFOA) as both a micellar electrokinetic chromatography (MEKC) reagent for separation of neutral explosives and as the complexation reagent for mass spectrometric detection of PFOA-explosive complexes in the negative ion mode. High explosives that formed complexes with PFOA included RDX, HMX, tetryl, and PETN. Some nitroaromatics were detected as molecular ions. Detection limits in the high parts per billion range and linear calibration responses over two orders of magnitude were obtained. For proof of concept, the technique was applied to the quantitative analysis of high explosives in sand samples. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Innovative scheme for high-repetition-rate imaging of CN radical.

PubMed

Satija, Aman; Ruesch, Morgan D; Powell, Michael S; Son, Steven F; Lucht, Robert P

2018-02-01

We have employed, to the best of our knowledge, a novel excitation scheme to perform the first high-repetition-rate planar laser-induced fluorescence (PLIF) measurements of a CN radical in combustion. The third harmonic of a Nd:YVO 4 laser at 355 nm due to its relatively large linewidth overlaps with several R branch transitions in a CN ground electronic state. Therefore, the 355 nm beam was employed to directly excite the CN transitions with good efficiency. The CN measurements were performed in premixed CH 4 -N 2 O flames with varying equivalence ratios. A detailed characterization of the high-speed CN PLIF imaging system is presented via its ability to capture statistical and dynamical information in these premixed flames. Single-shot CN PLIF images obtained over a HMX pellet undergoing self-supported deflagration are presented as an example of the imaging system being applied towards characterizing the flame structure of energetic materials.

A systematic tandem mass spectrometric study of anion attachment for improved detection and acidity evaluation of nitrogen-rich energetic compounds.

PubMed

Gaiffe, Gabriel; Bridoux, Maxime C; Costanza, Christine; Cole, Richard B

2018-01-01

The development of rapid, efficient, and reliable detection methods for the characterization of energetic compounds is of high importance to security forces concerned with terrorist threats. With a mass spectrometric approach, characteristic ions can be produced by attaching anions to analyte molecules in the negative ion mode of electrospray ionization mass spectrometry (ESI-MS). Under optimized conditions, formed anionic adducts can be detected with higher sensitivities as compared with the deprotonated molecules. Fundamental aspects pertaining to the formation of anionic adducts of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), 1,3,5-trinitro-1,3,5-triazinane (RDX), pentaerythritol tetranitrate (PETN), nitroglycerin (NG), and 1,3,5-trinitroso-1,3,5-triazinane energetic (R-salt) compounds using various anions have been systematically studied by ESI-MS and ESI tandem mass spectrometry (collision-induced dissociation) experiments. Bracketing method results show that the gas-phase acidities of PETN, RDX, and HMX fall between those of HF and acetic acid. Moreover, PETN and RDX are each less acidic than HMX in the gas phase. Nitroglycerin was found to be the most acidic among the nitrogen-rich explosives studied. The ensemble of bracketing results allows the construction of the following ranking of gas-phase acidities: PETN (1530-1458 kJ/mol) > RDX (approximately 1458 kJ/mol) > HMX (approximately 1433 kJ/mol) > nitroglycerin (1427-1327.8 kJ/mol). Copyright © 2017 John Wiley & Sons, Ltd.

VH-92A Presidential Helicopter (VH-92A)

DTIC Science & Technology

2015-12-01

HMX - 1) and support the President worldwide and the Vice President primarily inside the National Capital Region. Mission tasking encompasses two (2...Factor: 19% of Total Aircraft Inventory (TAI) Squadrons: Marine Helicopter Squadron One ( HMX -1) Helicopters per (active) squadron: 16 Monthly Flight

Conservation of gene linkage in dispersed vertebrate NK homeobox clusters.

PubMed

Wotton, Karl R; Weierud, Frida K; Juárez-Morales, José L; Alvares, Lúcia E; Dietrich, Susanne; Lewis, Katharine E

2009-10-01

Nk homeobox genes are important regulators of many different developmental processes including muscle, heart, central nervous system and sensory organ development. They are thought to have arisen as part of the ANTP megacluster, which also gave rise to Hox and ParaHox genes, and at least some NK genes remain tightly linked in all animals examined so far. The protostome-deuterostome ancestor probably contained a cluster of nine Nk genes: (Msx)-(Nk4/tinman)-(Nk3/bagpipe)-(Lbx/ladybird)-(Tlx/c15)-(Nk7)-(Nk6/hgtx)-(Nk1/slouch)-(Nk5/Hmx). Of these genes, only NKX2.6-NKX3.1, LBX1-TLX1 and LBX2-TLX2 remain tightly linked in humans. However, it is currently unclear whether this is unique to the human genome as we do not know which of these Nk genes are clustered in other vertebrates. This makes it difficult to assess whether the remaining linkages are due to selective pressures or because chance rearrangements have "missed" certain genes. In this paper, we identify all of the paralogs of these ancestrally clustered NK genes in several distinct vertebrates. We demonstrate that tight linkages of Lbx1-Tlx1, Lbx2-Tlx2 and Nkx3.1-Nkx2.6 have been widely maintained in both the ray-finned and lobe-finned fish lineages. Moreover, the recently duplicated Hmx2-Hmx3 genes are also tightly linked. Finally, we show that Lbx1-Tlx1 and Hmx2-Hmx3 are flanked by highly conserved noncoding elements, suggesting that shared regulatory regions may have resulted in evolutionary pressure to maintain these linkages. Consistent with this, these pairs of genes have overlapping expression domains. In contrast, Lbx2-Tlx2 and Nkx3.1-Nkx2.6, which do not seem to be coexpressed, are also not associated with conserved noncoding sequences, suggesting that an alternative mechanism may be responsible for the continued clustering of these genes.

High Pressure-Temperature Phase Diagram of 1,1-diamino-2,2-dinitroethylene

NASA Astrophysics Data System (ADS)

Bishop, Matthew; Chellappa, Raja; Liu, Zhenxian; Preston, Daniel; Sandstrom, Mary; Dattelbaum, Dana; Vohra, Yogesh; Velisavljevic, Nenad

2013-06-01

1,1-diamino-2,2-dinitroethelyne (FOX-7) is a less sensitive energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ) . In this study, we have investigated the high P-T stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra confirmed the known α --> β (110 °C) and β --> γ (160 °C) phase transitions; as well as, indicated an additional phase transition, γ --> δ (210°C), with the δ phase being stable up to 250 °C prior to melt/decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa revealed that the α --> β transition occurs at 180 °C, while β --> β + δ phase transition shifted to 300 °C with suppression of γ phase. Decomposition was observed above 325 °C. Based on multiple high P-T measurements, we have established the first high P-T phase diagram of FOX-7. This work was, in part, supported by the US DOE under contract No. DE-AC52-06NA25396 and Science Campaign 2 Program. MB acknowledges additional support from the NSF BD program. Use of NSLS (DE-AC02-98CH10886) beamline U2A (COMPRES, No.EAR01-35554, CDAC).

On the mechanism of influence of explosive compounds: Destruction process on sensitivity of these compounds to mechanic impacts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Filin, V.P.; Loboyko, B.G.; Averin, A.N.

1996-05-01

The results of investigations into sensitivity of the HMX-based explosive compound samples to mechanic stimuli are shown in the presented report. As a result of experimental studies it was illustrated, that explosives deformation and destruction processes under mechanical stimuli are accompanied by occurrence of different electric phenomena. The hypothesis on possible influence of electric phenomena occurring under deformation and destruction on the mechanism of formation of zones with high density of energy is discussed in the report. {copyright} {ital 1996 American Institute of Physics.}

Ignition criterion for heterogeneous energetic materials based on hotspot size-temperature threshold

NASA Astrophysics Data System (ADS)

Barua, A.; Kim, S.; Horie, Y.; Zhou, M.

2013-02-01

A criterion for the ignition of granular explosives (GXs) and polymer-bonded explosives (PBXs) under shock and non-shock loading is developed. The formulation is based on integration of a quantification of the distributions of the sizes and locations of hotspots in loading events using a cohesive finite element method (CFEM) developed recently and the characterization by Tarver et al. [C. M. Tarver et al., "Critical conditions for impact- and shock-induced hot spots in solid explosives," J. Phys. Chem. 100, 5794-5799 (1996)] of the critical size-temperature threshold of hotspots required for chemical ignition of solid explosives. The criterion, along with the CFEM capability to quantify the thermal-mechanical behavior of GXs and PBXs, allows the critical impact velocity for ignition, time to ignition, and critical input energy at ignition to be determined as functions of material composition, microstructure, and loading conditions. The applicability of the relation between the critical input energy (E) and impact velocity of James [H. R. James, "An extension to the critical energy criterion used to predict shock initiation thresholds," Propellants, Explos., Pyrotech. 21, 8-13 (1996)] for shock loading is examined, leading to a modified interpretation, which is sensitive to microstructure and loading condition. As an application, numerical studies are undertaken to evaluate the ignition threshold of granular high melting point eXplosive, octahydro-1,3,5,7-tetranitro-1,2,3,5-tetrazocine (HMX) and HMX/Estane PBX under loading with impact velocities up to 350 ms-1 and strain rates up to 105 s-1. Results show that, for the GX, the time to criticality (tc) is strongly influenced by initial porosity, but is insensitive to grain size. Analyses also lead to a quantification of the differences between the responses of the GXs and PBXs in terms of critical impact velocity for ignition, time to ignition, and critical input energy at ignition. Since the framework permits

Combustion Mechanisms of Very High Burn Rate (VHBR) Propellant. Phase II.

DTIC Science & Technology

1995-09-01

potassium salt of B10H1 2-. The Kraton slate and the Hycar slate both contain RDX as the oxidizer, while the PEG slate contains HMX and TAGN in the... polyacrylate (Hycar), hydroxy-terminated polybutadiene, and a mixture of styrene and ethylene-butylene (Kraton). As might be expected, when all else is equal...proprietary formulations of Teledyne-McCormick-Selph (TMS), designated H498 and H466. In H498, a potassium cation is utilized, while in H466, an

Pressure-coupled combustion response model for solid propellants based on Zeldovich-Novozhilov approach

NASA Technical Reports Server (NTRS)

Harstad, K. G.; Strand, L. D.

1987-01-01

An exact analytical solution is given to the problem of long-time propellant thermal response to a specified pressure oscillation. Coupling to the gas phase is made using the quasisteady Zeldovich-Novozhilov approximation. Explicit linear and lowest order (quadratic) nonlinear expressions for propellant response are obtained from the implicit nonlinear solutions. Using these expressions, response curves are presented for an ammonium perchlorate composite propellant and HMX monopropellant.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Willey, Trevor M.; Lauderbach, Lisa; Gagliardi, Franco

HMX-based explosives LX-10 and PBX-9501 were heated through the β-δ phase transition. Ultra-small angle x-ray scattering (USAXS) and molecular diffraction were simultaneously recorded as the HMX was heated. Mesoscale voids and structure dramatically change promptly with the β-δ phase transition, rather than with other thermal effects. Also, x-ray induced damage, observed in the USAXS, occurs more readily at elevated temperatures; as such, the dose was reduced to mitigate this effect. Optical microscopy performed during a similar heating cycle gives an indication of changes on longer length scales, while x-ray microtomography, performed before and after heating, shows the character of extensivemore » microstructural damage resulting from the temperature cycle and solid-state phase transition.« less

Shock initiation of an ɛ-CL-20-estane formulation

NASA Astrophysics Data System (ADS)

Tarver, C. M.; Simpson, R. L.; Urtiew, P. A.

1996-05-01

The shock sensitivity of a pressed solid explosive formulation, LX-19, containing 95.2% by weight epsilon phase 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (HNIW) and 4.8% Estane binder, was determined using the wedge test and embedded manganin pressure gauge techniques. This formulation was shown to be slightly more sensitive than LX-14, which contains 95.5% HMX and 4.5% Estane binder. The measured pressure histories for LX-19 were very similar to those obtained using several HMX-inert binder formulations. An Ignition and Growth reactive flow model for LX-19 was developed which differed from those for HMX-inert binder formulations only by a 25% higher hot spot growth rate.

Deflagration rates of secondary explosives under static MPa - GPa pressure

NASA Astrophysics Data System (ADS)

Zaug, Joseph; Young, Christopher; Glascoe, Elizabeth; Maienschein, Jon; Hart, Elaine; Long, Gregory; Black, Collin; Sykora, Gregory; Wardell, Jeffrey

2009-06-01

We discuss our measurements of the chemical reaction propagation rate (RPR) as a function of pressure using diamond anvil cell (DAC) and strand burner technologies. Materials investigated include HMX and RDX crystalline powders, LX-04 (85% HMX and 15% Viton A), and Comp B (63% RDX, 36% TNT, 1% wax). The anomalous correspondence between crystal structure, including in some instances isostructural phase transitions, on pressure dependant RPRs of TATB, HMX, Nitromethane, and Viton are elucidated using micro -IR and -Raman spectroscopies. The contrast between DAC GPa and strand burner MPa regime measurements yields insight into explosive material burn phenomena. Here we highlight pressure dependent physicochemical mechanisms that appear to affect the deflagration rate of precompressed energetic materials.

Large-Scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) Simulations of the Molecular Crystal alphaRDX

DTIC Science & Technology

2013-08-01

potential for HMX / RDX (3, 9). ...................................................................................8 1 1. Purpose This work...6 dispersion and electrostatic interactions. Constants for the SB potential are given in table 1. 8 Table 1. SB potential for HMX / RDX (3, 9...modeling dislocations in the energetic molecular crystal RDX using the Large-Scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) molecular

Erosivity of LOVA Propellants

DTIC Science & Technology

1981-09-01

ant was a mixture of RDX with a KRATON binder. Two propellants (80% RDX-PU and 80% HMX- CTBN ) had heat inputs greater than the M735 projectile with a...LOVA propellants [80% RDX-PU and 80% HMX.- CTBN ) would require a wear-reducing additive to keep wear comparable to M735 and M774. The other LOVA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skidmore, Cary Bradford; Preston, Daniel N.

These are a set of slides for educational outreach to children on high explosives science. It gives an introduction to the elements involved in this science: carbon, hydrogen, nitrogen, and oxygen. Combined, these form the molecule HMX. Many pictures are also included to illustrate explosions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burnham, A K; Weese, R K; Andrzejewski, W J

Decomposition kinetics are determined for HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and CP (2-(5-cyanotetrazalato) pentaammine cobalt (III) perchlorate) separately and together. For high levels of thermal stress, the two materials decompose faster as a mixture than individually. This effect is observed both in high-temperature thermal analysis experiments and in long-term thermal aging experiments. An Arrhenius plot of the 10% level of HMX decomposition by itself from a diverse set of experiments is linear from 120 to 260 C, with an apparent activation energy of 165 kJ/mol. Similar but less extensive thermal analysis data for the mixture suggests a slightly lower activation energy formore » the mixture, and an analogous extrapolation is consistent with the amount of gas observed in the long-term detonator aging experiments, which is about 30 times greater than expected from HMX by itself for 50 months at 100 C. Even with this acceleration, however, it would take {approx}10,000 years to achieve 10% decomposition at {approx}30 C. Correspondingly, negligible decomposition is predicted by this kinetic model for a few decades aging at temperatures slightly above ambient. This prediction is consistent with additional sealed-tube aging experiments at 100-120 C, which are estimated to have an effective thermal dose greater than that from decades of exposure to temperatures slightly above ambient.« less

A two-phase model for aluminized explosives on the ballistic and brisance performance

NASA Astrophysics Data System (ADS)

Kim, Wuhyun; Gwak, Min-cheol; Lee, Young-hun; Yoh, Jack J.

2018-02-01

The performance of aluminized high explosives is considered by varying the aluminum (Al) mass fraction in a heterogeneous mixture model. Since the time scales of the characteristic induction and combustion of high explosives and Al particles differ, the process of energy release behind the leading detonation wave front occurs over an extended period of time. For simulating the performance of aluminized explosives with varying Al mass fraction, HMX (1,3,5,7-tetrahexmine-1,3,5,7-tetrazocane) is considered as a base explosive when formulating the multiphase conservation laws of mass, momentum, and energy exchanges between the HMX product gases and Al particles. In the current study, a two-phase model is utilized in order to determine the effects of the Al mass fraction in a condensed phase explosive. First, two types of confined rate stick tests are considered to investigate the detonation velocity and the acceleration ability, which refers to the radial expansion velocity of the confinement shell. The simulation results of the confined rate stick test are compared with the experimental data for the Al mass fraction range of 0%-25%, and the optimal Al mass fraction is provided, which is consistent with the experimental observations. Additionally, a series of plate dent test simulations are conducted, the results of which show the same tendency as those of the experimental tests with varying Al mass fractions.

Transferability of electronic structure of four energetic materials by using single crystal and high resolution X-ray diffraction experiments

NASA Astrophysics Data System (ADS)

Chen, Yu-Sheng

The electronic structures of four energetic materials, trinitrodiazapentalene (C6H3N5O6, TNDAP), beta-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (C4H8N8O8, beta-HMX), 1,3,3-trinitroazetidine (C3H4N4O6, TNAZ), and hexahydro-1,3,5-trinitro-1,3,5-s-triazine (C3H6N6O6, RDX), have been analyzed using Hansen-Coppens multipole refinements, using high resolution X-ray diffraction data collected at low temperature, as well as from theoretical calculated structure factors from the solid state phase using density functional theory (DFT), plus B3LYP level theory, and the 6-31G* basis set. However, when comparing both the deformation density and the electrostatic potentials from the theoretical results in TNDAP and TNAZ, they disagree with the experimental results. Therefore, those results have been deposited in appendices A4 and A6, for future reference. In HMX and RDX the theoretical results are in good agreement with experimental results. The physical properties derived from the electronic structure in these four energetic materials, such as multipole populations, the values of the electron density and its Laplacian of the electron density at the bond critical points, have also been calculated using "Atoms in Molecules" (AIM) theory both from the solid state phase calculation, and the experiment, as well as directly calculated from the free molecule in the gas phase. The electron density and the magnitude of its Laplacian from the gas phase are always larger than for the solid state phase calculation and the experiment. This may be due to the packing effect. The transferability of the experimental electronic structure of the NO 2 groups from HMX to TNDAP, TNAZ and RDX are also presented here. Even though the major populated multipoles are robust (small e.s.d.'s), these are few in number, compared with other lower populated multipoles for which the populations span a larger range. Since the deformation electron density distributions are reconstructed using linear

Development of a flyer design to perform plate impact shock-release-shock experiments on explosives

NASA Astrophysics Data System (ADS)

Finnegan, Simon; Ferguson, James; Millett, Jeremy; Goff, Michael

2017-06-01

A flyer design to generate a shock-release-shock loading history within a gas gun target was developed before being used to study the response of an HMX based explosive. The flyer consisted of two flyer plates separated by a vacuum gap. This created a rear free surface that, with correct material choice, allowed the target to release to close to ambient pressure between the initial shock and subsequent re-shock. The design was validated by impacting piezoelectric pin arrays to record the front flyer deformation. Shots were performed on PCTFE targets to record the shock states generated in an inert material prior to subjecting an HMX based explosive to the same loading. The response of the explosive to this loading history was recorded using magnetic particle velocity (PV) gauges embedded within the targets. The behavior during the run to detonation is compared with the response to sustained shocks at similar input pressures.

Morphological effects on sensitivity of heterogeneous energetic materials

NASA Astrophysics Data System (ADS)

Roy, Sidhartha; Rai, Nirmal; Sen, Oishik; Udaykumar, H. S.

2017-06-01

The mesoscale physical response under shock loading in heterogeneous energetics is inherently linked to the microstructural characteristics. The current work demonstrates the connection between the microstructural features of porous energetic material and its sensitivity. A unified levelset based framework is developed to characterize the microstructures of a given sample. Several morphological metrics describing the mesoscale geometry of the materials are extracted using the current tool including anisotropy, tortuosity, surface to volume, nearest neighbors, size and curvature distributions. The relevant metrics among the ones extracted are identified and correlated to the mesoscale response of the energetic materials under shock loading. Two classes of problems are considered here: (a) field of idealized voids embedded in the HMX material and (b) real samples of pressed HMX. The effects of stochasticity associated with void arrangements on the sensitivity of the energetic material samples are shown. In summary, this work demonstrates the relationship between the mesoscale morphology and shock response of heterogeneous energetic materials using a levelset based framework.

