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.

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)

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).

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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(-).

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.

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.

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.

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.

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.

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

Molecular dynamics study of binding energies, mechanical properties, and detonation performances of bicyclo-HMX-based PBXs.

PubMed

Qiu, Ling; Xiao, Heming

2009-05-15

To investigate the effect of polymer binders on the monoexplosive, molecular dynamics simulations were performed to study the binding energies, mechanical properties, and detonation performances of the bicyclo-HMX-based polymer-bonded explosives (PBXs). The results show that the binding energies on different crystalline surfaces of bicyclo-HMX decrease in the order of (010)>(100)>(001). On each crystalline surface, binding properties of different polymers with the same chain segment are different from each other, while those of the polymers in the same content decrease in the sequence of PVDF>F(2311)>F(2314) approximately PCTFE. The mechanical properties of a dozen of model systems (elastic coefficients, various moduli, Cauchy pressure, and Poisson's ratio) have been obtained. It is found that mechanical properties are effectively improved by adding small amounts of fluorine polymers, and the overall effect of fluorine polymers on three crystalline surfaces of bicyclo-HMX changes in the order of (010)>(001) approximately (100). In comparison with the base explosive, detonation performances of the PBXs decrease slightly, but they are still superior to TNT. These suggestions may be useful for the formulation design of bicyclo-HMX-based PBXs.

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

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.

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.

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.

Preparation and Properties of Surface-Coated HMX with Viton and Graphene Oxide

NASA Astrophysics Data System (ADS)

Wang, Jingyu; Ye, Baoyun; An, Chongwei; Wu, Bidong; Li, Hequn; Wei, Yanju

2016-07-01

To improve the safety performance of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) particles, the new carbon material graphene oxide (GO) and Viton were used to coat HMX via a solvent-slurry process. For comparison, the HMX/Viton/graphite (HMX/Viton/G) and HMX/Viton composites were also prepared by the same process. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and differential scanning calorimetry (DSC) were employed to characterize the morphology, composition, and thermal decomposition of samples. The impact sensitivity and shock wave sensitivity of HMX-based composites were also measured and analyzed. The results of SEM, XRD, and XPS indicate that the cladding layer of HMX-based composites is successfully constructed. HMX/Viton/GO composites exhibit better thermal stability compared to HMX and HMX/Viton. The results show that both impact and shock wave sensitivities of HMX/Viton/GO composites are much lower than that of HMX/Viton. In addition, GO sheets exhibit a better desensitizing effect than G sheets. These combined properties suggest that nano-GO has good compatibility with explosives and can be utilized as a desensitizer in HMX particles.

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

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.

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.

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

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.

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.

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.

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

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

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.

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

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.

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.

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

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

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

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.

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

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.

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.

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.

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

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.

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.}

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 discussed in detail. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced biodegradation of cyclotetramethylenetetranitramine (HMX) under mixed electron-acceptor condition.

PubMed

Boopathy, R

2001-02-01

The biodegradation of cyclotetramethylenetetranitramine, commonly known as 'high melting explosive' (HMX), under various electron-acceptor conditions was investigated using enrichment cultures developed from the anaerobic digester sludge of Thibodaux sewage treatment plant. The results indicated that the HMX was biodegraded under sulfate reducing, nitrate reducing, fermenting, methanogenic, and mixed electron accepting conditions. However, the rates of degradation varied among the various conditions studied. The fastest removal of HMX (from 22 ppm on day 0 to < 0.05 ppm on day 11) was observed under mixed electron-acceptor conditions, followed in order by sulfate reducing, fermenting, methanogenic, and nitrate reducing conditions. Under aerobic conditions, HMX was not biodegraded, which indicated that HMX degradation takes place under anaerobic conditions via reduction. HMX was converted to methanol and chloroform under mixed electron-acceptor conditions. This study showed evidence for HMX degradation under anaerobic conditions in a mixed microbial population system similar to any contaminated field sites, where a heterogeneous population exists.

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.

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.

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.

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

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.

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

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.}

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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

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.

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

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

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

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.

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.

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.

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.

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.

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.

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.

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.

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

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 conditions.

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

TIME-SEQUENCED X-RAY OBSERVATION OF A THERMAL EXPLOSION

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

Tringe, J. W.; Molitoris, J. D.; Kercher, J. R.

The evolution of a thermally-initiated explosion is studied using a multiple-image x-ray system. HMX-based PBX 9501 is used in this work, enabling direct comparison to recently-published data obtained with proton radiography [1]. Multiple x-ray images of the explosion are obtained with image spacing of ten microseconds or more. The explosion is simultaneously characterized with a high-speed camera using an interframe spacing of 11 mus. X-ray and camera images were both initiated passively by signals from an embedded thermocouple array, as opposed to being actively triggered by a laser pulse or other external source. X-ray images show an accelerating reacting frontmore » within the explosive, and also show unreacted explosive at the time the containment vessel bursts. High-speed camera images show debris ejected from the vessel expanding at 800-2100 m/s in the first tens of mus after the container wall failure. The effective center of the initiation volume is about 6 mm from the geometric center of the explosive.« less

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

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.

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.

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

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.

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.

Relationship between pressure and reaction violence in thermal explosions

NASA Astrophysics Data System (ADS)

Smilowitz, L.; Henson, B. F.; Rodriguez, G.; Remelius, D.; Baca, E.; Oschwald, D.; Suvorova, N.

2017-01-01

Reaction violence of a thermal explosion is determined by the energy release rate of the explosive and the coupling of that energy to the case and surroundings. For the HMX and TATB based secondary high explosives studied, we have observed that temperature controls the time to explosion and pressure controls the final energy release rate subsequent to ignition. Pressure measurements in the thermal explosion regime have been notoriously difficult to make due to the extreme rise in temperature which is also occurring during a thermal explosion. We have utilized several different pressure measurement techniques for several different secondary high explosives. These techniques include commercially available piezoelectric and piezoresistive sensors which we have utilized in the low pressure (sub 30 MPa) range of PBX 9502 thermal explosions, and fiber Bragg grating sensors for the higher pressure range (up to GPa) for PBX9501 experiments. In this talk, we will compare the measurement techniques and discuss the pressures measured for the different formulations studied. Simultaneous x-ray radiography measurements of burn velocity will also be shown and correlations between pressure, burn velocity, and reaction violence will be discussed.

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

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.

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.

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.

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

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

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.

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.

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

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.

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.

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.

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

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).

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.

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.

Time-sequenced X-ray Observation of a Thermal Explosion

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

Tringe, J W; Molitoris, J D; Smilowitz, L

The evolution of a thermally-initiated explosion is studied using a multiple-image x-ray system. HMX-based PBX 9501 is used in this work, enabling direct comparison to recently-published data obtained with proton radiography [1]. Multiple x-ray images of the explosion are obtained with image spacing of ten microseconds or more. The explosion is simultaneously characterized with a high-speed camera using an interframe spacing of 11 {micro}s. X-ray and camera images were both initiated passively by signals from an embedded thermocouple array, as opposed to being actively triggered by a laser pulse or other external source. X-ray images show an accelerating reacting frontmore » within the explosive, and also show unreacted explosive at the time the containment vessel bursts. High-speed camera images show debris ejected from the vessel expanding at 800-2100 m/s in the first tens of {micro}s after the container wall failure. The effective center of the initiation volume is about 6 mm from the geometric center of the explosive.« less

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

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.

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.

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

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

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.

Eigenvalue Detonation of Combined Effects Aluminized Explosives

NASA Astrophysics Data System (ADS)

Capellos, Christos; Baker, Ernest; Balas, Wendy; Nicolich, Steven; Stiel, Leonard

2007-06-01

This paper reports on the development of theory and performance for recently developed combined effects aluminized explosives. Traditional high energy explosives used for metal pushing incorporate high loading percentages of HMX or RDX, whereas blast explosives incorporate some percentage of aluminum. However, the high blast explosives produce increased blast energies, with reduced metal pushing capability due to late time aluminum reaction. Metal pushing capability refers to the early volume expansion work produced during the first few volume expansions associated with cylinder wall velocities and Gurney energies. Our Recently developed combined effects aluminized explosives (PAX-29C, PAX-30, PAX-42) are capable of achieving excellent metal pushing and high blast energies. Traditional Chapman-Jouguet detonation theory does not explain the observed detonation states achieved by these combined effects explosives. This work demonstrates, with the use of cylinder expansion data and thermochemical code calculations (JAGUAR and CHEETAH), that eigenvalue detonation theory explains the observed behavior.

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

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.

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

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: RDXRDX>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.

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

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

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

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.

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.

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.

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.

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.

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.

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.

Plant tissue analysis for explosive compounds in phytoremediation and phytoforensics.

PubMed

Karnjanapiboonwong, Adcharee; Mu, Ruipu; Yuan, Yuan; Shi, Honglan; Ma, Yinfa; Burken, Joel G

2012-01-01

Plant tissue analysis methods were evaluated for six explosive compounds to assess uptake and phytoforensic methods development to quantify explosives in plant to obtain the plant data for the evaluation of explosive contamination in soil and groundwater. Four different solvent mixtures containing acetonitrile or methanol were tested at variable extraction ratios to compare the extraction efficiency for six explosive compounds: 2,4,6-trinitrotoluene (TNT), pentaerythritoltetranitrate (PETN), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2-amino-4,6-dinitrotoluene (2ADNT), and 2,4-Dinitroanisole (DNAN), in Laurel Willow (Salix pentandra) stem and range grass Big Bluestem (Andropogon gerardii) using LC-MS/MS. Plant tissues were spiked with 500 ng/g of explosives and extracted using ultrasonically-assisted solvent extraction. With the ratio of fresh plant mass to solvent volume of 1:20 for willow and 1:40 for big bluestem grass, results indicated that all explosives in willow except HMX were extracted at higher than 73.3% by using 20 mL of methanol, 50:50 (v/v) methanol:water, or acetonitrile, whereas HMX was extracted with the highest recovery of 61.3% by 20 mL of acetonitrile. In big bluestem grass, the most effective solvents were 20 mL of either methanol or 50:50 (v/v) methanol:water for PETN extraction with a recovery of higher than 101.2% and 20 mL of 50:50 (v/v) methanol:water for HMX, RDX, TNT, 2ADNT, and DNAN extraction with a recovery of 83.8%, 104.4%, 97.5%, 80.7%, and 108.2%, respectively. However, unlike methanol and acetonitrile, 50:50 (v/v) methanol:water provided no problem of leading or split peak in chromatogram; therefore, it was preferred in the test and performed a method validation. Results indicated that 50:50 (v/v) methanol:water provided good repeatability and recovery and method detection limits at 0.5-20 ng/g fresh weight or 8.8-61.3 ng/g dry weight. Overall, results suggested that solvent extraction efficiency of explosives in plant was influenced by plant species and solvent used, and method presented here was believed to provide the preliminary data with respect to the analysis of simultaneous explosives in plants with LC-MS/MS.

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.

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).

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.

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 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.

Plasmonic enhanced terahertz time-domain spectroscopy system for identification of common explosives

NASA Astrophysics Data System (ADS)

Demiraǧ, Yiǧit; Bütün, Bayram; Özbay, Ekmel

2017-05-01

In this study, we present a classification algorithm for terahertz time-domain spectroscopy systems (THz-TDS) that can be trained to identify most commonly used explosives (C4, HMX, RDX, PETN, TNT, composition-B and blackpowder) and some non-explosive samples (lactose, sucrose, PABA). Our procedure can be used in any THz-TDS system that detects either transmission or reflection spectra at room conditions. After preprocessing the signal in low THz regime (0.1 - 3 THz), our algorithm takes advantages of a latent space transformation based on principle component analysis in order to classify explosives with low false alarm rate.

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 to primarily include pore collapse and growth phase to primarily include post-collapse grain burning. We are able to track late-time, post-collapse burning due to the unique loading conditions employed in these calculations. We find that (dF/dt)gr > (dF/dt)ig for all pressures considered. (dF/dt)gr changes more significantly from 25 to 38 GPa (from 0.05/µs to >10-100/µs) than from 15 to 25 GPa (from 0.005/µs to 0.05/µs). There is a three order-of-magnitude difference in the reaction from 15 to 38 GPa just after pore collapse. This is qualitatively consistent with fitting the (macroscopic) Ignition and Growth model to high pressure shock initiation data, where much larger reaction fractions are needed to capture the early stages of reaction. Calculated burn rates demonstrate better agreement with data at intermediate times in the growth phase for 15 to 25 GPa and late times for 30 GPa then at any time in the growth phase for 38 GPa. Our calculations are much higher than burn rate data at the earliest times in the growth phase for all pressures, which may reflect the higher localized pressures and temperatures just after pore collapse in the ignition phase. Our calculations with spherical, conical, and elliptical pores show that the influence of morphology on reaction rate is pressure dependent and the most influential pore shapes at lower pressures aren't the same at higher pressures in the regime studied. Altogether these studies provide the basis for developing microstructure-aware models that can be used to design new explosives with optimal performance-safety characteristics. Such models can be used to guide additive manufacturing of explosives and fully exploit their disruptive nature.

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.

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.

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.

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.

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.

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

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.

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)

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

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

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.

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.

Double Shock Experiments on PBX Explosive JOB-9003

NASA Astrophysics Data System (ADS)

Zhang, Xu

2017-06-01

One-dimensional plate impact experiments have been performed to study the double shock to detonation transition and Hugoniot state in the HMX-based explosive JOB-9003. The flyer was a combination with sapphire and Kel-F which could pass two different pressure waves into PBX Explosive JOB-9003 sample after impact. The particle velocities at interface and different depths in the PBX JOB-9003 sample were measured with Al-based electromagnetic particle velocity gauge technique, thus obtaining particle velocity - time diagram. According to the diagram, the corresponding Hugoniot state can be determined based on the particle velocity and shock wave velocity in the sample. Comparing with the single shock experiments, PBX Explosive JOB-9003 shows desensitization features due to the pre-pressed shock wave, the shock to detonation transition distance is longer than those single shock experiments.

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.

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.

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.

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

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.

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.

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.

Detonation Characteristics of Mixtures of HMX and Emulsion Explosives

DTIC Science & Technology

1989-04-01

and an aqueous emulsion explo- sive have been determined. The emulsion explosive consisted of amonium - nitrate , sodium- nitrate and water in the...1989 D Cb ID A Final Report C14 Approved for public release; distribution unlimited. AIR FORCE WEAPONS LABORATORY Air Force Systems Command Kirtland...TERMS (ContInue on nvwn Nf ocosury and idsŘ by block number) FIELD GROUP SUB-GROUP Explosives; Ammonium Nitrate ;- 19 01Emulsion Explosives; ( 07 04

Shock initiation of 2,4-dinitroimidazole (2,4-DNI)

NASA Astrophysics Data System (ADS)

Urtiew, P. A.; Tarver, C. M.; Simpson, R. L.

1996-05-01

The shock sensitivity of the pressed solid explosive 2,4-dinitroimidazole (2,4-DNI) was determined using the embedded manganin pressure gauge technique. At an initial shock pressure of 2 GPa, several microseconds were required before any exothermic reaction was observed. At 4 GPa, 2,4-DNI reacted more rapidly but did not transition to detonation at the 12 mm deep gauge position. At 6 GPa, detonation occurred in less than 6 mm of shock propagation. Thus, 2,4-DNI is more shock sensitive than TATB-based explosives but is considerably less shock sensitive than HMX-based explosives. An Ignition and Growth reactive flow model for 2,4-DNI based on these gauge records showed that 2,4-DNI exhibits shock initiation characteristics similar to TATB but reacts faster. The chemical structure of 2,4-DNI suggests that it may exhibit thermal decomposition reactions similar to nitroguanine and explosives with similar ring structures, such as ANTA and NTO.

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.

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.

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.

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.

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.

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.

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.

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.

Quantifying the stability of trace explosives under different environmental conditions using electrospray ionization mass spectrometry.

PubMed

Sisco, Edward; Najarro, Marcela; Samarov, Daniel; Lawrence, Jeffrey

2017-04-01

This work investigates the stability of trace (tens of nanograms) deposits of six explosives: erythritol tetranitrate (ETN), pentaerythritol tetranitrate (PETN), cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (HMX), 2,4,6-trinitrotoluene (TNT), and 2,4,6-trinitrophenylmethylnitramine (tetryl) to determine environmental stabilities and lifetimes of trace level materials. Explosives were inkjet printed directly onto substrates and exposed to one of seven environmental conditions (Laboratory, -4°C, 30°C, 47°C, 90% relative humidity, UV light, and ozone) up to 42 days. Throughout the study, samples were extracted and quantified using electrospray ionization mass spectrometry (ESI-MS) to determine the stability of the explosive as a function of time and environmental exposure. Statistical models were then fit to the data and used for pairwise comparisons of the environments. Stability was found to be exposure and compound dependent with minimal sample losses observed for HMX, RDX, and PETN while substantial and rapid losses were observed in all conditions except -4°C for ETN and TNT and in all conditions for tetryl. The results of this work highlight the potential fate of explosive traces when exposed to various environments. Published by Elsevier B.V.

Quantifying the Stability of Trace Explosives under Different Environmental Conditions using Electrospray Ionization Mass Spectrometry

PubMed Central

Sisco, Edward; Najarro, Marcela; Samarov, Daniel; Lawrence, Jeffrey

2017-01-01

This work investigates the stability of trace (tens of nanograms) deposits of six explosives: erythritol tetranitrate (ETN), pentaerythritol tetranitrate (PETN), cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (HMX), 2,4,6-trinitrotoluene (TNT), and 2,4,6-trinitrophenylmethylnitramine (tetryl) to determine environmental stabilities and lifetimes of trace level materials. Explosives were inkjet printed directly onto substrates and exposed to one of seven environmental conditions (Laboratory, −4 °C, 30 °C, 47 °C, 90 % relative humidity, UV light, and ozone) up to 42 days. Throughout the study, samples were extracted and quantified using electrospray ionization mass spectrometry (ESI-MS) to determine the stability of the explosive as a function of time and environmental exposure. Statistical models were then fit to the data and used for pairwise comparisons of the environments. Stability was found to be exposure and compound dependent with minimal sample losses observed for HMX, RDX, and PETN while substantial and rapid losses were observed in all conditions except −4 °C for ETN and TNT and in all conditions for tetryl. The results of this work highlight the potential fate of explosive traces when exposed to various environments. PMID:28153227

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.

UPTAKE AND TRANSFORMATION OF EXPLOSIVES BY EASTERN COTTONWOOD (POPULUS DELTOIDES)

EPA Science Inventory

The 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-tetraazocine (HMX) have been extensively used by the United States military to manufacture munitions. Since World War II, both the commissioning an...

The evolution of solid density within a thermal explosion. I. Proton radiography of pre-ignition expansion, material motion, and chemical decomposition

NASA Astrophysics Data System (ADS)

Smilowitz, L.; Henson, B. F.; Romero, J. J.; Asay, B. W.; Saunders, A.; Merrill, F. E.; Morris, C. L.; Kwiatkowski, K.; Grim, G.; Mariam, F.; Schwartz, C. L.; Hogan, G.; Nedrow, P.; Murray, M. M.; Thompson, T. N.; Espinoza, C.; Lewis, D.; Bainbridge, J.; McNeil, W.; Rightley, P.; Marr-Lyon, M.

2012-05-01

We report proton transmission images obtained during direct heating of a sample of PBX 9501 (a plastic bonded formulation of the explosive nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)) prior to the ignition of a thermal explosion. We describe the application of proton radiography using the 800 MeV proton accelerator at Los Alamos National Laboratory to obtain transmission images in these thermal explosion experiments. We have obtained images at two spatial magnifications and viewing both the radial and the transverse axes of a solid cylindrical sample encased in aluminum. During heating we observe the slow evolution of proton transmission through the samples, with particular detail during material flow associated with the HMX β-δ phase transition. We also directly observe the loss of solid density to decomposition associated with elevated temperatures in the volume defining the ignition location in these experiments. We measure a diameter associated with this volume of 1-2 mm, in agreement with previous estimations of the diameter using spatially resolved fast thermocouples.

MESOSCALE MODELING OF DEFLAGRATION-INDUCED DECONSOLIDATION IN POLYMER-BONDED EXPLOSIVES

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

Springer, H K; Glascoe, E A; Reaugh, J E

Initially undamaged 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 the evolution of deflagration-induced damage during the transition to convective burning is not well understood. The objective of this study is to investigate the role of microstructure and initial pressurization on deconsolidation. We performed simulations using the multi-physics hydrocode, ALE3D. HMX-Viton A served as our model explosive.more » A Prout-Tompkins chemical kinetic model, Vielle's Law pressure-dependent burning, Gruneisen equation-of-state, and simplified strength model were used for the HMX. The propensity for deconsolidation increased with increasing defect size and decreasing initial pressurization, as measured by the increase in burning surface area. These studies are important because they enable the development of continuum-scale damage models and the design of inherently safer explosives.« less

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 explicit tracking of the influences of microstructure, loading, and mechanical constraints, the calculations also show the effects of stress wave reflection and confinement condition on the ignition behaviors of GXs and PBXs.

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

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.

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 reactions of aluminum and explosive decomposition products in a post-detonation environment

NASA Astrophysics Data System (ADS)

Tappan, Bryce C.; Manner, Virginia W.; Lloyd, Joseph M.; Pemberton, Steven J.

2012-03-01

In order to determine the reaction behavior of Al in RDX or HMX/cast-cured binder formulations shortly after the passage of the detonation, a series of cylinder tests was performed on formulations comprising of varying binder systems and either 3.5 μm spherical Al or LiF (an inert salt with a similar molecular weight and density to 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 Research, Development and Engineering Laboratory at Picatinny have recently coined the term "combined effects" explosives for materials such as these; 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 early post-detonation environment are analyzed. Reaction rates of Al metal are investigated via comparison of predicted performance based on thermoequilibrium calculations. The detonation velocities, wall velocities, and parameters at the CJ plane are some of the parameters that will be discussed.

