Theoretical design of new bridge-ring insensitive high energy compounds by selected normal Diels-Alder reactions between NH2-substituted oxazoles and NO2/NF2/NHNO2-substituted ethylenes/acetylenes

In this work, NH₂-substituted oxazoles and NO₂/NF₂/NHNO₂-substituted ethylenes/acetylenes were designed and used as dienes and dienophiles, respectively, in order to develop new bridge-ring insensitive high energy compounds through the Diels-Alder reaction between them. The reaction type, reaction feasibility and performance of reaction products were investigated in detail theoretically. The results showed that dienes most possibly react with dienophiles through the HOMO-diene controlled normal Diels-Alder reaction at relatively low energy barrier. Tetranitroethylene could react with the designed dienes much more easily than other dienophiles, and was employed to further design 29 new bridge-ring energetic compounds. Due to high heat of formation, density and oxygen balance, all designed bridge-ring energetic compounds have outstanding detonation performance, 16 of them have higher energy than HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and 2 others even possess comparative energy with the representative of high energy compounds CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane). The predicted average h₅₀ value of these bridge-ring energetic compounds is 83 cm, showing their low impact sensitivity. The NH₂ groups could obviously impel the proceeding of Diels-Alder reactions, but would slightly decrease the energy and sensitivity performance. In all, the new designed bridge-ring compounds have both high energy and low sensitivity, and may be produced through Diels-Alder reactions at relatively low energy barrier. This paper may be helpful for the theoretical design and experiment synthesis of new advanced insensitive high energy compounds.     

Nitro-tetrazole based high performing explosives: Recent overview of synthesis and energetic properties

Heterocyclic skeleton (Azoles) and different energetic groups containing high performing explosives are highly emerged in recent years to meet the challenging requirements of energetic materials in both military and civilian applications with improved performance. For this purpose tetrazole (Azole) is identified as an attractive heterocyclic backbone with energetic functional groups nitro (-NO₂), nitrato (-ONO₂), nitrimino (-NNO₂), and nitramino (–NH–NO₂) to replace the traditionally used high performing explosives. The tetrazole based compounds having these energetic functional groups demonstrated advanced energetic performance (detonation velocity and pressure), densities, and heat of formation (HOF) and became a potential replacement of traditional energetic compounds such as RDX. This review presents a summary of the recently reported nitro-tetrazole energetic compounds containing poly-nitro, di/mono-nitro, nitrato/nitramino/nitrimino, bridged/bis/di tetrazole and nitro functional groups, describing their preparation methods, advance energetic properties, and further applications as high-performing explosives, especially those reported in the last decade. This review aims to provide a fresh concept for designing nitro-tetrazole based high performing explosives together with major challenges and perspectives.     

Hyperspectral imaging and remote trace detection of cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5 d] imidazole (BCHMX) compared with traditional explosives using laser induced fluorescence

cis-1,3,4,6-Tetranitrooctahydroimidazo-[4,5 d] imidazole (BCHMX) is an advanced energetic compound that expected to spread worldwide in the near future. Since, no approved remote detection methods were reported in current literature for this material, we performed hyper-spectral imaging and laser induced fluorescence (LIF) to a BCHMX sample under low laser fluence for determining the optimum laser wavelength used in any future BCHMX-LIF based remote detection systems. For this purpose, an experimental setup consisted of a sun spectrum lamp and hyper-spectral camera was built to illuminate and image white powder samples of BCHMX in comparison with the traditional explosives, HMX (1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane), RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), PETN (2,2-Bis[(nitroxy)methyl]propane-1,3-diyldinitrate). The imaging reveals strong BCHMX sample absorption contrast among other samples at wavelength ranging from 400 to 410 nm. When light source was replaced by a 405 nm laser diode illuminator, a strong BCHMX sample LIF at the spectral range from 425 to 700 nm was observed under low laser fluence condition of 0.1 mJ/cm². Finally, we demonstrated successfully the ability of the 405 nm LIF and the hyperspectral imaging technique to detect finger print traces of BCHMX on white cellulose fabric from a distance of 15 m and a detection limit of 1 μg/cm².     