Annual Report to Congress - Fiscal Year 2002, from the Strategic Environmental Research and Development Program

DTIC Science & Technology

2003-03-01

and Catabolic Enzymes Involved in Phytoremediation of the Nitro-Substituted Explosives TNT, RDX, and HMX . . . . . A-48 CU-1318 – Engineering Transgenic...1317 Identification of Metabolic Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro-Substituted Explosives TNT, RDX, and HMX...A A-48 PROJECT SUMMARY PROJECT TITLE & ID: Identification of Metabolic Routes and Catabolic Enzymes Involved in Phytoremediation of the Nitro

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Lu; Hanson, David E

Here we present the results on the study of surface properties of {beta}-HMX crystal utilizing molecular simulations. The surface polarity of three principal crystal surfaces are investigated by measuring the water contact angles. The calculated contact angles agree excellently with the values measured by experiment and show that the surface polarity of three crystal surfaces are different. The free energies and forces of detaching an Estane chain with and without nitroplasticizer from the three principal crystal surfaces were calculated using umbrella sampling technique. We find that the detaching free energy/force increases with the increasing HMX surface polarity. In addition, ourmore » results also show that nitroplasticizer plays an important role in the adhesion forces between Estane and HMX surfaces.« less

Small scale thermal violence experiments for combined insensitive high explosive and booster materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rae, Philip J; Bauer, Clare L; Stennett, C

A small scale cook-off experiment has been designed to provide a violence metric for both booster and IHE materials, singly and in combination. The experiment has a simple, axisymmetric geometry provided by a 10 mm internal diameter cylindrical steel confinement up to 80 mm in length. Heating is applied from one end of the sample length creating pseudo 1-D heating profile and a thermal gradient across the sample(s). At the opposite end of the confinement to the heating block, a machined groove provides a point of rupture that generates a cylindrical fragment. The displacement of the external face of themore » fragment is detected by Heterodyne Velocimetry. Proof of concept experiments are reported focusing on HMX and TATB formulations, and are described in relation to confinement, ullage and heating profile. The development of a violence metric, based upon fragment velocity records is discussed.« less

A Comparative Study of Very High Burning Rate Materials - HIVELITE compositions 300511 and 300435

DTIC Science & Technology

1982-08-01

explosives and more or as sensitive as RDX and HMX . Thermal Sensitivity Differential Thermal Analysis/Thermogravimetric Analysis (DTA/TGA) Simultaneous...impact than Comp B end RDX but is less sensitive than lead azide. HIVELITE 30051i on the other hand, is less sensitive than Comp B and RDX on the ERL...represents the alpha to beta phase transition of KNO 3 . This endotherm is followed by four exotherms with peaks at 538 K (265*C), 567 K (2940C), 598 K

Study of the laser-induced decomposition of energetic materials at static high-pressure by time-resolved absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hebert, Philippe; Saint-Amans, Charles

2013-06-01

A detailed description of the reaction rates and mechanisms occurring in shock-induced decomposition of condensed explosives is very important to improve the predictive capabilities of shock-to-detonation transition models. However, direct measurements of such experimental data are difficult to perform during detonation experiments. By coupling pulsed laser ignition of an explosive in a diamond anvil cell (DAC) with time-resolved streak camera recording of transmitted light, it is possible to make direct observations of deflagration phenomena at detonation pressure. We have developed an experimental set-up that allows combustion front propagation rates and time-resolved absorption spectroscopy measurements. The decomposition reactions are initiated using a nanosecond YAG laser and their kinetics is followed by time-resolved absorption spectroscopy. The results obtained for two explosives, nitromethane (NM) and HMX are presented in this paper. For NM, a change in reactivity is clearly seen around 25 GPa. Below this pressure, the reaction products are essentially carbon residues whereas at higher pressure, a transient absorption feature is first observed and is followed by the formation of a white amorphous product. For HMX, the evolution of the absorption as a function of time indicates a multi-step reaction mechanism which is found to depend on both the initial pressure and the laser fluence.

A laser-based FAIMS detector for detection of ultra-low concentrations of explosives

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.; Sychev, Alexey V.; Tugaenko, Anton V.; Bogdanov, Artem S.; Perederiy, Anatoly N.; Spitsyn, Eugene M.

2014-06-01

A non-contact method for analyzing of explosives traces from surfaces was developed. The method is based on the laser desorption of analyzed molecules from the surveyed surfaces followed by the laser ionization of air sample combined with the field asymmetric ion mobility spectrometry (FAIMS). The pulsed radiation of the fourth harmonic of a portable GSGG: Cr3+ :Nd3+ laser (λ = 266 nm) is used. The laser desorption FAIMS analyzer have been developed. The detection limit of the analyzer equals 40 pg for TNT. The results of detection of trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX) and cyclotetramethylenetetranitramine (HMX) are presented. It is shown that laser desorption of nitro-compounds from metals is accompanied by their surface decomposition. A method for detecting and analyzing of small concentrations of explosives in air based on the laser ionization and the FAIMS was developed. The method includes a highly efficient multipass optical scheme of the intracavity fourthharmonic generation of pulsed laser radiation (λ = 266 nm) and the field asymmetric ion mobility (FAIM) spectrometer disposed within a resonator. The ions formation and detection proceed inside a resonant cavity. The laser ion source based on the multi-passage of radiation at λ = 266 nm through the ionization region was elaborated. On the basis of the method the laser FAIMS analyzer has been created. The analyzer provides efficient detection of low concentrations of nitro-compounds in air and shows a detection limit of 10-14 - 10-15 g/cm3 both for RDX and TNT.

Importance of the gas phase role to the prediction of energetic material behavior: An experimental study

NASA Astrophysics Data System (ADS)

Ali, A. N.; Son, S. F.; Asay, B. W.; Sander, R. K.

2005-03-01

Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6mm±0.4mm exists below which ignition by CO2 laser is not possible at the tested irradiances of 29W /cm2 and 38W/cm2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials.

Toxicity and uptake of cyclic nitramine explosives in ryegrass Lolium perenne.

PubMed

Rocheleau, Sylvie; Lachance, Bernard; Kuperman, Roman G; Hawari, Jalal; Thiboutot, Sonia; Ampleman, Guy; Sunahara, Geoffrey I

2008-11-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) are cyclic nitramines used as explosives. Their ecotoxicities have been characterized incompletely and little is known about their accumulation potential in soil organisms. We assessed the toxicity and uptake of these explosives in perennial ryegrass Lolium perenne L. exposed in a Sassafras sandy loam (SSL) or in a sandy soil (DRDC, CL-20 only) containing contrasting clay contents (11% and 0.3%, respectively). A 21-d exposure to RDX, HMX or CL-20 in either soil had no adverse effects on ryegrass growth. RDX and HMX were translocated to ryegrass shoots, with bioconcentration factors (BCF) of up to 15 and 11, respectively. In contrast, CL-20 was taken up by the roots (BCF up to 19) with no translocation to the shoots. These studies showed that RDX, HMX, and CL-20 can accumulate in plants and may potentially pose a risk of biomagnification across the food chain.

SERDP ER-1376 Enhancement of In Situ Bioremediation of Energetic Compounds by Coupled Abiotic/Biotic Processes:Final Report for 2004 - 2006

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Comfort, Steve; Fredrickson, Herbert L.

2007-08-07

This project was initiated by SERDP to quantify processes and determine the effectiveness of abiotic/biotic mineralization of energetics (RDX, HMX, TNT) in aquifer sediments by combinations of biostimulation (carbon, trace nutrient additions) and chemical reduction of sediment to create a reducing environment. Initially it was hypothesized that a balance of chemical reduction of sediment and biostimulation would increase the RDX, HMX, and TNT mineralization rate significantly (by a combination of abiotic and biotic processes) so that this abiotic/biotic treatment may be a more efficient for remediation than biotic treatment alone in some cases. Because both abiotic and biotic processes aremore » involved in energetic mineralization in sediments, it was further hypothesized that consideration for both abiotic reduction and microbial growth was need to optimize the sediment system for the most rapid mineralization rate. Results show that there are separate optimal abiotic/biostimulation aquifer sediment treatments for RDX/HMX and for TNT. Optimal sediment treatment for RDX and HMX (which have chemical similarities and similar degradation pathways) is mainly chemical reduction of sediment, which increased the RDX/HMX mineralization rate 100 to150 times (relative to untreated sediment), with additional carbon or trace nutrient addition, which increased the RDX/HMX mineralization rate an additional 3 to 4 times. In contrast, the optimal aquifer sediment treatment for TNT involves mainly biostimulation (glucose addition), which stimulates a TNT/glucose cometabolic degradation pathway (6.8 times more rapid than untreated sediment), degrading TNT to amino-intermediates that irreversibly sorb (i.e., end product is not CO2). The TNT mass migration risk is minimized by these transformation reactions, as the triaminotoluene and 2,4- and 2,6-diaminonitrotoluene products that irreversibly sorb are no longer mobile in the subsurface environment. These transformation rates are

Ab initio study of energy transfer rates and impact sensitivities of crystalline explosives.

PubMed

Bernstein, Jonathan

2018-02-28

Impact sensitivities of various crystalline explosives were predicted by means of plane wave-density functional theory calculations. Crystal structures and complete vibrational spectra of TATB, PETN, FOX7, TEX, 14DNI, and β-HMX molecular crystals were calculated. A correlation between the phonon-vibron coupling (which is proportionally related to the energy transfer rate between the phonon manifold and the intramolecular vibrational modes) and impact sensitivities of secondary explosives was found. We propose a method, based on ab initio calculations, for the evaluation of impact sensitivities, which consequently can assist in screening candidates for chemical synthesis of high energetic materials.

Reactive Behavior of Explosive Billets in Deflagration Tube of Varied Confinements

NASA Astrophysics Data System (ADS)

Hu, Haibo; Guo, Yingwen; Li, Tao; Fu, Hua; Shang, Hailin; Wen, Shanggang; Qiu, Tian; LaboratoryShock Wave; Detonation Physics Research Team

2017-06-01

The deflagration process of small size cylinder billets of pressed HMX-based explosive JO-9159 and the deflagration tube wall deformation is recorded by combined pressure velocity-meter high-speed frame photographic and radiographic diagnostic system. The influence of confinement structure strength on deflagration evolution behavior is compared with analysis of convective flame propagation along the slot between explosive billet and confinement wall.The follow-up reaction inside the cracks on the initiation site end surface on the side surfaces and between the end surfaces of explosive billets is restored with the analysis results of post experimental explosive billet remains.

Ab initio study of energy transfer rates and impact sensitivities of crystalline explosives

NASA Astrophysics Data System (ADS)

Bernstein, Jonathan

2018-02-01

Impact sensitivities of various crystalline explosives were predicted by means of plane wave-density functional theory calculations. Crystal structures and complete vibrational spectra of TATB, PETN, FOX7, TEX, 14DNI, and β-HMX molecular crystals were calculated. A correlation between the phonon-vibron coupling (which is proportionally related to the energy transfer rate between the phonon manifold and the intramolecular vibrational modes) and impact sensitivities of secondary explosives was found. We propose a method, based on ab initio calculations, for the evaluation of impact sensitivities, which consequently can assist in screening candidates for chemical synthesis of high energetic materials.

Strengthening and Stiffening of Plastic Bonded Explosives Under Pressure and Metal-Like Mechanical Properties

DTIC Science & Technology

2005-11-01

Plastizer TG( 0C) PAX2A HMX CAB BDNPAIF -37a 85% 6% 9% PBS 9501 SUCROSE ESTANE BDNPAIF -41 (Bb 94% 3% 3% PBX 9501 HMX ESTANE BDNPAIF -41 (Bb 95% 2.5% 2.5...Material MPa PSI PAX2A 23* 3400 PBS 9501 63** 9200 PBX 9501 31** 4500 LX-14 63** 9200 Aluminum 100+ 14,500 Steel 241+ 35,000 *(69 MPa) and a strain rate

Numerical optimization of Ignition and Growth reactive flow modeling for PAX2A

NASA Astrophysics Data System (ADS)

Baker, E. L.; Schimel, B.; Grantham, W. J.

1996-05-01

Variable metric nonlinear optimization has been successfully applied to the parameterization of unreacted and reacted products thermodynamic equations of state and reactive flow modeling of the HMX based high explosive PAX2A. The NLQPEB nonlinear optimization program has been recently coupled to the LLNL developed two-dimensional high rate continuum modeling programs DYNA2D and CALE. The resulting program has the ability to optimize initial modeling parameters. This new optimization capability was used to optimally parameterize the Ignition and Growth reactive flow model to experimental manganin gauge records. The optimization varied the Ignition and Growth reaction rate model parameters in order to minimize the difference between the calculated pressure histories and the experimental pressure histories.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weese, R K; Burnham, A K; Maienschein, J L

Dimensional changes related to temperature cycling of the beta and delta polymorphs of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) are important for a variety of applications. The coefficient of thermal expansion (CTE) of the beta and delta phases are measured and reported in this work over a temperature range of -20 C to 215 C. In addition, dimensional changes associated with the phase transition were measured, both through the transition and back down. Initially, differential scanning calorimetry (DSC) was used to investigate back conversion of the delta phase to the beta phase polymorph. The most successful approach was first to measure the amount ofmore » the beta to delta conversion, then after a given cooling period a repeat analysis, to measure the heat consumed by a second pass through the beta to delta phase transition. In addition, TMA is used to measure the dimensional change of a 0.20-gram sample of HMX during its initial heating and then three days later during a 2nd heating. This HMX shows the beta to delta phase transition a second time, thereby confirming the back conversion from delta to beta phase HMX.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pahl, R. J.; Trott, W. M.; Snedigar, S.

A series of gas gun tests has been performed to examine contributions to energy release from micron-sized and nanometric aluminum powder added to sieved (212-300{mu}m) HMX. In the absence of added metal, 4-mm-thick, low-density (64-68% of theoretical maximum density) pressings of the sieved HMX respond to modest shock loading by developing distinctive reactive waves that exhibit both temporal and mesoscale spatial fluctuations. Parallel tests have been performed on samples containing 10% (by mass) aluminum in two particle sizes: 2-{mu}m and 123-nm mean particle diameter, respectively. The finely dispersed aluminum initially suppresses wave growth from HMX reactions; however, after a visiblemore » induction period, the added metal drives rapid increases in the transmitted wave particle velocity. Wave profile variations as a function of the aluminum particle diameter are discussed.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Castaneda, Jaime N.; Pahl, Robert J.; Snedigar, Shane

A series of gas gun tests has been performed to examine contributions to energy release from micron-sized and nanometric aluminum powder added to sieved (212-300{micro}m) HMX. In the absence of added metal, 4-mm-thick, low-density (64-68% of theoretical maximum density) pressings of the sieved HMX respond to modest shock loading by developing distinctive reactive waves that exhibit both temporal and mesoscale spatial fluctuations. Parallel tests have been performed on samples containing 10% (by mass) aluminum in two particle sizes: 2-{micro}m and 123-nm mean particle diameter, respectively. The finely dispersed aluminum initially suppresses wave growth from HMX reactions; however, after a visiblemore » induction period, the added metal drives rapid increases in the transmitted wave particle velocity. Wave profile variations as a function of the aluminum particle diameter are discussed.« less

Field Demonstration of Biologically Active Zone Enhancement (BAZE) for In Situ RDX Degradation in Groundwater

DTIC Science & Technology

2010-07-01

Used Defense Site GAC granular activated carbon HA health advisory HFCS high fructose corn syrup HMX octahydro-1,3,5,7-tetranitro 1,3,5,7... fructose corn syrup (HFCS) by injection is another innovative alternative and was demonstrated at Milan Army Ammunition Plant. Data needed for comparison...tetrazocine HPLC high pressure liquid chromatograph HVAC heating, ventilation, and air conditioning ID inside diameter IW injection well MNX

Final Programmatic Environmental Impact Statement for Defense Threat Reduction Agency (DTRA) Activities on White Sands Missile Range, New Mexico. Volume 1

DTIC Science & Technology

2007-03-01

similar in structure to HMX. HMX is used to implode fissionable material in nuclear devices to achieve critical mass and as a component of plastic...extent of DTRA activities on WSMR and reduce the Department of Defense capability to control and eliminate weapons of mass destruction. The Final...safeguarding the United States and its allies from weapons of mass destruction (WMD). DTRA maintains a number of test beds and target types at White Sands

Shock-Induced Shear Bands in an Energetic Molecular Crystal: Application of Shock-Front Absorbing Boundary Conditions to Molecular Dynamics Simulations

DTIC Science & Technology

2008-07-17

orthorhombic unit cell in space group Pbca that contains eight molecules - polymorph .12 An RDX molecule is depicted in Fig. 1a and a projection of the...tions of crystalline cyclotetramethylene tetranitramine HMX Refs. 26 and 27 and RDX . In the case of RDX the Smith-Bharadwaj potential25 not only...However, NEMD studies of shock waves in - HMX by Jaramillo et al.27 revealed a gradual transition from dislocation-mediated plasticity to deformation

Ultraviolet Resonance Raman Enhancements in the Detection of Explosives

DTIC Science & Technology

2009-06-01

nitramines (e.g., RDX , HMX ) and aromatic compounds (e.g., DNT, TATB, TNT). 1. Types of Explosives and Chemical Composition Due to stability...resonance Raman spectra of TNT, RDX , HMX , and PETN using 40 UV wavelengths from 210 to 280 nm using a 90 collection geometry [32]. This study includes...Raman can result in a dramatic increase in the Raman scattering efficiency of select band(s) associated with the electronic transition . Other than

Treatment of Explosives Residues from Range Activities

DTIC Science & Technology

2009-09-01

on the specific proportions of peat moss and crude soybean oil in the PMSO. Detections of TNT, HMX, and the RDX degradation products MNX, DNX, and...83 Table 5.8.1-1. Summary of explosive compound detections in all samples collected over the duration of the demonstration...reduced 12- to 50-fold, depending on the depth. Dissolved TNT and HMX were not detected with enough frequency to allow calculation of fluxes of these

Biodegradation of the cyclic nitramine explosives RDX, HMX, and CL-20.

PubMed

Crocker, Fiona H; Indest, Karl J; Fredrickson, Herbert L

2006-11-01

Cyclic nitramine explosives are synthesized globally mainly as military munitions, and their use has resulted in environmental contamination. Several biodegradation pathways have been proposed, and these are based mainly on end-product characterization because many of the metabolic intermediates are hypothetical and unstable in water. Biodegradation mechanisms for cyclic nitramines include (a) formation of a nitramine free radical and loss of nitro functional groups, (b) reduction of nitro functional groups, (c) direct enzymatic cleavage, (d) alpha-hydroxylation, or (e) hydride ion transfer. Pathway intermediates spontaneously decompose in water producing nitrite, nitrous oxide, formaldehyde, or formic acid as common end-products. In vitro enzyme and functional gene expression studies have implicated a limited number of enzymes/genes involved in cyclic nitramine catabolism. Advances in molecular biology methods such as high-throughput DNA sequencing, microarray analysis, and nucleic acid sample preparation are providing access to biochemical and genetic information on cultivable and uncultivable microorganisms. This information can provide the knowledge base for rational engineering of bioremediation strategies, biosensor development, environmental monitoring, and green biosynthesis of explosives. This paper reviews recent developments on the biodegradation of cyclic nitramines and the potential of genomics to identify novel functional genes of explosive metabolism.

Fast emission spectroscopy for monitoring condensed carbon in detonation products of oxygen-deficient high explosives

NASA Astrophysics Data System (ADS)

Poeuf, Sandra; Baudin, Gerard; Genetier, Marc; Lefrançois, Alexandre; Cinnayya, Ashwin; Laurent, Jacquet

2017-06-01

A new thermochemical code, SIAME, dedicated to the study of high explosives, is currently being developed. New experimental data relative to the expansion of detonation products are required to validate the code, and a particular focus is made on solid carbon products. Two different high explosive formulations are used: a melt-cast one (RDX/TNT 60/40 % wt.) and a pressed one (HMX/VitonR 96/4 % wt.). The experimental setup allows the expansion of the products at pressures below 1 GPa in an inert medium (vacuum, helium, nitrogen and PMMA). The results of fast emission dynamic spectroscopy measurements used to monitor the detonation carbon products are reported. Two spectral signatures are identified: the first is associated to ionized gases and the second to carbon thermal radiation. The experimental spectral lines are compared with simulated spectra. The trajectory of the shock wave front is continuously recorded with a high frequency interferometer. Comparisons with numerical simulations on the hydrodynamic code Ouranoshave been done. These two measurements, using the different inert media, enable to make one step forward in the validation of the detonation products equation of state implemented in the SIAME code.

Electron-doping by hydrogen in transition-metal dichalcogenides

NASA Astrophysics Data System (ADS)

Oh, Sehoon; Im, Seongil; Choi, Hyoung Joon

Using first-principles calculations, we investigate the atomic and electronic structures of 2H-phase transition-metal dichalcogenides (TMDC), 2H-MX2, with and without defects, where M is Mo or W and X is S, Se or Te. We find that doping of atomic hydrogen on 2H-MX2 induces electron doping in the conduction band. To understand the mechanism of this electron doping, we analyze the electronic structures with and without impurities. We also calculate the diffusion energy barrier to discuss the spatial stability of the doping. Based on these results, we suggest a possible way to fabricate elaborately-patterned circuits by modulating the carrier type of 2H-MoTe2. We also discuss possible applications of this doping in designing nano-devices. This work was supported by NRF of Korea (Grant No. 2011-0018306) and KISTI supercomputing center (Project No. KSC-2016-C3-0052).

