臺灣博碩士論文加值系統

鈦和鈦合金因具有無毒、生物相容性、抗菌性等特性，被廣泛應用在航太及醫療領域，鈦金屬容易在表面自然形成氧化鈦薄膜，鈦的氧化膜具良好的化學穩定性，可保護底層合金不被外在環境因素腐蝕。
本研究為了增進鈦合金生物相容性及機械性質，採用陰極電弧蒸鍍技術(Cathodic Arc Evaporation, CAE)於鈦合金(Ti-6Al-4V)表面鍍製鈦鋯鉭(TiZrTa)薄膜，再透過雷射的高能量密度特性在鈦鋯鉭薄膜表面形成直線、圓形、棋盤三種紋理，以獲得規律的表面微結構之鈦鋯鉭氧化層。進而探討雷射表面紋理氧化對表面形貌的影響，以及抗菌性與生物相容性。
本研究使用掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 觀察試片表面與截面在經過雷射處理後的變化，搭配能量分散式光譜分析儀(EDS)進行表面元素成分分析，再利用X射線光電子能譜儀(X-ray Photoelectron Spectroscope,XPS)、X光繞射分析儀(X-Ray Diffractometer, XRD)觀察薄膜化學鍵結態、晶體結構及結晶相分析；利用雷射顯微鏡和水接觸角量測儀(Water Contact Angle, WCA)量測薄膜表面粗糙度與親疏水性，最後用金黃色葡萄球菌(Staphylococcus aureus, S.a)進行抗菌分析，小鼠纖維母細胞(L929)及小鼠骨肉瘤細胞(MG-63)進行細胞毒性分析及細胞相容性分析，判斷是否具有生物相容性。
根據研究結果經過雷射紋理氧化之試片，表層會形成規律的凹痕紋理微結構，因此表面粗糙度比純薄膜高，並且擁有較高粗糙度之紋理表面呈現親水性，較適合細胞生長，雷射產生的高溫使表面氧化，生成Ta2O5、Ti2O3、TiO2、V2O5、V2O3、ZrO2、Al2O3等氧化物，其中Ta2O5可抑制細菌生長，而生物學實驗中未表現出明顯的抗菌優勢，並且具有輕微的細胞毒性，但細胞活力有顯著提升。
本研究中80s經過雷射處理後獲得疏水性及較低的粗糙度，雖然會使細菌附著，但卻讓此雷射紋理之間距適合細胞生長，因此短時間內的生物相容性有較優異的表現；而50c則是擁有親水性及最高的粗糙度，濕潤性不利於細菌生長但高粗糙度適合細胞黏附、繁殖，因此在長時間的生物相容性有較優異的表現。

Titanium and titanium alloys are widely used in aerospace and medical fields due to their non-toxicity, biocompatibility, and antibacterial properties. Titanium metal can naturally form a titanium oxide film on its surface, which exhibits excellent chemical stability and protects the underlying alloy from corrosion by external environmental factors.
In this study, in order to enhance the biocompatibility and mechanical properties of titanium alloys, a titanium zirconium tantalum (TiZrTa) thin film was deposited on the surface of titanium alloy (Ti-6Al-4V) using the Cathodic Arc Evaporation (CAE) technique. Subsequently, laser surface texturing with high energy density was employed to create three different patterns: straight lines, circles, and chessboards, on the surface of the TiZrTa-coated titanium alloy, aiming to obtain regular surface microstructures of the TiZrTa oxide layer. The influence of laser surface texturing and oxidation on the surface morphology, as well as the antibacterial properties and biocompatibility, were investigated.
In this study, the surface and cross-section of the samples after laser treatment were observed using a Scanning Electron Microscope (SEM). Energy Dispersive X-ray Spectroscopy (EDS) was used for surface elemental composition analysis. X-ray Photoelectron Spectroscopy (XPS) and X-ray Diffractometer (XRD) were employed to analyze the chemical bonding state, crystal structure, and crystalline phases of the thin films. Laser microscopy and a Water Contact Angle (WCA) measurement device were used to measure the surface roughness and hydrophobicity/hydrophilicity of the thin films. Antimicrobial analysis was performed using Staphylococcus aureus (S.a) bacteria, and cell toxicity and biocompatibility analyses were conducted using mouse fibroblast cells (L929) and mouse osteosarcoma cells (MG-63) to determine the biological compatibility.
According to the research findings, the samples subjected to laser surface texturing exhibited regular concave microstructures, resulting in higher surface roughness compared to the pure thin film. The textured surfaces with higher roughness showed hydrophilicity, making them more favorable for cell growth. The high temperature generated by the laser led to surface oxidation, forming oxides such as Ta2O5,Ti2O3,TiO2,V2O5,V2O3,ZrO2 and Al2O3. Among these, Ta2O5 demonstrated the ability to inhibit bacterial growth. However, the biological experiments did not show significant antibacterial advantages, and there was a slight cytotoxicity. Nevertheless, the cell viability was significantly improved.
In this study, the sample 80s, after laser treatment, achieved hydrophobicity and lower roughness. Although it promoted bacterial adhesion, the optimized spacing of the laser texturing favored cell growth, leading to better short-term biocompatibility performance. On the other hand, sample 50c exhibited hydrophilicity and the highest roughness, which hindered bacterial growth due to its wetting nature. However, the high roughness facilitated cell attachment and proliferation, resulting in superior long-term biocompatibility performance.

