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Using electrochemical impedance spectroscopy

to predict the corrosion resistance of
unexposed coated metal panels
ARTICLE in PROGRESS IN ORGANIC COATINGS SEPTEMBER 2009
Impact Factor: 2.36 DOI: 10.1016/j.porgcoat.2009.04.009
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Progress in Organic Coatings 66 (2009) 834
Contents lists available at ScienceDirect
Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat
Using electrochemical impedance spectroscopy to predict the corrosion

resistance of unexposed coated metal panels
F. Louis Floyd a , Sundaresan Avudaiappan b , Jason Gibson b , Bhaumik Mehta b , Pauline Smith c ,
Theodore Provder d, , John Escarsega e
a
PO Box 31208; Independence, OH 44131, United States

Eastern Michigan University; Ypsilanti, MI, United States
U.S. Army Research Lab; Aberdeen Proving Grounds, MD, United States
d
Polymer & Coatings Consultants, LLC, Solon, OH, United States
e
US Army Research Lab; Aberdeen Proving Grounds, MD, United States
b
c
a r t i c l e
i n f o
Article history:
Received 1 April 2008
Received in revised form 19 March 2009
Accepted 23 April 2009
Keywords:
Corrosion
Electrochemical impedance spectroscopy
Salt fog testing
Pretreatment
Primer
Topcoat
a b s t r a c t
The goal of the current work was to determine if electrochemical impedance spectroscopy (EIS) testing
of a series of coated but unexposed metal panels could predict the corrosion results of other sections of
the same coated panels that were subjected to both continuous and cyclic corrosion testing. Variables
included metal, pretreatment, primer, and topcoat. EIS results were shown to be strongly dependent
upon the time-of-residence in the electrochemical cell prior to commencement of testing, and to the
choice of electrolyte used in the cell. Good correlations between EIS and corrosion testing were seen for
topcoat effects, but not for pretreatment effects. EIS results appear to relate mostly to barrier properties
rather than electrochemical properties of coatings. It is suggested that the variation seen in EIS solution
resistance values (Rs ) can be utilized to quantify total system error. Total error was estimated by three
techniques: total Rs variation, panel replicate variation, and EIS reading replication. The three approaches
yielded similar results: total error for equivalent circuit components expressed in log10 form was on the
order of 50%, expressed as percent standard deviation.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Electrochemical impedance spectroscopy (EIS) scans have been
used for over 40 years to measure the properties of coated metal
panels, and to infer relative performance of those coated panels
in corrosive or other environments. There are several hundred references in the literature to EIS scans of coated metals, including
journals, books, and government contract reports. Only a few are
cited here, to provide context for the present report.
Activity in this eld started in the 1940s (see Bacon et al. [1] for
example) and proceeded slowly until 1970s, after which it accelerated sharply with the introduction by Solatron (UK) and Princeton
Applied Research (U.S.) of automated EIS instruments. Todays suppliers include Solatron, Zahner, Eco-Chemie, and Radiometer who
all use frequency response analyzers; AMETEK (formerly PAR) who
use a lock-in amplier, and Gamry who use sub-harmonic sampling
with discrete Fourier Transform. The present study employs Gamry
instrumentation.
Corresponding author. Tel.: + 1 440 914 0611.

E-mail address: tprovder@att.net (T. Provder).
0300-9440/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2009.04.009
EIS scans are accomplished by vertically mounting an open

cylindrical cell containing electrolyte and the various electrodes
onto a horizontal at coated panel, attaching the electrodes, electrically isolating the entire system, pushing the start button.
The instrument applies an AC voltage (typically 10 mV in amplitude), measures the resulting current and calculates the resulting
impedance, all as a function of AC frequency from high (MHz) to low
(mHz). There is a phase lag between applied voltage and measured
current, which produces both a real and imaginary component to
the impedance measured at each frequency.
Results are commonly reported as a plot of imaginary vs. real
components of impedance (Nyquist plots) or impedance vs. frequency and phase angle vs. frequency (Bode plots). One can also
calculate the values of various circuit components from a model
equivalent circuit applied to the results. Later sections consider
these in greater detail.
It is generally agreed among workers in the eld that to be valid,
EIS measurements must adhere to the following four rules [2]:
Causality: the observed response is due only to the applied perturbation (no signicant spurious signals).
Linearity: system obeys Ohms Law, dE/dl = Z. Impedance (Z)
is independent of the magnitude of the applied perturbation.

F.L. Floyd et al. / Progress in Organic Coatings 66 (2009) 834
[Requires small amplitudes, on the order of 10 mV of applied

perturbation.]
Stability: system does not change over time, and returns to its
original state after the perturbation is removed. [E and I after a
run are the same as before the run.]
Continuity: nite values exist for highest and lowest frequencies,
and are continuous in between.
Unfortunately, it is fairly common for publications on EIS measurements of coated panels to overlook one or more of the above
rules.
Fig. 1. Equivalent circuit model with two time constants.
1.1. Tutorials and critical reviews

Taylor [3] provides a good basic introduction on the use of EIS
measurements to observe the changes in lm properties over time
while immersed in an electrolyte solution, such as the decline in
resistance and increase in capacitance caused by the absorption of
water. On the other hand, Al-Janabi, et al., [4] report that in some
circumstances impedance (Z) can actually increase at long exposure
times, which they attribute to the clogging of pores with corrosion
products. There is an example of such behavior in the present work.
Geenen [5] provides an excellent summary of EIS techniques for
studying coatings, covering the behavior of the individual circuit
components with increasing exposure time, and the role of aws in
the lm by measuring the effect of laser-induced model aws. The
present authors found this work to be lucid, comprehensive, and
quite helpful.
Tait [6] has written an excellent text on electrochemical corrosion testing, including EIS measurements, covering not only theory
but also step-by-step practice in the use of the various techniques.
The text also covers experimental error and the need for replication (he asserts a minimum of ve). In this context, Tait cautions
the reader to not discard extreme values (aka yers, outliers) unless
they are the result of known causes.
Amirudin and Thierry [7], of the Swedish Corrosion Institute,
provide an excellent critical review of the use of EIS measurements
to study the degradation of coated metals. They caution that just
because many equivalent circuits of varying complexity can be
employed does not necessarily mean that they are valid, have been
conrmed by other techniques, or represent physical reality. They
also assert that a number of commonly accepted practices are not
yet settled, viz., the signicance of the coating resistance, the utility of the breakpoint frequency, and the alternate use of constant
phase elements and capacitance in equivalent circuits.
Silverman [8] provides a recent tutorial on and critical review
of the use of electrochemical techniques to predict corrosion
behavior. He notes that the demand for quicker assessments of
corrosion behavior prompted the development of electrochemical
techniques, which can produce useful results in 13 days. He also
notes that while the technique is easy to use, the interpretation of
results can be quite difcult. He likens the difculty in trying to
solve for several unknowns using only one equation. As such, he is
one of the few authors to point out that EIS measurements cannot of
themselves provide all the information needed to reliably predict
corrosion results, but must instead be used in combination with
other techniques to provide the desired results. This view is echoed
by Fontana [9], Haynes [10], Baboian [11], and Silverman [12].
1.2. Equivalent circuit models
On occasion, an equivalent circuit model has been employed to
calculate circuit components which are claimed to relate separately
to the coatings and the substrate (or interface). The most common
form of circuit model is a two-time-constant model with resistances
and capacitances related to each of the coating and the substrate
(or interface). All models also contain an uncompensated solution

resistance which is presumed to be invariant.
In 1993 Mansfeld [13] described the use of a simple twotime-constant equivalent circuit for the interpretation of EIS
measurements of coated aluminum panels, and the use of those
circuit components to determine the protective properties of
coatings and their degradation with exposure time in corrosive
environments. Considerable data scatter was shown for the circuit components, and smoothing suggestions were offered. He also
introduced a pitting model for aluminum alloys, that involved a
different model circuit that correlated nicely with the observed
growth rate of the pits.
Kern et al. [14] recently proposed an alternate model to account
for blistering that employs an additional set of capacitances and
resistance in parallel with the elements shown in Fig. 1.
In the present work, we chose to go with the simpler model as
shown in Fig. 1, since it provided an adequate t to our data.
1.3. Rapid electrochemical assessment of paint (REAP; aka
AC/DC/AC tests)
In 1996, Kendig et al., [15] rst proposed that one could combine
EIS measurements with DC-driven delamination experiments to
provide a rapid assessment of paint quality applied to steel (REAP;
aka AC/DC/AC test). Their process involved running an EIS scan initially, and then again after 24 h of immersion in 0.5 M NaCl solution.
A parallel cathodic delamination experiment is run to determine
delamination rate from a scribe. The DC potential of the sample is
held either at OCP or at 0.600 V vs. SCE if no stable OCP could
be obtained. The results are combined via multiple regression into
a model that correlates to continuous salt fog results, although
the data scatter is rather large. One EIS equipment manufacturer
(Gamry) has automated this process for their instruments.
Suay et al. [16] picked up on the concept in 2003 and developed a
different cycle to accomplish the same mission, also on steel. Suays
process involves running an EIS scan (1.5 h), followed by a cathodic
polarization test driven by an applied DC voltage (3 V relative to
OCP; 30 min), followed by a relaxation period of an hour, then followed by another EIS scan (1.5 h). The sequence is repeated 20
times. The results are combined with a parallel measure of cathodic
delamination test that involves exposure to voltage of 0.60 V vs.
Ag/AgCl for 24 h, then taping the scribe to determine the extent of
delamination from the scribe. This is said to provide meaningful
results in as little as a few days.
In 2005, Poelman et al. [17], applied Suays technique to coatings
for aluminum, and reported good results.
1.4. Other uses of EIS
Various authors have used EIS measurements to characterize
the utility of pretreatments [1820],

10
the value of inhibitive pigmentation [21] in coatings,

time-to-failure derived from coating capacitance [22],
the utility of corrosion inhibitors for steel in concentrated NaOH
solution [23] (however, the paper reveals that the DC polarization
technique is far more informative and useful for the evaluation of
inhibitors than is EIS),
adhesion (delamination) of coatings exposed to corrosive environments [24] (the interlayer resistance (R2 ) was shown to
correlate well with separate blister test results),
thresholds for failure during immersion testing [25]: using the
lowest frequency, Z > 109 implies excellent corrosion protection,
109 > Z > 107 implies adequate protection, while Z < 107 implies
poor corrosion protection,
the damage to coatings caused by abrasion [26], and
the quantity of water absorbed in a lm from capacitance values,
via the BrasherKingsbury [27] equation (results comparable to
gravimetric methods):
Vw =
(log Ct /C0 )
log w
(1)
where, Vw = volume fraction of absorbed water at time t,

