臺灣博碩士論文加值系統

摘要
本研究探討2205雙相不銹鋼（簡稱2205DSS）表面沈積2mg/cm2氯化鈉及置於500vppm NaCl(g) 的流動氣氛加熱爐，溫度550~850℃之高溫腐蝕。
實驗結果顯示2205DSS之高溫腐蝕動力學遵守拋物線定律，腐蝕反應速率隨溫度的上升而加速。高溫腐蝕後之腐蝕生成物，由外而內分別為Fe2O3、Fe3O4、Cr2O3及FeCr2O4之腐蝕皮膜結構，不同溫度下其生成物之順序並無明顯相異之處，唯850℃之試片於氧化皮膜脫落後的試片表層較容易檢測到SiO2及NiO。在雙相結構腐蝕順序實驗中，表面沈積2mg/cm2氯化鈉的試片其腐蝕順序與α、γ相無關，為全面性的腐蝕，但於500vppm NaCl(g) 的流動氣氛下，亦無法分辨α、γ相的腐蝕順序但可發現γ相較α相有較快速腐蝕的現象。

Abstract
The objective of this study is to figure out the hot corrosion behavior of 2205 duplex stainless steel (2205 DSS) within the temperature range from 550 to 850℃ in the static air condition with 2mg/cm2 NaCl deposit , and in the air atmospheres condition with a constant flow rate of 500vppm NaCl(g) respectively.
Experimental results show that the hot corrosion kinetics met the parabolic rate law and the corrosion rate increased constantly with increasing temperature. The scales formed included Fe2O3/Fe3O4/Cr2O3 and FeCr2O4 from outer layer to inner layer. The sequence of formation is independent of the environment temperature, but the SiO2 and NiO can be found in the substrate of 850℃specimen. Experimental results also show that the corrosion sequence in two phase structure of 2205 DSS was too much conformity and without distinction in the 2mg/cm2 NaCl deposit and in the air atmospheres condition with a constant flow rate of 500vppm NaCl(g). For the case of constant flow rate of 500vppm NaCl(g) condition, the corrosion rate in the γ phase was greater than that in the α phase.

目錄
第一章 前言 1
第二章 文獻回顧 4
　2.1 雙相不銹鋼簡介 4
2.1.1 雙相不銹鋼的發展與種類 7
2.1.2 合金元素對雙相不銹鋼之影響 10
2.1.3 雙相不銹鋼的抗腐蝕性質 13
　2.2 熱力學資料 17
　2.3 含氯氣氛中之高溫腐蝕及熱腐蝕 33
2.3.1 氯氧化反應 33
2.3.2 溫度對高溫腐蝕之影響 37
2.3.3 腐蝕產物之生成相 41
2.3.4 沈積2mg/cm2氯化鈉之高溫腐蝕 42
　2.4 腐蝕產物之色澤 50
第三章 實驗方法 51
　3.1 實驗流程 51
　3.2 試片準備 53
　3.3 氯化鈉誘發之高溫腐蝕實驗 55
3.3.1 氯化鈉沈積作業 55
3.3.2 高溫腐蝕實驗作業 55
3.3.3 雙相腐蝕順序觀察實驗作業 57
　3.4 分析設備與方法 59
3.4.1 分析設備 59
3.4.2 分析方法 60
第四章 實驗結果 64
　4.1 腐蝕型態外觀 64
　4.2 XRD分析 67
　4.3 截面金相 73
　4.4 腐蝕動力學 77
　4.5 腐蝕皮膜分析 83
　4.6 短時間高溫腐蝕 94
第五章 討論 110
　5.1 沈積氯化鈉之高溫腐蝕反應機制 110
　5.2 腐蝕皮膜組成及型態 117
　5.3 溫度的影響 120
　5.4 α相與γ相的腐蝕順序探討 122
　5.5 與其他合金之比較 125
第六章 結論 129
參考文獻 131
附錄 2205 DSS腐蝕前後成份分析表 138

