硅酸盐学报

热水浴还原法制备Gd₂O₂S：Pr闪烁陶瓷及性能优化

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杜永笑 ¹^,² , 罗朝华 ² , 孙靖涵 ¹^,² , 庄翊君 ² , 刘永福 ² , 孙鹏 ² , 蒋俊 ²

硅酸盐学报 | 研究论文 2024,52(3): 812-819

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硅酸盐学报 |研究论文 2024 , 52 (3) : 812 -819

热水浴还原法制备Gd₂O₂S：Pr闪烁陶瓷及性能优化

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杜永笑¹^,², 罗朝华², 孙靖涵¹^,², 庄翊君², 刘永福², 孙鹏², 蒋俊²

作者信息

^1．宁波大学材料科学与化学工程学院，浙江宁波 315211

^2．中国科学院宁波材料技术与工程研究所，浙江宁波 315201

通讯作者:

罗朝华（1984—），男，博士，研究员。

作者简介:

杜永笑（1995—），女，硕士研究生。

Preparation and Performance of Gd₂O₂S:Pr Scintillation Ceramics by Hot Water-Bath Reduction

Yongxiao DU¹^,², Zhaohua LUO², Jiinghan SUN¹^,², Yijun ZHUANG², Yongfu LIU², Peng SUN², Jun JIANG²

Affiliations

^1.School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang, China

^2.Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China

Corresponding Author:

LUO Zhaohua (1984-), male, Ph.D., Professor. E-mail: luozhaohua@nimte.ac.cn

DU Yongxiao (1995-), female, Master candidate. E-mail: duyongxiao@nimte.ac.cn

出版时间: 2024-03-20 doi: 10.14062/j.issn.0454-5648.20230520

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摘要

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硫氧化钆（Gd₂O₂S, GOS）闪烁陶瓷是一种具有高光输出、低余辉与高X射线阻止能力的闪烁材料，被广泛用于核医学影像和安全检查等领域。然而，GOS粉体合成过程复杂，组分精确配比与第二相难以控制，导致高品质GOS闪烁陶瓷制备依然存在较大挑战。针对这些问题和挑战：此项研究采用热水浴还原法制备了不同摩尔配比的（Gd_1-_xPr_x）₂O₂S闪烁陶瓷材料，探究了不同形貌、粒度的氧化钆（Gd₂O₃）原料对Gd₂O₂S粉体的显微结构和光学性能影响。结果表明：亚微米级Gd₂O₃相较于纳米Gd₂O₃所合成的Gd₂O₂S：Pr粉体及闪烁陶瓷都具有更高的荧光强度，通过弱还原气氛下预烧结与热等静压后处理之后的Gd₂O₂S闪烁陶瓷具有较高的下相对密度和光学性能。在Pr³⁺掺杂量（摩尔分数）x=0.2%时，闪烁陶瓷荧光强度达到最大值，并且在513 nm波长处透过率达到31%。本研究成功开发了一种简单而成本低廉的陶瓷制备工艺，该工艺无副产物污染，有望基于此工艺，大规模生产高性能Gd₂O₂S闪烁陶瓷。

关键词

闪烁陶瓷 / 硫氧化钆 / 氧化钆 / 显微结构 / 光学性能

Abstract

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Introduction

Gadolinium oxysulfide (Gd₂O₂S, GOS) scintillation ceramics as luminescent materials are widely used in nuclear medical imaging and security inspections due to their high light output, low afterglow, and strong X-ray stopping capability. However, the synthesis process of GOS powder is intricately complex, having some challenges for achieving accurate component ratios and controlling the second-phase impurities, thus leading to difficulties in producing high-quality GOS scintillation ceramics. In this paper, GOS precursor powders were firstly synthesized by a hot water bath reduction method with sub-micron and nano-scale gadolinium oxide (Gd₂O₃) as raw materials, and Gd₂O₂S:Pr scintillation ceramics were subsequently prepared by a two-step sintering method (i.e., atmospheric pressure pre-sintering and HIP post-treatment). In addition, the microstructure and optical properties of the powder and ceramics were also characterized.

Methods

Gd₂O₂S:Pr phosphors were synthesized by a hot water bath reduction method. Gd₂O₃ (99.999%, Ganzhou Berier New Materials Co., Ltd., China), Pr₆O₁₁ (99.995%, Ganzhou Berier New Materials Co., Ltd., China), and concentrated H₂SO₄ (AR, Shanghai Macklin Biochemical Co., Ltd., China) were used as high-quality raw materials. Gd₂O₃ and Pr₆O₁₁ were firstly weighed according to (Gd_1-_xPr_x)₂O₂S (x=0.001-0.010), and then mixed with a diluted sulfuric acid solution at a molar ratio of Gd₂O₃:H₂SO₄ of 1∶1. The suspension was stirred and uniformed by a magnetic stirrer. Also, the suspension was heated in a hot water bath at 90 ℃ for 150 min. After the reaction was completed, the suspension was cooled to room temperature, and then the suspension was filtered, washed/dried, ground and sieved. Finally, the ground powders were calcined in a tube furnace, The resulting mixture was subsequently calcined in a tube furnace under a 20% hydrogen-nitrogen mixture reduction atmosphere at 750 ℃ for 6 h to yield the gadolinium oxide sulfide powders.

