CORROSION SCIENCE
Lifetime Prediction for Organic Coatings
on Steel and a Magnesium Alloy
Using Electrochemical Impedance Methods✫
J.R. Scully* and S.T. Hensley**
ABSTRACT
Electrochemical impedance studies were conducted on an
epoxy polyamide-coated AISI 1010 steel (UNS G10100) and
an epoxy/chromate conversion-coated magnesium (Mg) alloy
ZE41A-T5 (UNS M16410). Results were compared to
evaluate the general applicability of various impedance-
derived measures of coating performance for radically
different metal substrates. Both coating systems were
immersed in room-temperature aqueous sodium chloride
(NaCl) solution of near neutral pH. Correlation of impedance
parameters obtained early in exposure with long-term visual
appearance demonstrated that low-frequency impedance
(< 10 mHz), coating resistance, breakpoint frequency, phase
angle minimum, and saddle frequency associated with the
phase angle minimum forecasted the long-term performance
of both systems. Impedance-based parameters adequately
estimated the defect areas associated with corrosion sites
that penetrated the organic coating but were unable to
estimate the areas associated with coating blisters. More
conservative impedance-based criteria had to be used for the
coated Mg alloy than for the coated steel in predicting long-
term performance. It was hypothesized that differences in the
critical impedance thresholds resulted from rapid Mg
✫
Submitted for publication August 1993; in revised form, April 1994.
Presented as paper no. 359 at CORROSION/93, March 1993, New
Orleans, LA.
* Center for Electrochemical Science and Engineering, Department of
Materia!s Science and Engineering, Thornton Hall, University of Virginia,
Charlottesville, VA, 22903-2442.
** Center for Electrochemical Science and Engineering, Department of
Materia!s Science and Engineering, Thornton Hall, University of Virginia,
Charlottesville, VA, 22903-2442. Present address: International Paper,
Texarkana, TX, 75572.
0010-9312/94/000167/$5.00+$0.50/0
CORROSION–Vol. 50, No. 9 © 1994, NACE International
oxidation and reduction of water reaction rates that occurred
at even the smallest defect sites and from the greater
solubility of magnesium hydroxide (Mg[OH]2). These findings
imply that more conservative coating performance criteria
than traditionally envisioned for steel in neutral salt water
might be necessary for Mg.
KEY WORDS: breakpoint frequency, coating resistance,
corrosion, electrochemical impedance, epoxy, impedance, life
prediction, magnesium, ocean water, sodium chloride, steel,
UNS G10100, UNS M16410, ZE41A-T5
INTRODUCTION
The notion that the corrosion performance of an
organic coated metal could be evaluated by
characterization of its ionic resistance first was proven
by Bacon, et al.1 Mayne found that the modest
inhibition of corrodant (oxygen [O2] and water) ingress
afforded by organic coatings could not explain the
protection mechanism of organic coatings on steel.2 A
protective coating restricts interaction between anodic
and cathodic sites at the coating-metal interface partly
by impeding penetration of the electrolyte but, more
importantly, by minimizing formation of a bulk
electrolyte phase at the coating-metal interface. Anodic
and cathodic electron transfer reactions occur readily
in the presence of a bulk electrolyte phase. These
processes result in corrosion product formation and
hydroxyl ion generation, respectively. Hydroxyl ions
and corrosion products both are capable of inducing
coating disbondment. Therefore, coating damage and
delamination occur at coating defects or coated areas
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CORROSION SCIENCE
of low resistance. Thus, the main role of a barrier-type
organic coating is to adhere to the substrate and
maintain high ionic resistance, which inhibits the ability
of local anodes and cathodes to support electron
transfer reactions at appreciable rates.
A review of the literature in 1979 suggested
coatings with a “critical” or threshold resistance of
< 107 Ω per cm2 of measured surface area are not
protective.3-4 Consequently, determination of the
electrical resistance of the coating, the defect area of
the coating, and the anodic-to-cathodic site density
provides a figure of merit describing the degree of
protection provided by a coating.
Electrochemical impedance provides a means to
estimate some of the important electrical and physical
coating parameters mentioned above. Although
electrochemical impedance spectroscopy (EIS)
methods have been applied to the study of electro-
chemical processes for more than three decades, they
first were used to probe the frequency dependence of
the electrical and electrochemical characteristics of
coated metal surfaces in the early 1980s.5-6 Studies
aimed at exploring the utility of impedance techniques
for lifetime prediction of coatings on steels demon-
strated that certain impedance parameters measured
after several weeks of exposure correlated well with
the coating performance after > 1 y.7-8 Important
impedance parameters included the low-frequency
(LF) impedance magnitude (e.g., ≤ 10 mHz), coating
resistance (Rd), and breakpoint frequency.
Tait, et al., found aerosol coating cans had
service lifetimes > 2 y when the pore resistance of the
coating was > 109 Ω-cm2 after 100 days of exposure.9
Lifetimes were < 1 y when the corrosion resistance
was < 107 Ω-cm2 within the same period.9 These
results were generalized for tin-free steel with an
organic coating, coated tin-plate steel as well as
organic-coated aluminum.
In agreement with Leidheiser’s review3-4 and Tait’s
findings,9 Scully found epoxy polyamide-coated steel
performed well for several years if the LF impedance
(e.g., at 1 mHz and 10 mHz) observed in the first
several months was > 107 Ω-cm2.7
While several correlations exist for barrier coatings
on steel, less information is available for coated
magnesium (Mg).
Conversion-coated and anodized Mg alloy AZ31
with an epoxy coating also has been examined by
impedance methods.10 Samples were exposed for 60
days. LF impedance at 10 mHz of > 108 Ω-cm2 were
obtained for 2 or 3 layers of an epoxy resin coating
(1)
UNS numbers are listed in Metals and Alloys in the Unified Numbering
System, published by the Society of Automotive Engineers (SAE) and
cosponsored by ASTM.
†
Trade name.
706
(16 µm to 20 µm thick) over conversion-coated or
anodized Mg.10 It was proposed that the anodized
substrate provided excellent bonding for an organic
coating, but that a final epoxy resin thickness of 16 µm
to 20 µm was required to properly seal the pores in the
anodized layer.10 The LF impedance was a good
measure of coating performance. However, impedance
values have not been correlated extensively with
coating lifetimes for coated Mg because of the
relatively short exposure periods used.
Moreover, critical or threshold impedance values
used as indicators to forecast a high probability of
coating failure after much longer exposure have not
been compared for organic coatings on steel and Mg.
The present study had three objectives. The first
was to assess the utility of equivalent circuit models
developed for coated steel for use with coated Mg. The
second was to determine whether the most significant
impedance parameters in terms of ability to forecast
long-term performance for coated steel applied equally
well to Mg. The third was to determine whether the
critical or threshold impedance values obtained at early
exposure times forecasted later performance.
EXPERIMENTAL PROCEDURES
AND DATA INTERPRETATION
Materials
Cold-rolled AISI 1010 steel (UNS G10100)(1)
was coated with an epoxy polyamide primer coating
(Mil-24441) by a dip application process described by
ASTM Standard D 823.11
Composition of the steel was 0.08% to 0.13 %
carbon (C), 0.3% to 0.6 % manganese (Mn), 0.04%
phosphorus (P), and 0.05% sulfur (S). Panels first were
degreased in xylene. Coatings then were applied in
25-µm to 30-µm increments for each dip. EIS studies
were done for nominal coating thicknesses of 25 µm,
55 µm, 150 µm, and 180 µm. Exposures were
conducted in ASTM artificial ocean water (ASTM
Standard D 1141) at room temperature.12 Experimental
details have been given elsewhere.7
Composition of the Mg alloy ZE41A-T5 (UNS
M16410) was 3.5% to 5.0% zinc (Zn), 0.75% to 1.75%
cerium (Ce), 0.4% to 1.0% zirconium (Zr), 0.15% Mn,
0.10% copper (Cu), 0.01% nickel (Ni), 0.30 total
others, and balance Mg.
The Mg alloy was chromate conversion-coated in
a dichromate bath in accordance with AMS 2475E.13 A
baked-on epoxy (Araldite 961†) was applied subse-
quently to 25-µm to 37-µm thicknesses. Panels then
were degreased in 1,1,1-trichloroethane. Tests were
conducted in aerated 5% sodium chloride (NaCI) at
room temperature.
A subset of the total population of replicate panels
was treated in boiling oil (Canadian Exxon 2380†), at
CORROSION–SEPTEMBER 1994

