近年來人們對羥基磷灰石(Hydroxyapatite；HA)的合成進行相當多的研究，羥基磷灰石為人體骨骼中的磷酸鈣鹽類的主要成分，目前大量用以取代醫療材料表面之塗層，並能促使骨質增生與誘導的作用，有效修復缺損組織。用於替代人體組織的生醫材料須具有機械耐久性、優異耐腐蝕性與優良的生物相容性等，能使植入材料能暫時或永久留於人體而不產生排斥。微弧氧化（MAO）是一種新近發展的技術，此技術相對火焰噴塗法較簡便，可在鈦表面產生多孔、相對粗糙且牢固附著的氧化鈦薄膜。此製程將電化學氧化與水性電解浴中的高壓火花處理相結合，電解浴還含有溶解鹽形式的改質元素（例如鈣和磷），以摻入所得塗層中。含有Ca和P離子的多孔膜也可以增強植體與骨頭之間的結合力和支抗。而依靠電參數的調整或電控制方式的選擇，可以對塗層的生長和微觀結構獲得進一步的改善。本研究選用的鈦合金為Ti6Al4V，通過調節微弧氧化法的實驗條件，如電壓和處理時間，製備氫氧基磷灰石薄膜。使用掃描式電子顯微鏡(SEM)、能量散射光譜儀(EDS)、X光繞射儀(XRD)，X射線光電子光譜(XPS)等儀器，來測量塗層的表面形貌、元素結構及結晶成份等分析，也利用 Tafel 測試來評估塗層的耐腐蝕性，通過在不同電位下測量電流來繪製極化曲線，然後使用Tafel 斜率分析來推斷腐蝕速率和其他電化學參數，利用 EIS 測試塗層的界面特性，包括電荷轉移阻抗、電解質擴散阻抗等。掃描式電子顯微鏡(SEM)顯示出在添加不同濃度的醋酸鋅下，呈現出不一樣的塗層形貌。X光繞射儀(XRD)表明沉積的生成物結晶體為氫氧基磷灰石及磷酸鈣組成。以相同電壓下且摻雜不同濃度的鋅進行微弧氧化。X射線光電子光譜(XPS)證明本研究成功成長氫氧基磷灰石之塗層結構。本研究利用微弧氧化法製備了具有良好結構和生物相容性的氫氧基磷灰石薄膜，為其在醫學應用中的潛在應用提供了實驗基礎。未來的研究可進一步探討植入材料方面的應用潛力。

In recent years, there has been substantial research on the synthesis of hydroxyapatite (HA), a major component of calcium phosphate salts in human bones. HA is widely used to coat the surfaces of medical materials, promoting bone growth and inducing effective tissue repair. Biomedical materials intended for substitution in human tissues must possess mechanical durability, excellent corrosion resistance, and superior biocompatibility to allow the implant to remain in the body temporarily or permanently without eliciting rejection.
Micro-arc oxidation (MAO) is a recently developed technique, that offers a simpler alternative to flame spraying. It can generate porous, relatively rough, and firmly adherent titanium oxide films on titanium surfaces. This process combines electrochemical oxidation with high-voltage spark treatment in an aqueous electrolyte bath containing dissolved salts of modifying elements (such as calcium and phosphorus) for incorporation into the resulting coating. The porous film containing Ca and P ions can enhance the bonding strength and resistance between the implant and bone. Further improvement in the coating's growth and microstructure can be achieved by adjusting the electrical parameters or selecting specific electro-control modes.
In this study, Ti6Al4V was chosen as the substrate, and different thicknesses of hydroxyapatite films were prepared by adjusting the experimental conditions of the micro-arc oxidation process, such as voltage and anodic treatment time. The surface morphology, elemental structure, and crystalline composition of the coatings were analyzed using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Additionally, the hydrophilicity and corrosion resistance of the coatings were investigated through contact angle measurements and Tafel tests, respectively. Tafel analysis involved measuring current at different potentials to construct polarization curves, followed by Tafel slope analysis to infer corrosion rates and other electrochemical parameters. Electrochemical impedance spectroscopy (EIS) was employed to evaluate the coating's interface characteristics, including charge transfer resistance and electrolyte diffusion impedance.
SEM images revealed distinct coating morphologies with the addition of different concentrations of zinc acetate. XRD confirmed the crystalline composition of the deposited product as tricalcium phosphate (TCP) and HA. Micro-arc oxidation was conducted at the same voltage with varying concentrations of zinc. XPS confirmed the successful preparation of the hydroxyapatite (HA) coating structure in this study.
This research successfully utilized the micro-arc oxidation method to prepare hydroxyapatite films with good structure and biocompatibility, laying an experimental foundation for their potential applications in the field of medicine. Future studies may further explore the application potential of these coatings in implant materials.

