核用耐铅铋腐蚀涂层的研究进展

doi:10.15541/jim20250372

摘要/Abstract

摘要： 铅铋共晶合金(LBE)凭借其高沸点、高导热性及优良安全性能,已成为加速器驱动先进核能系统(ADANES)和铅冷快堆(LFR)的核心冷却剂,但其在高温环境下引发的氧化腐蚀、溶解腐蚀及冲刷腐蚀耦合问题,严重威胁结构材料的服役寿命,制约了先进核能技术的工程化应用。表面涂层技术可在保留基体固有性能的基础上提升耐蚀性,是缓解LBE腐蚀的关键技术途径之一。本文系统综述了核用耐LBE腐蚀涂层的研究进展,首先从腐蚀机理入手,阐明了溶解氧、温度、流速与辐照等多因素协同作用对材料腐蚀的影响规律;进而按金属、陶瓷及复合三大体系,分析解析了FeCrAl(Y)、高熵合金、Al₂O₃、MAX相及梯度复合涂层的耐蚀机制、性能优势与失效行为。研究表明：FeCrAl(Y) 涂层通过“基体-氧化膜”协同作用形成连续 Al₂O₃ 隔离层,其耐蚀性和力学性能与 Cr、Al 含量相关;高熵合金涂层利用晶格畸变与多组元协同氧化抑制腐蚀介质的内扩散,但面临高温相分解与辐照脆化等问题;Al₂O₃ 等陶瓷涂层热力学稳定,可为基底提供有效防护,但在高温环境中因非晶晶化、界面匹配及自修复缺失等而易失效。复合结构涂层通过“金属过渡层+陶瓷功能层”梯度设计,有望实现高结合、高韧性、高阻隔等功能一体化。未来研究需聚焦环境-成分-工艺的耦合调控、多因素服役评价与寿命预测模型,为先进核能系统提供长时可靠防护解决方案。

关键词: 铅冷快堆, 铅铋共晶, 涂层, 耐腐蚀性, 综述

Abstract: Lead-bismuth eutectic (LBE), with its high boiling point, excellent thermal conductivity, and favorable safety properties, has become the core coolant for accelerator-driven advanced nuclear energy systems (ADANES) and lead-cooled fast reactors (LFRs). However, the coupled issues of oxidation corrosion, dissolution corrosion, and erosion corrosion induced by its high-temperature environment severely threaten the service life of structural materials, and hinder the engineering implementation of advanced nuclear technology. Surface coating technology, which enhances corrosion resistance while preserving the inherent properties of the substrate, has emerged as a key strategy to mitigate LBE corrosion. This paper provides a systematic review of research progress on corrosion-resistant coatings for nuclear applications against LBE corrosion. Starting from corrosion mechanisms, the influence of synergistic factors, including dissolved oxygen, temperature, flow velocity, and irradiation, on corrosion behavior are elucidated. Coatings are classified into three major systems, i.e. metallic, ceramic, and composite, and the corrosion resistance mechanisms, performance advantages, and failure behaviors of FeCrAl(Y), high-entropy alloys, Al₂O₃, MAX phases, and gradient composite coatings are analyzed. Research indicates that FeCrAl(Y) coatings form a continuous Al₂O₃ barrier layer through “matrix-oxide film” synergistic effect, with corrosion resistance and mechanical properties correlated to Cr and Al content. High-entropy alloy coatings suppress inward diffusion of corrosion species through lattice distortion and multi-component synergistic oxidation, yet they are susceptible to like high-temperature phase decomposition and irradiation embrittlement. Thermodynamically stable ceramic coatings like Al₂O₃ provide effective substrate protection, yet tend to fail in high-temperature environments due to amorphous crystallization, interface mismatch, and lack of self-healing. Composite-structured coatings with a gradient architecture of “metal transition layers + ceramic functional layers” present a promising approach for integrating high adhesion, high toughness, and high barrier properties. Future efforts should focus on coupled regulation of environment-composition-process, multi-factor service evaluation, and lifetime prediction models to deliver long-term reliable protection solutions for advanced nuclear energy systems.

