臺灣博碩士論文加值系統

金屬具有高機械強度，比起其他高分子或陶瓷材料更適合製作骨科內外需承載的固定裝置，為應用廣泛的生醫材料(Biomedical materials)，但目前製作植入材的製程，如鍛造(forging)等，普遍都存在著制式化的弊病，無法客製化製作符合病患所需之植入材，這樣制式的產品可能會影響預期的醫療效果。而新興之積層製造技術(additive manufacturing)又稱為快速成形技術，即具有高函工效率，同時金屬積層製造技術更具有可以製作複雜工件及可結合製圖技術之優勢，即能根據病患原骨骼或所需部位調整、設計出符合個人的植入材，提升治療品質。但積層製造工件比起傳統鍛造製程，具有較高的表面粗糙度，而過高的表面粗糙度會影響細胞貼附能力，為了增函生物相容性，積層技術必頇面對二次函工之挑戰。故本研究比較鍛造及電子束熔融(electron beam melting, EBM)樣品經過表面處理之差異，利用電拋光步驟降低表面粗糙度，再進行陽極氧化處理提升生物相容性，同時在樣品表面電鍍沉積銅粒子，預計在植體表面創造適合骨細胞貼附及
助長骨組織生長的環境，並得到抗菌的植體表面，降低手術感染風險，避免手術感染後的二次手術造成病患負擔。經電拋光及陽極處理後， 藉由掃描式電子顯微鏡(scanning electron microscopy, SEM)觀察到樣品表面多孔性形貌，微米級孔洞中產生奈米孔洞，表面粗糙度(Ra)由34.58 μm 提高至38.86 μm。並以雙束型聚焦離子束(dual-beam focused ion beam, DB-FIB)製備TEM 試片，再由球面像差修正掃描穿透式電子顯微鏡(transmission electron microscopy, STEM)確認電鍍之銅粒子為單晶，並以平板培養確認0.2 V 電鍍銅6 min 可對大腸桿菌(Escherichia coli, E. coil)抑菌，提高時間至8 min 以上可達抗菌；另以x 光光電子能譜儀(x-ray photoel ectronspectrometer, XPS)分析表面浸泡模擬體液後之表面處理樣品表面Ca/P/Ti，確認經由表面處理可促進Ca/P 沉積。

Comparison with polymer or ceramic materials, metal has higher mechanical strength. It is widely used in biomedical materials, such as orthopedic implant and fixing devices. Currently, medical implants were generally produced in large quantities and standardization for reducing the cost. However, these are not customized for individual patients, which may bring on some side medical effects not as expected. The technique of metal additive manufacturing (AM), unlike traditional processing techniques of subtraction, is highly concerned in recent years processed by stacking method to solve the bottlenecks and limitations of traditional manufactures. Combined with illustration or drawing technology, AM can produce customized workpieces with
more complicated shape. However, metal additive manufacturing workpieces has higher surface roughness than conventional forging processes, and excessive surface roughness will affect cell attachment ability. In order to increase biocompatibility, metal additive manufacturing must face the challenge of secondary processing. Therefore, This study adopted electropolishing and anodic titanium oxidation (ATO) to promote osteocytes attachment on the EBM titanium surface, and Cu electroplating to
obtain antibacterial property. The scanning electron microscopy (SEM) images showed the micro/nano-textured structure of surface morphology, increasing the surface Ra from 34.58 μm to 38.86 μm. Antibacterial tests demonstrated that Cu electroplating at the potential of 0.2 V for 6min presented inhibitory property against Escherichia coli and bactericidal property as increasing to8 min. In addition, the above surface-treated EBM titanium revealed improved deposition of hydroxyapatite (Ca/P)layer by in vitro bioactivity test using simulated body fluid.

