臺灣博碩士論文加值系統

Fe5Mn3CoCr中熵合金為近年來所被提出之新穎合金，此合金在產生形變時可表現出相變誘導塑性效應(Transformation induced plasticity)而發揮卓越的強度及延性，其良好之機械性質甚至優於傳統CoCrFeMnNi等莫耳高熵合金，但在腐蝕環境中之抗蝕性質依舊未知。因此本篇將CoCrFeMnNi高熵合金及Fe5Mn3CoCr中熵合金在不同環境中所呈現的腐蝕電化學特性進行分析，並探討兩者的極化破壞過程。在循環極化測試中，採用的腐蝕環境為不同pH值(3, 6, 9, 12)和溫度(10oC, 40oC, 70oC)的3.5wt%氯化鈉水溶液以及0.1M硫酸水溶液。實驗結果顯示，在3.5wt%氯化鈉水溶液中，CoCrFeMnNi高熵合金的鈍化區間明顯大於Fe5Mn3CoCr中熵合金，但二者之腐蝕電流密度並無顯著差異。在0.1M硫酸水溶液中，Fe5Mn3CoCr中熵合金的腐蝕電流密度較CoCrFeMnNi高熵合金高。在3.5wt%氯化鈉水溶液進行循環極化試驗後，可觀察到CoCrFeMnNi高熵合金所留下的蝕孔形貌，其是由介在物的崩解並擴展而產生;Fe5Mn3CoCr中熵合金則是呈現條線狀的腐蝕形貌，此形貌是由蝕孔相接形成。在0.1M硫酸水溶液進行循環極化試驗後，CoCrFeMnNi高熵合金之腐蝕型態為晶界腐蝕與加凡尼腐蝕;而Fe5Mn3CoCr中熵合金呈現分支狀組織，此一腐蝕形貌主要來自於ε麻田散相的溶解。

In recent years, Fe5Mn3CoCr medium entropy alloy (MEA) has been reported as an alloy system which shows transformation-induced plasticity effect during deformation. The excellent strength and ductility combination of this alloy is even better than CoCrFeMnNi high entropy alloy (HEA), but the corrosion behavior is still unknown. In this study, the corrosion behavior of CoCrFeMnNi HEA and Fe5Mn3CoCr MEA were investigated. The environments chose for the cyclic polarization measurement were 3.5wt% NaCl solution with different pH values (pH=3, 6, 9, 12) and temperatures (10oC, 40oC, 70oC) and 0.1M H2SO4 solution. The results show that, compared with CoCrFeMnNi HEA, Fe5Mn3CoCr MEA the had smaller passivation region in every test environment, but the two substrate had almost the same corrosion current density value in 3.5wt% NaCl solution without any adjustment. In 0.1M H2SO4 solution, the corrosion current density of Fe5Mn3CoCr MEA is higher than CoCrFeMnNi HEA. The surface morphologies of CoCrFeMnNi HEA after polarization measurement in 3.5wt% NaCl solution exhibited a pitting appearance, which was resulted from the disintegration of inclusions on surface; Fe5Mn3CoCr MEA showed “lath-shaped” corrosion morphologies which were caused by the connection of pits. After cyclic polarization in 0.1M H2SO4 solution, CoCrFeMnNi HEA showed intergranular corrosion and galvanic corrosion morphologies; Fe5Mn3CoCr MEA showed “branch-like” corrosion morphologies which is attributed to the dissolution of ε martensite.

摘要 I
Abstract II
目錄 III
圖目錄 VI
表目錄 X
第一章 前言 1
第二章 文獻回顧 2
2-1 腐蝕概論 2
2-1-1 腐蝕的意義 2
2-1-2 腐蝕分類 2
2-1-2-1均勻腐蝕(Uniform corrosion) 2
2-1-2-2孔蝕(Pitting corrosion) 3
2-1-2-3間隙腐蝕(Crevice corrosion) 4
2-1-2-4晶界腐蝕(Intergranular corrosion) 5
2-1-2-5加凡尼腐蝕(Galvanic corrosion) 6
2-1-2-6選擇性腐蝕(Selective leaching) 8
2-1-2-7 沖磨腐蝕(Erosion corrosion) 8
2-1-2-8應力腐蝕(Stress corrosion) 9
2-1-3 腐蝕熱力學 9
2-1-4腐蝕動力學 11
2-1-4-1腐蝕速率介紹 11
2-1-4-2極化介紹 12
2-1-4-3循環極化理論 14
2-2 高熵合金簡介 14
2-2-1高熵合金起源 14
2-2-2高熵合金定義 15
2-2-3 高熵合金之混合熵 15
2-2-4高熵合金之效應 16
2-2-5 高熵合金之抗腐蝕性質研究 19
2-3 TRIP/TWIP簡介 26
2-3-1 TRIP鋼與TWIP鋼 26
2-3-2 Fe50Mn30Co10Cr10 TRIP雙相高熵合金簡介 26
第三章 實驗方法 28
3-1實驗流程 28
3-2實驗內容 30
3-2-1試片製作 30
3-2-2結構分析 30
3-2-3成分分析 30
3-2-4電化學測試 31
3-2-5表面形貌觀察 32
3-2-6 腐蝕產物分析 32
第四章 結果與討論 33
4-1結構及元素分析 33
4-2電化學試驗 38
4-2-1 循環極化-不同pH值之氯化鈉環境 38
4-2-1-1 CoCrFeMnNi高熵合金在不同pH值氯化鈉水溶液之循環極化 38
4-2-1-2 Fe5Mn3CoCr中熵合金在不同pH值氯化鈉水溶液之循環極化 43
4-2-2 循環極化-不同溫度之氯化鈉環境 46
4-2-3 循環極化-硫酸環境 49
4-2-3-1 CoCrFeMnNi高熵合金在0.1M硫酸水溶液之循環極化 49
4-2-3-2 Fe5Mn3CoCr中熵合金在0.1M硫酸水溶液之循環極化 50
4-2-4動電位極化總比較 52
4-3 腐蝕形貌觀察 54
4-3-1 不同pH值之氯化鈉環境 54
4-3-2 不同溫度之氯化鈉環境 63
4-3-3 硫酸環境 70
4-4 氯化鈉環境之腐蝕機制探討 72
4-4-1 CoCrFeMnNi高熵合金之腐蝕機制 72
4-4-2 Fe5Mn3CoCr中熵合金之腐蝕機制 74
4-5 酸性氯化鈉環境之腐蝕產物分析 76
第五章 結論 82
第六章 未來展望 83
參考文獻 84

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