CORROSION SC IENCE

1988 Whitney Award Lecture

The Whitney Award is for a contribution to science, such as the development of improvement of a
theory that pro vides a more fundamental understanding of corrosion phenomena and/or the prevention
of corrosion. An individual may qualify who has made a recognized national or international
contribution to corrosion science through some form of education or works that lead to a better
understanding of the science of corrosion.

Don't Be Afraid of Electrochemical

Techniques But Use Them with Care!*

F. M ans feld*

ABSTRACT
As electrochemical techniques for corrosion research, monitoring,
and control become more sophisticated, and improved software
for the performance and analysis of electrochemical tests
becomes available, more detailed information about corrosion be-
havior can be obtained from such tests. It is important, however,
to consider the background and limitations of even such routine
tests as polarization techniques. While improved instrumentation
and the availability of commercial software have made it much
easier to carry out electrochemical corrosion tests, it is important
to plan the performance and analysis of such tests carefully. It is
pointed out that neglecting the effects of the uncompensated re-
sistance ("ohmic drop") can cause severe distortions of polariza-
tion curves, underestimation of corrosion rates, and changes in
the true scan rate of a potentiodynamic curve. Positive feedback
and the interrupter technique can be used to eliminate such er-
rors. The choice of the correct scan rate is an important factor in
the performance of potentiodynamic tests.
Electrochemical impedance spectroscopy (EIS) has broad-
ened the range of corrosion phenomena which can be studied
using electrochemical techniques. Examples of EIS applications
include the evaluation of corrosion behaviors of polymer-coated
metals and anodized Al alloys. EIS can be used as a quality con-
trol test for anodized Al surfaces and for chromate-conversion-
coated Al alloys. It is pointed out that it is on/y possible to use the
full power of the EIS technique if suitable models for the imped-
ance behavior and fitting programs for the analysis of EIS data
are developed. Examples for such models and software are given
for polymer-coated steel and anodized Al. A model which
describes the localized corrosion behaviors of Al alloys and Al-
based metal matrix composites is also presented.
INTRODUCTION
Considering the electrochemical nature of corrosion processes, it
is not surprising that the application of electrochemical techniques
has been so successful in the evaluation of the kinetics and the
mechanisms of corrosion processes. The constant improvement of
instrumentation and the recent development of software for the
performance and analysis of electrochemical tests have made the
use of electrochemical techniques even more successful. The in-
troduction of new techniques, such as electrochemical impedance
spectroscopy (EIS), has made it possible to study the corrosion
behavior of systems such as polymer-coated metals and anodized
Al, which could not be evaluated previously with traditional DC
techniques. While great progress is being made in the application
of electrochemical techniques in corrosion research, monitoring,
and control, it seems that often the background and the limitations
of these techniques are not considered carefully in the planning
and the analysis of electrochemical tests. In this paper, examples
of the application of different electrochemical techniques wilt be
given. It will be pointed out that greater care is necessary in the
performance of routine tests such as potentiodynamic polarization,
where the effects of the uncompensated resistance and scan rate
are often ignored. The application of EIS has so far resulted in the
publication of a large amount of experimental data without much
interpretation. The need for the development of suitable models
which describe the observed corrosion behavior and allow the
transition from the present data collection stage to the data analy-
sis stage will be demonstrated.
ELECTROCHEMICAL TECHNIQUES

Polarization Techniques
Presented at CORROSION/88, St. Louis, Missouri, March 1988. The application of polarization techniques, such as poten-
*Corrosion and Environmental Effects Laboratories, Dept. of Materials Science and tiostatic and potentiodynamic polarization, has been very success-
Engineering, University of Southern California, Los Angeles, California 90089- ful in evaluating such basic phenomena as passivity and the ef-
0241. fects of alloying and the use of inhibitors on the kinetics of the
0010-9312/88100223/$3.00/0
856 1988, National Association of Corrosion Engineers CORROSIONDecember 1988
 CORRO SION SC IE NCE

Rx Ru
2000

Rp 1500
CE REF WE

FIGURE 1. Equivalent circuit for the simplest case of a corroding

1000
electrode. E
500
electrochemical reactions which determine the corrosion behavior.
The development of the potentiostat allowed the detailerf study of
such systems, with Olivier's paper on the passivation behavior of 0
FeCr alloys probably being the first.' The late 1950s and 1960s
can be called "the polarization curve years," since the literature
was dominated by the results which were obtained with polariza- 500
tion techniques.

Today, the recording of polarization curves has become rou-

tine, with software being available for the performance and analy-
sis of such tests. While the availability of such software greatly
simplifies the experimental task of recording polarization curven, it 1 (mA/cm 2 )
also produces the potential danger that investigators, especially
the novice investigator, will assume that "standard tests" can be FIGURE 2. Polarization curves for steel in 0.02 M H 2 SO 4 with (Curve
applied to all systems with equal success. However, it is quite ap- 1) and without (Curve 2) compensation of the ohmic drop (from
parent that questions about the correct scan rate and the possible Reference 6).
errors which could result from the uncompensated resistance have
to be carefully considered for each corrosion system. This can be
seen from the schematic representation of the simplest corrosion
system, which is shown in Figure 1. A genera) knowledge of the
values of the uncompensated resistance (R), the polarization re- Ru= Const
sistance (R p ), and the electrode capacitance (C) can be used to
estimate the relative errors resulting from these effects and to ap-
W
ply measures to minimize these errors.
PPI
J 1-
Effects of the Uncompensated Resistance z
1- W
Errors caused by the uncompensated resistance 2-5 result
from the distortion of the polarization curve where a linear term
z cc
W
1 x R. is added to the potential E log 1 curve. If this error is not 1-
recognized, erroneous values of the Tafel slopes b a and b. and 0 0
the corrosion current densities (i corr ) will be obtained. As shown in a
Figure 2, 6 the experimental value of the potential E er; ,, at which
passivation occurs, is also affected by the ohmic drop. If such un-
corrected values were to be used for thermodynamic calculations,
incorrect conclusions would be reached. As Figure 2 shows, the
entire polarization curve for steel in 0.02 M H 2 SO 4 is affected by
the ohmic drop. In extreme cases, it is possible that the active- TIME
passive transition is entirely missed because of the ohmic drop
which might shift this transition out of the polarization range, which FIGURE 3. Time dependence of the electrode potential E the
is used in "standard tests." Of course, the presence of a pitting Current 1 and the ohmic drop lR at constant applied potential E. PP ,
potential would also be overlooked in such a case. (from Reference 7).