Experimental and computational investigation of microwave interferometry (MI) for detonation front characterization

NASA Astrophysics Data System (ADS)

Mays, Owen; Tringe, Joe; Souers, Clark; Lauderbach, Lisa; Baluyot, Emer; Converse, Mark; Kane, Ron

2017-06-01

Microwave interferometry (MI) presents several advantages over more traditional existing shock and deflagration front diagnostics. Most importantly, it directly interrogates these fronts, instead of measuring the evolution of containment surfaces or explosive edges. Here we present the results of MI measurements on detonator-initiated cylinder tests, as well as on deflagration-to-detonation transition experiments, with emphasis on optimization of signal strength through coupling devices and through microwave-transparent windows. Full-wave electromagnetic field finite element simulations were employed to better understand microwave coupling into porous and near full theoretical maximum density (TMD) explosives. HMX and TATB-based explosives were investigated. Data was collected simultaneously at 26.5 GHz and 39 GHz, allowing for direct comparison of the front characteristics and providing insight into the dielectric properties of explosives at these high frequencies. MI measurements are compared against detonation velocity results from photonic Doppler velocimetry probes and high speed cameras, demonstrating the accuracy of the MI technique. Our results illustrate features of front propagation behavior that are difficult to observe with other techniques. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

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.

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.

Ultra-violet and visible absorption characterization of explosives by differential reflectometry.

PubMed

Dubroca, Thierry; Moyant, Kyle; Hummel, Rolf E

2013-03-15

This study presents some optical properties of TNT (2,4,6-trinitrotoluene), RDX, HMX and tetryl, specifically their absorption spectra as a function of concentration in various solvents in the ultraviolet and visible portion of the electromagnetic spectrum. We utilize a standoff explosives detection method, called differential reflectometry (DR). TNT was diluted in six different solvents (acetone, acetonitrile, ethanol, ethyl acetate, methanol, and toluene), which allowed for a direct comparison of absorption features over a wide range of concentrations. A line-shape analysis was adopted with great accuracy (R(2)>0.99) to model the absorption features of TNT in differential reflectivity spectra. We observed a blue shift in the pertinent absorption band with decreasing TNT concentration for all solvents. Moreover, using this technique, it was found that for all utilized solvents the concentration of TNT as well as of RDX, HMX, and tetryl, measured as a function of the transition wavelength of the ultra-violet absorption edge in differential reflectivity spectra shows three distinct regions. A model is presented to explain this behavior which is based on intermolecular hydrogen bonding of explosives molecules with themselves (or lack thereof) at different concentrations. Other intermolecular forces such as dipole-dipole interactions, London dispersion forces and π-stacking contribute to slight variations in the resulting spectra, which were determined to be rather insignificant in comparison to hydrogen bonding. The results are aimed towards a better understanding of the DR spectra of explosives energetic materials. Copyright © 2012 Elsevier B.V. All rights reserved.

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

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 in energetic materials. The studies here illustrate this for modestly sized systems and modest periods; however, ReaxFF calculations of reactive processes have already been reported on systems with approximately 10(6) atoms. Thus, with suitable computational facilities, one can study the atomistic level chemical processes in complex systems under extreme conditions.

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.

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.

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.

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

Wemhoff, A P; Burnham, A K; Nichols III, A L

The reduction of the number of reactions in kinetic models for both the HMX 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 wellmore » 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 multi-step Arrhenius model, and can contain up to 90% less 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 multi-step Arrhenius approach, while up to 11% using a Prout-Tompkins cookoff model.« less

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.

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.

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.

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

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

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

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

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 could allow the sustainable use of live fire training ranges by enhancing biodegradation of explosives in situ and preventing them from migrating to through the vadose zone to underlying ground water and off-site.

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.

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

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

Sollier, A., E-mail: arnaud.sollier@cea.fr; Bouyer, V.; Hébert, P.

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 pressuremore » 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.« less

3-nitro-1,2,4-triazol-5-one: A less sensitive explosive

DOEpatents

Lee, Kien-Yin; Coburn, M.D.

1987-01-30

A less sensitive explosive, 3-nitro-1,2,4-triazol-5-one. The compound 3-nitro--1,2,4-triazol-5-one (NTO) has a crystal density of 1.93 g/cm/sup 3/ and calculated detonation velocity and pressure equivalent to those of RDX. It can be prepared in high yield from inexpensive starting materials in a safe synthesis. Results from initial small-scale sensitivity tests indicate that NTO is less sensitive than RDX and HMX in all respects. A 4.13 cm diameter, unconfined plate-dent test at 92% of crystal density gave the detonation pressure predicted for NTO by the BKW calculation. 3 tabs.

3-nitro-1,2,4-triazol-5-one, a less sensitive explosive

DOEpatents

Lee, Kien-Yin; Coburn, Michael D.

1988-01-01

A less sensitive explosive, 3-nitro-1,2,4-triazol-5-one. The compound 3-nitro-1,2,4-triazol-5-one (NTO) has a crystal density of 1.93 g/cm.sup.3 and calculated detonation velocity and pressure equivalent to those of RDX. It can be prepared in high yield from inexpensive starting materials in a safe synthesis. Results from initial small-scale sensitivity tests indicate that NTO is less sensitive than RDX and HMX in all respects. A 4.13 cm diameter, unconfined plate-dent test at 92% of crystal density gave the detonation pressure predicted for NTO by the BKW calculation.

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.

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.

Computer code for the optimization of performance parameters of mixed explosive formulations.

PubMed

Muthurajan, H; Sivabalan, R; Talawar, M B; Venugopalan, S; Gandhe, B R

2006-08-25

LOTUSES is a novel computer code, which has been developed for the prediction of various thermodynamic properties such as heat of formation, heat of explosion, volume of explosion gaseous products and other related performance parameters. In this paper, we report LOTUSES (Version 1.4) code which has been utilized for the optimization of various high explosives in different combinations to obtain maximum possible velocity of detonation. LOTUSES (Version 1.4) code will vary the composition of mixed explosives automatically in the range of 1-100% and computes the oxygen balance as well as the velocity of detonation for various compositions in preset steps. Further, the code suggests the compositions for which least oxygen balance and the higher velocity of detonation could be achieved. Presently, the code can be applied for two component explosive compositions. The code has been validated with well-known explosives like, TNT, HNS, HNF, TATB, RDX, HMX, AN, DNA, CL-20 and TNAZ in different combinations. The new algorithm incorporated in LOTUSES (Version 1.4) enhances the efficiency and makes it a more powerful tool for the scientists/researches working in the field of high energy materials/hazardous materials.

Computational Overlap Coupling Between Micropolar Linear Elastic Continuum Finite Elements and Nonlinear Elastic Spherical Discrete Elements in One Dimension

DTIC Science & Technology

2013-01-01

Cracking in asphalt pavement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Figure 2. 2D...metallic binder, figure 1(b)), particulate energetic materials (explosive crystalline grains with polymeric binder, figure 1(c)), asphalt pavement (stone...explosive HMX grains and at grain-matrix interfaces (2). (d) Cracking in asphalt pavement . 2 (i) it is limited by current computing power (even

Elasticity of crystalline molecular explosives

DOE PAGES

Hooks, Daniel E.; Ramos, Kyle J.; Bolme, C. A.; ...

2015-04-14

Crystalline molecular explosives are key components of engineered explosive formulations. In precision applications a high degree of consistency and predictability is desired under a range of conditions to a variety of stimuli. Prediction of behaviors from mechanical response and failure to detonation initiation and detonation performance of the material is linked to accurate knowledge of the material structure and first stage of deformation: elasticity. The elastic response of pentaerythritol tetranitrate (PETN), cyclotrimethylene trinitramine (RDX), and cyclotetramethylene tetranitramine (HMX), including aspects of material and measurement variability, and computational methods are described in detail. Experimental determinations of elastic tensors are compared, andmore » an evaluation of sources of error is presented. Furthermore, computed elastic constants are also compared for these materials and for triaminotrinitrobenzene (TATB), for which there are no measurements.« less

Modeling shock responses of plastic bonded explosives using material point method

NASA Astrophysics Data System (ADS)

Shang, Hailin; Zhao, Feng; Fu, Hua

2017-01-01

Shock responses of plastic bonded explosives are modeled using material point method as implemented in the Uintah Computational Framework. Two-dimensional simulation model was established based on the micrograph of PBX9501. Shock loading for the explosive was performed by a piston moving at a constant velocity. Unreactive simulation results indicate that under shock loading serious plastic strain appears on the boundary of HMX grains. Simultaneously, the plastic strain energy transforms to thermal energy, causing the temperature to rise rapidly on grain boundary areas. The influence of shock strength on the responses of explosive was also investigated by increasing the piston velocity. And the results show that with increasing shock strength, the distribution of plastic strain and temperature does not have significant changes, but their values increase obviously. Namely, the higher the shock strength is, the higher the temperature rise will be.

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.

A method for fast safety screening of explosives in terms of crystal packing and molecular stability.

PubMed

Hu, Xiaohua; Chen, Nana; Li, Weichen

2016-07-01

Safety prediction is crucial to the molecular design or the material design of explosives, and the predictions based on any single factor alone will cause much inaccuracy, leading to a desire for a method on multi-bases. The presented proposes an improved method for fast screening explosive safety by combining a crystal packing factor and a molecular one, that is, steric hindrance against shear slide in crystal and molecular stability, denoted by intermolecular friction symbol (IFS) and bond dissociation energy (BDE) of trigger linkage respectively. Employing this BDE-IFS combined method, we understand the impact sensitivities of 24 existing explosives, and predict those of two energetic-energetic cocrystals of the observed CL-20/BTF and the supposed HMX/TATB. As a result, a better understanding is implemented by the combined method relative to molecular stability alone, verifying its improvement of more accurate predictions and the feasibility of IFS to graphically reflect molecular stacking in crystals. Also, this work verifies that the explosive safety is strongly related with its crystal stacking, which determines steric hindrance and influences shear slide.

Performance characteristics and statistics of a laser initiated microdetonator

NASA Technical Reports Server (NTRS)

Yang, L. C.

1979-01-01

The test results of 320 units of the laser initiated microdetonator are summarized. The commercially fabricated units used a lead styphnate/lead azide/HMX (1 mg/17.5 mg/13.5 mg) explosive train design contained in a miniature aluminum can and completed with a glass-metal seal window. The test parameters were the high and low laser energy, high and low temperature, laser pulse duration, laser wavelength and nuclear radiation (5 x 10 to the 6th rads of 1 MeV gamma ray). The performance parameters were the laser energy for ignition and the actuation response time. Included also is a description of the development of a flexible, continuously advanced train of explosive devices by using the units, miniature optics and fiber optics.

Assessment of soil toxicity from an antitank firing range using Lumbricus terrestris and Eisenia andrei in mesocosms and laboratory studies.

PubMed

Robidoux, Pierre Yves; Dubois, Charles; Hawari, Jalal; Sunahara, Geoffrey I

2004-08-01

Earthworm mesocosms studies were carried out on a explosives-contaminated site at an antitank firing range. Survival of earthworms and the lysosomal neutral red retention time (NRRT), a biomarker of lysosomal membrane stability, were used in these studies to assess the effect of explosives-contaminated soils on the earthworms Lumbricus terrestris and Eisenia andrei under field conditions. Toxicity of the soils samples for E. andrei was also assessed under laboratory conditions using the earthworms reproduction test and the NRRT. Results indicate that the survival was reduced up to 40% in certain explosive-contaminated soil mesocosms following 10 days of exposure under field conditions, whereas survival was reduced up to 100% following 28 days of exposure under laboratory conditions. Reproduction parameters such as number of cocoons and number of juveniles were reduced in many of the selected contaminated soils. Compared to the reference, NRRT was significantly reduced for E. andrei exposed to explosive-contaminated soils under both field and laboratory conditions, whereas for L. terrestris NRRT was similar compared to the reference mesocosm. Analyses showed that HMX was the major polynitro-organic compound in soils. HMX was also the only explosive detected in earthworm tissues. Thus, results from both field mesocosms and laboratory studies, showed lethal and sub-lethal effects associated to soil from the contaminated area of the antitank firing range.

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.

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

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.

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.

Detonation Performance Analyses for Recent Energetic Molecules

NASA Astrophysics Data System (ADS)

Stiel, Leonard; Samuels, Philip; Spangler, Kimberly; Iwaniuk, Daniel; Cornell, Rodger; Baker, Ernest

2017-06-01

Detonation performance analyses were conducted for a number of evolving and potential high explosive materials. The calculations were completed for theoretical maximum densities of the explosives using the Jaguar thermo-chemical equation of state computer programs for performance evaluations and JWL/JWLB equations of state parameterizations. A number of recently synthesized materials were investigated for performance characterizations and comparisons to existing explosives, including TNT, RDX, HMX, and Cl-20. The analytic cylinder model was utilized to establish cylinder and Gurney velocities as functions of the radial expansions of the cylinder for each explosive. The densities and heats of formulation utilized in the calculations are primarily experimental values from Picatinny Arsenal and other sources. Several of the new materials considered were predicted to have enhanced detonation characteristics compared to conventional explosives. In order to confirm the accuracy of the Jaguar and analytic cylinder model results, available experimental detonation and Gurney velocities for representative energetic molecules and their formulations were compared with the corresponding calculated values. Close agreement was obtained with most of the data. Presently at NATO.

Short Term Innovative Research Program: Nanoengineered Reactive Materials for Tunable Ignition and Energy Release

DTIC Science & Technology

2009-01-01

Background Most conventional explosives can be roughly categorized into two classes – molecular materials and intermolecular composites. Molecular...materials refer to species such as the nitroalkanes (e.g. nitromethane ) and cyclic nitramines (e.g. TNAZ, RDX, HMX) that release chemical energy...alternative to conventional explosives that has been gaining increasing interest have been termed reactive materials, and are defined as systems in

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

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.

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.

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.

On-site comprehensive analysis of explosives using HPLC-UV-PAED

NASA Astrophysics Data System (ADS)

Marple, Ronita L.; LaCourse, William R.

2004-03-01

High-performance liquid chromatography with ultra violet and photo-assisted electrochemical detection (HPLC-UV-PAED) has been developed for the sensitive and selective detection of explosives in ground water and soil extracts. Fractionation and preconcentration of explosives is accomplished with on-line solid phase extraction (SPE), which minimizes sample pretreatment and enables faster and more accurate on-site assessment of a contaminated site. Detection limits are equivalent or superior (i.e., <1 part-per-trillion for HMX) to those achieved using the Environmental Protection Agency (EPA) Method 8330. This approach is more broadly applicable, as it is capable of determining a wider range of organic nitro compounds. Soil samples are extracted using pressurized fluid extraction (PFE), and this technique is automatable, field-compatible, and environmentally friendly, adding to the overall efficiency of the methodology.

Fluorescence quenching as an indirect detection method for nitrated explosives.

PubMed

Goodpaster, J V; McGuffin, V L

2001-05-01

A novel approach based on fluorescence quenching is presented for the analysis of nitrated explosives. Seventeen common explosives and their degradation products are shown to be potent quenchers of pyrene, having Stern-Volmer constants that generally increase with the degree of nitration. Aromatic explosives such as 2,4,6-trinitrotoluene (2,4,6-TNT) are more effective quenchers than aliphatic or nitramine explosives. In addition, nitroaromatic explosives are found to have unique interactions with pyrene that lead to a wavelength dependence of their Stern-Volmer constants. This phenomenon allows for their differentiation from other nitrated explosives. The fluorescence quenching method is then applied to the determination of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine(HMX), 2,4,6-TNT, nitromethane, and ammonium nitrate in various commercial explosive samples. The samples are separated by capillary liquid chromatography with post-column addition of the pyrene solution and detection by laser-induced fluorescence. The indirect fluorescence quenching method shows increased sensitivity and selectivity over traditional UV-visible absorbance as well as the ability to detect a wider range of organic and inorganic nitrated compounds.

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.

One-Dimensional Thermal Violence Cook-Off Test

NASA Astrophysics Data System (ADS)

Cook, Malcolm; Stennett, Christopher; University of Cranfield, Shrivenham, Swindon, SN6 8LA Team; AWE plc, Aldermaston, Reading Bershire, RG7 4PR, UK Team

2017-06-01

The One-Dimensional Thermal Violence (ODTV) test is designed to quantify and rank the violence of HE charges when heated to elevated temperatures. The test design consists of a central spherical explosive pellet encased in two aluminium barrel shaped halves, fitted with a copper sealing ring, encased by two aluminium locking rings placed over them from either end. The outer surface of the capsule is heated uniformly by placing in a pre-heated molten solder bath. This allows the time-to-explosion to be recorded for different initial bath temperatures. The ODTV capsule can hold samples up to 30mm in diameter. Diagnostics include both thermocouples and Photon Dopler Velocimetry (PDV). A series of live firings have been carried out on a range of bespoke HMX/HTPB explosives. These include HMX/HTPB mix ratios of 95/5, 92/8, 90/10, 88/12 and 85/15. These tests showed that the ODTV capsule had sufficient confinement and size that it could capture the spectrum of events expected from these formulations. It has been demonstrated that the deformation of the heater cup (that houses the molten solder) can be used as an additional violence metric along with the fragmentation and PDV wall velocities of the aluminium ODTV capsule.

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.

Aspects of the Application of Cavity Enhanced Spectroscopy to Nitrogen Oxides Detection

PubMed Central

Wojtas, Jacek; Mikolajczyk, Janusz; Bielecki, Zbigniew

2013-01-01

This article presents design issues of high-sensitive laser absorption spectroscopy systems for nitrogen oxides (NOx) detection. Examples of our systems and their investigation results are also described. The constructed systems use one of the most sensitive methods, cavity enhanced absorption spectroscopy (CEAS). They operate at different wavelength ranges using a blue—violet laser diode (410 nm) as well as quantum cascade lasers (5.27 μm and 4.53 μm). Each of them is configured as a one or two channel measurement device using, e.g., time division multiplexing and averaging. During the testing procedure, the main performance features such as detection limits and measurements uncertainties have been determined. The obtained results are 1 ppb NO2, 75 ppb NO and 45 ppb N2O. For all systems, the uncertainty of concentration measurements does not exceed a value of 13%. Some experiments with explosives are also discussed. A setup equipped with a concentrator of explosives vapours was used. The detection method is based either on the reaction of the sensors to the nitrogen oxides directly emitted by the explosives or on the reaction to the nitrogen oxides produced during thermal decomposition of explosive vapours. For TNT, PETN, RDX and HMX a detection limit better than 1 ng has been achieved. PMID:23752566

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

Modeling the Propagation of Shock Waves in Metals

NASA Astrophysics Data System (ADS)

Howard, W. Michael

2005-07-01

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 bulk modulus depends on pressure, density and temperature. The calculation of the melt temperature is based on the Lindermann law. At melt the yield strength and bulk 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 gives 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. We also discuss the dependence of our results upon our material model for aluminum.

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

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.

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.

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.

Elucidation of high sensitivity of δ-HMX: New insight from first principles simulations

NASA Astrophysics Data System (ADS)

Kuklja, Maija M.; Tsyshevsky, Roman V.; Sharia, Onise

2017-01-01

Understanding of a significant difference in sensitivities of β and δ phases of cyclotetramethylene-tetranitramine (HMX) has been long one of the challenges in the field of high energy density materials. Despite many experimental and theoretical efforts to explain the high sensitivity of the δ phase, convincing reasons behind the HMX behavior remained unclear. We established that the presence of a polar surface in δ-HMX has fundamental implications for stability and overall chemical behavior of the material. A comparative quantum-chemical analysis of decomposition mechanisms in polar δ-HMX and nonpolar β-HMX discovered a considerable difference in dominating dissociation reactions, activation barriers, and reaction rates. The polarization-induced charge transfer offered a logical explanation for different sensitivity of β-HMX and δ-HMX polymorphs to detonation initiation. Our conclusions also removed long-standing contradictions and explained a large range of experimental data on thermal decomposition of HMX.

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.

Minutes of the Explosives Safety Seminar (22nd) Held in Anaheim, California on 26-28 August 1986. Volume 2

DTIC Science & Technology

1986-08-01

the U.S. Customs thermionic acetone vapor detector and a non -commercial Gas Chromatograph with electron capture detection as the main types. Each had...detector would only detect RDX or HMX or other explosives that had residual solvent with an alpha keto group like acetone or methylethyl ketone...8217.’=- evaluation for both vapor and non -vapor methods. The NAVSEA was not prepared to engage in r comprehensive study but did fund a reviev of improved

Continuation of the Ecological Risk Assessment of Explosive Residues in Rodents, Reptiles, Amphibians, Fish and Invertebrates: An Integrated Laboratory and Field Investigation Related to Live-Fire Ranges in the Department of Defense

DTIC Science & Technology

2008-08-01

malicum strain HAAP-1 isolated from a methanogenic mixed culture. Current Microbiology 48:332-340. Army. 1985h. HMX: Acute toxicity tests in...explosives: biotransformation versus mineralization. Applied Microbiology and Biotechnology 54:605-618. Hawari J, Halasz A, Sheremata T, Beaudet S...triazine (RDX) with municipal anaerobic sludge. Applied and Environmental Microbiology 66:2652-2657. Kudo, H., and Y. Oki. 1984. Microtus species

The microbial composition and metabolic potential of the ovine rumen

USDA-ARS?s Scientific Manuscript database

The rumen is efficient at biotransforming nitroaromatic explosive compounds, such as TNT, RDX, and HMX, which have been used widely in US military munitions. These compounds are present in > 4,000 military items, from large bombs to very small igniters. However, their manufacturing processes have g...

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.

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.

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.

Rapid identification and desorption mechanisms of nitrogen-based explosives by ambient micro-fabricated glow discharge plasma desorption/ionization (MFGDP) mass spectrometry.

PubMed

Tian, CaiYan; Yin, JinWei; Zhao, ZhongJun; Zhang, Yinchenxi; Duan, YiXiang

2017-05-15

A novel technique of micro-fabricated glow discharge plasma desorption/ionization mass spectrometry was investigated for the first time in negative ion mode in this study. Negative ion micro-fabricated glow discharge plasma desorption/ionization mass spectrometry (NI-MFGDP-MS) was successfully applied to identify trace explosives in open air. Six explosives and explosives-related compounds were directly analyzed in seconds with this ion source. The ions of [M-H] - were predominant for 2-methyl-1,3,5-trinitrobenzene (trinitrotoluene, TNT) and 2,4,6-trinitrophenol (picric acid), and [M+NO 3 ] - were dominant ions for 1,3,5-trinitro-perhydro-1,3,5-triazine (cyclonite, RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (octogen, HMX), 1,2,3-trinitroxypropane (nitroglycerin, NG), and pentaerythritol tetranitrate (PETN). The limits of detection (LOD) were from 87.5pgmm -2 to 0.4 fg mm -2 and the relative standard deviation (RSD) ranged between 5.8% and 16.8% for the explosives involved in this study. The reliability of NI-MFGDP-MS was characterized by the analysis of a picric acid-RDX-PETN mixture and a mixture of RDX-pond water. NI-MFGDP-MS and ESI-MS were compared with these explosives and along with collision induced dissociation (CID) experiments. The results showed that electron capture, proton abstraction reaction, nucleophilic attack, ion-molecule attachment, decomposition and anion attachment took place during the NI-MFGDP-MS measurement. These findings provide a guideline and a supplement to the chemical libraries for rapid and accurate detection of explosives. The method shows great potential for fast, in situ, on-line and high throughput detection of explosives in the field of antiterrorism. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

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.

