2Cr13钢离子渗氮和WCrAlTiSiN离子镀复合处理及电化学行为.pdf

WCIAIIISINION(1)13/-141doi:10.11933/1007-9289.202210050021SS.2024Feb.CHINASURFACEENGINEERING2024年2 月No.1Vol.37国面中表第37 卷#第1期程2Cr13钢离子渗氮和WCrAITiSiN离子镀复合处理及电化学行为卢金鹏1张念武2王政伟1张哲浩3邵明昊4李杨1何永勇3（1.烟台大学核装备与核工程学院烟台264005;2.中国船级社青岛分社上青岛266072;3.清华大学摩擦学国家重点实验室北京100084;4.烟台大学机电汽车工程学院烟台264005)摘要：马氏体不锈钢的常规表面改性方法基本局限在单一化学热处理或镀膜，对表面性能的提升有限。对2 Cr13不锈钢进行离子渗氮与多弧离子镀WCrAITiSiN纳米多层涂层复合强化处理，研究其在天然海水环境中的耐腐蚀性能。采用不同的表面强化工艺，即未处理（Untreated）、低温渗氮处理（LPN）、高温渗氮处理（HPN）、单一镀膜处理（Coating）、低温渗氮十镀膜处理（LPN+C）和高温渗氮十镀膜处理（HPN+C）。采用X射线衍射、光学显微镜、透射电子显微镜和维氏硬度计对不同样品的组织结构、化学成分和硬度等进行表征。采用电化学阻抗法和动态电位极化法对2 Cr13在天然黄海海水中的电化学行为进行测试。试验结果表明：WCrAITiSiN涂层可在一定程度上提升腐蚀性能，但是溶液中的CI通过较薄单一涂层的缺陷侵入基体。LPN样品因渗氮层的存在提升了一定的耐腐蚀性能，而HPN样品因为渗氮温度过高而导致CrN大量析出，使得样品表面出现“贫Cr”现象，耐腐蚀性能下降。复合处理样品的渗氮层-WCrAITiSiN涂层可形成保护屏障，有效阻止电荷转移和电流从阳极流向阴极，提高2 Cr13钢在海水环境中的耐腐蚀性能。通过离子渗氮-多弧离子镀WCrAITiSiN纳米涂层复合强化方法可有效提升马氏体不锈钢在海水中的耐腐蚀性能。关键词：氮化物涂层；离子渗氮；多弧离子镀；显微硬度；电化学腐蚀中图分类号：TG174；T G 115Electrochemical Behavior of 2Cr13 Steels by Duplex Treatment ofPlasma Nitriding and WCrAITiSiN Ion Plating2LU JinpengZHANG NianwuWANG Zhengwei1ZHANG Zhehao3SHAO MinghaoLI Yang IHHE Yongyong34(1.School of Nuclear Equipment and Nuclear Engineering,Yantai University,Yantai 264005,China;2.China Classification Society Qingdao Branch,Qingdao 266072,China;3.State Key Laboratory of Tribology,Tsinghua University,Beijing 100084,China;4.School of Electromechanical Automobile Engineering,Yantai University,Yantai 264005,China)Abstract:The poor corrosion resistance of 2Crl3 steel significantly affects its service life in marine environments,such aspetrochemical,naval,and ocean engineering.Currently,strengthening methods for martensitic stainless steel are mainly limited to asingle chemical heat treatment or coating,and there is relatively litle research on composite treatment processes,especially nitriding基金项目：国家自然科学基金（52 17 5192）。Fund:National Natural Science Foundation of China(52175192).收稿日期：2 0 2 2-10-0 5；修改日期：2 0 2 3-0 5-2 4；接受日期：2 0 2 3-0 6-0 5；上线日期：2 0 2 3-12-15。Received October 5,2022;Revised May 24,2023;Accepted in revised form June 5,2023;Available online December 15,2023.引用格式：卢金鹏，张念武，王政伟，等.2 Cr13钢离子渗氮和WCrAITiSiN离子镀复合处理及电化学行为。中国表面工程，2 0 2 4，37(1)：137-147.Citation format:LU Jinpeng,ZHANG Nianwu,WANG Zhengwei,et al.Electrochemical behavior of 2Cr13 steels by duplex treatment of plasma nitriding and138面表中2024年程国and nano-multilayer coating.Plasma nitriding and multi-arc ion plating(WCrAITiSiN multilayer coating)were used for the compositestrengthening of 2Cr13 martensitic stainless steel,and its corrosion resistance in the natural Yellow Seawater environment was studied.2Cr13 was subjected