Ct = coatings capacitance at time t, C0 = coating capacitance at time
zero, and w = dielectric constant of water (80).
ment, such systems can be rapidly re-wet (minutes to hours) after

drying.
Murray [36] also suggested that critical measurement indicators are dependent on the paint system being studied. This reects
the fact that different kinds of coatings exhibit differing modes of
failure.
2. Experimental
2.1. Terminology
Equivalent Circuit Model. Fig. 1 represents a two-time-constant
model that is used in this paper for analyzing EIS measurements,
where
Rs solution resistance (aka uncompensated resistance Ru ),
R1 coating resistance (aka blister resistance Rb , pore resistance
Rp ),
R2 interfacial resistance (aka charge transfer resistance Rct , corrosion resistance Rcor , polarization resistance Rp ),
C1 coating capacitance (aka Cc ), and
C2 double-layer capacitance (aka Cdl ).
In this context:
1.5. Data variability and replication

Variability in data is a common problem with EIS measurements,
although few authors address the issue. Both Tait et al. [28] (perspective of thin lm can liners) and Murray [29] (perspective of
thick lm industrial maintenance and marine coatings) warn of this,
insisting on considerable replication because EIS measurements are
notoriously difcult to reproduce. Mansfeld [13] reported the same
problem for more conventional (few mils) coatings thicknesses.
Martin et al. [30] warns of the general problem of data variability with any work concerning coatings, while Tait [6] suggests that
all measured data for a given sample be considered valid unless
specically proved otherwise.
All insist on a high degree of replication, on the order of 10 or
so replicates. While their arguments are well-founded in the literature (see for example Mann et al. [31], Whittaker and Besuner
[32]), most acknowledge in private discussions that time and cost
considerations usually prevent such niceties in industrial research.
As a (grudging) compromise, they agree that one should employ at
least three replicates in order allow one to identify and reasonably
reject outlying values, which can greatly smooth the data over time
and experimental variables. In the present work, we employ three
replicates.
Shi, et al. [33], employed EIS to detect early degradation of topcoated systems due to articial weathering, with moderate success.
Although not directly related to the corrosion issue, this paper is an
excellent representation of the variability of data that one actually
observes during EIS measurements, showing considerable variation
over time that appears as cyclical wave patterns. Some of the variability may be due to the use of an abnormally high AC amplitude of
100 mV, even though a few others have chosen similar amplitudes
for high performance coatings. [34,35]
1.6. Miscellaneous observations on EIS measurements
Murray [29] showed that once a panel is removed from a corrosive environment and then dried, it can take up to 10 days of soaking
to re-establish the saturated water level and EIS characteristics that
existed before drying. This was a very surprising nding, since most
workers in the eld assume that once electrolyte pathways are
established in a coating lm via exposure to a corrosive environ-
Rs is associated with the electrolyte solution, and is assumed to

be invariant during the AC scan, regardless of sample or residence
time in the cell;
R1 and C1 are associated with the coating lm;
R2 and C2 are associated with the substrate and/or possibly the
interface between substrate and coating.
Initial values for circuit components is the designation for AC
scans that commence as quickly as possible after the electrolyte is
added to the cell. In some sections, this is also referred to as time
zero or t = 0.
Equilibrium values for circuit components is the designation
for the AC scans that occur 48 h after the electrolyte is added to the
cell. In some sections, this is also referred to as equilibrium time
or t = equil. While we experimentally determined that about 4 h of
soak time was sufcient to approximate equilibrium, we chose to
go with the 48 h time interval to be on the safe side, and because
we had complete data sets for this soak time.
2.2. Corrosion testing
All panels were coated and tested in B 117 and GM 9540 corrosion tests by Pauline Smith of ARL. Appendix B contains a detailed
description of the various coatings and treatments used in this
study.
Coated panels were cut into sections, and one set subjected to each of continuous salt fog testing (ASTM B 117;
5% NaCl electrolyte) and cyclic corrosion (GM 9540; 0.5%
NaCl, 0.1% CaCl2 , 0.075% NaHCO3 electrolyte) testing. Observations were recorded every 200 h in continuous and every 10
cycles in cyclic testing up to 1000 h and 50 cycles, respectively.
Each panel was evaluated for scribe creep by ASTM method
D-1654-92. Ratings for each time interval or cycle interval were
made on separate panels. The scribe creep ratings are then summed
over all interval hours of exposure for continuous salt fog testing or summed over all intervals of cycle times of exposure to
give the values indicated in the sum column. See Appendix B,
Table 5. By preserving the individual totals, one can calculate the
panel to panel variation for the entire data set and use the infor-

mation to lter the rest of the data for actual paint variations
vs. panel variations. Averages would simply compress the differences and make the differences less credible or harder to believe.
It was found that technique best represented what one saw visually if one laid out the panels and compared them one paint to
another. This also had the advantage of removing judgment from
picking any particular point in the continuum. The authors found
this summation technique superior to alternatives for clearly seeing
noise vs. coatings differences. This summation approach previously has been successfully used by the authors in this manner
[37].
The GM 9540 test involves the following sequence in a 24 h cycle:
6 h at 50 C and 100% RH;
15 min in contact with an electrolyte solution (0.5% NaCl, 0.1%
CaCl2 , 0.075% NaHCO3 );
17 h, 45 min drying at 60 C and 50% RH.
Note: operators report that it is common to encounter a precipitate with the GM 9540 electrolyte, and therefore perform
continuous mixing of that electrolyte. The precipitate was found
to be CaCO3 . However, with electrochemical testing this was unacceptable due to fouling of the EIS cell, so we resorted to a nal
ltration step to remove the precipitate before commencing EIS
testing with the GM 9540 electrolyte.
2.3. EIS testing (Unexposed coated panels provided by Pauline
Smith of ARL)
Following is a brief summary of the essential elements in the
testing protocols, as provided by Gamry:
Measure Eoc and allow it to stabilize.
Apply a DC voltage equal to the measured value of Eoc .
In addition to the DC voltage, apply a small sinusoidal voltage
(10 mV) perturbation of xed frequency and measure the current
response.
Calculate the impedance and the phase shift.
Repeat the measurement at a wide range of frequencies (1 mHz
to 100 kHz).
Model the electrochemical process with a two-time-constant
model using resistors capacitors. Adjust the value of the circuit
elements to t the model to the EIS data.
Record the data in a spreadsheet, and convert to log10 transform
for subsequent analysis.
The EIS instrumentation used in our studies is a Gamry (Warminster, PA) MultEchem 4 Electrochemistry System consisting of 4 FAS2
Femtostats for EIS measurements in a parallel multiplexing mode
with EIS300 Electrochemical Impedance Spectroscopy Software.
ZView Electrochemical Analysis software (Scribner Associates, Inc.,
Southern Pines, NC) was used to interpret and illustrate the AC data.
2.4. Assumptions
Every investigation carries with it a series of assumptions, which
may derive from hard science, convention, and biases and opinions of the experimenters. It is important to make assumptions as
explicit as possible to avoid (or clarify) problems later on with the
results and interpretations. Here are ours:
AC impedance results can be modeled adequately with a twotime-constant model, from which the various valid circuit
elements can be extracted.
11
Higher resistance values are better. This view derives from a barrier model of lm protection: better lms will resist passage of
both water and ions more than poorer lms.
Lower capacitance values are better. This is because water absorption increases coating capacitance. This view also derives from a
barrier model of lm protection.
Higher corrosion testing values are better. This is a simple consequence of using an ASTM scale where higher numbers represent
better performance.
Corrosion test results for a series of coatings (including replicates)
are best reported as the sum of all replicate panels at all time intervals for which corrosion results are recorded. Such totals were
found to be the most robust way of expressing system results, and
tend to reduce the errors involved in any single interval rating.
Correlation coefcients (r2 ) are considered compelling only if
they exceed 0.70 (+ or ), and are usually indicated in spreadsheets by bold numbers and a colored background (blue or green).
Sometimes we had to reject extreme value data. Standard techniques were used to accomplish this in the few cases where it was
required.
2.5. Abbreviations and terms used in this report
Avg: mean calculated for given group of panels.
TC, tc, Tpct: Topcoat utilized. Average of topcoated panels compared to average of untopcoated panels.
Tpct DTL-C: Comparison of panels topcoated with DTL vs. those
topcoated with C. In Table 6 and later, the designation is for the
difference between the two topcoated alternatives.
no TC, no tc, no Tpct: no topcoat utilized only primer and
pretreatment. Average of untopcoated panels calculated for comparisons to average of topcoated panels.
Primer only: alternative label for untopcoated. Includes primer
and pretreatment.
Pretreatment only: no primer and no topcoat.
no ctg: no coating; alternate reference to pretreatment only.
Pretreatments, primer, and topcoats are all described in detail
in Appendix III. Abbreviations of the long ofcial names are used in
the report to facilitate reading.
BC: basecoat (aka pretreatment in other sections of this
report).
BC + Pr: pretreatment plus primer (aka no topcoat).
BC + Pr + TC: fully coated panels (aka topcoated).
TC1 : topcoat 1 (aka topcoat DTL).
TC2 : topcoat 2 (aka topcoat C).
3. Results and discussion
3.1. Corrosion test results
3.1.1. Pretreatment effects (cf. Tables 1, 4, 5, 9)
The reader should note that the present section deals with rank
orders only. Subsequent sections deal with various quantitative
correlations. The reader should see Appendix A. for descriptions
of pretreatments and coatings studied. See Appendix B for Tables
416. Note that the numbers in parentheses in the tables indicate
negative numbers.
3.1.2. Steel vs. aluminum
Pretreatment corrosion rankings for various coating conditions on aluminum and steel are summarized in Table 1.
There were insufcient panel comparisons for the steel substrate to draw any broad conclusions other than pretreatment
P60 is superior to alternatives. As a result, the balance of

