Corrosion rate electrochemical determination

Anodic Protection Corrosion of metals, and their alloys, exposed to a given environment requires at least two separate electrochemical (anodic and cathodic) reactions. The corrosion rate is determined at the intersection of these two reactions (see Fig. 25-2a). 

The anode and cathode corrosion currents, fcorr.A and fcorr,B. respectively, are estimated at the intersection of the cathode and anode polarization of uncoupled metals A and B. Conventional electrochemical cells as well as the polarization systems described in Chapter 5 are used to measure electrochemical kinetic parameters in galvanic couples. Galvanic corrosion rates are determined from galvanic currents at the anode. The rates are controlled by electrochemical kinetic parameters like hydrogen evolution exchange current density on the noble and active metal, exchange current density of the corroding metal, Tafel slopes, relative electroactive area, electrolyte composition, and temperature. 

The droplet height varied between 400 and 1100 pm. The local corrosion rates were determined by EIS and electrochemical polarization measurements. An increase in corrosion rate was observed with decreasing electrolyte thickness below 800 pm. The increase of the corrosion rate was due to the decrease of the diffusion layer thickness, resulting in an increase in oxygen reduction rate. 

Carbon steel reinforcement corrosion rates are determined using in situ electrochemical corrosion techniques. These techniques have advantages and disadvantages, and are complementary to some extent. Electrochemical impedance spectroscopy (EIS) is an AC method particularly suited for coated metal corrosion rates. 

Corrosion occurs at a rate determined by equilibrium between opposing electrochemical reactions. The rate of any given electrochemical process depends on the rates of two conjugate reactions proceeding at the surface of the metal. Transfer of metal atoms from the lattice to the solution (anodic reaction) with the liberation of electrons and consumption of these electrons by some depolarisers (cathodic reaction). When these two reactions are in equilibrium, the flow of electrons from each reaction of balanced and no net electron flow (current) occurs. Various methods are available for the determination of dissolution rate of metals in corrosive environments but electrochemical methods employing polarisation techniques are by far most widely used. The corrosion rate (CR) is evaluated by mass loss method considering uniform corrosion. The Corrosion rate is determined by the following formula as per standard [102]. 

ASTM G 96, Practice for On-Line Monitoring of Corrosion in Plant Equipment (Electrical and Electrochemical Methods)—This standard outlines procedures for online corrosion monitoring in operating systems. The test methods described in this standard are used to determine the cumulative metal loss (electrical resistance method) or instantaneous corrosion rates (electrochemical method). Reference 15 provides a summary of electrical resistance and polarization resistance theory. 

The corrosion of Mg is thus only partly electrocheniical, and electrochemical measurements predict [31] corrosion rates, P , lower than the real corrosion rate, as determined for example by hydrogen evolution. The apparent electrochemical valence, (1 + A ), is determined by the quantity (2PJPy. For example Petty et al. [29] measured the apparent valence to be 1.5 in 150 g/L NaCl. If this was the only important effect, electrochemical measurements should always underestimate the actual corrosion rate by a constant fraction (which might depend on solution). 

Corrosion Rate by CBD Somewhat similarly to the Tafel extrapolation method, the corrosion rate is found by intersecting the extrapolation of the linear poi tion of the second cathodic curve with the equihbrium stable corrosion potential. The intersection corrosion current is converted to a corrosion rate (mils penetration per year [mpy], 0.001 in/y) by use of a conversion factor (based upon Faraday s law, the electrochemical equivalent of the metal, its valence and gram atomic weight). For 13 alloys, this conversion factor ranges from 0.42 for nickel to 0.67 for Hastelloy B or C. For a qmck determination, 0.5 is used for most Fe, Cr, Ni, Mo, and Co alloy studies. Generally, the accuracy of the corrosion rate calculation is dependent upon the degree of linearity of the second cathodic curve when it is less than... 

