CN108707880B - 一种用于医用金属材料的表面改性方法 - Google Patents

一种用于医用金属材料的表面改性方法 Download PDF

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CN108707880B
CN108707880B CN201810486087.6A CN201810486087A CN108707880B CN 108707880 B CN108707880 B CN 108707880B CN 201810486087 A CN201810486087 A CN 201810486087A CN 108707880 B CN108707880 B CN 108707880B
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刘莹
王军
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Abstract

本发明公开了一种用于医用金属材料的表面改性方法，包括：S1金属材料磨抛及清洗；S2在金属材料表面生成氧化物薄膜或混合氧化物薄膜；S3采用溶胶凝胶法在金属材料表面进一步制备TiO2薄膜，完成对金属材料的表面改性。其在保证金属材料的机械性能及TiO2薄膜生物相容性的基础上，通过原位表面改性技术，对金属材料表面进行前处理，提高TiO2薄膜与金属材料的界面结合力，从而提高金属材料使用过程中的稳定性和安全性。

Description

一种用于医用金属材料的表面改性方法
技术领域
本发明涉及材料技术领域，尤其涉及一种医用金属材料的“两步法”表面改性方法。
背景技术
金属材料因具有良好的机械性能而广泛用于血管支架、骨科及心脏瓣膜等领域，然而在与活体组织接触时，金属材料表面离子释放往往会产生不利的宿主反应和材料反应，医用金属材料的生物相容性有待进一步提高。
表面改性技术是在不改变基体材料性质的基础上，通过对材料表面成分和微观结构的调控，提高材料的性质。薄膜技术是一种重要的表面改性技术，近年来，利用TiO2薄膜良好的生物相容性，通过薄膜技术在医用金属材料表面制备TiO2薄膜，改善医用金属材料的生物相容性，已取得了较大的进展，其主要工作在于通过溅射法、等离子体浸没离子注入与沉积技术、溶胶-凝胶法等薄膜制备方法和技术在医用金属材料表面制备TiO2薄膜，研究薄膜材料的制备工艺、微观结构与生物相容性之间的关系。
发明内容
本发明的目的是提供一种用于医用金属材料的表面改性方法，有效解决现有技术中金属材料与改性薄膜材料界面之间结合力不够的技术问题。
本发明提供的技术方案如下：
一种金属材料的表面改性方法，包括：
S1金属材料磨抛及清洗；
S2 在金属材料表面生成氧化物薄膜或混合氧化物薄膜；
S3 采用溶胶凝胶法在金属材料表面进一步制备TiO2薄膜，完成对金属材料的表面改性。
进一步优选地，在步骤S2中，采用预先配置的混合酸溶液对金属材料进行钝化，在其表面生成氧化物薄膜。
进一步优选地，在步骤S2中，采用高温热处理的方法在金属材料表面生成混合氧化物薄膜。
进一步优选地，在步骤S3中包括：
S31 采用钛酸四丁酯为原料配制TiO2溶胶；
S32 通过浸渍式提拉法在金属材料表面形成TiO2薄膜。
在本发明提供的用于医用金属材料的表面改性方法中，首先，在金属材料表面生成氧化物或混合氧化物薄膜，增加金属材料表面的粗糙度和表面能；之后，进一步在金属材料表面制备TiO2薄膜，完成对金属材料进行了两步改性，使其同时具备亲水性（含有羟基）。其在保证金属材料的机械性能及TiO2薄膜生物相容性的基础上，通过原位表面改性技术，对金属材料表面进行前处理，提高TiO2薄膜与金属材料的界面结合力，从而提高金属材料使用过程中的稳定性和安全性。尤其在医用技术领域，采用该表面改性方法处理后，表面的TiO2薄膜与基底的金属材料之间具有良好结合力的同时具有良好的血液相容性，在血管支架、骨科和心脏瓣膜等领域都具有应用前景。
附图说明
下面将以明确易懂的方式，结合附图说明优选实施方式，对金属材料表面改性方法的上述特性、技术特征、优点及实现方式予以进一步说明。
图1为本发明中金属材料的表面改性方法流程示意图；
图2为本发明中对金属材料改性后的结构示意图。
附图标记说明:
1-金属材料，2-氧化物薄膜或混合氧化物薄膜，3-TiO2薄膜。
具体实施方式
下面结合附图和实例进一步说明本发明的实质内容，但本发明的内容并不限于此。
如图1所示，本发明提供了一种金属材料的表面改性方法，具体包括：S1 金属材料磨抛及清洗；S2 在金属材料表面生成氧化物薄膜或混合氧化物薄膜；S3 采用溶胶-凝胶法在金属材料表面进一步制备TiO2薄膜，完成对金属材料的表面改性，改性后的金属材料结构如图2所示。
在步骤S2中，可以采用预先配置的混合酸溶液对金属材料进行钝化，在其表面生成氧化物薄膜，具体，首先，在烧杯中配制混合酸溶液，混合酸成分包括体积比为5-20%的硝酸和1-5%的氢氟酸水溶液；之后，将经打磨抛光的金属材料放置到盛有混合酸溶液的烧杯中，并将烧杯放置于恒温水浴锅（温度30-55℃）中30-90min（分钟），在金属材料表面生成氧化物薄膜。另外，在该步骤中，还可以采用高温热处理的方法在金属材料表面生成混合氧化物薄膜，具体，将金属材料置于高温炉（温度500~700℃）中1~3h（小时），在金属材料表面生成混合物氧化膜。
在步骤S3中包括：S31 采用钛酸四丁酯为原料配制TiO2溶胶；具体，将钛酸四丁酯溶入部分无水乙醇，充分搅拌，得到溶液a；将适量的浓硝酸、蒸馏水加入到部分无水乙醇，得到溶液b；在搅拌过程中，将溶液b缓慢加入到溶液a中，继续搅拌，得到TiO2溶胶，陈化24小时以上用于制备薄膜。S32 通过浸渍式提拉法在金属材料表面形成TiO2薄膜，具体，浸渍时间20-200s，提拉速度为500-3000μm/min，每次镀膜后进行热处理，镀膜过程重复1-4次，300℃-600℃进行退火处理1-3h。
实施例一
将清洗干净的医用金属材料316L不锈钢，在体积比为10%的硝酸和2%的浓硝酸中50℃水浴60min，表面生成氧化铬薄膜，完成对不锈钢的原位表面改性；在配制好的TiO2溶胶中，通过浸渍式提拉法制备TiO2薄膜，其中，提拉速度为1000 μm/min，退火温度为500℃，退火时间为1h，完成对不锈钢的表面改性。
改性后的医用金属材料316L不锈钢表面均方根粗糙度为6.078 nm，接触角为41.3°，原位表面改性后的氧化物表面与TiO2薄膜间结合力增加，且亲水性TiO2薄膜具有良好的血液相容性。
实施例二
将清洗干净的医用金属材料316L不锈钢，在马弗炉中700℃热处理60min，表面生成氧化铬和氧化铁的混合薄膜，完成对不锈钢的原位表面改性；在配制好的TiO2溶胶中，通过浸渍式提拉法制备TiO2薄膜，其中，提拉速度为1000μm/min，退火温度为500℃，退火时间为1h，完成对不锈钢的表面改性。
改性后的医用金属材料316L不锈钢表面均方根粗糙度为12.499 nm，接触角为35.2°，原位表面改性后的混合物氧化物表面与TiO2薄膜间结合力增加，同时亲水性TiO2薄膜具有良好的血液相容性。
应当说明的是，上述实施例均可根据需要自由组合。以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (1)

