Linear polarization technique Tafel

Electrochemical corrosion techniques are essential to predict service life in chemical and construction industries. The following direct current (dc) electrochemical methods are used in corrosion engineering practice linear polarization technique, Tafel extrapolation, and open circuit potential vs. time measurements. The alternating current (ac) technique is electrochemical impedance spectroscopy (EIS). This technique uses alternating current to measure frequency-dependent processes in corrosion and estimates the change of polarization resistance as a function of time. 

Ehiring corrosion (oxidation) process, both anodic and cathodic reaction rates are coupled together on the electrode surface at a specific current density known ds icorv This is an electrochemical phenomenon which dictates that both reactions must occur on different sites on the metal/electrolyte interface. For a uniform process under steady state conditions, the current densities at equilibrium are related as o = — c = ieorr Ecorr- Assume that corrosion is uniform and there is no oxide film deposited on the metal electrode surface otherwise, complications would arise making matters very complex. The objective at this point is to determine both Ecorr and icorr either using the Tafel Extrapolation or Linear Polarization techniques. It is important to point out that icorr cannot be measured at Ecorr since ia = —ic and current wfll not flow through an external current-measuring device [3]. 

The study of uniform corrosion and studies assuming corrosion uniformity are probably the most widespread application of electrochemical measurements both in the laboratory and in the field. The widespread use of these electrochemical techniques does not mean that they are without complications. Both linear polarization and Tafel extrapolation need special precautions for their results to be valid. The main complications or obstacles in performing polarization measurements can be summarized in the following categories ... 

Many different electrochemical and non-electrochemical techniques exist for the study of corrosion and many factors should be considered when selecting a technique. Corrosion rate can be determined by Tafel extrapolation from a potentiodynamic polarization curve. Corrosion rate can also be determined using the Stem-Geary equation from the polarization resistance derived from a linear polarization or an electrochemical impedance spectroscopy (EIS) experiment. Techniques have recently been developed to use electrochemical noise for the determination ofcorrosion rate. Suscephbility to localized corrosion is often assessed by the determination of a breakdown potenhal. Other techniques exist for the determinahon of localized corrosion propagahon rates. The various electrochemical techniques will be addressed in the next section, followed by a discussion of some nonelectrochemical techniques. 

Recall that both Tafel slopes are positive in this form of the equation. The Stern-Geary equation is the basis for the linear polarization method in which the polarization resistance is determined typically by scanning the potential from a value slightly below the corrosion potential to one slightly above the corrosion potential. It is an extremely easy technique that has been put to considerable use in corrosion monitoring. The polarization resistance can be determined by a simple two-point measurement at values above... 

The Steam-Geary equation requires both the anodic and cathodic slopes to remain constant. For accurate measurements, it is necessary for the Tafel constants, and be, to be determined independendy using the Tafel technique. The slope of a linear polarization curve is controlled mainly by Ieo - Assuming that b and b are in the range of 120 mV, Eq. (5.24) reduces to ... 

Aqueous corrosion is electrochemical in nature. It is therefore possible to measure corrosion rate by employing electrochemical techniques. Two methods based on electrochemical polarization are available The Tafel extrapolation and linear polarization. Electrochemical methods permit rapid and precise corrosion-rate measurement and may be used to measure corrosion rate in systems that cannot be visually inspected or subject to weight-loss tests. Measurement of the corrosion current while the corrosion potential is varied is possible with the apparatus shown in Figure 1.4. 

The measurements typically are carried out at polarizations intermediate between the linear and the Tafel ranges (therefore, at relatively low current densities), and the system is completely characterized without significant damage to the specimen surface. Several variations and improvements of this basic idea were also proposed. The disadvantage of this technique is that the roots of the equations are sometimes complex numbers. 

H2SO4 in which the potential was scanned from —20 to -1-20 mV relative to the OCP. A relatively linear response is observed in this potential range. From Fig. 4, the polarization resistance can be found to be 80 cm. Using the Tafel slopes for this system determined from the potentiodynamic polarization curve given in Fig. 3 and the polarization resistance taken from Fig. 4, the corrosion rate is found to he 1.4 x 10 A cm , which is close to the value determined hy the Tafel extrapolation technique. 

Figure 31.1 shows a classic electrochemically measured Tafel polarization diagram [33. The Tafel analysis is performed by extrapolating the linear portions of both cathodic and anodic curves on a log (current) versus potential plot to their point of intersection. This intersection point provides both the corrosion potential con and the corrosion current density for the system unperturbed. This is a very simple yet powerful technique for quantitatively characterizing a corrosion process. The Tafel equation can be simplified to provide Eq. (7) by approximation using a power series expansion. 

The error of the Tafel-plot technique due to the neglect of the double-layer effect was reported to be unpredictable. The doublelayer effect distorts both the anodic and cathodic polarization curves, not necessarily to the same degree this results in possible cancellation or enhancement of the error caused by the doublelayer effect. Furthermore, because the Tafel lines are distorted and may not even have a truly linear portion in any potential range, the results strongly depend on the rather arbitrary drawing of a straight line through the data points. 

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