采用X射线光电子能谱(XPS)研究了AISI304不锈钢在含(MoO4/2-+Cl-)的模拟闭塞电池中形成钝化膜的组成与结构及MoO4/2-抑制局部腐蚀的机理.结果表明:在闭塞区内AISI304不锈钢表面钝化膜的外层主要有MoO4/2-、CrO3、CrCl3、CrOOH、Fe2O3、γ-FeOOH、Fe(OH)3、CrO4/2-、Cr(OH)3、NiCl2、FeCl2和FeCl3;溅射5 min时膜内层主要有MoCl3、CrO2、FeCl2、FeCl3以及少量的FeO.MoO4/2-对钝化膜的影响在于:MoO4/2-迁入闭塞区后吸附在金属表面上,可取代或部分取代吸附在钢表面的Cl-,并与Fe2+在蚀孔内反应生成不容性的FeMoO4而沉积到蚀孔壁上,有助于蚀孔的再钝化,从而抑制腐蚀的进一步扩展;MoO4/2-的吸附能使水合氧化亚铁沉淀膜由阴离子选择性变为阳离子选择性,使H+可以从膜下扩散出去,而Cl-难以扩散到膜下富集,从而使MoO4/2-具有缓蚀作用
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