8YSZ陶瓷在模拟压水堆水环境中的耐腐蚀性能

doi:10.15541/jim20230513

无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 803-809.DOI: 10.15541/jim20230513

8YSZ陶瓷在模拟压水堆水环境中的耐腐蚀性能

范武刚¹(), 曹雄², 周响², 李玲², 赵冠楠², 张兆泉¹()

1.中国科学院上海硅酸盐研究所, 上海 200050
2.上海核工程研究设计院股份有限公司, 上海 200233

收稿日期:2023-11-03 修回日期:2024-01-10 出版日期:2024-07-20 网络出版日期:2024-01-22
通讯作者: 张兆泉, 研究员. E-mail: zhangzq@mail.sic.ac.cn
作者简介:范武刚(1978-), 男, 副研究员. E-mail: fanwugang@mail.sic.ac.cn
基金资助:
国家重大科技专项基金(2017ZX06002004)

Anticorrosion Performance of 8YSZ Ceramics in Simulated Aqueous Environment of Pressurized Water Reactor

FAN Wugang¹(), CAO Xiong², ZHOU Xiang², LI Ling², ZHAO Guannan², ZHANG Zhaoquan¹()

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Shanghai Nuclear Engineering Research and Design Institute Co., Ltd., Shanghai 200233, China

Received:2023-11-03 Revised:2024-01-10 Published:2024-07-20 Online:2024-01-22
Contact: ZHANG Zhaoquan, professor. E-mail: zhangzq@mail.sic.ac.cn
About author:FAN Wugang (1978-), male, associated professor. E-mail: fanwugang@mail.sic.ac.cn
Supported by:
National Science and Technology Major Project of China(2017ZX06002004)

摘要/Abstract

摘要：

8%(摩尔分数)Y₂O₃稳定ZrO₂(8YSZ)陶瓷具有优异的氧离子电导率和低热导率, 在燃料电池、热障涂层、隔热等领域都有重要应用。然而它作为压水堆的堆内隔热或结构材料, 在事故条件下的水腐蚀机制和耐腐蚀性能目前尚不明晰。本研究在350 ℃/17.4 MPa, 0.3 μg/L溶解氧(DO)的动水循环模拟压水堆水环境中, 系统考察了8YSZ陶瓷的质量、物相、显微结构、力学性能以及溶液成分随腐蚀时间的变化, 并探讨了腐蚀机制。研究发现8YSZ陶瓷的质量随腐蚀时间的延长先增大后减小, 并会受表面粗糙度的影响。增重归因于水分子进入陶瓷后形成了Zr-OH和Y-OH团簇, 而失重是由金属阳离子析出和晶粒溶解所导致的。物相分析显示立方结构的8YSZ腐蚀后未往四方相或单斜相转变, 这与四方相或部分稳定的氧化锆的相变失效不同。表面及断面形貌变化显示水分子可沿缺陷或微裂纹进入陶瓷内部, 破坏晶界, 使受腐蚀影响区域由穿晶断裂变为沿晶断裂。腐蚀前后8YSZ陶瓷的压缩强度和抗弯强度未明显改变, 而维氏硬度略有降低, 这与陶瓷表层形成的大量腐蚀坑有关。表面抛光样品腐蚀1050 h时的单位表面积的质量变化率为-0.108×10^-3mg∙cm^-2∙h^-1, 腐蚀坑深度仅为30.8 μm。这些结果表明8YSZ陶瓷具有优良的耐水腐蚀性能, 有望用于压水堆内的隔热或结构材料。

关键词: 8YSZ陶瓷, 亚临界水, 腐蚀行为, 微观结构, 力学性能

Abstract:

