Tafel Slopes and Corrosion Rates from Polarization Resistance Measurements* FLORIAN MANSFELD* Abstract ‘A new analysis of polarization curves in the non-Tafel region in the vicinity of the corrosion potential is described which allows calculation of the polarization resistance (Fp) and the Tal slopes (band bic). From these data instantaneous corrosion rates are calculated. Experimental data for the systern Fe/IN HaSO, are analyzed by the proposed method and by computer least square analy The good ‘agreement observed suggests that all important corrosion parameters (corrosion potential, corrosion ‘current, Tafel slopes) can be obtained by the proposed analysis. These parametors are used for ‘mechanistic considerations which explain the observation time corrosion current. The basis of the polarization resistance technique first described by Wagner and Traud' and Stern and co- workers? * is the relation babe a - Dab 1B a Kor F506, #B0) Wye 234+ B)Rp Ry which is valid as long as the relation between current (1) and potential (9) can be expressed as: Kou foxp 23(6-Geon) -2.3(6- Scorn) eg 226-H00 gy In Equations (1) and (2), leore and Gcorr are corrosion current and corrosion potential, ba and be are anodic and cathodic Tafel slopes, and Rp = (d9/dl)écorr is the slope of potential-current plot at the corrosion potential. Rp is often called polarization resistance. Some of the problems associated with the use of the polarization resistance method have been discussed recently by Prazak* and by Oldham and Mansfeld’ In many applications Ry has been determined incorrectly as the slope of the potential-current curve at ¢ # Gcore- Conse- quently, erroneous Ry values have been used to calculate corrosion currents, While this error is often not recognized, it is commonly believed that the major limitation of the polarization resistance technique lies in the fact that the factor Dabe pete 23ba +e) has to be known in order to determine Ieory from Equation (1). Oldham and Mansfeld’ have shown recently that the corrosion current (Icoex) can be determined accurately “Presented at the NACE Corrosion Research Conference, Anaheim, California, March 19.21, 1973. Science Center, Rockwell International, Thousand Oaks, CA. Vol. 29, No. 10, October, 1973 wendence of corrosion potential and without knowledge of the factor B by graphical analysis of polarization curves in the range used in the polarization resistance technique. However, it still seems desirable to obtain simultaneously the Tafel slopes (bj and be) and polarization resistance (Rp). In doing so, one could accu- rately determine Iegyr a8 a function of time, electrolyte composition, temperature, or other parameters. A deter- mination of Ieorr, corr» Da, and be as a function of such parameters in a potential range where no changes in the surface structure of the test electrode due to polarization are to be expected is of additional interest, since from such data conclusions about corrosion mechanisms could be drawn, Progress of such attempts, which has been reported elsewhere,” will be summarized in the following. Background of Analysis, of Polarization Curves Combination of Equations (1) and (2) leads to 1 babe 1 2.3 by +b. Ry which can be written after rearrangement as babe 2.3A9, a 23 Rp where Od = - écorr- Since the right hand side of Equation (4) depends only on the Tafel slopes (by and be), it should be possible to obtain bg and be from plots of Rpl vs 6. Figure 1a shows a plot of the right side of Equation (4) vs Ag for various anodic Tafel slopes (by = 40, 60, or 120 mV) at a constant cathodic Tafel slope (be = 120 mV). It can been seen that the curvature of the plot depends on the ratio of the Tafel slopes by and be. In Figure 1b it has been assumed that anodic and cathodic Tafel slopes are 397equal (by = be = b). Note the different curvature at cathodic potentials (Ag < 0) in Figure 1a and Figure 1b. ‘These examples show that different kinetic behavior of a corroding metal, as expressed by different combinations of Tafel slopes, can be recognized based on plots according to Equation 4. ‘The corrosion current (Icorz) can then be calculated from the measured polarization curve in the following four steps which are based on Equations (1) and (2): 1. Determine the polarization resistance Rp from: di 1 Boson by drawing a tangent at A¢ = 0. 