Cathodic protection principles

Some years after Davy s death, Faraday examined the corrosion of cast iron in sea water and found that it corrodes faster near the water surface than deeper down. In 1834 he discovered the quantitative connection between corrosion weight loss and electric current. With this discovery he laid the scientific foundation of electrolysis and the principles of cathodic protection. 

Two areas of passivity are located in Fig. 2-2 where Fe has a very low corrosion rate. In contrast to cathodically protected metals in groups I and II, the corrosion rate of anodically passivated metals in groups III and IV cannot in principle be zero. In most cases the systems belong to group IV where intensified weight loss corrosion or local corrosion occurs when U > U" There are only a few metals belonging to group III e.g., Ti, Zr [44] and A1 in neutral waters free of halides. 

Practical measurements providing data on corrosion risk or cathodic protection are predominantly electrical in nature. In principle they concern the determination of the three principal parameters of electrical technology voltage, current, and resistance. Also the measurement of the potential of metals in soil or in electrolytes is a high-resistance measurement of the voltage between the object and reference electrode and thus does not draw any current (see Table 3-1). 

Differences in temperature and concentration can in principle lead to corrosion cell formation, but have little effect below the water line. On the other hand, they have to be taken into account in the interior corrosion of containers and tanks in relation to their service operation (see Section 2.2.4.2). Generally the action of corrosion cells can be reduced or eliminated by cathodic protection. 

Galvanic corrosion is the enhanced corrosion of one metal by contact with a more noble metal. The two metals require only being in electrical contact with each other and exposing to the same electrolyte environment. By virtue of the potential difference that exists between the two metals, a current flows between them, as in the case of copper and zinc in a Daniell cell. This current dissolves the more reactive metal (zinc in this case), simultaneously reducing the corrosion rate of the less reactive metal. This principle is exploited in the cathodic protection (Section 53.7.2) of steel structures by the sacrificial loss of aluminum or zinc anodes. 

In principle, cathodic protection can be applied to all the so-called engineering metals. In practice, it is most commonly used to protect ferrous materials and predominantly carbon steel. It is possible to apply cathodic protection in most aqueous corrosive environments, although its use is largely restricted to natural near-neutral environments (soils, sands and waters, each with air access). Thus, although the general principles outlined here apply to virtually all metals in aqueous environments, it is appropriate that the emphasis, and the illustrations, relate to steel in aerated natural environments. 

In recent years it has been regarded as somewhat passe to refer to Sir Humphrey Davy in a text on cathodic protection. However, his role in the application of cathodic protection should not be ignored. In 1824 Davy presented a series of papers to the Royal Society in London in which he described how zinc and iron anodes could be used to prevent the corrosion of copper sheathing on the wooden hulls of British naval vessels. His paper shows a considerable intuitive awareness of what are now accepted as the principles of cathodic protection. Several practical tests were made on vessels in harbour and on sea-going ships, including the effect of various current densities on the level of protection of the copper. Davy also considered the use of an impressed current device based on a battery, but did not consider the method to be practicable. 

In principle, all metals may be protected by cathodic protection. In practice, it is not always relevant either because the metals are, to all intents and purposes, naturally immune to corrosion (the noble metals) and often not used as engineering materials or, being base metals, they are well protected by... 

PRINCIPLES OF CATHODIC PROTECTION Table 10.4 Recommended protection potentials for other metals ... 

The thermodynamic and electrode-kinetic principles of cathodic protection have been discussed at some length in Section 10.1. It has been shown that, if electrons are supplied to the metal/electrolyte solution interface, the rate of the cathodic reaction is increased whilst the rate of the anodic reaction is decreased. Thus, corrosion is reduced. Concomitantly, the electrode potential of the metal becomes more negative. Corrosion may be prevented entirely if the rate of electron supply is such that the potential of the metal is lowered to the value where it is found that anodic dissolution does not occur. This may not necessarily be the potential at which dissolution is thermodynamically impossible. 

A consequence of cathodic protection in seawater is the formation of a protective calcareous scale . The increased local pH at the steel surface caused by hydroxyl production (a product of the cathodic reaction) favours the deposition of a mixed scale of CaCO, and Mg(OH)2. This scale is beneficial since it is protective and non-conducting, thus reducing the cathodic current density. Ensuring a high current density in the early period of operation will encourage calcareous scale deposition and thus reduce the current requirements in the long term (see Section 10.1 Principles of Cathodic Protection ). 

The latter part of this chapter has dealt with the design considerations for a sacrificial anode cathodic protection system. It has outlined the important parameters and how each contributes to the overall design. This is only an introduction and guide to the basic principles cathodic protection design using sacrificial anodes and should be viewed as such. In practice the design of these systems can be complex and can require experienced personnel. 

The complexity of the systems to be protected and the variety of techniques available for cathodic protection are in direct contrast to the simplicity of the principles involved, and, at present the application of this method of corrosion control remains more of an art than a science. However, as shown by the potential-pH diagrams, the lowering of the potential of a metal into the region of immunity is one of the two fundamental methods of corrosion control. 

In principle, cathodic protection can be used for a variety of applications where a metal is immersed in an aqueous solution of an electrolyte, which can range from relatively pure water to soils and to dilute solutions of acids. Whether the method is applicable will depend on many factors and, in particular, economics — protection of steel immersed in a highly acid solution is theoretically feasible but too costly to be practicable. It should be emphasised that as the method is electrochemical both the structure to be protected and the anode used for protection must be in both metallic and electrolytic contact. Cathodic protection cannot therefore be applied for controlling atmospheric corrosion, since it is not feasible to immerse an anode in a thin condensed film of moisture or in droplets of rain water. 

A typical soil resistivity survey is shown in Fig. 10.22. Soil resistivities will normally indicate whether a cathodic-protection system is advisable in principle and whether impressed current or sacrificial anode schemes in particular are preferable. It may, as a result of the survey, be considered desirable to apply protection to the whole line or to limit protection to certain areas of low soil resistivity or hot spots . 

Although the principles of cathodic protection are essentially simple and were in fact first outlined by Sir Humphry Davy in 1824, the application of the method to practical problems remains more of an art than a science. A properly designed cathodic protection system will be both economical and effective. On the other hand an incorrectly designed scheme will be inefficient, uneconomical and under certain circumstances may accelerate corrosion instead of controlling it. 

The measurement of current densities in the vicinity of a cathodically protected structure is a comparatively new principle used chiefly to monitor the effectiveness of offshore protection systems. These measurements are undertaken by twin half-cell devices either installed for stationary use or moved about the structure by diver or remote controlled vehicle. 

Before considering the principles of this method, it is useful to distinguish between anodic protection and cathodic protection (when the latter is produced by an external e.m.f.). Both these techniques, which may be used to reduce the corrosion of metals in contact with electrolytes, depend upon the electrochemical mechanisms that result from changing the potential of a metal. The appropriate potential-pH diagram for the Fe-H20 system (Section 1.4) indicates the magnitude and direction of the changes in the potential of iron immersed in water (pH about 7) necessary to make it either passive or immune in the former case the stability of the metal depends on the formation of a protective film of metal oxide (passivation), whereas in the latter the metal itself is thermodynamically stable and egress of metal ions from the lattice into the solution is thus prevented. 

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