Detonation Performance Testing of LX-19

NASA Astrophysics Data System (ADS)

Vincent, Samuel; Aslam, Tariq; Jackson, Scott

2015-06-01

CL-20 was developed at the Naval Surface Weapons Center at China Lake, CA in the mid 80's. Being less sensitive than PETN, but considerably more powerful than HMX, it is the highest energy and density compound known among organic chemicals. LX-19 was developed at LLNL in the early 90's. It is a high-energy plastic bonded explosive, composed of 95.8 wt% CL-20 and 4.2 wt% Estane binder, and is similar to LX-14 (composed of HMX and Estane), but with greater sensitivity characteristics with use of the more energetic CL-20 explosive. We report detonation performance results for unconfined cylindrical rate sticks of LX-19. The experimental diameter effects are shown, along with detonation front shapes, and reaction zone profiles for different test diameters. This data is critical for calibration to Detonation Shock Dynamics (DSD). LA-UR-15-20672.

Solid-solid phase transformation via internal stress-induced virtual melting, significantly below the melting temperature. Application to HMX energetic crystal.

PubMed

Levitas, Valery I; Henson, Bryan F; Smilowitz, Laura B; Asay, Blaine W

2006-05-25

We theoretically predict a new phenomenon, namely, that a solid-solid phase transformation (PT) with a large transformation strain can occur via internal stress-induced virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. We show that the energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking which does not affect the thermodynamics or kinetics of the solid-solid transformation. Thus, virtual melting represents a new mechanism of solid-solid PT, stress relaxation, and loss of coherence at a moving solid-solid interface. It also removes the athermal interface friction and deletes the thermomechanical memory of preceding cycles of the direct-reverse transformation. It is also found that nonhydrostatic compressive internal stresses promote melting in contrast to hydrostatic pressure. Sixteen theoretical predictions are in qualitative and quantitative agreement with experiments conducted on the PTs in the energetic crystal HMX. In particular, (a) the energy of internal stresses is sufficient to reduce the melting temperature from 551 to 430 K for the delta phase during the beta --> delta PT and from 520 to 400 K for the beta phase during the delta --> beta PT; (b) predicted activation energies for direct and reverse PTs coincide with corresponding melting energies of the beta and delta phases and with the experimental values; (c) the temperature dependence of the rate constant is determined by the heat of fusion, for both direct and reverse PTs; results b and c are obtained both for overall kinetics and for interface propagation; (d) considerable nanocracking, homogeneously distributed in the transformed material, accompanies the PT, as predicted by theory; (e) the nanocracking does not

Investigation of explosives mechanic impact sensitivity on the samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loboyko, B.G.; Alekseev, A.V.; Litvinov, B.V.

1996-05-01

Several results of investigation into HMX-based explosive compound sensitivity to mechanic impact on the samples are presented. Mechanic loading of samples was effected by dynamic insertion of a pin. Alternation of physical state of explosive compound on account of preliminary thermal treatment or destruction of samples increased their sensitivity considerably. {copyright} {ital 1996 American Institute of Physics.}

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

NASA Astrophysics Data System (ADS)

Bishop, M. M.; Chellappa, R. S.; Liu, Z.; Preston, D. N.; Sandstrom, M. M.; Dattelbaum, D. M.; Vohra, Y. K.; Velisavljevic, N.

2014-05-01

1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and α → β (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → (~210 °C), with the δ phase being stable up to ~251 °C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 °C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa.

ALE3D Simulation and Measurement of Violence in a Fast Cookoff Experiment with LX-10

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClelland, M A; Maienschein, J L; Howard, W M

We performed a computational and experimental analysis of fast cookoff of LX-10 (94.7% HMX, 5.3% Viton A) confined in a 2 kbar steel tube with reinforced end caps. A Scaled-Thermal-Explosion-eXperiment (STEX) was completed in which three radiant heaters were used to heat the vessel until ignition, resulting in a moderately violent explosion after 20.4 minutes. Thermocouple measurements showed tube temperatures as high as 340 C at ignition and LX-10 surface temperatures as high as 279 C, which is near the melting point of HMX. Three micro-power radar systems were used to measure mean fragment velocities of 840 m/s. Photonics Dopplermore » Velocimeters (PDVs) showed a rapid acceleration of fragments over 80 {micro}s. A one-dimensional ALE3D cookoff model at the vessel midplane was used to simulate the heating, thermal expansion, LX-10 decomposition composition, and closing of the gap between the HE (High Explosive) and vessel wall. Although the ALE3D simulation terminated before ignition, the model provided a good representation of heat transfer through the case and across the dynamic gap to the explosive.« less

A novel method for the measurement of the von Neumann spike in detonating high explosives

NASA Astrophysics Data System (ADS)

Sollier, A.; Bouyer, V.; Hébert, P.; Doucet, M.

2016-06-01

We present detonation wave profiles measured in T2 (97 wt. % TATB) and TX1 (52 wt. % TATB and 45 wt. % HMX) high explosives. The experiments consisted in initiating a detonation wave in a 15 mm diameter cylinder of explosive using an explosive wire detonator and an explosive booster. Free surface velocity wave profiles were measured at the explosive/air interface using a Photon Doppler Velocimetry system. We demonstrate that a comparison of these free surface wave profiles with those measured at explosive/window interfaces in similar conditions allows to bracket the von Neumann spike in a narrow range. For T2, our measurements show that the spike pressure lies between 35.9 and 40.1 GPa, whereas for TX1, it lies between 42.3 and 47.0 GPa. The numerical simulations performed in support to these measurements show that they can be used to calibrate reactive burn models and also to check the accuracy of the detonation products equation of state at low pressure.

Three-dimensional Mesoscale Simulations of Detonation Initiation in Energetic Materials with Density-based Kinetics

NASA Astrophysics Data System (ADS)

Jackson, Thomas; Jost, A. M.; Zhang, Ju; Sridharan, P.; Amadio, G.

2017-06-01

In this work we present three-dimensional mesoscale simulations of detonation initiation in energetic materials. We solve the reactive Euler equations, with the energy equation augmented by a power deposition term. The reaction rate at the mesoscale is modelled using a density-based kinetics scheme, adapted from standard Ignition and Growth models. The deposition term is based on previous results of simulations of pore collapse at the microscale, modelled at the mesoscale as hot-spots. We carry out three-dimensional mesoscale simulations of random packs of HMX crystals in a binder, and show that the transition between no-detonation and detonation depends on the number density of the hot-spots, the initial radius of the hot-spot, the post-shock pressure of an imposed shock, and the amplitude of the power deposition term. The trends of transition at lower pressure of the imposed shock for larger number density of pore observed in experiments is reproduced. Initial attempts to improve the agreement between the simulation and experiments through calibration of various parameters will also be made.

Survival and reproduction of enchytraeid worms, Oligochaeta, in different soil types amended with energetic cyclic nitramines.

PubMed

Dodard, Sabine G; Sunahara, Geoffrey I; Kuperman, Roman G; Sarrazin, Manon; Gong, Ping; Ampleman, Guy; Thiboutot, Sonia; Hawari, Jalal

2005-10-01

Hexanitrohexaazaisowurtzitane (CL-20), a new polycyclic polynitramine, has the same functional nitramine groups (N-NO2) as the widely used energetic chemicals hexahydro-1,3,5-trinitro-1,3,5-triazacyclohexane (royal demolition explosive [RDX]) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (high-melting explosive [HMX]). Potential impacts of CL-20 as an emerging contaminant must be assessed before its use. The effects of CL-20, RDX, or HMX on adult survival and juvenile production by potworms Enchytraeus albidus and Enchytraeus crypticus were studied in three soil types, including Sassafras sandy loam (1.2% organic matter [OM], 11% clay, pH 5.5), an agricultural soil (42% OM, 1% clay, pH 8.2), and a composite agricultural-forest soil (23% OM, 2% clay, pH 7.9) by using ISO method 16387 (International Standard Organization, Geneva, Switzerland). Results showed that CL-20 was toxic to E. crypticus with median lethal concentration values for adult survival ranging from 0.1 to 0.7 mg/kg dry mass (DM) when using the three tested soils. In addition, CL-20 adversely affected juvenile production by both species in all soils tested, with median effective concentration (EC50) values ranging from 0.08 to 0.62 mg/kg DM. Enchytraeus crypticus and E. albidus were similarly sensitive to CL-20 exposure in the composite agricultural-forest soil, which supported reproduction by both species and enabled comparisons. Correlation analysis showed weak or no relationship overall among the soil properties and reproduction toxicity endpoints. Neither RDX nor HMX affected (p > 0.05) adult survival of either species below 658 and 918 mg/kg DM, respectively, indicating that CL-20 is more toxic to enchytraeids than RDX or HMX. Examination of data shows that CL-20 should be considered as a potential reproductive toxicant to soil invertebrates, and that safeguards should be considered to minimize the potential for release of CL-20 into the environment.

Density Distributions of Cyclotrimethylenetrinitramines (RDX)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffman, D M

2002-03-19

As part of the US Army Foreign Comparative Testing (FCT) program the density distributions of six samples of class 1 RDX were measured using the density gradient technique. This technique was used in an attempt to distinguish between RDX crystallized by a French manufacturer (designated insensitive or IRDX) from RDX manufactured at Holston Army Ammunition Plant (HAAP), the current source of RDX for Department of Defense (DoD). Two samples from different lots of French IRDX had an average density of 1.7958 {+-} 0.0008 g/cc. The theoretical density of a perfect RDX crystal is 1.806 g/cc. This yields 99.43% of themore » theoretical maximum density (TMD). For two HAAP RDX lots the average density was 1.786 {+-} 0.002 g/cc, only 98.89% TMD. Several other techniques were used for preliminary characterization of one lot of French IRDX and two lot of HAAP RDX. Light scattering, SEM and polarized optical microscopy (POM) showed that SNPE and Holston RDX had the appropriate particle size distribution for Class 1 RDX. High performance liquid chromatography showed quantities of HMX in HAAP RDX. French IRDX also showed a 1.1 C higher melting point compared to HAAP RDX in the differential scanning calorimetry (DSC) consistent with no melting point depression due to the HMX contaminant. A second part of the program involved characterization of Holston RDX recrystallized using the French process. After reprocessing the average density of the Holston RDX was increased to 1.7907 g/cc. Apparently HMX in RDX can act as a nucleating agent in the French RDX recrystallization process. The French IRDX contained no HMX, which is assumed to account for its higher density and narrower density distribution. Reprocessing of RDX from Holston improved the average density compared to the original Holston RDX, but the resulting HIRDX was not as dense as the original French IRDX. Recrystallized Holston IRDX crystals were much larger (3-500 {micro}m or more) then either the original class 1 HAAP

Sampling for Explosives Residues at Fort Greely, Alaska. Reconnaissance Visit July 2000

DTIC Science & Technology

2001-11-01

on lands withdrawn from the public domain under the Military Lands With- drawal Act (PL 106 -65). The Army has pledged to implement a program to...from the public domain under the Military Lands Withdrawal Act (Public Law 106 -65); the withdrawal of land was recently renewed. As part of the...option fuse Pellet booster comp A5 (RDX (98.5%)and stearic acid (1.5%) 8 g Lead charge PBXN -5 (HMX 95% and Binder 5%) 152 mg Detonator assembly HMX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Preston, Daniel N; Peterson, Paul D; Kien - Yin, Lee

Structural damage in energetic materials plays a significant role in the probability of nonshock initiation events. Damage may occur in the form of voids or cracks either within crystals or in binder-rich regions between crystals. These cracks affect whether hotspots generated by impact will quench or propagate under non-shock insult. For this study, we have separately engineered intracrystalline and inter-crystalline cracks in to the HMX-based PBX 9501. Intra-crystalline cracks were created by subjecting HMX to forward and reverse solid-to-solid phase transformations prior to formulation. Inter-crystalline cracks were induced by compressing formulated samples of PBX 9501 at an average strain ratemore » of 0.00285 S{sup -1}. Both sets of pre-damaged explosives were then impact tested using the LANL Type 12 Drop Weight-Impact Machine and their sensitivities compared to nondamaged PBX 9501. Results of these tests clearly show significant differences in sensitivity between damaged and non-damaged PBX 9501.« less

Nanoscale Heat Conduction in Crystalline Solids

NASA Astrophysics Data System (ADS)

Christenson, Joel; Phillips, Ronald

Heat conduction in crystalline solids occurs through the motion of molecular-scale vibrations, or phonons. In continuum scale problems, there are sufficient phonon-phonon interactions for local equilibrium to be established, and heat conduction is accurately described by Fourier's law. However, at length scales comparable to the phonon mean free path, Fourier's law becomes inaccurate, and more fundamental descriptions of heat transfer are required. We are investigating the viability of the phonon Boltzmann Transport Equation (BTE) to describe heat conduction in nanoscale simulations of the high-explosive material β-HMX. By using a combination of numerical and analytic solutions of the BTE, we demonstrate the existence of physical behavior that is not qualitatively captured by the classical Fourier's law in the nanoscale regime. The results are interpreted in terms of continuum-scale simulations of shock-induced collapse of air-filled pores in β-HMX, which is believed to be a precursory step towards complete detonation of the material.

Influence of crystal characteristics on the shock sensitivities of cyclotrimethylene trinitramine, cyclotetramethylene tetranitramine, and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetra-cyclo[5,5,0,03,1105,9]dodecane immersed in liquid

NASA Astrophysics Data System (ADS)

Li, Hongzhen; Xu, Rong; Kang, Bing; Li, Jinshan; Zhou, Xiaoqing; Zhang, Chaoyang; Nie, Fude

2013-05-01

The shock sensitivities of differently qualified cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine(HMX), and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetra-cyclo[5,5,0,03,1105,9]dodecane (CL-20) immersed in liquid were determined by the large-scale gap tests, for systemic discussion on the influences of crystal characteristics on them. As a result, it shows that (1) the immersion of crystals in liquid leads to an obvious sensitivity decrease; (2) for all three explosives, their shock sensitivities are lowered with increasing their crystal apparent densities or decreasing their particle sizes, and almost not affected by particle morphologies; (3) the crystal twins are readily formed for HMX and the most distinct factor influencing its shock sensitivities; (4) it is found that the crystal apparent density affects most obviously the shock sensitivities for RDX and CL-20; and (5) CL-20, HMX, and RDX are less and less sensitive to shock, suggesting chemical components are also a determining factor.

Numerical simulation of double front detonations in a non-ideal explosive with varying aluminum concentration

NASA Astrophysics Data System (ADS)

Kim, Wuhyun; Gwak, Min-Cheol; Yoh, Jack; Seoul National University Team

2017-06-01

The performance characteristics of aluminized HMX are considered by varying the aluminum (Al) concentration in a hybrid non-ideal detonation model. Two cardinal observations are reported: a decrease in detonation velocity with an increase in Al concentration and a double front detonation (DFD) feature when aerobic Al reaction occurs behind the front. While experimental studies have been reported on the effect of Al concentration on both gas-phase and solid-phase detonations, the numerical investigations were limited to only gas-phase detonation for the varying Al concentration. In the current study, a two-phase model is utilized for understanding the volumetric effects of Al concentration in the condensed phase detonations. A series of unconfined and confined rate sticks are considered for characterizing the performance of aluminized HMX with a maximum Al concentration of 50%. The simulated results are compared with the experimental data for 5%-25% concentrations, and the formation of DFD structure under varying Al concentration (0%-50%) in HMX is investigated.

Density-based kinetics for mesoscale simulations of detonation initiation in energetic materials

NASA Astrophysics Data System (ADS)

Jackson, Thomas Luther; Zhang, Ju

2017-07-01

In this work we present one- and two-dimensional mesoscale simulations of detonation initiation in energetic materials. We solve the reactive Euler equations, with the energy equation augmented by a power deposition term. The reaction rate at the mesoscale is modelled using a density-based kinetics scheme, adapted from standard 'Ignition and Growth' models. The deposition term is based on previous results of simulations of void collapse at the microscale, modelled at the mesoscale as hot spots. For an isolated hot spot in a homogeneous medium, it is found that a critical size of the hot spots exists. If the hot spots exceed the critical size, initiation of detonation can be achieved. For sub-critical hot-spot sizes, we show that it takes a collection of hot spots to achieve detonation. We also carry out two-dimensional mesoscale simulations of random packs of HMX crystals in a binder, and show that the transition between no detonation and detonation depends on the number density of the hot spots, the initial radius of the hot spot, the post-shock pressure of an imposed shock, and the amplitude of the power deposition term.

Numerical and experimental study of thermal explosions in LX-10 and PBX 9501: Influence of thermal damage on deflagration processes

NASA Astrophysics Data System (ADS)

Tringe, J. W.; Kercher, J. R.; Springer, H. K.; Glascoe, E. A.; Levie, H. W.; Hsu, P.; Willey, T. M.; Molitoris, J. D.

2013-07-01

We employ in-situ flash x-ray imaging, together with a detailed multiphase convective burn model, to demonstrate how explosives' binder characteristics influence the burning processes in thermal explosions. Our study focuses on the HMX-based explosives LX-10 and PBX 9501. While the HMX (cyclotetramethylene-tetranitramine) crystallite size distributions for these two explosives are nearly identical before heating, our experiments and simulations indicate that after heating, variations result due to differences in binder composition. Post-ignition flash x-ray images reveal that the average density decreases at late times more rapidly in PBX 9501 than LX-10, suggesting a faster conductive burning rate in PBX-9501. Heated permeability measurements in LX-10 and PBX 9501 demonstrate that the binder system characteristics influence the evolution of connected porosity. Once ignited, connected porosity provides pathways for product gas heating ahead of the reaction front and additional surface area for burning, facilitating the transition from conductive to convective burning modes. A multiphase convective burn model implemented in the ALE3D code is used to better understand the influence on burn rates of material properties such as porosity and effective thermally damaged particle size. In this context, particles are defined as gas-impermeable binder-coated crystallites and agglomerations with a set of effective radii reff. Model results demonstrate quantitative agreement with containment wall velocity for confined PBX 9501 and LX-10, and qualitative agreement with density as a function of position in the burning explosive. The model predicts a decrease in post-ignition containment wall velocity with larger radii in reff. These experimental data and model results together provide insight into the initiation and propagation of the reaction wave that defines the convective burn front in HMX-based explosives, a necessary step toward predicting violence under a broad range of

Analysis of microstructure-dependent shock dissipation and hot-spot formation in granular metalized explosive

NASA Astrophysics Data System (ADS)

Chakravarthy, Sunada; Gonthier, Keith A.

2016-07-01

Variations in the microstructure of granular explosives (i.e., particle packing density, size, shape, and composition) can affect their shock sensitivity by altering thermomechanical fields at the particle-scale during pore collapse within shocks. If the deformation rate is fast, hot-spots can form, ignite, and interact, resulting in burn at the macro-scale. In this study, a two-dimensional finite and discrete element technique is used to simulate and examine shock-induced dissipation and hot-spot formation within low density explosives (68%-84% theoretical maximum density (TMD)) consisting of large ensembles of HMX (C4H8N8O8) and aluminum (Al) particles (size ˜ 60 -360 μm). Emphasis is placed on identifying how the inclusion of Al influences effective shock dissipation and hot-spot fields relative to equivalent ensembles of neat/pure HMX for shocks that are sufficiently strong to eliminate porosity. Spatially distributed hot-spot fields are characterized by their number density and area fraction enabling their dynamics to be described in terms of nucleation, growth, and agglomeration-dominated phases with increasing shock strength. For fixed shock particle speed, predictions indicate that decreasing packing density enhances shock dissipation and hot-spot formation, and that the inclusion of Al increases dissipation relative to neat HMX by pressure enhanced compaction resulting in fewer but larger HMX hot-spots. Ensembles having bimodal particle sizes are shown to significantly affect hot-spot dynamics by altering the spatial distribution of hot-spots behind shocks.

