Cathodic polarisation

Fig. 1.31 Shape of cathodic polarisation curve when transport overpotential is rate controlling, (a) Effect of velocity on ( l and corrosion rate, (b) effect of concentration on tY and corrosion rate and (c) effect of position and slope of anodic curve (after Stern...

Bardal, E., pH and Potential Measurements on Mild Steel and Cast Iron During Periodic Cathodic Polarisation at 20°C and 90°C , Corros. Sci., 11, 371 (1971)... 

Increase in velocity may increase the rate by bringing the cathode reactant more rapidly to the surface of the metal thus decreasing cathodic polarisation, and by removing metal ions thus decreasing anodic polarisation. 

Fig. 1.65 Potential/time curves for cathodically polarised and unpolarised iron in 1 0 n NaCl at 25 C. Curve a unpolarised Fe curve b Fe polarised cathodically at 20 nA/cm, pFt = 6 2 curve c Fe polarised cathodically at 20/iA/cm, pFt = 8-9 and curve d Fe polarised cathodically at 40/iA/cm, pFt = 6-2 (potentials vs. S.H.E.) (after Pryor )...

It follows from (1) that the more negative metal, at a bimetallic junction, can be subject to more aggravated attack because of this lowered cathodic polarisation. In part, this may result from the greater ease of replenishment of dissolved oxygen under conditions where the ratio of surface area to electrolyte volume is very high. Rosenfel d has also produced evidence to show that rapid convective mixing in the condensed layer, under conditions of lowered relative humidity which permit rapid evaporation, further hastens the arrival of dissolved oxygen at the cathode and results in an additional... 

The driving force of a thermogalvanic corrosion cell is therefore the e.m.f. attributable to these four effects, but modified by anodic and cathodic polarisation of the metal electrodes as a result of local action corrosion processes. 

Electrochemical corrosion of metals Since the aggressiveness of salt melts is governed by redox equilibria, and is often controlled by composition of the external atmosphere, effects analogous to electrochemical or oxygen-concentration corrosion in aqueous systems can occur in salt melts. Tomashov and Tugarinov determined cathodic polarisation curves in fused chlorides and concluded that the cathodic reactions of impurities could be represented as ... 

In the case of CaCl2 and NaCl, the order corresponds with the corrosion behaviour expected from cathodic polarisation curves . The order of aggressiveness of chlorides can also be explained on the basis of redox potentials of the melts, calculated on thermodynamic grounds from the free energies of formation of the appropriate oxides and chlorides . The order of aggressiveness of nitrates is complicated by passivity effects , while that of alkalis in contact with air is... 

Fig. 3.14 Idealised form of a potentiostatic anodic polarisation curve ABCDE for stainless steels as determined in sulphuric acid solution. PQ and P Q arc two cathodic polarisation curves that lead to passivity and corrosion, respectively...

Polarisation from an external source may also affect the range of passivity. Cathodic polarisation may depress the potential from the passive to the active region (see Fig. 3.14) and thus care should be taken to avoid contact with any other corroding metal. Anodic polarisation, on the other hand, can stabilise passivity provided that the potential is not increased into the range of transpassivity (see Fig. 3.14) and anodic protection is quite feasible. 

Although tests on smooth specimens indicate that cathodic protection of maraging steel is possible, tests on specimens with pre-existing cracks indicate a greater sensitivity to hydrogen embrittlement during cathodic polarisation . The use of cathodic protection on actual structures must therefore be applied with caution, and the application of less negative potentials than are indicated to be feasible in smooth specimen tests is to be recommended if it is assumed that structures contain crack-like defects. 

Turning now to the acidic situation, a report on the electrochemical behaviour of platinum exposed to 0-1m sodium bicarbonate containing oxygen up to 3970 kPa and at temperatures of 162 and 238°C is available. Anodic and cathodic polarisation curves and Tafel slopes are presented whilst limiting current densities, exchange current densities and reversible electrode potentials are tabulated. In weak acid and neutral solutions containing chloride ions, the passivity of platinum is always associated with the presence of adsorbed oxygen or oxide layer on the surface In concentrated hydrochloric acid solutions, the possible retardation of dissolution is more likely because of an adsorbed layer of atomic chlorine ... 

