臺灣博碩士論文加值系統

本研究第一部份探討的是 Ti50Ni50-xFex (x = 1, 2 and 3)形狀記憶合金於林格氏液中腐蝕浸出合金表面離子釋出及表面性質，利用感應耦合電漿質譜分析儀、X光繞射分析儀、電化學測試及X光光電子能譜儀進行分析。感應耦合電漿質譜分析儀實驗結果得知Ti50Ni50-xFex形狀記憶合金Ni及Fe離子腐蝕浸出濃度皆高於Ti離子濃度。電化學結果顯示Ti50Ni50-xFex形狀記憶合金抗腐蝕性隨合金中Fe原子含量的增加而下降。X光光電子能譜儀結果指出Ti50Ni50-xFex形狀記憶合金表面主要是由TiO2氧化物所構成並形成一薄膜層，而NiO及Fe2O3氧化物也會在金屬表面形成，破壞TiO2氧化層的完整性，造成大量的Ni及Fe離子釋出，導致Ni及Fe離子釋出量高於Ti離子。Ti50Ni50-xFex形狀記憶合金中金屬離子的釋出具有一定的風險，必須要在Ti50Ni50-xFex形狀記憶合金表面進行改質，方可成為具有潛力之生醫材料。
本研究的第二部份探討不同比例之乙烯醋酸乙烯酯粉末(EVA powder)摻混幾丁聚醣(Chitosan, CS)複合膜(EVA powder/CS)改質316L不鏽鋼表面，探討複合膜試片表面性質及抗凝血性。根據傅立葉轉換紅外光光譜儀與X光光電子能譜儀結果顯示隨著EVA powder添加量越多，表面之烷基(-CH3)及矽氧基(-Si-O-Si)疏水官能基團強度越大，使水接觸值也會隨之提升。牛血清蛋白測試中觀察得知，當EVA powder/CS添加比例小於5時，EVA powder/CS複合膜較純幾丁聚醣薄膜具有較低的牛血清蛋白吸附量，有效改善純幾丁聚醣薄膜試片表面之抗凝血性質。然而當EVA powder/CS添加比例大於8時，EVA powder/CS複合膜表面逐漸不平整導致牛血清吸附量提高，使抗凝血效果降低。因此EVA powder/CS複合膜選擇適當的比例會使複合膜試片具有較佳的疏水性、平滑表面及較低的牛血清蛋白吸附量，方可成為良好的生醫材料。

The first part of this study is to investigate the selective leaching and surface characteristics of Ti50Ni50-xFex(x = 1, 2, and 3) shape memory alloys using inductively coupled plasma mass spectrometry, X-ray diffractometry, electrochemical tests, and X-ray photoelectron spectroscopy. In our results, the concentrations of Ni and Fe ions selectively leached from each specimen were considerably higher than that of Ti ions. Electrochemical tests revealed a gradual deterioration in the corrosion resistance of Ti50Ni50-xFex SMAs as the Fe content in the alloys was increased. X-ray photoelectron spectroscopy results indicate that the surface of each specimen is primarily made up of passive TiO2 films. NiO and Fe2O3 oxides, which also formed on the surface of Ti50Ni50-xFex SMAs, deteriorated the uniformity and undermined the protective effect of TiO2 films, resulting in the highly selective leaching of Ni and Fe ions. Ti50Ni50-xFex SMAs possess a number of favorable properties than other SMAs; however, high concentrations of selectively leached Ni and Fe ions may pose a risk in biomedical applications, particular used in implant materials. The second part of this study is to investigate the surface characteristics and anticoagulant properties of 316L stainless steel coated with ethylene vinyl acetate powder (EVA)/chitosan (CS) composite films, using various EVA powder/CS rations, for biomedical applications. The Fourier transform infared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results showed that in the EVA powder/CS composite films, the signals of the –CH3 and –Si-O-Si hydrophobic functional groups became more significant when the EVA powder content increased, resulting in a higher water contact angle. The results of the bicinchoninic acid (BCA) protein assay showed that EVA powder/CS composite films with EVA powder/CS content ratios lower than 5 possessed lower adsorption concentrations of bovine serum albumin than chitosan films, suggesting that the anticoagulant properties of the EVA powder/CS composite films deteriorated significantly because its surface morphology became rougher with abundant protuberances. Therefore, EVA powder/CS compsite films with appropriate EVA powder/CS content ratios are good candidate materials for biomedical applications because they possess advantages such as hydrophobic properties, smooth surface morphologies, and a low capacity for protein adsorption.