The ohmic drop can cause problems in even a simple poten-

tiostatic test, where a constant potential is applied and the current
is monitored as a function of time. As shown in Figure 3, 7 the
changes of the current 1 with time lead to a time-dependent ohmic
drop (IR u ) as a result of which the true electrode potential E t
shows a time-dependent difference from the applied potential
E appl . Such effects could explain differences in the results obtained
by different investigators in supposedly identical tests or in a se-
ries tests performed by the same investigator with slightly different
arrangement of working electrode (WE) and reference electrode
(REF). Especially in studies on the effect of the applied potential
on the susceptibility to stress corrosion cracking (SCC), the effect
of the ohmic drop can be severe, if small changes in E, lead to
large changes in SCC behavior.
The uncompensated resistance R also affects the true scan
rate s a in a potentiodynamic experiment. 8 In the Tafel region, s a
will become smaller as the current 1 increases; while in the active-
passive transition region, s a can be larger than the applied scan
rate S app i. The error 6 caused by R. has been given as:'
6 = (Sappi Se6)"Sapp) = R ^/(R^ + R p ) (1)
For the theoretical case of an electrode with the Tafel slopes
b a = 40 mV and b. = 120 mV, i corr = 1 mA/cm 2 , and R = 1
ohm, this error exceeds 95% for an anodic polarization of 120 mV
and 65% for a cathodic polarization of 240 mV. This case, which
represents iron in 1 M H 2 SO 4 , shows that for larger polarizations,

CORROSIONVol. 44, No. 12 857

CORROSION SCIENCE

most of the applied potential results in the ohmic drop with very
little polarization of the electrode surface.
The ohmic drop in polarization measurements can be elimi-
nated in various ways. It can be subtracted from the measured
polarization curve after the measurement using a constant value of
R. which had been either calculated from the cell geometry and
the electrolyte conductivity or measured with a current or potential
pulse or by one of the techniques discussed below. The disadvan-
tage to this approach is that it has to assume a constant value of
R. (which, most likely, is not true for the anodic polarization curve)
and that the scan rate error cannot be corrected by subtracting the
ohmic drop after recording the polarization curve. The ohmic drop
can also be subtracted from the measured polarization curve
mathematically by curve fitting to the Tafel equation. However, the
limitations are the same.
The techniques which are available commercially for the mSec 10.2 mS/divl
compensation of R during the measurement are the positive
feedback and the interrupter techniques. The backgrounds of both
a SCE REF,
MV = 160 mV,
techniques have been described in the electrochemical literature I - 0.34 mA, Ru - 470 ohm.
and will therefore not be discussed in this paper. However, a few
comments regarding the application of these techniques need to
be made here. The positive feedback technique is relatively easy
to apply; however, changing values of R during the measurement
will lead to instabilities of the potentiostat and possible measure-
ment loss. The use of this technique over a wide potential range is
therefore considered to be of only very limited value in corrosion
studies.
en
The interrupter technique avoids the limitations of the positive
0
feedback technique by continuous sampling of the value of R and
subtraction of the ohmic drop IR. However, a detailed study of
the application of this technique in corrosion studies has shown
that it is very difficult to apply and that a number of experimental
considerations have to be made very carefully. This study was
conducted for steel and stainless steel (SS) in ethanolic HCI as a
model solution, which combines relatively low conductivity with mSec I0.05mS/div)
moderate corrosivity, both of which can be varied by varying the
HCI concentration. Data have also been obtained for the anodic b Pt WIRE REF,
and cathodic polarization behavior of AISI 11 304 SS in pure
)
tV = 525 mV,
hydrazine. 4 It was found that the interrupter frequency and the
I = 0.34 mA, Ru = 1.54 kohm.
band width of the potentiostat have to be adjusted to the charac-
teristics of the system given in Figure 1 in order to obtain mean-
ingful results.
A recording of the impedance spectrum in the high-frequency
range provides data which can be used for these adjustments.
Such data, of course, also provide the values of R. at the times of
the measurement. Adjustment of the potentiostat band width is
possible for the Solartront Model 1286. Another very important
aspect which was discovered in this study was that reference elec-
trodes such as the SCE cannot be used in the interrupter tech-
nique. Figure 4 shows traces of the potential decay during the in-
terrupter period, which were recorded which an oscilloscope. Such
observations are essential for the correct application of the inter-
rupter technique. Trace A obtained with a SCE as the REF does
not show the correct shape, despite the Pact that all potentiostat
settings were applied correctly. R, which was determined as 1.5
mSec (0.1mS/divl
kohm from the EIS data, was calculated from Trace A to be 0.47
kohm. Capacitive coupling of the SCE with a Pt wire, which im- C SCE+Pt WIRE
proves the high-frequency response, 9 results in the expected AV - 560 mV,
shape of the potential decay curve (Trace C), but the calculated I - 0.31 mA, Ru - 1.81 kohm.
value of R = 1.81 kohm is too large. Only when the SCE is elim-
inated and a Pt wire is used as the REF, the correct decay curve FIGURE 4. Potential decay during interruption of the applied
and the correct R value can be recorded (Trace B). potential for different reference e lectrodes.
The uncompensated resistance also affects measurements of
the polarization resistance R P in a small polarization range around
the corrosion potential. 2 The experimental value R P " is the sum of with high corrosion rates (low R p ) and good to moderate conduc-
the true value R P and R. (R 1; = R P + P u ). The error caused by tivities (low R) and in systems with low corrosion rates (high R P)

R is equal to R/R p and can have similar magnitudes in systems and low conductivities (high R). Figure 5 shows an example for
measurements of R P for the system Fe/EtOH + 0.01 N HCI. The
1 ' 1 American Iran and Steel Institute (AISI), Washington, DC. ohmic drop was eliminated during the measurement with the posi-
tRegistered trede name. tive feedback technique. Neglect of the contribution of R. would

858 CORROSIONDecember 1988



CO RROSION SCIENCE

400
150

Fe
0.01 N HCVEtON i 100
22 C 200
Eleetrod. Surtaw: 2.0 em'
50

-40 -30 -20 -10 I ---^^__

^ +10 +20 +30 +40
Uncomp^nbd
y > 0
I(mV)
R. = 357
C -50 E
Componstbd
-100
(R n = 212f1) -200
=74n W
-150

