Energetic Co-Crystal of a Primary Metal-Free Explosive with BTF. Ideal Pair for Co-Crystallization

Co-crystallization is an elegant technique to tune the physical properties of crystalline solids. In the field of energetic materials, co-crystallization is currently playing an important role in the engineering of crystals with improved performance. Here, based on an analysis of the structural features of the green primary explosive, tetramethylammonium salt of 7-oxo-5-(trinitromethyl)-4,5,6,7-tetrahydrotetrazolo[1,5-a][1,3,5]triazin-5-ide (1), a co-former such as the powerful secondary explosive, benzotrifuroxan (BTF, 2), has been proposed to improve it. Compared to the original 1, its co-crystal with BTF has a higher detonation pressure and velocity, as well as an initiating ability, while the impact sensitivity and thermal stability remained at about the same level. Both co-formers, 1 and 2, and co-crystal 3 were characterized by single-crystal X-ray diffraction and their crystal packing was analyzed in detail by the set of approaches, including periodic calculations. In the co-crystal 3, all intermolecular interactions were significantly redistributed. However, no new types of intermolecular interactions were formed during co-crystallization. Moreover, the interaction energies of structural units in crystals before and after co-crystallization were approximately the same. A similar trend was observed for the volumes occupied by structural units and their densifications. The similar nature of the organization of the crystals of the co-formers and the co-crystal gives grounds to assert that the selected co-formers are an ideal pair for co-crystallization, and the invariability of the organization of the crystals was probably responsible for the preservation of some of their properties.

INFLUENCE OF DETONATION PRESSURE OF EXPLOSIVE COMPOSITIONS ON HEAT OF EXPLOSION

К настоящему времени накоплен большой объём калориметрических данных о теплоте (энергии) взрыва Q различных взрывчатых веществ (ВВ) и взрывчатых составов (ВС). Получены зависимости Q от начальной плотности ВВ Q(ρ0). Однако, на практике давление детонации в основном заряде можно менять, вызывая пересжатую детонацию, за счёт инициирования основного заряда мощным ВВ, поэтому практический интерес представляют зависимости теплоты взрыва от давления детонации Q(Р), которые можно получить на основе имеющихся зависимостей Q(ρ0) для индивидуальных ВВ, распространив их на ВС. Приведена методика определения зависимостей для расчёта теплоты взрыва различных ВС, включая алюминийсодержащие, как при нормальной так и при пересжатой детонации A large volume of calorimetric data on the heat energy Q of explosion for various explosives (Es) and explosive compositions (EC) has been accumulated by now. The dependences of Q on the initial ES density Q (ρ0) are obtained. However, the detonation pressure in the base charge can be changed in practice causing super compressed detonation, due to the initiation of the base charge by a powerful explosive; therefore, the dependences of the explosion heat on the detonation pressure Q (P), which can be obtained on the basis of the available dependences Q (ρ0) for individual explosives is of practical interest as they can be applied to EC. A method to determine the dependences for calculating the heat of explosion of various aircraft, including aluminum-containing ones, both during normal and super compressed detonation is presented.

Energetic Windmill: Computational insight into planar guanidine-based nitroazole-substituted compounds as energetic materials

In this work, we designed a series of energetic materials with a windmill-like structure based on guanidine and nitroazole, and optimized them at the B3LYP/6-311G** level using density functional theory (DFT). According to the optimization results, 6 molecules with planar structures were screened out from 28 molecules and their regularities were summarized. We calculated their geometry, natural bond orbital (NBO) charge, frontier molecular orbital, molecular surface electrostatic potential, and thermochemical parameters. In addition, their properties such as density, enthalpy of formation, detonation velocity, detonation pressure and impact sensitivity are also predicted. The result shows that this series of compounds is a promising new type of energetic material, especially compound 1 has superior detonation velocity and detonation pressure (D=9720m/s, P=41.9GPa).

Design and Selection of Pyrazolo[3,4-d][1,2,3] Triazole-based High-energy Materials

In this study, we design a series of bridged energetic compounds based on pyrazolo[3,4-d][1, 2, 3]triazole to screen potential energetic materials with excellent detonation properties and acceptable sensitivities. The electronic structures, heats of formation, detonation velocity, detonation pressure, and impact sensitivity of the designed compounds were calculated using density functional theory. The results showed that the designed compounds have high positive heats of formation in the range of 1035.4 (A7) to 2851.4 kJ mol−1 (D2). Moreover, the designed compounds have high crystal densities and heats of detonation, which significantly enhance detonation pressures and velocities. The detonation pressures and velocities are in the ranges of 6.23 (A1) to 9.65 km s−1 (D3) and 15.7 to 43.9 GPa (E8), respectively. The impact sensitivity data also suggest that the designed compounds have impact sensitivities in an acceptable range. Considering detonation pressures, detonation velocities, and impact sensitivities, six compounds (C3, C5, D3, D5, E3, and F3) were screened as potential materials with high energy density, excellent detonation properties, and low impact sensitivities. Finally, the electronic structures of the screened compounds were simulated to provide further understanding on the physicochemical properties of these compounds.

