Zr含量对磁控溅射NiCrZr薄膜结构及耐蚀性的影响
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摘要
目的在316L不锈钢基体表面磁控溅射Ni CrZr薄膜,提高其在3.5%NaCl溶液中的耐蚀性。方法采用非平衡磁控溅射技术,在316L不锈钢基体上,用Ni Cr(原子比80:20)复合靶和纯Zr靶制备了不同Zr含量的Ni CrZr薄膜。采用XRD、原子力显微镜、扫描电镜和Gamry电化学工作站,分别分析了Ni Cr Zr薄膜的物相组成、表面形貌、表面粗糙度、截面形貌、元素组成、厚度以及在3.5%NaCl溶液中的电化学腐蚀性能。结果随着Zr靶功率的增加,薄膜中Zr含量不断增加,薄膜的组织结构不断细化,表面粗糙度由4.91 nm减小到了2.79 nm。薄膜主要由Cr3Ni2、Cr1.2Ni0.8Zr、Cr2Zr、CrO3、Ni Cr O4和ZrO2相组成,表明薄膜容易在空气中氧化。此外,随着Zr含量的增加,与316L基体相比,Ni Cr Zr薄膜在3.5%NaCl溶液中的腐蚀电流减小,腐蚀电位增大。当Zr原子分数为24.73%时,NiCrZr薄膜可以在溶液中形成稳定的钝化膜,从而表现出最佳的耐蚀性,腐蚀电流密度达到最小值13.10nA/cm2,与316L基体相比减小了95%。结论 Zr含量的增加可以使薄膜变得更加细密,有效阻隔电解质与基体的接触,从而提高涂层的耐蚀性。
The work aims to form NiCrZr film on the 316 L stainless steel by magnetron sputtering to improve the corrosionresistance in 3.5%NaCl solution. NiCrZr films with different Zr contents were prepared on 316 L stainless steel substrates withNiCr(80 at% : 20 at%) composite target and pure Zr target by unbalanced magnetron sputtering. The phase composition, surfacemorphology, roughness, cross-sectional morphology, composition of the elements, thickness and the corrosion resistance in3.5%Na Cl solution were analyzed by XRD, AFM, SEM and Gamry electrochemical workstation, respectively. With the increaseof Zr target power, the content of Zr in the film increased, the microstructure of the film was refined, and the surface roughnesswas reduced from 4.91 to 2.19 nm. The films were mainly composed of Cr3 Ni2, Cr1.2 Ni0.8 Zr, Cr2 Zr, CrO3, NiCrO4 and ZrO2, sothe film was easily oxidized in air. Furthermore, with the increase of Zr content, the corrosion current of NiCrZr film in3.5%NaCl solution decreased and the corrosion potential increased compared with the 316 L substrate. When the Zr content was24.73%(at%), the NiCrZr thin films exhibited the best corrosion resistance due to the formation of stable passivation layer in3.5%NaCl solution, and the corrosion current density reached a minimum value of 13.10 nA/cm2, which was reduced by 19 times compared with 248.5 nA/cm2 of 316 L. Thus, the increase of the Zr content can make the film denser, and can effectivelyimprove the corrosion resistance of the coating by impeding the contact between the electrolyte and the substrate.
The work aims to form NiCrZr film on the 316 L stainless steel by magnetron sputtering to improve the corrosionresistance in 3.5%NaCl solution. NiCrZr films with different Zr contents were prepared on 316 L stainless steel substrates withNiCr(80 at% : 20 at%) composite target and pure Zr target by unbalanced magnetron sputtering. The phase composition, surfacemorphology, roughness, cross-sectional morphology, composition of the elements, thickness and the corrosion resistance in3.5%Na Cl solution were analyzed by XRD, AFM, SEM and Gamry electrochemical workstation, respectively. With the increaseof Zr target power, the content of Zr in the film increased, the microstructure of the film was refined, and the surface roughnesswas reduced from 4.91 to 2.19 nm. The films were mainly composed of Cr3 Ni2, Cr1.2 Ni0.8 Zr, Cr2 Zr, CrO3, NiCrO4 and ZrO2, sothe film was easily oxidized in air. Furthermore, with the increase of Zr content, the corrosion current of NiCrZr film in3.5%NaCl solution decreased and the corrosion potential increased compared with the 316 L substrate. When the Zr content was24.73%(at%), the NiCrZr thin films exhibited the best corrosion resistance due to the formation of stable passivation layer in3.5%NaCl solution, and the corrosion current density reached a minimum value of 13.10 nA/cm2, which was reduced by 19 times compared with 248.5 nA/cm2 of 316 L. Thus, the increase of the Zr content can make the film denser, and can effectivelyimprove the corrosion resistance of the coating by impeding the contact between the electrolyte and the substrate.
引文
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[3]刘通,孙桂芳,张永康.45#钢表面激光合金化NiCrAl2O3涂层的组织及耐磨性能研究[J].表面技术,2016,45(10):64-69.LIU Tong,SUN Gui-fang,ZHANG Yong-kang.Microstructure and wear resistance of NiCr-Al2O3 coating alloyed with 45#steel laser[J].Surface technology,2016,45(10):64-69.