Theoretical study of an energetic material di-1H-1,3,4-triazole derivatives

Computations by density functional theory (DFT) method are performed on a series of di-1H-1,3,4-triazole derivatives with different substituents and linkages. The heat of formation (HOF) is predicted by the designed isodesmic reactions. The predicted results reveal that –N₃ and –NN– groups are effective structural units for increasing the HOF values of the di-1H-1,3,4-triazole derivatives. The HOMO–LUMO gap is affected by the substituents and linkage groups. Detonation performance is evaluated using the Kamlet–Jacobs approach based on the calculated density and HOF. The results indicate that –NO₂, –NF₂, –NH–, –NH–NH– and –NN– groups are helpful for enhancing the detonation properties of di-1H-1,3,4-triazole derivatives. The bond dissociation energy and bond order of the weakest bonds are analyzed to investigate their stability. It is observed that the –CH₂–, –CH₂–CH₂– and –CHCH– groups are effective structural units for improving the stabilities of these derivatives. Considering the detonation performance and the stability, five compounds are screened as the potential candidates for high energy density materials.     

Preparation and characterization of HMX/NH2-GO composite with enhanced thermal safety and desensitization

To improve the safety of HMX, HMX/NH₂-GO composite was prepared with aqueous ammonia functionalized graphene oxide (NH₂-GO). The composite was characterized by SEM, Zeta potential, XPS, Raman spectrum, XRD, HPLC, DSC and BAM sensitivity test. The results indicated that the functionalization with aqueous ammonia can enhance the interaction between GO and HMX, and more efficiently desensitize the explosive. The optimal impact sensitivity of the HMX/NH₂-GO composite can be not less than 40 J, which is also the most insensitivity compared to the previous reports prepared by coating desensitization with non-energetic desensitized material. Moreover, the potential reason for the different impact and friction sensitivity was also discussed, which may bring a novel perspective to achieve the desensitization of energetic material.     

Synthesis and properties of novel nitro-based thermally stable energetic compounds

This paper reviews the achievements in the field of synthesis of new thermally resistant explosive compounds in the years 2009 through 2019. The performance characteristics of these compounds (sensitivity, thermal decomposition parameters, and detonation parameters) were compared with those of 1,3,5-triamino-2,4,6-trinitrobenzene, which still seems to be an unrivalled model of a thermally resistant and generally low-sensitivity explosive material. New thermally stable explosives (TSEs) were found among macromolecular compounds with tri- and dinitrophenyl groups, nitro and amine-nitro derivatives of azoles, and polynitro derivatives of calixarenes. Some of them match TATB in terms of thermal resistance and additionally have higher detonation parameters.     

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 ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-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.     

Insensitive energetic microspheres DAAF/RDX fabricated by facile molecular self-assembly

Insensitive energetic materials are promising in the defense weapons field. However, energetic materials still suffer from great challenges and the concern about their safety limits their utilization. In this work, insensitive energetic explosive 3,3′-diamino-4,4′-azoxyfurazan/hexahydro-1,3,5-trinitro-1,3,5-triazine (DAAF/RDX) microspheres were fabricated by self-assembly method. Rod-like DAAF/RDX was prepared by mechanical ball milling for comparison. DAAF/RDX composites with different mass ratios (90:10, 80:20, and 70:30) were obtained. The morphologies and structures of as-obtained DAAF/RDX composites were characterized by scanning electron microscopy (SEM), powder x-ray diffraction (PXRD) and fourier transform infrared spectroscopy (FT-IR). The results showed that DAAF/RDX microspheres exhibited regular shaped microspheres with sizes from 0.5 to 1.2 μm. There was no crystal transition during the modification process. The thermal properties of as-obtained materials were then evaluated by differential scanning calorimetry (DSC) and materials studio software. DAAF/RDX microspheres showed an advanced decomposition peak temperature compared with rod-like DAAF/RDX. The binding energy and peak temperature values at zero β_i (T_P0) of DAAF/RDX (90:10) increased by 36.77 kJ/mol, 1.6 °C, and 58.11 kJ/mol, 12.3 °C compared to DAAF/RDX (80:20) and DAAF/RDX (70:30), indicating the better thermal stability of DAAF/RDX (90:10). The characteristic drop height (H₅₀) of DAAF/RDX (higher than 100 cm) composites was higher than that of raw RDX (25 cm), suggesting significant improvements in mechanical safety. The preparation of DAAF/RDX microspheres is promising for the desensitization of RDX and useful for the formation of other materials and future wide applications.     

