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Article(id=1240631735122195237, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240631729627648823, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.03.031, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1700841600000, receivedDateStr=2023-11-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773719255476, onlineDateStr=2026-03-17, pubDate=1717171200000, pubDateStr=2024-06-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773719255476, onlineIssueDateStr=2026-03-17, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773719255476, creator=13701087609, updateTime=1773719255476, updator=13701087609, issue=Issue{id=1240631729627648823, tenantId=1146029695717560320, journalId=1235980550691926019, year='2024', volume='44', issue='3', pageStart='1', pageEnd='181', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773719254166, creator=13701087609, updateTime=1773724083554, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1240651985603580488, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240631729627648823, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1240651985603580489, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240631729627648823, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=145, endPage=148, ext={EN=ArticleExt(id=1240631735470322493, articleId=1240631735122195237, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Microstructure and Corrosion Resistance of Laser Cladded Coating of Medium-Entropy Alloy CoCrNi on Surface of Stainless Steel for Automobile, columnId=1236276108207902848, journalTitle=Mining and Metallurgical Engineering, columnName=MATERIALS, runingTitle=null, highlight=null, articleAbstract=

In order to improve surface hardness and corrosion resistance of 304 stainless steel, a medium-entropy alloy (CoCrNi) coating was prepared on the surface of 304 stainless steel by laser cladding, and phase composition, element distribution and corrosion resistance of the cladded coating were studied. The results show that the treatment has achieved good metallurgical bonding between the cladded CoCrNi coating and the substrate, with no cracks, pores and other defects. The cladded coating is composed of single FCC phase, and exhibits dendrite and inter-dendrite structure. The elements are uniformly distributed on the cladded coating without obvious segregation. The uniform distribution of Cr element plays a positive role in improving corrosion resistance of the coating. The CoCrNi coating has its polarization resistance (101.65 kΩ) higher than that of 304 substrate (90.56 kΩ), and also significantly higher corrosion resistance.

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为提升车用304不锈钢的表面硬度及耐蚀性，采用激光熔覆技术在304不锈钢表面制备了CoCrNi中熵合金熔覆层，并研究了熔覆层的相组成、元素分布及耐蚀性能。结果表明，CoCrNi中熵合金熔覆层与基体形成了良好的冶金结合，无裂纹、气孔等缺陷；熔覆层由单一FCC相组成，组织为枝晶、枝晶间结构，各元素在熔覆层中均匀分布，无明显偏析现象，Cr元素的均匀分布对提升涂层耐蚀性具有积极作用；CoCrNi中熵合金熔覆层的极化电阻（101.65 kΩ）高于304基体的极化电阻（90.56 kΩ），耐蚀性明显高于304基体。

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曾东保（1980—），男，江西人，讲师，主要研究方向为机械设计及其自动化。E-mail：

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曾东保（1980—），男，江西人，讲师，主要研究方向为机械设计及其自动化。E-mail：

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曾东保（1980—），男，江西人，讲师，主要研究方向为机械设计及其自动化。E-mail：

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（a）熔覆层顶端；（b）结合区形貌

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样品名称Rs/ΩRct/ΩQdl/（μF·cm-2·sn-1）Rp/kΩ
304不锈钢基体0.701 3080.015 0590.56
中熵合金熔覆层10.133×1055.99×10-5101.65
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304不锈钢基体和CoCrNi中熵合金熔覆层的EIS拟合结果

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样品名称Rs/ΩRct/ΩQdl/（μF·cm-2·sn-1）Rp/kΩ
304不锈钢基体0.701 3080.015 0590.56
中熵合金熔覆层10.133×1055.99×10-5101.65
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汽车用不锈钢表面激光熔覆CoCrNi中熵合金熔覆层微观组织及耐蚀性研究
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曾东保 1 , 何毅鹏 2 , 廖文宇 3
矿冶工程杂志 | 材料 2024,44(3): 145-148
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矿冶工程杂志 | 材料 2024, 44(3): 145-148
汽车用不锈钢表面激光熔覆CoCrNi中熵合金熔覆层微观组织及耐蚀性研究
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曾东保1 , 何毅鹏2, 廖文宇3
作者信息
  • 1.江西制造职业技术学院，江西　南昌　330095
  • 2.南华大学　机械工程学院，湖南　衡阳　421001
  • 3.上汽大众汽车有限公司，上海　201805

