Aeration cell

As discussed above, deposits can cause accelerated localized corrosion by creating differential aeration cells. This same phenomenon occurs with a biofilm. The nonuniform nature of biofilm formation creates an inherent differential, which is enhanced by the oxygen consumption of organisms in the biofilm. 

Figure 2.6 Differential aeration cell at a waterline. Water contains sodium chloride.

The oxidation products are almost insoluble and lead to the formation of protective films. They promote aeration cells if these products do not cover the metal surface uniformly. Ions of soluble salts play an important role in these cells. In the schematic diagram in Fig. 4-1 it is assumed that from the start the two corrosion partial reactions are taking place at two entirely separate locations. This process must quickly come to a complete standstill if soluble salts are absent, because otherwise the ions produced according to Eqs. (2-21) and (2-17) would form a local space charge. Corrosion in salt-free water is only possible if the two partial reactions are not spatially separated, but occur at the same place with equivalent current densities. The reaction products then react according to Eq. (4-2) and in the subsequent reactions (4-3a) and (4-3b) to form protective films. Similar behavior occurs in salt-free sandy soils. 

Both reactions indicate that the pH at the cathode is high and at the anode low as a result of the ion migration. In principle, the aeration cell is a concentration cell of H ions, so that the anode remains free of surface films and the cathode is covered with oxide. The J U curves in Fig. 2-6 for anode and cathode are kept apart. Further oxidation of the corrosion product formed according to Eq. (4-4) occurs at a distance from the metal surface and results in a rust pustule that covers the anodic area. Figure 4-2 shows the steps in the aeration cell. The current circuit is completed on the metal side by the electron current, and on the medium side by ion migration. 

Fig. 4-2 Schematic representation of the electrical and chemical processes in an aeration cell.

It is a consequence of the action of different pH values in the aeration cell that these cells do not arise in well-buffered media [4] and in fast-flowing waters [5-7]. The enforced uniform corrosion leads to the formation of homogeneous surface films in solutions containing Oj [7-9]. This process is encouraged by film-forming inhibitors (HCOj, phosphate, silicate, Ca and AP ) and disrupted by peptizing anions (CP, SO ") [10]. In pure salt water, no protective films are formed. In this case the corrosion rate is determined by oxygen diffusion [6,7,10]... 

Coatings of less noble metals than the substrate metal (e.g., Zn on Fe) are only protective if the corrosion product of the metal coating restricts the corrosion process. At the same time, the formation of aeration cells is hindered by the metal coating. No corrosion occurs at defects. Additional cathodic protection to reduce the corrosion of the metal coating can be advantageous. Favorable polarization properties and low protection current requirements are possible but need to be tested in individual cases. The possibility of damage due to blistering and cathodic corrosion must be heeded. 

Concentration cells have two similar electrodes in contact with a solution of differing composition. The two kinds of concentration cells are salt concentration cells and differential aeration cells [186]. 

Differential Aeration Cells. This type of concentration cell is more important in practice than is the salt concentration cell. The cell may be made from two electrodes of the same metal (i.e., iron), immersed completely in dilute sodium chloride solution (Figure 4-433). The electrolyte around one electrode (cathode) is thoroughly aerated by bubbling air. Simultaneously the electrolyte around the other electrode is deaerated by bubbling nitrogen. The difference in oxygen concentration causes a difference in potential. This, in turn, initiates the flow of current. This type of cell exists in several forms. Some of them are as follows [188]. 

Figure 4-434. Differential aeration cell illustrated by waterline corrosion. (From Ref. [165].)...

The deposit partially shields the steel surface, creating a differential aeration cell (Figure 4-435). 

Air—Water Interface. This is another good example of a differential aeration cell (Figure 4-436). Here the water at the surface contains more oxygen than the water slightly below the surface. This difference in concentration can cause preferential attack just below the waterline. 

Figure 53.4 Crevice corrosion driven by (a) a differential aeration cell and (b) a differential metal ion concentration cell...