Excited electronic state decomposition mechanisms and dynamics of nitramine energetic materials and model systems

NASA Astrophysics Data System (ADS)

Greenfield, Margo

Energetic materials play an important role in aeronautics, the weapon industry, and the propellant industry due to their broad applications as explosives and fuels. RDX (1,3,5-trinitrohexahydro-s-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) are compounds which contain high energy density. Although RDX and HMX have been studied extensively over the past several decades a complete understanding of their decomposition mechanisms and dynamics is unknown. Time of flight mass spectroscopy (TOFMS) UV photodissociation (ns) experiments of gas phase RDX, HMX, and CL-20 generate the NO molecule as the initial decomposition product. Four different vibronic transitions of the initial decomposition product, the NO molecule, are observed: A2Sigma(upsilon'=0)←X 2pi(upsilon"=0,1,2,3). Simulations of the rovibronic intensities for the A←X transitions demonstrate that NO dissociated from RDX, HMX, and CL-20 is rotationally cold (˜20 K) and vibrationally hot (˜1800 K). Conversely, experiments on the five model systems (nitromethane, dimethylnitramine (DMNA), nitropyrrolidine, nitropiperidine and dinitropiperazine) produce rotationally hot and vibrationally cold spectra. Laser induced fluorescence (LIF) experiments are performed to rule out the possible decomposition product OH, generated along with NO, perhaps from the suggested HONO elimination mechanism. The OH radical is not observed in the fluorescence experiments, indicating the HONO decomposition intermediate is not an important pathway for the excited electronic state decomposition of cyclic nitramines. The NO molecule is also employed to measure the dynamics of the excited state decomposition. A 226 nm, 180 fs light pulse is utilized to photodissociate the gas phase systems. Stable ion states of DMNA and nitropyrrolidine are observed while the energetic materials and remaining model systems present the NO molecule as the only

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aviles-Ramos, Cuauhtemoc

A thermal decomposition model for PBX 9501 (95% HMX, 2.5% Estane® binder, 2.5% BDNPA/F nitro-plasticizer) was implemented by Dickson, et. al. The objective in this study is to estimate parameters associated with this kinetics model so it can be applied to carry out thermal ignition predictions for LX-07 (90% HMX, 10% Viton binder). LX-07 thermal ignition experiments have been carried out using the “Sandia Instrumented Thermal Ignition Apparatus”, SITI. The SITI design consists of solid cylinders (1” diameter × 1” height) of high explosive (HE) confined by a cylindrical aluminum case. An electric heater is wrapped around the outer surfacemore » of the case. This heater produces a temperature heating ramp on the outer surface of the case. Internal thermocouples measure the HE temperature rise from the center to locations close to the HE-aluminum interface. The energetic material is heated until thermal ignition occurs. A two–dimensional axisymmetric heat conduction finite element model is used to simulate these experiments. The HE thermal decomposition kinetics is coupled to a heat conduction model trough the definition of an energy source term. The parameters used to define the HE thermal decomposition model are optimized to obtain a good agreement with the experimental time to thermal ignition and temperatures. Also, heat capacity and thermal conductivity of the LX-07 mixture were estimated using temperatures measured at the center of the HE before the solid to solid HMX phase transition occurred.« less

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bishop, M. M.; Chellappa, R. S.; Liu, Z.

Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C),more » with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..« less

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

DOE PAGES

Bishop, M. M.; Chellappa, R. S.; Liu, Z.; ...

2014-05-07

Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C),more » with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..« less

Detonation wave profiles measured in plastic bonded explosives using 1550 nm photon doppler velocimetry (PDV)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gustavsen, Richard L; Bartram, Brian D; Sanchez, Nathaniel

2009-01-01

We present detonation wave profiles measured in two TATB based explosives and two HMX based explosives. Profiles were measured at the interface of the explosive and a Lithium-Fluoride (LiF) window using 1550 nm Photon Doppler Velocimetry (PDV). Planar detonations were produced by impacting the explosive with a projectile launched in a gas-gun. The impact state was varied to produce varied distance to detonation, and therefore varied support of the Taylor wave following the Chapman-Jouget (CJ) or sonic state. Profiles from experiments with different support should be the same between the Von-Neumann (VN) spike and CJ state and different thereafter. Comparisonmore » of profiles with differing support, therefore, allows us to estimate reaction zone lengths. For the TATB based explosive, a reaction zone length of {approx} 3.9 mm, 500 ns was measured in EDC-35, and a reaction zone length of {approx} 6.3 mm, 800 ns was measured in PBX 9502 pre-cooled to -55 C. The respective VN spike state was 2.25 {+-} 0.05 km/s in EDC-35 and 2.4 {+-} 0.1 km/s in the cooled PBX 9502. We do not believe we have resolved either the VN spike state (> 2.6 km/s) nor the reaction zone length (<< 50 ns) in the HMX based explosives.« less

NQR Line Broadening Due to Crystal Lattice Imperfections and Its Relationship to Shock Sensitivity

NASA Astrophysics Data System (ADS)

Caulder, S. M.; Buess, M. L.; Garroway, A. N.; Miller, P. J.

2004-07-01

The hydrodynamic hot spot model is used to explain the difference between shock sensitive and shock insensitive explosives. Among the major factors that influence the shock sensitivity of energetic compounds are the quality and particle size of the energetic crystals used to formulate the cast plastic bonded explosive. As do all energetic compounds, RDX and HMX exhibit internal crystal defects the magnitude and type of which depend on the manufacturing process used to synthesize and re-crystallize the energetic compound. Nuclear Quadrupole Resonance (NQR) spectroscopy was used to determine the crystal quality of RDX, HMX and CL-20 obtained from various manufacturers. The NQR experimental results are discussed. Cast plastic bonded explosives were made using the RDX and HMX obtained from the various manufacturers and subsequently subjected to the NOL large-scale gap test (LSGT). The results of the LSGT are discussed and correlated with the NQR results. A relationship between the crystal defect density and shock initiation pressure of the plastic bonded explosive is developed and discussed.

BMP regulates regional gene expression in the dorsal otocyst through canonical and non-canonical intracellular pathways

PubMed Central

2016-01-01

The inner ear consists of two otocyst-derived, structurally and functionally distinct components: the dorsal vestibular and ventral auditory compartments. BMP signaling is required to form the vestibular compartment, but how it complements other required signaling molecules and acts intracellularly is unknown. Using spatially and temporally controlled delivery of signaling pathway regulators to developing chick otocysts, we show that BMP signaling regulates the expression of Dlx5 and Hmx3, both of which encode transcription factors essential for vestibular formation. However, although BMP regulates Dlx5 through the canonical SMAD pathway, surprisingly, it regulates Hmx3 through a non-canonical pathway involving both an increase in cAMP-dependent protein kinase A activity and the GLI3R to GLI3A ratio. Thus, both canonical and non-canonical BMP signaling establish the precise spatiotemporal expression of Dlx5 and Hmx3 during dorsal vestibular development. The identification of the non-canonical pathway suggests an intersection point between BMP and SHH signaling, which is required for ventral auditory development. PMID:27151948

Ignition behavior of an aluminum-bonded explosive (ABX)

NASA Astrophysics Data System (ADS)

Hardin, D. Barrett; Zhou, Min; Horie, Yasuyuki

2017-01-01

We report the results of a study on the ignition behavior of a novel concept and design of a heterogeneous energetic material system called ABX, or aluminum-bonded explosives. The idea is to replace the polymeric binder in polymer-bonded explosives (PBX) with aluminum. The motivation of this study is that a new design may have several desirable attributes, including, among others, electrical conductivity, higher mechanical strength, enhanced integrity, higher energy content, and enhanced thermal stability at elevated temperatures. The analysis carried out concerns the replacement of the Estane binder in a HMX/Estane PBX by aluminum. The HMX volume fraction in the PBX and HMX is approximately 81%. 2D mesoscale simulations are carried out, accounting for elasticity, viscoelasticity, elasto-viscoplasticity, fracture, internal friction, and thermal conduction. Results show that, relative to the PBX, the aluminum bonded explosives (ABX) show significantly less heating and lower ignition sensitivity under the same loading conditions. The findings appear to confirm the expected promise of ABX as a next-generation heterogeneous energetic material system with more desirable attributes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Austin, Ryan A.; Barton, Nathan R.; Reaugh, John E.

A numerical model is developed to study the shock wave ignition of HMX crystal. The model accounts for the coupling between crystal thermal/mechanical responses and chemical reactions that are driven by the temperature field. This allows for the direct numerical simulation of decomposition reactions in the hot spots formed by shock/impact loading. The model is used to simulate intragranular pore collapse under shock wave loading. In a reference case: (i) shear-enabled micro-jetting is responsible for a modest extent of reaction in the pore collapse region, and (ii) shear banding is found to be an important mode of localization. The shearmore » bands, which are filled with molten HMX, grow out of the pore collapse region and serve as potential ignition sites. The model predictions of shear banding and reactivity are found to be quite sensitive to the respective flow strengths of the solid and liquid phases. In this regard, it is shown that reasonable assumptions of liquid-HMX viscosity can lead to chemical reactions within the shear bands on a nanosecond time scale.« less

Distinct transcriptomes define rostral and caudal serotonin neurons

PubMed Central

Wylie, Christi J.; Hendricks, Timothy J.; Zhang, Bing; Wang, Lily; Lu, Pengcheng; Leahy, Patrick; Fox, Stephanie; Maeno, Hiroshi; Deneris, Evan S.

2012-01-01

The molecular architecture of developing serotonin (5HT) neurons is poorly understood yet its determination is likely to be essential for elucidating functional heterogeneity of these cells and the contribution of serotonergic dysfunction to disease pathogenesis. Here, we describe the purification of postmitotic embryonic 5HT neurons by flow cytometry for whole genome microarray expression profiling of this unitary monoaminergic neuron type. Our studies identified significantly enriched expression of hundreds of unique genes in 5HT neurons thus providing an abundance of new serotonergic markers. Furthermore, we identified several hundred transcripts encoding homeodomain, axon guidance, cell adhesion, intracellular signaling, ion transport, and imprinted genes associated with various neurodevelopmental disorders that were differentially enriched in developing rostral and caudal 5HT neurons. These findings suggested a homeodomain code that distinguishes rostral and caudal 5HT neurons. Indeed, verification studies demonstrated that Hmx homeodomain and Hox gene expression defined an Hmx+ rostral subtype and Hox+ caudal subtype. Expression of engrailed genes in a subset of 5HT neurons in the rostral domain further distinguished two subtypes defined as Hmx+En+ and Hmx+En-. The differential enrichment of gene sets for different canonical pathways and gene ontology categories provided additional evidence for heterogeneity between rostral and caudal 5HT neurons. These findings demonstrate a deep transcriptome and biological pathway duality for neurons that give rise to the ascending and descending serotonergic subsystems. Our databases provide a rich, clinically relevant, resource for definition of 5HT neuron subtypes and elucidation of the genetic networks required for serotonergic function. PMID:20071532

Exploring hydride-π interactions and their tuning by σ-hole bonds: an ab initio study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Asadollahi, Soheila; Mousavian, Parisasadat

2018-01-01

In the present work, ab initio calculations are performed to investigate the geometry, interaction energy and bonding properties of binary complexes formed between metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CH3) and a series of π-acidic heteroaromatic rings. In all the resulting complexes, the heteroaromatic ring acts as a Lewis acid (electron acceptor), while the H atom of the HMX molecule acts as a Lewis base (electron donor). The nature of this interaction, called 'hydride-π' interaction, is explored in terms of molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. The results show that the interaction energies of these hydride-π interactions are between -1.24 and -2.72 kcal/mol. Furthermore, mutual influence between the hydride-π and halogen- or pnicogen-bonding interactions is studied in complexes in which these interactions coexist. For a given π-acidic ring, the formation of the pnicogen-bonding induces a larger enhancing effect on the strength of hydride-π bond than the halogen-bonding.

Health assessment for Louisiana Army Ammunition Plant, Shreveport, Webster County, Louisiana, Region 6. CERCLIS No. LA0213820533. Preliminary report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1989-04-10

The Louisiana Army Ammunition Plant (LAAP) is listed on the National Priorities List. The site is a 15,000-acre Federal facility located in Shreveport (Webster Parish), Louisiana. On-site ground water beneath 16 unlined surface impoundments near the southern boundary is contaminated. Access to LAAP is restricted and under 24-hour security. Contaminants include 2,4,6-trinitrotoluene (TNT), cyclonite (RDX), trinitrobenzene (TNB), and homocyclonite (HMX). Preliminary on-site sampling results have identified TNT (493,133 ppm in sediment/subsoil, 483,556 ppm in sludge, 1,033 ppm in surface soil, 7 ppm in surface water, and 18 ppm in ground water), RDX (60,224 ppm in sediment/subsoil, 602 ppm in surfacemore » soil, 60,224 ppm in sludge, and 14 ppm in ground water), TNB (2 ppm in surface water and 8 ppm in ground water), and HMX (4 ppm in ground water). Based on available information, the site is considered to be of potential public health concern because of the risk to human health caused by the possibility of human exposure to hazardous substances.« less

On Predicting the Crystal Structure of Energetic Materials From Quantum Mechanics

DTIC Science & Technology

2008-12-01

DE ABSTRACT A quantum-mechanically-based potential energy function that describes interactions of dimers of the explosive ...method is capable of producing force fields for interactions of the molecular crystalline explosive RDX, and appears to be suitable to enable reliable...Ridge, TN. Byrd, E.F.C., Scuseria, G.E., Chabalowski, C.F., 2004: “An ab initio study of solid nitromethane , HMX, RDX and CL20: Successes and

Laser Desorption of Explosives Traces with Low Vapors Pressure

NASA Astrophysics Data System (ADS)

Akmalov, A. E.; Chistyakov, A. A.; Kotkovskii, G. E.

In this work comparison of the desorption effectiveness of picosecond and nanosecond laser sources (λ = 266, 532 nm) were carried out to investigate the possibility of creating a non-contact sampling device for detectors of explosives on the principles of ion mobility spectrometry (IMS) and field asymmetric ion mobility spectrometry (FAIMS). The results of mass spectrometric studies of TNT (2,4,6-Trinitrotoluene), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), RDX (1,3,5-Trinitro-1,3,5-triazacyclohexane) laser desorption from a quartz substrate are presented. It is shown that the most effective laser source is a Nd:YAG3+ laser (λ = 266 nm; E = 1 mJ; τ = 5-10 ns; q = 108 W/cm2). The typical desorbed mass is 2 ng for RDX, 4-6 ng for TNT and 0.02 ng HMX per single laser pulse. The results obtained make it possible to create a non-contact portable laser sampling device operating in frequency mode with high efficiency.

RDX/HMX Plant Design

DTIC Science & Technology

1981-05-01

coating process in Explosives Manufacturing Line 2. The end products of the initial design effort are process flow diagrams, piping and...instrumentation diagrams, motor control schedules, interlock logic diagrams, piping installation drawings, typical instrument Installation details, equipment...structures, equipment, utilities, and process piping extending 1.5 m (5 ft) beyond the building or area were not included in the scope of work. Nitrolysis

High strength forgeable tantalum base alloy

NASA Technical Reports Server (NTRS)

Buckman, R. W., Jr.

1975-01-01

Increasing tungsten content of tantalum base alloy to 12-15% level will improve high temperature creep properties of existing tantalum base alloys while retaining their excellent fabrication and welding characteristics.

On the violence of thermal explosion in solid explosives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chidester, S.K.; Tarver, C.M.; Green, L.G.

Heavily confined cylinders of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and triaminotrinitrobenzene (TATB) were heated at rates varying from 2 C/min to 3.3 C/h. Fourteen of the cylinders were hollow, and inner metallic liners with small heaters attached were used to produce uniform temperatures just prior to explosion. A complex thermocouple pattern was used to measure the temperature history throughout the charge and to determine the approximate location where the runaway exothermic reaction first occurred. The violence of the resulting explosion was measured using velocity pin arrays placed inside and outside of the metal confinement cylinders, flash x-rays, overpressure gauges, and fragment collection techniques.more » Five cylinders were intentionally detonated for violence comparisons. The measured temperature histories, times to explosion, and the locations of first reaction agreed closely with those calculated by a two-dimensional heat transfer code using multistep chemical decomposition models. The acceleration of the confining metal cylinders by the explosion process was accurately simulated using a two-dimensional pressure dependent deflagration reactive flow hydrodynamic mode. The most violent HMX thermal explosions gradually accelerated their outer cases to velocities approaching those of intentional detonations approximately 120 {micro}m after the onset of explosion. The measured inner cylinder collapse velocities from thermal explosions were considerably lower than those produced by detonations. In contrast to the HMX thermal reactions, no violent thermal explosions were produced by the TATB-based explosive LX-17. A heavily confined, slowly heated LX-17 test produced sufficient pressure to cause a 0.1 cm bend in a 2 cm thick steel plate.« less

Reaction Buildup of PBX Explosives JOB-9003 under Different Initiation Pressures

NASA Astrophysics Data System (ADS)

Zhang, Xu; Wang, Yan-fei; Hung, Wen-bin; Gu, Yan; Zhao, Feng; Wu, Qiang; Yu, Xin; Yu, Heng

2017-04-01

Aluminum-based embedded multiple electromagnetic particle velocity gauge technique has been developed in order to measure the shock initiation behavior of JOB-9003 explosives. In addition, another gauge element called a shock tracker has been used to monitor the progress of the shock front as a function of time, thus providing a position-time trajectory of the wave front as it moves through the explosive sample. The data are used to determine the position and time for shock to detonation transition. All the experimental results show that: the rising-up time of Al-based electromagnetic particle velocity gauge was very fast and less than 20 ns; the reaction buildup velocity profiles and the position-time for shock to detonation transition of HMX-based PBX explosive JOB-9003 with 1-8 mm depth from the origin of impact plane under different initiation pressures are obtained with high accuracy.

Skyrmion-based high-frequency signal generator

NASA Astrophysics Data System (ADS)

Luo, Shijiang; Zhang, Yue; Shen, Maokang; Ou-Yang, Jun; Yan, Baiqian; Yang, Xiaofei; Chen, Shi; Zhu, Benpeng; You, Long

2017-03-01

Many concepts for skyrmion-based devices have been proposed, and most of their possible applications are based on the motion of skyrmions driven by a dc current in an area with a constricted geometry. However, skyrmion motion driven by a pulsed current has not been investigated so far. In this work, we propose a skyrmion-based high-frequency signal generator based on the pulsed-current-driven circular motion of skyrmions in a square-shaped film by micromagnetic simulation. The results indicate that skyrmions can move in a closed curve with central symmetry. The trajectory and cycle period can be adjusted by tuning the size of the film, the current density, the Dzyaloshinskii-Moriya interaction constant, and the local in-plane magnetic anisotropy. The period can be tuned from several nanoseconds to tens of nanoseconds, which offers the possibility to prepare high-frequency signal generator based on skyrmions.

High-Purity Glasses Based on Arsenic Chalcogenides

DTIC Science & Technology

2001-06-01

Chemical interaction of chalcogenides and some impurities (CS 2, TeO2 ) with the quartz glass at high temperature leads to the thin layers formation...UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADPO1 1523 TITLE: High-Purity Glasses Based on Arsenic Chalcogenides...Materials Vol. 3, No. 2, June 2001, p. 341 - 349 HIGH-PURITY GLASSES BASED ON ARSENIC CHALCOGENIDES M. F. Churbanov, I. V. Scripachev, G. E. Snopatin, V. S

Low-pressure barrier discharge ion source using air as a carrier gas and its application to the analysis of drugs and explosives.

PubMed

Usmanov, Dilshadbek T; Yu, Zhan; Chen, Lee Chuin; Hiraoka, Kenzo; Yamabe, Shinichi

2016-02-01

In this work, a low-pressure air dielectric-barrier discharge (DBD) ion source using a capillary with the inner diameter of 0.115 and 12 mm long applicable to miniaturized mass spectrometers was developed. The analytes, trinitrotoluene (TNT), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), 1,3,5,7-tetranitroperhydro-1,3,5,7-tetrazocine (HMX), pentaerythritol tetranitrate (PETN), nitroglycerine (NG), hexamethylene triperoxide diamine (HMTD), caffeine, cocaine and morphine, introduced through the capillary, were ionized by a low-pressure air DBD. The ion source pressures were changed by using various sizes of the ion sampling orifice. The signal intensities of those analytes showed marked pressure dependence. TNT was detected with higher sensitivity at lower pressure but vice versa for other analytes. For all analytes, a marked signal enhancement was observed when a grounded cylindrical mesh electrode was installed in the DBD ion source. Among nine analytes, RDX, HMX, NG and PETN could be detected as cluster ions [analyte + NO3 ](-) even at low pressure and high temperature up to 180 °C. The detection indicates that these cluster ions are stable enough to survive under present experimental conditions. The unexpectedly high stabilities of these cluster ions were verified by density functional theory calculation. Copyright © 2016 John Wiley & Sons, Ltd.

Development of an Analytical Method for Explosive Residues in Soil,

DTIC Science & Technology

1987-06-01

confirm peak identities. The eluent for both columns should be 50:50 methanol-water. The elution time for all the analytes of interest on the LC -18 column...nitrate at 1.77 min for LC -8, 1.73 min for LC -DP, and 1.80 for LC -1. 23 Table A2. Instrument calibration results for HMX. Concentration Solution Soil* Peak ...LCT 12 AUG 2 0 W 1M 2j TNT Owl ""r’ L ,,,O MRYX TN L DNS 2 HMX 0 12 LC -CN 110 KMX S 8 TETRYL 6 RDXW 4 DNB and TNB 0 Approved for public release

An NQR Study of TNT Characteristics.

