鎂合金具有生物可降解特性與良好的生物相容性，並且其機械性質與骨頭相匹配，可作為新的可降解骨科植體，但由於未經處理的鎂合金在人體環境中降解腐蝕過快，並且腐蝕伴隨的副產物，氫氣、高濃度的鹼性離子與鎂離子可能會導致周邊骨組織的發炎反應，因此本研究將透過表面處理減緩腐蝕與提高材料的生物相容性。
實驗首先透過微弧氧化處理在鎂合金基材上形成一多孔鈍化層，其成分主要為氧化鎂與矽氧化鎂，此陶瓷氧化塗層可防止腐蝕液體接觸基材，提升材料的抗腐蝕能力，本研究藉由添加氟化物以及調整最終電壓值，最佳化塗層的腐蝕阻抗。微弧氧化塗層表面散布的孔洞可增加其粗糙度與表面積，並且塗層中最外層的氫氧化鎂可透過氫鍵與聚乙烯亞胺(Polyethyleneimine,PEI)結合，分枝型態的PEI具有一級胺可與羧基交聯形成醯胺鍵，因此棓酸(Gallic acid, GA)，一種多功能性的天然酚類分子，即可固定在微弧氧化塗層上，儘管鎂合金表面已有一層氧化保護層，但水溶液下的棓酸依然會破壞塗層的結構腐蝕鎂合金，所以接枝反應必須在非水溶液下進行，確保抗腐蝕性不被破壞。
經由FT-IR、XPS與親水角實驗證實，本研究成功將PEI與GA固定在微弧氧化塗層上，並且藉由表面型態、酸鹼值變化、氫氣釋放與電化學實驗確認此製程不會破壞塗層和降低抗腐蝕能力，在體外細胞實驗，發現經由PEI與GA修飾後的組別具有最好的生物相容性，且能夠促進骨細胞的貼附行為，而GA又可再接上含有胺基的功能性分子，如: 血管內皮生長因子(VEGF)，此研究成功發展出第一個將棓酸修飾在生醫鎂合金微弧氧化塗層的方法。

Magnesium alloys are biodegradable materials with good biocompatibility. Its mechanical properties are close to human’s natural bone and thus magnesium alloys are good candidates of biodegradable bone implants. However, the unmodified magnesium alloys may suffer from the rapid corrosion in the physiological environment. Moreover, the byproducts of the corrosion, such as hydrogen, high concentration of metallic and alkaline ions, will cause the inflammatory of the osseous tissue. Thus, this research utilized surface modification to decrease the corrosion rate and improve the biocompatibility.
First, micro arc oxidation (MAO) process created a porous and passivated coating on the magnesium alloy. The coating, mainly composed of MgO and Mg2SiO4, could inhibit the corrosive solution contacting with the substrates to increase the corrosion resistance. In this study, by modulating the components of the electrolytes and the final voltages, the highest corrosion resistance of MAO coating could be obtained. Second, the scattering pores of MAO coating could increase surface roughness and area. In addition, Mg(OH)2 covered the outmost part of the coating which provide great sites for combining Polyethyleneimine (PEI) through hydrogen bond. The amine group of PEI could further react with the carboxyl group of gallic acid (GA), a natural and multifunctional phenolic molecule, by forming amide bond. Although there was a protective layer on the magnesium alloy, under the aqueous condition, GA still would break the structure of the MAO coating. Therefore, the grafting reaction must process in the non-aqueous solution to ensure the sufficient corrosion resistance.
In this study, PEI and GA were successfully immobilized onto the MAO coating confirmed by FT-IR, XPS and contact angle. The corrosion resistance was assessed by the surface morphology, the variation of the pH value, the releasement of the hydrogen and the electrochemical tests indicating that the immobilization wouldn’t decline the quality of the MAO coating. In vitro tests, the cell cytotoxicity and adhesion tests found that PEI and GA modified group had the best biocompatibility and can stimulate osteoblastic-like cells adhesion. Moreover, GA can further combine with some biofuctional molecules, such as vascular endothelial growth factor (VEGF). In conclusion, this study successfully developed a method for immobilizing GA onto MAO coating of biodegradable magnesium alloy for the first time.

中文摘要 I
Abstract II
致謝 IV
Table of contents V
List of tables VIII
List of figures IX
Chapter 1 introduction 1
1.1 Biodegradable Orthopedic Implants 1
1.2 Magnesium Alloys 3
1.3 The comparison of surface treatment for magnesium 5
1.4 Strategies to improve micro arc oxidation coating 6
1. Choice of electrolytes 9
2. Process parameters and conditions 10
3. Sealing and post treatments 10
1.5 The biologic coatings for orthopedic implants 11
1.6 Molecules immobilized on magnesium 13
1.7 Polyethyleneimine 15
1.8 Phenolic molecules 16
1.9 Motivation 18
Chapter 2 Materials and Methods 19
2.1 Experimental equipment and materials 19
2.1.1 Magnesium specimens 19
2.1.2 Experimental Materials 19
2.1.3 Experimental Equipment 20
2.2 Experimental Methods 21
2.2.1 Micro Arc Oxidation coating 21
2.2.2 Polyethyleneimine Coating 21
2.2.3 Immobilization of Gallic Acid 22
2.3 Experimental Setup 23
2.4 Material Characterizations 23
2.4.1 Surface morphology and chemical composition 23
2.4.2 AFM measurements 24
2.4.3 Phase composition measurement 24
2.4.4 Functional group measurement 24
2.4.5 X-ray photoelectron spectroscopy 24
2.4.6 Water contact angle 25
2.4.7 Secondary immobilizing ability 25
2.5 Corrosion resistance analysis 26
2.5.1 Electrochemical test 26
2.5.2 Hydrogen releasement tests 26
2.5.3 pH value enhancement tests 27
2.6 Cell Culture 27
2.7 In vitro tests 28
2.7.1 Cytotoxicity tests 28
2.7.2 Cell adhesion tests 28
2.7.3 Hemolysis tests 29
Chapter 3 Results 30
3.1 The effects of the electrolyte for MAO coating 30
3.2 The effects of the final voltage in MAO process 36
3.3 MAO coating immobilized with PEI and GA: Part 1 Materials analysis 41
3.4 MAO coating immobilized with PEI and GA: Part 2 Materials corrosion resistance analysis 50
3.5 MAO coating immobilized with PEI and GA: Part 3 In vitro tests 52
Chapter 4 Discussion 58
4.1 The optimization of MAO coating 58
4.2 MAO coating immobilized with PEI and GA: Material analysis 61
4.3 MAO coating immobilized with PEI and GA: The evaluation of corrosion behavior 64
4.4 MAO coating immobilized with PEI and GA: The performance of biological response 66
Conclusion 70
References 71

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