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研究生： 吳汶育
Wu, Wen-Yu
論文名稱： 鍍層鎂鋅合金顯微組織及機械性質與生醫應用特性研究
A Study of Microstructure, Mechanical Properties and Biomedical Application of Coated Mg-Zn Alloy
指導教授： 洪飛義
Hung, Fei-Yi
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2022
畢業學年度： 110
語文別： 中文
論文頁數： 109
中文關鍵詞： 鎂合金 、陽極氧化 、降解 、機械性質 、生物相容性
外文關鍵詞： Mg alloy, anodic oxidation, degradation, mechanical properties, biocompatibility
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    • 目前臨床上多以不鏽鋼及鈦合金作為骨科植入材，但其機械性質與人骨差異甚大，易產生應力遮蔽效應，且患者痊癒後須進行二次手術取出植入物；而鎂合金機械性質與人骨相近，有助於骨組織的復原和再生，且其具有生物可降解性，可避免二次手術帶來的感染風險與醫療成本。然而鎂合金降解過快，存在大量析氫引發周圍組織發炎問題，為當前鎂合金植入材所面臨的最大挑戰，而藉由適當合金元素添加及表面處理，可有效延緩降解並優化機械性質。
    本研究選用ZKX500鎂合金，改良傳統陽極氧化方式對其進行表面處理，於其表面生成磷酸鹽鍍層，並導入雙層表面處理，以磷酸鹽鍍層為基礎再塗覆一層高分子明膠，可以改善鎂合金降解特性。在體外降解實驗結果中，明膠塗層易與基材剝離，反而會加劇材料內部腐蝕，而磷酸鹽鍍層則會與模擬體液反應形成保護層，能有效地延緩鎂合金降解。此外，磷酸鹽鍍層厚度約為800奈米，適合應用在尺寸小、表面結構精度高之醫材。
    為進一步評估降解導致機械性質劣化的程度，將經過陽極氧化的鎂合金浸泡於人工模擬體液後，進行拉伸、衝擊、疲勞等機械性質試驗。在經過四週的浸泡後，拉伸試驗結果顯示，強度及延性雖有衰退的趨勢，但仍優於人骨且符合醫材規範，衝擊韌性則僅有輕微衰退，而耐疲勞性受降解影響較大，但仍能展現出磷酸鹽鍍層有緩解劣化的作用。此外，生物相容性測試結果顯示，磷酸鹽鍍層適合細胞貼附與生長，在生物體內無明顯不良反應。
    藉由陽極氧化方式在鎂合金表面生成磷酸鹽鍍層，能延緩鎂合金降解，減少降解後機械性質的劣化，並改善其生物相容性，且磷酸鹽鍍層及鎂合金可於人體內自行降解並代謝，其降解產物與人體骨骼成分相近，有助於骨骼修復。鎂合金及磷酸鹽鍍層降解特性、機械性質等相關數據可提供臨床應用參考。

    Mg-based implant can be detected by X-ray, which is conducive to postoperative follow-up. Its properties are closer to human bones, and thus stress shielding effect can be avoided. Also, a second surgery is unnecessary due to its biodegradability. However, the high degradation rate is the biggest challenge to Mg-based implants, so surface treatment should be performed. In this study, ZKX500 Mg alloy is used. The non-toxic and eco-friendly anodic oxidation method is adopted to improve corrosion resistance.
    The results show that the anodic coating mainly consisted of Mg3(PO4)2. After anodic oxidation, the coating and ion-exchanged layer form and slow down the degradation. The results of the tensile test and impact test show coated specimens maintain good strength, ductility, and toughness after immersing in SBF. Anodic coating is also an excellent surface for cells to attach and proliferate. In the animal implantation experiment, coated Mg bone screw can support the injured part for at least 3 months.

    中文摘要 I 英文延伸摘要 III 誌謝 XIII 總目錄 XIV 表目錄 XVIII 圖目錄 XIX 第一章 前言 1 第二章 文獻回顧 3 2-1 生物醫用材料 3 2-1-1 生醫材料的種類 3 2-1-2 骨科植入材的選擇 4 2-2 生醫鎂合金 5 2-2-1 生醫鎂合金的優勢 6 2-2-2 生醫鎂合金的限制 7 2-3 鎂合金元素添加效應 7 2-4 鎂合金腐蝕機制 8 2-5 鎂合金表面處理 10 2-5-1 表面處理方法 10 2-5-2 雙層表面處理 11 2-6 明膠特性及應用 12 2-7 鎂合金拉伸機械性質 13 2-8 鎂合金衝擊韌性 14 2-9 鎂合金疲勞特性 14 2-10 動物試驗 15 2-11 研究目的 16 第三章 實驗方法與步驟 21 3-1 實驗架構 21 3-2 材料表面處理 21 3-2-1 陽極氧化磷酸鹽鍍層 22 3-2-2 明膠塗層 22 3-3 微觀形貌觀察與組成分析 23 3-3-1 表面微觀形貌與元素分析 23 3-3-2 相組成分析 23 3-3-3 橫截面微觀結構與元素分佈 24 3-3-4 化學組成分析 24 3-4 體外降解試驗 24 3-4-1 電化學試驗 25 3-4-2 浸泡試驗 26 3-5 降解後機械性質試驗 27 3-5-1 微硬度試驗 27 3-5-2 拉伸試驗 27 3-5-3 衝擊試驗 28 3-5-4 旋轉疲勞試驗 29 3-6 細胞貼附性試驗 30 3-7 動物試驗 30 第四章 結果與討論 40 4-1 磷酸鹽鍍層特性 40 4-1-1 磷酸鹽鍍層形貌及相組成 40 4-1-2 磷酸鹽鍍層形成機制 41 4-1-3 磷酸鹽鍍層TEM分析 42 4-2 明膠塗層特性 43 4-2-1 明膠交聯反應 43 4-2-2 明膠塗層化學組成分析 44 4-3 體外降解行為探討 44 4-3-1 動電位極化曲線 44 4-3-2 浸泡試驗 45 4-3-3 鎂合金及磷酸鹽鍍層降解機制 46 4-3-4 明膠塗層腐蝕行為 47 4-4 降解前後機械性質探討 48 4-4-1 微硬度試驗 48 4-4-2 拉伸試驗 48 4-4-3 衝擊韌性試驗 49 4-4-4 旋轉疲勞試驗 50 4-5 細胞貼附性探討 51 4-6 動物體內植入試驗 52 4-7 鎂合金表面處理應用特性評估 53 4-7-1 單層表面處理 53 4-7-2 雙層表面處理 53 第五章 結論 102 參考文獻 104

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