硅酸盐学报

硼硅酸盐核废料玻璃在深地质处置过程中腐蚀机理研究进展

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张宇轩 ¹^,² , 马瑞 ¹^,² , 崔秀涛 ² , 吴楠楠 ¹ , 欧阳顺利 ¹^,²

硅酸盐学报 | 综合评述 2024,52(5): 1749-1760

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硅酸盐学报 |综合评述 2024 , 52 (5) : 1749 -1760

硼硅酸盐核废料玻璃在深地质处置过程中腐蚀机理研究进展

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张宇轩¹^,², 马瑞¹^,², 崔秀涛², 吴楠楠¹, 欧阳顺利¹^,²

作者信息

^1．广州航海学院，广州 510725

^2．内蒙古科技大学材料与冶金学院，内蒙古包头 014010

通讯作者:

欧阳顺利（1983—），男，博士，教授。

作者简介:

张宇轩（1995—），男，博士研究生。

Corrosion Mechanism of Borosilicate Nuclear Waste Glass During Deep Geological Disposal: A Short Review

Yuxuan ZHANG¹^,², Rui MA¹^,², Xiutao CUI², Nannan WU¹, Shunli OUYANG¹^,²

Affiliations

^1.Guangzhou Maritime University, Guangzhou 510725, China

^2.School of Material and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, Inner mongolia, China

Corresponding Author:

OUYANG Shunli (1983-), male, Ph.D., Professor. E-mail: ouyangshunli01@163.com

ZHANG Yuxuan (1995-), male, Doctoral candidate. E-mail: ldu2013yuxuan@outlook.com

出版时间: 2024-05-20 doi: 10.14062/j.issn.0454-5648.20230568

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摘要

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在放射性核废料深地质处置过程中，硼硅酸盐玻璃是目前国际上首选的固化材料。但是在10⁵~10⁶年的时间尺度上不能排除地下水对玻璃侵蚀，因此需要进行玻璃在水溶液环境中的长时间腐蚀机制的研究。研究过程发现，大多数玻璃最终都会以一个及其缓慢的残余速率腐蚀，因此可以使利用玻璃在深地质处置核废料。本综述针对硼硅酸盐核废料玻璃现有的腐蚀现象、行为及模型进行了总结，并讨论其中存在的问题，为玻璃长期腐蚀性研究提出可能的研究设想。

关键词

核废料玻璃 / 腐蚀 / 化学亲和力模型 / 蚀变层

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The possibility and potential impact of a nuclear accident are a subject of debate and a key factor in public concern for nuclear facilities virtually since the first reactor. Although nuclear power plants have several built-in physical barriers to maintain the safety of the system, they are designed to prevent radioactive isotopes from escaping into the environment. However, the experiences for past few decades indicate that nuclear accidents can happen. The radioactive waste produced by nuclear power plants also threatens the natural environment and human health. It can exist in the natural environment for up to 100 000 years. Deep geological disposal of spent fuel and radioactive waste is the most feasible and safe option. The permanent disposal of highly radioactive nuclear waste is to place it in a container that can be isolated from the natural environment until the radioactivity of the fission products reducing to a safe level. The short-term and long-term corrosion mechanism of glass is one of the key points. The current research is to use various methods to simulate the short-term and long-term behaviors of the glass body in different geological environments. However, there is a lack of effective connections between various experiments. In just a few decades after the vitrified body is buried, countless problems that are not considered in the disposal of waste glass are discovered. The current situation is that existing research results lag far behind actual needs. From this point of view, research related to the corrosion of solidified glass is not a precautionary measure, but an urgent one that cannot be delayed.