164°F (73.3°C), 232°F (111.1°C), and 300°F (148.9°C)
prior to exposure in 5% NaCI at room temperature.
This treatment was implemented to simulate exposure
to aircraft engine fluids. Virtually no long-term adverse
effect of the oil treatment was detected for the panels
tested. Oil inhibited the corrosion of bare ZE41A-T5.
Degradation of the total population of coated Mg
panels was dominated by the initiation and growth of
coating defects that were more or less independent of
the oil pretreatment. The present work was intended to
address the forecasting ability of impedance methods
regardless of the exact processing conditions.
Experimental Methods
EIS data were collected over a frequency range of
1 mHz or 10 mHz to 65 kHz or 100 kHz. Spectra were
acquired at selected times during the exposure period.
Earlier steel work was performed using either a B.C.
1200† potentiostat and Solartron 1250† frequency
response analyzer (FRA).7 Coated Mg was investi-
gated using either a Princeton Applied Research 273A†
potentiostat with a 5310† lock-in analyzer, or a PAR
273A† potentiostat/Solartron 1255† FRA. Data
acquisition was achieved using internal software7 in the
former case and either the PAR 388† software or
ZPLOT† in the latter. A three-electrode electrochemical
configuration was used with a clamp-on electrolyte cell
attached by a rubber O-ring. A 13-cm2 test area was
used for steel specimens. A 10-cm2 test area was used
for coated Mg. A silver-silver chloride (Ag-AgCI)
reference electrode exposed to the NaCI solution was
used in both cases, along with a platinized mesh
counter electrode.
Experiments were conducted at the open-circuit
potential (OCP). OCP obtained for the uncoated alloys
was applied potentiostatically in cases where coatings
of high integrity made determination of a stable OCP
difficult. In the case of AISI 1010 steel, OCP of the
bare steel was –0.6 to –0.7 VAg-AgCI. In the case of the
Mg alloy, the chromate conversion-coated OCP was
≈ –1.6 VAg-AgCI. Alternating current (AC) amplitudes of
10 mV were applied. For high-quality coatings, this
amplitude was increased to 100 mV or 300 mV to
improve the signal-to-noise ratio. Some caution is
warranted with the use of large amplitudes since the
coating could be damaged, and nonlinearities in the
EIS response might be introduced.
Panels were rated visually at various times periods
(steel) and after 120 days (Mg) using the system
described by ASTM Standard D 610 for corrosion
sites14 or for blisters given by ASTM Standard D 714.15
However, the area scale used for D 610 also was
applied to blisters. This scale is 9 (0.03%), 8 (0.1%),
7 (0.3%), 6 (1%), 5 (3%), 4 (10%), 3 (16%), 2 (33%),
and 1 (50%), where the percent in parenthesis is the
area percent corroded or blistered.
CORROSION–Vol. 50, No. 9
CORROSION SCIENCE
(a)
(b)
FIGURE 1. Electrical equivalent circuit models describing
coated metal systems: (a) defect-free coating and (b) organic
coating containing defects. (Rt = charge transfer resistance
associated with corrosion at exposed metal sites).
Data Analysis
The equivalent electrical circuit models in Figures
1(a) and (b) were used for coated steel and Mg.
For the coated Mg system, the EIS circuit
parameters associated with Figure 1 were determined
with a commercially available software. Capacitances
were modeled either as ideal capacitors (C) such that
the admittance = j␻C, where ␻ is the frequency in
rad/s, j = [–1]1/2, or as constant-phase elements
(admittance = j␻nYo where 0 < n < 1 and Yo is a
parameter describing the apparent capacitance.
Circuit parameters were determined by a nonlinear
least-squares fitting analysis procedure.
For coated steel, impedance parameters were
obtained using an iterative procedure whereby the
synthetic spectra for selected impedance parameters
were compared to experimental spectra and updated
until a good correspondence was achieved.16 In this
procedure, intrinsic area-specific resistances and
capacitances (coating defect [rd], corrosion charge
transfer resistance [rt], and double-layer capacitance
[Cdl]) were held constant.16 The defect area (Ad) was
varied to model the increasing coating porosity associ-
ated with various thicknesses of epoxy polyamide on
steel.16
The defect area could be estimated from the high-
frequency and low-frequency breakpoints (fh and fl,
respectively), which have been defined by Hack and
Scully16 and Haruyama, et al.17
fl is favored for small defect areas.16 fh and fl are
linear functions of defect area over a broad range of
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CORROSION SCIENCE
FIGURE 2. Rd as a function of exposure time for epoxy
polyamide-coated steel for various coating thicknesses. Results
are shown for replicate specimens at each thickness.
