Pitting of metals

In deriving Eq. (36), and hence Eq. (38), it was assumed that the induction time is dominated by the time required to accumulate a critical areal concentration of cation vacancies (i.e., the formation time of the vacancy condensate). However, as evident from Fig. 33, the induction time may exceed the vacancy condensation time by the amount required for the film to dissolve locally and rupture. We previously lumped these effects into the relaxation time, r, and for the pitting of metals such as iron, copper, nickel, and stainless steels, which form very thin barrier layers, this approximation appears to be reasonable, in that Eq. (36) accounts for the experimental data very well. It is possible, however, to envision a case where the time... 

Utilization. For example, Be and the chalcophile elements, As, Cd, Hg, Pb, and Se, which are released during coal combustion or leached from coal waste products, can present significant environmental hazards halogens such as Cl and F can cause severe boiler corrosion and volatilized Ni, Ti, or V can cause corrosion and pitting of metal surfaces. On the positive side, some trace elements (e.g., Ge, Zn, U, and Au) may eventually prove to be economic by-products of coal utilization, while other elements (e.g., B) may be useful in helping to understand depositional environments and to correlate coal seams (7.8). 

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. 

Zsklarska-Smialowska Z 1986 Pitting Corrosion of Metals (Flouston, TX National Association of Corrosion Engineers)... 

Cemented carbides play a cmcial role in the recovery of metallic ores and nonmetals by underground or open-pit mining practices, recovery of minerals such as coal (qv), potash, and trona, and drilling for oh and gas. The methods of excavation can be broadly classified into three types rotary... 

Two types of localized corrosion are pitting and crevice corrosion. Pitting corrosion occurs on exposed metal surfaces, whereas crevice corrosion occurs within occluded areas on the surfaces of metals such as the areas under rivets or gaskets, or beneath silt or dirt deposits. Crevice corrosion is usually associated with stagnant conditions within the crevices. A common example of pitting corrosion is evident on household storm window frames made from aluminum alloys. 

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. 

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. 

Ancient iron structures sometimes show no sign of corrosion or at most, very little. The clean atmosphere of past centuries may be responsible in that it allowed a very thin adherent layer of oxide to develop on the surface [22], This layer very often protects against even today s increasingly aggressive industrial pollutants Very often the conditions of the initial corrosion are the ones that determine the lifespan of metals [23], A well-known example is the sacred pillar of Kutub in Delhi, which was hand forged from large iron blooms in 410 a.d. In the pure dry air, the pillar remains free of rust traces but shows pitting corrosion of the iron... 

The important beneficial effects that substrate roughness can bring were firmly established in the late sixties and early seventies, principally as a result of work in two areas. The first was associated with the electroless deposition of metals onto plastics such as ABS and polypropylene. In the process the plastics must be etched in a way which produces pits on a micrometre scale. Such a topography had been shown to be a necessary, but not sufficient condition for adequate adhesion [40]. 

Loch, n. hole, opening cavity eye pore prison, -blende, /. perforated screen or diaphragm. -eisen, n. puncher, pimch. locben, v.t. perforate, punch, pierce, locherig, a. full of holes, perforated, porous. Locherstelle,/. open place, gap, hole. Loch-frass, m. pitting (as of metals), -karte,/. punch (ed) card, -kultur,/. (Bact.) stab culture. -scheibe, /. perforated disk, apertured disk. 

Microbiocides may be toxic to humans therefore, care must be taken when used. When selecting the microbiocide, the field engineer can obtain pertinent information on chemicals from the service company providing the chemicals. The microbiocide selected must be compatible with the system in which it is being used. Some chemicals such as quaternary amines have dual functions one as microbiocides and the other as film-forming corrosion inhibitors. Insufficient concentrations of this type of chemical may not be enough to coat the whole surface of metal and can cause pitting corrosion. The selection must also depend on chemicals that can produce the desired control in minimum time limits and... 

The most important mechanism involved in the corrosion of metal is electrochemical dissolution. This is the basis of general metal loss, pitting corrosion, microbiologically induced corrosion and some aspects of stress corrosion cracking. Corrosion in aqueous systems and other circumstances where an electrolyte is present is generally electrochemical in nature. Other mechanisms operate in the absence of electrolyte, and some are discussed in Section 53.1.4. 

Pitting of passive metals such as the stainless steels, aluminium alloys, etc., in the presence of specific ions, e.g. Ci ions Dezincification deaiuminification graphitisation... 

On the other hand, pit initiation which is the necessary precursor to propagation, is less well understood but is probably far more dependent on metallurgical structure. A detailed discussion of pit initiation is beyond the scope of this section. The two most widely accepted models are, however, as follows. Heine, etal. suggest that pit initiation on aluminium alloys occurs when chloride ions penetrate the passive oxide film by diffusion via lattice defects. McBee and Kruger indicate that this mechanism may also be applicable to pit initiation on iron. On the other hand, Evans has suggested that a pit initiates at a point on the surface where the rate of metal dissolution is momentarily high, with the result that more aggressive anions... 

Unfortunately, there is no general theory that will explain all the forms of localised attack that occur with the variety of metal/environment systems encountered in practice, e.g. the mechanism of the pitting of stainless steels in Cl -containing solutions is quite different from the dezincification of brass in a fresh natural water. Nevertheless, many of the following factors play an important part in most forms of localised attack ... 

Localised attack can, however, occur on a surface of metal that is apparently uniform, and this occurs particularly with the highly passive metals that depend on a thin invisible protective film of oxide for their corrosion resistance. In such cases submicroscopic defects in the passive film may form the sites at which pits are initiated, thus giving rise to a situation similar to that shown in Fig. 1.46. 

The development of acidity within an occluded cell is by no means a new concept, and it was used by Hoar s as early as 1947 in his Acid Theory of Pitting to explain the pitting of passive metals in solutions containing Cl ions. According to Hoar the Cl ions migrate to the anodic sites and the metal ions at these sites hydrolyse with the formation of HCl, a strong acid that inhibits the formation of a protective film of oxide or hydroxide. Edeleanu and Evans followed the pH changes when aluminium was made anodic in Cl solutions and found that the pH decreased from 8-8 to 5-3. 

The importance of occluded cells cannot be overemphasised, and Brown considers that pitting, crevice corrosion, intergranular attack, filiform corrosion and hydrogen cracking are characterised by local acidification due to hydrolysis of metal ions, and that this phenomenon is of major significance in the overall mechanism. 

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