Pitting surface and

The effect of convection on the pitting behaviour of stainless steel 304 is in total contrast to that of pure iron, in that removal of the metal salt film leads to the repassivation of the metal surface. Harb [113] has recently investigated the pitting-convection behaviour of single pits in a pH 3.5 solution of 0.1 M Na2S04 and 0.2 M NaCl. Basing his analysis on the concept of a critical Peclet number [113], he showed that high Peclet numbers (Pe > 10) favour removal of the dissolution products from the pit surface and subsequent repassivation, whilst for flow rates and/or pit radii for which... 

Low alloy steels (4000-8000 series) Surface oxidation and pitting, surface and intergranular Reddish-brown oxide (rust)... 

Qualitative examples abound. Perfect crystals of sodium carbonate, sulfate, or phosphate may be kept for years without efflorescing, although if scratched, they begin to do so immediately. Too strongly heated or burned lime or plaster of Paris takes up the first traces of water only with difficulty. Reactions of this type tend to be autocat-alytic. The initial rate is slow, due to the absence of the necessary linear interface, but the rate accelerates as more and more product is formed. See Refs. 147-153 for other examples. Ruckenstein [154] has discussed a kinetic model based on nucleation theory. There is certainly evidence that patches of product may be present, as in the oxidation of Mo(lOO) surfaces [155], and that surface defects are important [156]. There may be catalysis thus reaction VII-27 is catalyzed by water vapor [157]. A topotactic reaction is one where the product or products retain the external crystalline shape of the reactant crystal [158]. More often, however, there is a complicated morphology with pitting, cracking, and pore formation, as with calcium carbonate [159]. 

Leaky valves are also a cause of erosion. Most turbine erosion-corrosion problems come from damage that takes place when the unit is not running. A shght steam leak into the turbine will let the steam condense inside the turbine, and salt from the boiler water will settle on the inside surfaces and cause pitting, even of the stainless blading. There must be two valves with a drain between them, i.e., a block valve on the header and an open drain in the line before it reaches the closed trip-throttle valve. 

Corrosion products and deposits. All sulfate reducers produce metal sulfides as corrosion products. Sulfide usually lines pits or is entrapped in material just above the pit surface. When freshly corroded surfaces are exposed to hydrochloric acid, the rotten-egg odor of hydrogen sulfide is easily detected. Rapid, spontaneous decomposition of metal sulfides occurs after sample removal, as water vapor in the air adsorbs onto metal surfaces and reacts with the metal sulfide. The metal sulfides are slowly converted to hydrogen sulfide gas, eventually removing all traces of sulfide (Fig. 6.11). Therefore, only freshly corroded surfaces contain appreciable sulfide. More sensitive spot tests using sodium azide are often successful at detecting metal sulfides at very low concentrations on surfaces. 

Pits form grooves or furrows on wall surfaces on stainless steels (Figs. 7.5 and 7.6). Contents leak out of pit interiors and depassivate areas immediately below the active corrosion sites. Grooves form, fol-... 

Stress-corrosion cracks tend to branch along the metal surfaces. Typically, evidence of corrosion, such as accumulations of corrosion products, is not observed, although stains in the cracked region may be apparent. Stress-corrosion cracks tend to originate at physical discontinuities, such as pits, notches, and corners. Areas that may possess high-residual stresses, such as welds or arc strikes, are also susceptible. 

This method is generally not capable of achieving a uniform standard of cleanliness on structural steel. It is not effective in removing intact mill scale or corrosion products from pitted surfaces. The durability of subsequent coats is therefore variable and unpredictable, and depends on the thoroughness of the operation and the exact nature of the contaminants left on the surface. The method should be confined to non-aggressive environments or where short-term durability is economically acceptable. 

Fig. l.S(a) Grain boundary intersecting an etched metallographic surface and (b) etch pit at a dislocation interseaing an etched metallographic surface... 

Gear lubricants In addition to the usual oxidation and corrosion inhibitors, lubricants for heavily loaded gears almost always contain EP additives containing sulphur, chlorine or phosphorus. In order to function, these additives must react locally with the metal surfaces, and yet the extent of the reaction should not be such that it could be described as corrosive, or promote fatigue pitting . These EP additives may be quite safe with ferrous metal surfaces, but may cause severe corrosion on copper alloys, e.g. on bronze worm wheels if for any reason excessive temperatures arise. 

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