臺灣博碩士論文加值系統

本研究在探討三式英高鎳超合金(包括Inconel 939(In-939), René 77, René 108合金)在溫度550~850℃，於H2/H2S混合氣氛及H2/H2S/H2O混合氣氛下之腐蝕行為。結果顯示，所有英高鎳超合金的腐蝕動力學皆遵守拋物線型定律，且腐蝕反應速率皆隨溫度上升而加快，其中，在H2/H2S混合氣氛之腐蝕速率皆比H2/H2S/H2O混合氣氛慢，而腐蝕速率之高低因合金的種類而異，其中In-939最快、René 77次之，而René 108最慢。英高鎳超合金在兩種不同氣氛下主要生成內、外兩層腐蝕層，且各層皆生成複雜的腐蝕物，包括外層以硫化鎳(Ni3S2)及少量硫化鈷(Co9S8/Co6S5)，而René 77更生成硫化鈷鉬(CoMo2S4)，而內層主要為硫化鎳鉻(NiCr2S4)、硫化鉻(Cr2S3/Cr3S4)及少量的硫化鋁(Al2S3)，且René 77在H2/H2S/H2O混合氣氛下更有微量的氧化鋁(Al2O3)生成；由白金指標實驗得知，所有白金皆位於內層與外層腐蝕層之間，這表示外層硫化物生成主要是由陽(鎳、鉻及鈷等)離子向外擴散所致，而內層腐蝕物的形成主要是由陰離子向內擴散所致。

The purpose of this thesis is to study the corrosion behavior of three Nickel base superalloys (containing In-939, René 77, René 108) over the temperature range 550~850oC in H2/H2S and H2/H2S/H2O mixed gases. The corrosion kinetics of all superalloys followed the parabolic rate law at all temperatures, and the corrosion rate constants increased with increasing temperature. René 108 exhibited the best corrosion resistance among the three alloys studied, while In-939 has the faster corrosion rates. The scales formed in H2/H2S mixed gases on the three alloys were duplex and heterophasic, consisting of the outer layer of mostly nickel sulfide (Ni3S2), cobalt sulfide (Co9S8/Co6S5), and also minor (CoMo2S4) (René 77 only). On the other hand, the inner layer was a heterophasic mixture of mostly (NiCr2S4), (Cr2S3/Cr3S4), and minor (Al2S3). The scales formed on all alloys in the H2/H2S/H2O gas mixture were similar to those of in H2/H2S mixed gases except for that minor amount of Al2O3 was also detected in the inner layer of René 77. Platinum markers were always located at the interface between the inner and outer scales, suggesting that the outer scale grew by outward transport of cations (Ni, Cr, and Co) and the inner scale grew by the inward diffusion of

總目錄
總目錄 ……………………….…………………………..… I
表目錄 ……………………….…………………………..… III
圖目錄 ……………………….…………………………..… IV
摘要 (中文)……………….…………………………..…. VII
摘要 (英文)……………….…………………………..…. ⅤIII
第一章 前言………………….…………………………..… 1
第二章 文獻回顧……………………….………………….. 5
第三章 實驗步驟……………………….………………….. 10
3-1 試片成分與製作………….……………………….. 10
3-2 硫化腐蝕實驗……….…………………………..… 10
3-3 實驗觀察與分析………….……………………..… 18
第四章 實驗結果…………………………….…………….. 19
4-1 材料之金相顯微組織…………………………..…. 19
4-2 H2/H2S混合氣氛硫化腐蝕….……………..…..….. 19
4-2-1 腐蝕動力學……………………...……….… 19
4-2-2 腐蝕物表面型態與組成分析………….…... 32
4-2-3 短時間硫化實驗…………………………… 49
4-2-4 白金指標實驗…………………………....… 56
4-3 H2/H2S/H2O混合氣氛硫化腐蝕….…………...….. 60
4-3-1 腐蝕動力學…………….…………………... 60
4-3-2 腐蝕物表面型態與組成分析…...……….… 67
4-3-3 短時間硫化實驗…………….……………... 89
4-3-4 白金指標實驗……………………………… 93
第五章 討論…………………………….………………….. 95
第六章 結論…………………………….………………….. 105
第七章 參考文獻……………………….………………….. 107
表目錄
表-1 三式鎳基超合金之化學成份表(wt%)………….….. 11
表-2 不同氣氛下的氣體分壓值(a) H2/H2S, (b) H2/H2S/ H2O…………………………………………………... 15
表-3 三式合金於(a) H2/H2S混合氣氛及(b) H2/H2S/H2O混合氣氛各溫度硫化反應常數(kp值, 單位:g2/cm4/sec)及顯示性活化能(kJ/mole)。…………. 28
表-4 三式合金於(a) H2/H2S混合氣氛及(b) H2/H2S/H2O混合氣氛下腐蝕後表面的X-rays分析。……………
表-5 表面腐蝕物型態之EDX分析。…………………….