Shock initiation performance of NTO-based polymer bonded explosive

3-nitro-1,2,4-tri-azol-5-one (NTO) is a high energy insensitive explosive. To study the shock initiation process of NTO-based polymer bonded explosive JEOL-1 (32%octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 32% NTO, 28% Al and 8% binder system), the cylinder test, the gap experiments and numerical simulation were carried out. Firstly, we got the detonation velocity (7746 m/s) and the parameters of Jones-Wilkins-Lee (JWL) equation of state (EOS) for detonation product by cylinder test and numerical simulation. Secondly, the Hugoniot curve of unreacted explosive for JEOL-1 was obtained calculating the data of pressure and time at different Lagrangian positions. Then the JWL EOS of unreacted explosive was obtained by utilizing the Hugoniot curve as the reference curve. Finally, we got the pressure growth history of JEOL-1 under shock wave stimulation and the parameters of the ignition and growth reaction rate equation were obtained by the pressure-time curves measured by the shock-initiation gap experiment and numerical simulation. The determined trinomial ignition and growth model (IG model) parameters can be applied to subsequently simulation analysis and design of insensitive ammunition with NTO-based polymer bonded explosive.     

Prediction of concentration of toxic gases produced by detonation of commercial explosives by thermochemical equilibrium calculations

An adverse effect resulting from explosive mine blasts is the production of toxic nitrogen oxides (NO and NO₂) and carbon monoxide (CO). The empirical measurements of the concentration of toxic gases showed that it depends not only on the composition of an explosive and properties of its ingredients but also on several other parameters, such as volume of blasting chamber, explosive charge mass and design, confinement characteristics, surrounding atmosphere, etc. That explains why measured concentrations of toxic gases reported in literature significantly differ.In this paper, we discuss the possibility of theoretical prediction of the concentration of toxic gases by thermochemical equilibrium calculation applying two models: ideal detonation model and deflagration model. It can be demonstrated that thermochemical calculations can provide a good estimation of the measured concentrations and reproduce experimentally obtained effects of additives on the production of toxic gases. It was also found that the ideal detonation model applies to heavily confined explosive charges, while the deflagration model is more suitable for low detonation velocity explosives with light confinement.     

Theoretical calculation and experimental study on the interaction mechanism between TKX-50 and AP

The combination of 5,5′-bistetrazole-1,1′-diolate (TKX-50) and ammonium perchlorate (AP) can make greater use of the chemical energy of TKX-50 based energetic materials. The research on the interaction mechanism between TKX-50 and AP is very important for designing TKX-50-AP compounds and judging the formation feasibility of composite particles, which can lay a theoretical foundation for the preparation of TKX-50-AP mixed crystals and the application of TKX-50 in propellant, propellant and explosive. Herein, in order to research the interaction mechanism between TKX-50 and AP, density-functional theory calculation was applied to optimize three configurations of TKX-50-AP compounds. The geometry structure, electrostatic potential and binding energy of the compounds were predicted, and the electronic density topological analysis was also carried out. Then TKX-50-AP mixed crystals structures were constructed, and the radial distribution function of H–O and H–N in mixed crystals was calculated. Finally, solvent/non-solvent method was applied to prepare TKX-50-AP composites, and the infrared spectroscopy and the non-isothermal decomposition performance of the composites were characterized. Results show that the superposition of positive charges in TKX-50 molecule and negative charges in AP makes the electrostatic potential distributions of TKX-50-AP compounds different from that of TKX-50 and AP. The interaction energies of TKX-50-AP 1, TKX-50-AP 2 and TKX-50-AP 3 are 39.743 kJ/mol, 61.206 kJ/mol and 27.702 kJ/mol, respectively. The interaction between TKX-50 molecules and AP molecules in TKX-50-AP mixed crystals both depends on hydrogen bonds and van der Waals force, and the number and strength of hydrogen bonds are significantly greater than that of van der Waals force. The composition of AP and TKX-50 makes the absorption peak of the five-membered rings and NH₃OH⁺ of TKX-50 shift to low wavenumber in the infrared spectroscopy. In general, TKX-50 interacts with AP via hydrogen bonds and van der Waals force, and the calculated results are in good agreement with the experimental results. The composition of TKX-50 and AP can also prolong the decomposition process.     

