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CORROSION SCIENCE

Factors Influencing the Rate


of Cathodic Disbonding of Coatings

U. Steinsmo* and J.I. Skar**

ABSTRACT However, the relevancy of the ASTM G 8 test


has been questioned. The necessity of using high-
Cathodic disbonding on coated steel panels was studied. quality, thick-film coatings for installations under
The coating was applied by airless spraying on blast- water also has been questioned. Costs for these
cleaned steel surfaces. The importance of electrolyte, systems are high (i.e., $60/m2 to $70/m2).
polarization potential, dry film thickness, and temperature Hence, the quality, economy, and environmental
was investigated. The time dependence of disbonding was impact of coatings must be optimized. To do this,
determined in a long-term test in natural seawater. reliable test methods are needed to qualify new
Implications of the test results for the relevance of the
systems for seawater application.
ASTM G 8 test were reviewed.
In the present work, the importance of film
KEY WORDS: ASTM G 8, British Standard 3900, carbon thickness, potential, temperature (T), electrolyte, and
steel, cathodic disbondment, coatings, electrolyte, film, time dependence on the cathodic disbonding process
organic coatings, polarization, potential, seawater, steel, were investigated. The data were compared with
temperature available literature data. Test results were reviewed
with respect to the relevancy of the ASTM G 8 test. A
INTRODUCTION comparison with the British Standard (BS) 3900 test
also was made.2
Cathodic disbonding (i.e. Ioss of adhesion as a result
of a cathodic reaction underneath a paint film) is the EXPERIMENTAL
main degradation mechanism for cathodically
protected coated steel exposed to seawater. The
28-day ASTM G 8 test usually is applied to structures
Specimen Preparation
off the Norwegian coast to assess the ability of a The steel specimens were made of cold-rolled
paint to resist cathodic disbonding.1 The ASTM G 8 low-alloy carbon (C) steel (max. 0.18% C, 0.60%
test generally is considered an accelerated test lithium, max. 1.1% manganese) Specimens were
because the applied potential is as low as 1,450 mV degreased and blast-cleaned prior to coating. The
to 1,550 mV vs a copper-copper sulfate (Cu-CuSO4) maximum roughness was 66 m 10 m.
reference electrode. The coatings were applied by airless spraying at
a pressure of 140 bar (14 MPa) to 150 bar (15 MPa)
with an 18/80 nozzle. Two coats were applied to get
the desired dry film thickness. The first coat was

Submitted for publication February 1994; in revised form, May 1994.
* SINTEF Corrosion Center, N-7034, Trondheim, Norway.
cured 1 day before the second coat was applied. The
** Norsk Hydro a.s., Box 2560, N-3901, Porsgrunn, Norway. final curing time varied, but was never < 60 days and
0010-9312/94/000213/$5.00+$0.50/0
934 1994, NACE International CORROSIONDECEMBER 1994
CORROSION SCIENCE

was always the same for the panels used to study the
influence of one parameter. The coatings included
two model paints made in the laboratory and two
commercial paints.3 The dry film thickness was
measured using a magnetic coating thickness gauge.
The variation in thickness on each test panel was
found to be < 8%.

Test Setup
Test specimens 75 mm by 75 mm were given an
intentional circular holiday 4 mm in diameter in the
center. The specimens were exposed to the electro-
FIGURE 1. Test setup. (A, plastic cell; B, steel specimen;
lyte at the free corrosion potential or were polarized
C, coating; D, rubber gasket; E, salt bridges; F, rubber stopper;
using a potentiostat. To avoid contamination with
G, H-inlet/outlet of circulating electrolyte; I, beaker with Pt
chlorine (Cl2) at potentials below 1,000 mVSCE, the counter electrode; J, saturated calomel reference electrode;
platinum (Pt) counter electrode was kept in a and K, potentiostat).
separate beaker. The beaker was connected to the
cell containing the working electrode by means of a
salt bridge. The effect of Cl2 contamination was
investigated in a separate test. The exposed area
was limited by pressing a plastic cell with a rubber
gasket against the coated steel surface (Figure 1).
The cells were mounted in a series forming a loop.
The electrolyte was circulated through the loop by a
pump to keep T constant during the test. The
electrolytes were 0.25 M sodium chloride (NaCl),
0.5 M NaCl, ASTM D 1141 artificial seawater,4 and
the ASTM G 8 solution.
A long-term exposure test in natural seawater
also was performed. In this test, panels 200 mm by
200 mm were coupled to a zinc sacrificial anode
with a potential varying from 1,000 mVAg-AgCI to
1,040 mVAg-AgCI (silver-silver chloride electrode in
seawater).
Specimens then were removed from the test
loop, and the disbonded area was determined by
lifting with a knife, according to the ASTM G 8 test.
The border between the disbonded and nondisbonded
area was distinct. The diameter of the disbonded
area was determined using a slide calliper. For each FIGURE 2. Average disbonded area for: Epoxy 1 (), Epoxy
specimen, 8 diameters were measured. The average 2 (+), vinyl-tar (), and epoxy-tar (). Exposure time = 21 days,
diameter was used to calculate the disbonded area potential = 1,400 mVSCE, T = 25.0C 0.5C.
(excluding the area of the holiday).

