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.     

Shock initiation performance of NTO-based polymer bonded explosive

3-nitro-1,2,4-tri-azol-5-one (NTO) is a high energy insensitive explosive. To study the shock initiation process of NTO-based polymer bonded explosive JEOL-1 (32%octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 32% NTO, 28% Al and 8% binder system), the cylinder test, the gap experiments and numerical simulation were carried out. Firstly, we got the detonation velocity (7746 m/s) and the parameters of Jones-Wilkins-Lee (JWL) equation of state (EOS) for detonation product by cylinder test and numerical simulation. Secondly, the Hugoniot curve of unreacted explosive for JEOL-1 was obtained calculating the data of pressure and time at different Lagrangian positions. Then the JWL EOS of unreacted explosive was obtained by utilizing the Hugoniot curve as the reference curve. Finally, we got the pressure growth history of JEOL-1 under shock wave stimulation and the parameters of the ignition and growth reaction rate equation were obtained by the pressure-time curves measured by the shock-initiation gap experiment and numerical simulation. The determined trinomial ignition and growth model (IG model) parameters can be applied to subsequently simulation analysis and design of insensitive ammunition with NTO-based polymer bonded explosive.     

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.     

Thermal hazard assessment of TKX-50-based melt-cast explosive

In the present study, thermal hazards of TNT and DNAN used as the molten binder in TKX-50-based melt-cast explosives were comparatively studied through accelerating rate calorimeter (ARC) and Cook-off experiments. Two kinds of ARC operation modes were performed to investigate the thermal safety performance under adiabatic conditions (HWS mode) and constant heating (CHR mode). The obtained results demonstrated that at both heating modes, DNAN/TKX-50 outperformed TNT/TKX-50 from the thermal safety point of view. However, the sensitivity to heat of the samples was reverse because of the different heating modes. In addition, the results of thermal hazard assessment obtained from the cook-off experiment complied with ARC analysis which indicated the molten binder TNT replaced by DNAN would reduce the hazard of the TKX-50 melt cast explosive. Furthermore, the results of cook-off experiments also showed that DNAN/TKX-50 outperformed TNT/TKX-50 from the aspect of thermal stability, which was consistent with the result of CHR mode because of the similar heating process.     

Preparation and characterization of HMX/EVA/hBNNSs micro-composites with improved thermal stability and reduced sensitivity

Hexagonal boron nitride nanosheets(HBNNSs)have huge potential in the field of coating materials owing to their remarkable chemical stability,mechanical strength and thermal conductivity.Thin-layer hBNNSs were obtained by a liquid-phase exfoliation of h-BN powders and incorporated into EVA coatings for improving the safety performance of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX).HBNNSs and ethylene-vinyl acetate copolymer(EVA)were introduced to HMX by a solvent-slurry process.For com-parison,the HMX/EVA and HMX/EVA/graphene(HMX/EVA/G)composites were also prepared by a similar process.The morphology,crystal form,surface element distribution,thermal decomposition property and impact sensitivity of HMX/EVA/hBNNSs composites were contrastively investigated.Results showed that as prepared HMX/EVA/hBNNSs composites were well coated with hBNNSs and EVA,and exhibited better thermal stability and lower impact sensitivity than that of HMX/EVA and HMX/EVA/G composites,suggesting superior performance of desensitization of hBNNSs in explosives.     

Burning rate and other characteristics of strontium titanate (SrTiO3) supplemented AP/HTPB/Al composite propellants

In a quest of search for a new burning rate modifier for composite propellant, strontium titanate (SrTiO₃), a perovskite oxide has been chosen for evaluation in a composite propellant formulation based on its other catalytic applications. Initially, SrTiO₃ was characterized for particle size, morphology and material/phase identification (using XRD). By varying SrTiO₃ content in a standard composite propellant, different compositions were prepared and their performance and processing parameters like the end of mix (EOM) viscosity, mechanical properties, density, burning rate, pressure exponent (n-value), etc. were measured. The results reveal that 2% SrTiO₃ causes more than 12% enhancement in propellant burning rate (at 70 ksc pressure) in comparison to the standard propellant composition. The pressure exponent also increases to 0.46, whereas the standard composition was having its value as 0.35.     

Microcrack- and microvoid-related impact damage and ignition responses for HMX-based polymer-bonded explosives at high temperature

Investigating the damage and ignition behaviors of polymer-bonded explosive (PBX) under a coupled impact and high-temperature loading condition is required for the safe use of charged PBXs. An improved combined microcrack and microvoid model (CMM) was developed for better describing the thermal effects of deformation, damage, and ignition responses of PBXs. The main features of the model under typical dynamic loadings (i.e. uniaxial tension and compression, and lateral confinement) at different initial temperature were first studied. And then the effects of temperature on impact-shear sensitivity of HMX-based PBXs were investigated. The results showed that the ignition threshold velocity of shear-crack hotspots exhibits an increase from 260 to 270 to 315–325 m/s when initial temperature increases from 301 to 348 K; and then the threshold velocity decreases to 290–300 m/s with the initial temperature continually increasing to 378 K. The predicted ignition threshold velocity level of the explosives under coupled impact and high temperature loading conditions were consistent with the experimental data.     