2. Multiply the current I measured at a certain value Ag by 2.3 Rp and plot 2.3 Rpl vs¢. 3. Determine from this plot the Tafel slopes (by and bb.) by curve fitting using theoretical curves calculated for various values of by and be 4, Calculate Igor from Equation (1) using the Rp value determined in Step 1 and the Tafel slopes determined in Step 3. Experimental Results Curve Fitting This new type of analysis of polarization curves of corroding metals, described above, has been used for iron (99.9%, Johnson, Matthey and Co.) in IN Hp$O,. The polarization curves have been measured in the potentio- dynamic mode using a sweep rate of 30 mV/min., and in general, Ag = +25 mV. Duration of the experiment was 24 hours. Figure 2 shows some of the polarization curves obtained at various times of the experiment. From these curves the polarization resistance (Rp) was determined as the slope of the curve at Ag = 0. A plot of 2.3 Rpl vs Ad ‘was then constructed according to Step 2, and compared to theoretical curves for various combinations of by and be. Results are shown in Figure 3a for the run recorded after 10 minutes and in Figure 3b for the run recorded after 290 ‘minutes. From Figure 3a the values of by and be which fit the measured curve best are estimated to be by = 30 mV and be = 95 mV, while from Figure 3b one finds by = 55 mV and be = 105 mV. Since the values of the Tafel slopes used to calculate the theoretical curves have been varied in steps of $ mV, Tafel slopes could only be determined within +5 mV, Sometimes itis somewhat difficult to decide which Tafel slopes fit a curve best, and the error in determination of b, oF be of both values will be larger than Sm. While the calculations necessary for Steps 1 to 4 could be carried out best using a computer (described below), the theoretical curves can be computed quickly using desk top calculators. Once a set of theoretical curves corresponding to the right side of Equation 4 has been calculated, they ‘can be used for analysis of any recorded polarization curve. Results of the analysis of polarization curves by curve fitting for the system Fe/IN HO, are summarized in Figure 4, While there are some fluctuations of the cathodic 398, 0 = woh [=o mw xf yo | Ye GA ooh a 4 4 Cy 60 fo 1 1 a) asa s an oy , 7 / y, val MY 4 wef ip | y . y ao | 1 L sate) FIGURE 1 — Plots of right side of Equation (4) vs Ap = 0 carr tor various combinations of Tafel slopes. (a) be = 120 mV, and (b) by = be = B. Tafel slope (be), there seems to be an increase of the anodic Tafel slope (b,) with time, The factor B = babe/2.3(ba + bc). which correlates polarization resistance (Rp) and corrosion current (Ieors) increases by about a factor of 2 from 9.9 mV to 19.7 mV during the 24-hour period. For qualitative measurements of the corrosion current of the system Fe/IN H,SOq one CORROSION-NACET T Fe/W HS 0 win 120 ain == 290 nin 1260 win // 1 (na) atm) FIGURE 2 ~ Experimental polarization curves for iron in 1N HS0, a @ function of time. could have used a value of B= 13 mV as calculated from literature values (by = 40 mV, be = 120 mV). However, if Tafel slopes are unknown, or if precise values of corrosion currents and of Tafel slopes are to be obtained as a function of time, then the method described here should be very usefl Finally, the values of the inverse polarization resistance (Ry!) and the corrosion current (lege) = BRp! are shown in Figure 4 for the 24-hour test. The corrosion current increases by about a factor of 10 in the first 6 hours of the experiment and then levels off, Similar results have been reported by Chin and Nobe® and Bamartt.2"° Since the factor B