目錄
中文摘要 I
Abstract III
致謝 V
目錄 VI
圖目錄 VIII
表目錄 X
第一章 緒論 1
1-1 前言 1
第二章 基礎理論與文獻回顧 4
2-1 生醫材料 4
2-1-1 生醫材料簡介 4
2-1-2 生醫材料種類 4
2-2 生物相容性 5
2-3 鈦合金特性介紹 5
2-3-1 高生物相容性 5
2-3-2 耐腐蝕性 5
2-3-3 多彩的氧化膜 6
2-3-4 比強度高 6
2-4 表面處理介紹 8
2-5 氫氧基磷灰石 12
2-6 植入材披覆氫氧基磷灰石的優點 13
2-7 改善氫氧基磷灰石剝落之方法 14
2-8 文獻回顧 15
第三章 實驗方法與分析設備 24
3-1 實驗材料 24
3-2 實驗方法 24
3-3 試片製備 24
3-4 微弧氧化處理 25
3-5 HA與Zn-HA塗層的量測 26
3-6 表面性能分析 26
3-7 儀器原理 28
第四章 實驗結果與討論 43
4-1 掃描式電子顯微鏡（Scanning Electron Microscopy, SEM） 43
4-1-1 體外生物相容性測試之SEM分析 44
4-2 能量散射光譜儀(EDS) 45
4-2-1 體外生物相容性測試之EDS分析 45
4-3 X光繞射儀（X-Ray Diffraction, XRD） 46
4-3-1 體外生物相容性測試之XRD分析 47
4-4 X光電子能譜儀（X-ray Photoelectron Spectrometer, XPS） 48
4-4-1 體外生物相容性測試之XPS分析 49
4-5 塗層製備的理論模型 50
4-6 塔佛試驗 (Tafel test) 52
4-7 電化學阻抗分析儀 (Electrochemical impedance spectroscopy, EIS) 53
第五章 結論與未來展望 73
5-1 結論 73
5-2 未來展望 74
參考文獻 75

圖目錄
圖 2-1 增加表面粗糙度目的與相關處理方法 21
圖 2-2 常用的表面改質方法 21
圖 3-1 電解液藥品圖 33
圖 3-2 實驗架構 33
圖 3-3 實驗設備設置圖 34
圖 3-4 微弧氧化實驗示意圖 34
圖 3-5 X 光繞射儀 (XRD) 35
圖 3-6 X 射線光電子光譜 (XPS) 35
圖 3-7 掃描式電子顯微鏡(SEM)及能量散射光譜儀(EDS) 36
圖 3-8 電化學分析儀 36
圖 3-9 雷射共軛焦 37
圖 4-1 在相同電壓和時間且不同濃度之 HA、Zn-HA塗層的 SEM 圖 55
圖 4-2 為浸泡 SBF 後，在相同電壓和時間且不同濃度之 HA、Zn-HA塗層的SEM 圖 56
圖 4-3 在相同電壓和時間且不同濃度之 HA、Zn-HA塗層的 EDS 圖 57
圖 4-4 為浸泡 SBF 後，在相同電壓和時間且不同濃度之 HA、Zn-HA塗層的EDS 圖 58
圖 4-5 在相同電壓和時間且不同濃度之 HA、Zn-HA塗層的 XRD 圖 59
圖 4-6 為浸泡 SBF 後，在相同電壓和時間且不同濃度之 HA、Zn-HA塗層的XRD 圖 60
圖 4-7 HA 塗層在電壓 150V 下之 XPS 全譜圖 61
圖 4-8 為浸泡 SBF 後，HA 塗層在電壓 150V 下之 XPS 全譜圖 62
圖 4-9 在相同時間不同濃度且電壓 150V 下之 XPS Ca (2p)分峰圖 63
圖 4-10 為浸泡 SBF 後，在相同時間不同濃度且電壓 150V 下之 XPS Ca (2p)分峰圖 64
圖 4-11 在相同時間不同濃度且電壓 150V 下之 XPS O (1s)分峰圖 65
圖 4-12 為浸泡 SBF 後，在相同時間不同濃度且電壓 150V 下之 XPS O (1s)分峰圖 66
圖 4-13 在相同時間不同濃度且電壓 150V 下之 XPS Zn (2p)分峰圖 67
圖 4-14 為浸泡 SBF 後，在相同時間不同濃度且電壓 150V 下之 XPS Zn (2p)分峰圖 68
圖 4-15 HA、Zn-HA 塗層的 Tafel 極化曲線圖 69
圖 4-16 比較 HA、Zn-HA塗層在相同時間、相同電壓且不同濃度的電化學阻抗之奈奎斯圖(Nyquist plot) 70
圖 4-17 比較 HA、Zn-HA塗層在相同時間、相同電壓且不同濃度的電化學阻抗之波德圖(Bode plot) 71
圖 4-18 HA、Zn-HA塗層的等校電路模擬模型 72

表目錄
表 2-1 生物醫用金屬材料必需具備的基本條件 21
表 2-2 生物活性的影響因素 22
表 2-3 鈦合金表面處理後具有性能 22
表 2-4 氫氧基磷灰石之物理與化學性質 23
表 3-1 製備1000ml人體模擬體液各組成的添加順序、添加量及純度 26
表 3-2 電解液配方表 38
表 3-3 實驗耗材與設備儀器 39
表 4-1 為 HA、Zn-HA塗層的腐蝕電位、腐蝕電流與腐蝕速率 69
表 4-2 為 HA、Zn-HA塗層的溶液電阻、電容與極化電阻 72

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