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Article(id=1240648784707899576, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240648781595725960, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.05.030, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1714233600000, receivedDateStr=2024-04-28, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773723320413, onlineDateStr=2026-03-17, pubDate=1727712000000, pubDateStr=2024-10-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773723320413, onlineIssueDateStr=2026-03-17, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773723320413, creator=13701087609, updateTime=1773723320413, updator=13701087609, issue=Issue{id=1240648781595725960, tenantId=1146029695717560320, journalId=1235980550691926019, year='2024', volume='44', issue='5', pageStart='1', pageEnd='184', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773723319672, creator=13701087609, updateTime=1773824608750, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241073618831078097, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240648781595725960, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241073618831078098, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1240648781595725960, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=148, endPage=152, ext={EN=ArticleExt(id=1240648787916542256, articleId=1240648784707899576, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Microstructure and Wear Resistance of FeCoCrNiMn High-Entropy Alloy Coating by High-Speed Laser Cladding Technology, columnId=1236276108207902848, journalTitle=Mining and Metallurgical Engineering, columnName=MATERIALS, runingTitle=null, highlight=null, articleAbstract=

A FeCoCrNiMn high-entropy alloy (HEA) coating was prepared on the 201 stainless steel surface by adopting high-speed laser cladding technology, and then the microstructure, phase distribution, microhardness of FeCoCrNiMn coating, as well as its wear properties in dry sliding condition were all investigated. It is found that such laser cladded FeCoCrNiMn HEA coating consists of a single FCC structure, with no obvious cracks observed. It also forms a good metallurgical bond with the substrate. The microhardness of the coating is around (439±2.1) HV, nearly two times that of 201 stainless steel substrate, and the strengthening mechanisms mainly include strengthening by grain refinement and solid solution strengthening. Also, the FeCoCrNiMn coating presents an obviously better wear resistance than 201 stainless steel, with an average friction factor of 0.246 and a specific wear rate of about 2.59×10-6 mm3/(N·m). The wear mechanisms for it include adhesive and abrasive wear. It is concluded that such FeCoCrNiMn HEA coating prepared by high-speed laser cladding technology can significantly improve the surface hardness, wear resistance and service life of machine components.

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采用高速激光熔覆技术在201不锈钢表面制备了FeCoCrNiMn高熵合金熔覆层，研究了FeCoCrNiMn高熵合金熔覆层显微组织、相分布、显微硬度及干滑动磨损性能。结果表明，FeCoCrNiMn高熵合金熔覆层由单一的FCC固溶体组成，熔覆层未产生明显裂纹等缺陷，并与基体形成了良好的冶金结合。FeCoCrNiMn高熵合金熔覆层的显微硬度（439±2.1）HV，约为201不锈钢基体显微硬度的2倍。涂层的强化机制主要为细晶强化和固溶强化。高速激光熔覆技术制备的FeCoCrNiMn高熵合金熔覆层具有良好的耐磨性，平均摩擦因数为0.246，比磨损率2.59×10-6 mm3/（N·m），磨损机理为黏着磨损和磨粒磨损，其耐磨性明显优于201不锈钢基体。采用高速激光熔覆技术制备的FeCoCrNiMn高熵合金熔覆层可显著提升机床部件的表面硬度、耐磨损性能和服役寿命。

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王海威（1981—），男，河南项城人，硕士，副教授，主要研究方向为纳米结构材料的设计、制备及组装。E-mail：

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王海威（1981—），男，河南项城人，硕士，副教授，主要研究方向为纳米结构材料的设计、制备及组装。E-mail：

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王海威（1981—），男，河南项城人，硕士，副教授，主要研究方向为纳米结构材料的设计、制备及组装。E-mail：

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（a）涂层顶部；（b）涂层中部；（c）涂层底部

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（a）FeCoCrNiMn高熵合金涂层的微观形貌；（b）Fe元素；（c）Cr元素；（d）Mn元素；（e）Ni元素；（f）Co元素

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（a）201不锈钢基体；（b）FeCoCrNiMn高熵合金涂层

