Pitting in steel

Figure 5. The pitting in steel Figure 6. Microcrack in steel...

Figure 9.18 Differential aeration leading to pitting in steel (a) before and (b) after corrosion...

Dissolved oxygen is significantly more corrosive than carbon dioxide. Dissolved oxygen in pure water at 65°C is found to be six times more corrosive than a molar equivalent concentration of carbon dioxide. The combined corrosion caused by O2 and CO2 is twice that caused individually by oxygen and CO2. Oxygen is known to produce rust and pitting in steel equipment. Oxygen picks... 

Fig. 2 Fully developed pitting in track (hardened structural steel)...

Molybdenum improves the corrosion resistance of stainless steels that are alloyed with 17—29% chromium. The addition of 1—4% molybdenum results in high resistance to pitting in corrosive environments, such as those found in pulp (qv) and paper (qv) processing (33), as weU as in food preparation, petrochemical, and poUution control systems. 

Low Cement, Ultra-Low Cement, and No-Cement Castables are classified on the basis of calcium oxide content. These are 1—2.5, 0.2—1.0, and 0.2% CaO maximum, respectively. In the latter case the lime content is not a result of a hydrauHc setting cement constituent but comes from aggregate impurities. The insulating class is also subdivided. This division is shown in Table 14. Refractories used in steel-pouring pits are classified under ASTM C435 (Table 15). 

Crevice Corrosion. Crevice corrosion is intense locali2ed corrosion that occurs within a crevice or any area that is shielded from the bulk environment. Solutions within a crevice are similar to solutions within a pit in that they are highly concentrated and acidic. Because the mechanisms of corrosion in the two processes are virtually identical, conditions that promote pitting also promote crevice corrosion. Alloys that depend on oxide films for protection (eg, stainless steel and aluminum) are highly susceptible to crevice attack because the films are destroyed by high chloride ion concentrations and low pH. This is also tme of protective films induced by anodic inhibitors. 

The stainless steels contain appreciable amounts of Cr, Ni, or both. The straight chrome steels, types 410, 416, and 430, contain about 12, 13, and 16 wt % Cr respectively. The chrome—nickel steels include type 301 (18 wt % Cr and 9 wt % Ni), type 304 (19 wt % Cr and 10 wt % Ni), and type 316 (19 wt % Cr and 12 wt % Ni). Additionally, type 316 contains 2—3 wt % Mo which gready improves resistance to crevice corrosion in seawater as well as general corrosion resistance. AH of the stainless steels offer exceptional improvement in atmospheric conditions. The corrosion resistance results from the formation of a passive film and, for this reason, these materials are susceptible to pitting corrosion and to crevice corrosion. For example, type 304 stainless has very good resistance to moving seawater but does pit in stagnant seawater. 

Area effects in galvanic corrosion are very important. An unfavorable area ratio is a large cathode and a small anode. Corrosion of the anode may be 100 to 1,000 times greater than if the two areas were the same. This is the reason why stainless steels are susceptible to rapid pitting in some environments. Steel rivets in a copper plate will corrode much more severely than a steel plate with copper rivets. 

Figure 2.23 Shallow pitting in crevice areas on a 304 stainless steel coupon exposed to a misting atmosphere. Note the relatively clean areas where the washer teeth contacted the coupon surface. (Magnification 7.5x.)...

Flgure 6.8 Scalloped, partially undercut pits in a cross section of a 316 stainless steel tube. 

Stainless steels tend to pit in acid solutions. Pits form local areas of metal loss associated with breakdown of a protective oxide layer. Breakdown is stimulated by low pH as well as by the decrease of dissolved oxygen in occluded regions. Small, active pit sites form and remain stable because of the large ratio of cathodic surface area (unattacked metal surface) to the pit area. Active corrosion in the pit cathodically protects immediately adjacent areas. If conditions become very severe, pitting will give way to general attack as more and more of the surface becomes actively involved in corrosion. 

Figure 53.3 illustrates a pit in a stainless steel such as type 534 or 316 austenitic alloy. Pitting starts at heterogeneity in the steel surface, such as an outcropping sulfide inclusion, the shielded region beneath a deposit or even a discontinuity in the naturally present oxide film caused by a scratch or embedded particle of abrasive grit. This initiation phase of pitting corrosion may take seconds... 

More recently, Fontana and Greene measured the current between a pit in stainless steel and the surrounding metal the pit was allowed to form, and cut out from the surrounding metal (the cathode), its edge was insulated and it was then replaced in the hole with a suitable connection for measuring the current flow between the pit and the surrounding metal. These workers showed that under certain conditions was about a thousand times... 

Suzuki, Yamake and Kitamura determined the pHs, chloride ion concentrations, metal ion concentrations and the potentials of artificial pits in Fe, Cr, Ni and Mo, and in three austenitic stainless steels during anodic polarisation in 0-5 N NaCl at 70°C. In the case of the pure metals the pH values were found to be lower than those calculated from the metal ion concentrations (Table 1.17), and the experimentally determined pHs were as follows ... 

Table 1.18 pH, chloride ion concentration and potential for artificial pits in stainless steels ... 

Videm, K., Pitting Corrosion of Aluminium in Contact with Stainless Steel , Proc. Conf. on Corrosion Reactor Mater., Salzburg, Austria, 1, 391 (1962) C.A., 60, 1412g Lyon, D. H., Salva, S. J. and Shaw, B. C., Etch Pits in Germanium Detection and Effects , J. Electrochem. Soc., 110, 184c (1963)... 

Szklarska-Smialowska, Z., Electron Microprobe Study of the Effect of Sulphide Inclusions on the Nucleation of Corrosion Pits in Stainless Steels , Br. Corros. J., S, 159 (1970) Weinstein, M. and Speirs, K., Mechanisms of Chloride-activated Pitting Corrosion of Martensitic Stainless Steels , J. Electrochem. Soc., 117, 256 (1970)... 

Development of Pits in Stainless Steel inO-5 n NaCl + 0 -1 n H2SO4 Solution , Corns. Sci., 12, 925 (1972)... 

It should be made clear that all the rates of rusting in the atmosphere just quoted, relate to average general penetration and take no account of pitting. Serious pitting of steel exposed to atmospheric corrosion is uncomm.on on simple test plates, but it may be necessary to allow for this in some practical cases, where local attack may be occasioned by faulty design and other factors. 

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