Tafel slopes measurements

The sohd line in Figure 3 represents the potential vs the measured (or the appHed) current density. Measured or appHed current is the current actually measured in an external circuit ie, the amount of external current that must be appHed to the electrode in order to move the potential to each desired point. The corrosion potential and corrosion current density can also be deterrnined from the potential vs measured current behavior, which is referred to as polarization curve rather than an Evans diagram, by extrapolation of either or both the anodic or cathodic portion of the curve. This latter procedure does not require specific knowledge of the equiHbrium potentials, exchange current densities, and Tafel slope values of the specific reactions involved. Thus Evans diagrams, constmcted from information contained in the Hterature, and polarization curves, generated by experimentation, can be used to predict and analyze uniform and other forms of corrosion. Further treatment of these subjects can be found elsewhere (1—3,6,18). 

The effects of adsorbed inhibitors on the individual electrode reactions of corrosion may be determined from the effects on the anodic and cathodic polarisation curves of the corroding metaP . A displacement of the polarisation curve without a change in the Tafel slope in the presence of the inhibitor indicates that the adsorbed inhibitor acts by blocking active sites so that reaction cannot occur, rather than by affecting the mechanism of the reaction. An increase in the Tafel slope of the polarisation curve due to the inhibitor indicates that the inhibitor acts by affecting the mechanism of the reaction. However, the determination of the Tafel slope will often require the metal to be polarised under conditions of current density and potential which are far removed from those of normal corrosion. This may result in differences in the adsorption and mechanistic effects of inhibitors at polarised metals compared to naturally corroding metals . Thus the interpretation of the effects of inhibitors at the corrosion potential from applied current-potential polarisation curves, as usually measured, may not be conclusive. This difficulty can be overcome in part by the use of rapid polarisation methods . A better procedure is the determination of true polarisation curves near the corrosion potential by simultaneous measurements of applied current, corrosion rate (equivalent to the true anodic current) and potential. However, this method is rather laborious and has been little used. 

The exact calculation of icorr for a given time requires simultaneous measurements of Rp and anodic and cathodic Tafel slopes (/> and be). Computer programs have been developed for the determination of precise values of /corr according to Eqs. (2) and (3). Experimental values of Rp (2p contain a contribution from the uncompensated solution resistance... 

Applications of Rp techniques have been reported by King et al. in a study of the corrosion behavior of iron pipes in environments containing SRB. In a similar study, Kasahara and Kajiyama" used Rp measurements with compensation of the ohmic drop and reported results for active and inactive SRB. Nivens et al. calculated the corrosion current density from experimental Rp data and Tafel slopes for 304 stainless steel exposed to a seawater medium containing the non-SRB Vibrio mtriegens. 

A qualitative measure of the corrosion rate can be obtained from the slope of the curves in Fig. 2. Z INT is given in units of s ohm" . Owing to the presence of the uncompensated ohmic resistance and lack of values for Tafel slopes [Eq. (2)], data in Fig. 2 should be viewed as indicative of significant changes in corrosion rates. Corrosion loss remained low during the first 2 months, followed by a large increase for both flushed samples and controls. The corrosion rate increased when the surface pH reached values of 1 or less. Total corrosion loss as determined from integrated Rp data was less for the control than for the flushed sample. 

Elucidation of the actual values of key diagnostic parameters that have been used for a long time by ORR experimentahsts, including primarily the measured Tafel slope and the reaction order with regard to O2, and their predictive power regarding the ORR mechanism. 

What is behind the apparent disagreements between Tafel slopes and reaction orders reported from recent investigations of the ORR at PEFC cathode catalysts and the slopes and reaction orders measured earlier for model systems of low Pt surface area Is the ORR process at a dispersed Pt catalyst possibly different in nature from the ORR process at low-surface-area Pt ... 

Is there a way to verify experimentally not only that the measured low Tafel slope of 60mV/decade in the fuel-cell-relevant potential range is fully explainable by an intrinsic slope of 120 mV/decade for ORR at Pt metal, but also that this intrinsic Tafel slope can be experimentally verified within the fuel-cell-relevant potential range In fact, an elegant response to this challenge has recently been provided by impedance spectra measured for the ORR process at Pt/C in a PEFC cathode... 

At 60 minutes only, dc potentiodynamic curves were determined from which the corrosion current was obtained by extrapolation of the anodic Tafel slope to the corrosion potential. The anodic Tafel slope b was generally between 70 to 80 mV whereas the cathodic curve continuously increased to a limiting diffusion current. The curves supported impedance data in indicating the presence of charge transfer and mass transfer control processes. The measurements at 60 minutes indicated a linear relationship between and 0 of slope 21mV. This confirmed that charge transfer impedance could be used to provide a measure of the corrosion rate at intermediate exposure times and these values are summarised in Table 1. 

The use of the impedance technique in the study of polymer coated steel, has been thoroughly described elsewhere. The present paper compares this technique with that of harmonic analysis, originally proposed by Meszaros ). The authors have presented preliminary data using the latter technique(3) wherein the early stages of polymer breakdown have been studied. The current paper extends this work to polymers which have been immersed for a considerable period of time. The harmonic method gives information not available from the impedance technique in the Tafel slopes and the corrosion current are directly measurable. A brief summary of the harmonic method and the equations used are given below. 

It can be seen that it was again difficult to obtain results from specimens where no stable rest potential could be measured. The harmonic currents in all cases were low and for certain specimens were of the same order as the distortion resulting from the input sine wave. The Tafel slopes obtained were in general anomalously high and the corrosion rates varied over several orders of magnitude. 

The actual current passed / = 2F/4Jt,[H + ]exp[ — J pAE] since two electrons are transferred for every occurrence of reaction I. Equation (1.64) constitutes the fundamental kinetic equation for the hydrogen evolution reaction (her) under the conditions that the first reaction is rate limiting and that the reverse reaction can be neglected. From this equation, we can calculate the two main observables that can be measured in any electrochemical reaction. The first is the Tafel slope, defined for historical reasons as ... 

---