Passivity transition region

Fig. 61. Cluster pattern observed during the electrodissolution of a Fe ring electrode in the active/passive transition region under potentiostatic conditions. The RE was located in the plane of the WE. (a) and (b) Snapshots taken during two successive oscillations of the total current, (c) Spatiotemporal plot of the azimuthal intensity. (Reproduced with permission from B. J. Green and J. L. Hudson, Phys. Rev. E 63 (2001) 026214, (2001) by the American Physical Society).

Figure 4. 16. Impedance spectra for iron in 1M H2SO4 at various potentials within the active dissolution and active-to-passive transition regions as determined using a negative impedance converter (NIC). Impedance values are given in ohms (electrode diameter = 0.5 cm), and the arrows indicate the direction of decreasing frequency. (After Epelboin et al. [1975]).

The fluctuations of anodic current were investigated in a different way by Podesta et al. [20], who showed that in an H2SO4 (1 M) chloride-containing solution a high sulfur-bearing steel (AISI 303) exhibits some anodic current oscillations in a close potential range determined at the active-passive transition region. These oscillations are kept undamped for a particular value of the electrode potential at... 

Initially, the curve conforms to the Tafel equation and curve AB which is referred to as the active region, corresponds with the reaction Fe- Fe (aq). At B there is a departure from linearity that b omes more pronounced ns the potential is increased, and at a potential C the current decreases to a very small value. The current density and potential at which the transition occurs are referred to as the critical current density, and the passivation potential Fpp, respectively. In this connection it should be noted that whereas is determined from the active to passive transition, the Flade potential Ef is determined from the passive to active transition... 

Fig. 1.39 Schematic anodic polarisation curve for a metal. Region AB describes active dissolution of the metal. BC is the active/passive transition, with passivation commencing at B. Passivation is complete only at potentials higher than C. The metal is passive over the range CD...

Another contribution of the potentiostatic technique to s.c.c. studies has been the report that cracking prevails essentially at two potential levels for metals showing an active-passive transition. These potentials are located near the top and bottom of the passive region. Along the same lines, Uhlig and his co-workers have determined critical ranges of potential for s.c.c. , although their theoretical interpretation differs from that of the other references cited. 

Active Loop the region of an anodic polarisation curve of a metal comprising the active region and the active-passive transition. 

The limits of transition region BC are not very distinct and depend on the experimental conditions. At high potential scan rates (short duration of the experiment), passivation will start later (i.e., potential will be somewhat more positive, and for a short time the currents may be higher than i ). 

In the presence of oxidizing species (such as dissolved oxygen), some metals and alloys spontaneously passivate and thus exhibit no active region in the polarization curve, as shown in Fig. 6. The oxidizer adds an additional cathodic reaction to the Evans diagram and causes the intersection of the total anodic and total cathodic lines to occur in the passive region (i.e., Ecmi is above Ew). The polarization curve shows none of the characteristics of an active-passive transition. The open circuit dissolution rate under these conditions is the passive current density, which is often on the order of 0.1 j.A/cm2 or less. The increased costs involved in using CRAs can be justified by their low dissolution rate under such oxidizing conditions. A comparison of dissolution rates for a material with the same anodic Tafel slope, E0, and i0 demonstrates a reduction in corrosion rate... 

For the case shown in Fig. 8, the anodic and cathodic Evans lines intersect at three points. The polarization curve for this situation appears unusual, although it is fairly commonly observed with CRAs. At low potentials, the curve is identical to that shown in Fig. 5. However, just above the active-passive transition, another Ecmi appears followed by a loop and yet a third ECljU before the passive region is observed. The direction (anodic or cathodic) of the applied current density for each region shown in the polarization curve of Fig. 8 is indicated, showing that the loop consists of cathodic current. The origin of the cathodic loop is the... 

Passive regions close to active-passive transitions as for nickel-chromium-iron alloy 600 or steel in caustic solutions (Figure 6.58).143 144... 

After a first sweep towards the positive which is not shown in the diagram and which is dominated by the dissolution of the airfoimed oxide layer, a sweep in the positive direction starts at the negative potential end of the cathodic part of the curve. In the first part, from A to the corrosion potential B where the curve becomes anodic, Hj evolution is the most important process. In this region both samples are very similar. The corrosion potential at B is nearly the same for unimplanted, with Cr implanted and with Ar bombarded iron. From B to C the anodic dissolution of the metal takes place and at C the active to passive transition starts. Here one observes the most significant difference between the two samples. The critical current density for passivation of implanted iron is more than one order of... 

The extents of the passive potential regions have been reduced for all materials except pure chromium, and the curves for 90 and 100 wt% nickel indicate that an active-to-passive state transition no longer occurs. The magnitude of the influence of the chloride ions is emphasized by comparing the current densities for each alloy at 200 mV (SHE) with and without chloride ions present. 

In the transition region between active dissolution and passive behavior a transformation process from a film of adsorbed iron hydroxide species into the passive oxide film takes place. . The potential when this transformation is completed is called the Flade potential p. For iron the transformation process may be formulated schematically by the equation ... 

Based on the same principle, the corrosion resistance of metals and alloys with polarization curves having active-passive transitions can be greatly improved by an impressed anodic current initially equal to or greater than the critical current for passivity. The potential of the metal moves into the passive region... 

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