Gd2O2S:Tb闪烁陶瓷的制备与结构: 水浴合成中H2SO4/Gd2O3摩尔比的影响

doi:10.15541/jim20220542

无机材料学报 ›› 2023, Vol. 38 ›› Issue (4): 452-460.DOI: 10.15541/jim20220542

Gd₂O₂S:Tb闪烁陶瓷的制备与结构: 水浴合成中H₂SO₄/Gd₂O₃摩尔比的影响

吴俊林¹^,²(), 丁继扬¹^,³, 黄新友³, 朱丹阳¹^,², 黄东¹^,³, 代正发¹, 杨文钦⁴^,⁵, 蒋兴奋⁴^,⁵, 周健荣⁴^,⁵, 孙志嘉⁴^,⁵, 李江¹^,²()

1.中国科学院上海硅酸盐研究所, 透明光功能无机材料重点实验室, 上海 201899
2.中国科学院大学材料科学与光电工程中心, 北京 100049
3.江苏大学材料科学与工程学院, 镇江 212013
4.散裂中子源科学中心, 东莞 523803
5.中国科学院高能物理研究所, 核探测与核电子学国家重点实验室, 北京 100049

收稿日期:2022-09-16 修回日期:2022-10-13 出版日期:2023-04-20 网络出版日期:2022-12-30
通讯作者: 李江, 研究员. E-mail: lijiang@mail.sic.ac.cn
作者简介:吴俊林(1998-), 男, 硕士研究生. E-mail: wujunlin20@mails.ucas.ac.cn

Fabrication and Microstructure of Gd₂O₂S:Tb Scintillation Ceramics from Water-bath Synthesized Nano-powders: Influence of H₂SO₄/Gd₂O₃ Molar Ratio

WU Junlin¹^,²(), DING Jiyang¹^,³, HUANG Xinyou³, ZHU Danyang¹^,², HUANG Dong¹^,³, DAI Zhengfa¹, YANG Wenqin⁴^,⁵, JIANG Xingfen⁴^,⁵, ZHOU Jianrong⁴^,⁵, SUN Zhijia⁴^,⁵, LI Jiang¹^,²()

1. Key Laboratory of Transparent Opto-functional Inorganic Materials, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3. School of Material Science and Engineering, Jiangsu University, Zhenjiang 212013, China
4. Spallation Neutron Source Science Center, Dongguan 523803, China
5. State Key Laboratory of Particle Detection and Electronics, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

Received:2022-09-16 Revised:2022-10-13 Published:2023-04-20 Online:2022-12-30
Contact: LI Jiang, professor. E-mail: lijiang@mail.sic.ac.cn
About author:WU Junlin (1998-), male, Master candidate. E-mail: wujunlin20@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(12175254);National Natural Science Foundation of China(U1832119);National Key R&D Program of China(2021YFE0104800);International Partnership Program of Chinese Academy of Sciences(121631KYSB20200039);International Cooperation Project of Shanghai Science and Technology Commission(20520750200);National Centre for Research and Development(WPC2/1/SCAPOL/2021)

摘要/Abstract

摘要：

Gd₂O₂S:Tb闪烁陶瓷以其明亮的绿色发光、高能量转换效率和高中子俘获截面而广泛应用于中子成像和工业无损检测等领域, 但Gd₂O₂S:Tb陶瓷中存在的Gd₂O₃第二相影响其闪烁性能。本工作以H₂SO₄和Gd₂O₃为原料, 采用水浴法合成Gd₂O₂S:Tb前驱体, 研究了H₂SO₄与Gd₂O₃的摩尔比(n)对前驱体和Gd₂O₂S:Tb粉体性能的影响。前驱体的化学组成随n增大而变化：2Gd₂O₃·Gd₂(SO₄)₃·xH₂O(n<2.00)、Gd₂O₃·2Gd₂(SO₄)₃·xH₂O (2.25≤n≤2.75)和Gd₂(SO₄)₃·8H₂O(n=3.00), 经过空气煅烧和氢气还原后, 所有的粉体均形成Gd₂O₂S相。Gd₂O₂S:Tb粉体的形貌与前驱体的相组成密切相关, 随着n增大, Gd₂O₂S:Tb粉体的XEL强度增加呈现出两个阶段, 对应前驱体的相转变阶段。采用真空预烧结合热等静压烧结制备了Gd₂O₂S:Tb陶瓷, 相较于n为2.00、2.25、2.50, 其他n制备的Gd₂O₂S:Tb陶瓷都达到了较高的相对密度和XEL强度, 不同n制备的陶瓷中都存在Gd₂O₃第二相, n增大有利于减少陶瓷内部的第二相, 为进一步消除Gd₂O₂S:Tb陶瓷中的第二相提供了思路。

关键词: 水浴法, H₂SO₄与Gd₂O₃摩尔比, Gd₂O₂S:Tb纳米粉体, 闪烁陶瓷

Abstract:

The Gd₂O₂S:Tb scintillation ceramics is extensively used for neutron radiography and industrial non-destructive testing due to its bright green emission, high intrinsic conversion efficiency and high thermal neutron capture cross-section. However, the existence of Gd₂O₃ secondary phase in Gd₂O₂S ceramics impedes the scintillation property. In this work, The Gd₂O₂S:Tb precursors were synthesized in water-bath with H₂SO₄ and Gd₂O₃ as starting materials. Molar ratio of H₂SO₄ to Gd₂O₃ defined as n was adjusted to synthesize the precursors., which influence on the properties of the precursors and powders was studied. Chemical composition of the precursors changes with the increase of n, from 2Gd₂O₃·Gd₂(SO₄)₃·xH₂O (n<2.00) to Gd₂O₃·2Gd₂(SO₄)₃·xH₂O (2.25≤n≤2.75), and to Gd₂(SO₄)₃·8H₂O (n=3.00). After being calcined and reduced, all the powders form pure Gd₂O₂S phase. Morphology of the Gd₂O₂S:Tb powders is closely related to the phase composition of the precursor. Increasement of the XEL intensity shows two stages with n increase, corresponding to the phase transition of the precursor, respectively. The Gd₂O₂S:Tb scintillation ceramics were therefore fabricated by vacuum pre-sintering and HIP post-treatment. The ceramics were fabricated from the powders prepared with different n, achieving high relative density and XEL intensity, except the ceramics fabricated from the powders prepared with the n=2.00, 2.25, 2.50. The increase of n is beneficial to the removal of the Gd₂O₃ secondary phase from the Gd₂O₂S:Tb ceramics. This work provides a way for eliminating the secondary phase in Gd₂O₂S:Tb scintillation ceramics.

Key words: water-bath method, molar ratio of H₂SO₄ to Gd₂O₃, Gd₂O₂S:Tb nanopowder, scintillation ceramics

中图分类号:

TQ174

吴俊林, 丁继扬, 黄新友, 朱丹阳, 黄东, 代正发, 杨文钦, 蒋兴奋, 周健荣, 孙志嘉, 李江. Gd₂O₂S:Tb闪烁陶瓷的制备与结构: 水浴合成中H₂SO₄/Gd₂O₃摩尔比的影响[J]. 无机材料学报, 2023, 38(4): 452-460.

WU Junlin, DING Jiyang, HUANG Xinyou, ZHU Danyang, HUANG Dong, DAI Zhengfa, YANG Wenqin, JIANG Xingfen, ZHOU Jianrong, SUN Zhijia, LI Jiang. Fabrication and Microstructure of Gd₂O₂S:Tb Scintillation Ceramics from Water-bath Synthesized Nano-powders: Influence of H₂SO₄/Gd₂O₃ Molar Ratio[J]. Journal of Inorganic Materials, 2023, 38(4): 452-460.

图/表 9

Fig. 1 XRD patterns of the products prepared with different n of H2SO4 and Gd2O3 in hot water bath at 90 ℃ for 2 h

Fig. 2 XRD patterns of the products calcined in air at 600 ℃ for 3 h from the precursors prepared with different n

Fig. 3 XRD patterns of the products calcined in air and reduced in H2 at 750 ℃ for 2 h from the precursors prepared with different n

Fig. 4 FESEM morphologies of Gd2O2S: Tb powders with different n (a) n=1.00; (b) n=1.25; (c) n=1.50; (d) n=1.75; (e) n=2.00; (f) n=2.25; (g) n=2.50; (h) n=2.75; (i) n=3.00

Fig. 5 XEL spectra and normalized integral intensity curves in the range of 350-700 nm of Gd2O2S:Tb powders with different n (a) XEL spectra; (b) Normalized integral intensity curves; Colorful figures are available on website

Fig. 6 Relative densities of Gd2O2S:Tb ceramics vacuum pre-sintered at 1300 ℃ for 3 h and HIP post-treatment at 1450 ℃ for 3 h fabricated from the powders with different n

Fig. 7 FESEM micrograph and EDS patterns (white area) of the Gd2O2S:Tb ceramics vacuum pre-sintered at 1300 ℃ for 3 h and HIP post-treatment at 1450 ℃ for 3 h fabricated from the powders prepared with n=1.00

Fig. 8 FESEM morphologies of Gd2O2S:Tb ceramics fabricated from the powders prepared with different n (a) n=1.00; (b) n=1.25; (c) n=1.50; (d) n=1.75; (e) n=2.00; (f) n=2.25; (g) n=2.50; (h) n=2.75; (i) n=3.00

Fig. 9 XEL spectra and normalized integral intensity curves in the range of 350-700 nm of Gd2O2S:Tb ceramics fabricated from the powders with different n (a) XEL spectra; (b) Normalized integral intensity curves; Colorful figures are available on website

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Gd₂O₂S:Tb闪烁陶瓷的制备与结构: 水浴合成中H₂SO₄/Gd₂O₃摩尔比的影响

Fabrication and Microstructure of Gd₂O₂S:Tb Scintillation Ceramics from Water-bath Synthesized Nano-powders: Influence of H₂SO₄/Gd₂O₃ Molar Ratio

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