defect areas, with certain simplifying assumptions. 16
Breakpoint frequency also is dependent on the coating
dielectric constant and resistivity, and these param-
eters are unlikely to remain constant or change with
time so as to offset each other perfectly. Therefore, the
approximating nature of the breakpoint frequency
approach cannot be overemphasized.
For larger defect areas, fh is used.16-17 A phase
angle minimum (⌽min), occurring at intermediate
frequencies, also can be exploited to examine coating
deterioration. ⌽min arises as a result of a separation of
the coating and interfacial resistive-capacitive (RC)
time constants depicted in Figure 1(b) with
deterioration. The frequency associated with ⌽min (fmin)
and ⌽min itself have been found useful for character-
izing coatings on metals.18 fmin is proportional to the
defect area raised to the 1/2 power, and tan ⌽min is
inversely proportional to the defect area raised to the
1/2 power.18 Use of a combination of fmin and ⌽min
provides a method for distinguishing between changes
in coating defect resistivity and defect area.18 The
formal derivations used for fh and the saddle frequency
analysis methods have been discussed elsewhere.16-20
Controversy exists as to how sensitive fh is to the
area associated with blisters.19-20 If the coating
resistivity (␳) is the same over blisters and well-bonded
coated areas, then a decrease in the defect resistance
of the coating (Rd) and, concurrently, an increase in fh
does not occur with disbondment.19 Central to this
controversy, then, is the value of ␳ and its meaning. It
has been asserted that ␳ remains high over delamina-
ted areas of the coating.6,19 However, these claims are
based on the measurement of the resistivity of
detached films and not that of actual blisters. It is true
that delaminated coatings with a high ␳ are less likely
to be detected by the breakpoint frequency analysis
708
method.6,19 However, Haruyama, et al., pointed out that
a low value of ␳ at blisters can be accounted for by the
electromigration of Cl– or Na+ to the anodic or cathodic
sites under the blister to maintain charge neutrality.17
Others have argued that the approach is suited
particularly well to coating defects such as pores that
are open to the electrolyte.16 For these types of
defects, it is theorized that ␳ approaches the resistivity
near or even below that of the external electrolyte
(12 Ω-cm to 25 Ω-cm), which is much less than that of
the intact coating.16 It is well established that occluded
sites may lead to increased ionic concentrations if the
long diffusion length minimizes the transport of soluble
corrosion products into the external solution. With
these possibilities and limitations in mind, the data for
the coated steel and Mg systems could be analyzed.
RESULTS AND DISCUSSION
EIS Characterization
of Epoxy Polyamide-Coated Steel
The EIS responses of various coating thicknesses
on steel have been reported elsewhere.7 Rd as a
function of exposure time is shown in Figure 2 for a
variety of coating thicknesses. Gradual decreases in
resistance were observed for all coatings. Very low
initial Rd values were observed for thin coatings (20 µm
and 55 µm) almost immediately. Corrosion sites were
detected visually at early times for single-layer
coatings. Multilayer coatings, especially the 116-µm-
thick and 150-µm-thick coatings showed no visible
signs of deterioration until well after 100 days.
Significant changes in the EIS response occurred
before this time. The low initial values of Rd for the thin
coatings (≤ 25 µm) were best accounted for by an
increased population of pre-existing defect areas with a
decreasing number of coating layers and, hence, a
decreasing total coating thickness.
In the case of the 20-µm-thick coating, an intrinsic
␳ value of 1010 Ω-cm to 1014 Ω-cm results in an area
specific Rd of 107 Ω-cm to 1011 Ω-cm2 for a 10-µm
coating. An alternative view is that a 20-µm-thick
coating containing an equal population of substrate
penetrating coating defects as a 200-µm-thick coating
should have produced an Rd value that is only one-
tenth of the 200-µm coating’s Rd based on difference in
thickness. Rd for the 180-µm-thick coating was
109 Ω-cm2 just after exposure, implying that a
108 Ω-cm2 resistance should have been obtained for
the 20-µm-thick coating. Thus, the observed extremely
low Rd for the single and 2-layer coating thicknesses
just after exposure could not be accounted for by
geometric changes in coating thickness alone. Such
behavior would be described best by pre-existing open
defects or pores that penetrated to the metal substrate.
Hence, Rd was a good measure of the initial defect
CORROSION–SEPTEMBER 1994
 CORROSION SCIENCE