RESULTS AND DISCUSSION


1141), ASTM G 8 solution with Cl2 gas, and ASTM G
Importance of the Electrolyte 8 solution without Cl2. The paints tested were two
The ASTM G 8 test specified an electrolyte commercial products (epoxy-tar and vinyl-tar) and
consisting of 1 wt% of the following salts: NaCI, two model paints (desginated Epoxy 1 and Epoxy 2).
sodium sulfate (Na2SO4), and sodium carbonate Results are shown in Figure 2. The data shown are
(Na2CO3), which is quite different from seawater. The the average of three specimens. The variation in the
electrolyte had pH = 10 and conductivity = 34 mS/cm. disbonded area most likely was a result of variation in
During the test, Cl2 gas (potentiostatic polarization) the average dry film thickness from one electrolyte to
was produced at the counter electrode. To determine another.
the importance of the electrolyte, four paint films were A consistent finding was that thicker coatings
tested in 3% NaCI, artificial seawater (ASTM D had lower disbonding rates. For the thickness range

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The similarity between the results obtained in the


four different electrolytes tested could be explained
by the fact that the Na concentration and O2
concentration was about the same in seawater, in
3 wt% NaCI, and in the ASTM G 8 solution (Table 1).
However, the chloride (Cl) concentration
increased as the electrolyte was changed from ASTM
G 8 and from NaCl to seawater (Table 1). Studies by
Leidheiser and Wang have indicated that the type of
anion in the electrolyte had no significant influence
on cathodic disbonding. This conclusion was based
on a comparison of NaCI, sodium bromide (NaBr),
and sodium fluoride (NaF).5 The present test results
were in accordance with this observation.
The difference in pH between the electrolytes
(Table 1) and the Cl2 gas produced at the counter
electrode was found to have no effect on the rate of
disbonding for the coatings studied.

Temperature Dependence
The disbonded area as a function of T is shown
FIGURE 3. Cathodic disbonding for Epoxy 1 vs dry film thick- in Figure 4 in an Arrhenius plot. There is some
ness in 0.25 M NaCl. T = 20.0C 0.5C, potential = free scatter in the data as a result of variation in dry film
corrosion potential ( 700 mVSCE), and exposure time = 191 h.
thickness and paint film properties. The correlation
coefficient for the straight line was 0.88. The slope of
the curve gave the activation energy for the disbond-
ing process. For the paint studied, the activation
TABLE 1 energy was found to be 33 kJ/mol 5 kJ/mol.
O2, Na, Cl Concentration, This was lower than the values obtained by
and pH for the Electrolytes Studied Leidheiser and Catino for a 12.5 m polybutadiene
O2 Na Cl coating in 0.5 M NaCI (i.e., 56.5 kJ/mol).7 The
Electrolyte (ppm) (M) (M) pH polarization potential in this case was 920 mVSCE.
Applied on galvanized steel and exposed to 0.5 M
ASTM D 1141 6.8 0.45 0.56 8.2
3 wt% NaCl 6.9 0.51 0.51 7 NaCI, polybutadiene has been found to have an
ASTM G 8 6.7 0.50 0.17 10 activation energy of 39.8 kJ/mol.9
Hence, data available indicated the disbonding
process has an activation energy from 30 kJ/mol to
60 kJ/mol. The data implied that increasing T from
75 m to 300 m, the disbonded area was linearly 10C to 20C would increase the disbonding rate
dependent on the dry film thickness (Figure 3). 1.5 to 2.4 times, respectively. In spite of the strong
Figure 3 also shows that decreasing the dry film dependence of the cathodic disbonding process on T,
thickness of Epoxy 1 from 300 m to 100 m the ASTM G 8 test specifies T between 21C and
increased the disbonded area 4 times. 25C. Testing at 25C rather than 21C may give a
Taking the variation in the dry film thickness into 40% larger disbonded area. Hence, testing at
account, it was concluded that there was no ambient T should be avoided.
significant difference in disbonding rates in the four The disbonding rate for the Epoxy 1 coating
electrolytes for any of the coatings investigated. tested was ~ 100 times higher than the disbonding
Studies on the effect of the electrolyte on the rate rate of the commercial paints applied offshore. T
of cathodic disbonding have shown that cations have dependence observed was in agreement with test
a strong influence on the rate of cathodic disbond- results obtained for commercial paint films,
ing.5-8 The rate increased as the electrolyte changed however.10
in the order: calcium chloride (CaCI2)-lithium chloride
(LiCI)-NaCl-potassium chloride (KCI)-rubidium Effect of Polarization Potential
chloride (RbCI)-cesium chloride (CsCI). The rate of Results showed the disbonded area increased
cathodic disbonding also has been found to increase as the polarization potential decreased (or became
with increasing oxygen (O2) concentration.6 more negative), as illustrated in Figure 5. The data