摘要 I
Abstract II
致謝 IV
目錄 V
圖目錄 VIII
表目錄 XI
第一章 前言 1
第二章 文獻回顧 2
2.1形狀記憶合金 (Shape Memory Alloys, SMAs) 2
2.1.1形狀記憶效應 (Shape Memory Effect, SME) 2
2.1.2超彈性 (Superelasticity) 3
2.2生醫材料 (Biomedical Materials) 4
2.2.1醫用金屬材料 (Biomedical Metallic Materials) 5
2.2.2 形狀記憶合金於生醫材料相關研究 5
2.3電化學腐蝕 6
2.3.1塔弗極化曲線(Tafel Curve) 6
2.3.2腐蝕 7
2.4幾丁聚醣 (Chitosan, CS) 8
2.5 幾丁聚醣生醫材料之相關應用 9
2.6不鏽鋼 (Stainless Steel) 10
2.7 316L不鏽鋼於生醫材料之相關應用 11
2.8乙烯醋酸乙烯酯 (Ethylene Vinyl Acetate copolymers, EVA) 12
第三章 實驗步驟 20
3.1 Ti50Ni50-xFex(x=1, 2 and 3)形狀記憶合金離子腐蝕浸出之研究 20
3.1.1 Ti50Ni50-xFex形狀記憶合金配製和熔煉 20
3.1.2 Ti50Ni50-xFex形狀記憶合金X光繞射分析 20
3.1.3 Ti50Ni50-xFex形狀記憶合金之腐蝕浸出 20
3.1.4 Ti50Ni50-xFex形狀記憶合金之電化學分析測試 21
3.1.5 Ti50Ni50-xFex形狀記憶合金之X光光電子能譜儀分析 21
3.2 幾丁聚醣/乙烯醋酸乙烯酯粉末複合膜改質316L不鏽鋼表面 22
3.2.1 不同比例之EVA powder/CS複合膜凝膠溶液之製備 22
3.2.2 316 L不鏽鋼表面預處理 22
3.2.3 316 L不鏽鋼表面接枝EVA powder/CS複合膜 22
3.2.4 EVA powder/CS複合膜試片FTIR-ATR測試 23
3.2.5 EVA powder/CS複合膜試片表面型態觀察 23
3.2.6 EVA powder/CS複合膜試片水接觸測試 23
3.2.7 EVA powder/CS複合膜試片表面元素組成分析 23
3.2.8 EVA powder/CS複合膜試片牛血清蛋白吸附測試 23
3.2.9 EVA powder/CS複合膜試片毒性測試 24
3.3 實驗藥品 25
第四章 結果與討論 36
4.1 Ti50Ni50-xFex形狀記憶合金腐蝕浸出及表面性質之研究 36
4.1.1 Ti50Ni50-xFex形狀記憶合金X光繞射分析 36
4.1.2 Ti50Ni50-xFex形狀記憶合金感應耦合電漿質譜分析儀( ICP-MS)分析 36
4.1.3 Ti50Ni50-xFex形狀記憶合金電化學Tafel極化曲線數據分析 36
4.1.4 Ti50Ni50-xFex形狀記憶合金X光光電子能譜儀(XPS)分析 37
4.1.5 Ti50Ni50-xFex形狀記憶合金腐蝕浸出綜合討論 38
4.2 EVA powder/CS複合膜改質316L不鏽鋼之表面性質研究 38
4.2.1 EVA powder/CS複合膜試片FTIR-ATR分析 39
4.2.2 EVA powder/CS複合膜試片水接觸分析 40
4.2.3 EVA powder/CS複合膜試片表面型態分析 40
4.2.4 EVA powder/CS複合膜試片X光光電子能譜儀分析 40
4.2.5 EVA powder/CS複合膜試片牛血清蛋白吸附測試 41
