臺灣博碩士論文加值系統

本研究係利用三價鉻化成膜的製程參數、電化學性質、表面微結構分析、鹽霧試驗以及化成膜液的老化等問題，進行一系列之探討與研究。
研究項目共分為三個部分，第一部分為探討三價鉻化成膜之製程參數，在鋅電鍍製程方面，使用鹼性無氰化物電鍍液；其最佳條件為: 電流密度3.0A/dm2、溫度30℃、電鍍時間30分鐘，以X-Ray膜厚機測試為10μm。化成皮膜製作方面: 浸泡時間以30~60秒、濃度12.0 v/v %、溫度在室溫、pH值控制在1.8±0.2時獲得最佳製程參數。
第二部分為探討化成反應時間對三價鉻化成膜表面形貌與電化學性質影響之研究: 利用OCP方法瞭解化成膜生成的機制，EIS測得皮膜結構，得知三價鉻化成膜計有內、中、外三層結構和皮膜緻密性大小。利用極化曲線法快速測得皮膜耐蝕性質，SEM得知鈍化膜厚度為約50~200 nm、AFM能測得表面粗糙度分佈之微結構。
第三部分為探討電鍍生產過程中鐵、銅離子的累積影響化成膜液的老化問題之研究: 利用不同濃度鐵離子及銅離子添加於三價鉻化成膜液，探討鍍鋅試片經化成後之皮膜抗腐蝕之研究。其結果顯示，由於鐵離子濃度之增高，皮膜之耐蝕性則降低，濃度增至140.0 mg/L開始明顯影響三價鉻鈍化膜之耐蝕性，造成皮膜表面裂紋增加。同時由於銅離子濃度提高至9.0 mg/L則開始嚴重影響三價鉻化成膜的耐蝕性，使用SIMS和XPS觀察皮膜則變厚，且形成氧化銅越多，導致皮膜結構更鬆散，造成三價鉻鈍化膜耐蝕性之下降。本研究成果可供電鍍產業在三價鉻化成製程滾鍍與吊鍍生產上之參考，監控銅、鐵離子濃度藉以提高品質。

This dissertation investigated the manufacturing factors that affect the quality of Cr (III)-based conversion coatings on zinc coated steel surface by the morphology, and electrochemistry techniques.
In the first section of the dissertation, an optimal preparation condition of alkide noncyanide zincplating process were found as: current density 3.0A/dm2, electroplating time 30 min, dipping time 30~60 sec, bath concentration 12%, bath temperature 25~30℃, pH value 2.0 ± 0.1. Salt spray results showed that the Cr (III)-based conversion coatings have better anticorrosion property than that of the Cr (VI) conversion coating.
The second section of the dissertation investigated the effects of immersion time on morphology and electrochemical properties of the Cr (III)-based conversion coatings on zinc coated steel surface. By means of the nondestructive measurement technique, corrosion properties can be quickly evaluated by using an EIS, In addition, the roughness profile was monitored by SEM、AFM.
The third part of the dissertation discussed the effects of contamination of pollution ions on the corrosion properties of Cr (III)-coated films on zinc. The ferric and copper ions were individually added to Cr (III) conversion coating solution, effects of anticorrosion properties were correlated. Results showed that the increase of ferric ion concentration to 140 mg/L would decrease the corrosion properties. Moreover, cracks were noticed as the increase of film thickness. Increase of the copper ion concentration accelerated the growth of the film. For the case of copper compound concentration raised to 9.0 mg/L of copper ion, the corrosion result on Cr (III)-based conversion coatings has improved.