The use of impedance electrochemical techniques to study corrosion mechanisms and to determine corrosion rates is an emerging technology. Elec trode impedance measurements have not been widely used, largely because of the sophisticated electrical equipment required to make these measurements. Recent advantages in micro-elec tronics and computers has moved this technique almost overnight from being an academic experimental investigation of the concept itself to one of shelf-item commercial hardware and computer software, available to industrial corrosion laboratories. 

Although important contributions in the use of electrical measurements in testing have been made by numerous workers it is appropriate here to refer to the work of Stern and his co-workerswho have developed the important concept of linear polarisation, which led to a rapid electrochemical method for determining corrosion rates, both in the laboratory and in plant. Pourbaix and his co-workers on the basis of a purely thermodynamic approach to corrosion constructed potential-pH diagrams for the majority of metal-HjO systems, and by means of a combined thermodynamic and kinetic approach developed a method of predicting the conditions under which a metal will (a) corrode uniformly, (b) pit, (c) passivate or (d) remain immune. Laboratory tests for crevice corrosion and pitting, in which electrochemical measurements are used, are discussed later. 

It is evident from previous considerations (see Section 1.4) that the corrosion potential provides no information on the corrosion rate, and it is also evident that in the case of a corroding metal in which the anodic and cathodic sites are inseparable (c.f. bimetallic corrosion) it is not possible to determine by means of an ammeter. The conventional method of determining corrosion rates by mass-loss determinations is tedious and over the years attention has been directed to the possibility of using instantaneous electrochemical methods. Thus based on the Pearson derivation Schwerdtfeger, era/. have examined the logarithmic polarisation curves for potential breaks that can be used to evaluate the corrosion rate however, the method has not found general acceptance. 

Neufeld, P. and Queenan, E. D., Frequency Dependence of Polarisation Resistance Measured with Square Wave Alternating Potential , Br. Corros. J., 5, 72-75, March (1970) Fontana, M. G., Corrosion Engineering, 3rd edn., McGraw-Hill, pp 194-8 (1986) Dawson, J. L., Callow, L. M., Hlady, K. and Richardson, J. A., Corrosion Rate Determination By Electrochemical Impedance Measurement , Conf. On-Line Surveillance and Monitoring of Process Plant, London, Society of Chemical Industry (1977)... 

The measurement of corrosion current has provided, as is well known, a quite useful electrochemical technique for determining corrosion rates. However, contrary to homogeneous corrosion, pitting corrosion is a typical heterogeneous reaction on a metal surface, so that it is difficult to estimate the actual corrosion state from the usual corrosion current data. 

That is, to determine the correct corrosion rates in pitting corrosion, as shown in Fig. 37, it is necessary to know the local corrosion currents on the electrode surface. The corrosion current observed is, however, obtained as the total current, which is collected by the lead wire of the electrode. From the usual electrochemical measurement, we can thus determine only an average corrosion current (i.e., the corrosion rate). Hence if we can find some way to relate such an average rate to each local corrosion rate, the local corrosion state can be determined even with the usual electrochemical method. 

A simplification of the polarization resistance technique is the linear polarization technique in which it is assumed that the relationship between E and i is linear in a narrow range around E . Usually only two points ( , 0 are measured and B is assumed to have a constant value of about 20 mV. This approach is used in field tests and forms the basis of commercial corrosion rate monitors. Rp can also be determined as the dc limit of the electrochemical impedance. Mansfeld et al. used the linear polarization technique to determine Rp for mild steel sensors embedded in concrete exposed to a sewer environment for about 9 months. One sensor was periodically flushed with sewage in an attempt to remove the sulfuric acid produced by sulfur-oxidizing bacteria within a biofilm another sensor was used as a control. A data logging system collected Rp at 10-min intervals simultaneously for the two corrosion sensors and two pH electrodes placed at the concrete surface. Figure 2 shows the cumulative corrosion loss (Z INT) obtained by integration of the MRp time curves as ... 