參考文獻
1. P.L. Daniel, J.L. Barna, and J.D. Blue, Proceedings National Waste Processing Conference, p.221 (1986).
2. J.A. Harris, W.G. Lipscomb, and G.D. Smith, Corrosion/87, NACE International, p.402 (1987).
3. H.H. Krause, Corrosion/91, NACE International, p.242 (1991).
4. 林建勝，鐵鎳鉻系合金於氯化鈉沈積鹽之熱腐蝕，國立台灣科技大學碩士論文，民國85年。
5. Y. Shinata, F. Takahashi, and K. Hashiura, “NaCl-induced Hot Corrosion of Stainless Steels,” Mater. Sci. Eng., p.87, p.399 (1987).
6. N. Hiramatsu, Y. Uematsu, T. Tanaka, and M. Kinugasa, “Effects of Alloying Elements on NaCl-Induced Hot Corrosion of Stainless Steels,” Mater. Sci. Eng., A120, p.319 (1989).
7. C.-J. Wang, J.-W. Lee, and C.-H. Kao, “NaCl-induced Hot Corrosion of Stainless Steel and Fe-Mn-Al-C Alloy ,” Corrosion Prevention for Industrial Safety and Environmental Control Vol.1, pp.141-146, Ed. by S.L.I. Chan and W.T. Tsai, Corrosion Engineering Association of the R.O.C, Kaohsiung (1995).
8. G.Y. Lai, in “High Temperature Corrosion of Engineering Alloys,” ASM, p.175 (1990).
9. J. Charles, “structure and Mechanical Properties of Duplex Stainless Steels,” 4th international conference duplex 94 stainless steel, Glasgow, Scotland, p.KI (Nov., 1994).
10. Robert N Gunn, in “Duplex Stain Steels Microstructur : Properties and Applications,” Abington Publishing (1997).
11. M. Barteri, F. Mancia, and A. Tamba, Corrosion, p.58(1987).
12. C. Ericsson, “De rostfria Duplexstalens forsta ar,” No 6, Bergsmannen (1988).
13. J. Charles, “Superduplex stainless steels:structure and properties,” Duplex Stainless Steels 91, vol.1, Beaune Bourgogne, France, pp.23-30 (October 1991).
14. P. Combrade and J.P. Audouard, “Duplex Stainless Steels and Localized Corrosion Resistance,” ibid, pp.257-281.
15. J.M. Hauser, “High Ductility Low-Nickel Duplex Stainless Steel for Lighter Transport Vehicles,” International Congress Stainless Steel 99 Science and Market 3rd European Congress, vol.1, Chia Laguna Sardinia, Italy, pp.85-94 (June 1999)
16. 謝曉華，「不銹鋼在水溶液中的抗蝕性」，防蝕工程，第4卷，第一期，第32頁，民國七十九年。
17. 邱將明，「不銹鋼的種類與特性」，工業材料，第97期，第78~98頁，民國八十四年。
18. 蕭禎傑，Fe-Cr-Ni雙相不銹鋼低溫時效脆化之研究，國立清華大學核子工程研究所材料組博士論文，民國八十三年。
19. 劉宏義，合金元素及製程參數對雙相不銹鋼機械性質與耐蝕性質影響之研究，國立成功大學材料科學與工程系博士論文，民國九十年。
20. 蔡文達，雙相不銹鋼的基本特性，雙相不銹鋼之應用與耐蝕性質研討會講義，國立成功大學成功校區材料系視聽教室，第A1~A25頁，民國八十八年三月十九~二十日。
21. J.S. Kim, W.H.A Peelen, K. Hemmes, and R.C. Makkus, “Effect of Alloying Element on the Contact Resistance and the Passivation Behavior of Stainless Steels,”Corrosion Science, vol. 44, p640 (2002).
