臺灣博碩士論文加值系統

鎂合金的化學性質活潑，屬於易遭受腐蝕的金屬，因此防蝕處理成為鎂合金在應用的過程中所需探討的重要課題。本研究探討利用冷噴銲處理在AZ80鎂合金表面噴銲IN265、301不銹鋼、純鋁膜層後對AZ80鎂合金表面性質之影響，包括顯微組織、機械性質及腐蝕性質。
研究結果發現，在微觀結構及機械性質方面，冷噴銲處理形成的膜層為非緻密的膜層，在膜層內部會有少許孔隙。冷噴銲純鋁會使得AZ80鎂合金表面有明顯加工硬化的現象，故造成AZ80母材表面硬度值提升；冷噴銲IN625及301不銹鋼會使得AZ80鎂合金表面產生再結晶現象，造成鎂合金表面晶粒細化；而由於高溫及再結晶現象，晶粒內差排數量減少，故使得AZ80母材表面硬度值僅有些微上升。在磨耗試驗上，冷噴銲膜層皆提高了AZ80鎂合金的耐磨耗性，以IN625膜層抗磨耗性最佳，301不銹鋼膜層次之，再者為純鋁噴銲層。
在腐蝕性質方面，在NaCl水溶液環境中，IN625膜層及301不銹鋼膜層皆大幅提升了AZ80母材抗蝕性；且從循環極化曲線可看出IN625膜層及301不銹鋼膜層對孔蝕的再癒合能力佳，對於抗蝕性極差的AZ80鎂合金有大幅的改善。在泥漿沖刷的環境中，不論膜層或母材在低角度沖蝕中造成的破壞會大於高角度沖蝕，但不論於何種沖刷角度，IN625膜層、301不銹鋼膜層及純鋁噴銲層皆大幅提升了AZ80母材抗沖蝕性。
另外，經熱處理後的冷噴銲純鋁試片，在膜層與AZ80母材的界面處會產生交互擴散形成連續相之介金屬化合物，Mg17Al12及Al3Mg2，其硬度皆高於基材與噴銲層。而將AZ80鎂合金經冷噴銲純鋁粉後再進行陽極處理，可在試片表面得到一層高硬度氧化鋁層，此氧化層大幅改善了純鋁膜層在NaCl水溶液環境中的抗蝕性。

It is commonly recognized that magnesium possesses poor corrosion resistance because of its high oxidation potential and porous oxide structure. The corrosion resistance is the most important topic for magnesium alloys application.
The thesis aims to investigate how cold spray influences the properties of magnesium alloy, including microstructure, mechanical and corrosion property. The sprayed substrate is AZ80 magnesium alloy. IN625, 301 stainless steel and aluminum powder is used to spraying on the surface.
In the study, the coating formed by cold spray treatment has some holes, and is a non-dense film. AZ80 substrate occurred grain refinement after spray IN625 and 301 stainless steel process. For the aluminum coating, it was observed that after coating process, substrate surface is obviously harder than after coating IN625 process.
As to the corrosion behavior, the result of the potential-dynamic polarization curve tests reveals that, whether in the IN625 or the Al coating, the corrosion resistance are better than magnesium substrate. In the wear and erosion test, the cold spray coating are to improve the wear and erosion resistance of AZ80 magnesium alloy.
After annealing, the AZ80 alloy interacts with Al coating to form Mg17Al12 and Al3Mg2 compound at the interface. After anodizing, on the aluminum coating surface formed a high hardness alumina layer that has excellent corrosion resistance than aluminum coating.