DTIC Science & Technology

1977-09-01

RDX , HMX , a r d some of t he heavy me t al 3~~: id~.s h~~’n for rn.nn ye.~rs been use d as rn~~lit~~ry nii p lns i n’t-~~~~, Thr p h y s i c a l...ambient temperatures of more than one coexisting crystal phase. This polymorphism is known to occur in TNT , HMX and PbN3, and is responsible for a...specific problems of TNT polymorphism and phase transitions were researched . This is one of the problems which is relevant to present day concerns . The

Deflagration Rates and Molecular Bonding Trends of Statically Compressed Secondary Explosives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaug, J M; Foltz, M F; Hart, E

2010-03-09

We discuss our measurements of the chemical reaction propagation rate as a function of pressure. Materials investigated have included CL-20, HMX, TATB, and RDX crystalline powders, LX-04, Comp B, and nitromethane. The anomalous correspondence between crystal structure, including in some instances isostructural phase transitions, on pressure-dependant RPRs of TATB, HMX, Nitromethane, CL-20, and PETN have been elucidated using micro-IR and -Raman spectroscopies. Here we specifically highlight pressure-dependent physicochemical mechanisms affecting the deflagration rate of nitromethane and epsilon-CL-20. We find that pressure induced splitting of symmetric stretch NO{sub 2} vibrations can signal the onset of increasingly more rapid combustion reactions.

Maisotsenko cycle applications for multistage compressors cooling

NASA Astrophysics Data System (ADS)

Levchenko, D.; Yurko, I.; Artyukhov, A.; Baga, V.

2017-08-01

The present study provides the overview of Maisotsenko Cycle (M-Cycle) applications for gas cooling in compressor systems. Various schemes of gas cooling systems are considered regarding to their thermal efficiency and cooling capacity. Preliminary calculation of M-cycle HMX has been conducted. It is found that M-cycle HMX scheme allows to brake the limit of the ambient wet bulb temperature for evaporative cooling. It has demonstrated that a compact integrated heat and moisture exchange process can cool product fluid to the level below the ambient wet bulb temperature, even to the level of dew point temperature of the incoming air with substantially lower water and energy consumption requirements.

A Novel Multiscale QM-MD-SPH Computational Method for Heterogeneous Multicomponent Reactive Systems

DTIC Science & Technology

2017-11-30

The first-principle study on the equation of state of hmx under high pressure. Science China Physics, Mechanics and Astronomy , 54(5):831–835, 2011...J J Monaghan, J C Lattanzio. A refined particle method for astrophysical problems. Astronomy and astrophysics 149 (1985): 135-143. 133 [148] J J...Monaghan. Smoothed particle hydrodynamics. Annual review of astronomy and astrophysics 30.1 (1992): 543-574. [149] J P Morris. A study of the

Carbon nanotube transistor based high-frequency electronics

NASA Astrophysics Data System (ADS)

Schroter, Michael

At the nanoscale carbon nanotubes (CNTs) have higher carrier mobility and carrier velocity than most incumbent semiconductors. Thus CNT based field-effect transistors (FETs) are being considered as strong candidates for replacing existing MOSFETs in digital applications. In addition, the predicted high intrinsic transit frequency and the more recent finding of ways to achieve highly linear transfer characteristics have inspired investigations on analog high-frequency (HF) applications. High linearity is extremely valuable for an energy efficient usage of the frequency spectrum, particularly in mobile communications. Compared to digital applications, the much more relaxed constraints for CNT placement and lithography combined with already achieved operating frequencies of at least 10 GHz for fabricated devices make an early entry in the low GHz HF market more feasible than in large-scale digital circuits. Such a market entry would be extremely beneficial for funding the development of production CNTFET based process technology. This talk will provide an overview on the present status and feasibility of HF CNTFET technology will be given from an engineering point of view, including device modeling, experimental results, and existing roadblocks. Carbon nanotube transistor based high-frequency electronics.

Biodegradation of nitro-substituted explosives 2,4,6-trinitrotoluene, hexahydro-1,3,5-trinitro-1,3,5-triazine, and octahydro-1,3,5,7-tetranitro-1,3,5-tetrazocine by a phytosymbiotic Methylobacterium sp. associated with poplar tissues (Populus deltoides x nigra DN34).

PubMed

Van Aken, Benoit; Yoon, Jong Moon; Schnoor, Jerald L

2004-01-01

A pink-pigmented symbiotic bacterium was isolated from hybrid poplar tissues (Populus deltoides x nigra DN34). The bacterium was identified by 16S and 16S-23S intergenic spacer ribosomal DNA analysis as a Methylobacterium sp. (strain BJ001). The isolated bacterium was able to use methanol as the sole source of carbon and energy, which is a specific attribute of the genus Methylobacterium. The bacterium in pure culture was shown to degrade the toxic explosives 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazene (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5-tetrazocine (HMX). [U-ring-(14)C]TNT (25 mg liter(-1)) was fully transformed in less than 10 days. Metabolites included the reduction derivatives amino-dinitrotoluenes and diamino-nitrotoluenes. No significant release of (14)CO(2) was recorded from [(14)C]TNT. In addition, the isolated methylotroph was shown to transform [U-(14)C]RDX (20 mg liter(-1)) and [U-(14)C]HMX (2.5 mg liter(-1)) in less than 40 days. After 55 days of incubation, 58.0% of initial [(14)C]RDX and 61.4% of initial [(14)C]HMX were mineralized into (14)CO(2). The radioactivity remaining in solution accounted for 12.8 and 12.7% of initial [(14)C]RDX and [(14)C]HMX, respectively. Metabolites detected from RDX transformation included a mononitroso RDX derivative and a polar compound tentatively identified as methylenedinitramine. Since members of the genus Methylobacterium are distributed in a wide diversity of natural environments and are very often associated with plants, Methylobacterium sp. strain BJ001 may be involved in natural attenuation or in situ biodegradation (including phytoremediation) of explosive-contaminated sites.

Ignition and Growth Modeling of Shock Initiation of Different Particle Size Formulations of PBXC03 Explosive

NASA Astrophysics Data System (ADS)

Hussain, Tariq; Liu, Yan; Huang, Fenglei; Duan, Zhuoping

2016-01-01

The change in shock sensitivity of explosives having various explosive grain sizes is discussed. Along with other parameters, explosive grain size is one of the key parameters controlling the macroscopic behavior of shocked pressed explosives. Ignition and growth reactive flow modeling is performed for the shock initiation experiments carried out by using the in situ manganin piezoresistive pressure gauge technique to investigate the influences of the octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) particle size on the shock initiation and the subsequent detonation growth process for the three explosive formulations of pressed PBXC03 (87% HMX, 7% 1,3,5-trichloro-2,4,6-trinitrobenzene (TATB), 6% Viton by weight). All of the formulation studied had the same density but different explosive grain sizes. A set of ignition and growth parameters was obtained for all three formulations. Only the coefficient G1 of the first growth term in the reaction rate equation was varied with the grain size; all other parameters were kept the same for all formulations. It was found that G1 decreases almost linearly with HMX particle size for PBXC03. However, the equation of state (EOS) for solid explosive had to be adjusted to fit the experimental data. Both experimental and numerical simulation results show that the shock sensitivity of PBXC03 decreases with increasing HMX particle size for the sustained pressure pulses (around 4 GPa) as obtained in the experiment. This result is in accordance with the results reported elsewhere in literature. For future work, a better approach may be to find standard solid Grüneisen EOS and product Jones-Wilkins-Lee (JWL) EOS for each formulation for the best fit to the experimental data.

Biodegradation of Nitro-Substituted Explosives 2,4,6-Trinitrotoluene, Hexahydro-1,3,5-Trinitro-1,3,5-Triazine, and Octahydro-1,3,5,7-Tetranitro-1,3,5-Tetrazocine by a Phytosymbiotic Methylobacterium sp. Associated with Poplar Tissues (Populus deltoides × nigra DN34)

PubMed Central

Van Aken, Benoit; Yoon, Jong Moon; Schnoor, Jerald L.

2004-01-01

A pink-pigmented symbiotic bacterium was isolated from hybrid poplar tissues (Populus deltoides × nigra DN34). The bacterium was identified by 16S and 16S-23S intergenic spacer ribosomal DNA analysis as a Methylobacterium sp. (strain BJ001). The isolated bacterium was able to use methanol as the sole source of carbon and energy, which is a specific attribute of the genus Methylobacterium. The bacterium in pure culture was shown to degrade the toxic explosives 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazene (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5-tetrazocine (HMX). [U-ring-14C]TNT (25 mg liter−1) was fully transformed in less than 10 days. Metabolites included the reduction derivatives amino-dinitrotoluenes and diamino-nitrotoluenes. No significant release of 14CO2 was recorded from [14C]TNT. In addition, the isolated methylotroph was shown to transform [U-14C]RDX (20 mg liter−1) and [U-14C]HMX (2.5 mg liter−1) in less than 40 days. After 55 days of incubation, 58.0% of initial [14C]RDX and 61.4% of initial [14C]HMX were mineralized into 14CO2. The radioactivity remaining in solution accounted for 12.8 and 12.7% of initial [14C]RDX and [14C]HMX, respectively. Metabolites detected from RDX transformation included a mononitroso RDX derivative and a polar compound tentatively identified as methylenedinitramine. Since members of the genus Methylobacterium are distributed in a wide diversity of natural environments and are very often associated with plants, Methylobacterium sp. strain BJ001 may be involved in natural attenuation or in situ biodegradation (including phytoremediation) of explosive-contaminated sites. PMID:14711682

Modeling Nonlinear Elastic-plastic Behavior of RDX Single Crystals During Indentation

DTIC Science & Technology

2012-01-01

single crystals has also been probed using shock experiments (6, 12) and molecular dynamics simulations (12–14). RDX undergoes a polymorphic phase...Patterson, J.; Dreger, Z.; Gupta, Y. Shock-wave Induced Phase Transition in RDX Single Crystals. J. Phys. Chem. B 2007, 111, 10897–10904. 17. Bedrov, D...and Volume Compression of β - HMX and RDX . In Proc. Int. Symp. High Dynamic Pressures; Commissariat a l’Energie Atomique: Paris, 1978; pp 3–8. 24

New Synthetic Approaches to TAT

DTIC Science & Technology

1990-03-30

stabilized externally by resonance stabilization of electron withdrawing substituents placed on all four Nitrogen aL,.ms (T,- N -:, ...7; 4- N -NO2 HMX, etc...or internally by ring carbonyl groups adja- cent to the ring- N -atoms (amide resonance). 1. Cyclization experiments on methylene-bisacetamide (MBA4...more, the high instability of the desired 8-membered [8]ane- N 4 system, and the difficulty to apply proper cond’tion-. what the final products can

Genetic evidence for conserved non-coding element function across species–the ears have it

PubMed Central

Turner, Eric E.; Cox, Timothy C.

2014-01-01

Comparison of genomic sequences from diverse vertebrate species has revealed numerous highly conserved regions that do not appear to encode proteins or functional RNAs. Often these “conserved non-coding elements,” or CNEs, can direct gene expression to specific tissues in transgenic models, demonstrating they have regulatory function. CNEs are frequently found near “developmental” genes, particularly transcription factors, implying that these elements have essential regulatory roles in development. However, actual examples demonstrating CNE regulatory functions across species have been few, and recent loss-of-function studies of several CNEs in mice have shown relatively minor effects. In this Perspectives article, we discuss new findings in “fancy” rats and Highland cattle demonstrating that function of a CNE near the Hmx1 gene is crucial for normal external ear development and when disrupted can mimic loss-of function Hmx1 coding mutations in mice and humans. These findings provide important support for conserved developmental roles of CNEs in divergent species, and reinforce the concept that CNEs should be examined systematically in the ongoing search for genetic causes of human developmental disorders in the era of genome-scale sequencing. PMID:24478720

High performance network and channel-based storage

NASA Technical Reports Server (NTRS)

Katz, Randy H.

1991-01-01

In the traditional mainframe-centered view of a computer system, storage devices are coupled to the system through complex hardware subsystems called input/output (I/O) channels. With the dramatic shift towards workstation-based computing, and its associated client/server model of computation, storage facilities are now found attached to file servers and distributed throughout the network. We discuss the underlying technology trends that are leading to high performance network-based storage, namely advances in networks, storage devices, and I/O controller and server architectures. We review several commercial systems and research prototypes that are leading to a new approach to high performance computing based on network-attached storage.

Symposium on Explosives and Pyrotechnics, 13th, Hilton Head Island, SC, Dec. 2-4, 1986, Proceedings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1987-01-01

The present conference on explosive and pyrotechnic technologies discusses the shock-sensitivity of RDX, the thermodynamic properties of RDX, TNT, nitroglycerine, and HMX energetic molecules, the dynamic resistivity of exploding conductors, the decomposition of azides, the critical shock-initiation energy of emulsion explosives, actuator valve optimization, pyrotechnic aerosolization from novel imbibed liquid matrices, tetrazole initiators, and polymeric binders for red phosphorus pellets. Also discussed are channel-effect studies, the dynamic desensitization of coal mine explosives, the electromagnetic and electrostatic protection of explosives, the reliability of fuze explosive trains, the hazardous properties of explosive chemicals, the emulsification of an explosive with a chemical foamingmore » agent, and low energy ignition of HMX using a foil bridge.« less

Determination of enthalpies of formation of energetic molecules with composite quantum chemical methods

DOE PAGES

Manaa, M. Riad; Fried, Laurence E.; Kuo, I-Feng W.

2016-02-01

We report gas-phase enthalpies of formation for the set of energetic molecules NTO, DADE, LLM-105, TNT, RDX, TATB, HMX, and PETN using the G2, G3, G4, and ccCA-PS3 quantum composite methods. Calculations for HMX and PETN hitherto represent the largest molecules attempted with these methods. G3 and G4 calculations are typically close to one another, with a larger difference found between these methods and ccCA-PS3. Furthermore there is significant uncertainty in experimental values, the mean absolute deviation between the average experimental value and calculations are 12, 6, 7, and 3 kcal/mol for G2, G3, G4, and ccCA-PS3, respectively.

Nitramine smokeless propellant research

NASA Technical Reports Server (NTRS)

1977-01-01

A transient ballistics and combustion model was derived to represent the closed vessel experiment that is widely used to characterize propellants. The model incorporates the nitramine combustion mechanisms. A computer program was developed to solve the time dependent equations, and was applied to explain aspects of closed vessel behavior. It is found that the rate of pressurization in the closed vessel is insufficient at pressures of interest to augment the burning rate by time dependent processes. Series of T-burner experiments were performed to compare the combustion instability characteristics of nitramine (HMX) containing propellants and ammonium perchlorate (AP) propellants. It is found that the inclusion of HMX consistently renders the propellant more stable.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manaa, M. Riad; Fried, Laurence E.; Kuo, I-Feng W.

We report gas-phase enthalpies of formation for the set of energetic molecules NTO, DADE, LLM-105, TNT, RDX, TATB, HMX, and PETN using the G2, G3, G4, and ccCA-PS3 quantum composite methods. Calculations for HMX and PETN hitherto represent the largest molecules attempted with these methods. G3 and G4 calculations are typically close to one another, with a larger difference found between these methods and ccCA-PS3. Furthermore there is significant uncertainty in experimental values, the mean absolute deviation between the average experimental value and calculations are 12, 6, 7, and 3 kcal/mol for G2, G3, G4, and ccCA-PS3, respectively.

High-throughput GPU-based LDPC decoding

NASA Astrophysics Data System (ADS)

Chang, Yang-Lang; Chang, Cheng-Chun; Huang, Min-Yu; Huang, Bormin

2010-08-01

Low-density parity-check (LDPC) code is a linear block code known to approach the Shannon limit via the iterative sum-product algorithm. LDPC codes have been adopted in most current communication systems such as DVB-S2, WiMAX, WI-FI and 10GBASE-T. LDPC for the needs of reliable and flexible communication links for a wide variety of communication standards and configurations have inspired the demand for high-performance and flexibility computing. Accordingly, finding a fast and reconfigurable developing platform for designing the high-throughput LDPC decoder has become important especially for rapidly changing communication standards and configurations. In this paper, a new graphic-processing-unit (GPU) LDPC decoding platform with the asynchronous data transfer is proposed to realize this practical implementation. Experimental results showed that the proposed GPU-based decoder achieved 271x speedup compared to its CPU-based counterpart. It can serve as a high-throughput LDPC decoder.

Sensitivity Characterization of Pressed Energetic Materials using Flyer Plate Mesoscale Simulations

NASA Astrophysics Data System (ADS)

Rai, Nirmal; Udaykumar, H. S.

Heterogeneous energetic materials like pressed explosives have complicated microstructure and contain various forms of heterogeneities such as pores, micro-cracks, energetic crystals etc. It is widely accepted that the presence of these heterogeneities can affect the sensitivity of these materials under shock load. The interaction of shock load with the microstructural heterogeneities may leads to the formation of local heated regions known as ``hot spots''. Chemical reaction may trigger at the hot spot regions depending on the hot spot temperature and the duration over which the temperature can be maintained before phenomenon like heat conduction, rarefaction waves withdraws energy from it. There are different mechanisms which can lead to the formation of hot spots including void collapse. The current work is focused towards the sensitivity characterization of two HMX based pressed energetic materials using flyer plate mesoscale simulations. The aim of the current work is to develop mesoscale numerical framework which can perform simulations by replicating the laboratory based flyer plate experiments. The current numerical framework uses an image processing approach to represent the microstructural heterogeneities incorporated in a massively parallel Eulerian code SCIMITAR3D. The chemical decomposition of HMX is modeled using Henson-Smilowitz reaction mechanism. The sensitivity characterization is aimed towards obtaining James initiation threshold curve and comparing it with the experimental results.

Application of vacuum stability test to determine thermal decomposition kinetics of nitramines bonded by polyurethane matrix

NASA Astrophysics Data System (ADS)

Elbeih, Ahmed; Abd-Elghany, Mohamed; Elshenawy, Tamer

2017-03-01

Vacuum stability test (VST) is mainly used to study compatibility and stability of energetic materials. In this work, VST has been investigated to study thermal decomposition kinetics of four cyclic nitramines, 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-HNIW, CL-20), bonded by polyurethane matrix based on hydroxyl terminated polybutadiene (HTPB). Model fitting and model free (isoconversional) methods have been applied to determine the decomposition kinetics from VST results. For comparison, the decomposition kinetics were determined isothermally by ignition delay technique and non-isothermally by Advanced Kinetics and Technology Solution (AKTS) software. The activation energies for thermolysis obtained by isoconversional method based on VST technique of RDX/HTPB, HMX/HTPB, BCHMX/HTPB and CL20/HTPB were 157.1, 203.1, 190.0 and 176.8 kJ mol-1 respectively. Model fitting method proved that the mechanism of thermal decomposition of BCHMX/HTPB is controlled by the nucleation model while all the other studied PBXs are controlled by the diffusion models. A linear relationship between the ignition temperatures and the activation energies was observed. BCHMX/HTPB is interesting new PBX in the research stage.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weese, R K; Burnham, A K

Dimensional changes related to temperature cycling of the {beta} and {delta} polymorphs of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) are important for a variety of applications. The coefficient of thermal expansion (CTE) of the {beta} and {delta} phases are measured over a temperature range of -20 C to 215 C by thermo-mechanical analysis (TMA). Dimensional changes associated with the phase transition were also measured, and the time-temperature dependence of the dimensional change is consistent with phase transition kinetics measured earlier by differential scanning calorimetry (DSC). One HMX sample measured by TMA during its initial heating and again three days later during a second heatingmore » showed the {beta}-to-{delta} phase transition a second time, thereby indicating back conversion from {delta}-to-{beta} phase HMX during those three days. DSC was used to measure kinetics of the {delta}-to-{beta} back conversion. The most successful approach was to first heat the material to create the {delta} phase, then after a given period at room temperature, measure the heat absorbed during a second pass through the {beta}-to-{delta} phase transition. Back conversion at room temperature follows nucleation-growth kinetics.« less

DWT-Based High Capacity Audio Watermarking

NASA Astrophysics Data System (ADS)

Fallahpour, Mehdi; Megías, David

This letter suggests a novel high capacity robust audio watermarking algorithm by using the high frequency band of the wavelet decomposition, for which the human auditory system (HAS) is not very sensitive to alteration. The main idea is to divide the high frequency band into frames and then, for embedding, the wavelet samples are changed based on the average of the relevant frame. The experimental results show that the method has very high capacity (about 5.5kbps), without significant perceptual distortion (ODG in [-1, 0] and SNR about 33dB) and provides robustness against common audio signal processing such as added noise, filtering, echo and MPEG compression (MP3).

