Cathode under cathodic protection

Unprotected steel corrodes at a rate which is generally assumed to be 0.1 to 0.2mm per annum. Factors that influence the actual rate of corrosion include the maintenance program applied by the owner - particularly preservation of protective coatings, efficiency of cathodic protection systems in ballast tanks, corrosive properties of the cargo carried and environmental factors such as temperature and humidity. Under extreme conditions it has been known for the annual rate of corrosion on unprotected steel exposed on both surfaces to approach 1mm. 

Figure 2-11 shows weight loss rate-potential curves for aluminum in neutral saline solution under cathodic protection [36,39]. Aluminum and its alloys are passive in neutral waters but can suffer pitting corrosion in the presence of chloride ions which can be prevented by cathodic protection [10, 40-42]. In alkaline media which arise by cathodic polarization according to Eq. (2-19), the passivating oxide films are soluble ... 

In the cathodic protection of storage tanks, potentials should be measured in at least three places, i.e., at each end and at the top of the cover [16]. Widely different polarized areas arise due to the small distance which is normally the case between the impressed current anodes and the tank. Since such tanks are often buried under asphalt, it is recommended that permanent reference electrodes or fixed measuring points (plastic tubes under valve boxes) be installed. These should be located in areas not easily accessible to the cathodic protection current, for example between two tanks or between the tank wall and foundations. Since storage tanks usually have several anodes located near the tank, equalizing currents can flow between the differently loaded anodes on switching off the protection system and thus falsify the potential measurement. In such cases the anodes should be separated. 

Cathodic protection can be used to protect steel in concrete (see Chapter 19). There is no fear of damage by H2 evolution due to porosity of the mortar. Local corrosion attack can be observed under extreme conditions due to porosity (water/ cement ratio = 1) and polarization (f/jq = -0.98 V) with portland cement but not with blast furnace cement, corresponding to field IV in Fig. 2-2 [53]. However, such conditions do not occur in practice. 

Hydrogen is involved in cathodic protection with magnesium anodes on account of the high contribution of self-corrosion. This must be considered in its use in closed containers, e.g., boilers. In enamelled boilers there is no danger from deflagration of the oxy-hydrogen gas under normal service conditions [2] however safety requirements must be observed [28,29], particularly with routine maintenance work. 

Cathodic protection stations frequently operate under conditions that are continually changing. These include ... 

Cathodic protection installations must be tested when commissioned and at least annually. The potentials should be measured at several points on the bottom of the tank with special probes under the oil, and the height of the electrolyte solution should be checked. The off potential and the protection potential as in Section 2.4 are the means for checking the protection criterion according to Eq. (2-39). 

The installation of electrically insulating foils under the base of the tank or in its vicinity interferes with cathodic protection. 

In the tidal zone and the spray zone (known as the splash zone), cathodic protection is generally not very effective. Here thick coatings or sheathing with corrosion-resistance materials (e.g., based on NiCu) are necessary to prevent corrosion attack [4]. The coatings are severely mechanically stressed and must be so formed that repair is possible even under spray conditions. Their stability against cathodic polarization (see Section 17.2), marine growths, UV rays and seawater must be ensured [4,5]. 

The use of corrosion-resistant materials and the application of corrosion protection measures are in many cases the reason that industrial plants and structures can be built at all. This is particularly so in pipeline technology. Without cathodic protection and without suitable coating as a precondition for the efficiency of cathodic protection, long-distance transport of oil and gas under high pressures would not be possible. Furthermore, anodic protection was the only protective measure to make possible the safe operation of alkali solution evaporators (see Section 21.5). 

It remains to be determined whether the previous experiments , which have been interpreted as confirming the cathodic protection of aluminium by zinc, can be truly interpreted in this fashion or whether they are due to the accumulation of Zn in the electrolyte. Under laboratory conditions, and under some practical conditions in stagnant solutions or in recirculating systems, the latter explanation is quite likely. 

In static air-free sea water the potential of iron or steel reaches a steady-statevalueof —0-75 V (v5. S.C.E., = 0-246 V) which should be compared with the more noble potential of —0-61 V observed under conditions of high velocity and aeration (Table 2.16). This potential of —0-75 V for iron in sea water is important in the practice of cathodic protection. 

Moisture Aims are frequently found under unbonded protective coatings of asphalt and plastic tapes. The nature and origin of this water is still unknown but is of great interest because of its relationship to bond failure, microbial utilisation of asphalt and hydrocarbons, and efficiency of cathodic protection. ... 

Cathodic protection applications in fresh water include use of ferrite-coated niobium , and the more usual platinum-coated niobium . Platinised niobium anodes have been used in seawater, underground and in deep wells " and niobium connectors have been used for joining current leads Excellent service has been reported in open-seawater, where anodic potentials of up to 120V are not deleterious, but crevice corrosion can occur at 20 to 40V due to local surface damage, impurities such as copper and iron, and under deposits or in mud ... 

In common with many of the alloy-environment systems described so far, if the alloy is not susceptible to stress-corrosion cracking under constant stress or stress intensity, then little or no effect of environment on fatigue crack growth is observed. In these cases, frequency, R ratio and potential within the passive or cathodically protected ranges for titanium have no effect on growth rates. 

Fig. 10.5 Polarisation diagram representing corrosion and cathodic protection when the cathodic process is under mass transfer control. The values of fcorr and /cor, are lower than when there is no mass transfer restriction, i.e. when the cathodic kinetics follow the dotted line...

Some metals are amphoteric. That is, they form simple cations (in acid solutions) and soluble oxyanions (in alkaline solution) only in the mid-pH range is a protective film stable. Since cathodic protection produces alkali at the structure s surface, it is important to restrict the polarisation, and thereby the amount of hydroxyl ion produced, in these cases. Thus both lead and aluminium will suffer cathodic corrosion under cathodic protection if the potential is made excessively electro negative. 

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. 

It is clear that to ensure adequate protection of a structure under cathodic protection it is necessary to measure its electrode potential. This can only be achieved by using a reference electrode placed in the same environment as the structure and measuring the e.m.f. of the cell so formed. Since the electrode potentials of different types of reference electrode vary, it is clear that the measured e.m.f. will also vary according to the particular reference electrode used. It follows that the potential measured must always be recorded with respect to the reference electrode deployed, which must always be stated. 

The higher the pH of the seawater the greater will be the proportion of carbonate ions present (since as the pH increases, so the H concentration decreases, thereby moving the equilibrium to the right). It follows that at a surface under cathodic protection, the hydroxyl ion produced has the effect of increasing the local carbonate ion concentration. 

---