area of the coating. Indeed, assuming penetration of

the electrolyte in a single pre-existing pore and that this
defect resistance dominated Rd described by Figure 1,
an initial defect area of ≈ 10–4 cm2 is suggested.
As discussed earlier, fh increases linearly with
increasing defect area under certain simplifying
assumptions. Figures 3 and 4 illustrate the differences
in breakpoint frequency observed as a function of
exposure time for the 55-µm-thick coatings compared
to the 150-µm-thick coatings. Visual indications
(ASTM D 610 rating of 9) of as little as 0.03% actively
corroding area (4 x 10–3 cm2) were not detected until
after 100 days of exposure in both cases, yet fh was
sensitive enough to pick up increases in the coating
defect area. These data indicate that the breakpoint FIGURE 3. Relationship between breakpoint frequency and
frequency analysis method is a useful approach for exposure time for a 55-µm-thick epoxy polyamide-coated
quantifying the development of low resistance defect steel. Results are shown for replicate specimens.
areas prior to visual observation of corrosion. A
correlation exists between breakpoint frequency and
visual assessment of defect area, but a rigorous
assessment of whether blistered areas were detected
accurately by the breakpoint frequency was not
possible using these data.
A model was developed subsequently to describe
the influence of small defect areas of extremely low
intrinsic resistivity on the EIS response of coated
metals.16 This model was based on the assumption
that decreases in Rd and increases in breakpoint
frequency correspond strictly with the growth of
localized pre-existing corrosion sites of low intrinsic
resistivity (e.g., approaching that of the bulk electro-
lyte). This model was not intended to describe the
growth of large delaminated areas nor that of blisters in
cases where the magnitude of ␳ of the detached FIGURE 4. Relationship between breakpoint frequency and
coating remains high. The model accurately represen- exposure time for a 146-µm- to 160-µm-thick epoxy polyamide-
ted cases where the actively corroding area was of coated steel. Results are shown for replicate specimens.
similar dimensions as the area of low resistance
associated with the pores in the coating.
Figures 5 and 6 show synthetic computer-
generated EIS data in the Bode magnitude and phase impedance spectrum was collected immediately after
angle formats that resulted strictly from changes in immersion to avoid delamination and corresponding
defect area. The assumed circuit model parameters unknown changes in the defect area. The known
are given in Figure 7. All resistance and capacitance defect area in this case increased instantaneously
parameters remained fixed, except for the defect area from essentially zero to 1% with the intentionally
(Ad), which was assumed to have a low initial resistivity applied flaw. Figure 8 shows the experimental EIS
representative of the bulk electrolyte. The resulting data before and after drilling the hole along with the
synthetic EIS data was strikingly similar to that synthetic data resulting from the model fit. Good
observed during the degradation of actual coatings. agreement was obtained by applying the parameters
The high- (fh) and low- (fl) frequency breakpoints indicated in Figure 7. While this approach could not
identified with the open circles in Figure 6 increase account for all types of defects in coated metal
linearly with defect area, and saddle frequency (fmin) systems, it demonstrates the superiority of EIS over
with defect area to the 1/2 power with fl saturating visual methods for detecting and ranking small actively
above 0.001% defect area. Tan ⌽min decreases with corroding areas associated with direct penetration of
increasing defect area to the 1/2 power. the coating on metals. Coating performance and
To verify the assumptions in this model, a small quality control of coatings may be assessed using
hole was drilled in a well-coated steel panel. An these procedures.

