| 研究生: |
林士桂 Lin, Shih-Guei |
|---|---|
| 論文名稱: |
熱力學計算輔助快削鋼之硫化錳介在物形貌控制技術 CALPHAD-assisted morphology control of manganese sulfide inclusions in free-cutting steels |
| 指導教授: |
林士剛
Lin, Shih-Kang |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 材料科學及工程學系 Department of Materials Science and Engineering |
| 論文出版年: | 2016 |
| 畢業學年度: | 104 |
| 語文別: | 英文 |
| 論文頁數: | 94 |
| 中文關鍵詞: | 快削鋼 、硫化錳 、CALPHAD 、凝固路徑 、高溫實驗 |
| 外文關鍵詞: | Free-cutting steels, MnS inclusions, CALPHAD, Solidification path, High-temperature experiments |
| 相關次數: | 點閱:85 下載:4 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
為了要滿足工業上對於鋼鐵切削性質日益漸增的需求,開發具有良好切削性質的快削鋼材是必需的。硫化錳介在物為易切削物質之一,煉鋼過程中可藉由硫與錳元素的添加來形成硫化錳。硫化錳可以破壞鐵基體的連續性而使切屑易斷,當含硫化錳之鋼材受剪切外力作用時,其可做為應力集中源降低鋼材的切削抗力,進而增加鋼材的切削性質並降低切削刀具的磨損。硫系快削鋼的切削性能受其中硫化錳形狀、尺寸及分佈決定,因此在鋼材凝固的過程中,硫化錳的形成機制需要被謹慎的評估。硫化錳主要是鋼液經由共晶或偏晶反應所形成,而對切削性質較有利的球狀硫化錳是鋼液經偏晶反應形成的富硫化錳液態後續凝固而成的。但是這兩個反應的溫度差異(“∆T”)甚小,微量合金元素的添加即會影響硫化錳形成反應之相平衡溫度進而改變鋼液的凝固路徑使得共晶反應的硫化錳生成。
為了能夠精準地控制硫化錳的形貌,本研究使用熱力學計算方法(Calculation of phase diagram, CALPHAD) 搭配高週波感應高溫熔煉實驗。根據TCFE7商用熱力學鐵基資料庫,模擬Fe-Mn-S三元及Fe-C-Si-Mn-S五元合金系統之鋼液的凝固路徑,進一步評估硫含量對硫化錳形貌的影響。此外;根據合金元素添加對“∆T”的改變情形,有系統性的評估合金元素對硫化錳形貌的影響,並將其概分為三類:C, Si, Nb, Cr, V和Mo為共晶反應穩定劑;Al, Cu和O為偏晶反應穩定劑;Ta, Zr, Ni, N, P, W, H, Ar, B和Co為惰性添加劑。其中O為超強的偏晶反應穩定劑,可以顯著的增加球狀的硫化錳的形成。結合高溫實驗與理論熱力學計算,提出控制硫化錳析出形貌、尺寸及分布的材料設計原則,開發更具良好切削性質的快削鋼材並優化其冶煉工藝技術。
It is necessary to develop new free-cutting steels with good machinability in order to meet the ever-increasing demand for machining efficiency in industry. The addition of sulfur (S) can improve the machinability of steel by forming manganese sulfide (MnS) inclusions. These inclusions lower the shear strength of steel such that the cutting resistance is reduced, with MnS being the stress raiser. Since the morphology and the uniformity of the MnS inclusions critically determine the machinability of steels, the reactions involving MnS formation during solidification need to be carefully assessed, especially with regard to whether they are eutectic or monotectic reactions. Globular MnS is formed from the MnS-rich liquid (L2) through a monotectic reaction, which provides a greater benefit for machining. However, the temperature difference (“∆T”) between these two reactions is so close that doping elements may alter the solidification path of the liquid steel, and may result in a eutectic reaction.
In this study, we focus on establishing the relationships between alloying elements and solidified microstructures by utilizing both the calculation of phase diagram (CALPHAD) method and high-temperature experiments with an atmosphere-controlled high-frequency induction furnace. Based on a commercial thermodynamic database, TCFE7, we simulated the solidification path of the pure Fe-Mn-S ternary system and some alternative paths with alloying elements carbon (C) and silicon (Si) to further evaluate the effects of S content on the microstructure of MnS. Moreover, we also systematically evaluated the effects of various alloying elements on the microstructure of MnS based on their effects on changing “∆T”. These alloying elements can be categorized into three groups: C, Si, Nb, Cr, V, and Mo are eutectic-stabilizers, O, Cu and Al are monotectic-stabilizers, and Ta, Zr, Ni, N, P, W, H, Ar, B, and Co are inert dopants, which do not noticeably change the microstructure of MnS. Among these, oxygen (O) is identified as a super-strong monotectic-stabilizer, and the addition of oxygen addition can drastically enhance the monotectic-type MnS, which is desirable for free-cutting steels. The thermodynamic predictions agree closely with the results of high-temperature experiments. With the combined efforts of thermodynamic calculations and high-temperature experiments, the morphology, size, and uniformity of MnS inclusions can be optimized for the development of better free-cutting steels.