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

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 binder is important within the context of using a cohesive traction-separation model for the delamination of a crystal-binder system.« less

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 binder is important within the context of using a cohesive traction-separation model for the delamination of a crystal-binder system.« less

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.

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.

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.

Novel laser induced photoacoustic spectroscopy for instantaneous trace detection of explosive materials.

PubMed

El-Sharkawy, Yasser H; Elbasuney, Sherif

2017-08-01

Laser photoacoustic spectroscopy (LPAS) is an attractive technology in terms of simplicity, ruggedness, and overall sensitivity; it detects the time dependent heat generated (thermo-elastic effect) in the target via interaction with pulsed optical radiation. This study reports on novel LPAS technique that offers instant and standoff detection capabilities of trace explosives. Over the current study, light is generated using pulsed Q-switched Nd:YAG laser; the generated photoacoustic response in stimulated explosive material offers signature values that depend on the optical, thermal, and acoustical properties. The generated acoustic waves were captured using piezoelectric transducer as well as novel customized optical sensor with remotely laser interferometer probe. A digital signal processing algorithm was employed to identify explosive material signatures via calculation of characteristic optical properties (absorption coefficient), sound velocity, and frequency response of the generated photoacoustic signal. Customized LPAS technique was employed for instantaneous trace detection of three main different high explosive materials including TNT, RDX, and HMX. The main outcome of this study is that the novel customized optical sensor signals were validated with traditional piezoelectric transducer. Furthermore, the customized optical sensor offered standoff detection capabilities (10cm), fast response, high sensitivity, and enhanced signal to noise ratio. This manuscript shaded the light on the instant detection of trace explosive materials from significant standoffs using novel customized LPAS technique. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental and Modeling Studies of Crush, Puncture, and Perforation Scenarios in the Steven Impact Test

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

Vandersall, K S; Chidester, S K; Forbes, J W

2002-06-28

The Steven test and associated modeling has greatly increased the fundamental knowledge of practical predictions of impact safety hazards for confined and unconfined explosive charges. Building on a database of initial work, experimental and modeling studies of crush, puncture, and perforation scenarios were investigated using the Steven impact test. The descriptions of crush, puncture, and perforation arose from safety scenarios represented by projectile designs that ''crush'' the energetic material or either ''puncture'' with a pinpoint nose or ''perforate'' the front cover with a transportation hook. As desired, these scenarios offer different aspects of the known mechanisms that control ignition: friction,more » shear and strain. Studies of aged and previously damaged HMX-based high explosives included the use of embedded carbon foil and carbon resistor gauges, high-speed cameras, and blast wave gauges to determine the pressure histories, time required for an explosive reaction, and the relative violence of those reactions, respectively. Various ignition processes were modeled as the initial reaction rate expression in the Ignition and Growth reaction rate equations. Good agreement with measured threshold velocities, pressure histories, and times to reaction was calculated for LX-04 impacted by several projectile geometries using a compression dependent ignition term and an elastic-plastic model with a reasonable yield strength for impact strain rates.« less

Characterization of Hypervelocity Metal Fragments for Explosive Initiation

NASA Astrophysics Data System (ADS)

Yeager, John; Bowden, Patrick; Guildenbecher, Daniel; Olles, Joseph

2017-06-01

The off-normal detonation behavior of two plastic-bonded explosive (PBX) formulations was studied using explosively-driven aluminum fragments moving at hypersonic velocity. Witness plate materials, including copper and polycarbonate, were used to characterize the distribution of particles, finding that the aluminum did not fragment homogeneously but rather with larger particles in a ring surrounding finer particles. Digital holography experiments were conducted to measure three-dimensional shape and size of the fastest-moving fragments, which ranged between 100 and 700 microns and traveled between 2 and 3.5 km/s. Crucially, these experiments showed variability in the fragmentation in terms of the number of fragments at the leading edge of the fragment field, indicating that both single and multiple shock impacts could be imparted to the target material. Lower density PBX 9407 (RDX-based) was initiable at up to 4.5 inches, while higher density PBX 9501 (HMX-based) was only initiable at up to 0.25 inches. This type of data is critical for safety experiments and hydrocode simulations to quantify shock-to-detonation transition mechanisms and the associated risk-margins for these materials.

Portable thin layer chromatography for field detection of explosives and propellants

NASA Astrophysics Data System (ADS)

Satcher, Joe H.; Maienschein, Jon L.; Pagoria, Philip F.; Racoveanu, Ana; Carman, M. Leslie; Whipple, Richard E.; Reynolds, John G.

2012-06-01

A field deployable detection kit for explosives and propellants using thin layer chromatography (TLC) has been developed at Lawrence Livermore National Laboratory (LLNL). The chemistry of the kit has been modified to allow for field detection of propellants (through propellant stabilizers), military explosives, peroxide explosives, nitrates and inorganic oxidizer precursors. For many of these target analytes, the detection limit is in the μg to pg range. A new miniaturized, bench prototype, field portable TLC (Micro TLC) kit has also been developed for the detection and identification of common military explosives. It has been demonstrated in a laboratory environment and is ready for field-testing. The kit is comprised of a low cost set of commercially available components specifically assembled for rapid identification needed in the field and identifies the common military explosives: HMX, RDX, Tetryl, Explosive D or picric acid, and TNT all on one plate. Additional modifications of the Micro TLC system have been made with fluorescent organosilicon co-polymer coatings to detect a large suite of explosives.

A DFT-D Study on Structural, Electronic, Thermodynamic, and Mechanical Properties of HMX/MPNO Cocrystal under High Pressure

NASA Astrophysics Data System (ADS)

Lin, He; Chen, Jian-Fu; Cui, Yu-Ming; Zhang, Zhen-Jiang; Yang, Dong-Dong; Zhu, Shun-Guan; Li, Hong-Zhen

2017-04-01

An investigation on the structural, electronic, thermodynamic, and mechanical properties of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)/2-methylpyridine-N-oxide (MPNO) cocrystal was carried out from 0 to 100 GPa by using a dispersion-corrected density functional theory (DFT-D) method. Our calculated crystal structure is in excellent agreement with experimental results at ambient pressure. Based on the analysis of lattice parameters, lattice angles, bond lengths, bond angles, and dihedral angles under high pressure, we observe that HMX molecules in the cocrystal bulk are seriously distorted but MPNO molecules remain relatively unchanged. Hydrogen bond lengths are greatly shortened under high pressure. In addition, with the increase in pressure, the bandgap decreases gradually. However, it increases suddenly at 70 GPa. Some important hydrogen bonds between HMX and MPNO are also observed in the density of states spectrum. According to the thermodynamic analysis, this cocrystal is more easily prepared under low pressure. Finally, we characterized its mechanical properties and the results show that this cocrystal is malleable in nature. We expect that this research can provide a fundamental basis for further HMX cocrystal design and preparation.

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.

Statistical Hotspot Model for Explosive Detonation

NASA Astrophysics Data System (ADS)

Nichols, Albert

2005-07-01

The presence and need for energy localization in the ignition and detonation of high explosives is a corner stone in our understanding of explosive behavior. This energy localization, known as hot spots, provides the match that starts the energetic response that is integral to the detonation. In our model, we use the life cycle of a hot spot to predict explosive response. This life cycle begins with a random distribution of inhomogeneities in the explosive that we describe as a potential hot spot. A shock wave can transform these into hot spots that can then grow by consuming the explosive around them. The fact that the shock wave can collapse a potential hot spot without causing ignition is required in order to model phenomena like dead pressing. The burn rate of the hot spot is taken directly from experimental data. In our approach we do not assume that every hot spot is burning in an identical environment, but rather we take a statistical approach to the burning process. We also do not make a uniform temperature assumption in order to close the mixture equation of state, but track the flow of energy from reactant to product. Finally, we include both the hot spot burn model and a thermal decomposition path, required to explain certain long time behaviors. Building on work performed by Reaugh et. al., we have developed a set of reaction parameters for an HMX based heterogeneous explosive. These parameters have been determined from computer models on the micron scale, and experimental data. This model will be compared to experimental rate stick data. This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

The measured temperature and pressure of EDC37 detonation products

NASA Astrophysics Data System (ADS)

Ferguson, J. W.; Richley, J. C.; Sutton, B. D.; Price, E.; Ota, T. A.

2017-01-01

We present the experimentally determined temperature and pressure of the detonation products of EDC37; a HMX based conventional high explosive. These measurements were performed on a series of cylinder tests. The temperature measurements were undertaken at the end of the cylinder with optical fibres observing the bare explosive through a LiF window. The temperature of the products was measured for approximately 2 µs using single colour pyrometry, multicolour pyrometry and also using time integrated optical emission spectroscopy with the results from all three methods being broadly consistent. The peak temperature was found to be ≈ 3600 K dropping to ≈ 2400 K at the end of the measurement window. The spectroscopy was time integrated and showed that the emission spectra can be approximated using a grey body curve between 520 - 800 nm with no emission or absorption lines being observed. The pressure was obtained using an analytical method which requires the velocity of the expanding cylinder wall and the velocity of detonation. The pressure drops from an initial CJ value of ≈ 38 GPa to ≈ 4 GPa after 2 µs.

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 work of Hatler et. al., and the reactive temperature rise will be obtained from Mader's work. Finally, the assessment of when a detonation occurs will be derived from Bowden and Yoffe's thermal explosion theory (hot spot).« 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.

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.

Optical ordnance system for use in explosive ordnance disposal activities

NASA Technical Reports Server (NTRS)

Merson, J. A.; Salas, F. J.; Helsel, F.M.

1994-01-01

A portable hand-held solid state rod laser system and an optically-ignited detonator have been developed for use in explosive ordnance disposal (EOD) activities. Laser prototypes from Whittaker Ordnance and Universal Propulsion have been tested and evaluated. The optical detonator contains 2-(5 cyanotetrazolato) pentaamine cobalt(III) perchlorate (CP) as the DDT column and the explosive Octahydro- 1,3,5,7 - tetrazocine (HMX) as the output charge. The laser is designed to have an output of 150 mJ in a 500 microsecond pulse. This output allows firing through 2000 meters of optical fiber. The detonator can also be ignited with a portable laser diode source through a shorter length of fiber.

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.

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.

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.

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

Degradation Mechanisms of Poly(ester urethane) Elastomer

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

Edgar, Alexander S.

This report describes literature regarding the degradation mechanisms associated with a poly(ester urethane) block copolymer, Estane® 5703 (Estane), used in conjunction with Nitroplasticizer (NP), and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane, also known as high molecular weight explosive (HMX) to produce polymer bonded explosive PBX 9501. Two principal degradation mechanisms are reported: NO2 oxidative reaction with the urethane linkage resulting in crosslinking and chain scission events, and acid catalyzed hydrolysis of the ester linkage. This report details future work regarding this PBX support system, to be conducted in late 2017 and 2018 at Engineered Materials Group (MST-7), Materials Science and Technology Division, Los Alamos Nationalmore » Laboratory. This is the first of a series of three reports on the degradation processes and trends of the support materials of PBX 9501.« less

HMX based enhanced energy LOVA gun propellant.

PubMed

Sanghavi, R R; Kamale, P J; Shaikh, M A R; Shelar, S D; Kumar, K Sunil; Singh, Amarjit

2007-05-08

Efforts to develop gun propellants with low vulnerability have recently been focused on enhancing the energy with a further improvement in its sensitivity characteristics. These propellants not only prevent catastrophic disasters due to unplanned initiation of currently used gun propellants (based on nitrate esters) but also realize enhanced energy levels to increase the muzzle velocity of the projectiles. Now, in order to replace nitroglycerine, which is highly sensitive to friction and impact, nitramines meet the requirements as they offer superior energy due to positive heat of formation, typical stoichiometry with higher decomposition temperatures and also owing to negative oxygen balance are less sensitive than stoichiometrically balanced NG. RDX has been widely reported for use in LOVA propellant. In this paper we have made an effort to present the work on scantily reported nitramine HMX based LOVA gun propellant while incorporating energetic plasticizer glycidyl azide polymer to enhance the energy level. HMX is known to be thermally stable at higher temperature than RDX and also proved to be less vulnerable to small scale shaped charge jet attack as its decomposition temperature is 270 degrees C. HMX also offers improved impulse due to its superior heat of formation (+17 kcal/mol) as compared to RDX (+14 kcal/mol). It has also been reported that a break point will not appear until 35,000 psi for propellant comprising of 5 microm HMX. Since no work has been reported in open literature regarding replacement of RDX by HMX, the present studies were carried out.

Unreacted Hugoniots for porous and liquid explosives

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

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

1993-08-01

Numerous authors have measured the Hugoniots of a variety of granular explosives pressed to different densities. Each explosive at each density was typically then treated as a unique material having its own Hugoniot. By combining methods used by Hayes, Sheffield and Mitchell (for describing the Hugoniot of HNS at various densities) with Hermann`s P-{alpha} model, 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. We discuss application of this method to several materials including HMX, PETN, TNT,more » and Tetryl, as well as HNS. We also show that the ``Universal Liquid Hugoniot`` can be used to calculate the unreacted Hugoniot for liquid explosives. With this method only the ambient pressure sound speed and density are needed to predict the Hugoniot. Applications presented include nitromethane and liquid TNT.« less

The Combustion of HMX. [burning rate at high pressures

NASA Technical Reports Server (NTRS)

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

1980-01-01

The burn rate of HMX was measured at high pressures (p more than 1000 psi). The self deflagration rate of HMX was determined from 1 atmosphere to 50,000 psi. The burning rate shows no significant slope breaks.

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

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.

Portable SERS Instrument for Explosives Monitoring

DTIC Science & Technology

2006-04-01

RDX, HMX, TNT, and TNB in UMCD groundwater…………………………………………………………………... 15 Figure 12. SERS (left) and colorimetry (right) methods set up on a...desk at ALAAP…... 20 Figure 13. SERS (left) and colorimetry (right) apparatus installed in the CPT truck…… 21 Figure 14. The Explosives Washout...for TNT in water……………………………... 29 Figure 17. Comparison of SERS and colorimetry field and laboratory results………….. 34 Figure 18. Comparison of SERS

Diffusion and drive-point sampling to detect ordnance-related compounds in shallow ground water beneath Snake Pond, Cape Cod, Massachusetts, 2001-02

USGS Publications Warehouse

LeBlanc, Denis R.

2003-01-01

Diffusion samplers and temporary drive points were used to test for ordnance-related compounds in ground water discharging to Snake Pond near Camp Edwards at the Massachusetts Military Reservation, Cape Cod, MA. The contamination resulted from artillery use and weapons testing at various ranges upgradient of the pond.The diffusion samplers were constructed with a high-grade cellulose membrane that allowed diffusion of explosive compounds, such as RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) and HMX (Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), into deionized water inside the samplers. Laboratory tests confirmed that the cellulose membrane was permeable to RDX and HMX. One transect of 22 diffusion samplers was installed and retrieved in August-September 2001, and 12 transects with a total of 108 samplers were installed and retrieved in September-October 2001. The diffusion samplers were buried about 0.5 feet into the pond-bottom sediments by scuba divers and allowed to equilibrate with the ground water beneath the pond bottom for 13 to 27 days before retrieval. Water samples were collected from temporary well points driven about 2-4 feet into the pond bottom at 21 sites in December 2001 and March 2002 for analysis of explosives and perchlorate to confirm the diffusion-sampling results. The water samples from the diffusion samplers exhibited numerous chromatographic peaks, but evaluation of the photo-diode-array spectra indicated that most of the peaks did not represent the target compounds. The peaks probably are associated with natural organic compounds present in the soft, organically enriched pond-bottom sediments. The presence of four explosive compounds at five widely spaced sites was confirmed by the photo-diode-array analysis, but the compounds are not generally found in contaminated ground water near the ranges. No explosives were detected in water samples obtained from the drive points. Perchlorate was detected at less than 1 microgram per liter in two drive-point samples collected at the same site on two dates about 3 months apart. The source of the perchlorate in the samples could not be related directly to other contamination from Camp Edwards with the available information. The results from the diffusion and drive-point sampling do not indicate an area of ground-water discharge with concentrations of the ordnance-related compounds that are sufficiently elevated to be detected by these sampling methods. The diffusion and drive-point sampling data cannot be interpreted further without additional information concerning the pattern of ground-water flow at Snake Pond and the distributions of RDX, HMX, and perchlorate in ground water in the aquifer near the pond.

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

The role and importance of porosity in the deflagration rates of HMX-based materials

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

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

The deflagration behavior of thermally damaged HMX-based materials will be discussed. Strands of material were burned at pressures ranging from 10-300 MPa using the LLNL high pressure strand burner. Strands were heated in-situ and burned while still hot; temperatures range from 90-200 C and were chosen in order to allow for thermal damage of the material without significant decomposition of the HMX. The results indicate that multiple variables affect the burn rate but the most important are the polymorph of HMX and the nature and thermal stability of the non-HE portion of the material. Characterization of the strands indicate thatmore » the thermal soak produces significant porosity and permeability in the sample allowing for significantly faster burning due to the increased surface area and new pathways for flame spread into the material. Specifically, the deflagration rates of heated PBXN-9, LX-10, and PBX-9501 will be discussed and compared.« less

Characterization of hypervelocity metal fragments for explosive initiation

DOE PAGES

Yeager, John D.; Bowden, Patrick R.; Guildenbecher, Daniel R.; ...

2017-07-17

The fragment impact response of two plastic-bonded explosive (PBX) formulations was studied using explosively driven aluminum fragments. A generic aluminum-capped detonator generated sub-mm aluminum particles moving at hypersonic velocities. The ability of these fragments to initiate reaction or otherwise damage two PBX materials was assessed using go/no-go experiments at standoff distances of up to 160 mm. Lower density PBX 9407 (RDX-based) was initiable at up to 115 mm, while higher density PBX 9501 (HMX-based) was only initiable at up to 6 mm. Several techniques were used to characterize the size, distribution, and velocity of the particles. Witness plate materials, includingmore » copper and polycarbonate, and backlit high speed video were used to characterize the distribution of particles, finding that the aluminum cap did not fragment homogeneously but rather with larger particles in a ring surrounding finer particles. Finally, precise digital holography experiments were conducted to measure the three-dimensional shape and size of the fastest-moving fragments, which ranged between 100 and 700 μm and traveled between 2.2 and 3.2 km/s. Crucially, these experiments showed variability in the fragmentation in terms of the number of fragments at the leading edge of the fragment field, indicating that both single and multiple shock impacts could be imparted to the target material. As a result, these types of data are critical for safety experiments and hydrocode simulations to quantify shock-to-detonation transition mechanisms and the associated risk-margins for these materials.« less

Characterization of hypervelocity metal fragments for explosive initiation

NASA Astrophysics Data System (ADS)

Yeager, John D.; Bowden, Patrick R.; Guildenbecher, Daniel R.; Olles, Joseph D.

2017-07-01

The fragment impact response of two plastic-bonded explosive (PBX) formulations was studied using explosively driven aluminum fragments. A generic aluminum-capped detonator generated sub-mm aluminum particles moving at hypersonic velocities. The ability of these fragments to initiate reaction or otherwise damage two PBX materials was assessed using go/no-go experiments at standoff distances of up to 160 mm. Lower density PBX 9407 (RDX-based) was initiable at up to 115 mm, while higher density PBX 9501 (HMX-based) was only initiable at up to 6 mm. Several techniques were used to characterize the size, distribution, and velocity of the particles. Witness plate materials, including copper and polycarbonate, and backlit high speed video were used to characterize the distribution of particles, finding that the aluminum cap did not fragment homogeneously but rather with larger particles in a ring surrounding finer particles. Finally, precise digital holography experiments were conducted to measure the three-dimensional shape and size of the fastest-moving fragments, which ranged between 100 and 700 μm and traveled between 2.2 and 3.2 km/s. Crucially, these experiments showed variability in the fragmentation in terms of the number of fragments at the leading edge of the fragment field, indicating that both single and multiple shock impacts could be imparted to the target material. These types of data are critical for safety experiments and hydrocode simulations to quantify shock-to-detonation transition mechanisms and the associated risk-margins for these materials.

Increasing Fe0-mediated HMX destruction in highly contaminated soil with didecyldimethylammonium bromide surfactant.

PubMed

Park, Jeong; Comfort, Steve D; Shea, Patrick J; Kim, Jong Sung

2005-12-15

Mixtures of energetic compounds pose a remediation problem for munitions-contaminated soil. Although treatment with zerovalent iron (Fe0) can be effective, RDX and TNT are more readily destroyed than HMX. Adding didecyldimethylammonium bromide (didecyl) at 2% w/v with 3% (w/v) Fe0 to a 20% slurry of Los Alamos National Laboratory soil containing solid-phase HMX (45 000 mg/kg) resulted in >80% destruction within 6 days. Because the HMX concentration did not increase in solution and the didecyl equilibrium concentration was well below the critical micelle concentration, we conclude thatthe solution primarily contained didecyl monomers. The adsorption isotherm for didecyl on iron is consistent with electrostatic adsorption of monomers and some hydrophobic partitioning at low equilibrium concentrations. Fe0 pretreated with didecyl was superior to Fe0 alone or mixed with didecyl in removing HMX from solution, but it was less effective than Fe0 + didecyl when solid-phase HMX was present. Reseeding HMX to mimic dissolution indicated an initial high reactivity of didecyl-pretreated Fe0, but the reaction slowed with each HMX addition. In contrast, reaction rates were lower but reactivity was maintained when Fe0 and didecyl were added together and didecyl was included in fresh HMX solutions. Destruction of solid-phase HMX requires low didecyl concentrations in solution so that hydrophobic patches are maintained on the iron surface.

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.

Small-scale Detonation Velocity Measurement of Select CL-20 Cocrystals

NASA Astrophysics Data System (ADS)

Vuppuluri, Vasant; Gunduz, I. Emre; Son, Steven F.

2017-06-01

The challenge of developing novel energetic materials makes cocrystallization using existing energetic molecules useful. Cocrystallization of CL-20 with other high explosives such as HMX has been demonstrated previously to yield novel energetic materials and may have favorable detonation performance. However, detonation performance characterization of these cocrystals is challenging due to limited availability of material. Also, the contribution of bonding energy between coformers contained within the cocrystal is not well-understood. We present the comparison of steady detonation velocities of CL-20 cocrystals to their corresponding physical mixtures using microwave interferometry. With less than 1.5 g of the cocrystal material contained within 6.52 mm diameter charges, shot-to-shot variation in detonation velocity of only about 100 m/s are achievable with this technique. This variation is adequate to resolve relatively small differences between physical mixed explosive molecules and cocrystals.

