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CorrosionScience,Vol. 38, No. 12,pp.

2073-2082,1996
Pergamon Copyright 0 1996ElsevierScienceLtd
Printed in Great Britain. All rights reserved
0010-938X/96$15.00+0.00

PII: s0010-938x(%)ooo34-0

ON ELECTROCHEMICAL TECHNIQUES FOR INTERFACE


INHIBITOR RESEARCH

C. CA0

Key State Laboratory for Corrosion and Protection, Institute of Corrosion and Protection of Metals, The Chinese
Academy of Sciences, 62 Wencui Road Shenyang 110015, China

Abstract-The electrochemical behavior related to different modes of inhibition effect is discussed for interface
inhibitors. The action coefficients of an inhibitor on the anodic and cathodic reactions (f, andf,, respectively) of a
corrosion process are defined. An equation is deduced which denotes that if the inhibition effect is caused by
geometrically blocking the surface of metal electrode by adsorbed inhibitive species, the corrosion potential in the
inhibitor-containing solution will be nearly equal to that in the solution without the inhibitor. In this case the
inhibition efficiency (7) equals the coverage (0) of the adsorbed species and can be estimated by polarization
resistance (R,) measurements. In addition, the plot of q vs the “relative coverage” (p) estimated from interfacial
capacitance measurements will be a straight line through the original point of the coordinate. If the inhibition is not
due to the geometric blocking effect, which can be judged by the noticeable shift of corrosion potential as the
inhibitor is added into the solution, then q cannot be estimated by R, and does not equal 0. Instead, transfer
resistance (R,) can always be employed to estimate inhibition efficiency whatever the mode of the inhibition effect. It
is argued that theoretically no Tafelian straight lines can be measured in solutions with interface inhibitors unless 0
is independent of the electrode potential E or_&andf, of the inhibitor change linearly with E. Equations of faradaic
admittance at the corrosion potential in inhibitor-containing solution for different modes of inhibition effect are
deduced. In addition to the estimation of R,, R, and interfacial capacitance, information on the adsorption of the
inhibitive species can also be gathered by EIS measurement. In the case of the geometric blocking effect, the EIS
display in the inhibitor-containing solution will be similar to that in the black solution when q is low, while a single
capacitive loop will display when q is high. If the inhibition is not due to the geometric blocking effect, two time
constants will be involved in the EIS display measured in the inhibitive-containing solution no matter what the
displays of EIS in the blank solution are, and in this case the effect of E on 0 can be predicted based on the EIS and
polarization curve measurements. Copyright 0 1996 Elsevier Science Ltd
Keywords: C. acid inhibition.

NOMENCLATURE

B in inhibitor-containing solution
Cinh concentration of an inhibitor in solution
Cd interfacial capacitance of a metal electrode in inhibitor-containing solution
q the value of Cd when the surface of the metal electrode is wholly covered by the
adsorbed inhibitive species
the value of Cd without inhibitor in solution
q - cs,

Manuscript received 18 August 1995.

2073
C. Cao

corrosion potentials without and with an inhibitor in solution, respectively


E corr-E,,,,, shift of corrosion potential due to addition of an inhibitor
action coefficients of an inhibitor on the anodic and cathodic reactions of a
corrosion process, respectively
polarization current density
anodic and cathodic current densities without inhibitor in solution,
respectively
anodic and cathodic current densities with an inhibitor in solution, respectively
faradaic current density
corrosion current densities without and with an inhibitor in solution,
respectively
proportional coefficients between corrosion current density and the reciprocal
of polarization resistance without and with an inhibitor in solution,
respectively
gas constant
polarization resistances without and with an inhibitor in solution, respectively
transfer resistances without and with an inhibitor in solution respectively
transfer resistance of electrode surface portion covered by adsorbed inhibitive
species
subscript denoting steady state
faradaic admittances of electrode in solutions without and with an inhibitor,
respectively
Faradaic admittance of electrode surface portion covered by adsorbed
inhibitive species
Tafelian slopes of anodic and cathodic reactions, respectively, in a solution
without inhibitor
Tafelian slopes of anodic and cathodic reactions in solution with an inhibitor
relative coverage of adsorbed inhibitive species on the surface of metal
electrode
inhibition efficiency
coverage of adsorbed inhibitive species on the surface of metal electrode
circular frequency

