高放废物地质处置库近场环境中碳钢腐蚀产物演化研究进展

doi:10.11902/1005.4537.2026.195

中国腐蚀与防护学报

2026, Vol. 46

Issue (5): 1343-1352 CSTR: 32134.14.1005.4537.2026.195 DOI: 10.11902/1005.4537.2026.195

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高放废物地质处置库近场环境中碳钢腐蚀产物演化研究进展

谢敬礼¹^,², 王友志³, 乔书振³, 牛佳雨³, 郝龙³(

), 曹胜飞¹^,², 王俭秋³

^1.核工业北京地质研究院北京 100029
^2.国家原子能机构高放废物地质处置创新中心北京 100029
^3.中国科学院金属研究所中国科学院核用材料与安全评价重点实验室沈阳 110016

Recent Advances in Evolution of Carbon Steel Corrosion Products in Near-field Environment of Geological Repositories for High-level Radioactive Waste

XIE Jingli¹^,², WANG Youzhi³, QIAO Shuzhen³, NIU Jiayu³, HAO Long³(

), CAO Shengfei¹^,², WANG Jianqiu³

^1.Beijing Research Institute of Uranium Geology, Beijing 100029, China
^2.CAEA Innovation Center for Geological Disposal of High-level Radioactive Waste, Beijing 100029, China
^3.CAS Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

引用本文:

谢敬礼, 王友志, 乔书振, 牛佳雨, 郝龙, 曹胜飞, 王俭秋. 高放废物地质处置库近场环境中碳钢腐蚀产物演化研究进展[J]. 中国腐蚀与防护学报, 2026, 46(5): 1343-1352.
Jingli XIE, Youzhi WANG, Shuzhen QIAO, Jiayu NIU, Long HAO, Shengfei CAO, Jianqiu WANG. Recent Advances in Evolution of Carbon Steel Corrosion Products in Near-field Environment of Geological Repositories for High-level Radioactive Waste[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(5): 1343-1352.

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摘要:

碳钢因具有良好的力学性能、工程可加工性和成本优势，被广泛用作高放废物地质处置库处置容器、外包装及相关工程构件的候选材料。处置库近场环境在长期演化过程中将经历由有氧向缺氧、由非饱和向再饱和以及由氧化性向还原性的转变，进而控制碳钢腐蚀产物的组成和相变行为。本文综述了处置初期有氧阶段、残余氧耗尽过渡阶段和长期缺氧阶段碳钢表面腐蚀产物的相组成、形成机制及演化路径，讨论了地下水化学组成和缓冲/回填材料典型组分对FeOOH、Fe₂O₃、Fe(OH)₂、Fe₃O₄、绿锈、FeCO₃和FeS等腐蚀产物形成与转化的影响。进一步分析了腐蚀产物演化对钢—膨润土/黏土岩界面反应、近场氧化还原条件和工程屏障长期性能的潜在影响，并对未来碳钢腐蚀产物演化研究的发展方向进行了展望。

关键词 ：高放废物, 地质处置, 近场环境, 碳钢, 腐蚀产物

Abstract：

Carbon steel has attracted widespread attention as a candidate material for metallic containers, overpacks, and related engineering components in geological repositories for high-level radioactive waste, owing to its favorable mechanical properties, engineering processability, and cost-effectiveness. During long-term repository evolution, the near-field environment is expected to transition from aerobic to anaerobic conditions, from unsaturated to re-saturated states, and from oxidizing to reducing conditions, thereby controlling the composition and phase-transformation behavior of carbon steel corrosion products. This paper reviews the phase composition, formation mechanisms, and evolution pathways of corrosion products formed on carbon steel surfaces during the initial aerobic stage, the transitional oxygen-depletion stage, and the long-term anoxic stage. It also discusses the influences of groundwater chemistry and typical components of buffer/backfill materials on the formation and transformation of corrosion products, including FeOOH, Fe₂O₃, Fe(OH)₂, Fe₃O₄, green rust, FeCO₃, and FeS. Furthermore, the potential impacts of corrosion product evolution on steel-bentonite/claystone interfacial reactions, near-field redox conditions, and the long-term performance of engineered barriers are analyzed. Finally, future research directions concerning the evolution of corrosion products on carbon steel are discussed.