FIGURE 5. R P measurements for iron in ethanolic 0.01 N HCI with

and without compensation of the ohmic drop. -400

have led to an underestimation of corrosion rates by a factor of

five. Haruyama and Tsuru have proposed a corrosion monitor -600
based on the impedance method which measures R at a high -1 0 1 2 3 4 5
frequency and R. + R p = R p " at a low frequency. 10 An electronic
circuit subtracts R. from R P ' and outputs R. An instrument based
on this concept is now available commercially. (2) Log I li ( 1 in uA/cm 2
FIGURE 6. Potentiodynamic polarization curves obtained at differ-
Effects of Scan Rate ent scan rates for AIS/ 430 SS in 1 N H2 SO 4 (aqueous); scan rate
The effects of the scan rate on the anodic polarization curves (mV/s): 0.03 (Curve 1), 0.17 (Curve 2), 0.34 (Curve 3), and 1.00
of AISI 430 SS in 1 N H 2 SO 4 (aqueous) and in 1 N H 2 SO 4 (meth- (Curve 4).
anol) are shown in Figures 6 and 7. Curve 2 in Figure 6 repre-
sents the scan rate used in ASTMt 31 Standard G5. Both sets of
data show that the effect of scan rate is small in the active region 4
and the active-passive transition region where currents are large,
but large in the passive region where currents are smaller. Since
the values of R P and C in Figure 1 are potential-dependent, it fol-
lows that the response of the system in Figure 6 to changes in the
2
applied potential will be potential-dependent. This discussion also
shows that the experimental polarization curves can depend, to a
significant degree, on the polarization conditions and that numeri-
cal analysis of such data resulting in system specific data can only
be conducted for results obtained with scan rates which are suffi-
ciently small. For these reasons, the use of so-called corrosion E
behavior diagrams results in meaningless data and should be dis-
continued. In most cases, these measurements reflect only the
response of the system to the usually very arbitrary polarization
v -2
conditions with very little, if any, useful kinetic information. W

Localized Corrosion
Polarization techniques have also been applied for the evalu-
ation of localized corrosion phenomena. The pitting potential E pt
and the protection potential E prot have been used to characterize
the susceptibility of metals and alloys to pitting corrosion. The dif-
ference between E prot and the corrosion potential E go has been
used to assess the danger of localized corrosion occurring. How-
ever, both values are affected by the experimental conditions to a
degree which depends on the corrosion system, with SSs and Al
alloys being the extremes on either side. The problem with the
approach of ranking the susceptibility to pitting based on E pit be-
comes apparent for Al alloys, where in aerated NaCI, E p , t equals
E co , r . AAt 4) Al 2024 has a more noble E pit , but suffers more dam-
age from pitting in NaCI than AA Al 6061 or Al 7075, which have a
more negative E pi ,.
j 2 >Rohrback Cosasco Model 9030 Corrater, Rohrback Cosasco Systems, Santa Fe
Springs, California.
(3) American Society for Testing and Materials (ASTM), Philadelphia. Pennsylvania.
(4) Aluminum Association (AA), Washington, DC.
-4
-6
Loglil ( I in uA/cm 2 )
FIGURE 7. Potentiodynamic polarization curves obtained at differ-
ent scan rates for AIS/ 430 SS in 1 N H2 SO 4 (methanol); scan rate
(mV/s): 0.03 (Curve 1), 0.17 (Curve 2), 0.34 (Curve 3), and 1.00
(Curve 4).
From an engineering standpoint, it seems much more impor-
tant to determine pit growth rates than the possibility that pitting
can occur. Hunkeler and Boehni 11 have developed a method for
the determination of pit growth rates based on a metal foil tech-
nique. Based on the results obtained with this new technique; they
were able to determine the growth law for pits in Al in the form

