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研究生： 林榮信
Lin, Rong-Sin
論文名稱： 含銅碳鋼於氯化鈉水溶液中之腐蝕性質研究
Corrosion behavior of copper-containing carbon steels in NaCl solution
指導教授： 蔡文達
Tsai, Wen-Ta
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： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 88
中文關鍵詞： 含銅碳鋼 、浸泡試驗 、動電位極化曲線 、交流阻抗頻譜
外文關鍵詞： coppering-containing steels, immersion test, potentiodynamic polarization curves, electrochemical impedance spectroscopy
相關次數： 點閱：147  下載：5 
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    • 本研究係探討銅的添加對碳鋼於3.5 wt% NaCl水溶液中之耐蝕性的影響，以浸泡試驗計算其腐蝕重量損失，利用動電位極化曲線及交流阻抗頻譜量測以了解其電化學耐蝕性質，並利用X光繞射分析儀（X-ray diffraction, XRD）及X光光電子能譜儀（X-ray photoelectron spectroscopy, XPS）分析定電位測試後表面腐蝕產物之結晶結構與化學組態。
    浸泡試驗結果顯示，在酸性溶液中，不含銅之SS400有最大的腐蝕重量損失，且隨著Cu含量的增加，其重量損失也隨之下降；在中性及鹼性溶液中，SS400仍有較高之腐蝕量，顯示銅的添加可降低碳鋼之重量損失，且在此環境中，重量損失量並未隨銅含量的增加而明顯減少。動電位極化曲線量測結果指出，腐蝕電位（corrosion potential, Ecorr）不因鋼材銅含量不同而改變，但會隨pH值增加而減小，且含銅碳鋼相較於SS400有較低之陽極電流密度，而當pH值大於10時，於陽極區皆可見鈍化現象。交流阻抗頻譜分析(electrochemical impedance spectroscopy, EIS)結果顯示，在pH = 2之條件下，隨著碳鋼含銅量增加，其極化阻抗（polarization resistance, Rp）可由130 ohm-cm2增加至958 ohm-cm2；於pH = 12之情況下，含有4.5 wt% Cu之碳鋼其阻抗可達3166 ohm-cm2，且當溶液pH值提升，鋼材之阻抗值也隨之提升。此外，施加定電位於-0.7 VSCE持續30分鐘後由XPS分析結果發現，含銅碳鋼表面含有鐵的氧化物、銅及銅的氧化物。綜合上述研究成果，銅的添加有助提升於碳鋼在3.5 wt% NaCl水溶液中之耐蝕性質，尤以酸性條件下，有更加明顯之趨勢。

    The corrosion behavior of Cu-containing carbon steels in various acidity 3.5 wt% NaCl solution was investigated. By immersion test to calculated the weight loss. The properties of electrochemical corrosion behavior were obtained from potentiodynamic polarization curves and electrochemical impedance spectroscopy. The corrosion products’ crystal structure and chemical bonding energy after potentiostat testing obtained from the X-ray diffraction and X-ray photoelectron spectroscope.
    The immersion test showed that the weight loss of SS400 steel was higher than that of Cu-containing carbon steels in acidic solution. The weight loss of the Cu-containing carbon steels is decreased with increasing Cu content of the carbon steel. Furthermore, the weight loss of SS400 steel was still higher than that of Cu-containing carbon steels in neutral or basic solution. Potentiodynamic polarization curves showed that the corrosion potential (Ecorr) of Cu-containing carbon steels did not change greatly by adding various Cu content in carbon steel. However, the corrosion potential of Cu-containing carbon steels decreased as the pH value of solution increased. In case of anodic region, the anodic current density of Cu-containing carbon steels was lower than that of SS400 steel. There was a passivation region could be observed in the anodic curves with the pH value of solution was more than 10. The electrochemical impedance spectroscopy (EIS) results indicated that the polarization resistance (Rp) of Cu-containing carbon steel varied from 130 ohm-cm2 to 958 ohm-cm2, depending on the Cu content, in acidic solution (pH = 2). On the other hand, the results also shows that the Rp was increased as the solution pH increased. A significant increase in Rp (3166 ohm-cm2) could be obtained for 4.5 wt% Cu in carbon steel, in basic solution (pH = 12). After potentiostatic test at -0.7 VSCE for 30 minutes, iron oxide, Cu oxide and Cu could be formed on the Cu-containing carbon steels, as confirmed by X-ray photoelectron spectroscopy (XPS) analysis According to the results, the corrosion resistance could be improved by adding Cu element for carbon steels in 3.5 wt% NaCl solution, especially under acidic solution.