INTRODUCTION
Electrochemical techniques such as polarization curve measurement, polarization resistance
measurement and electrochemical impedance spectroscopy (EIS) measurement are
commonly employed in inhibitor research. For example, corrosion current densities or
inhibition efficiencies are often estimated by extrapolation of polarization curves to
corrosion potentials or by calculations based on polarization resistance measurements. In
some cases, equations of adsorption isotherms of interface inhibitors are obtained from
plots of the inhibition efficiencies vs concentrations of the inhibitors (Cinh)studied. The
applicability of these techniques in interface inhibitor research requires further
consideration. Though electrochemical impedance at corrosion potential is frequently
measured in inhibitor research, it appears that little attention has been paid to the
theoretical interpretation of the measured EIS.
Lorenz and Mansfeld’ classified the modes of the inhibition effect of interface inhibitors
Interface inhibitor research 2075

into three categories: that caused by the geometric blocking effect of adsorbed inhibitive
species on the metal surface; that due to the effect of blocking the active sites on the metal
surface by adsorbed inhibitive species; and that due to the electro-catalytic effect of the
inhibitor or its reaction products. It has been discussed* in the case of the first mode that the
inhibition effect comes from the reduction of the reaction area on the surface of the
corroding metal, whereas for the other two modes the inhibition effects are due to the
changes in the average activation energy barriers of the anodic and cathodic reactions of the
corrosion process. Thus the electrochemical behavior and the interpretation of the
measured electrochemical data will be not the same for all the modes. With respect to this
point, some considerations are briefly discussed here.

SHIFT OF CORROSION POTENTIAL


If the rates of the anodic and cathodic reactions of a corrosion process for a metal in an
acid solution without inhibitors (the blank solution) follow Tafel’s law, then the anodic and
cathodic current densities of the corrosion process can be described in terms of the following
equations:

Z, = k,exp(EIB& Z, = -M-E/&) (1)


Here the direction of the cathodic reaction is taken as negative and Z, is a negative value. At
the corrosion potential (Z&J,
Z, = k,exp(&,,,lB,) = -Zc = M-&,/B,) = Zcorr (2)
Hence the polarization curve of a metal electrode can be written as equation (3):

Z = ZcorrexpKE - &.dBal - ev[-(E - &rr)lBcl (3)


When an inhibitor is added into the solution, the anodic and cathodic current densities
at the same potential as that for Z, and Z, will be

Z; =faL 1:=_L& (4)


Here faand fcare the action coefficients of the inhibitor on the anodic and cathodic reactions
of the corrosion process, respectively.f;:< 1 if the inhibitor retards the reaction i andf; > 1 if
it accelerates the reaction i at the given potential. They are functions of electrode potential
E. At the corrosion potential in the inhibitor-containing solution, E= E’,,,, and
Z, = IZcl= I’,,,,. Then it can be deduced that
A&,,, = B&/U% + BcYn(f,/fc)E~,,, (5)

Here A&,,, = E,,, - &,,,. For the case of the geometric blocking effect, fa=fc=l-0,
theoretically AEcorrwill be zero. This means that if the inhibition is due to the geometric
blocking effect, the shift of corrosion potential will be negligible as the inhibitor is added to
the solution. At the same time it is impossible that the active sites on the metal surface are the
same for both the anodic and cathodic reactions of the corrosion process. Thus in the case of
the active sites blocking effect, usually the values of faand fcare different and a noticeable
shift of corrosion potential will be observed as the inhibitor is added to the solution. The
same situation is also true for the case of the electro-catalytic effect, since it is usual that the
catalytic effects of an inhibitor cannot be the same for two different reactions. Nevertheless,
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log 111(A/cm’)