CORROSIONVol. 44, No. 12 859

CORR OSION SCIENCE

i p = ip t b- ', where b was 0.5. It was found further 12 13 that cer-

tain anions which increase E P;1 could increase or decrease pit
growth rates depending on the type and concentration of the anion
added. The accelerating effect resulted from the increase of the
conductivity of the electrolyte in the pit. These results show that
very important information concerning the lifetime of structural ma-
terials which is not available from E, 1 or E P ,o , can be obtained with
this foil technique. This technique, therefore, deserves much wider
use in studies of pitting phenomena.
iii
Electrochemical Impedance Spectroscopy (EIS)
The author has discussed the background of the EIS tech-
nique and its application in corrosion studies in 1981 14 and 1982 15
and has given in 1981 with W. J. Lorenz a comparison of the re-
sults of corrosion rate measurements obtained with DC and AC
techniques. 16 The author was the first to introduce the term elec-
trochemical impedance spectroscopy (EIS)," 18 thereby replacing
the previously used term AC impedance.
Since its introduction by I. Epelboin and coworkers (see, for
example, Reference 19), EIS has become very popular and has
been applied to all types of corrosion phenomena. Certain sys-
tems such as polymer-coated metals and anodized Al which were
difficult to study with DC techniques have received renewed atten-
tion. This fast development of EIS is surprising and somewhat
worrisome, since the technique itself is not easy to apply and the
data are often difficult to interpret. Most papers published so far
consist of the experimental results without much discussion of
their significance. Often, the EIS data are of a peculiar shape and FIGURE 8. lnhomogeneous surface model with equivalent circuit
cannot be fit to any of the existing models. It is therefore neces- (from Reference 24).
sary to evaluate methods which can be used to determine whether
the experimental data meet the requirements for real impedance
data namely linearity, causality, and stability. In addition, the data
need to be finite in the frequency range between infinity and zero.
N
The Kramers-Kronig (K-K) transforms 2 have been considered as
a method for the validation of experimental data. 21 However, re-
EU
cent considerations 22 z 3 have shown that the impedance data for
many practical systems such as welt-inhibited solutions, polymer-
coated metals, and anodized Al do not reach a DC limit in the fre- 'N_
quency range which is experimentally accessible. An analysis with
the K-K transforms would therefore suggest that these data are
E
1
invalid impedance data, despite the fact that the data fit very well
to a theoretical model. Various examples of this situation have
been given by Shih and Mansfeld. 22,23 Alternative methods for the V 0 200 400 600 800 1000
validation of experimental data therefore need to be examined.
Re()/ Qcm 2
The Inhomogeneous Surface Model
FIGURE 9. Simulated impedance spectra as a function of R MO
based on the model in Figure 8 (from Reference 24).
In order to advance the analysis of experimental EIS data,
models have to be developed which are based on the physical
and chemical properties of the corrosion systems studied. Many of rotation speed. The fit to the model in Figure 8 is shown as a
investigators have reported depressed semicircles in Nyquist plots, solid line. Excellent agreement is observed for all three rotation
and a number of suggestions have been made as to the reason speeds. The Bode plots in Figure 11 show more clearly the char-
for this deviation from the expected ideal behavior. However, only acteristic features of the EIS data. It has been recommended 25 to
very recently, Juettner, et al 24 have been able to develop a model use Bode plots as standard plots, since all experimental data are
which can explain such depressed semicircles as the results of the equally represented and since the phase angle is a very sensitive
simultaneous occurrence of charge transfer and transport pro- indication of the occurrence of additional time constants in the im-
cesses in neutral aerated media. Figure 8 shows this "inhomo- pedance spectrum. The quality of a fit to a theoretical model can
geneous surface model," which assumes that metal dissolution be judged best on the basis of the phase angle. Addition of 10 -2
occurs on parts of the corroding metal which are covered with cor- M hexan(1,6)-biphosphonic acid (HBP) as an inhibitor leads to im-
rosion products, while oxygen reduction occurs in the pores of the pedance spectra, which are shown in Figure 12 as a function of
oxide film. The equivalent circuit consists of the charge transfer exposure time and in Figure 13 as a function of rotation speed.
resistance Z Me and the transport resistances Z N , which describes The spectra in Figures 12 and 13 could be called depressed
the Nernstian diffusion of oxygen, Z 5 , which describes the inhomo- semicircles, but closer inspection shows that the high-frequency
geneous transport to the pores, and Z por , which describes the dif- part which contains the influence of the transport phenomena is
fusion of oxygen in the pores. C is the electrode capacitance. Sim- different from the low-frequency part. It should be pointed out that
ulation of the impedance as a function of R M8 shows that with for these complicated spectra, determination of the capacitance C
decreasing values of R Me , two depressed semicircles occur from the frequency of the maximum of the imaginary part of
(Figure 9). In Figure 10, experimental data for a rotating iron disk the impedance Im(Z) and the diameter R p of the semicircle as
electrode in aerated 0.5 M Na 2 SO 4 , pH 8, are shown as a function C = 1/2irf rt1e ,R, is impossible. Many of the very high capacitance

860 CORROSIONDecember 1988

 CORROSION SCIENCE.

2400
N
E N
E 1600 0.5 Hz
G
iN
G
5 Hz
E IN 800
E 0.5Hz
tQ 0.05 Hz

"0 200 400 600 800 1000 0

Re(Z)/Qcm2
FIGURE 10. Impedance spectra for iron in aerated 0.5 M Na 2 SO 4
pH = 8 as a function of the rotation speed of the disk (RDE) (from
0 800 1600 2400 3200 4000
Re(2)1S2cm 2
, FIGURE 12. lmpedance spectra for iron (RDE) in aerated 0.5 M
Na 2 SO 4 pH = 8 containing 10 -2 M HBP for an exposure time of 10
,

Reference 24). h (Curve 1) and 28 h (Curve 2) (from Reference 24).

5 3000

E 4
E
U
u 2000
G 3 IN_ 0.05 Hz
IN 2
E
1
1000 0.5 Hz QQ
0.005 Hz
0 1
00
1000 2000 3000 4000 5000
0
Re (2) /S2cm 2
FIGURE 13. Same as in Figure 12, but for three different rotation
a speeds: Curve 1 = 0 s 1 , Curve 2= 4 s 1 , Curve 3 = 14 S 1 (from
Reference 24).
90

Polymer Coatings
m The most successful application of EIS has probably been in
N the evaluation of the corrosion behavior of polymer-coated metals.
L-

Today, most of the leading automotive manufacturers, steel com-

panies, and producers of paint systems are using EIS for the eval-
45 uation of the performance of various paint systems on steel or gal-
vanized steel. The equivalent circuit shown in Figure 14 can
explain most of the impedance spectra reported so far. The coat-
ing capacitance C. depends on the ratio e /d, where d is the coat-
ing thickness. Its changes with exposure time to a corrosive me-
dium can be used to determine the electrolyte uptake which
changes the dielectric constant e. The changes of R om , which has
01 been called pore resistance by Mansfeld and Kendig, 26-29 have
been used to rank the performance of different coating systems.
-3 -2 -1 0 1 2 3 4 5
Recently, Haruyama, et a1 30 have suggested that R P0 can be used
b log (f / s -1 ) to determine the delaminated area A d under a paint film. Assum-
ing that the specific value R 0 ohm cm 2 of the coating does not
( )

FIGURE 11. Bode plots for the data in Figure 10 at 4 Hz (from change with exposure time, A d can be calculated from the experi-
Reference 24).
mental data for R P0 (ohm) = R P /A d . The interfacial impedance Z ;

has different properties for different paint systems. Mansfeld and

values reported in the literature probably result from this incorrect
method of calculation.
The model parameters in Figure 8 can only be obtained by a
fit of the experimental data to the model. Because of the large
number of fit parameters, Juettner, et al 24 found it necessary to
make certain assumptions concerning the values of some parame-
ters and fit the others. Very good agreement between the corro-
sion rates determined from the value of R Me and from solution
analysis by atomic absorption has been observed. 24
Kendig found that a simple combination of a polarization resis-
tance R P in parallel with a double-layer capacitance C d , applies for
thin paint films on steel and Al alloys, while a transmission line-
type impedance appears when a phosphate layer is applied on the
steel under the paint film. 26-29 It is interesting that the properties of
this latter impedance depend on the size of the phosphate crys-
tals. This fact suggests that the EIS measurements can be used
as a quality control test for such coating systems containing phos-
phate layers. It is, in principle, possible to calculate the size of the
corroding area under the coating from the experimental values of

