Zr基块体非晶合金疏水性表面制备及其生物相容性研究

The combined quality in their mechanical and chemical properties gives great advantages for Zr-based bulk metallic glasses (BMGs) to be an excellent choice for biomedical applications. However, the applications are limited due to their hydrophillic surfaces. Studies on the fabrication of hydrophobic surface and its biocompatibility in Zr-based BMGs have the significance of science and also promote their applications. In this work, the preparation technologies of hydrophobic surfaces, with different contact angles, on Zr-based BMGs will be investigated firstly. Secondly, the effect of hydrophobicity on bio-corrosion behaviors will be studied. Thirdly, cellular behaviors will be researched by adhesion and proliferation of the human umbilical vein endothelial cell on the surfaces with different hydrophobicity. Finally, blood compatibility will be evaluated by hemolysis analysis, coagulation test and platelet adhesion investigation. Based on the experimental researches, the inherent relationship between the microstructure, hydrophobicity and biocompatibility will be revealed, and the mechanism of hydrophobicity on its biocompatibility can be also discussed. This study will provide theoretical and experimental basis for developing newly BMGs with high biocompatibility.

Zr基非晶合金因其自身优良特性在生物医疗领域存在巨大应用前景，但亲水性的表面使应用受到限制。研究Zr基非晶合金疏水性表面构建及其对生物相容性的作用机制不但具有重要的科学意义，而且将有力促进非晶合金的实际应用。本课题通过研究Zr基非晶合金疏水性表面的制备工艺，实现疏水性的可控制备；研究疏水性对其生物腐蚀性能的影响；通过考察内皮细胞在其表面的粘附和繁殖行为研究疏水性对细胞行为作用；采用动态凝血性能、血小板粘附行为和溶血性能实验研究疏水表面的血液相容性。在实验研究的基础上，揭示非晶合金表面微观结构-疏水程度-生物相容性三者间的内在关联，探讨疏水性对其生物相容性的作用机制，为探索具有高生物相容性的新型非晶合金提供理论与试验依据。

Zr基非晶合金因其自身优良特性在生物医疗领域存在潜在应用，但亲水性表面使其应用受到限制，研究Zr基非晶合金疏水性表面构建及其生物相容性具有重要的意义。.本项目采用3.5 wt.% NaCl溶液进行电化学蚀刻，在Zr46Cu46Al8 非晶合金表面实现超疏水，在3.5 wt.% NaCl中自腐蚀电流密度下降三个数量级、抑制率为99.6%。在0.03 M NaCl和0.20 M NaBr混合溶液中电化学刻蚀Zr46Cu46Al8非晶合金制备了超双疏表面，在PBS中自腐蚀电流密度下降一个数量级，阻抗提高12.6倍。在0.5 wt.% KCl中电化学刻蚀Zr46Cu46Al8和Zr46(Cu4.5/5.5Ag1/5.5)46Al8非晶合金获得超疏水。在SBF中两种材料自腐蚀电流密度均下降一个数量级；细菌粘附减少，并具有较强的杀菌性、前者杀菌更优；可降低血小板粘附，抗凝血能力优异。在2.2 M HCl中对Zr46Cu46Al8非晶合金化学刻蚀，在40 min-9 h大范围时间内均能获得超疏水。该表面可有效抑制血小板和细菌粘附，具有优异的杀菌和抗凝血性能。在0.25 M NaBr中电化学刻蚀制备了Zr56Al16Co28非晶合金超疏水表面。该表面能有效抑制血小板粘附，溶血率仅为0.24%；经SBF浸泡6天后自腐蚀电流密度仅下降一个数量级，腐蚀抑制率为96.3%。在0.25 M NaBr中对Zr56Al16(Co0.75Ag0.25)28非晶合金进行电化学刻蚀后实现超疏水，经SBF溶液浸泡3天后仍能保持良好的耐蚀性。以上两种材料均具有良好的机械耐久性和化学稳定性，都能有效抑制平滑肌细胞和细菌粘附，但含Ag样品杀菌能力更强。在Zr56Al16Co28非晶合金表面电镀制备了超疏水Zn/pDop/SA涂层。该表面不仅减少了细菌粘附，在模拟人体溶液中浸泡后可实现超疏水到亲水性转变，进而促进细胞生长。最后将电化学刻蚀和电化学沉积相结合创新性的同时在Zr基非晶合金阳极和阴极实现超疏水。.本研究结果为高生物相容性Zr基非晶合金开发提供了新思路，为非晶合金医用材料的探索提供了重要基础数据和实验依据，有利于推动非晶合金在生物医用领域的实际应用。