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样品名称磨损体积/mm3比磨损率/[mm3·（N·m）-1]
201不锈钢基体6.83×10-64.82×10-6
FeCoCrNiMn熔覆层3.01×10-62.59×10-6
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高熵合金涂层和201不锈钢基体的磨损体积和比磨损率

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样品名称磨损体积/mm3比磨损率/[mm3·（N·m）-1]
201不锈钢基体6.83×10-64.82×10-6
FeCoCrNiMn熔覆层3.01×10-62.59×10-6
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高速激光熔覆FeCoCrNiMn高熵合金熔覆层组织及耐磨性研究
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王海威 , 肖文波
矿冶工程杂志 | 材料 2024,44(5): 148-152
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矿冶工程杂志 | 材料 2024, 44(5): 148-152
高速激光熔覆FeCoCrNiMn高熵合金熔覆层组织及耐磨性研究
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王海威 , 肖文波
作者信息
  • 南昌航空大学　科技学院，江西　共青城　332020

    • 王海威（1981—），男，河南项城人，硕士，副教授，主要研究方向为纳米结构材料的设计、制备及组装。E-mail：

Microstructure and Wear Resistance of FeCoCrNiMn High-Entropy Alloy Coating by High-Speed Laser Cladding Technology
Haiwei WANG , Wenbo XIAO
Affiliations
  • College of Science and Technology, Nanchang Aviation University, Gongqingcheng 332020, Jiangxi, China
出版时间: 2024-10-01 doi: 10.3969/j.issn.0253-6099.2024.05.030
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摘要
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采用高速激光熔覆技术在201不锈钢表面制备了FeCoCrNiMn高熵合金熔覆层，研究了FeCoCrNiMn高熵合金熔覆层显微组织、相分布、显微硬度及干滑动磨损性能。结果表明，FeCoCrNiMn高熵合金熔覆层由单一的FCC固溶体组成，熔覆层未产生明显裂纹等缺陷，并与基体形成了良好的冶金结合。FeCoCrNiMn高熵合金熔覆层的显微硬度（439±2.1）HV，约为201不锈钢基体显微硬度的2倍。涂层的强化机制主要为细晶强化和固溶强化。高速激光熔覆技术制备的FeCoCrNiMn高熵合金熔覆层具有良好的耐磨性，平均摩擦因数为0.246，比磨损率2.59×10-6 mm3/（N·m），磨损机理为黏着磨损和磨粒磨损，其耐磨性明显优于201不锈钢基体。采用高速激光熔覆技术制备的FeCoCrNiMn高熵合金熔覆层可显著提升机床部件的表面硬度、耐磨损性能和服役寿命。

高速激光熔覆  /  熔覆层  /  相组成  /  耐磨性  /  高熵合金  /  FeCoCrNiMn  /  显微硬度

A FeCoCrNiMn high-entropy alloy (HEA) coating was prepared on the 201 stainless steel surface by adopting high-speed laser cladding technology, and then the microstructure, phase distribution, microhardness of FeCoCrNiMn coating, as well as its wear properties in dry sliding condition were all investigated. It is found that such laser cladded FeCoCrNiMn HEA coating consists of a single FCC structure, with no obvious cracks observed. It also forms a good metallurgical bond with the substrate. The microhardness of the coating is around (439±2.1) HV, nearly two times that of 201 stainless steel substrate, and the strengthening mechanisms mainly include strengthening by grain refinement and solid solution strengthening. Also, the FeCoCrNiMn coating presents an obviously better wear resistance than 201 stainless steel, with an average friction factor of 0.246 and a specific wear rate of about 2.59×10-6 mm3/(N·m). The wear mechanisms for it include adhesive and abrasive wear. It is concluded that such FeCoCrNiMn HEA coating prepared by high-speed laser cladding technology can significantly improve the surface hardness, wear resistance and service life of machine components.