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).

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.

A general framework for numerical simulation of improvised explosive device (IED)-detection scenarios using density functional theory (DFT) and terahertz (THz) spectra.

PubMed

Shabaev, Andrew; Lambrakos, Samuel G; Bernstein, Noam; Jacobs, Verne L; Finkenstadt, Daniel

2011-04-01

We have developed a general framework for numerical simulation of various types of scenarios that can occur for the detection of improvised explosive devices (IEDs) through the use of excitation using incident electromagnetic waves. A central component model of this framework is an S-matrix representation of a multilayered composite material system. Each layer of the system is characterized by an average thickness and an effective electric permittivity function. The outputs of this component are the reflectivity and the transmissivity as functions of frequency and angle of the incident electromagnetic wave. The input of the component is a parameterized analytic-function representation of the electric permittivity as a function of frequency, which is provided by another component model of the framework. The permittivity function is constructed by fitting response spectra calculated using density functional theory (DFT) and parameter adjustment according to any additional information that may be available, e.g., experimentally measured spectra or theory-based assumptions concerning spectral features. A prototype simulation is described that considers response characteristics for THz excitation of the high explosive β-HMX. This prototype simulation includes a description of a procedure for calculating response spectra using DFT as input to the Smatrix model. For this purpose, the DFT software NRLMOL was adopted. © 2011 Society for Applied Spectroscopy

Electronic tongue for nitro and peroxide explosive sensing.

PubMed

González-Calabuig, Andreu; Cetó, Xavier; Del Valle, Manel

2016-06-01

This work reports the application of a voltammetric electronic tongue (ET) towards the simultaneous determination of both nitro-containing and peroxide-based explosive compounds, two families that represent the vast majority of compounds employed either in commercial mixtures or in improvised explosive devices. The multielectrode array was formed by graphite, gold and platinum electrodes, which exhibited marked mix-responses towards the compounds examined; namely, 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), pentaerythritol tetranitrate (PETN), 2,4,6-trinitrotoluene (TNT), N-methyl-N,2,4,6-tetranitroaniline (Tetryl) and triacetone triperoxide (TATP). Departure information was the set of voltammograms, which were first analyzed by means of principal component analysis (PCA) allowing the discrimination of the different individual compounds, while artificial neural networks (ANNs) were used for the resolution and individual quantification of some of their mixtures (total normalized root mean square error for the external test set of 0.108 and correlation of the obtained vs. expected concentrations comparison graphs r>0.929). Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of Temperature Profile on Reaction Violence in Heated, Self-Ignited, PBX-9501

NASA Astrophysics Data System (ADS)

Asay, Blaine; Dickson, Peter; Henson, Bryan; Smilowitz, Laura; Tellier, Larry

2001-06-01

Historically, the location of ignition in heated explosives has been implicated in the violence of subsequent reactions. This is based on the observation that typically, when an explosive is heated quickly, ignition occurs at the surface, leading to premature failure of confinement, a precipitous drop in pressure, and failure of the reaction. During slow heating, reaction usually occurs near the center of the charge, and more violent reactions are observed. Many safety protocols use these global results in determining safety envelopes and procedures. We have conducted instrumented experiments with cylindrical symmetry and precise thermal boundary conditions which have shown that the temperature profile in the explosive, along with the time spent at critical temperatures, and not the location of ignition, are responsible for the level of violence observed. Microwave interferometry was used to measure case expansion velocities and reaction violence. We are using the data in a companion study to develop better kinetic models for HMX and PBX 9501. Additionally, the spatially- and temporally-resolved temperature data are being made available for those who would like to use them.

Vibrational Energy in Molecules and Nanoparticles: Applications to Energetic Materials

DTIC Science & Technology

2009-01-30

of vibrational energy in a polyatomic molecule, nitromethane . Work on water and amino acids partially supported by AFOSR are developmental in nature...have characterized the surface vibrations of HMX explosive and their interaction with polymer binders. We have introduced a major improvement in SFG...Vibrational energy in nitromethane and benzene E. Time resolved spectroscopy of chemistry in flash-heated nanoenergetic materials F. Complete

Long-Wave Infrared (LWIR) Molecular Laser-Induced Breakdown Spectroscopy (LIBS) Emissions of Thin Solid Explosive Powder Films Deposited on Aluminum Substrates.

PubMed

Yang, Clayton S-C; Jin, Feng; Trivedi, Sudhir B; Brown, Ei E; Hommerich, Uwe; Tripathi, Ashish; Samuels, Alan C

2017-04-01

Thin solid films made of high nitro (NO 2 )/nitrate (NO 3 ) content explosives were deposited on sand-blasted aluminum substrates and then studied using a mercury-cadmium-telluride (MCT) linear array detection system that is capable of rapidly capturing a broad spectrum of atomic and molecular laser-induced breakdown spectroscopy (LIBS) emissions in the long-wave infrared region (LWIR; ∼5.6-10 µm). Despite the similarities of their chemical compositions and structures, thin films of three commonly used explosives (RDX, HMX, and PETN) studied in this work can be rapidly identified in the ambient air by their molecular LIBS emission signatures in the LWIR region. A preliminary assessment of the detection limit for a thin film of RDX on aluminum appears to be much lower than 60 µg/cm 2 . This LWIR LIBS setup is capable of rapidly probing and charactering samples without the need for elaborate sample preparation and also offers the possibility of a simultaneous ultraviolet visible and LWIR LIBS measurement.

Impact of surface energy on the shock properties of granular explosives.

PubMed

Bidault, X; Pineau, N

2018-01-21

This paper presents the first part of a two-fold molecular dynamics study of the impact of the granularity on the shock properties of high explosives. Recent experimental studies show that the granularity can have a substantial impact on the properties of detonation products {i.e., variations in the size distributions of detonation nanodiamonds [V. Pichot et al., Sci. Rep. 3, 2159 (2013)]}. These variations can have two origins: the surface energy, which is a priori enhanced from micro- to nano-scale, and the porosity induced by the granular structure. In this first report, we study the impact of the surface-energy contribution on the inert shock compression of TATB, TNT, α-RDX, and β-HMX nano-grains (triaminotrinitrobenzene, trinitrotoluene, hexogen and octogen, respectively). We compute the radius-dependent surface energy and combine it with an ab initio-based equation of state in order to obtain the resulting shock properties through the Rankine-Hugoniot relations. We find that the enhancement of the surface energy results in a moderate overheating under shock compression. This contribution is minor with respect to porosity, when compared to a simple macroscopic model. This result motivates further atomistic studies on the impact of nanoporosity networks on the shock properties.

Impact of surface energy on the shock properties of granular explosives

NASA Astrophysics Data System (ADS)

Bidault, X.; Pineau, N.

2018-01-01

This paper presents the first part of a two-fold molecular dynamics study of the impact of the granularity on the shock properties of high explosives. Recent experimental studies show that the granularity can have a substantial impact on the properties of detonation products {i.e., variations in the size distributions of detonation nanodiamonds [V. Pichot et al., Sci. Rep. 3, 2159 (2013)]}. These variations can have two origins: the surface energy, which is a priori enhanced from micro- to nano-scale, and the porosity induced by the granular structure. In this first report, we study the impact of the surface-energy contribution on the inert shock compression of TATB, TNT, α-RDX, and β-HMX nano-grains (triaminotrinitrobenzene, trinitrotoluene, hexogen and octogen, respectively). We compute the radius-dependent surface energy and combine it with an ab initio-based equation of state in order to obtain the resulting shock properties through the Rankine-Hugoniot relations. We find that the enhancement of the surface energy results in a moderate overheating under shock compression. This contribution is minor with respect to porosity, when compared to a simple macroscopic model. This result motivates further atomistic studies on the impact of nanoporosity networks on the shock properties.

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

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.

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.

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.

Remedial action suitability for the Cornhusker Army Ammunition Plant site

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

Nonavinakere, S.; Rappa, P. III

1995-12-31

Numerous Department of Defense (DOD) sites across the nation are contaminated with explosive wastes due to munitions production during World War II, Korean Conflict and Vietnam Conflict. Production activities included explosives manufacturing, loading, packing, assembling, machining, casting and curing. Contaminants often present at these sites include TNT, RDX, HMX, Tetryl 2,4-DNT, 2,6-DNT, 1,3-DNB, 1,3,5-TNB and nitrobenzene. The Cornhusker Army Ammunition Plant (CAAP) is one such DOD site that has been determined to be contaminated with explosives. The CAAP is located approximately 2 miles west of the City of Grand Island in Hall County, Nebraska. The plant produced artillery, bombs, boosters,more » supplementary charges and various other experimental explosives. The purpose of this paper is to provide an overview of the site background, review of the remedial alternatives evaluation process and rationale behind the selection of present remedial action.« less

Acute and chronic toxicity of the new explosive CL-20 to the earthworm (Eisenia andrei) exposed to amended natural soils.

PubMed

Robidoux, Pierre Yves; Sunahara, Geoffrey I; Savard, Kathleen; Berthelot, Yann; Dodard, Sabine; Martel, Majorie; Gong, Ping; Hawari, Jalal

2004-04-01

Monocyclic nitramine explosives such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are toxic to a number of ecological receptors, including earthworms. The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is a powerful explosive that may replace RDX and HMX, but its toxicity is not known. In the present study, the lethal and sublethal toxicities of CL-20 to the earthworm (Eisenia andrei) are evaluated. Two natural soils, a natural sandy forest soil (designated RacFor2002) taken in the Montreal area (QC, Canada; 20% organic carbon, pH 7.2) and a Sassafras sandy loam soil (SSL) taken on the property of U.S. Army Aberdeen Proving Ground (Edgewood, MD, USA; 0.33% organic carbon, pH 5.1), were used. Results showed that CL-20 was not lethal at concentrations of 125 mg/kg or less in the RacFor2002 soil but was lethal at concentrations of 90.7 mg/kg or greater in the SSL soil. Effects on the reproduction parameters such as a decrease in the number of juveniles after 56 d of exposure were observed at the initial CL-20 concentration of 1.6 mg/kg or greater in the RacFor2002 soil, compared to 0.2 mg/kg or greater in the SSL soil. Moreover, low concentrations of CL-20 in SSL soil (approximately 0.1 mg/kg; nominal concentration) were found to reduce the fertility of earthworms. Taken together, the present results show that CL-20 is a reproductive toxicant to the earthworm, with lethal effects at higher concentrations. Its toxicity can be decreased in soils favoring CL-20 adsorption (high organic carbon content).

Thermodynamics of HMX Polymorphs and HMX/RDX Mixtures

DOE PAGES

Myint, Philip C.; Nichols, Albert L.

2016-12-09

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

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

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.

Effect of viscoplasticity on ignition sensitivity of an HMX based PBX

NASA Astrophysics Data System (ADS)

Hardin, D. Barrett; Zhou, Min

2017-01-01

The effect of viscoplastic deformation of the energetic component (HMX) on the mechanical, thermal, and ignition responses of a two-phase (HMX and Estane) PBX is analyzed. PBX microstructures are subjected to impact loading from a constant velocity piston traveling at a rate of 50 to 200 m/s. The analysis uses a 2D cohesive finite element framework, the focus of which is to evaluate the relative ignition sensitivity of the materials to determine the effect of the viscoplasticity of HMX on the responses. To delineate this effect, two sets of calculations are carried out; one set assumes the HMX grains are fully hyperelastic, and the other set assumes the HMX grains are elastic-viscoplastic. Results show that PBX specimens with elastic-viscoplastic HMX grains experience lower average and peak temperature rises, and as a result, show lower numbers of hotspots. An ignition criterion based on a criticality threshold obtained from chemical kinetics is used to quantify the ignition behavior of the materials. The criterion focuses on hotspot size and temperature to determine if a hotspot will undergo thermal runaway. It is found that the viscoplasticity of HMX increases the minimum load duration, mean load duration, threshold loading velocity, and total input energy required for ignition.

Detection of Buried Mines and Unexploded Ordnance (UXO)

DTIC Science & Technology

2007-04-20

http://www.apopo.org/newsite/content/index.htm Ref-3 Block, M., R. Medina , and R. Albanese. Analysis of data determining whether European honey...News Service, September 30. http://www.purdue.edu/UNS/html4ever/2005/050930.Cooks.explosives.html Brannon, James. M., Patrick Deliman, Carlos Ruiz...James. M., Patrick Deliman, Carlos Ruiz, Cynthia Price, Mohammed Qasim, Jeffrey A. Gerald, Charolett Hayes, and Sally Yost. 1999. HMX adsorption and TNT

Ecological Risk Assessment of Perchlorate in Avian Species, Rodents, Amphibians and Fish

DTIC Science & Technology

2008-08-01

triazine (RDX) by Acetobacterium malicum strain HAAP-1 isolated from a methanogenic mixed culture. Current Microbiology 48:332-340. Army. 1985h. HMX...Microbial degradation of explosives: biotransformation versus mineralization. Applied Microbiology and Biotechnology 54:605-618. Hawari J...hexahydro-1, 3,5-trinitro-1,3,5-triazine (RDX) with municipal anaerobic sludge. Applied and Environmental Microbiology 66:2652-2657. Kudo, H., and Y

Analysis of explosives using corona discharge ionization combined with ion mobility spectrometry-mass spectrometry.

PubMed

Lee, Jihyeon; Park, Sehwan; Cho, Soo Gyeong; Goh, Eun Mee; Lee, Sungman; Koh, Sung-Suk; Kim, Jeongkwon

2014-03-01

Corona discharge ionization combined with ion mobility spectrometry-mass spectrometry (IMS-MS) was utilized to investigate five common explosives: cyclonite (RDX), trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), cyclotetramethylenetetranitramine (HMX), and 2,4-dinitrotoluene (DNT). The MS scan and the selected ion IMS analyses confirmed the identities of the existing ion species and their drift times. The ions observed were RDX·NO3(-), TNT(-), PETN·NO3(-), HMX·NO3(-), and DNT(-), with average drift times of 6.93 ms, 10.20 ms, 9.15 ms, 12.24 ms, 11.30 ms, and 8.89 ms, respectively. The reduced ion mobility values, determined from a standard curve calculated by linear regression of (normalized drift times)(-1) versus literature K0 values, were 2.09, 1.38, 1.55, 1.15, 1.25, and 1.60 cm(2) V(-1) s(-1), respectively. The detection limits were found to be 0.1 ng for RDX, 10 ng for TNT, 0.5 ng for PETN, 5.0 ng for HMX, and 10 ng for DNT. Simplified chromatograms were observed when nitrogen, as opposed to air, was used as the drift gas, but the detection limits were approximately 10 times worse (i.e., less sensitivity of detection). © 2013 Elsevier B.V. All rights reserved.

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.

Identification of HMX1 target genes: A predictive promoter model approach

PubMed Central

Boulling, Arnaud; Wicht, Linda

2013-01-01

Purpose A homozygous mutation in the H6 family homeobox 1 (HMX1) gene is responsible for a new oculoauricular defect leading to eye and auricular developmental abnormalities as well as early retinal degeneration (MIM 612109). However, the HMX1 pathway remains poorly understood, and in the first approach to better understand the pathway’s function, we sought to identify the target genes. Methods We developed a predictive promoter model (PPM) approach using a comparative transcriptomic analysis in the retina at P15 of a mouse model lacking functional Hmx1 (dmbo mouse) and its respective wild-type. This PPM was based on the hypothesis that HMX1 binding site (HMX1-BS) clusters should be more represented in promoters of HMX1 target genes. The most differentially expressed genes in the microarray experiment that contained HMX1-BS clusters were used to generate the PPM, which was then statistically validated. Finally, we developed two genome-wide target prediction methods: one that focused on conserving PPM features in human and mouse and one that was based on the co-occurrence of HMX1-BS pairs fitting the PPM, in human or in mouse, independently. Results The PPM construction revealed that sarcoglycan, gamma (35kDa dystrophin-associated glycoprotein) (Sgcg), teashirt zinc finger homeobox 2 (Tshz2), and solute carrier family 6 (neurotransmitter transporter, glycine) (Slc6a9) genes represented Hmx1 targets in the mouse retina at P15. Moreover, the genome-wide target prediction revealed that mouse genes belonging to the retinal axon guidance pathway were targeted by Hmx1. Expression of these three genes was experimentally validated using a quantitative reverse transcription PCR approach. The inhibitory activity of Hmx1 on Sgcg, as well as protein tyrosine phosphatase, receptor type, O (Ptpro) and Sema3f, two targets identified by the PPM, were validated with luciferase assay. Conclusions Gene expression analysis between wild-type and dmbo mice allowed us to develop a PPM that identified the first target genes of Hmx1. PMID:23946633

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 ear malformation, most cases of which remain unexplained. PMID:22736458

Determination of nitroaromatic and nitramine type energetic materials in synthetic and real mixtures by cyclic voltammetry.

PubMed

Üzer, Ayşem; Sağlam, Sener; Tekdemir, Yasemin; Ustamehmetoğlu, Belkıs; Sezer, Esma; Erçağ, Erol; Apak, Reşat

2013-10-15

Nitro-explosives contain reducible aromatic -NO2 groups or cyclic >N-NO2 bonds that may undergo reductive cleavage. This work reports the development of a cyclic voltammetric (CV) assay for nitro-aromatics (trinitrotoluene (TNT), dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)) using a glassy carbon electrode. This determination was first used for these energetic materials by resolving current responses of reduction potentials primarily due to one constituent but partly contributed by other constituents. Calibration curves of current intensity versus concentration were linear in the range of 30-120 mg L(-1) for RDX with a limit of detection (LOD) of 10.2 mg L(-1), 40-120 mg L(-1) for HMX (LOD=11.7 mg L(-1)), 40-120 mg L(-1) for TNT (LOD=11.2 mg L(-1)), and 40-140 mg L(-1) for DNT (LOD=10.8 mg L(-1)). Results showed that the CV method could provide a sensitive approach for the simultaneous determination of RDX and TNT in synthetic and real mixtures. Deconvolution of current contributions of mixtures at peak potentials of constituents was performed by multiple linear regression. The proposed method was successfully applied to the analysis of military explosives comp A5 and octol, and method validation was performed both against HPLC on a comp B (TNT+RDX) sample and against GC-MS on real post-blast residual samples containing both explosives. Copyright © 2013 Elsevier B.V. All rights reserved.

New directions in the science and technology of advanced sheet explosive formulations and the key energetic materials used in the processing of sheet explosives: Emerging trends.

PubMed

Talawar, M B; Jangid, S K; Nath, T; Sinha, R K; Asthana, S N

2015-12-30

This review presents the work carried out by the international community in the area of sheet explosive formulations and its applications in various systems. The sheet explosive is also named as PBXs and is a composite material in which solid explosive particles like RDX, HMX or PETN are dispersed in a polymeric matrix, forms a flexible material that can be rolled/cut into sheet form which can be applied to any complex contour. The designed sheet explosive must possess characteristic properties such as flexible, cuttable, water proof, easily initiable, and safe handling. The sheet explosives are being used for protecting tanks (ERA), light combat vehicle and futuristic infantry carrier vehicle from different attacking war heads etc. Besides, sheet explosives find wide applications in demolition of bridges, ships, cutting and metal cladding. This review also covers the aspects such as risks and hazard analysis during the processing of sheet explosive formulations, effect of ageing on sheet explosives, detection and analysis of sheet explosive ingredients and the R&D efforts of Indian researchers in the development of sheet explosive formulations. To the best of our knowledge, there has been no review article published in the literature in the area of sheet explosives. Copyright © 2015 Elsevier B.V. All rights reserved.

Task Order 7. Use of activated carbon for treatment of explosives-contaminated groundwater at the Milan Army Ammunition Plant (MAAP). Final report, Apr 89-May 90

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

Dennis, R.M.; Wujcik, W.J.; Lowe, W.L.

1990-05-01

The primary objective of this task was to determine the feasibility of using GAC to treat ground water contaminated by explosives at the Milan Army Ammunition Plant (MAAP) in Milan, Tennessee. Laboratory GAC isotherm studies were conducted and two carbons, Atochem, Inc. GAC 830 and Calgon Filtrasorb 300, were selected for further testing in continuous flow GAC columns. Three pilot scale continuous flow GAC column tests were performed at MAAP using the two carbons selected from the laboratory GAC isotherm studies. The results from the laboratory and pilot studies are presented in this report. They show that concurrent removal ofmore » explosives such as TNT, RDX, HMX, Tetryl, and nitrobenzenes from ground water using continuous flow granular activated carbon is feasible.« less

Acute occupational poisoning by octogen: first case report.

PubMed

Testud, François; Descotes, Jacques; Le Meur, Brigitte

2006-01-01

Octogen (HMX) is a polynitramine explosive closely related to hexogen, a known occupational toxin in military munitions plants. No acute human poisoning with octogen has ever been reported. A 28-year-old man with no history of epilepsy was admitted to the Emergency Department for seizures that had developed during the night after a full working day when he manually sieved large amounts of dry octogen. On admission, the clinical examination was normal and all other examinations could not substantiate the development of essential or secondary epilepsy. Elevated octogen concentrations were measured in his plasma, which confirmed occupational exposure to the explosive. The rarity of acute human poisonings by octogen is due to the infrequent use of this explosive and, more importantly, its very low oral bioavailability. However, acute poisoning can occur, but should be easily avoided by implementing adequate preventive measures.

