Synthesis and Characteristics of Bis(nitrofurazano)furazan (BNFF), an Insensitive Material with High Energy‐Density

The insensitive compound bis(nitrofurazano)furazan (BNFF) with high energy‐density was synthesized by three‐step reactions and fully characterized. The key reduction reaction was discussed. BNFF has a high crystal density (1.839 g cm⁻³) and a low melting point (82.6 °C). BNFF is insensitive to impact and friction and has similar detonation velocity (8680 m s⁻¹) and detonation pressure (36.1 GPa) compared to RDX.     

4,5‐Bis(5‐tetrazolyl)‐1,2,3‐triazole: Synthesis and Performance

4,5‐Bis(5‐tetrazolyl)‐1,2,3‐triazole (BTT) was synthesized by a new method. Its structure was characterized by IR and ¹³C NMR spectroscopy and elemental analysis (EA). The thermal stability of BTT was investigated by TG‐DSC technique. The kinetic parameters including activation energy and pro‐exponential factor were calculated by Kissinger equation. The combustion heat, detonation products, hygroscopicity, impact, and friction sensitivity were also measured. The formation heat, detonation pressure, and detonation velocity of BTT were calculated. BTT has high detonation pressure and detonation velocity (P=35.36 GPa, D=8.971 km s⁻¹). BTT has potential application prospect as environmentally friendly gas generant, insensitive explosive and solid propellant.     

Preparation and Properties of An Insensitive Booster Explosive Based on LLM‐105

A new insensitive booster explosive based on 2,6‐diamino‐3,5‐dinitropyrazing‐1‐oxide (LLM‐105) was prepared by a solvent‐slurry process with ethylene propylene diene monomer (EPDM) as binder. SEM (scanning electron microscopy) was employed to characterize the morphology and particle size of LLM‐105 and molding powder. The mechanical sensitivity, thermal sensitivity, shock wave sensitivity, and detonation velocity of the LLM‐105/EPDM booster were also measured and analyzed. The results show that both mechanical sensitivity and thermal sensitivity of LLM‐105/EPDM are much lower than that of conventional boosters, such as PBXN‐5 and A5. Its shock wave sensitivity is also lower than that of PBXN‐5 and PBXN‐7. When the density of charge is 95 % TMD, its theoretical and measured detonation velocities are 7858 m s⁻¹ and 7640 m s⁻¹, respectively. These combined properties suggested that LLM‐105/EPDM can be used as an insensitive booster.     

Energetic Derivatives of 2‐Nitrimino‐5,6‐dinitro‐benzimidazole

2‐Nitrimino‐5,6‐dinitrobenzimidazole ( 1 ) was synthesized by nitration of 2‐aminobenzimidazole at ambient temperature in good yield. In order to explore new insensitive explosives four energetic nitrogen‐rich 1 : 1 salts such as the guanidinium ( 1a ), aminoguanidinium ( 1b ), triaminoguanidinium ( 1c ) and hydroxylammonium ( 1d ) were synthesized either by facile acid/base or in situ metathesis reaction. In addition 2‐nitrobenzimidazole ( 2 ) was synthesized by the reaction of 2‐aminobenzimidazole using potassium hyperoxide in THF. Different nitration methods were tested to obtain a theoretically 2,4,5,6,7‐pentanitrobenzimidazole but only the already known 4,5,6,7‐tetranitrobenzimidazol‐2‐one ( 3 ) could be isolated. All synthesized compounds were characterized especially by low temperature X‐ray diffraction, CHN elemental analysis and ¹H and ¹³C NMR spectroscopy. The heat of formation of all new synthesized compounds was calculated using CBS‐4M electronic enthalpies in combination with the atomization method to calculate their detonation parameters with the EXPLO 5 V5.05 computer code.     

