Polarization pits

After thermalization, the electron may recombine with a positive ion or be captured by a molecule forming a negative ion, or it may be locked in a trap the role of which may be played by fluctuation cavities or structural disturbances in the medium, or by polarization pits that the electron digs when it interacts with surrounding molecules. Such captured electrons are called solvated electrons (in water they are sometimes called hydrated electrons).31,32 According to the data obtained in picosecond pulsed-radiolysis sets,33 34 the solvation time of an electron is 2 x 10-12 s in water and —10 11 s in methanol. 

Comparative electrochemical Cyclic Polarization ("pitting") scans in aerated 3.5% NaCl, for aluminum alloy samples. 

In an electrochemical polarization experiment on a passive system tire onset of localized dissolution can be detected by a steep current increase at a very distinct anodic potential (tire pitting potential, —see figure... 

In the potential range catliodic to one frequently observes so-called metastable pitting. A number of pit growtli events are initiated, but tire pits immediately repassivate (an oxide film is fonned in tire pit) because the conditions witliin tire pit are such that no stable pit growtli can be maintained. This results in a polarization curve witli strong current oscillations iU [Pg.2728]

Evidence of localized corrosion can be obtained from polarization methods such as potentiodynamic polarization, EIS, and electrochemical noise measurements, which are particularly well suited to providing data on localized corrosion. When evidence of localized attack is obtained, the engineer needs to perform a careful analysis of the conditions that may lead to such attack. Correlation with process conditions can provide additional data about the susceptibility of the equipment to locaHzed attack and can potentially help prevent failures due to pitting or crevice corrosion. Since pitting may have a delayed initiation phase, careful consideration of the cause of the localized attack is critical. Laboratory testing and involvement of an... 

Figure 2-11 shows weight loss rate-potential curves for aluminum in neutral saline solution under cathodic protection [36,39]. Aluminum and its alloys are passive in neutral waters but can suffer pitting corrosion in the presence of chloride ions which can be prevented by cathodic protection [10, 40-42]. In alkaline media which arise by cathodic polarization according to Eq. (2-19), the passivating oxide films are soluble ... 

If the technical regulations are adhered to for constructional steels in neutral waters, there are no conditions for H-induced corrosion. On the other hand, hardened and high-strength materials with hardnesses above HV 350 are very susceptible [60,82,92], since anodic polarization encourages crack formation in saline media and anodic pitting occurs with acid products of hydrolysis [93]. 

Oxygen dissolved in aqueous solutions, even in very low concentrations, is a leading cause of corrosion problems (i.e., pitting) in drilling. Its presence also accelerates the corrosion rate of other corrodents such as hydrogen sulfide and carbon dioxide. Oxygen plays a dual role both as a cathodic depolarizer and an anodic polarizer or passivator. Within a certain range of concentration the... 

The aggressive ions either break down the protective films or prevent their formation and, in effect, increase the corrosion rate. In presence of chloride and sulfate ions the corrosion attack is more localized and, as a result, causes deep pitting. Inhibitive ions, on the other hand, tend to limit the attack and decrease the corrosion rate by forming protective films. The film is similiar to adherent carbonate-containing rust, which polarizes the anodic areas. When aggressive and inhibitive ions are present together, the aggressive ions, if present in sufficient quantities, interfere with the deposition of the protective layers. 

Electrochemical noise A variety of related techniques are now available to monitor localized corrosion. No external polarization of the corroding metal is required, but the electrical noise on the corrosion potential of the metal is monitored and analyzed. Signatures characteristic of pit initiation, crevice corrosion and some forms of stress corrosion cracking is obtained. 

A process in which a substance gains entry into a cell. Endocytic mechanisms are crucial for a variety of cellular functions such as the uptake of nutrients, regulation of cell surface expression of receptors, maintenance of cell polarity, and more. Receptor-mediated endocytosis via clathrin-coated pits is the most studied endocytic process, which is important for regulation of the time and magnitude of signals generated by a variety of cell-surface receptors. 

Figure 11. Schematic diagram of anodic polarization curve of passive-metal electrode when sweeping electrode potential in the noble direction. The dotted line indicates the polarization curve in the absence of Cl-ions, whereas the solid line is the polarization curve in the presence of Cl ions.7 Ep, passivation potential Eb, breakdown potential Epit> the critical pitting potential ETP, transpassive potential. (From N. Sato, J, Electrochem. Soc. 129, 255, 1982, Fig. 1. Reproduced by permission of The Electrochemical Society, Inc.)...

