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.     

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.     

Recent progress on transition metal oxides and carbon-supported transition metal oxides as catalysts for thermal decomposition of ammonium perchlorate

As a main oxidizer in solid composite propellants, ammonium perchlorate (AP) plays an important role because its thermal decomposition behavior has a direct influence on the characteristic of solid com-posite propellants. To improve the performance of solid composite propellant, it is necessary to take measures to modify the thermal decomposition behavior of AP. In recent years, transition metal oxides and carbon-supported transition metal oxides have drawn considerable attention due to their extraor-dinary catalytic activity. In this review, we highlight strategies to enhance the thermal decomposition of AP by tuning morphology, varying the types of metal ion, and coupling with carbon analogue. The enhanced catalytic performance can be ascribed to synergistic effect, increased surface area, more exposed active sites, and accelerated electron transportation and so on. The mechanism of AP decom-position mixed with catalyst has also been briefly summarized. Finally, a conclusive outlook and possible research directions are suggested to address challenges such as lacking practical application in actual formulation of solid composite propellant and batch manufacturing.     

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.     

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.     

固体推进剂裂纹摩擦热点形成细观模型分析

分析机械撞击载荷作用下复合固体推进剂内部裂纹摩擦形成热点过程。研究在压应力与剪切应力作用下闭合裂纹滑移、扩展、摩擦生热、热扩散、推进剂热分解及与气相产物相互作用。利用断裂力学、热传导、推进剂热分解动力学方法,建立裂纹摩擦热点细观模型。通过模型数值计算,探讨推进剂裂纹摩擦产生高温热点的过程和条件。分析计算表明裂纹摩擦和扩展可导致推进剂形成高温热点。     

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.     

Performance study of jute-epoxy composites/sandwiches under normal ballistic impact

This study is undertaken to explore the use of natural fiber Jute-epoxy (JE), Jute-epoxy-rubber (JRE) sandwich composite for ballistic energy absorption. Energy absorbed and residual velocities for these composites are evaluated analytically and through Finite Element Analysis (FEA). FE analysis of JE plates is carried out for different thicknesses (3, 5, 10 and 15 mm). JE plates and JRE sandwiches having the same thickness (15 mm) are fabricated and tested to measure residual velocity and energy absorbed. The analytical results are found to agree well with the results of FE analysis with a maximum error of 9%. The study on JE composite plate reveals that thickness influences the energy absorption. Experimental and FE analysis study showed that JRE sandwiches have better energy absorption than JE plates. Energy absorption of a JRE sandwich is about 71% greater than JE plates. Damages obtained from FEA and testing are in good agreement. SEM analysis confirms composites failed by fiber rupture and fragmentation.     

Preparation of ammonium nitrate-based solid composite propellants supplemented with polyurethane/nitrocellulose blends binder and their thermal decomposition behavior

To improve the performance of solid composite propellants (SCPs) supplemented with ammonium nitrate (AN) as an oxidizer, the incorporation of energetic ingredients such as explosives, energetic binders or catalysts is a common effective approach. For this purpose, polyurethane (PU), a typical inert binder, was mixed with nitrocellulose (NC) as an energetic polymer. Numerous composite solid propellant compositions based on AN and NC-modified polyurethane binder with different NC ratios were prepared. The prepared formulations were characterized using Fourier transform infrared spectroscopy (FTIR), RAMAN spectroscopy, X-ray diffraction (XRD), electron densimetry, thermogravimetric (TG) analysis, and differential scanning calorimetry (DSC). A kinetic study was then performed using the iterative Kissinger-Akahira-Sunose (It-KAS), Flynn-Wall-Ozawa (It-FWO), and non-linear Vyazovkin integral with compensation effect (VYA/CE) methods. The theoretical performances, such as theoretical specific impulse, adiabatic flame temperature, and ideal exhaust gaseous species, were also determined using the NASA Lewis Code, Chemical Equilibrium with Application (CEA). Spectroscopic examinations revealed the existence of NC and full polymerization of PU in the prepared propellants. According to density tests, the density of the propellant increases as the nitrocellulose component increases. According to the thermal analysis and kinetics study, the increase in NC content catalyzed the thermal decomposition of the AN-based composite solid propellants. Based on the theoretical study, increasing the amount of NC in the propellant increased the specific impulse and, as a result, the overall performance.     

