Corrosion phenomenon Current

A cut or scratch of the film applied on polarized p>anel allows again the flow of protective electrical current metallic zinc is oxidized and the film is sealed again. A substantial difference with other types of coatings is that the corrosive phenomenon does not occur under the film adjacent to the cut (undercutting). 

Despite the several mathematical models being developed for describing corrosion problems and their solutions, each model has its own degree of accuracy, which depends on the chosen variables and conditions, and numerical method for determining relevant parameters that describe a particular corrosion phenomenon. Comprehensive reviews of models for describing a particular problem, such as crevice cathodic protection, pitting growth rate, current and potential attenuation are available in the literature [2,3,18,25-32]. 

An electrochemical reaction is said to be polarized or retarded when it is limited by various physical and chemical factors. In other words, the reduction in potential difference in volts due to net current flow between the two electrodes of the corrosion cell is termed polarization. Thus, the corrosion cell is in a state of nonequilibrium due to this polarization. Figure 4-415 is a schematic illustration of a Daniel cell. The potential difference (emf) between zinc and copper electrodes is about one volt. Upon allowing current to flow through the external resistance, the potential difference falls below one volt. As the current is increased, the voltage continues to drop and upon completely short circuiting (R = 0, therefore maximum flow of current) the potential difference falls toward about zero. This phenomenon can be plotted as a polarization diagram shown in Figure 4-416. 

The dissolution of zinc in a mineral acid is much faster when the zinc contains an admixture of copper. This is because the surface of the metal contains copper crystallites at which hydrogen evolution occurs with a much lower overpotential than at zinc (see Fig. 5.54C). The mixed potential is shifted to a more positive value, E mix, and the corrosion current increases. In this case the cathodic and anodic processes occur on separate surfaces. This phenomenon is termed corrosion of a chemically heterogeneous surface. In the solution an electric current flows between the cathodic and anodic domains which represent short-circuited electrodes of a galvanic cell. A. de la Rive assumed this to be the only kind of corrosion, calling these systems local cells. 

This phenomenon, however, is not difficult to understand in view of the mechanism of dissolution under such conditions. Since the number of active sites increases linearly with current density and these sites are characterized by a film structure (or thickness or both) different from that at the OCP, one could expect corresponding increases in the corrosion rate. However, as was mentioned earlier, the active surface area in the pits increases with time, and hence one should expect the corrosion rate to increase correspondingly. Therefore, since the effect is not time dependent, one... 

Considerable progress has been made during the past decade toward a better insight into the basic concepts and mechanism involved in metallic dissolution and corrosion. More emphasis has been placed on the "fundamental particles (metallic ions, electrons, and electron acceptors) and on the use of current-voltage characteristics. The wide recognition of dissolution and corrosion as electrode processes, and the idea of a polyelectrode exhibiting a mixed potential, have augmented the use of electrochemical techniques in the study and interpretation of corrosion phenomena. There is even some evidence that the phenomenon of passivity may soon be clarified. 

Electrochemical potentlostat measurements have been performed for the corrosion of iron, carbon steel, and stainless steel alloys in supercritical water. The open circuit potential, the exchange or corrosion current density, and the transfer coefficients were determined for pressures and temperatures from ambient to supercritical water conditions. Corrosion current densities increased exponentially with temperature up to the critical point and then decreased with temperature above the critical point. A semi-empirical model is proposed for describing this phenomenon. Although the current density of iron exceeded that of 304 stainless steel by a factor of three at ambient conditions, the two were comparable at supercritical water conditions. The transfer coefficients did not vary with temperature and pressure while the open circuit potential relative to a silver-silver chloride electrode exhibited complicated behavior. 

Polarization behavior relates to the kinetics of electrochemical processes. Study of the phenomenon requires techniques for simultaneously measuring electrode potentials and current densities and developing empirical and theoretical relationships between the two. Before examining some of the simple theories, experimental techniques, and interpretations of the observed relationships, it is useful to characterize the polarization behavior of several of the important electrochemical reactions involved in corrosion processes. 

Overvoltage depends on the current density. When a cathodic current is appHed to the electrode, the electrons accumulate in the metal as a result of slow charge transfer. This phenomenon causes cathodic polarization, t], to be negative. Conversely, when electrons are removed from the metal like anodic polarization (corrosion), the polarization is positive. 

Electrochemical tests are specific tests conducted with the aim to evaluate the corrosion current. As mentioned before, corrosion, and so material loss, is a phenomenon including electrochemical reactions and electron transfer. This transfer can be translated into an electrical current that can be measured by using accurate instrumentation, often in remote control by specialised software. 

---