Application of a new computational method to determine

corrosion current density in a cathodically protected system

I.QAMAR S. W.HUSAIN
In the present paper a numerical approach to determine the corrosion current density of a cathodically protected metal is explained. In this method three independent relationships are established and numerical evaluation of the unknowns is carried out by using electrochemical data obtained very close to the protection potential. The results obtained using hypothetical data are shown to be comparable with another method proposed by Meas and Fujioka. The present method, however, has an advantage over this method in that no prior knowledge of the corrosion current density of the unprotected metal (I e) is required. Because of this restriction, it is shown that the method of Meas and Fujioka is sensitive to slight inaccuracies in the value of Ie used. On the other hand, the present method implicitly calculates the value of Ie. Manuscript received 9 July 1991; in final form 8 August 1991. The authors are at the Dr A. Q. Khan Research Laboratories, PO Box 502, Rawalpindi, Pakistan.

Published by Maney Publishing (c) IOM Communications Ltd

INTRODUCTION
The kinetics of an electrochemical corrosion process where only one anodic and one cathodic reaction take place is described by the following equations 11 =101 {exp[2'3(EEd/b1a] -exp[ -2'3(EEd/b1e]}
.. (l)

PROPOSED METHOD
Generally three polarisation regimes can be defined, as pointed out by Meas and Fujioka,6 which allow us to simplify equations (I) and (2): regime I: E is close to E 1 regime 2: E is close to E2 regime 3: E is away from E1 and E2 . In order to illustrate the application of our proposed method, we have developed equations for regime I only. The method, however, is general and can be applied to other regimes as well. For regime I, E - E 1 is very small and exponentials in equation (1) are approximated by the first term of the series expansion (exp(y) = y). Also, as E - E2 would be a large negative quantity, the contribution of the first exponential in equation (2) can be neglected. These approximations lead to the following equations 11 =2'3I01B(EE1)
(3) (4)

12 = 102{exp[23(E - E2)/b2a] - exp [- 2'3(E - E2)/b2e]}

. (2)

where 101 and 102 are the exchange current densities, E 1 and E2 are the equilibrium potentials and b1 and b2 are the Tafel slopes for reactions I and 2 respectively. The partial current density 11 is known as the corrosion current density and determines the rate at which the metal is corroding at a potential E. The current density measured externally in the circuit is the ~um of the two partial current densities and special techniques must be used to determine the value of the partial current densities. At equilibrium corrosion potential Ee, the two partial current densities are equal and thus the externally measured current is zero. The corrosion current density Ie at Ee represents the corrosion rate of a metal in the absence of any polarisation. The determination of Ie has been dealt with extensively over the years and many methodsl-4 have been developed. The present. authors have introduced a new computational methodS to calculate Ie from electrochemical data. In the present paper we apply our method to determine corrosion current density I ep for a system which is cathodically protected at a potential Eep The method is applied considering the restriction that a complete electrochemical corrosion experiment is not feasible for cathodically protected systems since it is undesirable to carry out measurements away from the protection potential. The problem has also been addressed by Meas and Fujioka.6 Their method (referred to below as the MF method), however, requires that Ie be known. Our method, on the other hand, does not require a prior knowledge of Ie. In the following we explain our method and show its utility with an example. The results of our method are compared with those obtained from the MF method. Figure I represents graphically the various terms used in this paper.

12 = -102 exp(- 2'3(E - E2)/b2c)

where B = (bla + b1e)/blab1e' The total current density will now be the sum of partial current densities given by equations (3) and (4). Using the definition of corrosion current density Ie (i.e. Ie = 11 = 12 at E =:= Ee), the total current density can be written as I=Ie+2'3I01BP-Ie I=Ie+B1P-Ie P=E-Ee B1 =2'3101B B2 =23/b2c It is to be noted that the value of the corrosion current density I ep at cathodic protection potential Eep is the partial current at Pep = Eep - Ee and is given by the following equation I ep = Ie + B 1 Pep

exp(-2'3P/b2e) exp(-B2P)

(5)

which can be rewritten as

(6)

where the following designations hold

(7)

Equation (6) has three unknowns Ie, Bb and B2 In our proposed method we formulate three independent equations \
British Corrosion Journal 1992 Vol. 27 NO.2 125

126

Qamar and Husain

Computation

of corrosion current in cathodically

protected

system

B1 from equation SS=

(8) using equations function takes the form

(11) and (9), the SS (12)

I (Ij-G(B22

Eep
E1

102

101 I ep

Ie

log(Current

Density)

Schematic representation of various terms used in electrode kinetics: thick solid curve is experimentally determin'ed polarisation curve; thin solid lines are Tafel lines; crosses represent the three measurement points used to determine corrosion current density at an applied protection potential Ecp

Published by Maney Publishing (c) IOM Communications Ltd

where G(B2) is another function of B2 only. The value of B2 for which the SS function is minimum is determined by solving equation (12) using Newton's method. Once B2 is known, Ie is calculated using equation (11), B1 using equation (9) and finally I cp using equation (7). It should be noted that the three unknowns Ic,Bb and B2 could be determined using equation (6) alone by inserting three data points and solving the resulting simultaneous equations. However, such a technique will be highly sensitive to the accuracy of the three data points. In practice such accuracy can not be achieved. To improve the confidence in the results, the number of experimental data points must be increased and consequently the method should be flexible enough to accommodate all the data points. This can easily be done using our proposed method. It is to be noted that the MF method is based on a simultaneous solution of equations (6) and (8) with the requirement that the value of Ie be known.