The Gd₂O₂S:Pr powders obtained were formed in a 15 mm cylindrical mold under uniaxial dry pressing at 10 MPa and then treated by cold isostatic pressing (CIP) at 200 MPa. Subsequently, the green bodies were pre-sintered in a flowing hydrogen-nitrogen atmosphere at 1 350 ℃ for 2 h, and HIP post-treatment was performed in argon at 1 600 ℃ and 180 MPa for 2 h. The sintered ceramics were polished and annealed for coming characterizations.

Results and discussion

The microstructure of Gd₂O₂S:Pr powders prepared with submicron-sized particles of Gd₂O₃ and nano-sized particles of Gd₂O₃ was examined, respectively. The results reveal differences in particle size and morphology between the two powders. Gd₂O₂S:Pr powder derived from submicron-sized Gd₂O₃ powder has irregular columnar particles and sheet-like structures, whereas that prepared with nano-sized Gd₂O₃ powder is coralloid particles. The fluorescence emission spectrum of the ceramics is consistent with that of the powders although the excitation peak partially obscures by the absorption peak. High-temperature sintering gradually eliminates the differences in particle size and leads to the formation of dense sintered bodies in the ceramics. Consequently, the discrepancy in fluorescence intensity caused by differences in particle size is reduced. Specifically, ceramics prepared with Gd₂O₃ nano-powder display a low fluorescence intensity, while those produced with Gd₂O₃ submicron-sized powder exhibites a high fluorescence intensity. To further investigate the factors influencing the optical properties of the ceramics, the doping concentration of Pr³⁺ was explored. Fluorescence and XEL spectroscopy tests were conducted on Gd₂O₂S:xPr (x=0.1%, 0.2%, 0.4%, 0.6%, 0.8%, and 1.0%) ceramics prepared using Gd₂O₃ submicron-sized powder with different Pr³⁺ doping concentrations. The experimental results reveal that the fluorescence and XEL spectral intensities reach their maximum values when the Pr³⁺ doping concentration is 0.2%. The SEM images demonstrate that the ceramics prepared using submicron-sized Gd₂O₃ powder have a dense structure with well-defined grain boundaries and uniform grain sizes. The EDS element distribution results confirm the effective doping of Pr element into the host lattice. Gd₂O₂S:Pr ceramic prepared exhibits a high transmittance.

Conclusions

The utilization of Gd₂O₃ submicron-sized powder resulted in Gd₂O₂S:Pr powder and the scintillation ceramics displayed a higher fluorescence intensity, compared to that synthesized with Gd₂O₃ nano-sized powder. Furthermore, Gd₂O₂S scintillation ceramics pre-sintered in a weak reducing atmosphere and subsequently sintered in a hot isostatic pressing exhibited improved density and optical properties. The maximum fluorescence intensity of the scintillation ceramics was achieved at a Pr³⁺ doping concentration x of 0.2%. In addition, the scintillation ceramics achieved a transmittance of 31% at a wavelength of 513 nm. This study developed a simple and cost-effective ceramic preparation process without any byproduct pollution, thereby offering a promising potential for large-scale production of high-performance Gd₂O₂S scintillation ceramics.

Key words

scintillation ceramics / gadolinium oxysulfide / gadolinium oxide / microstructure / optical performance

引用本文

杜永笑, 罗朝华, 孙靖涵, 庄翊君, 刘永福, 孙鹏, 蒋俊. 热水浴还原法制备Gd₂O₂S：Pr闪烁陶瓷及性能优化. 硅酸盐学报, 2024 , 52 (3) : 812 -819 . DOI: 10.14062/j.issn.0454-5648.20230520

Yongxiao DU, Zhaohua LUO, Jiinghan SUN, Yijun ZHUANG, Yongfu LIU, Peng SUN, Jun JIANG. Preparation and Performance of Gd₂O₂S:Pr Scintillation Ceramics by Hot Water-Bath Reduction[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (3) : 812 -819 . DOI: 10.14062/j.issn.0454-5648.20230520

基金

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浙江省“尖兵”“领雁”研发攻关计划(2022C01046)
浙江省自然科学基金(LZ23A040001)

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2024年第52卷第3期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230520

接收时间：2023-07-23
首发时间：2026-10-22
出版时间：2024-03-20

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收稿日期：2023-07-23
修回日期：2023-09-14

基金

浙江省“尖兵”“领雁”研发攻关计划(2022C01046)

浙江省自然科学基金(LZ23A040001)

作者信息

^1．宁波大学材料科学与化学工程学院，浙江宁波 315211

^2．中国科学院宁波材料技术与工程研究所，浙江宁波 315201

通讯作者:

罗朝华（1984—），男，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230520

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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