电火花沉积FeCoCrNiCu高熵合金涂层的组织结构与耐蚀性
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摘要
目的通过在45Mn2钢表面进行电火花沉积Fe CoCrNiCu高熵合金涂层,改变其表面性能。方法采用真空吸铸法制备直径为3mm的Fe CoCrNiCu高熵合金电极,采用电火花沉积技术,在45Mn2钢表面制备高熵合金沉积层。通过X射线衍射仪(XRD)、光学显微镜(OM)、扫描电子显微镜(SEM)等分析研究沉积层的相组成、表面形貌、表面粗糙度和显微组织。通过三电极体系对涂层进行极化曲线和电化学阻抗谱(EIS)测试,分析其在3.5%NaCl溶液中的电化学腐蚀行为。结果制备的Fe CoCrNiCu涂层连续、均匀,具有简单的FCC结构,表面呈银灰色橘皮状,厚度约为25μm。涂层表面凸凹不平,为典型的"溅射状"花样形貌,表面粗糙度均方根偏差Rq约为4μm。极化曲线表明,高熵沉积层自腐蚀电位为-0.548 V,较45Mn2基材正移约180m V,腐蚀电流密度为1.59μA/cm~2,约为基材的1/6。电化学阻抗谱EIS测试结果显示,Fe CoCrNiCu高熵合金沉积层较45Mn2基材具有更大的容抗弧半径和极化电阻,其模拟电路可以用R(Q(R(QR)))表示。结论电火花沉积技术是一种极具发展潜力的高熵合金涂层制备技术,制备的Fe CoCrNiCu高熵合金涂层可有效提高基材的耐蚀性能。
The work aims to deposit FeCoCrNiCu high-entropy alloy coating on 45Mn2 steel to improve the surface properties. FeCoCrNiCu high-entropy alloy rod with a dimeter of 3 mm was prepared by copper mold suction casting and the FeCoCrNiCu high-entropy alloy coating was deposited on 45Mn2 steel surface by electro-spark deposition technique. The phase composition, surface morphologies and microstructures of the deposited coatings were analyzed by optical microscope(OM),X-ray diffraction(XRD), and scanning electron microscopy(SEM). The electrochemical corrosion behaviors of the deposited coating in 3.5%NaCl were measured by polarization curves and electrochemical impedance spectroscopy. The prepared FeCoCr Ni Cu coating was continuous and uniform with a simple FCC structure. The surface was silver-gray orange peel and about25 μm thick. The surface of the coating was uneven and showed typical "sputtering" pattern. The root mean square deviation(Rq) of the surface roughness was about 4 μm. The polarization curves showed that the self-corrosion potential of the high-entropy deposits was-0.548 V, which was 180 mV higher than that of 45Mn2 substrates, and the corrosion current density was 1.59 μA/cm~2, which was about 1/6 of that of the substrates. The EIS results of electrochemical impedance spectroscopy showed that the FeCoCrNiCu high-entropy alloy deposit had larger capacitive arc radius and polarization resistance than 45Mn2 substrate, and the analog circuit could be expressed by R(Q(R(QR)). Electro-spark deposition(ESD) is a promising technology for preparing high-entropy alloy coatings. The high-entropy FeCoCrNiCu coating prepared can effectively improve the corrosion resistance of the substrate.
The work aims to deposit FeCoCrNiCu high-entropy alloy coating on 45Mn2 steel to improve the surface properties. FeCoCrNiCu high-entropy alloy rod with a dimeter of 3 mm was prepared by copper mold suction casting and the FeCoCrNiCu high-entropy alloy coating was deposited on 45Mn2 steel surface by electro-spark deposition technique. The phase composition, surface morphologies and microstructures of the deposited coatings were analyzed by optical microscope(OM),X-ray diffraction(XRD), and scanning electron microscopy(SEM). The electrochemical corrosion behaviors of the deposited coating in 3.5%NaCl were measured by polarization curves and electrochemical impedance spectroscopy. The prepared FeCoCr Ni Cu coating was continuous and uniform with a simple FCC structure. The surface was silver-gray orange peel and about25 μm thick. The surface of the coating was uneven and showed typical "sputtering" pattern. The root mean square deviation(Rq) of the surface roughness was about 4 μm. The polarization curves showed that the self-corrosion potential of the high-entropy deposits was-0.548 V, which was 180 mV higher than that of 45Mn2 substrates, and the corrosion current density was 1.59 μA/cm~2, which was about 1/6 of that of the substrates. The EIS results of electrochemical impedance spectroscopy showed that the FeCoCrNiCu high-entropy alloy deposit had larger capacitive arc radius and polarization resistance than 45Mn2 substrate, and the analog circuit could be expressed by R(Q(R(QR)). Electro-spark deposition(ESD) is a promising technology for preparing high-entropy alloy coatings. The high-entropy FeCoCrNiCu coating prepared can effectively improve the corrosion resistance of the substrate.
