本研究係以探討低溫型三元系DMSO2-ZnCl2-MoCl5融熔鹽電解質浴以不同電解型式電解鍍鉬，以製備具耐腐蝕性之含鉬鍍層為目的。本實驗所選用之工作電極為SS304不鏽鋼、參考電極為Zn/ZnCl2、對極為金屬鉬圓柱。

In this study, the low temperature ternary (DMSO2-ZnCl2-MoCl5) molten salt system for electrodepositing Mo by different electrolytic types was selected in order to obtain Mo layer which can resist corrosion as purpose.

一、 緒論 1
1.1 前言 1
1.2 電化學系統 3
1.3 電化學之相關參數說明 5
1.4 熔融鹽之定義 7
1.5 熔融鹽之電化學行為 13
1.6 循環伏安法(Cycle voltammetry) 15
1.7 熔融鹽輸送性質探討 17
1.8 耐腐蝕測試-塔弗極化曲線 20
1.9 研究動機與目的 26
二、 文獻回顧 27
2.1 不鏽鋼表面處理技術 27
2.2 定電流電鍍與定電位電鍍 31
2.3 脈衝電鍍 (plused electrodeposition) 32
2.4 金屬沉積機構 (mechanism of metal deposition) 34
2.5 鹽浴組成(DMSO2-ZnCl2) 38
2.6 電解沉積鉬之技術發展 42
三、 實驗方法與步驟 53
3.1 實驗藥品與設備 53
3.2 實驗架構 57
四、 結果與討論 69
4.1 三元系(DMSO2-ZnCl2-MoCl5)熔融鹽輸送性質 69
4.2 不同電解型式之電解沉積鉬鍍層 79
4.3 三元系(DMSO2-ZnCl2-MoCl5)熔融鹽鍍鉬層厚度分析 110
4.4 耐腐蝕測試-塔弗極化曲線 118
四、 結論 124
五、 未來展望 131
六、 參考文獻 130

1.S. Senderoff, G.W. Mellors, Science 153,1575,(1996).
2.S. Senderoff, G.W. Mellors, J, Electrochem. Soc. 114, 586, (1967).
3.A. Girginov, T.Z. Tzvetkoff, M.Bojinov, J.Appl. Electrochem. 25,993, (1995).
4.B. Aladjov, A. Stoyanova, J.R. Selman, Y.P. Lin, in: N. Masuko, T. Osaka,Y. Ito(Eds), Electrochemical Technology : Innovations and New Developments, Kodansha/Gordon and Breach, Tokyo, p. 301,(1996).
5.Hironori Nakajima, Toshiyuki Nohira, Rika Hagiwara, Electrochimical Acta
51, 3776-3780, (2006).
6.許信儀, 低溫型熔融鹽電解質輸送特性及相關應用之研究. 國立雲林科技大學,博士論文,(2003).
7.Gale, D.G.L.a.R.J., Molten Salt Techniques, Vol. 1, (1983).
8.Gale, D.G.L.a.R.J., Molten Salt Techniques, Vol. 2, (1983).
9.吳溪煌 校閱,田福助 編著,電化學理論與應用,新科技書局(2000).
10.曾群安, 林景崎, 陳鐿夫, 以循環伏安法解析電化學回收金屬銦之最佳化條件設定, 國立中央大學,碩士論文,(2010)
11.周政偉, 含EMIC 低溫型熔融鹽電解質之輸送特性及白金鍍層之電解披覆研究. 國立雲林科技大學，碩士論文, (2006).
12.張國億, 低溫型熔融鹽電解質浴脈衝電解鎢之研究. 國立雲林科技大學,碩士論文, (2007).
13.陳威統, 高溫型熔融鹽電解質浴電解製備美金屬之研究. 國立雲林科技大學,　碩士論文, (2012).