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CORROSION SCIENCE
FIGURE 5. Bode magnitude plot showing the theoretical effect
of various percentages of defect area on the simulated
impedance behavior of a coated steel with a total area of
10 cm2. Hypothetical defect areas are indicated on the plot
using both area % and the ASTM D 610 scale.
One other parameter associated with the
characterization of coatings by EIS should be
mentioned. This parameter was the LF impedance
associated with the impedance plateau seen at
frequencies below ≈ 10 mHz in Figure 5. If this
parameter were determined near the direct current
(DC) limit, it would become a LF resistance similar to
the DC resistance reported in earlier studies.1 The
circuit model shown in Figure 1(b) indicates that LF
impedance would be dominated by the sum Rs + Rd +
Rt as frequency approaches zero. Hence, the LF
resistance is a combined measure of Rd and the
corrosion resistance for conductive electrolytes.
FIGURE 7. Equivalent circuit component intrinsic parameter values used in Figures 5, 6, and 8.
710
FIGURE 6. Bode phase angle plot showing the theoretical
effect of various percentages of defect area on the simulated
impedance phase angle behavior of a coated steei with a total
area of 10 cm2. Hypothetical defect areas are indicated using
both area % and the ASTM D 610 scale.
Decrease of the LF impedance < 108 Ω-cm2 as shown
in Figure 9 correlates well with the ability to measure
a stable OCP with a high-impedance voltmeter.
Measurement of a stable OCP is also a qualitative
indicator of the presence of active defects. Moreover,
the ability to measure a stable OCP should rely on
some minimum required defect area.
EIS Characterization
of the Coated Mg Alloy
Conversion-coated Mg alloy ZE41A-T5 was tested
with the 25-µm- to 37-µm-thick Araldite epoxy coatings.
Impedance behavior was dominated by the random
CORROSION–SEPTEMBER 1994
 CORROSION SCIENCE

presence of pre-existing defects for nominally identical

panels. The following results focus on detection and
monitoring of these defects, as well as on the issue of
lifetime prediction.
Figures 10 and 11 illustrate the EIS response of
two coated specimens as a function of selected
exposure times. The solid lines represent a computer
fit to the circuit models depicted in Figures 1(a) and (b).
The data were described readily using the same circuit
model developed for coated steel. For the specimen
containing a natural defect (Figure 11[a]), a significant
change in the LF impedance (< 10–1 Hz) was observed
after 65 days. At this time, ⌽min was observed at
intermediate frequencies, fl increased with time, and
the capacitive response observed at 10 days exposure
time became resistive. Using the framework developed
from the synthetic analysis of Figures 5 through 7, FIGURE 8. Impedance magnitude data for an epoxy-coated
these changes indicated the existence and growth of steel in ASTM artificial seawater. Solid lines represent synthetic
data developed using the circuit parameters given in Figure 7
active defects. In contrast, the impedance response in
for selected defect areas which give the fit shown. ∆ and ❏
the case of limited defect formation and growth symbols indicate experimental data at two defect areas.
remained almost completely capacitive, although a
small separation of the LF and HF time constants was
indicated by the appearance of ⌽min at intermediate
frequencies (Figure 10). Figures 12 and 13 illustrate
the relationship between various coating parameters
(Rd, charge transfer or corrosion resistance [Rt], and
OCP) as a function of exposure time for the defect-free
and naturally defective cases. OCP of the bare ZE41A-
T5 Mg alloy was –1.57 VAg-AgCI. Similar OCP values
were observed for natural defects and freshly abraded
alloys. In the case of the coating containing the natural
defect, OCP approached this value by 65 days. An
ASTM D 610 rating of 6 (1% active area, or ~ 0.1 cm2)
was obtained at 120 days, which was roughly
consistent with an electrochemically determined active
area of 1.3 x 10–2 cm2. This active area was obtained
by dividing Cdl (µF) determined from a fit to the circuit
model shown in Figure 1(b) by the area specific value FIGURE 9. LF impedance behavior (at 1 mHz and 10 mHz) and
of Cdl, determined for the bare Mg alloy (30 µF/cm2 to OCP as a function of exposure time for 160-µm-thick epoxy-
50 µF/cm2) in 5% NaCI. In the case of the bare Mg coated steel.
alloy, the circuit model consisted of a parallel RCdl
combination and a solution resistance (Rs) in series.
OCP of the bare Mg alloy was not reached in the case
of the defect-free coated Mg alloy (Figures 10 and 12) exposure time always were consistent with increases
even after 120 days, consistent with its high imped- in breakpoint and saddle frequencies and with
ance. For this panel, an ASTM D 610 rating of 10 was decreases in ⌽min. However, it was difficult to obtain a
obtained (10–2% or less active area, ~ 10–3 cm2), which quantitative measure of defect area from these
was consistent with a calculated electrochemically parameters without a number of assumptions, as
active area of 10–5 cm2 obtained using capacitance discussed previously. Utilization of Cdl to determine
data in the manner described above. area requires the assumption of an area specific
Given the question surrounding the ability of EIS to capacitance. The 50 µF/cm2 value found for bare Mg in
detect defect area on coated metals, a test of the 5% NaCI was used even though the chemistry at the
degree of correlation of the ASTM D 610 and D 714 base of a pore was unknown. Figures 14 and 15
ratings with electrochemically detected defect area was examine the correlation between the impedance-based
undertaken. The most direct EIS measure of defect active area and the visually determined defect area
area is the interfacial capacitance. Increases in Cdl with evaluated by ASTM D 610 and D 714, respectively.