    總目錄 中文摘要 I Abstract III 致謝 V 總目錄 VII 表目錄 IX 圖目錄 X 第一章 前言 1 第二章 文獻回顧 3 2.1 含銅鋼之背景 3 2.2 含銅鋼的腐蝕 3 2.2.1 酸性環境 3 2.2.2 中性環境 6 2.2.3 鹼性環境 7 第三章 實驗方法與步驟 24 3.1 試驗材料 24 3.2 基材特性分析 27 3.3 試驗溶液 27 3.4 浸泡試驗 28 3.5 電化學性質測試 28 3.6 定電位測試（potentiostatic test） 31 第四章 結果與討論 32 4.1 鋼材之基本性質 32 4.2 浸泡試驗結果 37 4.3 鋼材在NaCl水溶液中的耐蝕性質分析結果 41 4.4 鋼材表面腐蝕生成物分析結果 60 4.5 溶液中pH值改變對鋼材耐蝕性質之影響 65 4.6 鋼材銅含量對其耐蝕性質之影響 78 第五章 結論 81 參考文獻 83   表目錄 表2－1　不同銅含量之碳鋼於10 wt% H2SO4溶液中改變浸置時間的交流阻抗頻譜分析結果[9]。 9 表3－1 實驗材料化學成分組成（wt%）。 25 表4－1 鋼材於不同pH之3.5 wt% NaCl水溶液經浸泡14天後之腐蝕速率。 39 表4－2 由動電極化曲線結果計算之腐蝕電位（Ecorr）、腐蝕電流密度（icorr）、極化阻抗（Rp）及腐蝕速率（corrosion rate）。 68 表4－3 交流阻抗頻譜分析之阻抗值。 69   圖目錄 圖2－1 不同銅含量之碳鋼於10 wt% H2SO4溶液之動電位極化曲線[9]。 10 圖2－2 不同銅含量之碳鋼於10 wt% H2SO4溶液之交流阻抗頻譜分析[9]。 11 圖2－3 不同銅含量之碳鋼於10 wt% H2SO4溶液浸泡6小時後之XPS分析結果（a）碳鋼、（b）與（c）分別為含銅量0.2與0.35 wt%之含銅碳鋼[9]。 12 圖2－4 不同含銅含量之碳鋼在42 wt% H2SO4水溶液中浸泡24小時之腐蝕速率與銅含量關係圖[7]。 13 圖2－5 不同含銅含量之碳鋼於在42 wt% H2SO4水溶液中浸泡24小時之動電位極化曲線[7]。 14 圖2－6 含銅不銹鋼於除氧之0.1 M H2SO4水溶液中之動電位極化曲線[23]。 15 圖2－7 不同銅含量之麻田散體不銹鋼於10 wt%之HCl水溶液中之動電位極化曲線[8]。 16 圖2－8 不含銅之低碳鋼與含銅低碳鋼在5 wt% NaCl環境中進行加速循環腐蝕試驗之重量損失量與循環次數之關係圖[25]。 17 圖2－9 低碳鋼於合成自來水中之（a）動電位極化曲線、（b）為由動電位極化曲線計算而得之腐蝕速率[12]。 18 圖2－10 含銅碳鋼於合成自來水中浸泡3小時之Cu元素之EPMA分析結果，可發現銹層與基材界面Cu富集之現象[12]。 19 圖2－11 不同銅含量之不銹鋼在0.05 M NaCl水溶液中之開路電位（a）Austenite及（b）Ferrite[6]。 20 圖2－12 不同銅含量之不銹鋼在0.05 M NaCl水溶液中之動電位極化曲線（a）Austenite及（b）Ferrite[6]。 21 圖2－13 純鐵、純銅與鐵銅合金在含有0.01 M NaCl之Ca(OH)2溶液(pH =10)之極化曲線[10]。 22 圖2－14 於0.01 M NaCl之Ca(OH)2溶液(pH =10)中施加-0.1 VSSE極化10分鐘之陽極電流密度（a）純鐵與鐵銅合金、（b）將（a）之y軸放大[11]。 23 圖3－1 研究架構流程圖。 26 圖3－2 動電位極化曲線阻抗值計算方式。 30 圖4－1 不含銅SS400碳鋼、含銅鋼種A690及特製B、C、D鋼種之XRD繞射分析結果。 