在AZ31镁合金表面制备锌钙磷酸盐(Zn?Ca?P)涂层和铈掺杂锌钙磷酸盐(Zn?Ca?Ce?P)涂层。采用X射线能谱(EDS)、光电子能谱(XPS)、X射线衍射(XRD)、电子探针(EPMA)和扫描电镜(SEM)以及析氢实验和电化学测试技术研究涂层的化学成分、形貌和腐蚀性能。结果表明：两种膜层主要是磷酸盐(Zn3(PO4)2·4H2O)、Mg3(PO4)2、Ca3(PO4)2晶体簇和少量的MgF2和CaF2非晶颗粒组成。CePO4的形成使Zn?Ca?Ce?P膜层更加致密，并具有更好的耐蚀性。两种涂层只能在浸泡前期为AZ31镁基体提供保护作用，随着浸泡时间延长，涂层与基体界面之间电偶腐蚀的发生加快了腐蚀速率。Ce的添加促进了Ca的均匀分布和磷化膜的形成。因此，Zn?Ca?Ce?P涂层具有作为镁合金底涂层的应用前景。
Zinc calcium phosphate (Zn?Ca?P) coating and cerium-doped zinc calcium phosphate (Zn?Ca?Ce?P) coating were prepared on AZ31 magnesium alloy. The chemical compositions, morphologies and corrosion resistance of coatings were investigated through energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), electron probe micro-analysis (EPMA) and scanning electron microscopy (SEM) together with hydrogen volumetric and electrochemical tests. The results indicate that both coatings predominately contain crystalline hopeite (Zn3(PO4)2·4H2O), Mg3(PO4)2 and Ca3(PO4)2, and traces of non-crystalline MgF2 and CaF2. The Zn?Ca?Ce?P coating is more compact than the Zn?Ca?P coating due to the formation of CePO4, and displays better corrosion resistance than the Zn?Ca?P coating. Both coatings protect the AZ31 Mg substrate only during an initial immersion period. The micro-galvanic corrosion between the coatings and their substrates leads to an increase of hydrogen evolution rate (HER) with extending the immersion time. The addition of Ce promotes the homogenous distribution of Ca and formation of hopeite. The Zn?Ca?Ce?P coating has the potential for the primer coating on magnesium alloys.
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