Self-corrosion

The anodes are generally not of pure metals but of alloys. Certain alloying elements serve to give a fine-grained structure, leading to a relatively uniform metal loss from the surface. Others serve to reduce the self-corrosion and raise the current yield. Finally, alloying elements can prevent or reduce the tendency to surface film formation or passivation. Such activating additions are necessary with aluminum. 

On the other hand, the difference between the theoretical and the usable current content due to self-corrosion is not negligible. This effect is taken care of... 

The rate of self-corrosion of zinc anodes is relatively low. In fresh cold water, it amounts to about 0.02 g m h , corresponding to a corrosion rate of 25 /rm a. In cold seawater, the value is about 50% higher [10]. These figures refer to stagnant water. In flowing water the corrosion rates are significantly greater. Zinc is not practically suited for use in warm waters because of its tendency to passivate. 

Pure aluminum cannot be used as an anode material on account of its easy passivatability. For galvanic anodes, aluminum alloys are employed that contain activating alloying elements that hinder or prevent the formation of surface films. These are usually up to 8% Zn and/or 5% Mg. In addition, metals such as Cd, Ga, In, Hg and T1 are added as so-called lattice expanders, these maintain the longterm activity of the anode. Activation naturally also encourages self-corrosion of the anode. In order to optimize the current yield, so-called lattice contractors are added that include Mn, Si and Ti. 

Magnesium anodes usually consist of alloys with additions of Al, Zn and Mn. The content of Ni, Fe and Cu must be kept very low because they favor selfcorrosion. Ni contents of >0.001% impair properties and should not be exceeded. The influence of Cu is not clear. Cu certainly increases self-corrosion but amounts up to 0.05% are not detrimental if the Mn content is over 0.3%. Amounts of Fe up to about 0.01% do not influence self-corrosion if the Mn content is above 0.3%. With additions of Mn, Fe is precipitated from the melt which on solidification is rendered harmless by the formation of Fe crystals with a coating of manganese. The addition of zinc renders the corrosive attack uniform. In addition, the sensitivity to other impurities is depressed. The most important magnesium alloy for galvanic anodes is AZ63, which corresponds to the claims in Ref. 22. Alloys AZ31 and M2 are still used. The most important properties of these alloys are... 

Low pH values favor self-corrosion, displace the rest potential to more negative values, reduce polarization, and lead to uniform material consumption pH values above 10.5 act opposite to this. Below pH 5.5 to 5.0, the current yield is so low that their use is impracticable. 

In the application of magnesium anodes for enamelled boilers, the consumption rate of the anodes is determined less by current supply than by self-corrosion. The calculation of life from data on protection current requirement, /, and anode mass, m, is difficult because the a value is so low. 

In oxygen-free water, the self-corrosion is practically solely due to hydrogen evolution... 

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. 

With unprotected comparison test pieces, the corrosion rate was 4 mm a , which from cell current measurements indicated that the self-corrosion was 50%. 

The current yield of aluminum depends on the composition of the water and the operating conditions it usually lies between a = 0.8 and 0.9 (see Section 6.2.3). Self-corrosion occurs, as with Mg, with hydrogen evolution. 

It should be noted that when metals like zinc and aluminium are used as sacrificial anodes the anode reaction will be predominantly 10.18a and 10.186, although self-corrosion may also occur to a greater or lesser extent. Whereas the e.m.f. between magnesium, the most negative sacrificial anode, and iron is =0-7 V, the e.m.f. of power-impressed systems can range from 6 V to 50 V or more, depending on the power source employed. Thus, whereas sacrificial anodes are normally restricted to environments having a resistivity of <6 000 0 cm there is no similar limitation in the use of power-impressed systems. 

The electrochemical impedance gradually decreases but does not vary very much with the DDTC concentration increasing. It indicates that DDTC takes part in the electrochemical reaction and the reaction rate increases as the DDTC concentration enhances. As contrasted with it, the passivation of the collector-salts of reaction production on the mineral electrode further inhibits the anodic reaction so that the electrochemical resistance is wholly much bigger than that of self-corrosive reaction in the absence of DDTC. 

Abstract The flotation mechanism is discussed in the terms of corrosive electrochemistry in this chapter. In corrosion the disolution of minerals is called self-corrosion. And the reaction between reagents and minerals is treated as inhibition of corrosion. The stronger the ability of inhibiting the corrosion of minerals, the stronger the reagents react with minerals. The two major tools implied in the research of electrochemical corrosion are polarization curves and EIS (electrochemistry impedance spectrum). With these tools, pyrite, galena and sphalerite are discussed under different conditions respectively, including interactions between collector with them and the difference of oxidation of minerals in NaOH solution and in lime. And the results obtained from this research are in accordance with those from other conventional research. With this research some new information can be obtained while it is impossible for other methods. 

As is known to all, the flotation mechanism of sulphide minerals can be explained based on electrochemistry because sulphide minerals have the semiconductor character and a series of electrochemistry reaction occurring in solution. After these reactions, the surface of sulphide minerals changes and forms a new phase. We called it as self-corrosion of sulphide minerals. As before, the essence of the reaction between the collector and the minerals is the formation of the hydrophobic entity on the mineral surface, and then minerals can be floated. We can find that the reaction between the collector and the minerals is similar to the depression on mineral self-corrosion. In the corrosion, we called this effect as inhibition, and this kind of reagent is an inhibiting reagent. There are many studies on corrosion, especially its research method and theory. Thus, we can get some new information on the mechanism of sulphide flotation from corrosive electrochemistry. 

There existed oxidation-reduction reactions with the same reaction speed on the sulphide mineral surface in water. One is the self-corrosion of sulphide mineral. Another is the reduction of oxygen. If the equilibrium potential for the anodic reaction and the cathodic reaction are, respectively, E and, and the mineral electrode potential is E, the relationship among them is as follows ... 

One more recent use of aluminium is in cathodic protection. In this application, the alloy sacrificially corrodes, i.e. is anodic and thus prevents corrosion of the structure to which it is electrically connected. In order for these alloys to be efficient, they must undergo little self-corrosion, but corrode uniformly when stimulated by galvanic contact. 

Equation (7.1) expresses also that the total corrosion rate of the less noble metal ( oorrA) cousists of a Contribution of galvanic corrosion (/g iv) and a contribution of self-corrosion due to the cathodic reaction on the same metal (/catA)- The corrosion current densities of a galvanic couple are finally derived by dividing the corrosion... 

Crucial properties of sacrificial anodes are listed in Tables 10.15 and 10.16. In aluminium, Hg (or alternatively In to avoid pollution of the environment) contributes to reduced tendency to passivation. In Zn anodes, the content of Fe (among some other species) should be kept very low to avoid self-corrosion. As regards anode testing, see Reference [10.25]. 

For solution of the following tasks b)- e) we assume complete protection of the container continuously for all the 10 years, we disregard self-corrosion of the anode, and the calculation is to be based on the data given in Figure 2 and in the text. 

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