口試委員會審定書 ........................................................................................................... I
致謝 ............................................................................................................................... IX
摘要 .................................................................................................................................V
Abstract .......................................................................................................................... VII
第一章 前言 ................................................................................................................ - 1 -
第二章 文獻回顧 ........................................................................................................ - 3 -
2-1 鎂與鎂合金簡介 ........................................................................................... - 3 -
2-1-1 鎂與鎂合金........................................................................................ - 3 -
2-1-2 鎂與鎂合金的腐蝕特性.................................................................... - 4 -
2-1-3 鎂合金的分類.................................................................................... - 5 -
2-2 冷噴銲製程 ................................................................................................... - 6 -
2-2-1 冷噴銲製程原理................................................................................ - 7 -
2-2-2 冷噴銲製程參數與堆積效率.......................................................... - 10 -
2-2-3 冷噴銲製程設備之演進.................................................................. - 15 -
2-3 鋁陽極處理 ................................................................................................. - 19 -
2-3-1 陽極處理.......................................................................................... - 19 -
2-3-2 封孔處理.......................................................................................... - 21 -
2-4 腐蝕與電化學 ............................................................................................. - 22 -
2-4-1 腐蝕的定義與型態.......................................................................... - 22 -
2-4-2 金屬的電化學腐蝕.......................................................................... - 25 -
2-4-3 腐蝕電化學量測.............................................................................. - 26 -
2-4-4 開路電位(Open Circuit Potential) ................................................... - 27 -
2-4-5 循環極化法(Cyclic Polarization) .................................................... - 28 -
第三章 實驗方法 ...................................................................................................... - 31 -
X
3-1 實驗流程圖 ................................................................................................. - 31 -
3-2 試片之準備 ................................................................................................. - 32 -
3-2-1 鎂合金母材...................................................................................... - 32 -
3-2-2 冷噴銲粉末...................................................................................... - 32 -
3-2-3 冷噴銲製程...................................................................................... - 33 -
3-2-4 冷噴銲試片之熱處理...................................................................... - 33 -
3-2-5 冷噴銲試片之陽極處理.................................................................. - 34 -
3-3 微觀結構觀察分析 ..................................................................................... - 35 -
3-3-1 OM金相觀察 ................................................................................... - 35 -
3-3-2 SEM顯微組織觀察 ......................................................................... - 35 -
3-3-3 EPMA成分分析 .............................................................................. - 36 -
3-3-4 X-Ray繞射分析 ............................................................................... - 36 -
3-4 機械性質分析 ............................................................................................. - 37 -
3-4-1 微硬度試驗...................................................................................... - 37 -
3-4-2 磨耗試驗.......................................................................................... - 37 -
3-5腐蝕性質分析 .............................................................................................. - 39 -
3-5-1 鹽霧試驗.......................................................................................... - 39 -
3-5-2 電化學試驗...................................................................................... - 39 -
3-5-3 濕式沖蝕試驗.................................................................................. - 40 -
第四章 結果與討論 .................................................................................................. - 41 -
4-1微觀結構觀察分析 ...................................................................................... - 41 -
4-1-1 X-Ray繞射分析 ............................................................................... - 41 -
4-1-2 OM金相觀察及SEM顯微組織觀察 ............................................. - 43 -
4-1-3 EPMA成分分析 .............................................................................. - 48 -
4-2機械性質分析 .............................................................................................. - 49 -
4-2-1 維克氏硬度試驗.............................................................................. - 49 -
XI
4-2-2 磨耗試驗.......................................................................................... - 51 -
4-3腐蝕性質分析 .............................................................................................. - 54 -
4-3-1 鹽霧試驗.......................................................................................... - 54 -
4-3-2 電化學試驗...................................................................................... - 55 -
4-3-3 濕式沖蝕試驗.................................................................................. - 58 -
4-4 冷噴銲試片之熱處理 ................................................................................. - 64 -
4-4-1巨觀觀察及微觀結構觀察............................................................... - 64 -
4-4-2 EDX及EPMA分析 ........................................................................ - 67 -
4-4-3維克氏硬度試驗............................................................................... - 72 -
4-5 冷噴銲鋁試片之陽極處理 ......................................................................... - 73 -
4-5-1 SEM微觀結構觀察 ......................................................................... - 73 -
4-5-2 EPMA成分分析 .............................................................................. - 74 -
4-5-3 X-Ray繞射分析 ............................................................................... - 75 -
4-5-4維克氏硬度試驗............................................................................... - 76 -
4-5-5電化學試驗....................................................................................... - 77 -
4-5-6鹽霧試驗........................................................................................... - 78 -
4-6 噴銲層厚度對工件比重之影響 ................................................................. - 79 -
第五章 結論 .............................................................................................................. - 81 -
參考文獻 .................................................................................................................... - 83 -

1. 楊智超，鎂合金材料特性及新製程發展，工業材料，152（1999）72。
2. 王建義，超輕量鎂合金開發，工業材料，184（2002）132。
3. Pattison, J., et al.,‥Cold gas dynamic manufacturing: A non-thermal approach to freeform fabrication ‥International Journal of Machine Tools and Manufacture Vol. 47, 2007, pp. 627-634.
