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研究生: 陳姸熹
Chen, Yen-Hsi
論文名稱: 液態穿透式電子顯微鏡探討鎂鋅鈣合金的局部腐蝕行為與成分變化
Discussion of Localized Corrosion Behavior and Composition Variation of Mg-Zn-Ca Alloy Using Liquid TEM Technology
指導教授: 徐邦昱
Hsu, Bang-Yu
共同指導: 陳引幹
Chen, In-Gann
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: 87
中文關鍵詞: 鎂鋅鈣合金 、局部腐蝕 、腐蝕行為 、微米電偶腐蝕 、liquid TEM
外文關鍵詞: Mg-Zn-Ca alloy, localized corrosion, corrosion behavior, micro-galvanic coupling, liquid TEM
相關次數: 點閱:290  下載:0 
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  • 鎂加入鋅、鈣製成鎂基材的合金材料,具有良好的生物相容性(biocompatibility),生物可降解性(biodegradability)和生物可吸收性(bio-absorbability),在醫用植入材料界備受矚目,如骨釘或支架。純鎂在人體中的腐蝕速率過快,而鎂、鋅、鈣三種元素會形成介金屬化合物(IMC),提升材料的抗腐蝕能力。文獻中常見探討鎂合金腐蝕行為的傳統技術包含掃描電子顯微鏡(SEM)、X光繞射儀(XRD)和釋氫試驗(hydrogen evolution test),然而,皆無法看到腐蝕過程之影像以及臨場成分分析。為了解鎂鋅鈣合金的抗腐蝕機制,本文將引入新穎的研究方法—液態穿透式電子顯微鏡技術(liquid TEM),以微米至奈米(micro-to-nano)尺度的視角觀察鎂鋅鈣合金分別在水與氯化鈉水溶液中腐蝕之現象,包含臨場(in-situ)影像、成分分布變化等,特別是探討文獻中鮮少討論之鎂合金第二相(secondary phase)變化,進而推得腐蝕機制。
    本研究之鎂鋅鈣合金材料由金屬中心(MIRDC)提供,包含鑄錠、粉末及粉末熱壓成型塊材,其中粉末之微觀結構較為穩定,是由介金屬化合物第二相Ca2Mg6Zn3 (IM1)呈網狀分布,將不規則形狀的鎂基材隔開,故作為腐蝕機制探討之對象。鎂鋅鈣合金粉末經DI water腐蝕後,可發現微米級的氧化鎂相,推測是鎂基材和水中的氧氣反應產生。而Ca2Mg6Zn3 (IM1)則不會被腐蝕,但可能有微量溶解,且出現因為周圍鎂基材被腐蝕而失去支撐之隨時間向外擴散的現象。
    當溶液中有氯離子時,會使鎂基材被腐蝕形成易溶於水的MgCl2,亦導致Ca2Mg6Zn3 (IM1)產生變化。推測其中大部分的鎂和鈣以離子的形式存在於溶液中,鋅則形成難溶於水的非晶Zn-rich相(可能為ZnO)覆蓋在試片上,或許有機會作為披覆的鈍化層,阻擋剩餘的鎂合金與腐蝕液直接接觸,進而降低腐蝕速率。

    In order to realize the corrosion mechanism of degradable Mg-Zn-Ca alloy at micro-to-nano scale, liquid TEM as a novel technique performing a liquid environment via an isolated sandwich chip structure was introduced. Galvanic corrosion, which can be considered as a kind of localized corrosion, was observed to occur in DI water and NaCl solutions due to corrosion potential difference between the Mg matrix and the secondary phase, intermetallic compound Ca2Mg6Zn3 (IM1). Moreover, IM1 was discovered that it became a Zn-rich phase after immersed in NaCl solutions. This has not been widely discussed.

    摘要 I 致謝 V 表目錄 IX 圖目錄 XI 第一章 緒論 1 1-1 前言 1 1-2 研究動機 2 第二章 文獻回顧 3 2-1 醫用鎂合金 3 2-1-1 醫用鎂合金研究與發展現況 3 2-1-2 鎂鋅鈣合金腐蝕機制 6 2-2 Liquid TEM技術 23 2-2-1 Liquid cell結構 23 2-2-2 Liquid TEM的前景與展望 27 第三章 實驗方法與儀器設備 31 3-1 藥品與材料 31 3-1-1 鑄造鎂鋅鈣合金(as-cast Mg-Zn-Ca alloy) 31 3-1-2 鎂鋅鈣合金粉末 31 3-1-3 鎂鋅鈣合金熱壓成型塊材 32 3-2 使用設備與實驗方法 33 3-2-1 設備 33 3-2-2 實驗流程 36 3-2-3 分析軟體 37 第四章 結果與討論 38 4-1 鎂鋅鈣合金微觀結構分析 38 4-1-1 X光繞射儀分析 38 4-1-2 鑄造鎂鋅鈣合金(as-cast Mg-Zn-Ca alloy) 41 4-1-3 鎂鋅鈣合金粉末 44 4-1-4 鎂鋅鈣合金熱壓成型塊材 47 4-1-5 結論 49 4-2 鎂鋅鈣合金之微觀臨場腐蝕分析(DI water) 50 4-2-1 鑄造鎂鋅鈣合金經DI water腐蝕 50 4-2-2 鎂鋅鈣合金粉末經DI water腐蝕 53 4-2-3 鎂鋅鈣合金熱壓成型塊材經DI water腐蝕 55 4-2-4 結論 57 4-3 氯化鈉水溶液作為腐蝕液之濃度對鎂鋅鈣合金粉末的影響 58 4-3-1 鎂鋅鈣合金粉末經0.2 g/L氯化鈉水溶液腐蝕 58 4-3-2 鎂鋅鈣合金粉末經1 g/L氯化鈉水溶液腐蝕 61 4-3-3 鎂鋅鈣合金粉末經5 g/L氯化鈉水溶液腐蝕 64 4-3-4 結論 66 4-4 鎂鋅鈣合金粉末之腐蝕機制探討 67 4-4-1 鎂鋅鈣合金粉末之腐蝕產物推測 67 4-4-2 鎂鋅鈣合金粉末在DI water中腐蝕隨時間之成分定性分析 72 4-4-3 結論(機制推測) 77 第五章 總結論 80 參考文獻 82 附錄 87

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