高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (4): 607.doi: 10.7503/cjcu20160013

• 研究论文: 无机化学 • 上一篇    下一篇

CaF2微晶玻璃的一步法制备及Eu3+离子探针特性

王彩萍, 李友芬(), 张一东   

  1. 北京化工大学材料电化学过程与技术实验室, 北京 100029
  • 收稿日期:2016-01-08 出版日期:2016-04-10 发布日期:2016-03-22
  • 作者简介:联系人简介: 李友芬, 女, 博士, 副教授, 主要从事无机非金属方面的研究. E-mail: yfli@ mail. buct. edu. cn
  • 基金资助:
    国家自然科学基金(批准号: 51372012)资助

Preparation of Glass Ceramics Containing CaF2 by One-step Method and Analysis of the Fluorescent Probe of Eu3+ Ion

WANG Caiping, LI Youfen*(), ZHANG Yidong   

  1. Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2016-01-08 Online:2016-04-10 Published:2016-03-22
  • Contact: LI Youfen E-mail:yfli@ mail. buct. edu. cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No. 51372012)

摘要:

以组成为n(SiO2)∶n(Al2O3)∶n(CaO)∶n(CaF2)∶n(NaF)∶n(B2O3)=40∶20∶10∶10∶15∶5的微晶发光玻璃为基质, 采用一步析晶法制备了CaF2析晶相. 利用X射线衍射仪(XRD)、 扫描电子显微镜(SEM)、 X射线能量散射谱仪(EDS)和荧光分光光度计等对样品结构、 组成及光谱性能进行分析, 探讨了Eu3+掺杂浓度和析晶温度对微晶玻璃发光性能的影响. 实验结果表明, 在850 ℃下处理可获得分布均匀、 粒径尺寸为200 nm的CaF2析晶相, 微晶玻璃的发光强度是基质玻璃的1.7倍. 微晶玻璃的发射光谱在590, 614, 652和700 nm出现发射峰, 分别对应Eu3+5D0-7FJ(J=1,2,3,4)跃迁. 通过对 5D0-7F15D0-7F2跃迁强度的分析以及Judd-Ofelt理论参数Ω2值的计算可知Eu3+周围晶体场在析晶前后对称性发生变化. 机理分析表明, 析晶处理后Eu3+从高声子能量的Si-O环境进入低声子能量的Ca-F环境中, 说明Eu3+可作为荧光探针研究微晶玻璃晶体结构的变化.

关键词: 微晶玻璃, 荧光探针, 发射光谱, 局域环境

Abstract:

Transparent glass-ceramics with composition n(SiO2)∶n(Al2O3)∶n(CaO)∶n(CaF2)∶n(NaF)∶n(B2O3)=40∶20∶10∶10∶15∶5 were fabricated via traditional melting technique with one-step method. X-ray diffraction(XRD) results of as-prepared glass-ceramics confirmed the existence of CaF2 phase. Scanning electron microscopy(SEM) observation showed that the CaF2 crystalline phase had a size of 200 nm and dispersed in the amorphous phase. The fluorescence intensity of glass ceramics was 1.7 times that of the glass. The emission spectrum showed several luminescence peaks at 590 nm(5D07F1), 614 nm(5D07F2), 652 nm(5D07F3) and 700 nm(5D07F4), which are attributed to the Eu3+ ion transition. The intensity ratio of 5D0 -7F2 transition to the 5D0 -7F1 transition and Ω2 of Judd-Ofelt parameters were used to measure the rare earth ion site symmetry. The data revealed that Eu3+ ions are embedded into Ca-F environment from Si-O environment during the crystallization process. Therefore Eu3+ can be applied to investigate the microstructures of glass-ceramic crystal as a fluorescence probe.

Key words: Glass ceramic, Fluorescence probe, Emission spectrum, Local environment

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