Key words: LFR, LBE, coatings, corrosion resistance, review

中图分类号:

TL34

刘春帆, 陈科, 葛芳芳, 黄庆. 核用耐铅铋腐蚀涂层的研究进展[J]. 无机材料学报, DOI: 10.15541/jim20250372.

LIU Chunfan, WANG Renda, CHEN Ke, HUANG Qing, GE Fangfang. Research Progress on LBE Corrosion Resistant Coatings[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250372.

参考文献

[1] YANG L, ZHAN W.A closed nuclear energy system by accelerator-driven ceramic reactor and extend AIROX reprocessing.Science China Technological Sciences, 2017, 60(11): 1702.
[2] LORUSSO P, BASSINI S, DEL NEVO A, et al. GEN-IV LFR development: Status & perspectives. Progress in Nuclear Energy, 2018, 105: 318.
[3] FIORI F, ZHOU Z.A study on the Chinese nuclear energy options and the role of ADS reactor in the Chinese nuclear expansion.Progress in Nuclear Energy, 2016, 91: 159.
[4] ZHANG J.A review of steel corrosion by liquid lead and lead-bismuth.Corrosion Science, 2009, 51(6): 1207.
[5] ZHANG J, LI N.Review of the studies on fundamental issues in LBE corrosion.Journal of Nuclear Materials, 2008, 373(1): 351.
[6] AUGER T, LORANG G, GUéRIN S, et al. Effect of contact conditions on embrittlement of T91 steel by lead-bismuth. Journal of Nuclear Materials, 2004, 335(2): 227.
[7] GONG X, SHORT M P, AUGER T,et al. Environmental degradation of structural materials in liquid lead- and lead-bismuth eutectic-cooled reactors. Progress in Materials Science, 2022, 126: 100920.
[8] MüLLER G, HEINZEL A, KONYS J, et al. Results of steel corrosion tests in flowing liquid Pb/Bi at 420-600 °C after 2000 h. Journal of Nuclear Materials, 2002, 301(1): 40.
[9] FETZER R, WEISENBURGER A, JIANU A,et al. Oxide scale formation of modified FeCrAl coatings exposed to liquid lead. Corrosion Science, 2012, 55: 213
[10] CHEN Q, BAI F, WANG P,et al. Microstructure response and lead-bismuth eutectic corrosion behavior of 11Cr1Si ferritic/martensitic steel after Au-ion irradiation. Corrosion Science, 2022, 198: 110101.
[11] FRAZER D, QVIST S, PARKER S, et al. Degradation of HT9 under simultaneous ion beam irradiation and liquid metal corrosion. Journal of Nuclear Materials, 2016, 479: 382.
[12] YAO C, ZHANG H, CHANG H, et al. Structure of surface oxides on martensitic steel under simultaneous ion irradiation and molten LBE corrosion. Corrosion Science, 2022, 195: 109953.
[13] SHI H, WANG H, FETZER R,et al. Influence of Si addition on the corrosion behavior of 9 wt.% Cr ferritic/martensitic steels exposed to oxygen-controlled molten Pb-Bi eutectic at 550 and 600 °C. Corrosion Science, 2021, 193: 109871.
[14] ZHANG H, LIU X, XU Y, et al. Comparison investigation on corrosion of SIMP and T91 steels exposed to liquid LBE at 450 ℃: The role of Si on reducing oxidation rate. Corrosion Science, 2023, 225: 111553.
[15] ZHUANG Y, ZHANG X, ZENG X, et al. The influence of Y addition on oxide layers of 15-15Ti-Y steel exposed to static Pb-Bi alloys with containing oxygen. Journal of Nuclear Materials, 2024, 588: 154806.
[16] LUO W, HUANG Q, LUO L, et al. Effect of minor addition of Ce on microstructure and LBE corrosion resistance for CLAM steel. Corrosion Science, 2022, 209: 110796.