Increasing the Utility of the Copper Cylinder Expansion Test

DTIC Science & Technology

2012-04-01

hydrocode [20–22]. The simulations were run in axially-symmetric, two-dimensional coordinates. The explosive was modeled with the JWL EoS and pro...1968, Livermore, Califor- nia, USA. [6] W. C. Davis, Calibration of a JWL Equation of State, Los Alamos National Laboratory Quarterly Report, M-9-QR-88...CP620, 954. [12] P. W. Merchant, S. J. White, A. M. Collyer, A WBL-Consis- tent JWL Equation of State for the HMX-Based Explosive EDC37 from Cylinder

High performance and highly reliable Raman-based distributed temperature sensors based on correlation-coded OTDR and multimode graded-index fibers

NASA Astrophysics Data System (ADS)

Soto, M. A.; Sahu, P. K.; Faralli, S.; Sacchi, G.; Bolognini, G.; Di Pasquale, F.; Nebendahl, B.; Rueck, C.

2007-07-01

The performance of distributed temperature sensor systems based on spontaneous Raman scattering and coded OTDR are investigated. The evaluated DTS system, which is based on correlation coding, uses graded-index multimode fibers, operates over short-to-medium distances (up to 8 km) with high spatial and temperature resolutions (better than 1 m and 0.3 K at 4 km distance with 10 min measuring time) and high repeatability even throughout a wide temperature range.

Simulation Learning PC Screen-Based vs. High Fidelity

DTIC Science & Technology

2011-08-01

D., Burgess, L., Berg, B . and Connolly, K . (2009). Teaching mass casualty triage skills using iterative multimanikin simulations. Prehospital...SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON USAMRMC a. REPORT U b . ABSTRACT U...learning PC screen-based vs. high fidelity – progress chart Attachment B . Approved Protocol - Simulation Learning: PC-Screen Based (PCSB) versus High

Competency-Based Adult High School Curriculum Project.

ERIC Educational Resources Information Center

Singer, Elizabeth

This compilation of program materials serves as an introduction to and overview of Florida's Brevard Community College's (BCC's) Competency-Based Adult High School Completion Project, which was conducted to teach administrators, counselors, and teachers how to organize and implement a competency-based adult education (CBAE) program; to critique…

High resolution PFPE-based molding High resolution PFPE-based molding High resolution PFPE-based molding techniques for nanofabrication of high pattern density sub-20 nm features: A fundamental materials approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, Stuart S; Samulski, Edward; Lopez, Renee

2010-01-01

ABSTRACT. Described herein is the development and investigation of PFPE-based elastomers for high resolution replica molding applications. The modulus of the elastomeric materials was increased through synthetic and additive approaches while maintaining relatively low surface energies (<25 mN/m). Using practically relevant large area master templates, we show that the resolution of the molds is strongly dependant upon the elastomeric mold modulus. A composite mold approach was used to form flexible molds out of stiff, high modulus materials that allow for replication of sub-20 nm post structures. Sub-100 nm line grating master templates, formed using e-beam lithography, were used to determinemore » the experimental stability of the molding materials. It was observed that as the feature spacing decreased, high modulus composite molds were able to effectively replicate the nano-grating structures without cracking or tear-out defects that typically occur with high modulus elastomers.« less

NTO-Picryl Constitutional Isomers—A DFT Study

NASA Astrophysics Data System (ADS)

Türker, Lemi; Çelik Bayar, Çağlar

2012-01-01

The quantum chemical properties and the detonation performance of some new explosives, 5-nitro-4-picryl-2,4-dihydro-3H-1,2,4-triazol-3-one (class A) and 5-nitro-2-picryl-2,4-dihydro-3H-1,2,4-triazol-3-one (class B), and their constitutional isomers have been investigated theoretically using the density functional theory (DFT) 6-31G(d,p) method. All of the constitutional isomers were found to be more sensitive than 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) and TNT but more insensitive than RDX and HMX. Their detonation performance is higher than that of NTO and TNT and all except two had lower detonation performance than RDX and HMX.

Equations of State and High-Pressure Phases of Explosives

NASA Astrophysics Data System (ADS)

Peiris, Suhithi M.; Gump, Jared C.

Energetic materials, being the collective name for explosives, propellants, pyrotechnics, and other flash-bang materials, span a wide range of composite chemical formulations. Most militarily used energetics are solids composed of particles of the pure energetic material held together by a binder. Commonly used binders include various oils, waxes, and polymers or plasticizers, and the composite is melt cast, cured, or pressed to achieve the necessary mechanical properties (gels, putties, sheets, solid blocks, etc.) of the final energetic material. Mining, demolition, and other industries use liquid energetics that are similarly composed of an actual energetic material or oxidizer together with a fuel, that is to be mixed and poured for detonation. Pure energetic materials that are commonly used are nitroglycerine, ammonium nitrate, ammonium or sodium perchlorate, trinitrotoluene (TNT), HMX, RDX, and TATB. All of them are molecular materials or molecular ions that when initiated or insulted undergoes rapid decomposition with excessive liberation of heat resulting in the formation of stable final products. When the final products are gases, and they are rapidly produced, the sudden pressure increase creates a shock wave. When decomposition is so rapid that the reaction moves through the explosive faster than the speed of sound in the unreacted explosive, the material is said to detonate. Typically, energetic materials that undergo detonation are known as high explosives (HEs) and energetic materials that burn rapidly or deflagrate are known as low explosives and/or propellants.

Model-based Clustering of High-Dimensional Data in Astrophysics

NASA Astrophysics Data System (ADS)

Bouveyron, C.

2016-05-01

The nature of data in Astrophysics has changed, as in other scientific fields, in the past decades due to the increase of the measurement capabilities. As a consequence, data are nowadays frequently of high dimensionality and available in mass or stream. Model-based techniques for clustering are popular tools which are renowned for their probabilistic foundations and their flexibility. However, classical model-based techniques show a disappointing behavior in high-dimensional spaces which is mainly due to their dramatical over-parametrization. The recent developments in model-based classification overcome these drawbacks and allow to efficiently classify high-dimensional data, even in the "small n / large p" situation. This work presents a comprehensive review of these recent approaches, including regularization-based techniques, parsimonious modeling, subspace classification methods and classification methods based on variable selection. The use of these model-based methods is also illustrated on real-world classification problems in Astrophysics using R packages.

High dynamic range image acquisition based on multiplex cameras

NASA Astrophysics Data System (ADS)

Zeng, Hairui; Sun, Huayan; Zhang, Tinghua

2018-03-01

High dynamic image is an important technology of photoelectric information acquisition, providing higher dynamic range and more image details, and it can better reflect the real environment, light and color information. Currently, the method of high dynamic range image synthesis based on different exposure image sequences cannot adapt to the dynamic scene. It fails to overcome the effects of moving targets, resulting in the phenomenon of ghost. Therefore, a new high dynamic range image acquisition method based on multiplex cameras system was proposed. Firstly, different exposure images sequences were captured with the camera array, using the method of derivative optical flow based on color gradient to get the deviation between images, and aligned the images. Then, the high dynamic range image fusion weighting function was established by combination of inverse camera response function and deviation between images, and was applied to generated a high dynamic range image. The experiments show that the proposed method can effectively obtain high dynamic images in dynamic scene, and achieves good results.

Development of highly sensitive and selective antibodies for the detection of the explosive pentaerythritol tetranitrate (PETN) by bioisosteric replacement.

PubMed

Hesse, Almut; Biyikal, Mustafa; Rurack, Knut; Weller, Michael G

2016-02-01

An improved antibody against the explosive pentaerythritol tetranitrate (PETN) was developed. The immunogen was designed by the concept of bioisosteric replacement, which led to an excellent polyclonal antibody with extreme selectivity and immunoassays of very good sensitivity. Compounds such as nitroglycerine, 2,4,6-trinitrotoluene, 1,3,5-trinitrobenzene, hexogen (RDX), 2,4,6-trinitroaniline, 1,3-dinitrobenzene, octogen (HMX), triacetone triperoxide, ammonium nitrate, 2,4,6-trinitrophenol and nitrobenzene were tested for potential cross-reactivity. The detection limit of a competitive enzyme-linked immunosorbent assay was determined to be around 0.5 µg/l. The dynamic range of the assay was found to be between 1 and 1000 µg/l, covering a concentration range of three decades. This work shows the successful application of the bioisosteric concept in immunochemistry by exchange of a nitroester to a carbonate diester. The antiserum might be used for the development of quick tests, biosensors, microtitration plate immunoassays, microarrays and other analytical methods for the highly sensitive detection of PETN, an explosive frequently used by terrorists, exploiting the extreme difficulty of its detection. Copyright © 2015 John Wiley & Sons, Ltd.

Carbon nanotube transistor based high-frequency electronics

NASA Astrophysics Data System (ADS)

Schroter, Michael

At the nanoscale carbon nanotubes (CNTs) have higher carrier mobility and carrier velocity than most incumbent semiconductors. Thus CNT based field-effect transistors (FETs) are being considered as strong candidates for replacing existing MOSFETs in digital applications. In addition, the predicted high intrinsic transit frequency and the more recent finding of ways to achieve highly linear transfer characteristics have inspired investigations on analog high-frequency (HF) applications. High linearity is extremely valuable for an energy efficient usage of the frequency spectrum, particularly in mobile communications. Compared to digital applications, the much more relaxed constraints for CNT placement and lithography combined with already achieved operating frequencies of at least 10 GHz for fabricated devices make an early entry in the low GHz HF market more feasible than in large-scale digital circuits. Such a market entry would be extremely beneficial for funding the development of production CNTFET based process technology. This talk will provide an overview on the present status and feasibility of HF CNTFET technology will be given from an engineering point of view, including device modeling, experimental results, and existing roadblocks.

Anaerobic biotransformation of explosives in aquifer slurries amended with ethanol and propylene glycol.

PubMed

Adrian, Neal R; Arnett, Clint M

2007-01-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6-trinitrotoluene (TNT) are explosives that are frequently found as environmental contaminants on military installations. Hydrogen has been shown to support the anaerobic transformation of these explosives. We investigated ethanol and propylene glycol as electron donors for providing syntrophically produced H2 for stimulating the anaerobic biodegradation of explosives in contaminated soil. The study was conducted using anoxic microcosms constructed with slurries of the contaminated soil and groundwater. The addition of 5mM ethanol and propylene glycol enhanced the biodegradation of RDX and HMX relative to the control bottles. Ethanol was depleted within about 20 days, resulting in the transient formation of hydrogen, acetate, and methane. The hydrogen headspace concentration increased from 8 ppm to 1838 ppm before decreasing to background concentrations. Propylene glycol was completely degraded after 15 days, forming hydrogen, propionate, and acetate as end-products. The hydrogen headspace concentrations increased from 56 ppm to 628 ppm before decreasing to background concentrations. No methane formation was observed during the incubation period of 48 days. Our findings indicate the addition of ethanol and propylene to the aquifer slurries increased the hydrogen concentrations and enhanced the biotransformation of RDX and HMX in the explosive-contaminated soil.

Comparison of Pumped and Diffusion Sampling Methods to Monitor Concentrations of Perchlorate and Explosive Compounds in Ground Water, Camp Edwards, Cape Cod, Massachusetts, 2004-05

USGS Publications Warehouse

LeBlanc, Denis R.; Vroblesky, Don A.

2008-01-01

Laboratory and field tests were conducted at Camp Edwards on the Massachusetts Military Reservation on Cape Cod to examine the utility of passive diffusion sampling for long-term monitoring of concentrations of perchlorate and explosive compounds in ground water. The diffusion samplers were constructed of 1-inch-diameter rigid, porous polyethylene tubing. The results of laboratory tests in which diffusion samplers were submerged in containers filled with ground water containing perchlorate, RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) indicate that concentrations inside the diffusion samplers equilibrated with concentrations in the containers within the 19-day-long test period. Field tests of the diffusion samplers were conducted in 15 wells constructed of 2- or 2.5-inch-diameter polyvinyl chloride pipe with 10-foot-long slotted screens. Concentrations of perchlorate, RDX, and HMX in the diffusion samplers placed in the wells for 42 to 52 days were compared to concentrations in samples collected by low-flow pumped sampling from 53 days before to 109 days after retrieval of the diffusion samples. The results of the field tests indicate generally good agreement between the pumped and diffusion samples for concentrations of perchlorate, RDX, and HMX. The concentration differences indicate no systematic bias related to contaminant type or concentration levels.

Mesoscale Modeling of Deflagration-Induced Deconsolidation in Polymer-Bonded Explosives

NASA Astrophysics Data System (ADS)

Springer, H. Keo; Reaugh, J. E.; Glascoe, E. A.; Kercher, J. R.; Friedman, G.

2011-06-01

Initially intact polymer-bonded explosives can transition from conductive burning to more violent convective burning via rapid deconsolidation at higher pressures. The pressure-dependent infiltration of cracks and pores, i.e., damage, by product gases at the burn-front is a key step in the transition to convective burning. However, the relative influence of pre-existing damage and deflagration-induced damage on the transition to convective burning is not well understood. The objective of this study is to investigate the role of explosive constituent properties, microstructure, and deflagration velocity on deconsolidation. We performed simulations using the multi-physics hydrocode, ALE3D. HMX was used as the model energetic grain. We used a JWL form for the unreacted and reacted equation-of-state of the HMX. Simplified strength and failure models were used for the HMX and the binder. The propensity for deconsolidation increased with increasing grain volume fraction, increasing porosity, decreasing binder strength, and increasing deflagration velocity. These studies are important because they enable the development of deflagration-induced damage models, as well as the design of inherently safer explosives. This work performed under the auspices of the U.S. DOE by LLNL under Contract DE-AC52-07NA27344. This work was funded by the Joint DoD/DOE Munitions Technology Development Program.

Research On Bi-Based High-Temperature Superconductors

NASA Technical Reports Server (NTRS)

Banks, Curtis; Doane, George B., III; Golben, John

1993-01-01

Brief report describes effects of melt sintering on Bi-based high-temperature superconductor system, as well as use of vibrating-sample magnetometer to determine hysteresis curves at 77 K for partially melt-sintered samples. Also discussed is production of high-temperature superconducting thin films by laser ablation: such films potentially useful in detection of signals of very low power.

High-Pressure Design of Advanced BN-Based Materials.

PubMed

Kurakevych, Oleksandr O; Solozhenko, Vladimir L

2016-10-20

The aim of the present review is to highlight the state of the art in high-pressure design of new advanced materials based on boron nitride. Recent experimental achievements on the governing phase transformation, nanostructuring and chemical synthesis in the systems containing boron nitride at high pressures and high temperatures are presented. All these developments allowed discovering new materials, e.g., ultrahard nanocrystalline cubic boron nitride (nano-cBN) with hardness comparable to diamond, and superhard boron subnitride B 13 N₂. Thermodynamic and kinetic aspects of high-pressure synthesis are described based on the data obtained by in situ and ex situ methods. Mechanical and thermal properties (hardness, thermoelastic equations of state, etc.) are discussed. New synthetic perspectives, combining both soft chemistry and extreme pressure-temperature conditions are considered.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pavlenko, A A; Maksimenko, E V; Chernyshova, L V

Experimental results on stand-off detection of HMX traces at various surfaces using the method of active spectral imaging in the IR region are reported. (laser applications and other topics in quantum electronics)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parab, Niranjan D.; Roberts, Zane A.; Harr, Michael H.

Fracture of crystals and subsequent frictional heating are associated with formation of hot spots in energetic composites such as polymer bonded explosives (PBXs). Traditional high speed optical imaging methods cannot be used to study the dynamic sub-surface deformation and fracture behavior of such materials due to their opaque nature. In this study, high speed synchrotron X-ray experiments are conducted to visualize the in situ deformation and fracture mechanisms in PBXs manufactured using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and hydroxyl-terminated polybutadiene (HTPB) binder. A modified Kolsky bar apparatus was used to apply controlled dynamic compression on the PBX specimens, and a high speedmore » synchrotron X-ray phase contrast imaging (PCI) setup was used to record the in situ deformation and failure in the specimens. The experiments show that synchrotron X-ray PCI provides a sufficient contrast between the HMX crystals and the doped binder, even at ultrafast recording rates. Under dynamic compression, most of the cracking in the crystals was observed to be due to the tensile stress generated by the diametral compression applied from the contacts between the crystals. Tensile stress driven cracking was also observed for some of the crystals due to the transverse deformation of the binder and superior bonding between the crystal and the binder. In conclusion, the obtained results are vital to develop improved understanding and to validate the macroscopic and mesoscopic numerical models for energetic composites so that eventually hot spot formation can be predicted.« less

Detection of explosives by positive corona discharge ion mobility spectrometry.

PubMed

Tabrizchi, Mahmoud; Ilbeigi, Vahideh

2010-04-15

In this work, thermal decomposition has been used to detect explosives by IMS in positive polarity. Explosives including Pentaerythritol Tetranitrate (PETN), Cyclo-1,3,5-Trimethylene-2,4,6-Trinitramine (RDX), 2,4,6-Trinitrotoluene (TNT), 2,4-Dihydro-5-nitro-3H-1,2,4-triazol-3-one (NTO), 1,3,5,7-Tetranitro-1,3,5,7-tetrazocine (HMX), have been evaluated at temperatures between 150 and 250 degrees C in positive polarity in air. Explosives yield NO(x) which causes NO(+) peak to increase. Additional peaks may be used to identify the type of explosive. The limit of detection for RDX, HMX, PETN, NTO, and TNT were obtained to be 1, 10, 40, 1000, and 1000 ng, respectively. 2009 Elsevier B.V. All rights reserved.

Effectiveness of laser sources for contactless sampling of explosives

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.

2016-05-01

A mass-spectrometric study of photo processes initiated by ultraviolet (UV) laser radiation in explosives adsorbed on metal and dielectric substrates has been performed. A calibrated quadrupole mass spectrometer was used to determine a value of activation energy of desorption and a quantity of explosives desorbed by laser radiation. A special vacuumoptical module was elaborated and integrated into a vacuum mass-spectrometric system to focus the laser beam on a sample. It has been shown that the action of nanosecond laser radiation set at q= 107 - 108 W/cm2, λ=266 nm on adsorbed layers of molecules of trinitrotoluene (TNT ) and pentaerytritoltetranitrate (PETN) leads not only to an effective desorption, but also to the non-equilibrium dissociation of molecules with the formation of nitrogen oxide NO. The cyclotrimethylenetrinitramine (RDX) dissociation products are observed only at high laser intensities (q> 109 W/cm2) thus indicating the thermal nature of dissociation, whereas desorption of RDX is observed even at q> 107 W/cm2 from all substrates. Desorption is not observed for cyclotetramethylenetetranitramine (HMX) under single pulse action: the dissociation products NO and NO2 are registered only, whereas irradiation at 10Hz is quite effective for HMX desorption. The results clearly demonstrate a high efficiency of nanosecond laser radiation with λ = 266 nm, q ~ 107 - 108 W/cm2, Epulse= 1mJ for desorption of molecules of explosives from various surfaces.

Detonation Reaction Zones in Condensed Explosives

NASA Astrophysics Data System (ADS)

Tarver, Craig M.

2006-07-01

Experimental measurements using nanosecond time resolved embedded gauges and laser interferometric techniques, combined with Non-Equilibrium Zeldovich - von Neumann - Doling (NEZND) theory and Ignition and Growth reactive flow hydrodynamic modeling, have revealed the average pressure/particle velocity states attained in reaction zones of self-sustaining detonation waves in several solid and liquid explosives. The time durations of these reaction zone processes are discussed for explosives based on pentaerythritol tetranitrate (PETN), nitromethane, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), triaminitrinitrobenzene(TATB) and trinitrotoluene (TNT).

Investigation of the efficiency of regenerative cooling of the ramjet combustor by gasification products of energy-intensive material

NASA Astrophysics Data System (ADS)

Averkov, I. S.; Arefyev, K. Yu.; Baykov, A. V.; Yanovskiy, L. S.

2017-01-01

The results of mathematical modeling of the thermal state of combustion chambers with regenerative cooling for ramjet engines of promising flying vehicles are presented. The cooling of combustion chambers by the gasification products of a combined charge of the energy-intensive material is considered, where the polyethylene is used as a stuff, and the HMX-based compounds are used as the active substance. The flow rates of the cooling eneregy-intensive material are determined, which provide acceptable levels of temperatures of combustion chambers at various modes of engines operation are determined.

A high-rate PCI-based telemetry processor system

NASA Astrophysics Data System (ADS)

Turri, R.

