Molecular Dynamics Simulation of Shock Response of CL-20 Co-crystals Containing Void Defects

To investigate the effect of void defects on the shock response of hexanitrohexaazaisowurtzitane(CL-20)co-crystals,shock responses of CL-20 co-crystals with energetic materials ligands trinitrotoluene(TNT),1,3-dinitrobenzene(DNB),solvents ligands dimethyl carbonate(DMC) and gamma-butyrolactone(GBL)with void were simulated,using molecular dynamics method and reactive force field.It is found that the CL-20 co-crystals with void defects will form hot spots when impacted,significantly affecting the decomposition of molecules around the void.The degree of molecular fragmentation is relatively low under the reflection velocity of 2 km/s,and the main reactions are the formation of dimer and the shedding of nitro groups.The existence of voids reduces the safety of CL-20 co-crystals,which induced the sensitivity of energetic co-crystals CL-20/TNT and CL-20/DNB to increase more significantly.Detonation has occurred under the reflection velocity of 4 km/s,energetic co-crystals are easier to polymerize than solvent co-crystals,and are not obviously affected by voids.The results show that the energy of the wave decreases after sweeping over the void,which reduces the chemical reaction frequency downstream of the void and affects the detonation performance,especially the solvent co-crystals.

Dinitrophenyl-oxadiazole compounds:Design strategy,synthesis,and properties of a series of new melt-cast explosives

Melt-cast explosives are the most widely used energetic materials in military composite explosives,researchers have been unremittingly exploring high-energy and insensitive melt-cast explosives.In this work,a series of dinitrophenyl-oxadiazole compounds were designed and prepared.These compounds have an ideal low melting point(80-97℃),good detonation performance(detonation velocity D=6455-6971 m/s,detonation pressure P=18-19 GPa)and extreme insensitive nature(impact sensitivity≥60 J,friction sensitivity>360 N).All these compounds were well characterized by nuclear magnetic resonance,fourier transform infrared spectroscopy,elemental analysis.Compounds 2,3 were unambiguously confirmed by X-ray single crystal diffraction analysis.As a result,their overall properties are superior to traditional melt-cast explosives trinitrotoluene(TNT)and dinitroanisole(DNAN)which may have excellent potential applications in insensitive melt-cast explosives.

Fluorinated semi-interpenetrating polymer networks for enhancing the mechanical performance and storage stability of polymer-bonded explosives by controlling curing and phase separation rates

Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.

Assessing the energy release characteristics during the middle detonation reaction stage of aluminized explosives

Afterburning behind the detonation front of an aluminized explosive releases energy on the millisecond timescale,which prolong the release of detonation energy and the energy release at different stages also shows significant differences.However,at present,there are few effective methods for evaluating the energy release characteristics of the middle reaction stage of such explosives,which can have a duration of tens to hundreds of microseconds.The present work demonstrates an approach to assessing the midstage of an aluminized explosive detonation based on a water push test employing a high degree of confinement.In this method,the explosive is contained in a steel cylinder having one end closed that is installed at the bottom of a transparent water tank.Upon detonation,the gaseous products expand in one direction while forcing water ahead of them.The resulting underwater shock wave and the interface between the gas phase products and the water are tracked using an ultra-high-speed framing and streak camera.The shock wave velocity in water and the expansion work performed by the gaseous detonation products were calculated to assess the energy release characteristics of aluminized explosives such as CL-20 and RDX in the middle stage of the detonation reaction.During the middle stage of the detonation process of these aluminized explosives,the aluminum reaction reduced the attenuation of shock waves and increased the work performed by gas phase products.A higher aluminum content increased the energy output while the presence of oxidants slowed the energy release rate.This work demonstrates an effective means of evaluating the performance of aluminized explosives.

