单分散二氧化硅微球及核壳结构材料的制备与研究
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摘要
近年来,核壳结构材料的制备成为材料科学中的一个重要研究领域。核壳结构材料,一般由固态的核和围绕其周围包覆完好的壳组成。相对于单一组分的材料来说,核壳结构具有独特的性质从而具有更广泛的应用价值,近年来引起较多的关注。核壳材料的结构、尺寸和大小具有良好的可控性,从而可以方便的调控其磁学、光学、力学、热学、电学、催化等性质。核壳材料可作为制备中空材料的前驱体,还可将昂贵材料包覆在廉价材料上,以降低其成本。近几年,化学组成相同、粒径及表面性质均一的单分散SiO_2微球常被用作模板制备核壳结构的复合微球,但仍存在一些球形度不高、粒度不均一等缺点,目前的改进工作主要集中于制备单分散性较好、球形度较高的、粒度小且均一分布的SiO_2粉体,并利用单分散SiO_2微球组建核壳结构材料。
本文首先以St(o|¨)ber法为基础,制备单分散SiO_2微球,利用透射电子显微镜(TEM)和粒度分析仪对样品的形貌和粒度进行表征,系统地考察了以氨水为催化剂时,不同反应条件对SiO_2粒径和分散性的影响,并对其反应机制进行了探讨;在此基础上,以制备的单分散SiO_2微球为核,采用溶胶-凝胶法合成了核-壳结构粉体,包括SiO_2@Y_2O_3,SiO_2@YAG:Ce~(3+)等,并对核壳结构粉体的形貌、结构、性质进行表征。研究结果如下:
(1)利用St(o|¨)ber法,以醇为溶剂,正硅酸乙酯在氨水催化下水解、缩聚,并进行一系列的后处理得到SiO_2微球。研究结果表明,溶剂(醇)的种类不仅影响SiO_2颗粒的分散性,而且随醇碳链增长,SiO_2微球的粒径增大,粒径分布变宽。随着反应液中正硅酸乙酯浓度、水浓度、氨水浓度及体系温度的变化,生成的SiO_2微球的粒径呈规律性的变化。
(2)利用溶胶-凝胶法,以单分散SiO_2为核合成了SiO_2@Y_2O_3核壳结构粉体。XRD和TEM结果表明,SiO_2表面的Y_2O_3结晶良好,且不与SiO_2核发生反应,随煅烧温度的升高,衍射峰强度增加,但并未产生新的衍射峰,这种核-壳结构的粉体表面致密,厚度均匀,保持了单分散SiO_2微球的形貌特征,壳的厚度可以通过沉积次数进行调控。
(3)利用溶胶-凝胶法,以单分散SiO_2为核合成了SiO_2@YAG:Ce~(3+)核壳结构粉体。XRD和TEM结果表明,当煅烧温度为800℃时,SiO_2微球表面的YAG:Ce~(3+)结晶完好,非晶SiO_2核不与YAG:Ce~(3+)壳层发生反应,核-壳结构SiO_2@YAG:Ce~(3+)粉体具有完美的球形(粒径约为300 nm),表面光滑不团聚,壳的厚度可以通过沉积次数进行调控。
In recent years, there has been intense interest in the fabrication of core/shell materials in the field of material science. Core-shell materials, often made up of a solid core surrounded by a well-defined shell layer, are known to exhibit unique and advanced properties over single-component nanoparticles, making them attractive for use in a wide range of applications, and are therefore of extensive scientific and technological interest. The structure, size, and composition of these particles can be easily altered in a controllable way to tailor their magnetic, optical, mechanical, thermal, electrical, and catalytic properties. The core-shell particles can be used as a precursor form to produce hollow spheres or to lower the cost of precious materials by coating them on inexpensive cores. Nowadays, the most commonly used to be the nuclear is monodisperse SiO_2, such microspheres have the same chemical composition, particle size and surface properties. The improvements focused on the preparation of monodisperse, particle size is small and homogeneous SiO_2 powder, and used monodisperse SiO_2 microspheres form a class of core-shell powder, which has a potential research value and potential applications.
In this article, monodispersed silica particles templates were produced by Stober method. The morphology and size of the particles were characterized by transmission electron microscopy (TEM) and particle size analyzer. We had studied the effections of different agents and reaction conditions of ethanol on the SiO_2 particle size and dispersion in the ammonia catalyst, and discussed its mechanism. Secondly, we had synthesised core-shell powder for monodisperse SiO_2 is the nuclear using the sol-gel method, including SiO_2@Y_2O_3, SiO_2@YAG:Ce~(3+), etc., and the core-shell powders were characterized by transmission electron microscopy (TEM) and X-ray powder diffraction. The results are as follows:
(1) Microspheres SiO_2 were prepared by hydrolysis of tetraethoxy silane (TEOS) in alcohol-water mixed solvents using ammonia as catalyst. The results show that the monodispers of silicon dioxide will be affected by the alcohols, and with the alcohol carbon chain growth, SiO_2 microspheres increased size, size distribution broadens.The particle size of SiO_2 microspheres had changed, with the different of reaction solution, ethyl silicate concentration, water concentration, ammonia concentration and system temperature.
(2) Core-shell powder SiO_2@Y_2O_3 were synthesised by sol-gel method. XRD and TEM indicated that Y_2O_3 did not reaction with SiO_2 nuclear, The diffraction peak intensity increased with the sintering temperature, but did not produce new diffraction peaks, The core-shell structured phosphor particles were smooth and uniform, maintained the morphology of monodisperse SiO_2. The thickness of the shells could be easily controlled by changing the number of deposition cycles.
