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研究生:吳亞竹
研究生(外文):Wu, Yazhu
論文名稱:電鍍三價鉻黑色膜製程開發及特性研究
論文名稱(外文):The Study Of Characterization And Process Development At Electordepositing Black Trivalent Chromium Coating
指導教授:葛明德葛明德引用關係
指導教授(外文):Ger, Mingder
口試委員:葛明德白清源林招松侯光煦劉益銘
口試委員(外文):Ger, MingderBai, ChingyuanLin, ChaosungHou, KunghsuLiu, Yiming
口試日期:2012-05-14
學位類別:碩士
校院名稱:國防大學理工學院
系所名稱:化學工程碩士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:99
中文關鍵詞:電鍍三價鉻黑色膜耐蝕性黑化度
外文關鍵詞:Electrodeposition trivalent chromium platingBlack coatingCorrosion resistance
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本研究目的為利用電鍍的技術開發具有裝飾性和功能性的三價鉻黑色膜,此三價鉻黑色膜在太陽能板與光學儀器等產品上有相當的應用性。傳統鉻鍍層以六價鉻為鍍液成分。而六價鉻做為金屬材料之防護已有數十年的歷史。六價鉻鍍層的防蝕機制,主要是由一層薄的緻密層及一層厚的多孔層組成,由於六價鉻具有自我修復能力,在多孔層缺陷內產生許多修補腐蝕之物質,共同和鈍化膜一起達到防蝕功能,但六價鉻易造成環境污染並會對人體致癌,不易進行產品回收,因此,世界各國近年極力發展取代六價鉻的鈍化處理技術。本研究以鐵片為基材,將三價鉻離子還原在基材表面上,從中獲得黑色之鍍膜。黑色鍍層主要注重在特殊功能性上,黑色具有顏色區別、暗色調隱蔽、裝飾性色彩以及消光、散熱、太陽能吸收等光學和熱功能的目的。
  研究中探討電流密度、電鍍時間及黑化劑濃度對黑色膜各項性質之影響,包含以黑度計量測黑化度、SEM觀察表面型態、EDS量測黑化膜的組成成分、XRD分析三價鉻黑色膜之結構、UV-NIR absorption spectrometer對光的吸收度,並以電化學方法測試耐蝕性。由實驗結果得知:在電流密度高於(約30A/dm2)及電鍍1分鐘基材表面能得到黑色均勻與附著性良好的三價鉻黑色膜,此三價鉻黑色膜之組成成分主要以CoP、Cr(OH)3、CoO及Cr2O3為主,此外在電流密度30A/dm2以上所製備之三價鉻黑色膜具有較佳之耐蝕性。

This study aims to technology develop a decorative and functional, and black trivalent chromium coating using electroplating. The black trivalent chromium coating has considerable in applicability solar thermal collector and optical apparatus. In this study, a galvanized iron sheet substrate was used as the substrate. The trivalent chromium ions were reduced on the substrate surface to from the black coating. The influence of current density, electroplating time, and the concentration of black addition agent on the properties of black film was investigated. Spectra scan colorimeter was employed to measure the black level. Scanning electron microscopy(SEM) with X-ray energy dispersive spectronmetry(EDS) was used to examine the surface morphology ans composition of the black film. The crystal structure of the film was obtained via X-ray diffraction. UV-Visible-Near IR spectrometer was used to measure the optical absorption, and electrochemical approach was used to analyze the corrosion behavior of the black trivalent Cr coating.
The experimental results show that when a uniformly black trivalent chromium coating can be formed on the substrate when the current density was controlled at higher 30A/dm2 and electroplating for 1min. The black coating adheres well to the substrate. The black coating is mainly composed of CoP, Cr(OH)3、Cr2O3 and CrP Moreover, the black trivalent chromium coating produced at the corrent density over 30A/dm2, have better corrosion resistance than others.

致謝 i
摘要 iii
Abstract iv
目錄 v
表目錄 viii
圖目錄 ix
1. 緒論 1
1.1 研究動機 1
1.2 研究目的 2
2. 文獻回顧與理論基礎 3
2.1電鍍鉻的發展及現狀 3
2.1.1六價鉻電鍍之發展 3
2.1.2三價鉻電鍍之發展 4
2.2電鍍黑鉻技術之發展 6
2.3電化學機制原理 11
2.3.1 水溶液電化學反應 11
2.3.2 混合電位理論 11
2.3.3 極化曲線 12
2.3.4 金屬活化與鈍化 13
3. 實驗方法 16
3.1鍍液與電鍍黑鉻技術開發 16
3.1.1 試片準備與前處理 16
3.1.2 黑化電鍍液配製 16
3.1.3 電鍍黑鉻處理 17
3.2鍍層材料特性檢測與分析 18
3.2.1不同操作參數對鍍層表面型態之評估 18
3.2.2 腐蝕性質測試 21
3.2.3鍍層成分分析 21
3.2.4黑化度分析 24
4.結果與討論 28
4.1操作參數與三價鉻黑色膜特性研究 28
4.1.1電流密度對三價鉻黑色膜之影響 28
4.1.2電鍍時間對三價鉻黑色膜之影響 33
4.1.3溫度對三價鉻黑色膜之影響 39
4.1.4 pH值對三價鉻黑色膜之影響 44
4.2黑化鍍液濃度與三價鉻黑色膜特性研究 49
4.2.1主鹽濃度之影響 49
4.2.2鈷離子之影響 54
4.2.3黑化劑之影響 59
4.2.4介面活性劑之影響 64
4.3電鍍三價鉻黑色膜反應機制探討 69
黑化層成長機構解析 78
5.結論 80
6.未來展望 81
參考文獻 82
自傳 87


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