    • 曾东保（1980—），男，江西人，讲师，主要研究方向为机械设计及其自动化。E-mail：

Microstructure and Corrosion Resistance of Laser Cladded Coating of Medium-Entropy Alloy CoCrNi on Surface of Stainless Steel for Automobile
Dongbao ZENG1 , Yipeng HE2, Wenyu LIAO3
Affiliations
  • 1.Jiangxi Technical College of Manufacturing, Nanchang 330095, Jiangxi, China
  • 2.School of Mechanical Engineering, University of South China, Hengyang 421001, Hunan, China
  • 3.SAIC VOLKSWAGEN Automotive Co Ltd, Shanghai 201805, China
出版时间: 2024-06-01 doi: 10.3969/j.issn.0253-6099.2024.03.031
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摘要
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为提升车用304不锈钢的表面硬度及耐蚀性，采用激光熔覆技术在304不锈钢表面制备了CoCrNi中熵合金熔覆层，并研究了熔覆层的相组成、元素分布及耐蚀性能。结果表明，CoCrNi中熵合金熔覆层与基体形成了良好的冶金结合，无裂纹、气孔等缺陷；熔覆层由单一FCC相组成，组织为枝晶、枝晶间结构，各元素在熔覆层中均匀分布，无明显偏析现象，Cr元素的均匀分布对提升涂层耐蚀性具有积极作用；CoCrNi中熵合金熔覆层的极化电阻（101.65 kΩ）高于304基体的极化电阻（90.56 kΩ），耐蚀性明显高于304基体。

高熵合金  /  熔覆层  /  表面处理  /  激光熔覆  /  CoCrNi  /  中熵合金  /  耐蚀性  /  304不锈钢  /  汽车用材料

In order to improve surface hardness and corrosion resistance of 304 stainless steel, a medium-entropy alloy (CoCrNi) coating was prepared on the surface of 304 stainless steel by laser cladding, and phase composition, element distribution and corrosion resistance of the cladded coating were studied. The results show that the treatment has achieved good metallurgical bonding between the cladded CoCrNi coating and the substrate, with no cracks, pores and other defects. The cladded coating is composed of single FCC phase, and exhibits dendrite and inter-dendrite structure. The elements are uniformly distributed on the cladded coating without obvious segregation. The uniform distribution of Cr element plays a positive role in improving corrosion resistance of the coating. The CoCrNi coating has its polarization resistance (101.65 kΩ) higher than that of 304 substrate (90.56 kΩ), and also significantly higher corrosion resistance.