Electrochemical impedance, weight loss, and potentiodyne techniques can be used to determine the corrosion rates of carbon steel and the activities of both sulfate-reducing bacteria and acid-producing bacteria in a water injection field test. A study revealed that the corrosion rates determined by the potentiodyne technique did not correlate with the bacterial activity, but those obtained by electrochemical impedance spectroscopy (EIS) were comparable with the rates obtained by weight loss measurements [545]. 

In this study, ion implantation and RBS analyses were important tools used to complement electrochemical measurements. Without the combination of both types of measurements, important information would have been lost. Electrochemical analysis alone would not show the inactive Pt while RBS analysis alone would have made determination of corrosion rates much more tedious. 

The electrochemical approach has the advantage of speed and relative simplicity. The disadvantage is that one obtains the corrosion rate under the conditions chosen—a fresh electrode and solution—i.e., corrosion in the shortterm. Real corrosion situations are more complex. At longer times, the metal becomes partly covered with an oxide and other coatings the solution or moisture film contains components not there in a laboratory situation. However, the Stern-Geary electrochemical approach allows at least a relative determination of the corrosion rate for a series of situations. It is simple and it is fast. 

The impossibility of a direct measurement of corrosion rate using electrochemical testing would seem to be discouraging. Application of mixed potential theory allows determination of the corrosion rate using a method known as Tafel extrapolation. 

The information required to predict electrochemical reaction rates (i.e., experimentally determined by Evans diagrams, electrochemical impedance, etc.) depends upon whether the reaction is controlled by the rate of charge transfer or by mass transport. Charge transfer controlled processes are usually not affected by solution velocity or agitation. On the other hand, mass transport controlled processes are strongly influenced by the solution velocity and agitation. The influence of fluid velocity on corrosion rates and/or the rates of electrochemical reactions is complex. To understand these effects requires an understanding of mixed potential theory in combination with hydrodynamic concepts. 

However, since this corrosion reaction is short-circuited on the corroding surface, no current will flow in any external measuring circuit. Consequently, a direct electrochemical measurement of the corrosion current (convertible to corrosion rate by the application of Faraday s law) cannot be made. Despite this limitation, electrochemical techniques can be used to decouple the two half-reactions, thereby enabling each to be separately and quantitatively studied. This involves the determination of the current-potential relationships for each half-reaction. Subsequently, the behavior under electrochemically unperturbed (open-circuit or natural corrosion) conditions can be reconstructed by extrapolation of these relationships to Ecorr-... 

Figure 16 Illustration of the procedure used to evaluate fuel corrosion performance in a nuclear waste vault (A) fuel corrosion rate as a function of radiation dose rate [from (B) in Figure 15] (B) calculated radiation dose rate decay curve (C) fuel corrosion rates as a function of time in a waste vault. The dashed line indicates that there is a limit to the acceptable extrapolation of rates determined electrochemically.

Thus the key parameters influencing the corrosion rate under deposits will be the deposit porosity, which determines the available surface area of material for corrosion, and the deposit tortuosity, which along with porosity will modify the fluxes of diffusing species within pores. Readers interested in a more extensive discussion are referred to other sources (17). Here we concentrate on a brief discussion of electrochemical methods of investigating the properties of deposits as a basis for eventual modeling. 

The direct electrochemical measurement of such low corrosion rates is difficult and limited in accuracy. However, electrochemical techniques can be used to establish a database against which to validate rates determined by more conventional methods (such as weight change measurements) applied after long exposure times. Blackwood et al. (29) used a combination of anodic polarization scans and open circuit potential measurements to determine the dissolution rates of passive films on titanium in acidic and alkaline solutions. An oxide film was first grown by applying an anodic potential scan to a preset anodic limit (generally 3.0 V), Fig. 24, curve 1. Subsequently, the electrode was switched to open-circuit and a portion of the oxide allowed to chemically dissolve. Then a second anodic... 

In the determination of corrosion rates by electrochemical techniques the corrosion current density /corr in pa/cm2 is measured which is written as ... 

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