to ion nitriding using an LDMC-20F pulsed glow discharge ion-nitriding furnace.The sample was placed on thecathode of a nitriding furnace,and the internal pressure of the furnace was reduced to 10 Pa.The voltage was adjusted to 750 V with aduty cycle of 73%,and the temperature was adjusted to 440 or 480C.The internal NH3 pressure was maintained at 350 Pa,and thesample was heat-treated for 5 h.Untreated,“LPN,and HPN samples were deposited with(W,Cr,Al,Ti,Si)N multilayer coatingsusing an industrial HCCE-280 cathodic arc evaporation system.Three W(99.99%),three Cr(99.99%),one Al-Ti-Si,and one Al-Tialloy targets were selected.The current parameters for each target were adjusted according to the desired deposition rate.A very thinCr bonding layer was deposited on the polished surface of the sample in an argon atmosphere,followed by the deposition of a CrNtransition layer in a nitrogen atmosphere.Subsequently,in a mixed atmosphere of argon and nitrogen,a CrTiAiSiN layer wasdeposited on three Cr,one Al-Ti,and one Al-Ti-Si targets.Finally,multiple nanoscale WCrAITiN layers were prepared as theoutermost layer using programmed alternating deposition of WCrAITiN and CrWAITiN layers enriched with W and Cr,respectively.The structure,chemical composition,and hardness of the samples were characterized using X-ray diffraction,optical microscopy,transmission electron microscopy,and Vickers hardness testing.The results show that the nitrided sample is mainly composed ofe-Fe2-3N,-Fe4N,and an phases.The surface of the LPN and the HPN samples formed hardened layers of 50 and 90 m thicknesses,respectively.The WCrAITiN coating,with a thickness of 2.3 m,was composed of CrN,W2N,TiN,and AIN phases.The surfacehardness of the untreated sample was low and could not provide sufficient support,leading to an unsatisfactory hardness of the coatedsample.Afer the composite treatment,the surface hardness of 2Cr13 steel increased from approximately 250 HVo.1 to 2 100 HVo.1.The electrochemical behavior of 2Cr13 in natural Yellow Seawater was tested using electrochemical impedance spectroscopy andpotentiodynamic polarization.The results show that all samples exhibited a single equivalent circuit in the EIS spectra.Compared tothe other samples,the“LPN+C sample exhibited excellent corrosion resistance.Compared to the untreated sample,the Ecor value ofthe LPN+C sample increased from-6.54x10-1 V to-4.79x10-I V,the Icor value and corrosion rate decreased by a single order ofmagnitude,while Ret increased by a single order of magnitude.The nitrided layer and WCrAITiSiN coating can formed a protectivebarrier,effectively blocking charge