硅烷化处理对镁合金表面微弧氧化涂层降解性能的影响

doi:10.12068/j.issn.1005-3026.2025.20250013

摘要/Abstract

摘要：

采用电沉积、真空浸渍和常规浸渍3种工艺对Mg-0.45Zn-0.45Ca合金上的微弧氧化涂层进行硅烷偶联剂(KH550)硅烷化处理.通过扫描电镜、维氏硬度计和电化学测试等，研究了硅烷化处理工艺对医用镁合金表面微弧氧化涂层的缺陷封闭效果和在模拟体液（SBF）中长期降解性能的影响.结果表明，3种工艺均可在微弧氧化涂层表面获得硅烷薄膜.其中，利用电沉积可制备出厚度为1.5~7 μm的硅烷膜层，对微弧氧化涂层有很好的封闭效果，且可有效提高涂层的硬度和附着力.此外，电沉积工艺处理的涂层在模拟体液中浸泡3个月后仍可有效保护镁合金基体，满足可降解生物医用镁合金的需求.因此，利用微弧氧化和KH550硅烷电沉积处理的Mg-0.45Zn-0.45Ca合金具有成为可降解镁合金植入物的潜力.

关键词: 镁合金, 涂层, 硅烷, 电沉积, 长期降解性能

Abstract:

Three types of processes， including electrodeposition， vacuum impregnation， and conventional immersion， were used to modify the micro-arc oxidation （MAO） coatings on Mg-0.45Zn-0.45Ca alloys using KH550 silane.The effects of these silanization processes on the sealing effect for the defects within the MAO coating on the surface of medical magnesium alloys and the long-term degradation performance of the coating in simulated body fluid （SBF） were studied by scanning electron microscopy， Vickers hardness tester， and electrochemical measurements.The results show that silane films can be successfully prepared on the surface of the MAO coating using these three types of processes.Among them， the silane film with a thickness of 1.5~7 μm can be fabricated by electrodeposition， which shows a superior sealing effect to the MAO coating and can enhance the hardness and adhesion strength of the coating.Besides， the MAO coating prepared by electrodeposition after immersion for three months in SBF can effectively protect the magnesium substrate， satisfying the requirements for the biodegradable biomedical magnesium alloys.Therefore， the Mg-0.45Zn-0.45Ca alloy with KH550 silanization electrodeposition and MAO has the potential to be used as degradable magnesium alloys implants.

Key words: magnesium alloy, coating, silane, electrodeposition, long-term degradation performance

中图分类号:

TG 17

张涛, 刘闯, 张一, 王福会. 硅烷化处理对镁合金表面微弧氧化涂层降解性能的影响[J]. 东北大学学报（自然科学版）, 2025, 46(8): 105-112.

Tao ZHANG, Chuang LIU, Yi ZHANG, Fu-hui WANG. Effect of Silanization on Degradation Performance of Micro-arc Oxidation Coatings on Magnesium Alloys Surfaces[J]. Journal of Northeastern University(Natural Science), 2025, 46(8): 105-112.

图/表 10

表1 Mg-0.45Ca-0.45Zn合金的成分（质量分数） ((mass fraction) %)

Table 1 Compositions of Mg-0.45Ca-0.45Zn alloys

Mn	Cu	Zn	Si	Ca	Al	Fe	Mg
0.036	0.000 4	0.60	0.037	0.31	0.026	0.003	余量

图1 PEO涂层及不同工艺制备的PEO/KH550复合涂层的SEM图像（a）—PEO涂层；（b）—常规浸渍制备的PEO/KH550复合涂层；（c）—真空浸渍制备的PEO/KH550复合涂层；（d）—电沉积制备的PEO/KH550复合涂层.

Fig.1 SEM images of PEO coating and PEO/KH550 composite coatings prepared by different processes

图2 不同工艺制备的PEO/KH550复合涂层的FTIR谱

Fig.2 FTIR spectrum of PEO/KH550 composite coatings prepared by different processes

图3 PEO涂层及不同工艺制备的PEO/KH550复合涂层的维氏硬度和附着力（a）—维氏硬度；（b）—附着力.

Fig.3 Vickers hardness and adhesion of PEO coating and PEO/KH550 composite coatings prepared by different processes

图4 PEO涂层及不同工艺制备的PEO/KH550复合涂层的极化曲线

Fig.4 Polarization curves of PEO coating and PEO/KH550 composite coatings prepared by different processes

表3 动电位极化曲线拟合结果 (polarization curves)

Table 3 Fitting results of potentiodynamic

样品	i_corr/(µA·cm^-2)	E_corr/V	E_b/V
PEO	0.029	-1.91	-1.62
PEO/KH550 常规浸渍	0.028	-1.74	-1.32
PEO/KH550电沉积	0.002	-1.78	-1.21
PEO/KH550 真空浸渍	0.062	-1.79	-1.34

图5 PEO涂层及不同工艺制备的PEO/KH550复合涂层在SBF中浸泡不同天数的阻抗谱（a）—PEO涂层；（b）—常规浸渍制备的PEO/KH550复合涂层；（c）—真空浸渍制备的PEO/KH550复合涂层；（d）—电沉积制备的PEO/KH550复合涂层.

Fig.5 Impedance spectrum of PEO coating and PEO/KH550 composite coatings prepared by different processes after immersion in SBF for different days

图6 电化学阻抗谱的等效电路图（a）—无感抗行为的Nyquist图的拟合电路图；（b）—有感抗行为的Nyquist图的拟合电路图.

Fig.6 Equivalent circuits of electrochemical impedance spectrum

图7 降解速率与浸泡时间的关系

Fig.7 Relationship between degradation rate and immersion time

图8 PEO涂层及不同工艺制备的PEO/KH550复合涂层在SBF中浸泡不同天数后的形貌

Fig.8 Morphology of PEO coating and PEO/KH550 composite coatings prepared by different processes after immersion in SBF for different days

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