Abstract
A review is presented of the history of the development of the Point Defect Model (PDM) for the growth and breakdown of passive films that form on the surfaces of reactive metals in contact with corrosive, condensed phase environments. The PDM has passed through three generations, with each successive generation addressing issues that have arisen from experiment. Thus, the first Generation model (PDM-I), which was developed in the late 1970s/early 1980s, assumed that the passive film was a single defective oxide layer that contained cation vacancies and oxygen vacancies that were generated and annihilated at the metal/film and film/solution interfaces. This model was inspired by the work by Wagner on high temperature oxidation. As with gas-phase systems, the film was assumed not to dissolve. However, it soon became evident that this model could not account for the properties of the passive state on metals in contact with aqueous environments and, accordingly a Generation II model (PDM-II) was developed to address these issues. PDM-II incorporated the bi-layer structure of the film comprising a defective oxide (or hydride) barrier layer that grows into the metal and an outer layer that forms by precipitation of material from the reaction of cations transmitted through the barrier layer with species in the environment (including water, CO 2−3 , HS−, etc.), introduced metal interstitials to the suite of defects, recognized barrier layer dissolution, and recognized the need to classify reactions as to whether they are lattice conservative or non-conservative. PDM-II has enjoyed considerable success and the author knows of no instance where it has been demonstrated to be at odds with experiment when confluence between experiment and theory has been demonstrated. A Generation III model (PDM-III) has been recently developed to extend the theory to those cases (e.g., the valve metals) where the outer layer is so resistive that it controls the impedance of the interface and hence the corrosion rate. A fourth generation model that will describe passivity on alloys is now under development. The experimental evidence upon which each generation is based is reviewed.
Similar content being viewed by others
References
Macdonald, D.D., Pure Appl. Chem., 1999, vol. 71, p. 951.
Uhlig H., in Passivity of Metals, Frankenthal, R.P. and Kruger, J., Eds., Princeton, NJ: The Electrochemical Society, 1978, p. 1.
Schönbein, C, Pogg. Ann., 1836, vol. 37, p. 390. Reprinted in 1965.
Faraday, M., Experimental Researches in Electricity, vol. 2, p. 234 (reprinted 1965), NY: Dover.
Schultze, J.W. and Lohrengel, M.M., Electrochim. Acta, 2000, vol. 45, p. 2499.
Olsson, C.-O.A. and D. Landolt, D., Electrochim. Acta, 2003, vol. 48, p. 1093.
Heiligenberg, S. (International Symposium on Passivity), Germany; Z. Elektrochem., 1958, vol. 62, pp. 619–827.
The Second International Symposium on Passivity, Toronto, Canada; J. Electrochem. Soc., 1963, vol. 110; ibid, 1964, vol. 111.
The Third International Symposium on Passivity, Cambridge, UK, 1970; Electrochim. Acta., 1970, vol. 15; ibid, 1971, vol. 16.
The Fourth International Symposium on Passivity, Airlie, VA; published as Passivity of Metals, Frankenthal, R.P. and Kruger, J., Eds., Princeton, NJ: The Electrochemical Society, 1978.
The Fifth International Symposium on Passivity, Bombannes, France, 1983; published as Passivity of Metals and Semiconductors, Froment, M., Ed., Amsterdam: Elsevier, 1983.
The Sixth International Symposium on Passivity, Sapporo, Japan, 1989; published as Passivity of Metals and Semiconductors, Sato, N. and Hashimoto, K., Eds., Oxford, UK: Pergamon Press, 1990.
The Seventh International Symposium on Passivity, Passivation of Metals and Semiconductors, Clausthal, Germany, 1994; published as a Special Issue of Mater. Sci. Forum, Heusler, K., Ed., 1995, pp. 185–188.
The Eighth International Symposium on Passivity of Metals and Semiconductors, Jasper, Alberta, Canada, May 9–14, 1999; Symposium Proceedings published by The Electrochemical Society, Ives, M.B., Ed., 2001.
Guntherschulze, A. and Betz, H., Z. Phys., 1931, vol. 68, p. 145.
Guntherschulze, A. and Betz, H., Z. Elekrochem., 1931, vol. 37, p. 726.
Guntherschulze, A. and Betz, H., Z. Phys., 1934, vol. 92, p. 367.
Verwey, E.J.W., Physica, 1935, vol. 2, p. 1059.
Cabrera, N. and Mott, N.F., Rep. Progr. Phys., 1948–1949, vol. 12, p. 163.
Fehlner, F.P. and Mott, N.F., Oxidat. Met., 1970, vol. 2, p. 59.
Young, L., Anodic Oxide Films, London: Academic Press, 1961.
Sato, N. and Cohen, M., J. Electrochem. Soc., 1964, vol. 111, p. 512.
Vetter, K.J., Electrochim. Acta, 1971, vol. 16, p. 1923.
Vetter, K.J. and Gorn, F., Electrochim. Acta, 1973, vol. 18, p. 321.