4.2.6 EVA powder/CS複合膜試片毒性測試分析 42
4.2.7 EVA powder/CS複合膜試片綜合討論 42
第五章 結論 69
參考文獻 70
附錄 79

圖2.1 形狀記憶合金之形狀記憶效應及超彈性示意圖[11] 13
圖2.2 形狀記憶合金之形狀記憶效應示意圖[11] 13
圖2.3 單向形狀記憶效應示意圖[15] 14
圖2.4 雙向形狀記憶效應示意圖[15] 14
圖2.5 形狀記憶合金之形狀記憶效應示意圖[16] 14
圖2.6 溫度大於Af的應力應變示意圖[17] 15
圖2.7 溫度小於Af的應力應變示意圖[17] 15
圖2.8 標準電化學原理圖[35] 16
圖2.9 Tafel外插法、Tafel區與電流關係圖[36] 16
圖2.10 塔弗極化曲線示意圖[35] 17
圖2.11 線性外插法與電流關係圖[36] 17
圖2.12 不同類型金屬腐蝕示意圖[37] 18
圖2.13 幾丁質去乙醯化為幾丁聚醣示意圖 19
圖2.14 可再分散乳膠粉示意圖 19
圖3.1 Ti50Ni50-xFex 形狀記憶合金腐蝕浸出實驗流程圖 29
圖3.2 真空電弧熔煉爐(VAR) 30
圖3.3 X光繞射分析儀 31
圖3.4 感應耦合電漿質譜儀構造圖[74] 31
圖3.5 電化學反應測試示意圖 32
圖3.6 X光光電子能譜儀(XPS) 32
圖3.7 316L不鏽鋼表面改質之實驗流程圖 33
圖3.8 316L不鏽鋼表面預處理 34
圖3.9 傅利葉紅外線轉換光譜圖 (FTIR-ATR) 35
圖2.1 形狀記憶合金之形狀記憶效應及超彈性示意圖[11] 13
圖2.2 形狀記憶合金之形狀記憶效應示意圖[11] 13
圖2.3 單向形狀記憶效應示意圖[15] 14
圖2.4 雙向形狀記憶效應示意圖[15] 14
圖2.5 形狀記憶合金之形狀記憶效應示意圖[16] 14
圖2.6 溫度大於Af的應力應變示意圖[17] 15
圖2.7 溫度小於Af的應力應變示意圖[17] 15
圖2.8 標準電化學原理圖[35] 16
圖2.9 Tafel外插法、Tafel區與電流關係圖[36] 16
圖2.10 塔弗極化曲線示意圖[35] 17
圖2.11 線性外插法與電流關係圖[36] 17
圖2.12 不同類型金屬腐蝕示意圖[37] 18
圖2.13 幾丁質去乙醯化為幾丁聚醣示意圖 19
圖2.14 可再分散乳膠粉示意圖 19
圖3.1 Ti50Ni50-xFex 形狀記憶合金腐蝕浸出實驗流程圖 29
圖3.2 真空電弧熔煉爐(VAR) 30
圖3.3 X光繞射分析儀 31
圖3.4 感應耦合電漿質譜儀構造圖[74] 31
圖3.5 電化學反應測試示意圖 32
圖3.6 X光光電子能譜儀(XPS) 32
圖3.7 316L不鏽鋼表面改質之實驗流程圖 33
圖3.8 316L不鏽鋼表面預處理 34
圖3.9 傅利葉紅外線轉換光譜圖 (FTIR-ATR) 35
圖3.10 水接觸角儀器 35
圖4.1 Ti50Ni49Fe1、Ti50Ni48Fe2及Ti50Ni47Fe3形狀記憶合金之XRD圖 46
圖4.2 Ti50Ni50-xFex形狀記憶合金試片於林格氏液腐蝕浸出後 (a) Ti、(b) Ni及(c) Fe離子濃度圖 47
圖4.3 Ti50Ni49Fe1、Ti50Ni48Fe2及Ti50Ni47Fe3 形狀記憶合金之Tafel極化曲線圖 48
圖4.4 (a) Ti50Ni49Fe1、(b) Ti50Ni48Fe2及(c) Ti50Ni47Fe3 形狀記憶合金之XPS全能譜(Survey)圖 49