14.Chao-Chen Yang, Min-Fong Shu, Electrodepositon of Zinc from binary ZnCl2-DMSO2 molten electrolyte at room temperature. Z.Naturforsch. 62a, 754-760,(2007)
15.M.F. Shu, H.Y. Hsu, C.C. Yang. Z. Naturforsch. 58a,451,(2003)
16.徐明豐, 室溫型熔融鹽電解質離子之輸送特性及其磁性薄膜之製備. 國立雲林科技大學, 博士論文, (2006)　
17.William L.Wade, Jr., Gordon Sand. Mo-permalloy film deposited on a continuous wire substrate. Brisf Communications,(1971)
18.C.C. Nee, W. Kim, and R.weil. Pulse Electrodeposition of Ni-Mo alloys. J. Electrochem. Soc.135. 5. (1988)
19.E.J. Podlaha, M. Matlosz and D. Landolt. Electrodeposition of High Mo Content Ni-Mo alloys under forced convection. Electrochem. Soc. 140, 10, (1993)
20.楊肇政, 許信儀. 低溫型熔融鹽電解鍍鉬之研究. 國立雲林科技大學科技學刊, 第9卷, 第3期, 199-206,(2000).
21.Tetsuya Tsuda, Charles L. Hussey, Gery R. Stafford. Electrodeposition of Al-Mo alloys from the Leiws Acidic Aluminum Chloride-1-ethyl-3-methylimidazolium Chloride molten salt. J. Electrochemical Soc. 151,6,(2004).
22.Tetsuya Tsuda, Charles L. Hussey, Gery R. Stafford. Electrodeposition of Al－Mo –Mn alloys from the Leiws Acidic AlCl3-EtMeImCl molten salt. J. Electrochemical Soc. 152,9, (2005).
23.Hironori Nakajima, Toshiyuki Nohira, Eika Hagiwara. Electrodeposition of metallic molybdenum film in ZnCl2-NaCl-KCl-MoCl3 system at 250℃. Electrochimica Acta 51, 3776-3780, (2006).
24.J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, in: J. Chastain,Physical R.C. King Jr. (Eds.), Handbook of X-ray Photoelectron Spectroscopy,Electronics, Inc., Eden Prairie, Minnesota, (1995).
25.Tetsuya Tsuda, Satoshi Arimoto, Susumu Kuwabata, Charles L. Hussey. Electrodeposition of Al–Mo–Ti ternary alloys in the Lewis Acidic Aluminum Chloride–1-Ethyl-3-methylimidazolium Chloride room-temperature ionic liquid. Journal of The Electrochemical Society, 155 (4) D256-D262 (2008).
26.Koji NITTA, Masatoshi MAJIMA, Shinji INAZAWA, Kan KITAGAWA, Toshiyuki NOHIRA Rika HAGIWARA. Electrodeposition of Molybdnum from molten salt. Electronics 2010 J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomeben, in:J. Chastain, R. C. King, Jr. (Eds.), Handbook of X-ray Photoelectron Spectroscopy , Physical Electronics, Inc. Eden Parairie, Minnesota,(1995).
27.R. A. Carpio, L. A. King, R. E. Lindstrom, J. C. Nardi, and C. L. Hussey, J. Electrochem. Soc., 126,1644 (1979)
28.Y. Lwadate, K. Lgarashi, and J. Mochinaga, J. Electrochem. Soc., 133, 1162 (1986)
29.E. R. Van Artsdalen and I. S. Yaffe, J. Phys. Chem., 59, 118(1955)
30.D.S. Newman, R. T. Tillack, D. P. Morgan, and W.C. Wan, J Electrochem Soc, 124, 856,(1977)
31.D.S. Newman, W. Rohr, and D. Kirklin, J. Electrochem. Soc, 119,797,(1972)
32.A. J. Easteal and C. A. Angell, J. Phys. Chem., 74, 3987,(1970)
33.L. A. King and F. R. Duke, J. electrochem. Soc., 111, 717,(1964)
34.F. R. Duke and Lynn Bissell, J. Electrochem. Soc., 111, 717,(1964)
35.“電化學’’,熊楚強, 王月著, 文京圖書有限公司
36.“腐蝕控制’’, 鮮祺振著, 徐氏基金會
37.“腐蝕及其防制’’, 柯賢文, 全華科技圖書有限公司
38.“防蝕技術’’, 劉富雄, 全華科技圖書有限公司
39.Denny A. Jones, “Principles And Prevention of Corrosion’’ 2nd ed. (Prentice-Hall, Inc. 1996)
40.Ashby, Michael F and David R. H. Jones.’’Chapter 12’’ Engineering Materials 2
41.C.C. Yang and M.F. Shu, Z. Naturforsh. 60a, 444,(2005)
42.D. L. Thomes, J. Y. Cheng, and D. N. Bennion, J. Electrochem. Soc. 135, 2674,(1988)
43.A. J. Bard and L. R. Faulkner, second edition”Electrochemical methods; fundamentals and applications”, John wiley and Sons, New York(2001)
44.E.H Phelps, Corrosion, 18, 239t ,(1962).
