Direct ink writing of 3D-Honeycombed CL-20 structures with low critical size

3D-Honeycombed CL-20 structures with low critical size of detonation have been fabricated successfully for intelligent weapon systems using a micro-flow direct ink writing (DIW) technology. The CL-20-based explosive ink for DIW technology was prepared by a two-component adhesive system with waterborne polyurethane (WPU) and ethyl cellulose (EC). Not only the preparation of the explosive ink but also the principle of DIW process have been investigated systematically. The explosive ink displayed strong shear-thinning behavior that permitted layer-by-layer deposition from a fine nozzle onto a substrate to produce complex shapes. The EC content was varied to alter the pore structure distribution and rheological behavior of ink samples after curing. The deposited explosive composite materials are of a honeycombed structure with high porosity, and the pore size distribution increases with the increase of EC content. No phase change was observed during the preparation process. Both WPU and EC show good compatibility with CL-20 particles. Apparently high activation energy was realized in the CL-20-based composite ink compared with that of the refined CL-20 due to the presence of non-energetic but stable WPU. The detonation performance of the composite materials can be precisely controlled by an adjustment in the content of binders. The 3D honeycombed CL-20 structures, which are fabricated by DIW technology, have a very small critical detonation size of less than 69 μm, as demonstrated by wedge shaped charge test. The ink can be used to create 3D structures with complex geometries not possible with traditional manufacturing techniques, which presents a bright future for the development of intelligent weapon systems.     

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.     

Sandwich structure for enhancing the interface reaction of hexanitrohexaazaisowurtzitane and nanoporous carbon scaffolds film to improve the thermal decomposition performance

Improving the thermal decomposition performance of hexanitrohexaazaisowurtzitane (CL-20) by appropriate methods is helpful to promote the combustion performance of CL-20-based solid propellants. In this study, we synthesized a sandwich structure of CL-20 and nanoporous carbon scaffolds film (NCS) and emphatically studied the thermal decomposition performance of the composite structure. Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal decomposition process of the composite structure. The kinetic parameters of thermal decomposition were calculated by the thermal dynamic analysis software AKTS. These results showed that the thermal decomposition performance of the sandwich structure of CL-20 and NCS was better than CL-20. Among the tested samples, NCS with a pore size of 15 nm had the best catalytic activity for the thermal decomposition of CL-20. Moreover, the thermal decomposition curve of the composite structure at the heating rate of 1 K/min was deconvoluted by mathematical method to study the thermal decomposition process. And a possible catalytic mechanism was proposed. The excellent thermal decomposition performance is due to the sandwich structure enhances the interface reaction of CL-20 and NCS. This work may promote the extensive use of CL-20 in the field of solid rocket propellant.     

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.     

Burning characteristics of high density foamed GAP/CL-20 propellants

The monolithic foamed propellants with high densities were prepared by casting and two-step foaming processes. Glycidyl azide polymer (GAP) and isocyanate were used as the binder system and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW, CL-20) was employed as the energetic component. The newly designed formulation containing 60 % CL-20 produced a force constant of 1077 J/g and low flame temperature of 2817 K. Two foamed propellants with densities of 1.32 g/cm³ and 1.53 g/cm³ were fabricated by a confined foaming process and examined by closed bomb tests. The results revealed that porosity significantly affects burning performance. A size effect on combustion behaviors was observed for the foamed propellant with 5.56 % porosity, and a double-hump progressive dynamic vivacity curve was obtained. At last, the 30 mm gun test was carried out to demonstrate the interior ballistic performance, and the muzzle velocity increased by 120 m/s at the same maximum chamber pressure when monolithic propellant was added in the charge.     

Construction and Properties of Structure-and Size-controlled Micro/Nano-energetic Materials

The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development of the construction strategies for achieving zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) micro/nanostructures from energetic molecules is introduced. Also, an overview of the unique properties induced by micro/nanostructures and size effects is provided. Special emphasis is focused on the size-dependent properties that are different from those of the conventional micro-sized energetic materials, such as thermal decomposition, sensitivity, combustion and detonation, and compaction behaviors. A conclusion and our view of the future development of micro/nano-energetic materials and devices are given.     