12
this discussion is focused exclusively on the aluminum panels.
4. EIS testing of coated panels: equivalent circuit element

analysis results
3.1.3. B 117
In continuous testing, there was agreement in rank order among
fully coated, primer only, and pretreatment only conditions for all
of the pretreatments. The effect of adding coatings to the pretreatments was to reduce their differences and increase their longevity,
but did not alter their rank orders.
We utilized the Z-view software to calculate the equivalent

circuit elements for each experiment, based on the measured
impedance vs. frequency results, and based on a two-time-constant
model.
The equivalent circuit elements for the two-time-constant
model consist of Rs (solution resistance), R1 (coating resistance),
C1 (coating capacitance), R2 (substrate or interface resistance), and
C2 (substrate or interface capacitance).
We chose to transform all the circuit element data to log10 values, because of the variable magnitudes involved, and because of
the magnitude of total error involved in the various measurements.
Once we made this transformation of the data, meaningful results
became much more visually obvious.
3.1.4. GM 9540
In cyclic testing, three of the pretreatments showed agreement
in rank order among the coatings situations, while the DOD treatment was higher in rank order uncoated than it was coated. The
single deviation for DOD was its inferior performance once coated.
3.1.5. Cyclic vs. continuous
The only deviation in agreement between the corrosion tests
was the same inferior performance of fully coated DOD in cyclic
testing. Otherwise, the agreement between cycles was nearly perfect. This was surprising, considering all the work published on the
deciencies of continuous vs. cyclic testing.
Interestingly, the Alodine 5700 showed essentially zero protection by itself in both continuous and cyclic testing. However, once
coated, its performance rose to the bottom end of the performance
of the other coated systems in B 117 testing, but closed only about
half the gap in cyclic testing.
3.2. Correlations
Table 4 shows the regression coefcients for B 117continuous vs.
GM 9540 cyclic testing for various subsets of data: all panels, full
coatings systems, primer plus pretreatment only, and pretreatment
only (i.e., uncoated). The overall correlation for all panels between
the two tests is r = .727 (see Table 4), which is common for such
a correlation between cyclic and continuous testing (informal poll
among colleagues in the industry).
For aluminum panels, it is interesting that the correlation starts
high for the pretreatment only set (r = .922), improves slightly
as one adds primer (r = .983), then declines sharply as one adds
topcoat (r = .601). This means that the difference between cyclic
and continuous exposure is minimal for pretreatment only and
pretreatment + primer, and increases as one adds topcoats to the
pretreated metal. A similar result is seen for steel panels.
The aluminum panels in B 117 continuous testing show an
excellent correlation (r > .9) between pretreatment only, pretreatment + primer, and the fully coated system. This strongly suggests
that the pretreatment is the controlling layer in subsequent continuous corrosion testing of coated panels.
However, the aluminum panels in GM 9540 cyclic testing show
an excellent correlation between pretreatment only and pretreatment + primer (r = 1), but a poor correlation for the fully coated
system (r .5). This suggests that there are factors contributed by
the topcoat that are modifying the relative performance of the pretreatments in subsequent cyclic corrosion testing.
Table 5 shows the corrosion results for all aluminum panels for
all time intervals of observation. To summarize the data, we chose
to sum all observations for a given system for all time intervals
to represent the nal corrosion rating for that system. We then
averaged the results for each subset of pretreatments to arrive at
the rating for that variable. Next, there were three samples with
pretreatment + primer (no topcoat), and four samples with pretreatment only. These data were then utilized for comparison to
electrochemical results later in this report.
The data set for steel was much smaller, and will not be extensively discussed in this report.
4.1. Plots of circuit elements vs. soak time

Supplementary material contains plots of the various circuit elements as a function of soak time in the electrochemical cell.
4.1.1. B 117 electrolyte
As will be discussed later in Section 7, the solution resistance values calculated from EIS measurements do not likely represent any
physical signicance, but instead probably represent total system
error. Therefore Rs values will not be discussed further here.
Most systems showed an increase in coatings resistance (R1 )
as soak time increased, although a few showed a slight decrease.
Likewise, interfacial resistance (R2 ) showed a general increase in
resistance vs. soak time.
Coating capacitance (C1 ) was either at, or jumped to a higher
value during early soak times, then remained constant thereafter. It
should be noted that none of the capacitance measurements in this
study showed evidence of water clustering as asserted by Geneen
[5], among others, even though our soak times were similar to others reported in the literature.
Topcoat DTL showed a denite tendency to absorb more water
than the topcoat C, as evidenced by the higher coating capacitance
for topcoat DTL. Double layer capacitance (C2 ) also showed either
at or early jumps in capacitance as a function of soak time. Topcoat
DTL again showed a much higher C2 than topcoat C, suggesting more
water absorption.
GM 9540 Electrolyte. With GM 9540 electrolyte, coating resistance values were largely at vs. soak time in the cell, in contrast to
the B 117 electrolyte. Surprisingly, topcoat DTL showed higher coating resistance values than topcoat C. The pretreatment only panels
showed the lowest R1 values, as expected.
Interfacial resistance (R2 ) values were largely at during soak
time, except for topcoat DTL, which started high, then dropped
about two orders of magnitude within the rst few hours of soaking.
Coating capacitance (C1 ) was essentially at for all systems as
a function of soak time. The pretreatment only samples were consistently four orders of magnitude higher in capacitance than the
various coated samples, suggesting that they were more water sensitive than the coatings in this electrolyte.
Double layer capacitance (C2 ) showed the same behavior as coating capacitance (C1 ).
4.2. Circuit element data analysis (see Appendix B)
4.2.1. Time-of-soak
The rst issue is to determine how long it takes to achieve equilibrium in the EIS cell (aka t = equil), once electrolyte has been
added, and then to compare those equilibrium results with ones

13
Table 1
Pretreatment corrosion rankings for various coating conditions (summarized from Table 15).
Situation
B 117 ranking
GM 9540 ranking
Aluminum
Fully coated
No topcoat
Pretreatment only
DOD > A1200 > NAVAIR > A5700 > none

A1200 > NAVAIR > A5700
DOD A1200 > NAVAIR A5700
A1200 > NAVAIR > DOD A5700 none

A1200 = NAVAIR A5700
DOD > A1200 NAVAIR A5700
Steel
fully coated
No topcoat
P60 > none

P60 > DOD
P60 > none

P60 > DOD
Note: DOD in bold face under GM 9540 ranking is sole deviation from otherwise excellent rank order agreement between tests, and among coatings
situations.
Table 2
Solution resistance measured by DC multi-meter using B 117 electrolyte.
Paint ID
Cell residence time (h)
Multi-meter DC measurements
Conductance (mS)
Solution resistance (m)
Solution resistance Rs 100
RM-7-3
RM-7-3
RM-7-3
RM-7-3
RM-7-3
0
4
8
48
72
76.4
72.9
75.3
75.8
76.3
0.0131
0.0173
0.0132
0.0132
0.0132
1.31
1.73
1.32
1.32
1.32
17.4
275
252.7
117.8
10
RM-8-1
RM-8-1
RM-8-1
RM-8-1
RM-8-1
0
4
8
48
72
76.2
76.3
76
76.1
77.1
0.0131
0.0131
0.0132
0.0132
0.0131
1.31
1.31
1.32
1.32
1.31
5.16
194.2
165.2
7.26
14.87
RM-8-2
RM-8-2
RM-8-2
RM-8-2
RM-8-2
0
4
8
48
72
75.4
76.4
76.2
76.6
77
0.0133
0.0131
0.0131
0.0131
0.0131
1.33
1.31
1.31
1.31
1.31
11.42
11.08
247.8
13.26
15.02
RM-8-3
RM-8-3
RM-8-3
RM-8-3
RM-8-3
0
4
8
48
72
71.2
76.4
76
67.9
79.4
0.014
0.0131
0.0132
0.0147
0.0126
1.4
1.31
1.32
1.47
1.26
8.16
315.4
273
1.57
16.21
measured as soon as the electrolyte is added to the cell (aka t = 0 or

initial time).
We found that equilibrium is achieved in less than 4 h of immersion in the cell, after which responses vs. soak time are at (see
supplementary material for illustrations). Thus, our choice of the
long soak times (24 or 48 h) for equilibrium values is justied.
4.2.2. Solution resistance
The solution resistance values (Rs ) are not invariant or independent on experimental details as theory requires. Rs decline about
an order of magnitude between t = 0 and t = equilibrium for B 117
electrolyte, and about half an order of magnitude for GM 9540
electrolyte.
Table 3
Topcoat effects with indicated electrolytes.
B 117 electrolyte
t=0
GM 9540 electrolyte
t = equil
Corrosion testing
None > tp
EIS testing
Rs
R1
R2
C1
C2
tp > none
tp > none
tp > none
None > tp
None > tp
t=0
tp > none
tp > none
tp > none
tp > none
Similar
Rs values from impedance measurements bear little resemblance to those measured with a DC multi-meter, either in
magnitude or consistency over time. Separate multi-meter readings
of Rs are essentially constant over time (see Table 2).
Although not specically listed here, results with GM 9540 electrolyte showed a similar story to that seen with the B 117 electrolyte
(Table 3).
It is our view that the variations seen with Rs values in EIS measurements do not represent any physical signicance, but rather
represent the total system error for AC measurements. As a result,
we have not attempted to draw any other conclusions relating to
Rs .
Capacitance shows the greatest differentiation with B 117 electrolyte, while resistance shows the greatest differentiation with GM
9540 electrolyte.
For aluminum panels, none of the circuit components correlate
well with corresponding corrosion test results. Steel panels are an
exception, but with very small data sets.
t = equil
4.3. Topcoat effects
tp > none
Similar
tp > none
None > > tp
None > > > tp
None > tp
AC equiv circ solution resistance ()
tp > none
Similar
tp > none
Similar
Similar
tp: average of two topcoats; none: no topcoat was used (i.e., primer plus pretreatment).
In corrosion testing (both continuous and cyclic), topcoat C was

clearly superior to topcoat DTL. In EIS testing, C was also superior to
DTL for all circuit elements, for both initial and equilibrium times,
and for both electrolytes. This was the single most consistent result
in this study. (Tables 7, 8, 11, 12)
In B 117 testing, there was a slight advantage for leaving the
topcoat off, while in GM 9540 testing, there was a slight advantage

14
for using a topcoat. However, in EIS testing, the story was mixed for
using a topcoat vs. none.
With B 117 electrolyte, resistance values supported using a topcoat, while capacitance values argued for leaving it off. This might
suggest that the topcoats were relatively water sensitive in this
electrolyte.
With GM 9540 electrolyte, such differences as existed were all
in favor of using a topcoat, which was consistent with corrosion
test results. The differences were most pronounced with resistance
readings. This suggests that there was no difference in water sensitivity with or without topcoat with the GM 9540 electrolyte.
4.4. Pretreatment effects (see Tables 5, 7, 8, 9, 11, 12)
4.4.1. B 117 electrolyte
At t = 0, fully coated systems showed no signicant differences
for the various pretreatments for any of the circuit elements.
Removing the topcoat resulted in resistance values showing the
order
At t = equil, no useful differentiation was seen for the fully coated

and primer only panels. For pretreatment only, resistance values
cleanly differentiated DOD as being better than the rest, but could
not differentiate the rest. None of these results agreed well with
corrosion test results.
In some cases, the no pretreatment samples appear to compete
successfully with the various pretreatments. We speculate that the
reason may lie in the nature of the AC test itself. Our results suggest
that AC impedance testing primarily measures lm properties of
the coatings systems, rather than the electrochemical state of the
metallic substrate. This suggests that one needs some kind of DC
measurement of the electrochemical component in order to complete the picture, and adequately predict the corrosion resistance
of a wide variety of systems. This is in agreement with the views
of several previous workers: Silverman [8,12], Fontana [9], Haynes
and Baboian [10] and Baboian [11].
5. Electrolyte effects
A1200A5700 NAVAIR
5.1. The choice of electrolyte plays a denite role in the AC results
while capacitance values showed the order
When one considers the composition of the two electrolytes, this

is not all that surprising. The B 117 electrolyte is strongly corrosive
(5% NaCl), while the GM 9540 electrolyte is strongly passivating [37]
(0.5% NaCl + 0.1% CaCl2 + 0.075% NaHCO3 ). In fact, bicarbonate has
been shown to be one of the stronger inorganic passivating agents
presently known.
Separate from the passivation issue, bicarbonate can form precipitates with both iron and aluminum, providing a pore-plugging
mechanism even during immersion. In addition, the GM 9540 electrolyte forms precipitates on its own (CaCO3 ), and must be ltered
prior to use. This is in agreement with previous work by Al-Janabi
et al. [4].
One might therefore reasonably speculate that the choice of
electrolyte plays at least some role in the differing results that one
observes for cyclic vs. continuous corrosion testing. It would be
interesting to conduct corrosion tests using the reverse electrolytes,
to determine the relative role that the electrolyte plays vs. the cycle.
NAVAIRA1200 > A5700.