transfer and current flow from anode to cathode.this improved the corrosion resistance of 2Cr13steel in seawater.The composite reinforcement method of ion nitriding and multi-arc ion plating with nanocoating can effectivelyenhance the surface hardness and corrosion resistance of martensitic stainless steel,particularly in seawater environments,therebyextending the service life of martensitic stainless-steel parts in marine applications.Keywords:nitrided coating;plasma nitriding;multi-arc ion plating;microhardness;electrochemical corrosion0前言2Cr13钢是一种应用范围很广泛的马氏体不锈钢，具有较高的强度和良好的力学性能，主要应用于承受冲击载荷较多兼具一定耐蚀性要求的零件。但2 Cr13钢耐磨性和耐腐蚀性较差，不仅限制其在石油化工和海洋工程等领域的应用，也严重影响其使用寿命-3。提高2 Cr13马氏体不锈钢零件的耐腐蚀性，延长零件的使用寿命对工业生产水平的提升具有重要意义。硬质涂层在金属材料防氧化腐蚀方面的发展十分迅速。在工件涂覆一层或多层硬质涂层可以有效地提高材料的硬度、耐腐蚀性能和耐摩擦性能4.5。在物理沉积技术发展的过程中，发现CrN基涂层具有优越的性能，因此在工业中被广泛使用6-8 。研究发现，在CrN 基涂层中加入Ti9、A 1l 10 1、w l 1-12 和 Sil13等元素可以进一步提高涂层的性能，比如，具有优秀化学稳定性和韧性的 CTTiNl14和 CTAIN 涂层15-16 。制造业的快速发展对涂层的性能也有了更高的要求。在工业领域中TiN、Cr N系列的涂层使用较多，缺少对WN系列的纳米多层涂层的研究。在CrN膜层中添加Ti、A l、W 和Si等元素，可以形成具有多种相的纳米涂层，这种涂层相比传统的TiN、CrN涂层来说，硬度更高，耐腐蚀和耐摩擦性能更好，而且具有更好的膜基结合力。BELIARDOUH等17 研究表明，CrCr NCr A IN多层膜具有优秀的耐摩擦性和耐腐蚀性。CHIPATECUA 等18 研究表明物理气相沉积的方法在不锈钢表面沉积CrN涂层可以大大提高在氯化物中的耐腐蚀性。KABIR等10 研究表明在CrN涂层中掺入Al，可以形成致密的铬铝氧化物保护膜，这些富含Al和Cr的氧化物对金属表面具有出色的保护效果，并且可以在氧化过程中阻止氧的向内扩散和金属阳离子的向外扩散。另外，Ti的掺入会提高涂层的磨损性能，提高CrN基涂层的致密性14。HUANG等19 研究表139卢金鹏，等：2 Cr13钢离子渗氮和WCrAITiSiN离子镀复及电化学行为第1期明CrWN涂层表现出优异的力学性能和耐磨性，W元素的存在提高了涂层的整体性能，随着W含量的增加，晶格膨胀和硬度增加。硬质涂层可以给基体带来更好的耐腐蚀性能和耐摩擦性能2 0 ，但是由于涂层本身的硬度要高于基体的表面硬度，如果基体的承载能力不够，有可能会导致涂层失效。而且涂层比较薄，长时间置放于含有CI的溶液中时，也很难抵挡CI的腐蚀，所以具有较好耐腐蚀性的氮化强化层会很好地解决这个问题2 1-2 。HE和 LI 等2 3-2 采用离子渗氮方法对2Cr13表面进行处理，结果表明经过渗氮处理样品的表面硬度、耐腐蚀性和耐摩擦性得到较大的提升。若在涂层沉积之前，先对基体进行渗氮处理，涂层与基体之间的结合力得到提高，承载能力也会大为提升2 7-31。WANG 和 LI 等32-34 在经过渗氮前处理的AISI316L钢上沉积WCrAITiSiN复合涂层，将不同处理的样品进行电化学腐蚀和摩擦磨损试验后，试验结果表明，离子渗氮方法可以在样品表面形成均匀而致密的渗氮层，复合处理后的样品表现出优异的耐腐蚀性能和耐摩擦性。较高的Cr含量使奥氏体不锈钢本身就具有不错的耐腐蚀性，可以应用在恶劣的腐蚀环境下，而马氏体不锈钢比奥氏体不锈钢Cr含量低，导致马氏体不锈钢更适合应用在轻度腐蚀的场合中。目前2 Cr13钢的强化处理基本局限在单一渗氮或镀膜，复合处理的工艺应用较少。本文以2 Cr13钢为研究对象，进行离子渗氮和WCrAITiSiN涂层复合强化，并研究复合强化后样品在海水中的电化学行为。1试验准备1.1样品制备使用电火花线切割机（EDWC）将2 Cr13马氏体不锈钢棒材切割成厚度8 mm，直径2 5mm的样品，2 Cr13化学成分（质量分数）如表1所示。对样品表面进行打磨，抛光后表面粗糙度Ra Coating HPN+C LPN HPN Untreated。复合强化层可以有效抵御腐蚀介质的侵入，有效改善马氏体不锈钢在海洋环境中的服役情况。参考文献1黄朝军，梁文萍，缪强，等.2 Cr13不锈钢的硼碳共渗及其摩擦学性能.热处理，2 0 19，34(6)：1-9.HUANG Chaojun,LIANG Wenping,MIAO Qiang,et al.Borcarburizing and resulting tribological property for2Cr13 stainless steelJJ.Heat Treatment,2019,34(6):1-9.(in Chinese)2 WANG X,FAN L,DING K,et al.Pitting corrosion of2Cr13 stainless steel in deep-sea environmentJJ.Journalof Materials Science&Technology,2021,64:187-194.3 DALMAU 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