Shock-induced energy localization and reaction growth considering chemical-inclusions effects for crystalline explosives

Chemical inclusions significantly alter shock responses of crystalline explosives in macroscale gap experiments but their microscale dynamics origin remains unclear.Herein shock-induced energy localization,overall physical responses,and reactions in a-1,3,5-trinitro-1,3,5-triazinane(a-RDX)crystal entrained various chemical inclusions were investigated by the multi-scale shock technique implemented in the reactive molecular dynamics method.Results indicated that energy localization and shock reaction were affected by the intrinsic factors within chemical inclusions,i.e.,phase states,chemical compositions,and concentrations.The atomic origin of chemical-inclusions effects on energy localization is dependent on the dynamics mechanism of interfacial molecules with free space volume,which includes homogeneous intermolecular compression,interfacial impact and shear,and void collapse and jet.As introducing various chemical inclusions,the initiation of those dynamics mechanisms triggers diverse decay rates of bulk RDX molecules and hereby impacts on growth speeds of final reactions.Adding chemical inclusions can reduce the effectiveness of the void during the shock impacting.Under the shockwave velocity of 9 km/s,the parent RDX decay rate in RDX entrained amorphous carbon decreases the most and is about one fourth of that in RDX with a vacuum void,and solid HMX and TATB inclusions are more reactive than amorphous carbon but less reactive than dry air or acetone inclusions.The lessdense shocking system denotes the greater increases in local temperature and stress,the faster energy liberation,and the earlier final reaction into equilibrium,revealing more pronounced responses to the present intense shockwave.The quantitative models associated with the relative system density(RD_(sys))were proposed for indicating energy-localization mechanisms and evaluating initiation safety in the shocked crystalline explosive.RD_(sys)is defined by the density ratio of defective RDX to perfect crystal after dynamics relaxation and reveals the global density characteristic in shocked systems filled with chemical inclusions.When RD_(sys)is below 0.9,local hydrodynamic jet initiated by void collapse dominates upon energy localization instead of interfacial impact.This study sheds light on novel insights for understanding the shock chemistry and physical-based atomic origin in crystalline explosives considering chemical-inclusions effects.

Research on the quasi-isentropic driving model of aluminized explosives in the detonation wave propagation direction

Taking CL-20(Hexanitrohexaazaisowurtzitane)-based aluminized explosives with high gurney energy as the research object, this research experimentally investigates the work capability of different aluminized explosive formulations when driving metal flyer plates in the denotation wave propagation direction.The research results showed that the formulations with 43 μm aluminum(Al) powder particles(The particle sizes of Al powder were in the range of 2~43 μm) exhibited the optimal performance in driving flyer plates along the denotation wave propagation direction. Compared to the formulations with Al powder 13 μm, the formulations with Al powder 2 μm delivered better performance in accelerating metal flyer plates in the early stage, which, however, turned to be poor in the later stage. The CL-20-based explosives containing 25% Al far under-performed those containing 15% Al. Based on the proposed quasi-isentropic hypothesis, relevant isentropy theories, and the functional relationship between detonation parameters and entropy as well as Al reaction degree, the characteristic lines of aluminized explosives in accelerating flyer plates were theoretically studied, a quasi-isentropic theoretical model for the aluminized explosive driving the flyer plate was built and the calculation methods for the variations of flyer plate velocity, Al reaction degree, and detonation product parameters with time and axial positions were developed. The theoretical model built is verified by the experimental results of the CL-20-based aluminized explosive driving flyer plate. It was found that the model built could accurately calculate the variations of flyer plate velocity and Al reaction degree over time. In addition, how physical parameters including detonation product pressure and temperature varied with time and axial positions was identified. The action time of the positive pressure after the detonation of aluminized explosives was found prolonged and the downtrend of the temperature was slowed down and even reversed to a slight rise due to the aftereffect reaction between the Al powder and the detonation products.

Effects of temperature, particle size, and air humidity on sensibility of typical high-energetic explosives

The production and utilization of high-energetic explosives often pose a range of safety hazards,with sensitivity being a key factor in evaluating these risks.To investigate how temperature,particle size,and air humidity affect the responsiveness of commonly used high-energetic explosives,a series of BAM(Bundesanstalt für Materialforschung und-prüfung)impact and friction sensitivity tests were carried out to determine the critical impact energy and critical load pressure of four representative high-energetic explosives(RDX,HMX,PETN and CL-20)under different temperatures,particle sizes,and air humidity conditions.The experimental findings facilitated an examination of temperature and particle size affecting the sensitivity of high-energetic explosives,along with an assessment of the influence of air humidity on sensitivity testing.The results clearly indicate that high-energetic explosives display a substantial decline in critical reaction energy when subjected to micrometre-sized particles and an air humidity level of 45%at a temperature of 90℃.Furthermore,it was noted that the critical reaction energy of high-energetic explosives diminishes with an increase in temperature within 25℃−90℃.In the same vein,as the particle sizes of high-energetic explosives increase,so does the critical reaction energy for micrometre-sized particles.High air humidity significantly affects the sensitivity testing of high-energetic explosives,emphasizing the importance of refraining from conducting sensitivity tests in such conditions.