Preparation and property of CL-20/BAMO-THF energetic nanocomposites

A sol-gel freezing-drying method was utilized to prepare energetic nanocomposites based on 2, 4, 6, 8, 10, 12-hexanitro-2, 4, 6, 8, 10, 12-hexaazaisowurtzitane (CL-20) with 3, 3-Bis (azidomethyl) oxetane-tetrahydrofuran copolymer (BAMO-THF) as energetic gel matrix. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman, Fourier-transform infrared spectroscopy (FT-IR) and differential thermal analyser (DTA) were utilized to characterize the structure and property of the resultant energetic nanocomposites. Compared with raw CL-20, the average particle sizes of CL-20 in CL-20/BAMO-THF energetic nanocomposites were decreased to nano scale and the morphologies of CL-20 were also changed from prismatic to spherical. FT-IR detection revealed that CL-20 particles were recrystallized in BAMO-THF gel matrix during the freezing-drying process. The thermal decomposition behaviors of the energetic nanocomposites were investigated as well. The thermolysis process of CL-20/BAMO-THF nanocomposites was enhanced and the activation energy was lower compared with that of raw CL-20, indicating that CL-20/BAMO-THF nanocomposites showed high thermolysis activity. The impact sensitivity tests indicated that CL-20/BAMO-THF energetic nanocomposites presented low sensitivity performance.     

Study of simple plane wave generator with an air-metal barrier

Plane wave generators (PWGs) are used to accelerate flyer plates to high velocities with their generated plane waves, which are widely used in the test of dynamic properties of materials. The traditional PWG is composed of two explosives with different detonation velocities. It is difficult to implement the related fabrication processes and control the generated waves due to its complicated structures. A simple plane wave generator is presented in this paper, which is composed of two identical cylindrical high explosive (HE) charges and an air-metal barrier. A theoretical model was established based on two different paths of the propagation of detonation waves, based on which the size of air-metal barrier was calculated for a given charge. The corresponding numerical simulations were also carried out by AUTODYN-2D^® based on the calculated results, which were used to compare with the theoretical calculations. A detonation wave with a flatness of 0.039 μs within the range of 70-percent diameter of the main charge was obtained through the simulations.     

Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

A differential/integral method to estimate the kinetic parameters (apparent activation energy E_a and pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane (HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy (E_a) obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion (T_b) and adiabatic time-to-explosion (t_TIad) based on Kooij formula are used to calculate the values of T_b and t_TIad to evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of E_a and A of decomposition reaction of HNIW are 3(1 − α)[−ln(1 − α)]^2/3, 152.73 kJ mol⁻¹ and 10^11.97 s⁻¹, respectively, and the values of self-accelerating decomposition temperature (T_SADT), T_b and t_TIad are 486.55 K, 493.11 K and 52.01 s, respectively.     

Ni-Zn铁氧体粉末的溶胶-凝胶合成及微波性能

以硝酸铁、硝酸镍、硝酸锌、柠檬酸和氨水为原料,用溶胶-凝胶法合成了不同组成的Ni-Zn铁氧体粉末。利用热分析、X射线衍射等手段研究了干凝胶热分解行为。利用网络分析仪对铁氧体粉末的电磁性能进行了表征,考察了铁氧体的组成与其电磁性能之间的关系。结果表明,溶胶-凝胶法合成的铁氧体粉末的μ″值随测试频率的提高和Ni-Zn铁氧体中锌含量的增加而减小。     

Experimental and numerical investigations of interface properties of Ti6Al4V/CP-Ti/Copper composite plate prepared by explosive welding

Explosive welding technique is widely used in many industries. This technique is useful to weld different kinds of metal alloys that are not easily welded by any other welding methods. Interlayer plays an important role to improve the welding quality and control energy loss during the collision process. In this paper, the Ti6Al4V plate was welded with a copper plate in the presence of a commercially pure titanium interlayer. Microstructure details of welded composite plate were observed through optical and scanning electron microscope. Interlayer-base plate interface morphology showed a wavy structure with solid melted regions inside the vortices. Moreover, the energy dispersive spectroscopy analysis in the interlayer-base interface reveals that there are some identified regions of different kinds of chemical equilibrium phases of Cu–Ti, i.e. CuTi, Cu₂Ti, CuTi₂, Cu₄Ti, etc. To study the mechanical properties of composite plates, mechanical tests were conducted, including the tensile test, bending test, shear test and Vickers hardness test. Numerical simulation of explosive welding process was performed with coupled Smooth Particle Hydrodynamic method, Euler and Arbitrary Lagrangian-Eulerian method. The multi-physics process of explosive welding, including detonation, jetting and interface morphology, was observed with simulation. Moreover, simulated plastic strain, temperature and pressure profiles were analysed to understand the welding conditions. Simulated results show that the interlayer base plate interface was created due to the high plastic deformation and localized melting of the parent plates. At the collision point, both alloys behave like fluids, resulting in the formation of a wavy morphology with vortices, which is in good agreement with the experimental results.     