A Constitutive Modeling and Experimental Effect of Shock Wave on the Microstructural Sub-strengthening of Granular Copper

Micro-sized copper powder (99.95%; O≤0.3) has been shock-processed with explosives of high detonation velocities of the order of 7.5km/s to observe the structural and microstructural sub-strengthening. Axisymmetric shock-consolidation technique has been used to obtain conglomerates of granular Cu. The technique involves the cylindrical compaction system wherein the explosive-charge is in direct proximity with the powder whereas the other uses indirect shock pressure with die-plunger geometry. Numeric simulations have been performed on with Eulerian code dynamics. The simulated results show a good agreement with the experimental observation of detonation parameters like detonation velocity, pressure, particle velocity and shock pressure in the reactive media. A pin contactor method has been utilized to calculate the detonation pressure experimentally. Wide angled x-ray diffraction studies reveal that the crystalline structure (FCC) of the shocked specimen matches with the un-shocked specimen. Field emissive scanning electron microscopic examination of the compacted specimens show a good sub-structural strengthening and complement the theoretical considerations. Laser diffraction based particle size analyzer also points towards the reduced particle size of the shock-processed specimen under high detonation velocities. Micro-hardness tests conducted under variable loads of 0.1kg, 0.05kg and 0.025kg force with diamond indenter optical micrographs indicate a high order of micro-hardness of the order of 159Hv. Nitrogen pycnometry used for the density measurement of the compacts shows that a compacted density of the order of 99.3% theoretical mean density has been achieved.

Model for Calculating Seismic Wave Spectrum Excited by Explosive Source

To reveal the characteristics and laws of the seismic wavefield amplitude-frequency excited by explosive source, the method for computing the seismic wave spectrum excited by explosive was studied in this paper. The model for calculating the seismic wave spectrum excited by explosive source was acquired by taking the seismic source model of spherical cavity as the basis. The results of using this model show that the main frequency and the bandwidth of the seismic waves caused by the explosion are influenced by the initial detonation pressure, the adiabatic expansion of the explosive, and the geotechnical parameters, which increase with the reduction of initial detonation pressure and the increase of the adiabatic expansion. The main frequency and the bandwidth of the seismic waves formed by the detonation of the explosives in the silt clay increase by 23.2% and 13.6% compared to those exploded in the silt. The research shows that the theoretical model built up in this study can describe the characteristics of the seismic wave spectrum excited by explosive in a comparatively accurate way.

Theoretical studies of novel high energy density materials based on oxadiazoles

In this study, 32 energetic compounds were designed using oxadiazoles (1,2,5-oxadiazole, 1,3,4-oxadiazole) as the parent by inserting different groups as well as changing the bridge between the parent. These compounds had high-density and excellent detonation properties. The electrostatic potentials of the designed compounds were analyzed using density functional theory (DFT). The structure, heat of formation (HOF), density, detonation performances (detonation pressure P , detonation velocity D , detonation heat Q ), and thermal stability of each compound were systematically studied based on molecular dynamics. The results showed that the -N 3 group has the greatest improvement in HOF. For the detonation performances, the directly linked, -N=N-, -NH-NH- were beneficial when used as a bridge between 1,2,5-oxadiazole and 1,3,4-oxadiazole, and it can also be found that bridge changing had little effect on the trend of detonation performance, while energetic groups changing influenced differently. The designed compounds (except for A2 , B2 , B4 ) all had higher detonation properties than TNT, A6 ( D = 9.41 km s -1 , P = 41.86 GPa, Q = 1572.251 cal g -1 ) was the highest, followed D6 had poorer performance ( D = 8.96 km s -1 , P = 37.46 GPa, Q = 1354.51 cal g -1 ).

Molecular Design of Long Intra-annular Nitrogen Chains：3H-tetrazolo[1,5-d]tetrazole-Based High-Energy-Density Materials

Energetic compounds containing long nitrogen chain, have been a research hotspot. Fused heterocycles are stable due to their aromatic systems. The compound obtained by combining long nitrogen chain and fused ring can not only retain good energetic property, but also ensure better stability. This work designed eight fused heterocycle-based energetic compounds, 3H-tetrazolo[1,5-d]tetrazole (1) and its derivatives (2-8), containing a nitrogen chain with seven nitrogen atoms. The HOF, thermal stability, and energetic properties of these compounds were studied by using the DFT method. The results show that the introduction of -NO2, -N3, -NF2, -ONO2, -NHNO2 groups increased the density, HOF, detonation velocity, and detonation pressure greatly. The densities of 3, 5, 7, and 8 fall within the range designated for high-energy-density materials. The calculated detonation velocity of the compounds 3 and 8 are up to 9.86 km s-1 and 9.78 km s-1, which are superior to that of CL-20. The kinetic study of the thermal decomposition mechanism indicates that the N-R bonds maybe not the weakest bonds of these compounds. The tetrazole ring opening of the heterocycle-based energetic compounds, followed by N2 elimination is predicted to be the primary decomposition channel, whether or not they have substituent groups.