CORROSIONVol. 44, No. 12 861

CORROSION SCIENCE
FIGURE 14. Equivalent circuits for the corrosion behavior of a
coated metal.
C dl , if a constant value of the specific double-layer capacitance
C d ; such as 30 F/cm 2 is assumed. However, for coatings of the
thickness range which is used in practical applications and which
are free of intentional defects, it is often difficult to measure the
part of the impedance spectrum which corresponds to Z,, since it
occurs at very high impedance values and at very low frequencies.
Figure 15 shows the time dependence of the pore resistance
R 50 of a polybutadiene film on steel during exposure to aerated
0.5 N NaC1. 27 Also shown are data for a free film, for which R Po
was found to be independent of exposure time. The changes of
R po depend very much on the surface preparation of the steel sur-
face. Mansfeld and Kendig 26.29 have suggested that this strong
effect of surface preparation results from the different amounts of
corrosion occurring on surfaces which have been cleaned well and
passivated and those which are more reactive. The corrosion
products are assumed to apply pressure to the coating film, which
then develops increasing amounts of defects which reduces R P0 .
Using Haruyama's argument, 30 it can be concluded that the
changes of R po reflect the differences in the degree of delamina-
tion, which depend on the type of surface preparation. Figure 16
shows indeed that the values of R P0 change with time in the same
manner as the corroding area (CORR) and the delaminated area
(DEL), as determined visually according to ASTM Standard D 610.
Both interpretations can be used to explain the results shown in
Figure 16.
Anodized Aluminum
EIS has also provided new and more detailed information
concerning the corrosion protection by anodic films such as anod-
ized layers on Al and its alloys. 3 ' -38 The effects of anodizing and
862 CORROSIONDecember 1988
POLISHED
O POUSHED+ DEGREASED
0 HOT ALKAUNE
A ALKALINE DERUST
A CONC. HNO3
INH. HCI
FREE FILM
Z
O
2
0
a
0
a
0
O
J
TIME. DAYS
FIGURE 15. Time dependence of R Po for coated steel with different
surface pretreatment procedures and for a free film.
sealing procedures, alloy chemistry, and outdoor exposure have
been studied recently by Mansfeld and Kendig 17,31-33 and Lorenz
and coworkers. 31-36 As early as 1962, Hoar and Wood have stud-
ied the sealing of porous oxide films on Al with bridge measure-
ments. 37 They arrived at the equivalent circuit (EC) in Figure 17
for the unsealed [Figure 17(a)] and the partially sealed [Figure
17(b)] porous layer. Koda, et a1 38 have proposed the EC in Figure
17(c) for Al which was anodized in 2% oxalic acid. Lorenz, et al
used the same EC for a discussion of impedance spectra for Al
which was anodized in sulfuric acid and sealed in hot water. 35
The results obtained by Hoar and Wood 37 demonstrate the
typical requirements for the collection of impedance data for anod-
ized Al alloys over a sufficient wide frequency range to determine
all the elements of the EC in Figure 17. Impedance spectra calcu-
lated for the experimental results reported by Hoar and Wood, 37
who did not display their data in impedance plots, are shown in
Figure 18. The results for the unsealed surface show that the ca-
pacitance C o = 10 -9 F/cm 2 of the outer porous layer can only be
detected at frequencies exceeding 10 8 Hz. The use of test elec-
trodes with a larger surface area will move the capacitive region of
the spectra to lower frequencies. Mansfeld and coworkers have
been using electrodes with areas of 20 cm 2 . The occurrence of a
third time constant at --1000 Hz or the DC limit at 10 6 Hz in Fig-
ure 18 have not been confirmed by more recent studies of undam-
aged surfaces. 3 ' -36 . 38 The simulated impedance spectra in Figure
18 demonstrate the need for accurate measurements in a very
wide frequency range, which typically extends from more than 100
kHz to 10 mHz or less. This requires the automatic adjustment of
the gain of the current amplifier 39 and the use of a capacitively
coupled wire reference electrode. 9
Mansfeld and Kendig have reported a systematic study of the
effects of the anodizing [sulfuric acid (SAA) vs chromic acid
(CAA)] and sealing [hot water (HW) vs dichromate (DCh)] treat-
ments and alloy chemistry (AA Al Alloys 2024, 6061, and 7075)
and have proposed to use EIS as a quality control test. 31,32 Im-
pedance spectra were collected as a function of exposure time to
aerated 0.5 N NaCI. Figure 19 gives the impedance spectra for
 CORROSION SCIENCE

0
6 1 1 ' 1 1 ' 1 1 1 ' 1 '

LOG R po 1010 STEEL/0.5 N NaCI

O E coli POLISHED. COATED
5 ACORR 100
DEL
0.03

0.1 r 4 200 0
0 v
0.3 a

1
3 300 E

3 og
0 10 0 2 400 W
wW
C 16

33 1 500

50

0 II 600
0 2 4 6 8 10 12 14 16 18
t(DAYS)

FIGURE 16. Time dependence of R, the corroded area CORR, the delaminated area DEL, and the
corrosion potential E. O.

8
FILM SUR FACE
ALUMINUM HOAR AND WOOD MODEL
Al/Nl ACETATE SEALING
OXIDE (CO) 6
S>
'ORE (R 1 ) L - 24 h
0
S4
N

N
ARRIER g 2

n
'ER (R 2 , C2) I J UNSEALED \
ALUMINUM 0

Co 90

R^
C2
WWQ eo
R2 w0
a R1
Co ^_ X 45

R^ w
C2 NSEALED
C1,1 C1,2
d

b R1,1 R1,2 R2
C1
Rn C2
O F 1 1 1 1 1 1 t 1 1 i
-1 0 1 2 3 4 5 6 7 8 9
LOG 2IIf (f In Hz)
FIGURE 18. Bode plots for SAA Al with sealing in Ni acetate (data
from Reference 37, Table 2) for EC in Figure 17(b).