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(a) (b)

FIGURE 10. Impedance response for an low initial defect Araldite-coated Mg alloy after various exposure times
in 0.5% NaCI solution. The symbols show experimental data, and the solid line indicates the computer fit to the
model shown in Figure 1.

(a) (b)
FIGURE 11. Impedance response for a high initial defect Araldite-coated Mg alloy after various exposure times
in 0.5% NaCI solution. The symbols show experimental data, and the solid line indicates the computer fit to the
model shown in Figure 1.

Results were presented for the entire population of
coated Mg alloy panels after exposure for 120 days.
EIS data was acquired at 120 days for active-area
determination, and panels were removed immediately
and rated visually. Each solid circle represents such a
data pair. The dotted line indicates the corroded area
prescribed by the numerical rating system given by the
D 610 standard. The same size index also was applied
to blisters to give the D 714 rating. Electrochemically
corroded areas somewhat underestimated the visual
D 610 ratings (Figure 14), especially when the visual
rating was < 4, but qualitatively followed visual
assessments. This underestimation may have resulted
from inaccuracies in the assumed value of Cdl that
were used to calculate the active area, from the fact
that all corroded sites detected visually were not active

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FIGURE 12. Changes in selected impedance parameters as a

function of exposure time for a low initial defect Araldite-coated
FIGURE 13. Changes in selected impedance parameters as a
Mg alloy after various exposure times in 0.5% NaCI solution.
function of exposure time for a high initial defect Araldite-
See Figure 10.
coated Mg alloy after various exposure times in 0.5% NaCl
solution. See Figure 11.

on day 120, or from the fact that AC signal was not

distributed uniformly on all of the visually detected
active area.
Such qualitative agreement was not observed in
the case of blisters (D 714 concept with D 610 defect
area scale). Also, the sum of blister and corroded
areas did not yield meaningful correlations. An inability
to sense blisters occurred either as a result of an
incorrect area specific capacitance assumption,
because blisters observed visually at the end of the
test were not necessarily electrochemically active at
the time of the EIS measurement to detect active area,
or as a result of a high ␳ value over the blister site.
Results did confirm, as with the case of coated steel,
that extremely small actively corroding areas could be
sensed using EIS. The lack of agreement in the case
of blisters will require further investigation. FIGURE 14. Relationship between ASTM D 610 visual rating
Simplistic interpretations of EIS results also yield after 120 days exposure and electrochemical active area
useful information regarding corrosion processes. The derived from Cdl at 120 days for an Araldite-coated Mg alloy.
LF impedance obtained at 82 mHz decreased steadily
with exposure time in the case of the panel indicating
the presence of defects. It was clear from the equiva-
lent circuit model in Figure 1(b) that the near-DC performance were not observed for the epoxy-coated
impedance magnitude obtained at this frequency was steels.5 Hence, Cc did not appear to be an effective
a measure of both Rd and Rt, as mentioned previously. measure of corrosion performance for these coated
Changes in OCP also correlated well with the trend metals in NaCl solution.
toward coating damage. The lower the LF impedance, In summary, the models shown in Figures 1(a)
the closer OCP of the coated system was to OCP and (b) appeared to be appropriate for coated Mg. The
obtained for a bare ZE41A-T5 Mg alloy. same impedance parameters found useful for coated
Some comments should be made concerning the steel correlated to coating performance and growth of
usefulness of coating capacitance (Cc) as a predictor of defect area for a coated Mg alloy.
coating damage. Increases in Cc were observed with
exposure time. However, changes in Cc that clearly Lifetime Prediction Correlations
forecasted the degradation process were not evident The critical or threshold impedance magnitude
for the Araldite-coated Mg alloy. Similarly, strong below which failure of the coated metal occurred at
correlations between changes in Cc and coating some later date was examined. An ideal impedance

