Abstract
In an acidic nitrate solution containing no less than 10−4 mol/l Ag+, potentiostatic anodic dissolution of silver from its alloy with gold (up to 35 at. %) already in about 10 s is limited by the solid-phase mutual diffusion of the components. A number of diffusion-kinetic dissolution models taking into account contributions from the liquid-phase mass transfer, segregation in the surface layer, microroughness of the surface, shift of the alloy-solution interface, as well as the relaxation of nonequilibrium vacancies into a transient dissolution current are considered. The diffusivities and mutual diffusivities of the components, concentrations of nonequilibrium vacancies, and thickness of the diffusion zone estimated in terms of these models are compared. The effect of the overpotential and alloy composition is discussed. The main source of nonequilibrium monovacancies in the amount 14 orders as high as the equilibrium one is found to be the dissolution of silver. The efficiency of the sinks, among which the formation of bivacancies seemingly dominates, is not high, which predetermines the slowness of relaxation processes in the solid-phase diffusion zone.
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REFERENCES
Losev, V.V. and Pchelnikov, A.P., Itogi Nauki Tekhniki. Elektrokhimiya, 1979, vol. 15, p. 62.
Kaiser, H., Alloy Dissolution. Chemical Industries, New York: Basel, 1987, vol. 28 (Corrosion Mechanism), p. 85.
Marshakov, I.K., Vvedenskii, A.V., Kondrashin, V.Yu., and Bokov, G.A., Anodnoe rastvorenie i selektivnaya korroziya splavov (Anodic Dissolution and Selective Corrosion of Alloys), Voronezh: Izd. VGU, 1988.
Losev, V.B., Pchelnikov, A.P., and Marshakov, A.I., Itogi Nauki Tekhniki. Elektrokhimiya, 1984, vol. 21, p. 77.
Wen, C.J., Ho, C., Boukamp, B.A., et al., Int. Metals Rev., 1981, vol. 26, no.6, p. 253.
Lantelme, F., Iwadate, Y., Shi, Y., et al., J. Electroanal. Chem., 1985, vol. 107, no.2, p. 229.
Vvedenskii, A.V., Marshakov, I.K., and Storozhenko, V.N., Elektrokhimiya, 1994, vol. 30, no.4, p. 459.
Vvedenskii, A.V., Stekolnikov, Yu.A., Tutukina, N.M., and Marshakov, I.K., Elektrokhimiya, 1982, vol. 18, no.12, p. 1646.
Bobrinskaya, E.V., Vvedenskii, A.V., and Marshakov, I.K., Elektrokhimiya, 1999, vol. 35, no.10, p. 1202.
Bobrinskaya, E.V. and Vvedenskii, A.V., Elektrokhimiya, 2001, vol. 37, no.9, p. 1102.
Bokshtein, B.S., Bokshtein, S.Z., and Zhukhovitskii, L.A., Termodinamika i kinetika diffuzii v tverdykh telakh (Thermodynamics and Kinetics of Diffusion in Solids), Moscow: Metallurgiya, 1974.
Physical Metallurgy, Cahw, R.W. and Haasen, P., Eds., Amsterdam: North-Holland Physics, 1983, vols. 1 and 2.
Geguzin, Ya.E., Diffuzionnaya zona (Diffusion Zone), Moscow: Nauka, 1973.
Borovskii, I.K., Gurov, K.P., Marchukova, I.D., and Ugaste, Yu.E., Protsessy vzaimnoi diffuzii v splavakh (Mutual Diffusion Processes in Alloys), Moscow: Nauka, 1979.
Bokshtein, B.S., Kopetskii, I.V., and Shvindlerman, L.S., Termodinamika i kinetika granits zeren v metallakh (Thermodynamics and Kinetics of Grain Boundaries in Metals), Moscow: Metallurgiya, 1986.
Kaibyshev, O.A. and Valiev, R.Z., Granitsy zeren i svoistva metallov (Grain Boundaries and Metal Properties), Moscow: Metallurgiya, 1984.
Bokshtein, S.Z., Stroenie i svoistva metallicheskikh splavov (Structure and Properties of Metal Alloys), Moscow: Metallurgiya, 1971.
Suvorov, A.L., Defekty v metallakh (Defects in Metals), Moscow: Nauka, 1984.
Ermakov, S.S., Fizika metallov i defekty kristallicheskogo stroeniya (Physics of Metals and Defects of Crystalline Structure), Leningrad: Izd. LGU, 1989.
Vvedenskii, A.V., Marshakov, I.K., Stekolnikov, Yu.A., and Anokhina, I.V., Zashch. Met., 1985, vol. 21, no.3, p. 346.
Anokhina, I.V., Vvedenskii, A.V., Stekolnikov, Yu.A., and Marshakov, I.K., Zashch. Met., 1986, vol. 22, no.5, p. 705.
Zartsyn, I.D., Vvedenskii, A.V., and Marshakov, I.K., Elektrokhimiya, 1994, vol. 30, no.5, p. 544.
Wachter, A., J. Amer. Chem. Soc., 1932, vol. 54, p. 4609.
Wagner, C. and Engelhgard, G., Z. Phys. Chem., 1932, vol. 159, p. 241.
Kozaderov, O.A. and Vvedenskii, A.V., Kondens. sredy mezhfaz. granitsy, 2003, vol. 5, no.1, p. 32.
Kozaderov, O.A. and Vvedenskii, A.V., Zashch. Met., 2005, vol. 41, no.3, p. 1.
Pickering, H.W. and Wagner, C., J. Electrochem. Soc., 1967, vol. 114, no.7, p. 698.
Raleigh, D.O. and Growe, H.R., J. Electrochem. Soc., 1967, vol. 116, no.1, p. 40.
Larikov, L.N. and Isaichev, V.I., Diffuziya v metallakh i splavakh (Diffusion in Metals and Alloys), Kiev: Naukova Dumka, 1987.
Orlov, A.N. and Trushin, Yu.V., Energii tochechnykh defektov v metallakh (Energies of Point Defects in Metals), Moscow: Energoizdat, 1983.
Scheblykina, G.E., Bobrinskaya, E.V., and Vvedenskii, A.V., Zashch. Met., 1998, vol. 34, no.1, p. 11.
Kozaderov, O.A. and Vvedenskii, A.V., Elektrokhimiya, 2001, vol. 37, no.8, p. 929.
Vvedenskii, A.V., Elektrokhimiya, 1991, vol. 27, no.2, p. 256.
Vvedenskii, A.V. and Marshakov, I.K., Electrochim. Acta, 1991, vol. 36, no.8, p. 905.
Vvedenskii, A.V. and Marshakov, I.K., Elektrokhimiya, 1995, vol. 31, no.2, p. 257.
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Translated from Zashchita Metallov, Vol. 41, No. 4, 2005, pp. 360–371.
Original Russian Text Copyright © 2005 by Kozaderov, Sazhneva, Koroleva, Vvedenskii.
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Kozaderov, O.A., Sazhneva, O.V., Koroleva, O.V. et al. Solid-Phase Diffusion at a Potentiostatic Dissolution of Silver Alloyed with Gold. Prot Met 41, 329–340 (2005). https://doi.org/10.1007/s11124-005-0047-7
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DOI: https://doi.org/10.1007/s11124-005-0047-7