Assessment of portable FTIR and Raman spectroscopy for the detection of 2,3-dimethyl-2,3-dinitrobutane(DMDNB)in plastic explosives

The Marplex Convention was established to prevent the manufacture of unmarked plastic explosives and stipulates that a volatile detection agent must be added at the time of manufacture.However,to-date,laboratory testing remains the internationally accepted practice for identifying and quantifying the taggants stipulated in the Convention.In this project,portable FTIR and Raman instruments were tested for their ability to detect 2,3-dimethyl-2,3-dinitrobutane(DMDNB),the chemical marker incorporated in plastic explosives that are manufactured within Australia.While both FTIR and Raman instruments detected solid DMDNB(98%purity),field analysis of plastic explosives at an Australian Defence establishment showed that both FTIR and Raman spectra were matched the relevant explosive(RDX or PETN),rather than the DMDNB taggant.For all three plastic explosives tested,the concentration of DMDNB was measured by SPME-GC-MS to be between 1.8 and 2%,greater than the minimum 1%concentration stipulated by the Marplex Convention.Additional testing with a plastic explosive analogue confirmed that the minor absorption peaks that would characterize low concentrations of DMDNB were masked by absorption bands from other compounds within the solid.Thus,while both FTIR and Raman spectroscopy are suitable for detection of plastic explosives,neither rely on the presence of DMDNB for detection.It is likely that similar results would be found for other taggants stipulated by the Marplex Convention,given they are also present in concentrations less than 1%.

Research Progress in Detection of Explosives by Chemical Colorimetric Method

This article reviews the current application status and research progress of colorimetric detection methods based on chemical colorimetry in the detection of explosives.It mainly introduced colorimetric sensors,colorimetric sensor arrays,and chemical colorimetric sensors based on novel material substrates.The application prospect of chemical colorimetric method in the field of explosives detection was prospected.

Ordered Solidification Technique Under Low Pressures in the Loading of Molten Explosives

In order to improve the quality of loading and make the ammuni- tion safe in use,a new loading technique of ordered solidification has been studied.The study shows that the adoption of this new technique makes the charge more compact and brings about a satisfactory supplement of liquid ex- plosives,thus increasing the charge density,which is most advantageous to the crimination of pores,cavities,gaps at the bottom and in loose struc- tures.The physical mechanical properties of the charge are hence greatly im- proved,and the sensitivity of the charge to environmental stimulations is much lowered.

Pyrolysis of CL20-BTF Co-crystal via ReaxFF-lg Reactive Force Field Molecular Dynamics Simulations

To obtain detailed information on the potential energy, the evolution of species, the initial reaction paths, and thermal decomposition products, we conducted simulations on pyrolysis process of CL20/BTF co-crystal using the ReaxFF/lg reaction force field, with temperature set at 2000 K to 3000 K. With the analysis of evolution curves of potential energy based on exponential function, we obtain the overall characteristic time. Via a description of the total package reaction with classical Arrhenius law, we obtain the activation energy of CL20/BTF co-crystal： Ea=60.8 kcal/mol. Based on the initial path of CL20/BTF co-crystal thermal decomposition we studied, we conclude that N-NO2 bond of CL20 molecules breaks first, working as a dominant role in the initial stage of thermal decomposition under the condition of different temperatures, and that all CL20 molecules completely decompose before BTF molecular regardless of different temperatures. We also find that the main products of CL20/BTF co-crystal are NO2, NO, NO3, HNO, O2, N2, H2O, CO2, N2O, and HONO, etc., on which the temperature forms certain influence.

Detonation Behavior of Intermolecular Explosives EAR

In order to find out the detonation mechanism of intermolecular explosives (IMX), the EAR15 explosive is studied by the experiments and numerical modeling. The results show that EAR15 is a nonideal explosive, since in the detonation reaction zone both reacted and unreacted ammonium nitrate (AN) absorb the energy through the interface, resulting in the characteristic of nonideal detonation. In our tests, only 19%-49% active AN takes part in reaction, the rest behaves as the inert at the detonation wave front.