[1] B.-J. Lee, B. Sundman, S. Kim, and K.-G. Chin, "Thermodynamic Calculations on the Stability of Cu2S in Low Carbon Steels," ISIJ International, vol. 47, pp. 163-171, 2007.
[2] Z. Li and D. Wu, "Effect of Free-cutting Additives on Machining Characteristics of Austenitic Stainless Steels," Journal of Materials Science & Technology, vol. 26, pp. 839-844, 2010.
[3] S. Kalpakjian and S. R. Schmid, Manufacturing Processes for Engineering Materials, 5th ed. : Pearson education, 2008.
[4] J. Fujiwara, "Cutting Mechanism of Sulfurized Free-Machining Steel," 2012.
[5] G. Anan, T. Tsuji, A. Yoshida, and K. Shiihashi, "High Strength Lead Free Steels for Fracture Splitting Connecting Rods," Kobe Steel Engineering Reports, vol. 56, 2006.
[6] Retrieved from "http://yanfeimoxing.blog.163.com/."
[7] Retrieved from "http://www.oastore.com.tw/."
[8] Retrieved from "http://museum.csc.com.tw/."
[9] H. Fredriksson and U. Akerlind, Materials Processing during Casting: John Wiley & Sons, Ltd, 2006.
[10] R. Kiessling and N. Lange, Non-metallic inclusions in steel: Metals Society, 1978.
[11] L. Yan, L. Zhilin, Z. Chengwei, and Z. Yingchun, "Influence of valence electron structures of phase and biphase interfaces of sulfides on hot brittleness in steel," Science in China Series E-Engineering & Materials Science, vol. 47, pp. 488-504, 2004.
[12] C. E. Sims and F. B. Dahle, "The Effect of Aluminum on the Properties of Medium Carbon Cast Steel," Transactions of the American Foundrymen's Society, vol. 46, pp. 65-132, 1938.
[13] A. I. H. Committee and P. K. Trojan, "Inclusion-Forming Reactions," ASM Handbook, vol. 15 - Casting, 2008; 2010.
[14] Y. Ito, N. Masumitsu, and K. Matsubara, "Formation of Manganese Sulfide in Steel," Transactions of the Iron and Steel Institute of Japan, vol. 21, 1981.
[15] K. Oikawa, H. Ohtani, K. Ishida, and T. Nishizawa, "The Control of the Morpholog of MnS Inclusions in Steel during Solidification," ISIJ International, vol. 35, 1995.
[16] K. Oikawa, K. Ishida, and T. Nishizawa, "Effect of Titanium Addition on the Formation and Distribution of MnS Inclusions in Steel during Solidification," ISIJ International, vol. 37, pp. 332-338, 1997.
[17] Z.-K. Liu, "First-Principles Calculations and CALPHAD Modeling of Thermodynamics," Journal of Phase Equilibria and Diffusion, vol. 30, pp. 517-534, 2009.
[18] W. F. Smith, Structure and properties of engineering alloys: McGraw-Hill Education, 1993.
[19] J. Szekely, "Steelmaking and industrial ecology - Is steel a green material?," ISIJ International, vol. 36, pp. 121-132, 1996.
[20] H. Yaguchi, "Effect of soft additives (Pb/Bi) on machinability of low carbon resulphurised free machining steels," Materials Science and Technology, vol. 5, pp. 255-267, 1989.
[21] M. A. Krishtal, A. A. Borgardt, and Y. D. Yashin, "Effect of lead on the machinability of free-cutting steel," Metal Science and Heat Treatment, vol. 19, pp. 178-180, 1977.
[22] H. Yaguchi, "Effect of soft additives (Pb, Bi) on formation of built-up edge," Materials Science and Technology, vol. 4, pp. 926-931, 1988.
[23] "Directive 2002/95/EC of the European Parliament and of the council of 27 January 2003 on the restriction of the use of certain hazardous substances in electrical and electronic equipment," Official Journal of the European Union, 2003.
[24] "Directive 2003/108/EC of the European Parliament and of the Council of 8 December 2003 amending Directive 2002/96/EC on waste electrical and electronic equipment (WEEE)," Official Journal of the European Union, 2003.
[25] "Machinability Enhancement of Non-Leaded Free Cutting Steels," 2006.
[26] M. Hashimura, A. Mizuno, and K. Miyanishi, "Effect of MnS distribution on machinability in low-carbon free-cutting steel," Iron and Steel Technology, vol. 6, pp. 45-51, 2009.
[27] M. Toshiyuki, T. Kunikazu, and S. Tetsuo, "Development of Free Cutting Steel without Lead Addition to Replace AISI12L14," JFE TECHNICAL REPORT, vol. 15, 2010.
[28] M. Hashimura, K. Miyanishi, and A. Mizuno, "Development of Low-Carbon Lead-Free Free-Cutting Steel Friendly to Environment," Nippon Steel Technical Report, vol. 96, 2007.