45.M. Stern, J. Electrochem. Soc., 102, 609,(1955)
46.M. Stern, J. Electrochem. Soc., 102, 663,(1955)
47.M. Stern. and A.L. Geary, J. Electrochem. Soc., 104,56,(1957)
48.M. Stern, J. Electrochem. Soc., 104, 559,(1957)
49.M. Stern, J. Electrochem. Soc., 104, 645,(1957)
50.M. Stern and R.M. Roth, J. Electrochem. Soc., 104, 390,(1957)
51.M. Stern, J. Electrochem. Soc., 104, 600,(1957)
52.M. Stern, Corrosion., 14, 440t(1958)
53.D.L. Grimmett, M. Schwartz and K. Nobe, J. Electrochem. Soc., 137, 3414,(1990)
54.B.N. Popov, K. M. Yin and R.E. White, ibid., 140, 1321,(1993)
55.K.M. Yin, S.L. Jan, C.C. Lee, Surf. Coat. Technol, 88, 219,(1996)
56.Gerhard Ett, Eliasbete J. Pessine, Electrochimca Acta, 44, 2859,(1999)
57.S.K. Ghosh, A.K. Grovera, G.K. Dey, M.K. Totlani, Surf. Coat. Technol., 126, 48,(2000)
58.Roy, S. and D. Landolt, J. Electrochem. Soc., 27(3),299, (1997).
59.Yin, K, Surface and Coating Technology, 88, 162,(1997)
60.Aroyo, M. et al., Plating and Surface Finishing,82,5,(1995)
61.T. P. Moffat, J Electrochem. Soc., 141, L115, (1994).
62.Y. Katayama, S. Dan, T. Miura, and T. Kishi, J Electrochem. Soc. 148, C102,(2001)
63.R.T. Carlin, P.C. Trulove, and H.C. De Long, J. Electrochem. Soc., 143 2747,(1996)
64.M.H. Allahyarzadeha, B. Roozbehania, A. Ashrafi. Electrodeposition of high Mo content amorphous/nanocrystalline Ni–Mo alloys using-ethyl-3-methyl- imidazolium chloride ionic liquid as an additive. Electrochimica Acta 56, 10210–10216, (2011).
65.M.H. Allahyarzadeh, B. Roozbehani, A. Ashrafi, S.R. Shadizadeh. Electrodeposition of high Mo content amorphous/nanocrystalline Ni–Mo alloys using 1-methyl-imidazolium chloride ionic liquid as an additive. Surface &; Coatings Technology.,206, 137–142, (2011)


66.M. H. Allahyarzadeh, B. Roozbehani, A. Ashrafi, S. R. Shadizadeh,
A. Seddighian, and E. Kheradmanda. A Novel Aspect of Two Imidazolium-Based Ionic Liquids in Electrodeposition of Amorphous/Nanocrystalline Ni-Mo Journal of The Electrochemical Society, 159 (8), D473-D478 (2012).
67.張奇龍, 基礎材料實驗報告腐蝕電化學分析, 明道大學, (2007).