increases only slowly with time, the values of Teor and Rp" show essentially similar behavior. Computer Analysis ‘The analysis of polarization curves in Steps 1 to 4 requires accurate determination of Rp by graphical means (Step 1), and a decision about which theoretical curves best fit the experimental curves (Step 3). In order to evaluate whether the experimental data of Figure 3 have been analyzed correctly by the method proposed here, they were also analyzed by the method of linear least squares using a computer program which is described in the Appendix. Some advantages of this computer program deserve to be listed here. Tafel slopes can be obtained in the mixed potential region where no Tafel lines are observed (Ag! < 60 mV). Anodic and cathodic Tafel lines can be calculated even if data have been recorded only at Ag 0. The calculated error of by, be, Rp, and Iegrr indicates how T T 7 e290 ain t= tonin by = ssa 0+ Wav volo” “eo be = 120m o 7 b, = 1050 Db, = 300 o) Dy = AO ° v bg 2007 7 ssnv sok | sah 4 oe 2, = 6a ©, = 3001 ° , Sa sab 4 seh 4 a o | ao 4 cok 4 401 e v 4 40} ¥ 4 v vf? al L L -« 1 L L S30 a8 a 7a 0 a 16 7 700 . satan ° sete FIGURE 3 ~ Experimental curves (solid line) and theoretical cures, superimposed in order to ‘obtain best values of By and be. (a) 10 minutes, and (3) 290 minutes. Vol. 29, No. 10, October, 1973 399eC 4509) Co elon) FIGURE 4 — Time behavior of corrosion parameters of iron in NH,S04, TABLE 1 ~Corr much experimental scatter is involved. If the computer does not find a solution for a given set of experimental data, then the scatter of the data is too large or Equation 2 is not obeyed due to concentration polarization, excess IR drop ‘or other complications discussed. Table 1 summarizes the results obtained for Fe/ IN H,SO, over a 24-hour period and compares results ob- tained by the new method based on curve fitting and by ‘computer analysis. In general, good agreement is found, especially for the polarization resistance (Rp), differences amounting to 43% in the average, Good agreement has also been found for the anodic Tafel slope (b,), while differ- ences for the cathodic Tafel slope (be) are somewhat larger. It will be seen, however, that in cases where differences between be values obtained by the two different analyses, are large, the error of the be value obtained by computer solutions is also large, indicating poor experimental data. Finally, good agreement is also found for the corrosion current (Ieorr), Which is found to increase during the first 6 hours of the experiment and then to stay more or less constant, It has been shown by the author” that good agreement was observed between the average corrosion current density (cd) for the 24-hour test and the average corrosion ed calculated from the amount of iron deter- mined in the test solution after the test, which corresponds to 2.28 ma/em? (5700 mdd). n Parameters of Iron in IN S03 Time core by be a ‘oor {rind (mv wsScE) (ov) (ov) SB (va) 10 493 20 95 15.04 068 art 13649 1560-0.10 081 +0.03 40 428 20 20 9.76 097 3et7 1047 992 40.18 1.2440.23 59 84 40 100 7a1 1.68 4546 129245 777 £068 125 #0.26, 120 480 55 105 482 225 eatz2 1572127 4.77 £0.09 4.11208 191 483 6 8s 3.33 467 ata cate 3424001 3.14 +0.28 228 496 50 80 3.33 4.10 4782 sate 361 #002 3574020 21 486 55 105 323 486 eats 12943 321 40.06 5.76 41.80 250 98 6s 105 290 sor 4645 esto 3.18 £008 3694045 aot 490 55 110 282 565 sot7 a5t16 3.02 +004 4.644078 1363 506 70 90 asi 487 ant 70+? 