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

Modeling The Shock Initiation of PBX-9501 in ALE3D

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

Leininger, L; Springer, H K; Mace, J

The SMIS (Specific Munitions Impact Scenario) experimental series performed at Los Alamos National Laboratory has determined the 3-dimensional shock initiation behavior of the HMX-based heterogeneous high explosive, PBX 9501. A series of finite element impact calculations have been performed in the ALE3D [1] hydrodynamic code and compared to the SMIS results to validate the code predictions. The SMIS tests use a powder gun to shoot scaled NATO standard fragments at a cylinder of PBX 9501, which has a PMMA case and a steel impact cover. The SMIS real-world shot scenario creates a unique test-bed because many of the fragments arrivemore » at the impact plate off-center and at an angle of impact. The goal of this model validation experiments is to demonstrate the predictive capability of the Tarver-Lee Ignition and Growth (I&G) reactive flow model [2] in this fully 3-dimensional regime of Shock to Detonation Transition (SDT). The 3-dimensional Arbitrary Lagrange Eulerian hydrodynamic model in ALE3D applies the Ignition and Growth (I&G) reactive flow model with PBX 9501 parameters derived from historical 1-dimensional experimental data. The model includes the off-center and angle of impact variations seen in the experiments. Qualitatively, the ALE3D I&G calculations accurately reproduce the 'Go/No-Go' threshold of the Shock to Detonation Transition (SDT) reaction in the explosive, as well as the case expansion recorded by a high-speed optical camera. Quantitatively, the calculations show good agreement with the shock time of arrival at internal and external diagnostic pins. This exercise demonstrates the utility of the Ignition and Growth model applied in a predictive fashion for the response of heterogeneous high explosives in the SDT regime.« less

JAGUAR Procedures for Detonation Behavior of Explosives Containing Boron

NASA Astrophysics Data System (ADS)

Stiel, Leonard; Baker, Ernest; Capellos, Christos

2009-06-01

The JAGUAR product library was expanded to include boron and boron containing products. Relationships of the Murnaghan form for molar volumes and derived properties were implemented in JAGUAR. Available Hugoniot and static volumertic data were analyzed to obtain constants of the Murnaghan relationship for solid boron, boron oxide, boron nitride, boron carbide, and boric acid. Experimental melting points were also utilized with optimization procedures to obtain the constants of the volumetric relationships for liquid boron and boron oxide. Detonation velocities for HMX - boron mixtures calculated with these relationships using JAGUAR are in closer agreement with literature values at high initial densities for inert (unreacted) boron than with the completely reacted metal. These results indicate that boron mixtures may exhibit eigenvalue detonation behavior, as observed by aluminized combined effects explosives, with higher detonation velocities than would be achieved by a classical Chapman-Jouguet detonation. Analyses of calorimetric measurements for RDX - boron mixtures indicate that at high boron contents the formation of side products, including boron nitride and boron carbide, inhibits the energy output obtained from the detonation of the formulation.

Physical and Chemical Microstructural Damage in Pressed CL-20 explosives

NASA Astrophysics Data System (ADS)

Demol, Gauthier; Sandusky, Harold W.

1999-06-01

Based upon its molecular composition, its structure, and its heat of formation, it was expected that CL-20 (hexanitrohexaazaisowurtzitane) would be more energetic and more sensitive than RDX and HMX. Reports of batch-to-batch variations in the sensitivity of neat CL-20 have led to its sensitivity being ranked in the range between the sensitivity of RDX and that of PETN. The ultimate utility of CL-20 as an ingredient in explosive and propellant formulations will depend upon the ability to understand the factors that are responsible for this batch-to-batch variability, and to control the sensitivity in formulations within acceptable limits. This work is a characterization of CL-20 at various stages in its life cycle. The evolution of damage from the initial neat crystals of CL-20 to the ready-to-use pressed pellets will be described. This characterization includes physical documentation using light microscopy and Scanning Electron Microscopy. Spatially resolved chemical analysis is also performed using Fourier-Transform Infrared Spectroscopy.

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.

Effect of Temperature Profile on Reaction Violence in Heated and Self-Ignited PBX 9501

NASA Astrophysics Data System (ADS)

Asay, Blaine; Dickson, Peter; Henson, Bryan; Smilowitz, Laura; Tellier, Larry

2002-07-01

Historically, the location of ignition in heated explosives has been implicated in the violence of subsequent reactions. This is based on the observation that typically, when an explosive is heated quickly, ignition occurs at the surface, leading to premature failure of confinement, a precipitous drop in pressure, and failure of the reaction. During slow heating, reaction usually occurs near the center of the charge, and more violent reactions are observed. Many safety protocols use these global results in determining safety envelopes and procedures. We are conducting instrumented experiments with cylindrical symmetry and precise thermal boundary conditions which are beginning to show that the temperature profile in the explosive, along with the time spent at critical temperatures, and not the location of ignition, are responsible for the level of violence observed. Microwave interferometry was used to measure case expansion velocities which can be considered a measure of reaction violence. We are using the data in a companion study to develop better kinetic models for HMX and PBX 9501. Additionally, the spatially- and temporally-resolved temperature data are being made available for those who would like to use them.

Using molecular recognition of beta-cyclodextrin to determine molecular weights of low-molecular-weight explosives by MALDI-TOF mass spectrometry.

PubMed

Zhang, Min; Shi, Zhen; Bai, Yinjuan; Gao, Yong; Hu, Rongzu; Zhao, Fenqi

2006-02-01

This study presents a novel method for determining the molecular weights of low molecular weight (MW) energetic compounds through their complexes of beta-cyclodextrin (beta-CD) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) in a mass range of 500 to 1700 Da, avoiding matrix interference. The MWs of one composite explosive composed of 2,6-DNT, TNT, and RDX, one propellant with unknown components, and 14 single-compound explosives (RDX, HMX, 3,4-DNT, 2,6-DNT, 2,5-DNT, 2,4,6-TNT, TNAZ, DNI, BTTN, NG, TO, NTO, NP, and 662) were measured. The molecular recognition and inclusion behavior of beta-CD to energetic materials (EMs) were investigated. The results show that (1) the established method is sensitive, simple, accurate, and suitable for determining the MWs of low-MW single-compound explosives and energetic components in composite explosives and propellants; and (2) beta-CD has good inclusion and modular recognition abilities to the above EMs.

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.

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

Perry, William L; Gunderson, Jake A; Dickson, Peter M

There has been a long history of interest in the decomposition kinetics of HMX and HMX-based formulations due to the widespread use of this explosive in high performance systems. The kinetics allow us to predict, or attempt to predict, the behavior of the explosive when subjected to thermal hazard scenarios that lead to ignition via impact, spark, friction or external heat. The latter, commonly referred to as 'cook off', has been widely studied and contemporary kinetic and transport models accurately predict time and location of ignition for simple geometries. However, there has been relatively little attention given to the problemmore » of localized ignition that results from the first three ignition sources of impact, spark and friction. The use of a zero-order single-rate expression describing the exothermic decomposition of explosives dates to the early work of Frank-Kamanetskii in the late 1930s and continued through the 60's and 70's. This expression provides very general qualitative insight, but cannot provide accurate spatial or timing details of slow cook off ignition. In the 70s, Catalano, et al., noted that single step kinetics would not accurately predict time to ignition in the one-dimensional time to explosion apparatus (ODTX). In the early 80s, Tarver and McGuire published their well-known three step kinetic expression that included an endothermic decomposition step. This scheme significantly improved the accuracy of ignition time prediction for the ODTX. However, the Tarver/McGuire model could not produce the internal temperature profiles observed in the small-scale radial experiments nor could it accurately predict the location of ignition. Those factors are suspected to significantly affect the post-ignition behavior and better models were needed. Brill, et al. noted that the enthalpy change due to the beta-delta crystal phase transition was similar to the assumed endothermic decomposition step in the Tarver/McGuire model. Henson, et al., deduced the kinetics and thermodynamics of the phase transition, providing Dickson, et al. with the information necessary to develop a four-step model that included a two-step nucleation and growth mechanism for the {beta}-{delta} phase transition. Initially, an irreversible scheme was proposed. That model accurately predicted the spatial and temporal cook off behavior of the small-scale radial experiment under slow heating conditions, but did not accurately capture the endothermic phase transition at a faster heating rate. The current version of the four-step model includes reversibility and accurately describes the small-scale radial experiment over a wide range of heating rates. We have observed impact-induced friction ignition of PBX 9501 with grit embedded between the explosive and the lower anvil surface. Observation was done using an infrared camera looking through the sapphire bottom anvil. Time to ignition and temperature-time behavior were recorded. The time to ignition was approximately 500 microseconds and the temperature was approximately 1000 K. The four step reversible kinetic scheme was previously validated for slow cook off scenarios. Our intention was to test the validity for significantly faster hot-spot processes, such as the impact-induced grit friction process studied here. We found the model predicted the ignition time within experimental error. There are caveats to consider when evaluating the agreement. The primary input to the model was friction work over an area computed by a stress analysis. The work rate itself, and the relative velocity of the grit and substrate both have a strong dependence on the initial position of the grit. Any errors in the analysis or the initial grit position would affect the model results. At this time, we do not know the sensitivity to these issues. However, the good agreement does suggest the four step kinetic scheme may have universal applicability for HMX systems.« less

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.

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.

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

Proceedings of the International Symposium on Detonation (9th) Held in Portland, Oregon on 28 August - 1 September 1989. Volume 2,

DTIC Science & Technology

1989-09-01

Excited Ram. in Spectra of Shock-Compressed Triaminotrinitrobenzene W. M. Trott and A, M,Renlund................................................. 153...Cochairmen: Paul Cooper and Hyla Napaden sky Physical and Chemical Nature of Hot Spots in TATB and HMX J, Sharma, B, C. Beard, J. Forbes, C. S. Coffey...Secondary Explosives A. M. Renlund, P. L. Stanton, and W . M. Trott ..... ................................. 1118 POSTER PAPERS Organizer and Chairman: Robert

Explosive Ordnance Disposal Proficiency Range and Multi-Purpose Contingency Training Area

DTIC Science & Technology

2007-04-01

1,3,5-trimethylene-2,4,6-trinitramine (RDX), cyclo-1,3,5,7- tetramethylene-2,4,6,8-tetra-nitramine [HMX], tetryl, and picric acid ; inorganic compounds...nitrogen oxides, which cause acid rain. Ir. addition, nitrogen oxide emissions contribute to the problem of global warming and also r;ombine with...of sUlfur oxide and nitrogen oxides, which cause acid ram. Ji:, addition, nitrogen oxide emis~ions contribute to the probl!llll of global warming

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 observed product. Pump-probe transients of the resonant A←X (0-0) transition of the NO molecule show a constant signal indicating these materials decompose faster than the time duration of the 226 nm laser light. Calculational results together with the experimental results indicate the energetic materials decompose through an internal conversion to very highly excited (˜5 eV of vibrational energy) vibrational states of their ground electronic state, while the model systems follow an excited electronic state decomposition pathway.

A micro-macro coupling approach of MD-SPH method for reactive energetic materials

NASA Astrophysics Data System (ADS)

Liu, Gui Rong; Wang, Guang Yu; Peng, Qing; De, Suvranu

2017-01-01

The simulation of reactive energetic materials has long been the interest of researchers because of the extensive applications of explosives. Much research has been done on the subject at macro scale in the past and research at micro scale has been initiated recently. Equation of state (EoS) is the relation between physical quantities (pressure, temperature, energy and volume) describing thermodynamic states of materials under a given set of conditions. It plays a significant role in determining the characteristics of energetic materials, including Chapman-Jouguet point and detonation velocity. Furthermore, EoS is the key to connect microscopic and macroscopic phenomenon when simulating the macro effects of an explosion. For instance, an ignition and growth model for high explosives uses two JWL EoSs, one for solid explosive and the other for gaseous products, which are often obtained from experiments that can be quite expensive and hazardous. Therefore, it is ideal to calculate the EoS of energetic materials through computational means. In this paper, the EoSs for both solid and gaseous products of β-HMX are calculated using molecular dynamics simulation with ReaxFF-d3, a reactive force field obtained from quantum mechanics. The microscopic simulation results are then compared with experiments and the continuum ignition and growth model. Good agreement is observed. Then, the EoSs obtained through micro-scale simulation is applied in a smoothed particle hydrodynamics (SPH) code to simulate the macro effects of explosions. Simulation results are compared with experiments.

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

Small-scale deflagration cylinder test with velocimetry wall-motion diagnostics

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

Hooks, Daniel E; Hill, Larry G; Pierce, Timothy H

Predicting the likelihood and effects of outcomes resultant from thermal initiation of explosives remains a significant challenge. For certain explosive formulations, the general outcome can be broadly predicted given knowledge of certain conditions. However, there remain unexplained violent events, and increased statistical understanding of outcomes as a function of many variables, or 'violence categorization,' is needed. Additionally, the development of an equation of state equivalent for deflagration would be very useful in predicting possible detailed event consequences using traditional hydrodynamic detonation moders. For violence categorization, it is desirable that testing be efficient, such that it is possible to statistically definemore » outcomes reliant on the processes of initiation of deflagration, steady state deflagration, and deflagration to detonation transitions. If the test simultaneously acquires information to inform models of violent deflagration events, overall predictive capabilities for event likelihood and consequence might improve remarkably. In this paper we describe an economical scaled deflagration cylinder test. The cyclotetramethylene tetranitramine (HMX) based explosive formu1lation PBX 9501 was tested using different temperature profiles in a thick-walled copper cylindrical confiner. This test is a scaled version of a recently demonstrated deflagration cylinder test, and is similar to several other thermal explosion tests. The primary difference is the passive velocimetry diagnostic, which enables measurement of confinement vessel wall velocities at failure, regardless of the timing and location of ignition.« less

Spark-safe low-voltage detonator

DOEpatents

Lieberman, Morton L.

1989-01-01

A column of explosive in a low-voltage detonator which makes it spark-safe ncludes an organic secondary explosive charge of HMX in the form of a thin pad disposed in a bore of a housing of the detonator in an ignition region of the explosive column and adjacent to an electrical ignition device at one end of the bore. The pad of secondary charge has an axial thickness within the range of twenty to thirty percent of its diameter. The explosive column also includes a first explosive charge of CP disposed in the housing bore in the ignition region of the explosive column next to the secondary charge pad on a side opposite from the ignition device. The first CP charge is loaded under sufficient pressure, 25 to 40 kpsi, to provide mechanical confinement of the pad of secondary charge and physical coupling thereof with the ignition device. The explosive column further includes a second explosive charge of CP disposed in the housing bore in a transition region of the explosive column next to the first CP charge on a side opposite from the pad of secondary charge. The second CP charge is loaded under sufficient pressure, about 10 kpsi, to allow occurrence of DDT. The first explosive CP charge has an axial thickness within the range of twenty to thirty percent of its diameter, whereas the second explosive CP charge contains a series of increments (nominally 4) each of which has an axial thickness-to-diameter ratio of one to two.

Spark-safe low-voltage detonator

DOEpatents

Lieberman, M.L.

1988-07-01

A column of explosive in a low-voltage detonator which makes it spark-safe includes an organic secondary explosive charge of HMX in the form of a thin pad disposed in a bore of a housing of the detonator in an ignition region of the explosive column and adjacent to an electrical ignition device at one end of the bore. The pad of secondary charge has an axial thickness within the range of twenty to thirty percent of its diameter. The explosive column also includes a first explosive charge of CP disposed in the housing bore in the ignition region of the explosive column next to the secondary charge pad on a side opposite from the ignition device. The first CP charge is loaded under sufficient pressure, 25 to 40 kpsi, to provide mechanical confinement of the pad of secondary charge and physical coupling thereof with the ignition device. The explosive column further includes a second explosive charge of CP disposed in the housing bore in a transition region of the explosive column next to the first CP charge on a side opposite from the pad of secondary charge. The second CP charge is loaded under sufficient pressure, about 10 kpsi, to allow occurrence of DDT. The first explosive CP charge has an axial thickness within the range of twenty to thirty percent of its diameter, whereas the second explosive CP charge contains a series of increments (nominally 4), each of which has an axial thickness-to-diameter ratio of one to two. 2 figs.

Optimization of biological and instrumental detection of explosives and ignitable liquid residues including canines, SPME/ITMS and GC/MSn

NASA Astrophysics Data System (ADS)

Furton, Kenneth G.; Harper, Ross J.; Perr, Jeannette M.; Almirall, Jose R.

2003-09-01

A comprehensive study and comparison is underway using biological detectors and instrumental methods for the rapid detection of ignitable liquid residues (ILR) and high explosives. Headspace solid phase microextraction (SPME) has been demonstrated to be an effective sampling method helping to identify active odor signature chemicals used by detector dogs to locate forensic specimens as well as a rapid pre-concentration technique prior to instrumental detection. Common ignitable liquids and common military and industrial explosives have been studied including trinitrotoluene, tetryl, RDX, HMX, EGDN, PETN and nitroglycerine. This study focuses on identifying volatile odor signature chemicals present, which can be used to enhance the level and reliability of detection of ILR and explosives by canines and instrumental methods. While most instrumental methods currently in use focus on particles and on parent organic compounds, which are often involatile, characteristic volatile organics are generally also present and can be exploited to enhance detection particularly for well-concealed devices. Specific examples include the volatile odor chemicals 2-ethyl-1-hexanol and cyclohexanone, which are readily available in the headspace of the high explosive composition C-4; whereas, the active chemical cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX) is not. The analysis and identification of these headspace 'fingerprint' organics is followed by double-blind dog trials of the individual components using certified teams in an attempt to isolate and understand the target compounds to which dogs are sensitive. Studies to compare commonly used training aids with the actual target explosive have also been undertaken to determine their suitability and effectiveness. The optimization of solid phase microextraction (SPME) combined with ion trap mobility spectrometry (ITMS) and gas chromatography/mass spectrometry/mass spectrometry (GC/MSn) is detailed including interface development and comparisons of limits of detection. These instrumental methods are being optimized in order to detect the same target odor chemicals used by detector dogs to reliably locate explosives and ignitable liquids.

Thermal behavior and compatibility study of dihydroxylammonium 3,4-dinitraminofurazan

NASA Astrophysics Data System (ADS)

Huang, Haifeng; Shi, Yameng; Yu, Yao; Yang, Jun

2018-04-01

A large number of nitramino-featured energetic salts have been reported and some of them show promising properties. Among them, the dihydroxylammonium 3,4-dinitraminofurazan (HADNAF) is easy to synthesize and shows high calculated detonation performances and acceptable thermal stability. The non-isothermal kinetics parameters of HADNAF including the apparent activation energy (E) and pre-exponential factor (A) of the exothermic decomposition reaction, and activation entropy (ΔS≠), activation enthalpy (ΔH≠), activation Gibbs free energy (ΔG≠) at TP0 of the reaction and the critical temperature of thermal explosion (Tb) were obtained by Kissinger's and Ozawa's method, respectively. Additionally, the compatibility of HADNAF with other materials (e.g. TNT, RDX, HMX, B, Mg) was tested by DSC method.

Numerical Simulation of Pre-heated Confined PBX Charge Under Low Velocity

NASA Astrophysics Data System (ADS)

Hu, Cai; Wu, Yanqing; Huang, Fenglei; Liu, Yan; Explosion; damage Team

2017-06-01

Impact sensitivity and thermal safety are very important for explosive safety usage.To investigate the effect of thermal softening on impact sensitivity of HMX-based PBX, a finite element model aiming at pre-heated confined PBX charge sbujected to bullets impact has been established. The predicted ignition starting area of the explosive charge was evaluated based on volume strain and equivalent strain contours. It showed that the ignition starting area moves towards the center of the explosives from the surface with increase of heating temperature. The threshold velocity does not increase monotonically with the pre-heating temperature increases. Instead, the threshold velocity rises till 360 m/s when the cook-off temperature is lower than 75°, then decreases the increased temperature. The results imply that our PBX has the lowest impact sensitivity at about 75°. These numerical results agree very well with the corresponding experiment results conducted by Dai et al. The influence of thermal softening on the impact sensitivity has been analyzed. As the strength decreases, more impact energy will be absorbed. At the same time, shear resistance ability will be weaken and volume compression work may play a more important role to ignition. China National Nature Science Foundation (11572045), ``Science Challenging Program'' (JCKY2016212A501), opening fund from Safety ammunition research and Development Center (RMC2015B03).

Desorption and Transformation of Nitroaromatic (TNT) and Nitramine (RDX and HMX) Explosive Residues on Detonated Pure Mineral Phases

DTIC Science & Technology

2011-11-01

surface area measurements were used to compare the pristine and detonated mineral surfaces and to determine if the extreme heat and/or pressures of...gas (N2) in a liquid nitrogen atmosphere (−194.8°C). Results from six relative pressure points were reduced to surface area values applying BET theory...include the minerals quartz, calcite, and dolomite . However, in some detonated Ottawa sand samples the highest intensity peak for calcite at 29° 2Θ

Performance characteristics of a laser initiated microdetonator

NASA Technical Reports Server (NTRS)

Yang, L. C.

1981-01-01

The test results of 320 units of a laser initiated microdetonator are summarized. The commercially fabricated units used a lead styphnate/lead azide/HMX (1 mg/13.5 mg) explosive train design contained in a miniature aluminum can that was capped with a glass-metal seal window. The test parameters were the laser energy, temperature, laser pulse duration, laser wavelength and nuclear radiation (5,000,000 rad of 1 MeV gamma rays). The performance parameters were the laser energy for ignition and the actuation response time.

Design of New Bridge-Ring Energetic Compounds Obtained by Diels-Alder Reactions of Tetranitroethylene Dienophile.

PubMed

He, Piao; Mei, Hao-Zheng; Wu, Le; Yang, Jun-Qing; Zhang, Jian-Guo; Cohen, Adva; Gozin, Michael

2018-03-29

The density functional theory method was employed to calculate three-dimensional structures for a series of novel explosophores. The design of new molecules (DA1-DA12) was based on the bridge-ring structures that could be formed via Diels-Alder (DA) reaction of selected nitrogen-rich dienes and tetranitroethylene dienophile. The feasibility of the proposed DA reactions was predicted on the basis of the molecular orbital theory. The strong interactions between the HOMO of dienes, with electron-donating groups (Diene2, Diene6, and Diene8), and the LUMO of tetranitroethylene dienophile suggested thermodynamically favorable formation of the desired DA reaction products. In addition to molecular structures of the explored DA compounds, their physicochemical and energetic properties were also calculated in detail. Due to compact bridge-ring structures, new energetic molecules have highly positive heats of formation (up to 1124.90 kJ·mol -1 ) and high densities (up to 2.04 g·cm -3 ). Also, as a result of all-right ratios of nitrogen and oxygen, most of the new compounds possess high detonation velocities (8.28-10.02 km·s -1 ) and high detonation pressures (30.87-47.83 GPa). Energetic compounds DA1, DA4, and DA12 exhibit a superior detonation performance over widely used HMX explosive, and DA5, DA7, and DA10 could be comparable to the state-of-the-art CL-20 and ONC explosives. Our proposed designs and synthetic methodology should provide a platform for the development of novel energetic materials with superior performance.

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

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, and morphology prediction of cocrystal.

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.

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

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

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

Yeager, John D.; Bowden, Patrick R.; Guildenbecher, Daniel R.