22. J.Charles, “The duplex stainless steels : material to meet your needs,” Duplex Stainless Steels 91, vol.1, Beaune Bourgogne, France, pp.3-47 (October 1991).
23. William F.Smith原著，李春穎、許煙明、陳忠仁等譯，材料科學與工程，第二版，McGraw-Hill Inc.，民國八十三年。
24. J.M. Nicholls, “Corrosion Properties of Duplex Stainless Steels : General Corrosion, Pitting and Crevice Corrosion,” 4th International Conference Duplex 94 Stainless Steels, Glasgow, Scotland, p.K, (Nov., 1994).
25. N. Birks and G.H. Meier, in “Introduction to High Temperature Oxidation of Metals,” Edward Arnold, London, p.17 (1983).
26. C. Wagner, Z. Phys. Chem., pp.21-25 (1933).
27. B. Chattopadhyay and G.C. Wood, “The Transient Oxidation of Alloys,” Oxid. Met., 2, No. 4, p.373 (1970).
28. E.T. Turkdogan, in “Physical Chemistry of High Temperature Technology,” Harcourt Brace Jovanovich, New York (1980).
29. Y. Ihara, H. Ohgame, K. Sakiyama, and K. Hashimoto , ”The Corrosion Behaviour of Iron in Hydrogen Chloride Gas and Gas Mixtures of Hydrogen Chloride and Oxygen at High Temperatures,” Corros. Sci., 21, No.12, P.805 (1981).
30. O. Kub and E.L. Evans, in “Metallurgical Thermochemistry,” Pergamion, New York, p.225 (1958).
31. Y.N. Chang and F.I. Wei, “High-Temperature Chlorine Corrosion of Metals and Alloys,” J. Mater. Sci., 26, p.3693 (1991).
32. D.R. Stull and H. Prophet, “JANAF Thermochemical Table,” NSRDS-NBS37, U.S. Dept. Commer., Washington, D.C. (1971).
33. O. Kubaschewski, E.L. Evans, and C.B. Alcock, in “Metallurgical Thermochemistry,” 4th edition, Pergamon, New York, pp.421~429 (1967).
34. 化學大辭典編輯委員會，英、中、日化學大辭典，總召集人:高阿輝，高立圖書有限公司，民國82年。
35. U. Seybolt, “Internal Oxidation in Heat-Resisting Stainless Steels Caused by Presence of Halides,” Oxidation of Metals, 2, No.2, p.161 (1970).
36. Y. Kawahara, “high temperature corrosion mechanisms and effect of alloying elements for materials used in waste incineration environment,” Corros. Sci., Vol.44, pp.223-245 (2002).
37. Y. Shinata, “Accelerated Oxidation Rate of Chromium Induced by Sodium Chloride,” Oxid. Met., 27, Nos.5/6, p.315 (1987).
38. Y. Shinata, M. Hara, and T. Nakagawa, “Accelerated Oxidation of Chromium by Trace of Sodium Chloride Vapor,” Materials Transactions, JIM, 32, No.10, p.969 (1991).
39. M.K. Hossain and S.R.J. Saunders, “A Microstructural study of the Influence of NaCl Vapor on the Oxidation of a Ni-Cr-Al Alloy at 850℃,” Oxid. Met., Vol.12, pp.1-3 (1978).
40. C.T. sims, W.C. Hagel, in ”The super allays,” John Wiley and sons, New York, pp.287-315 (1972).
41. Y. Shinata, “Accelerated Oxidation Rate of Chromium Induced by Sodium Chloride,” Oxide of Metals., Vol 27, pp.315-332 (1987).
42. D. Renusch, B. Veal, K. Natesan, and M. Grimsditch, “Transient Oxidation in Fe-Ni-Cr Alloys: A Raman-Scattering Study,” Oxid. Met., 46, Nos.5/6, p.365 (1996).
43. N. Hiramatsu, Y. Uematsu, T. Tanaka, and M. Kinugasa, “Effects of Alloying Elements on NaCl-Induced Hot Corrosion of Stainless Steels,” Mater. Sci. Eng., A120, p.319 (1989).
