熔盐法低温合成掺钕ZrSiO4陶瓷的物相演变和化学稳定性

doi:10.15541/jim20220775

无机材料学报 ›› 2023, Vol. 38 ›› Issue (8): 910-916.DOI: 10.15541/jim20220775 CSTR: 32189.14.10.15541/jim20220775

所属专题：【结构材料】核用陶瓷（202409）

熔盐法低温合成掺钕ZrSiO₄陶瓷的物相演变和化学稳定性

刘建¹^,²(), 王凌坤¹^,², 许保亮¹^,², 赵倩¹^,², 王耀萱¹^,², 丁艺¹^,², 张胜泰¹^,²^,³(), 段涛¹^,²()

1.西南科技大学核废物与环境安全省部共建协同创新中心, 绵阳 621010
2.西南科技大学国防科技学院, 环境友好能源材料国家重点实验室, 绵阳 621010
3.中国工程物理研究院核物理与化学研究所高级陶瓷创新研究团队, 绵阳 621900

收稿日期:2022-12-28 修回日期:2023-02-22 出版日期:2023-08-20 网络出版日期:2023-03-17
通讯作者: 段涛, 教授. E-mail: duant@ustc.edu.cn; 张胜泰, 助教. E-mail: 1045477738@qq.com
作者简介:刘建(1995-), 男, 硕士研究生. E-mail: 1977812990@qq.com
基金资助:
国家自然科学基金项目(U2167221);国家自然科学基金项目(21906133);国家自然科学基金项目(22176157);四川省科技厅四川省青年科技创新研究团队(2021JDTD0019);国防基础科学研究计划(JCKY2019404D001)

Nd-doped ZrSiO₄ Ceramics: Synthesis in Molten Salt at Low Temperature, Phase Evolution and Chemical Stability

LIU Jian¹^,²(), WANG Lingkun¹^,², XU Baoliang¹^,², ZHAO Qian¹^,², WANG Yaoxuan¹^,², DING Yi¹^,², ZHANG Shengtai¹^,²^,³(), DUAN Tao¹^,²()

1. National Co-Innovation Center for Nuclear Waste Disposal and Environmental Safety, Southwest University of Science and Technology, Mianyang 621010, China
2. State Key Laboratory of Environment-friendly Energy Materials, School of National Defence Science & Technology, Southwest University of Science and Technology, Mianyang 621010, China
3. Innovation Research Team for Advanced Ceramics, Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, China

Received:2022-12-28 Revised:2023-02-22 Published:2023-08-20 Online:2023-03-17
Contact: DUAN Tao, professor. E-mail: duant@ustc.edu.cn; ZHANG Shengtai, assistant.E-mail: 1045477738@qq.com
About author:LIU Jian(1995-), male, Master candidate. E-mail: 1977812990@qq.com
Supported by:
National Natural Science Foundation of China(U2167221);National Natural Science Foundation of China(21906133);National Natural Science Foundation of China(22176157);Sichuan Youth Science and Technology Innovation Research Team of Sichuan Provincial Science and Technology Department(2021JDTD0019);National Defense Basic Scientific Research Project(JCKY2019404D001)

摘要/Abstract

摘要：

相较于传统固相烧结方法, 熔盐在较低的温度下提供了快速的传质和成核过程, 可合成用于固化高放废物(HLW)的陶瓷固化体。本工作采用熔盐法(MSS)在不同烧结温度(1100、1200、1300、1400、1500 ℃)和不同烧结时间(3、6、9、12、15 h)下制备了掺Nd的锆石(ZrSiO₄)陶瓷(Zr_1-_xNd_xSiO_4-_x_/2(0≤x≤0.1)), 并采用静态浸出试验(PCT)研究掺Nd的ZrSiO₄陶瓷在模拟地质处置环境下的化学稳定性。在熔盐与氧化物最佳摩尔比为10 : 1、烧结温度为1200 ℃、烧结时间为6 h的较温和条件下, 利用熔盐法成功合成了Zr_1-_xNd_xSiO_4-_x_/2, 可将Nd在ZrSiO₄中的固溶摩尔分数提高到8%, 结果显示MSS法能够降低陶瓷合成温度, 缩短合成时间, 提高固溶量。ZrSiO₄陶瓷对三价锕系核素的固化机理为晶格固化。浸出实验结果显示, Nd的归一化浸出率（LR_Nd）低至~10^-5g·m^-2·d^-1。浸出前后ZrSiO₄陶瓷未发生物相演变, 展现出较好的结构稳定性。浸出模型显示Nd浸出归因于陶瓷表面层发生溶解。研究结果表明, MSS法是一种高效的合成陶瓷固化体的手段。

关键词: 固化, 锆石, 熔盐, 化学稳定性

Abstract:

