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稀土化合物纳米材料的合成与性质研究

Synthesis and Properties of Rare Earth Compounds Nanomaterials

【作者】 林松竹

【导师】 董相廷;

【作者基本信息】 长春理工大学 , 材料物理与化学, 2013, 博士

【摘要】 稀土纳米发光材料在高分辨显示、荧光标记、生物成像、诊断和治疗等方面具有重要的应用价值。以磷酸盐为基质的稀土发光材料已受到研究者的广泛关注。目前稀土磷酸盐纳米发光材料的研究主要集中在纳米粒子方面,而稀土磷酸盐一维纳米材料的制备研究鲜见报道。因此,制备一维磷酸盐纳米材料并探索其性质是重要的研究课题。稀土配合物是金属有机配合物的一种,稀土配合物掺杂高分子材料是一类很有价值的功能材料,这种材料兼具稀土离子的发光特性和高分子材料的特性,提高了配合物的稳定性,制备的材料具有良好的发光性能。将稀土配合物掺入高分子中制成的纳米纤维是一种新型的发光材料,有重要的研究价值。稀土族石榴石型铁氧体晶体的物理和化学性能稳定,被认为是最有应用前景的新一代磁光记录介质。本论文主要研究内容为:(1)采用水热法制备了具有良好光学性质的Eu3+离子掺杂的稀土磷酸盐纳米晶材料,研究了不同合成条件对纳米稀土磷酸盐的晶体结构、形貌和尺寸、以及发光性能的影响和调控规律。结果显示,纳米磷酸盐的发光性质与所制备的纳米材料的结构和形貌有关,通过改变纳米晶的结构来控制发光性能是可行的。(2)通过Ce3+对Tb3+的传能实现高效发光已经为人们所认可。本文采用水热法,通过控制温度和表面活性剂合成了不同尺寸和形貌的CePO4:Tb3+内米棒材料,研究了加入不同量的CTABi(十六烷基三甲基溴化铵)以及改变反应温度对产物的尺寸、晶体结构和形貌的影响,取得了一些重要的结论和创新性成果。(3)采用静电纺丝法,合成了Eu(TTA)3ECIP/PS纳米纤维,研究了不同合成条件对纤维的影响,在此基础上,研究了不同配合物掺杂浓度的纳米纤维的发光性质,以及对氧气传感的性质,发现氧气对发光的猝灭作用具有线性关系,配合物在聚合物中分散均匀,而且响应时间和恢复时间短,是氧气传感的优良材料。同时我们探索了利用双收集板法制备定向复合纤维的方法,并探索了形成机理。(4)采用溶胶-凝胶法合成了稀土掺杂的石榴石铁氧体(TbY)3Fe5012,分析了其结构及形成机理,研究了稀土掺杂对磁性能的影响。

【Abstract】 Rare earth doped luminescent nanomaterials have important applications in high-resolution display, fluorescence label, biological imaging, diagnosis and therapy of diseases and etc. Rare earth phosphors using phosphates as matrix have attracted considerable attention of the researchers. Nowadays, the researches on rare earth phosphates luminescent nanomaterials are focused on the morphology of nanoparticles. The investigation on one-dimensional rare earth phosphates nanomaterials is rarely reported. Therefore, the fabrication of one-dimensional rare earth ions-doped rare earth phosphates will be a meaningful subject. Rare earth coordination compounds-doped polymers are a kind of very valuable functional materials that have both the luminescence properties of rare earth ions and the characteristics of polymer materials. The prepared materials have excellent luminescent properties and high stability. Nanofibers prepared by doping of rare earth coordination compounds in the polymer are a new kind of luminescent materials, and have become a new and important subject of study. Rare earth doped garnet type ferrite is considered as a kink of the most promising media of magneto-optical recording, due to its stability performance of physical and chemistry characters.The main research contents of this thesis are:(1) Eu3+doped phosphates fluorescent nanomaterials with excellent luminescent properties were prepared by hydrothermal method. The influences of synthesis conditions on sizes, crystal structures and morphologies of the phosphates nanomaterials were investigated. The results showed that the luminescent properties of the phosphates nanomaterials were related with the structure and morphology of the as-prepared nanomaterials. And it was practicable to control the luminescent properties of the phosphates nanomaterials by changing the structure of the nanocrystalline.(2) Energy transfer from Ce3+to Tb3+is known and can be found in many luminescent materials. In this dissertation, CePO4:Tb3+nanorods were prepared via hydrothermal method. Sizes, crystal structures and morphologies of the products were investigated by introducing different amounts of CTAB and altering the reaction temperature. Some new meaningful results are obtained.(3) The Eu(TTA)3ECIP/PS composite nanofibers were fabricated by electrospinning. The influences of synthesis conditions on sizes and morpHologies of the composite fibers were investigated. On this basis, we researched the luminescent and oxygen-sensing properties of the composite fibers with different doping concentrations. Experimental data suggested that the Eu(TTA)3ECIP/PS nanofibers exhibited a high sensitivity towards oxygen with a good linear relationship. In addition, the Eu(TTA)3ECIP/PS nanofibers owned a quick response along with its excellent atmospHere insensitivity and pHotobleaching resistance. All these results suggested that the Eu(TTA)3ECIP/PS system were promising candidates for oxygen sensing optical sensors. At the same, we explored the method to prepare the aligned fibers with double collectors. The formation mechanism of the aligned fibers between the collectors was also discussed.(4)(TbY)3Fe5O12with garnet structure were produced via sol-gel method. The structure and formation mechanism were studied. Also, we investigated the influence of rare earth doping on the magnetic properties of the nanoparticles.

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