Oxidation of Metals

, Volume 47, Issue 1–2, pp 139–203 | Cite as

Oxidation of the intermetallics MoSi2 and TiSi2—A comparison

  • S. Melsheimer
  • M. Fietzek
  • V. Kolarik
  • A. Rahmel
  • M. Schütze
Article

Abstract

The oxidation behavior of two MoSi2 variants, one Mo-rich and one Si-rich, and TiSi2 was investigated between 1000 and 1400°C in air, oxygen and an 80/20-Ar/O2 mixture. A protective SiO2 scale develops on MoSi2 in all atmospheres in the temperature range investigated. The SiO2 modification changes around 1300°C from tridymite to cristobalite. This change in SiO2 modification seems to cause an enhanced formation of SiO2 and evaporation of MoO3. The SiO2 grows at the MoSi2-scale interface. In air a two-layer scale grows on TiSi2 between about 1000 and 1200°C with an inner inwards growing fine-grain mixture of SiO2 + TiO2 and an outer outward-growing TiO2 partial layer. TiN formation in the transient oxidation is responsible for the formation of the inner mixed partial layer because in N -free atmospheres a scale of a SiO2 matrix with some Ti oxide precipitates inside is formed. A one-layer scale structure similar as that in N-free atmosphere is found on TiSi2 in air at T > 1200°C. In oxygen the TiO2 precipitates grow as needles mostly oriented perpendicular to the surface. Due to the faster oxygen transport in TiO2 compared with SiO2, these TiO2 needles act as “oxygen pipes,” causing an enhanced oxidation of TiSi2 in front of these needles. The SiO2 scale dissolves about 1–2% TiO2. This doping causes a mixed oxygenand Si transport with the consequence that the SiO2 scale on TiSi2 grows partly by oxygen transport inwards and Si transport outwards. The SiO2 modification is cristobalite over the entire temperature range investigated.

