Cyclic anodic passivation

F ie 7.9 Schematic representation of a cyclic anodic polarization curve of an active-passive material in a chloride-containing environment pitting potential ( pu) and protection potential ( p ) are identified [1]... 

ASTM G 61 Standard Test Method for Conducting Potentiodynamic Polarization Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys Provides information on conducting cyclic anodic polarization tests. Useful procedure for evaluating pitting and crevice corrosion susceptibility. Can be modified for other alloys that exhibit passive behavior. 

Upon an increase of the anodic reverse potential finally up to 8 V versus Li the cyclic voltammogran corresponding to Fig. 9 remains unchanged, showing that the passivating layer at the electrode also protects the solvents (PC and DME) from being oxidized. Subsequent deposition and dissolution of lithium at the passivated electrodes remains possible when the electrode is passivated but the cycling efficiency decreases. 

Mechanism 3 involves NiOH in at least three reactions, and Ni(OH)2 as the active Ni reactant in solution. Since increasing the concentration of the complex-ant(s) in solution will reduce the concentration of both unhydrolyzed and hydrolyzed metal ions, arguments of complexation cannot be readily employed to either support or discount this mechanism. However, it has been this author s experience in formulating electroless Co-P solutions with various complexants for Co2+ that improper complexation which results in even a faint precipitate of hydrolyzed cobalt ions yields an inactive electroless Co-P solution. Furthermore, anodic oxidation of hypo-phosphite at Ni anodes does not proceed at a significant rate under conditions where the surface is most probably covered with a passive film of nickel oxide [48], e.g. NiO.H20, which would be expected to oxidize the reducing agent via a cyclic redox mechanism. 

Figure 24 Schematic Evans diagram and polarization curve illustrating the origin of the negative hysteresis observed upon cyclic polarization for materials that do not pit. Line a represents the (unchanging) cathodic Evans line. Line b represents the anodic Evans line during the anodically directed polarization, while line c represents the anodic Evans line for the material after its passive film has thickened because of the anodic polarization. The higher corrosion potential observed for the return scan (E (back)) is due to the slowing of the anodic dissolution kinetics.

Anodic dissolution of hard alloys has been enhanced by the application of ultrasound, apparently because of the increase in cavitation and the hydrodynamic pressure resulting in an increase in current density. The cyclic nature of the hydrodynamic pressure helps to remove passivating oxide films from the surface of the workpiece, thereby raising the process efficiency. This increase in current density resulting from the application of ultrasonic vibrations was most evident in hard alloys containing appreciable quantities of Ti and Ta carbides [117]. 

The tip and substrate current spikes in Figure 46 are generally well correlated (particularly at times greater than 8 s), suggesting that the breakdown of the passive layer (substrate current) involves the release of Fe2+ from the iron surface, which was detected by reduction to Fe(0) at the tip UME. Evidence for the presence of Fe(0) at the tip came from the visual observation of a reddish-brown film at the electrode surface after such measurements and cyclic voltammograms (CVs) recorded with the tip positioned close to the iron surface, before and after a corrosion experiment. Prior to corrosion measurements, the tip CV displayed features consistent only with the reduction of TCA, while after corrosion the CV also showed a cathodic wave, possibly due to the reduction of Fe2+ to Fe and a corresponding anodic stripping peak. The latter occurred at the same potential as the anodic dissolution of iron, and was thus attributed to the reoxidation of Fe(0). Denuault and Tan (68,69) used a similar approach to identify the dissolution products for mild steel subjected to an acidic corrosive environment. In contrast to the work of Wipf and Still, the tip electrode was used only as a detector and not as an initiator of the corrosion process. CVs recorded with the tip placed close to the substrate detected the presence of Fe2+ and H2. 

Cyclic potentiodynamic polarization used in determining pitting potential consists of scanning the potential to more anodic and protection potentials during the forward and return scans and compare the behavior at different potentials under identical conditions. The polarization curve of an alloy (with or without coating showing active-passive behavior may be obtained in a chosen medium as a function of chloride concentration). E, or Ep represent pitting potential or breakdown potential,... 

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