The fragment impact response of two plastic-bonded explosive (PBX) formulations was studied using explosively driven aluminum fragments. A generic aluminum-capped detonator generated sub-mm aluminum particles moving at hypersonic velocities. The ability of these fragments to initiate reaction or otherwise damage two PBX materials was assessed using go/no-go experiments at standoff distances of up to 160 mm. Lower density PBX 9407 (RDX-based) was initiable at up to 115 mm, while higher density PBX 9501 (HMX-based) was only initiable at up to 6 mm. Several techniques were used to characterize the size, distribution, and velocity of the particles. Witness plate materials, includingmore » copper and polycarbonate, and backlit high speed video were used to characterize the distribution of particles, finding that the aluminum cap did not fragment homogeneously but rather with larger particles in a ring surrounding finer particles. Finally, precise digital holography experiments were conducted to measure the three-dimensional shape and size of the fastest-moving fragments, which ranged between 100 and 700 μm and traveled between 2.2 and 3.2 km/s. Crucially, these experiments showed variability in the fragmentation in terms of the number of fragments at the leading edge of the fragment field, indicating that both single and multiple shock impacts could be imparted to the target material. As a result, these types of data are critical for safety experiments and hydrocode simulations to quantify shock-to-detonation transition mechanisms and the associated risk-margins for these materials.« less

Superfund record of decision (EPA Region 7): Cornhusker Army Ammunition Plant, Operable Unit 1, Hall County, Grand Island, NE, September 29, 1994

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

NONE

1995-04-01

The decision document presents the selected interim remedial action for the groundwater operable unit at the Cornhusker Army Ammunition Plant (CAAP). Operable Unit One encompasses the explosives groundwater plume(s), both on-post and off-post. Explosives of concern in the contaminant plume include RDX, TNT, HMX, and their decomposition products. The objective of the interim action is to contain the plume and prevent further migration of contaminants, and does not encompass full restoration of the plume of contaminated groundwater. The recommended alternatives provide an approach to containing and removing contaminant mass from the groundwater plume. This approach will control further migration ofmore » the plume and reduce the levels of the contamination in groundwater.« less

Non-Newtonian behavior observed via dynamic rheology for various particle types in energetic materials and simulant composites

NASA Astrophysics Data System (ADS)

Choi, Jong Han; Lee, Sangmook; Lee, Jae Wook

2017-02-01

The rheological properties of polymer composites highly filled with different filler materials were examined using a stress-controlled rheometer with a parallel-plate configuration, for particle characterization of the filler materials in plastic (polymer) bonded explosive (PBX). Ethylene vinyl acetate (EVA) with dioctyl adipate (DOA) was used as the matrix phase, which was shown to exhibit Newtonian-like behavior. The dispersed phase consisted of one of two energetic materials, i.e., explosive cyclotrimethylene trinitramine (RDX) or cyclotetramethylene tetranitramine (HMX), or a simulant (Dechlorane) in a bimodal size distribution. Before the test, preshearing was conducted to identify the initial condition of each sample. All examined filled polymer specimens exhibited yield stress and shear-thinning behavior over the investigated frequency range. The complex viscosity dependence on the dynamic oscillation frequency was also fitted using an appropriate rheological model, suggesting the model parameters. Furthermore, the temperature dependency of the different filler particle types was determined for different filler volume fractions. These comparative studies revealed the influence of the particle characteristics on the rheological properties of the filled polymer.

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.

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.

In Situ Imaging during Compression of Plastic Bonded Explosives for Damage Modeling

NASA Astrophysics Data System (ADS)

Yeager, John; Manner, Virginia; Patterson, Brian; Walters, David; Cordes, Nikolaus; Henderson, Kevin; Tappan, Bryce; Luscher, Darby

2017-06-01

The microstructure of plastic bonded explosives (PBXs) is known to influence behavior during insults such as deformation, heating or initiation to detonation. Obtaining three-dimensional microstructural data can be difficult due in part to fragility of the material and small feature size. X-ray computed tomography (CT) is an ideal characterization technique but the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient x-ray contrast to differentiate between the components. Here, we have formulated several PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7- tetrazocine (HMX) crystals and low-density binder systems. The full three-dimensional microstructure of these samples has been characterized using microscale CT during uniaxial mechanical compression in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and material flow. Additionally, the segmented, 3D images were meshed for finite element simulation. Initial results of the mesoscale modeling exhibit qualitatively similar delamination. Los Alamos National Laboratory - LDRD.

Influence of 2,4,6-trinitrotoluene (TNT) concentration on the degradation of TNT in explosive-contaminated soils by the white rot fungus Phanerochaete chrysosporium.

PubMed Central

Spiker, J K; Crawford, D L; Crawford, R L

1992-01-01

The ability of Phanerochaete chrysosporium to bioremediate TNT (2,4,6-trinitrotoluene) in a soil containing 12,000 ppm of TNT and the explosives RDX (hexahydro-1,3,5-trinitro-1,3,5- triazine; 3,000 ppm) and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine; 300 ppm) was investigated. The fungus did not grow in malt extract broth containing more than 0.02% (wt/vol; 24 ppm of TNT) soil. Pure TNT or explosives extracted from the soil were degraded by P. chrysosporium spore-inoculated cultures at TNT concentrations of up to 20 ppm. Mycelium-inoculated cultures degraded 100 ppm of TNT, but further growth was inhibited above 20 ppm. In malt extract broth, spore-inoculated cultures mineralized 10% of added [14C]TNT (5 ppm) in 27 days at 37 degrees C. No mineralization occurred during [14C]TNT biotransformation by mycelium-inoculated cultures, although the TNT was transformed. PMID:1444437

Continuous engineering of nano-cocrystals for medical and energetic applications.

PubMed

Spitzer, D; Risse, B; Schnell, F; Pichot, V; Klaumünzer, M; Schaefer, M R

2014-10-10

Cocrystals, solid mixtures of different molecules on molecular scale, are supposed to be tailor made materials with improved employability compared to their pristine individual components in domains such as medicine and explosives. In medicine, cocrystals are obtained by crystallization of active pharmaceutical ingredients with precisely chosen coformers to design medicaments that demonstrate enhanced stability, high solubility, and therefore high bioavailability and optimized drug up-take. Nanoscaling may further advance these characteristica compared to their micronsized counterparts - because of a larger surface to volume ratio of nanoparticles. In the field of energetic materials, cocrystals offer the opportunity to design smart explosives, combining high reactivity with significantly reduced sensitivity, nowadays essential for a safe manipulation and handling. Furthermore, cocrystals are used in ferroelectrics, non-linear material response and electronic organics. However, state of the art batch processes produce low volume of cocrystals of variable quality and only have produced micronsized cocrystals so far, no nano-cocrystals. Here we demonstrate the continuous preparation of pharmaceutical and energetic micro- and nano-cocrystals using the Spray Flash Evaporation process. Our laboratory scale pilot plant continuously prepared up to 8 grams per hour of Caffeine/Oxalic acid 2:1, Caffeine/Glutaric acid 1:1, TNT/CL-20 1:1 and HMX/Cl-20 1:2 nano- and submicronsized cocrystals.

Continuous engineering of nano-cocrystals for medical and energetic applications

NASA Astrophysics Data System (ADS)

Spitzer, D.; Risse, B.; Schnell, F.; Pichot, V.; Klaumünzer, M.; Schaefer, M. R.

2014-10-01

Cocrystals, solid mixtures of different molecules on molecular scale, are supposed to be tailor made materials with improved employability compared to their pristine individual components in domains such as medicine and explosives. In medicine, cocrystals are obtained by crystallization of active pharmaceutical ingredients with precisely chosen coformers to design medicaments that demonstrate enhanced stability, high solubility, and therefore high bioavailability and optimized drug up-take. Nanoscaling may further advance these characteristica compared to their micronsized counterparts - because of a larger surface to volume ratio of nanoparticles. In the field of energetic materials, cocrystals offer the opportunity to design smart explosives, combining high reactivity with significantly reduced sensitivity, nowadays essential for a safe manipulation and handling. Furthermore, cocrystals are used in ferroelectrics, non-linear material response and electronic organics. However, state of the art batch processes produce low volume of cocrystals of variable quality and only have produced micronsized cocrystals so far, no nano-cocrystals. Here we demonstrate the continuous preparation of pharmaceutical and energetic micro- and nano-cocrystals using the Spray Flash Evaporation process. Our laboratory scale pilot plant continuously prepared up to 8 grams per hour of Caffeine/Oxalic acid 2:1, Caffeine/Glutaric acid 1:1, TNT/CL-20 1:1 and HMX/Cl-20 1:2 nano- and submicronsized cocrystals.

Continuous engineering of nano-cocrystals for medical and energetic applications

PubMed Central

Spitzer, D.; Risse, B.; Schnell, F.; Pichot, V.; Klaumünzer, M.; Schaefer, M. R.

2014-01-01

Cocrystals, solid mixtures of different molecules on molecular scale, are supposed to be tailor made materials with improved employability compared to their pristine individual components in domains such as medicine and explosives. In medicine, cocrystals are obtained by crystallization of active pharmaceutical ingredients with precisely chosen coformers to design medicaments that demonstrate enhanced stability, high solubility, and therefore high bioavailability and optimized drug up-take. Nanoscaling may further advance these characteristica compared to their micronsized counterparts – because of a larger surface to volume ratio of nanoparticles. In the field of energetic materials, cocrystals offer the opportunity to design smart explosives, combining high reactivity with significantly reduced sensitivity, nowadays essential for a safe manipulation and handling. Furthermore, cocrystals are used in ferroelectrics, non-linear material response and electronic organics. However, state of the art batch processes produce low volume of cocrystals of variable quality and only have produced micronsized cocrystals so far, no nano-cocrystals. Here we demonstrate the continuous preparation of pharmaceutical and energetic micro- and nano-cocrystals using the Spray Flash Evaporation process. Our laboratory scale pilot plant continuously prepared up to 8 grams per hour of Caffeine/Oxalic acid 2:1, Caffeine/Glutaric acid 1:1, TNT/CL-20 1:1 and HMX/Cl-20 1:2 nano- and submicronsized cocrystals. PMID:25300652

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

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

Modeling Three-Dimensional Shock Initiation of PBX 9501 in ALE3D

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

Leininger, L; Springer, H K; Mace, J

A recent SMIS (Specific Munitions Impact Scenario) experimental series performed at Los Alamos National Laboratory has provided 3-dimensional shock initiation behavior of the HMX-based heterogeneous high explosive, PBX 9501. A series of finite element impact calculations have been performed in the ALE3D [1] hydrodynamic code and compared to the SMIS results to validate and study code predictions. These SMIS tests used a powder gun to shoot scaled NATO standard fragments into a cylinder of PBX 9501, which has a PMMA case and a steel impact cover. This SMIS real-world shot scenario creates a unique test-bed because (1) SMIS tests facilitatemore » the investigation of 3D Shock to Detonation Transition (SDT) within the context of a considerable suite of diagnostics, and (2) many of the fragments arrive at the impact plate off-center and at an angle of impact. A particular goal of these model validation experiments is to demonstrate the predictive capability of the ALE3D implementation of the Tarver-Lee Ignition and Growth reactive flow model [2] within a fully 3-dimensional regime of SDT. The 3-dimensional Arbitrary Lagrange Eulerian (ALE) hydrodynamic model in ALE3D applies the Ignition and Growth (I&G) reactive flow model with PBX 9501 parameters derived from historical 1-dimensional experimental data. The model includes the off-center and angle of impact variations seen in the experiments. Qualitatively, the ALE3D I&G calculations reproduce observed 'Go/No-Go' 3D Shock to Detonation Transition (SDT) reaction in the explosive, as well as the case expansion recorded by a high-speed optical camera. Quantitatively, the calculations show good agreement with the shock time of arrival at internal and external diagnostic pins. This exercise demonstrates the utility of the Ignition and Growth model applied for the response of heterogeneous high explosives in the SDT regime.« less

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.

Collapse of elongated voids in porous energetic materials: Effects of void orientation and aspect ratio on initiation

NASA Astrophysics Data System (ADS)

Rai, Nirmal Kumar; Schmidt, Martin J.; Udaykumar, H. S.

2017-04-01

The sensitivity of porous energetic materials depends on mesostructural heterogeneities such as voids, defects, cracks, and grain boundaries. The mesostructure of pressed explosives contains voids of arbitrary shapes including elongated voids of various orientations and aspect ratios. Mesoscale simulations to date have analyzed the effect of void morphology on the sensitivity of energetic materials for idealized shapes such as cylindrical, conical, and elliptical. This work analyzes the sensitivity behavior of elongated voids in an HMX matrix subject to shock loading. Simulations show that sensitivity of elongated voids depends strongly on orientation as well as aspect ratio. Ranges of orientations and aspects ratios are identified that enhance or inhibit initiation. Insights obtained from single elongated void analyses are used to identify sensitive locations in an imaged mesostructure of a pressed explosive sample.

Development of a Molecularly Imprinted Polymer-Based Sensor for the Electrochemical Determination of Triacetone Triperoxide (TATP)

PubMed Central

Mamo, Samuel Kassahun; Gonzalez-Rodriguez, Jose

2014-01-01

The explosive triacetone triperoxide (TATP), which can be prepared from commercially readily available reagents following an easy synthetic procedure, is one of the most common components of improvised explosive devices (IEDs). Molecularly-imprinted polymer (MIP) electrochemical sensors have proved useful for the determination of different compounds in different matrices with the required sensitivity and selectivity. In this work, a highly sensitive and selective molecularly imprinted polymer with electrochemical capabilities for the determination of TATP has been developed. The molecular imprinting has been performed via electropolymerisation onto a glassy carbon electrode surface by cyclic voltammetry from a solution of pyrrole functional monomer, TATP template and LiClO4. Differential Pulse Voltammetry of TATP, with LiClO4 as supporting electrolyte, was performed in a potential range of −2.0 V to +1.0 V (vs. Ag/AgCl). Three-factor two-level factorial design was used to optimise the monomer concentration at 0.1 mol·L−1, template concentration at 100 mmol·L−1 and the number of cyclic voltammetry scan cycles to 10. The molecularly imprinted polymer-modified glassy carbon electrode demonstrated good performance at low concentrations for a linear range of 82–44,300 μg·L−1 and a correlation coefficient of r2 = 0.996. The limits of detection (LoD) and quantification (LoQ) achieved were 26.9 μg·L−1 and 81.6 μg·L−1, respectively. The sensor demonstrated very good repeatability with precision values (n = 6, expressed as %RSD) of 1.098% and 0.55% for 1108 and 2216 μg·L−1, respectively. It also proved selective for TATP in the presence of other explosive substances such as PETN, RDX, HMX, and TNT. PMID:25490589

Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3

DOE PAGES

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

2012-07-20

The vertical and adiabatic ionization potential (IP V and IP A) and vertical electron affinity (EA V) for six explosives (RDX, HMX, TNT, PETN, HMTD, and TATP) have been studied by ab initio computational methods. The IPV was calculated using MP2 and CBS-QB3 while the IP A was calculated with B3LYP, CAM-B3LYP, ω B97XD, B2PLYP, and MP2. RDX and TNT IP A’s were also reported using CBS -QB3. Excluding results by CBS-QB3, B3LYP and B2PLYPD provided superior and more consistent results for calculating the IP. The EA V were calculated using the same methods however B3LYP performed the worst inmore » this case with MP2 and B2PLYPD predicting values closest to those made by CBS-QB3, which was used a reference due to lacking experimental data. Basis set effects were evaluated using 6- 31+G(d,p), 6-311+G(d,p), and 6-311+(3df,2p) for both IP and EA. 6-31+G(d,p) gave satisfactory results for calculating both IP however 6-311+G(3df,2p) had improved results in calculating the EA. The four nitro containing compounds had exothermic reduction potentials while the peroxides were unfavorable. Additionally, it was seen that RDX, HMX, TATP and HMTD were unstable in their reduced forms. Results are aimed to assist detection and screening methods.« less

Detection and identification of substances using noisy THz signal

NASA Astrophysics Data System (ADS)

Trofimov, Vyacheslav A.; Zakharova, Irina G.; Zagursky, Dmitry Yu.; Varentsova, Svetlana A.

2017-05-01

We discuss an effective method for the detection and identification of substances using a high noisy THz signal. In order to model such a noisy signal, we add to the THz signal transmitted through a pure substance, a noisy THz signal obtained in real conditions at a long distance (more than 3.5 m) from the receiver in air. The insufficiency of the standard THz-TDS method is demonstrated. The method discussed in the paper is based on time-dependent integral correlation criteria calculated using spectral dynamics of medium response. A new type of the integral correlation criterion, which is less dependent on spectral characteristics of the noisy signal under investigation, is used for the substance identification. To demonstrate the possibilities of the integral correlation criteria in real experiment, they are applied for the identification of explosive HMX in the reflection mode. To explain the physical mechanism for the false absorption frequencies appearance in the signal we make a computer simulation using 1D Maxwell's equations and density matrix formalism. We propose also new method for the substance identification by using the THz pulse frequency up-conversion and discuss an application of the cascade mechanism of molecules high energy levels excitation for the substance identification.

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

Fluorescence-based sensing of 2,4,6-trinitrotoluene (TNT) using a multi-channeled poly(methyl methacrylate) (PMMA) microimmunosensor.

PubMed

Charles, Paul T; Adams, Andre A; Howell, Peter B; Trammell, Scott A; Deschamps, Jeffrey R; Kusterbeck, Anne W

2010-01-01

Fluorescence immunoassays employing monoclonal antibodies directed against the explosive 2,4,6-trinitrotoluene (TNT) were conducted in a multi-channel microimmunosensor. The multi-channel microimmunosensor was prepared in poly (methyl methacrylate) (PMMA) via hot embossing from a brass molding tool. The multi-channeled microfluidic device was sol-gel coated to generate a siloxane surface that provided a scaffold for antibody immobilization. AlexaFluor-cadaverine-trinitrobenzene (AlexaFluor-Cad-TNB) was used as the reporter molecule in a displacement immunoassay. The limit of detection was 1-10 ng/mL (ppb) with a linear dynamic range that covered three orders of magnitude. In addition, antibody crossreactivity was investigated using hexahydro-1,3,5-triazine (RDX), HMX, 2,4-dinitrotoluene (DNT), 4-nitrotoluene (4-NT) and 2-amino-4,6-DNT.

Fluorescence-based Sensing of 2,4,6-Trinitrotoluene (TNT) Using a Multi-channeled Poly(methyl methacrylate) (PMMA) Microimmunosensor

PubMed Central

Charles, Paul T.; Adams, Andre A.; Howell, Peter B.; Trammell, Scott A.; Deschamps, Jeffrey R.; Kusterbeck, Anne W.

2010-01-01

Fluorescence immunoassays employing monoclonal antibodies directed against the explosive 2,4,6-trinitrotoluene (TNT) were conducted in a multi-channel microimmunosensor. The multi-channel microimmunosensor was prepared in poly (methyl methacrylate) (PMMA) via hot embossing from a brass molding tool. The multi-channeled microfluidic device was sol-gel coated to generate a siloxane surface that provided a scaffold for antibody immobilization. AlexaFluor-cadaverine-trinitrobenzene (AlexaFluor-Cad-TNB) was used as the reporter molecule in a displacement immunoassay. The limit of detection was 1–10 ng/mL (ppb) with a linear dynamic range that covered three orders of magnitude. In addition, antibody crossreactivity was investigated using hexahydro-1,3,5-triazine (RDX), HMX, 2,4-dinitrotoluene (DNT), 4-nitrotoluene (4-NT) and 2-amino-4,6-DNT. PMID:22315573

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

A full scale hydrodynamic simulation of pyrotechnic combustion

NASA Astrophysics Data System (ADS)

Kim, Bohoon; Jang, Seung-Gyo; Yoh, Jack

2017-06-01

A full scale hydrodynamic simulation that requires an accurate reproduction of shock-induced detonation was conducted for design of an energetic component system. A series of small scale gap tests and detailed hydrodynamic simulations were used to validate the reactive flow model for predicting the shock propagation in a train configuration and to quantify the shock sensitivity of the energetic materials. The energetic component system is composed of four main components, namely a donor unit (HNS + HMX), a bulkhead (STS), an acceptor explosive (RDX), and a propellant (BKNO3) for gas generation. The pressurized gases generated from the burning propellant were purged into a 10 cc release chamber for study of the inherent oscillatory flow induced by the interferences between shock and rarefaction waves. The pressure fluctuations measured from experiment and calculation were investigated to further validate the peculiar peak at specific characteristic frequency (ωc = 8.3 kHz). In this paper, a step-by-step numerical description of detonation of high explosive components, deflagration of propellant component, and deformation of metal component is given in order to facilitate the proper implementation of the outlined formulation into a shock physics code for a full scale hydrodynamic simulation of the energetic component system.

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

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

A generalized crystal-cutting method for modeling arbitrarily oriented crystals in 3D periodic simulation cells with applications to crystal-crystal interfaces

NASA Astrophysics Data System (ADS)

Kroonblawd, Matthew P.; Mathew, Nithin; Jiang, Shan; Sewell, Thomas D.

2016-10-01

A Generalized Crystal-Cutting Method (GCCM) is developed that automates construction of three-dimensionally periodic simulation cells containing arbitrarily oriented single crystals and thin films, two-dimensionally (2D) infinite crystal-crystal homophase and heterophase interfaces, and nanostructures with intrinsic N-fold interfaces. The GCCM is based on a simple mathematical formalism that facilitates easy definition of constraints on cut crystal geometries. The method preserves the translational symmetry of all Bravais lattices and thus can be applied to any crystal described by such a lattice including complicated, low-symmetry molecular crystals. Implementations are presented with carefully articulated combinations of loop searches and constraints that drastically reduce computational complexity compared to simple loop searches. Orthorhombic representations of monoclinic and triclinic crystals found using the GCCM overcome some limitations in standard distributions of popular molecular dynamics software packages. Stability of grain boundaries in β-HMX was investigated using molecular dynamics and molecular statics simulations with 2D infinite crystal-crystal homophase interfaces created using the GCCM. The order of stabilities for the four grain boundaries studied is predicted to correlate with the relative prominence of particular crystal faces in lab-grown β-HMX crystals. We demonstrate how nanostructures can be constructed through simple constraints applied in the GCCM framework. Example GCCM constructions are shown that are relevant to some current problems in materials science, including shock sensitivity of explosives, layered electronic devices, and pharmaceuticals.

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.

Application of paper spray ionization for explosives analysis.