圖目錄
圖-1 H2/H2S混合氣實驗裝置圖…………………………. 12
圖-2 H2/H2S/H2O混合氣實驗裝置圖……………………... 14
圖-3 三式合金經由 HNO3:HCl=1:3的腐蝕液腐蝕後之金相組織照片(a) In-939, (b) René 77 及 (c) René 108.....………………………………………………... 20
圖-4 In-939原材表面之X-ray分析……………………… 22
圖-5 三式合金於H2/H2S混合氣腐蝕各溫度之重量增加變化量與時間的平方根關係圖 (a) In-939, (b) René 77 及 (c) René 108..…..…………………….……… 23
圖-6 三式合金於H2/H2S混合氣腐蝕各溫度之重量增加變化量與時間的平方根關係圖 (a) 550℃, (b) 600℃, (c) 700℃, (d) 800℃ 及 (e) 850℃.…………….. 25
圖-7 三式合金於H2/H2S混合氣硫化腐蝕速率常數與溫度倒數之Arrhenius圖..…..……………………....… 31
圖-8 In-939在H2/H2S混合氣氛於溫度(a) 550℃硫化腐蝕102.47小時,(b) 850℃硫化腐蝕1.27小時的表面形態..…...…………………………….…………….... 36
圖-9 René 77在H2/H2S混合氣氛於溫度(a) 600℃硫化腐蝕195.43小時,(b) 800℃硫化腐蝕3小時後的表面型態…...……………………………………………... 37
圖-10 René 108在H2/H2S混合氣氛於溫度(a) 550℃硫化腐蝕299.88小時,(b) 850℃硫化腐蝕8.53小時後的表面形態……………………………………..……... 38
圖-11 In-939於H2/H2S混合氣氛下溫度850℃硫化腐蝕1.27小時之X-光繞射分析圖….…………..……….. 40
圖-12 (a)~(f)為In-939於H2/H2S混合氣氛下溫度600℃硫化腐蝕18.18小時後的BEI橫截面及X-光元素分佈.…………………...……………………………….. 41
圖-13 René 77於H2/H2S混合氣氛下溫度600℃硫化腐蝕195.4小時之X-光繞射分析圖……………….…….. 44
圖-14 (a)~(g)為René 77於H2/H2S混合氣氛下溫度700℃硫化腐蝕31.85小時後的BEI橫截面及X-光元素分佈………………………………………..…...…. 45
圖-15 René 108於H2/H2S混合氣氛下溫度800℃硫化腐蝕13.3小時之X-光繞射分析圖………………...…. 50
圖-16 (a)~(h)為Rene’108於H2/H2S混合氣氛下溫度800℃硫化腐蝕13.3小時後的BEI橫截面及X-光元素分佈……………………….…………………………. 51
圖-17 In-939於H2/H2S混合氣氛下溫度600℃硫化腐蝕10分鐘之(a) X-光繞射分析圖, (b)表面型態………………….……………………………...….. 55
圖-18 René 77於H2/H2S混合氣氛下溫度700℃硫化腐蝕5分鐘之(a) X-光繞射分析圖, (b)表面型態…..……………………………………………….... 57
圖-19 René 108於H2/H2S混合氣氛下溫度600℃硫化腐蝕20分鐘之(a) X-光繞射分析圖, (b)表面型態…………..……………………………………..….. 58
圖-20 René 77於H2/H2S混合氣氛下於溫度800℃硫化腐蝕3.65小時的橫截面圖…………………………….. 59
圖-21 三式合金於H2/H2S/H2O混合氣腐蝕各溫度之重量增加變化量與時間的平方根關係圖 (a) In-939, (b) René 77 及 (c) René 108…………………………… 61
圖-22 三式合金於H2/H2S/H2O混合氣腐蝕各溫度之重量增加變化量與時間的平方根關係圖 (a) 550℃, (b) 600℃, (c) 700℃, (d) 800℃ 及 (e) 850℃….…….... 63
圖-23 三式合金於H2/H2S/H2O混合氣硫化腐蝕速率常數與溫度倒數之Arrhenius圖…..…….……………….. 66