1.一种用于医用金属材料的表面改性方法，其特征在于，所述表面改性方法中包括：
S1金属材料磨抛及清洗；
S2在金属材料表面生成氧化物薄膜或混合氧化物薄膜；
S3采用溶胶凝胶法在金属材料表面进一步制备TiO2薄膜，完成对金属材料的表面改性；
在步骤S2中，采用预先配置的混合酸溶液对金属材料进行氧化的方法在其表面生成氧化物薄膜；具体，首先，在烧杯中配制混合酸溶液，混合酸成分包括体积比为5-20％的硝酸和1-5％的氢氟酸水溶液；之后，将经打磨抛光的金属材料放置到盛有混合酸溶液的烧杯中，并将烧杯放置于恒温水浴锅中30-90min，在金属材料表面生成氧化物薄膜；
或在步骤S2中，采用高温热处理的方法在金属材料表面生成混合氧化物薄膜，具体，将金属材料置于高温炉中1～3h，在金属材料表面生成混合物氧化膜；
在步骤S3中包括：
S31采用钛酸四丁酯为原料配制TiO2溶胶；具体，将钛酸四丁酯溶入部分无水乙醇，充分搅拌，得到溶液a；将适量的浓硝酸、蒸馏水加入到部分无水乙醇，得到溶液b；在搅拌过程中，将溶液b缓慢加入到溶液a中，继续搅拌，得到TiO2溶胶，陈化24小时以上用于制备薄膜；
S32通过浸渍式提拉法在金属材料表面形成TiO2薄膜，具体，浸渍时间20-200s，提拉速度为500-3000μm/min，每次镀膜后进行热处理，镀膜过程重复1-4次，300℃-600℃进行退火处理1-3h。
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