Potential drop passive film

For metals such as chromium and alloys such as stainless steel, the plot of potential versus corrosion rate above the range is shown in Figure 20.67. Figure 20.68 shows a sudden sharp drop in corrosion above some critical potential. Despite a high level of anode polarization above V, the corrosion rate drops precipitously due to the formation of a thin, protective oxide film as a barrier to the anodic dissolution reaction. Resistance to corrosion above is termed passivity. The drop in corrosion rate above can be as much as 10 to 10 times below the maximum rate in the active state. With increasing corrosion potential, the low corrosion rate remains constant until at a relatively high potential the passive film break down, and the normal increase in corrosion rate resumes in a transpassive region. 

As already mentioned, salt-containing liquid solvents are typically used as electrolytes. The most prominent example is LiPF6 as a conductive salt, dissolved in a 1 1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) as 1 molar solution. It should be mentioned that this electrolyte is not thermodynamically stable in contact with lithium or, for example, LiC6. Its success comes from the fact that it forms an extremely stable passivation layer on top of the electrode, the so-called solid-electrolyte interface (SEI) [35], Key properties of such SEI layers are high Li+ and very low e conductivity - that is, they act as additional electrolyte films, where the electrode potential drops to a level the liquid electrolyte can withstand [36],... 

In-depth selective etching of silicon in alkaline solutions can also utilize the difference in the passivation potentials between p- and ra-type materials [135,138, 180, 222, 223]. In this method, as shown in Fig. 36i, an anodic voltage sufficient to cause passivation of ra-Si is applied through an ohmic contact. Because of the potential drop in the reversely biased pn junction, the potential of the p-Si maintains at a potential negative to the passivation potential and is etched. Upon complete removal of the p-Si, the junction disappears and the etch stops because the ra-Si is passivated. A current peak, corresponding to the formation of the passive oxide film on the ra-Si, occurs when the p-ra interface is reached. This current peak signals the onset of the etch stop. Extra control can be obtained by applying... 

If the passive film cannot be reestablished and active corrosion occurs, a potential drop is established in the occluded region equal to IR where R is the electrical resistance of the electrolyte and any salt film in the restricted region. The IR drop lowers the electrochemical potential at the metal interface in the pit relative to that of the passivated surface. Fluctuations in corrosion current and corrosion potential (electrochemical noise) prior to stable pit initiation indicates that critical local conditions determine whether a flaw in the film will propagate as a pit or repassivate. For stable pit propagation, conditions must be established at the local environment/metal interface that prevents passive film formation. That is, the potential at the metal interface must be forced lower than the passivating potential for the metal in the environment within the pit. Mechanisms of pit initiation and propagation based on these concepts are developed in more detail in the following section. 

These factors can be discussed with reference to the polarization curves for the initial and changing conditions within the occluded region. The combined effects of a potential drop into the pit and the effect of the lowered pH, which raises Epp and increases icrit, are also analyzed by reference to Fig. 7.6 (Ref 20). As previously assumed, the solid anodic curve is taken as representative of a stainless steel in an environment of pH = 1. The dashed extension again represents the anodic polarization behavior in the absence of a passive film. At a potential, Ecorr (or Epot if the potential is maintained potentiostatically), the passive current density would be iCOrr,pass and the active corrosion current density would be iCorr,act- Assume that a small flaw through the passive film is associated with an (IR), drop that lowers the potential in the bottom of the flaw to E,. Since this potential is higher than the passivating potential, Epp, this flaw should immediately repassivate and not propagate. 

If the flaw in the passive film is smaller in cross section and greater in depth, then with reference to Fig. 7.6, the resulting increase in resistance can lead to an (IR)2 potential drop that decreases the potential in the bottom of the flaw and/or pit to E2. Then passivity cannot be maintained, and the corrosion current density increases to i2 in the active range. The local corrosion rate is much higher, and a stable pit is initiated at the much higher current density. When the pH of the bulk envi-... 

There is also evidence that the beneficial effect of molybdenum is to interfere with pit propagation. If the mechanism is active at the initiation of localized breakdown of the passive film, then, effectively, pitting will not occur. Based on the low solubility of molybdenum chloride, Mo03, and polymolybdates in acid solutions, one mechanism proposes that molybdenum enhances the formation of salt films of these species within the pit. This can decrease the IR potential drop to the pit... 

In the opposite case, hv > g, photons produce electron-hole pairs. Accumulation of holes at the oxide surface increases the local potential drop which may cause a fast photocorrosion. Ion migration is enhanced in the thin film, corrosion is enhanced, and altogether a fast dissolution of metal takes place by a photoelectro-chemical process in the passive film. An example is given for Ti [160]. This technique can be used for microstructuring of Ti- or Al surfaces [104]. On the other hand, anodic metal ion dissolution competes with the opposite anodic film forming ITR of oxygen ions. Therefore, in dependence on the special conditions, laser induced oxide growth may overcome pit formation [160]. 

Pickering and coworkers [31, 34, 35] have demonstrated both experimentally and computationally that for systems that meet the criteria of the IR theory, lA is predicted. The amount of potential drop increases as one moves into the crevice because of the current leaving the crevice. If the geometry, solution conductivity, and passive current density of the material in the environment conspire to create sufficient ohmic drop, then the potential of some portion of the material within the crevice falls to the primary passive potential. Under these circumstances, the passive film is not stable and active dissolution occurs. The potential difference between the applied potential and the primary passivation potential is referred to as IR. Deeper still into the crevice the ohmic drop leads to decreased dissolution as the overpotential for the anodic reaction decreases. Thus, ohmic drop is responsible for the initiation and stabihzation of crevice corrosion according to this model. 

A further barrier to corrosion reactions is provided by electrical resistance. When the anodic and cathodic reactions at the metal surface take place with locally different current densities, resistance in the current circuits can cause a measurable drop in potential (resistance polarization). This resistance polarization is a linear function of the current. Resistance polarization frequently arises through the formation of passive films. The resulting relationship between the change in potential and the current usually no longer follows Ohm s law, but instead is subject to a logarithmic relationship. 

The development of pits starts with a crack or a hole of atomic dimension in the passive film caused, e.g., by tensions or by local chemical dissolution of the fihn. Permanent pitting corrosion can start above a critical potential and a critical concentration of the chloride ions. Above these critical values repassivation is prevented by the adsorption of the aggressive anions in the crack or the hole. The small dimensions of the crack or hole stabilize the large potential drop between active and passive surface. 

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