Crevice corrosion mechanisms

The crevice corrosion mechanism is very similar to that of pitting with respect to the autocatalytic propagation. However, the causes of initiation, the morphology and the penetration of pitting are quite different from that of crevice corrosion (Figure 6.21).16... 

Rupture of Organic Protective Films This condition differs from other causes of localized corrosion since these protective films are nonconductors and, as such, do not support the cathodic reaction. After the rupture in the coating, corrosion may progress under the coating by crevice corrosion mechanisms, resulting in further damage. 

Metal-matrix composites are thought to corrode by a crevice corrosion mechanism with the crevice forming at the fibre/matrix interface (Cosgrave and Hinton 1991). They have studied the corrosion behaviour of an Al alloy 6061/boron metal-matrix composite in 0.1 M NaCl solution. As shown in fig. 11, the presence of lOOOppm CeCls in the test solution, significantly reduced the corrosion rate of the composite, particularly at long immersion times. After testing with CeCls present, a thick opaque yellow film of hydrated Ce oxide was observed on the surface of the composite. Cosgrave and Hinton concluded that the presence of this film was responsible for the corrosion protection, and that the... 

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. 

Surface defects, if sufficiently severe, may result in failure by themselves. More commonly, they act as triggering mechanisms for other failure modes. For example, open laps or seams may lead to crevice corrosion or to concentration sites for ions that may induce stress-corrosion cracking. 

General description. Incomplete penetration describes the condition in which the weld fails to reach the bottom of the weld joint, resulting in a notch located at the root of the weld (Fig. 15.12). This critical defect can substantially reduce the intrinsic mechanical strength of the joint and can combine with environmental factors to produce corrosion fatigue (Chap. 10), stress-corrosion cracking (Chap. 9), or crevice corrosion (Chap. 2). 

Copper has excellent resistance to some corrosive environments, including fresh waters and fluoride-containing atmospheres. Alloying is necessary to achieve good strength, but copper limiting with steel for strength is an alternative (BS 5624). Copper and some of its alloys are susceptible to crevice corrosion, but the mechanism is different from that which affects stainless steels. 

The various types of localised corrosion have been enumerated in Table 1.2 in Section 1.1, and many of them are dealt with in some detail in other sections of this volume. For this reason this section will be confined to a consideration of the factors that give rise to crevice corrosion, filiform corrosion, pitting, selective leaching and erosion-corrosion and of the mechanisms of these forms of localised attack. 

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. 

Most cases of crevice corrosion take place in near-neutral solutions in which dissolved oxygen is the cathode reactant, but in the case of copper and copper alloys crevice corrosion can occur owing to differences in the concentration of Cu ions however, in the latter the mechanism appears to be different, since attack takes place at the exposed surface close to the crevice and not within the crevice in fact, the inside of the crevice may actually be cathodic and copper deposition is sometimes observed, particularly in the Cu-Ni alloys. Similar considerations apply in acid solutions in which the hydrogen ion is the cathode reactant, and again attack occurs at the exposed surface close to the crevice. 

At first sight the mechanism of crevice corrosion appears to be simply the formation of a differential aeration cell in which the freely exposed metal outside the crevice is predominantly cathodic whilst the metal within the crevice is predominantly or solely anodic the large cathode current acts on the small anodic area thus resulting in intense attack. However, although differential aeration plays an important role in the mechanism, the situation in reality is far more complex, owing to the formation of acid within the crevice. 

Fig, 1.50 Mechanism of crevice corrosion at. for example, the steel joint shown in Fig. 1.49cr when immersed in a chloride solution after Reference 22... 

Griess has observed crevice corrosion of titanium in hot concentrated solutions of Cl , SOj I ions, and considers that the formation of acid within the crevice is the major factor in the mechanism. He points out that at room temperature Ti(OH)3 precipitates at pH 3, and Ti(OH)4 at pH 0-7, and that at elevated temperatures and at the high concentrations of Cl ions that prevail within a crevice the activity of hydrogen ions could be even greater than that indicated by the equilibrium pH values at ambient temperatures. Alloys that remain passive in acid solutions of the same pH as that developed within a crevice should be more immune to crevice attack than pure titanium, and this appears to be the case with alloys containing 0-2% Pd, 2% Mo or 2[Pg.169]

Pitting may be defined as a limiting case of localised attack in which only small areas of the metal surface are attacked whilst the remainder is largely unaffected, and this definition is applicable irrespective of the mechanism involved dezincification, crevice corrosion and impingement attack can all result in pitting, although the mechanisms of these three processes are quite different. 

In recent years the mechanism of crevice has been mathematically modelled and a more thorough understanding of the corrosion processes has been evolved . From such mathematical modelling it is feasible to predict critical crevice dimensions to avoid crevice corrosion determined with relatively simple electrochemical measurements on any particular stainless steel. 

The corrosion problems associated with mechanical fixtures are often one of two types, i.e. crevice corrosion or bimetallic corrosion ", which have been dealt with in some detail in Sections 1.6 and 1.7, respectively. 

Finally, mechanical joints, e.g. nuts, bolts, rivets etc., are still important joining methods for which attention must be given to compatibility to avoid dissimilar metal corrosion problems and crevice corrosion " . ... 

In addition to the basic corrosion mechanism of attack by acetic acid, it is well established that differential oxygen concentration cells are set up along metals embedded in wood. The gap between a nail and the wood into which it is embedded resembles the ideal crevice or deep, narrow pit. It is expected, therefore, that the cathodic reaction (oxygen reduction) should take place on the exposed head and that metal dissolution should occur on the shank in the wood. 

Localized, concentration-cell corrosion (differential aeration corrosion), occurring as Tuberculation corrosion Crevice corrosion Under-deposit corrosion Pitting corrosion All forms of localized, concentration-cell corrosion are indirect attack type corrosion mechanisms. They result in severe metal wastage and can also induce other corrosion mechanisms, e.g. Stress corrosion Corrosion fatigue... 

Polarization techniques have also been used to determine mechanisms by which microorganisms induce localized corrosion in the forms of pitting or crevice corrosion. In most cases itpit was determined in the presence and absence of bacteria, itpit provides data as to the tendency for pitting, but not the rate for pit propagation. Salvarezza et ah " and De Mele... 

MIC almost always acts in concert with other corrosion mechanisms and may, at times, appear to be crevice corrosion, underdeposit acid attack, oxygen-concentration cell corrosion, ion-concentration cell corrosion, and CO2... 

Stainless steel generally withstands polluted sea water and polluted brackish water better than copper-base alloys. Substituting an austenitic stainless screen for silicon-bronze trash racks has resulted in greatly improved service at a west coast power plant. Normally stainless steel screens, because of the crevices involved (where the wires cross), are not recommended for use in sea water. This alteration of the usual corrosion mechanism, presumably related to the hydrogen sulfide content of polluted sea water, needs to be studied. 

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