8% (molar fraction) Y₂O₃ stabilized ZrO₂ (8YSZ) ceramics have important applications in fuel cells, thermal barrier coatings, as well as thermal insulation due to their excellent oxygen ionic conductivity and low thermal conductivity. However, their corrosion resistance to water and their behaviors as thermal insulation or structural material in pressurized water reactors during accidents are not fully understood. This study systematically examined the mass, crystal phase, microstructure, mechanical properties, and solution composition of 8YSZ ceramics over time in a dynamic water environment at 350 ℃/17.4 MPa with 0.3 μg/L dissolved oxygen, aiming to simulate a pressurized water reactor environment. It is found that the mass of 8YSZ ceramics increases firstly and then decreases with corrosion duration time. The mass change is influenced by the surface roughness. The weight gain is attributed to the formation of Zr-OH and Y-OH clusters by the entry of water molecules into the ceramics, whereas the weight loss is caused by the metal cations leaching and the dissolution of grains. Phase analysis demonstrates that the cubic 8YSZ after corrosion does not undergo any phase transformation towards tetragonal or monoclinic phases, which is different from the degradation mechanism of tetragonal or partially stabilized zirconia. Changes in surface and cross-section morphology indicate that water molecules enter the interior of the ceramics along defects or microcracks, producing grain boundary damage and changing the fracture mode in the corrosion-affected region from transgranular to intergranular fracture. Compressive and flexural strengths of this ceramics after corrosion do not change significantly, while the Vicker’s hardness decreases slightly, which are related to the formation of pits in the surface layer. As a consequence, depth of the corrosion pit after 1050 h is only 30.8 μm, and the mass change rate of per unit surface area is -0.108×10^-3 mg∙cm^-2∙h^-1, consolidating excellent water corrosion resistance of 8YSZ ceramic. Therefore, 8YSZ ceramics are promising for thermal insulation or structural materials in pressurized water reactors.

Key words: 8YSZ ceramic, subcritical water, corrosion behavior, microstructure, mechanical property

中图分类号:

TQ174

范武刚, 曹雄, 周响, 李玲, 赵冠楠, 张兆泉. 8YSZ陶瓷在模拟压水堆水环境中的耐腐蚀性能[J]. 无机材料学报, 2024, 39(7): 803-809.

FAN Wugang, CAO Xiong, ZHOU Xiang, LI Ling, ZHAO Guannan, ZHANG Zhaoquan. Anticorrosion Performance of 8YSZ Ceramics in Simulated Aqueous Environment of Pressurized Water Reactor[J]. Journal of Inorganic Materials, 2024, 39(7): 803-809.

图/表 7

图1 8YSZ陶瓷的质量变化比例和单位表面积的质量变化速率

Fig. 1 Mass change ratio and mass change rate of per unit surface area of 8YSZ ceramics

图2 8YSZ陶瓷腐蚀前及腐蚀不同时间后的XRD谱图

Fig. 2 XRD patterns of 8YSZ ceramics before and after corrosion for different periods (a) 2θ=20°-80°; (b) 2θ=28°-38°

图3 8YSZ陶瓷腐蚀前及腐蚀不同时间后的Raman谱图

Fig. 3 Raman spectra of 8YSZ ceramics before and after corrosion for different periods

图4 8YSZ陶瓷腐蚀前及腐蚀不同时间后表面(a, c, e, g)和断面(b, d, f, h)的SEM照片

Fig. 4 SEM images for surfaces (a, c, e, g) and cross sections (b, d, f, h) of 8YSZ ceramics before and after corrosion for different periods (a, b) 0 h; (c, d) 350 h; (e, f) 700 h; (g, h) 1050 h

图5 8YSZ陶瓷腐蚀前及腐蚀不同时间后的力学性能

Fig. 5 Mechanical properties of 8YSZ ceramics before and after corrosion for different periods (a) Viker’s harness; (b) Fracture toughness; (c) Bending strength; (d) Compression strength

表1 腐蚀前后回路水中化学成分的含量(mg/L)

Table 1 Contents of chemical compositions in water circulation before and after corrosion tests (mg/L)

Corrosion time/h	Zr	Y	Fe	Cr	Ni
0	0	-	0	-	0
350	0.04	0.01	-	-	0.01
700	0.01	-	0.01	0.01	0.05
1050	0.01	-	0.01	0.02	0.09

图6 8YSZ陶瓷在动态亚临界水中的腐蚀机制示意图

Fig. 6 Schematic drawing of corrosion mechanism for 8YSZ ceramics in dynamic subcritical water

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8YSZ陶瓷在模拟压水堆水环境中的耐腐蚀性能

Anticorrosion Performance of 8YSZ Ceramics in Simulated Aqueous Environment of Pressurized Water Reactor

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