一种镍基高温合金的高温<strong>HCl</strong>腐蚀行为

doi:10.11900/0412.1961.2023.00070

金属学报

2025, Vol. 61

Issue (5): 770-782 DOI: 10.11900/0412.1961.2023.00070

研究论文

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一种镍基高温合金的高温HCl腐蚀行为

周一鸣¹^,², 韩勇军³, 谢光²(

), 郑伟², 肖炎彬³, 潘阳³, 张健²(

)

1 中国科学技术大学材料科学与工程学院沈阳 110016
2 中国科学院金属研究所师昌绪先进材料创新中心沈阳 110016
3 中国船舶集团有限公司第七〇五研究所西安 710077

High-Temperature Corrosion Behavior of a Nickel-Based Superalloy in HCl-Containing Atmosphere

ZHOU Yiming¹^,², HAN Yongjun³, XIE Guang²(

), ZHENG Wei², XIAO Yanbin³, PAN Yang³, ZHANG Jian²(

)

1 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
2 Shi -changxu Innovation Center for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
3 The 705 Research Institute of China State Shipbuilding Corporation Limited, Xi'an 710077, China

引用本文:

周一鸣, 韩勇军, 谢光, 郑伟, 肖炎彬, 潘阳, 张健. 一种镍基高温合金的高温HCl腐蚀行为[J]. 金属学报, 2025, 61(5): 770-782.
Yiming ZHOU, Yongjun HAN, Guang XIE, Wei ZHENG, Yanbin XIAO, Yang PAN, Jian ZHANG. High-Temperature Corrosion Behavior of a Nickel-Based Superalloy in HCl-Containing Atmosphere[J]. Acta Metall Sin, 2025, 61(5): 770-782.

全文: PDF(4390 KB) HTML

摘要:

针对极端环境中材料面临的高温、高浓度HCl的苛刻工况，采用XRD、SEM、EDS和EPMA等研究手段，研究了一种镍基高温合金在960 ℃、5%HCl + 0.5%O₂ + Ar (体积分数)气氛条件下的热腐蚀行为，腐蚀时间长达200 h。通过对比不同时间的腐蚀动力学曲线、腐蚀产物种类及分布、截面腐蚀层结构及元素分布，在分析高温合金腐蚀规律的基础上，初步探讨了高温HCl腐蚀机理。结果表明，960 ℃高温下，合金动力学曲线可分为2段：0~75 h及75~200 h，随时间延长，2段曲线均呈先上升后下降的趋势，生成了大量含Mo、Ti、Cr的挥发性氯化物；腐蚀层中，外层富Cr和Ti的氧化物层保护性较差；没有形成连续的Al₂O₃层；富Ta尖晶石相层具有降低金属离子外扩散的作用；未在试片截面腐蚀层中观察到明显的氯化物富集。研究表明，960 ℃高温下，除了气氛中的HCl、O₂以外，通过氯化-氧化过程，而非中温下的活化氧化过程，生成的Cl₂同样参与了反应，并起到加速氧化的作用。

关键词 ：镍基高温合金, 高温HCl腐蚀, 氯化, 氧化, 氯化物

Abstract：

Superalloys are widely used in aviation, aerospace, energy, transportation, and petrochemical industries due to their excellent properties, such as high-temperature strength, plasticity, fracture toughness, oxidation resistance, and hot corrosion resistance. They are primarily employed in aircraft engines and gas turbines within aviation, marine, and power generation sectors. Furthermore, due to the unique properties of superalloys and continuous advancements of superalloy technology, their applications are expanding into increasingly extreme service environments. In order to simulate the harsh working conditions of materials under high temperature and high concentration HCl environment, the hot corrosion behavior of a nickel-based superalloy was investigated at 960 ^oC in a mixed atmosphere of 5%HCl + 0.5%O₂ + Ar (volume fraction) using XRD, SEM, EDS, and EPMA techniques. Hot corrosion tests were conducted for 200 h. Analysis of corrosion kinetics, types and distribution of corrosion products, and cross-sectional elemental mapping revealed two distinct stages (0-75 h and 75-200 h), both showing an initial increase followed by a decrease in corrosion rate. Volatile chlorides containing Mo, Ti, and Cr formed extensively. The corrosion layer exhibited a poorly protective (Cr, Ti)-rich oxide layer, while no continuous Al₂O₃ layer was observed. The Ta-rich spinel layer inhibited outward diffusion of metal ions. The corrosion layer of the experimental alloy did not exhibit any significant chloride concentration on its cross-section. In addition to HCl and O₂ in the atmosphere, Cl₂ generated through chlorination and oxidation processes reacted with the alloy and played an important role in accelerating oxidation at 960 ^oC, without evidence of intermediate-temperature activated oxidation.

Key words： nickel-based superalloy high-temperature HCl-containing corrosion chlorination oxidation chloride

收稿日期: 2023-02-20

ZTFLH:

TG132.3

基金资助:国家重点研发计划项目(2021YFA1600603);航空发动机及燃气轮机基础科学中心项目(P2022-C-IV-001-001);国家自然科学基金项目(52271042);国家自然科学基金项目(51911530154);国家自然科学基金项目(91860201);国家自然科学基金项目(U2141206);两机基础研究项目(J2019-VI-0010-0124)

通讯作者: 谢光，gxie@imr.ac.cn，主要从事高温合金研发及同步辐射应用研究；
张健，jianzhang@imr.ac.cn，主要从事高温合金研发

Corresponding author: XIE Guang, professor, Tel: (024)23748882, E-mail: gxie@imr.ac.cn;
ZHANG Jian, professor, Tel: (024)23911196, E-mail: jianzhang@imr.ac.cn

作者简介: 周一鸣，男，1998年生，博士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2023.00070 或 https://www.ams.org.cn/CN/Y2025/V61/I5/770

图1 热腐蚀实验试片尺寸

图2 高温HCl腐蚀实验设备示意图

图3 镍基高温合金热处理态显微组织的SEM像

图4 镍基高温合金在960 ℃含5%HCl气氛中腐蚀0~200 h的动力学曲线散点及分段拟合结果

图5 镍基高温合金在960 ℃含5%HCl气氛中腐蚀不同时间后的表面宏观形貌

图6 镍基高温合金表面剥落面积随腐蚀时间的变化

图7 镍基高温合金在960 ℃含5%HCl气氛中腐蚀不同时间后表面腐蚀产物的XRD谱、设备冷凝端挥发性腐蚀产物的实物图及其XRD谱

表1 镍基高温合金在960 ℃含5%HCl气氛中腐蚀不同时间后腐蚀产物的XRD物相分析结果

图8 镍基高温合金在960 ℃含5%HCl气氛中腐蚀不同时间后表面微观形貌的SEM背散射电子(BSE)像

图9 镍基高温合金在960 ℃含5%HCl气氛中腐蚀不同时间后截面形貌的SEM-BSE像

图10 镍基高温合金腐蚀产物厚度随腐蚀时间的变化

图11 镍基高温合金腐蚀不同时间后截面沿晶界内氧化形貌的SEM-BSE像

图12 镍基高温合金在960 ℃含5%HCl气氛中腐蚀不同时间后截面形貌的SEM-BSE像及EPMA元素面分布

图13 不同元素M不同温度下的反应Gibbs自由能变化(ΔG)

图14 在960 ℃条件下Al、Ti、Cr氧化及氯化反应的ΔG

表2 镍基高温合金主要元素对应的氯化物的熔点和沸点[23] (K)

图15 在960 ℃条件下不同氯化物被氧化的ΔG

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