4. D.S. Tawil, “Corrosion and surface protection developments”, magnesium technology in Proceedings of the Conference, 1986.
5. William F. Smith, “Structure and Properties of Engineering Alloys”, 2nd Edition, McGraw-Hill Science/Engineering/Math, 1993.
6. 邱六合、林信安，“鎂合金腐蝕與表面處理”，工業材料，186期, 2002, pp.118-119.
7. G.L.Song, A.Atrens, X.L.Wu, B.Zhang, “Corrosion behaviour of AZ21, AZ501 and AZ91 in sodium chloride”, Corrosion Science, Vol.40(10), 1998, pp.1769-1791.
8. GL Song, A Atrens, “Magnesium corrosion mechanisms”, Proceeding of The 12th Asia-Pacific Corrosion Control Conference 2001, Vol.1, pp.499-516.
9. 戴光勇，鎂合金表面處理技術〈上〉，材料與社會，24,1988,pp.57.
10. Alkhimov, A.P., V.F. Kosarev, and A.N. Papyrin,‥A method of cold gas dynamic deposition‥. Doki. Akad. Nauk SSSR.Vol. 315, 1990, pp. 1062-1065.
11. Klinkov, S.V., V.F. Kosarev, and M. Rein,‥Cold spray deposition: Significance of particle impact phenomena‥. Aerospace Science and Technology.Vol. 9, 2005, pp. 582-591.
12. Steenkiste, T.H.V., J.R. Smith, and R.E. Teets, ‥Aluminum coatings via kinetic spray with relatively large powder particles‥. Surface and Coatings Technology Vol. 154, 2002, pp. 237-252.
- 84 -
13. Livingstone, I.H.G., K. Verolme, and C.J. Hayhurst, ‥Predicting the fragmentation onset velocity for different metallic projectiles using numerical simulations‥. International Journal of Impact Engineering Vol. 26, 2001, Pp. 453-464.
14. Stradling, G.L., et al.,‥Ultra-high velocity impacts: cratering studies of microscopic impacts from 3 km/s to 30 km/s‥. International Journal of Impact Engineering.Vol. 14, 1993, pp. 719-727.
15. Gilmore, D., et al. ‥Particle velocity and deposition efficiency in the cold spray process‥. Journal of Thermal Spray Technology.Vol. 8, 1999, pp. 576-582.
16. Papyrin, A.,‥Cold spray technology‥, ed. V. Kosarev, et al., 2007.
17. Schmidt, T., et al.,‥Development of a generalized parameter window for cold spray deposition‥. Acta Materialia.Vol. 54, 2006, pp. 729-742.
18. Jodoin, B., F. Raletz, and M. Vardelle,‥Cold spray modeling and validation using an optical diagnostic method‥. Surface and Coatings Technology.Vol. 200, 2006, pp. 4424-4432.
19. Jen, T.-C., et al.,‥Numerical investigations on cold gas dynamic spray process with nano and microsize particles‥. International Journal of Heat and Mass Transfer Vol. 48, 2005, pp. 4384-4396.
20. Pattison, J., et al.,‥Cold gas dynamic manufacturing: A non-thermal approach to freeform fabrication ‥International Journal of Machine Tools and Manufacture Vol. 47, 2007, pp. 627-634.