Fig. I. Polarization curves of Armco Fe in I mol/L HCI with various added concentrations (mmol/
L) of N,N-dipropynoxy methyl butyl amine (PMBA): 1-O; 2-0.04; 34.08; 4-I

-400
I

_.-.J
-I

Fig. 2. Polarization curves of Armco Fe in 0.5 mol/L HzS04 with various added concentrations
(mmol/L) of N,N-dipropynoxy methyl butyl amine (PMBA): 1-O; 24.04; 34.08; 4-0.24; 5-l.

in the case of the active sites blocking effect, both the values offa and& cannot be larger than
1, while in the case of the electro-catalytic effect, sometimes one of theh values may be larger
than 1 if the inhibitor accelerates one of the reactions of the corrosion process. From a
comparison of the corrosion potentials and the polarization curves measured in the
solutions with and without an inhibitor, the modes of the inhibition effect of the inhibitor
can be ascertained in most cases. It should be noted that in practice the mode of inhibition
effect depends not only on the inhibitor, but also on the anion in the solution. Figure l3
shows the polarization curves of Armco Fe in 1 mol/L HCl with various concentrations of
N,N-dipropynoxy methyl butyl amine (PMBA). In the HCl solution the inhibition effect of
PMBA on Fe is caused by the geometric blocking effect. Figure 23 shows the polarization
curves in 0.5 mol/L HIS04 with various concentrations of PMBA. Based on the discussion
above, the inhibition for this system cannot be caused by the geometric blocking effect, but
may be due in the main to the active sites blocking effect.
It is obvious that only in the case of the geometric blocking effect does the inhibition
Interface inhibitor research 2077

Table 1. Corrosion potentials (SCE) of Armco Fe in 1mol/L HCl with additions of various concentrations of
dodecylamine (DDA)

Concentration of DDA (mol/L) 0 5 x 10-s 10-4 5 x 10-4 10-j

Ear, (mv) -483 -481 -482 -482 -483

efficiency (q) equal the coverage of the adsorbed inhibitive species (0) on the metal surface.
To verify this point, one can study the relationship between rl and relative coverage (u). The
latter is estimated by interfacial capacitance measurements according to the following
equation:4
/_L= 1 - cd/c; = /W (6)
Here Cd and Ci are the interfacial capacitance of the metal electrode in solutions with
and without the inhibitor, and the expression of the coefficient 1 is
J = 1 - c;fc; (7)
C$ is the interfacial capacitance of the electrode when 0 equals 1. If q equals 0, the plot of u
vs q must be a straight line passing through the origin. For example, the corrosion potentials
of Armco Fe in 1 mol/L HCl with various concentrations of dodecylamine (DDA) are listed
in Table 1.’ They are nearly the same for each solution. Thus one can ascertain that the
inhibition of DDA on Fe in HCl solution should be caused by the geometric blocking effect.
The plot of u vs r~for this system is shown in Fig. 3. A straight line through the origin is
obtained. From the slope of the line one can estimate the value of cSd that cannot be
measured directly. Thus in this case one can study the adsorption isotherm by the plot of q vs
ci&. For other two inhibition modes, q is a certain function of 0, but not equal to it; an
incorrect conclusion will be obtained if one studies the adsorption isotherm based on the
relationship between q and cinh.

