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.     

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.     

Recent advances in catalytic combustion of AP-based composite solid propellants

Composite solid propellants (CSPs) have widely been used as main energy source for propelling the rockets in both space and military applications. Internal ballistic parameters of rockets like characteristic exhaust velocity, specific impulse, thrust, burning rate etc., are measured to assess and control the performance of rocket motors. The burn rate of solid propellants has been considered as most vital parameter for design of solid rocket motors to meet specific mission requirements. The burning rate of solid propellants can be tailored by using different constituents, extent of oxidizer loading and its particle size and more commonly by incorporating suitable combustion catalysts. Various metal oxides (MOs), complexes, metal powders and metal alloys have shown positive catalytic behaviour during the com-bustion of CSPs. These are usually solid-state catalysts that play multiple roles in combustion of CSPs such as reduction in activation energy, enhancement of rate of reaction, modification of sequences in reaction-phase, influence on condensed-phase combustion and participation in combustion process in gas-phase reactions. The application of nanoscale catalysts in CSPs has increased considerably in recent past due to their superior catalytic properties as compared to their bulk-sized counterparts. A large surface-to-volume ratio and quantum size effect of nanocatalysts are considered to be plausible reasons for improving the combustion characteristics of propellants. Several efforts have been made to produce nanoscale combustion catalysts for advanced propellant formulations to improve their energetics. The work done so far is largely scattered. In this review, an effort has been made to introduce various combustion catalysts having at least a metallic entity. Recent developments of nanoscale combustion catalysts with their specific merits are discussed. The combustion chemistry of a typical CSP is briefly discussed for providing a better understanding on role of combustion catalysts in burning rate enhancement. Available information on different types of combustion nanocatalysts is also presented with critical comments.     

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。     

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。     

Vapor-phase decomposition of dimethyl methylphosphonate (DMMP), a sarin surrogate,in presence of metal oxides

Chemical warfare agents (CWA) are stockpiled in large quantities across the globe. Agents stored in inaccessible facilities need to be destroyed rapidly without dispersing the compounds to surrounding areas. Metal-based energetic formulations are used in such prompt defeat applications to rapidly decompose the CWA by generating a high temperature environment. An alternate, and possibly a more effective decomposition pathway could be provided by chemicidal action of aerosolized condensed combustion products, which typically consist of metal oxides. Toxic fumes that escape the high tem-perature blast zone can be neutralized by smoke generated during combustion, depending on the par-ticle size, surface characteristics, chemical properties, and concentration of this smoke. This review considers relevant experimental and modeling studies quantifying decomposition of CWA comprising organophosphorus compounds and their surrogates on the surface of various metal oxides. Dimethyl methylphosphonate (DMMP), a sarine surrogate, was used most commonly for such experiments. Many reported efforts focused on the mechanisms of adsorption of DMMP to various metal oxides and initial reaction steps cleaving various bonds from the chemisorbed molecules. For selected oxides, these ex-periments were supported by quantum-mechanical calculations. In other studies, the capacity of oxide surfaces to adsorb and decompose DMMP was quantified. In most cases, porous catalysts were used although limited experimental data are available for aerosolized nonporous oxide particles. The reported experimental data applicable to scenarios involving prompt decomposition of CWA are summarized. It is noted that information is lacking describing respective heterogeneous reaction kinetics. Preliminary estimates of aerosolized smoke particle concentrations required to destroy CWA are made considering gas phase diffusion rates and reported values of the oxide capacity to decompose CWA or their surrogates.     

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.     

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.     

非壅塞固体火箭冲压发动机及其贫氧推进剂

研究了非壅塞固体火箭冲压发动机的工作特性。研制出了能量高、燃速高、燃速压强指数高、低压燃烧性能好的铝镁贫氧推进剂配方。采用连管式试验与数值分析相结合的方法 ,对非壅塞固体火箭冲压发动机性能进行了系统的研究     

Theoretical calculation and experimental study on the interaction mechanism between TKX-50 and AP

The combination of 5,5′-bistetrazole-1,1′-diolate (TKX-50) and ammonium perchlorate (AP) can make greater use of the chemical energy of TKX-50 based energetic materials. The research on the interaction mechanism between TKX-50 and AP is very important for designing TKX-50-AP compounds and judging the formation feasibility of composite particles, which can lay a theoretical foundation for the preparation of TKX-50-AP mixed crystals and the application of TKX-50 in propellant, propellant and explosive. Herein, in order to research the interaction mechanism between TKX-50 and AP, density-functional theory calculation was applied to optimize three configurations of TKX-50-AP compounds. The geometry structure, electrostatic potential and binding energy of the compounds were predicted, and the electronic density topological analysis was also carried out. Then TKX-50-AP mixed crystals structures were constructed, and the radial distribution function of H–O and H–N in mixed crystals was calculated. Finally, solvent/non-solvent method was applied to prepare TKX-50-AP composites, and the infrared spectroscopy and the non-isothermal decomposition performance of the composites were characterized. Results show that the superposition of positive charges in TKX-50 molecule and negative charges in AP makes the electrostatic potential distributions of TKX-50-AP compounds different from that of TKX-50 and AP. The interaction energies of TKX-50-AP 1, TKX-50-AP 2 and TKX-50-AP 3 are 39.743 kJ/mol, 61.206 kJ/mol and 27.702 kJ/mol, respectively. The interaction between TKX-50 molecules and AP molecules in TKX-50-AP mixed crystals both depends on hydrogen bonds and van der Waals force, and the number and strength of hydrogen bonds are significantly greater than that of van der Waals force. The composition of AP and TKX-50 makes the absorption peak of the five-membered rings and NH₃OH⁺ of TKX-50 shift to low wavenumber in the infrared spectroscopy. In general, TKX-50 interacts with AP via hydrogen bonds and van der Waals force, and the calculated results are in good agreement with the experimental results. The composition of TKX-50 and AP can also prolong the decomposition process.     

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。     

点火瞬态过程对复合固体推进剂力学响应特性的影响

根据一个有效的非线性粘弹模型,导出复合固体推进剂微分形式本构方程和应变速率关系式。分析表明点火瞬态过程中压强与推进剂应变、升压速率与推进剂应变速率之间呈线性关系,线性系数均为推进剂初始模量。     

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.     

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).     

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。     

固体火箭发动机长期贮存热载荷的有限元分析方法

分析了固体火箭发动机药柱在长期贮存过程中,由于温度载荷谱的变化所引起的力学响应。基于粘弹性积分蠕变型本构关系,推导了能分析粘弹结构的热载荷的有限元模型,并用它分析了梁、厚壁圆筒与真实固体火箭发动机的热应力问题。     

材料性能对固体发动机结构完整性的影响

基于描述粘弹性材料特性的Burgers模型的本构关系以及基于该本构关系下的有限元方法 ,根据温度载荷和内压载荷的特点 ,分别建立了分析某固体发动机材料性能参数对结构完整性影响的有限元模型。应用MSC/NAS TRAN结构分析软件 ,详细分析了在温度和内压载荷作用下固体发动机材料性能参数对结构完整性的影响。在温度载荷的作用下 ,主要影响结构完整性的是推进剂的泊松比与热膨胀系数 ;在内压载荷作用下 ,主要影响结构完整性的是包覆层和推进剂的泊松比以及推进剂的初始模量。所得的结论可为固体发动机的生产设计提供参考     

THE CREEP-DAMAGE MODELING CORRELATED TO TEMPERATURE FOR COMPOSITE SOLID PROPELLANT

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