摘要


沿晶應力腐蝕龜裂(Intergranular Stress Corrosion Cracking, IGSCC)是沸水式反應器中常見的材料老化劣化問題之一。根據文獻資料與實務經驗，若將不鏽鋼管件之電化學腐蝕電位(Electrochemical Corrosion Potential, ECP)控制在低於 -230 mVSHE，則能有效抑制沿晶應力腐蝕龜裂的發生。目前抑制IGSCC的技術只要以加氫水化學(Hydrogen Water Chemistry, HWC)搭配催化性被覆的貴重金屬添加(Noble Metal Chemical Addition, NMCA)為主，尚有以氧化鈦、氧化鋯等抑制性被覆技術(Inhibitive Protective Coating, IPC)。
本研究以氧化鋯為研究對象。首先我們先用熱水沉積法被覆二氧化鋯在304不鏽鋼試片的表面，來評估此被覆二氧化鋯層在模擬沸水式反應器環境的防蝕效益。接著，為了要了解此熱水沉積法被覆之二氧化鋯層在模擬沸水式反應器裡的耐久度，我們在不同水化學環境、流速150cc/min的高溫環境下進行四個禮拜的耐久度測試。最後，同時為了瞭解此被覆層在不同環境流速下的防蝕效益，我們也以低中高三種不同環境流速來測試此被覆試片的腐蝕行為。
根據實驗結果顯示，此二氧化鋯被覆層在高溫、不同水化學條件、最高流速150cc/min的環境底下長達28天後，其腐蝕電流和腐蝕電位並無明顯改變，且仍然維持其優異的保護性質，降低試片的腐蝕電流和腐蝕電位。

目錄
摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VIII
表目錄 XV
第一章 前言 1
1.1研究背景 1
1.2 研究目的 2
1.3 論文結構 4
第二章 文獻回顧 5
2.1 現今核能界材料使用所遭遇到的挑戰 5
2.2 核電廠輕水式反應器LWR水化學應用與保護關連性 7
2.3 不鏽鋼組件在高溫形成氧化膜的特性 10
2.3.1 高溫純水中不鏽鋼表面氧化層結構 10
2.3.2高溫純水中不銹鋼表面氧化膜成長機制 20
2.3.3拉曼散射光譜分析 30
2.4 抑制性被覆(Inhibitive Protective Coating, IPC) 32
2.4.1 溶膠凝膠法(Sol-gel) 32
2.4.2 電漿噴灑法(Plasma Spray) 33
2.4.3 合金添加法(Alloying) 34
2.4.4 化學添加法(Chemical Addition) 35
2.4.5 抑制性覆膜機制 39
2.5 不鏽鋼在高溫含過氧化氫環境下的電化學行為 43
2.6高流速對電化學腐蝕電位( ECP )的影響 46
2.7高流速對抑制性被覆膜的影響 48
2.8 現今防蝕技術與運轉經驗 51
第三章 基礎理論 55
3.1 應力腐蝕龜裂 55
3.1.1 應力腐蝕龜裂肇因 56
3.1.2 應力腐蝕龜裂之型態 58
3.1.3 應力腐蝕龜裂之現代理論 58
3.1.4 防治方法 63
3.2 混合電位理論 67
3.2.1 混合電位模式(Mixed Potential Model, MPM) 67
3.2.2 影響ECP大小的重要參數 71
3.2.3 電化學腐蝕電位與應力腐蝕龜裂關係 72
3.3 BWR防蝕技術簡介 73
3.3.1 伊凡斯圖(Evan’s Diagram) 73
3.3.2 加氫水化學 74
3.3.3貴重金屬添加(NMCA) 75
3.3.4 抑制性被覆(IPC) 76
第四章 研究方法 80
4.1 實驗方法與流程 80
4.2 試片準備 81
4.3 敏化程度測試 82
4.4 預長氧化膜 83
4.5 抑制性氧化鋯被覆 83
4.6 實驗設備 84
4.6.1 模擬BWR水循環系統 84
4.6.2氧化鋯被覆系統 85
4.6.3 參考電極製作 87
4.7 表面分析 88
4.7.1 輝光放電分光儀(Glow Discharge Spectrometer, GDS) 88
4.7.2 SEM表面微結構分析與EDX成分分析 88
4.7.3 拉曼光譜儀(Raman Spectroscopy) 88
4.7.4 感應式耦合電漿質譜分析(ICP-MS) 89
4.8 高溫電化學分析 90
4.8.1 預長氧化膜電化學腐蝕電位(ECP)監測 91
4.8.2 動態電位極化掃描 91
4.8.3表面被覆處理耐久度測試和低中高流速測試 92
第五章 實驗結果 93
5.1 敏化測試 93
5.2 預長氧化膜結果分析 94
5.2.1 掃描式電子顯微鏡 (SEM) 94
5.2.2 雷射拉曼散射光譜 (LRS) 98
5.3 IPC試片表面分析 100
5.3.1 掃描式電子顯微鏡 (SEM) 100
5.3.2 感應耦合電漿質譜分析 (ICP-MS) 104
5.3.3 雷射拉曼散射光譜 (LRS) 104
5.4 電化學分析 107
5.5 高溫電化學分析─二氧化鋯耐久度測試之動態電位極化掃描 109
5.5.1 溶氧濃度極化曲線 110
5.5.2 不同過氧化氫濃度極化曲線 117
5.5.3 溶氫濃度極化曲線 133
5.6 高溫電化學分析─不同流速之動態電位極化掃描 139
5.6.1 溶氧濃度極化曲線 140
5.6.2 不同過氧化氫濃度極化曲線 142
5.6.3 溶氫濃度極化曲線 147
第六章 結論 149
6.1 結論 149
第七章 未來工作 151
參考文獻 153

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