Galvanic cells corrosion compared

Both resistance of the electrolyte and polarization of the electrodes limit the magnitude of current produced by a galvanic cell. For local-action cells on the surface of a metal, electrodes are in close proximity to each other consequently, resistance of the electrolyte is usually a secondary factor compared to the more important factor of polarization. When polarization occurs mostly at the anodes, the corrosion reaction is said to be anodically controlled (see Fig. 5.7). Under anodic control, the corrosion potential is close to the thermodynamic potential of the cathode. A practical example is impure lead immersed in sulfuric add, where a lead sulfate film covers the anodic areas and exposes cathodic impurities, such as copper. Other examples are magnesium exposed to natural waters and iron immersed in a chromate solution. 

Schematic of grain boundary region in a 2XXX alloy. Precipitation of the very-high-copper-content precipitates on the boundary causes a copper-depleted zone on either side of the boundary. The difference in the electrochemical potentials of the copper-depleted zone and the copper-rich matrix form a strong galvanic cell with a potential difference of about 0.12 V. Furthermore, the anodic copper-depleted zone is small in area compared with the area of the cathodic grain matrix, resulting in a high driving force for rapid intergranular corrosion. (Courtesy of Alcoa Technical Center, Edward L. Colvin.)...

The importance of concrete cracks in rebar corrosion has also been highlighted by Niirnberger. Both carbonation and chloride ion diffusion, two important processes associated with rebar corrosion, can proceed more rapidly into the concrete along the crack faces, compared with uncracked concrete. Niirnberger argued that corrosion in the vicinity of the crack tip could be accelerated further by crevice corrosion effects and galvanic cell formation. The steel in the crack will tend to be anodic relative to the cathodic (passive) zones in uncracked... 

Figure 6.12 compares the corrosion rates and potentials of an uncoupled and galvanically coupled differential aeration cell of equal electrode area. The corrosion rates were estimated by mixed potential theory. With two uncoupled electrodes, on the nitrogen side of the differential aeration cell the anodic reaction is iron dissolution ... 

Galvanic corrosion (also called "dissimilar metal corrosion" or wrongly "electrolysis") refers to corrosion damage induced when two dissimilar materials are coupled in a corrosive electrolyte. In a bimetallic couple, the less noble material becomes the anode and tends to corrode at an accelerated rate, compared with the uncoupled condition and the more noble material will act as the cathode in the corrosion cell. 

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