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研究生： 黃嫈庭
Huang, Ying-Ting
論文名稱： 熱壓延與表面處理對醫療級可降解型鎂鋅合金機械性質與生醫應用特性研究
A Study on Mechanical Properties and Biomedical Application Characteristics of Hot-rolling and Surface Modify Medical Degradable Mg-Zn alloy
指導教授： 洪飛義
Hung, Fei-Yi
呂傳盛
Lui, Truan-Sheng
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： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 91
中文關鍵詞： 鎂合金 、壓延 、生物降解 、表面處理 、動物試驗
外文關鍵詞： Mg alloy, rolling, biodegradable, surface treatment, animal experiment
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    • 目前臨床上金屬植入醫材以不鏽鋼與鈦合金為主，當患者痊癒後需二次手術將其取出，不僅有再次感染的風險，也會造成醫療成本的增加。鎂合金具有良好的生物相容性及可被人體吸收的降解特性，且降解產物能促進新生骨的成長，機械性質與人骨接近，能避免應力遮蔽效應，是理想的骨科植入醫材。然而鎂合金降解過快，析出大量氫氣造成組織發炎，是現今鎂合金醫材開發所面臨的問題。透過適當的合金元素添加以及表面改質，能有效強化鎂合金的力學性質並減緩降解速率。
    本研究選用ZKX500鎂合金，探討熱處理以及壓延製程對材料微觀組織與機械性質之影響。在拉伸機械性質分析中，鎂合金在經過壓延及退火熱處理後，仍然保有良好機械強度，且延性顯著提升。為了改善降解特性，導入雷射改質、化學鍍金、磷酸化成處理等表面處理方法。實驗結果顯示，雷射改質可在材料表面生成氧化膜以減緩降解速率，而化學鍍金會使鍍層與鎂基材產生電位差，導致嚴重的迦凡尼腐蝕，值得注意的是，經由磷酸化成製程得到的磷酸鹽皮膜，有助於提升材料抗腐蝕能力。為進一步評估降解造成機械性質的衰退程度，將磷酸化的鎂合金進行浸泡實驗後的拉伸測試，結果顯示在經過四週的模擬人工體液浸泡後，儘管強度及延性有隨時間而衰退的趨勢，但其機械性質仍優於人骨。在生物相容性測試中，顯示磷酸鹽皮膜不具生物毒性，且表面對細胞初期的貼附性佳。
    最後，將壓延鎂合金板加工成實心骨釘及4孔骨板，再經過磷酸化成處理後，進行動物體內實驗。將骨釘骨板植入蘭嶼黑豬右前肢，在術後經過1個月有觀察到氣腔產生，但豬隻能正常行走並無任何異狀。植入3個月後，骨釘幾乎完全降解消失，骨板仍保有完整性，且在骨板外層有新生組織，顯示鎂骨板有助於骨折的恢復。
    磷酸表面處理後，能使鎂合金擁有良好耐腐蝕性及生物相容性，在植入生物體後能自行降解並代謝，不需二次手術取出，並有新生骨產生，相關數據可提供臨床應用參考。

    Magnesium-based biodegradable implants that can be absorbed by humans promote osteoblastic activity during the degradation and inhibit the formation of osteoclasts. Moreover, magnesium can be detected by X-rays, and this can help doctors to perform postoperative diagnosis and treatment, which is beneficial for patients. This study focus on microstructure, mechanical properties, corrosion properties and animal experiment of ZKX500 Mg alloy prepared through hot rolling and surface treatment.
    The results show that rolling and heat treatment process can maintain excellent mechanical properties and also reduce the in vitro corrosion rate. Phosphate conversion coating can also slow down the corrosion rate. The tensile test and impact test after immersion test show that the mechanical properties retained well with phosphate coating. The mini-pig implantation test shows that bone plate can provide sufficient support at least for 3 month. The relevant results can serve as a reference for use of the material in biomedical applications.

    中文摘要 II Abstract IV 致謝 XI 總目錄 XII 表目錄 XVI 圖目錄 XVII 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 生醫材料的發展 3 2-1-2 骨科生醫材料的選擇 4 2-2 鎂合金材料特性 5 2-3 生醫用鎂合金材料的優點 6 2-4 生醫用鎂合金材料應用限制 7 2-5 鎂合金腐蝕機制 8 2-6 鎂合金元素添加效應 9 2-6-1 鋅 9 2-6-2 鋯 10 2-6-3 鈣 10 2-7 材料破壞韌性 11 2-8 壓延加工 11 2-9 鎂合金表面改質技術 12 2-10 細胞實驗 13 2-11 動物實驗 14 2-12 研究目的 15 第三章 實驗方法與步驟 21 3-1 實驗架構 21 3-2 材料製備 21 3-2-1 熱處理條件 21 3-2-2 熱壓延製程 21 3-2-3 表面處理 22 3-2 微觀組織觀察 22 3-3 相組成分析 23 3-4 機械性質試驗 23 3-4-1 硬度試驗 23 3-4-2 拉伸試驗 23 3-4-3 破壞韌性試驗 24 3-5 體外降解試驗 24 3-5-1 電化學試驗 24 3-5-2 浸泡試驗 25 3-5-3 浸泡後拉伸 26 3-5-4 浸泡後衝擊 26 3-6 細胞相容性試驗 26 3-6-1 細胞毒性測試 26 3-6-2 貼附試驗 28 3-7 動物試驗 29 第四章 結果與討論 37 4-1 熱處理與熱壓延製程 37 4-1-1 鎂合金微觀組織特性 37 4-1-2 X光繞射與相分析 37 4-1-3 硬度量測 38 4-1-4 拉伸性質分析 38 4-1-5 破壞韌性 38 4-1-6 動電位極化曲線試驗 39 4-2 表面層應用性與界面特性 39 4-2-1 雷射表面改質特性 39 4-2-2 化學鍍金膜特性 40 4-2-3 磷酸皮膜特性 41 4-3 降解行為探討 42 4-3-1 動電位極化曲線試驗 42 4-3-2 浸泡試驗 43 4-4 體外仿生特性探討 44 4-4-1 動電位極化曲線試驗 44 4-4-2 浸泡試驗 44 4-4-3 浸泡後拉伸強度劣化機制 45 4-4-4 浸泡後衝擊強度劣化機制 45 4-5 體外細胞相容性 46 4-5-1 細胞毒性測試 46 4-5-2 細胞貼附測試 46 4-6 動物體內植入試驗 47 4-7 鎂醫材表面製程應用性 48 第五章 結論 85 參考文獻 87

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