PubMed

Tsai, Chia-Wei; Tipple, Christopher A; Yost, Richard A

2017-10-15

A desired feature in the analysis of explosives is to decrease the time of the entire analysis procedure, including sampling. A recently utilized ambient ionization technique, paper spray ionization (PSI), provides the possibility of combining sampling and ionization. However, an interesting phenomenon that occurs in generating negatively charged ions pose some challenges in applying PSI to explosives analysis. The goal of this work is to investigate the possible solutions for generating explosives ions in negative mode PSI. The analysis of 2,4,6-trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) was performed. Several solvent systems with different surface tensions and additives were compared to determine their effect on the ionization of explosives. The solvents tested include tert-butanol, isopropanol, methanol, and acetonitrile. The additives tested were carbon tetrachloride and ammonium nitrate. Of the solvents tested, isopropanol yielded the best results. In addition, adding ammonium nitrate to the isopropanol enhanced the analyte signal. Experimentally determined limits of detection (LODs) as low as 0.06 ng for PETN, on paper, were observed with isopropanol and the addition of 0.4 mM ammonium nitrate as the spray solution. In addition, the explosive components of two plastic explosive samples, Composition 4 and Semtex, were successfully analyzed via surface sampling when using the developed method. The analysis of explosives using PSI-MS in negative ion mode was achieved. The addition of ammonium nitrate to isopropanol, in general, enhanced the analyte signal and yielded better ionization stability. Real-world explosive samples were analyzed, which demonstrates one of the potential applications of PSI-MS analysis. Copyright © 2017 John Wiley & Sons, Ltd.

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.

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

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.

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.

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.

Transient processes in the combustion of nitramine propellants

NASA Technical Reports Server (NTRS)

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

1978-01-01

A transient combustion model of nitramine propellants is combined with an isentropic compression shock formation model to determine the role of nitramine propellant combustion in DDT, excluding effects associated with propellant structural properties or mechanical behavior. The model is derived to represent the closed pipe experiment that is widely used to characterize explosives, except that the combustible material is a monolithic charge rather than compressed powder. Computations reveal that the transient combustion process cannot by itself produce DDT by this model. Compressibility of the solid at high pressure is the key factor limiting pressure buildups created by the combustion. On the other hand, combustion mechanisms which promote pressure buildups are identified and related to propellant formulation variables. Additional combustion instability data for nitramine propellants are presented. Although measured combustion response continues to be low, more data are required to distinguish HMX and active binder component contributions. A design for a closed vessel apparatus for experimental studies of high pressure combustion is discussed.

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 of cyclic nitramines in water is sufficient to cause ring cleavage followed by spontaneous decomposition to form the final products.

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

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).

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, these mutant Hmx1 alleles represent the first mouse models of a recently-discovered Oculo-Auricular syndrome caused by mutation of the orthologous human gene. PMID:19379485

The evolution of solid density within a thermal explosion II. Dynamic proton radiography of cracking and solid consumption by burning

NASA Astrophysics Data System (ADS)

Smilowitz, L.; Henson, B. F.; Romero, J. J.; Asay, B. W.; Saunders, A.; Merrill, F. E.; Morris, C. L.; Kwiatkowski, K.; Grim, G.; Mariam, F.; Schwartz, C. L.; Hogan, G.; Nedrow, P.; Murray, M. M.; Thompson, T. N.; Espinoza, C.; Lewis, D.; Bainbridge, J.; McNeil, W.; Rightley, P.; Marr-Lyon, M.

2012-05-01

We report proton transmission images obtained subsequent to the laser assisted thermal ignition of a sample of PBX 9501 (a plastic bonded formulation of the explosive nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)). We describe the laser assisted thermal ignition technique as a means to synchronize a non-linear thermal ignition event while preserving the subsequent post-ignition behavior. We have obtained dynamic proton transmission images at two spatial magnifications and viewed both the radial and transverse axis of a solid cylindrical sample encased in aluminum. Images have been obtained with 3 to 15 μs temporal resolution and approximately 100 μm spatial resolution at the higher magnification. We observe case expansion from very early in the experiment, until case fragmentation. We observe spatially anisotropic features in the transmission which we attribute to cracking in the solid explosive, in agreement with previous measurements conducted on two dimensional samples with optical viewing. Digital analysis of the images also reveals spatially isotropic features which we attribute to the evolution of the loss of density by burning subsequent to thermal ignition.

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.

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)-

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.

Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

PubMed

Wang, XinJie; Wu, YanQing; Huang, FengLei

2017-01-05

A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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

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

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.

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

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

Comparison of the LLNL ALE3D and AKTS Thermal Safety Computer Codes for Calculating Times to Explosion in ODTX and STEX Thermal Cookoff Experiments

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

Wemhoff, A P; Burnham, A K

2006-04-05

Cross-comparison of the results of two computer codes for the same problem provides a mutual validation of their computational methods. This cross-validation exercise was performed for LLNL's ALE3D code and AKTS's Thermal Safety code, using the thermal ignition of HMX in two standard LLNL cookoff experiments: the One-Dimensional Time to Explosion (ODTX) test and the Scaled Thermal Explosion (STEX) test. The chemical kinetics model used in both codes was the extended Prout-Tompkins model, a relatively new addition to ALE3D. This model was applied using ALE3D's new pseudospecies feature. In addition, an advanced isoconversional kinetic approach was used in the AKTSmore » code. The mathematical constants in the Prout-Tompkins code were calibrated using DSC data from hermetically sealed vessels and the LLNL optimization code Kinetics05. The isoconversional kinetic parameters were optimized using the AKTS Thermokinetics code. We found that the Prout-Tompkins model calculations agree fairly well between the two codes, and the isoconversional kinetic model gives very similar results as the Prout-Tompkins model. We also found that an autocatalytic approach in the beta-delta phase transition model does affect the times to explosion for some conditions, especially STEX-like simulations at ramp rates above 100 C/hr, and further exploration of that effect is warranted.« less

Standoff detection of explosive molecules using nanosecond gated Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chung, Jin Hyuk; Cho, Soo Gyeong

2013-06-01

Recently, improvised explosive device (IED) has been a serious threat for many countries. One of the approaches to alleviate this threat is standoff detection of explosive molecules used in IEDs. Raman spectroscopy is a prospective method among many technologies under research to achieve this goal. It provides unique information of the target materials, through which the ingredients used in IEDs can be analyzed and identified. The main problem of standoff Raman spectroscopic detection is the large background noise hindering weak Raman signals from the target samples. Typical background noise comes from both ambient fluorescent lights indoor and sunlight outdoor whose intensities are usually much larger than that of Raman scattering from the sample. Under the proper condition using pulse laser and ICCD camera with nanosecond pulse width and gating technology, we succeed to separate and remove these background noises from Raman signals. For this experiment, we build an optical system for standoff detection of explosive molecules. We use 532 nm, 10 Hz, Q-switching Nd:YAG laser as light source, and ICCD camera triggered by laser Qswitching time with proper gate delay regarding the flight time of Raman from target materials. Our detection system is successfully applied to detect and identify more than 20 ingredients of IEDs including TNT, RDX, and HMX which are located 10 to 54 meters away from the system.

Pre-ignition confinement and deflagration violence in LX-10 and PBX 9501

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

Tringe, J. W., E-mail: tringe2@llnl.gov; Glascoe, E. A.; McClelland, M. A.

In thermal explosions of the nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)-based explosives LX-10 and PBX-9501, the pre-ignition spatial and temporal heating profile defines the ignition location. The ignition location then determines the extent of inertial confinement and the violence of the resulting deflagration. In this work, we present results of experiments in which ∼23 g cylinders of LX-10 and PBX 9501 in thin-walled aluminum confinement vessels were subjected to identical heating profiles but which presented starkly different energy release signatures. Post-explosion LX-10 containment vessels were completely fragmented, while the PBX 9501 vessels were merely ruptured. Flash x-ray radiography images show that the initiation locationmore » for the LX-10 is a few mm farther from the end caps of the vessel relative to the initiation location of PBX 9501. This difference increases deflagration confinement for LX-10 at the time of ignition and extends the pressurization time during which the deflagration front propagates in the explosive. The variation in the initiation location, in turn, is determined by the thermal boundary conditions, which differ for these two explosives because of the larger coefficient of thermal expansion and greater thermal stability of the Viton binder in LX-10 relative to the estane and bis(2,2-dinitropropyl) acetal/formal binder of the PBX 9501. The thermal profile and initiation location were modeled for LX-10 using the hydrodynamics and structures code ALE3D; results indicate temperatures in the vicinity of the ignition location in excess of 274 °C near the time of ignition. The conductive burn rates for these two explosives, as determined by flash x-ray radiography, are comparable in the range 0.1–0.2 mm/μs, somewhat faster than rates observed by strand burner experiments for explosives in the temperature range 150–180 °C and pressures up to 100 MPa. The thinnest-wall aluminum containment vessels presented here rupture at lower pressures, in the range 10 MPa, suggesting that moderately higher temperatures and pressures are present near the deflagration front. For these explosives, however the most important property for determining deflagration violence is the degree of inertial confinement.« less

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.

Micro-blast waves using detonation transmission tubing

NASA Astrophysics Data System (ADS)

Samuelraj, I. Obed; Jagadeesh, G.; Kontis, K.

2013-07-01

Micro-blast waves emerging from the open end of a detonation transmission tube were experimentally visualized in this study. A commercially available detonation transmission tube was used (Nonel tube, M/s Dyno Nobel, Sweden), which is a small diameter tube coated with a thin layer of explosive mixture (HMX + traces of Al) on its inner side. The typical explosive loading for this tube is of the order of 18 mg/m of tube length. The blast wave was visualized using a high speed digital camera (frame rate 1 MHz) to acquire time-resolved schlieren images of the resulting flow field. The visualization studies were complemented by computational fluid dynamic simulations. An analysis of the schlieren images showed that although the blast wave appears to be spherical, it propagates faster along the tube axis than along a direction perpendicular to the tube axis. Additionally, CFD analysis revealed the presence of a barrel shock and Mach disc, showing structures that are typical of an underexpanded jet. A theory in use for centered large-scale explosions of intermediate strength (10 < Δ {p}/{p}_0 ≲ 0.02) gave good agreement with the blast trajectory along the tube axis. The energy of these micro-blast waves was found to be 1.25 ± 0.94 J and the average TNT equivalent was found to be 0.3. The repeatability in generating these micro-blast waves using the Nonel tube was very good (± 2 %) and this opens up the possibility of using this device for studying some of the phenomena associated with muzzle blasts in the near future.

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.

Development of electrochemical sensors for trace detection of explosives and for the detection of chemical warfare agents

NASA Astrophysics Data System (ADS)

Berger, T.; Ziegler, H.; Krausa, Michael

2000-08-01

A huge number of chemical sensors are based on electrochemical measurement methods. Particularly amperometric sensorsystems are employed for the fast detection of pollutants in industry and environment as well as for analytic systems in the medical diagnosis. The large number of different applications of electrochemical sensors is based on the high sensitivity of electrochemical methods and on the wide of possibilities to enhance the selectivity by variation of electrochemical and chemical parameters. Besides this, electrochemical sensorsystems are frequently simple to operate, transportable and cheap. Up to now the electrochemical method of cyclic voltammetry is used only seldom for sensors. Clearly the efficiency of cyclic voltammetry can be seen at the sensorsystem for the detection of nitro- and aminotoluenes in solids and waters as presented here. The potentiodynamic sensors system can be employed for the fast and easy risk estimation of contaminated areas. Because of the high sensitivity of electrochemical methods the detection of chemical substances with a low vapor pressure is possible also. The vapor pressure of TNT at room temperature is 7 ppb for instances. With a special electrochemical set-up we were able to measure TNT approximately 10 cm above a TNT-sample. In addition we were able to estimate TNT in the gaseous phase approximately 10 cm above a real plastic mine. Therefore it seems to be possible to develop an electrochemical mien detection. Moreover, we present that the electrochemical detection of RDX, HMX and chemical warfare agents is also possible.

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

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.

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.

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.

Analysis of organic compounds in aqueous samples of former ammunition plants

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

Levsen, K.; Preiss, A.; Berger-Preiss, E.

1995-12-31

In Germany, a large number of sites exist where ammunition was produced before and in particular during World War II. These former production sites represent a particular threat to the environment because these plants were constructed and operated under war conditions, where production was far more important than protection of the health of the (in general forced) workers and the environment. New approaches are presented for the extraction and analysis of explosives and related compounds in aqueous samples from former ammunition production sites. Quantitative extraction of nitro aromatics but also of the polar nitroamines such as RDX and HMX ismore » achieved by solid phase extraction with styrene-divinylbenzene polymers (Lichrolut EN). Proton nuclear magnetic resonance ({sup 1}H-NMR) has been used to identify and quantify unknowns in ammunition waste water. Finally, automated multiple development (AMD) high performance thin layer chromatography was applied for the first time to the analysis of this compound class.« less

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.

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.

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

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.

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

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.

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

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

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

Detonation Velocity Calculations of Explosives with Slowly-Burning Constituents

NASA Astrophysics Data System (ADS)

Howard, W. Michael; Souers, P. Clark; Fried, Laurence E.

1997-07-01

The thermochemical code Equilbrium CHEETAH has been modified to allow partial reaction of constituents and partial flow of heat. Solid or liquid reactants are described by Einstein oscillators, whose temperatures can be changed to allow heat transfer. Hydroxy-terminated-poly-budadiene, mixed with RDX or HMX, does not react, as shown by the effect on the calculated detonation velocity. Aluminum and ammonium perchlorate in composites also do not react. Only partial heat flow also takes place in the unreacted materials. These results show that the usual assumption of total burn in a thermochemical code is probably incorrect, at least in the sonic reaction zone that drives the detonation velocity. A kinetic code would be the logical extension of this work.

Growth and defects of explosives crystals

NASA Astrophysics Data System (ADS)

Cady, H. H.

Large single crystals of PETN, RDX, and TNT can be grown easily from evaporating ethyl acetate solutions. The crystals all share a similar type of defect that may not be commonly recognized. The defect generates conical faces, ideally mosaic crystals, and may account for the 'polymorphs' of TNT and detonator grades of PETN. TATB crystals manufactured by the amination of trichlorotrinitrobenzene in dry toluene entrain two forms of ammonium chloride. One of these forms causes 'worm holes' in the TATB crystals that may be the reason for its unusually low failure diameters. Strained HMX crystals form mechanical twins that can spontaneously revert back to the untwinned form when the straining force is removed. Large strains or temperatures above 100 C lock in the mechanical twins.

Fate of CL-20 in sandy soils: degradation products as potential markers of natural attenuation.

PubMed

Monteil-Rivera, Fanny; Halasz, Annamaria; Manno, Dominic; Kuperman, Roman G; Thiboutot, Sonia; Ampleman, Guy; Hawari, Jalal

2009-01-01

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH(2)=N-C(=N-NO(2))-CH=N-CHO or its isomer N(NO(2))=CH-CH=N-CO-CH=NH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil.

Development and qualification testing of a laser-ignited, all-secondary (DDT) detonator

NASA Technical Reports Server (NTRS)

Blachowski, Thomas J.; Krivitsky, Darrin Z.; Tipton, Stephen

1994-01-01

The Indian Head Division, Naval Surface Warfare Center (IHDIV, NSWC) is conducting a qualification program for a laser-ignited, all-secondary (DDT) explosive detonator. This detonator was developed jointly by IHDIV, NSWC and the Department of Energy's EG&G Mound Applied Technologies facility in Miamisburg, Ohio to accept a laser initiation signal and produce a fully developed shock wave output. The detonator performance requirements were established by the on-going IHDIV, NSWC Laser Initiated Transfer Energy Subsystem (LITES) advanced development program. Qualification of the detonator as a component utilizing existing military specifications is the selected approach for this program. The detonator is a deflagration-to-detonator transfer (DDT) device using a secondary explosive, HMX, to generate the required shock wave output. The prototype development and initial system integration tests for the LITES and for the detonator were reported at the 1992 International Pyrotechnics Society Symposium and at the 1992 Survival and Flight Equipment National Symposium. Recent results are presented for the all-fire sensitivity and qualification tests conducted at two different laser initiation pulses.

Ability of thermochemical calculation to treat organic peroxides

NASA Astrophysics Data System (ADS)

Osmont, Antoine; Baudin, Gérard; Genetier, Marc

2017-06-01

Since 3 years, the CEA Gramat is developing a new thermochemical code, called SIAME, funded by DGA to help French defense industry at conceiving new explosives compositions. It enables the calculation of CJ detonation and deflagration points and combustion of explosives. The accuracy of the code has been checked on several compositions containing PETN, RDX, HMX, TNT, NTO. The error on the velocity of detonation is 3%. To enlarge the domain of validity of the code, organic peroxides have been considered. It is known that thermochemical simulation is in failure regarding compounds as simple as hydrogen peroxide. The computed velocity of detonation is 5720 m/s when shock planar impact gives 6150 m/s. The same discrepancy is found for TATP, with a calculated value at 5870 m/s when 5290 has been measured. Detonation velocity of TATP has been measured at two different densities. These velocities agree with other published values. A closer look at the enthalpy of formation of TATP has revealed that it comes from an article of 1932. Ab initio computations have given a totally different value, leading to better agreement with experiment.

Metagenomic Survey of a Military-Impacted Lagoon in Puerto Rico

NASA Astrophysics Data System (ADS)

Davila-Santiago, L.; DeLeon-Rodriguez, N.; LaSanta-Pagan, K. Y.; Kurt, Z.; Padilla-Crespo, E.; Hatt, J.; Spain, J.; Konstantinidis, K.; Massol-Deya, A.

2016-02-01

Military practices have left a legacy of contamination worldwide. In Puerto Rico, the east part of the populated Vieques Island was used for over fifty years as a bombing range by the Navy. A year after the base was closed in 2003, the impacted area was designated as a Superfund site. Previous studies have shown elevated levels of heavy metals, explosives (e.g. RDX, TNT, HMX), and other toxic chemicals at the site. The Anones Lagoon, located in the middle of the bombing range is one of the most polluted spots within the site. Intermittently, the lagoon is connected through a channel to the Caribbean Sea. In order to describe the microbial diversity and its potential contribution to natural attenuation of explosives, sediment samples have been collected since 2005. Sediment from reference lagoons (San Juan and Cabo Rojo) have also been sampled and analyzed in parallel for comparisons. Total DNA was extracted and sequenced using Ilumina My-Seq platform. Results indicate that Gammaproteobacteria were abundant in all lagoons samples but the Vieques lagoon harbors overall different microbial taxa. Alpha diversity analysis showed that Anones was less diverse compared to the pristine Cabo Rojo lagoon. Importantly, a clear shift was seen in the Anones Lagoon in 2013 compared to 2005, were Halomonas spp. became dominant (up to 25%) while other groups like Marinobacter showed signs of enrichment as well. Interestingly, these groups have been shown to degrade explosive-related chemicals in tropical sediments. Functional gene annotation of the Anones metagenome showed the presence of RDX degradation genes such as cytochrome p450. This study is the first comparative metagenomic survey of lagoons in Puerto Rico that explored the microbial diversity and biodegradation potential at Vieques.

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

Biostimulation and microbial community profiling reveal insights on RDX transformation in groundwater

DOE PAGES

Wang, Dongping; Boukhalfa, Hakim; Marina, Oana; ...

2016-11-17

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a high explosive released to the environment as a result of weapons manufacturing and testing worldwide. At Los Alamos National Laboratory, the Technical Area (TA) 16 260 Outfall discharged high-explosives-bearing water from a high-explosives-machining facility to Cañon de Valle during 1951 through 1996. These discharges served as a primary source of high-explosives and inorganic-element contamination in the area. Data indicate that springs, surface water, alluvial groundwater, and perched-intermediate groundwater contain explosive compounds, including 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). RDX has been detected in the regional aquifer in several wells, and a corrective measures evaluation ismore » planned to identify remedial alternatives to protect the regional aquifer. Perched-intermediate groundwater at Technical Area 16 is present at depths from 650 ft to 1200 ft bgs. In this study, we examined the microbial diversity in a monitoring well completed in perched-intermediate groundwater contaminated by RDX, and examined the response of the microbial population to biostimulation under varying geochemical conditions. Results show that the groundwater microbiome was dominated by Actinobacteria and Proteobacteria. A total of 1,605 operational taxonomic units (OTUs) in 96 bacterial genera were identified. Rhodococcus was the most abundant genus (30.6%) and a total of 46 OTUs were annotated as Rhodococcus. One OTU comprising 25.2% of total sequences was closely related to a RDX -degrading strain R. erythropolis HS4. A less abundant OTU from the Pseudomonas family closely related to RDX-degrading strain P. putida II-B was also present. Biostimulation significantly enriched Proteobacteria but decreased/eliminated the population of Actinobacteria. Consistent with RDX degradation, the OTU closely related to the RDX-degrading P. putida strain II-B was specifically enriched in the RDX-degrading samples. Analysis of the accumulation of RDX-degradation products reveals that during active RDX degradation, there is a transient increase in the concentration of the degradation products MNX, DNX, TNX, and NDAB. The accumulation of these degradation products suggests that RDX is degraded via sequential reduction of the nitro functional groups followed by abiotic ring-cleavage. Here, the results suggest that strict anaerobic conditions are needed to stimulate RDX degradation under the TA-16 site-specific conditions.« less

Biostimulation and microbial community profiling reveal insights on RDX transformation in groundwater

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

Wang, Dongping; Boukhalfa, Hakim; Marina, Oana

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a high explosive released to the environment as a result of weapons manufacturing and testing worldwide. At Los Alamos National Laboratory, the Technical Area (TA) 16 260 Outfall discharged high-explosives-bearing water from a high-explosives-machining facility to Cañon de Valle during 1951 through 1996. These discharges served as a primary source of high-explosives and inorganic-element contamination in the area. Data indicate that springs, surface water, alluvial groundwater, and perched-intermediate groundwater contain explosive compounds, including 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). RDX has been detected in the regional aquifer in several wells, and a corrective measures evaluation ismore » planned to identify remedial alternatives to protect the regional aquifer. Perched-intermediate groundwater at Technical Area 16 is present at depths from 650 ft to 1200 ft bgs. In this study, we examined the microbial diversity in a monitoring well completed in perched-intermediate groundwater contaminated by RDX, and examined the response of the microbial population to biostimulation under varying geochemical conditions. Results show that the groundwater microbiome was dominated by Actinobacteria and Proteobacteria. A total of 1,605 operational taxonomic units (OTUs) in 96 bacterial genera were identified. Rhodococcus was the most abundant genus (30.6%) and a total of 46 OTUs were annotated as Rhodococcus. One OTU comprising 25.2% of total sequences was closely related to a RDX -degrading strain R. erythropolis HS4. A less abundant OTU from the Pseudomonas family closely related to RDX-degrading strain P. putida II-B was also present. Biostimulation significantly enriched Proteobacteria but decreased/eliminated the population of Actinobacteria. Consistent with RDX degradation, the OTU closely related to the RDX-degrading P. putida strain II-B was specifically enriched in the RDX-degrading samples. Analysis of the accumulation of RDX-degradation products reveals that during active RDX degradation, there is a transient increase in the concentration of the degradation products MNX, DNX, TNX, and NDAB. The accumulation of these degradation products suggests that RDX is degraded via sequential reduction of the nitro functional groups followed by abiotic ring-cleavage. Here, the results suggest that strict anaerobic conditions are needed to stimulate RDX degradation under the TA-16 site-specific conditions.« less

Biostimulation and microbial community profiling reveal insights on RDX transformation in groundwater.