Study of nano-nitramine explosives: preparation,sensitivity and application

Nano-nitramine explosives (RDX, HMX, CL-20) are produced on a bi-directional grinding mill. The scanning electron microscope (SEM) observations show that the prepared particles are semi-spherical, and the narrow size distributions are characterized using the laser particle size analyzer. Compared with the micron-sized samples, the nano-products show obvious decrease in friction and impact sensitivities. In the case of shock sensitivities, nano-products have lower values by 59.9% (RDX), 56.4% (HMX), and 58.1% (CL-20), respectively. When nano-RDX and nano-HMX are used in plastic bonded explosives (PBX) as alternative materials of micron-sized particles, their shock sensitivities are significantly decreased by 24.5% (RDX) and 22.9% (HMX), and their detonation velocities are increased by about 1.7%. Therefore, it is expected to promote the application of nano-nitramine explosives in PBXs and composite modified double-based propellants (CMDBs) so that some of their properties would be improved.     

Performances and direct writing of CL-20 based ultraviolet curing explosive ink

A new type of explosive ink formulation that can be quickly cured was prepared with unsaturated polyester as binder,styrene as active monomer,2,4,6-trimethylbenzoyl-diphenylphosphine oxide as photoinitiator,and hexanitrohexaazaisowurtzitane (CL-20) as the main explosive.Then the explosive ink direct writing technology was used to charge the micro-sized energetic devices,the curing mechanism of the explosive ink was discussed,and the microstructure,safety performance and explosive transfer performance of the explosive ink molded samples were tested and analyzed.Results indicate that the composite material has a fast curing molding speed,its hardness can reach 2H within 8 min.The crystal form of CL-20 in the molded sample is still ε type.The CL-20 based W-curing explosive ink formulation has good compatibility,its apparent activation energy is increased by about 3.5 kJ/mol.The composite presents a significant reduction in impact sensitivity and its characteristic drop height can reach 39.8 cm,which is about 3 times higher than the raw material.When the line width of charge is 1.0 mm,the critical thickness of the explosion can reach 0.015 mm,and the explosion velocity is 7129 m/s when the charge density is 1.612 g/cm3.     

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.     

Enhancing the explosive characteristics of a Semtex explosive by involving admixtures of BCHMX and HMX

A well-known ternary plastic explosive, Czech Semtex 1H, contains a mixture of PETN and RDX softened by SBR. In this work, BCHMX was used to replace PETN in Semtex 1H to form Sem-BC+RDX. In addition, another mixture based on BCHMX and HMX as energetic fillers bonded by the polymeric matrix of Semtex 1H (Sem-BC+HMX) was studied. The particle size distribution of each individual explosive was determined to obtain the optimum mixing conditions. Friction and impact sensitivities were determined. The velocity of detonation was reported practically and the detonation properties were calculated by EXPLO5 code. The explosive strength of each sample was measured by the ballistic mortar test. The conclusion confirms that the velocity of detonation of Sem-BC+HMX was the highest in comparison with the prepared samples. Sem-BC+RDX has the least impact and frictions sensitivities. Sem-BC+RDX has higher detonation velocity, detonation properties and explosive strength than Semtex 1H. Addition of BCHMX in Semtex 1H as a replacement for PETN is the candidate to produce a high performance advanced Czech plastic explosive.     

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 intermolecular hydrogen bonding in FOX-7 is responsible for limited solubility in most of organic solvents. Large solubility differences of FOX-7 with HMX and CL-20 restricts it's 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/FOX-7 (4:1) co-crystals. The fine powdered materials obtained were characterized by SEM, powder XRD, Raman spectroscopy, 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 solid-solid phase transformation in the co-crystals as they were observed in pristine materials. The thermal stability calculated in terms of activation barrier for decomposition, revealed the CL-20/FOX-7 co-crystal to be intermediately 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.     

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.     

Structure design and property adjustment of new cage rich-nitrogen pentazolyltetraazacubanes as potential high energy density compounds

In this study, based on two attractive energetic compounds pentazole (PZ) and tetraazacubane (TAC), a new family of high energy and high nitrogen compounds pentazolyltetraazacubanes were designed. Then, a different number of NH₂ or NO₂ groups were introduced into the system to further adjust the property. The structures, properties, and the structure-property relationship of designed molecules were investigated theoretically. The results showed that all nine designed compounds have extremely high heat of formation (HOF, 1226-2734 kJ/mol), good density (1.73–1.88 g/cm³), high detonation velocity (8.30–9.35 km/s), high detonation pressure (29.8–39.7 GPa) and acceptable sensitivity (ΔV: 41-87 ų). These properties could be effectively positive adjusted by replacing one or two PZ rings by NH₂ or/and NO₂ groups, especially for the energy and sensitivity performance, which were increased and decreased obviously, respectively. As a result, two designed pentazolyltetraazacubanes were predicted to have higher energy and lower sensitivity than the famous high energy compound in use 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, while two others have better combination property than 1,3,5-Trinitro-1,3,5-triazacyclohexane. In all, four new pentazolyltetraazacubanes with good combination performance were successfully designed by combining PZ with TAC, and the further property adjustment strategy of introducing a suitable amount of NH₂/NO₂ groups into the system. This work may help develop new cage energetic compounds.     

