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Title: Zinc Treatment Effects on Corrision Behavior of 302 Stainless Steel in High Temperature, Hydrogenated Water

Authors:
;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930097
Report Number(s):
BNL-80735-2008-JA
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Corrosion Science; Journal Volume: 48; Journal Issue: 9
Country of Publication:
United States
Language:
English
Subject:
national synchrotron light source

Citation Formats

Ziemniak,S., and Hanson, M. Zinc Treatment Effects on Corrision Behavior of 302 Stainless Steel in High Temperature, Hydrogenated Water. United States: N. p., 2006. Web. doi:10.1016/j.corsci.2005.10.014.
Ziemniak,S., & Hanson, M. Zinc Treatment Effects on Corrision Behavior of 302 Stainless Steel in High Temperature, Hydrogenated Water. United States. doi:10.1016/j.corsci.2005.10.014.
Ziemniak,S., and Hanson, M. Sun . "Zinc Treatment Effects on Corrision Behavior of 302 Stainless Steel in High Temperature, Hydrogenated Water". United States. doi:10.1016/j.corsci.2005.10.014.
@article{osti_930097,
title = {Zinc Treatment Effects on Corrision Behavior of 302 Stainless Steel in High Temperature, Hydrogenated Water},
author = {Ziemniak,S. and Hanson, M.},
abstractNote = {},
doi = {10.1016/j.corsci.2005.10.014},
journal = {Corrosion Science},
number = 9,
volume = 48,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}
  • Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 C were found to lower the corrosion rate of austenitic stainless steel (UNS S30400) by about a factor of five, relative to a non-zinc baseline test after 10,000 hr. Characterizations of the corrosion oxide layer via grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy in combination with argon ion milling and target factor analysis, confirmed the presence of two spinel oxide phases and minor amounts of recrystallized nickel. Based on the distribution of the three oxidized alloying constituents (Fe, Cr, Ni) with respect tomore » depth and oxidation state, it was concluded that: (a) corrosion occurs in a non-selective manner, but approximately 30% of the oxidized iron is released to the water, and (b) the two spinel oxides exist as a ferrite-based outer layer (Ni{sub 0.1}Zn{sub 0.6}Fe{sub 0.3})(Fe{sub 0.95}Cr{sub 0.05}){sub 2}O{sub 4} on top of a chromite-based inner layer (Ni{sub 0.1}Zn{sub 0.2}Fe{sub 0.7})(Fe{sub 0.4}Cr{sub 0.6}){sub 2}O{sub 4}. These results suggest that immiscibility in the Fe{sub 3}O{sub 4}-ZnFe{sub 2}O{sub 4} binary may play a role in controlling the zinc content of the outer layer. On the other hand, the lower corrosion rate caused by zinc additions is believed to be a consequence of corrosion oxide film stabilization due to the substitution reaction equilibrium: z Zn{sup 2+}(aq) + FeCr{sub 2}O{sub 4}(s) {approx} z Fe{sup 2+}(aq) + (Zn{sub z}Fe{sub 1-z})Cr{sub 2}O{sub 4}(s). The liquid-solid distribution coefficient for the reaction, defined by the ratio of total zinc to iron ion concentrations in solution divided by the Zn(II)/Fe(II) ratio in the solid, z/(1-z), was found to be 0.184. This interpretation is consistent with the benefits of zinc treatment being concentration dependent.« less
  • Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 C were found to reduce the corrosion rate of Alloy 600 (UNS N06600) by about 40% relative to a non-zinc baseline test [2]. Characterizations of the corrosion oxide layer via SEM/TEM and grazing incidence X-ray diffraction confirmed the presence of a chromite-rich oxide phase and recrystallized nickel. The oxide crystals had an approximate surface density of 3500 {micro}m{sup -2} and an average size of 11 {+-} 5 nm. Application of X-ray photoelectron spectroscopy with argon ion milling, followed by target factor analyses, permitted speciatedmore » composition vs. depth profiles to be obtained. Numerical integration of the profiles revealed that: (1) alloy oxidation occurred non-selectively and (2) zinc(II) ions were incorporated into the chromite-rich spinel: (Zn{sub 0.55}Ni{sub 0.3}Fe{sub 0.15})(Fe{sub 0.25}Cr{sub 0.75}){sub 2}O{sub 4}. Spinel stoichiometry places the trivalent ion composition in the single phase oxide region, consistent with the absence of the usual outer, ferrite-rich solvus layer. By comparison with compositions of the chromite-rich spinel obtained in the non-zinc baseline test, it is hypothesized that zinc(II) ion incorporation was controlled by the equilibrium for 0.55 Zn{sup 2+}(aq) + (Ni{sub 0.7}Fe{sub 0.3})(Fe{sub 0.3}Cr{sub 0.7}){sub 2}O{sub 4}(s) {r_equilibrium} 0.40 Ni{sup 2+}(aq) + 0.15 Fe{sup 2+}(aq) + (Zn{sub 0.55}Ni{sub 0.3}Fe{sub 0.15})(Fe{sub 0.3}Cr{sub 0.7}){sub 2}O{sub 4}(s). It is estimated that only 8% of the Ni(II) ions generated during non-selective oxidation of the alloy were retained as Ni(II) in the corrosion layer; the remainder either recrystallized to Ni(0) (38%) or were released to the aqueous phase (54%).« less
  • The corrosion behavior of an austenitic stainless steel (UNS S30400) has been characterized in a 10,000 hour test conducted in hydrogenated, ammoniated water at 260 C. The corrosion kinetics were observed to follow a parabolic rate dependency, the parabolic rate constant being determined by chemical descaling to be 1.16 mg dm{sup -2} hr{sup -1/2}. X-ray photoelectron spectroscopy, in combination with argon ion milling and target factor analysis, was applied to provide an independent estimate of the rate constant that agreed with the gravimetric result. Based on the distribution of the three oxidized alloying constituents (Fe, Cr, Ni) with respect tomore » depth and elemental state, it was found that: (a) corrosion occurs in a non-selective manner, and (b) the corrosion film consists of two spinel oxide layers--a ferrite-based outer layer (Ni{sub 0.2}Fe{sub 0.8})(Fe{sub 0.95}Cr{sub 0.05}){sub 2}O{sub 4} on top of a chromite-based inner layer (Ni{sub 0.2}Fe{sub 0.8})(Cr{sub 0.7}Fe{sub 0.3}){sub 2}O{sub 4}. These compositions agree closely with the solvi phases created by immiscibility in the Fe{sub 3}O{sub 4}-FeCr{sub 2}O{sub 4} binary, implying that immiscibility plays an important role in the phase separation process.« less
  • Samples of austenitic stainless steel 18-10 were exposed to different surface treatment (milling, machine rectification, paper polishing, and electrolytic polishing). The autoclave tests in water (300 deg C) and in water vapor (400 deg C, 200 kg/cm/sup 2/) comprised periods up to 2000 hr. The behavior of the electrolytically polished samples was sharply drstinguished from samples having other treatment. But, whereas the electrolytic polishing causes a very significant improvement in water at 300 deg C, the treatment has no effect in vapor at 400 deg C. (tr-auth)