Kirchheim, R., Electrochim. Acta, 1987, vol. 32, p. 1619.
Chao, C.-Y., Lin, L.-F., and Macdonald, D.D., J. Electrochem. Soc., 1981, vol. 128, p. 1187.
Macdonald, D.D., Biaggio, S.R., and Song, H., J. Electrochem. Soc., 1992, vol. 139, p. 170.
Heusler, K.E., Corros. Sci., 1990, vol. 31, p. 597.
Engell, H.J., Electrochim. Acta, 1977, vol. 22, p. 987.
Sato, N., in Passivity of Metals, Frankenthal, R.P. and Kruger, J., Eds., Princeton, N.J.: The Electrochemical Society, 1978, p. 29.
Olsson, C.-O.A., Hamm, D., and Landolt, D., J. Electrochem. Soc., 2000, vol. 147, p. 4093.
Olsson, C.-O.A., Verge, M.-G., and Landolt, D., J. Electrochem. Soc., 2004, vol. 151, p. B652.
Verge, M.-G., Olsson, C.-O.A., and Landolt, D., Corros. Sci., 2004, vol. 46, p. 2583.
Macdonald, D.D., Theory of the Transpassive State, H. H. Uhlig Award Lecture, The Electrochemical Society Spring Meeting, San Francisco, CA, 2001.
Macdonald, D.D., The Holy Grail: Deterministic Prediction of Corrosion Damage Thousands of Years into the Future, Proc. Int. Workshop Pred. Long Term Corros. Behav. Nucl. Waste Systs. (Commissariat a l’Energie Atomique and Pennsylvania State University), Cadarache, France, Nov. 26–29 (2001); Euro. Fed. Corros. Publ., Ferron, D. and Macdonald, D.D., Eds., 2003, no. 36, pp. 75–90.
Tsuchiya, H., Fujimoto, S., Chihara, O., and Shibata, T., Electrochim. Acta, 2002, vol. 47, p. 4357.
Sunseri, C., Piazza, S., and DiQuarto, F., J. Electrochem. Soc., 1990, vol. 137, p. 2411.
Pensado-Rodrguez, O., Urquidi-Macdonald, M., Flores, J.R., and Macdonald, D.D., Bilayer Film Structure Modeling for Lithium Dissolution in Alkaline Solutions, in Passivity and Its Breakdown, Natishan, P.M. et al., Eds., Proc. Electrochem. Soc., 1997, vols. 97–26, p. 870.
Pensado-Rodriguez, O., Flores, J., Urquidi-Macdonald, M., and Macdonald, D.D., J. Electrochem. Soc., 1999, vol. 146, pp. 1326–1335.
Park, P., Urquidi-Macdonald, M., and Macdonald, D.D., ICONE (12th Int. Conf. Nucl. Eng., “Nuclear Energy—Powering the Future”), Hyatt Regency Crystal City, Arlington, VA, USA, April 25–29, 2004, Paper ICONE12-49098.
Tsuchiya, H., Fujimoto, S., Chihara, O., and Shibata, T., Electrochim. Acta, 2002, vol. 47, p. 4357.
Macdonald, D.D., Sun, A., Priyantha, N., and Jayaweera, P., J. Electroanal. Chem., 2004, vol. 572, p. 421.
Liu, J., Marx, B.M., and Macdonald, D.D., Analysis of Electrochemical Impedance Data for Iron in Borate Buffer Solutions, Nuclear Waste Management: Accomplishments of the Environmental Management Science Program, Wang, P. and Zachry, T., Eds.; ACS Symposium Series 943; Washington, DC: American Chemical Society, 2006.
Sikora, E. and Macdonald, D.D., Electrochim. Acta, 2002, vol. 48, p. 69.
Macdonald, D.D. and Cragnolino, G.A., Corrosion and Erosion-Corrosion of Steam Cycle Materials, in Water Technology for Thermal Power Systems, Cohen, P., Ed., New York, NY: ASME, 1989, Chapter 9.
Sikora, E., Sikora, J., and Macdonald, D.D., The Point Defect Model vs. the High Field Model for Describing the Growth of Passive Films, Herbert, K.R. and Thompson, G.E., Eds. (Proc. 7th Int. Symp. Oxide Films on Metals and Alloys VII), 1994, vols. 94–25, p. 139.
Eley, D.D. and Wilkinson, P.R., Proc. Roy. Soc (London) Ser. A, 1960, vol. 254, p. 327.
Macdonald, D., J. Electrochem. Soc., 1992, vol. 139, p. 3434.
Macdonald, D.D. and Engelhardt, G.R., Predictive Modeling of Corrosion, in Shreir’s Corrosion, Richardson, J.A. et al., Eds., 2010, vol. 2, pp. 1630–1679.
Wagner, C., J. Electrochem. Soc., 1952, vol. 99, p. 369.
