【作者】 郭效德；

【导师】 李凤生； 宋洪昌；

【作者基本信息】 南京理工大学 ， 材料学， 2007， 博士

【摘要】 高燃速推进剂广泛应用于高速动能弹、机载导弹、反坦克导弹等快速反应武器，因此高燃速推进剂是固体推进剂最热门的研究方向之一。采用一种膏体状推进剂粘结小球药而制备的复式结构体的高燃速推进剂具有燃烧速度高和燃烧稳定等特点。本文主要针对这种新型推进剂的配方设计及燃烧特性进行了系统的理论和实验研究。首先，分析讨论了小球粘结高燃速推进剂燃烧性能设计原理及方法，采用基于推进剂化学结构与特征反应关系的燃速预估程序和REAL热力学系统软件分别计算了组分含量与黏结剂和小球药燃烧性能、能量性能的关系，分析了推进剂燃烧性能、能量性能设计时组分含量的选择原则。根据小球粘结高燃速推进剂配方设计的特点，在综合了双基推进剂和复合推进剂部分制备工序的基础上，提出了常温、无溶剂、二步挤压制备小球粘结高燃速推进剂工艺。其次，分别研究了组分含量、小球药形态、结构及与黏结剂质量比对小球粘结高燃速推进剂燃烧性能的影响。实验结果表明：当膏体状黏结剂配方中NC、NG、AP含量增加，膏体状黏结剂燃速增大，推进剂燃速也增大；而随着小球药配方中NG／NC比例增大，小球药燃速增大，推进剂燃速下降。其内在规律是膏体状黏结剂与小球药燃速差越大，推进剂燃速越高，反之亦然。小球药粒径越小、表面越粗糙，则推进剂燃速越高。膏体状黏结剂与小球药质量比越小，推进剂燃速也越高，但二者质量比小到一定数值后易造成推进剂燃烧不稳定，根据理论分析，膏体状黏结剂与小球药质量比至少应大于41：59。然后，系统研究了铅、铜、铁化合物不同组合的催化剂对小球粘结高燃速推进剂主要组分热分解和燃烧性能的催化特性。实验结果表明：在铅、铜复合的基础上加入含铁的化合物，可使双基黏结剂的热分解峰大幅度提前，显示了较好的催化效果；同样可显著促进AP的热分解，特别是亚铁氰化铅／铜铬氧化物复合不仅使AP高温分解峰温提前了133.4℃，而且使低温分解峰温提前了55.1℃，是催化AP热分解中效果较好的一种催化剂组合。同时采用铅／铁／铜复合催化剂，可以较大幅度降低小球粘结高燃速推进剂在高压区间内的压强指数，特别是亚铁氰化铅／亚铬酸铜组合显示了对小球粘结高燃速推进剂较好的催化效果。对小球粘结高燃速推进剂燃烧及熄火照片分析表明，小球粘结高燃速推进剂燃烧熄火表面不是一个简单的曲面，而是由小球药表面熔化而又相互粘结成具有一定厚度的多孔气透性结构的燃烧表面层，在该燃烧层内就可能发生一定程度的对流燃烧，其燃烧过程也有别于一般改性双基推进剂，可分为六个区，即凝聚相加热区、亚表面反应区、燃烧表面区、多孔透气区、颗粒流动区和产物区。最后，对小球粘结高燃速推进剂发动机进行了实验研究和数据分析，结果表明，小球粘结高燃速推进剂在不同条件下有三种燃烧类型。类似于普通双基推进剂的平行层燃烧类型，类似于超高燃速推进剂的对流燃烧类型，以及介于二者之间的“有限对流燃烧”类型。可用一无量纲数值r大小和压强来判断新型高燃速推进剂出现三种类型燃烧的条件，在压强较小和r≈1.0时该推进剂在发动机内是类平行层进行燃烧；在压强较高和r＞1.4时该推进剂在发动机内是类对流燃烧；在压强适中和r≈1.1～1.3时，该推进剂在发动机内是有限对流燃烧。同一种推进剂在不同的条件下可出现这三种不同的燃烧类型，是小球粘结高燃速推进剂燃烧特性的新颖之处。同时，这也为小球粘结高燃速推进剂提供了广阔的应用领域。更多还原