CORROSION–Vol. 50, No. 9 713

CORROSION SCIENCE
FIGURE 15. Relationship between blister area determined
using ASTM D 610 rating scale after 120 days exposure and
electrochemical active area derived from Cdl at 120 days for an
Araldite-coated Mg alloy.
parameter would forecast the long-term performance
even if determined very early in the exposure period.
Coating performance was forecast using impedance
parameters determined as early as 14 days in the case
of coated steel.7 However, to minimize uncertainty
about the issue of minimum exposure time, a uniform
time period of 65 days was selected. Impedance
parameters determined at this time were compared to
visual ratings obtained later.
To resolve whether the threshold impedance
magnitude which signals coating failure at some later
time was the same for coated steel and the Mg alloy,
impedance parameters obtained at 65 days exposure
were compared to the visual appearance after 120
days for both systems. Impedance parameters
examined included the LF impedance, Rd, fl, fh, and fmin.
Panels were rated visually at 120 days according to
ASTM standard D 610. An ASTM D 610 rating of 5
(3% corroded area) was defined arbitrarily as coating
failure for the purpose of this comparison.
Figure 16 shows the relationship between LF
impedance at 65 days and the D 610 visual rating after
120 days for both epoxy polyamide-coated steel and
Araldite-coated Mg alloy. Steel specimens with a LF
resistance < ≈ 105 Ω-cm2 at 65 days met the failure
criterion. Steel specimens with a LF resistance < 5 x
105 Ω-cm2 in 65 days met the same failure criterion in
600 days (Figure 17). However, any coated steel
specimens with a LF resistance > 106 Ω-cm2 survived
for 600 days without failure. This was similar to the
older resistance criterion of 107 Ω-cm2.3-4,9 Hence, the
threshold LF resistance for steel was ≈ 106 Ω-cm2 to
107 Ω-cm2 for the failure criterion arbitrarily chosen
here. In the case of the coated Mg alloy, specimens
with a 65-day LF resistance ≤ 4 x 108 Ω-cm2 were
714
FIGURE 16. Correlation between ASTM D 610 rating at 120
days and LF impedance after 65 days exposure time for an
Araldite-coated Mg alloy and epoxy polyamide-coated steel.
liable to fail (2 of 4 replicate panels failed, while 1 had
a rating of 6). For the coated Mg alloy with a LF
resistance > 4 x 108 Ω-cm2 at 65 days, only 1 of 3
panels approached failure with a 120-day rating of 6.
Hence, the threshold LF resistance for the Araldite-
coated Mg alloy clearly was ≥ 109 Ω-cm2. Exposure for
> 120 days may have resulted in the need for an even
higher impedance to avoid failure. An exact value
could not be proposed at this time because of an
inadequate data set for statistical analysis.
Figure 18 shows the relationship between Rd at
65 days and the D 610 visual rating after 120 days for
both epoxy polyamide-coated steel and Araldite-coated
Mg alloy. Steel specimens with Rd < ≈ 104 Ω-cm2 at
65 days met the failure criterion. Steel specimens with
Rd < 3 x 105 Ω-cm2 (65 days) met the same failure
criterion after 600 days of exposure. However, any
coated steel specimens with Rd > 106 Ω-cm2 survived
for 600 days exposure in ASTM ocean water without
failure. Hence, the threshold Rd for epoxy polyamide-
coated steel was ≈ 106 Ω-cm2 to 107 Ω-cm2 given the
failure criterion chosen here. This also was consistent
with former criteria. In the case of coated Mg,
specimens with a 65-day Rd < ≈ 108 Ω-cm2 were likely
to fail (2 of 6 replicate panels failed, while 2 had a
rating of 6, or were near failure). Moreover, 3 of 3
coated Mg panels with Rd > 108 Ω-cm2 did not fail in the
120-day period. A Rd threshold of ~ 109 Ω-cm2 was
suggested by these results for the coated Mg system.
A similar trend was observed with regard to the
breakpoint and saddle frequencies. A breakpoint
frequency > 104 Hz signaled imminent coating failure
for the steel, while any significant separation of time
constants at all so that fmin and ⌽min emerged including
fmin > 102 Hz signaled failure for the Mg alloy.
CORROSION–SEPTEMBER 1994