The pretreatment only samples showed the following order for
all circuit elements:
DOD A1200NAVAIR.
As a reminder, corrosion testing ranked the pretreatments for
all coatings systems:
DOD > A1200 > NAVAIR > A5700 > none.
Thus the corrosion results do not agree well with these t = 0, B
117 electrolyte, EIS results, except possibly for the uncoated (pretreatment only) panels.
At t = equil, the fully coated systems showed a weak differentiation with resistance
R1 : A1200ODNAVAIRnone > A5700
R2 : A1200DODnone > NAVAIRA5700
but a consistently strong differentiation with capacitance
readings:DOD >>> A1200NAVAIRnone >>> A5700.
Removing the topcoat resulted in variable rankings, while the
pretreatment only samples showed a very consistent result for all
circuit elements:NAVAIRA1200 DOD.
Only the capacitance results with fully coated systems seemed
to agree well with the corrosion results.
4.4.2. GM 9540 Electrolyte
At t = 0, fully coated systems showed no differences in capacitance values, and variable rankings in resistance values
R1 : NAVAIR > DOD A5700 A1200 > none
R2 : A5700 > DOD > A1200 > none NAVAIR
When one removes the topcoat, only R2 shows any differentiation
A1200 > NAVAIR A5700.
For the pretreatment only samples, capacitance values showed
no differentiation while resistances values provided consistent
rankings:
DOD > A5700 > NAVAIR > A1200.
None of the EIS testing with GM 9540 electrolyte at t = 0 agreed
well with cyclic corrosion rankings.
5.2. B 117 electrolyte

R1 and R2 actually increase with soak time with B 117 electrolyte.
This was true for topcoated, primer only and pretreatment only conditions. There was also a tendency for topcoat C to show this trend
more than topcoat DTL. We did of course re-check our data to make
sure that we had not inadvertently inverted the two-time intervals.
This is in agreement with the hole-plugging theory advanced by
Al-Janabi mentioned above.
C1 and C2 tended to increase with soak time as expected. Unexpected was that this trend was strongly present for topcoat DTL and
only to a minor extent for topcoat C. This suggests that topcoat DTL
is far more water sensitive than topcoat C.
In the absence of topcoat, and in the absence of primer (pretreatment only), capacitance showed only a minor increase with
soak time. This suggests that the topcoat is the only element in the
system that shows signicant water sensitivity.
5.3. GM 9540 electrolyte
R2 showed the strongest differentiation principally between
topcoats at t = 0; however at t = equilibrium, the differences were
small. Capacitance showed relatively little differentiation at either
time interval, and little change as a function of soak time. This
might be viewed as support for the pore-plugging theory for this
electrolyte.

6. Correlations
6.1. Corrosion vs. electrochemical testing
For aluminum panels in B 117 electrolyte vs. continuous salt
fog testing, none of the electrochemical parameters correlated with
corrosion testing for either soak time. However, steel panels showed
good correlations for R2 (both soak times), R1 (t = 0 only), and C2
(t = equil only).
For aluminum panels in GM 9540 electrolyte vs. cyclic testing,
none of the electrochemical parameters correlated with corrosion
testing for either soak time. However, steel panels showed good
correlations for R2 (t = 0 only) and Rs (t = equil only). Unfortunately,
the fortuitous correlations with salt spray for steel panels in GM
9540 electrolyte casts suspicion on the correlations with R2 and Rs .
6.2. Continuous vs. cyclic corrosion tests
A signicant, but imperfect, correlation exists between continuous (B 117) and cyclic (GM 9540) tests for both steel and aluminum
panels. The overall correlation is about r = 0.72.
6.3. Pretreatment vs. coating
There appears to be a strong correlation between pretreatment
only and fully coated systems, suggesting that quick-screening
might be accomplished with pretreatment only panels. For B 117
testing, the correlation is excellent, while for cyclic testing, there
is one strong exception: DOD performs far worse (relatively) when
coated than uncoated.
6.4. Topcoating
For aluminum, the presence of a topcoat detracts from the correlation between continuous and cyclic test results. In the absence
of topcoat (primer only), the correlation increases to greater than
0.9.
For steel, there is no topcoat effect. However, the sample size is
quite small.
7. Assessment of system error
The solution resistance (Rs ) is assumed in all models to be invariant, and independent of all experimental variables. If true, then
any observed variation in Rs can be considered to be solely due
to total experimental error, including sample preparation and
electrochemical testing. Our AC measurements show that log10 Rs
varies on the order of 50%, expressed as percent standard deviation of all log Rs values for all panels, substrates, and electrolytes.
Meanwhile, solution resistance as measured by DC was essentially constant.
A separate calculation, based only on replicate AC readings on
duplicate panels, produces the following estimates of error (as
%S.D.):
log10 Rs 20%
log10 R1 50%
log10 R2 41%
log10 C1 31%
log10 C2 27%
The reader should note that these values represent only the
error associated with electrochemical measurements, and do not
include all the other experimental steps. However, they are all
within the same order of magnitude as the total log10 Rs speculation above.
The reader is cautioned to take this error issue seriously when
attempting to develop any correlations between electrochemical
15
measurements and actual corrosion test results. While error is

only infrequently discussed in the open literature on EIS measurements, that minority view is very likely representative of EIS
data in general.
8. Summary and conclusions
The goal of this work was to determine if EIS testing of unexposed
coated metal panels could predict the corrosion results of other
sections of the same coated panels that were separately subjected
to continuous (B 117) and cyclic (GM 9540) corrosion testing.
The panels of interest were prepared at the US Army Research
Laboratory, and represent a combination of two metals (aluminum and steel), ve pretreatments, one primer (solventborne
epoxy) and two topcoats (solventborne urethanes). Details of the
panels and their coatings and pretreatments can be found in
Appendix A. EIS testing was conducted with both the B 117 electrolyte and the GM 9540 electrolyte at both initial (t = 0) and
equilibrium (t = equil) times after adding the electrolyte to the
cell. Comparisons were then made between each corrosion test
and its corresponding EIS test conducted with the same electrolyte.
Equivalent circuit components were calculated from a twotime-constant model, and were expressed as the log10 transform
due to their large magnitudes. This transformation simplied the
data so that one could readily see component effects on the circuit
elements. The elements calculated were solution resistance (Rs ),
coating resistance (R1 ), interface resistance (R2 ), coating capacitance (C1 ) and interface capacitance (C2 ).
Within the context of the panels tested, following is a summary
of our ndings and interpretations:
The EIS results depended strongly on the time-of-residence in the
electrochemical cell prior to commencement of AC scans (soak
time), requiring at least 4 h to achieve equilibrium, after which
results remained essentially constant up to the maximum of 48 h
tested.
The EIS results also depended strongly on the choice of electrolyte
used in the AC cell, suggesting that corrosion differences seen
between continuous and cyclic corrosion testing may be due in
part to the electrolyte used separate from the cycle employed.
Corrosion test results were therefore compared to the EIS results
obtained with the corresponding electrolyte.
EIS testing clearly demonstrated the same superiority of topcoat C
over topcoat DTL seen in corrosion testing. This was the strongest
effect seen in this study. Descriptions of the two topcoats can be
found in Appendix A topcoat C is MIL-C-53039; topcoat DTL is
MIL-DTL-64159.
EIS testing showed good correlation with corrosion testing for the
topcoat vs. no topcoat series. In corrosion testing, B 117 showed
a slight preference for leaving the topcoat off, while GM 9540
showed a slight advantage for using a topcoat. In EIS testing with
B 117 electrolyte, the capacitance values agreed while the resistance values disagreed with the corrosion results. EIS testing with
GM 9540 electrolyte showed broad agreement with the corresponding corrosion results.
EIS testing could not accurately predict the relative performance
of the various pretreatments seen in corrosion testing. There was
one exception where capacitance readings with B 117 electrolyte
at t = equil did provide good correlation to B 117 corrosion testing.
The results broke down as follows:
B 117 electrolyte, t = 0 poor correlation to B 117 testing
B 117 electrolyte, t = equil capacitance had good correlation to
B 117
GM 9540 electrolyte, t = 0 poor correlation to GM 9540 testing