Key words

oxidation MoSi2 TiSi2 air oxygen O and Si transport in SiO2 

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References

  1. 1.
    H. Ryssel, inLexikon Elektronik und Mikroelektronik, Hrsg. von D. Sautter and H. Weinerth, eds., “Silicide” (Düsseldorf, 1990).Google Scholar
  2. 2.
    D. Levy, J. P. Ponpon, A. Grob, and R. Stuck,Appl. Phys. A 38, 23 (1985).Google Scholar
  3. 3.
    B. L. Crowder and S. Zirinsky,IEEE J. Solid-State Circuits SC-14, 291–293 (1979).Google Scholar
  4. 4.
    S. P. Murarka, D. B. Fraser, A. K. Sinha, and H. J. Levinstein,IEEE J. Solid-State Circuits SC-15, 474–482 (1980).Google Scholar
  5. 5.
    S. P. Murarka,Thin Solid Films 140, 35 (1986).Google Scholar
  6. 6.
    S. Melsheimer, Oxidationsverhalten der Disilicide TiSi2 und MoSi2 als Struktur- und Beschichtungswerkstoffe bei hohen Temperaturen, Dissertation RWTH Aachen, 1996.Google Scholar
  7. 7.
    R. W. Bartlett, P. R. Gage, and P. A. Larssen,Trans. Met. Soc. AIME 230, 1528 (1964).Google Scholar
  8. 8.
    V. E. Ivanov, E. P. Nechiporenko, V. I. Zmij, V. M. Krivoruchko, L. F. Verkho-robin, O. M. Aleksandrov, A. S. Mitrofanov, and N. S. Poltavtsev,Neorg. Mater. 1, 1354 (1965).Google Scholar
  9. 9.
    J. B. Berkowitz-Mattuck,Stability of Ceramic Materials at Temperatures to 2000°C, WADD Technical Report 60-377, Contract No. AF 33(616)-6154, Project No. 7350, 1960.Google Scholar
  10. 10.
    J. B. Berkowitz-Mattuck and R. R. Dils,J. Electrochem. Soc. 112, 583 (1965).Google Scholar
  11. 11.
    R. W. Bartlett and P. R. Gage,Trans. Met. Soc. AIME 233, 968 (1965).Google Scholar
  12. 12.
    R. W. Bartlett, J. W. McCamont, and P. R. Gage,J. Am. Cer. Soc. 48, 551 (1965).Google Scholar
  13. 13.
    D. A. Berztiss, R. R. Cerchiara, E. A. Gulbransen, F. S. Pettit, and G. H. Meier,Mat. Sci. Eng. A 155, 165 (1992).Google Scholar
  14. 14.
    L. N. Lie, W. A. Tiller, and K. C. Saraswat,J. Appl. Phys. 56, 2127 (1984).Google Scholar
  15. 15.
    T. Mochizuki and M. Kashiwagi,J. Electrochem. Soc. 127, 1128 (1980).Google Scholar
  16. 16.
    Binary Alloy Phase Diagrams, 2nd ed., T. B. Massalski, ed. (Am. Soc. Metals, Metals Park, Ohio, 1990).Google Scholar
  17. 17.
    F. N. Schwettmann, R. A. Graff, and M. Kolodney,J. Electrochem. Soc. 118, 1973 (1971).Google Scholar
  18. 18.
    J. B. Berkowitz-Mattuck, P. E. Blackburn, and E. J. Felten,Trans. Met. Soc. AIME 233, 1093 (1965).Google Scholar
  19. 19.
    O. Rubisch,Ber. Dtsch. Keram. Ges. 41, 120 (1964).Google Scholar
  20. 20.
    A. F. Hollemann and E. Wiberg,Lehrbuch der Anorganischen Chemie (Walter de Gruyter, Berlin and New York, 1985), p. 752.Google Scholar
  21. 21.
    H. Schnabel,Zur Pulvermetallurgie des Molybdändisilizids, Dissertation TH, Karlsruhe, 1965.Google Scholar
  22. 22.
    K. Reinmuth,Die Reaktionen hochschmelzender Silizide mit Stickstoff und Sauerstoff, Dissertation TH, Karlsruhe, 1968.Google Scholar
  23. 23.
    E. Fitzer, K. Reinmuth, and H. Schnabel,Arch. Eisenhüttenw.40, 895. (1969).Google Scholar
  24. 24.
    K. L. Luthra,Oxid. Met. 36, 475 (1991).Google Scholar
  25. 25.
    A. Rahmel and P. J. Spencer,Oxid. Met. 35, 53 (1991).Google Scholar
  26. 26.
    R. C. DeVries, R. Roy, and E. F. Osborn,Trans. Br. Cer. Soc. 53, 525 (1954).Google Scholar
  27. 27.
    A. G. Revesz,Phys. Stat. Sol. 57, 235, 657 (1980).Google Scholar
  28. 28.
    G. R. Blair, H. Levin, and R. E. O'Brien,J. Am. Cer. Soc. 48, 430 (1965).Google Scholar
  29. 29.
    The Si-SiO 2 System, P. Balk, ed., Materials Science Monographs32 (Elsevier, New York, 1988).Google Scholar
  30. 30.
    The Physics and Chemistry of SiO 2 and the Si-SiO 2 Interface, C. R. Helms and B. E. Deal, eds. (Plenum Press, New York, 1988).Google Scholar
  31. 31.
    E. A. Irene,CRC Crit. Rev. Solid State Mater. Sci. 14, 175 (1988).Google Scholar
  32. 32.
    E. Fitzer, J. Schlichting, and F. K. Schmidt,High-Temp. High Pres. 2, 553 (1970).Google Scholar
  33. 33.
    S. Becker, A. Rahmel, and M. Schütze,Solid State Ionics 53-56, 280 (1992).Google Scholar
  34. 34.
    K. P. Wild,Das Zunderverhalten der Disilizide der Metalle der 4., 5. und 6. Nebengruppe und ihrer Mischsysteme, Dissertation Universität Karlsruhe, 1973.Google Scholar
  35. 35.
    R. Roy, R. C. DeVries, D. E. Rase, M. W. Shafer, and E. F. Osborn, inPhase Diagrams for Ceramists, E. M. Levin, C. R. Robbins, and H. F. McMurdie, eds. (The Am. Cer. Soc., Columbus, Ohio, 1964), Fig. 115, p. 69.Google Scholar
  36. 36.
    E. Fitzer, inWarmfeste und korrosionsbeständige Sinterwerkstoffe. 2. Plansee-Seminar, Reutte/Tirol, F. Benesovsky, ed. (Berlin, 1955), pp. 56–79.Google Scholar