Thermobaric and enhanced blast explosives(TBX and EBX)

In this review, excerpts from the literature of thermobaric(TBX) and enhanced blast explosives(EBX) that are concentrated on studies that include their compositions, properties, reactive metal components, modeling and computations are presented.

Effects of Al/O on pressure properties of confined explosion from aluminized explosives

Pressure histories were tested in a 500-L chamber to identify the pressure load in confined explosion from aluminized explosives. Different aluminized explosives with Al/O, ranging from 0.25 to 1.23, were used. The recorded pressure curves could express the reflection of initial shock wave and the after burning combustion of aluminum. As there is no objective way to gain quasi-static pressure(P_(QS)),method of multipoint averaging was used in smoothing the original pressure curves to gain the P_(QS). The P_(QS),rising time of pressure(t_(QS)) which stands for the duration of the initial reflected shock wave, and attenuation coefficient(ω) which stands for the supportive effects of the combustion of aluminum to the P_(QS) are used to characterize the pressure load in the confined explosion from aluminized explosives. The research results showed that the Al/O significantly affected the three characteristic quantities. With the increase of Al/O, the P_(QS) increased at first and decreased later, gaining maximum at Al/O=0.99; the t_(QS)sustained growth and the ω decreased at first and increased later, gaining minimum at AI/O=0.99.

Thermal decomposition and kinetics of plastic bonded explosives based on mixture of HMX and TATB with polymer matrices

This work describes thermal decomposition behaviour of plastic bonded explosives(PBXs) based on mixture of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX) and 2,4,6-triamino-1,3,5-trinitrobenzene(TATB)with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis(STA) and differential scanning calorimetry(DSC) to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis(TGA) indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn—Wall—Ozawa(FWO) and Kissinger-Akahira-Sunose(KAS)methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.

Effect of energy content of the nitraminic plastic bonded explosives on their performance and sensitivity characteristics

Information about the forty nine nitraminic plastic bonded explosives(PBXs)and different nitramines were collected.Fillers of these PBXs are nitramines 1,3,5-trinitro-1,3,5-triazinane(RDX)and β-1,3,5,7-tetranitro-1,3,5-tetrazocane(β-HMX),cis-1,3,4,6-tetranitro-octahydroimidazo-[4,5-d]imidazole(bicyclo-HMX,BCHMX)and e-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(e-HNIW,CL-20)which are bonded by polyfluoro-elastomers,polydimethyl-siloxane,poly-glycidyl azide,polyisobutylene,polystyrene-butadiene,poly-acrylonitrile-butadiene and hydroxyl-terminated polybutadiene in addition to a melt cast compositions based on 2,4,6-trinitrotoluene.For thirty two of these PBXs the relationships are specified and analyzed between heats of their combustion and relative explosive strengths;by means of these relationships it might be possible to estimate,which groupings in the macromolecule of binder could be liable to their primary fission in the PBXs initiation.Similarly,for forty two of these explosives,the relationships are described and analyzed between their enthalpies of formation and impact sensitivities;here is especially attention paid to PBXs filled by BCHMX.Specific rate constants from Vacuum Stability Test(VST)of four nitramines and twenty PBXs are introduced into relationships with their enthalpies of formation.Regarding to all the mentioned cases,increasing of energy content of the studied explosives leads to increase of the relative explosive strength or initiation reactivity,respectively.Exception with the opposite trend,the outputs of VST are for BCHMX,where in PBXs are matrices with the esteric plasticizers or the energetic poly-glycidyl azide.Admixture of RDX or HMX,respectively,into the BCHX PBXs gives ternary PBXs whose thermal stability,in the sense of applied VST,is higher comparing to the original binary explosives.

Preparation of reduced sensitivity co-crystals of cyclic nitramines using spray flash evaporation