high-entropy alloy  /  cladded coating  /  surface treatment  /  laser cladding  /  CoCrNi  /  medium-entropy alloy  /  corrosion resistance  /  304 stainless steel  /  automobile material
曾东保, 何毅鹏, 廖文宇. 汽车用不锈钢表面激光熔覆CoCrNi中熵合金熔覆层微观组织及耐蚀性研究. 矿冶工程杂志, 2024 , 44 (3) : 145 -148 . DOI: 10.3969/j.issn.0253-6099.2024.03.031
Dongbao ZENG, Yipeng HE, Wenyu LIAO. Microstructure and Corrosion Resistance of Laser Cladded Coating of Medium-Entropy Alloy CoCrNi on Surface of Stainless Steel for Automobile[J]. Mining and Metallurgical Engineering, 2024 , 44 (3) : 145 -148 . DOI: 10.3969/j.issn.0253-6099.2024.03.031
正文
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高熵合金作为一种多主元素合金，具有优异机械性能、热稳定性和优异耐蚀性能[1-3]。CoCrNi中熵合金源于FeCoCrNiMn高熵合金，但CoCrNi中熵合金的强度和耐蚀性显著优于FeCoCrNiMn高熵合金，因此，CoCrNi中熵合金受到广泛关注[4-6]。由于Cr或Ni等钝化元素的加入，CoCrNi中熵合金在腐蚀环境中具有独特的化学稳定性[7]。CoCrNi中熵合金具有优异的力学性能和耐腐蚀性，已广泛应用于汽车、航空航天、冶金设备等领域[8-11]。
在钢材表面制备CoCrNi中熵合金熔覆层可显著提高钢材综合性能。激光熔覆作为一种先进的表面改性技术，具有组织致密、热影响区小、稀释率低等优点，被广泛应用于汽车用不锈钢表面改性及强化等领域[12]。文献[13]采用激光熔覆技术在1045钢表面制备CoCrNi中熵合金熔覆层，分别研究了熔覆层的微观结构、耐磨性及耐蚀性能，结果表明，涂层为单相FCC结构，并具有多段动电位极化行为，具有良好的耐蚀性。文献[14]采用激光选区熔化技术制备了含有铁基非晶材料的CoCrNi中熵合金，结果表明，当铁基非晶材料含量达到7%时，CoCrNi中熵合金具有优异的耐蚀性。
本文选取等物质的量比的Cr、Co、Ni高纯度粉末，采取激光熔覆技术在304不锈钢表面制备CoCrNi中熵合金熔覆层，分别对中熵合金熔覆层的相组成、元素分布、显微硬度及耐蚀性进行研究，以期制备出具有优异耐蚀性的涂层，拓展中熵合金的应用范围。
1　试验方法
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1.1　材料及试验参数
选用尺寸为200 mm×100 mm×10 mm的304不锈钢为基材。在激光熔覆前，采用碳化硅砂纸对基材进行打磨，去除表面氧化物和夹杂物，随后用丙酮清洗，充分干燥。采用粒径为20～50 μm的Cr、Co、Ni高纯度球形粉末作为激光熔覆的原料。制备中熵合金熔覆层前，将粉末在80 ℃真空干燥12 h。采用TruDiode 3006光纤激光系统进行加工，并采用预制粉末的方式制备中熵合金熔覆层，预制粉末厚度约1.2 mm，搭接率40%，保护器流量18 L/min。激光功率2 000 W，扫描速度600 mm/min，光斑直径3.6 mm。
1.2　金相及显微组织
采用线切割机切取金相试样，并采用砂纸打磨金相试样，随后采用金刚石抛光膏进行抛光，直至表面没有明显划痕。采用X射线衍射仪（XRD）分析中熵合金熔覆层的相组成。采用金相显微镜观察中熵合金熔覆层的金相组织形貌。采用场发射扫描电子显微镜和能谱仪表征熔覆层的微观组织和元素分布。
1.3　电化学腐蚀及显微硬度
选择3.5%NaCl人工海水作为测试介质，在电化学工作站上采用三电极系统（铂电极，参比电极，工作电极）测试304不锈钢基体和CoCrNi中熵合金熔覆层的电化学腐蚀性能。待测样品用环氧树脂固定，待测面积为1 cm×1 cm。试验在室温（22±1）℃下进行，测试循序依次为：开路电位测试、电化学阻抗谱测试和动电位极化曲线测试。电化学阻抗谱测试在开路电位下进行，交流幅值为10 mV，外部测试频率为10-2～105Hz。进行极化曲线测试时，扫描速度为0.5 mV。采用ZsimpWin软件对EIS曲线和极化曲线进行Tafel拟合。采用1.0 V恒电位极化（Vs OCP）测量钝化膜生长引起中熵合金熔覆层样品的电流衰减行为，总测试时间为3 600 s。每个电化学试验重复3次，以确保重复性。
2　试验结果与讨论
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2.1　相组成及微观结构
图1为CoCrNi中熵合金熔覆层和304不锈钢基体的XRD衍射图谱。可以看出，熔覆层的相组成为面心立方相（FCC），最强衍射峰为（111）晶面。有研究表明，FCC相在（111）平面上排列极为致密，晶粒各向异性极强，动态钝化倾向极强[15]。此外，原子通常在（111）面取向上具有更紧密的排列形式和更强的结合能，因此可以表现出更高的力学性能和优异耐磨性[16]。与标准PDF卡（PDF#47-1405）相比，中熵合金熔覆层的衍射峰均有不同程度的左移，这与激光熔覆过程中快速凝固引起的晶格畸变相关[17]。
图2为CoCrNi熔覆层的截面金相组织形貌。由图2可见，CoCrNi熔覆层与304不锈钢基体具有良好的冶金结合，熔覆层内部组织均匀，未产生裂纹、气孔、晶粒粗化等缺陷。CoCrNi熔覆层沿截面竖直向上方向呈现出沿温度梯度方向定向凝固，并呈现典型的胞状晶→树枝晶→等轴晶的晶体形态转变，这是温度梯度分布差异较大引起的[18]。当液相的实际温度低于结晶平衡温度时会产生这种现象。在基体与熔覆层的结合区生成了一层平面晶，这是由于温度梯度与凝固速率的比值较大[19]。
