【作者】 杨毅；

【导师】 李凤生； 宋洪昌；

【作者基本信息】 南京理工大学 ， 材料学， 2003， 博士

【摘要】 纳米／微米复合技术是纳米材料领域的一门新型技术。利用该技术可以获得纳米粒子无团聚、纳米功能特性得到充分发挥、纳米粒子在体系中分散较好的纳米复合粒子。本文选择了在军民各领域应用较广泛的、在纳米材料领域比较典型的几种材料，通过复合粒子的三种复合形式的研究，分别对颗粒复合型和膜复合型纳米／微米复合粒子的复合技术及其复合原理进行了研究；在对前面两者研究的基础上，把两种复合方式进行了有机的结合，制备出了性能优异的纳米壳／膜／微米核型的功能复合粒子。通过对颗粒复合型、膜复合型及纳米颗粒壳／膜／核复合型三方面的粒子设计方法的全面研究，为制备新型的纳米功能复合粒子提供了新的思路，为粒子复合技术提供了较好的理论依据和实验基础。 首先，以RDX和Al粉作为原材料，研究了纳米／微米复合技术中的颗粒复合型材料的制备方法及其对复合材料的结构性能的影响。采用自制的YLG型高效研磨机，通过调节不同的液体研磨介质（水、乙醇），制备出了复合效果不同、结构性能有差异的两种颗粒复合型的RDX／Al超细复合粒子。用激光粒度测试仪、SEM、DSC、XRD及爆热量热计等仪器对复合粒子粒度、粒子形貌、热力学性能、粒子组分及爆热等进行了较全面的研究。结果表明：在水中研磨有助于粒子的复合，而在乙醇中研磨则有利于粒子的超细化和分散。在乙醇中研磨样品由于高能物质（C₂H₅O）₃Al的生成，有效地防止了金属铝粉的氧化，其爆热提高明显。为了解释这些现象，提出了超细复合模型及超细RDX／Al复合炸药热分解模型，其结论与实验结果符合得很好。 其次，以TiO₂和SiO₂为复合对象，分别制备了纳米SiO₂薄膜包覆纳米TiO₂的纳米复合粒子（膜复合型）和纳米TiO₂粒子沉积复合在自制的单分散球形SiO₂粒子表面的复合粒子（颗粒复合型），研究了两种复合技术的原理和实验方法，以及所制备的两种纳米复合粒子的优异特性。在对几种保健食品的灭菌保鲜的实验中，发现两种复合粒子都比纯的纳米TiO₂有更好的效果。其中，添加膜复合型纳米粒子的样品的菌落总数最少，具有最优的作用效果，其菌落总数为各食品企业标准菌落总数的0.25％～0.7％，是相应空白样的0.52％～0.97％，为纯纳米TiO₂粉样品菌落总数的33.3％～83.3％。。 以上述两方面的理论分析、实验技术和实验结果为基础，选取纳米Fe₂O₃和金属铝粉为复合材料，首先运用成膜复合技术，将自行选取合成的无机膜材料包覆在活化摘要博士论文后的金属铝粉粒子表面，形成对活性金属粒子有很好“保护”作用的纳米薄膜/金属铝复合粒子:然后再次运用颗粒复合型粒子复合技术，将纳米FeZO3粒子沉积复合在纳米膜/金属铝复合粒子的表面，形成了以纳米Fe203催化粒子为外层，活性金属铝为内核，纳米常温惰性薄膜为中间层的纳米壳/膜/微米核型的功能复合粒子。这种功能复合粒子既具有高效的催化作用，又具有很好的能量性能。将该新型复合粒子应用到固体火箭推进剂中，发现使推进剂的能量性能和燃烧性能都得到了较大提高。该技术目前已经申请国防发明专利，专利批准号为:03 105599.0。更多还原

【Abstract】 The nanometer/micrometer composite technology, by which nanometer composite materials with low aggregation of nanometer particles can be prepared, is a new kind of technology in nanometer material field. With the technology, the functional characteristics of nanometer particles can be brought into play adequately. Several kinds of typical materials in nanometer field are chosen to prepare functional nanometer materials in this dissertation. Based on the study of grain composite particles and membrane composite particles, a new kind of functional nanometer composite particle is prepared in the form of nanometer grain/nanometer membrane/micrometer core particle. Through the study of nanometer grain and membrane composite technology separately, as well as the organically combination of grain and membrane composite technology, the theoretical basis and experimental foundation are presented for particles compounding.First, the grain composite technology was studied with the materials of RDX and Al powder. The RDX/Al superfine composite powder was prepared with an YLG model stirring grinding machine. The grinding media (water and alcohol) were compared and studied during the grinding process. The particle composition and their diameters, appearances of the composite particles and their properties of thermodynamics and explosive heat were studied by using the particle diameter sizer, SEM, DSC, XRD and explosive heat testing machine respectively. The study results indicated that the water grinding media may benefit the compounding of particles, while the alcohol grinding media may benefit the superfining and dispersing of particles for the energetic(C2H5O)3Al sample, which was gained in alcohol media. Accordingly the explosive heat was improved of sample ground in alcohol. In order to explain this phenomena, models on the superfining and compounding of particles and the thermolysis of superfine RDX/Al composite explosive were proposed and the models are well in accord with the experiment results.Second, the membrane and grain composite technologies were studied for compounding materials of TiO2 and SiO2. The nanometer composite particles of nanometer TiO2 covered by nanometer SiO2 membrane as well as nanometer TiO2 particles precipitated on auniform dispersed micrometer SiO2 sphere particle were prepared respectively. The sterilization experiments on several health care foods indicated that the two kinds of nanometer composite particles showed much better sterilization effect than the pure nanometer TiO2. While the samples added with nanometer TiO2/SiO2 membrane composite particles resulted in the lowest bacteria number. After 60 days, the total bacteria numbers of the samples containing membrane composite powder were only 50 to 120 units per gram, only 0.25%~0.7% of the enterprise standards of corresponding health care food, 0.52%~0.97% of the bacteria numbers of blank samples and 33.3%~83.3% of those of samples containing pure nanometer TiO2 powder.Based on the theoretical analysis and the experimental results of the two above-mentioned study, a new kind of composite particles in the form of nanometer grain/membrane/micrometer core particle was prepared by combined the grain and membrane composite technology organically. Nanometer Fe2O3 and micrometer Al were experimented to prepare the grain/membrane/core composite particles. The membrane, which was proved can protect the metal core particles from oxidation, was formed in the preparing process of composite particles. After the composite particle of inorganic membrane covering Al powder is formed, nanometer Fe2O3 is deposited on the surface of membrane. Accordingly the nanometer grain/nanometer membrane/micrometer core particle with catalytic and energetic function is achieved. The application experiments on solid propellant indicated that the decomposition of propellant is accelerated, and that the combustion heat is increased distinctively. A patent has been applied to protect the novel technology, and the patent authorization number is 03105599.0.更多还原