PubMed

Wang, Dongping; Boukhalfa, Hakim; Marina, Oana; Ware, Doug S; Goering, Tim J; Sun, Fengjie; Daligault, Hajnalka E; Lo, Chien-Chi; Vuyisich, Momchilo; Starkenburg, Shawn R

2017-04-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a high explosive released to the environment as a result of weapons manufacturing and testing worldwide. At Los Alamos National Laboratory, the Technical Area (TA) 16 260 Outfall discharged high-explosives-bearing water from a high-explosives-machining facility to Cañon de Valle during 1951 through 1996. These discharges served as a primary source of high-explosives and inorganic-element contamination in the area. Data indicate that springs, surface water, alluvial groundwater, and perched-intermediate groundwater contain explosive compounds, including 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). RDX has been detected in the regional aquifer in several wells, and a corrective measures evaluation is planned to identify remedial alternatives to protect the regional aquifer. Perched-intermediate groundwater at Technical Area 16 is present at depths from 650 ft to 1200 ft bgs. In this study, we examined the microbial diversity in a monitoring well completed in perched-intermediate groundwater contaminated by RDX, and examined the response of the microbial population to biostimulation under varying geochemical conditions. Results show that the groundwater microbiome was dominated by Actinobacteria and Proteobacteria. A total of 1,605 operational taxonomic units (OTUs) in 96 bacterial genera were identified. Rhodococcus was the most abundant genus (30.6%) and a total of 46 OTUs were annotated as Rhodococcus. One OTU comprising 25.2% of total sequences was closely related to a RDX -degrading strain R. erythropolis HS4. A less abundant OTU from the Pseudomonas family closely related to RDX-degrading strain P. putida II-B was also present. Biostimulation significantly enriched Proteobacteria but decreased/eliminated the population of Actinobacteria. Consistent with RDX degradation, the OTU closely related to the RDX-degrading P. putida strain II-B was specifically enriched in the RDX-degrading samples. Analysis of the accumulation of RDX-degradation products reveals that during active RDX degradation, there is a transient increase in the concentration of the degradation products MNX, DNX, TNX, and NDAB. The accumulation of these degradation products suggests that RDX is degraded via sequential reduction of the nitro functional groups followed by abiotic ring-cleavage. The results suggest that strict anaerobic conditions are needed to stimulate RDX degradation under the TA-16 site-specific conditions. © 2016 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

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.

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 intermolecular interactions with in the crystal lattice of β phase HMX and is much larger (100X) than that of simple conformational changes. The evidence of a straightforward one step mechanism is not supported by this research. Solid-solid phase transition kinetics is very complexed. There are many factors that contribute to an overall reaction mechanism. The initial assumptions that were chosen to allow simple manipulation of the HMX phase transition data prove to be too limiting. The rate constant by definition should in fact be constant, however, our data reflects it is not (refer to k vs time plot in Appendix 2). The assumption of a first order, simple single step reaction is a good starting point for the study of HMX phase transition kinetics, but further analysis should be done with other reaction orders and multiple step mechanisms. Understanding the kinetics of β phase HMX will clearly help the custodian understand the limitations of storage and use of this compound.« less

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.

Synthesis, Chemical and Physical Characterization of TKX-50

NASA Astrophysics Data System (ADS)

Klapoetke, Thomas

2015-06-01

TKX-50 (bis(hydroxylammonium) 5,5'-bis(tetrazolate-1 N-oxide)) is one of the most promising ionic salts as a possible replacement for RDX. The thermal behavior of TKX-50 (bis(hydroxylammonium) 5,5'-(tetrazolate-1 N-oxide)) and the kinetics of its thermal decomposition were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The calculated results of the detonation parameters and equations of state for the detonation products (EOS DP) of explosive materials TKX-50 and MAD-X1 and several of their derivatives were obtained using the computer program EXPLO5 V.6.01. These values were also calculated for standard explosive materials which are commonly used such as TNT, PETN, RDX, HMX as well as for the more powerful explosive material CL-20 to allow comparisons to be made. The determination of the detonation parameters and EOS DP was conducted both for explosive materials having the maximum crystalline density and for porous right up to 50% in volume materials. The influence of the content of plastic binder polyisobutylene used (up to 20% in volume) on all of the investigated properties was also examined. Calculated results on shock wave loading of different inert barriers in a wide range of their dynamic properties under explosion on their surfaces of concrete size charges of different explosive materials in various initial states were obtained with the use of the one-dimensional computer hydrocode EP. Barriers due to materials such as polystyrene, textolite, magnesium, aluminum, zinc, copper, tantalum or tungsten were examined (Fig. 1). Initial values of pressure and other parameters of loading on the interface explosive-barrier were determined in the process of conducted calculations. Phenomena of propagation and attenuation of shock waves in barrier materials were considered too for all possible situations. From these calculations, an essentially complete overview of the explosion properties and characteristics of shock wave action onto barriers was obtained for several new and also for several standard explosive materials as a comparison. Work done in collaboration with Golubev/Fischer/Stierstorfer/Bohanek/Dobrilovic.

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.

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.

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

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.

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

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)

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

Ignition threshold of aluminized HMX-based PBXs

NASA Astrophysics Data System (ADS)

Miller, Christopher; Zhou, Min

2017-06-01

We report the results of micromechanical simulations of the ignition of aluminized HMX-based PBX under loading due to impact by thin flyers. The conditions analyzed concern loading pulses on the order of 20 nanoseconds to 0.8 microseconds in duration and impact piston velocities on the order of 300-1000 ms-1. The samples consist of a stochastically similar bimodal distribution of HMX grains, an Estane binder, and 50 μm aluminum particles. The computational model accounts for constituent elasto-vicoplasticity, viscoelasticity, bulk compressibility, fracture, interfacial debonding, fracture, internal contact, bulk and frictional heating, and heat conduction. The analysis focuses on the development of hotspots under different material settings and loading conditions. In particular, the ignition threshold in the form of the James relation and the corresponding ignition probability are calculated for the PBXs containing 0%, 6%, 10%, and 18% aluminum by volume. It is found that the addition of aluminum increases the ignition threshold, causing the materials to be less sensitive. Dissipation and heating mechanism changes responsible for this trend are delineated. Support by DOE NNSA SSGF is gratefully acknowledged.

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.

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.

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.

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.

Remedial Investigation Report for Lake City Army Ammunition Plant. Volume 1

DTIC Science & Technology

1990-06-01

EXPLOSIVE COMPOUNDS 1 3-DNB ɘ 61 ɘ.61 ɘ.61 ɘ.61 ɘ.61 1 73 135-7N6 11 7 ɘ.56 ɘ.56 ɘ.56 ɘ.56 0.7 *J 3.24 ə 30 ə 30 ə,30 ə.30 ə.30 POX ɘ...COMPOUNDS * 5- TNB I37 ɘ.56 ɘ. 56 ɘ 56 ɘ. 56 ɘ,56 HMX 17 4 ə.,30 ə 30 < 1 340 ᝻,30 ə.30 POX IS0 1.67 ɘ.63 ɘ.63 ɘ.63 1 84 OTHERS (ALL NO OR...Torkelson and Rowe 1031 5-209 Evidence suggests that 1,1,2-TCA is embryo toxic to chicken eggs (Elovaara 1979). I,I,2-TCA was found to be weakly mutagenic

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

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

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

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.

Shear Band Formation in Plastic-Bonded Explosives (PBX)

NASA Astrophysics Data System (ADS)

Dey, Thomas N.; Johnson, James N.

1997-07-01

Adiabatic shear bands can be a source of ignition and lead to detonation. At low to moderate deformation rates, 10--1000 s-1, two other mechanisms can also give rise to shear bands. These mechanisms are: softening caused by micro-cracking and (2) a constitutive response with a non-associated flow rule as is observed in granular material such as soil. Brittle behavior at small strains and the granular nature of HMX suggest that PBX-9501 constitutive behavior may be similar to sand. A constitutive model for each of these mechanims is studied in a series of calculations. A viscoelastic constitutive model for PBX-9501 softens via a statistical crack model, based on the work of Dienes (1986). A sand model is used to provide a non-associated flow rule. Both models generate shear band formation at 1--2% strain at nominal strain rates at and below 1000 s-1. Shear band formation is suppressed at higher strain rates. The sand model gives qualitative agreement for location and orientation of shear bands observed in a punch experiment. Both mechanisms may accelerate the formation of adiabatic shear bands.

Aluminum nanoparticles burning - still a puzzle?

NASA Astrophysics Data System (ADS)

Gromov, A. A.; Popenko, E. M.

2009-09-01

The experimental data on the aluminum nanopowders (nAl) combustion in oxidizing media (air, propellants AP∗/HTPB†/Al/HMX‡, and energetic compositions) assuming the phenomenon of nitrides formation with the high yield is generalized. In the present work, the nAl produced by electrical explosion of wires was studied. The temperature, burning rate, and radiation were measured at combustion and the actual burning process was recorded by a videocamera. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and chemical analysis were performed on the both initial powders and final condensed products. It was experimentally proved that the combustion process of aluminum nanoparticles was two staged independently of burning conditions in nitrogen-containing media. The formation of nitrides in presence of molecular nitrogen is the determining stage in the particles combustion. A qualitative discussion is given on the kinetic limitation for AlN (AlON) oxidation due to rapid condensation and encapsulation of solid AlN (AlON).

New perspectives in the PAW/GIPAW approach: J(P-O-Si) coupling constants, antisymmetric parts of shift tensors and NQR predictions.

PubMed

Bonhomme, Christian; Gervais, Christel; Coelho, Cristina; Pourpoint, Frédérique; Azaïs, Thierry; Bonhomme-Coury, Laure; Babonneau, Florence; Jacob, Guy; Ferrari, Maude; Canet, Daniel; Yates, Jonathan R; Pickard, Chris J; Joyce, Siân A; Mauri, Francesco; Massiot, Dominique

2010-12-01

In 2001, Pickard and Mauri implemented the gauge including projected augmented wave (GIPAW) protocol for first-principles calculations of NMR parameters using periodic boundary conditions (chemical shift anisotropy and electric field gradient tensors). In this paper, three potentially interesting perspectives in connection with PAW/GIPAW in solid-state NMR and pure nuclear quadrupole resonance (NQR) are presented: (i) the calculation of J coupling tensors in inorganic solids; (ii) the calculation of the antisymmetric part of chemical shift tensors and (iii) the prediction of (14)N and (35)Cl pure NQR resonances including dynamics. We believe that these topics should open new insights in the combination of GIPAW, NMR/NQR crystallography, temperature effects and dynamics. Points (i), (ii) and (iii) will be illustrated by selected examples: (i) chemical shift tensors and heteronuclear (2)J(P-O-Si) coupling constants in the case of silicophosphates and calcium phosphates [Si(5)O(PO(4))(6), SiP(2)O(7) polymorphs and α-Ca(PO(3))(2)]; (ii) antisymmetric chemical shift tensors in cyclopropene derivatives, C(3)X(4) (X = H, Cl, F) and (iii) (14)N and (35)Cl NQR predictions in the case of RDX (C(3)H(6)N(6)O(6)), β-HMX (C(4)H(8)N(8)O(8)), α-NTO (C(2)H(2)N(4)O(3)) and AlOPCl(6). RDX, β-HMX and α-NTO are explosive compounds. Copyright © 2010 John Wiley & Sons, Ltd.

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.

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.

Shock Initiation of Wedge-shaped Explosive Measured with Smear Camera and Photon Doppler Velocimetry

NASA Astrophysics Data System (ADS)

Gu, Yan

2017-06-01

Triaminotrinitrobenzene (TATB) is an important insensitive high explosive in conventional weapons due to its safety and high energy. In order to have an insight into the shock initiation performance of a TATB-based insensitive high explosive (IHE), experimental measurements of the particle velocity histories of the TATB-based Explosive using Photon Doppler Velocimetry and shock wave profile of the TATB-based explosive using High Speed Rotating Mirror Smear Camera had been performed. In this paper, we would describe the shock initiation performance of the TATB-based explosive by run-to-detonation distance and the particle velocity history at an initialization shock of about 7.9 GPa. The parameters of hugoniot of unreacted the TATB-based explosive and Pop relationship could be derived with the particle velocity history obtained in this paper.

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

Combined use of direct analysis in real-time/Orbitrap mass spectrometry and micro-Raman spectroscopy for the comprehensive characterization of real explosive samples.

PubMed

Bridoux, Maxime C; Schwarzenberg, Adrián; Schramm, Sébastien; Cole, Richard B

2016-08-01

Direct Analysis in Real Time (DART™) high-resolution Orbitrap™ mass spectrometry (HRMS) in combination with Raman microscopy was used for the detailed molecular level characterization of explosives including not only the charge but also the complex matrix of binders, plasticizers, polymers, and other possible organic additives. A total of 15 defused military weapons including grenades, mines, rockets, submunitions, and mortars were examined. Swabs and wipes were used to collect trace (residual) amounts of explosives and their organic constituents from the defused military weapons and micrometer-size explosive particles were transferred using a vacuum suction-impact collection device (vacuum impactor) from wipe and swap samples to an impaction plate made of carbon. The particles deposited on the carbon plate were then characterized using micro-Raman spectroscopy followed by DART-HRMS providing fingerprint signatures of orthogonal nature. The optical microscope of the micro-Raman spectrometer was first used to localize and characterize the explosive charge on the impaction plate which was then targeted for identification by DART-HRMS analysis in both the negative and positive modes. Raman spectra of the explosives TNT, RDX and PETN were acquired from micrometer size particles and characterized by the presence of their characteristic Raman bands obtained directly at the surface of the impaction plate nondestructively without further sample preparation. Negative mode DART-HRMS confirmed the types of charges contained in the weapons (mainly TNT, RDX, HMX, and PETN; either as individual components or as mixtures). These energetic compounds were mainly detected as deprotonated species [M-H](-), or as adduct [M + (35)Cl](-), [M + (37)Cl](-), or [M + NO3](-) anions. Chloride adducts were promoted in the heated DART reagent gas by adding chloroform vapors to the helium stream using an "in-house" delivery method. When the polarity was switched to positive mode, DART-HRMS revealed a very complex distribution of polymeric binders (mainly polyethylene glycols and polypropylene glycols), plasticizers (e.g., dioctyl sebacate, tributyl phosphate), as well as wax-like compounds whose structural features could not be precisely assigned. In positive mode, compounds were identified either as protonated molecules or ammonium adduct species. These results clearly demonstrate the complementarity of micro-Raman microscopy combined with DART-MS. The former technique provides structural information on the type of explosives present at the surface of the sample, whereas the latter provides not only a confirmation of the nature of the explosive charge but also useful additional information regarding the nature of the complex organic matrix of binders, plasticizers, polymers, oils, and potentially other organic additives and contaminants present in the sample. Combining these two techniques provides a powerful tool for the screening, comprehensive characterization, and differentiation of particulate explosive samples for forensic sciences and homeland security applications. Graphical Abstract Comprehensive characterization of explosive particles collected from swipe samples by micro-Raman and DART™-HRMS.

Comparison of no-purge and pumped sampling methods for monitoring concentrations of ordnance-related compounds in groundwater, Camp Edwards, Massachusetts Military Reservation, Cape Cod, Massachusetts, 2009-2010

USGS Publications Warehouse

Savoie, Jennifer G.; LeBlanc, Denis R.

2012-01-01

Field tests were conducted near the Impact Area at Camp Edwards on the Massachusetts Military Reservation, Cape Cod, Massachusetts, to determine the utility of no-purge groundwater sampling for monitoring concentrations of ordnance-related explosive compounds and perchlorate in the sand and gravel aquifer. The no-purge methods included (1) a diffusion sampler constructed of rigid porous polyethylene, (2) a diffusion sampler constructed of regenerated-cellulose membrane, and (3) a tubular grab sampler (bailer) constructed of polyethylene film. In samples from 36 monitoring wells, concentrations of perchlorate (ClO4-), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), the major contaminants of concern in the Impact Area, in the no-purge samples were compared to concentrations of these compounds in samples collected by low-flow pumped sampling with dedicated bladder pumps. The monitoring wells are constructed of 2- and 2.5-inch-diameter polyvinyl chloride pipe and have approximately 5- to 10-foot-long slotted screens. The no-purge samplers were left in place for 13-64 days to ensure that ambient groundwater flow had flushed the well screen and concentrations in the screen represented water in the adjacent formation. The sampling methods were compared first in six monitoring wells. Concentrations of ClO4-, RDX, and HMX in water samples collected by the three no-purge sampling methods and low-flow pumped sampling were in close agreement for all six monitoring wells. There is no evidence of a systematic bias in the concentration differences among the methods on the basis of type of sampling device, type of contaminant, or order in which the no-purge samplers were tested. A subsequent examination of vertical variations in concentrations of ClO4- in the 10-foot-long screens of six wells by using rigid porous polyethylene diffusion samplers indicated that concentrations in a given well varied by less than 15 percent and the small variations were unlikely to affect the utility of the various sampling methods. The grab sampler was selected for additional tests in 29 of the 36 monitoring wells used during the study. Concentrations of ClO4-, RDX, HMX, and other minor explosive compounds in water samples collected by using a 1-liter grab sampler and low-flow pumped sampling were in close agreement in field tests in the 29 wells. A statistical analysis based on the sign test indicated that there was no bias in the concentration differences between the methods. There also was no evidence for a systematic bias in concentration differences between the methods related to location of the monitoring wells laterally or vertically in the groundwater-flow system. Field tests in five wells also demonstrated that sample collection by using a 2-liter grab sampler and sequential bailing with the 1-liter grab sampler were options for obtaining sufficient sample volume for replicate and spiked quality assurance and control samples. The evidence from the field tests supports the conclusion that diffusion sampling with the rigid porous polyethylene and regenerated-cellulose membranes and grab sampling with the polyethylene-film samplers provide comparable data on the concentrations of ordnance-related compounds in groundwater at the MMR to that obtained by low-flow pumped sampling. These sampling methods are useful methods for monitoring these compounds at the MMR and in similar hydrogeologic environments.

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.

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

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.

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.

Shock compression and flash-heating of molecular adsorbates on the picosecond time scale

NASA Astrophysics Data System (ADS)

Berg, Christopher Michael

An ultrafast nonlinear coherent laser spectroscopy termed broadband multiplex vibrational sum-frequency generation (SFG) with nonresonant suppression was employed to monitor vibrational transitions of molecular adsorbates on metallic substrates during laser-driven shock compression and flash-heating. Adsorbates were in the form of well-ordered self-assembled monolayers (SAMs) and included molecular explosive simulants, such as nitroaromatics, and long chain-length alkanethiols. Based on reflectance measurements of the metallic substrates, femtosecond flash-heating pulses were capable of producing large-amplitude temperature jumps with DeltaT = 500 K. Laser-driven shock compression of SAMs produced pressures up to 2 GPa, where 1 GPa ≈ 1 x 104 atm. Shock pressures were estimated via comparison with frequency shifts observed in the monolayer vibrational transitions during hydrostatic pressure measurements in a SiC anvil cell. Molecular dynamics during flash-heating and shock loading were probed with vibrational SFG spectroscopy with picosecond temporal resolution and sub-nanometer spatial resolution. Flash-heating studies of 4-nitrobenzenethiolate (NBT) on Au provided insight into effects from hot-electron excitation of the molecular adsorbates at early pump-probe delay times. At longer delay times, effects from the excitation of SAM lattice modes and lower-energy NBT vibrations were shown. In addition, flash-heating studies of alkanethiolates demonstrated chain disordering behaviors as well as interface thermal conductances across the Au-SAM junction, which was of specific interest within the context of molecular electronics. Shock compression studies of molecular explosive simulants, such as 4-nitrobenzoate (NBA), demonstrated the proficiency of this technique to observe shock-induced molecular dynamics, in this case orientational dynamics, on the picosecond time scale. Results validated the utilization of these refined shock loading techniques to probe the shock initiation or first bond-breaking reactions in molecular explosives such as delta-HMX: a necessary study for the development of safer and more effective energetic materials.

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.

A study of the composition of the products of laser-induced breakdown of hexogen, octogen, pentrite and trinitrotoluene using selected ion flow tube mass spectrometry and UV-Vis spectrometry.

PubMed

Sovová, Kristýna; Dryahina, Kseniya; Spanel, Patrik; Kyncl, Martin; Civis, Svatopluk

2010-05-01

Four types of explosives were studied using a combination of Laser Induced Breakdown Spectroscopy (LIBS) and Selected Ion Flow Tube Mass Spectrometry (SIFT-MS). The LIBS technique uses short laser pulses (ArF excimer laser) as the energy source to convert small amounts samples into plasma and to produce the emission from their molecular fragments or atoms. SIFT-MS is a novel method for absolute quantification based on chemical ionization using three precursor ions, with the capability to determine concentrations of trace gases and vapours of volatile organic compounds in real time. This is the first time that SIFT-MS has been used to study the release of NO, NO(2), HCN, HNO(3), HONO, HCHO and C(2)H(2) after a laser-induced breakdown of pure explosive compounds HMX (1,3,5,7-tetranitro-1,3,5,7-tetraazacyclo-octane), RDX (1,3,5-trinitro-2-oxo-1,3,5-triazacyclo-hexane), PETN (pentaerithrityl-tetranitrate) and TNT (2,4,6-trinitrotoluene) in solid form. The radiation emitted after excitation was analysed using a time resolving UV-Vis spectrometer with a ICCD detector. Electronic bands of the CN radical (388 nm), the Swan system of the C(2) radical (512 nm), the NH radical (336 nm), the OH radical (308.4 nm) and atomic lines of oxygen, nitrogen and hydrogen were identified. Vibrational and excitation temperatures were determined from the intensity distributions and a scheme of chemical reactions responsible for the formation of the observed species was proposed.

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.