CN103628052B - 一种钛合金微孔骨表面二氧化钛薄膜涂层的制备方法 - Google Patents
一种钛合金微孔骨表面二氧化钛薄膜涂层的制备方法 Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 57
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 20
- 239000007888 film coating Substances 0.000 title claims abstract description 13
- 238000009501 film coating Methods 0.000 title claims abstract description 13
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 8
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- 229910000756 V alloy Inorganic materials 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
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- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
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Abstract
本发明涉及一种钛合金微孔骨表面二氧化钛薄膜涂层的制备方法。Ti6A14V合金人工骨在人体体液环境所形成的具有防御保护性的二氧化钛薄膜稳定性、耐久性差，导致Ti6A14V合金中的有毒元素A1、V析出。本发明将一定摩尔比的TiPT（异丙氧基钛):C3H8O(无水异丙醇):HCL(盐酸):H2O(水)搅拌均匀并陈化得到二氧化钛(TiO2)溶胶。并使用浸渍提拉法在钛合金微孔骨表面合成二氧化钛薄膜涂层，所生成的TiO2可以对基底提供有效的防腐性保护,增强材料的耐腐蚀性能，能极好地保护Ti6A14V合金表面不剥离。该方法制作的TiO2薄膜方法简单，成本低廉，具有潜在的生物医用领域的应用价值。
Description
技术领域
本发明涉及医用生物活性复合材料，特别涉及一种钛合金微孔骨表面二氧化钛薄膜涂层的制备方法。
背景技术
Ti6A14V合金具有比强度高，耐蚀性能优异，高温抗蠕变性能和无磁性等优良的性能，是目前最为常用的人工骨植入体和手术器械的生物医学材料。
然而,当Ti6A14V合金人工骨长期处于人体体液环境中时,其表面将会自发形成的具有防御保护性的二氧化钛薄膜，所生成的TiO2薄膜稳定性、耐久性差,且极可能被剥离甚至溶解于人体中,导致Ti6A14V合金中的有毒元素A1、V析出,并且随着这层TiO2薄膜的破坏,Ti6A14V合金表面的腐蚀作用将会加剧。由于Ti6A14V合金存在的磨损、腐蚀、植入感染问题，常常导致人工骨植入失败。
目前，各种已采用的Ti6A14V合金表面改性的方法均没有能够达到理想的临床应用效果，主要问题是表面结合强度不够或制造成本高。因此，继续探索新的在Ti6A14V合金表面制备涂层的方法，仍然是非常重要的前沿课题。
发明内容
本发明是为了改变现有的技术不足，而制备一种保护Ti6A14V合金微孔骨的耐腐蚀性能良好的二氧化钛薄膜涂层。
本发明的目的通过下述技术方案实现：
步骤1.将TiPT、C3H8O、HCL和H2O混合，它们之间的摩尔比为1.0:9.1:0.15:1.1，并用磁力搅拌器搅拌20分钟，保持温度在0-150C下陈化12-18小时，得到二氧化钛溶胶。
步骤2.将Ti6A14V合金微孔骨浸入上述二氧化钛溶胶中24-48小时，温度保持在15-250C。
步骤3.取合金微孔骨样品浸泡在40ml的0.5mol/l硝酸溶液中10-15天，温度保持在50-700C，所述的合金微孔骨样品大小为10mm*30mm*1mm。
步骤4.将Ti6A14V合金微孔骨样品以3cm/min的速度慢慢从硝酸水溶液中取出来并在常温下冷却，从而完成薄膜涂层的制备。
本发明的有益效果：
利用该方法形成的具有防御保护性的TiO2薄膜稳定性、耐久性好,能保护Ti6A14V合金微孔骨在人体中不容易剥离甚至溶解。
该方法制作的TiO2薄膜方法简单，成本低廉，具有潜在的生物医用领域的应用价值。
附图说明
图1为Ti6A14V合金微孔骨表面的二氧化钛薄膜涂层厚随浸入时间而变化图。
具体实施方式
下面通过附图和实施例，对本发明的技术方案做进一步的详细描述。
本发明的原理是利用计算机技术对微孔结构进行力学研究,优化出力学性能最好的微孔结构，利用Ti6A14V合金粉末激光烧结成型人工微孔骨。本发明中采用Ti6A14V合金微孔骨样品大小为10mm*30mm*1mm。将一定摩尔比的TiPT（异丙氧基钛):C3H8O(无水异丙醇):HCL(盐酸):H2O(水)搅拌均匀并陈化得到二氧化钛(TiO2)溶胶。并使用浸渍提拉法在钛合金微孔骨表面合成二氧化钛薄膜涂层，所生成的TiO2薄膜稳定性和耐久性好,能极好地保护Ti6A14V合金表面不剥离。
实例1
1.先将摩尔比TiPT（异丙氧基钛):C3H8O(无水异丙醇):HCL(盐酸):H2O(水)=1.0:9.1:0.15:1.1用磁力搅拌器搅拌20分钟，其温度保持在00C陈化12小时。
2.然后将Ti6A14V合金微孔骨浸入上述钛溶液中24小时，其温度保持在150C。
3.再将Ti6A14V合金微孔骨样品大小为10mm*30mm*1mm浸泡在40ml的0.5mol/l的硝酸溶液中10天，温度保持在500C。
4.Ti6A14V合金微孔骨样品以约3cm/min的速度慢慢从硝酸水溶液中拿出来在常温下冷却。
产品经扫描电子显微镜JEM-1400/1011测定，Ti6A14V合金微孔骨表面二氧化钛薄膜涂层厚度为8.48μm。经X射线衍射仪（日本理学）及其化学分析化得出Ti6A14V合金微孔骨表面二氧化钛的含量为10.1%。