(3) Core-shell powder SiO_2@YAG:Ce~(3+) were synthesised by sol-gel method, XRD and TEM indicated that the YAG:Ce~(3+) did not reaction with the SiO_2 nuclear, and YAG:Ce~(3+)has crystaled in the SiO_2 surface at the sintering temperature 800℃, and the core-shell structured phosphor particles were smooth and uniform, maintained the morphology of monodisperse SiO_2 (about 300 nm). The thickness of the shells could be easily controlled by changing the number of deposition cycles.
本文首先以St(o|¨)ber法为基础,制备单分散SiO_2微球,利用透射电子显微镜(TEM)和粒度分析仪对样品的形貌和粒度进行表征,系统地考察了以氨水为催化剂时,不同反应条件对SiO_2粒径和分散性的影响,并对其反应机制进行了探讨;在此基础上,以制备的单分散SiO_2微球为核,采用溶胶-凝胶法合成了核-壳结构粉体,包括SiO_2@Y_2O_3,SiO_2@YAG:Ce~(3+)等,并对核壳结构粉体的形貌、结构、性质进行表征。研究结果如下:
(1)利用St(o|¨)ber法,以醇为溶剂,正硅酸乙酯在氨水催化下水解、缩聚,并进行一系列的后处理得到SiO_2微球。研究结果表明,溶剂(醇)的种类不仅影响SiO_2颗粒的分散性,而且随醇碳链增长,SiO_2微球的粒径增大,粒径分布变宽。随着反应液中正硅酸乙酯浓度、水浓度、氨水浓度及体系温度的变化,生成的SiO_2微球的粒径呈规律性的变化。
(2)利用溶胶-凝胶法,以单分散SiO_2为核合成了SiO_2@Y_2O_3核壳结构粉体。XRD和TEM结果表明,SiO_2表面的Y_2O_3结晶良好,且不与SiO_2核发生反应,随煅烧温度的升高,衍射峰强度增加,但并未产生新的衍射峰,这种核-壳结构的粉体表面致密,厚度均匀,保持了单分散SiO_2微球的形貌特征,壳的厚度可以通过沉积次数进行调控。
(3)利用溶胶-凝胶法,以单分散SiO_2为核合成了SiO_2@YAG:Ce~(3+)核壳结构粉体。XRD和TEM结果表明,当煅烧温度为800℃时,SiO_2微球表面的YAG:Ce~(3+)结晶完好,非晶SiO_2核不与YAG:Ce~(3+)壳层发生反应,核-壳结构SiO_2@YAG:Ce~(3+)粉体具有完美的球形(粒径约为300 nm),表面光滑不团聚,壳的厚度可以通过沉积次数进行调控。
In recent years, there has been intense interest in the fabrication of core/shell materials in the field of material science. Core-shell materials, often made up of a solid core surrounded by a well-defined shell layer, are known to exhibit unique and advanced properties over single-component nanoparticles, making them attractive for use in a wide range of applications, and are therefore of extensive scientific and technological interest. The structure, size, and composition of these particles can be easily altered in a controllable way to tailor their magnetic, optical, mechanical, thermal, electrical, and catalytic properties. The core-shell particles can be used as a precursor form to produce hollow spheres or to lower the cost of precious materials by coating them on inexpensive cores. Nowadays, the most commonly used to be the nuclear is monodisperse SiO_2, such microspheres have the same chemical composition, particle size and surface properties. The improvements focused on the preparation of monodisperse, particle size is small and homogeneous SiO_2 powder, and used monodisperse SiO_2 microspheres form a class of core-shell powder, which has a potential research value and potential applications.
In this article, monodispersed silica particles templates were produced by Stober method. The morphology and size of the particles were characterized by transmission electron microscopy (TEM) and particle size analyzer. We had studied the effections of different agents and reaction conditions of ethanol on the SiO_2 particle size and dispersion in the ammonia catalyst, and discussed its mechanism. Secondly, we had synthesised core-shell powder for monodisperse SiO_2 is the nuclear using the sol-gel method, including SiO_2@Y_2O_3, SiO_2@YAG:Ce~(3+), etc., and the core-shell powders were characterized by transmission electron microscopy (TEM) and X-ray powder diffraction. The results are as follows:
(1) Microspheres SiO_2 were prepared by hydrolysis of tetraethoxy silane (TEOS) in alcohol-water mixed solvents using ammonia as catalyst. The results show that the monodispers of silicon dioxide will be affected by the alcohols, and with the alcohol carbon chain growth, SiO_2 microspheres increased size, size distribution broadens.The particle size of SiO_2 microspheres had changed, with the different of reaction solution, ethyl silicate concentration, water concentration, ammonia concentration and system temperature.
(2) Core-shell powder SiO_2@Y_2O_3 were synthesised by sol-gel method. XRD and TEM indicated that Y_2O_3 did not reaction with SiO_2 nuclear, The diffraction peak intensity increased with the sintering temperature, but did not produce new diffraction peaks, The core-shell structured phosphor particles were smooth and uniform, maintained the morphology of monodisperse SiO_2. The thickness of the shells could be easily controlled by changing the number of deposition cycles.
(3) Core-shell powder SiO_2@YAG:Ce~(3+) were synthesised by sol-gel method, XRD and TEM indicated that the YAG:Ce~(3+) did not reaction with the SiO_2 nuclear, and YAG:Ce~(3+)has crystaled in the SiO_2 surface at the sintering temperature 800℃, and the core-shell structured phosphor particles were smooth and uniform, maintained the morphology of monodisperse SiO_2 (about 300 nm). The thickness of the shells could be easily controlled by changing the number of deposition cycles.
引文
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