Chan, D.Y.C., Healy, T.W, Supasiti, T., and Usui, S., J. Coll. Interface Sci., 2006, vol. 296, p. 150.
Yates, D.E., Levine, S., and Healy, T.W., J. Chem. Soc. Faraday I, 1974, vol. 70, p. 1807.
Yates, D.E. and Healy, T.W., J. Colloid Interface Sci., 1976, vol. 55, p. 9.
Chan, D.Y.C., Healy, T.W., Perram, J.W., and White L.R., J. Chem. Soc. Faraday I, 1975, vol. 71, p. 1046.
Healy, T.W. and White, L.R., Adv. Colloid Interface Sci., 1978, vol. 9, p. 303.
Ismail, K., Sikora, E., and Macdonald, D.D., J. Electrochem. Soc., 1998, vol. 145, p. 3141.
Bao, J. and Macdonald, D.D., J. Solid State Electrochem., in press.
Nordsveen, M., Nesic, S., Nyborg, R., and Stangeland, A., Corrosion, 2003, vol. 59, p. 443.
Rosas-Camacho, O., Urquidi-Macdonald, M., and Macdonald, D.D., ECS Trans., 2009, vol. 19, no. 29, p. 143.
Macdonald, D.D., Al-Rafaie, M., and Engelhardt, G.R., J. Electrochem. Soc., 2001, vol. 148, p. B343.
Urquidi-Macdonald M., and Macdonald, D.D., Transients in the Growth of Passive Films on High Level Nuclear Waste Canisters, Proc. Int. Workshop Pred. Long Term Corros. Behav. Nucl. Waste Systs. (Commissariat a l’Energie Atomique and Pennsylvania State University), Cadarache, France, Nov. 26–29, 2002, pp. 165–178.
Macdonald, D., J. Electrochem. Soc., 2006, vol. 153, p. B213.
Lee, J.-B., General Corrosion and Localized Corrosion of Waste Package Outer Barrier, Report ANL-EBSMD-000003 REV 01, Office of Civilian Radioactive Waste Management, US Dept. Energy, June 2003.
Jang, H.-J., Park, C.-J., and Kwon, H.-S., Met. Mater. Int., 2009, vol. 15, p. 57.
Jang, H.-J. and Kwon, H.-S., Trans. ECS, 2007, vol. 3, no. 24, p. 1.
Kirchheim, R., Heine, B., Fischmeister, H., Hofmann, S., Knote, K., and Stoltz, U., Corros. Sci., 1989, vol. 29, no. 7, p. 899.
Kamrunnahar, M., Bao, J.-E., and Macdonald, D.D., Corros. Sci., 2005, vol. 47, no. 12, p. 3111.
Lewis, J.E. and Plumb, R.C., J. Electrochem. Soc., 1958, vol. 105, p. 496.
Zhang, L., Macdonald, D.D., Sikora, E., and Sikora, J., J. Electrochem. Soc., 1998, vol. 145, p. 898.
Burstein, T. and Davenport, A.J., J. Electrochem. Soc., 1989, vol. 136, p. 936.
Macdonald, D.D. and Engelhardt, G.R., The Point Defect Model for Bi-Layer Passive Films, ECS Trans, 2010, vol. 28, no. 24, p. 123.
Ai, J., Chen, Y.-Z., Urquidi-Macdonald, M., and Macdonald, D.D., J. Electrochem. Soc., 2007, vol. 154, p. C52.
Ai, J., Chen, Y.-Z., Urquidi-Macdonald, M., and Macdonald, D.D., J. Electrochem. Soc., 2007, vol. 154, p. C43.
Macdonald, D.D. and Smedley, S.I., An Electrochemical Impedance Analysis of Passive Films on Ni(111) in Phosphate Buffer Solutions, Electrochim. Acta, 1990, vol. 135, p. 1949.
Zhang, L. and Macdonald, D.D., Segregation of Alloying Elements in Passive Systems. I. XPS Studies on the Ni-W System, Electrochim. Acta, 1998, vol. 43, p. 2661.
Zhang, L. and Macdonald, D.D., Segregation of Alloying Elements in Passive Systems. II. Numerical Simulation, Electrochim. Acta, 1998, vol. 43, p. 2673–2685.
Vankeerberghen, M., private communication, A JRT Meeting, ONDRAI-NIRAS, Brussels, Belgium, 2010.
Urquidi-Macdonald, M., Normand, B., Mendy, H., and Macdonald, D.D., to be published.
Jung, Y.W., Byun, J.S., Woo, D.H., and Kim, Y.D., Thin Solid Films, 2009, vol. 517, p. 3726.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in Russian in Elektrokhimiya, 2012, Vol. 48, No. 3, pp. 259–284.
The article is published in the original.
Rights and permissions
About this article
Cite this article
Macdonald, D.D. Some personal adventures in passivity—A review of the point defect model for film growth. Russ J Electrochem 48, 235–258 (2012). https://doi.org/10.1134/S1023193512030068
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1023193512030068