The present day weapon technology demands novel energetic materials that exhibit simultaneous high explosive yield and reduced sensitivity.This article demonstrates application of spray evaporation to prepare reduced sensitive co-crystals of high performance nitramine explosives like HMX and CL-20 with a relatively less insensitive explosive 1,1-diamino-2,2-dinitroethylene or FOX-7.Stronger intermolecurar hydrogen bonding in FOX-7 is responsible for limited solubility in nost of o rganic solvents.Large solubility differences of FOX-7 with HMX and CL-20 restricts ifs co-crystallization through classical methods that yields thermodynamically favorable product.Spray flash evaporation,a kinetic crystallization method,has been therefore adopted and could successfully produce CL-20/FOX-7(2:1) and HMX/FQX-7(4:1) co-crystals.The fine powdered materials obtained were characterized by SEM,powder XRD,Raman spectro scopy,DSC-TGA etc.Multipoint Raman spectra showed consistent occurrence of spectral features indicating stoichiometric co-existence of ingredients in the crystal lattices.DSC analysis showed absence of all thermally assisted solidsolid phase transformation in the co-crystals as they were observed in pristine materials.The thermal stability calculated in terms of activation barrier fordecomposition,revealed the CL-20/FOX-7 co-crystal to be interlediately stable on comparison to their constituents while,the HMX/FOX-7 co-crystal is more stable.Compared to pure HMX and CL-20,both the co-crystals have shown higher insensitivity to impact force,suggesting them to be suitable for future generation insensitive munitions.

Explosion temperature mapping of emulsion explosives containing TiH_(2)powders with the two-color pyrometer technique

In the study,the two-color pyrometer technique was used to measure the transient temperature field of emulsion explosives with different contents of TiH_(2)powders.The experimental results showed that the introduction of TiH_(2)powders could significantly increase the explosion temperature and fireball duration of emulsion explosive.When emulsion explosives were ignited,the average explosion temperature of pure emulsion explosive continuously decreased while emulsion explosives added with TiH_(2)powders increased at first and then decreased.When the content of TiH_(2)powders was 6 mass%,the explosion average temperature reached its maximum value of 3095 K,increasing by 43.7%as compared with that of pure emulsion explosive.In addition,the results of air blast experiment and explosion heat test showed that the variation trends of shock wave parameters,explosion heat and theoretical explosion temperature of emulsion explosives with different contents of TiH_(2)powders were basically consistent with that of explosion temperature measured by the two-color pyrometer technique.In conclusion,the two-color pyrometer technique would be conducive to the formula design of emulsion explosive by understanding the explosion temperature characteristics.

Influence of an emulsifier on the pressure desensitization of emulsion explosives

The desensitization degree of emulsion explosives （EE） was calculated with the peak pressure of explosion shock waves tested in water. To an explosive, the less the desensitization degree, the better the compression resistance, so the compression resistance of an explosive can be compared and analyzed quantificationally with the desensitization degree. The influence of an emulsifier on the pressure desensitization of EE was studied, including the content and category of emulsifiers. Three kinds of emulsifiers （Span-80, compound emulsifier, and T-152） were used in the tests. The experimental results show that both the content and category of emulsifiers make a great effect on the pressure desensitization of EE. The desensitization degree of EE reduces with the emulsifier content being increased, but there is an optimal content of an emulsifier for the compression resistance of EE. While the content of Span-80 reaches 4wt%, the desensitization degree of EE becomes a minimal value, and augments somewhat if the emulsifier content is increased more. That is to say, the compression resistance of EE becomes the highest while the content of Span-80 is 4wt%, and the compression resistance will decline if the content of Span-80 is increased more. The compression resistance of the explosive emulsified by compound emulsifier is the highest among all the explosives, when the content of the whole components and manufacturing engineering are kept invariable.

Effect of metal powders on explosion of fuel-air explosives with delayed secondary igniters

In order to improve the energy level of fuel air explosive(FAE) with delayed secondary igniters, high energetic metal powders were added to liquid fuels mainly composed of ether and isopropyl nitrate.Metal powders’ explosive properties and reaction mechanisms in FAE were studied by high-speed video,pressure test system, and infrared thermal imager. The results show that compared with pure liquid fuels, the shock wave overpressure, maximum surface fireball temperature and high temperature duration of the mixture were significantly increased after adding high energetic metal powder. The overpressure values of the liquid-solid mixture at all measuring points were higher than that of the pure liquid fuels. And the maximum temperature of the fireball was up to 1700C, which was higher than that of the pure liquid fuels. After replacing 30% of aluminum powder with boron or magnesium hydride, the shock wave pressure of the mixture was further increased. The high heat of combustion of boron and the hydrogen released by magnesium hydride could effectively increase the blast effect of the mixture. The improvement of the explosion performance of boron was better than magnesium hydride. It shows that adding high energetic metal powder to liquid fuels can effectively improve the explosion performance of FAE.