Energetic Residues from the Detonation of IMX‐104 Insensitive Munitions

The development of insensitive munitions by NATO countries is an ongoing effort. Less‐sensitive ingredients in both explosives and propellants will ensure the protection of deployed troops against an unwanted reaction to an external stimulus on the munitions stockpile. In the US Army, current efforts are directed towards the development of melt cast insensitive explosive formulations. Various formulations, mainly based on DNAN and NTO, have been developed and are now being fielded. Our research goal is to measure the deposition rate of energetics compounds from various insensitive munitions detonation scenarios. Our hypothesis is that the relative insensitiveness of these formulations leads to slightly higher deposition rates than conventional explosive formulations. This paper describes detonation residues research on mortar rounds containing IMX‐104 explosive. Analyses indicate that high‐order detonation residues are slightly greater for this formulation than for conventional munitions. However, blow‐in‐place detonations (BIPs) resulted in much higher residues deposition, indicating that a larger donor charge is required for efficient detonation. The highly soluble compound NTO was particularly problematic, with BIP deposition approaching 95 % of the original load. Toxicological studies of NTO are not finalized, leaving considerable uncertainty regarding the feasibility of approving these rounds for distribution.     

Ignition and Growth Modeling of LX‐17 Hockey Puck Experiments

Detonating solid plastic bonded explosives (PBX) formulated with the insensitive molecule triaminotrinitrobenzene (TATB) exhibit measurable reaction zone lengths, curved shock fronts, and regions of failing chemical reaction at abrupt changes in the charge geometry. A recent set of “hockey puck” experiments measured the breakout times of diverging detonation waves at ambient temperature LX‐17 (92.5% TATB plus 7.5% Kel‐F binder) and the breakout times at the lower surfaces of 15 mm thick LX‐17 discs placed below the detonator‐booster plane. The LX‐17 detonation waves in these discs grow outward from the initial wave leaving regions of unreacted or partially reacted TATB in the corners of these charges. This new experimental data is accurately simulated for the first time using the Ignition and Growth reactive flow model for LX‐17, which is normalized to detonation reaction zone, failure diameter and diverging detonation data. A pressure‐cubed dependence for the main growth of reaction rate yields excellent agreement with experiment, while a pressure‐squared rate diverges too quickly and a pressure‐quadrupled rate diverges too slowly into the LX‐17 below the booster equatorial plane.     

The Shock Initiation Threshold of HNS as a Function of its Density

The shock initiation threshold of hexanitrostilbene (HNS) pellets with different densities has been investigated by performing small‐scale gap tests. As the sensitivity of HNS strongly depends on the density of the pellet, the density was varied in a range that the pellet material can be expected to be insensitive by means of no initiation at pressure loads of 2.6 GPa. In the case of HNS we observed that the material became insensitive at densities larger than 1.65 g cm⁻³. Further, we found that the pressure loads can be increased from 2.6 GPa to 3.29 GPa for densities increasing from ϱ=1.65 g cm⁻³ to ϱ=1.70 g cm⁻³ (98% TMD) without detonation of the HNS pellet.     

Silicon Fuel in High Performance Explosives

In an effort to improve the insensitive munition (IM) response but maintain performance of aluminized formulations, silicon was investigated as a possible replacement for aluminum. An RDX‐based silicon explosive was developed in which nearly 90 % reaction of silicon to silicon dioxide was realized by 7 volume expansions as measured by the 2.54 cm diameter copper cylinder expansion test. In spite of the low nitramine loading in the formulation (79 wt.‐%), the corresponding Gurney constant for the explosive was 2.81±0.02 km s⁻¹, which is superior to Composition A‐3 under the same experimental conditions (91 % RDX, 2.69±0.02 km s⁻¹). Energy calculations from detonation calorimetry also indicate reaction of the silicon, which was further confirmed by both silicon metal and silicon dioxide in the analyzed residue. The energy release, despite it being equivalent to a highly loaded explosive, was found to lag behind the rate of A‐3. This indicates silicon oxidation may occur sometime after lighter gas reactions in the reaction front, but is fast enough to impart work in the copper cylinder test.     

