玻璃温室用稀土、过渡金属离子掺杂氟氧化物微晶玻璃的研究

发布时间：2019-01-18 14:05

【摘要】：在当今世界,日益增长的能源需求已逐渐“全球化”。人们都在寻找能够替代化石燃料的新型能源。太阳能作为新兴的可再生能源,取之不尽用之不竭,既不耗材又具有环境友好性。我们是农业大国,提高农作物的单位产量是当务之急。近几年国家大力倡导的光伏农业,就是将太阳能的相关技术广泛应用于现代农业种植之中。当前,温室用的采光材料不具备收集特定波长光的能力。对于绿色植物,叶绿素主要吸收的光谱区有两个,一个是波长640~680 nm的红光部分,另一个是波长430~500 nm的蓝光部分。至于紫外线植物吸收的比较少,过强反而会损伤植物细胞。我们希望通过光谱转光,将更多地太阳光转至光合作用最需要的红光部分,使光合作用效率更高,提高农作物的产量。目前农用转光材料主要以转光膜为主,但薄膜材料自身的透光性差以及污染严重等问题阻碍了转光膜的进一步应用。相比之下玻璃材料具有优良的热稳定性及化学性能,而且能够更好的适应变化的外界环境,使用寿命也更长。微晶玻璃是在制备成功基质玻璃的基础上进行一步二次热处理过程,析出特定的纳米颗粒。氟氧化物微晶玻璃兼具有氧化物微晶玻璃和氟化物微晶玻璃的优点,析出的氟化物晶粒尺寸小,使微晶玻璃既保持了高度的透明,又具备了特殊的光学性能。本论文主要研究了玻璃温室用稀土离子以及过渡金属元素掺杂的氟氧化物玻璃及微晶玻璃材料的制备和发光性能,探讨了一些离子匹配的可行性分析,并对其中的光谱转换机理做了分析:1.氟氧化物玻璃陶瓷的制备。微晶玻璃的制备是建立在基础玻璃制备的基础之上,进行一定条件的二次热处理完成的。通过参考对比,我们选择了硅酸盐的氟氧化物玻璃作为发光的基质材料,并成功制备出了在机械性能、微观结构和光学性能方面都符合要求的微晶玻璃。2.Ce3+,Er3+,Yb3+三掺氟氧玻璃陶瓷的制备。在基质为50Si O2-20Al2O3-20Ca F2-10Na F的氟氧玻璃陶瓷中掺杂Ce3+,Er3+,Yb3+离子,通过Ce3+,Er3+之间的下转换和Er3+,Yb3+之间的上转换,将吸收的紫外光和吸收的近红外光都转到Er3+的主发射668nm的红橙光。Ce3+自身的发光属于宽带发光,在400-500 nm范围内的蓝光也可被叶绿素吸收用于光合作用。3.Ce3+,Mn2+,Yb3+三掺氟氧化物玻璃陶瓷的制备。在基质为50Si O2-20Al2O3-20Ca F2-10Na F的氟氧化物硅酸盐玻璃中,我们掺入Ce3+,Mn2+,Yb3+离子。Mn2+的发光属于宽带发光。Ce3+,Mn2+之间的能量传递也要比Ce3+,Er3+之间的能量传递更显著。因此这种材料更具有应用前景。总之,通过稀土离子和过渡金属离子掺杂,实现上下转换发光。将光合作用不能利用的紫外和近红外光转到可见范围内,将有助于光合作用效率的提高。我们制备的无机掺杂材料将有助于提高光合作用利用光能的效率,具有广泛的应用前景。
[Abstract]:In today's world, growing energy demand has been gradually "globalized". People are looking for new sources of energy that can replace fossil fuels. As a new renewable energy source, solar energy is inexhaustible and environmentally friendly. We are a big agricultural country and it is urgent to increase the unit output of crops. In recent years, photovoltaic agriculture, which has been strongly advocated by our country, is widely used in modern agriculture. Currently, greenhouse lighting materials do not have the ability to collect specific wavelengths of light. For green plants, there are two main spectral regions of chlorophyll absorption, one is the red part of 640 ~ 680 nm, the other is the blue part of 430 nm. As for UV plants absorb less, too strong will damage the plant cells. We hope to transfer more sunlight to the red part of photosynthesis through spectral conversion, so as to increase the efficiency of photosynthesis and increase the yield of crops. At present, the conversion film is mainly used in agriculture, but its poor transmittance and serious pollution hinder the further application of the film. By contrast, glass materials have excellent thermal stability and chemical properties, and can adapt to the changing environment better, the service life is longer. Glass-ceramics are prepared on the basis of the successful matrix glass through one-step and two-step heat treatment process, precipitating specific nanoparticles. Fluoride oxide glass-ceramics have the advantages of both oxide glass-ceramics and fluoride glass-ceramics, and the size of fluoride precipitates is small, which makes the glass-ceramics have high transparency and special optical properties. In this paper, the preparation and luminescence properties of rare earth ions and transition metal elements doped fluoride oxide glass and glass-ceramics in glass greenhouses are studied, and the feasibility analysis of some ion matching is discussed. The spectral conversion mechanism is analyzed as follows: 1. Preparation of fluoride oxide Glass Ceramics. The preparation of glass-ceramics is based on the preparation of the basic glass and the secondary heat treatment is carried out under certain conditions. By reference and comparison, we selected silicate fluoride oxide glass as the luminescent matrix material, and successfully prepared glass-ceramics which meet the requirements in mechanical properties, microstructure and optical properties. 2.Ce3, Er3, Preparation of Yb3 _ 3 Fluorine-doped Glass Ceramics. Ce3, Er3, Yb3 ions are doped in fluorinated glass ceramics with 50Si O2-20Al2O3-20Ca F2-10Na F matrix, and the downconversion between Ce3 and Er3 and the upconversion between Er3 and Yb3 are carried out. The absorption of ultraviolet light and the absorption of near-infrared light are transferred to the main emitting red orange light of 668nm in Er3. The luminescence of Ce3 itself belongs to broadband luminescence, and the blue light in the range of 400-500 nm can also be absorbed by chlorophyll for photosynthesis. 3.Ce3, Mn2, Preparation of Yb3 trifluoride doped Glass Ceramics. In the fluoride oxide silicate glass with 50Si O2-20Al2O3-20Ca F2-10Na F matrix, we doped Ce3, Mn2, Yb3 ions. The luminescence of Mn2 belongs to broadband luminescence. The energy transfer between Ce3 and Mn2 is more significant than that between Ce3 and Er3. Therefore, this material has more application prospect. In a word, the upper and lower conversion luminescence is realized by doping rare earth ions and transition metal ions. The efficiency of photosynthesis will be improved by transferring ultraviolet and near-infrared light which cannot be used in photosynthesis to visible range. The inorganic doped materials we prepared will help to improve the efficiency of photosynthesis in the utilization of light energy and have a wide application prospect.
【学位授予单位】：河南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ171.733

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