臺灣博碩士論文加值系統

本研究利用直流電鍍法在SC-CO2的條件下製備鎳磷合金。發現在SC-CO2下鍍層中磷含量與電流效率會大量的降低，推測是由於中間產物磷化氫可能會溶解於SC-CO2中。雖然在超臨界的狀態下，增加鍍液中亞磷酸含量可以提高鍍層中磷含量，但卻會造成電流效率的下降。在表面形貌方面，利用SC-CO2電鍍法可得較緻密且平整的鍍層，且隨著壓力的上升，表面粗糙度會逐漸下降至20.4MPa的23nm；但增加鍍液中亞磷酸濃度卻會使表面的粗糙度上升。在抗腐蝕的測試中，腐蝕電流隨著操作壓力上升而下降，且鍍膜在經400oC退火後腐蝕電流會再些微下降；常壓鍍膜由9.8μA下降至7.9μA，20.4MPa之鍍膜由5.2μA下降至3.9μA，顯示利用SC-CO2電鍍之鍍膜擁有較好的抗腐蝕力。鍍膜的機械強度由常壓的556Hv提昇至10.2MPa下的650Hv；而1.2M之亞磷酸硬度較0.2M提昇50%。經退火後，可由XRD圖發現磷化鎳(Ni3P)的波峰，使合金鍍層硬度向上提昇，常壓為810Hv，10.2MPa為895HV，亞磷酸濃度1.2M為1024HV。
此外利用複合電鍍來製備磷化鎳合金，發現在超臨界下，硬度並無太大的增加，這是由於添加分散劑會降低SC-CO2之溶解度，以至於失去超臨界電鍍所帶來的好處。

Nickel-phosphorus (Ni-P) alloys were prepared by electroplating under supercritical carbon dioxide (SCCO2) in this study. Under SCCO2, phosphorus content and current efficiency were dramatically decreased as a result of dissolution of the intermediate, PH3. Adding more phosphorous acid is useful for increasing phosphorus content in deposit layer but decreasing current efficiency. Roughness gradually decreased with pressure increased but concentration of phosphorous acid decreased. Corrosion test was examined by polarization curve. Higher pressure and concentration of phosphorous acid made better corrosion resistance. Corrosion current was 9.8μA at atmosphere, and 5.2μA at 20.4MPa. After heat treatment, corrosion current may further decreased As pressure increased, the micro-hardness of the Ni-P alloys increases to 650Hv at 10.2MPa, and becomes decreasing with further increasing pressure. Micro-hardness of the Ni-P alloys increases of 50% with 1.2M phosphorous acid comparing to atmosphere. Hardness further increased after heat treatment.
Composite plating is also used in this study to produce Ni-P alloy. The dispersant used in this study inhibited the dissolution of SCCO2 which caused no benefit in micro-hardness of as-plated deposit. After annealing, more phosphorus powder in deposit layer made harder deposit.

中文摘要 I
Abstract II
目錄 III
圖目錄 VII
表目錄 XII
第二章、文獻回顧與分析介紹 3
2-1電鍍 3
2-1-1 電鍍的基本介紹 3
2-1-2 合金電鍍機制 6
2-1-3 複合鍍共沉積機制與原理 7
2-2 鎳磷合金 9
2-2-1鎳磷合金的沉積機制 10
2-2-2鎳磷合金的製備 11
2-2-3鎳磷合金的微硬度 12
2-2-4鎳磷合金的結構 13
2-2-5鎳磷合金的抗腐蝕力 14
2-3 超臨界電鍍 15
2-3-1超臨界流體 15
2-3-2超臨界二氧化碳 18
2-3-3界面活性劑 19
2-3-4超臨界電鍍 23
2-3-5 SC-CO2之溶解度 27
2-4 腐蝕實驗 30
2-4-1 腐蝕的基本介紹 30
2-4-2 電化學測試法 (Polarization Curve) 35
2-5 研究動機與目的 37
第三章 實驗方法與步驟 38
3.1 藥品與儀器 38
3-1-1 藥品 38
3-1-2 實驗儀器 38
3-2 實驗流程與方法 39
3-3超臨界電鍍系統 40
3-4 實驗流程(鎳磷合金之電鍍) 41
3-4-1 電鍍前處理 41
3-4-2 鎳磷合金電鍍 42
3-4-2-1 改變操作壓力 43
3-4-2-2 提昇超臨界下鍍層中的磷含量 44
3-4-3 退火(Annealing) 50
3-5 電導度量測與試片分析 51
3-5-1 電導度的量測 51
3-5-2 腐蝕實驗 53
第四章 結果與討論 55
4-1電導度與乳化的討論 55
4-2電化學行為探討 59
4-2-1改變操作壓力 59
4-2-2 改變亞磷酸濃度 62
4-3 鎳磷合金鍍膜探討 66
4-3-1 改變操作壓力對鍍膜的影響 66
4-3-1-1 組成分析與電流效率 66
4-3-1-2 表面形貌分析 67
4-3-1-3結晶構造分析 73
4-3-1-4機械強度分析 77
4-3-1-5腐蝕試驗 80
4-3-2 改變亞磷酸濃度對鍍膜的影響 84
4-3-2-1組成分析與電流效率 84
4-3-2-2 表面形貌分析 85
4-3-2-3 結晶構造分析 90
4-3-2-4機械強度分析 93
4-3-2-5腐蝕試驗 95
4-4 鎳磷合金鍍膜探討 (複合電鍍) 99
4-4-1研磨參數對磷粉粒徑的影響 99
4-4-2組成分析 101
4-4-3形貌分析 102
4-4-4機械強度分析 106
4-4-5 腐蝕試驗 108
第五章 結論與未來展望 112
5-1結論 112
5-2未來與展望 113
參考文獻 115

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