【作者】 马振叶；

【导师】 李凤生； 宋洪昌；

【作者基本信息】 南京理工大学 ， 材料学， 2004， 博士

【摘要】 固体推进剂是军事和航天技术的重要领域，一直为国内外研究者所重视。目前，高能和高燃速推进剂是最热门的研究方向。在提高固体推进剂燃速的众多方法中，采用纳米催化剂被认为是最有前途的方法之一。本研究在总装预研课题“固体推进剂用纳米材料的处理与应用研究”项目经费的资助下对纳米氧化物进行了研究。为了提高纳米氧化物对AP热分解的催化性能，采用对其进行表面改性、掺杂混合、与高氯酸铵（AP）直接复合等方法来进行研究。本文工作主要包括： 1．以Fe₂O₃为例，研究对纳米氧化物进行表面改性的方法，并分析了改性处理对纳米Fe₂O₃催化AP热分解的影响。该部分采用的表面改性方法主要包括以下3种： ● 在油相中制备纳米Fe₂O₃粒子同时用合适的表面活性剂对其进行表面改性；其中纳米Fe₂O₃粒子的制备方法选用两相体系法，表面活性剂选用油酸。 ● 首先在水相中制备纳米Fe₂O₃粒子，然后在油相中用合适的表面活性剂对其进行表面改性；其中纳米Fe₂O₃粒子的制备方法选用凝胶-溶胶法，表面活性剂选用醋酸。 ● 在水相中制备纳米Fe₂O₃粒子的同时选择合适的表面活性剂对其进行表面改性；其中纳米Fe₂O₃粒子的制备方法选用强迫水解法，表面活性剂分别选用油酸钠，十二烷基苯磺酸钠和硬脂酸。 结果表明，上述3种方法均可获得粒径小、分散性好的纳米Fe₂O₃粒子。表面改性处理能提高纳米Fe₂O₃粒子对AP热分解的催化性能。 2．对过渡金属氧化物（TMO）和稀土氧化物（REO）这两类常用的氧化物进行了掺杂混合，并研究了纳米混合氧化物对AP热分解的催化性能。主要內容包括： ● 在不同的掺杂混合比例下，将Fe₂O₃、CuO和Co₂O₃这3种TMO分别进行两两混合，并研究了纳米TMO／TMO混合氧化物对AP热分解的催化性能； ● 按1:1的质量比，将3种TMO（Fe₂O₃、CuO和Co₂O₃）与3种REO（CeO₂、Nd₂O₃和Y₂O₃）分别进行两两混合制得纳米TMO／REO混合氧化物，并研究了其对AP热分解的催化性能。 结果表明，两种氧化物混合后，其对AP热分解的催化效果表现为三种效应：正协同效应、无协同效应和负协同效应，主要取决于混合氧化物的成分与混合比例。 3．采用溶剂-非溶剂法制备了纳米氧化物／AP复合粒子，研究了复合粒子的热分解性能。其中选择的氧化物为TMO（Fe₂O₃，CuO，Co₂O₃）和REO（Nd₂O₃和Y₂O₃）。结果表明，制备以纳米氧化物为核、AP为壳的纳米复合粒子，可有效地解决纳米氧化物的分散性问题并提高其与AP的接触面积，进而提高纳米氧化物对AP热分解的催化性能。4.以FeZO3为例，研究了将纳米氧化物与AP的复合处理对复合推进剂燃烧性能的影 响。结果表明，纳米FeZO:与妙的复合处理能有效提高复合推进剂的燃烧性能， 使复合推进剂的燃速提高，压力指数降低。5.以Al粉为例，研究了金属添加剂与AP的复合处理对复合推进剂燃烧性能的影响。 结果表明，AI粉与”的复合处理能有效提高复合推进剂的热分解性能和燃烧性 能。此外，本文还研究了将FeZO3和Al粉都与AP复合处理对复合推进剂的燃烧 性能的影响，结果表明，将FeZO:和Al粉同时与AP复合处理后，复合推进剂的 燃速高于添加任何一种复合粒子的复合推进剂的燃速，但压力指数也增大。关键词:纳米粒子，氧化物，催化剂，固体推进剂，高氯酸钱，铝粉，FeZO3，表面 改性，复合推进剂更多还原

【Abstract】 Solid propellant is an important research field of military affairs and spaceflight technology. Now solid propellant with high energy and high burning rate is one of the most pop aspects. Among those methods to improve the burning rate of solid propellant, the nanometer-sized catalyst has been considered as one kind of most prospective methods. In this dissertation, we conduct the research on the nanometer-sized oxide catalyst under the support of national chief equipment ministry fund. In order to improve the catalytic performance of nanometer-sized oxide on the thermal decomposition of AP, the methods of the surface modification, doped mixing and composite with AP directly of nanometer-sized oxide are studied. Those main works are as follows:1. Take example for ferric oxide (Fe2O3), the surface-modification (SM) techniques of nanometer-sized(NMS) oxides were investigated and the catalytic activity of surface-modified NMS oxides on the thermal decomposition of ammonium perchlorate (AP) was analyzed. The SM techniques applied to Fe2O3 include: Modify the nanometer-sized Fe2O3 particles in oil/water two-phase system during their preparation by applying appropriate surfactant, In this dissertation, the NMS particles preparation method and surfactant are the two-phase system method and the oleic acid respectively. Prepare the NMS Fe2O3 particles in water phase firstly, and then modify the prepared Fe2O3 particles in oil phase by using certain surfactant, In this section, the NMS particles preparation method and surfactant are the Gel-Sol method and the acetic acid respectively. Modify the NMS Fe2O3 particles in water system during their preparation by applying appropriate surfactant. In this section, the NMS particles preparation method is force hydrolysis method and the surfactants are sodium oleic acid, DBS and stearic acid respectively. The results show that the NMS Fe2O3 particles with narrow size distribution can be obtained by using the three SM techniques discussed above. The SM process can improve the catalytic activity of NMS Fe2O3 particles on the thermal decomposition of AP. Among those SM techniques, the first technique can achieve better effect.2. Mix the transition metal oxide (TMO) and rare earth oxide(REO) and analyze the catalytic activity of those mixtures on the thermal decomposition of AP. Main worksinclude: Mix the random two kinds of material among three TMOs including theCuO and CO2O3 with different rate, and then analyze the catalytic activity of those mixtures on the thermal decomposition of AP. Mix random one kind of TMO (Fe2O3, CuO and Co2O3) and one kind of REO (CeO2, Nd2O3 and Y2O3) and analyze the catalytic activity of those mixtures on the thermal decomposition of AP. The results show that the catalytic activity of oxide mixtures on the thermal decomposition AP exhibit three kinds of cooperation action determined by the component and proportion of the mixtures. The three cooperation action are positive, zero and negative cooperation action respectively.3. The oxide/AP composite NMS particles were prepared by the solvent-nonsolvent method and their catalytic performance on the thermal decomposition of AP was analyzed. In this section, the applied oxides include Fe2O3, CuO, CO2O3, Nd2O3 and Y2O3. The results show that the preparing the oxide/AP composite particles not only improve the dispersed capability of NMS oxide particles, but also augments the contacting area of NMS oxide particles with AP. Hence the catalytic activity of NMS oxide particles on the thermal decomposition of AP can achieve obvious improvement.4. Take example for Fe2O3, the composite process of Fe2O3 and AP on the combustion performance of composite propellant was analyzed. The results show that the composite process of Fe2O3 and AP can improve the burning rate and decrease the pressure index of composite propellant.5. Take example for Al, the composite process of Al and AP on the combustion performance of composite propellant was analyzed. The results show that the composite pro更多还原