16
GM 9540 electrolyte, t = equil poor correlation to GM 9540

testing.
The corrosion of coated metal panels seems to be largely controlled by the pretreatment used. The addition of coatings serves
to reduce the differences between pretreatments, but does not
alter their rank order. Unfortunately, the equivalent circuit elements measured by EIS do not provide a similar clear-cut result,
and do not generally correlate with the corrosion results.
Pair-wise analysis provides better insight than overall regression
or rank order correlations, due to the relatively high systematic
error involved in EIS testing.
The solution resistance (Rs ) measured by EIS was highly variable and bore no resemblance to that measured by conventional
DC techniques, which was essentially constant as theory suggests. We therefore speculate that Rs as measured by EIS may be
employed as a measure of total experimental error (metal consistency, pretreatment, coatings preparation and application, and
EIS measurements).
EIS testing is probably providing information largely on the barrier component of corrosion, and little on the electrochemical
(inhibiting) component. In contrast, an earlier report demonstrated that DC measurements can be employed to quantify the
electrochemical component separately from the barrier component [812].
8.1. Recommendations
It is presently unclear how much of the difference seen between
continuous and cyclic corrosion testing is due to the cycle, and how
much is due to the choice of electrolyte. Given the differences seen
in EIS testing with the two different electrolytes, it would be useful
to conduct corrosion testing of well-characterized coating systems
on both steel and aluminum using opposite electrolytes: GM 9540
electrolyte in continuous testing and B 117 electrolyte in the cyclic
test. This would help to separate the electrolyte effects from the
cycle effects in corrosion testing results.
Acknowledgments
This work was supported by the U.S. Department of the Army,
Tank-Automotive and Armaments Command (TACOM), contract no.
DDAE07-03-C-L127 and the Army Research Laboratory (ARL) contract no. DAAD19-03-2-0013.
The authors would like to acknowledge the contributions of the
following people in completing this study:
I. Carl Handsy of the U.S. Department of the Army, TankAutomotive and Armaments Command, Warren, MI for very useful
technical discussions during our testing.
Martin Donbrosky, Jr., Chemir Analytical Services, Ypsilanti, MI.,
for technical discussions and support of some of the laboratory
work.
Appendix A.
A.1. Pretreatments and coatings studied (descriptions provided by
Pauline Smith of ARL)
A.1.1. Metal pretreatment
Conversion coatings: Typically, conversion coatings are thin and
are below a half-micron () in thickness. Coating weights are
inversely dependent on the inherent corrosion resistance of the aluminum alloy. The following conversion coatings were employed in
the present study:
Alodine 1200S is a chromate control, and based on chromic
acid, uorides, and ferricyanide. The lm is mostly chromium
oxide/aluminum oxide. The chromium oxide in the lm consists

of about half trivalent and half hexavalent chromium. It is one of
the best treatments from an historically performance stand point.
Treatment weight is 40 70 mg/sq. ft. on AA-2024-T3.
Navair TCP is based on zirconium uoride and trivalent
chromium sulfate; it is one of the best all-around chromate alternatives. The lm is mostly zirconium oxide/aluminum oxide with
approximately 35% by weight trivalent chromium and complexes
with the zirconium compound. Treatment weight is 3050 mg/sq.
ft. on AA-2024-T3.
Alodine 5700 is based on zirconium oxide and titanium uoride;
it is one of the best non-chrome conversion coatings. It functions as
an adhesion promoter and must be coated to offer corrosion protection. The lm is mostly zirconium oxide/titanium oxide/aluminum
oxide. Treatment weight is usually below 15 mg/sq. ft.
All three pretreatments were deposited by the same traditional
process used for the chromate control, Alodine 1200S. The only
stipulation is that TCP and Alodine 5700 are not used with silicate cleaners in the process. They were deposited by immersion,
spray or wipe-on, at ambient (7580 F) temperatures. Depending
on the condition of the metals, (mill marks, ink, oil), the usual procedure is to solvent wipe or vapor degrease with acetone or methyl
ethyl ketone, followed with a hot, mildly alkaline, non-silicate, nonetching aluminum cleaner. Then, an acid etch and desmit, and then
into the conversion coating solution. Better results are obtained
when there is 1.510 min of contact time with the conversion coating solution.
Alodine 1200S has the lowest pH and is the most active solution;
therefore, it generally has the shortest reaction time of 1.53.0 min.
Next is Alodine 5700, with a 3.05.0 min contact and the TCP is
usually within 5.0 min. The contact times are longer for spray processing than for immersion processing.
Wash primer. DoD-P-15328 is formulated as a low-solid,
solvent-base that contains polyvinyl butyral, phosphoric acid and
zinc chromate. It serves to promote adhesion and minimize corrosion.
Wash primers are characteristically thin 0.50.7 mil (1
mil = 0.001 in.), cross-linked coatings applied by HVLP spraying directly to the bare metal substrate to provide protection from
corrosion and promote adhesion.
The CARC system application specication, MIL-C-53072C
requires that metal surfaces on tactical vehicles be treated to
improve adhesion and corrosion resistance prior to coating with
an epoxy primer and a camouage topcoat. In original equipment
manufacturer (OEM) processes, the surface treatment is generally
performed by a ve-stage immersion process, for instance, zinc
phosphate prescribed in TT-C-490.
The purpose of the DoD-P-15328D wash primer is to enhance
corrosion resistance, through the passivation of the metal surface. In the U.S. Armys Chemical Agent Resistant Coating (CARC)
System, the metal surface is coated with a wash primer, overcoated with an epoxy primer and followed by a camouage
urethane topcoat. Several coating procedures specify the use of
the wash primer, DoD-P-15328D, as a surface treatment prior to
the application of an epoxy primer and polyurethane topcoat CARC
system.
The material is furnished in two components. Component A has
polyvinyl butyral, zinc chromate, magnesium silicate and phosphoric acid in Component B.
A.2. Primer
MIL-P-53022 is the current solvent-based, epoxy primer, formulated with corrosion inhibiting pigments. This specication
covers a ash drying, corrosion inhibiting epoxy primer for
ferrous and nonferrous metals. The primer is lead and chro-

mate free and meets the air pollution requirements for solvent
emissions.
The material is furnished in two components. Component A
is a pigmented bisphenol type epoxy resin. Component B is an
aliphatic polyamide epoxy resin adduct. Applied by HVLP spraying, DFT of 0.00120.0015 in. Pigments are Titanium dioxide, Zinc
phosphate, corrosion inhibiting pigments (zinc complex Sicorin
RZ) and magnesium silicates. Pigments = 54%, vehicle solids = 23%,
volatiles = 22%, density = 13.0.
A.3. Topcoats
MIL-DTL-64159, type II, is formulated with a novel pigment
package and uses polymeric beads for attening agents. It is the
water-dispersible, aliphatic polyurethane coatings. It is the nish
coat on all military tactical equipment, which includes ground, aviation and related support assets. The materials are free of hazardous
air pollutants (HAP-free), lead, chromate (hexavalent chromium),
and have a maximum volatile organic compound (VOC) content of
220 g/L (1.8 lb/gal) as packaged.
The material is furnished in two components: Component A consists of a hydroxyl functional polyurethane dispersion, prime and
extender pigments, additives and solvents. Component B consists
of an aliphatic isocyanate prepolymer type that is dispersible in
water that may be combined with volatile solvents. The mixing
ratio shall be two parts of Component A to one part of Component
B. The extender pigments (attening agents) composed of polymer
based of polyurethane or urea formaldehyde condensation type
polymers or other polymeric composition. Applied by HVLP spray,
DFT 0.0020.00025 in.
Pigments = 34%, vehicle solids = 16%, volatiles = 50%, density = 11.0. PVC = 23.3.
MIL-C-53039 is the single component, solvent-based CARC, an
aliphatic polyurethane coating. It is used as a nish coat on military
combat equipment. The coating is lead and hexavalent chromium
free and has a maximum of 180 g/L (1.5 pounds/gallon) volatile
organic compounds with zero volatile hazardous air pollutants.
17
The material is a single package and consists of an aliphatic polyisocyanate prepolymer combined with volatile solvents, pigments,
extenders and additives. Iron oxides used as hiding pigments shall
be of synthetic origins and not naturally occurring. The titanium
dioxide is rutile, chalk resistant. No lead or hexavalent chromium
pigments used. The non-volatile vehicle shall be a hydroxyl terminated prepolymer reacted with an aliphatic polyisocyanate.
Applied by HVLP Spray the coating to a dry lm thickness
between 0.002 0.0002 inches (0.0508 0.00508 mm).
Pigments = 39%, vehicle solids = 22%, volatiles = 40%, density = 11.1.
Appendix B. B 117 and GM 9540 corrosion test results and
AC equivalent circuit element data
Table 4
Corrosion testing correlations B 117 continuous vs. GM 9540
cyclic tests.
ARL panel series
Regression correlations
r2 B 117 vs. GM 9540
Sample size
Aluminum
All panels
Full coatings systems
Primer plus pretreatment
Pretreatment only
0.724
0.601
0.983
0.922
18
10
3
4
Steel
All panels
Full coatings systems
Primer only
All panels
0.836
0.992
1.000
0.727
6
4
2
24
B 117
r2
Sample size
Al: pretreat only vs. primer + topcoat

Al: pretreat only vs. primer only
0.958
0.997
4
3
0.494
1.000
4
3
GM9540
Al: pretreat only vs. primer + topcoat
Al: pretreat only vs. primer only
18
Table 5
Corrosion testing results B 117 continuous and GM 9540 cyclic tests.
Panel ID
Substrate
Pretreatment
Primer
Topcoat
B 117 Continuous salt spray

200 h
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Fe 1018
Fe 1018
Fe 1018
Fe 1018
Fe 1018
Fe 1018
Alodine 1200
Alodine 1200
NAVAIR TCP
NAVAIR TCP
Alodine 5700
Alodine 5700
DoD-P-15328
DoD-P-15328
None
None
NAVAIR TCP
Alodine 1200
Alodine 5700
NAVAIR TCP
Alodine 1200
Alodine 5700
DoD-P-15328
None
None
None
Bonderite 952 P60
Bonderite 952 P60
Bonderite 952 P60
DoD-P-15328
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
None
None
None
None
None
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-DTL-64159
MIL-P-53039
MIL-DTL-64159
MIL-P-53039
MIL-DTL-64159
MIL-P-53039
MIL-DTL-64159
MIL-P-53039
MIL-DTL-64159
MIL-P-53039
None
None
None
None
None
None
None
Aircraft green
MIL-DTL-64159
MIL-P-53039
MIL-DTL-64159
MIL-P-53039
None
None
Mean
S.D.
%S.D.
Correlations
Notes: Corrosion
ratings for each
interval are made
on different
panels
ON
ON
00
ON
8
7
10
10
7
7
9
9
5
7
6
0
10
8
7
7
00
00
7
7
ON
ON
8
7
00
00
10
9
00
On
8
9
8
7
6
0
10
9
7
7
00
00
7
7
ON
ON
8
7
8
7
ON
ON
3
6
9
9
6
5
6
0
10
8
7
7
7
8
7
6
GM 9540 cyclic test