2002-07-01

The high performances reached by the Satellite on-board telemetry generation and transmission, as consequently, will impose the design of ground facilities with higher processing capabilities at low cost to allow a good diffusion of these ground station. The equipment normally used are based on complex, proprietary bus and computing architectures that prevent the systems from exploiting the continuous and rapid increasing in computing power available on market. The PCI bus systems now allow processing of high-rate data streams in a standard PC-system. At the same time the Windows NT operating system supports multitasking and symmetric multiprocessing, giving the capability to process high data rate signals. In addition, high-speed networking, 64 bit PCI-bus technologies and the increase in processor power and software, allow creating a system based on COTS products (which in future may be easily and inexpensively upgraded). In the frame of EUCLID RTP 9.8 project, a specific work element was dedicated to develop the architecture of a system able to acquire telemetry data of up to 600 Mbps. Laben S.p.A - a Finmeccanica Company -, entrusted of this work, has designed a PCI-based telemetry system making possible the communication between a satellite down-link and a wide area network at the required rate.

High Performance Oxides-Based Thermoelectric Materials

NASA Astrophysics Data System (ADS)

Ren, Guangkun; Lan, Jinle; Zeng, Chengcheng; Liu, Yaochun; Zhan, Bin; Butt, Sajid; Lin, Yuan-Hua; Nan, Ce-Wen

2015-01-01

Thermoelectric materials have attracted much attention due to their applications in waste-heat recovery, power generation, and solid state cooling. In comparison with thermoelectric alloys, oxide semiconductors, which are thermally and chemically stable in air at high temperature, are regarded as the candidates for high-temperature thermoelectric applications. However, their figure-of-merit ZT value has remained low, around 0.1-0.4 for more than 20 years. The poor performance in oxides is ascribed to the low electrical conductivity and high thermal conductivity. Since the electrical transport properties in these thermoelectric oxides are strongly correlated, it is difficult to improve both the thermoelectric power and electrical conductivity simultaneously by conventional methods. This review summarizes recent progresses on high-performance oxide-based thermoelectric bulk-materials including n-type ZnO, SrTiO3, and In2O3, and p-type Ca3Co4O9, BiCuSeO, and NiO, enhanced by heavy-element doping, band engineering and nanostructuring.

High resolution, MRI-based, segmented, computerized head phantom

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zubal, I.G.; Harrell, C.R.; Smith, E.O.

1999-01-01

The authors have created a high-resolution software phantom of the human brain which is applicable to voxel-based radiation transport calculations yielding nuclear medicine simulated images and/or internal dose estimates. A software head phantom was created from 124 transverse MRI images of a healthy normal individual. The transverse T2 slices, recorded in a 256x256 matrix from a GE Signa 2 scanner, have isotropic voxel dimensions of 1.5 mm and were manually segmented by the clinical staff. Each voxel of the phantom contains one of 62 index numbers designating anatomical, neurological, and taxonomical structures. The result is stored as a 256x256x128 bytemore » array. Internal volumes compare favorably to those described in the ICRP Reference Man. The computerized array represents a high resolution model of a typical human brain and serves as a voxel-based anthropomorphic head phantom suitable for computer-based modeling and simulation calculations. It offers an improved realism over previous mathematically described software brain phantoms, and creates a reference standard for comparing results of newly emerging voxel-based computations. Such voxel-based computations lead the way to developing diagnostic and dosimetry calculations which can utilize patient-specific diagnostic images. However, such individualized approaches lack fast, automatic segmentation schemes for routine use; therefore, the high resolution, typical head geometry gives the most realistic patient model currently available.« less

A High Performance COTS Based Computer Architecture

NASA Astrophysics Data System (ADS)

Patte, Mathieu; Grimoldi, Raoul; Trautner, Roland

2014-08-01

Using Commercial Off The Shelf (COTS) electronic components for space applications is a long standing idea. Indeed the difference in processing performance and energy efficiency between radiation hardened components and COTS components is so important that COTS components are very attractive for use in mass and power constrained systems. However using COTS components in space is not straightforward as one must account with the effects of the space environment on the COTS components behavior. In the frame of the ESA funded activity called High Performance COTS Based Computer, Airbus Defense and Space and its subcontractor OHB CGS have developed and prototyped a versatile COTS based architecture for high performance processing. The rest of the paper is organized as follows: in a first section we will start by recapitulating the interests and constraints of using COTS components for space applications; then we will briefly describe existing fault mitigation architectures and present our solution for fault mitigation based on a component called the SmartIO; in the last part of the paper we will describe the prototyping activities executed during the HiP CBC project.

Validation of highly reliable, real-time knowledge-based systems

NASA Technical Reports Server (NTRS)

Johnson, Sally C.

1988-01-01

Knowledge-based systems have the potential to greatly increase the capabilities of future aircraft and spacecraft and to significantly reduce support manpower needed for the space station and other space missions. However, a credible validation methodology must be developed before knowledge-based systems can be used for life- or mission-critical applications. Experience with conventional software has shown that the use of good software engineering techniques and static analysis tools can greatly reduce the time needed for testing and simulation of a system. Since exhaustive testing is infeasible, reliability must be built into the software during the design and implementation phases. Unfortunately, many of the software engineering techniques and tools used for conventional software are of little use in the development of knowledge-based systems. Therefore, research at Langley is focused on developing a set of guidelines, methods, and prototype validation tools for building highly reliable, knowledge-based systems. The use of a comprehensive methodology for building highly reliable, knowledge-based systems should significantly decrease the time needed for testing and simulation. A proven record of delivering reliable systems at the beginning of the highly visible testing and simulation phases is crucial to the acceptance of knowledge-based systems in critical applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burnham, A K; Weese, R K; Adrzejewski, W J

Accelerated aging tests play an important role in assessing the lifetime of manufactured products. There are two basic approaches to lifetime qualification. One tests a product to failure over range of accelerated conditions to calibrate a model, which is then used to calculate the failure time for conditions of use. A second approach is to test a component to a lifetime-equivalent dose (thermal or radiation) to see if it still functions to specification. Both methods have their advantages and limitations. A disadvantage of the 2nd method is that one does not know how close one is to incipient failure. Thismore » limitation can be mitigated by testing to some higher level of dose as a safety margin, but having a predictive model of failure via the 1st approach provides an additional measure of confidence. Even so, proper calibration of a failure model is non-trivial, and the extrapolated failure predictions are only as good as the model and the quality of the calibration. This paper outlines results for predicting the potential failure point of a system involving a mixture of two energetic materials, HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and CP (2-(5-cyanotetrazalato) pentaammine cobalt (III) perchlorate). Global chemical kinetic models for the two materials individually and as a mixture are developed and calibrated from a variety of experiments. These include traditional thermal analysis experiments run on time scales from hours to a couple days, detonator aging experiments with exposures up to 50 months, and sealed-tube aging experiments for up to 5 years. Decomposition kinetics are determined for HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and CP (2-(5-cyanotetrazalato) pentaammine cobalt (III) perchlorate) separately and together. For high levels of thermal stress, the two materials decompose faster as a mixture than individually. This effect is observed both in high-temperature thermal analysis experiments and

High School Students' Concepts of Acids and Bases.

ERIC Educational Resources Information Center

Ross, Bertram H. B.

An investigation of Ontario high school students' understanding of acids and bases with quantitative and qualitative methods revealed misconceptions. A concept map, based on the objectives of the Chemistry Curriculum Guideline, generated multiple-choice items and interview questions. The multiple-choice test was administered to 34 grade 12…

Carbon Nanofiber-Based, High-Frequency, High-Q, Miniaturized Mechanical Resonators

NASA Technical Reports Server (NTRS)

Kaul, Anupama B.; Epp, Larry W.; Bagge, Leif

2011-01-01

High Q resonators are a critical component of stable, low-noise communication systems, radar, and precise timing applications such as atomic clocks. In electronic resonators based on Si integrated circuits, resistive losses increase as a result of the continued reduction in device dimensions, which decreases their Q values. On the other hand, due to the mechanical construct of bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonators, such loss mechanisms are absent, enabling higher Q-values for both BAW and SAW resonators compared to their electronic counterparts. The other advantages of mechanical resonators are their inherently higher radiation tolerance, a factor that makes them attractive for NASA s extreme environment planetary missions, for example to the Jovian environments where the radiation doses are at hostile levels. Despite these advantages, both BAW and SAW resonators suffer from low resonant frequencies and they are also physically large, which precludes their integration into miniaturized electronic systems. Because there is a need to move the resonant frequency of oscillators to the order of gigahertz, new technologies and materials are being investigated that will make performance at those frequencies attainable. By moving to nanoscale structures, in this case vertically oriented, cantilevered carbon nanotubes (CNTs), that have larger aspect ratios (length/thickness) and extremely high elastic moduli, it is possible to overcome the two disadvantages of both bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonators. Nano-electro-mechanical systems (NEMS) that utilize high aspect ratio nanomaterials exhibiting high elastic moduli (e.g., carbon-based nanomaterials) benefit from high Qs, operate at high frequency, and have small force constants that translate to high responsivity that results in improved sensitivity, lower power consumption, and im - proved tunablity. NEMS resonators have recently been demonstrated using topdown

Python based high-level synthesis compiler

NASA Astrophysics Data System (ADS)

Cieszewski, Radosław; Pozniak, Krzysztof; Romaniuk, Ryszard

2014-11-01

This paper presents a python based High-Level synthesis (HLS) compiler. The compiler interprets an algorithmic description of a desired behavior written in Python and map it to VHDL. FPGA combines many benefits of both software and ASIC implementations. Like software, the mapped circuit is flexible, and can be reconfigured over the lifetime of the system. FPGAs therefore have the potential to achieve far greater performance than software as a result of bypassing the fetch-decode-execute operations of traditional processors, and possibly exploiting a greater level of parallelism. Creating parallel programs implemented in FPGAs is not trivial. This article describes design, implementation and first results of created Python based compiler.

High temperature deformation mechanisms of L12-containing Co-based superalloys

NASA Astrophysics Data System (ADS)

Titus, Michael Shaw

Ni-based superalloys have been used as the structural material of choice for high temperature applications in gas turbine engines since the 1940s, but their operating temperature is becoming limited by their melting temperature (Tm =1300degrees C). Despite decades of research, no viable alternatives to Ni-based superalloys have been discovered and developed. However, in 2006, a ternary gamma' phase was discovered in the Co-Al-W system that enabled a new class of Co-based superalloys to be developed. These new Co-based superalloys possess a gamma-gamma' microstructure that is nearly identical to Ni-based superalloys, which enables these superalloys to achieve extraordinary high temperature mechanical properties. Furthermore, Co-based alloys possess the added benefit of exhibiting a melting temperature of at least 100degrees C higher than commercial Ni-based superalloys. Superalloys used as the structural materials in high pressure turbine blades must withstand large thermomechanical stresses imparted from the rotating disk and hot, corrosive gases present. These stresses induce time-dependent plastic deformation, which is commonly known as creep, and new superalloys must possess adequate creep resistance over a broad range of temperature in order to be used as the structural materials for high pressure turbine blades. For these reasons, this research focuses on quantifying high temperature creep properties of new gamma'-containing Co-based superalloys and identifying the high temperature creep deformation mechanisms. The high temperature creep properties of new Co- and CoNi-based alloys were found to be comparable to Ni-based superalloys with respect to minimum creep rates and creep-rupture lives at 900degrees C up to the solvus temperature of the gamma' phase. Co-based alloys exhibited a propensity for extended superlattice stacking fault formation in the gamma' precipitates resulting from dislocation shearing events. When Ni was added to the Co-based compositions

High dynamic range emission measurements of shocked energetic materials: Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)

NASA Astrophysics Data System (ADS)

Bassett, Will P.; Dlott, Dana D.

2016-06-01

A new emission apparatus with high time resolution and high dynamic range was used to study shock-induced ignition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine in the form of ultrafine powder (4 ± 3 μm particle size), over a range of impact velocities (0.8-4.3 km s-1) and impact durations (2.5-16 ns). A graybody model was used to extract graybody emissivities and time-dependent temperatures from a few ns to 100 μs. The emission transients consisted of three parts: a 6700 K nanosecond burst during the shocks, a 4000-4500 K temperature spike near 0.3 μs followed by a ˜3300 K tail extending out to ˜100 μs. These temperatures varied remarkably little with impact velocity and duration, while the emission intensities and emissivities changed by over an order of magnitude. The emissivity changes were interpreted with a hot spot model, where hot spot temperatures reached a maximum of 6700 K and the hot spot volume fractions increased from 5% to 100% as impact velocity increased from 1 to 3 km s-1. Changing shock durations in the 2.5-16 ns range had noticeable effects on the microsecond emission. The 0.3 μs temperature spike was much smaller or absent with 2.5 ns shocks, but prominent with longer durations. An explanation for these effects was put forth that invoked the formation of carbon-rich clusters during the shock. In this view, cluster formation was minimal with 2.5 ns shocks, but longer-duration shocks produced increasingly larger clusters, and the 0.3 μs temperature spikes represented cluster ignition.

Multi-dimensional mesoscale simulations of detonation initiation in energetic materials with density-based kinetics

NASA Astrophysics Data System (ADS)

Jackson, Thomas Luther; Jost, Antoine M. D.; Zhang, Ju; Sridharan, Prashanth; Amadio, Guilherme

2018-03-01

In this work we present multi-dimensional mesoscale simulations of detonation initiation in energetic materials. We solve the reactive Euler equations, with the energy equation augmented by a power deposition term. The reaction rate at the mesoscale is modelled using density-based kinetics, while the deposition term is based on simulations of void collapse at the microscale, modelled at the mesoscale as hot spots. We carry out two- and three-dimensional mesoscale simulations of random packs of HMX crystals in a binder, and show that transition between no-detonation and detonation depends on the number density of the hot spots, the packing fraction, and the post-shock pressure of an imposed shock. In particular, we show that, for a fixed post-shock pressure, there exists a critical value of the number density of hot spots, such that when the number density is below this value a detonation wave will not develop. We highlight the importance of morphology to initiation by comparing with a homogeneous counterpart, and we compare relevant length scales by examining their corresponding power spectra. We also examine the effect of packing fraction and show that at low post-shock pressures there is significant variation in the initiation times, but that this variation disappears as the post-shock pressure is increased. Finally, we compare three-dimensional simulations with the experimental data, and show that the model is capable of qualitatively reproducing the trends shown in the data.

High-resolution, anthropomorphic, computational breast phantom: fusion of rule-based structures with patient-based anatomy

NASA Astrophysics Data System (ADS)

Chen, Xinyuan; Gong, Xiaolin; Graff, Christian G.; Santana, Maira; Sturgeon, Gregory M.; Sauer, Thomas J.; Zeng, Rongping; Glick, Stephen J.; Lo, Joseph Y.

2017-03-01

While patient-based breast phantoms are realistic, they are limited by low resolution due to the image acquisition and segmentation process. The purpose of this study is to restore the high frequency components for the patient-based phantoms by adding power law noise (PLN) and breast structures generated based on mathematical models. First, 3D radial symmetric PLN with β=3 was added at the boundary between adipose and glandular tissue to connect broken tissue and create a high frequency contour of the glandular tissue. Next, selected high-frequency features from the FDA rule-based computational phantom (Cooper's ligaments, ductal network, and blood vessels) were fused into the phantom. The effects of enhancement in this study were demonstrated by 2D mammography projections and digital breast tomosynthesis (DBT) reconstruction volumes. The addition of PLN and rule-based models leads to a continuous decrease in β. The new β is 2.76, which is similar to what typically found for reconstructed DBT volumes. The new combined breast phantoms retain the realism from segmentation and gain higher resolution after restoration.

Modeling Propagation of Shock Waves in Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howard, W M; Molitoris, J D

2005-08-19

We present modeling results for the propagation of strong shock waves in metals. In particular, we use an arbitrary Lagrange Eulerian (ALE3D) code to model the propagation of strong pressure waves (P {approx} 300 to 400 kbars) generated with high explosives in contact with aluminum cylinders. The aluminum cylinders are assumed to be both flat-topped and have large-amplitude curved surfaces. We use 3D Lagrange mechanics. For the aluminum we use a rate-independent Steinberg-Guinan model, where the yield strength and shear modulus depend on pressure, density and temperature. The calculation of the melt temperature is based on the Lindermann law. Atmore » melt the yield strength and shear modulus is set to zero. The pressure is represented as a seven-term polynomial as a function of density. For the HMX-based high explosive, we use a JWL, with a program burn model that give the correct detonation velocity and C-J pressure (P {approx} 390 kbars). For the case of the large-amplitude curved surface, we discuss the evolving shock structure in terms of the early shock propagation experiments by Sakharov.« less

Modeling Propagation of Shock Waves in Metals

NASA Astrophysics Data System (ADS)

Howard, W. M.; Molitoris, J. D.

2006-07-01

We present modeling results for the propagation of strong shock waves in metals. In particular, we use an arbitrary Lagrange Eulerian (ALE3D) code to model the propagation of strong pressure waves (P ˜ 300 to 400 kbars) generated with high explosives in contact with aluminum cylinders. The aluminum cylinders are assumed to be both flat-topped and have large-amplitude curved surfaces. We use 3D Lagrange mechanics. For the aluminum we use a rate-independent Steinberg-Guinan model, where the yield strength and shear modulus depend on pressure, density and temperature. The calculation of the melt temperature is based on the Lindermann law. At melt the yield strength and shear modulus is set to zero. The pressure is represented as a seven-term polynomial as a function of density. For the HMX-based high explosive, we use a JWL, with a program burn model that give the correct detonation velocity and C-J pressure (P ˜ 390 kbars). For the case of the large-amplitude curved surface, we discuss the evolving shock structure in terms of the early shock propagation experiments by Sakharov.

Unreacted equation of states of typical energetic materials under static compression: A review

NASA Astrophysics Data System (ADS)

Zhaoyang, Zheng; Jijun, Zhao

2016-07-01

The unreacted equation of state (EOS) of energetic materials is an important thermodynamic relationship to characterize their high pressure behaviors and has practical importance. The previous experimental and theoretical works on the equation of state of several energetic materials including nitromethane, 1,3,5-trinitrohexahydro-1,3,5-triazine (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX), hexanitrostilbene (HNS), hexanitrohexaazaisowurtzitane (HNIW or CL-20), pentaerythritol tetranitrate (PETN), 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105), triamino-trinitrobenzene (TATB), 1,1-diamino-2,2-dinitroethene (DADNE or FOX-7), and trinitrotoluene (TNT) are reviewed in this paper. The EOS determined from hydrostatic and non-hydrostatic compressions are discussed and compared. The theoretical results based on ab initio calculations are summarized and compared with the experimental data. Project supported by the National Natural Science Foundation of China (Grant Nos. 11174045 and 11404050).

High efficiency tantalum-based ceramic composite structures

NASA Technical Reports Server (NTRS)

Stewart, David A. (Inventor); Leiser, Daniel B. (Inventor); DiFiore, Robert R. (Inventor); Katvala, Victor W. (Inventor)

2010-01-01

Tantalum-based ceramics are suitable for use in thermal protection systems. These composite structures have high efficiency surfaces (low catalytic efficiency and high emittance), thereby reducing heat flux to a spacecraft during planetary re-entry. These ceramics contain tantalum disilicide, molybdenum disilicide and borosilicate glass. The components are milled, along with a processing aid, then applied to a surface of a porous substrate, such as a fibrous silica or carbon substrate. Following application, the coating is then sintered on the substrate. The composite structure is substantially impervious to hot gas penetration and capable of surviving high heat fluxes at temperatures approaching 3000.degree. F. and above.

Efficacy of problem based learning in a high school science classroom

NASA Astrophysics Data System (ADS)

Rissi, James Ryan

At the high school level, the maturity of the students, as well as constraints of the traditional high school (both in terms of class time, and number of students), impedes the use of the Problem-based instruction. But with more coaching, guidance, and planning, Problem-based Learning may be an effective teaching technique with secondary students. In recent years, the State of Michigan High School Content Expectations have emphasized the importance of inquiry and problem solving in the high school science classroom. In order to help students gain inquiry and problem solving skills, a move towards a problem-based curriculum and away from the didactic approach may lead to favorable results. In this study, the problem-based-learning framework was implemented in a high school Anatomy and Physiology classroom. Using pre-tests and post-tests over the material presented using the Problem-based technique, student comprehension and long-term retention of the material was monitored. It was found that Problem-based Learning produced comparable test performance when compared to traditional lecture, note-taking, and enrichment activities. In addition, students showed evidence of gaining research and team-working skills.

Energy-Based Tetrahedron Sensor for High-Temperature, High-Pressure Environments

NASA Technical Reports Server (NTRS)

Gee, Kent L.; Sommerfeldt, Scott D.; Blotter, Jonathan D.

