Steel corrosion potential

The subsequent oxide formation leads to a decrease in the overall oxidation rate, according to Equation 18.5. The value of n in this equation (which is the same as in the crack propagation rate. Equation 18.6) varies with the alloy chemistry (e.g., chromium content for a denuded grain boundary of Type 304 stainless steel), corrosion potential at the crack mouth, and the anionic activity in the bulk environment. 

Duplex stainless steels (ca 4% nickel, 23% chrome) have been identified as having potential appHcation to nitric acid service (75). Because they have a lower nickel and higher chromium content than typical austenitic steels, they provide the ductabdity of austenitic SS and the stress—corrosion cracking resistance of ferritic SS. The higher strength and corrosion resistance of duplex steel offer potential cost advantages as a material of constmction for absorption columns (see CORROSION AND CORROSION CONTROL). 

Foulants enter a cooling system with makeup water, airborne contamination, process leaks, and corrosion. Most potential foulants enter with makeup water as particulate matter, such as clay, sdt, and iron oxides. Insoluble aluminum and iron hydroxides enter a system from makeup water pretreatment operations. Some well waters contain high levels of soluble ferrous iron that is later oxidized to ferric iron by dissolved oxygen in the recirculating cooling water. Because it is insoluble, the ferric iron precipitates. The steel corrosion process is also a source of ferrous iron and, consequendy, contributes to fouling. 

Anodic Inhibitors. Passivating or anodic inhibitors produce a large positive shift in the corrosion potential of a metal. There are two classes of anodic inhibitors which are used for metals and alloys where the anodic shift in potential promotes passivation, ie, anodic protection. The fkst class includes oxidking anions that can passivate a metal in the absence of oxygen. Chromate is a classical example of an oxidking anodic inhibitor for the passivation of steels. 

This criterion is derived from the fact that the free corrosion potential in soil is generally I/cu Cuso4 -0-55 V. Ohmic voltage drop and protective surface films are not taken into consideration. According to the information in Chapter 4, a maximum corrosion rate for uniform corrosion in soil of 0.1 mm a can be assumed. This corresponds to a current density of 0.1 A m l In Fig. 2-9, the corrosion current density for steel without surface film changes by a factor of 10 with a reduction in potential of about 70 mV. To reduce it to 1 jum a (0.14 V would be necessary. The same level would be available for an ohmic voltage drop. With surfaces covered with films, corrosion at the rest potential and the potential dependence of corrosion in comparison with act contrary to each other so that qualitatively the situation remains the same. More relevant is... 

Corrosion likelihood (depassivation) Steel/concrete potential Uccso, (V)... 

Figure 4-422. Corrosion characteristics of iron and 18% Cr stainless steel in diiute sulfuric acid and as a function of soiution oxidizing power (corrosion potential). (From Ref. [187].)...

These values are roughly constant across a range of electrolyte environments except where noted but the variations between alloys, heat treatment conditions, etc. creates a range for each metal. For some metals such as iron and steel the range is low ( 100 mV), but for lead, nickel, stainless steels a range is given. The corrosion potential is reported with respect to the saturated calomel reference electrode. 

The corrosion potentials of metals and alloys are temperature dependent. The potential of a steel distillation column, heat exchanger or other item of plant varies in the temperature zones in which it is operating. Under some... 

Imoi, H., Saito, Y., Kobayashi, M. and Fujiyama, S., Pitting-corrosion-resistant Chromium Stainless Steel , Japan Kokai 7300, 221 (1973) C.A., 79, 22569a Sato, E., Tamura, T. and Okabe, T., Aluminium Anode for Cathodic Protection. 7 Pitting and Corrosion Potentials for Gallium in Sodium Chloride Solutions , Kinzoku Hyomen Gijutsu, 24, 82 (1973) C.A., T9, 12792d... 

The general form of the anodic polarisation curve of the stainless steels in acid solutions as determined potentiostaticaiiy or potentiodynamically is shown in Fig. 3.14, curve ABCDE. If the cathodic curve of the system PQ intersects this curve at P between B and C only, the steel is passive and the film should heal even if damaged. This, then, represents a condition in which the steel can be used with safety. If, however, the cathodic curve P Q also intersects ED the passivity is unstable and any break in the film would lead to rapid metal solution, since the potential is now in the active region and the intersection at Q gives the stable corrosion potential and corrosion current. 

The sometimes contradictory results from different workers in relation to the elements mentioned above extends to other elements . Some of these differences probably arise from variations in test methods, differences in the amounts of alloying additions made, variations in the amounts of other elements in the steel and the differing structural conditions of the latter. Moreover, the tests were mostly conducted at the free corrosion potential, and that can introduce further variability between apparently similar experiments. In an attempt to overcome some of these difficulties, slow strain-rate tests were conducted on some 45 annealed steels at various controlled potentials in three very different cracking environments since, if macroscopic... 

It is hardly surprising that the preparation of surfaces of plain specimens for stress-corrosion tests can sometimes exert a marked influence upon results. Heat treatments carried out on specimens after their preparation is otherwise completed can produce barely perceptible changes in surface composition, e.g. decarburisation of steels or dezincification of brasses, that promote quite dramatic changes in stress-corrosion resistance. Similarly, oxide films, especially if formed at high temperatures during heat treatment or working, may influence results, especially through their effects upon the corrosion potential. 

Fig. 10.6 Polarisation diagram showing the limited role hydrogen evolution plays at the corrosion potential of steel in aerated neutral solution, the larger role in determining cathodic protection currents and the dominant role in contributing to current requirements at very negative potenitals. The dotted line shows the total cathodic current due to oxygen reduction and...

Many passive metals suffer pitting attack when aggressive ions (usually chloride) enter the system. It is possible to forestall pitting, or to stop it once started, using cathodic protection. It is not necessary to polarise to the protection potential of the metal a negative shift of 100 mV from the natural corrosion potential in the environment will often be sufficient. This technique has been applied to various stainless steels and to aluminium . The philosophy is not unlike that applied to rebar in concrete. 

Although aluminium is a base metal, it spontaneously forms a highly protective oxide film in most aqueous environments, i.e. it passivates. In consequence, it has a relatively noble corrosion potential and is then unable to act as an anode to steel. Low level mercury, indium or tin additions have been shown to be effective in lowering (i.e. making more negative) the potential of the aluminium they act as activators (depassivators). Each element has been shown to be more effective with the simultaneous addition of zinc . Zinc additions of up to 5% lower the anode operating potential, but above this level no benefit is gained . Below 0 9 7o zinc there is little influence on the performance of aluminium anodes . Table 10.10 lists a number of the more common commercial alloys. 

Table 12.2 Corrosion potentials of substrates of coppter and steel, plated and unplated in same plating solutions. Deposition potential is accompanied by current density (A/m ) in parentheses the plated substrate s coating thickness was 2 5 fim. The final column gives the potential below which hydrogen evolution is possible only in the cuprocyanide is it observed...

Corrosion potentials in plating baths The standing potentials of steel and copper (before application of current) are shown in Table 12.2, together with the standing potential of the plated metal and the potential below which hydrogen should, in theory, be evolved. The potential of the cathode during deposition at a typical current density is also given. 

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