Fig. 1.47 Early form of the Evans differential aeration cell . (Courtesy U. R. Evans)...

It is evident from this description of the operation of the differential aeration cell that other factors must be involved if the differential aeration... 

Fig. 1.48 Examples of differential aeration cells (a) and (b) Differential aeration cells formed by the geometry of a drop of NaCl solution on a steel surface (c) differential aeration cells formed by the geometry of a vertical steel plate partly immersed in a NaCl solution. Increasing concentrations of Na2 CO3 decrease the anodic area (d) until at a sufficient concentration attack is confined to the water line (e) (/) shows the membrane of corrosion products formed at water...

At first sight the mechanism of crevice corrosion appears to be simply the formation of a differential aeration cell in which the freely exposed metal outside the crevice is predominantly cathodic whilst the metal within the crevice is predominantly or solely anodic the large cathode current acts on the small anodic area thus resulting in intense attack. However, although differential aeration plays an important role in the mechanism, the situation in reality is far more complex, owing to the formation of acid within the crevice. 

Fig. 1.52 Mechanism of filiform corrosion showing how atmospheric oxygen and watCT enter the active head through the film (lacquer) and how water leaves through the inactive tail. This results in a high concentration of oxygen at the V -shaped interface between the tail and the head, and to a differential aeration cell (after Uhlig )...

Saraby-Reintjes, A., Differential Aeration Cell , 7. Electro. Chem. Interfacial Eiectrochem., 37. 357 (1972) C.A., 77, 55484f... 

The rate of water flow is also most important. This determines the supply of oxygen to the rusting surface, and may remove corrosion products that would otherwise stifle further rusting. A plentiful oxygen supply to the cathodic areas will stimulate corrosion, but so may smaller supplies at a slow rate of flow, if this leads to the formation of differential aeration cells (see Section 1.6). 

Cables are frequently laid in ducting for protection, but are still susceptible to corrosion by aeration cells set up between the cables and the duct walls, and to attack by corrosive solutions, especially from concrete ducts. They are also prone to corrosion by organic acids from wooden ducting, and to galvanic corrosion with iron supports. Damage by insects and animals may also occur... 

Both iron- and copper-based alloys are corroded more easily on either side of the neutral pH band. In low pH conditions e.g. due to carbon dioxide, the acidic environments attack the alloys readily, causing damage both at the points of initial corrosion and perhaps, consequentially, further along the system, by screening the surface with corrosion products and permitting the development of differential aeration cells. 

Soil corrosion does not lend itself readily to direct study in the laboratory. However, indirect methods involving the action of differential aeration cells have yielded valuable information in comparing the probable corrosivities of different soils towards steel. The details of this technique were described by Denison , Ewing , Schwerdtfeger, and by Logan, Ewing and Denison ... 

Although each form of concentration cell may be considered a discrete form of corrosion, in practice, more than one type may occur simultaneously. These forms of corrosion are all characterized by localized differences in concentration of hydrogen, oxygen, chloride, sulfate, and other minerals, but especially oxygen (producing the so-called differential oxygen concentration cell, or differential-aeration cell). The basic mechanisms surrounding each of these specific forms of concentration cell corrosion are discussed next. 

Stainless steel also is susceptible to crevice corrosion and deposit attack. Differential aeration cells, formed between stagnant and well-aerated areas on the metal surface, may promote rapid attack. 

These forms of corrosion are all characterized by localized differences in concentration of hydrogen, oxygen, chloride, sulfate, etc., but especially oxygen (producing the so-called differential oxygen concentration cell or differential aeration cell). 

Discontinuities in the corrosion product film result in differential aeration cells, leading to pitting corrosion. A pitting rate of 0.25-0.38 mm/yr on bare steel and 0.5 mm/yr on steel with mill scale has been observed. Assuming the average corrosion rate of 0.125 mm/yr, the pitting factor works out to be 2 to 3 for... 

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