600 h
00
ON
ON
00
7
7
ON
ON
5
9
9
9
7
5
7
0
10
9
6
7
8
7
On
On
00
ON
On
00
4
8
ON
ON
Is)
ON
8
9
5
4
5
0
8
9
7
7
6
7
4
5
800 h
7
8
00
On
3
7
00
ON
7
5
8
9
5
4
5
0
8
9
7
5
5
7
7
5
00
00
7
8
4
7
00
ON
5
5
7
9
5
3
4
0
8
0
7
4
7
7
5
4
7
9
7
6
5
5
00
00
7
5
8
8
4
3
4
0
7
0
3
5
7
6
5
3
Sum
10 Cyc
65
70
61
59
47
56
71
72
44
49
66
71
45
38
43
0
71
52
51
49
56
58
48
43
9
10
ON
ON
ON
00
10
8
4
8
9
9
6
8
9
1
10
6
7
6
7
8
7
6
53.5
15.5
29.0%
AlSS
Alcyclic 1
FeSS
Fecyclic
20 Cyc
ON
ON
ON
ON
3
8
5
7
5
4
9
9
7
9
9
1
9
8
7
6
00
00
7
6
ON
ON
00
ON
5
6
5
5
3
4
9
8
5
7
7
0
9
8
5
5
00
00
6
5
30 Cyc
ON
ON
ON
ON
3
9
4
6
4
4
8
9
5
7
7
0
9
8
6
5
7
8
7
6
ON
ON
ON
00
4
5
5
4
3
3
9
9
4
7
7
0
8
4
5
5
7
7
6
4
40 Cyc
ON
ON
7
9
5
6
On
On
3
3
9
9
4
7
7
0
7
7
5
4
7
7
6
5
ON
ON
00
00
1
4
2
3
1
2
8
8
3
6
6
0
7
7
5
3
7
7
5
4
Sum
ON
ON
On
00
3
4
5
4
1
0
8
8
4
6
6
0
6
7
4
4
7
7
6
4
72
73
65
69
33
50
42
43
24
28
69
69
38
57
58
2
65
55
44
38
58
60
50
40
50.1
17.6
35.2%
2
1
3
4
5
6
7
8
14
13
16
17
18
20
19
21
22
28
10
9
11
12
23
15
400 h
Table 6
Analysis of circuit element results using B 117 electrolyte.
Panel ID
Substrate
Pretreatment
Primer
Topcoat
AC Impedance, unexposed, initial

log Rs
log R1
log C2
log Rs
log R1
log R2
log C1
log C2
(8.64)
(8.76)
(8.77)
(8.97)
(8.34)
(8.87)
(8.87)
(9.27)
(9.06)
(8.99)
(8.42)
(8.38)
(6.78)
(4.75)
(4.57)
1.37
3.03
2.49
2.78
1.59
2.86
1.66
2.74
1.13
2.90
2.49
2.52
2.49
0.68
0.69
7.72
7.72
0.21
8.02
0.22
7.71
7.47
7.21
6.50
7.94
(7.83)
7.61
7.03
4.49
4.26
(0.34)
(8.21)
(0.41)
(7.93)
0.24
(0.64)
(7.98)
(8.24)
0.05
(8.17)
(7.83)
(7.99)
(8.14)
(4.54)
(4.37)
0.11
(7.98)
(0.41)
(7.76)
0.26
(0.73)
(7.69)
(7.25)
0.05
(8.00)
(7.64)
(7.78)
5.27
(3.77)
(3.19)
Al 2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al 2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al 2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al 2024 T3
Al2024 T3
Alodine 1200
Alodine 1200
NAVAIR TCP
NAVAIR TCP
Alodine 5700
Alodine 5700
DoD-P-15328
DoD-P-15328
None
None
NAVAIR TCP
Alodine 1200
Alodine 5700
NAVAIR TCP
Alodine 1200
Alodine 5700
DoD-P-15328
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
None
None
None
None
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
None
None
None
None
None
None
None
3.23
3.22
3.01
3.13
2.71
3.41
3.13
3.43
3.21
3.42
0.80
2.40
2.72
0.67
0.74
2.01
2.01
3.07
3.22
3.01
3.13
2.71
3.41
3.13
4.60
3.04
3.25
0.80
2.25
2.25
0.67
0.74
panels
2.01
(7.01)
(8.64)
(8.94)
(8.59)
(8.97)
(8.34)
(8.87)
(8.87)
(9.09)
(9.06)
(8.99)
(8.42)
(8.38)
(6.78)
(4.75)
(4.57)
not
(7.01)
0.63
4.74
5.45
2.33
6.71
1.17
6.23
3.21
5.60
5.46
4.12
7.46
5.57
(2.00)
4.70
4.31
available
0.21
2.37
1.08
0.25
10
9
11
12
23
15
Fe1018
Fe1018
Fe1018
Fe1018
Fe1018
Fe1018
None
None
Bonderite 952 P60
Bonderite 952 P60
Bonderite 952 P60
DoD-P-15328
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
None
None
2.90
3.43
1.56
3.34
1.73
4.95
4.60
3.43
2.70
3.34
5.10
5.14
4.60
3.43
2.70
3.34
5.10
5.14
(8.45)
(8.54)
(8.72)
(8.57)
1.56
(1 1.52)
(8.45)
(8.54)
(8.72)
(8.57)
1.38
(1 1.52)
4.64
2.79
1.27
2.63
2.61
2.90
6.00
5.35
1.18
5.22
5.07
0.00
1.67
8.37
7.38
8.14
7.43
(2.00)
1.68
(4.37)
(0.22)
(8.03)
(7.89)
0.76
(7.96)
(3.19)
(0.22)
(7.92)
(7.68)
5.17
2.7
1.1
39.2%
3.0
1.2
40.7%
3.0
1.2
41.7%
(7.8)
2.6
32.6%
(7.8)
2.5
32.2%
2.2
1.0
44.1%
4.0
2.5
61.9%
5.0
4.2
84.8%
(4.2)
4.0
95.4%
(3.5)
4.5
125.5%
0.322
(0.540)
(0.540)
0.353
0.209
(0.006)
(0.212)
(0.442)
(0.287)
(0.791)
(0.518)
0.124
(0.051)
0.187
0.116
(0.048)
0.188
0.056
(0.306)
(0.517)
0.304
0.291
(0.005)
(0.196)
0.643
0.511
(0.060)
(0.284)
(0.384)
(0.246)
(0.492)
(0.336)
Correlations:
Notes: Corrosion
rating for each
interval are made
on different
panels
AlSS
Alcyclic
FeSS
Fecyclic
0.177
0.174
(0.310)
(0.510)
(0.560)
(0.293)
I (0.791)
(0.518)
log C1
2
1
3
4
5
6
7
8
14
13
16
17
18
20
19
21
22
Mean
S.D.
%S.D.
3.07
3.22
3.01
3.27
2.71
3.41
3.13
3.43
3.21
3.42
0.80
2.25
2.25
0.67
0.74
AC Impedance, unexposed, equilibrium
log R2
19
20
Pretreatment
Corrosion test results

B 117
Alodine 1200
NAVAIRTCP
Alodine 5700
DODP-15328
None
Sum of differences
Mean values top three
B 117
GM 9540
Tpct DTL-C
No Tpct
Tpct DTL-C
GM 9540
No Tpct
Average Tpct
Average Tpct
(5)
2
(9)
(1)
(5)
(18)
71
66
45
(1)
(4)
(17)
(1)
(4)
(27)
69
69
38
68
60
52
72
26
73
67
42
43
26
59
60
60
61
Topcoat
C DTL
C DTL
Average no topcoat average of all topcoats
With no topcoat:
Pretreatment
B 117
GM 9540

A1200 > NAVAIR > DOD A5700 > none
Alodine 1200 NAVAIR Alodine 5700
Table 7
Effects analysis of corrosion results B 117 continuous vs. GM 9540 continuous tests.
Pretreatment
Circuit component initial values using B 117 electrolyte

log Rs
Alodine 1200
NAVAIRTCP
Alodine 5700
DODP-15328
None
Sum of differences
log R1
log R2
log C1
log C2
Tpct DTL-C
No Tpct
Average
Tpct
Tpct DTL-C
No Tpct
Average
Tpct
Tpct DTL-C
No Tpct
Average
Tpct
Tpct DTL-C
No Tpct
Average
Tpct
Tpct DTL-C
No Tpct
0.02
(0.12)
(0.71)
(0.30)
(0.21)
(1.32)
2.40
0.80
2.72
3.23
3.07
3.06
3.28
3.32
(0.15)
(0.25)
(0.71)
(0.30)
(0.21)
(1.63)
2.25
0.80
2.25
3.14
3.14
3.06
3.28
3.32
(0.15)
(0.12)
(0.71)
(1.48)
(0.21)
(2.67)
2.25
3.14
0.80
2.25
0.12
3.07
3.06
3.87
3.14
(8.38)
0.20
0.53
0.40
(0.07)
1.19
(8.70)
(8.42)
(6.78)
0.30
(8.87)
(8.61)
(9.07)
(9.02)
(8.38)
0.38
0.53
0.23
(0.07)
1.37
(8.79)
(8.42)
(6.78)
1.97
3.12
1.77
3.11
1.77
3.09
(7.86)
(8.72)
C > DTL
C > DTL
Topcoated
pretreatments
similar
Average
topcoat > average
no topcoat
C > DTL
Topcoated
pretreatments
similar
Average topcoat > average

no topcoat
C > DTL
Topcoated
pretreatments
similar
Average
topcoat > average
no topcoat
(7.86)
Average
Tpct
(8.78)
(8.61)
(8.98)
(9.02)
(8.72)
C > DTL
Topcoated
pretreatments
similar
Average
topcoat < average
no topcoat
Topcoated
pretreatments
similar
Average
topcoat < average
no topcoat
Table 8
Effects analysis of equivalent circuit elements using B 117 electrolyte at t = 0.
21
22
Table 9
Effects analysis of equivalent circuit elements using B 117 electrolyte at t = equilibrium
Circuit component equilibrium values using B 117 electrolyte
Tpct DTL-C No Tpct