圖4.5 (a) Ti50Ni49Fe1、(b) Ti50Ni48Fe2及(c) Ti50Ni47Fe3 形狀記憶合金Ti 2p Orbital圖 50
圖4.6 (a) Ti50Ni49Fe1、(b) Ti50Ni48Fe2及(c) Ti50Ni47Fe3 形狀記憶合金Ni 2p Orbital圖 51
圖4.7 (a) Ti50Ni49Fe1、(b) Ti50Ni48Fe2及(c) Ti50Ni47Fe3 形狀記憶合金Fe 2p Orbital圖 52
圖4.8 316L不鏽鋼經不同時間Piranha Solution表面改質之FTIR-ATR圖 53
圖4.9 316L不鏽鋼經不同時間APTES表面改質之FTIR-ATR圖 53
圖4.10 316L不鏽鋼經APTES與戊二醛表面改質之FTIR-ATR圖 54
圖4.11 純幾丁聚醣(CS)之FTIR-ATR圖 54
圖4.12 EVA powder之FTIR-ATR圖 55
圖4.13 CS薄膜與EVA powder/CS複合膜之FTIR-ATR疊圖 55
圖4.14 CS薄膜及EVA powder/CS複合膜之水接觸角圖 56
圖4.15 (a) CS, (b)EVA1, (c)EVA3, (d)EVA5, (e)EVA8, (f)EVA10 複合膜之1000× SEM圖 57
圖4.16 CS薄膜之XPS全能譜(Survey)圖 58
圖4.17 EVA powder之XPS全能譜(Survey)圖 58
圖4.18 (a)EVA1, (b)EVA3, (c)EVA5, (d)EVA8, (e)EVA10 複合膜之XPS全能譜(Survey)圖 59
圖4.19 CS薄膜之C 1s軌域圖 60
圖4.20 EVA powder之C 1s軌域圖 60
圖4.21 (a)EVA1, (b)EVA3, (c)EVA5, (d)EVA8, (e)EVA10 複合膜之C 1s軌域圖 61
圖4.22 CS薄膜之N 1s軌域圖 62
圖4.23 EVA powder之N 1s軌域圖 62
圖4.24 (a)EVA1, (b)EVA3, (c)EVA5, (d)EVA8, (e)EVA10 複合膜之N 1s軌域圖 63
圖4.25 CS薄膜之O 1s軌域圖 64
圖4.26 EVA powder之O 1s軌域圖 64
圖4.27 (a)EVA1, (b)EVA3, (c)EVA5, (d)EVA8, (e)EVA10 複合膜之O 1s軌域圖 65
圖4.28 CS薄膜之Si 2p軌域圖 66
圖4.29 EVA powder之Si 2p軌域圖 66
圖4.30 (a)EVA1, (b)EVA3, (c)EVA5, (d)EVA8, (e)EVA10 複合膜之Si 2p軌域圖 67
圖4.31 CS薄膜及EVA powder/CS複合膜蛋白質(BSA)吸附圖 68
圖4.32 CS薄膜及EVA powder/CS複合膜毒性測試圖 68

表3.1 林格氏注射液成分表 27
表3.2 感應耦合電漿質譜分析儀參數 27
表3.3 電化學Tafel極化曲線參數 27
表3.4 磷酸鹽緩衝液(PBS)組成成分 28
表3.5 培養基(LB)組成成分 28
表4.1 Ti50Ni50-xFex 形狀記憶合金之腐蝕電流(Icorr)及腐蝕電位(Ecorr)結果 44
表4.2 Ti50Ni50-xFex 形狀記憶合金Ti離子軌域成份比例 44
表4.3 Ti50Ni50-xFex 形狀記憶合金Ni離子軌域成份比例 45
表4.4 Ti50Ni50-xFex 形狀記憶合金Fe離子軌域成份比例 45

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