圖-24 In-939在H2/H2S/H2O混合氣氛於溫度(a) 600℃硫化腐蝕14.50小時,(b) 850℃硫化腐蝕0.85小時後的表面型態………………………..………...………. 68
圖-25 René 77在H2/H2S/H2O混合氣氛於溫度(a) 600℃硫化腐蝕122.42小時,(b) 850℃硫化腐蝕1.07小時後的表面型態………………..…………..…………….. 70
圖-26 René 108在H2/H2S/H2O混合氣氛於溫度(a) 550℃硫化腐蝕202.2小時,(b) 700℃硫化腐蝕44.25小時後的表面型態………………………..…..………….. 71
圖-27 In-939於H2/H2S/H2O混合氣氛下溫度800℃硫化腐蝕1.52小時之X-光繞射分析圖…………………. 72
圖-28 (a)~(g)為In-939於H2/H2S/H2O混合氣氛下溫度700℃硫化腐蝕3小時後的BEI橫截面及X-光元素分佈………………………………………..……….... 73
圖-29 René 77於H2/H2S/H2O混合氣氛下溫度800℃硫化腐蝕1.42小時之X-光繞射分析圖…………………. 78
圖-30 (a)~(h)為René 77於H2/H2S/H2O混合氣氛下溫度700℃硫化腐蝕19.92小時後的BEI橫截面及X-光元素分佈…………………………...………………... 79
圖-31 René 108於H2/H2S/H2O混合氣氛下溫度700℃硫化腐蝕44.25小時之X-光繞射分析圖…………….. 83
圖-32 (a)~(i)為René 108於H2/H2S/H2O混合氣氛下溫度550℃硫化腐蝕202.2小時後的BEI橫截面及X-光元素分佈…..……………………………………..….. 84
圖-33 In-939於H2/H2S/H2O混合氣氛下溫度700℃硫化腐蝕5分鐘之(a) X-光繞射分析圖, (b)表面型態………………………………………………….…. 90
圖-34 René 77於H2/H2S/H2O混合氣氛下溫度700℃硫化腐蝕5分鐘之(a) X-光繞射分析圖, (b)表面型態…………………………...……………….……….. 91
圖-35 René 108於H2/H2S/H2O混合氣氛下溫度700℃硫化腐蝕5分鐘之(a) X-光繞射分析圖, (b)表面型態…………………………………………………….. 92
圖-35 René 77於H2/H2S/H2O混合氣氛下溫度800℃硫化腐蝕19.92小時的橫截面圖…..…………………….. 94
圖-36 Cr-S-O於溫度700℃之熱力學穩定相圖…………... 104

七、參考文獻
1. P. Elliott, A. A. Ansari, and R. Nabovi, Corr. Sci., 44 (1988) 544.
2. G. Y. Lai, High Temperature Corrosion of Engineering Alloys (High Temperature Alloys Haynes International, Inc. Kokomo, Indiana, USA 1990), P. 1.
3. 黃忠良, 金屬材料之高溫氧化與腐蝕, 第 1-16 頁, 台南, 復漢出版社, 民國七十七年.
4. William F. Smith, Structures and Properties of Engineering Alloys, (McGraw-Hill, New York, 1981) 420.
5. G. W. Goward, Materials Science and Technology, 2 (1986) 194.
6. S. Mrowec and K. Przybylski, High Temp. Mat. Processes 6 (1984) 1.
7. S. Mrowec and K. Przybylski, Oxid. Met. 23 (1985) 107.
8. L. Jian, C.Y. Yuh, and M. Farooque , ”Oxidation Behavior of Superalloys in Oxidation and Reducing Envioronment” , Corr. Sci. 42 (2000) 1573.