Fig. 3. Plot of Mvs 1 for Armco Fe in 1 mol/L HCl with dodecylamine (DDA) as the inhibitor.
2078 C. Cao

ON TAFEL PLOTS
Tafel slopes can be defined as follows:
fia = dE/dlogl,, /$, = -dE/dlog& (8)
If /l is a constant, then the anodic polarization curve will be a straight line in a semi-
logarithmic coordinate. Such straight line plots indicate that the rates of the reactions follow
the Tafel law. For a corroding metal electrode, if a Tafel straight line can be measured either
for an anodic or cathodic reaction, then the corrosion current density can be estimated by
extrapolating the Tafelian line to the corrosion potential. Now if in a solution without
inhibitors /.Ia and PC are constants, i.e. Tafel lines can be measured both for anodic and
cathodic reactions, then in the solution with an added inhibitor the apparent Tafelian slopes
can be deduced based on equation (4) and (8):
,t?; = Pa/[1 + Ba(d~~gf,lWl, B: = Ml - Bc(dbWWl (9)
At a given temperature& andf, are functions of 0, and in turn are functions of E, so jYa and
/I’=are not constants unless 0 is independent of E orf; values are linear functions of E. Thus
theoretically no straight line in semi-logarithmic plots of polarization curves can usually be
obtained in inhibitor-containing solutions. In our laboratory it was found that for every
interface inhibitor studied there was a critical potential at the anodic polarization curve,
when the electrode potential was higher than the critical potential, the polarization current
density then increased rapidly. Sometimes the critical potential is quite close to the corrosion
potential (for example, see Fig. 2). Unreliable results may be obtained in the estimation of
the corrosion current density by extrapolating poiarization curves to the corrosion potential
E corr in interface inhibitor research.

ON POLARIZATION RESISTANCE
Inhibition efficiency of an inhibitor is often estimated by polarization resistance
measurements based on the following equation:
7 = 1 - R,IR; (10)
where R’, and R, are the polarization resistance values measured in solutions with and
without the inhibitor, respectively. The author has demonstrated6 that if the anodic
dissolution of the corroding metal is the unique anodic reaction in the corrosion process,
then a relationship between the corrosion current density Z,,,, and the polarization
resistance R,, equation (1 1), always holds:
I corr = K/R, (11)
The general expression of the proportional coefficient K is as follows:

K = KdlnMdE),~O~~- (dWcl/d~)Ec,,,l-l (12)


By applying equation (12) to equation (3)

K = B&c/(/% + Bc) (13)


which is the proportional coefficient in Stern and Geary equation.’ In the inhibitor-
Interface inhibitor research 2079

containing solution, the proportional coefficient will be

K’ = [(Pa + Bc)lBaPc + (dlnfa/cWEs, - (dlnf,/dE)~Ln]-’ (14)

Usually it is different from that in the blank solution unless the inhibition is caused by the
geometric blocking effect. In the latter case& =fC = 1 - 0 and then K = K. Thus if AE,,,, is
noticeable the inhibition efficiency calculated by equation (10) may be incorrect.
It will be shown in the discussion of EIS at corrosion potential that though inhibition
efficiency cannot be always calculated based on the data of polarization resistance, data of
transfer resistance estimated by EIS measurements at corrosion potential can be employed
to calculate the inhibition efficiency in any case.

EIS MEASUREMENTS
In an inhibitor-containing solution, the most important state variables affecting the EIS
display of a corroding metal electrode at constant temperature is E and 0. The expression of
the faradaic admittance for a single anodic or cathodic reaction with two state variables is:’
yF(o)i = 1/ R:i -I- &/(a -I-j@), (i = a, C) (15)

Here
l/Rii = (aZ,!/aE),, = Z;‘lBi (16)

(17)

a = -(as/so),, (18)
and
J‘ = dO/dt (1%
The subscript “ss” denotes the steady state. Since at the steady state [ = 0, it follows that
dO/dE = - (a&lE)/(a~/X9) and equation (15) can be written as

YF~o) = l/R&,) +(a&/~),,(d@/W/(l +_Wa) (20)

At the corrosion potential, two reactions, anodic (a) and cathodic (c), are taking place
simultaneously at the surface of the metal electrode with the same rate, i.e. F, = lPCl= PC,,,.
The faradaic admittance of the electrode system is the sum of both reactions and can be
expressed as

yF(O) = l/R&) +B'/(l +jw/a) (21)

Here

B’ = W#@),, - (W~l/W,,l(WW (23)


In the case of the geometric blocking effect, [(aZ’,/L+@),,,,, - (a(Z’,@@),,,, = 0, and then
2080 C. Cao

Fig. 4. EIS of Armco Fe in 1mol/L HCI without (curve 1) and with the addition of 0.5 mmol/L
hexamine (HA) (curve 2).

