离子型硼笼类铝粉促燃剂结构性能协同设计及促燃机制

Developing liquid-solid high energy fuels containing nano-Al is a novel way as well as an important research direction due to the energy density limit of the existing high-density liquid hydrocarbon fuels. To solve the problem of incomplete combustion of nano-Al in ramjet engines arising from some key factors (essentially, poor dynamic conditions of combustion) which mainly comprise extremely short residence time, aluminum agglomeration, mismatch of liquid-solid multiscale-combustion, burning-promoting technology of nano-Al based on the regulation and control of structures of ionic boron cage compounds is presented. The regulation and control of structures of ionic boron cage compounds can be achieved by means of the design of anionic and cation. By the research on the coordinate regulation law amoung calorific value, density and burning-promoting performance, the coordinate regulation can be realized. Effects of ionic boron cage compounds on the conversion of nano-Al, composition and morphology of combustion products, dynamic behavior of combustion reaction of nano-Al will be investigated through the shock-induced ignition and combustion performance evaluation and design of thermogravimetric analysis. The intrinsic relationship between the structure and burning-promoting performance of ionic boron cage compounds will be determined, by which the burning-promoting mechanism can be revealed. Based on the research of this project, theoretical and scientific basis can be provided for the application of ionic boron cage compounds to liquid-solid high energy fuels. Moreover, this project will greatly promote the application of liquid-solid high energy fuels to ramjet engines.

现有液体高密度碳氢燃料能量密度已近极限，研制含铝液固高能燃料是提高燃料能量密度的新途径和重要发展方向。为了解决纳米铝粉在冲压发动机中因滞留时间短、铝粉团聚、液-固多尺度燃烧不匹配等（本质原因为铝粉燃烧动力学条件差）导致的铝粉燃烧不充分的问题，项目提出了基于离子型硼笼化合物结构调控促进铝粉燃烧的促燃剂技术。通过开展离子型硼笼化合物阴、阳离子设计实现其结构调控；通过研究离子型硼笼化合物结构与热值、密度和促燃性能的协同调控规律，实现各性能协同调控；利用高能燃料激光点火燃烧、热重分析实验，研究离子型硼笼化合物对铝粉燃烧转化率、凝相产物组成形貌、铝粉燃烧动力学行为的影响规律，关联离子型硼笼化合物的分子结构与促燃性能，揭示离子型硼笼类铝粉促燃剂的促燃机制。本项目将为离子型硼笼类铝粉促燃剂在液固高能燃料中的应用提供重要的理论基础和科学依据，并推动实现含铝液固高能燃料在冲压发动机中的应用。

现有液体高密度燃料能量已近极限，研制含铝液固高能燃料是重要发展方向。然而，铝粉燃烧不充分严重制约了含铝液固高能燃料的发展及应用。项目提出了离子型硼笼化合物作为铝粉促燃剂的解决思路。通过阴、阳离子改性调控离子型硼笼化合物结构，阐明了其对热值、密度和促燃性能的影响规律，掌握了性能调控方法，研究了离子型硼笼化合物对铝粉燃烧转化率、凝相产物组成形貌、铝粉燃烧动力学的影响规律，关联了结构与促燃性能，揭示了铝粉促燃剂的作用机制。主要过程及结果如下：.（1）采用热解反应合成了离子型硼笼母体化合物十氢十硼酸双四乙基铵，通过离子交换或复分解法引入镍、钴、铜等金属，进行阳离子调控，通过调变硼笼上硼氢的烷基取代基进行阴离子调控，设计合成出系列不同阴、阳离子调控的离子型硼笼化合物。扫描/透射电镜、红外等表明，制备的化合物在2438 cm-1和1088cm-1均出现了典型的硼笼特征吸收峰，其晶粒尺寸在一维上最低可至50 nm，整体呈不规则长块状形貌。.（2）研究了阴、阳离子结构调控对离子型硼笼化合物关键理化性能密度、热值和热稳定性等的影响规律，发现阳离子显著提高了密度，但略降低了热值，其中引入铜后的BTC密度和热值分别达0.93 g/cm3和48.87 MJ/kg、热分解温度为272.6℃，兼具高密度、高热值和适宜的热分解特性，而引入烷基阴离子密度和热值均有所下降。.（3）离子型硼笼化合物的结构对含铝液固高能燃料燃烧性能影响显著。从燃烧峰温看，BNE和BTC整体效果最佳。含不同离子型硼笼化合物的高能燃料热解和燃烧产生的小分子的速率明显不同，且部分离子型硼笼化合物可促进燃料二次燃烧。BTC添加后，铝粉的氧化反应活化能降低40.5 kJ/mol，从而提升了铝粉的燃烧性能。.项目为离子型硼笼类铝粉促燃剂在液固高能燃料中的应用提供了重要的理论基础和科学依据，相关成果成功应用于固体推进剂及火炸药，显著提升了武器射程和毁伤威力，为国防武器装备建设作出了重要贡献。