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化学进展 2020, Vol. 32 Issue (4): 406-416 DOI: 10.7536/PC190732 前一篇   后一篇

• •

钛及钛合金表面羟基磷灰石涂层结合强度及稳定性

林巧霞1, 殷萌1, 魏延1, 杜晶晶1, 陈维毅1,2, 黄棣1,2,**()   

  1. 1. 太原理工大学生物医学工程学院生物医学工程系 纳米生物材料与再生医学研究中心 太原 030024
    2. 太原理工大学生物医学工程研究所 材料强度与结构冲击山西省重点实验室 太原 030024
  • 收稿日期:2019-07-25 修回日期:2019-12-27 出版日期:2020-04-05 发布日期:2020-03-30
  • 通讯作者: 黄棣
  • 作者简介:
    * 通信作者 Corresponding author e-mail:
  • 基金资助:
    国家自然科学基金项目(11632013, 11502158, 11802197, 11902214); 山西省重点研发国际合作项目(201803D421060); 山西省自然科学基金项目(201801D221439)
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The Bonding Strength and Stability Between Hydroxyapatite Coating and Titanium or Titanium Alloys

Qiaoxia Lin1, Meng Yin1, Yan Wei1, Jingjing Du1, Weiyi Chen1,2, Di Huang1,2,**()   

  1. 1. Research Center for Nano-biomaterials & Regenerative Medicine, Department of Biomedical Engineering, College of Biomedical Engineering, Taiyuan University of Technology, Taiyuan 030024, China;
    2. Institute of Applied Mechanics & Biomedical Engineering, Shanxi Key Laboratory of Materials Strength & Structural Impact, Taiyuan University of Technology, Taiyuan 030024, China;
  • Received:2019-07-25 Revised:2019-12-27 Online:2020-04-05 Published:2020-03-30
  • Contact: Di Huang
  • Supported by:
    The work was supported by the National Natural Science Foundation of China(11632013, 11502158, 11802197, 11902214); the International Cooperation Project Foundation of Shanxi Province(201803D421060); the Natural Science Foundation for Young Scientist of Shanxi Province(201801D221439)

钛(Ti)及其合金凭借优异的机械性能和良好的生物相容性,一直是骨和牙种植体的主要临床应用材料。由于钛及其合金自身的生物惰性,不易与周围骨组织进行快速的骨整合,因此其表面的生物活性有待进一步提高。羟基磷灰石(HA)是人体骨和牙齿的主要无机成分,具有良好的生物活性和生物相容性,受其力学性能的制约,常被作为涂层材料覆盖在钛基体表面,用以提高植入体的生物活性。但一直存在涂层与基体界面结合强度低和涂层力学稳定性差的问题,成为限制其临床广泛应用的主要因素。本文从涂层结构设计、成分设计及制备方法等方面,就国内外改善钛基底与HA涂层界面结合性能的研究现状和发展动态作一综述,为高性能钛植入体的制备和应用提供参考。

关键词： 钛植入体, 羟基磷灰石涂层, 结合强度, 稳定性

Titanium (Ti) and Ti alloys have been the main clinical application materials for bone and dental implants due to their excellent mechanical properties and good biocompatibility. However, it is not easy to achieve rapid osseointegration with surrounding bone tissues because of the biological inertia of titanium materials. Therefore, the biological activity of implant surface is further required. Hydroxyapatite (HA) is the main inorganic component of human bones and teeth, which has good bioactivity and biocompatibility. But restricted by its own brittleness, HA is often used as a coating material to cover the surface of Ti substrates to improve the biological activity of implants. However, the problems of weak bonding strength between coating and substrate and poor mechanical stability of coating have been the main factors limiting the wide clinical applications of HA coated titanium implants. From the aspects of coating structure, composition and preparation method, the research status and development trend of improving the interface bonding strength between Ti substrate and HA coating at home and abroad are summarized, which could provide a reference for the preparation and application of high-performance titanium implants.