A Novel Insensitive High Explosive 3,4‐Bis (Aminofurazano) Furoxan

A novel insensitive high explosive 3,4‐bis (aminofurazano) furoxan (BAFF) was prepared using 3‐amino‐4‐acylchloroximinofurazan (ACOF) as a precursor. The molecular and crystal structures of BAFF were characterized by IR, MS, ¹H NMR, ¹³C NMR, elemental analysis, and single crystal X‐ray diffraction. The single crystal structure of BAFF recrystallized from water is monoclinic, space group P 21/c, and ρ_c=1.745 g cm⁻³, and that recrystallized from ethanol is triclinic, space group P 1, and ρ_c=1.737 g cm⁻³. BAFF has multiple crystal forms. The calculated detonation velocity by BKW code is 8100 m s⁻¹ (ρ=1.795 g cm⁻³, theoretical density calculated by quantum chemistry) and the experimental value is 7177 m s⁻¹ (ρ=1.530 g cm⁻³, charge density). The tested values of impact, friction, and electrostatic spark sensitivity show that BAFF is insensitive.     

A Novel Cocrystal Explosive of HNIW with Good Comprehensive Properties

In order to improve the safety of the high explosive 2,4,6,8,10,12‐hexanitrohexaazaisowurtzitane (HNIW), we cocrystallized HNIW with the insensitive explosive DNB (1,3‐dinitrobenzene) in a molar ratio 1 : 1 to form a novel cocrystal explosive. Structure determination showed that it belongs to the orthorhombic system with space group Pbca. Therein, layers of DNB alternate with bilayers of HNIW. Analysis of interactions in the cocrystal indicated that the cocrystal is mainly formed by hydrogen bonds and nitro‐aromatic interactions. Moreover, the thermal behavior, sensitivity, and detonation properties of the cocrystal were evaluated. The results implied that the melting point of the cocrystal is 136.6 °C, which means an increase of 45 °C relative that of pure DNB. The predicted detonation velocity and detonation pressure of the cocrystal are 8434 m s⁻¹ and 34 GPa, respectively, which are similar to that of the reported HNIW/TNT cocrystal, but its reduced sensitivity (H₅₀=55 cm) makes it an attractive ingredient in HNIW propellant formulations.     

Tetrazolyl Triazolotriazine: A New Insensitive High Explosive

A triazolotriazine carbonitrile ( 1 ) was formed by diazotization of 3‐amino‐5‐cyano‐1,2,4‐triazole followed by treatment with nitroacetonitrile. Cyclization of the C≡N bond with sodium azide results in a tetrazolyl triazolotriazine ( 2 ). Formation of the sodium salt of 2 , followed by metathesis with [PPN][Cl] resulted in the organic salt 3 . Compounds 1 , 2 , and 3 were characterized by elemental analysis and infrared, ¹H, and ¹³C{¹H} NMR spectroscopy and 1 and 3 were characterized by single‐crystal X‐ray diffraction. Compound 2 has a density of 1.819 g cm⁻¹, is thermally stable up to 305 °C, and is insensitive to impact, friction, and electrical discharge. The detonation pressure and velocity of 2 are calculated to be 27.04 GPa and 8.312 km s⁻¹, respectively, making this a 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) replacement candidate.     

