臺灣博碩士論文加值系統

耐腐蝕性差是鎂合金的嚴重缺點，其原因為鎂合金本身之高化學活性特性，使其在一般環境中容易被腐蝕而破壞原有特性，這也限制了它們在海洋環境中的應用，故提高鎂合金的耐腐蝕性是非常重要之課題，而於鎂合金表面披覆塗層則是改善其耐腐蝕性差的有效技術之一。本研究利用溶膠凝膠法製備二氧化鈰(CeO2)/1H,1H,2H,2H-全氟辛基三乙氧基矽烷(1H,1H,2H,2H-perfluorooctyltriethoxysilane, FAS-13)複合性塗層於鎂合金表面，並經過常壓電漿噴射束(APPJ)之熱處理後，得到一無機/有機之抗腐蝕與疏水性膜層。膜層材料特性分析藉由水接觸角(WCA)與表面自由能計算與百格刀附著性測試及拉曼光譜儀，表面形貌觀察則由場發射掃描式電子顯微鏡(FE-SEM)得知，而膜層之耐腐蝕性就由電化學阻抗頻譜與動電位極化曲線分析得出。
　　根據分析結果顯示，在常壓電漿熱處理後之膜層為疏水性質且與基材之間附著性相當良好，而從表面形貌中觀察到膜層有裂縫的產生，並且由拉曼光譜儀分析膜層材料為立方螢石結構之二氧化鈰，然後從電化學阻抗頻譜可知相較於原始AZ91D鎂合金，在經過常壓電漿熱處理後之試片皆有較高腐蝕電位與較低之腐蝕電流密度。
　　最後將經常壓電漿熱處理後之試片於5 wt %之NaCl溶液中進行鹽霧測試24~72小時與鹽酸浸泡測試24~72小時，其抗蝕性結果顯示仍比原始之鎂合金要高上許多，故表示本實驗所鍍之膜層能有效地提升原始鎂合金之抗腐蝕能力。
關鍵字：AZ91D鎂合金、溶膠凝膠法、稀土金屬、抗腐蝕薄膜、疏水性

Poor corrosion resistance is a serious drawback of magnesium alloys which restricts their applications in industry and marine environments. To increase the anti-corrosion resistance of magnesium alloys is very important, and coating is one of the effective techniques for improvement in the poor corrosion resistance. This study used sol-gel method to prepare cerium oxide/perfluorooctyltriethoxysilane composite coating on magnesium alloy surface, and after heat treatment of Atmospheric Pressure Plasma Jet(APPJ) to get an inorganic/organic corrosion resistant and hydrophobic coatings.
　　The characteristic of the film was analyzed by Water Contact Angle (WCA) and Adhesion cross-cut test and Raman spectroscopy, surface morphology observed by Field Emission Scanning Electron Microscopy (FE-SEM), and corrosion resistance was confirmed by Electrochemical Impedance Spectroscopy (EIS).
　　According to the results, the film after heat treatment of APPJ is hydrophobic, and the adhesion of the film to the substrate is quite good. FE-SEM observed cracks on the film. Raman spectroscopy confirmed the film was cubic fluorite structure of cerium oxide. EIS showed that film after heat treatment of APPJ performed even better corrosion potential and lower corrosion current density than the original AZ91D alloy.
　　Finally, after salt spray test in 5 wt % NaCl solution for 24~72h and hydrochloric acid immersion test for 24~72h showed the better corrosion resistance than AZ91D alloy.
Keywords: magnesium alloys, sol-gel, rare earth oxides, anti-corrosion layers, hydrophobic

中文摘要 I
Abstract II
致謝 IV
目錄 V
圖索引 IX
表索引 XIV
第一章 緒論
1.1 前言 1
1.2 二氧化鈰防蝕膜層 1
1.3 研究動機 1
第二章 文獻回顧
2.1 鎂金屬 3
2.1.1 鎂金屬特性 3
2.1.2 鎂合金 4
2.1.3 不同元素添加對鎂金屬影響 5
2.1.4 鎂合金之腐蝕現象 8
2.2 二氧化鈰的基本性質 14
2.2.1 物理性質及晶體結構 14
2.2.2 光學性質 15
2.2.3 化學性質 16
2.3 親疏水性質介紹 25
2.3.1 親疏水定義 25
2.3.2 表面張力 29
2.4 二氧化鈰製備方法 34
2.4.1 物理法 34
2.4.2 化學法 36
2.5 溶膠-凝膠簡介 39
2.6 電漿簡介 43
2.6.1 電漿定義 43
2.6.2 電漿原理 44
第三章 實驗設備與方法
3.1 研究設計 46
3.2 實驗藥品 48
3.3 實驗設備 49
3.4 材料分析儀器 60
3.4.1 接觸角量測儀 (Contact Angle) 60
3.4.2 場發射掃描式電子顯微鏡 (FE-SEM) 61
3.4.3 顯微拉曼螢光譜儀 62
3.4.4 百格刀附著性測試 63
3.4.5 電化學測試 65
3.4.6 熱重分析儀 (TGA) 72
3.4.7 傅立葉紅外線光譜儀 (FT-IR) 73
3.4.8 光學發射光譜儀 (OES) 74
3.5 實驗程序 75
3.5.1 試片準備 75
3.5.2 氧化鈰水溶液製備與旋轉塗佈鍍膜 75
3.5.3 傳統熱處理與常壓電漿熱處理之程序 76
第四章 結果與討論
4.1 前言 78
4.2 各項參數選定 79
4.2.1 熱重分析與熱處理溫度訂定 79
4.2.2 常壓電漿熱處理溫度設定與OES物種分析 80
4.2.3 傳統熱處理與常壓電漿熱處理比較 85
4.2.4 溶膠溶液莫耳濃度 87
4.2.5 探討不同熱處理製程後之接觸角與表面自由能 89
4.2.6 探討不同熱處理製程後之膜層附著性 91
4.2.7 探討不同熱處理製程後之表面形貌 92
4.3 無添加FAS之不同熱處理製程 94
4.3.1 接觸角與表面自由能 94
4.3.2 膜層附著性 94
4.3.3 表面形貌分析 94
4.3.4 拉曼光譜儀分析 96
4.3.5 阻抗頻譜分析 96
4.4 添加FAS之不同熱處理製程 104
4.4.1 FAS介紹與熱重分析 104
4.4.2 接觸角與表面自由能 104
4.4.3 膜層附著性 105
4.4.4 表面形貌分析 105
4.4.5 傅立葉紅外線光譜儀分析 106
4.4.6 阻抗頻譜分析 107
4.4.7 動電位極化曲線分析 109
4.5 膜層腐蝕特性研究 117
4.5.1 鹽霧測試規範與機制 117
4.5.2 鹽霧測試之表面形貌 119
4.5.3 鹽霧測試之阻抗頻譜分析 123
4.5.4 鹽霧測試之傅立葉紅外線光譜儀分析 128
4.5.5 鹽酸浸泡測試之表面形貌 130
第五章 結論與未來展望
5.1 結論 133
5.2 未來展望 134
第六章 參考文獻 135

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