Alodine 1200
(1.65)
NAVAIRTCP
(0.28)
Alodine 5700
(1.27)
DODP-15328
(1.08)
None
(1.77)
Sum of differences
(6.06)
Topcoat
C DTL
log R2
log R1
log Rs
2.49
2.52
2.49
Tpct DTL-C No Tpct
Average
Tpct
Tpct DTL-C No Tpct
Average
Tpct
Tpct DTL-C No Tpct
Average
Tpct
Tpct DTL-C No Tpct
Average
Tpct
2.20
2.63
2.23
2.20
2.01
(0.71)
(4.39)
(5.07)
(2.39)
1.34
(11.21)
7.46
5.57
(2.00)
5.10
4.52
3.70
4.40
4.79
0.00
(7.81)
(7.49)
0.26
(1.44)
(16.49)
7.61
7.61
7.03
7.72
4.12
3.96
7.34
7.22
7.88
7.52
0.88
0.27
8.22
24.76
(7.83)
(7.99)
(6.78)
(4.27)
(4.17)
(0.20)
(8.11)
(4.06)
8.10
7.35
0.99
(0.44)
8.04
24.04
(7.64)
(7.78)
5.27
(3.93)
(4.09)
(0.24)
(7.47)
(3.97)
3.68
4.44
7.42
5.27
(7.53)
(2.88)
(3.39)
(2.75)
2.50
2.35
Pretreatment
C DTL
Topcoated pretreatments similar
Average all
topcoats average
no topcoat
log C2
log C1
Average
Tpct
C DTL
1200 >
none >
NAVAIR >
DOD >
5700
Average all
topcoats > average
no topcoat
C > DTL
1200 > DOD none > NAVAIR > 5700
Average all
topcoats average
no topcoat
C > DTL
DOD
1200
NAVAIR
none
5700
No topcoat average
all topcoats
DOD
NAVAIR
none
1200
5700
No topcoat > average
all topcoats
Pretreatment
Table 10
Analysis of equivalent circuit elements using GM 9540 electrolyte.
Panel ID
Al2024 T3
Al 2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al 2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al 2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Al2024 T3
Fe1018
Fe1018
Fe1018
Fe1018
Fe1018
Pretreatment
Alodine 1200
Alodine 1200
NAVAIR TCP
NAVAIR TCP
Alodine 5700
Alodine 5700
DoD-P-15328
DoD-P-15328
None
None
NAVAIR TCP
Alodine 1200
Alodine 5700
NAVAIR TCP
Alodine 1200
Alodine 5700
DoD-P-15328
None
None
Bonderite 952 P60
Bonderite 952 P60
DoD-P-15328
Primer
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
None
None
None
None
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
MIL-P-53022
Topcoat
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
None
None
None
None
None
None
None
MIL-DTL-64159
MIL-C-53039
MIL-DTL-64159
MIL-C-53039
None
Mean
S.D.
%S.D.
Notes: Ratings for
each interval are
made on
different panels
* Indicates
blisters in
unscribed region
** Indicates
severe edge
blistering
*** Indicates that
AC results are
guesses
AC impedance, unexposed, To
log R2
AC impedance, unexposed, equilibrium
log Rs
log R1
logC1
log C2
log R1
log R2
logC1
2.39
3.21
3.00
1.34
2.14
3.48
3.15
3.38
1.28
3.52
1.00
1.14
1.17
1.21
1.21
1.12
1.03
3.26
4.98
3.17
3.40
0.99
3.20
5.41
7.23
7.70
3.91
5.93
7.01
6.04
3.68
3.43
5.64
5.72
6.07
1.56
1.45
2.18
3.74
3.25
9.88
3.38
4.79
4.09
9.89
19.70
9.75
16.90
19.57
20.01
17.30
20.08
17.73
9.15
9.73
14.66
9.91
6.32
4.91
18.72
19.70
11.61
11.79
20.00
20.00
11.25
(11.25)
(8.79)
(8.41)
(8.95)
(9.64)
(9.04)
(8.63)
(9.04)
(9.11)
(13.53)
(8.41)
(8.45)
(8.39)
(4.86)
(4.43)
(4.88)
(6.57)
(9.47)
(9.40)
(9.47)
(9.33)
(8.77)
(8.28)
(8.65)
(8.81)
(8.70)
(8.21)
(8.92)
(8.67)
(8.63)
(8.60)
(8.99)
(8.53)
(8.59)
(8.56)
(4.68)
(5.10)
(4.56)
(4.70)
(4.74)
(9.09)
(8.41)
(8.57)
(8.95)
1.86
1.28
1.89
1.58
1.92
1.81
1.75
2.73
1.69
2.95
0.94
1.17
0.97
1.20
1.20
1.10
0.98
1.76
1.46
1.91
2.70
1.24
log Rs
6.85
5.31
7.22
4.77
6.68
5.03
6.23
4.27
2.93
3.63
4.64
4.77
5.30
1.48
1.34
1.38
3.40
6.18
4.43
6.63
4.11
3.79
8.40
7.88
8.60
8.29
8.05
7.99
7.60
7.62
6.83
8.16
7.59
7.60
7.60
5.06
4.63
5.03
18.52
7.71
7.86
8.53
8.08
9.07
(8.25)
(8.51)
(8.28)
(8.44)
(8.23)
(8.39)
(8.24)
(8.39)
(8.37)
(10.53)
(8.28)
(8.33)
(8.23)
(4.75)
(4.21)
(4.76)
(6.21)
(8.25)
(8.40)
(8.32)
(8.77)
(8.66)
log C2
(8.09)
(7.95)
(8.28)
(7.81)
(7.88)
(8.31)
(7.59)
(7.26)
(7.35)
(8.13)
(7.65)
(7.67)
(7.65)
(4.56)
(4.88)
(4.40)
(4.30)
(7.69)
(7.47)
(8.17)
(8.10)
(8.45)
2.30
1.19
51.6%
4.78
2.10
43.8%
14.49
5.09
35.2%
(8.58)
2.02
23.5%
(7.77)
1.69
21.7%
1.64
0.58
35.1%
4.56
1.74
38.1%
8.03
2.62
32.6%
(7.85)
1.50
19.1%
(7.26)
1.35
18.6%
0.356
0.589
0.137
(0.419)
(0.530)
0.180
0.593
0.483
(0.528)
Correlations :
(0.494)
Alcyclic
(0.020)
0.308
(0.235)
(0.014)
(0.146)
(0.253)
0.349
0.302
(0.078)
(0.192)
FeSS
Fecyclic
0.458
0.031
(0.186)
(0.469)
0.877
0.973
(0.729)
(0.380)
0.086
(0.072)
0.899
0.864
0.415
0.308
(0.426)
0.008
0.005
(0.232)
0.109
(0.354)
AlSS
2
1
3
4
5
6
7
8
14
13
16
17
18
20
19
21
22
10
9
11
12
15
Substrate
23
24
Pretreatment
B 117
Tpct DTL-C
Alodine 1200
NAVAIRTCP
Alodine 5700
DODP-15328
None
Sum of differences
(5)
2
(9)
(1)
(5)
(18)
60
GM 9540
No Tpct
71
66
45
Tpct DTL-C
(1)
(4)
(17)
(1)
(4)
(27)
60
61
B 117 all Tpct
GM 9540 All Tpct
No Tpct
69
69
38
135
120
103
143
52
145
134
83
85
52
59
Correlations to corrosion testing results

Results
Topcoat
Pretreatment
B 117
GM 9540
C > DTL
C DTL
tc no tc
With no topcoat:
DOD 1200 NAVAIR > 5700 none

1200 > NAVAIR DOD5700 none
tc no tc; sig improves results w/Alodine 5700
Alodine 1200 AVAIR Alodine 5700
Table 11
Effects analysis of corrosion results B 117 continuous vs. GM 9540 cyclic tests.
Pretreatment
Circuit component initial results using GM 9540 electrolyte

log Rs
Alodine 1200
NAVAIRTCP
Alodine 5700
DODP-15328
None
Sum of differences
Results
B 117
log R1
log R2
log C1
log C2
TpctDTL-C No Tpct
All Tpct
Tpct DTL-C
No Tpct
All Tpct
Tpct DTL-C
No Tpct
All Tpct
Tpct DTL-C
No Tpct
All Tpct
Tpct DTL-C
No Tpct
All Tpct
(0.81)
1.65
(1.34)
(0.23)
(2.24)
(2.97)
1.14
1.00
1.17
2.80
2.17
2.81
3.26
2.40
(2.21)
(0.47)
(2.02)
0.97
0.25
(3.48)
5.72
5.64
6.07
4.30
7.46
4.92
6.52
3.56
(9.81)
(7.15)
(0.44)
(2.77)
8.58
(11.59)
14.66
9.73
9.91
14.79
13.33
19.79
18.69
13.44
(2.45)
0.53
(0.60)
0.41
4.42
2.32
(8.45)
(8.41)
(8.39)
(10.02)
(8.68)
(9.34)
(8.84)
(11.32)
0.37
(0.11)
0.71
(0.05)
0.39
1.32
(8.59)
(8.53)
(8.56)
(8.46)
(8.75)
(8.57)
(8.65)
(8.79)
1.10
(0.62)
2.59
(0.14)
5.81
(0.98)
5.56
0.40
11.44
0.47
15.97
(0.27)
(8.41)
(0.80)
(9.35)
0.47
(8.56)
0.06
(8.59)
0.50
C DTL
C DTL
DOD > Alodine
1200 Alodine
5700 > none > Navair
C DTL
Navair > DOD > Alodine
5700 > Alodine
1200 > none
C > DTL
Alodine
700 > DOD > Alodine
1200 > none NAVAIR
C > DTL
None > Alodine
1200 >
Alodine
5700 > DOD NAVAIR
All similar
GM 9540
tc > no tc
tc > no tc
tc > no tc
tc > no tc
Table 12
Effects analysis of equivalent circuit elements using GM 9540 electrolyte at t = 0.
tc = no tc
25
26
Table 13
Effects analysis of equivalent circuit elements using GM 9540 electrolyte at t = equilibrium.
Pretreatment
Circuit component equilibrium results using GM 9540 I electrolyte