In contrast to conventional solid-phase sintering, molten salt method can provide a fast mass transfer and nucleation process at lower temperatures which has potential to synthesize the ceramic solid solution for immobilization of high-level nuclear waste (HLW). In this work, Nd-doped zircon (ZrSiO₄) ceramics (Zr_1-_xNd_xSiO_4-_x_/2(0≤x≤0.1)) were prepared by the molten salt synthesis(MSS) at different sintering temperatures (1100, 1200, 1300, 1400, 1500 ℃) for different sintering time (3, 6, 9, 12, and 15 h). Chemical stability of Nd-doped zircon ceramics in simulated geological disposal environment was studied by static leaching test (PCT). Zr_1-_xNd_xSiO_4-_x_/2 was synthesized by the molten salt method under the optimum molar ratio of molten salt to oxide at 10:1, sintering temperature at 1200 ℃ and sintering time of 6 h with the solid solution of Nd in ZrSiO₄ being increased to 8% (in mol). The MSS can reduce the synthetic temperature, shorten the sintering time and save the solid solution. The immobilizing mechanism of ZrSiO₄ ceramics for trivalent actinide nuclides is lattice immobilizing. Experimental results show that the normalized leaching rate (LR_Nd) of Nd is as low as ~10^-5g·m^-2·d^-1. ZrSiO₄ ceramics have no phase evolution before and after leaching, suggesting good structural stability. TLeaching model consolidates that Nd leaching is due to dissolution of the ceramic surface layer. Data from this study show that MSS is a promising method to synthesize ceramics solid solution.

Key words: immobilization, zircon, molten salt, chemical stability

中图分类号:

TQ174

刘建, 王凌坤, 许保亮, 赵倩, 王耀萱, 丁艺, 张胜泰, 段涛. 熔盐法低温合成掺钕ZrSiO₄陶瓷的物相演变和化学稳定性[J]. 无机材料学报, 2023, 38(8): 910-916.

LIU Jian, WANG Lingkun, XU Baoliang, ZHAO Qian, WANG Yaoxuan, DING Yi, ZHANG Shengtai, DUAN Tao. Nd-doped ZrSiO₄ Ceramics: Synthesis in Molten Salt at Low Temperature, Phase Evolution and Chemical Stability[J]. Journal of Inorganic Materials, 2023, 38(8): 910-916.

图/表 12

图1 掺钕ZrSiO4的MSS法合成路线

Fig. 1 Synthetic schematic of Nd-doped ZrSiO4 by MSS

图2 不同烧结温度(1100、1200、1300、1400、1500 ℃)下MSS法合成的ZrSiO4的XRD图谱

Fig. 2 XRD patterns of ZrSiO4 synthesized by MSS at different temperatures (1100, 1200, 1300, 1400, and 1500 ℃)

图3 1200 ℃不同烧结时间(3, 6, 9, 12, 15 h)MSS法合成ZrSiO4的XRD图谱

Fig. 3 XRD patterns of ZrSiO4 synthesized by MSS at 1200 ℃ for different time (3, 6, 9, 12, and 15 h)

图4 MSS法在不同熔盐与氧化物摩尔比下合成ZrSiO4的XRD图谱(1200 ℃/6 h)

Fig. 4 XRD patterns of ZrSiO4 synthesized by MSS with different molar ratios of molten salt to oxide (1200 ℃/6 h)

图5 MSS法合成ZrSiO4陶瓷固化体机理图

Fig. 5 Mechanism of ZrSiO4 ceramics synthesis by MSS

图6 在1200 ℃烧结6 h条件下MSS法合成Zr1-xNdxSiO4-x/2 (0≤x≤0.1)的XRD图谱

Fig. 6 XRD patterns of Zr1-xNdxSiO4-x/2 (0≤x≤0.1) synthesized by MSS at 1200 ℃ for 6 h

图7 Zr1-xNdxSiO4-x/2(0≤x≤0.1)晶格体积随Nd含量的变化

Fig. 7 Variation of lattice volume of Zr1-xNdxSiO4-x/2 (0≤x≤0.1) in contrast to Nd content

图8 Zr1-xNdxSiO4-x/2的微观形貌及其粒度分布

Fig. 8 Micromorphologies and correponding particle size distributions of Zr1-xNdxSiO4-x/2 (a) ZrSiO4; (b) Zr0.98Nd0.02SiO3.99; (c)Zr0.92Nd0.08SiO3.96; (d) Correponding particle size distribution

图9 Zr1-xNdxSiO4-x/2 (0.02≤x≤0.10)的归一化浸出率

Fig. 9 Normalized leaching rate of Zr1-xNdxSiO4-x/2 (0.02≤x≤0.10)

图10 ${{B}_{\text{Nd}}}$与浸出液接触时间的对数关系

Fig. 10 Logarithmic relationship of ${{B}_{\text{Nd}}}$ on the time of contact with leaching solution

图11 浸出42 d后Zr1-xNdxSiO4-x/2 (0.02≤x≤0.10)的XRD图谱

Fig. 11 XRD patterns of Zr1-xNdxSiO4-x/2 (0.02≤x≤0.10) after leaching for 42 d

图12 浸出42 d后Zr1-xNdxSiO4-x/2 (x=0.02, 0.08)的SEM形貌

Fig. 12 SEM images of Zr1-xNdxSiO4-x/2 (x=0.02, 0.08) after leaching for 42 d

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熔盐法低温合成掺钕ZrSiO₄陶瓷的物相演变和化学稳定性

Nd-doped ZrSiO₄ Ceramics: Synthesis in Molten Salt at Low Temperature, Phase Evolution and Chemical Stability

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