不同轧制态医用Zn-Li-Ce合金表面涂层特征及腐蚀行为研究

张源; 牛丽静; 张朋; 刘芸; 王子剑; 田亚强; 陈连生

doi:10.16490/j.cnki.issn.1001-3660.2025.16.008

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表面技术 ›› 2025, Vol. 54 ›› Issue (16) : 100-110. DOI: 10.16490/j.cnki.issn.1001-3660.2025.16.008

腐蚀与防护

不同轧制态医用Zn-Li-Ce合金表面涂层特征及腐蚀行为研究

张源, 牛丽静, 张朋, 刘芸^*, 王子剑, 田亚强, 陈连生

作者信息 +

Surface Coating Characteristics and Corrosion Properties of Zn-Li-Ce Alloys at Different Rolling States

ZHANG Yuan, NIU Lijing, ZHANG Peng, LIU Yun^*, WANG Zijian, TIAN Yaqiang, CHEN Liansheng

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摘要

目的锌基合金具有良好的生物降解性、可加工性和优异的生物功能性,但铸态锌合金存在局部腐蚀倾向,过度释放的Zn²⁺会造成局部组织毒性并对骨愈合/修复产生不利影响,难以满足临床植入的要求。方法通过光学显微镜（OM）、扫描电子显微镜（SEM）、X射线衍射仪（XRD）及动电位极化PDP/EIS等手段探究轧制态合金组织对其表面涂层特征及降解行为的影响。结果当轧制压下率为80%时,磷酸锌锶涂层锌合金表现出优异的耐蚀性能。这是由于适宜晶粒尺寸的轧制锌合金具有较高的晶界密度,在化学转化过程中Zn²⁺能够通过晶界更有效地释放到暴露的表面中,产生更多活性点,有利于促进表面形成均匀致密的磷酸锌锶涂层,有效地阻碍了侵蚀性离子与基体的直接接触,增强了合金的耐蚀性能;此外,轧制后的高密度晶界可作为腐蚀点蚀的屏障,阻碍腐蚀坑的进展,进一步增强基体对腐蚀的防御能力。结论随轧制压下率增加（20%、40%、60%和80%）,磷酸锌锶涂层锌合金在模拟体液中测得的电化学腐蚀速率（0.669、0.408、0.249和0.160 mm/a）及失重速率（0.0526、0.0313、0.0170和0.0121 mm/a）均呈现逐渐降低的趋势。其中,磷酸锌锶涂层锌合金在轧制压下率80%时获得最优异的耐蚀性能。

Abstract

Zinc-based alloys own good biodegradability, machinability and excellent biological functionality, but the excessive release of Zn²⁺ will cause the local toxicity and affect bone tissue healing, which is difficult to meet the requirements of medical implants. In this study, the novel Zn-Li-Ce zinc alloys were successfully prepared and coated with the zinc strontium phosphate conversion coatings. Besides, the morphology composition, elements distribution, thickness and corrosion resistance were elucidated by OM, SEM/EDS, XRD, 3D/CLSM, PDP and EIS. With the increase of the rolling reduction rate (20%, 40%, 60% and 80%), the surface morphology of coated alloys changed from large mass to small spherical and quadrilateral interwoven growth structure. It could be seen from the element distributions that with the increase of rolling reduction rates, the coverage and uniformity of coating components were improved. The electrochemical corrosion rates (0.669, 0.408, 0.249 and 0.160 mm/a) and static weight-loss rates (0.052 6, 0.031 3, 0.017 0 and 0.012 1 mm/a) of coated zinc alloys measured in simulated body fluids showed a gradual decreasing trend. Therein, the best excellent corrosion resistance of coated zinc alloys were obtained at the rolled-reduction of 80%. In the case of large deformation, the small angle grain boundary and the coexisting crystal boundary hindered the pit progress by changing the crystal orientation, thereby enhancing the corrosion resistance of the substrate. In addition, the hot-rolled Zn alloys owned high grain boundary densities, which induced the Zn²⁺ more efficiently to penetrate into the exposed surface through the grain boundaries during the chemical transformation process. The formation of a large number of activated particles was conducive to the formation of uniform and dense zinc-strontium phosphate coating on the surface, which effectively prevented the direct contact between the aggressive ions and the substrate, thereby enhancing the corrosion resistance of the alloy. In the early stage of corrosion, the protective effect of the coating could prevent the surface of the zinc alloy substrate from directly contacting the corrosion solution. With the prolongation of the corrosion process, the film layer of corrosion products was ultimately formed on the surface of the alloy, which effectively reduced the degradation rate of the zinc alloy. In the middle and late stages of corrosion, the degree of protection provided was also different due to the different adhesion between the coating and the substrate. Particularly, the coated zinc alloy with the large rolling pressure rate had the strong binding force and the good coating thickness and density, which could better protect the substrate from erosion, resulting in a uniform corrosion plane. Compared with traditional zinc alloys, the hot-rolled zinc alloys with zinc strontium phosphate conversion coatings have better corrosion resistance and controllable corrosion rates. The results obtained are of great significance for the research on the corrosion resistance of medical zinc alloys, and the zinc strontium phosphate coating coupled with hot-rolled may be an effective measure to decrease the corrosion rates of Zn-Li-Ce alloys, providing a promising way for the surface modification of degradable metals.

导出引用

张源, 牛丽静, 张朋, 刘芸, 王子剑, 田亚强, 陈连生. 不同轧制态医用Zn-Li-Ce合金表面涂层特征及腐蚀行为研究[J]. 表面技术. 2025, 54(16): 100-110 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.16.008

ZHANG Yuan, NIU Lijing, ZHANG Peng, LIU Yun, WANG Zijian, TIAN Yaqiang, CHEN Liansheng. Surface Coating Characteristics and Corrosion Properties of Zn-Li-Ce Alloys at Different Rolling States[J]. Surface Technology. 2025, 54(16): 100-110 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.16.008

中图分类号： TG174.4

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