log Rs
Results
B 117
log R2
log C1
log C2
All Tpct
Tpct DTL-C
No Tpct
All Tpct
Tpct DTL-C
No Tpct
All Tpct
Tpct DTL-C
No Tpct
All Tpct
Tpct DTL-C
No Tpct
All Tpct
0.58
0.31
0.10
(0.98)
(1.27)
(1.25)
1.57
1.74
1.87
2.24
2.32
1.54
2.45
1.65
(0.98)
(1.27)
3.39
4.77
4.64
5.30
6.08
5.99
5.85
5.25
3.28
0.52
0.31
0.06
(0.03)
(1.32)
(0.45)
7.60
7.59
7.60
8.14
8.44
8.02
7.61
7.49
0.26
0.16
0.16
0.15
2.16
2.89
(8.33)
(8.28)
(8.23)
(8.38)
(8.36)
(8.31)
(8.32)
(9.45)
(0.14)
(0.47)
0.42
(0.33)
0.78
0.27
(7.67)
(7.65)
(7.65)
(8.02)
(8.05)
(8.09)
(7.42)
(7.74)
4.90
(0.98)
5.98
0.81
7.60
(0.72)
8.20
0.84
(8.28)
(0.88)
(8.35)
0.65
(7.66)
(0.50)
(8.05)
(0.50)
Topcoat
C > DTL
1.20
1.20
1.10
1.17
1.72
1.00
(0.90)
Pretreatment
DTL C
C DTL
Alodine
1200 Navair Alodine
5700 > DOD none
GM 9540
C DTL
NAVAIR > Alodine
1200 Alodine
5700 > DOD none
C DTL
Alodine
1200
Navair
Alodine5700 >
DOD
none
None
>Alodine
1200
Navair
Alodine
5700 DOD
None >
DOD >
5700 >
NAVAIR >
1200
DOD
TC > no TC
TC no TC
TC > no TC
TC no TC
TC no TC
Alodine 1200
NAVAIRTCP
Alodine 5700
DODP-15328
None
Sum of differences
log R1
Tpct DTL-C No Tpct
Table 14a
Rank Order Results at t = 0.
Electrochemical results unexposed panels initial Rs
B 117
GM 9540
Average TC
Alodine 1200
2
NAVAIR
3
Alodine 5700
4
DOD
1
None
5
tpct DTL
2
tpctC
1
Average TC
tie
No TC
tie
Correlations within circuit elements
No TC
No Ctg
1
2
3
2
3
4
1
5
Average TC vs. no TC
Average TC vs. no ctg
No ctg vs. no TC
Average TC
No TC
No coating
Average TC
1
2
4
3
5
2
1
tie
tie
Pearsoncorrelationcoefficients
B 117
GM 9540
1.000
1.000
1.000
0.945
0.667
1.000
B 117
GM 9540
no TC
No Ctg
Average TC
no TC
No Ctg
1.5
1.5
3
2.5
2.5
4
1
5
3
5
4
2
1
2
1
1
2
2
3
1
2.5
2.5
4
1
5
B 117
B 117 vs. GM 9540
0.500
(0.205)
(0.866)
B 117 vs. GM 9540
0.700
0.866
0.975
0.700
0.866
0.368
Average TC
5
4
3
2
1
2
1
1
2
GM 9540
0.866
(0.975)
(1.000)
No TC
No Ctg
2.5
2.5
1
1.5
1.5
3
4
5
Variable
27
28
Table 14b
Rank order results at t = 0 (cont.).
Electrochemical results unexposed panels initial R1
Electrochemical results unexposed panels initial R2
B 117
B 117
GM 9540
Average TC
Alodine 1200
3.5
NAVAIR
3
Alodine 5700
5
DOD
5
none
2
tpct DTL
2
tpctC
1
Average TC
1
No TC
2
No Ctg
Average TC
no TC
No Ctg
Average TC
no TC
No Ctg
2
3
1
2.5
2.5
4
1
5
1
2
3
4
5
2
3
1
3.5
3.5
2
1
2
3
4
1
5
2
1
1
2
1.5
3
1.5
2.5
2.5
4
1
No ctg vs. no TC
Average TC
No TC
No coating
GM 9540
no TC
Tie
Tie
B 117
GM 9540
(0.961)
(0.529)
(0.866)
(0.500)
(0.949)
0.866
B 117
B117vs. GM 9540
0.000
0.949
(0.500)
B117vs. GM 9540
(0.121)
1.000
0.333
0.300
0.000
0.316
Average TC
2
1
3
4
5
2
1
1
2
GM 9540
0.500
0.100
(1.000)
no TC
No Ctg
1
2
3
4
3
2
1
5
Variable
Table 14c
Rank order results at t = 0.
Electrochemical results unexposed panels initial C2
B 117
B 117
Average TC
Alodine 1200
4
NAVAIR
3
Alodine 5700
5
DOD
1
None
2
tpct DTL
2
tpctC
1
Average TC
2
No TC
1
GM 9540
No Ctg
Average TC
No TC
No Ctg
Average TC
No TC
No Ctg
Average TC
No TC
No Ctg
2
1
3
3
2
4
1
2
3
5
4
1
1
2
3
4
2.5
2.5
1
5
3
4
5
2
1
Tie
Tie
2
1
2
1
3
3
2
4
1
3
2
1
5
4
3
1.5
1.5
1
2.5
4
2.5
5
No ctg vs. no TC
Average TC
no TC
No coating
GM 9540
No TC
1
2
Pearson correlation coefcients
B 117
GM 9540
1.000
0.983
1.000
0.982
(0.821)
(0.866)
Tie
Tie
B 117
B 117 vs. GM 9540
0.500
0.800
1.000
B 117 vs. GM 9540
0.300
0.500
0.632
(0.900)
0.000
0.316
GM 9540
0.866
(0.051)
(0.866)
Variable
Electrochemical results unexposed panels initial C1
29
30
Table 15a
Rank order results at t = equilibrium.
Variable
Electrochemical results - unexposed panels equilibrium Rs
Alodine1200
NAVAIR
Alodine 5700
DOD
No pretreatment
tpct DTL
tpctC
Average TC
No TC
B 117 Electrolyte
GM 9540 Electrolyte
Average TC
No TC
No Ctg
Average TC
No TC
No Ctg
Average TC
No TC
No Ctg
Average TC
No TC
No Ctg
2
3
4
1
5
2
1
tie
tie
1
2
3
2
3
4
1
1
2
4
3
5
2
1
tie
tie
1.5
1.5
3
2.5
2.5
4
1
1
2.5
4
2.5
5
2
1
2
1
1.5
1.5
4
3
2
2
4
2
5
5
4
3
1
2
2
1
1
2
1
2.5
2.5
1.5
1.5
3
4
5
No ctg vs. no TC
Average TC
No TC
No Coating
GM 9540
B 117
GM 9540
B 117
GM 9540
1.000
1.000
1.000
0.945
0.316
1.000
0.866
0.816
1.000
(0.866)
(0.872)
0.500
B 117 vs. GM 9540
B 117 vs. GM 9540
0.700
0.866
0.949
(0.564)
0.500
0.272
B 117
Table 15b
Rank order results at t = equlibrium (cont.).
Variable
Electrochemical results unexposed panels equilibrium R1

B 117 Electrolyte
Average TC
no TC
No Ctg
3.5
1
2
3.5
5
2
1
1
2
2.5
1
2.5
2
1
4
3
5
No ctg vs. no TC
Average TC
No TC
No Coating
Average TC
1
3
2
4
5
2
1
Tie
Tie
B 117 Electrolyte
GM 9540 electrolyte
no TC
No Ctg
Average TC
No TC
No Ctg
Average TC
No TC
No Ctg
2
3
1
2
3.5
3.5
1
5
4
2
2
5
2
2
1
2
1
1
2
3
1
2
4
3
5
3
1
2
4
5
2
1
1
2
2
2
2
2.5
4
2.5
1
5
B 117
GM 9540
B 117
GM 9540
0.803
0.316
0.756
0.500
(0.316)
0.000
(0.866)
(0.258)
0.982
*
(0.949)
*
B 117 vs. GM 9540
B 117 vs. GM 9540
0.462
(0.866)
(0.105)
0.335
Alodine 1200
NAVAIR
Alodine 5700
DOD
no pretreatment
tpct DTL
tpct C
Average TC
No Tc
Electrochemical results unexposed panels equilibrium R2
GM 9540 electrolyte
0.316
*Note correlation not meaningful, since one component is invariant.
31
32
Table 15c
Rank order results at t = equlibrium (cont.).
Electrochemical results unexposed panels equilibrium C1
Electrochemical results unexposed equilibrium C2
GM 9540 electrolyte
B 117 electrolyte
GM 9540 electrolyte
Variable
Average TC
no TC
No Ctg
Average TC
No TC
No Ctg
Average TC
no TC
No Ctg
Average TC
No TC
No Ctg
Alodine 1200
NAVAIR
Alodine 5700
DOD
No pretreatment
tpct DTL
tpct C
Average TC
no tc
2.5
2.5
5
1
4
2
1
2
1
2
1
3
1
2
4
3
5
3
3
3
3
1
2
1
Tie
Tie
2
2
2
2.5
4
2.5
1
5
3.5
2
5
1
3.5
2
1
2
1
2
1
3
2
1
4
3
5
1
2
3
5
4
2
1
Tie
Tie
2
2
2
1
2
3
4
5
No ctg vs. no TC
Average TC
no TC
No coating
Pearson correlations coefcients
B 117
GM 9540
B 117
GM 9540
0.866
0.467
0.655
*
*
*
1.000
0.480
0.982
*
0.983
*
B 11 7 vs. GM 9540
B 117 vs. GM 9540
(0.363)
*
(0.316)
(0.359)
*
0.600
B 117 Electrolyte

33
Table 16
Aluminum pretreatment rankings.
Test
Fully coated
No topcoat
Pretreatment only
Corrosion
Aluminum
B 117 (continuous)
GM 9540 (cyclic

A1200 > NAVAIR > DOD A5700 none
A1200 > NAVAIR > A5700

A1200 NAVAIR A5700
DOD A1200 > NAVAIR A5700

DOD > A1200 NAVAIR A5700
Steel
B 117 (continuous)
GM 9540 (cyclic)
P60 > none

P60 > none
P60 > DOD

P60 > DOD
n.a.
n.a.
All similar
All similar
All similar
All similar
All similar
A1200 A5700 NAVAIR

A1200 A5700 NAVAIR
A1200 A5700 NAVAIR
NAVAIR A1200 > A5700
NAVAIR A1200 > A5700
(Note: A5700 missing in this set)

DOD A1200 NAVAIR
DOD A1200 NAVAIR
DOD A1200 NAVAIR
DOD A1200 NAVAIR
DOD A1200 NAVAIR
All similar
NAVAIR > DOD A5700 A1200 > none
A5700 > DOD > A1200 > none NAVAIR
All similar
All similar
All similar
All similar
A1200 > NAVAIR A5700
All similar
All similar
All similar
DOD > A5700 > NAVAIR A1200
DOD > A5700 NAVAIR > A1200
All similar
All similar
B 117 electrolyte
Rs
R1
R2
C1
C2
all similar
A1200 none NAVAIR DOD > A5700
A1200 DOD none > NAVAIR A5700
DOD A1200 NAVAIR none A5700
DOD NAVAIR none A1200 A5700
All similar
NAVAIR > A1200 A5700
A1200 A5700 NAVAIR
All similar
A1200 NAVAIR A5700
(Note: A5700 missing in this set)

All similar
NAVAIR A1200 DOD
NAVAIR A1200 > DOD
NAVAIR A1200 DOD
NAVAIR A1200 DOD
GM 9540 Electrolyte
Rs
R1
R2
C1
C2
All similar
Rest > none
All similar
All similar
All similar
All similar
All similar
All similar
All similar
All similar
All similar
DOD > rest
DOD rest
All similar
All similar
Note: data below are for aluminum substrates only

EIS at t = 0
B 117 Electrolyte
Rs
R1
R2
C1
C2
GM 9540 Electrolyte
Rs
R1
R2
C1
C2
EIS at t = equil
Notes: designates tied rankings >, , increasing degree of better than DOD in bold in corrosion testing is sole deviation in rank order.
Appendix C. Supplementary data

Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.porgcoat.2009.04.009.
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Progress in Organic Coatings

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Using electrochemical impedance spectroscopy

Ink Systems, Inc.

Available from: Theodore Provder

This article appeared in a journal published by Elsevier. The attached

Author's personal copy

Contents lists available at ScienceDirect