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.     

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.     

Analysis on damage characteristics and detonation performance of solid rocket engine charge subjected to jet

To further explore the damage characteristics and impact response of the shaped charge to the solid rocket engine (SRE) in storage or transportation, protective armor was designed and the shelled charges model (SCM)/SRE with protective armor impacting by shaped charge tests were conducted. Air overpressures at 5 locations and axial acceleration caused by the explosion were measured, and the experimental results were compared with two air overpressure curves of propellant detonation obtained by related scholars. Afterwards, the finite element software AUTODYN was used to simulate the SCM impacted process and SRE detonation results. The penetration process and the formation cause of damage were analyzed. The detonation performance of TNT, reference propellant, and the propellant used in this experiment was compared. The axial acceleration caused by the explosion was also analyzed. By comprehensive comparison, the energy released by the detonation of this propellant is larger, and the HMX or Al particles contained in this propellant are more than the reference propellant, with a TNT equivalent of 1.168–1.196. Finally, advanced protection armor suggestions were proposed based on the theory of woven fabric rubber composite armor (WFRCA).     

过氧化氢发动机中的低频振荡

过氧化氢是现代液体火箭推进剂的重要发展方向。针对过氧化氢发动机试验中出现的低频振荡现象,通过建立发动机系统模型,对这种振荡现象进行了仿真和分析,成功实现了发动机的稳定工作。本文将有利于结合仿真和试验,促进过氧化氢发动机的研制。     

聚氨酯型复合推进剂的性能研究

本文研究聚氨酯型复合推进剂的力学性能和燃烧性能,给出了提高推进剂力学性能的有效途径,测试了推进剂燃烧性能的基本特征参数,采用光电子能谱(ESCA)对这种复合推进剂的界面作用机理进行了微观探讨.     

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。     

液体推进剂爆炸火球热传递参数的试验测量技术

介绍了液体推进剂爆炸火球的内部温度,辐射温升和辐射热流密度的试验测量方法,试验测量的计算机数据采集系统,并给出了５０ｋｇ,１００ｋｇ,３００ｋｇ液体推进剂（Ｎ２Ｏ４／ＵＤＭＨ）爆炸火球的热传递参数的部分测量结果。     

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.     

van der Pol 振子在负反馈作用下的动力性态分析

本文从非线性振动理论和反馈控制论的角度研究了ｖａｎｄｅｒＰｏｌ振子在负反馈作用下的动力性态,用中心流形法和形式级数法分析了ｖａｎｄｅｒＰｏｌ振子的局部稳定性和Ｈｏｐｆ分叉行为,用Ｒｕｎｇｅ─Ｋｕｔｔａ法给出了仿真结果。     

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.     

Thermodynamics and performance of Al/CuO nanothermite with different storage time

The storage stability of energetic materials is important for its application. Here, the storage stability of Al/CuO nanothermite, which was prepared by electrospray method and stored with different storage time, was systematically researched. The activation energy of Al/CuO nanothermite was calculated by differential scanning calorimetry (DSC). The ignition temperature and the curve pressure history of Al/CuO nanothermite was measured using ignition temperature measuring device and constant-volume pressurization tests, respectively. Further, the thermites were characterized by X-ray Diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and Transmission electron microscopy (TEM). The results show that the morphology of the thermites did not change significantly. The activation energy was decreased from 254.1 kJ/mol to 181.8 kJ/mol after storage for 13 months. When stored for 0, 7 and 13 months, the peak pressures of Al/CuO nanothermite were 685.8 kPa, 626.3 kPa and 625.5 kPa, respectively. In addition to the ignition temperature, it was 775 ℃, 739 ℃ and 754 ℃, respectively. This result indicated that the ignition and combustion properties of Al/CuO nano-thermite are obviously reduced when stored for a long time, at room temperature.     

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.     

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.     

复合固体推进剂颗粒填充模型及其统计特性分析

复合固体推进剂属于高填充比颗粒类复合材料,氧化剂和金属颗粒在基体中的随机分布使其在细观尺度具有非均质的特点。从细观尺度研究固体推进剂燃烧及力学性能时,必须考虑颗粒级配、空间分布和种类等因素的影响。采用分子动力学方法,以硝酸酯增塑聚醚高能复合固体推进剂为研究对象,将固体颗粒模型化为球形,生成其在基体内随机分布的颗粒填充模型。利用Monte-Carlo算法模拟计算颗粒填充模型细观结构的两点概率函数,并研究了颗粒填充体积分数、尺寸与级配等参数对其的影响规律。从统计意义上给出具有各态历经性、统计均匀性和各向同性特点的颗粒填充构型最小周期性代表体元尺寸,可有效减小后续研究的计算量,节约计算成本。所构建的推进剂细观几何构型及对最小周期性代表体元尺寸的计算为后续开展复合固体推进剂细观尺度燃烧、燃面处铝团聚及力学性能数值研究奠定了基础。     

