PrAlO3陶瓷的制备及性能研究

doi:10.15541/jim20230072

无机材料学报 ›› 2023, Vol. 38 ›› Issue (10): 1200-1206.DOI: 10.15541/jim20230072 CSTR: 32189.14.10.15541/jim20230072

所属专题：【结构材料】核用陶瓷（202409）

PrAlO₃陶瓷的制备及性能研究

顾军毅¹^,²(), 范武刚¹, 张兆泉¹(), 姚琴¹(), 展红全²

1.中国科学院上海硅酸盐研究所, 上海 200050
2.景德镇陶瓷大学材料科学与工程学院, 景德镇 333403

收稿日期:2022-02-13 修回日期:2023-03-29 出版日期:2023-10-20 网络出版日期:2023-06-01
通讯作者: 张兆泉, 研究员. E-mail: zhangzq@mail.sic.ac.cn;
姚琴, 高级工程师. E-mail: yaoqin@mail.sic.ac.cn
作者简介:顾军毅(1997-), 男, 硕士研究生. E-mail: 2020028013@stu.jci.edu.cn
基金资助:
国家重大科技专项基金(2017ZX06002004);国家自然科学基金(52062020)

Preparation and Thermal Property of PrAlO₃ Ceramics

GU Junyi¹^,²(), FAN Wugang¹, ZHANG Zhaoquan¹(), YAO Qin¹(), ZHAN Hongquan²

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, China

Received:2022-02-13 Revised:2023-03-29 Published:2023-10-20 Online:2023-06-01
Contact: ZHANG Zhaoquan, professor. E-mail: zhangzq@mail.sic.ac.cn;
YAO Qin, associate professor. E-mail: yaoqin@mail.sic.ac.cn
About author:GU Junyi (1997-), male, Master candidate. E-mail: 2020028013@stu.jci.edu.cn
Supported by:
National Science and Technology Major Project of China(2017ZX06002004);National Natural Science Foundation of China(52062020)

摘要/Abstract

摘要：

钙钛矿结构的铝酸镨(PrAlO₃)具有较高的稳定性并能提供可被其它镧系稀土离子掺杂的格位, 有望成为一种新型中子吸收材料基体, 目前对PrAlO₃的研究主要集中在单晶材料的制备方法及其光学、磁学等特性。本工作采用固相反应合成法, 以正硅酸乙酯(TEOS)作为液相助烧剂, 制备了高致密度钙钛矿相PrAlO₃陶瓷, 并采用XRD、SEM、顶杆法和激光闪光法系统表征了PrAlO₃陶瓷的显微结构及热物理性能。结果表明, 通过在1200 ℃预先合成PrAlO₃粉体并添加质量分数为0.4%~1.0%的TEOS作为液相助烧剂, 在1500 ℃左右烧结可获得相对密度大于99%的PrAlO₃陶瓷; 而未添加助烧剂获得的产物相对密度仅为96%。PrAlO₃陶瓷在亚临界温度360 ℃时的热导率为4.99 W·m^-1·K^-1, 优于Dy₂TiO₅和GdAlO₃陶瓷, 并且室温到800 ℃的线性热膨胀系数仅为10.2× 10^-6 K^-1。同时, PrAlO₃陶瓷的抗弯强度和维氏硬度分别达到95.55 MPa和7.95 GPa, 荧光光谱表现出Pr³⁺的特征发射峰。研究结果显示, 高密度钙钛矿相PrAlO₃陶瓷制备方法简单, 具有较好的热物性和力学性能, 作为一种稀土基中子吸收核用材料具有较好的应用前景。

关键词: PrAlO₃, 钙钛矿相, 热物性能, 核用材料

Abstract:

Perovskite-structured praseodymium aluminum oxide (PrAlO₃) exhibits high stability which has a site that can be doped with other rare earth ions, enabling it a promising new neutron-absorbing material matrix. However, the current research on PrAlO₃mainly focuses on the preparation methods of single crystal materials and their optical and magnetic property. Here, we firstly prepared a high-density perovskite phase PrAlO₃ ceramics by solid-phase reaction synthesis using tetraethyl orthosilicate (TEOS) as a liquid phase sintering aid, and then studied its microstructure and thermal property by XRD, SEM, push-rod technique, and laser flash method. The results showed that, by pre-synthesizing PrAlO₃powder at 1200 ℃ and adding 0.4%-1.0%(in mass) TEOS as a liquid phase sintering aid, PrAlO₃ ceramic with a relative density higher than 99% could be obtained at around 1500 ℃, while the relative density of the product without sintering aids was only 96%. The thermal conductivity of PrAlO₃ ceramic at a subcritical temperature of 360 ℃ was 4.99 W·m^-1·K^-1, superior to those of Dy₂TiO₅ and GdAlO₃ ceramics, and its linear thermal expansion coefficient from room temperature to 800 ℃ was only 10.2×10^-6K^-1. Moreover, the bending strength and Vickers hardness of PrAlO₃ ceramics reached 95.55 MPa and 7.95 GPa, respectively, and the fluorescence spectrum exhibited characteristic emission peaks of Pr³⁺. This study shows that high-density perovskite phase PrAlO₃ ceramics can be prepared by a convenient method with good thermophysical property and mechanical property. They exhibit good application prospects as a rare earth-based neutron-absorbing nuclear material.

