论文总字数：26678字

摘 要

钛合金由于具有良好且稳定的机械性能，常被用于医疗骨种植体中，而医用钛合金的结构与性质不同于自然骨，和人体组织相差较大，植入体内后与硬组织或软组织进行生物化学融合较困难，并且由于表面钝化膜的存在，钛合金与骨组织难以进行化学键结合，导致骨组织被纤维组织包围并与周围环境发生分离，致使外科手术失败，因此医用钛合金的表面改性技术具有较高的研究价值。本论文采用电沉积法在钛合金的表面制备羟基磷灰石涂层，并探讨了刻蚀液体系、电解液成分和沉积电压等工艺条件对涂层的形貌、生物活性以及耐蚀性的影响，得出以下结论：

HNO₃-HF的刻蚀液体系既可以保证试样不会过度腐蚀，也可以达到增加比表面积的目的，最适合钛片刻蚀。柠檬酸根能够使HA的晶粒由六棱柱状变为尖锥细棒状，晶粒尺寸显著减小，使得涂层更加均匀、致密，且不会改变涂层的成分。预计沉积电压为4V左右时，涂层具有较高的完整性且能在表面均匀分布，热震次数最佳，耐蚀性最好。当反应温度为40℃左右时，生物稳定性较好。

关键词：钛 生理环境 刻蚀 电沉积 羟基磷灰石涂层

Research on Surface Treatment Technology of Titanium Metal in Human Physiological Environment

Abstract

Titanium alloys are often used in medical bone implants because of their good and stable mechanical properties. The structure and properties of medical titanium alloys are different from natural bones, and they are quite different from human tissues. After implanted in the body, they are hard or soft. It is difficult to perform biochemical fusion, and due to the presence of a surface passivation film, it is difficult for chemical bonding between titanium alloy and bone tissue, resulting in bone tissue surrounded by fibrous tissue and separated from the surrounding environment, resulting in surgical failure. Surface modification technology has high research value. In this paper, electrodeposition is used to prepare hydroxyapatite coating on the surface of titanium alloy, and the process conditions such as etching solution system, electrolyte composition and deposition voltage are discussed to the coating morphology, biological activity and corrosion resistance. Influence, the following conclusions are drawn:

The etching solution system of HNO₃-HF can not only ensure that the sample will not be excessively corroded, but also achieve the purpose of increasing the specific surface area, which is most suitable for etching of titanium sheets. The citrate can change the HA grain from a hexagonal column shape to a tapered thin rod shape. The grain size is significantly reduced, making the coating more uniform and dense without changing the composition of the coating. It is expected that when the deposition voltage is about 4V, the coating has high integrity and can be evenly distributed on the surface, with the best number of thermal shocks and the best corrosion resistance. When the reaction temperature is about 40℃, the biological activity is better.

Key Words: Titanium; Physiological environment; Etch; Electro-deposition; HA

目 录

摘 要 I

Abstract II

目 录 III

第一章 绪论 1

1.1 引言 1

1.2 生物医用钛及钛合金简介 1

1.2.1钛及钛合金简介 1

1.2.2钛及钛合金的生物医学应用 2

1.3 钛及其合金的腐蚀 4

1.3.1钛的特殊腐蚀形态 4

1.3.2钛的点蚀机理 5

1.4 生物医用钛的常见表面改性技术 6

1.4.1机械方法 7

1.4.2物理方法 7

1.4.3化学方法 8

1.4.4其他方法 10

1.5 本课题的研究意义及内容 11

第二章 实验及研究方案 12

2.1 实验材料及仪器设备 12

2.2 实验步骤 13

2.2.1刻蚀液配置 13

2.2.2预处理 14

2.2.3电解液配置 14

2.2.4HA涂层制备 14

2.3 测试内容 15

2.3.1腐蚀速率测定 15

2.3.2使用金相显微镜观察刻蚀后Ti的表面形貌 16

2.3.3涂层物相测试 16

2.3.4涂层表面形貌测试 16

2.3.5结合强度测试 16

2.3.6生物稳定性测试 17

2.3.7极化曲线测试 17

第三章 实验结果及预测结果的讨论 19

3.1 刻蚀液的选择 19

3.1.1腐蚀速度分析 19

3.1.2表面形貌分析 20

3.1.3进一步实验预测 20

3.2 柠檬酸根的影响分析 21

3.2.1涂层的形貌和物相分析 21

3.2.2涂层的结合强度分析 22

3.3 沉积电压的影响分析 22

3.3.1表面形貌和物相分析 22

3.3.2结合强度分析 24

3.3.3耐蚀性分析 24

3.4 涂层生物稳定性分析 25

第四章 结论与展望 27

参考文献 28

致谢 31

第一章 绪论

1.1 引言

金属材料在生物领域方面也可用作医用材料，并且在很早之前就开始被使用。因其在人体中也能保持很好的稳定性，常常作为植入体植入人体中置换出已经磨损或病变的组织。表1-1列出了生物医用金属材料的发展史^[1]。

表1-1 生物医用材料的发展史

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