Thermochemical,Sensitivity and Detonation Characteristics of New Thermally Stable High Performance Explosives

The M06‐2X/6‐311G(d,p) and B3LYP/6‐311G(d,p) density functional methods and electrostatic potential analysis were used for calculation of enthalpy of sublimation, crystal density and enthalpy of formation of some thermally stable explosives in the gas and solid phases. These data were used for prediction of their detonation properties including heat of detonation, detonation pressure, detonation velocity, detonation temperature, electric spark sensitivity, impact sensitivity and deflagration temperature using appropriate methods. The range of different properties for these compounds are: crystal density 1.51–2.01 g cm⁻³, enthalpy of sublimation 346.4–424.7 kJ mol⁻¹, the solid phase enthalpy of formation 500.4–860.6 kJ mol⁻¹, heat of detonation 13.64–17.57 kJ g⁻¹, detonation pressure 33.0–37.0 GPa, detonation velocity 8.5–9.5 km s⁻¹, detonation temperature 5488–6234 K, electric spark sensitivity 7.89–9.47 J, impact sensitivity 21–38 J, deflagration temperature 560–586 K and power [%TNT] 207–276. The results show that two novel energetic compounds N,N′‐(diazene‐1,2‐diylbis(2,3,5,6‐tetranitro‐4,1‐phenylene))bis(5‐nitro‐4H‐1,2,4‐triazol‐3‐amine) (DDTNPNT3A) and 1,1′‐(diazene‐1,2‐diylbis(2,3,5,6‐tetranitro‐4,1‐phenylene))bis(3‐nitro‐1H‐1,2,4‐triazol‐5‐amine) (DDTNPNT5A) can be introduced as thermally explosives with high detonation performance.     

The Synthesis of Energetic Compound on 4,4′‐((2,4,6‐trinitro‐1,3‐phenylene)bis(oxy)) bis(1,3‐dinitrobenzene)(ZXC‐5): Thermally Stable Explosive with Outstanding Properties

The novel, thermally stable explosive 4,4′‐((2,4,6‐trinitro‐1,3‐phenylene)bis(oxy))bis(1,3‐dinitrobenzene) (Be referred to as ZXC‐ 5 in our laboratory) has been reported. ZXC‐5 can be synthesized by a simple synthetic method (The total synthesis of ZXC‐ 5 requires only two steps and the total yield of ZXC‐ 5 is more than 89 %) and shows the superior detonation performances (detonation pressure, detonation velocity, sensitivity toward mechanical stimuli, and temperature of decomposition). The structure of ZXC‐5 was characterized by multinuclear (¹H, ¹³C) NMR and mass spectrometry. The structure in the crystalline state was confirmed by low‐temperature single‐crystal X‐ray diffraction. From the calculated standard molar enthalpy of formation and the measured densities, the detonation properties were predicted by using the EXPLO5 V6.01 thermochemical computer code. The sensitivity of ZXC‐ 5 towards impact, electrostatic discharge, and friction were also measured.     

Detonation Products as a Function of Initiation Strength,ambient gas and binder systems of explosives charges

The way of initiating an insensitive high explosive can influence the start of a detonation reaction remarkably. In order to study the extent of this influence, different boosters and different booster structures for the initiation of explosive mixtures containing TNT and nitroguanidine (NQ) have been used. The experiments have been conducted in a 1.5 m³ containment from which the detonation products could be taken and analyzed. In those cases where we only used a 10 g RDX booster together with a detonation cap no. 8, we had not a complete detonation reaction by initiating cylindrical charges of TNT/NQ and TNT/AN. This means that unreacted TNT was analyzed in the solid residue, mainly consisting of carbon soot. On the other hand, we had a complete detonation using an additional booster of about 18 g detonation sheet, placed on the front side of the cylindrical explosive, having the same diameter as the explosive charge. Another part of the investigations deals with the determination of the influence of different argon pressures on the composition of the detonation gas and the solid residue. Between vacuum and one bar argon a strong change not only of the gas but also of the soot residue was measured. A stronger influence on the products was found using a confinement with glass tubes. The investigation of Al-containing charges exhibited a very different behavior compared with charges without Al. No more influence of vaccum or of different ambient gas pressure could be observed. By investigation of two composite explosive charges (PBX) containing binder systems of different energies and different oxygen balances, a great influence on the reaction of Al was found. The PBX charges with the better O₂-balance containing the energetic GAP-binder reacted nearly completely with the Al, opposite to the charge containing the polyisobutylene (PIB) binder system.     

