Pitting, steel corrosion

Schwenk, W., Theory of Stainless Steel Pitting , Corrosion, 20, 129 (1964)... 

Type 304 stainless steel pitting corrosion specimens... 

Inorganic inhibitors such as chromate, nitrite, nitrates, and arsenate are very efficient for ferrous alloys. They prevent stainless steel pitting corrosion by forming a monolayer or multilayer passivating films. For chromate, the film is formed by iron oxidation (anodic... 

Steel Pitting corrosion temperature. Crevice corrosion temperature,... 

Pitting occurs witli many metals in halide containing solutions. Typical examples of metallic materials prone to pitting corrosion are Fe, stainless steels and Al. The process is autocatalytic, i.e., by initial dissolution, conditions are established which furtlier stimulate dissolution inside tire pit tire metal (Fe in tire example of figure C2.8.6 dissolves. 

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. 

The second class of anodic inhibitors contains ions which need oxygen to passivate a metal. Tungstate and molybdate, for example, requke the presence of oxygen to passivate a steel. The concentration of the anodic inhibitor is critical for corrosion protection. Insufficient concentrations can lead to pitting corrosion or an increase in the corrosion rate. The use of anodic inhibitors is more difficult at higher salt concentrations, higher temperatures, lower pH values, and in some cases, at lower oxygen concentrations (37). 

Stainless steels attacked by sulfate reducers show well-defined pits containing relatively little deposit and corrosion product. On freshly corroded surfaces, however, black metal sulfides are present within pits. Rust stains may surround pits or form streaks running in the direction of gravity or flow from attack sites. Carbon steel pits are usually capped with voluminous, brown friable rust mounds, sometimes containing black iron sulfide plugs fFig. 6.10). 

Other passivating materials suffer pitting corrosion by chloride ions [62] in a way similar to stainless steels (e.g., Ti [63] and Cu [64]). The pitting potential for aluminum and its alloys lies between = -0.6 and -0.3 V, depending on the material and concentration of chloride ions [10,40-42]. 

Stainless steels in soil can only be attacked by pitting corrosion if the pitting potential is exceeded (see Fig. 2-16). Contact with nonalloyed steel affords considerable cathodic protection at f/jj < 0.2 V. Copper materials are also very resistant and only suffer corrosion in very acid or polluted soils. Details of the behavior of these materials can be found in Refs. 3 and 14. 

Nonuniform corrosion or pitting corrosion frequently occurs on steel structures in seawater and in soil. Nonuniform and pitting corrosion easily lead to damage in tanks, pipelines, water heaters, ships, buoys and pontoons, because these structures lose their functional efficiency when their walls are perforated (see Chapter 4). 

Which Alloy to Use. Unalloyed mild steel parts have been known to corrode at rates as high as 800 mils per year. The low-chrome steels, through 9-Cr, are sometimes much more resistant than mild steel. No corrosion has been reported, with both 2%-Cr and 5-Cr furnace tubes, whereas carbon steel tubes in the same service suffered severe coiTosion. The 12-Cr stainless steels are scarcely, if any, better than the low-chromes. But the 18-8 Cr-Ni steels, without molybdenum, are often quite resistant under conditions of low velocity although they are sometimes subject to severe pitting. 

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... 

Metals which owe their good corrosion resistance to the presence of thin, passive or protective surface films may be susceptible to pitting attack when the surface film breaks down locally and does not reform. Thus stainless steels, mild steels, aluminium alloys, and nickel and copper-base alloys (as well as many other less common alloys) may all be susceptible to pitting attack under certain environmental conditions, and pitting corrosion provides an excellent example of the way in which crystal defects of various kinds can affect the integrity of surface films and hence corrosion behaviour. 

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)... 

Tomashov, N. D., Chernova, G. P. and Marcova, O. N., Effect of Supplementary Alloying Elements on Pitting Corrosion Susceptibility of 18Cr-14Ni Stainless Steel , Corrosion, 20, 166 (1964)... 

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