CAA Al 7075 with a DCh or a HW seal and for an unsealed

surface. 31.32 The results for the HW sealed surface are very simi-
lar to those reported by Lorenz, et al"-as and Koda, et al. 38 How-
C R?
ever, the spectrum for the DCh sealed surface at frequencies ex-
ceeding 1 Hz is almost identical to that of the unsealed surface,
FIGURE 17. ECs for anodized Al alloys.
except for a shallow minimum of the phase angle at --10 Hz,

CORROSIONVol. 44, No. 12 863

CORROSION SCIENCE

90
f 1 . F)cb cl. f1C f

0 50
W Rb Rt tal
J

2 f
4
W RS FCb
N
Q 30 t.f
1
Cb Cp
Rb RP Rb
n
a T
x10 7 s
CAA Al 7075/0.5N NaCI
x10 6
w
6 6
14 x10 5 E
O
x
2
K 3 x104 N 4 -

x103 !V F
t72
0 ID UNSEALED,3h
J O ^ 0
2 HOT WATER SEAL, 20h
x 10 2 0
2 -

(3 DICHROMATE SEAL. 4h o.05

0.5
0 1 t I 1 t x 101
1 0 1 2 3 4 5
0
LOG w (w IN RAD/S) -2 0 2 4 6
FIGURE 19. Bode plots for CAA AA Al 7075 which was unsealed, LOG ca
dichromate (DCh) or hot water (HW) sealed.
90

which shows that two time constants occur also for the DCh
sealed surface. Despite these very small differences in the imped-
ance spectra, the corrosion resistance of the DCh-sealed surface O O O
during exposure to NaCI was superior to that of the unsealed sur- _ 60
face. This points to a difference in the sealing mechanism 31.32 w
1
The use of ASTM B457 which requires one measurement at 1000 (7
Hz would result in erroneous conclusions concerning the quality of
the DCh sealing procedure and the resulting corrosion resistance.
y 30
Based on the impedance data obtained for anodized Al alloys
after outdoor exposure for three years, Lorenz and coworkers 34 S
have proposed a modification of the EC in Figure 17(c) to take a
into account changes resulting from the observed corrosion phe-
nomena. The following two cases were considered: (1) penetration
of the outer porous layer without attack of the barrier layer -2 0 2 4 6
("passive pits"), and (2) penetration of both layers resulting in ac- LOG w(w in rad/s)
tive corrosion of the Al-base metal ("active pits"). Figures 20 and
21 show the corresponding ECs and typical impedance plots as a RS=1i2,R P =10 5 f.C p =10 -9 F
function of the area fraction F for which pitting occurred. 32 34 Lo-
renz, et aI 34 . 35 have observed impedance spectra for HW sealed Rb=10 9 2,Cb=5.10 -7 F
SAA Al 99.5 containing artificial pits during exposure to NaCI for
20 h, which were very similar to those shown in Figure 21. Mans- 0
feld and Kendig 31,32 have observed similar impedance spectra for
FIGURE 20. Schematic representation of damage to the outer
CAA Al 2024 with a DCh seal during exposure to NaCI for periods
exceeding 120 h. porous layer of anodized Al: (a) EC and (b) Bode plots as a function
of the area fraction F at which pitting occurred.
In a study on the effects of acid fog on the corrosion behavior
of various materials, Mansfeld, et a1 4 have recently exposed SAA
HW sealed Al at three sites in Southern California. After 15 in the capacitive region resulting from the outer porous layer is
months of exposure in Visalia, California, no damage was ob- slightly different from that of the ideal case (which would be 1 in
served; in fact, the properties of the outer porous layer seemed to a Bode plot), the parameter has been used for fitting purposes.
have improved, as can be seen by the changes of the impedance This deviation from ideal capacitive behavior is considered to re-
spectra compared to those of an unexposed blank in Figure 22. sult from the inhomogeneous nature of the anodized sealed sur-
The simple shape of these impedance plots suggests that the data face which contains the anodized layer and the sealed pores. Ta-
can be fit to the model shown in Figure 17(c). Software has been ble 1 shows the impedance parameters for the unexposed blank,
developed for the fitting of the experimental impedance data which the side of the sample which was facing upward, and that which
results in the numerical values of Cl, C2, and Al. Since the slope was facing downward.

864 CORROSIONDecember 1988

 CORROSION SC IEN CE

(1 FICb (1 - F)Cp

175
Jk
E

E
0

FAL!
c
..
N i[-\ \ 3//2 /1
N
W
fl \\ /^ / N
RCORR
T i15
tI -
a
-2 -1 0 1 2 3 4 5
LOG 1(1inHz)

6 FIGURE 22. Bode plots for anodized Al: Curve 1 = unexposed

blank; Curves 2 and 3 = after exposure for 15 months in Visalia,
California; Curve 2 = surface facing upward; Curve 3 = surface
N 4 facing downward.
F
(Do
2 (ai 0.001 TABLE 1
(1) 0.01 Impedance Data for Anodized Al After 15 Months
(4) 0.1 of the Exposure at Visalia, California

-2 0 2 4 6 Blank Facing Up Facing Down

LOG w
Cl (F/cm 2 ) 6.5 x 10 - ' 4.6 x 10 - ' 4.8 x 10 -e
R7 (ohmcm 2 ) 8.4 x 10' 5 8.2 x 10' 6 1.4 x 10"
90 al -0.9 -0.94 -0.94
C2 2.6x10-7 3.0x10 - ' 6.7x10-7
a2 -0.9 -0.94 -0.94

60
W Conversion Coatings
z
30
rn
-2 0 2 4 6
LOG w(w in radls)
b the presentation in a Bode plot have the advantage that the scat-
RS - 1Q. RF - 10 5 4. Cp - 10 -9 F.
Cb - 5.10 -7 F, Rb - 1094. RCORR - 10 5 Q. Cdf - 3.10'`
FIGURE 21. Schematic representation of damage to both oxide
layers on anodized Al: (a) EC and (b) Bode plots as a function of F.
The reststance R1 of the pores has increased about tenfold
during exposure for the side facing upward. This increase was
even higher for the surface facing downward. Apparently, the wet-
ting/drying cycles in an atmosphere which was not very corrosive
(despite earlier measurements of very low pH values in collected
fog samples) favors continued sealing of the pores in the outer
oxide Iayer. The decrease of the capacitance Cl of this film with
exposure time suggests that the film has thickened. These resuits
demonstrate again the detailed information which is available from
EIS data for cases where other methods for corrosion damage
analysis would not be sensitive enough to provide meaningful in-
formation. The capacitance of the barrier layer for the exposed
samples is difficult to determine in the measured frequency range
resulting from the large value of R1 and was therefore considered
not to be affected by the exposure test remaining at a constant
value of 0.3 to 0.7 p.F/cm 2 , which has been also reported by other
workers. 32-35
EIS has also been found to be very useful as a quality con-
trol test for chromate conversion coated Al alloys. 41 Figure 23
shows a scatter band for the impedance of AA Al 7075-T73, which
was coated with Alodinet 600 and then exposed to aerated 0.5 N
NaCI for 2 h. The scatter band was determined from the EIS data
for six samples which had been prepared with the same standard
procedure for the application of Alodine 600. The mean curve and
the curves for plus/minus two standard deviations from the mean
were calculated at each measured frequency. This procedure and
ter in the data can be evaluated at all frequencies. In Figure 23,
the scatter becomes larger at the lowest frequencies, where polar-
ization of the electrode can occur because of the drift of the corro-
sion potential. The EIS data in this frequency range were obtained
in a galvanostatic mode at 1 = 0. Figure 24 shows EIS data for a
sample which was not prepared according to the standard proce-
dure. Deviations occur from the standard plot in Figure 23 at the
highest and lowest frequencies. With increasing exposure time, a
shoulder in the impedance plot, which becomes more obvious
from the inspection of the phase angle (Figure 24), disappears,
the capacitance increases, and the impedance at the lowest fre-
quencies decreases. This strong time dependence of the imped-
ance itself is evidence that the conversion-coated surface is unsta-
bie and not very corrosion-resistant.
Localized Corrosion
The final example of the application of EIS in the author's
recent work concerns the detection and monitoring of localized
corrosion of Al alloys. 42-45 It has been observed that characteristic
changes occur in the capacitive part and at the lowest frequencies
of the impedance diagram when pitting or crevice corrosion ini-
1 Registered trede name.