Key words: PrAlO₃, perovskite phase, thermophysical property, nuclear materials

中图分类号:

TQ174

顾军毅, 范武刚, 张兆泉, 姚琴, 展红全. PrAlO₃陶瓷的制备及性能研究[J]. 无机材料学报, 2023, 38(10): 1200-1206.

GU Junyi, FAN Wugang, ZHANG Zhaoquan, YAO Qin, ZHAN Hongquan. Preparation and Thermal Property of PrAlO₃ Ceramics[J]. Journal of Inorganic Materials, 2023, 38(10): 1200-1206.

图/表 10

图1 T0粉体以及在氩氢混合气中不同温度煅烧后粉体的XRD谱图

Fig. 1 XRD patterns of T0 powder and powders calcined at different temperatures in Ar/H2 atmosphere

图2 不同TEOS浓度的PrAlO3陶瓷XRD谱图

Fig. 2 XRD patterns of PrAlO3 ceramics with different TEOS concentrations

图3 不同浓度TEOS样品的相对密度随烧结温度变化曲线

Fig. 3 Change of relative density with sintering temperature of samples with different concentrations of TEOS

图4 1200 ℃, Ar/H2气氛下烧结的 PrAlO3的 SEM-EDS照片和各元素分布图

Fig. 4 SEM-EDS image and elemental distributions of of PrAlO3 sintered at 1200 ℃ in Ar/H2 atmosphere

图5 不同温度烧结的T4样品的(a~d)表面和(a′~d′)断面的SEM照片

Fig. 5 SEM images of (a-d) areal surface and (a′-d′) fractural surface of T4 samples sintered at different temperatures (a, a′) 1430 ℃; (b, b′) 1460 ℃; (c, c′) 1500 ℃; (d, d′) 1600 ℃

图6 样品T4的平均晶粒尺寸与烧结温度的关系

Fig. 6 Relationship between average grain size and sintering temperature for T4 samples

表1 PrAlO3陶瓷烧结的力学性能

Table 1 Mechanical property of PrAlO3 prepared at different sintering temperatures

Sintering temperature/℃	Bending strength/MPa	Fracture toughness/(MPa·m^1/2)	Vickers hardness/GPa	Average grain size/μm
1500	88.47±4.14	0.81±0.02	7.95±0.43	5.51±1.84
1600	95.55±4.62	0.92±0.06	7.75±0.28	15.40±5.02

图7 不同温度烧结样品T4的热物理性能

Fig. 7 Thermophysical property of sample T4 sintered at different temperatures (a) Thermal expansion coefficient; (b) Thermal diffusivity; (c) Specific heat capacity; (d) Thermal conductivity

表2 不同控制棒360 ℃下热膨胀系数和热导率参数

Table 2 Thermal expansion coefficient and thermal conductivity parameters of different control rods at 360 ℃

Material	Density/ (g·cm^-3)	Thermal expansion coefficient/ (×10^-6, K^-1)	Thermal conductivity/ (W·m^-1·K^-1)
PrAlO₃	6.69	9.3	5.0
GdAlO₃^[31]	6.64	4.8±0.2	3.5±0.1
Tb₂TiO₅^[32]	6.89	6.8±0.2	1.3±0.1
B₄C^[33]	2.25	3.7±0.1	9.8±0.1
Ag-In-Cd^[34,35]	10.18	22.5 (25~500 ℃)	92.0±1.0

图8 1500 ℃烧结T4的荧光发射光谱

Fig. 8 Fluorescence emission spectrum of T4 sintered at 1500 ℃ Inset: photograph of PrAlO3 ceramic sample

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PrAlO₃陶瓷的制备及性能研究

Preparation and Thermal Property of PrAlO₃ Ceramics

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