[17] VAN DEN BOSCH J, HOSEMANN P, ALMAZOUZI A,et al. Liquid metal embrittlement of silicon enriched steel for nuclear applications. Journal of Nuclear Materials, 2010, 398(1): 116.
[18] DAI Y, BOUTELLIER V, GAVILLET D, et al. FeCrAlY and TiN coatings on T91 steel after irradiation with 72MeV protons in flowing LBE. Journal of Nuclear Materials, 2012, 431(1): 66.
[19] ZHANG W, ZHONG Y, QIU X, et al. Screening of the FeCrAl LBE corrosion-resistant coatings: The effect of Cr and Al contents. Surface and Coatings Technology, 2023, 462: 129477.
[20] PALM M.Concepts derived from phase diagram studies for the strengthening of Fe-Al-based alloys.Intermetallics, 2005, 13(12): 1286.
[21] ZHANG W, ZHOU M, DENG J,et al. Improved LBE corrosion resistance of the FeCrAl coating by the addition of trace Si element. Intermetallics, 2024, 166: 108197.
[22] ZHANG P, YAO Z, WANG X,et al. A novel FeCrAlW_x high entropy alloy coating for enhancing lead-bismuth eutectic corrosion resistance. Journal of Nuclear Materials, 2024, 589: 154844.
[23] ZHANG W, DENG J, ZHOU M, et al. Synergistic effect of simultaneous proton irradiation and LBE corrosion on the microstructure of the FeCrAl(Y)coatings. Corrosion Science, 2024, 229: 111874.
[24] WEI X S, JIN J L, JIANG Z Z, et al. FeCrMoWCBY metallic glass with high corrosion resistance in molten lead-bismuth eutectic alloy. Corrosion Science, 2021, 190: 109688.
[25] YANG J, SHI K, ZHANG W,et al. A novel AlCrFeMoTi high-entropy alloy coating with a high corrosion-resistance in lead-bismuth eutectic alloy. Corrosion Science, 2021, 187: 109524.
[26] YANG J, ZHANG F, CHEN Q,et al. Effect of Au-ions irradiation on mechanical and LBE corrosion properties of amorphous AlCrFeMoTi HEA coating: Enhanced or deteriorated? Corrosion Science, 2021, 192: 109862.
[27] YANG J, ZHOU M, LV L, et al. Influence of Si addition on the microstructure, mechanical and lead-bismuth eutectic corrosion properties of an amorphous AlCrFeMoTiSi_x high-entropy alloy coating. Intermetallics, 2022, 148: 107649.
[28] SHORT M P, BALLINGER R G.A Functionally Graded Composite for Service in High-Temperature Lead- and Lead-Bismuth-Cooled Nuclear Reactors—I: Design.Nuclear Technology, 2012, 177(3): 366.
[29] YANG J, LIANG J, WANG G, et al. Microstructure, mechanical properties and lead-bismuth eutectic corrosion behavior of FeCrAlTiNb high-entropy alloy coatings. Corrosion Science, 2023, 222: 111407.
[30] YANG J, ZHAO K, WANG G, et al. Influence of coating thickness on microstructure, mechanical and LBE corrosion performance of amorphous AlCrFeTiNb high-entropy alloy coatings. Surface and Coatings Technology, 2022, 441: 128502.
[31] DENG J, YANG J, LV L,et al. Corrosion behavior of refractory TiNbZrMoV high-entropy alloy coating in static lead-bismuth eutectic alloy: A novel design strategy of LBE corrosion-resistant coating? Surface and Coatings Technology, 2022, 448: 128884.
[32] WANG W, ZHU Z, YANG L,et al. Superior corrosion resistance of a slurry FeAl coating on 316LN stainless steel in 550 ℃ liquid lead-bismuth eutectic. Corrosion Science, 2024, 227: 111757.
[33] FERRé F G, MAIROV A, IADICICCO D,et al. Corrosion and radiation resistant nanoceramic coatings for lead fast reactors. Corrosion Science, 2017, 124: 80.