整体缝合夹芯结构复合材料力学性能

所设计的新型整体缝合泡沫夹芯复合材料结构,能够避免一般斜缝方式引起纤维交叉损坏的弊端。采用真空导入模塑工艺制备整体缝合泡沫夹芯结构复合材料,研究缝合结构、缝合方式以及缝合纱线用量对整体缝合泡沫夹芯复合材料平压力学性能和弯曲性能的影响。结果表明,新型缝合结构在保证平压力学性能的同时,相比于垂直缝合结构弯曲破坏载荷提高了94.4%;穿透缝合方式能够显著提高试样的平压强度和弯曲破坏载荷;随着缝合纱线用量的增加,整体缝合泡沫夹芯复合材料的压缩和弯曲性能显著提高。     

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.     

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.     

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.     

PMI泡沫夹层结构雷达天线罩间接热-结构耦合分析与实验研究

机载PMI泡沫夹层结构雷达天线罩在环境温度变化时将产生表面变形现象并影响其使用性能,但对天线罩热变形结果进行实时检测分析具有一定难度。通过ANSYS间接热-结构耦合法建立了分析模型,对天线罩进行了计算分析,采用热膨胀片状模型进行了理论分析,在此基础上,设计并开展了温度冲击实验研究。结果表明, PMI夹层结构天线罩的热-结构耦合变形综合应变趋势是棱边处膨胀程度最大,由边缘至天线罩透波面中心处,膨胀程度逐渐减小；间接热-结构耦合计算应变值与实测应变值之间平均相差35.08%,间接热-结构耦合分析方法与模型具有一定的可信性。     

基于背衬影响的水下声隐身夹芯复合材料结构设计

在考虑背衬影响的前提下,建立了3种典型水下声隐身夹芯复合材料的结构模型;从水声波动方程出发,推导了3种模型的传递矩阵、声反射系数和吸声系数,并通过试验验证了传递矩阵法的有效性;考虑吸声层厚度、密度、损耗因子、水层厚度等对声隐身性能的影响,应用数值方法对水下夹芯复合材料声隐身结构形式进行了设计,分析了各层材料参数对隐身结构反射系数和吸声系数的影响规律;在吸声层中附加了一层复合材料,有效地抑制了隐身结构的谐振峰,并研究了附加层的匹配位置,使隐身结构在不改变吸声层厚度的情况下获得了更好的声学性能.     

Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

A differential/integral method to estimate the kinetic parameters (apparent activation energy E_a and pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane (HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy (E_a) obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion (T_b) and adiabatic time-to-explosion (t_TIad) based on Kooij formula are used to calculate the values of T_b and t_TIad to evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of E_a and A of decomposition reaction of HNIW are 3(1 − α)[−ln(1 − α)]^2/3, 152.73 kJ mol⁻¹ and 10^11.97 s⁻¹, respectively, and the values of self-accelerating decomposition temperature (T_SADT), T_b and t_TIad are 486.55 K, 493.11 K and 52.01 s, respectively.     

基于表层及芯材阻尼特性的夹层结构导纳分析

针对复合材料夹层板结构,综合开展芯材材料阻尼特性动力学热分析(DMTA)试验、表层玻璃钢和芯材试件阻尼衰减特性研究,通过夹层板结构的模态激振试验得到结构的模态阻尼比。从结构动力学方程出发探讨了影响多自由度系统结构传递导纳的相关参量,试验对比分析了钢质板和复合材料夹层板两型结构的传递导纳特性,并研究了激振点与响应点间距对复合材料夹层结构传递导纳的影响。研究表明:当尺寸和边界条件相同时,影响结构传递导纳的主要因素是结构的固有频率和模态阻尼。试验还得到了复合材料夹层板较钢质板的基频提高值和传递导纳降低均值,该试验结果可为工程设计提供参考。     

轻质夹层复合吸声结构的制备工艺和水声性能

夹层复合吸声结构具有很强的可设计性,得到广泛的应用,但以往研究的此夹层结构的吸声芯材存在密度较大的问题。为此,设计了一种轻质夹层复合吸声结构,对该结构的制备工艺特别是芯材的制备工艺进行了设计,用玻璃钢作为表层材料、用柔性环氧树脂和聚氨酯改性环氧树脂的混合物为基体、空心玻璃微珠为填料、593和聚醚胺为固化剂所制备的多孔复合材料作为芯材来制备夹层复合吸声结构,制作了该结构的声学测试试件,在脉冲声管中测试了其水下声学性能。结果表明:所设计的夹层复合吸声结构具有较低的密度和良好的吸声性能,证明了该制备工艺设计的合理性。     

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.     

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.