2012-01-01

An acoustic energy-based probe has been developed that incorporates multiple acoustic sensing elements in order to obtain the acoustic pressure and three-dimensional acoustic particle velocity. With these quantities, the user can obtain various energy-based quantities, including acoustic energy density, acoustic intensity, and acoustic impedance. In this specific development, the probe has been designed to operate in an environment characterized by high temperatures and high pressures as is found in the close vicinity of rocket plumes. Given these capabilities, the probe is designed to be used to investigate the acoustic conditions within the plume of a rocket engine or jet engine to facilitate greater understanding of the noise generation mechanisms in those plumes. The probe features sensors mounted inside a solid sphere. The associated electronics for the probe are contained within the sphere and the associated handle for the probe. More importantly, the design of the probe has desirable properties that reduce the bias errors associated with determining the acoustic pressure and velocity using finite sum and difference techniques. The diameter of the probe dictates the lower and upper operating frequencies for the probe, where accurate measurements can be acquired. The current probe design implements a sphere diameter of 1 in. (2.5 cm), which limits the upper operating frequency to about 4.5 kHz. The sensors are operational up to much higher frequencies, and could be used to acquire pressure data at higher frequencies, but the energy-based measurements are limited to that upper frequency. Larger or smaller spherical probes could be designed to go to lower or higher frequency range

High-Performance and Self-Powered Deep UV Photodetectors Based on High Quality 2D Boron Nitride Nanosheets

PubMed Central

Rivera, Manuel; Rahaman, Mostafizur; Zhou, Andrew F.; Mohammed Alzuraiqi, Waleed; Feng, Peter

2017-01-01

High-quality two-dimensional (2D) crystalline boron nitride nanosheets (BNNSs) were grown on silicon wafers by using pulsed plasma beam deposition techniques. Self-powered deep ultraviolet (DUV) photodetectors (PDs) based on BNNSs with Schottky contact structures are designed and fabricated. By connecting the fabricated DUV photodetector to an ammeter, the response strength, response time and recovery time to different DUV wavelengths at different intensities have been characterized using the output short circuit photocurrent without a power supply. Furthermore, effects of temperature and plasma treatment on the induced photocurrent response of detectors have also been investigated. The experimental data clearly indicate that plasma treatment would significantly improve both induced photocurrent and response time. The BNNS-based DUV photodetector is demonstrated to possess excellent performance at a temperature up to 400 °C, including high sensitivity, high signal-to-noise ratio, high spectral selectivity, high speed, and high stability, which is better than almost all reported semiconducting nanomaterial-based self-powered photodetectors. PMID:29257098

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

High energy microelectromechanical oscillator based on the electrostatic microactuator

NASA Astrophysics Data System (ADS)

Baginsky, I.; Kostsov, Edvard; Sobolev, Victor

2008-03-01

Electrostatic high energy micromotor based on the ferroelectric films is studied as applied to microelectromechanical devices operating in vibrational mode. It is shown that the micromotor can be efficiently used in high frequency micromechanical vibrators that are used in high energy MEMS devices, such as micropumps, microvalves, microinjectors, adaptive microoptic devices etc.

Using a Web-based GIS to Teach Problem-based Science in High School and College

NASA Astrophysics Data System (ADS)

Metzger, E.; Lenkeit Meezan, , K. A.; Schmidt, C.; Taketa, R.; Carter, J.; Iverson, R.

2008-12-01

Foothill College has partnered with San Jose State University to bring GIS web mapping technology to the high school and college classroom. The project consists of two parts. In the first part, Foothill and San Jose State University have teamed up to offer classes on building and maintaining Web based Geographic Information Systems (GIS). Web-based GIS such as Google Maps, MapQuest and Yahoo Maps have become ubiquitous, and the skills to build and maintain these systems are in high demand from many employers. In the second part of the project, high school students will be able to learn about Web GIS as a real world tool used by scientists. The students in the Foothill College/San Jose State class will build their Web GIS using scientific data related to the San Francisco/San Joaquin Delta region, with a focus on watersheds, biodiversity and earthquake hazards. This project includes high school level curriculum development that will tie in to No Child Left Behind and National Curriculum Standards in both Science and Geography, and provide workshops for both pre-and in- service teachers in the use of Web GIS-driven course material in the high school classroom. The project will bring the work of professional scientists into any high school classroom with an internet connection; while simultaneously providing workforce training in high demand technology based jobs.

Detection of Explosives Using Differential Laser-Induced Perturbation Spectroscopy with a Raman-based Probe.

PubMed

Oztekin, Erman K; Burton, Dallas J; Hahn, David W

2016-04-01

Explosives detection is carried out with a novel spectral analysis technique referred to as differential laser-induced perturbation spectroscopy (DLIPS) on thin films of TNT, RDX, HMX, and PETN. The utility of Raman spectroscopy for detection of explosives is enhanced by inducing deep ultraviolet laser perturbation on molecular structures in combination with a differential Raman sensing scheme. Principal components analysis (PCA) is used to quantify the DLIPS method as benchmarked against a traditional Raman scattering probe, and the related photo-induced effects on the molecular structure of the targeted explosives are discussed in detail. Finally, unique detection is observed with TNT samples deposited on commonly available background substrates of nylon and polyester. Overall, the data support DLIPS as a noninvasive method that is promising for screening explosives in real-world environments and backgrounds. © The Author(s) 2016.

High-Performance Microsupercapacitors Based on Bioinspired Graphene Microfibers.

PubMed

Pan, Hui; Wang, Dawei; Peng, Qingfa; Ma, Jun; Meng, Xin; Zhang, Yaopeng; Ma, Yuning; Zhu, Shenmin; Zhang, Di

2018-03-28

The miniaturization of portable electronic devices has fueled the development of microsupercapacitors that hold great potential to complement or even replace microbatteries and electrolytic capacitors. In spite of recent developments taking advantage of printing and lithography, it remains a great challenge to attain a high energy density without sacrificing the power density. Herein, a new protocol mimicking the spider's spinning process is developed to create highly oriented microfibers from graphene-based composites via a purpose-designed microfluidic chip. The orientation provides the microfibers with an electrical conductivity of ∼3 × 10 4 S m -1 , which leads to a high power density; the energy density is sustained by nanocarbons and high-purity metallic molybdenum disulfide. The microfibers are patterned in-plane to fabricate asymmetric microsupercapacitors for flexible and on-chip energy storage. The on-chip microsupercapacitor with a high pattern resolution of 100 μm delivers energy density up to the order of 10 -2 W h cm -3 and retains an ultrahigh power density exceeding 100 W cm -3 in an aqueous electrolyte. This work provides new design of flexible and on-chip asymmetric microsupercapacitors based on microfibers. The unique biomimetic microfluidic fabrication of graphene microfibers for energy storage may also stimulate thinking of the bionic design in many other fields.

Neural network based feed-forward high density associative memory

NASA Technical Reports Server (NTRS)

Daud, T.; Moopenn, A.; Lamb, J. L.; Ramesham, R.; Thakoor, A. P.

1987-01-01

A novel thin film approach to neural-network-based high-density associative memory is described. The information is stored locally in a memory matrix of passive, nonvolatile, binary connection elements with a potential to achieve a storage density of 10 to the 9th bits/sq cm. Microswitches based on memory switching in thin film hydrogenated amorphous silicon, and alternatively in manganese oxide, have been used as programmable read-only memory elements. Low-energy switching has been ascertained in both these materials. Fabrication and testing of memory matrix is described. High-speed associative recall approaching 10 to the 7th bits/sec and high storage capacity in such a connection matrix memory system is also described.

High-efficient and high-content cytotoxic recording via dynamic and continuous cell-based impedance biosensor technology.

PubMed

Hu, Ning; Fang, Jiaru; Zou, Ling; Wan, Hao; Pan, Yuxiang; Su, Kaiqi; Zhang, Xi; Wang, Ping

2016-10-01

Cell-based bioassays were effective method to assess the compound toxicity by cell viability, and the traditional label-based methods missed much information of cell growth due to endpoint detection, while the higher throughputs were demanded to obtain dynamic information. Cell-based biosensor methods can dynamically and continuously monitor with cell viability, however, the dynamic information was often ignored or seldom utilized in the toxin and drug assessment. Here, we reported a high-efficient and high-content cytotoxic recording method via dynamic and continuous cell-based impedance biosensor technology. The dynamic cell viability, inhibition ratio and growth rate were derived from the dynamic response curves from the cell-based impedance biosensor. The results showed that the biosensors has the dose-dependent manners to diarrhetic shellfish toxin, okadiac acid based on the analysis of the dynamic cell viability and cell growth status. Moreover, the throughputs of dynamic cytotoxicity were compared between cell-based biosensor methods and label-based endpoint methods. This cell-based impedance biosensor can provide a flexible, cost and label-efficient platform of cell viability assessment in the shellfish toxin screening fields.

Low-Cost Bio-Based Carbon Fibers for High Temperature Processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul, Ryan Michael; Naskar, Amit

GrafTech International Holdings Inc. (GTI), under Award No. DE-EE0005779, worked with Oak Ridge National Laboratory (ORNL) under CRADA No. NFE-15-05807 to develop lignin-based carbon fiber (LBCF) technology and to demonstrate LBCF performance in high-temperature products and applications. This work was unique and different from other reported LBCF work in that this study was application-focused and scalability-focused. Accordingly, the executed work was based on meeting criteria based on technology development, cost, and application suitability. High-temperature carbon fiber based insulation is used in energy intensive industries, such as metal heat treating and ceramic and semiconductor material production. Insulation plays a critical rolemore » in achieving high thermal and process efficiency, which is directly related to energy usage, cost, and product competitiveness. Current high temperature insulation is made with petroleum based carbon fibers, and one goal of this protect was to develop and demonstrate an alternative lignin (biomass) based carbon fiber that would achieve lower cost, CO2 emissions, and energy consumption and result in insulation that met or exceeded the thermal efficiency of current commercial insulation. In addition, other products were targeted to be evaluated with LBCF. As the project was designed to proceed in stages, the initial focus of this work was to demonstrate lab-scale LBCF from at least 4 different lignin precursor feedstock sources that could meet the estimated production cost of $5.00/pound and have ash level of less than 500 ppm in the carbonized insulation-grade fiber. Accordingly, a preliminary cost model was developed based on publicly available information. The team demonstrated that 4 lignin samples met the cost criteria. In addition, the ash level for the 4 carbonized lignin samples was below 500 ppm. Processing as-received lignin to produce a high purity lignin fiber was a significant accomplishment in that most

Inquiry-Based Instruction and High Stakes Testing

NASA Astrophysics Data System (ADS)

Cothern, Rebecca L.

Science education is a key to economic success for a country in terms of promoting advances in national industry and technology and maximizing competitive advantage in a global marketplace. The December 2010 Program for International Student Assessment (PISA) ranked the United States 23rd of 65 countries in science. That dismal standing in science proficiency impedes the ability of American school graduates to compete in the global market place. Furthermore, the implementation of high stakes testing in science mandated by the 2007 No Child Left Behind (NCLB) Act has created an additional need for educators to find effective science pedagogy. Research has shown that inquiry-based science instruction is one of the predominant science instructional methods. Inquiry-based instruction is a multifaceted teaching method with its theoretical foundation in constructivism. A correlational survey research design was used to determine the relationship between levels of inquiry-based science instruction and student performance on a standardized state science test. A self-report survey, using a Likert-type scale, was completed by 26 fifth grade teachers. Participants' responses were analyzed and grouped as high, medium, or low level inquiry instruction. The unit of analysis for the achievement variable was the student scale score average from the state science test. Spearman's Rho correlation data showed a positive relationship between the level of inquiry-based instruction and student achievement on the state assessment. The findings can assist teachers and administrators by providing additional research on the benefits of the inquiry-based instructional method. Implications for positive social change include increases in student proficiency and decision-making skills related to science policy issues which can help make them more competitive in the global marketplace.

AIN-Based Packaging for SiC High-Temperature Electronics

NASA Technical Reports Server (NTRS)

Savrun, Ender

2004-01-01

Packaging made primarily of aluminum nitride has been developed to enclose silicon carbide-based integrated circuits (ICs), including circuits containing SiC-based power diodes, that are capable of operation under conditions more severe than can be withstood by silicon-based integrated circuits. A major objective of this development was to enable packaged SiC electronic circuits to operate continuously at temperatures up to 500 C. AlN-packaged SiC electronic circuits have commercial potential for incorporation into high-power electronic equipment and into sensors that must withstand high temperatures and/or high pressures in diverse applications that include exploration in outer space, well logging, and monitoring of nuclear power systems. This packaging embodies concepts drawn from flip-chip packaging of silicon-based integrated circuits. One or more SiC-based circuit chips are mounted on an aluminum nitride package substrate or sandwiched between two such substrates. Intimate electrical connections between metal conductors on the chip(s) and the metal conductors on external circuits are made by direct bonding to interconnections on the package substrate(s) and/or by use of holes through the package substrate(s). This approach eliminates the need for wire bonds, which have been the most vulnerable links in conventional electronic circuitry in hostile environments. Moreover, the elimination of wire bonds makes it possible to pack chips more densely than was previously possible.

Highly stretchable nanoalginate based polyurethane elastomers.

PubMed

Daemi, Hamed; Barikani, Mehdi; Barmar, Mohammad

2013-06-20

Highly stretchable elastomeric samples based on cationic polyurethane dispersions-sodium alginate nanoparticles (CPUD/SA) were prepared by the solution blending of sodium alginate and aqueous polyurethane dispersions. CPUDs were synthesized by step growth polymerization technique using N-methyldiethanolamine (MDEA) as a source of cationic emulsifier. The chemical structure and thermal-mechanical properties of these systems were characterized using FTIR and DMTA, respectively. The presence of nanoalginate particles including nanobead and nanorod particles were proved by SEM and EDX. It was observed that thermal properties of composites increased with increasing SA content. All prepared samples were known as thermoplastic-elastomers with high percentages of elongation. Excellent compatibility of prepared nanocomposites was proved by the DMTA data. Copyright © 2013 Elsevier Ltd. All rights reserved.

In Situ Imaging during Compression of Plastic Bonded Explosives for Damage Modeling.

PubMed

Manner, Virginia W; Yeager, John D; Patterson, Brian M; Walters, David J; Stull, Jamie A; Cordes, Nikolaus L; Luscher, Darby J; Henderson, Kevin C; Schmalzer, Andrew M; Tappan, Bryce C

2017-06-10

The microstructure of plastic bonded explosives (PBXs) is known to influence behavior during mechanical deformation, but characterizing the microstructure can be challenging. For example, the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient X-ray contrast to obtain three-dimensional data by in situ, absorption contrast imaging. To address this difficulty, we have formulated a series of PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and low-density binder systems. The binders were hydroxyl-terminated polybutadiene (HTPB) or glycidyl azide polymer (GAP) cured with a commercial blend of acrylic monomers/oligomers. The binder density is approximately half of the HMX, allowing for excellent contrast using in situ X-ray computed tomography (CT) imaging. The samples were imaged during unaxial compression using micro-scale CT in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and flow. Additionally, 2D slices from the segmented 3D images were meshed for finite element simulation of the mesoscale response. At low stiffness, the binder and crystal do not delaminate and the crystals move with the material flow; at high stiffness, marked delamination is noted between the crystals and the binder, leading to very different mechanical properties. Initial model results exhibit qualitatively similar delamination.

In situ imaging during compression of plastic bonded explosives for damage modeling

DOE PAGES

Manner, Virginia Warren; Yeager, John David; Patterson, Brian M.; ...

2017-06-10

Here, the microstructure of plastic bonded explosives (PBXs) is known to influence behavior during mechanical deformation, but characterizing the microstructure can be challenging. For example, the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient X-ray contrast to obtain three-dimensional data by in situ, absorption contrast imaging. To address this difficulty, we have formulated a series of PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and low-density binder systems. The binders were hydroxyl-terminated polybutadiene (HTPB) or glycidyl azide polymer (GAP) cured with a commercial blend of acrylic monomers/oligomers. The binder density is approximately half of the HMX, allowingmore » for excellent contrast using in situ X-ray computed tomography (CT) imaging. The samples were imaged during unaxial compression using micro-scale CT in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and flow. Additionally, 2D slices from the segmented 3D images were meshed for finite element simulation of the mesoscale response. At low stiffness, the binder and crystal do not delaminate and the crystals move with the material flow; at high stiffness, marked delamination is noted between the crystals and the binder, leading to very different mechanical properties. Initial model results exhibit qualitatively similar delamination.« less

In situ imaging during compression of plastic bonded explosives for damage modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manner, Virginia Warren; Yeager, John David; Patterson, Brian M.

Here, the microstructure of plastic bonded explosives (PBXs) is known to influence behavior during mechanical deformation, but characterizing the microstructure can be challenging. For example, the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient X-ray contrast to obtain three-dimensional data by in situ, absorption contrast imaging. To address this difficulty, we have formulated a series of PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and low-density binder systems. The binders were hydroxyl-terminated polybutadiene (HTPB) or glycidyl azide polymer (GAP) cured with a commercial blend of acrylic monomers/oligomers. The binder density is approximately half of the HMX, allowingmore » for excellent contrast using in situ X-ray computed tomography (CT) imaging. The samples were imaged during unaxial compression using micro-scale CT in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and flow. Additionally, 2D slices from the segmented 3D images were meshed for finite element simulation of the mesoscale response. At low stiffness, the binder and crystal do not delaminate and the crystals move with the material flow; at high stiffness, marked delamination is noted between the crystals and the binder, leading to very different mechanical properties. Initial model results exhibit qualitatively similar delamination.« less

In Situ Imaging during Compression of Plastic Bonded Explosives for Damage Modeling

PubMed Central

Manner, Virginia W.; Yeager, John D.; Patterson, Brian M.; Walters, David J.; Stull, Jamie A.; Cordes, Nikolaus L.; Luscher, Darby J.; Henderson, Kevin C.; Schmalzer, Andrew M.; Tappan, Bryce C.

2017-01-01

The microstructure of plastic bonded explosives (PBXs) is known to influence behavior during mechanical deformation, but characterizing the microstructure can be challenging. For example, the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient X-ray contrast to obtain three-dimensional data by in situ, absorption contrast imaging. To address this difficulty, we have formulated a series of PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and low-density binder systems. The binders were hydroxyl-terminated polybutadiene (HTPB) or glycidyl azide polymer (GAP) cured with a commercial blend of acrylic monomers/oligomers. The binder density is approximately half of the HMX, allowing for excellent contrast using in situ X-ray computed tomography (CT) imaging. The samples were imaged during unaxial compression using micro-scale CT in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and flow. Additionally, 2D slices from the segmented 3D images were meshed for finite element simulation of the mesoscale response. At low stiffness, the binder and crystal do not delaminate and the crystals move with the material flow; at high stiffness, marked delamination is noted between the crystals and the binder, leading to very different mechanical properties. Initial model results exhibit qualitatively similar delamination. PMID:28772998

Microbial Degradation of RDX and HMX

DTIC Science & Technology

2004-02-01

can be performed on aqueous solutions and soil leachates . In this 0 100 200 300 400 500 0 1 2 3 4 5 6 4- N D A B (µ m ol .k g- 1 ) Days 4- N D A B (µ... Phytoremediation and Natural Attenuation, Ed A. Singh and O. Ward. Vol. 1, Springer-Verlag (Book chapter) 2. Bonin, P.M.L., D. Bejan, L. Schutt, J. Hawari

High Density Polymer-Based Integrated Electgrode Array

DOEpatents

Maghribi, Mariam N.; Krulevitch, Peter A.; Davidson, James Courtney; Hamilton, Julie K.

2006-04-25

A high density polymer-based integrated electrode apparatus that comprises a central electrode body and a multiplicity of arms extending from the electrode body. The central electrode body and the multiplicity of arms are comprised of a silicone material with metal features in said silicone material that comprise electronic circuits.

Fast Reactions of Aluminum and Explosive Decomposition Products in a Post-Detonation Environment

NASA Astrophysics Data System (ADS)

Tappan, Bryce; Manner, Virginia; Lloyd, Joseph; Pemberton, Steven; Explosives Applications; Special Projects Team

2011-06-01

In order to determine the reaction behavior of Al in HMX/cast-cured binder formulations shortly after the passage of the detonation, a series of cylinder tests was performed on formulations with varying amounts of 2 μm spherical Al as well as LiF (an inert surrogate for Al). In these studies, both detonation velocity and cylinder expansion velocity are measured in order to determine exactly how and when Al contributes to the explosive event, particularly in the presence of oxidizing/energetic binders. The U.S. Army ARDEC at Picatinny has recently coined the term ``combined effects explosives'' for these materials as they demonstrate both high metal pushing capability and high blast ability. This study is aimed at developing a fundamental understanding of the reaction of Al with explosives decomposition products, where both the detonation and post-detonation environment are analyzed. Reaction rates of Al metal are determined via comparison of predicted performance based on thermoequilibrium calculations. The JWL equation of state, detonation velocities, wall velocities, and parameters at the C-J plane are some of the parameters that will be discussed.