微弧氧化-水热处理制备TiO2 HA生物活性涂层的研究

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3.0 赵德峰 2024-11-19 4 4 6.93MB 60 页 15积分

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摘要

钛及钛合金由于具有密度低、弹性模量低等优异的机械性能以及优良的生物

相容性和较高的耐腐蚀性，是目前广泛研究和应用的生物种植体材料。然而将其

植入到人体中存在结合强度低、生物活性差、愈合时间长等问题，并且其耐磨性

较差，植入人体后腐蚀严重，容易向肌体释放金属离子，对肌体不利。钛及其合

金的这些缺陷严重影响了钛种植体的临床成功率。因此，对钛及其合金进行表面

改性以完善其生物学性能迫在眉睫。

本课题以 Ti6-Al4-V 为研究对象，采用微弧氧化-水热处理法对钛合金进行表

面改性，在其表面生成一层含有羟基磷灰石（HA）的多孔 HA-TiO2生物活性陶

瓷氧化膜。通过微弧氧化制得的多孔结构有利于骨细胞的附着生长，在很大程度

上可以提高植入体与骨组织之间的结合强度。在微弧氧化的基础上，对植入体进

行水热处理，使氧化膜层表面生成一层羟基磷灰石(Hydroxyapatite,简称 HA)涂

层，创新性地提出在水热处理液中添加钙盐和磷盐的思路，获得了分布更加均

匀、形态更加统一的 HA 涂层，使得 Ti6-Al4-V 的生物活性有了很大提高。

本课题包括三个部分：

1) 微弧氧化制备富含钙磷元素的多孔陶瓷氧化膜

此试验以乙酸钙（Calcuim acetate,CA）、磷酸二氢钠(NaH2PO4)为钙源和磷

源，通过配制不同浓度乙酸钙和磷酸二氢钠的电解液，来研究电解液中钙盐、磷

盐浓度对膜层的影响。结果表明：

（1）在一定乙酸钙浓度和处理时间前提下，电解液中钙盐或者磷盐浓度的提高

导致微弧氧化过程中电流的提高，而电流的提高又导致膜层中孔洞直径增大，膜

层孔洞的增大导致膜层与基体的结合力降低。概括来讲，即膜层孔洞大小影响膜

层与基体的结合强度。

（2）随着微弧氧化处理时间的延长，膜层厚度增加，膜层表面孔洞直径变小。

这是随着处理时间的延长，膜层逐渐增厚，电流逐渐减小，从而出现封孔效应的

缘故。

2) 水热处理制备羟基磷灰石涂层

本文作者依据相关研究人员关于水热处理过程中钙、磷元素游离出膜层参与

HA 结晶的理论，大胆尝试水热处理液中添加钙盐、磷盐的方法。同时，对水热

处理中诸如温度、时间、PH 等工艺参数也进行了相关的研究。结果表明：

（1）随着温度的升高，HA 的直径逐渐增大。

（2）随着处理时间的延长，HA 的数量逐渐增多，尺寸逐渐增大。

（3）较高的水热处理液 PH 有利于 HA 结晶和形核。

（4）水热处理液中添加磷盐有助于 HA 结晶，但过多的磷盐使得片状 HA 增多。

（5）水热处理液中添加钙盐有助于 HA 结晶，但结晶出的 HA 为厚片状。

3) 模拟体液浸泡试验

本部分试验采用常用的 SBF(simulation body fluid,模拟体液)法对微弧氧化-水

热处理后的试样进行生物活性测试。通过对试样进行不同时间的 SBF 溶液浸泡试

验，以观察试样诱导羟基磷灰石的生成能力以及随时间的变化趋势。结果表明：

微弧氧化-水热处理后的试样，在 4天内便可诱导厚度可观的羟基磷灰石布满其表

面，表现出了很强的生物活性。

关键词：钛合金；表面改性；羟基磷灰石；微弧氧化；水热合成

ABSTRACT

Titanium and its alloys are most attractive metal biomaterial materials because of its

excellent mechanical characters such as lower density, good biocompatibility and

corrosion resistance. This metal and its alloys have been widely used and studied.

Unfortunately, titanium and its alloys cannot bond to bone due to its bad combining

intensity with human body, poor bioactivity, and time wasting in the bone healing. Also

titanium and its alloys are easy to release ion to body because corrosion in physiological

environment. All of these facts limited the clinical achievement ratio and widespread

development of implant technique. Therefore, surface modification of titanium and its

alloys that to improve its biological performance is imminent.

This studying takes Ti6-Al4-V as the research object. By using micro-arc oxidation -

water heat treatment method, hydorxyapatite (HA)-TiO2 coatings were prepared on the

surface of Ti6Al4V. Because of the MAO-coating's porous structure, it can not only

helps osteocytes adherent growth, but also benefits the blood circulation, also it can

improve the bond strength between implants and human body. After that, HA coatings

can be prepared on the surface of MAO-treated Ti6Al4V by using hydrothermal

treatment. The hydorxyapatite that on the surface and in the holes can enhance the

bioactive of Ti6-Al4-V.And hydrothermal treatment makes the hydorxyapatite

crystallize well.

This studying includes three parts:

1. Preparation porous ceramics oxidation film that rich in calcium and phosphate

elements.

In this membrane, electrolyte were prepared with different calcium acetate and

sodium dihydrogen phosphate(NaH2PO4) concentration and analysis impacts of calcium

acetate and sodium dihydrogen phosphate of electrolyte on the MAO film. The results

show that:

(1)On the premise of certain film thickness, with the increasing of calcium acetate or

sodium dihydrogen phosphate concentration of electrolyte, the current increased in the

MAO process. As a result, the hole diameter of the film increased and the combination

of the film and substrate is reduced.