图3为CoCrNi熔覆层SEM组织形貌及元素分布图。由图3可以看出，Co、Cr、Ni 3种元素在熔覆层内均匀分布，无明显偏析现象。Cr元素的均匀分布有利于CoCrNi熔覆层在腐蚀条件下形成致密的钝化膜，提升了CoCrNi熔覆层的耐蚀性能[20]。
此外，结合显微组织形貌及XRD结果可知，CoCrNi中熵合金熔覆层仅存在单一稳定的FCC固溶体相。
2.2　CoCrNi中熵合金熔覆层耐蚀性
图4为CoCrNi中熵合金熔覆层和304不锈钢基体在3.5%NaCl溶液中的电化学测试结果。由图4可以看出，CoCrNi中熵合金熔覆层在阳极区存在明显钝化行为。腐蚀电位（Ecorr）和腐蚀电流（icorr）可以分别反映材料在盐水介质中的热力学腐蚀倾向和动力学腐蚀倾向[21]。CoCrNi中熵合金熔覆层的腐蚀电位和腐蚀电流密度分别为-157.26 mV和1.56×10-7A/cm2，304不锈钢基体的腐蚀电位和腐蚀电流分别为-514.93 mV和1.62×10-6A/cm2。可以看出CoCrNi中熵合金熔覆层的腐蚀电位高于304不锈钢基体，腐蚀电流密度低于304不锈钢基体，表明中熵合金熔覆层具有更为优异的耐蚀性。
在电化学腐蚀过程中，钝化膜的稳定性对合金的抗腐蚀能力具有至关重要作用。图5为CoCrNi中熵合金熔覆层和304不锈钢基体的Nyquist图。电容弧的直径是判断材料耐腐蚀性的重要指标，耐腐蚀优异的材料具有更大的电容弧直径[22]。由图5可以看出，CoCrNi中熵合金熔覆层的电容弧直径远大于304不锈钢基体，说明CoCrNi中熵合金熔覆层具有较高的阻抗模量，表明CoCrNi中熵合金熔覆层的钝化膜在熔覆层与3.5%NaCl溶液之间起到了良好的屏障作用。
图6为CoCrNi中熵合金熔覆层和304不锈钢基体的阻抗模量/频率图。图7为CoCrNi中熵合金熔覆层和304不锈钢基体的相位角/频率图，其中低频部分的阻抗模量可以表示在电化学腐蚀过程中腐蚀介质在材料表面发生了离子入侵，阻抗模量越大，腐蚀程度越小，试样的耐腐蚀性能越好[23]。由图6可见，CoCrNi中熵合金熔覆层低频区的阻抗模量明显高于304不锈钢基体，因此3.5%NaCl溶液对其渗透性差，表明CoCrNi中熵合金熔覆层的耐蚀性很好。这与图5结果一致。相角值可以表征材料的耐蚀性，与材料的耐蚀性呈正相关。由图7可以看出，CoCrNi中熵合金熔覆层的相角值高于304不锈钢基体，表明CoCrNi中熵合金熔覆层具有更强的抗离子侵蚀和抗海水腐蚀能力。
根据图4中明显的钝化行为，选择Rs（QcRc）对阻抗结果进行拟合，结果如表1所示。其中Rs为溶液电阻，Qc和Qdl分别为熔覆层电容和双电层电容，Rc和Rct分别为钝化膜电阻和电荷转移电阻，Rp为极化电阻。CoCrNi中熵合金熔覆层的Rct为3×105Ω，表明其在3.5%NaCl溶液中对电化学反应的抑制能力强，这与图4中CoCrNi中熵合金熔覆层的阳极钝化行为相关。双电层电容Qdl可以反映材料表面钝化膜的致密程度，CoCrNi中熵合金熔覆层的钝化膜密度为5.99×10-5 μF/（cm2·sn-1），说明CoCrNi中熵合金熔覆层样品表面可以形成致密的钝化膜，对基体具有极强的保护能力。此外，CoCrNi中熵合金熔覆层Rp值为101.65 kΩ，说明CoCrNi中熵合金熔覆层表面生成的钝化膜能有效降低离子转移，抑制电偶腐蚀，具有良好的保护效果[24]。
3　结论
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1）采用激光熔覆技术在304不锈钢基体表面成功制备了CoCrNi中熵合金熔覆层，熔覆层组织致密、成分均匀、无裂纹气孔等缺陷，并与基体形成良好冶金结合。
2）CoCrNi中熵合金熔覆层的相组成为单一的FCC相，熔覆层中各元素分布均匀，无明显偏析；Cr元素的均匀分布提升了熔覆层的耐腐蚀性能。
3）在3.5%NaCl人工海水中，CoCrNi中熵合金熔覆层具有较高的腐蚀电位（-157.26 mV）和较低的腐蚀电流密度（1.56×10-7A/cm2），表现出较强的抗腐蚀能力；熔覆层表面存在钝化膜，极化电阻高（101.65 kΩ），对熔覆层、基体表现出很强的保护作用。
基金
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  • 国家自然科学基金(51975270)
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2024年第44卷第3期
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doi: 10.3969/j.issn.0253-6099.2024.03.031
  • 接收时间：2023-11-25
  • 首发时间：2026-03-17
  • 出版时间：2024-06-01
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  • 收稿日期：2023-11-25
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    1.江西制造职业技术学院，江西　南昌　330095
    2.南华大学　机械工程学院，湖南　衡阳　421001
    3.上汽大众汽车有限公司，上海　201805
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2种不同金属材料的力学参数
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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
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红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
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光柄菇属 Pluteus 5 2.39
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