图1所示为Ti6A14V合金微孔骨表面的二氧化钛薄膜涂层厚随浸入时间而变化图。（其中其它参数同实例1）
实例2
1.先将摩尔比TiPT（异丙氧基钛):C3H8O(无水异丙醇):HCL(盐酸):H2O(水)=1.0:9.1:0.15:1.1用磁力搅拌器搅拌20分钟，其温度保持在100C陈化15小时。
2.然后将Ti6A14V合金微孔骨浸入上述钛溶液中36小时，其温度保持在200C。
3.再将Ti6A14V合金微孔骨样品大小为10mm*30mm*1mm浸泡在40ml的0.5mol/l的硝酸溶液中12天，温度保持在600C。
4.Ti6A14V合金微孔骨样品以约3cm/min的速度慢慢从硝酸水溶液中拿出来在常温下冷却。
产品经扫描电子显微镜JEM-1400/1011测定，Ti6A14V合金微孔骨表面二氧化钛薄膜涂层厚度为10.8μm。经X射线衍射仪（日本理学）及其化学分析化得出Ti6A14V合金微孔骨表面二氧化钛的含量为10.3%。
实例3
1.先将摩尔比TiPT（异丙氧基钛):C3H8O(无水异丙醇):HCL(盐酸):H2O(水)=1.0:9.1:0.15:1.1用磁力搅拌器搅拌20分钟，其温度保持在150C陈化18小时。
2.然后将Ti6A14V合金微孔骨浸入上述钛溶液中48小时，其温度保持在250C。
3.再将Ti6A14V合金微孔骨样品大小为10mm*30mm*1mm浸泡在40ml的0.5mol/l的硝酸溶液中15天，温度保持在700C。
4.Ti6A14V合金微孔骨样品以约3cm/min的速度慢慢从硝酸水溶液中拿出来在常温下冷却。
产品经扫描电子显微镜JEM-1400/1011测定，Ti6A14V合金微孔骨表面二氧化钛薄膜涂层厚度为14.98μm。经X射线衍射仪（日本理学）及其化学分析化得出Ti6A14V合金微孔骨表面二氧化钛的含量为14.92%。
上述三例所制备得到表面带二氧化钛薄膜涂层的钛合金微孔骨其耐腐蚀性能测试：分别将Ti6A14V合金微孔骨大小为10mm*30mm*1mm表面未处理的样品，和按上述方法表面的二氧化钛薄膜涂层的样品置于盛有模拟人体体液(SimulatedBodyFluid,SBF)的密闭容器中浸泡40天,并模拟人体体液环境370C，采用经典三电极体系的电化学测试方法。实验结果显示，Ti6A14V合金微孔骨表面未处理的样品，其表面被破环并逐渐剥落。而经过二氧化钛薄膜涂层的样品基本没有腐蚀的现象。
Claims (1)
1.一种钛合金微孔骨表面二氧化钛薄膜涂层的制备方法，其特征在于该方法包括以下步骤：
步骤1.将TiPT、C3H8O、HCL和H2O混合，它们之间的摩尔比为1.0:9.1:0.15:1.1，并用磁力搅拌器搅拌20分钟，保持温度在0-15℃下陈化12-18小时，得到二氧化钛溶胶；
步骤2.将Ti6A14V合金微孔骨浸入上述二氧化钛溶胶中24-48小时，温度保持在15-25℃；
步骤3.取合金微孔骨样品浸泡在40ml的0.5mol/l硝酸溶液中10-15天，温度保持在50-70℃，所述的合金微孔骨样品大小为10mm*30mm*1mm；
步骤4.将Ti6A14V合金微孔骨样品以3cm/min的速度慢慢从硝酸水溶液中取出来并在常温下冷却，从而完成薄膜涂层的制备；
Ti6A14V合金微孔骨表面二氧化钛薄膜涂层厚度为8.48μm-14.98μm，Ti6A14V合金微孔骨表面二氧化钛的含量为10.1-14.92％。
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Effective date of registration: 20171025 Address after: 310018, Hangzhou economic and Technological Development Zone, Zhejiang, Hangzhou province 210 room, Pioneer Park, Hangzhou Dianzi University Patentee after: Hangzhou Charles Electronic Technology Co., Ltd. Address before: Hangzhou City, Zhejiang province 310018 Xiasha Higher Education Park No. 2 street Patentee before: Hangzhou Electronic Science and Technology Univ |
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Inventor after: Zhang Shuai Inventor after: Zong Wei Inventor before: Yan Lamei Inventor before: Zhou Shenghua Inventor before: Yuan Youwei |
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Effective date of registration: 20180314 Address after: 210046 Yanzi street and Yanlu No. 371, Qixia District, Nanjing, Jiangsu Patentee after: Nanjing jetech Biological Technology Co. Ltd. Address before: 310018, Hangzhou economic and Technological Development Zone, Zhejiang, Hangzhou province 210 room, Pioneer Park, Hangzhou Dianzi University Patentee before: Hangzhou Charles Electronic Technology Co., Ltd. |
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