(2)With the prolonging of MAO treating time, the thickness of film increased, the

diameter of hole became smaller. All above is the result of current reducing?

2. Preparation hydroxyapatite coating by hydrothermal treatment.

In this part, the author boldly attempt to add calcium acetate or sodium dihydrogen

phosphate into the solution of hydrothermal treatment on the theory that acetate and

sodium dihydrogen phosphate free from MAO film to crystallize hydorxyapatite. This

theory was summarized by the author after reading a lot of related documents.

Furthermore, the parameters of hydrothermal treatment, such as temperature, process

time, PH, etc., were studied. The results show that:

(1)The diameter of HA raised with increasing temperature of hydrothermal

treatment.

(2)When the process time of hydrothermal treatment was protract, the number and

size of HA gradually increased.

(3)Higher PH is conducive to HA nuclear and crystal.

(4)The solution with sodium dihydrogen phosphate can promote HA crystal. And

more sodium dihydrogen phosphate leaded to more sheet HA.

(5)Calcium acetate can help HA crystal when added into solution. And calcium

acetate lead to the thick sheet HA.

3. SBF soaking test

This test was used to check biological activity of sample which is prepared by

MAO and hydrothermal treatment by means of Simulation Body Fluid. The results

suggested that the sample had good biological activity.

Key words: Titanium alloys, Bioactivity, Hydroxyapatite, Micro-arc

oxidization, Hydrothermal treatment

中文摘要

ABSTRACT

第一章绪论............................................................................................................... 1

§1.1 引言................................................................................................................. 1

§1.2 常用的生物医用材料..................................................................................... 2

§1.2.1 生物医用金属材料................................................................................. 2

§1.2.2 生物医用陶瓷材料................................................................................. 3

§1.3 钛合金的组成和性能..................................................................................... 4

§1.4 羟基磷灰石..................................................................................................... 5

§1.5 常用的表面改性技术 ..................................................................................... 6

§1.6 论文研究意义与创新点 ................................................................................. 8

§1.6.1 论文研究意义......................................................................................... 8

§1.6.2 创新点..................................................................................................... 9

第二章微弧氧化制备富含钙磷元素的多孔陶瓷氧化膜........................................ 10

§2.1 实验材料与仪器........................................................................................... 11

§2.2 试验方法...................................................................................................... 14

§2.3 试验结果与分析........................................................................................... 14

§2.3.1 微弧氧化法制备的含钙磷氧化膜....................................................... 14

§2.3.2 不同钙盐磷盐质量比电解液对膜层的影响....................................... 19

§2.3.3 微弧氧化处理时间对膜层的影响....................................................... 24

§2.4 本章小结....................................................................................................... 28

§2.4.1 膜层形成机理...................................................................................... 28

§2.4.2 Ca、P 元素进入膜层机理 ................................................................... 29

§2.4.3 微弧氧化工艺对膜层影响总结.......................................................... 29

第三章水热处理制备羟基磷灰石涂层.................................................................... 31

§3.1 实验材料与仪器........................................................................................... 31

§3.2 试验方法....................................................................................................... 32

§3.3 试验结果与分析........................................................................................... 33

§3.3.1 处理液 PH 值对 HA 生长的影响 .......................................................... 33

§3.3.2 处理液磷盐的添加及其浓度对 HA 生长的影响 ................................ 35

§3.3.3 处理液钙盐的添加对 HA 生长的影响 ................................................ 38

§3.3.4 处理液同时添加钙盐和磷盐对 HA 生长的影响 ................................ 39

§3.3.5 水热处理时间对 HA 生长的影响 ........................................................ 40

§3.3.6 水热处理温度对 HA 生长的影响 ........................................................ 41

§3.4 本章小结....................................................................................................... 42

§3.4.1 水热处理促生 HA 的机理分析............................................................42

§3.4.2 本章结果总结....................................................................................... 43

第四章膜层的模拟体液浸泡研究............................................................................ 45

§4.1 试验方法....................................................................................................... 45

§4.1.1 模拟体液（SBF）的配制.................................................................... 45

§4.1.2 试样生物活性试验步骤....................................................................... 46

§4.2 试验结果及分析........................................................................................... 46

§4.2.1 表面形貌分析....................................................................................... 47

§4.2.2 物相组成析........................................................................................... 47

§4.3 SBF 诱导羟基磷灰石沉积过程和机理探讨 ............................................... 47

§4.3.1 羟基磷灰石形成过程分析................................................................... 48

§4.3.2 SBF 中羟基磷灰石形成机理探讨 ....................................................... 48

§4.4 本章小结 ....................................................................................................... 49

第五章总结与展望.................................................................................................... 52

§5.1 总结............................................................................................................... 52

§5.2 展望............................................................................................................... 52

参考文献..................................................................................................................... 54

在读期间公开发表的论文和承担科研项目及取得成果......................................... 57

致谢............................................................................................................................. 58

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摘要：

摘要钛及钛合金由于具有密度低、弹性模量低等优异的机械性能以及优良的生物相容性和较高的耐腐蚀性，是目前广泛研究和应用的生物种植体材料。然而将其植入到人体中存在结合强度低、生物活性差、愈合时间长等问题，并且其耐磨性较差，植入人体后腐蚀严重，容易向肌体释放金属离子，对肌体不利。钛及其合金的这些缺陷严重影响了钛种植体的临床成功率。因此，对钛及其合金进行表面改性以完善其生物学性能迫在眉睫。本课题以Ti6-Al4-V为研究对象，采用微弧氧化-水热处理法对钛合金进行表面改性，在其表面生成一层含有羟基磷灰石（HA）的多孔HA-TiO2生物活性陶瓷氧化膜。通过微弧氧化制得的多孔结构有利于骨细胞的附着生长，在很大...

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