[4]黄鹤,邱长军,陈勇,等.锆合金表面磁控溅射与多弧离子镀Cr涂层的高温抗氧化性能[J].中国表面工程,2018,31(2):51-58.HUANG He,QIU Chang-jun,CHEN Yong,et al.High temperature oxidation resistance of magnetron sputtering and multi-arc ion plating Cr films on zironium alloy[J].China surface engineering,2018,31(2):51-58.
[5]LI J,KONG D.Micro-structures and high-temperature friction-wear performances of laser cladded Cr-Ni coatings[J].Materials,2018,11(1):137.
[6]BEN MAHMUD T A,ATIEH A M,KHAN T I.The wear behavior of HVOF sprayed near-nanostructured WC-17%Ni(80/20)Cr coatings in dry and slurry wear conditions[J].Journal of materials engineering&performance,2017,26(7):3507-3515.
[7]张轲,牛焱,吴维.NiCr合金在含氯氧化性气氛中的高温腐蚀[J].材料工程,2005(1):12-15.ZHANG Ke,NIU Yan,WU Wei,High temperature corrosion of Ni Cr alloys in chlorination-oxidizing atmosphere[J].Journal of materials engineering,2005(1):12-15.
[8]HUNTZ A M,PUIG T,CONFIGNAL L,et al.Laser melting of an NiCr alloy precoated with carbon:hightemperature oxidation and wear resistance[J].Materials science&engineering A,1989,120(89):555-561.
[9]马青华,杨青松,周建奇.几种镍铬基合金涂层在海水中的腐蚀电化学行为[J].腐蚀科学与防护技术,2015,27(4):401-404.MA Qing-hua,YANG Qing-song,ZHOU Jian-qi.Corrosion electrochemical behavior of several nickel-chromiumbased alloy coatings in seawater[J].Corrosion science and protection technology,2015,27(4):401-404.
[10]RAJU V R,KüHN U,WOLFF U,et al.Corrosion behaviour of Zr-based bulk glass-forming alloys containing Nb or Ti[J].Materials letters,2002,57(1):173-177.
[11]CAI F,JIANG C,ZHANG Z,et al.Fabrication and characterization of Ni-Zr composite coatings using electrodepositing technique[J].Journal of alloys&compounds,2015,635:73-81.
[12]SAHU B P,SARANGI C K,MITRA R.Effect of Zr content on structure property relations of Ni-Zr alloy thin films with mixed nanocrystalline and amorphous structure[J].Thin solid film,2018,660:31-45.
[13]TANG J,ZHU Q,WANG Y,et al.Insights on the role of copper addition in the corrosion and mechanical properties of binary Zr-Cu metallic glass coatings[J].Coatings,2018,7(12):223-238.
[14]HU J,YANG L,CAO G,et al.On the oxidation behavior of(Zr,Nb)2Fe under simulated nuclear reactor conditions[J].Corrosion science,2016,112:718-723.
[15]吴自勤,王兵,孙霞.薄膜生长[M].北京:科学出版社,2001.WU Zi-qin,WANG Bing,SUN Xia.Film growth[M].Beijing:Science Press,2001.
[16]PILLIS M F,GERIBOLA G A,SCHEIDT G,et al.Corrosion of thin,magnetron sputtered Nb2O5 films[J].Corrosion science,2016,102:317-325.
[17]DELLA ROVERE C A,ALANO J H,SILVA R,et al.Characterization of passive films on shape memory stainless steels[J].Corrosion science,2012,57(2):154-161.
[18]LIU C,BI Q,LEYLAND A,et al.An electrochemical impedance spectroscopy study of the corrosion behaviour of PVD coated steels in 0.5 N NaCl aqueous solution:Part II:EIS interpretation of corrosion behaviour[J].Corrosion science,2003,45(6):1257-1273.
[19]王正曦,麻彦龙,吴海鹏,等.5182铝合金表面锆化膜的制备及其性能研究[J].表面技术,2018,47(9):206-213.WANG Zheng-xi,MA Yan-long,WU Hai-peng,et al.Preparation and properties of zorconium conversion coating on 5182 aluminum alloy[J].Surface technology,2018,47(9):206-213.
[20]WU Z,CAO Q,MA Y,et al.Thickness-dependent pitting corrosion behavior in Ni-Nb thin film metallic glass[J].Thin solid films,2014,564:294-298.
[21]JORCIN J B,ORAZEM M E,PéBéRE N,et al.CPEanalysis by local electrochemical impedance spectroscopy[J].Electrochimica acta,2006,51(8):1473-1479.
[22]BYK T V,GAEVSKAYA T V,TSYBULSKAYA L S.Effect of electrodeposition conditions on the composition,microstructure,and corrosion resistance of Zn-Ni alloy coatings[J].Surface&coatings technology,2008,202(24):5817-5823.
[23]MATTHES B,BROSZEIT E,AROMAA J,et al.Corrosion performance of some titanium-based hard coatings[J].Surface&coatings technology,1991,49(1):489-495.