【作者】 王艳萍；

【导师】 陆路德； 杨绪杰； 汪信；

【作者基本信息】 南京理工大学 ， 化学工程与技术， 2006， 博士

【摘要】 纳米材料的制备和应用是当今材料科学研究的热点之一。推进剂的燃烧性能是装药技术的核心，使用少量的燃烧催化剂是调节推进剂的燃烧性能的最佳途径。而通过催化剂对推进剂主要组分的热分解性能的影响可以予估其对推进剂燃烧性能的影响。本论文主要制备了纳米尺度的NiO，CuO等单一金属氧化物和LaFeO₃，LaCoO₃等系列钙钛矿型复合氧化物纳米晶，并考察了其对高氯酸铵（AP）热分解、推进剂燃烧性能的影响，为进一步开发催化性能优异的催化剂，提高火药装药的性能提供实验和理论基础。主要研究内容如下： 通过固相反应法制备了纳米NiO。用FTIR，XRD，EDS等手段分析了固相反应制备纳米NiO的可行性和反应历程。在固相反应过程中可以通过加入分散剂和控制热处理温度得到分散性良好的纳米NiO。同时与体相材料的比较表明：纳米NiO的红外吸收光谱呈现“红移”现象，紫外-可见光吸收光谱呈现“蓝移”现象。晶体的粒径随热处理温度的升高而增大、晶格畸变率随热处理温度的升高而降低。沿用制备纳米NiO的方法制备了包括CuO，Fe₂O₃，CuO·Fe₂O₃，CuFe₂O₄在内的Cu-Fe-O系统催化剂。 用氨基酸燃烧法制备了LaFeO₃，LaCoO₃，LaNiO₃，LaFe_0.2Co_<sub>0.8O₃，LaFe_0.5Co_0.5O₃LaFe_0.8Co_0.2O₃，NdFeO₃等系列钙钛矿结构的纳米晶。产物与原料的投入比例一致，没有偏析现象。根据XRD衍射的数据，运用Fullprof程序软件对衍射数据指标化，并计算了晶胞参数。同时用TEM，HRTEM，SEM，EDS，Raman等手段对产物进行表征。计算了焙烧过程中LaFeO₃和LaNiO₃晶粒增长的活化能。以LaFeO₃为例，对固相反应法和燃烧法产物做了比较，燃烧法制备的样品分散程度高于传统的固相法。以氨水为燃烧调节剂，可以提高产物的分散性。 详细考察了NiO，Cu-Fe-O系统催化剂，LaFeO₃，LaCoO₃，LaNiO₃，LaFe_0.2Co_0.8O₃，LaFe_0.5Co_0.5O₃LaFe_0.8Co_0.2O₃，NdFeO₃AP热分解的催化性能。结果表明以上各种纳米材料对AP的热分解均具有催化作用： （1）纳米NiO使AP的高温分解反应峰值温度下降了93℃，表观分解反应放热量由0.59kJ·g^-1增至1.4kJ·g^-1，分解反应活化能由188J·mol^-1降至120J·mol^-1。依据电子转移的理论初步探讨了纳米NiO对AP热分解的催化机理； （2）Cu-Fe-O系列催化剂对AP热分解的催化性能的实验表明，CuO·Fe₂O₃的催化性能明显优于单一的Fe₂O₃和CuO，这是Fe₂O₃和CuO两种催化剂协同作用的结果。CuFe₂O₄在AP热分解中表现了优于CuO·Fe₂O₃的催化性能，这可能与尖晶石特殊的结构有关； （3）LaFeO₃，LaCoO₃，LaNiO₃三种钙钛矿型纳米晶对AP热分解的催化性能依次更多还原

【Abstract】 In the past decades, the synthesis and application of novel nanomaterials have been studied extensively. The manipulation of combustion properties composes the core part in the technology of powders and explosives. Catalyzed combustion provides a most popular approach to improve the properties of powder and explosives, in particular for solid propellants. According to the thermal decomposition of the predominant components in composite propellants, the behavior of the catalysts can be derived. In this dissertation, a series of nanometer-sized catalysts including NiO, CuO, LaFeO₃, LaCoO₃, etc have been prepared, and their effects on ammonium perchlorate （AP） thermal decomposition and propellants combustion were investigated. The dissertation is mainly focused on:1. A solid state reaction method is employed to synthesis nanometer-sized NiO and the overall procedure was monitored by FTIR, XRD, and EDS. The impacts of dispersant and thermal treatment temperature were also discussed. In compared with bulk, infrared absorption band of NiO nanoparticles shifts to low wave number （red-shift） and UV-vis optical absorption is blue-shift 0.55eV. We attribute such phenomenon to the size growth of the obtained products and decrement of the lattice distortion at elevated temperature. Furthermore, oxides such as CuO, Fe₂O₃, CuO-Fe₂O₃, and CuFe₂O₄ were prepared in the same way.2. The glycine combustion method was used to synthesis LaFeO₃, LaCoO₃, LaNiO₃, LaFe_0.2Co_0.8O₃, LaFe_0.5Co_0.5O₃ LaFe_0.8Co_0.2O₃, and NdFeO₃ nanocrystals. Based on the XRD results, the Fullprof software were used to index the XRD data and calculate the crystal parameter. As the same time, the products were characterized by TEM, HERTEM, SEM, EDS. The activation energy of LaFeO₃ and LaNiO₃ nanocrystals formation during calcination were calculated. Compared with solid state method, the products of combustion method are more dispersed. Addition of ammonia improves the dispersity of the products.3. The catalysis of prepared products on AP thermal decomposition was investigated, by DTA and TG. The experimental results indicated that all prepared catalysts work for AP thermal decomposition in some degree:（1）. Addition of 2% of NiO nanoparticles in AP decreases the peak temperature of high temperature decomposition by 93℃ and increases the exothermic quantity of decomposition from 590J·g^-1 to 1.4kJ·g^-1. The activation energy of AP high temperature decomposition decreased from 188J·mol^-1 to 120J·mol^-1. The catalytic mechanism was更多还原