Abstract
The influence of shorting circuitry attachment between metal-oxide and oxideoxygen interfaces on the oxidation kinetics of copper, lithium-doped copper (Li: 400 ppm), and chromium-doped copper (Cr: 12 ppm) have been studied in dry air\((P_{O_2 } = 21.27kPa)\) in the temperature range of 523–1073 K. Oxide film or scale growth under short-circuiting as well as under normal oxidation conditions conforms to the parabolic rate law. The oxidation kinetics under short-circuiting resulted in decreased rates for Cu and Li-doped Cu up to a temperature of 773 K, while Cr-doped Cu exhibited an enhancement in rate compared to its normal oxidation in the same temperature range. However, above 873 K, all three systems under shorting circuitry attachment exhibited enhanced rates compared to their normal oxidation rates in conformity to the existing theoretical model. Use of additional resistances in series in the outer short-circuit Pt path have clearly established that below 773 K Mott's fieldinduced migration plays the most important role, while at elevated temperatures Wagner's electrochemical potential-gradient factor acts as the main driving force in the scale-growth process. The results have been interpreted on the basis of average defect concentration, the electrochemical potential gradient, electrical field gradient, and transport coefficient in the Cu2O layer.
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References
F. A. Kröger,The Chemistry of Imperfect Crystals,Vol. 3 (North-Holland, Amsterdam, 1974), p. 66.
W. H. Brattain,Rev. Modern Phys. 21, 203 (1951).
H. Dunwald, K. Hauffe, and C. Wagner,Z. Phys. Chem. 14B, 467 (1932).
H. Bloem,Philips Res. Repts. 13, 167 (1958).
S. Mrowec,Defects and Diffusion in Solids—An Introduction (Elsevier, Warszawa, 1980), p. 191.
J. Bardeen, W. H. Brattain, and W. Schokley,J. Chem. Phys. 14, 714 (1946).
P. Kofstad,Nonstoichiometry, Diffusion and Electrical Conductivity in Binary Metal Oxides (Wiley-Interscience, 1972), p. 328.
S. Mrowec and A. Stoklosa,Oxid. Met. 3, 291 (1971).
S. Mrowec, A. Stoklosa, and K. Godlewski,Crystal Lattice Defects 5, 239 (1971).
R. S. Toth, R. Klikson, and D. Trivich,Phys. Rev. 122, 482 (1961).
M. O'Keefe and W. J. Moore,J. Chem. Phys. 36, 3009 (1962).
W. J. Tomlinson and J. Yates,J. Phys. Chem. Solids 38, 1205 (1977).
V. Ananth, S. C. Bose, and S. C. Sircar,Scripta Met. 14, 687 (1980).
V. Ananth, S. C. Sircar, and S. K. Bose,Proc. Int. Conf. Corros. Sci. Tech. (ICMS '85), Calcutta S. K. Bose and U. K. Chatterjee eds. (Dept. of Met. Eng., I.I.T., Kharagpur, India, 1985), p. 320.
S. K. Bose, V. Ananth, and S. C. Sircar, Proc. 10th Congr. Metallic. Corros., Madras, Vol. 4 (Oxford and IBH, New Delhi, 1987), p. 3615.
S. K. Roy, S. K. Bose, and S. C. Sircar,Oxid. Met. 35, 1 (1991).
V. Ananth,Influence of Impressed Direct Current and Short-circuiting on the Oxidation of Copper and Iron and Reduction of Wüstite at High Temperatures, Ph.D. thesis (I.I.T., Kharagpur, India, 1985).