to solve for the unknowns. The first relationship by defining a least squares function

is obtained

RESULTS AND DISCUSSION

. (8) We use a typical system to illustrate the usefulness of the proposed method. The anodic reaction consists of the oxidation of Fe to Fe2 + and the cathodic reaction consists of reduction of H + to H2. The parameters for the anodic reaction are 7 101 =320 rnA m-2 E1

SS= I{li-[/c+B1Pi-Ic

exp(-B2Pi)]}2

where the summation is carried out over all the data points, i.e. i= I to N. The second relation is obtained by differentiating equation (6) and determining slope at the cathodic protection potential Pcp

(dI/dP)cp=B1

+B2Ic

exp(-B2Pcp)

(9)

= -500mV
mY/decade for the cathodic
2

The LHS of equation (9) is calculated as a numerical slope and depends only upon the experimental points. However, the RHS is evaluated analytically for a given set of the three parameters. Therefore the two sides of equation (9) are determined independently and would be equal when the choice of the three parameters is correct. The third relationship is obtained by integrating equation (6)

b1a=b1e=328 The parameters

reaction

are

102 = 14 rnA m E2=0

b2a = b2e = 123 m V/decade The Ec and Ie satisfying equation (5) are -237 mV and 1182 rnA m - 2 respectively. In order to test our method and compare it with the MF method, we use hypothetical data generated using equation (5) with the above parameters. In practice such data would be obtained experimentally. The data basically consist of three current values I(Pcp), I(P1), and I(P3). Note that only three data points have been used in order to have a valid comparison with the MF method. However, we recommend the use of as many experimental data points as possible to increase the reliability of the results. Additionally, it is desirable to keep PI and P3 close to Pcp, i.e. P d should be small. On the other hand the instrumental resolution imposes certain restrictions as to how small a value of P d can be applied. We have therefore

A=

Jp

fPN
1

IdP=Ic(PNexp(-B2P2)-

Pl)+!Bl(P~-

pi)

+Ic/B2[

exp(-B2PdJ

(10)

Similar to equation (9), the area A in equation (10), determined numerically using the trapezoidal rule, is independent of the integral evaluated for a given set of parameters. Equations (8)-(10) are thus the three relationships among the three parameters I c' B 1, and B 2' Eliminating B 1 from equations (9) and (10) gives

Ic=A/F(B2)
where F(B2) is a function Table 1 of B2 only. Eliminating

(11) Ie and

Comparison of calculated potentials Ecp

lcp, rnA m-2

corrosion current density

lep

at various cathodic protection

Applied potential,
mV

Present method 1078 899 451 54

MF

method 1078 898 450 52

Actual partial current density using equation (3) 1078 898

I c from the present method*, rnA m-2

-260 -300 -400 -490 *True value = 1182 British Corrosion Journal 1992

449
45

1182 1182. 1182 1182

Vol. 27

NO.2

Qamar and Husain Table 2 Effect of 1;" inaccuracy in Ie on the computed value of corrosion current density Iep using MF method
lcp, rnA m-2

Computation of corrosion current in cathodically protected system

127

Applied potential, mV -260 -300 -400 -490

Exact 1078 898 449 45

Computed 1093 921 528 334

Ee The solution is therefore more sensitive to the value of I e used in a region where cathodic protection is likely to be used, i.e. away from the corrosion potential. Although implicit in the above discussion, it cannot be overemphasised that our method generates the value of Ie (the corrosion current density of the freely corroding metal) the determination of which in itself is a major problem in electrochemical corrosion studies. As shown in the last column of Table 1, the values of Ie computed from the data at various potentials are the same as the exact value of Ie.

Published by Maney Publishing (c) IOM Communications Ltd

taken P d as 1 m V. A comparison of the results obt~ined using our method and the MF method is shown in Table 1. It is seen that the values of Icp obtained using the two methods are quite close to each other as well as to the true current obtained using equation (3). The proposed method has also been tested in the other regimes of applied potential. The results obtained are similar to those presented here and will not be discussed for the sake of brevity. It is interesting to note that, contrary to the assumption of Meas and Fujioka that I e is generally known and Tafel constants are not known, it is generally believed that the reverse is true. In fact the well known linear polarisation method2 used to calculate leis based on the assumption that Tafel constants are generally known. In addition, an accurate determination of leis generally a difficult task. We have -therefore tested the sensitivity of the MF method by introducing a certain degree of inaccuracy in the true value of Ie. The results thus obtained are shown in Table 2. A large error in I ep is observed at potentials near E1 whereas the error decreases as the protection potential approaches corrosion potential

CONCLUSIONS
The numerical approach used in the present paper to determine corrosion current density of a cathodically protected metal provides a reliable method for a wide range of applied potentials. The results are comparable to those obtained by another method developed by Meas and Fujioka.6 The main advantage of our method over the MF method is that it does not require a prior knowledge of Ie, the corrosion current density of the freely corroding metal. In fact our method generates the value of Ie, the determination of which is generally a problem.

REFERENCES
1. 2. 3. 4. 5. 6. 7.
J. TAFEL: Z. Phys. Chem., 1905, 50, 641. M. STERN and A. L. GEARY: J. Electrochem.

Soc., 1957, 104, 56.

J. JANKOWSKI and R. JUCHNIEWICZ: Corros. Sci., 1980, 20, 841. N. D. GREENE and R. H. GANDHI: Mater. Perform., 1982, 21, 34. I. QAMAR and s. W. HUSAIN: Br. Corros. J., 1990,25,202. Y. MEAS and J. FUJIOKA: Carras. Sci., 1990, 30, 929.

'Lectures on electrochemical corrosion'; New York, Plenum Press.

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British Corrosion Journal

1992 Vol. 27 NO.2