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.     

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.     

Fabrication and characterization of mussel-inspired layer-by-layer assembled CL-20-based energetic films via micro-jet printing

Three-dimensional (3D) micro-jet printing is a droplet deposition technique based on liquid-phase materials. To improve the deposition density and performance of energetic films with micro/nanoscale on an energetic chip, polydopamine (PDA) was utilized as a linker bridge to induce the in-situ self-assembly of CL-20-based energetic film via 3D micro-jet printing. The self-assembly was extensively characterized by confocal laser scanning microscopy (CLSM), SEM, power-XRD, XPS, and DSC. The performance of the self-assembled film was verified by the mechanical properties and detonation properties, and a possible self-assembly mechanism in the layer-by-layer micro-jet printing process was proposed. The results indicated PDA-induced self-assembly enhanced the physical entanglement between the binders and energetic crystal, reduced the porosity from 15.87% to 11.28%, and improved the elastic modulus and the detonation performance of the CL-20-based energetic film. This work proposes a novel and promising energetic film design and fabrication strategy to enhance the interaction between the energetic composite layers in the micro-jet printing process.     

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.     

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.     

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.     

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.     

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.     

Formulation development and characterization of cellulose acetate nitrate based propellants for improved insensitive munitions properties

Cellulose acetate nitrate (CAN) was used as an insensitive energetic binder to improve the insensitive munitions (IM) properties of gun propellants to replace the M1 propellant used in 105 mm artillery charges. CAN contains the energetic nitro groups found in nitrocellulose (NC), but also acetyl functionalities, which lowered the polymer's sensitivity to heat and shock, and therefore improved its IM properties relative to NC. The formulation, development and small-scale characterization testing of several CAN-based propellants were done. The formulations, using insensitive energetic solid fillers and high-nitrogen modifiers in place of nitramine were completed. The small scale characterization testing, such as closed bomb testing, small scale sensitivity, thermal stability, and chemical compatibility were done. The mechanical response of the propellants under high-rate uni-axial compression at, hot, cold, and ambient temperatures were also completed. Critical diameter testing, hot fragment conductive ignition (HFCI) tests were done to evaluate the propellants' responses to thermal and shock stimuli. Utilizing the propellant chemical composition, theoretical predictions of erosivity were completed. All the small scale test results were utilized to down-select the promising CAN based formulations for large scale demonstration testing such as the ballistic performance and fragment impact testing in the 105 mm M67 artillery charge configurations. The test results completed in the small and large scale testing are discussed.     

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.     

高官能度水性聚氨酯丙烯酸酯/纳米SiO2杂化材料的制备及性能

以聚己内酯二醇(PCL)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)和季戊四醇三丙烯酸酯(PETA)为原料,合成了高官能度水性聚氨酯丙烯酸酯WPUA。以WPUA为有机相,γ-甲基丙烯酰氧丙基三甲氧基硅烷(TMSPM)改性纳米SiO2为无机相,制备了水性光固化有机/无机纳米杂化体系。通过傅立叶变换红外光谱对合成产物进行了表征,并对杂化薄膜的表面形貌、热稳定性、光固化动力学及力学性能进行了分析。结果表明合成了预期产物,杂化体系中改性纳米SiO2分散均匀稳定;随着SiO2含量的增加,材料的热稳定性、力学性能均有明显提高;不同SiO2条件下体系均保持了较高的光固化速率和最终凝胶含量。     

Novel aluminum-based fuel: Facile preparation to improve thermal reactions

To improve the thermal properties of aluminum (Al) in the energetic system, a coated structure with ammonium perchlorate (AP) was prepared by a facile approach. And N, N-Dimethylformamide (DMF) was chosen as an ideal solvent based on heterogeneous nucleation theory and molecular dynamics simulation. This coated structure could enlarge the contact area and improve the reaction environment to enhance the thermal properties. The addition of AP could accelerate oxidation temperature of Al with around 17.5 °C. And the heat release of 85@15 composition rises to 26.13 kJ/g and the reaction degree is 97.6% with higher peak pressure (254.6 kPa) and rise rate (1.397 MPa/s). An ideal ratio with 15 wt% AP was probed primarily. The high energy laser-induced shockwave experiment was utilized to simulate the reaction behavior in hot field. And the larger activated mixture of coated powder could release more energy to promote the growth of shockwave with higher speed up to 518.7 ± 55.9 m/s. In conclusion, 85@15 composition is expected to be applied in energetic system as a novel metal fuel.     