J. Xue and R. Dieckmann,J. Phys. Chem. Solids 51, 1263 (1990).
V. Ananth, S. C. Sircar, and S. K. Bose,Trans. Jpn. Inst. Metals 26, 123 (1985).
S. K. Roy, V. Ananth, and S. K. Bose,Oxid. Met. 43, 185 (1995).
P. J. Jorgensen,Oxidation of Metals and Alloys, D. L. Douglass, ed. (ASM, Metals Park, Ohio, 1971, p. 157.
P. Kofstad,High Temperature Oxidation of Metals (Wiley, New York, 1966), p. 135.
D. O. Raleigh,J. Electrochem. Soc. 113, 782 (1966).
P. Kofstad,High Temperature Corrosion (Elsevier Applied Science, London and New York, 1988), p. 199.
R. N. Patnaik, S. K. Bose, and S. C. Sircar,Br. Corros. J. 12, 57 (1977).
A. T. Fromhold,Theory of Metal Oxidation, Vols. I, II (North-Holland, Amsterdam, 1976, 1980), p. 204.
A. T. Fromhold,J. Phys. Chem. Solids 33, 95 (1972).
H. Schmalzried,Solid State Reactions, translated by A. D. Pelton (Academic Press, New York, 1974), pp. 163, 180.
J. H. Eriksen and K. Hauffe, 5th Scand. Corros. Congr., Copenhagen, 1968, p. 38-I.
C. Ilschener-Gensch and C. Wagner,J. Electrochem. Soc. 105, 198 (1958).
N. Cabrera and N. F. Mott,Rept. Progr. Phys. 12, 163 (1949).
C. Wagner,Z. Phys. Chem. B21, 25 (1933);B312, 447 (1936).
C. Wagner,Atom Movements (ASM, Cleveland, Ohio, 1951), p. 151.
A. T. Fromhold,J. Phys. Soc. Jpn. 48, 2022 (1980).
S. K. Roy,Kinetics of Oxidation of Copper and Its Alloys at Low and Intermediate Temperatures, Ph.D. thesis (I.I.T., Kharagpur, 1976).
S. K. Roy and S. C. Sircar, Proc. Second National Conf on Corrosion and Its Control, SEAST, Calcutta, India, 1979, p. 93.
Ref. 24., p. 186.
Ref. 1. p.103.
J. A. Leroux and E. Raub,Z. Anorg. Allgem. Chem. 188, 205 (1930).
S. K. Mitra,Influence of Short-Circuiting and Static Charge Supply on the Oxidation Kinetics of Cu, Cu−Li and Cu−Cr Systems in the Temperature Range of 523–1173 K, Ph.D. thesis I.I.T. Kharagpur, India, 1991).
F. Gesmundo and F. Viani,J. Electrochem. Soc. 128, 460, 470 (1981);129, 622 (1982).
N. F. Mott and R. W. Gurney,Electronic Processes in Inonic Crystals (Dover, New York, 1964), p. 178.
O. Kubaschewski and C. B. Alcock,Metallurgical Thermochemistry, 5th ed. (Pergamon Press, 1989), pp. 379, 382.
L. V. Azaroff and J. J. Brophy,Electronic Processes in Materials (McGraw-Hill, New York, 1963), p. 345.
K. Hauffe,Oxidation of Metals (Plenum Press, New York, 1965).
Ref. 5., p. 190.
Ref. 5., p. 189.
J. Bénard and J. Talbot,C.R. Acad. Sci. Paris 225, 411 (1948).
F. P. Fehlner and N. F. Mott,Oxidation of Metals and Alloys D. L. Douglass, ed. (ASM, Metals Park, Ohio, 1971), p. 37.
M. J. Graham, D. Caplan, and R. J. Hussey,Can. Met. Q. 18, 283 (1979).
P. K. Krishnamurthy and S. C. Sircar,Acta Met. 16, 1461 (1968).
S. K. Roy, P. K. Krishnamurthy, and S. C. Sircar,Acta Met. 18, 519 (1970).
S. C. Kuiry,Studies on Kinetics of Iodide Film Growth on Pb, Ag and Their Doped Varieties in Iodine Atmosphere, Ph.D. thesis (I.I.T. Kharagpur, India, 1995).
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Bose, S.K., Mitra, S.K. & Roy, S.K. Effect of short-circuiting on the oxidation kinetics of copper and its doped varieties in the temperature range of 523–1073 K. Oxid Met 46, 73–107 (1996). https://doi.org/10.1007/BF01046885
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DOI: https://doi.org/10.1007/BF01046885