Abstract
The growth of thin (0–200 Å) oxide films on iron at 200 and 300 °C has been studied as a function of time and oxygen partial pressure using proton-induced X-ray emission (PIXE) and Auger electron spectroscopy (AES). Oxidation was found to be initially retarded by sulfur which had segregated onto the iron surfaces during preoxidation annealing, but only if the iron surface contained the maximum or near-maximum sulfur coverage (ca. one-half monolayer). During and immediately following the oxygen-sulfur interaction, oxide buildup appeared to be limited by a surface reaction (adsorption, ionization, or dissociation). For most of the oxidation period, pressure-dependent logarithmic oxide growth was observed at 200°C, and pressure-independent parabolic oxide growth at 300°C. Interpretation of the data indicated that oxide growth at 200°C may be limited by quantum mechanical tunneling of electronic species through the previously formed oxide film, and oxide growth at 300°C may be limited by ionic diffusion through the previously formed oxide film. Comparison of AES and PIXE data indicated that the oxide films formed at 200°C were uniform in thickness over the surface of the metal, whereas films formed at 300°C had relatively thin areas where sulfur had remained.
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References
W. E. Boggs, R. H. Kachik, and G. E. Pellissier,J. Electrochem Soc. 112, 539 (1965).
P. B. Sewell and M. Cohen,J. Electrochem. Soc. 111, 501 (1964).
P. B. Sewell and M. Cohen,J. Electrochem. Soc. 111, 508 (1964).
P. B. Sewell, D. F. Mitchell, and M. Cohen,Surf. Sci. 33, 535 (1972).
A. G. Goursat and W. W. Smeltzer,J. Electrochem. Soc. 120, 390 (1973).
R. J. Hussey and M. Cohen,Corros. Sci. 11, 699 (1971).
R. J. Hussey and M. Cohen,Corros. Sci. 11, 713 (1971).
E. J. Caule, K. H. Buob, and M. Cohen,J. Electrochem. Soc. 108, 829 (1961).
D. E. Davies, U. R. Evans, and J. N. Agar,Proc. R. Soc. 224, 443 (1954).
M. J. Graham and M. Cohen,J. Electrochem. Soc. 116, 1430 (1969).
Z. Szklarska-Smialowska and J. Jurek,Corrosion 32, 294 (1976).
N. Cabrera and N. F. Mott,Rep. Prog. Phys. 12, 163 (1949).
A. T. Fromhold, Jr. and E. L. Cook,Phys. Rev. 175, 877 (1968).
M. J. Graham, S. I. Ali, and M. Cohen,J. Electrochem. Soc. 117, 513 (1970).
A. M. Morgan and D. A. King,Surf. Sci. 23, 259 (1970).
J. Kruger, and H. T. Yolken,Corrosion 20, 29t (1964).
D. J. Young and M. J. Dignam,Oxid. Met. 5, 241 (1972).
C. F. Brucker and T. N. Rhodin,Surf. Sci. 57, 523 (1976).
G. W. Simmons and D. J. Dwyer,Surf. Sci. 48, 373 (1975).
A. J. Melmed and J. J. Carroll,J. Vac. Sci. Technol. 10, 164 (1972).
A. J. Pignocco and G. E. Pellissier,Surf. Sci. 7, 261 (1967).
J. M. Khan, D. L. Potter, and R. D. Worley,J. Appl. Phys. 37, 564 (1966).
R. R. Hart, F. W. Reuter III, H. P. Smith, and J. M. Khan,Phys. Rev. 179, 4 (1969).
G. C. Allen, I. T. Brown, and R. K. Wild,Oxid. Met. 12, 83 (1978).
K. Ueda and R. Shimizu,Surf. Sci. 43, 77 (1974).
W. E. Boggs, R. H. Kachik, and G. E. Pellissier,J. Electrochem. Soc. 114, 32 (1967).
N. Ramasubramanian, P. B. Sewell, and M. Cohen,J. Electrochem. Soc. 115, 12 (1968).
F. P. Fehlner and N. F. Mott,Oxid. Met. 2, 59 (1970).
I. M. Ritchie and G. L. Hunt,Surf. Sci. 15, 524 (1969).
R. Ghez,J. Chem. Phys. 58, 1838 (1973).
T. B. Grimley and B. M. W. Trapnell,Proc. R. Soc. A 234, 405 (1956).
A. T. Fromhold, Jr.,J. Phys. Chem. Solids 24, 1309 (1963).
N. F. Mott,Trans. Faraday Soc. 39, 472 (1940).
A. T. Fromhold, Jr. and E. L. Cook,Phys. Rev. 158, 600 (1967).
E. J. W. Verwey and P. W. Haayman,Physica 8, 979 (1941).
D. S. Tannhauser,J. Phys. Chem. Solids 23, 25 (1962).
A. T. Fromhold, Jr. and E. L. Cook,Phys. Rev. 163, 650 (1967).
K. F. Young and H. P. R. Frederikse,J. Phys. Chem. Ref. Data 2, 313 (1973).
Handbook of Chemistry and Physics, 44th ed. (CRC Press, Cleveland, 1963) pp. 2276–2280.
Handbook of Materials Science, Vol. III,Nonmetallic Materials and Applications, C. T. Lynch ed. (CRC Press, Cleveland, 1975), pp. 123–126.
C. J. Powell,Surf. Sci. 44, 29 (1974).
R. K. Wild,Corros. Sci. 17, 87 (1977).
J. Crank,The Mathematics of Diffusion (Oxford, Oxford, 1957), p 31, Eq. (3.15).
S. J. Wang and H. J. Grabke,Z. Metals 61, 597 (1970).
M. Aucouturier and M. Suzuki,Trans. Iron Steel Inst. Japan 7, 191 (1967).
W. E. Swartz, Jr. and D. M. Holloway,Appl. Spectrosc. 31, 210 (1977).
C. Leygraf and S. Ekelund,Surf. Sci. 40, 609 (1973).
T. J. Driscoll and P. B. Needham, Jr.,Oxid. Met. 13, 283 (1979).
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Driscoll, T.J. The initial oxidation of iron at 200° and 300° C and the effect of surface sulfur. Oxid Met 16, 107–131 (1981). https://doi.org/10.1007/BF00603747
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DOI: https://doi.org/10.1007/BF00603747