CORROSION-Vol. 44, No. 12 865

 CORROSION SCIENCE

0.5N NaCI. 2h
Al 7075-773IAIodlns 600
vo~ curve s 2a
N
2; 4
T
0
z_
3
N_

02

OL
-2 1 0 1 2
LOG 1(1 IN HZ)
FIGURE 25. EC for localized corrosion of Al alloys and Al-based
FIGURE 23. Scatter band for the impedance of AA Al 7075-773 metal matrix com posites.
coated with Alodine 600 determined for six samples after exposure
to 0.5 N NaCI for 2 h.

90

Al 7075-77310.5 N N*CI
8~mpN A11 75
7b

In 60$

0
1
J
0 1
C_
w
2
3
(3
T M- 3 45 0
2
N_ W W
N W
0
02 T 2 30
J S
a

0 I,
-2
___ /m/, i
-1 0 1 2
0 1
-3
1

-2 -1
1

0
1

1 2
S

LOG 1(1 IN HZ) LOG f (f IN HZ)

FIGURE 24. Bode plots for AA Al 7075-773 coated with Alodine 600 FIGURE 26. Schematic Bode plots for the EC in Figure 25: F = 0
by a nonstandard method: exposure in 0.5 N NaCI for 2h (Curve 1), (Curve 1) a nd F = 0.005 (Curve 2).
1 day (Curve 2), 2 days (Cu rve 3), a n d 7 days (Cu rv e 4).

tiate. The EC in Figure 25 has been developed based on the ex-

perimental data for Al alloys and Al-based metal matrix compos-
ites which were exposed to aerated 0.5 N NaCI. R p and C p
represent the passive surface, while R p and C P result from the
reactions in the growing pit. At the lowest frequencies, a transmis-
sion line-type impedance is observed, which is represented by the
element W in the EC. 42-45 F is the area fraction at which pitting is
observed. Figure 26 gives a theoretical example for the imped-
ance in the absence (F = 0) and the presence (F = 0.005) of pits
for typical values of the elements in the EC in Figure 25. 42 . 43 Pit-
ting results in a large increase of the impedance in the capacitive
region and the occurrence of an impedance element with a con-
stant slope in the log/Z/-log f diagram at low frequencies. The
phase angle has a second maximum at very low frequencies, as
discussed in detail elsewhere. 42-45 For the passive surface (F =
0), only one time constant was observed. Figure 27 shows EIS
data obtained in aerated 0.5 N NaCI for as-received AA Al 7075-
T6 and the same alloy after passivation in 1000 ppm CeCl 3 for 7
days. 42-45 The as-received alloy shows the characteristic changes
of the impedance for a pitted surface, which were illustrated in Fig-
ure 26. The passivated surface showed mainly capacitive behavior
until pitting occurred after -23 days. This result demonstrates that
passivation in CeCl 3 can produce surfaces which are very resis-
tant to localized attack. Therefore, this process has the potential of
replacing the toxic chromate conversion process.
Software has been developed which can be used to fit the
experimental data to the model in Figure 25. 46,47 Since for the
passive surface, the impedance is mainly capacitive, it is difficult
to obtain the DC limit of the impedance from which R P can be de-
termined. By observing the frequency dependence of the phase
angle, extrapolation of the impedance to the DC limit is possible
and R P can be calculated. 46 It is more difficult to extract the nu-
merical values of the elements in the model of Figure 25 from the
experimental impedance data. Using software written for analysis
of such data, 47 the values of R, R pjt e = R P , t /F and the total ca-
pacitance C, = C p + FC P;t have been obtained, as shown in Fig-
ure 28 for AA Al 7075-T6 as a function of exposure time to
NaCI. 43-45 It has not been possible so far to calculate the values of
F separately; however, the values of FC P , t can be determined from
plots such as that in Figure 28(b), assuming that C p does not
change when pitting occurs. The large increase of R P in Figure
28(a) when pits initiate suggests that the passive surface is catho-
dically protected by the growing pits. This discussion shows that it
is possible to detect the onset of pitting and to determine parame-
ters, which can be used to calculate pit growth rates from EIS data
obtained at the corrosion potential. 48 It has to be recognized, how-
ever, that the model shown in Figure 25 is only valid for Al and its
alloys. For Mg, the author and his coworkers have observed an
inductive loop in the impedance spectra when pitting occurred. 49

866 CORROSIONDecember 1988



CORROSION SCIENCE

90
1 -2 h 1 unhealud
2-4 d JAl 707546
3-2hC.Cl.k W
1. CeC1 3 treabed Al 7075-T6
4-23diN7075.76 75 2. As received Al 7075-T6
In 6
60
0

\N
Z W
5

1
N3 45 0
N Q
W
O 2 30 =
0. 4
2 ---- Pfttinp lor 1
LL
OL
-2 -1 0 1 2
LOG f (t IN HZ)

FIGURE 27. Bode plots for as-received and CeCl 3 treated AA Al

7075-T6 as a functio n of immersion time in 0.5 N NaCI. 2
- Pittlnp for 2
2 9
SUMMARY
1

The availability of improved instrumentation and software for

the performance and analysis of electrochemical tests has made it
0
more convenient to perform such tests and extract more detailed 10 20 30 40
information concerning corrosion kinetics and mechanisms. This
situation should not lead, however, to the neglect of certain limita- Tlme(days)
tions and experimental restraints in the application of electrochem- a
ical tests to the study of various corrosion systems.