[34] DOU P, KASADA R.Preliminary study on nano- and micro-composite sol-gel based alumina coatings on structural components of lead-bismuth eutectic cooled fast breeder reactors.Journal of Nuclear Materials, 2011, 409(3): 177.
[35] KASADA R, DOU P.Sol-gel composite coatings as anti-corrosion barrier for structural materials of lead-bismuth eutectic cooled fast reactor.Journal of Nuclear Materials, 2013, 440(1): 647.
[36] MIORIN E, MONTAGNER F, ZIN V,et al. Al rich PVD protective coatings: A promising approach to prevent T91 steel corrosion in stagnant liquid lead. Surface and Coatings Technology, 2019, 377: 124890.
[37] ZHONG Y, ZHANG W, CHEN Q, et al. Effect of LBE corrosion on microstructure of amorphous Al₂O₃ coating by magnetron sputtering. Surface and Coatings Technology, 2022, 443: 128598.
[38] GARCíA FERRé F, ORMELLESE M, DI FONZO F,et al. Advanced Al₂O₃ coatings for high temperature operation of steels in heavy liquid metals: a preliminary study. Corrosion Science, 2013, 77: 375.
[39] ZHU C, ZHOU M, LI Q,et al. Microstructural evolution and corrosion resistance of ZrO₂ coated ferrite/martensite steel in liquid lead-bismuth eutectic. Materials Today Communications, 2023, 35: 105603.
[40] WU Z Y, ZHAO X, LIU Y,et al. Lead-bismuth eutectic(LBE)corrosion behavior of AlTiN coatings at 550 and 600 ℃. Journal of Nuclear Materials, 2020, 539: 152280.
[41] HUANG S, PANG L, TAI P,et al. Lead-bismuth eutectic corrosion resistance of TiAlN coating after N⁵+ ion irradiation. Thin Solid Films, 2024, 791: 140224.
[42] WAN Q, WU Z Y, LIU Y, et al. Lead-bismuth eutectic(LBE)corrosion mechanism of nano-amorphous composite TiSiN coatings synthesized by cathodic arc ion plating. Corrosion Science, 2021, 183: 109264.
[43] SHI Q Q, YAN W, SHA W,et al. Corrosion resistance of self-growing TiC coating on SIMP steel in LBE at 600°C. Materials and Corrosion, 2016, 67(11): 1204.
[44] SHI H, AZMI R, HAN L,et al. Corrosion behavior of Al-containing MAX-phase coatings exposed to oxygen containing molten Pb at 600 °C. Corrosion Science, 2022, 201: 110275.
[45] YIN X, WANG H, XIAO J,et al. A high-entropy alloy nitride protective coating for fuel cladding in high temperature lead-bismuth eutectic alloy. Journal of Nuclear Materials, 2022, 568: 153888.
[46] ZHU Z, TAN J, ZHANG Z,et al. Corrosion behaviors of ODS-FeCrAl in oxygen-saturated lead-bismuth eutectic at 550 °C: Effects of grain boundaries and minor elements. Journal of Nuclear Materials, 2023, 587: 154710.
[47] WEISENBURGER A, HEINZEL A, MüLLER G, et al. T91 cladding tubes with and without modified FeCrAlY coatings exposed in LBE at different flow, stress and temperature conditions. Journal of Nuclear Materials, 2008, 376(3): 274.
[48] POPOVIC M P, CHEN K, SHEN H,et al. A study of deformation and strain induced in bulk by the oxide layers formation on a Fe-Cr-Al alloy in high-temperature liquid Pb-Bi eutectic. Acta Materialia, 2018, 151: 301.
[49] WEISENBURGER A, JIANU A, DOYLE S,et al. Oxide scales formed on Fe-Cr-Al-based model alloys exposed to oxygen containing molten lead. Journal of Nuclear Materials, 2013, 437(1): 282.