21. Li, C.-J. and W.-Y. Li,‥Deposition characteristics of titanium coating in cold spraying‥. Surface and Coatings Tecbnology.Vol. 167, 2003, pp.278-283.
22. Bray, M., A. Cockburn, and W. O Neill,‥The Laser-assisted Cold Spray process and deposit characterisation‥. Surface and Coatings Technology.Vol. 203, 2009, pp. 2851-2857.
- 85 -
23. Li, C.-J., et al.,‥A theoretical model for prediction of deposition efficiency in cold spraying‥. Thin Solid Films.Vol. 489, 2005, pp.79-85.
24. V.F. Kosarev, S.V. Klinkov, and A.A. Sova,“Recently patented facilities and applications in cold spray engineering”. Recent Patents on Engineering.Vol. 1, 2007, pp. 35-42.
25. T.H.V. Steenkiste,“Pseudo CMOS dynamic logic with delayed clocks”, in US20050211799 A1. 2005.
26. T.H.V. Steenkiste,“Spray system with combined kinetic spray and thermal spray ability”, in US20040058064A1. 2004.
27. S.V. Klinkov, et al.,“Deposition of multicomponent coatings by cold spray”. Surface & Coatings Technology.Vol. 202, 2008, pp. 5858-5862.
28. T.H.V. Steenkiste,“Replaceable throat insert for a kinetic spray nozzle ”, in US 20060038044A1. 2006.
29. .W. Kroemmer, P. Heinrich, and P. Richter,“Cold spraying - equipment and application trends.”, in ITSC 2003: International Thermal Spray Conference 2003: Advancing the Science and Applying the Technology. 2003 Orlando. pp. 97-102.
30. 陳佳莉，“陽極處理鋁合金表面處理應用”，台灣工業銀行，2007
31. 楊聰仁、蘇國祥，“鋁表面處理與應用之研究“，朝陽科技大學，碩士論文，民國95年
32. 施登士、陳正義，“不同製程參數對 AA1050 與AA5052陽極皮膜抗腐蝕能力的影響”，國立中央大學，碩士論文，民國九十九年
33. S.Werick, R.Pinner and P.G.Sheasby,“The surface treatment and finishing of aluminum and it’s alloys”, ASM International , Ohio, 1987, pp.829
34. V.Lopez, M.J.Bartolome, E.Escudero, E.Otero and J.A.Gonzalez, “Comparison by SEM, TEM, and EIS of hydrothermally sealed and cold sealed aluminum anodic oxides”, Journal of the Electrochemical Society, Vol 153, No 3, 2006, pp. 75-82
- 86 -
35. L.Hao and B.R.Cheng, “Sealing processes of anodic coatings—past present and future”, Metal finishing, Vol 98, 2000, pp. 8-18
36. 戴光勇，鎂合金表面處理技術（上），材料與社會，24（1988）57。
37. 許正勳、林昭宏，“偏壓參數對AISI 304不銹鋼電弧披覆TiAlCrN鍍膜特性之影響”，大同大學，碩士論文，民國九十七年
38. 鮮祺振,腐蝕理論與實驗,徐氏基金會出版社,民國七十九年。
39. Denny A. Jones, “Principles and prevention of corrosion”, Second Edition, Simon
40. 莊東漢，材料破損分析，五南圖書出版公司，民國九十七年。
41. W.S. Tait, “An introduction to electrochemical corrosion testing for practicing engineers and scientists”, Chapter 6, Racine,Wisconsin, 1994.
42. R. Bellman, Jr., and A. Lery, “ Erosion mechanism in Ductile Metals”, Wear, 70,1981,pp.1-27
43. A.V. Lery, “Solid Particle Erosion And Erosion-Corrosion of materials”, ASM International, 1995.
44. H.E. Friedrich, and B.L. Mordike, “Magnesium Technology”, Sprinnger-Verlag Berlin Heidelberg, 2006.