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.     

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.     

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。     

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.     

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。     

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.     

Investigation on the foaming behaviors of NC-based gun propellants

To prepare the porous NC-based (nitrocellulose-based) gun propellants, the batch foaming process of using supercritical CO₂ as the physical blowing agent is used. The solubilities of CO₂ in the single-base propellants and TEGDN (trimethyleneglycol dinitrate) propellants are measured by the gravimetric method, and SEM (scanning electron microscope) is used to observe the morphology of foamed propellants. The result shows that a large amount of CO₂ could be dissolved in NC-based propellants. The experimental results also reveal that the energetic plasticizer TEGDN exerts an important influence on the pore structure. The triaxial tensile failure mechanism for solid-state nucleation is used to explain the nucleation of NC-based propellants in the solid state. Since some specific foaming behaviors of NC-based propellants can not be explained by the failure mechanism, a solid-state nucleation mechanism which revises the triaxial tensile failure mechanism is proposed and discussed.     

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。     

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     

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。     

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.     

Fullerene bisadduct stabilizers: The effect of different addition positions on inhibiting the autocatalytic decomposition of nitrocellulose absorbed nitroglycerin

To explore the effect of different positions and number of pyrrolidine bound to the carbon cage on the stabilization effect of fulleropyrrolidine derivatives to nitrocellulose (NC)/nitroglycerine (NG), we synthesized N-(4-methoxy) phenylpyrrolidine-C₆₀ and four different of bis(N-(4-methoxy) phenylpyrrolidine)-C₆₀ compounds through Prato reaction. Their structures were characterized by UV–vis, ¹H NMR, ¹³C NMR, high-resolution mass spectroscopy, and single-crystal X-ray diffraction. Their stabilization effect to NC/NG were investigated using differential scanning calorimetry, methyl violet, vacuum stabilization effect, weight loss, and accelerating rate calorimeter tests. The results indicated these compounds had excellent stabilization effect to NC/NG. The stabilization effect of the fulleropyrrolidine bisadducts to NC/NG is significantly better than that of fulleropyrrolidine monoadduct and C₆₀. Moreover, the position where pyrrolidine binds to fullerene in fulleropyrrolidine bisadducts is different, and its stabilization effect to NC is also different. The stabilization effect order of different bisadduct isomers to nitrocellulose is as follows: e-edge > trans-2> cis-2> trans-3. Electron paramagnetic resonance (EPR) and FT-IR were used to study the stabilization mechanism of fulleropyrrolidine derivatives to NC/NG. The EPR results also show that fulleropyrrolidine bisadducts with different addition sites have different abilities to absorb nitroxide, and their ability is better than that of the monoadduct and C₆₀, which is consistent with the results of stabilization effect performance test.     

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.     

太阳能热推力器二次聚光器再生冷却过程

为克服太阳能热推力器折射式二次聚光器容易破裂的缺点,本文采用再生冷却技术,对二次聚光器与推力室进行了一体化设计,并对该过程进行了流动与传热仿真。仿真结果表明,该设计可有效地降低聚光器的工作温度至1600K以下,热应力分析表明可有效降低其破裂的可能性。同时该设计可预热推进剂至500K以上,提高了系统的能量利用效率。通过进一步对吸收腔内的热辐射分析发现,工质流动对吸收腔壁温影响较小,吸收腔壁面仍然可以维持2400-2600K的高温。     

聚氨酯/环氧树脂(PU/EP)AB-交联聚合物的研究

用二胺同时固化聚醚氨酯预聚物及环氧树脂,制得了PU/EP AB-交联聚合物(AB-CP)。以动态粘弹仪对其进行了表征,结果表明:形成AB-CP后,PU与EP相之间的相互作用大大加强(强于PU/EF IPN中PU与EP之间的作用),使PU链运动受到限制,其Tg移向高温区并形成了一个单一的Tg峰;研究了物料比、环氧值等对其动态力学谱(DMS)的影响。预期该化合物是一类有前途的增韧环氧树脂材料。     

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。     

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

ＴＨＥＣＲＥＥＰ－ＤＡＭＡＧＥＭＯＤＥＬＩＮＧＣＯＲＲＥＬＡＴＥＤＴＯＴＥＭＰＥＲＡＴＵＲＥＦＯＲＣＯＭＰＯＳＩＴＥＳＯＬＩＤＰＲＯＰＥＬＬＡＮＴＳｈｅｎＨｕａｉｒｏｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＡｅｒｏｓｐａｃｅＴｅｃｈｎｏｌｏｇｙ,１０８Ｌａｂｏ...