Immunity zone diagrams

Another way of looking at the theory of cathodic protection is to look at the Pourbaix diagram (Pourbaix, 1973 Morgan, 1990) for iron in chloride solution. This shows that there are conditions where steel corrodes, and areas where protective oxides form and an area of immunity to corro.sion depending upon the pH and the potential of the steel. Ideally we would like to depress the potential sufficiently to reach the immune zone (Figure 6.2). In practice we do not do that for reasons described in the Section 6.5 on control criteria. 

Pourbaix Diagrams. Plots of equilibrium pH vs electrochemical potential E describe the effects of aqueous corrosion on borosilicate and silicate glasses. They are applicable to weathering studies and to ground water attack on nuclear waste glasses. The diagrams display any immune zone between active corrosion... 

Although the zones of corrosion, immunity and passivity are clearly of fundamental importance in corrosion science it must be emphasised again that they have serious limitations in the solution of practical problems, and can lead to unfortunate misconceptions unless they are interpreted with caution. Nevertheless, Pourbaix and his co-workers, and others, have shown that these diagrams used in conjunction with E-i curves for the systems under consideration can provide diagrams that are of direct practical use to the corrosion engineer. It is therefore relevant to consider the advantages and limitations of the equilibrium potential-pH diagrams. 

The region of immunity [Fig. 1.15 (bottom)] illustrates how corrosion may be controlled by lowering the potential of the metal, and this zone provides the thermodynamic explanation of the important practical method of cathodic protection (Section 11.1). In the case of iron in near-neutral solutions the potential E = —0-62 V for immunity corresponds approximately with the practical criterion adopted for cathodically protecting the metal in most environments, i.e. —0-52 to —0-62V (vs. S.H.E.). It should be observed, however, that the diagram provides no information on the rate of charge transfer (the current) required to depress the potential into the region of immunity, which is the same (< —0-62 V) at all values of pH below 9-8. Consideration of curve//for the Hj/HjO equilibrium shows that as the pH... 

Fig. 1.38(Equilibrium potential-pH diagram for the Cr-H20 system and (< ) potential-pH diagram showing zones of corrosion, passivity and immunity (after Pourbaix )... 

As may be seen from the potential-pH diagram " (Fig. 6.3) platinum is immune from attack at almost all pH levels. Only in very concentrated acid solutions at high redox potentials (i.e. under oxidising conditions) is there a zone of corrosion. This accounts for the solubility of platinum in aqua regia. Platinum is also prone to complex-ion formation, and this can lead... 

The thermodynamic information is normally summarized in a Pourbaix diagram7. These diagrams are constructed from the relevant standard electrode potential values and equilibrium constants and show, for a given metal and as a function of pH, which is the most stable species at a particular potential and pH value. The ionic activity in solution affects the position of the boundaries between immunity, corrosion, and passivation zones. Normally ionic activity values of 10 6 are employed for boundary definition above this value corrosion is assumed to occur. Pourbaix diagrams for many metals are to be found in Ref. 7. 

Dissolution of the chlorides from the corrosion products is an essential part of the conservation process. It is essential that the artefact is immersed in an electrolyte that will not corrode the metal any further, while this dissolution is taking place. Corrosion scientists have developed redox potential - pH diagrams from thermodynamics in order to predict the most stable form of the metal. These diagrams are divided into three zones. Where metal ions are the most stable phase, this is classed as a zone of corrosion. If the metal itself is the most stable species, this is said to be the zone of immunity. The third zone is where solid metal compounds such as oxides, hydroxides, etc, are the most stable and may form a protective layer over the metal surface. This zone is termed passivity and the metal will not corrode as long as this film forms a protective barrier. The thickness of this passive layer may only be approximately 10 nm thick but as long as it covers the entire metal surface, it will prevent further corrosion. 

One frequently asked question concerning cathodic protection systems is what happens at the anode edge Is there a risk of accelerated corrosion This is a valid question and the risk is supported by the Pourbaix diagram which shows areas of imperfect passivity, pitting and corrosion around the immune and passive regions (Figure 7.2). However, the author knows of no atmospherically exposed reinforced concrete structure that is totally protected by cathodic protection. Most have anode zones that end before the reinforced concrete does. No cases of accelerated corrosion have been reported between zones or at the end of zones. 

Fig. l.lS(top) Equilibrium potemial-pH diagram for the Fe-HjO system showing the zones of stability of cations, anions and solid hydroxides (after Deltombe and Pourbaix ) and (bottom) simplified version showing zones of corrosion, immunity and passivity (curve / is the HjO/Hj equilibrium at Phj= 1 and cur s the Oj/HjO equilibrium at Poj = )... 

Figure 2.20 Pourbaix diagram for the iron-water system at 25°C showing nominal zones of immunity...

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