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.     

Recent advances in the synthesis and energetic properties of potassium-based potential green primary explosives

Primary explosives are utilized as a reliable initiator for secondary explosives in an extensive range of military and civilian operations. Heavy–metal–based primary explosives are moderate performing, more sensitive, and environmentally hazardous, posing a direct and indirect threat to health and safety. Therefore, heavy–metal–based primaries have been replaced by environment-friendly metal-based primary explosives, such as potassium complexes. This review presents not only a summary of the current progress of new-generation potassium-based primary explosives and their methods of preparation, energetic properties, and applications, but also a further comparison with traditional primary explosives. In addition, this work discusses the necessity of heavy metal–free primary explosives and the major challenges faced in replacing traditional primary explosives.     

制冷系统节能目标函数的研究

本文分析传统采用制冷系数(EER)作为节能指标的不准确性,提出采用(?)效率作为衡量制冷装置在不同工况下运行的节能指标。从(?)效率定义出发推导出带回热的制冷系统的(?)效率关系式,这为寻找装置最佳运行工况提供理论依据,并通过实验证实了理论的分析。     

Thermal decomposition of ammonium perchlorate catalyzed with CuO nanoparticles

Ammonium perchlorate (APC) is the most common oxidizer in use for solid rocket propulsion systems. However its initial thermal decomposition is an endothermic process that requires 102.5 J·g⁻¹. This manner involves high activation energy and could render high burning rate regime. This study reports on the sustainable fabrication of CuO nanoparticles as a novel catalyzing agent for APC oxidizer. Colloidal CuO nanoparticles with consistent product quality were fabricated by using hydrothermal processing. TEM micrographs demonstrated mono-dispersed particles of 15 nm particle size. XRD diffractogram demonstrated highly crystalline material. The synthesized colloidal CuO particles were effectively coated with APC particles via co-precipitation by using fast-crash solvent–antisolvent technique. The impact of copper oxide particles on APC thermal behavior has been investigated using DSC and TGA techniques. APC demonstrated an initial endothermic decomposition stage at 242 °C with subsequent two exothermic decomposition stages at 297.8 °C and 452.8 °C respectively. At 1 wt%, copper oxide offered decrease in initial endothermic decomposition stage by 30%. The main outcome of this study is that the two main exothermic decomposition peaks were merged into one single peak with an increase in total heat release by 53%. These novel features can inherit copper oxide particles unique catalyzing ability for advanced highly energetic systems.     

Tuning the reactivity of Al–Ni by fine coating of halogen-containing energetic composites

In this paper, various core-shell structured Al–Ni@ECs composites have been prepared by a spray-drying technique. The involved ECs refer to the energetic composites (ECs) of ammonium perchlorate/nitrocellulose (AP/NC, NA) and polyvinylidene fluoride/hexanitrohexaazaisowurtzitane (PVDF/CL-20, PC). Two Al–Ni mixtures were prepared at atomic ratios of 1:1 and 1:3 and named as Al/Ni and Al/3Ni, respectively. The thermal reactivity and combustion behaviors of Al–Ni@ECs composites have been comprehensively investigated. Results showed that the reactivity and combustion performance of Al–Ni could be enhanced by introducing both NA and PC energetic composites. Among which the Al/Ni@NA composite exhibited higher reactivity and improved combustion performance. The measured flame propagation rate (v = 20.6 mm/s), average combustion wave temperature (T_max = 1567.0 °C) and maximum temperature rise rate (γ_t = 1633.6 °C/s) of Al/Ni@NA are higher than that of the Al/Ni (v = 15.8 mm/s, T_max = 858.0 °C, and γ_t = 143.5 °C/s). The enhancement in combustion properties could be due to presence of the acidic gaseous products from ECs, which could etch the Al₂O₃ shell on the surface of Al particles, and make the inner active Al to be easier transported, so that an intimate and faster intermetallic reaction between Al and Ni would be realized. Furthermore, the morphologies and chemical compositions of the condensed combustion products (CCPs) of Al–Ni@ECs composites were found to be different depending on the types of ECs. The compositions of CCPs are dominated with the Al–Ni intermetallics, combining with a trace amount of Al₅O₆N and Al₂O₃.     

