转化液pH对医用Zn-Li-Ce合金表面涂层特征及生物降解行为的影响

Effects of conversion solution pH value on the surface coating characteristics and biodegradation behaviors of Zn-Li-Ce alloys

  • 摘要: 医用锌合金的腐蚀性能介于惰性铁基材料及可降解镁合金材料之间,并具有优异的生物相容性,在临床植入领域显示出巨大的应用潜力和发展前景。然而其非均匀腐蚀行为极易引发无预兆骤断及突发失效等科学难题。本文通过SEM、XRD、3D/CLSM及动电位极化测试等手段探究了转化液pH对锌合金表面涂层特征、产物组分及生物降解行为的影响。结果表明:随着转化液pH(2.25、2.50、3.00、3.25)的增加,合金表面涂层形貌由初始的片状转变为团簇绒球状,涂层厚度及致密度则呈现出先升高后降低的趋势,合金在模拟体液环境下腐蚀速率分别为0.475、0.303、0.206、0.235 mm/a,耐蚀性呈现出先升高后降低的趋势。原因如下:一方面pH的增加,H+的浓度有所下降,电解产生的离子处于平衡状态,涂层的形成比基材的溶解更占主导地位;另一方面适宜的酸性环境极易诱发合金表面活化,形成大量活性位点用于离子吸附/沉积,且形成的大量细小尺度团簇状晶体减少了溶液与基体的接触面积,进而延缓了合金的溶解速率。然而随着pH的逐渐增大,高浓度的OH-在溶液中会导致更多的Zn(PO42·2H2O沉积而抑制SrZn2(PO42物质的反应沉积,进而对涂层形貌产生明显改变,弱化合金在体液环境下的耐蚀性能。

     

    Abstract: The corrosion resistance of medical zinc alloy lies between that of an inert Fe substrate and a degradable Mg alloy. Combined with its excellent biocompatibility, zinc alloy shows great potential for clinical implantation. However, its non-uniform corrosion dissolution can easily trigger unpredictable fractures and abrupt failures, posing scientific and practical challenges. In this study, the effect of conversion liquid pH value on the surface coating characteristics and biodegradation behaviors was analyzed using SEM, XRD, 3D/CLSM and EIS tests. The results show that as the pH value of the conversion solution increases (2.25, 2.50, 3.00, 3.25), the coating morphology of the zinc alloy evolves from the initial flake to the globular cluster, while the coating thickness and density initially increase and then decrease. Correspondingly, the corrosion resistance of the alloy under simulated fluid environment is 0.475, 0.303, 0.206 and 0.235 mm/a, respectively. This trend can be attributed to two primary factors. First, the increase in pH value reduces the concentration of H+, bringing the electrolysis-generated ions closer to equilibrium and favoring the formation of the coating over substrate dissolution. Second, moderately acidic condition promotes surface activation of the alloy, generating numerous active sites for ion adsorption and deposition. The resulting fine, cluster-like crystals reduce the effective contact area between the solution and the matrix, thus slowing the dissolution rate under Hank’s electrolyte. However, at higher pH value levels, an elevated OH- concentration enhances the deposition of Zn (PO4)2·2H2O while suppressing the formation of SrZn2(PO4)2, leading to a significant change in coating morphology, and deteriorating the corrosion resistance of the alloy in a body fluid environment.

     

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