【Abstract】 High-burning-rate propellant is widely used in quick response weapons such ashypervelocity kinetic antitank missiles, aircraft-launched missile, antitank missiles,etc. High-burning-rate propellant is one of the hottest research directions in the field ofsolid propellant. The investigated high-burning-rate propellant is characterized by highburning rate and stable combustion, the duplex structure of wchich is fabricated bybinding small grain propellants together by pasty propellant. In the paper, the formuladesign and combustion behavior of the novel high-burning-rate propellant is investigatedboth theoretically and experimentally.Firstly, the principle and method of designing the combustion characteristics ofsmall grain-binding high-burning-rate propellant are analyzed and discussed, theburning behaviors and energy characteristic of the component content and binder andsmall grain propellant are respectively calculated by the estimating burning rateprocedure based on the chemical structure and characteristic of propellant, and theREALthermodynamics system software. The selection principle of component contentwhen designing the burning behavior and energy characteristic is analyzed. According tothe formula design of the small grain-binding high-buming-rate propellant as well as thepreparation processes of both double base propellant and composite propellant, thenovel process to prepare small grain-binding high-burning-rate propellant characterizedby the room temperature, solventlessness and two-step extruding is proposed.Secondly, the effects of the component content, small grain shape and structure,and the binder mass ratio of binder to small grain propellant on the burning behavior ofthe small grain-binding high-burning-rate propellant were respectively studied.Theexperimental results show that, the burning rate of pasty binder and the propellantincreases with the increasing the component content of NC, NG and AP and that as theratio of NC/NG in the small grain increases, the burning rate of small grain increasesbut the burning rate of the propellant redueces. The internal laws can be concluded thatthe greater burning rate difference between pasty binder and small grain is, the higherthe burning rate of the propellant is, vice versa.The smaller the particle size and the rougher the surface leads to the higher theburning rate of the propellant. The smaller the mass ratio of the pasty binder to smallgrain is, the higher the burning rate of the propellant is. But when the mass ratio isreduced to a certain value, it would easy to cause unstable combustion. Based ontheoretical analysis, the mass ratio of the pasty binder to small grain should be t higherthan 41: 59. The catalytic properties of the thermal decomposition and the burning behavior ofthe small grain-binding high- burning-rate propellant is systemically investigated.Experimental results that, ee the addition of iron composite into the lead/copper complexcatalyst significantly advances the peak temperature of double base binder thermaldecomposition, showing excellent catalytic performace., and also promotes the thermaldecomposition of AP. Especially the complex of lead ferrocyanide/C.C reducestemperature of AP higher temperature decomposition peak by 133.4℃and temperatureof AP lower temperature decomposition peak by 55.1℃, and is a good complex catalystin the catalytic thermal decomposition of AP. Moreover, using lead/iron/coppercomplex catalyst greatly reduces the pressure exponent in the higher pressure range ofthe small grain-binding high-burning-rate propellant. Remarkably, the complex of leadferrocyanide/C.C shows excellent catalytic effect on the small grain-bindinghigh-burning-rate propellant.The analyzed of the photos of the small grain-binding high-burning-rate propellantduring combustion and after extinguishing, the combustion extinguished surface is not asimple curved surface, but a surface with multi-perforated permeable structure composeof the melt and conglutinated small grain propellant, where convective combustion maybe exist, and its combustion can be divided into six different zones, condensed phaseheating zone, hypo-surface reaction zone, combustion surface zone, permeabilitymultiperforated zone, grain flowing zone and product zone.Under different conditions, the combustion of the small grain-bindinghigh-burning-rate propellant can be categorized into three types, i.e. parallel layercombustion similar to double base propellant, convective combustion similar to thesuper high-burning-rate propellant, and finite convective combustion between the twotypes. The dimensionless value r and pressure can be used to estimate when the threecombustion type appears. When the pressure is low and r≈1.0, the combustion in therocket motor is similar to parallel layer combustion; when the pressure is higher and r＞1.4, the combustion in the rocket motor is similar to the convective combustion; andwhen the pressure is moderate and r≈1.1～1.3, the combustion in the rocket motor isfinite convective combustion.The coclusion can be drawn that the same propellant hasthree different combustion types under different conditions, which is the difference ofthe small grain-binding high-burning-rate propellant from traditional propellant and willprovide a wider application field for high-burning-rate propellant.更多还原