Contents

1 Introduction

2 Structural design

2.1 Interface roughening

2.2 Interface nanocrystallization

2.3 Interface gradient design

3 Composition design

3.1 Inorganic ion addition

3.2 Metal and bioceramic addition

3.3 Other

4 Preparation

4.1 High-temperature preparation

4.2 Low-temperature preparation

4.3 Composite preparation

5 Conclusion and outlook

Key words: titanium implant, HA coating, bonding strength, stability
()
图1 物理吸附、化学键合和机械互锁的示意图[13]
Fig. 1 Schematic illustration of physical adsorption, chemical bonding, and mechanical interlocking[13]
图2 梯度涂层示意图[34]
Fig. 2 Schematic representation of the graded coating[34]
图3 HA沿OH通道c轴的透视图:报道了一些可能的取代离子, 两个三角形沿着c轴在相同水平处连接Ca(Ⅱ)离子[38]
Fig. 3 Perspective view along the c-axis of the OH channel environment. Some of the possible substituting ions are reported. The two triangles join Ca(Ⅱ) ions at the same level along the c-axis[38]
图4 PVD磁控溅射制备纯HA涂层和离子取代HA涂层的示意图[37]
Fig. 4 Schematic illustration of PVD magnetron sputtering for pure-HA and ion substituted-HA coatings[37]
图5 掺杂聚多巴胺的聚吡咯纳米线表面矿化形成磷酸钙的示意图 (a,b)多巴胺和吡咯通过电聚合沉积在Ti表面形成聚吡咯纳米线;(c,d)聚吡咯纳米线由于掺杂聚多巴胺而具有的儿茶酚基团促进磷酸钙晶体形成[56]
Fig. 5 The schematic illustration of formation of calcium phosphate biominerals on the polypyrrole nanowires doped with polydopamine. (a, b) the polypyrrole nanowires deposited on the biomedical titanium through the simultaneous electrical polymerization of dopamine and pyrrole. (c, d) catechol moiety on the surface of conducting polypyrrole nanowires doped with polydopamine assists calcium phosphate crystal formation[56]
图6 纤维增强增韧示意图 (A, C)被纤维增强的基体产生裂缝的两个视图;(B, D)A和C的透视图,以更好地理解“加强筋”作用[67]
Fig. 6 A typical representation of strengthening and toughening by fibres (A, C) represent two views of crack in a body being perturbed by fibres, (B, D) represent the see-through image of the body presented in A and C, for a better understanding of the reinforcement effects[67]
表1 HA涂层的高温制备法[13,37,68~73]
Table 1 Different high-temperature preparation methods to form HA coating[13,37,68~73]
High-temperature preparation
methods		 Advantages Disadvantages
Plasma spraying High deposition rates; low cost; fast bone healing Poor adhesion; non-uniformity in coating density; increase in residual stress; low crytallite which accelerates the dissolution of the coating in the body
Thermal spraying High deposition rates; low cost Poor adhesion; non-uniformity in coating
density; easy to dissolve
Pulsed laser deposition High deposition rates; ability to produce high
crystalline HA coating		 Lack of uniformity; low purity
Sputter soating Uniform coating thickness on flat substrates; dense coating; homogenous coating; high adhesion Low deposition rates; costly; produces
amorphous coatings
High-velocity suspension flame
spraying (HVSFS)		 High deposition rates; low cost; homogenous and
dense coating; fairly thin coating		 Poor adhesion; easy to dissolve
Hot isostatic pressing Produce dense coatings; homogeneous structure;
high uniformity; high precision		 Can not to coat complex substrates; high cost
表2 HA涂层的低温制备法[13,43,70,77~79]
Table 2 Different low-temperature preparation methods to form HA coating[13,43,70,77~79]
Low-temperature preparation
methods		 Advantages Disadvantages
Sol-gel Low cost;can coat complex shapes; simple deposition method; high purity; fairly good adhesion; very thin and high purity coating Some processes require controlled atmosphere processing; expensive raw materials; hard to control the porosity
Dip coating Can coat complex substrates; high surface
uniformity; good speed of coating;		 Requires high sintering temperatures;
thermal expansion mismatch; crack appearance
Biomimetic mineralization Can coat complex substrates; able to incorporate
bone growth stimulating factors and to form
bonelike apatite		 Obliges replacement and a constant pH of
simulated body fluid; time consuming
Electrophoretic/
electrochemical deposition		 Can coat complex shapes; uniform coating thickness; rapid deposition rates; low cost; high degree of
control on coating morphology and thickness		 Poor adhesion; challenging to produce
coatings without crack; involves high
sintering temperatures
Vacuum cold spray Can avoid oxidation and phase transition problems
during spraying;		 Cannot be used to prepare pure HA
coatings with good adhesion to substrates
图7 激光辅助冷喷涂系统示意图[88]
Fig. 7 Schematic diagram of laser-assisted cold spray system[88]
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