三维石英纤维增强氮化物基复合材料的烧蚀性能及显微结构

采用先驱体转化法制备了三维石英纤维增强氮化物基复合材料(3D SiO2f/Si3N4-BN),用等离子射流烧蚀方法研究了复合材料的烧蚀性能,运用扫描电镜及能谱仪对烧蚀表面微观形貌进行了观察和分析。结果表明氮化物基复合材料在高压高热流等离子体烧蚀下线烧蚀率为0.91mm/s,石英纤维熔融并被吹除带走了大量的热量,熔融层抑制了基体的机械剥蚀。基体由于强度高、升华温度高,延缓了熔融层的吹除,表明氮化物基复合材料是一种良好的耐高温烧蚀透波材料。     

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.     

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.     

新型起爆系统安全性计算机辅助分析

介绍了新型起爆系统,针对发射周期前、发射周期中和发射周期后安全距离内3个阶段建立了3棵安全性故障树并进行了数值计算。分析和计算结果表明,所设计的新型起爆系统符合美军标的相关规定,安全性失效率达到了美军标的要求,是高安全的起爆系统。该系统对推进钝感弹药引爆技术,特别是高新技术弹药的发展有重要意义。随着信息技术的发展,它将成为最先进的起爆系统。     

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.     

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.     

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.     

基于正弦高斯组合的UWB脉冲波形设计

针对美国FCC关于超宽带传输系统提出的辐射掩蔽特性,提出了一种基于正弦高斯组合的UWB脉冲波形设计新方案。以一组正弦高斯脉冲为基函数,利用最小均方误差准则(LSE)选取加权系数对基函数进行线性组合,通过调整基函数的载波频率和脉冲形成因子,对波形进一步优化。分析了TH-PPM UWB多用户系统的误码率性能。仿真结果表明,与高斯二阶微分脉冲、随机系数组合脉冲相比,基于正弦高斯组合脉冲具有更高的频谱利用率,误码性能更优。     

正弦高斯组合的UWB脉冲波形设计

针对美国FCC关于超宽带传输系统提出的辐射掩蔽特性,提出了一种基于正弦高斯组合的UWB脉冲波形设计新方案。以一组正弦高斯脉冲为基函数,利用最小均方误差准则(LSE)选取加权系数对基函数进行线性组合,通过调整基函数的载波频率和脉冲形成因子,对波形进一步优化。分析了TH-PPM UWB多用户系统的误码率性能。仿真结果表明,与高斯二阶微分脉冲、随机系数组合脉冲相比,基于正弦高斯组合脉冲具有更高的频谱利用率,误码性能更优。     

卫星导航系统的体系安全性分析方法

为了应对卫星导航系统内部复杂关系等体系特征为其安全分析带来的挑战、全面识别和分析卫星导航系统面临的体系安全威胁、提高系统的安全性和服务能力,基于功能依赖网络分析理论提出了从体系角度研究卫星导航系统安全性的建模方法,重点对导航系统内组件系统之间交互关系导致的危险传播、任意失效组合进行了后果分析和原因调查。仿真结果表明该方法能清晰地描述危险传播和失效组合的过程以及进行正逆向的推理分析,也证明了该方法在卫星导航系统安全分析问题上的潜力和适用性。     

Effects of total pressures and equivalence ratios on kerosene/air rotating detonation engines using a paralleling CE/SE method

In this paper, the kerosene/air rotating detonation engines(RDE) are numerically investigated, and the emphasis is laid on the effects of total pressures and equivalence ratios on the operation characteristics of RDE including the initiation, instabilities, and propulsive performance. A hybrid MPI + OpenMP parallel computing model is applied and it is proved to be able to obtain a more effective parallel performance on high performance computing(HPC) systems. A series of cases with the total pressure of 1 MPa, 1.5 MPa, 2 MPa, and the equivalence ratio of 0.9, 1, 1.4 are simulated. On one hand, the total pressure shows a significant impact on the instabilities of rotating detonation waves. The instability phenomenon is observed in cases with low total pressure (1 MPa) and weakened with the increase of the total pressure. The total pressure has a small impact on the detonation wave velocity and the specific impulse. On the other hand, the equivalence ratio shows a negligible influence on the instabilities, while it affects the ignition process and accounts for the detonation velocity deficit. It is more difficult to initiate rotating detonation waves directly in the lean fuel operation condition. Little difference was observed in the thrust with different equivalence ratios of 0.9, 1, and 1.4. The highest specific impulse was obtained in the lean fuel cases, which is around 2700 s. The findings could provide insights into the understanding of the operation characteristics of kerosene/air RDE.