引文
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[2]ZHANG Yong,ZUO Ting-ting,TANG Zhi,et al.Microstructures and properties of high-entropy alloys[J].Progress in materials science,2014,61:1-93.
[3]MIRACLE D B,SENKOV O N.A critical review of high entropy alloys and related concepts[J].Acta materialia,2017,122:448-511.
[4]CHEN Jian,ZHOU Xue-yang,WANG Wei-li,et al.Areview on fundamental of high entropy alloys with promising high-temperature properties[J].Journal of alloy and compounds,2018,760:15-30.
[5]YE Y F,WANG Q,LU Jian,et al.High-entropy alloy:challenges and prospects[J].Materials today,2016,19(6):349-362.
[6]LIU Jian,LIU Hao,CHEN Pei-jian,et al.Microstructural characterization and corrosion behaviour of AlCoCrFeNiTix high-entropy alloy coatings fabricated by laser cladding[J].Surface and coatings technology,2019,361:63-74.
[7]CHEN Li-jia,BOBZIN K,ZHOU Zheng,et al.Wear behavior of HVOF-sprayed Al0.6TiCrFeCoNi high entropy alloy coatings at different temperatures[J].Surface and coatings technology,2019,358:215-222.
[8]LIAO Wei-bing,LAN Si,GAO Li-bo,et al.Nanocrystalline high-entropy alloy(CoCrFeNiAl0.3)thin-film coating by magnetron sputtering[J].Thin solid films,2017,638:383-388.
[9]WANG Xiao-rong,WANG Zhao-qin,HE Peng,et al.Microstructure and wear properties of CuNiSiTiZr highentropy alloy coatings on TC11 titanium alloy produced by eletrospark-computer numerical control deposited process[J].Surface and coatings technology,2014,283:156-161.
[10]何艳玲,王彦芳,司爽爽,等.ZL101表面电火花沉积Zr基非晶涂层的组织结构[J].表面技术,2018,47(7):236-240.HE Yan-ling,WANG Yan-fang,SI Shuang-shuang,et al.Microstructure of electro-spark deposition Zr-based amorphous coating on ZL101[J].Surface technology,2018,47(7):236-240.
[11]王彦芳,司爽爽,宋增金,等.电火花沉积非晶涂层的组织结构与摩擦磨损性能[J].焊接学报,2018,39(7):121-124.WANG Yan-fang,SI Shuang-shuang,SONG Zeng-jin,et al.Microstructure and tribology behaviors of Zr-based amorphous coating on ZL101 by electro-spark deposition[J].Transactions of the China welding institution,2018,39(7):121-124.
[12]LI Q H,YUE T M,GUO Z N,et al.Microstructure and corrosion properties of AlCoCrFeNi high entropy alloy coatings deposited on AISI 1045 steel by the electrospark process[J].Metallurgical and materials transactions A,2013,44(4):1767-1778.
[13]WANG Xiao-rong,WANG Zhao-qin,LIN Tie-song,et al.Mass transfer trends of AlCoCrFeNi high-entropy alloy coatings on TC11 substrate via eletrospark-computer numerical control deposition[J].Journal of materials processing technology,2017,241:93-102.
[14]WANG Yu-sen,WANG Xiao-rong,WANG Zhao-qin,et al.Preparation and microstructure of AlCoCrFeNi highentropy alloy complex curve coatings[J].Metal science journal,2017,33(5):559-566.
[15]王小荣,王朝琴,何鹏,等.45钢表面高能微弧火花数控化沉积Al CoCrFeNi高熵合金[J].焊接学报,2016,37(10):73-76.WANG Xiao-rong,WANG Zhao-qin,HE Peng,et al.Numerical control deposition of AlCoCrFeNi highentropy alloy on 45 steel by high energy micro arc spark[J].Transactions of the China welding institution,2016,37(10):73-76.
[16]冯玉龙.电火花数控化沉积Fe Co Ni Cu Crx高熵合金涂层的微观结构及耐蚀性研究[D].兰州:兰州交通大学,2016.FENG Yu-long.Study on microstructure and corrosion resistance of FeCoNiCuCrx high entropy alloy coating prepared by electric spark numerical control deposition[D].Lanzhou:Lanzhou Jiaotong University,2016.
[17]YANG X,ZHANG Y.Prediction of high-entropy stabilized solid-solution in multi-component alloys[J].Materials chemistry&physics,2012,132(2-3):233-238.
[18]GUO Sheng,NG Chun,LU Jian,et al.Effect of valence electron concentration on stability of FCC or BCC phase in high entropy alloys[J].Journal of applied physics,2011,109:103505.