Borosilicate glass is currently a material of choice internationally for immobilizing high-level nuclear waste, including excess plutonium from dismantled nuclear weapons and highly radioactive liquid/solid waste from spent fuel reprocessing. In geological repositories, nuclear waste containing borosilicate glass is embedded in a multi-barrier containment system that should prevent water from entering the glass and the release of radioactive materials. However, groundwater corrosion of glass over long-term storage beyond geological time scales cannot be ruled out, so experimental glass corrosion studies, especially those dealing with corrosion mechanisms, are crucial to assess the long-term performance of glass. After long-term observation and experiments, the corrosion of glass in an aqueous solution environment is often divided into five stages, i.e., interdiffusion between solid and liquid stage, rapid initial reaction with the contact solution stage, corrosion rate decreases stage, residual rate stage and alteration recovery stage. Although these behaviors are not experienced by all materials under all corrosion conditions, one or more of the above can perfectly describe the corrosion process of the material. Three reactions usually occur during the reaction process, i.e., (1) hydration reaction (diffusion), water enters the glass as a complete molecule, (2) hydrolysis reaction, water reacts with the metal-oxygen bond in the glass to generate hydroxyl groups, and (3) ion exchange reaction, the modified cations in the glass are replaced by protons or other cations in the water. There is still controversy for the mechanism that controls the decrease in corrosion rate, but it is basically divided into two situations. One is due to the increase in the concentration of silicon at the interface, which causes the leaching rate to decrease, and another is due to the formation of a corrosion layer at the interface. Large molecules cannot be transferred. There are currently three most competitive models that are widely accepted. The first model is a chemical affinity model, which is based on the concept of "deviation from equilibrium" and can solve the problem of dissolution of the glass network, changes in pH value, precipitation of stable or metastable reaction products, and secondary problems at the interface (reaction zone) between glass and solution. Issues such as silicon oxide saturation and residual affinity of long-term reactions under near-saturated conditions; the second model is an alkali-proton exchange model to form a corrosion layer based on ion exchange reactions. The corrosion layer is considered as the ion exchange of protons with network modifiers such as Na⁺. The reaction produces products with silanol (Si—OH) groups. The silanol group is repolymerized to form the residual hydrated glass layer. The third model is a gel layer model, which believes that the corrosion layer formed can effectively protect the remaining glass from being corroded. It proposes the release of substances in the glass into the solution, that is, the corrosion rate is determined by the transmission characteristics of the "gel layer".

Summary and prospects

The corrosion of nuclear waste glass over long-time is undoubtedly the most complex problem in glass science to date. Because its components include dozens of oxides, there are cracks formed during the cooling stage, the geometry of the glass block is complex, the thermal, chemical and water boundary conditions are time-varying, involving many coupling phenomena. In addition, the time scale of deep geological disposal security assessment goes beyond direct verification. There is therefore a need to develop one or more rigorous, multi-scale theories to integrate basic understandings into models, which can be verified through dedicated experiments and compared with corrosion in natural or archaeological glass. Future models predicting a long-term corrosion of silicate glasses in aqueous environments should consider the spatial and temporal coupling of glass dissolution and silica precipitation and growth, controlling the transport of chemicals through the growing corrosion zone. Some specific issues include the evolution of porosity and structure over time in SAL, and how to control the transfer of materials between the aqueous solution and the glass; in the actual process, the nuclear fission products and actinides in the nuclear waste glass are what is the reaction during the glass corrosion process. Radioactive elements generate a large amount of heat during the placement process, and the ion irradiation they generate cause damage to the glass structure and SAL. The nucleation and growth of silicon dioxide at the reaction interface affect the glass dissolution rates and the use of ceramics and glass-ceramics for deep geological disposal of radioactive nuclear waste.

Key words

nuclear waste glass / corrosion / chemical affinity model / altered layer

引用本文

张宇轩, 马瑞, 崔秀涛, 吴楠楠, 欧阳顺利. 硼硅酸盐核废料玻璃在深地质处置过程中腐蚀机理研究进展. 硅酸盐学报, 2024 , 52 (5) : 1749 -1760 . DOI: 10.14062/j.issn.0454-5648.20230568

Yuxuan ZHANG, Rui MA, Xiutao CUI, Nannan WU, Shunli OUYANG. Corrosion Mechanism of Borosilicate Nuclear Waste Glass During Deep Geological Disposal: A Short Review[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (5) : 1749 -1760 . DOI: 10.14062/j.issn.0454-5648.20230568

基金

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国家自然科学基金(11964025; 11564031)

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2024年第52卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230568

接收时间：2023-08-02
首发时间：2026-10-22
出版时间：2024-05-20

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收稿日期：2023-08-02
修回日期：2023-08-19

基金

国家自然科学基金(11964025; 11564031)

作者信息

^1．广州航海学院，广州 510725

^2．内蒙古科技大学材料与冶金学院，内蒙古包头 014010

通讯作者:

欧阳顺利（1983—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230568

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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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