纳米TiO₂及TiO₂/PMMA复合材料的制备及其性能研究

【作者】 张宇婷；

【导师】 张明；

【作者基本信息】 扬州大学 ， 高分子化学与物理， 2010， 硕士

【摘要】 纳米TiO₂是一种新型多功能精细无机材料,具有熔点低、比表面积大、光吸收性能好等优越特性,从而广泛应用于功能陶瓷、油墨、高性能涂料、太阳能电池等诸多领域。有机/无机纳米杂化材料的组装以及相关的纳米技术在制备新型纳米复合材料中越来越受到研究者的关注。有机/无机纳米杂化材料是无机相和有机相互穿的网络结构,无机组分可改进有机组分的性能或使其功能化。由于纳米无机物与聚合物之间具有协同作用,使得高聚物基无机纳米杂化材料具有普通材料所没有的优良特性。本文采用水热合成法,制备了棒状纳米TiO₂以及掺杂稀土离子的纳米TiO₂,对其表面进行修饰并研究了其分散性。在本体聚合中添加TiO₂以及掺杂LaCl3、EuCl3的TiO₂来制备TiO₂/PMMA复合材料。重点考察了二氧化钛纳米粒子表面的有机改性,二氧化钛纳米粒子的填充量及外加电场对聚合物复合材料结构以及性能的影响。主要的研究结果如下:（1）通过水热合成法成功制备出形貌均一热稳定性较好的金红石型TiO₂纳米棒和掺杂稀土La和Eu的TiO₂纳米颗粒。掺杂稀土离子可以增大TiO₂纳米粒径,形状也由棒状向球形逐渐过渡,比表面积变小,稀土对TiO₂的掺杂降低了失重率,而晶型没有变化。（2）水热法制备TiO₂纳米颗粒的同时,采用聚甲基丙烯酸、油酸等不同有机物质进行表面修饰,以解决纳米TiO₂的团聚问题。结果发现油酸对TiO₂纳米颗粒的分散起到了很好的效果,PMA包裹对TiO₂纳米颗粒没有明显的分散效果。（3）将纳米TiO₂在本体聚合的过程中添加到聚甲基丙烯酸甲酯中。发现纳米TiO₂对聚甲基丙烯酸甲酯有很好的增韧作用。添加纳米TiO₂粒子会导致材料接触角变大,透光率降低。在电场的作用下PMMA及TiO₂/PMMA复合材料的力学和光学性能都明显提高。更多还原

【Abstract】 Nano-TiO₂ is a new multi-function fine inorganic material with many excellent features, such as low melting point, magnetic strength, large specific surface area, and excellent light absorption properties and etc. So far, nano-TiO₂ is widely used as functional ceramics, printing ink, high-performance coatings, solar cells and other areas. However, how to solve the reunion of nano-TiO₂ has been a hot topic. Organic / inorganic hybrid nano-materials, nano-assembly and related technology in the preparation of novel nano-composite materials have been aroused great concern. Inorganic and organic phase with each other through the network structure; inorganic components can improve the performance of organic components or their function, beacause of the synergic action between inorganic and polymer nano synergy can strengthen the bond among the two-phase capacity. Makes the polymer-based inorganic hybrid materials have properties which common materials do not have: Optical properties, mechanical properties, catalytic properties, etc.This paper mainly studies with titanium tetrachloride as the raw material by hydrothermal synthesis method, as a reasult rod-shaped powder and doping LaCl3, EuCl3 rare earth ion nano-TiO₂ powder was prepared. Meanwhile, to study the dispersivity of nano-TiO₂ with oleic acid, methyl methacrylate modified nano-TiO₂ on the surface. To make PMMA/TiO₂ composites, by adding TiO₂ and which is doped of LaCl3, EuCl3 into PMMA with in-situ bulk polymerization. The mechanisms of organic modified and effects on polymer matrix for nano-TiO₂ particles were studied such as mechanics, thermodynamics, morphology and so on. The main findings are as follows:（1） By hydrothermal method successfully prepared a diameter of about 15nm, 200nm length about the uniform morphology of rutile TiO₂ nanoparticles. The TiO₂ nanoparticles doping with rare earth La and Eu were prepared with the same way . Doping of rare earth ions can increase the size of TiO₂ nanoparticles, particle shape also changed from rod to spherical and the specific surface is smaller. Rare earth doping on the TiO₂ further improve the yield rate of weight loss.（2） Different substances on the surface modified TiO₂ nanoparticles, nano-TiO₂ aggregation to solve the problem. It was found that oleic acid on the dispersion of TiO₂ nanoparticles have played a very good results, the best concentration of 0.1M and modified 0.2M, PMA TiO₂ nanoparticles on the dispersion effect is not obvious.（3）By adding TiO₂ nanoparticles to the PMMA inside, the use of FE-SEM, impact properties, bending properties, contact angle, transmittance test for performance testing of the hybrid material, it is found that nano-TiO₂ particles on the polymer material has a good toughening effect. With the increasing amount of TiO₂ added the matrix micro-cracks increased, resulting in larger contact angle. Nano TiO₂ particles will reduce the light transmission rate of PMMA. Using the same method to add the rare earth ion doped into PMMA-TiO₂ hybrid materials tested and it is found that rare earth ions La and Eu doped TiO₂ nanoparticles can reduce the toughening effect.更多还原