  37. 37.
    C. D. Wirkus,J. Am. Cer. Soc. 49, 173 (1966).Google Scholar
  38. 38.
    P. I. Glushko, G. I. Postogvard, N. S. Pugachev, S. F. Dudnik, and V. P. Podtykan,Prot. Met. 13, 187 (1977).Google Scholar
  39. 39.
    J. Schlichting and S. Hoffmann,High Temp.-High Pres. 10, 349 (1978).Google Scholar
  40. 40.
    P. Meschter,Met. Trans. 23A, 1763 (1992).Google Scholar
  41. 41.
    R. W. Bartlettet al., Investigation of Mechanisms for Oxidation Protection and Failure of Intermetallic Coatings für Refractory Metals. Part I. Molybdenum Disilicide, Technical Documentary Report No. ADF-TDR-63-753, Part 1, Contract No. AF 33(657)-9170, June 1963.Google Scholar
  42. 42.
    C. E. Ramberg, P. Beatrice, K. Kurokawa, and W. L. Worrell,Mat. Res. Soc. Proc. 322, 243 (1994).Google Scholar
  43. 43.
    R. Beyers,J. Appl. Phys. 56, 147 (1984).Google Scholar
  44. 44.
    R. Beyers, R. Sinclair, and M. E. Thomas,Proc. Symp. High Temperature Materials Chemistry III Z. A. Munir and D. Cubicciotti, eds. (The Electrochemical Society, Pennington, NJ, 1986), pp. 1–3.Google Scholar
  45. 45.
    J. C. Schuster and H. Nowotny,Proc. 11th Int. Plansee Semin. 1 (1985), 889–911.Google Scholar
  46. 46.
    R. Beyers, R. Sinclair, and M. E. Thomas,J. Vac. Sci. Technol. B 2, 781 (1984).Google Scholar
  47. 47.
    S. Sambasivan and W. T. Petuskey,J. Mater. Res. 9, 2362 (1994).Google Scholar
  48. 48.
    W. J. J. Wakelkamp,Diffusion and Phase Relations in the System Ti-Si-C and Ti-Si-N, Dissertation, Eindhofen University of Technology, 1991.Google Scholar
  49. 49.
    H. J. Seifert,Thermodynamik und Phasengleichgewichte im System Ti-Si-C-N, Dissertation, Universität Stuttgart, 1993.Google Scholar
  50. 50.
    C. Sarioglu,Oxidation Behavior of MoSi 2 and MoSi 2-Based Composites at 500–1200°C, MS thesis, University of Pittsburgh, 1993.Google Scholar
  51. 51.
    P. J. Meschter,Met. Trans. 23A, 1763 (1992).Google Scholar
  52. 52.
    H. J. Grabke and G. H. Meier,Oxid. Met. 44, 147 (1995).Google Scholar
  53. 53.
    I. I. Kornilov and V. V. Glasova,Interaction of Refractory Transition Metals with Oxygen, (“Nauka,” Moskau, 1967).Google Scholar
  54. 54.
    R. Hörbe, O. Knacke, and K. E. Prescher,Erzmetall 14, 232 (1961).Google Scholar
  55. 55.
    E. P. EerNisse,Appl. Phys. Lett. 30, 290 (1977).Google Scholar
  56. 56.
    N. Birks and F. S. Pettit,Mat. Sci. Eng. A 143, 187 (1991).Google Scholar
  57. 57.
    J. Schlichting,Glastechn. Ber. 51, 21 (1978).Google Scholar
  58. 58.
    E. Fitzer and O. Rubisch,Elektrowärme 16, 163 (1958).Google Scholar
  59. 59.
    J. K. Srivastava, M. Prasad, and J. B. Wagner, Jr.,J. Electrochem. Soc. 132, 955 (1985).Google Scholar
  60. 60.
    H. A. Schaeffer, inEncyclopedia of Materials Science and Engineering, M. B. Bever, ed. (Pergamon Press, Oxford, 1986), p. 4393.Google Scholar
  61. 61.
    P. Kofstad,Nonstoichiometry, Diffusion, and Electrical Conductivity in Binary Metal Oxides (New York, 1972).Google Scholar
  62. 62.
    P. Kofstad,High Temperature Corrosion (New York, 1988).Google Scholar
  63. 63.
    S. Melsheimer, A. Rahmel, and M. Schütze,Oxid. Met., to be published.Google Scholar
  64. 64.
    W. J. Quadakkers, A. Elschner, H. Holsbrecher, K. Schmidt, W. Speier, and H. Nickel,Mikrochimica Acta 107, 197 (1992).Google Scholar
  65. 65.
    J. Jedlinski, M. J. Graham, G. I. Sproule, D. F. Mitchell, G. Borchardt, and A. Bernasik,Werkst. Korros. 46, 297 (1995).Google Scholar
  66. 66.
    N. S. Choudhury, H. C. Graham, and J. Hinze, inProperties of High Temperature Alloys, Z. A. Foroulis and F. S. Pettit, eds. (The Electrochem. Soc. 1976), p. 668.Google Scholar
  67. 67.
    C. Lang and M. Schütze,Oxid. Met.,46, 255 (1996).Google Scholar
  68. 68.
    S. Becker, A. Rahmel, M. Schorr, and M. Schütze,Oxid. Met. 38, 425 (1992).Google Scholar
  69. 69.
    H. Fietzek, Untersuchung der Hochtemperaturkorrosion von Titandisilicid mittels zeit- und t temperaturaufgelöster Röntgendiffraktometrie, Diplomarbeit Fachhochschule Karlsruhe, 1994.Google Scholar

Copyright information

© Plenum Publishing Corporation 1997

Authors and Affiliations

  • S. Melsheimer
    • 1
  • M. Fietzek
    • 2
  • V. Kolarik
    • 2
  • A. Rahmel
    • 3
  • M. Schütze
    • 3
  1. 1.A. T. Kearney Management ConsultantsDüsseldorfGermany
  2. 2.Fraunhofer-Institut für Chemische TechnologiePfinztalGermany
  3. 3.Karl-Winnacker-Institut der DECHEMA e.V.Frankfurt am MainGermany

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