氟化钙污泥制备高性能上转换发光微晶玻璃的研究

Preparation of high performance upconversion luminescent glass-ceramics by using calcium fluoride sludge

半导体行业产生的氟化钙(CaF_(2))污泥量大且含有絮凝剂等杂质,资源化利用难度大,现阶段主要处理方式为填埋。本文提出了将CaF_(2)污泥回收制备上转换发光微晶玻璃的资源化技术。将SiO_(2)、稀土Er_(2)O_(3)和Yb_(2)O_(3)引入到CaF_(2)污泥中,通过高温固相熔融法制备了一系列上转换发光微晶玻璃。采用X射线衍射、扫描电镜、荧光光谱等表征手段研究了不同含量CaF_(2)污泥和不同晶化温度对所得上转换发光微晶玻璃的结构、形貌、上转换发光峰位置、强度和荧光寿命等的作用规律。所得CaF_(2)基上转换发光微晶玻璃在980 nm激光激发下,能够发射出绿光(523和539 nm)和红光(655 nm)。原料质量配比为84.5%CaF_(2)污泥-10%SiO_(2)-0.5%Er_(2)O_(3)-5%Yb_(2)O_(3)且未晶化的微晶玻璃具有最大的绿光发射强度;经600℃晶化后,红光发射变强,说明晶化处理可调控CaF_(2)基上转换发光微晶玻璃的发射光谱。本文利用CaF_(2)污泥成功制备出高性能上转换发光微晶玻璃,为CaF_(2)污泥的高价值资源化利用提供了参考。

Calcium fluoride(CaF_(2))sludge in semiconductor industry is generated in large amounts and often contains impurities such as flocculants,which makes it difficult to reuse.Landfill is the main treatment method for CaF_(2)sludge at this stage.In this study,the recycling technology of CaF_(2)sludge to prepare upconversion luminescent glass ceramics was proposed.The preparation process was to introduce SiO_(2),rare earth oxides of Er_(2)O_(3)and Yb_(2)O_(3)into CaF_(2)sludge,and a series of upconversion luminescent glass ceramics were obtained by a high-temperature solid state melting method.The effects of different CaF_(2)sludge contents and crystallization temperatures on the structure,morphology,upconversion luminescence peak position,intensity,and fluorescence lifetime of the upconversion luminescence glass ceramics were studied by using X-ray diffractometer,scanning electron microscope,and fluorescence spectra.The obtained CaF_(2)-based upconversion luminescent glass ceramics emitted green(523 and 539 nm)and red light(655 nm)under 980 nm laser excitation.The uncrystallized glass ceramic with the raw material mass ratio of 84.5%CaF_(2)sludge-10%SiO_(2)-0.5%Er_(2)O_(3)-5%Yb_(2)O_(3)had the maximum green light emission intensity.After crystallization at 600℃,the red light emission became stronger,indicating that the emission spectra of the CaF_(2)-based upconversion luminescent glass ceramics can be adjusted by crystallization treatment.In this paper,the CaF_(2)sludge was successfully used to prepare the high-performance upconversion luminescent glass ceramics,which provides a reference for the high value resource utilization of CaF_(2)sludge.