3524001 3.23 +0.08 1415 503 80 no an 623 arta 120268 323 +002 7.18 £2.97 [Note First line results from curve fitting and second Hin 400 ults From computer analysis CORROSION NACEDiscussion It has been shown that contrary to common belief, Tafel slopes as well as polarization resistance values can be determined simultaneously from polarization curves in the vicinity of the corrosion potential. A comparison of data obtained with the method proposed here and from com- puter analysis of the experimental data has shown good agreement, especially when the scatter of experimental data is low, It is believed that this new analysis of polarization resistance data removes what had been assumed the major limitation of the polarization resistance technique. The corrosion potential, corrosion current, and anodic and cathodic Tafel slopes of a corroding metal obtained as described above, can be used for mechanistic considers. tions, Such an attempt can be seen in Figure 5, where anodic and cathodic Tafel lines have been plotted as a function of time based on the data obtained by computer solution, The rate of the anodic process (metal oxidation) at a given potential seems to increase as a function of time,() presumably due to an increase of the exchange cd for the Fe/Fe ® reaction and despite an enoblement of the reversible potential for this reaction as the Fe®* content of the solution increases (Grey = -440 + 30 log aye™* (mV vs SHE)). The rate of the cathodic reaction (reduction of HO" ions) at a given potential seems to increase in the first hours of the test and then decreases again. Asa result of these changes of the rates of oxidation and reduction reactions with time, the corrosion potential and corrosion current change as shown in Figure 4 and Table 1. Similar results and conclusions have been reached by Barnartt!® for FerrovacE in 1M NaHSO, Acknowledgment ‘The author acknowledges the help of E, Richard Cohen who formulated the computer analysis listed in the Appen- dix. References C, Wagner and W. Traud, Z, Elektrochem., 44, 391 (1938), 2M, Stern and A. L. Geary. J. Electrochem. Soc., 104, 56 (1987), 3. M. Stern and E, D. Weiser. Proc. Am, Soc. Test Mater., 59, 1280 (1959), 4. M, Prazak, Extended Abstracts, 231 Meeting of ISE (Formerly CITCE), Stockholm, Sweden (1972), K. B. Oldham and F. Mansfeld. Corrosion, 27, 434 (1971), KB, Oldham and F. Mansfeld. Corrosion Seience, (in press). F. Mansfeld. Electrochem. Soc.,120, 515 (1973), R. J. Chin and K, Nobe. J. Electrochem. Soc., 118, $45 (1911). S. Barnartt, Corrosion, 27, 467 (1971), S. Barnastt. J. Electrochem, Soc., 119, 812 (1972). Appendix Analysis of Polarization Curves by Least Squares Analysis From a relation between current (1) and potential (9) in the form: P -expt- \ a 2303 Rp vers) , since the area of the electrode increased during the exposure t0 S04 the correlation between currents and reaction rate can be only qualitative. Vol. 29, No, 10, October, 1973 FIGURE 5 — Time behavior of anodic and eathodie reactions for a corroding ron electrode in 1N H SOs, one wishes to find the parameters Rp, by, and be, and babe 2.303 (by * BIRp” leone = which are explained above (P’ = 2.30344). First ‘Then Equation (1) can be written sinh w P A SHED ar ay ‘The form of Equation (2) in terms of x and w provides the most convenient basis for numerical solution by nonlinear least squares or other alternative processes. Equation (2) is rewritten in the form. hw Pj W=HP)= AgeXPi —— @) where I; is the current measured at Py, Analysis begins with an initial guess for w, which is denoted w®. The improved estimate will be w= we +z. Then sinh(w° +2) P; fn y= fn A +x Pi +8 td nore (4) Expanding this in a Taylor series leads to: sinh WP, fn I= on Ag +x Py + en (s) 401In Equation (5), the unknown quantities (En Ag, x, and 2) appear linearly and may be solved for by the usual methods of linear least squares. Having done this a new estimate for w is wo +z. This may be taken as the new value of w° from which @ new z can be computed by repeating the process. The iteration is continued until the changes in the computed values of Ag, x, and w are sufficiently small, The polarization resistance (Rp) and the Tafel slopes can then be obtained as: 1 1 1 by = ——j be = 2303 A," wx w-x and the corrosion current (Igorr) can be calculated as lore = Aol 2w. ‘The error of Rp, ba, be, and Icqrr has been calculated using standard statistical formulae. Equation 5 has been, with minor modifications, programmed on APL. 402 CORROSION-NACE