Key words： high-level radioactive waste geological disposal near-field environment carbon steel corrosion products

收稿日期: 2026-06-30 32134.14.1005.4537.2026.195

ZTFLH:

TG172

基金资助:中核集团研发平台稳定支持科研项目(WDZC-2023-HDYY-102)

通讯作者: 郝龙，E-mail：lhao@imr.ac.cn, chinahaolong@126.com，研究方向为高放废物地质处置容器材料腐蚀与风险评估

Corresponding author: HAO Long, E-mail: lhao@imr.ac.cn, chinahaolong@126.com

作者简介: 谢敬礼，男，1984年生，博士，正高级工程师

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表1 不同国家高放废物处置概念及碳钢/铁基金属腐蚀产物关注点[2,4~13,19~22]

图1 高放废物地质处置环境中碳钢腐蚀产物生成及相变过程的典型演化路径及控制因子[11,12,23~47]

Corrosion product	Typical formation conditions	Significance in geological repositories
Fe₂O₃ (hematite/iron oxide)	Strongly oxidizing conditions, wet-dry cycling, or long-term oxidation environments	Generally not a dominant corrosion product during the long-term anoxic stage of deep geological disposal, but can serve as an indicator phase for early oxidation or external oxygen intrusion
FeOOH (e.g., goethite, lepidocrocite)	Oxic conditions, residual oxygen available, and early-stage oxidation environments	Usually indicates oxygen involvement in corrosion during the early disposal stage. These phases may undergo further reduction or transformation into Fe₃O₄, green rust, and other Fe(II)-bearing phases after oxygen depletion
β-FeOOH (akaganeite)	High Cl⁻ concentration, oxygen-containing environments, or localized oxidizing conditions	An important indicator of chloride-induced corrosion. Its presence in repository samples may suggest early-stage oxygenated chloride corrosion or localized oxidizing environments
Green rust (Fe(II)-Fe(III) layered double hydroxides)	Low-oxygen or mildly reducing environments; different types of green rust can form in the presence of Cl^-, SO $4 2 -$ , CO $3 2 -$ , and other anions	A key metastable corrosion product with strong redox activity. It may participate in the reductive immobilization of radionuclides such as Tc, Se, and U. Its presence indicates a transitional state with coexistence of Fe(II) and Fe(III)
Fe(OH)₂ (ferrous hydroxide)	Anoxic or low-oxygen conditions, near-neutral to alkaline groundwater; commonly formed during early anaerobic corrosion of carbon steel	An initial product of anaerobic corrosion, usually accompanied by H₂ generation. Due to its limited stability, it can subsequently transform into Fe₃O₄, green rust, FeCO₃, or FeS
Amorphous Fe(OH)ₓ / ferrihydrite-like products	Early oxidation, hydration, and rapid precipitation environments	Usually act as precursor phases that can further transform into FeOOH, Fe₃O₄, or more stable iron minerals. Their occurrence indicates immature and highly transformable corrosion products
Fe₃O₄ (magnetite)	Anoxic/low-oxygen conditions, alkaline or mildly alkaline environments; commonly formed during long-term anaerobic corrosion	One of the most important corrosion products in long-term carbon steel corrosion studies for geological disposal. A dense magnetite layer may reduce mass transport and corrosion rates; however, its electrical conductivity may influence electron transfer and corrosion processes
FeCO₃ (siderite)	Carbonate-rich groundwater containing HCO₃⁻/CO $3 2 -$ or CO₂; weakly acidic to neutral/mildly alkaline environments	Common in carbonate-bearing systems. It may form a relatively compact protective layer and reduce corrosion rates. Its presence indicates strong control of carbonate chemistry on corrosion product evolution
FeS (e.g., mackinawite and troilite-type iron sulfides)	Sulfide-containing environments; sulfate-reducing bacterial activity; possible formation under sulfur cycling conditions in Boom Clay, claystone, or bentonite systems	An important indicator of microbial corrosion and sulfide-induced corrosion. FeS can modify the electrical conductivity of corrosion layers and influence localized corrosion behavior, potentially promoting pitting or accelerated local corrosion
FeS₂ (pyrite/marcasite)	Long-term reducing sulfur-rich environments; further transformation of FeS phases	Represents a more stable stage of iron sulfide mineral evolution. Its formation indicates progressive stabilization of the Fe-S system but also suggests long-term influence of sulfur cycling on near-field geochemistry
Iron silicates / Fe-rich clay minerals (e.g., nontronite, chlorite alteration products)	Long-term reactions between Fe²⁺/Fe³⁺ released from steel corrosion and Si-, Al-, and Mg-bearing minerals in bentonite or claystone	Key products of long-term steel-bentonite/claystone interface evolution. Their formation may consume montmorillonite and modify the swelling capacity, permeability, and radionuclide retention capability of bentonite
Ca-bearing iron phases /Fe-Ca-Si hydrated products	Presence of cementitious materials, such as the Belgian Supercontainer concept or claystone-cement interfaces in disposal concepts	Reflect coupled interactions between carbon steel corrosion and high-pH cement porewater. They influence carbon steel passivation, corrosion product layer stability, and the long-term evolution of cement-based barriers

表2 高放废物地质处置近场环境中碳钢主要腐蚀产物总结[9~11,24,33,38]

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