I I I I I
,B ,
0 200 400 600 800 1000 I200 1400
Zr (V*cm*)

Fig. 5. EIS of Armco Fe in 1 mol/L HCI with added 1mmol/L dodecylamine (DDA).

YF(O) = l/R:(,) (24)

The faradaic admittance of the whole electrode in the inhibitor-containing solution is

Y;=(I-O)YF+OYF(O)=(~-O)YF+O/R:(~) (25)

Here Yr is the faradaic admittance of the metal electrode in the blank solution. Thus in
the case the value of 0 being small, i.e. if the inhibition efficiency is low, the EIS display in
the inhibitor-containing solution will be similar to that in the blank solution. On the other
hand, if the inhibition efficiency is high so that 1-O can be neglected, then from equation
(25)
Y; = O/R&, = l/R; (26)

The EIS display of the metal electrode in the inhibitor-containing solution will be a
single capacitive loop whatever the EIS display in the blank solution. In a wok’ carried out
in this laboratory, the measured values of corrosion potential of Armco Fe in 1 mol/L HCl
without inhibitors and in the same solution with the addition of 0.5 mmol/L hexylamine
(HA) or 1 mmol/L DDA are nearly -483 mV (SCE). This indicates that the inhibition
modes of both HA and DDA are the geometric blocking effects. The inhibition efficiency of
HA is rather low, namely 50%. The measured EIS displays for Fe in 1 mol/L HCl solution
with and without 0.5 mmol/L HA are shown in Fig. 4. They are similar to each other and the
value of transfer resistance in the blank solution is about one half of that in the solution with
HA. The inhibition efficiency of 1 mmol/L DDA is quite high, namely 94%. The EIS display
measured in this solution is shown in Fig. 5. It is a single capacitive arc, which confirms
equation (26).
Interface inhibitor research 208 I

Fig. 6. EIS of Armco Fe in 1 mol/L HCl with added 0.08 and 0.24 mmol/L PMBA.

80

60

IF
F”
c- 20
R
0
0
-20
Zr (fbcm2)
Fig. 7. EIS of Armco Fe in 0.5 mol/L HIS04 with added 0.08 and 0.24 mmol/L PMBA.

If the shift of corrosion potential AE,,, is noticeable, then the inhibition is caused by the
change of the activation energy barriers of the anodic and cathodic reactions of the
corrosion process. In this case the faradaic admittance of the corroding metal in the
inhibitor-containing solution can be expressed by
Y;; = l/R; + R/(1 +jo/a) (27)
Here

l/R: = (aZ;laE),, + (alZ:WE),, = Z~,,,BaScl(Ba + BJ (28)


B is defined by equation (23) and a is defined by equation (18). It has been demonstrated’
that when B’ is positive an inductive arc and when Z3’is negative a second capacitive arc will
display in the low frequency region. From polarization curve measurements at different
values of Cinh,one can obtain the sign of [(X,/i3@)-(alZ’,l/X9)]. Thus by combining the EIS
measurement at the corrosion potential with the polarization curve measurements, one can
obtain the sign of dO/dE. The EIS displays at corrosion potentials of Armco Fe in 1 mol/L
HCl with 0.08 and 0.24 mmol/L PMBA are shown in Fig. 6.3 They are all single capacitive
arcs consistent with the negligible shift of corrosion potential shown in Fig. 1. The EIS
displays shown in Fig. 7 refer to Armco Fe in 0.5 mol/L H2S04 with the addition of 0.08 and
0.24mmol/L PMBA. As discussed above, for Fe in a sulfuric solution the inhibition of
PMBA is not caused by the geometric blocking effect. The EIS displays in Fig. 7 all possess
two time constants with an inductive loop in the low frequency region, which denotes that
B > 0. It is obvious from Fig. 2 that [(aZ,/a) - (a(Z,l/~)] < 0. Thus it can be concluded that
for this system dO/dE < 0.
2082 C. Cao

