Advertisement

Deoxidation of Titanium Using Mg as Deoxidant in MgCl2-YCl3 Flux

  • Chenyi Zheng
  • Takanari OuchiEmail author
  • Akihiro Iizuka
  • Yu-ki Taninouchi
  • Toru H. Okabe
Article
First Online:
  • 23 Downloads

Abstract

To reduce the oxygen level in titanium (Ti) to less than 1000 mass ppm O, using magnesium as the deoxidant at 1300 K (1027 °C), the activity of the deoxidation product (MgO), i.e., aMgO, in the system must be reduced to less than 0.04, from a thermodynamic viewpoint. In this study, we developed a new deoxidation technique for Ti, by adding yttrium chloride (YCl3) to magnesium chloride (MgCl2) flux, which effectively decreases and maintains the aMgO in the system at a low level, via the formation of yttrium oxychloride (YOCl). Through thermodynamic assessment using a \( p_{{{\text{O}}_{ 2} }} {\text{-}}p_{{{\text{Cl}}_{ 2} }} \) diagram, as well as experiments, the deoxidation of Ti to an oxygen level below 1000 mass ppm O, via the reaction O (in Ti) + Mg + YCl3 → MgCl2 + YOCl, was confirmed. Furthermore, using the E-pO2− diagram of the M-O-Cl system (M = Y, Mg), the possibility of electrochemical deoxidation is discussed. In the MgCl2-YCl3 flux, Mg deposits on the Ti cathode and simultaneously deoxidizes it. The activity of the deoxidation product, MgO, decreases due to the formation of YOCl and/or the electrochemical oxidation of oxide ions on the carbon anode; thus, the deoxidation of Ti becomes feasible. This new deoxidation technique using rare-earth-containing MgCl2 flux can be applied to the recycling of Ti scraps, in the future.

This is a preview of subscription content, log in to check access.

Notes

Acknowledgments

The authors are grateful to Professors Hongmin Zhu and Osamu Takeda at Tohoku University for their valuable comments and helpful suggestions. This work was financially supported by the Japan Society for the Promotion of Science (JSPS), through a Grant-in-Aid for Scientific Research (S) (KAKENHI Grant No. 26220910).