FIGURE 17. Correlation between ASTM D 610 rating at 600
days and LF impedance after 65 days exposure time for epoxy
polyamide-coated steel.
It was clear from these results that more
conservative threshold impedance values would be
required for coated Mg compared to coated steel to
assure with any confidence a certain level of perform-
ance after a certain period of time. Therefore, caution
is required concerning the universal applicability of any
single threshold impedance value determined from a
certain coating-metal system. For instance, a DC
resistance value > 107 Ω-cm2 generally is viewed as
indicative of a good organic coating. Such a guideline
clearly may not apply to all alloys, coating systems, or
preparation procedures other than the ones actually
tested. A more conservative criterion perhaps should
be applied to coated Mg alloys.
Differences Between
Coated Mg and Steel
Although the existence of different impedance
threshold values was not surprising, the exact reason
was unclear. In the case of the comparison conducted
here, it was unlikely that the differences in performance
related to the differences in coating thicknesses (20 µm
to 37 µm for Mg as compared to 25 µm to 155 µm for
steel). For Mg, 20 µm to 37 µm has been shown to
provide excellent corrosion resistance when free of
defects.10 Four of 10 Araldite-coated Mg specimens
survived the 120-day test period with a perfect
ASTM D 610 rating of 10, implying that the coating
thickness in and of itself was not the cause. Rather, the
differences between coated steel and Mg reported
here more likely reflected the differences in corrosion
rate and controlling factors in the corrosion processes
for steel relative to Mg alloys in NaCI solutions.
The literature reports a corrosion rate of steel in
seawater of ~ 4 mpy.21 Commercial Mg alloys can
CORROSION–Vol. 50, No. 9
CORROSION SCIENCE
FIGURE 18. Correlation between ASTM D 610 rating at 120
days and Rd after 65 days exposure time for an Araldite-coated
Mg alloy and epoxy polyamide-coated steel.
corrode at several hundred times that rate in seawater,
mainly as a result of alloy impurities such as iron (Fe)
that facilitate the cathodic reduction of water reaction
at a high rate.21 A polarization resistance value (Rp) of
30 Ω-cm2 was obtained for the bare Mg alloy
investigated here, while several hundred Ω-cm2
typically is obtained for steel in aerated NaCI solution.
Moreover, corrosion of steels in NaCI of neutral pH is
controlled by the O2 reduction reaction.
It is reasonable to expect that O2 transport is
mass transport-controlled at small coating defects and
that this reactant may be depleted readily at corroded
sites. In the case of delamination or blistering of
coatings on steel, O2 must be transported relatively
long distances parallel to the metal surface through the
electrolyte to the delamination front. Alternatively, O2
must be transported through the organic coating
perpendicular to the steel surface to reach the
delamination front at much lower transport rates
through the polymer.7 In contrast, the primary cathodic
reaction in the case of Mg is the reduction of water.
This reaction is charge transfer-controlled in aqueous
NaCI solutions. Moreover, residual alloying impurities
such as Ni, Fe, and Cu accelerate the corrosion of
Mg.22 It is believed that these alloying elements
catalyze the reduction of water reaction, which leads to
hydroxyl ion production. Since this reaction is not mass
transport limited in aqueous solutions, corrosion of Mg
alloys may proceed rapidly at very small coating
defects. This may lead to rapid disbondment by both
corrosion product wedging as well as hydroxyl ion
production. In comparing steel to Mg from the stand-
point of hydroxyl ion production, an interfacial potential
equal to OCP for Mg in salt water would be analogous
to polarizing steel to –1.57 VAg-AgCI, not accounting for
715
CORROSION SCIENCE
possible differences in water reduction exchange
current densities. Coated steel at –1.57 VAg-AgCI would
have to be compared to coated Mg to obtain roughly
similar hydroxyl ion production rates and thereby
complete this comparison.
The fact that high initial impedance values were
required to insure good 120-day performance for the
Mg alloy implied that only the smallest of defect sites,
which presumably could be plugged with corrosion
products, could be tolerated in the case of coated Mg.
In fact, differences in oxide solubility also might explain
the inability of Mg to tolerate coating defects.
Magnesium hydroxide (Mg[OH]2) is considerably more
soluble than ferrous hydroxide (Fe[OH]2) at an
equivalent pH,23 rendering the “deactivation” of small
active sites by corrosion product precipitation more
difficult in the former case. The hydroxyl ion production
rate, greater solubility of corrosion products, and the
high oxidation rate of Mg all contribute to an inability to
tolerate larger natural defects. This discussion is
supported by the results since a ≥ 3% corroded area
often resulted in complete perforation of the Mg alloy
substrate (> 0.2 cm thick) in as few as 20 days. Hence,
successful use of coated Mg alloys requires a high-
integrity coating that minimizes defects.
CONCLUSIONS
❖ Results demonstrated the utility of EIS as well as
similar electrical equivalent circuit models for
evaluating the corrosion performance of barrier-type
coatings on steel and Mg alloy ZE41A-T5 in NaCl
solutions.
❖ Impedance parameters that were most capable of
forecasting long-term visually based performance of
coatings included LF impedance (≤ 10 mHz, 10 cm2
area), Rd, fl, fh, and fmin. Electrical equivalent circuit
analysis was required to extract some of these
parameters from the raw EIS spectra. However,
simplistic analysis of EIS data also was useful. For
instance, the easily determined LF impedance was a
measure of the combined sum of Rd, Rt, and Rs. This
parameter was a simple and effective measure of
multiple aspects related to the corrosion performance
of the coated metal system.
❖ Comparison of coated metal OCP values to those of
bare metals also provided a qualitative indication of
corrosion that complemented EIS-derived parameters.
❖ A threshold LF resistance value of 108 Ω-cm2 to
109 Ω-cm2 at 65 days forecasted failure when defined
by a 3% visually detected defect area after 120 days
for an Araldite-coated Mg alloy ZE41A-T5. For epoxy
polyamide-coated steel, a lower threshold LF
resistance of 107 Ω-cm2 forecasted failure using the
716
failure criterion chosen here. Results indicated a more
conservative impedance-based failure threshold may
be necessary for more electrochemically “active”
materials such as Mg-based alloys compared to those
currently envisioned for steels. However, results
showed excellent corrosion performance is possible for
coated Mg as long as coating defects are minimized
and high impedance values indicative of good barrier
qualities are maintained above such definable failure
thresholds.
ACKNOWLEDGMENTS
The authors acknowledge the assistance of
CDNSWC-Annapolis Division (formerly David Taylor
Research Center), H. Hack, Pratt & Whitney Aircraft
Co. of Canada, S. Yousri, and the Virginia Center for
Electrochemical Sciences and Engineering. J.R. Scully
was supported partially by the National Science
Foundation under contract DMR-9357463.
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CORROSION–SEPTEMBER 1994