high-speed laser cladding  /  cladded coating  /  phase composition  /  wear resistance  /  high-entropy alloy (HEA)  /  FeCoCrNiMn  /  microhardness
王海威, 肖文波. 高速激光熔覆FeCoCrNiMn高熵合金熔覆层组织及耐磨性研究. 矿冶工程杂志, 2024 , 44 (5) : 148 -152 . DOI: 10.3969/j.issn.0253-6099.2024.05.030
Haiwei WANG, Wenbo XIAO. Microstructure and Wear Resistance of FeCoCrNiMn High-Entropy Alloy Coating by High-Speed Laser Cladding Technology[J]. Mining and Metallurgical Engineering, 2024 , 44 (5) : 148 -152 . DOI: 10.3969/j.issn.0253-6099.2024.05.030
正文
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高熵合金是由5种或5种以上合金元素以等物质的量比组成的新型合金[1]。高熵合金的相组成通常为简单的固溶体结构，如面心立方、体心立方、密排六方结构和一些较为稳定的金属间化合物[2]。其中，FeCoCrNiMn高熵合金因其优越的力学性能、良好的耐磨性和耐腐蚀性能受到广泛研究[3]。目前，可采用磁控溅射、热喷涂、激光熔覆等技术制备FeCoCrNiMn高熵合金涂层[4]。其中，激光熔覆技术采用高能激光束加热金属基体表面的高熵合金粉末，熔化的金属粉末在基体表面形成涂层，该技术已成功应用于表面强化和再制造领域[5-7]。然而，由于激光熔覆技术涂层制备效率较低，表面粗糙度高，无法满足快速加工的要求。文献[8]提出了高速激光熔覆技术，以突破传统激光熔覆的低效率瓶颈。高速激光熔覆技术有望在表面改性方面发挥重要作用，实现气动活塞杆等旋转部件的耐磨、耐腐蚀防护涂层的制备[9-12]。研究表明，高速激光熔覆的高沉积速度和过冷却促进了超细晶结构的生长[13-14]。文献[15]研究了高速激光熔覆制备的FeCoCrNiMn高熵合金涂层在最大沉积速度3 m/min时的耐蚀性。然而，已有研究并没有系统分析FeCoCrNiMn高熵合金涂层的微观结构和耐磨性。本文综合评价了高速激光熔覆技术制备的FeCoCrNiMn高熵合金涂层的微观结构、相结构和磨损性能，可为高速激光熔覆制备高性能高熵合金耐磨涂层提供理论依据。
1　实验方法
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1.1　实验材料及工艺参数
实验所用基体材料为机床部件用201不锈钢钢管，基体外径200 mm，管壁厚度10 mm。涂层材料选用由气雾化法制备的等物质的量比的FeCoCrNiMn高熵合金粉末，粉末粒径53～105 μm。
采用高速激光熔覆技术以20 m/min的沉积速度制备FeCoCrNiMn高熵合金涂层，高纯氩气作为载气和保护气，流量16 L/min；激光功率3 500 W，搭接率50%，送粉速度15 g/min，光斑直径2.0 mm。
1.2　微观结构表征
将制备的FeCoCrNiMn高熵合金涂层加工成10 mm×10 mm×5 mm方形试样，然后进行常规研磨和抛光，采用王水（HCl与HNO3体积比3∶1）蚀刻FeCoCrNiMn高熵合金涂层横截面，用于微观结构表征。采用光学显微镜和扫描电子显微镜研究FeCoCrNiMn涂层的显微组织和元素分布。采用电子背散射衍射仪（EBSD）对涂层晶体取向进行表征。通过X射线衍射仪对涂层的相结构进行检测，扫描速率为2（°）/min，角范围为10°～90°。
使用维氏硬度计在涂层的横截面上进行显微硬度测试，测试载荷为200g，测试时间15 s。利用往复摩擦磨损试验机测试FeCoCrNiMn高熵合金涂层在载荷10 N下的摩擦性能，以半径3 mm的GCr15钢球为摩擦副，实验参数为往复长度7 mm，往复速度1 000 mm/min，持续时间20 min。FeCoCrNiMn高熵合金涂层的比磨损率可由公式（1）[16]进行计算：
