Abstract
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 [S.E. Ziemniak, M. Hanson, Corros. Sci., in press, doi:10.1016/j.corsci.2005.01.006]. 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 μm −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 speciated composition versus 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 0.55Ni 0.3Fe 0.15)(Fe 0.25Cr 0.75) 2O 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 2 + ( aq ) + ( Ni 0.7 Fe 0.3 ) ( Fe 0.3 Cr 0.7 ) 2 O 4 ( s ) ⇄ 0.40 Ni 2 + ( aq ) + 0.15 Fe 2 + ( aq ) + ( Zn 0.55 Ni 0.3 Fe 0.15 ) ( Fe 0.3 Cr 0.7 ) 2 O 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%).
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