摘要................................................................................................................................. i
Abstract .......................................................................................................................... ii
誌謝............................................................................................................................... iv
目錄................................................................................................................................ v
表目錄........................................................................................................................ viii
圖目錄........................................................................................................................... ix
第一章 緒論........................................................................................................ 1
1.1 前言........................................................................................................ 1
1.2 研究動機與目標.................................................................................... 2
第二章 理論基礎與文獻回顧............................................................................ 3
2.1 積層製造簡介........................................................................................ 3
2.1.1. 積層製造技術................................................................................ 3
2.1.2. 積層製造發展趨勢........................................................................ 3
2.1.3. 電子束熔融技術介紹.................................................................... 6
2.2 鈦合金簡介............................................................................................ 7
2.2.1. 純鈦................................................................................................ 7
2.2.2. 合金元素........................................................................................ 8
2.3 生醫材料介紹........................................................................................ 9
2.3.1. 人骨成分........................................................................................ 9
2.3.2. 生醫材料特性.............................................................................. 11
2.4 鈦合金表面處理.................................................................................. 13
2.4.1. 電解拋光介紹.............................................................................. 13
2.4.2. 陽極氧化鈦形成機制.................................................................. 16
2.4.3. 電化學沉積銅.............................................................................. 17
2.5 抗菌檢測介紹...................................................................................... 17
2.5.1. 細菌結構介紹.............................................................................. 17
2.5.2. 抗菌材料簡介.............................................................................. 19
2.5.3. 抗菌材料選擇.............................................................................. 22
2.5.4. 抗菌檢測規範.............................................................................. 24
2.5.5. 抗菌定義與計算.......................................................................... 27
2.6 檢測設備與原理.................................................................................. 28
2.6.1. 電子束熔融機台.......................................................................... 28
2.6.2. 掃描式電子顯微鏡(scanning electron microscopy, SEM) ......... 28
2.6.3. x 光能量散射光譜儀(energy dispersive spectroscopy, EDS) ..... 29
2.6.4. 雙束型聚焦離子束(dual-beam focused ion beam, DB-FIB) ...... 30
2.6.5. 穿透式電子顯微鏡(transmission elecetron microscopy, TEM) . 31
2.6.6. x 光繞射儀(x-ray diffractometer, XRD) ..................................... 32
2.6.7. x 射線光電子能譜儀(x-ray photoelectron spectrometer, XPS) .. 33
2.6.8. 感應耦合電漿質譜儀(inductively coupled plasma-mass
spectrometer, ICP-MS) ................................................................................ 34
2.6.9. 表面粗度測定機(Surface Roughness Tester) ............................. 35
2.6.10. 分光光度計( Ultraviolet/Visible Spectrophotometer, UV/Vis) ... 36
第三章 實驗方法與步驟.................................................................................. 37
3.1 研究架構.............................................................................................. 37
3.2 實驗藥品.............................................................................................. 37
3.3 實驗設備.............................................................................................. 38
3.4 分析試驗設備...................................................................................... 39
3.4.1. 電子束熔融機台(Electron beam melting machine) .................... 39
3.4.2. x 光繞射儀(x-ray diffractometer, XRD) ..................................... 39
3.4.3. 掃描式電子顯微鏡(scanning electron microscopy, SEM) ......... 39
3.4.4. 雙束型聚焦離子束(dual-beam focused ion beam, DB-FIB) ...... 40
3.4.5. 穿透式電子顯微鏡(transmission elecetron microscopy, TEM) . 40
3.4.6. x 光光電子能譜儀(x-ray photoelectron spectrometer, XPS) ...... 40
3.4.7. 感應耦合電漿質譜儀(inductively coupled plasma-mass
spectrometer, ICP-MS) ................................................................................ 40
3.4.8. 分光光譜儀(UV spectrophotometer, UV/Vis) ............................ 40
3.5 表面處理實驗流程.............................................................................. 40
3.5.1. 電解拋光...................................................................................... 40
3.5.2. 陽極氧化處理.............................................................................. 40
3.5.3. 電鍍銅.......................................................................................... 41
3.6 抗菌測試.............................................................................................. 41
3.6.1. 培養基.......................................................................................... 41
3.6.2. 培養基與試驗配製...................................................................... 41
3.6.3. 薄膜密著抗菌試驗...................................................................... 43
3.7 體外生物活性檢測........................................................................................ 43
第四章 實驗結果與討論.................................................................................. 47
4.1 EBM 及鍛造樣品之表面改質特性比較 ............................................ 47
4.1.1. 鍛造樣品之氧擴散能力與氧化層特性探討.............................. 47
4.1.1.1 不同陽極氧化參數之氧擴散能力分析...................... 47
4.1.1.2 不同陽極氧化參數之TEM 分析 ............................... 48
4.1.2. 表面形貌及微結構探討.............................................................. 50
4.1.2.1 電拋光後鍛造及EBM 樣品之SEM 分析 ................. 50
4.1.2.2 陽極氧化後鍛造及EBM 樣品之SEM 分析 ............. 50
4.1.2.3 EBM 不同結構樣品之表面特性分析 ................................ 50
4.1.3. 電流變化對表面粗糙度之影響.................................................. 58
4.1.3.1 電流與鈦離子釋出濃度之關係探討.......................... 58
4.1.3.2 EBM 不同結構樣品表面形貌與粗糙度之探討 ................ 59
4.1.3.3 電流與表面形貌之關係探討...................................... 60
4.2 電鍍銅特性分析及抗菌檢測.............................................................. 65
4.2.1. 不同電鍍參數之探討.................................................................. 65
4.2.1.1 改變電壓之表面形貌分析.......................................... 65
4.2.1.2 改變電鍍時間之表面形貌分析.................................. 65
4.2.1.3 電流與表面形貌之關係探討...................................... 65
4.2.2. EBM 不同結構樣品對表面形貌影響之探討 ............................ 69
4.2.2.1 電流與表面形貌之關係探討...................................... 69
4.2.2.2 電鍍銅與基材介面之TEM 分析 ............................... 69
4.3 EBM 樣品之抗菌檢測及生物相容性探討 ........................................ 73
4.3.1. EBM 不同結構樣品抗菌能力之探討 ........................................ 73
4.3.1.1 電鍍時間選擇.............................................................. 73
4.3.1.2 不同結構經電鍍之抗菌能力...................................... 73
4.3.1.3 樣品二次抗菌能力之探討.......................................... 73
4.3.2. 不同結構之生物相容性探討...................................................... 77
4.3.2.1 XPS 分析之表面沉積特性探討 ......................................... 77
4.3.2.2 SEM 表面形貌分析 ............................................................ 78
第五章 結論...................................................................................................... 80
參考文獻...................................................................................................................... 81
附錄.............................................................................................................................. 86
Extended Abstract ........................................................................................................ 87

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