激光与光电子学进展, 2023, 60 (21): 2116004, 网络出版: 2023-10-26  

Tm3+掺杂NaYbF4微晶在近红外光聚合中的应用

Application of NaYbF4∶Tm3+ Upconversion Microcrystals in Near-Infrared-Induced Photopolymerization
作者单位
1 江南大学化学与材料工程学院,江苏 无锡 214122
2 陕西师范大学材料科学与工程学院,陕西 西安 710119
摘要
上转换粒子(UCPs)辅助近红外光聚合(UCAP)作为一种新型光聚合方法在聚合化学中显示出潜在的应用价值,UCPs的上转换发光效率是影响其光聚合效率的关键因素。利用乙二胺四乙酸(EDTA)辅助的水热法合成了一系列NaYbF4∶Tm3+微晶体,探究了氟化钠(NaF)和EDTA含量、敏化剂掺杂比例以及水热温度对UCPs的形貌以及上转换发光强度的影响,并进一步研究了UCPs对近红外光聚合行为的影响。研究结果表明:氟源的加入会促进产物的相变并使长径比增大,适量的氟源可以增强上转换发光;此外,降低敏化剂掺杂浓度、提高反应温度以及降低配体的含量都可以在一定程度上增强UCPs的荧光强度。研究发现,增加近红外光光强可以有效提升粒子的荧光强度和紫外发射波段的占比,从而获得更快的聚合速率以及更高的官能团转化效率。最后,将最优条件下合成的UCPs应用于近红外光固化墨水直写3D打印,展现了其在3D打印领域的应用潜力。
Abstract
Upconverting particle (UCP)-assisted near-infrared (NIR) photopolymerization (UCAP) is a novel photopolymerization method, in which the upconversion luminescence efficiency of UCPs is the key factor that affects the photopolymerization efficiency. In this study, a series of NaYbF4∶Tm3+ microcrystals are synthesized by an ethylenediamine tetraacetic acid (EDTA)-assisted hydrothermal method, and the effects of adding sodium fluoride (NaF) and EDTA, the doping ratio of the sensitizer, and the hydrothermal temperature on the morphology and upconversion luminescence intensity of UCPs are investigated. Furthermore, the effects of UCPs on near-infrared photopolymerization are studied. The results indicate that the addition of the fluorine source promotes the phase transition and increases the aspect ratio of the crystals, and that a moderate amount of the fluorine source can enhance the upconversion luminescence of the product. In addition, decreasing the doped amount of the sensitizer, elevating the temperature, and decreasing the amount of ligand could each enhance the fluorescence intensity of UCPs to some extent. Moreover, increasing the intensity of NIR light could enhance the fluorescence intensity and the contribution of the UV emission band of the particles, resulting in a faster polymerization rate as well as a higher functional group conversion rate. Finally, the UCPs synthesized under optimal conditions could be successfully applied in direct 3D printing of NIR light-curable inks, demonstrating their application potential in 3D printing.

徐航, 胡鹏, 桑欣欣, 石峰, 刘仁. Tm3+掺杂NaYbF4微晶在近红外光聚合中的应用[J]. 激光与光电子学进展, 2023, 60(21): 2116004. Hang Xu, Peng Hu, Xinxin Sang, Feng Shi, Ren Liu. Application of NaYbF4∶Tm3+ Upconversion Microcrystals in Near-Infrared-Induced Photopolymerization[J]. Laser & Optoelectronics Progress, 2023, 60(21): 2116004.

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