Experimental study on the detonation process of a pulse detonation engine with ionized seeds

An experimental platform of a pulse detonation engine (PDE) was established to study the effect of different K₂CO₃ ionized seed mass contents on the detonation process. The pressure and ion concentration were detected in the detonation process of the PDE with different contents of ionized seeds. The initiation process of the PDE at different ignition frequencies was studied. The results show that the gas conductivity in the detonation process increased by adding ionized seeds to the PDE tube, and the conductivity increased with the increase in ionized seed mass content. With the increase in ionized seed mass content, the range of the conductivity decreased. The PDE was successfully ignited and formed a stable detonation wave at ignition frequencies of 5 Hz and 10 Hz, and the peak pressure of the stable detonation with the ignition frequency of 5 Hz was 17% higher than that with an ignition frequency of 10 Hz. The detonation wave intensity was weakened and degenerated to a shock wave that propagated in the tube without the fuel filled at the ignition frequency of 20 Hz.     

Numerical modelling of non-ideal detonation in ANFO explosives applying Wood-Kirkwood theory coupled with EXPLO5 thermochemical code

Ammonium nitrate and fuel oil (ANFO) based explosive is a classic example of non-ideal high explosives. Its detonation is characterized by a strong dependence of detonation parameters on explosive charge diameter, presence and characteristics of confinement, as well as incomplete consumption of explosive at the sonic point.In this work we propose a detonation model based on the Wood-Kirkwood (WK) theory coupled with the thermochemical code EXPLO5 and supplemented with reaction rate models. Our objective is to analyze the validity of the model for highly non-ideal ANFO explosives, with emphasis on effect of reaction rate models.It was found that both single-step and two-step pressure-based models can be calibrated to reproduce experimental detonation velocity-charge radius data of ANFO at radii significantly above the failure radius (i.e. for D/D_id > ∼0.6). Single-step pressure-based model, with the pressure exponent equal to 1.4, proved to be the most accurate, even in the vicinity of the failure radius. The impact of the rate models is most evident on temporal (and spatial) distribution of flow parameters in detonation driving zone, especially when it comes to the conversion and width of detonation driving zone.     

Studies on the flame propagation characteristic and thermal hazard of the premixed N2O/fuel mixtures

An experimental study was carried out to investigate the flame propagation and thermal hazard of the premixed N₂O/fuel mixtures, including NH₃, C₃H₈ and C₂H₄. The study provided the high speed video images and data about the flame locations, propagation patterns, overpressures and the quenching diameters during the course of combustion in different channels to elucidate the dynamics of various combustion processes. The onset decomposition temperature was determined using high-performance adiabatic calorimetry. It was shown that the order of the flame acceleration rate and thermal hazard was N₂O/C₂H₄>N₂O/C₃H₈>N₂O/NH₃.     

Preparation and characterization of HMX/EVA/hBNNSs micro-composites with improved thermal stability and reduced sensitivity

Hexagonal boron nitride nanosheets(HBNNSs)have huge potential in the field of coating materials owing to their remarkable chemical stability,mechanical strength and thermal conductivity.Thin-layer hBNNSs were obtained by a liquid-phase exfoliation of h-BN powders and incorporated into EVA coatings for improving the safety performance of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX).HBNNSs and ethylene-vinyl acetate copolymer(EVA)were introduced to HMX by a solvent-slurry process.For com-parison,the HMX/EVA and HMX/EVA/graphene(HMX/EVA/G)composites were also prepared by a similar process.The morphology,crystal form,surface element distribution,thermal decomposition property and impact sensitivity of HMX/EVA/hBNNSs composites were contrastively investigated.Results showed that as prepared HMX/EVA/hBNNSs composites were well coated with hBNNSs and EVA,and exhibited better thermal stability and lower impact sensitivity than that of HMX/EVA and HMX/EVA/G composites,suggesting superior performance of desensitization of hBNNSs in explosives.