激光粉末床熔融成形<strong>CoCrNi</strong>中熵合金的高温热腐蚀行为

doi:10.11902/1005.4537.2025.170

中国腐蚀与防护学报

2026, Vol. 46

Issue (1): 115-125 CSTR: 32134.14.1005.4537.2025.170 DOI: 10.11902/1005.4537.2025.170

增材制造与腐蚀专题

本期目录 | 过刊浏览

激光粉末床熔融成形CoCrNi中熵合金的高温热腐蚀行为

周小包¹, 王子腾², 任延杰¹^,²(

), 董少阳², 甘浪², 李聪²

^1.浙江科技大学智能制造与能源工程学院杭州 310023
^2.长沙理工大学能源与动力工程学院长沙 410076

Hot Corrosion Behavior of CoCrNi Medium-entropy Alloys Fabricated by Laser Powder Bed Fusion

ZHOU Xiaobao¹, WANG Ziteng², REN Yanjie¹^,²(

), DONG Shaoyang², GAN Lang², LI Cong²

^1.School of Intelligent Manufacturing and Energy Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, China
^2.Department of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410076, China

引用本文:

周小包, 王子腾, 任延杰, 董少阳, 甘浪, 李聪. 激光粉末床熔融成形CoCrNi中熵合金的高温热腐蚀行为[J]. 中国腐蚀与防护学报, 2026, 46(1): 115-125.
Xiaobao ZHOU, Ziteng WANG, Yanjie REN, Shaoyang DONG, Lang GAN, Cong LI. Hot Corrosion Behavior of CoCrNi Medium-entropy Alloys Fabricated by Laser Powder Bed Fusion[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(1): 115-125.

全文: PDF(17789 KB) HTML

摘要:

采用电化学阻抗谱技术研究激光粉末床熔融(LPBF)成形和轧制CoCrNi中熵合金(MEA)在650 ℃高温环境中受50%KCl + 50%Na₂SO₄ (质量分数)混合盐膜作用时的腐蚀行为。结果表明，LPBF成形合金在腐蚀周期内呈双容抗弧响应，而轧制合金在腐蚀初期呈双容抗特征，随着时间延长逐渐转变为扩散特征。微观表征显示，LPBF成形合金表面形成由Co₃O₄、NiO、Ni₃S₂和Cr₂O₃组成的多元产物层结构；而轧制合金表面仅生成单一Cr₂O₃，且伴随严重的内氧化。两种合金的晶界密度和晶界特征分布影响了金属原子和腐蚀介质的扩散行为，进而导致其电化学腐蚀行为及腐蚀产物膜结构存在差异。

关键词 ：热腐蚀, 激光粉末床熔融, CoCrNi中熵合金, 电化学阻抗谱, 微观组织

Abstract：

Herein, the corrosion behavior of two CoCrNi medium entropy alloys (MEA) with the same chemical composition, but prepared by laser powder bed fusion (LPBF) and rolling respectively, was comparatively investigated beneath a molten mixed salt film of 50%KCl + 50%Na₂SO₄ (mass fraction) at 650 ^oC by means of electrochemical impedance spectroscopy. The results reveal that the LPBF-fabricated alloy exhibits a double capacitive response, whereas the rolled alloy displays a transition from double capacitive characteristics to diffusion-dominated behavior with increasing corrosion time. Microscopic characterization shows that the LPBF-fabricated alloy surface forms a layered multi-product consisting of Co₃O₄, NiO, Ni₃S₂ and Cr₂O₃, while the rolled alloy surface generates only a single Cr₂O₃, accompanied by severe internal oxidation. The distinct corrosion behavior may be attributed to the influence of grain boundary density and grain boundary distribution characteristics on the metal atom diffusion and corrosive medium permeation, thereby affecting the characteristics of electrochemical impedance spectra and the composition and structure of corrosion product films.

Key words： hot corrosion laser powder bed fusion CoCrNi MEA electrochemical impedance spectroscopy microstructure

收稿日期: 2025-06-06 32134.14.1005.4537.2025.170

ZTFLH:

TG174

基金资助:国家自然科学基金(52171066);国家自然科学基金(52175129)

通讯作者: 任延杰，E-mail：yjren@zust.edu.cn，研究方向为中熵合金

作者简介: 周小包，1994年出生，2024年毕业于湘潭大学，获博士学位。现就职于浙江科技大学，讲师，主要研究方向为能源材料腐蚀与防护，近5 年以第一/通讯作者在Corrosion Science、Bioelectrochemistry 等期刊发表SCI论文8篇。
任延杰，1979 年出生，2008 年毕业于中国科学院金属研究所，获博士学位。现就职于浙江科技大学，教授、硕士生导师，中国腐蚀与防护学会高温专业委员会委员。主要从事动力电池关键材料、新能源材料、动力设备高温腐蚀与防护等方面的研究。先后主持国家自然科学基金、省自然科学基金等项目10余项。在国内外权威期刊上发表论文50 余篇，出版学术专著1 部、授权发明专利10余项。获湖南省科技进步三等奖2项、中国腐蚀与防护学会科学技术一、二等奖各1项。

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.170 或 https://www.jcscp.org/CN/Y2026/V46/I1/115

图1 LPBF用CoCrNi MEA粉末的形貌、粒径分布和扫描策略示意图

图2 熔盐电化学测试系统

图3 LPBF CoCrNi和轧制CoCrNi合金的金相显微结构和XRD谱图

图4 LPBF CoCrNi和轧制CoCrNi合金的EBSD结构表征图集

图5 LPBF CoCrNi MEA在高温盐膜腐蚀下的阻抗特征

图6 轧制CoCrNi MEA在高温盐膜腐蚀下的阻抗特征

图7 LPBF CoCrNi和轧制CoCrNi合金的拟合等效电路

表1 LPBF和轧制CoCrNi MEA在高温盐膜腐蚀下的电化学阻抗谱拟合参数

图8 LPBF和轧制CoCrNi MEA在50%KCl + 50%Na2SO4盐膜腐蚀48 h后的XRD图谱

图9 LPBF CoCrNi MEA在50%KCl + 50%Na2SO4盐膜腐蚀48 h后的截面形貌和元素EDS分布图

图10 轧制CoCrNi MEA在50%KCl + 50%Na2SO4盐膜腐蚀48 h后的截面形貌和元素EDS分布图

图11 LPBF与轧制CoCrNi MEA在50%KCl-50%Na2SO4熔融盐膜中的腐蚀机理示意图

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