含Ag抗菌双相不锈钢表面腐蚀产物的XPS分析
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摘要
采用X射线光电子能谱技术(XPS)研究了含Ag抗菌双相不锈铸钢在有菌环境中经电化学极化后的表面腐蚀产物。结果表明:添加纯Ag颗粒制备的不锈钢经1150℃固溶处理后,其钝化膜表层中的Ag主要以Ag2+氧化物和游离态的形式存在,Cr主要以CrO2,CrO3和Cr(OH)3形式存在,而添加150～300μm Cu-Ag中间合金颗粒制备的不锈钢经1150℃固溶处理后,其钝化膜表层中的Ag主要以Ag2+,Ag+和Ag2/3+氧化物形式存在,Cr以CrO2、Cr2O3和CrO3等多价态铬氧化物形式共存,且与前者相比,添加150～300μm Cu-Ag中间合金颗粒制备的材料其钝化膜中Cr2O3、钼氧化物和MoO42-的含量更多,而α-FeOOH和Cr(OH)3等氢氧化合物以及水合物的含量更少,表明其钝化膜的稳定性优于添加纯Ag颗粒制备的材料。
Silver-bearing antibacterial duplex stainless steels were prepared by adding silver granules(code name A) or 150～300 μm Cu-Ag particles(code name B) respectively. The two steels were then subjected to solid solution treatment at 1150 ℃. The surface passive films formed on the two steels after potentiodynamic polarization test in bacteria bearing liquid were analyzed by X-ray photoelectron spectroscopy(XPS). The results indicated that there exist silver as atomic Ag and oxide AgO, while chromium as CrO2, CrO3 and Cr(OH)3in the surface passive film of the steel A. However silver as oxides of AgO, Ag2 O and Ag3 O, while Cr as chromic oxides of multi-valence present in the surface passive film of the steel B. In comparison with the passive film on the steel A, that on the steel B has higher amount of Cr2O3, molybdenum oxides and MoO42-, but lower amount of hydroxides/hydrates, meaning that the stability of the passive film on the steel B is better.
Silver-bearing antibacterial duplex stainless steels were prepared by adding silver granules(code name A) or 150～300 μm Cu-Ag particles(code name B) respectively. The two steels were then subjected to solid solution treatment at 1150 ℃. The surface passive films formed on the two steels after potentiodynamic polarization test in bacteria bearing liquid were analyzed by X-ray photoelectron spectroscopy(XPS). The results indicated that there exist silver as atomic Ag and oxide AgO, while chromium as CrO2, CrO3 and Cr(OH)3in the surface passive film of the steel A. However silver as oxides of AgO, Ag2 O and Ag3 O, while Cr as chromic oxides of multi-valence present in the surface passive film of the steel B. In comparison with the passive film on the steel A, that on the steel B has higher amount of Cr2O3, molybdenum oxides and MoO42-, but lower amount of hydroxides/hydrates, meaning that the stability of the passive film on the steel B is better.
引文
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[14] Maurice V, Yang W P, Marcus P. X-Ray photoelectron spectrosco‐py and scanning tunneling microscopy study of passive films formed on(100)Fe-18Cr-13Ni single-crystal surfaces[J]. J. Elec‐trochem. Sci., 1998, 145(3):909
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[2] Santamaria M, Di Franco F, Di Quarto F, et al. Photoelectrochemi‐cal and XPS characterisation of oxide layers on 316L stainless steel grown in high-temperature water[J]. J. Solid State Electrochem.,2015, 19(2):3511
[3] Tardio S, Abel M L, Carr R H. Comparative study of the native ox‐ide on 316L stainless steel by XPS and ToF-SIMS[J]. J. Vac. Sci.Technol. A, 2015, 33(5):1
[4] Wang Y W, Jiang R J, Zhao J M. The properties of passive films formed on 316L and 316LN stainless steel in high-temperature and high-salinity solution[J]. J. Beijing Univ. Chem. Tech.(Nat. Sci.),2017, 44(5):72(王育武,姜瑞景,赵景茂. 316L和316LN不锈钢在高温高盐溶液中钝化膜的性能研究[J].北京化工大学学报(自然科学版),2017, 44(5):72)
[5] Xiang H L, Guo P P, Liu D. Microstructure and antibacterial proper‐ties of Ag-bearing duplex stainless steel[J]. Acta Metall. Sin., 2014,50:1210(向红亮,郭培培,刘东.含Ag抗菌双相不锈钢组织及抗菌性能研究[J].金属学报, 2014, 50:1210)
[6] Feng D M, Wang J Q, Wu W H. Introduction to Electronic Spectros‐copy(XPS/XAES/UPS)[M]. Beijing:National Defence Industry Press, 1992(冯大明,王建祺,吴文辉.电子能谱学(XPS/XAES/UPS)引论[M].北京:国防工业出版社, 1992)
[7] Liu S H. X-ray Photoelectron Spectroscopy Analysis[M]. Beijing:Science Press, 1988(刘世宏. X射线光电子能谱分析[M].北京:科学出版社, 1988)
[8] Liu G Q, Zhu Z Y, Ke W. The pitting of stainless and nickel-based alloys in acetic acid solution containing bromine ion[J]. Acta Metall. Sin., 2001, 37:275(刘国强,朱自勇,柯伟.不锈钢及镍基合金在含溴醋酸中的点蚀行为[J].金属学报, 2001, 37:275)
[9] Zhang L, Han E-H, Zhang Z E, et al. The corrosion of stainless steel and nickel base alloys in subcritical water condition[J]. Acta Metall.Sin., 2003, 39:649(张丽,韩恩厚,张召恩等.不锈钢及镍基合金在亚临界水环境中的腐蚀[J].金属学报, 2003, 39:649)
[10] Wang Z C, Zhang Y Z, Zhou S M, et al. Corrosion compositions of carbon steel under ion-selective coatings by XPS[J]. J. Chin. Soc.Corros. Prot., 2001, 21:273(王周成,张瀛洲,周绍民等.离子选择性涂层下碳钢表面腐蚀产物的XPS分析[J].中国腐蚀与防护学报, 2001, 21:273)
[11] Kumagai M, Myung S, Asaishi R, et al. High nitrogen stainless steel as bipolar plates for proton exchange membrane fuel cells[J]. J. Power Sources, 2008, 54(3):815
[12] He G, Gao Q W. Corrosion performance of enviroment-friendly chemical conversion films on mild steel[J]. Corros. Sci. Prot.Technol., 2009, 21:66(何刚,高勤卫.钢铁表面环保型杂多酸化学转化膜的耐蚀性[J].腐蚀科学与防护技术, 2009, 21:66)
[13] Huang C, Shih C. Effects of nitrogen and high temperature aging onσphase precipitation of duplex stainless steel[J]. Mater. Sci.Eng., 2005, A402(1/2):66
[14] Maurice V, Yang W P, Marcus P. X-Ray photoelectron spectrosco‐py and scanning tunneling microscopy study of passive films formed on(100)Fe-18Cr-13Ni single-crystal surfaces[J]. J. Elec‐trochem. Sci., 1998, 145(3):909
[15] Xu C C, Wu X M. Mechanism of MoO42-retarding the develop‐ment of the local corrosion in 304 stainless steel/Cl-solution[J].Chin. J. Mater. Res., 2002, 16:354(许淳淳,吴小梅. MoO42-抑制AISI304不锈钢局部腐蚀的机理[J].材料研究学报, 2002, 16:354)