[50] KIM S, LEE C-H, KIM T, et al. Effects of yttrium on the oxidation behavior of Fe13Cr6AlY alloys under 1200 °C steam. Journal of Alloys and Compounds, 2023, 960: 170642.
[51] LIANG J, YANG J, ZHANG W,et al. Corrosion behavior of magnetron sputtering Fe31Cr20Al17Ti16Nb16 high entropy coating in liquid lead-bismuth eutectic with different oxygen concentration at 500 °C. Surface and Coatings Technology, 2024, 480: 130579.
[52] ALI S, AHMED M, LIU B,et al. Microstructural stability and mechanical property of AlCrFeMoTi high-entropy amorphous alloy thin films under He+ ions irradiation. Surface and Coatings Technology, 2024, 487: 130952.
[53] CHARALAMPOPOULOU E, LAMBRINOU K, VAN DER DONCK T,et al. Early stages of dissolution corrosion in 316L and DIN 1.4970 austenitic stainless steels with and without anticorrosion coatings in static liquid lead-bismuth eutectic(LBE)at 500°C. Materials Characterization, 2021, 178: 111234.
[54] ZHANG T, MA J, LIU W, et al. Corrosion behavior of Al-O coating in oxygen-saturated lead-bismuth eutectic at 550 °C. Journal of Materials Research and Technology, 2024, 30: 4123.
[55] ZHANG Z, DUAN X, JIA D, et al. On the formation mechanisms and properties of MAX phases: A review. Journal of the European Ceramic Society, 2021, 41(7): 3851.
[56] BARSOUM M W.The M_N₊₁AX_N phases: A new class of solids: Thermodynamically stable nanolaminates. Progress in Solid State Chemistry, 2000, 28(1): 201.
[57] SOKOL M, NATU V, KOTA S, et al. On the Chemical Diversity of the MAX Phases. Trends in Chemistry, 2019, 1(2): 210.
[58] GONZALEZ‐JULIAN J. Processing of MAX phases: From synthesis to applications.Journal of the American Ceramic Society, 2020, 104(2): 659.
[59] BARNES L A, DIETZ RAGO N L, LEIBOWITZ L. Corrosion of ternary carbides by molten lead.Journal of Nuclear Materials, 2008, 373(1): 424.
[60] HEINZEL A, WEISENBURGER A, MüLLER G. Long-term corrosion tests of Ti₃SiC₂ and Ti₂AlC in oxygen containing LBE at temperatures up to 700 °C.Journal of Nuclear Materials, 2016, 482: 114.
[61] LAPAUW T, TUNCA B, JORIS J, et al. Interaction of M_n+1AX_n phases with oxygen-poor, static and fast-flowing liquid lead-bismuth eutectic. Journal of Nuclear Materials, 2019, 520: 258.
[62] LYU L, QIU X, YUE H,et al. Corrosion behavior of Ti₃SiC₂ in flowing liquid lead-bismuth eutectic at 500 ℃. Materials, 2022, 15(21): 7406.
[63] HEINZEL A, MüLLER G, WEISENBURGER A. Compatibility of Ti₃SiC₂ with liquid Pb and PbBi containing oxygen.Journal of Nuclear Materials, 2009, 392(2): 255.
[64] UTILI M, AGOSTINI M, COCCOLUTO G,et al. Ti₃SiC₂ as a candidate material for lead cooled fast reactor. Nuclear Engineering and Design, 2011, 241(5): 1295.
[65] LI Q, ZHONG Y, ZHANG W, et al. Microstructure, Mechanical Properties, and Lead-Bismuth Eutectic Corrosion Behaviors of FeCrAlY-Al₂O₃ Nanoceramic Composite Coatings. Coatings, 2024, 14(4): 393.
[66] 张顺蔺, 潘东, 尹星, 等. 多弧离子镀Al₂O₃-TiO₂/FeCrAl涂层的热冲击性能及在静态铅铋中的耐腐蚀行为研究. 核动力工程, 2024, 45(1): 90.
[67] HUANG S, PANG L, TAI P, et al. Study on Al₂O₃/Fe-Al gradient coating assisted prepared by ionic liquid for Lead-Bismuth eutectic corrosion resistance. Nuclear Materials and Energy, 2024, 38: 101623.