References

  1. 1.
    Abundance in Earth’s Crust. https://www.webelements.com/
  2. 2.
    [2] W. Kroll: J. Electrochem. Soc, 1940, vol. 78, pp. 35-47.CrossRefGoogle Scholar
  3. 3.
    F.H. Fore: Titanium-Physical Metallurgy, Processing, and Applications, ASM International, 2015.Google Scholar
  4. 4.
    [4] T. H. Okabe, C. Zheng, and Y. Taninouchi: Metall. Mater. Trans. B, 2018, vol. 49, pp. 1056–66.CrossRefGoogle Scholar
  5. 5.
    T.H. Okabe, Y. Taninouchi, and C. Zheng: Metall. Mater. Trans. B, 2018, vol. 49, pp. 3107–17.CrossRefGoogle Scholar
  6. 6.
    [6] T. H. Okabe, Y. Hamanaka, and Y. Taninouchi: Faraday Discuss., 2016, vol. 190, pp. 109-26.CrossRefGoogle Scholar
  7. 7.
    [7] Y. Taninouchi, Y. Hamanaka, and T. H. Okabe: Metall. Mater. Trans. B, 2016, vol. 47, pp. 3394-404.CrossRefGoogle Scholar
  8. 8.
    [8] T. H. Okabe, R. O. Suzuki, T. Oishi, and K. Ono: Mater. Trans. JIM, 1991, vol. 32, pp. 485–8.CrossRefGoogle Scholar
  9. 9.
    [9] T. H. Okabe, R. O. Suzuki, T. Oishi, and K. Ono: J. Iron Steel Inst. Japan, 1991, vol. 77, pp. 93–9 (in Japanese).CrossRefGoogle Scholar
  10. 10.
    [10] T. H. Okabe, T. Oishi, and K. Ono: J. Alloys Compd., 1992, vol. 184, pp. 43–56.CrossRefGoogle Scholar
  11. 11.
    [11] T. H. Okabe, M. Nakamura, T. Oishi, and K. Ono: Metall. Mater. Trans. B, 1993, vol. 24, pp. 449–55.CrossRefGoogle Scholar
  12. 12.
    M. Nakamura, T.H. Okabe, T. Oishi, and K. Ono: in Proceedings of the International Symposium on Molten Salt Chemistry and Technology, 1993, pp. 529–40.Google Scholar
  13. 13.
    [13] T. H. Okabe, T. Oishi, and K. Ono: Metall. Trans. B, 1992, vol. 23, pp. 583–90.CrossRefGoogle Scholar
  14. 14.
    [14] O. N. Carlson, J. A. Haefling, and F. A. Schmidt: J. Electrochem. Soc., 1960, vol. 107, pp. 540–5.CrossRefGoogle Scholar
  15. 15.
    [15] J. D. Corbett, J. D. Smith, and E. Garcia: J. Less Common Met., 1986, vol. 115, pp. 343–55.CrossRefGoogle Scholar
  16. 16.
    [16] T. H. Okabe, K. Hirota, Y. Waseda, and K. T. Jacob: J. Min. Mater. Process. Inst. Japan, 1998, vol. 114, pp. 813–8.Google Scholar
  17. 17.
    [17] H. Sano, M. Tashiro, T. Fujisawa, and C. Yamauchi: Mater. Trans. JIM, 1999, vol. 40, pp. 263–7.CrossRefGoogle Scholar
  18. 18.
    [18] O. Takeda, K. Nakano, and Y. Sato: Mater. Trans., 2014, vol. 55, pp. 334–41.CrossRefGoogle Scholar
  19. 19.
    [19] H. Hira: J. Jpn. Inst. Light Met., 2015, vol. 65, pp. 426–31 (in Japanese).CrossRefGoogle Scholar
  20. 20.
    [20] T. B. Massalski: Binary Alloy Phase Diagrams, 2nd ed., ASM International, Materials Park, OH, USA, 1990.Google Scholar
  21. 21.
    [21] O. Kubaschewski, and W. A. Dench: J. Inst. Met., 1953, vol. 82, pp. 87–91.Google Scholar
  22. 22.
    [22] K. Ono, and S. Miyazaki: J. Jpn. Inst. Met., 1985, vol. 49, 871–5 (in Japanese).CrossRefGoogle Scholar
  23. 23.
    R.L. Fisher: US Patent 4923531A, 1990.Google Scholar
  24. 24.
    R.L. Fisher: US Patent 5022935, 1991.Google Scholar
  25. 25.
    R.L. Fisher, and S.R. Seagle: US Patent 5211775 A, 1993.Google Scholar
  26. 26.
    R.L. Fisher, and S.R. Seagle: in Proceedings of the 7th World Conference on Titanium, 1993, vol. 3, pp. 2265–72.Google Scholar
  27. 27.
    [27] G. Z. Chen, D. J. Fray, and T. W. Farthing: Nature, 2000, vol. 407, pp. 361–4.CrossRefGoogle Scholar
  28. 28.
    [28] G. Z. Chen, D. J. Fray, and T. W. Farthing: Metall. Mater. Trans. B, 2001, vol. 32, pp. 1041–52.CrossRefGoogle Scholar
  29. 29.
    [29] S.-M. Han, Y.-S. Lee, J.-H. Park, G.-S. Choi, and D.-J. Min: Mater. Trans., 2009, vol. 50, no. 1, pp. 215-8.CrossRefGoogle Scholar
  30. 30.
    [30] J.-M. Oh, B.-K. Lee, C.-Y. Suh, S.-W. Cho, and J.-W. Lim: Powder Metall., 2012, vol. 55, pp. 402–4.CrossRefGoogle Scholar
  31. 31.
    [31] J.-M. Oh, K.-M. Roh, B.-K. Lee, C.-Y. Suh, W. Kim, H. Kwon, and J.-W. Lim: J. Alloys Compd., 2014, vol. 593, pp. 61–6.CrossRefGoogle Scholar
  32. 32.
    [32] J.-M. Oh, H. Kwon, W. Kim, and J.-W. Lim: Thin Solid Films, 2014, vol. 551, pp. 98-101.CrossRefGoogle Scholar
  33. 33.
    [33] K.-M. Roh, C.-Y. Suh, J.-M. Oh, W. Kim, H. Kwon, and J.-W. Lim: Powder Technol., 2014, vol. 253, pp. 266–9.CrossRefGoogle Scholar
