Influence of Incorporated Cl− in NiO on the Pitting Susceptibility of Nickel

Abstract
The pitting susceptibility of nickel in 0.08M Cl solutions (pH 4.0 ) has been determined by both potentiodynamic and potentiostatic techniques, the former giving a pitting potential and the latter an induction time, , for pit initiation. The potentiostatic approach is preferred because of the good reproducibility of results. Samples were prepassivated in non‐Cl or Cl containing solutions and then potentiostatically polarized in 0.08M Cl at different potentials and measured. For either pretreatment, decreased exponentially as the potential of pitting increased, i.e., . Oxides on samples prepassivated in Cl solution contain incorporated Cl and are significantly more resistant to pitting than those formed in Cl‐free solutions. This increase in pitting resistance for the Cl‐treated samples is in contrast to their decreased resistance to open‐circuit breakdown. Cl incorporation results in ∼2% expansion of the lattice leading to a more defective and thus less stable film towards open‐circuit breakdown. The results strongly suggest that Cl incorporated in the oxide lattice (as distinct from Cl in the electrolyte) is not a precursor to pit initiation since it actually increases the resistance to pitting.
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