Passivating potential concentration increase

In the case of the stainless steels, or other readily passivated metals, the rapid reduction of dissolved oxygen on the freely exposed surface will be sufficient to exceed the critical current density so that the metal will become passive with a potential greater than whereas the metal within the crevice will be active with a potential less than. The passivation of the freely exposed surface will be facilitated by the rise in pH resulting from oxygen reduction, whilst passivation within the crevice will be impeded by the high concentration of Cl ions (which increases the critical current density for passivation) and by the H ions (which increases the passivation potential E, see Section 1.4). 

Increasing concentrations of bicarbonate tended to raise the breakdown potentials but also increased the corrosion potentials. This, in combination with a high chloride concentration, high bicarbonate concentrations may raise the corrosion potentials such that they border on passivation breakdown. The increase in hysteresis loop size on potentiodynamic cycles with increasing bicarbonate concentration shows a lowered resistance to pitting attack and crevice corrosion. 

On the other hand, the passivation model, proposed by Palik et al. [80, 149], attributed the etch rate reduction to the easier formation of an oxide film on highly doped silicon. It is supported by a number of experimental observations. First, the difference between passivation potential and OCP decreases with increasing doping concentration, implying easier passivation... 

Metal atoms on the metal surface, as mentioned earlier, are soft acid, and hence they combine with anions of soft base on the metal surface. Once these metal surface atoms are ionized, they form metal ions such as iron ions and aluminum ions, and the metal surface turns to be hard acid. The metal ions then combine with anions of hard base such as hydroxide ions, OH, oxide ions, 02, and sulfate ions, SO4, to form insoluble metal oxides and salts of ionic bonding character. The two-dimensional concentration of surface metal ions increases with the electrode potential of the metal, and hence the metal surface gradually becomes harder in the Lewis acidity with increasing electrode potential until it combines with anions of hard base such as oxide ions to form a metal oxide film adhering firmly to the metal surface. The passivation potential of a metal is thus regarded as a threshold potential where the metal surface grows hard enough in the Lewis acidity to combine with a hard base of oxide ions. 

The effect of acid concentration on polarization of active-passive metals is shown in Fig. 4.8. Higher hydrogen ion concentration increases the critical anodic current density and decreases the passive potential range. Severe corrosion conditions present at higher acidity also increase current densities and corrosion rates at all potentials. Figure 4.9 presents the data for iron passivation in phosphoric acid/phosphate buffer solutions of... 

FIGURE 15.12 Schematic Evans diagram illustrating the influence of the rate of the reduction reaction (dotted lines) on active-passive behavior of a metal (solid line). ,ed> reversible potential for the reduction reaction oi, 02, 03, increasing exchange current densities for the reduction reaction (m/m+)> reversible potential for the M/M couple corr(i) and corr(2) are stable corrosion potentials. Concentration polarization is assumed to be absent. 

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