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.     

Light weight HTPB-clay nanocomposites(HCN)with enhanced ablation performance as inhibition materials for composite propellant

In the present study,organically modified Montmorillonite clay with polar moiety,the Cloisite 30B,is used for preparation of Hydroxyl terminated polybutadiene(HTPB)-clay nanocomposites(HCN)by dispersion of nanoclay in polymer matrix under high shear mixing.The nanocomposites thus prepared are evaluated in composite propellants as inhibitor material for their functional utility.Several inhibition formulations containing 5 wt％-15 wt％of nanoclay,with or without the conventional filler Sb2O3,were prepared.All these formulations were evaluated for their physical,mechanical,thermal,and ablative properties.Ablation rate and density of the compositions containing Cloisite 30B is around 23％and 5％lower respectively in comparison of the base composition.Strain capability of these compositions is twofold higher than that of base composition.These compositions have also been evaluated for their smoke generation tendency by measuring infra red(IR)attenuation in the wavelength range 1.3 μm-5.6 μm and 8 μm-13 μm and thereby compared with the base composition.The corresponding results confirmed that the compositions containing Cloisite 30B as filler have much lower IR attenuation than compositions with conventional filler,Sb2O3.Replacement of 5％Sb2O3 by nanoclay showed 8％reduction in IR attenuation rate which further reduced to 16％on replacement of 15％of Sb2O3.Interfacial bonding of HCN based inhibitors is also comparable or even better than conventional inhibitors.Precisely,the nanoclay composites with Cloisite 30B as filler exhibit all desirable properties of an inhibitor.     

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.     

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.     

先驱体转化致密SiC纳米复合材料的制备及其热电性能

以聚碳硅烷和锑改性聚硅烷为先驱体,利用先驱体转化SiC材料的富余自由碳高温石墨化的微观结构演变特点,采用热压烧结、先驱体浸渍—裂解法以及退火工艺制备出先驱体转化SiC纳米复合材料。采用SEM、TEM、XRD和Raman等测试手段表征和分析了相组成和微观结构,讨论了样品的热导率、电导率和塞贝克系数等热电参数随温度变化关系。研究表明,所得致密SiC纳米复合材料为n型热电材料。由于纳米石墨的作用,材料热导率抑制在4–8W/(m?K)范围。1600°C退火处理能够降低热导率,同时提高电导率和塞贝克系数绝对值,使先驱体转化法得到的SiC纳米复合材料无量纲热电优值ZT达到0.0028（650°C）,高于其他已报道的致密SiC/C复合材料和纳米复合材料体系。     

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.     

定应变作用下NEPE推进剂老化特性及寿命预估研究

为考察定应变作用下NEPE推进剂的老化特性,研究了20%定应变作用下NEPE推进剂贮存老化过程中力学性能、凝胶性能和界面性能的变化.研究结果表明:定应变作用下NEPE推进剂在贮存老化过程中最大抗拉强度降低,最大延伸率变化较小,其老化失效主要表现为强度的失效;定应变下NEPE推进剂的凝胶百分数和粘附功随老化时间的延长而降低,NEPE推进剂粘合剂基体的降解断裂和界面的"脱湿"是其主要的老化机理;定应变下NEPE推进剂的力学性能与细观性能的相关性研究表明,最大抗拉强度与凝胶百分数和粘附功存在相关关系,计算了其关系式,建立了由细观性能评估推进剂宏观力学性能的方法;选择最大抗拉强度下降30%时失效,20%定应变下NEPE推进剂的贮存寿命为8.3年.