Sulphates, which form part of the ash from the combustion of many fuels, are not harmful to high-alloy steels, but can become so if reduction to sulphide occurs. This leads to the formation of low melting point oxide-sulphide mixtures and to sulphide penetration of the metal. Such reduction is particularly easy if the sulphate can form a mixture of low melting point with some other substance. Reduction can be brought about by bad combustion, as demonstrated by Sykes and Shirley , and it is obviously important to avoid contact with inefficiently burnt fuels when sulphate deposits may be present. Reduction can also be brought about in atmospheres other than reducing ones and the presence of chlorides or vanadium pentoxide has been shown to be sufficient to initiate the reaction. It has also been shown that it can be initiated by prior cathodic polarisation in fused sodium sulphate. The effect of even small amounts of chloride on oxidation in the presence of sulphate is illustrated in Fig. 7.33 . 

In neutral solutions the application of cathodic polarisation prevents crack initiation and this could be taken to indicate that hydrogen embrittlement is not the operative mechanism, since the discharge and entry of hydrogen might be expected to fracture the specimen more readily. The beneficial effect of cathodic polarisation has been interpreted , however, to result from more rapid film repair in the alkaline catholyte generated by the cathode reaction. The film serves as a barrier to rapid hydrogen entry. Consistent with this is the observation that in an environment of low pH (e.g. 10 N HCl) where film formation would not be expected, cathodic polarisation has no effect upon crack propagation. 

The values of h, and b, i.e. The Tafel constants of the anodic and cathodic polarisation curves, first have to be measured directly in the laboratory or deduced by correlating values of AE/Ai measured on the plant with values deduced from corrosion coupons. The criticism is that the K value is likely to be inaccurate and/or to change markedly as conditions in the process stream change, i.e. the introduction of an impurity into a process stream could not only alter i but also the K factor which is used to calculate it. 

Figure 10.7 illustrates the use of an external power supply to provide the cathodic polarisation of the structure. The circuit comprises the power source, an auxiliary or impressed current electrode, the corrosive solution, and the structure to be protected. The power source drives positive current from the impressed current electrode through the corrosive solution and onto the structure. The structure is thereby cathodically polarised (its potential is lowered) and the positive current returns through the circuit to the power supply. Thus to achieve cathodic protection the impressed current electrode and the structure must be in both electrolytic and electronic contact. 

More negative than beginning of Tafel segment of cathodic polarisation (E - log /)... 

Where there is a perceived risk of crevice corrosion, cathodic protection can often be used to prevent its initiation. Once more a 100 mV cathodic polarisation will usually prove sufficient. However, it is doubtful whether cathodic protection can arrest crevice corrosion once started and, despite claims to the contrary, whether it could be effective in arresting stress-corrosion cracking. The problem lies in the fundamental difficulty of forcing cathodic current into an occluded area. 

The proof of protection is more difficult to establish in this case for two reasons. First, the object is to restore passivity to the rebar and not to render it virtually immune to corrosion. Second, it is difficult to measure the true electrode potential of rebars under these conditions. This is because the cathodic-protection current flowing through the concrete produces a voltage error in the measurements made (see below). For this reason it has been found convenient to use a potential decay technique to assess protection rather than a direct potential measurement. Thus a 100 mV decay of polarisation in 4 h once current has been interrupted has been adopted as the criterion for adequate protection. It will be seen that this proposal does not differ substantially from the decay criterion included in Table 10.3 and recommended by NACE for assessing the full protection of steel in other environments. Of course, in this case the cathodic polarisation is intended to inhibit pit growth and restore passivity, not to establish effective immunity. 

The anode material must provide a driving voltage sufficiently large to drive adequate current to enable effective cathodic polarisation of the structure. This requirement implies that the anode must have an operating potential that is more negative than the structure material to be protected. 

The irreversible behaviour of an aluminium electrode, which readily passes a current when cathodically polarised, but almost ceases to conduct when made the anode in certain aqueous solutions, has been known for over a century. 

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