A DFT Study on the Structures and Energies of Isomers of 4‐Amino‐1,3‐dinitro‐1,2,4‐triazol‐5‐one‐2‐oxide: New High Energy Density Compounds

Isomers of 4‐amino‐1,3‐dinitrotriazol‐5‐one‐2‐oxide (ADNTONO) are of interest in the contest of insensitive explosives and were found to have true local energy minima at the DFT‐B3LYP/aug‐cc‐pVDZ level. The optimized structures, vibrational frequencies and thermodynamic values for triazol‐5‐one N‐oxides were obtained in their ground state. Kamlet‐Jacob equations were used to evaluate the performance properties. The detonation properties of ADNTONO (D=10.15 to 10.46 km s⁻¹, P=50.86 to 54.25 GPa) are higher compared with those of 1,1‐diamino‐2,2‐dinitroethylene (D=8.87 km s⁻¹, P=32.75 GPa), 5‐nitro‐1,2,4‐triazol‐3‐one (D=8.56 km s⁻¹, P=31.12 GPa), 1,2,4,5‐tetrazine‐3,6‐diamine‐1,4‐dioxide (D=8.78 km s⁻¹, P=31.0 GPa), 1‐amino‐3,4,5‐trinitropyrazole (D=9.31 km s⁻¹, P=40.13 GPa), 4,4′‐dinitro‐3,3′‐bifurazan (D=8.80 km s⁻¹, P=35.60 GPa) and 3,4‐bis(3‐nitrofurazan‐4‐yl)furoxan (D=9.25 km s⁻¹, P=39.54 GPa). The  NH₂ group(s) appears to be particularly promising area for investigation since it may lead to two desirable consequences of higher stability (insensitivity), higher density, and thus detonation velocity and pressure.     

Detonation Properties of 1,3,5-Triamino-2,4,6-Trinitrobenzene when impacted by hypervelocity projectiles

This investigation analyzes the reaction of an insensitive high explosive with binder to hypervelocity impact by four projectiles of two types: rod and plate. The insensitive high explosive is composed of 92.5% 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and 7.5% Kel-F 800 binder, a vinylidene fluoride-chlorotrifluoroethylene copolymer. In this paper, for simplicity, we refer to this composition as “TATB”. Of the the impacting projectiles, three are steel-rod assemblies ranging in weight from 32.6 g to 34.6 g, and are composed of a steel rod 8 mm in diameter and 19 mm in length, of which 9 mm protrudes from a Polyzelux plastic holder. The fourth is a tantalum-plate assembly, weighing 23.9 grams and composed of a tantalum plate 24.2 mm in diameter and 1.5 mm in thickness mounted on a Polyzelux holder. The tantalum-plate experiment provides a highly efficient diverging detonation profile as predicted by similar previous investigations with flyer plates and TATB. The steel-rod experiments are compared to the tantalum-plate experiment to determine if detonation has occurred with the steel-rod impacts. The projectiles are accelerated by a two-stage, light-gas gun to velocities in the range of 3.1 km/s to 6.5 km/s (10,171 ft/s to 21,325 ft/s) and have bracketed the detonation threshold of the impacted TATB target. Comparisons of the TATB reaction data to a computer modeling of the experiment show that at 3.06 km/s, the computer model correctly predicts no initiation of detonation; at 4.75 km/s, the computer model correctly predicts a partial detonation; and at 5.67 km/s and 6.53 km/s, both the computer analyses and the experiments give divergent detonations.     