式中：V为涂层经干滑动磨损后的磨损体积，mm3；S为涂层的磨痕长度，mm；L为磨损过程中所施加的载荷，N。
2　实验结果讨论
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2.1　FeCoCrNiMn高熵合金涂层相组成分析
FeCoCrNiMn高熵合金涂层的XRD图谱如图1所示。由图1可见，FeCoCrNiMn高熵合金涂层由单一的面心立方晶格（FCC）固溶体组成。标准FCC固溶体的衍射峰角度分别为43.58°、50.79°和74.69°。而FeCoCrNiMn高熵合金涂层的衍射峰角度分别为43.78°、50.95°和74.99°，表明FeCoCrNiMn高熵合金涂层的FCC固溶体的衍射峰产生了偏移。
高速激光熔覆过程中存在较大热应力，导致FCC结构产生严重的晶格畸变；此外，高熵合金在凝固过程中同样会产生晶格畸变效应，导致衍射角发生偏移[17]。这种严重的晶格畸变效应产生固溶强化作用，从而提升FCC相的强度和硬度。
2.2　微观组织形貌
高速激光熔覆FeCoCrNiMn涂层的顶部-中部-底部金相组织形貌如图2所示。涂层顶部组织主要由枝晶和等轴晶组成，涂层组织细小，没有裂纹和气孔生成，表明所选用的工艺参数适用于高速激光熔覆高熵合金。涂层中部观察到枝晶和等轴晶生成，表明涂层内部晶体结构符合非平衡凝固过程中晶体生长规律。在涂层底部观察到基体与涂层结合区生成了一层较薄的平面晶，这是结合区温度梯度和冷却速度的比值较大，导致平面晶的生成[18]，并且涂层与基体间未形成孔隙、裂纹，表明基体与涂层间形成了良好的冶金结合。
FeCoCrNiMn高熵合金涂层SEM形貌及元素分布如图3所示。Fe、Co、Cr、Ni元素主要富集在枝晶，而Mn元素主要富集在枝晶间。这可由非平衡凝固过程中的固液分配系数来进行解释。文献[19]对Fe、Co、Cr、Ni、Mn的固液分配系数进行计算，Fe、Co、Cr、Ni的固液分配系数为1.02～1.06，而Mn元素的固液分配系数为0.75～0.83，固液分配系数小于1时，元素更倾向于在枝晶间富集，因此Mn元素存在枝晶间区域偏析。
FeCoCrNiMn高熵合金涂层的反极图如图4所示，由Channel 5软件分析后得知，FeCoCrNiMn熔覆层的晶粒尺寸为53.1 μm。高速激光熔覆过程中存在马拉高尼效应，导致FeCoCrNiMn高熵合金熔覆层的晶体取向产生随机性，因此没有形成明显的织构。
图5为FeCoCrNiMn高熵合金涂层局部晶粒之间的平均取向偏差（KAM）柱状分布图。KAM主要用于研究样品的局部塑性应变和位错密度[20]。KAM数值主要在0～1区间分布，经计算FeCoCrNiMn高熵合金涂层的KAM平均值为0.45。此外，KAM数值与几何必要位错（GND）相关。GND为非均匀变形中的统计储存位错形成的，其位错密度ρ可通过KAM值进行计算[21]：
式中：μ为EBSD实验的步长（1 μm）；b为伯格斯矢量（2.35×10-10）。经计算，FeCoCrNiMn高熵合金涂层的位错密度ρ为3.82×1015/m。较高的位错密度可以阻碍变形过程中裂纹扩展，提高材料的韧性[22]。
2.3　显微硬度
图6为涂层截面顶端到基体处的显微硬度曲线。FeCoCrNiMn涂层的显微硬度为（439±2.1）HV，201不锈钢基体的显微硬度为（231±2.3）HV。FeCoCrNiMn涂层具有较高显微硬度是固溶强化和细晶强化协同作用的结果。XRD结果（图1）表明，高熵合金涂层中的FCC相具有较强的晶格畸变效应，导致FCC相的固溶强化效应增大，从而引起其硬度升高[23]。此外，高速激光熔覆技术具有极快的冷却速度，凝固速度很快，晶粒得到细化，高熵合金涂层出现细晶强化作用[22]。因此，高熵合金涂层具有较高硬度是由固溶强化和细晶强化共同作用所致。
2.4　磨损实验
表1为FeCoCrNiMn高熵合金涂层和201不锈钢基体在往复滑动摩擦作用下的磨损体积和比磨损率。FeCoCrNiMn高熵合金涂层的比磨损率约为201不锈钢基体的53.73%，表明高熵合金涂层具有更优异的耐磨性。
