【作者】 李军伟；

【导师】 许鑫华；

【作者基本信息】 天津大学 ， 材料学， 2012， 博士

【摘要】 空心玻璃微珠（HGB）的表面功能化是提高HGB功能复合材料性能的关键。HGB可用于填充聚合物制备轻质高强复合材料，其关键是如何提高HGB和基体树脂之间的界面结合力。HGB也可作为载体，在其表面负载纳米材料构筑新型核壳复合结构，解决纳米材料易团聚、难分散的缺点，并可赋予HGB新的性能。本论文采用稀土材料对HGB进行表面改性，致力于研制HGB功能复合材料，对其开展微观结构和性能的研究。采用稀土镧络合物对HGB进行表面改性，通过溶液共混法制备PVDF/HGB复合材料，采用SEM、XRD、DSC测试方法研究PVDF/HGB复合材料的微观结构和结晶性能。SEM分析显示HGB经过稀土镧络合物表面改性后，与PVDF基体的界面结合力明显增强。XRD结果表明HGB的加入没有改变PVDF的结晶结构。采用Jeziorny法和Mo法对PVDF和PVDF/HGB复合材料的非等温结晶动力学进行了研究，结果表明：HGB抑制了PVDF的结晶，降低了复合材料的结晶速率。采用稀土离子对HGB进行表面改性，通过熔融共混法制备了PP/HGB、HDPE/HGB、PS/HGB和ABS/HGB四种复合材料，研究了复合材料的微观结构、力学性能和结晶性能。经稀土离子表面改性后的HGB与高分子基体树脂的界面结合力得到提高，复合材料的综合力学性能得到改善。硝酸钕表面改性的HGB可以促使PP产生少量β晶，但降低了PP的结晶速率。硝酸钕表面改性的HGB没有改变HDPE的晶型，其促使HDPE的相对结晶度增大。设计并制备了亚微米氧化锌包覆HGB复合结构，以HGB为载体，采用溶胶-凝胶法在HGB表面制备ZnO种子层，再在低温液相条件下，在生长液中生长有序的ZnO亚微米棒，制备得到ZnO包覆HGB复合结构。研究结果显示：在最佳反应条件下，HGB完全被ZnO亚微米棒包覆，ZnO亚微米棒具有良好的取向，截面呈六边形结构，平均直径为300～400nm，XRD分析表明ZnO亚微米棒为纤锌矿结构。ZnO种子层、生长液浓度和反应温度等条件影响复合结构的微观形貌。同时研究了稀土掺杂对HGB/ZnO复合结构的影响。采用均匀沉淀法制备稀土氧化物包覆HGB复合结构，控制适宜的生长液浓度、反应温度和反应时间等工艺参数可制备“梭形”纳米CeO₂包覆HGB复合结构，大部分CeO₂纳米棒垂直于HGB表面。同时制备并表征了HGB/Y2O₃、HGB/Dy₂O₃、HGB/Yb₂O₃和HGB/Y₂O₃:Eu³⁺复合结构。更多还原

【Abstract】 The key technology of hollow glass beads （HGB） composites is the surfacefunctionalization of HGB. The key to HGB filled polymer composites is how toimprove the interfacial bonding between HGB and matrix resin. The core-shellcomposite structure of HGB and nano-materials can solve the nanomaterialsdisadvantage of agglomerates and difficult to disperse. In this paper, the surfacemodification of the HGB was performed by using rare earth to committed to thedevelopment of the HGB functional composite material.PVDF/HGB composites were prepared by the method of solution blending usinglanthanum complex modified HGB. The morphology, structure and crystallizationkinetics of the PVDF and the PVDF/HGB composites were investigated by SEM,XRD and DSC, respectively. The results of SEM showed that the surface modificationof the HGB by using the lanthanum complex improved the interaction between theHGB and the PVDF. The results of XRD indicated alpha was the predominant phasein the PVDF and the crystal structure for the PVDF was not changed by the HGB. Inaddition, the Jeziorny and the Mo methods were used to analyze the non-isothermalcrystallization kinetics, the results indicated that the presence of the HGB decreasedthe crystallization rates of the PVDF.PP/HGB, HDPE/HGB, PS/HGB and ABS/HGB composites were prepared bythe method of melt blending using rare earth ions modified HGB, and themicrostructure, mechanical properties and/or crystalline performance of compositeswere studied. The results showed that the interfacial bonding between HGB andpolymer matrix could be significantly improved after superficial treatment of HGBwith the rare earth ion, and the mechanical properties of the composites wereimproved too. The results showed that the HGB modified by neodymium nitrate had anucleating effect on the matrix and promoted the formation of β-crystals ofpolypropylene, but the crystallization rate of polypropylene was decreased by addingHGB. In addition, the HGB modified by neodymium nitrate can increases thecrystallinity of HDPE.Uniform and oriented ZnO submicronrods on the surface of HGB werefabricated by using a seed growth process in aqueous solution of zinc nitrate andhexamethylenetetramine at low temperature. The structure and morphology ofas-obtained ZnO submicronrod-coated hollow glass microspheres （HGB/ZnO）composites were analyzed by using XRD and SEM. The results showed that all the HGB were coated with a well-aligned layer of ZnO submicronrods and the ZnOsubmicronrods possessed relatively uniform hexagonal rod structures and standperpendicular. Moreover, the ZnO submicronrods were affected by a variety ofgrowth conditions such as the ZnO seed layers and growth solution concentration andthe solution temperature. In addition, HGB/rare earth doped ZnO composites werestudied.Rare earth oxide coated HGB composites were prepared by using homogeneousprecipitation method. The “fusiform” nano-CeO₂coated HGB composites can befabricated under the optimal conditions. Most of CeO2nano-rods vertically in theHGB surface. In addition, the composites of HGB/Y2O3, HGB/Dy₂O₃, HGB/Yb₂O₃and HGB/Y₂O₃:Eu³⁺were prepared and characterized, respectively.更多还原