Electrochemical corrosion rate measurement methods

Electrochemical Corrosion-Rate Measurement Methods and the Uniform-Corrosion Consideration... 

The corrosion process is observed as a series of events which all contribute to the overall corrosion rate. Measurement of rest potential fluctuations between two identical electrodes of potential fluctuations with respect to a fixed reference can be carried out. The electrochemical noise output spectrum is analysed using digitised data. The interpretation requires electrochemical expertise, and the method is therefore usually provided as a specialised service. 

Table 15.6 Physical and Electrochemical Methods for Corrosion Rate Measurements...

Several electrochemical and physical methods can be used to measure the corrosion rate of the system. Some of the commonly used methods are listed in Table 15.6. The use of these electrochemical tools in monitoring the corrosion rate of cathodicaUy protected structures was reviewed by several researchers [75—80]. More information and the scope of corrosion rate measurements of cathodicaUy polarized metal structures by electrochemical techniques can be obtained in the reviews by Jankowski [81,82]. 

Where, W is weight loss (mg), A is area of the specimen (cm ), D is density of the specimen (gm/cm ), T is exposure time (hours) and unit pm/year is micro-metre/year. Indirect methods of corrosion rate measurement involve anodic/ cathodic reaction, consideration of current potential relationship or polarisation resistance values. Tafel extrapolation method is the most popular laboratory methods for measuring corrosion rate of a metal from electrochemical data in a corrosive medium. 

Chang and Wei (1990) used electrochemical and conversion-electron Mossbauer spectroscopy (CEMS) methods to study the corrosion behavior of electrodeposited Fe tZnj, wherej = 0.15-0.85,on 1010 steel immersed in a 0.1% NaCl solution at room temperature for 2 weeks. The corrosion rate measured by metal weight loss and electrochemical methods revealed that the Feo,25Zno,75 specimen was more corrosion resistant than the others. CEMS analysis showed that the corrosion product of the pure 1010 steel and the higher iron-containing Fe-Zn alloys on steel in 0.10% NaCl solution is (3-FeOOH. 

Corrosion in brownstock and post-oxygen washers has been investigated by Bennett and Magar [795] using electrochemical procedures. Their results showed that corrosion is affected by pH, chloride concentration, temperature, and aeration. These tests were complemented with instantaneous corrosion rate measurements by linear polarization resistance methods and by weight loss tests. 

The main concept that most of the corrosion data interpretation is based on was first introduced by Wagner and Traud (1938), according to which galvanic corrosion is an electrochemical process with anodic and cathodic reactions taking place as statistically distributed events at the corroding surface. The corresponding partial anodic and cathodic currents are balanced so that the overall current density is zero. This concept has proven to be very useful, since it allowed all aspects of corrosion to be included into the framework of electrochemical kinetics. Directly deduced from this were the methods of corrosion rate measurement by Tafel line extrapolation, or the determination of the polarization resistance Rp from the slope of the polarization curve at the open circuit corrosion potential... 

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. 

Indirect methods of corrosion rate measurement involve aspects of the electrochemical process other than metal dissolution. These measurements involve cathodic reactions, such as the evolution of hydrogen, or consider current-potential relationships, such as polarization curves or polarization resistance values. 

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. 

Electrochemical tests This group includes the various electrochemical tests that have been proposed and used over the last fifty or so years. These tests include a number of techniques ranging from the measurement of potential-time curves, electrical resistance and capacitance to the more complex a.c. impedance methods. The various methods have been reviewed by Walter . As the complexity of the technique increases, i.e. in the above order, the data that are produced will provide more types of information for the metal-paint system. Thus, the impedance techniques can provide information on the water uptake, barrier action, damaged area and delamination of the coating as well as the corrosion rate and corroded area of the metal. However, it must be emphasised that the more comprehensive the technique the greater the difficulties that will arise in interpretation and in reproducibility. In fact, there is a school of thought that holds that d.c. methods are as reliable as a.c. methods. 

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. 

Measurements of corrosion rates and other parameters connected with corrosion processes are important, first as indicators of the corrosion resistance of metallic materials and second because such measurements are based on general and fundamental physical, chemical, and electrochemical relations. Hence improvements and innovations in methods applied in corrosion research are likely to benefit basic disciplines as well. A method for corrosion measurements can only provide reliable data if the background of the method is fully understood. Failure of a method to give correct data indicates a need to revise assumptions regarding the basis of the method, which sometimes leads to the discovery of as-yet unnoticed phenomena. 

In spite of the fact that corrosion measurements have been made for a century and electrochemical methods used for about a half century, there is still a need for the development ofnew methods which would, e.g., predict long-term corrosion rates and that of internal corrosion that could lead to disastrous breakdowns. 

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 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... 

Electrochemical techniques alone cannot reveal all the relevant aspects of chromate inhibition, and key characterization experiments involving surface analysis, solution analysis, or other techniques are required to help understand inhibition. For this reason, several useful nonelectrochemical techniques are also discussed. These techniques provide a means for examining the effects of inhibition under free corrosion conditions where electrochemical methods are not well suited for measuring corrosion rate. 

Chapter 4 describes how the electrical nature of corrosion reactions allows the interface to be modeled as an electrical circuit, as well as how this electrical circuit can be used to obtain information on corrosion rates. Chapter 5 focuses on how to characterize flow and how to include its effects in the test procedure. Chapter 6 describes the origins of the observed distributions in space and time of the reaction rate. Chapter 7 describes the applications of electrochemical measurements to predictive corrosion models, emphasizing their use in the long-term prediction of corrosion behavior of metallic packages for high-level nuclear waste. Chapter 8 outlines the electrochemical methods that have been applied to develop and test the effectiveness of surface treatments for metals and alloys. The final chapter gives experimental procedures that can be used to illustrate the principles described. 

The methods of measuring corrosion rates in the course of testing corrosion inhibitors are conventional weight loss, electrochemical techniques such as linear polarization resistance, potentiodynamic polarization, AC impedance, and electrochemical potential or current noise. 

The electrochemical methods of measurement of corrosion rates have been described in Chapter 1. Some features of these methods are noted below ... 

In another study [35], the electrochemical emission spectroscopy (electrochemical noise) was implemented at temperatures up to 390 °C. It is well known that the electrochemical systems demonstrate apparently random fluctuations in current and potential around their open-circuit values, and these current and potential noise signals contain valuable electrochemical kinetics information. The value of this technique lies in its simplicity and, therefore, it can be considered for high-temperature implementation. The approach requires no reference electrode but instead employs two identical electrodes of the metal or alloy under study. Also, in the same study electrochemical noise sensors have been shown in Ref. 35 to measure electrochemical kinetics and corrosion rates in subcritical and supercritical hydrothermal systems. Moreover, the instrument shown in Fig. 5 has been tested in flowing aqueous solutions at temperatures ranging from 150 to 390 °C and pressure of 25 M Pa. It turns out that the rate of the electrochemical reaction, in principle, can be estimated in hydrothermal systems by simultaneously measuring the coupled electrochemical noise potential and current. Although the electrochemical noise analysis has yet to be rendered quantitative, in the sense that a determination relationship between the experimentally measured noise and the rate of the electrochemical reaction has not been finally established, the results obtained thus far [35] demonstrate that this method is an effective tool for... 

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