In the potential region where nonequilibrium fluctuations are kept stable, subsequent pitting dissolution of the metal is kept to a minimum. In this case, the passive metal apparently can be treated as an ideally polarized electrode. Then, the passive film is thought to repeat more or less stochastically, rupturing and repairing all over the surface. So it can be assumed that the passive film itself (at least at the initial stage of dissolution) behaves just like an adsorption film dynamically formed by adsorbants. This assumption allows us to employ the usual double-layer theory including a diffuse layer and a Helmholtz layer. 

Generally, for ideally polarized electrodes, the plots of the electrode potential against either the chemical potential of the component in question or its activity are referred to as the Esin and Markov plots the slope of the plot is called the Esin and Markov coefficient.82 Aogaki etal.19 first established the expression of the critical pitting potential with respect to the composition of the solution (i.e., the Esin and Markov relations corresponding to the critical condition of the instability obtained in the preceding sections) and also verified them experimentally in the case of Ni dissolution in NaCl solution. 

Fig. 3—Measurement of surface by HDI surface reflectance analyzer. In electromagnetic radiation (light), the polarization direction is defined as the direction of the electric field vector. The incident polarization of the light can be controlled. The instrument uses a variety of detectors to analyze the reflected polarization state of the light. (U.S. Patent 6,134,011). (a) Plane of the disk The SRA uses a fixed 60 degree (from the surface normal) angle of incidence. The plane of incidence is the same as the paper plane (b) Pit on a surface detected by reflected light channels of HDI instrument (c) Scratches on disk surface measured by HDI surface reflectance analyzer (d) Particles on the surface of disk detected by reflected light (black spot) and by scattered light (white spot) [8].

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... 

Ringas and Robinson performed electrochemical tests on stainless steels and mild steels in three cultures of SRB. In all cases pitting resistance was lower in cultures of SRB. Potentiodynamic polarization... 

It was learned that pitting-type metal and semiconductor corrosion is attended by the generation of noise seen in the form of dynamic irregularities in the changes of the anodic potential and current density. Thus, electrochemical noise studies were applied to the corrosion and passivation of metals and to their activation by external chemical (activating additives in the electrolyte) or electrochemical (anodic or cathodic polarization) agents. 

The second procedure is different from the previous one in several aspects. First, the metallic substrate employed is Au, which does not show a remarkable dissolution under the experimental conditions chosen, so that no faradaic processes are involved at either the substrate or the tip. Second, the tip is polarized negatively with respect to the surface. Third, the potential bias between the tip and the substrate must be extremely small (e.g., -2 mV) otherwise, no nanocavity formation is observed. Fourth, the potential of the substrate must be in a region where reconstruction of the Au(lll) surface occurs. Thus, when the bias potential is stepped from a significant positive value (typically, 200 mV) to a small negative value and kept there for a period of several seconds, individual pits of about 40 nm result, with a depth of two to four atomic layers. According to the authors, this nanostructuring procedure is initiated by an important electronic (but not mechanical) contact between tip and substrate. As a consequence of this interaction, and stimulated by an enhanced local reconstruction of the surface, some Au atoms are mobilized from the Au surface to the tip, where they are adhered. When the tip is pulled out of the surface, a pit with a mound beside it is left on the surface. The formation of the connecting neck between the tip and surface is similar to the TILMD technique described above but with a different hnal result a hole instead of a cluster on the surface (Chi et al., 2000). 

Other electrochemical techniques covered include measurements of the corrosion potential, the redox potential, the polarization resistance, the electrochemical impedance, electrochemical noise, and polarization curves, including pitting scans. A critical review of the literature concerned with the application of electrochemical techniques in the study of MIC is available [1164]. 

Figure 8. An Fe-17Cr stainless steel surface near a handle-shaped inclusion observed by AFM in 0.5M NaCl. (a) Surface at the corrosion potential of -240 mV (SCE). (b) Surface after application of a potential pulse of I s to 650 mV to initiate pitting, then anodically polarized at ISO mV (SCE). The pitting potential is approximately 350 mV. (Reprinted from Ref. 30 by permission of The Institute of Materials. London.)...

In research laboratories, potential is often used as the critical value for comparison purposes. A pitting potential is determined at a given suitable constant temperature, recording the anodic polarization curve while keeping other factors constant (Fig. 11). 

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