It can be seen from equations (22) and (28) that it is correct to use transfer resistance
rather than polarization resistance in calculating inhibition efficiency, because the
proportional coefficient between corrosion current density and the reciprocal of transfer
resistance, AMPa + B& is the same for both the solutions with and without inhibitors.
Thus R, and R’, in equation (10) should be replaced by Rt and Rt.

CONCLUSIONS
1. If the shift of corrosion potential due to addition of an interface inhibitor is negligible,
the inhibition is most probably caused by a geometric blocking effect of the adsorbed
inhibitive species on the surface of the corroding metal. It can be further confirmed by the
plot of inhibition efficiency 7 vs relative coverage u estimated from the interfacial
capacitance of the metal electrode. In the case of the geometric blocking effect, 9 equals
the coverage of adsorbed species 0 and the plot of n vs q should be a straight line passing
through the original point of the coordinate.
2. Theoretically, no Tafelian straight line can be found in inhibitor-containing solutions,
unless the coverage 0 of the adsorbed inhibitive species is independent of E or the action
coefficients of the inhibitor on the electrode reactions of the corrosion process are linear
functions of E.
3. Unless the inhibition is caused by the geometric blocking effect, polarization
resistance is not suitable to be employed in calculating corrosion current densities or
inhibition efficiency. Instead, transfer resistance can always be used for calculation of
inhibition efficiency in interface inhibitor research.
4. In interface inhibitor research, EIS measured at the corrosion potential can offer much
information; transfer resistance can be estimated from EIS measurement and inhibition
efficiency can be then calculated. The values of interfacial capacitance which can be
employed to calculate the relative coverage p of the adsorbed species are estimated from EIS
measurements. EIS analysis can offer additional evidence for the inhibition mode of the
inhibitor studied. In the case of the geometric blocking effect, the EIS display will be a single
capacitive loop if the inhibition efficiency is high and similar to that in the blank solution if
the inhibition efficiency is low. If the inhibition is not caused by the geometric blocking effect
the EIS display will possess two time constants. In this case, combined with polarization
curve measurements, the sign of d@/dE can be ascertained.

Acknowledgemenrs-The present paper is a part of the results of the key project “Study on Interface Inhibitors”
supported by the NSF of China.

REFERENCES
1. W. J. Lorenz and F. Mansfeld, Proc. 6th Symp. European Inhibition of Corrosion., University of Ferrara,
Ferrara, p. 23 (1985).
2. Ch. Cao, 7th Asian-Pa@ Corrosion Control Conf., Beijing, p. 901 (1991).
3. J. Wang, Doctoral dissertation, Insfitute Corrosion Protection Meet., Academic Sinica (1991).
4. T. Muarakawa, S. Nagaura and N. Hackerman, Corros. Sci. 7, 79 (1967).
5. Ch. Cao, M. Zhang and H. Lin, Corros. Sci. Prof. Technol. 4, 1 (1992).
6. Ch. Cao, Sh. Song and Y Wang, Corrosion 45, 99 (1989).
I. M. Stern and A. L. Geary, J. electrochem. Sot. 104, 56 (1957).
8. Ch. Cao, Electrochim. Acta 35, 831 (1990).
9. M. Zhang, Ch. Cao and H. Lin, J. Chin. Sot. Corros. ProI. 13, 101 (1993).

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