摘要... i
Abstract... ii
誌謝... iv
目錄... v
表目錄... vii
圖目錄... viii
第一章 緒論... 1
1.1 前言... 1
1.2 文獻回顧...2
1.2.1 生醫材料之特性... 2
1.2.2 鈦合金植入物之應用與研究... 3
1.2.3 陰極電弧蒸鍍原理(Cathodic Arc Evaporation, CAE)... 6
1.2.4 薄膜成長機制... 8
1.2.5 薄膜結構... 9
1.2.6 無毒金屬薄膜研究... 11
1.2.7 光纖雷射工作原理... 16
1.2.8 雷射表面織構處理與生物學性質... 18
1.3 研究動機與目的... 23
第二章 研究方法... 24
2.1 實驗流程... 24
2.2 實驗方法... 25
2.2.1 鍍膜前處理與步驟... 25
2.2.2 雷射設備... 27
2.3 參數設計... 28
2.3.1 TiZrTa薄膜製程設計... 28
2.3.2 雷射圖案參數設計... 29
2.4 試片表面結構與成分分析... 31
2.4.1 掃描式電子顯微鏡(Scanning Electron Microscope, SEM)... 31
2.4.2 化學分析電子能譜儀(Electron Spectroscope for Chemical Analysis,ESCA)...32
2.4.3 X光繞射分析儀(X-Ray Diffractometer,XRD)... 33
2.5 薄膜表面性質分析... 35
2.5.1 雷射顯微鏡(Laser Microscope)... 35
2.5.2 水接觸角量測儀(Water Contact Angle, WCA)... 36
2.6 生物實驗分析... 37
2.6.1 金黃色葡萄球菌(Staphylococcus aureus, S.a)抗菌性分析... 37
2.6.2 老鼠纖維母細胞(L929)毒性分析... 38
2.6.3 老鼠纖維母細胞(L929)細胞相容性分析... 39
2.6.4 小鼠骨肉瘤細胞(MG-63)毒性分析... 40
第三章 結果與討論... 41
3.1 試片表面結構與成分分析... 41
3.1.1 試片表面形貌分析... 41
3.1.2 試片表面成分分析... 44
3.1.3 試片截面分析... 48
3.1.4 XPS化學鍵結態與成分分析... 50
3.1.5 X光繞射分析... 59
3.2 薄膜表面性質分析... 60
3.2.1 表面粗糙度分析... 60
3.2.2 水接觸角量測分析... 62
3.3 生物實驗分析... 65
3.3.1 金黃色葡萄球菌(Staphylococcus aureus, S.a)抗菌性分析... 65
3.3.2 老鼠纖維母細胞(L929)毒性分析... 67
3.3.3 老鼠纖維母細胞(L929)細胞相容性分析... 68
3.3.4 小鼠骨肉瘤細胞(MG-63)毒性分析... 69
第四章 結論... 70
參考文獻... 72
Extended Abstract... 84 

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