Studies on Advanced RDX/TATB Based Low Vulnerable Sheet Explosives with HTPB Binder

Hydroxyl‐terminated polybutadiene (HTPB) based sheet explosives incorporating insensitive 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) as a part replacement of cyclotrimethylene trinitramine (RDX) have been prepared during this work. The effect of incorporation of TATB on physical, thermal, and sensitivity behavior as well as initiation by small and high caliber shaped charges has been determined. Composition containing 85% dioctyl phthalate (DOP) coated RDX and 15% HTPB binder was taken as control. The incorporation of 10–20% TATB at the cost of RDX led to a remarkable increase in density (1.43→1.49 g cm⁻³) and tensile strength (10→15 kg cm⁻²) compared to the control composition RDX/HTPB(85/15). RDX/TATB/HTPB based compositions were found less vulnerable to shock stimuli. Shock sensitivity was found to be of the order of 20.0–29.2 GPa as against 18.0 GPa for control composition whereas their energetics in terms of velocity of detonation (VOD) were altered marginally. Differential scanning calorimeter (DSC) and thermogravimetry (TG) studies brought out that compositions undergo major decomposition in the temperature region of 170–240 °C.     

Quantum Chemical Studies on the Structure and Performance Properties of 1,3,4,5‐Tetranitropyrazole: A Stable New High Energy Density Molecule

Molecular orbital calculations were performed for the geometric and electronic structures, band gap, thermodynamic properties, density, detonation velocity, detonation pressure, stability and sensitivity of 1,3,4,5‐tetranitropyrazole ( R23 ). The calculated density (approx. 2060 kg m⁻³), detonation velocity (approx. 9.242 km s⁻¹) and detonation pressure (approx. 41.30 GPa) of the model compound are appearing to be promising compared to hexahydro‐1,3,5‐trinito‐1,3,5‐triazine (RDX) and octahydro‐1,3,5,7‐tetranitro‐l,3,5,7‐tetrazocine (HMX). Bader’s atoms‐in‐molecules (AIM) analysis was also performed to understand the nature of the intramolecular N ⋅⋅⋅ O interactions and the strength of trigger X NO₂ bonds (where XC, N) of the optimized structure computed from the B3LYP/aug‐cc‐pVDZ level.     

Detonation Measurements on Damaged LX‐04

We have applied thermal insults on LX‐04 at 185 °C and found that the material expanded significantly, resulting in a bulk density reduction of 12%. Subsequent detonation experiments (three cylinder tests) were conducted on the thermally damaged LX‐04 samples and pristine low‐density LX‐04 samples and the results showed that the fractions reacted were close to 1.0. The thermally damaged LX‐04 and pristine low‐density LX‐04 showed detonation velocities of 7.7–7.8 mm μs⁻¹, significantly lower than that (8.5 mm μs⁻¹) of pristine high‐density LX‐04. Detonation energy densities for the damaged LX‐04, low‐density pristine LX‐04, and hot cylinder shot of LX‐04 were 6.48, 6.62, and 6.58 kJ cm⁻³, respectively, lower than the detonation energy density of 8.11 kJ cm⁻³ for the high density pristine LX‐04. The break‐out curves for the detonation fronts showed that the damaged LX‐04 had longer edge lags than the high density pristine LX‐04, indicating that the damaged explosive is less ideal.     

On the Unreacted Hugoniots of Three Plastic Bonded Explosives

There is a continuing interest in determining the detonation characteristics of loaded plastic‐bonded explosives (PBXs). Within the UK, the relevant government agencies wish to better understand the response of insensitive high explosives. This has required more detailed investigation of the transit of reaction from the unreacted state to products. The starting condition for shock to detonation transition (SDT), before application of a kinetic scheme to describe reaction, is thus the unreacted Hugoniot for the material. In this work, three PBXs, manufactured by BAE Land Systems, are investigated and modelled. All contain RDX in differing quantities in an HTPB binder. One of them contains aluminium. Two of the materials have the same weight percentage of filler and binder but differ in the grain size distribution entrained. The experimental Hugoniots are presented, and a composite equation of state is derived using an engineering model, and a model based on continuum mixture theory. Both are shown to describe the measurements well. Further applications of the technique are described and future uses are outlined.