  34. 34.
    [34] J.-M. Oh, I.-H. Choi, C.-Y. Suh, H. Kwon, J.-W. Lim, and K.-M. Roh: Met. Mater. Int., 2016, vol. 22, no. 3, pp. 488–92.CrossRefGoogle Scholar
  35. 35.
    [35] S.-J. Kim, J.-M. Oh, and J.-W. Lim: Met. Mater. Int., 2016, vol. 22, no. 4, pp. 658–62.CrossRefGoogle Scholar
  36. 36.
    [36] Y. Zhang, Z. Z. Fang, Y. Xia, Z. Huang, H. Lefler, T. Zhang, P. Sun, M. L. Free, and J. Guo: Chem. Eng. J., 2016, vol. 286, pp. 517–27.CrossRefGoogle Scholar
  37. 37.
    [37] Y. Xia, Z. Z. Fang, P. Sun, Y. Zhang, T. Zhang, and M. Free: J. Mater. Sci., 2017, vol. 52, pp. 4120–8.CrossRefGoogle Scholar
  38. 38.
    [38] J. Reitz, C. Lochbichler, and B. Friedrich: Intermetallics, 2011, vol. 19, pp. 762–8.CrossRefGoogle Scholar
  39. 39.
    [39] M. Bartosinski, S. Hassan-Pour, B. Friedrich, S. Ratiev, and A. Ryabtsev: Mater. Sci. Eng., 2016, vol. 143, 012009.Google Scholar
  40. 40.
    [40] B. M. Moon, J. H. Seo, H. J. Lee, K. H. Jung, J. H. Park, and H. D. Jung: J. Alloys Compd., 2017, vol. 727, pp. 931–9.CrossRefGoogle Scholar
  41. 41.
    [41] T. Yahata, T. Ikeda, and M. Maeda: Metall. Trans. B, 1993, vol. 24, pp. 599–604.CrossRefGoogle Scholar
  42. 42.
    [42] J.-M. Oh, K.-M. Roh, and J.-W. Lim: Int. J. Hydrogen Energy, 2016, vol. 41, pp. 23033–41.CrossRefGoogle Scholar
  43. 43.
    [43] Y. Su, L. Wang, L. Luo, X. Jiang, J. Guo, and H. Fu: Int. J. Hydrogen Energy, 2009, vol. 34, pp. 8958–63.CrossRefGoogle Scholar
  44. 44.
    [44] Y. Zhang, Z. Z. Fang, P. Sun, T. Zhang, Y. Xia, C. Zhou, and Z. Huang: J. Am. Ceram. Soc., 2016, vol. 138, pp. 6916–9.Google Scholar
  45. 45.
    [45] Y. Zhang, Z. Z. Fang, Y. Xia, P. Sun, B. V. Devener, M. Free, H. Lefler, and S. Zheng: Chem. Eng. J., 2017, vol. 52, pp. 299–310.CrossRefGoogle Scholar
  46. 46.
    [46] Y. Xia, Z. Z. Fang, Y. Zhang, H. Lefler, T. Zhang, P. Sun, and M. Free: Mater. Trans., 2017, vol. 58, no. 3, pp. 355–60.CrossRefGoogle Scholar
  47. 47.
    Y. Waseda, and M. Isshiki (eds.): Purification Process and Characterization of Ultra High Purity Metals, 3rd ed., Springer, Berlin, Germany, 2001, pp. 3–37.Google Scholar
  48. 48.
    [48] T. H. Okabe, K. Hirota, E. Kasai, F. Saito, Y. Waseda, and K. T. Jacob: J. Alloys Compd., 1998, vol. 279, pp. 184–91.CrossRefGoogle Scholar
  49. 49.
    Roskill: Rare Earths: Global Industry, Markets and Outlook to 2026, 16th ed., 2049 Information Services, London, UK, 2016.Google Scholar
  50. 50.
    [50] I. Barin: Thermochemical Data of Pure Substances, 3rd ed., Wiley-VCH., Weinheim, Germany, 1995.CrossRefGoogle Scholar
  51. 51.
    [51] S. M. Pang, S. H. Yan, Z. A. Li, D. H. Cheng, H. L. Xu, and B. Zhao: Chin. J. Rare Met., 2011, vol. 35, pp. 440–50 (in Chinese).Google Scholar
  52. 52.
    M.W. Chase: NIST-JANAF Thermochemical Tables, 4th ed., American Institute of Physics, 1998.Google Scholar
  53. 53.
    [53] Y. B. Patrikeev, G. I. Novikov, and V. V. Badovskii: Russ. J. Phys. Chem., 1973, vol. 47, p. 284.Google Scholar
  54. 54.
    [54] M. Su, and B. Qiu: Acta Metall. Sin., 1966, vol. 9, pp. 142–7 (in Chinese).Google Scholar
  55. 55.
    [55] C. J. Rosa: Metall. Trans., 1970, vol. 1, pp. 2517-22.Google Scholar
  56. 56.
    H.E. Swanson, E. Tatge, and R.K. Fuyat: Standard X-ray Diffraction Powder Patterns, National Bureau of Standards, 1962, p. 51.Google Scholar
  57. 57.
    [57] D. H. Templeton, and G. F. Carter: J. Phys. Chem., 1954, vol. 58, pp. 940–4.CrossRefGoogle Scholar
  58. 58.
    D.E. Partin, and M. O’keeffe: J. Solid State Chem., 1991, vol. 95, pp. 176–83.Google Scholar
  59. 59.
    [59] R. Littlewood: J. Electrochem. Soc, 1962, vol. 109, pp. 525–34.CrossRefGoogle Scholar

Copyright information

© The Minerals, Metals & Materials Society and ASM International 2019

Authors and Affiliations

  • Chenyi Zheng
    • 1
    • 2
  • Takanari Ouchi
    • 1
    Email author
  • Akihiro Iizuka
    • 1
    • 2
  • Yu-ki Taninouchi
    • 1
  • Toru H. Okabe
    • 1
  1. 1.Institute of Industrial ScienceThe University of TokyoTokyoJapan
  2. 2.Department of Materials Engineering, Graduate School of EngineeringThe University of TokyoTokyoJapan

Personalised recommendations

Cite article

Buy options