FeCoCrNiMn高熵合金涂层和201不锈钢基体在干摩擦磨损条件下的摩擦因数随时间变化曲线如图7所示。FeCoCrNiMn高熵合金涂层的平均摩擦因数为0.246，201不锈钢基体的平均摩擦因数为0.362，高熵合金涂层具有较低的摩擦因数。在磨损初始阶段，高熵合金涂层具有较高的硬度和抗变形能力，导致涂层与摩擦副间产生较大摩擦力，因此高熵合金涂层的摩擦因数在初始阶段波动较为明显；随着磨损的持续，涂层与摩擦副间的摩擦力降低，摩擦因数下降并趋于平稳。而不锈钢基体硬度较低，抗变形能力较差，在磨损过程中表面不断发生切削和脱落，磨损面的粗糙度不断增加，摩擦因数逐渐升高。
为了研究FeCoCrNiMn高熵合金涂层在干滑动磨损条件下的磨损机理，采用扫描电子显微镜观察高熵合金涂层和201不锈钢基体的磨损形貌，见图8。
201不锈钢基体的磨损表面存在大量黏着痕和犁沟，表明其主要磨损机制为黏着磨损和磨粒磨损。201不锈钢基体硬度较低，在磨损过程中容易与摩擦副发生冷焊，导致基体与摩擦副粘连并引起材料脱落，从而产生黏着磨损；此外，脱落的碎屑重新进入磨损体系，进一步加剧了磨粒磨损。
在FeCoCrNiMn高熵合金涂层的磨痕表面同样观察到黏着痕和犁沟，但黏着痕显著减少。FeCoCrNiMn高熵合金涂层具有较高的硬度和抗变形能力，可有效减少涂层因冷焊作用而引起的脱落，使黏着磨损趋势减弱。并且根据Archard定律[24]，材料的硬度与耐磨性成正比，因此，FeCoCrNiMn高熵合金涂层的耐磨性显著优于201不锈钢基体。FeCoCrNiMn高熵合金涂层的磨损机理为黏着磨损和磨粒磨损，且以磨粒磨损为主。
3　结论
收起
1）FeCoCrNiMn高熵合金涂层与201不锈钢基体呈现良好的冶金结合，涂层无裂纹等缺陷。高熵合金涂层的相组成为单一的FCC固溶体结构，涂层组织由等轴晶和枝晶组成。
2）FeCoCrNiMn高熵合金涂层和201不锈钢基体的显微硬度分别为（439±2.1）HV和（231±2.3）HV。FeCoCrNiMn高熵合金涂层的强化机制为固溶强化和细晶强化。
3）FeCoCrNiMn高熵合金涂层和201不锈钢基体的平均摩擦因数分别为0.246和0.362，比磨损率分别为2.59×10-6 mm3/（N·m）和4.82×10-6 mm3/（N·m）。高速激光熔覆技术制备的FeCoCrNiMn高熵合金涂层具有优异的耐磨性，其磨损机理为磨粒磨损和黏着磨损，且磨粒磨损为主要磨损机制。
基金
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  • 国家自然科学基金(12064027)
  • 江西省教育厅科技项目(GJJ2204302; GJJ2204305)
  • 江西省高层次高技能领军人才培养工程(2022-63)
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2024年第44卷第5期
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doi: 10.3969/j.issn.0253-6099.2024.05.030
  • 接收时间：2024-04-28
  • 首发时间：2026-03-17
  • 出版时间：2024-10-01
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  • 收稿日期：2024-04-28
基金
国家自然科学基金(12064027)
江西省教育厅科技项目(GJJ2204302; GJJ2204305)
江西省高层次高技能领军人才培养工程(2022-63)
作者信息
    南昌航空大学　科技学院，江西　共青城　332020
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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
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多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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