It has been pointed out that in the performance of potentiody-

namic polarization curves more attention needs to be paid to the 1. CsC13 itwted Al 7075-TO
effects of the uncompensated resistance, which can cause signifi- 2 2. As rsaetvsd Al 7075-TO
cant distortions of such curves and affect the true scan rate. Even
in a potentiostatic test, the true electrode potential might not be
constant because of a time-dependent ohmic drop. The interrupter ^. a
technique can be used to eliminate the ohmic drop during these
measurements; however, it is difficult to apply correctly. v 4

The introduction of EIS as a toot for corrosion research has

greatly increased the range of corrosion phenomena which can be
studied with electrochemical techniques. The results published so
far are more qualitative, and the need for the development of mod-
els for the observed impedance behavior has been pointed out.
Various models have been proposed recently, among them is the
inhomogeneous surface model which describes the often observed
"depressed semicircles" in Nyquist plots. Models have also been
established for the corrosion behavior of polymer-coated metals
and anodized Al alloys. EIS has been proposed as a quality con-
trol test for these systems and for chromate conversion coatings
on Al alloys. It has been shown that EIS can also be used for the
detection and monitoring of localized corrosion of Al alloys and
Al-based metal matrix composites. The need for the development
of software for fitting of the experimental data to a specific model
and the extraction of the parameters which describe the corrosion
behavior has been pointed out.
ACKNOWLEDGMENT
The author's work in the evaluation and application of electro-
chemical techniques in corrosion research would not have been
possible without the help and encouragement of many colleagues
and coworkers. Among these are G. Lauer, E. Parry, K. Oldham,
S. Gilman, M. Salomon, M. Kendig, S. Jeanjaquet, the late S.
Tsai, J. Kenkel, W. Lorenz, K. Juettner, H. Shih, S. Kim, and last,
but not least, H. H. Uhlig, who convinced the author that corrosion
research is a subject worth dedicating an entire career to.
200
100- t Pfteig br 1
10 20 30 40
b
FIGURE 28. Time dependence of the parameters of the EC in Figure
25 for the data in Figure 27: (a) Rp and RP;t, e = Rp;,,F and (b) C t _
C P + FC,,1 .
A major part of the work discussed here was carried out at
the Rockwell International Science Center (Thousand Oaks, Cali-
fornia) with partial funding under the Rockwell International R&D
Project. Funding was also received from the National Science
Foundation, the Office of Naval Research, the Naval Air Develop-
ment Center, and the Army Research Office. The US Senior Sci-
entist Award given by the Alexander von Humboldt Foundation in
1979 made repeated visits to W. J. Lorenz's laboratory in Karls-
ruhe, West Germany, and the establishment of a very fruitful coop-
eration possible. The involvement in the activities of the Corrosion
Division of The Electrochemical Society, and Committees T-3L of
NACE and G1 of ASTM gave an awareness of the possibilities
which electrochemical techniques can fulfill in corrosion research,
monitoring, and control.

CORROSIONVol. 44, No. 12 867

CORROSION SCIENCE

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1986.
30. S. Haruyama, M. Asari, T. Tsuru, Proc. Corrosion Protection by Organic Coat-
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p. 265, 1986.
36. W. Paatsch, W. J. Lorenz, K. Juettner, Metalloberflaeche, Vol. 41, p. 6. 1987.
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9. F. Mansfeld, S. Lin, Y. C. Chen, H. Shih, J. Electrochem. Soc., Vol. 135, p. 906, No. 803, Erlangen, West Germany, September 1983.
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12. F. Hunkeler, H. Boehni, Werkst. Korros., Vol. 32, p. 129, 1981. Al after Exposure in California," to be published.
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74, NACE, Houston, Texas. 44. F. Mansfeld, S. Lin, S. Kim, H. Shih, "Surface Modification of Al Alloys and Al-
19. I. Epelboin, C. Gabrielli, M. Keddam, H. Takenouti, ASTM STP, 727,p. 150, 1981. based Metal Matrix Composites by Chemical Passivation," submitted to Electro-
20. R. L. van Meirhaeghe, E. C. Dutoit, F. Cardon, W. P. Gomes, Electrochim. Acta, chim. Acta.
Vol. 21, p. 39, 1976. 45. F. Mansfeld, S. Lin, S. Kim, H. Shih, "Electrochemical Impedance Spectroscopy
21. D. D. Macdonald, M. Urquidi, J. Electrochem. Soc., Vol. 132, p. 2316, 1985; M. as a Monitoring Tool for Passivation and Localized Corrosion of Al Alloys," Proc.
Urquidi-Macdonald, S. Real, D. D. Macdonald, J. Electrochem. Soc., Vol. 133, p. Symp. Electrochem. Methods in Corrosion Research, Zuerich, Switzerland, July
2018, 1986. 1988, to be published in Metals Forum.
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Validation of Experimental Impedance Data?," Corrosion, in press. Very Low Corrosion Rates," submitted to Corros. Sci.
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the Validation of Impedance Data," Corros. Sci., in press. Cases of Localized Corrosion," submitted to Corrosion.
24. K. Juettner, W. J. Lorenz, M. W. Kendig, F. Mansfeld, J. Electrochem. Soc., Vol. 48. F. Mansfeld, S. Lin, S. Kim, H. Shih, "Pitting and Passivation of Al Alloys and
135, p. 332, 1988. Al-Based Metal Matrix Composites," Proc. Transient Techniques in Corrosion
25. F. Mansfeld, Corrosion, Vol. 44, p. 558, 1988. Science, The Electrochemical Society, Chicago, Illinois, October 1988.
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27. M. W. Kendig, F. Mansfeld, S. Tsai, Corros. Sci., Vol. 23, p. 317, 1983. Magnesium," submitted to J. Coatings Tech.
28. F. Mansfeld, M. W. Kendig, ASTM STP, 866, p. 122, 1985.

868 CORROSION-December 1988