磷碳键的构建

含有磷碳键的有机磷化合物广泛应用于农药、医药、塑料添加剂等领域,构建磷碳键是有机磷化学研究的基本问题之一．概要的评述了Michaelis-Arbuzov反应、Becker反应、过渡金属催化反应和含磷氢键化合物对不饱和烯炔的加成等几种形成磷碳键的化学反应．     

偶联剂在固体推进剂填料改性中的应用研究

本文采用硅烷类和钛酸酯类偶联剂对固体推进剂中的硝酸铵填料进行表面改性。改性后的硝酸铵接触角增大,表面张力降低且具有明显的疏水性。并证实偶联剂可以增强填料与粘结体系之间的界面相互作用。     

Research on the influences of confining pressure and strain rate on NEPE propellant: Experimental assessment and constitutive model

In order to study the influences of confining pressure and strain rate on the mechanical properties of the Nitrate Ester Plasticized Polyether (NEPE) propellant, uniaxial tensile tests were conducted using the self-made confining pressure system and material testing machine. The stress-strain responses of the NEPE propellant under different confining pressure conditions and strain rates were obtained and analyzed. The results show that confining pressure and strain rate have a remarkably influence on the mechanical responses of the NEPE propellant. As confining pressure increases (from 0 to 5.4 MPa), the maximum tensile stress and ultimate strain increase gradually. With the coupled effects of confining pressure and strain rate, the value of the maximum tensile stress and ultimate strain at 5.4 MPa and 0.0667 s⁻¹ is 2.03 times and 2.19 times of their values under 0 MPa and 0.00333 s⁻¹, respectively. Afterwards, the influence mechanism of confining pressure on the NEPE propellant was analyzed. Finally, based on the viscoelastic theory and continuous damage theory, a nonlinear constitutive model considering confining pressure and strain rate was developed. The damage was considered to be rate-dependent and pressure-dependent. The constitutive model was validated by comparing experimental data with predictions of the constitutive model. The whole maximum stress errors of the model predictions are lower than 4% and the corresponding strain errors are lower than 7%. The results show that confining pressure can suppress the damage initiation and evolution of the NEPE propellant and the nonlinear constitutive model can describe the mechanical responses of the NEPE propellant under various confining pressure conditions and strain rates. This research can lay a theoretical foundation for analyzing the structural integrity of propellant grain accurately under working pressure loading.     

一类非线性动力系统的时滞反馈分叉控制

对时滞控制作用下的参数激励van der Pol-Duffing方程进行了研究,着重研究了时滞参数对该类参数激励系统的1/2亚谐共振-主参数共振分叉响应控制。首先采用摄动法从理论上推导出时滞动力系统的分叉响应方程,再采用数值模拟的方法研究了时滞参数对系统分叉响应的影响。研究结果表明,适当选取时滞参数,不仅可以改变分叉响应曲线的拓扑形态,还可以平移分叉响应曲线,即使其分叉提前或滞后,还能同时满足这两种要求。     

围压下固体推进剂的破坏机理分析

贴壁浇筑的固体发动机推进剂药柱在点火状态下处于三向围压状态,而环向承受拉应变,亟待对围压下推进剂的破坏机理展开研究。基于自研的围压加载试验系统,通过开展推进剂在不同围压、温度和应变率下的单轴拉伸试验来研究围压、温度和应变率的耦合作用对推进剂力学行为的影响。针对围压下推进剂的力学响应特征,通过细观力学仿真进一步研究围压下推进剂的破坏形式,同时借助电镜扫描试验分析推进剂试样断面的形貌特征,通过试验和仿真相结合的手段分析了围压下推进剂的破坏机理。研究结果表明,围压下推进剂的损伤界面显著减少,且随着围压载荷的逐渐增加,推进剂的损伤形式从以颗粒脱湿为主转变为以颗粒破碎为主。     

单基发射药的热自燃数值模拟与其剩余能量变化研究

建立了单基发射药柱热自燃的数学模型 ,根据模型利用数值模拟的方法计算了单基发射药的中心温度与其剩余能量 ,并对中心温度的模拟结果与实验结果进行了比较。解决了其热分解动力学参数的非唯一性问题 ,为装填有单基发射药各种弹药的热自燃计算提供了依据