臺灣博碩士論文加值系統

本研究主要探討無氰鍍鋅三價鉻化成膜老化，釐清三價鉻鍍液老化的關鍵因素，提供線上吊鍍與滾鍍系統三價鉻鍍液管理之參考。藉由管理化成液中銅、鋅離子含量與pH值範圍，可以有效增加三價鉻鍍液使用壽命，降低生產成本。
本實驗以化成膜巨觀形貌觀察其顏色變化，線性極化掃描檢測化成膜抗蝕性，電化學交流阻抗分析化成膜結構與皮膜阻抗，化成膜長時間耐蝕性以鹽霧測試觀察，由電子顯微鏡觀察微結構並使用X光電子能譜儀分析化成膜厚度及組成成份。
添加鋅與銅離子之研究結果顯示，鋅與銅離子容忍度分別低於12500 ppm與30 ppm。當雜金屬濃度超過容忍度時，化成膜外觀顏色變淡且有斑駁；線性極化掃描顯示化成膜腐蝕電流都有增加的趨勢；電化學交流阻抗分析中皮膜阻抗大幅降低，膜層結構複雜，鹽霧測試無法通過24小時；微觀結構表面形貌顯示化成膜披覆性不佳，造成基材裸露；由X光電子能譜儀分析發現化成膜厚度較薄且組成成份中鉻的氧化物比例下降，顯示當雜金屬濃度過高會導致化成膜組成與結構改變導致耐蝕性能下降。
化成液pH值對化成膜影響之研究，結果顯示pH值對化成膜外觀顏色影響最大；電化學交流阻抗檢測顯示高pH值化成膜相對結構鬆散；鹽霧腐蝕測試平均耐鹽霧時間縮短但仍維持120小時以上水準；由開環電位發現pH值升高成膜驅動力會變小，使得最佳成膜參數改變造成化成膜耐蝕性降低。
放大實驗觀察雜金屬影響的效應，結果顯示主要金屬離子消耗與鋅、銅金屬生成的速率極為緩慢，因此本系統之配方使用壽命很長，但是需要搭配pH值的調控，容忍度在pH 2.0到pH 2.3之間，都可以保持生產線上要求的耐鹽霧時間48小時以上。

This study was to explore non-cyanide zinc trivalent chromate film aging and clarify the trivalent chromium bath a key factor in aging. Provide a reference for the trivalent chromium solution management system which was using hanging plating and barrel plating. By managing copper, zinc ion content in the solution and the range of solution pH, can effectively increase the trivalent chromium solution life, reduce production costs.
In this experiment, using linear-polarized scanning to detect the corrosion resistance of film, electrochemical impedance to analysis structure and resistance. Observed the corrosion resistance of the film for a long time in salt spray test. Using electron microscope to observe the micro-structure, X-ray photoelectron spectroscopy to analysis the thickness and composition of the film.
Zinc-ions and copper-ions were added to the study showed that tolerance of zinc-ions and copper-ions were less than 12500 ppm and 30 ppm. When the concentration of mixed metal exceed the tolerance, the appearance of the film the color fades and there is mottled. Linear-polarization scanning showed that the corrosion of the film was increased. Electrochemical impedance analysis showed that the impedance of coating has greatly reduced, and the structure of the film was complex. Salt spray test was less than 24 hours. Microstructure morphology test showed that of the film has poor display of the coated, resulting in the substrate exposed. By the X-ray photoelectron spectroscopy analysis, when the thickness of film was thin, the composition ratio of chromium oxide were decreased. It indicated that when the complex of metal concentration is too high, it will lead to change in film composition and structure of the corrosion performance.
The study of pH value on the impact of film showed that the pH value has the greatest impact of the film color appearance. Electrochemical impedance analysis showed that the structure of film was loose when pH value was high. The average time of salt spray test was decreased, but still maintain the 120 hours or more hours. By the OCP test showed that when pH value increased, the driving force will become smaller. It makes the best parameters change, resulting in reduced corrosion resistance of the film.
Amplification Experimental observe the effect of the complex metal showed that consumption rate of primary metal ions and the production rate of zinc-ions and copper-ions were very slow. Therefore, formulation of this system has a long service life, but it is need to control the pH value between 2.0 to 2.3. The salt spray time is more than 48 hours. It can meet the requirements of the production line.

誌謝 ii
摘要 iii
ABSTRACT iv
目錄 vi
表目錄 viii
圖目錄 ix
1.緒論 1
1.1 前言 1
1.2 研究動機與目的 2
2.文獻回顧 3
2.1 電鍍鋅之發展 3
2.2 鉻酸鹽化成膜之發展 3
2.3 三價鉻成膜機制 4
2.4 化成液中雜金屬離子之影響 5
3.原理介紹 6
3.1 化成處理之原理 6
3.2 線性極化掃描法 6
3.3 電化學交流阻抗頻譜法 7
3.4 X光光電子能譜儀 10
3.5 序列式感應偶合電漿原子發散光譜儀 10
4.實驗方法 13
4.1 實驗藥品 13
4.2 實驗儀器 13
4.3 三價鉻試片製作的流程 14
4.3.1 線性極化檢測 16
4.3.2 電化學交流阻抗檢測 17
4.3.3微結構分析 17
4.3.4縱深成份分析 17
4.3.5 鹽霧腐蝕測試 17
4.3.6 序列式感應耦合電漿原子發散光譜儀檢測 18
5.結果與討論 19
5.1 化成液中鋅離子對皮膜的影響 19
5.2 鍍液中銅離子對皮膜的影響 44
表5. 4添加不同濃度銅離子之化 46
5.3化成液pH值對皮膜的影響 62
5.4 三價鉻鍍液先導生產之研究 75
6.結論與未來展望 81
6.1結論 81
6.2未來展望 82
參考文獻 83
自傳 87

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