[29] T. Akasawa, H. Sakurai, M. Nakamura, T. Tanaka, and K. Takano, "Effects of free-cutting additives on the machinability of austenitic stainless steels," Journal of Materials Processing Technology, vol. 143-144 (1), pp. 66-71, 2003.
[30] T. Araki and S. Yamamoto, "Machinability of Steel and Metallugical Factors," Tetsu-to-Hagane, vol. 57, pp. 1912-1932, 1971.
[31] H. Fredriksson and M. Hillert, "Eutectic and Monotectic Formation of MnS in Cast Irons," Journal of the Iron and Steel Institute, vol. 209, pp. 109-113, 1971.
[32] L. K. Bigelow and M. C. Flemings, "Sulfide inclusions in steel," Metallurgical Transactions B, vol. 6B, pp. 275-283, 1975.
[33] "Thermo-Calc Software TCFE7 Steels/Fe-alloys database version 7 (Accessed 23 Aug 2013)."
[34] S. Chen, W. Cao, Y. Yang, F. Zhang, K. Wu, Y. Du, et al., "Calculation and application of liquidus projection," Rare metals, vol. 25, 2006.
[35] F. N. Rhines, Phase Diagrams in Metallurgy. New York, United States: McGraw-Hill Book company, Inc., 1956.
[36] J. W. Gibbs, "On the Equilibrium of Heterogeneous Substances," Transactions of the Connecticut Academy of Arts and Sciences, 1875~1878.
[37] W. D. Callister, Materials Science and Engineering: An Introduction, 7 ed.: John Wiley & Sons, Inc, 2006.
[38] D. A. Stephenson and J. S. Agapiou, Metal Cutting Theory and Practice, 2005.
[39] Production flow chart. Available: http://www.csc.com.tw/csc_e/pd/prs.htm
[40] H. Fredriksson and M. Hillert, "Formation of MnS Inclusions in Steel," Scandinavian Journal of Metallurgy, p. 125, 1973.
[41] M. Wakoh, T. k. Sawai, and S. Mizoguchi, "Effect of S Content on the MnS Precipitation in Steel with Oxide Nuclei," ISIJ International, vol. 36, pp. 1014-1021, 1996.
[42] "Effect of Titanium Addition on the Formation and Distribution of MnS Inclusions in Steel during Solidification," ISIJ International, vol. 37, pp. 332-338, 1997.
[43] Y.-B. Kang, M.-S. Kim, S.-W. Lee, J.-W. Cho, M.-S. Park, and H.-G. Lee, "A Reaction Between High Mn-High Al Steel and CaO-SiO2-Type Molten Mold Flux: Part II. Reaction Mechanism, Interface Morphology, and Al2O3 Accumulation in Molten Mold Flux," Metallurgical and Materials Transactions B, vol. 44B, pp. 309-316, 2012.
[44] Horiba, "Carbon/Sulfur Combustion Analyzer for Solid Materials EMIA series."
[45] Horiba, "Nitrogen/Oxygen Analyzer EMGA-920."
[46] J.-O. Andersson, T. Helander, L. Höglund, P. F. Shi, and B. Sundman, "Thermo-Calc and DICTRA, Computational tools for materials science," Calphad, vol. 26, pp. 273-312, 2002.
[47] E. Scheil, Z. Metallkd, vol. 34, pp. 70-72, 1942.
[48] S.-L. Chen, Y. Yang, S.-W. Chen, X.-G. Lu, and Y. A. Chang, "Solidification Simulation Using Scheil Model in Multicomponent Systems," Journal of Phase Equilibria and Diffusion, vol. 30, pp. 429-434, 2009.
[49] D. Dilner, H. Mao, and M. Selleby, "Thermodynamic assessment of the Mn-S and Fe-Mn-S systems," CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry, vol. 48, pp. 95-105, 2015.
[50] E. T. Turkdogan, "Fundamentals of steelmaking," 1996.
[51] D.-C. Madeleine, Microstructure of Steels and Cast Irons: Springer; 2004 edition, 2004.
[52] S. Nakamura, "Progress in the Manufacturing Technology and Quality of Free-machining Steels," ISIJ, Tokyo, p. 187, 1984.
[53] Z. Li and D. Wu, "Effect of free-cutting additives on machining characteristics of austenitic stainless steels," J. Mater. Sci. Technol., vol. 26, pp. 839-844, 2010.
[54] K. Oikawa, S.-I. Sum, and K. Ishida, "The effects of addition of deoxidation elements on the morphology of (Mn,Cr)S inclusions in stainless steel," Journal of Phase Equilibria and Diffusion, vol. 20, 1999.
[55] "Behaviors of manganese-sulfide in aluminum-killed steel solidified uni-directionally in steady state dendrite structure and inclusions," ISIJ International, vol. 34, pp. 896-905, 1994.
[56] H. Liu and W. Chen, "Effect of total oxygen content on the machinability of low carbon resulfurized free cutting steel," steel research int., vol. 83, 2012.