33 圖4－2 不含銅SS400碳鋼、含銅鋼種A690及特製B、C、D鋼種之OM金相圖：（a）S (SS400)、（b）A(A690)、（c）B、（d）C及（e）D。 34 圖4－3 編號D鋼種之SEM及EDS分析結果。（a）基材SEM影像、（b）第二相、（c）析出物及（d）EDS結果。 35 圖4－4 鐵-銅二元相圖[34]。 36 圖4－5 不同銅含量鋼材於不同pH值3.5 wt% NaCl水溶液之浸泡試驗重量損失量及腐蝕速率結果。 40 圖4－6 不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 2）中的極化曲線圖。 45 圖4－7　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 2）中的交流阻抗頻譜分析（a）Nyquist及（b）Bode圖。 46 圖4－8　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 4）中的極化曲線圖。 48 圖4－9　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 4）中的交流阻抗頻譜分析（a）Nyquist及（b）Bode圖。 49 圖4－10　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 6）中的極化曲線圖。 51 圖4－11　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 6）中的交流阻抗頻譜分析（a）Nyquist及（b）Bode圖。 52 圖4－12　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 10）中的極化曲線圖。 54 圖4－13　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 10）中的交流阻抗頻譜分析（a）Nyquist及（b）Bode圖。 55 圖4－14　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 12）中的極化曲線圖。 57 圖4－15　不同銅含量鋼材在3.5 wt% NaCl水溶液（pH = 12）中的交流阻抗頻譜分析（a）Nyquist及（b）Bode圖。 58 圖4－16 測試鋼種經定電位測試後之XRD分析結果。 62 圖4－17 基材經XPS分析之圖譜（a）Fe 2p3/2及（b）Cu 2p3/2。 63 圖4－18 鋼材經定電位試驗後之XPS分析圖譜（a）Fe 2p3/2及（b）Cu 2p3/2。 64 圖4－19 各式碳鋼於3.5 wt% NaCl水溶液中的腐蝕電位（Ecorr）及腐蝕電流密度（icorr）隨銅含量及溶液pH值之趨勢圖。 70 圖4－20 Fe-H2O系統於25 oC下之Pourbaix diagram[37]。 71 圖4－21 測試鋼種在不同pH值之3.5 wt% NaCl水溶液中的極化曲線圖（a）SS400及（b）含4.5 wt% Cu特製鋼材。 72 圖4－22 編號S鋼種在不同pH值之3.5 wt% NaCl水溶液中的交流阻抗頻譜分析（a）Nyquist及（b）Bode圖。 73 圖4－23 編號D鋼種在不同pH值之3.5 wt% NaCl水溶液中的交流阻抗頻譜分析（a）Nyquist及（b）Bode圖。 75 圖4－24 測試鋼種在不同pH值之3.5 wt% NaCl水溶液中的阻抗值之（a）直流訊號及（b）交流訊號圖。 77

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