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.     

直接挤出成型用环氧树脂的流变性及其可打印性

直接挤出成型制造适用于任何含或不含添加剂的膏状或凝胶状复合材料,对复合材料制造技术具有深远意义。通过探讨热固性环氧树脂的流变学行为与挤出成型特性,得出热固性环氧树脂在直接挤出成型制造应用中的通用性流变学参数。通过向复合材料中加入增稠剂,对其流变学行为进行设计。结果表明:在高剪切速率(50 s~(-1))和低剪切速率(0.01 s~(-1))下,添加30%纳米黏土的环氧树脂的流变学行为较适合挤出式3D打印工艺。利用龙门式气动挤出式3D打印机,对复合材料的打印成型质量进行试验分析和验证。结合试验结果探讨了喷头高度对复合材料成型质量的影响,并且提出适用于喷头高度临界值的计算方法。探讨了挤出率、剪切速率等因素对成型质量的作用规律。针对多层打印问题,提出包含补偿系数的多层打印的临界喷头高度的计算方法。以上研究对促进基于复合材料的挤出式3D打印具有积极意义。     

A quasi-isentropic model of a cylinder driven by aluminized explosives based on characteristic line analysis

A quasi-isentropic study on the process of driving a cylinder with aluminized explosives was carried out to examine the influence of the aluminum (Al) reaction rate on cylinder expansion and the physical parameters of the detonation products. Based on the proposed quasi-isentropic hypothesis and relevant isentropic theories, the characteristic lines of aluminized explosives driving a cylinder were analyzed, and a quasi-isentropic model was established. This model includes the variation of the cylinder wall velocity and the physical parameters of the detonation products with the Al reaction degree. Using previously reported experimental results, the quasi-isentropic model was verified to be applicative and accurate. This model was used to calculate the physical parameters for cylinder experiments with aluminized cyclotrimethylenetrinitramine explosives with 15.0 % and 30.0 % Al content. The results show that this quasi-isentropic model can be used not only to calculate the cylinder expansion rule or Al reaction degree, but also to calculate the physical parameters of the detonation products in the process of cylinder expansion. For explosives with 15.0 % and 30.0 % Al, 24.3 % and 18.5 % of the Al was found to have reacted at 33.9 μs and 34.0 μs, respectively. The difference in Al content results in different reaction intensity, occurrence time, and duration of two forms of reaction (diffusion and kinetic) between the Al powder and the detonation products; the post-detonation burning reaction between the Al powder and the detonation products prolongs the positive pressure action time, resulting in a continuous rise in temperature after detonation.     

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.     

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.     

Evaluation of effectiveness of polymer coatings in reducing blast-induced deformation of steel plates

Incorporating elastomers such as polymers in protective structures to withstand high energetic dynamic loads, has gained significant interest. The main objective of this study is to investigate the influence of a Polyurea coating towards the blast-induced response in steel plates. As such, Polyurea coated steel plates were tested under near-field blast loads, produced by the detonation of 1 kg of spherical nitromethane charges, at a standoff distance of 150 mm. Mild steel (XLERPLATE 350) and high-strength steel (BIS80) plates with thicknesses of 10 mm were Polyurea coated with thicknesses of 6 mm and 12 mm on either the front (facing the charge) or the back face. The deformation profiles were measured using 3D scanning. Numerical simulations were performed using the non-linear finite element code LS-DYNA. The strain-dependent behaviour of the steel and Polyurea were represented by Johnson-cook and Money-Rivlin constitutive models, respectively. The numerical models were validated by comparing the plate deflection results obtained from the experiments and were then used in the subsequent parametric study to investigate the optimum thickness of the Polyurea coating. The results indicate that back face coating contributes towards an approximately 20% reduction in the residual deformation as well as the absence of melting of the Polyurea layer, while the front-face coating can be used a means of providing additional standoff distance to the steel plates.