Passive film growth mechanisms

The scratch repassivation technique discussed above may be more useful for studying SCC than pitting [107]. This is because natural pitting is often initiated at defect sites in the passive film that are electronic or chemical in nature. Such sites are not necessarily probed by a mech inical scratch. Scratching can simulate SCC where mechanical film rupture processes are operative and anodic dissolution controls the SCC process. In general, once the passive film is mechanically disturbed at some potential, an electrochemical current can be measured that will decay back to a low level when repassivation has occurred. A measure of the crack growth rate, V, (cm/s) can be obtained from these data... 

The generally accepted model for passive film growth, illustrated in Fig. 3-14, is of field-assisted film formation, which is essentially a modified Cabrera-Mott model originally established for gaseous oxidation and the formation of thin oxide films in a gas at low temperature (Cabrera and Mott, 1948-1949 Fehlner and Mott, 1970). This classical theory describes the growth, in the direction perpendicular to the surface, of an oxide layer completely covering the substrate surface, by a hopping mechanism. The... 

The local dissolution rate, passivation rate, film thickness and mechanical properties of the oxide are obviously important factors when crack initiation is generated by localised plastic deformation. Film-induced cleavage may or may not be an important contributor to the growth of the crack but the nature of the passive film is certain to be of some importance. The increased corrosion resistance of the passive films formed on ferritic stainless steels caused by increasing the chromium content in the alloy arises because there is an increased enhancement of chromium in the film and the... 

Many theories on the formation mechanisms of PS emerged since then. Beale et al.12 proposed that the material in the PS is depleted of carriers and the presence of a depletion layer is responsible for current localization at pore tips where the field is intensified. Smith et al.13-15 described the morphology of PS based on the hypothesis that the rate of pore growth is limited by diffusion of holes to the growing pore tip. Unagami16 postulated that the formation of PS is promoted by the deposition of a passive silicic acid on the pore walls resulting in the preferential dissolution at the pore tips. Alternatively, Parkhutik et al.17 suggested that a passive film composed of silicon fluoride and silicon oxide is between PS and silicon substrate and that the formation of PS is similar to that of porous alumina. 

Solid-solid Adhesion Solid suspension, adhesion, cohesion, corrosion, passivation, epitaxial growth, wear, friction, diffusion, thin films, delamination, creep, mechanical stability, durability, solid state devices, blend and alloy, charge transfer, nucleation and growth abrasion... 

Macdougall, B., Graham, M.J., Growth and stability of passive films, in Corrosion mechanisms in theory and practice, P. Marcus and J. Oudar (eds.), Marcel Dekker, Inc., pp. 143-173, 1995. 

A somewhat alternative analysis of pitting attributes pit initiation to the activation of defects in the passive film, defects such as those induced during film growth or those induced mechanically due to scratching or stress. The pit behavior is analyzed in terms of the product, xi, a parameter in which x is the pit or crevice depth (cm), and i is the corrosion current density (A/cm2) at the bottom of the pit (Ref 21). Experimental measurements confirm that, for many metal/environment systems, the active corrosion current density in a pit is of the order of 1 A/cm2. Therefore, numerical values for xi may be visualized as a pit depth in centimeters. A defect becomes a pit if the pH in the pit becomes sufficiently low to prevent maintaining the protective oxide film. Establishing the critical pH, for a specific oxide, will depend on the depth (metal ions trapped by diffiisional constraints), the current density (rate of generation of metal ions) and the external pH. In turn, the current density will be determined by the local electrochemical potential established by corrosion currents to the passive external cathodic surface or by a potentiostat. Once the critical condition for dissolution of the oxide has been reached, the pit becomes deeper and develops a still lower pH by further hydrolysis. 

Representative environments for which SCC has been reported in carbon steels are included in Table 7.7. The sensitivity of these steels to changes in composition and environment are illustrated by the effects of potential in Fig. 7.78 to 7.80 and by the slow strain-rate data of Fig. 7.82 and 7.83. These data support the conclusion that environment cracking is related to the susceptibility of the passive films to crack under stress, to the subsequent crack growth due to anodic dissolution and/or hydrogen embrittlement during the period of exposure of the alloy substrate, and to rates of repassivation of the exposed areas. Actual crack-front growth mechanisms are discussed in some detail in a later section. 

Crack-tip growth mechanisms have been proposed that do not involve dislocation movement explicitly, but rather, in response to the stress field at the crack tip, interstitial atoms diffuse to the region of the stress field to reduce the stress substitutional atoms also will diffuse to the tip if the local stress is thereby reduced. Crack-tip growth would be increased if this local change in alloy composition enhances dissolution during slip displacement or alters the passive film such that it is more easily ruptured by dislocations emerging to the surface. That is, there is continuously produced at the crack tip a film that is more easily ruptured than the more stable passive film on the sides of the crack (Ref 158). 

Summary. Scanning tunneling microscopy (STM) provides new possibilities to explore the link between the structure and the properties of thin oxide overlayers (passive films) formed electrochemically on well-defined metal surfaces. Passive oxide films protect many metals and alloys against corrosion. A better understanding of the growth mechanisms, the stability, and the degradation of passive films requires precise structural data. Recently, new results on the atomic structure of passive films have been obtained by STM. The important questions of crystallinity, epitaxy and the nature of defects have been addressed. Data on the structure of passive films on Ni, Cr, Fe, Al, and Fe-Cr alloys are reviewed with enq>hasis on atomically resolved structures. Ihe perspectives of future developments are discussed. 

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