臺灣博碩士論文加值系統

本研究嘗試使用不同方法在經微弧氧化處理後之鈦及鈦合金多孔二氧化鈦陶瓷膜表面製備氫氧基磷灰石。本論文分為兩部分：第一部分以自製的氫氧基磷灰石靶材，利用射頻磁控濺鍍技術將氫氧基磷灰石披覆於二氧化鈦多孔陶瓷膜表面。第二部分在微弧氧化電解液中添加Ca2+、PO43-離子，製備富含鈣、磷成份之多孔二氧化鈦陶瓷膜，再使用水熱法誘導陶瓷膜中Ca2+、PO43-離子，在表面成核，形成氫氧基磷灰石。本研究目的在能於鈦合金表面製備具耐蝕性、親水性與具生物活性的結構。所得陶瓷膜利用電化學阻抗頻譜儀(EIS)分析其耐蝕性，水滴接觸角儀分析表面親水性，並以掃描式電子顯微鏡(SEM)觀察不同方法之表面形貌、微細形狀測定儀(α-step)分析表面粗糙度及膜厚、X光繞射儀(XRD)觀察陶瓷膜的結構及相組成，最後使用MTT法檢測比較，經不同方法處理後之鈦陶瓷膜表面細胞增殖率。
第一部分研究結果顯示：射頻磁控濺鍍氫氧基磷灰石薄膜為非晶相結構，其細胞增殖能力雖次於經水熱處理之微弧氧化陶瓷膜，但仍較基材優異。第二部分研究結果顯示: 電解液中添加Ca2+、PO43-離子在定電壓400V處理下具有較高的鈣、磷含量、表面粗糙度及親水性，且經水熱法後，除可在表面形成氫氧基磷灰石結晶外，還可保留陶瓷膜原本的粗糙多孔形貌，且具有較佳的細胞增殖能力。

With different methods, this study aims to fabricate hydroxyapatite on the titanium and its alloy surface by use of microarc oxidation treatment. The paper is composed of two parts. The first part is that RF magnetron sputtering technology and self-made targets were used to produce hydroxylapatite covering the surface of titanium and its alloy. The second part is that a coating containing rich calcium and phosphorus composition was formed on the surface of titanium and its alloy by means of Ca2+, PO43-ions added in the electrolyte; and then, the surface was treated with a hydrothermal method in order to obtain rich content of hydroxylapatite.
The study also aims to prepare the titanium and its alloy with better corrosion resistance, hydrophilic property and biologically active structure. The corrosion resistance of oxide coating was analyzed by Electrochemical Impedance Spectroscopy (EIS). Hydrophilic property was investigated by water contact angle. Furthermore, the morphology, microstructure, chemical composition and phase structures of coating were studied by FSEM-EDS and XRD. Surface roughness and thickness were examined by micro-shape analyzer (α-step) analysis. In addition, the MTT assay was used to explore the cell proliferation rate.
The first part of the study shows that the surface made from the RF magnetron sputtering treatment has amorphous hydroxyapatite structure. Moreover, its cell proliferation is worse than that of the secondary part; however, it is still superior to the surface of substrate. More importantly, the surface obtained from the second part appears better hydrophilic property, richer calcium and phosphorus content, favored surface roughness and higher cell proliferation.

摘要 i
Abstract ii
致謝 iv
目錄 v
圖目錄 viii
表目錄 xi
第一章 緒論 1
1.1 前言 1
1.2 研究動機及目的 2
1.3 研究架構 3
第二章 文獻回顧與理論 5
2.1 鈦、鈦合金及其氧化物 5
2.2 氫氧基磷灰石 9
2.3 植入金屬與骨組織 13
2.4 各種披覆氫氧基磷灰石方法 14
2.4.1 電漿噴鍍法(plasma spraying) 14
2.4.2 鹼處理法(alkali treatment) 15
2.4.3 電泳法(electrophoretic) 15
2.4.4 射頻磁控濺鍍法(RF magnetron sputtering) 16
2.4.4.1 射頻磁控濺鍍氫氧基磷灰石 16
2.4.4.2 射頻磁控濺射鍍膜原理 16
2.4.5 微弧氧化法(Microarc oxidation) 20
2.4.5.1 微弧氧化簡介 20
2.4.5.2 鈦及鈦合金微弧氧化 21
2.4.6 水熱法(Hydrothermal) 23
2.4.6.1 水熱法簡介 23
2.4.6.2 微弧氧化鈦陶瓷膜水熱處理 24
第三章 研究方法與原理 25
3.1 微弧氧化實驗步驟 25
3.1.1試片前處理 25
3.1.2 鍍液組成與電壓控制 26
3.2 水熱法實驗步驟 27
3.3 射頻磁控濺鍍氫氧基磷灰石實驗步驟 28
3.3.1 氫氧基磷灰石靶材製作步驟 28
3.3.2 濺鍍實驗步驟 29
3.3.2.1 微弧氧化試片濺鍍前處理 29
3.3.2.2濺鍍氫氧基磷灰石步驟 29
3.4體外細胞培養實驗步驟 32
3.5 鍍膜分析及量測 36
3.5.1 表面形貌分析 36
3.5.2 成分分析 37
3.5.3 鍍層晶相分析 38
3.5.4 膜層厚度量測 39
3.5.5 膜層親水性測試 40
3.5.6 膜層表面粗糙度分析 41
3.5.7 耐蝕性測試 42
3.6 細胞培養 44
3.7 實驗使用之材料及藥品 45
3.7.1 材料 45
3.7.2 藥品 45
第四章 結果與討論 47
4.1 射頻磁控濺鍍氫氧基磷灰石 47
4.1.1 氫氧基磷灰石靶材壓製 47
4.1.2 濺鍍氫氧基磷灰石 48
4.1.3 氫氧基磷灰石薄膜晶相及EDX成分分析 49
4.1.4 氫氧基磷灰石薄膜表面及橫截面分析 50
4.2 定電壓對微弧氧化膜之影響 51
4.3 純鈦及Ti-6Al-4V微弧氧化 52
4.3.1 表面及橫截面形貌分析 52
4.3.2 純鈦及Ti-6Al-4V表面粗糙度分析 56
4.3.3 純鈦及Ti-6Al-4V微弧氧化XRD分析 57
4.3.4 純鈦及Ti-6Al-4V膜層表面及橫截面EDX成分分析 59
4.3.5 純鈦及Ti-6Al-4V膜層動電位極化耐蝕性分析 63
4.4 微弧氧化膜水熱處理 69
4.4.1 水熱前後XRD分析 69
4.4.2 表面形貌分析 71
4.4.3 水熱前後EDX-Mapping分析 80
4.4.4 水滴接觸角分析 85
4.5 細胞增殖實驗分析 87
第五章 結論與未來建議 89
5.1 結論 89
5.2 未來建議 90
參考文獻 91

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