中文摘要 i
英文摘要 ii
誌謝iv
目錄v
表目錄viii
圖目錄ix
第一章 緒論1
1.1前言1
1.2文獻回顧3
1.2.1電鍍鋅之發展3
1.2.2鉻酸鹽化成皮膜之發展 3
1.2.3三價鉻鈍化膜成膜之機制 4
1.2.4六價鉻與三價鉻化成膜的比較7
1.3研究動機9
第二章 理論探討10
2.1鹼性無氰化物鍍鋅原理10
2.2化成處理原理11
2.3溶解度積(Ksp)及沉澱原理11
2.4電化學交流阻抗頻譜原理12
2.5線性極化掃描原理15
2.6二次離子質譜原理17
2.7化學分析電子術原理17
2.8鹽霧試驗18
第三章 實驗方法19
3.1藥品19
3.2鹼性鍍鋅試片與化成膜試片製作21
3.3實驗步驟23
3.3.1第一部分 三價鉻化成膜製程參數最適化之研究23
3.3.2第二部分 化成反應時間對三價鉻化成膜的表面形貌
與電化學性質之探討24
3.3.3第三部份 三價鉻藥液老化問題之研究25
3.3.3.1三價鉻藥液分別加入不同濃度之鐵離子25
3.3.3.2三價鉻藥液分別加入不同濃度之銅離子25
3.3.3.3電鍍工廠三價鉻藥液污染離子含量之追蹤25
3.4實驗設備26
3.4.1鹽霧試驗機26
3.4.2電化學性質檢測設備27
3.4.2.1電鍍槽27
3.4.2.2恆電位儀28
3.4.2.3交流阻抗頻譜檢測28
3.4.3化成膜微結構分析儀29
3.4.3.1掃瞄式電子顯微鏡29
3.4.3.2原子力顯微鏡30
3.4.3.3 X-Ray螢光膜厚儀30
3.4.3.4成分縱深分析儀31
3.4.3.5金屬含量分析儀31
第四章 三價鉻化成膜製程之最適化研究 32
4.1鹼性無氰化物鍍鋅製程32
4.2三價鉻化成膜製程35
4.2.1濃度變化因子 35
4.2.1.1線性極化掃瞄分析35
4.2.1.2交流阻抗頻譜分析38
4.2.2 pH值變化因子42
4.2.2.1線性極化掃瞄分析42
4.2.2.2交流阻抗頻譜分析44
4.2.3溫度變化因子48
4.2.3.1線性極化掃瞄分析48
4.3小結論 50
第五章 化成反應時間對三價鉻化成膜之表面形貌與電化學
性質的影響51
5.1開環電位量測51
5.2化成反應時間對三價鉻化成膜之表面形貌變化53
5.3化成反應時間對三價鉻化成膜之電化學性質的影響59
5.3.1線性極化掃瞄分析59
5.3.2交流阻抗頻譜分析62
5.4化成反應時間對三價鉻化成膜之鹽霧試驗的影響 65
5.5小結論 68
第六章 探討電鍍工廠污染離子對三價鉻化成藥液之老化行為69
6.1三價鐵離子對三價鉻化成膜之腐蝕研究70
6.1.1線性極化掃描分析70
6.1.2交流阻抗頻譜分析72
6.1.3掃瞄式電子顯微鏡表面形態分析77
6.1.4二次離子質譜分析80
6.1.5光電子能譜分析81
6.1.6小結論83
6.2添加銅離子對鍍鋅三價鉻化成膜抗蝕之研究84
6.2.1線性極化掃描分析84
6.2.2交流阻抗頻譜分析86
6.2.2.1交流阻抗等效電路分析 86
6.2.3掃瞄式電子顯微鏡表面形態分析91
6.2.4二次離子質譜分析94
6.2.5小結論95
6.3電鍍工廠三價鉻製程之老化研究96
6.3.1電鍍工廠三價鉻化成吊鍍生產線之
鉻、鐵、銅含量追蹤97
6.3.2電鍍工廠三價鉻化成滾鍍生產線之
鉻、鐵、銅含量追蹤99
6.3.3小結論101
第七章 結論102
7.1第一部份102
7.2第二部份102
7.3第三部份102
7.4未來與展望103
參考文獻 104
附錄
A.符號(公式)彙編109
B.作者簡介111
C.最近四年發表 SCI國際期刊及學術研討會112
D.最近四年參與教育部推動技專校院與產業園區
產學合作計畫一覽表 113
E.最近四年得獎或研究成果114

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