Formation and characterization of core-shell CL-20/TNT composite prepared by spray-drying technique

The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene (CL-20/TNT) composite was prepared by spray-drying method in which sensitive high energy explosive (CL-20) was coated with insensitive explosive (TNT). The structure and properties of different formulations of CL-20/TNT composite and CL-20/TNT mixture were characterized by scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Laser particle size analyzer, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impact sensitivity test and detonation performance. The results of SEM, TEM, XPS and XRD show that ϵ-CL-20 particles are coated by TNT. When the ratio of CL-20/TNT is 75/25, core-shell structure is well formed, and thickness of the shell is about 20–30 nm. And the analysis of heat and impact show that with the increase of TNT content, the TNT coating on the core-shell composite material can not only catalyze the thermal decomposition of core material (CL-20), but also greatly reduce the impact sensitivity. Compared with the CL-20/TNT mixture (75/25) at the same ratio, the characteristic drop height of core-shell CL-20/TNT composite (75/25) increased by 47.6% and the TNT coating can accelerate the nuclear decomposition in the CL-20/TNT composites. Therefore, the preparation of the core-shell composites can be regarded as a unique means, by which the composites are characterized by controllable decomposition rate, high energy and excellent mechanical sensitivity and could be applied to propellants and other fields.     

Coating processes towards selective laser sintering of energetic material composites

This research aims to contribute to the safe methodology for additive manufacturing (AM) of energetic materials. Coating formulation processes were investigated and evaluated to find a suitable method that may enable selective laser sintering (SLS) as the safe method for fabrication of high explosive (HE) compositions. For safety and convenience reasons, the concept demonstration was conducted using inert explosive simulants with properties quasi-similar to the real HE. Coating processes for simulant RDX-based microparticles by means of PCL and 3,4,5-trimethoxybenzaldehyde (as TNT simulant) are reported. These processes were evaluated for uniformity of coating the HE inert simulant particles with binder materials to facilitate the SLS as the adequate binding and fabrication method. Suspension system and single emulsion methods gave required particle near spherical morphology, size and uniform coating. The suspension process appears to be suitable for the SLS of HE mocks and potential formulation methods for active HE composites. The density is estimated to be comparable with the current HE compositions and plastic bonded explosives (PBXs) such as C4 and PE4, produced from traditional methods. The formulation method developed and understanding of the science behind the processes paves the way toward safe SLS of the active HE compositions and may open avenues for further research and development of munitions of the future.     

Nanothermite colloids: A new prospective for enhanced performance

Nanothermites (metal oxide/metal) can offer tremendously exothermic self sustained reactions. CuO is one of the most effective oxidizers for naonothermite applications. This study reports on two prospectives for the manufacture of CuO nanoparticles. Colloidal CuO particles of 15 nm particle size were developed using hydrothermal synthesis technique. Multiwalled carbon nanotubes (MWCNTs) with surface are 700 m²/g was employed as a substrate for synthesis of CuO-coated MWCNTs using electroless plating. On the other hand, aluminium particles with combustion heat of 32000 J/g is of interest as high energy density material. The impact of stoichiometric nanothermite particles (CuO/Al & Cuo-coated MWCNTs/Al) on shock wave strength of Al/TNT nanocomposite was evaluated using ballistic mortar test. While CuO-coated MWCNTs decreased the shock wave strength by 15%; colloidal CuO enhanced the shock wave strength by 30%. The superior performance of colloidal CuO particles was correlated to their steric stabilization with employed organic solvent. This is the first time ever to report on fabrication, isolation, and integration of stablilized colloidal nanothermite particles into energetic matrix where intimate mixing between oxidizer and metal fuel could be achieved.     

Dielectric constant predictions for energetic materials using quantum calculations

The dielectric constant (DC) is one of the key properties for detection of threat materials such as Improvised Explosive Devices (IEDs). In the present paper, the density functional theory (DFT) as well as ab-initio approaches are used to explore effective methods to predict dielectric constants of a series of 12 energetic materials (EMs) for which experimental data needed to experimentally determine the dielectric constant (refractive indices) are available. These include military grades energetic materials, nitro and peroxide compounds, and the widely used nitroglycerin. Ab-initio and DFT calculations are conducted. In order to calculate dielectric constant values of materials, potential DFT functional combined with basis sets are considered for testing. Accuracy of the calculations are compared to experimental data listed in the scientific literature, and time required for calculations are both evaluated and discussed. The best functional/basis set combinations among those tested are CAM-B3LYP and AUG-cc-pVDZm, which provide great results, with accuracy deviations below 5% when calculated results are compared to experimental data.     

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.