9. J. Huang, H. Fang, X. Fu, F. Huang, H. W, Q. Zhang, S. Deng, and J. Zu , ”High Temperature Oxidation Behavior and Mechanism of a New Type of Wrought Ni-Fe-Cr-Al Superalloy up to 1300℃” , Oxid. Met. 53 (2000) 273.
10. W. Kai, D. L. Douglass, and F. Gesmundo , ”The High Temperature Corrosion of Fe-Nb Alloys in a H2/H2O/H2S Gas Mixture” , Oxid. Met. 37 (1992) 389.
11. 李泰維, 海洋大學材料工程研究所碩士論文, 2000.
12. Chester T. Sims and William C. Hagel, The Superalloys, (NY :Wiley-Interscience, New York, 1972) p. 33-77.
13. 張宏睿, 國立台灣大學材料科學與工程學研究所碩士論文, 1998.
14. S. Mrowec, M. Danielewski, E. Godlewska, and K. Godlewski, in Oxidation of High-Temperature Intermetallics, ed. T. Grobstein and J. Doychak, TMS Publication USA, p. 147 (1998).
15. K. N. Strafford, Metall. Reviews 14 (1969) 153.
16. H. Habazaki, J. Dabek, K. Hashimoto, S. Mrowec, and M. Danielewski , ”The Sulfidation and Oxidation Behavior of Sputter-Deposited Amorphous Al-Mo Alloy At High Temperature” , Corr. Sci. 34 (1993) 183.
17. Z. Grzesik, H. Habazaki, K. H ashimoto, and S. Mrowec , ”The Sulphidation Behavior of Mo-Al Alloys with Low Aluminum Contents” , Corr. Sci. 36 (1994) 1499.
18. Chichang Shing, D. L. Douglass, and F. Gesmundo , ”Sulfidation Behavior of Al-Modified MP35N Alloys” , Oxid. Met. 35 (1991) 295.
19. G. C. Wood and F. H. Stott, Mat. Sci. and Tech. 3 (1987) 519.
20. G. Wang, D. L. Douglass, and F. Gesmundo, Oxid. Met. 35 (1991) 279.
21. M. F. Chen and D. L. Douglass , ”Effect of Some Ternary Additions on the Sulfidation of Ni-Mo Alloys” , Oxid. Met. 32 (1989) 185.
22. B. Gleeson, D. L. Douglass, and F. Gesmundo , ”A Comprehensive Investigation of the Sulfidation Behavior of Binary Co-Mo Alloys” , Oxid. Met. 33 (1990) 425.
23. R. V. Carter, D. L. Douglass, and F. Gesmundo, Oxid. Met. 31 (1989) 341.
24. B. Gleeson, D. L. Douglass, and F. Gesmundo, Oxid. Met. 31 (1989) 209.
25. G. Wang, D. L. Douglass, and F. Gesmundo, Oxid. Met. 35 (1991) 279.
26. H. Mitsui, H. Habazaki, K. Hashimoto, and S. Mrowec , ”The Sulfidation and Oxidation Behavior of Sputter-Deposited Amorphous Al-Ta Alloy At High Temperature” , Corr. Sci. 39 (1997) 59.
27. C. Fang, H. Yakuwa, and M. Miyasaka , ”Sulfidation Properties of Ni-20Cr and Ni-13.5Co-20Cr Alloys At 873k under Low Sulfur Pressures in H2S-H2 Atmospheres” , Oxid. Met. 53 (2000) 597.
28. C. Fang, H. Yakuwa, M. Miyasaka, and T. Narita, “Sulfidation Mechanism of Ni-20Cr and Ni-13.5Co-20Cr Alloys At 873k under Low Sulfur Pressures in H2S-H2 Atmospheres” , Oxid. Met. 54 (2000) 173.
29. C. Fang, H. Yakuwa, M. Miyasaka, and T. Narita , ”Phase Diagram of the Ni-Cr-S System at 873k between 10-4 and 10-8 Pa” , Oxid. Met. 54 (2000) 163.
30. P. D. Zelanko and G. Simkovich, Oxidation of Metals 8 (1974) 343.
31. S. Mrowec, T. Werber, and M. Zastawnik, Corros. Met. 6 (1966) 47.
32. D. J. Young, W. W. Smelter, and J. S. Kirkaldy, J. Electrochem. Soc. 120 (1973) 1221.