44. S. Kim and M.J. McNallan, “Mixed Oxidation of Iron-Chrominum Alloys in Gas Containing Oxygen and Chlorine at 900 to 1200K,” Corrosion (NACE), 46, No.9, p.746 (1990).
45. Yutaka. Shinata, Fujio. Takahashi, and Kokichi. Hashiura, ”NaCl-induced-Hot Corrosion-of-Stainless-Steels,” Material Science and Engineering, 87, pp.399-405 (1987).
46. F. Gesmundo and F. Viani, Corr. Sci., Vol.18, pp.217-231 (1978).
47. H.S. Hsu, Oxid. Met., Vol.26, pp.315-332 (1986).
48. B. Schmid, N. Aas, Q. Grong, and R. Qdegard, Oxid. Met., Vol.57, Nos. 1/2, pp.115-130 (2002).
49. G. Chaudron and H. Forestier, ”Etude de la decomposition du protooxyde de fer. Anomalies de dilatation correlatives de son instabilite,” Comptes rendus., Vol.178, pp.2173-2176 (1924).
50. 魏家傑，鐵鉻合金沉積氯化鈉及氯化鈣混合鹽之高溫腐蝕研究, 國立台灣科技大學碩士論文，民國九十二年。
51. 陳海誠，鐵鉻鎳合金於氯化鹽環境之高溫熱腐蝕機制,國立台灣科技大學碩士論文，民國九十二年。
52. 吳烈宗，鐵鎳鉻合金及鉻鉬鋼披覆氯化鈉之熱腐蝕，國立台灣科技大學碩士論文，民國八十八年。
53. 李清祺，鎳鉻合金於氯化鈉之高溫腐蝕反應機制，國立台灣科技大學碩士論文，民國八十七年。
54. 郭質良，現代化學名詞術語大辭典，廣文書局有限公司，民國六十四年。
55. ASTM G54-81, ”Standard Practice for Sample Static Oxidation Testing”.
56. C.J. Wang, Y.C. Chang, and Y.H. Su, ”The Hot Corrosion of Fe-based Alloys with pre-coating NaCl/Na2SO4 Mixtures at 750℃,” Oxidation of Metals, Vol.59, Nos.1/2, pp.115-133 (2003).
57. 王朝正、涂宗漢，「低碳鋼於氯化鈉之熱腐蝕機制及熱浸鋁之防制改善」，防蝕工程，第九卷，第四期，第225頁，民國八十四年。
58. P.A. Labum, J. Covington, K. Kinroda, G. Welsch, and T.E. Mitchell, Met. Trans., Vol.13, p.2103 (1982).
59. G.C. Wood, I.G. Wright, T. Hodgkiess, and D.P. Whittle, Workstoffe Korrosion, Vol.21, p.900 (1971).
60. 涂成一、蔡文達，雙相不銹鋼的晶界腐蝕性質，雙相不銹鋼之應用與耐蝕性質研討會講義，國立成功大學成功校區材料系視聽教室，第J1~J23頁，民國八十八年三月十九~二十日。
61. 劉勝擁、李正隆、高景海、彭宗平，「雙相鐵錳鋁合金在800℃之氧化特性」，防蝕工程，第八卷，第三期，第140~148頁，民國八十三年。
62. 黃忠良，金屬材料之高溫氧化與腐蝕，第50-63頁，台南，復漢出版社，民國七十七年。
63. J.D. Mckinley, Jr., and K.E. Shuler, “Kinetics of the High-Temperature Heterogeneous reaction of Chlorine and Nickel between 1200 and 1700。K,” J. Chem. Phys., 28, No.6, p.1207 (1958).
64. 何天佐，鐵鎳鉻不銹鋼於硫氯混合鹽之熱腐蝕，國立台灣科技大學碩士論文，民國九十年。