936 CORROSIONDECEMBER 1994


CORROSION SCIENCE

indicated there might be a linear relationship between


polarization potential and disbonding rate. The
scatter in the data, however, were significant, at least
at the lower potentials (i.e., < 1,000 mVSCE). A linear
relationship between potential and disbonded area
was in accordance with results obtained by Jin,
et al.11 Kendig, et al., also found that the disbonding
rate increased as the potential decreased to more
negative values, but he also found that the rate
leveled at ~ 1,000 mVSCE. The lowest potential
studied by Kendig was 1,050 mVSCE.12
The most important result common to all of the
investigations was the strong potential dependence
shown for the cathodic disbonding process. Results
from the present study showed that decreasing the
potential from 1,000 mVSCE to 1,400 mVSCE
increased the disbonding rate 1.6 times (Figure 5).
Jin, et al., found that decreasing the potential from
1,000 mVSCE to 1,400 mVSCE increased the
disbonding rate 2 times.11
However, the ASTM G 8 test does not specify
the polarization potential. The test specifies an FIGURE 4. Cathodic disbonding for Epoxy 1 vs 1/T in 0.5 M
applied potential in the range 1,450 mVCu-CuSO4 to NaCl. Polarization potential = 700 mVSCE, exposure time =
1,550 mVCu-CuSO4 and specifies that the reference 240 h, dry film thickness = 233 m 13 m.
electrode may be positioned anywhere in the beaker,
except that it should be at least 38 mm from the test
specimen.
Because of the potential drop, the specimen may
be polarized to a potential higher than the applied
potential. If Method B in the ASTM G 8 test is
specified, the dwell potential should be determined.
This potential corresponds to the polarization
potential, assuming that a storage oscilloscope with a
high sampling rate is used to measure the potential.
In many cases, however, the dwell potential is not
measured. Even when dwell potential is measured, it
often is not taken into account when test results are
interpreted.
In addition, the method described for determina-
tion of the dwell potential can give too positive a
potential value. The lack of information regarding the
polarization potential implies that the test results give
only limited information about the ability of the paint
film to resist cathodic disbonding. For example, it is
difficult to compare results from different tests.
On a cathodically protected steel structure, the
polarization potential may be as low as 1,000 mVSCE. FIGURE 5. Disbonded area vs potential in 0.5 M NaCl at
The BS 3900 test specifies a polarization potential of 25.0C 0.5C. Exposure time = 240 h, dry film thickness =
1,000 mVSCE 5 mVSCE.2 Hence, the BS 3900 test is 255 m 12 m.
not accelerated with respect to the potential, and the
test period is considerably longer than for the ASTM
G 8 test (26 weeks and 30 days, respectively).
the time it takes for the cathodic disbonding process
Time Dependence to initiate). After the delay time, the disbonded area
Time dependence of the cathodic disbonding has been found to increase linearly with time or the
process is characterized by an initial delay time (i.e., disbonded distance from the defect to increase

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FIGURE 7. Disbonded area vs time for Epoxy 1 in natural


FIGURE 6. Disbonded area for Epoxy 1 vs 0.5 M NaCl. seawater. Polarization potential = 1,020 mV Ag-AgCl
Polarization potential = 700 mVSCE, T = 20C 1C, and dry 20 mVAg-AgCl (seawater), T =10C 2C, and dry film thickness
film thickness = 252 m 6 m. = 239 m 2 m.

linearly with the square root of time. Figure 6 shows 12 mm to 21 mm (i.e., a difference of 9 mm). How-
the time dependence for the model paint Epoxy 1 in a ever, this result was far better than the reproducibility
short-term test. These data were in accordance with given for the ASTM G 8 test. According to the ASTM
results obtained by several authors.6-7,11-13 G 8 test, results should not be considered suspect
Extending the test period to 500 days, however, unless they differ by > 25 mm.
indicated that a shift occurred in the disbonding rate
after ~ 200 days of exposure (Figure 7). Because of A New Approach for Testing Susceptibility
the scatter in the data, an exponential or linear to Cathodic Disbonding
increase in the disbonded area over time could not The acceptance criteria for the cathodic
be excluded. The indicated shift in the disbonding disbonding test in the Norwegian offshore sector
rate over time implied that the coating found to be today is 5 mm max. Only one specimen has to be
superior during a 28-day test might not have been tested. The reproducibility of the ASTM G 8 test is
found superior after a longer and more relevant claimed to be no better than 12.5 mm. This is not
exposure time. satisfactory if a high level of accuracy is desired.
To improve reproducibility of the test, the
Reproducibility of Test Results following additional requirements should be included:
An essential question with respect to testing is The polarization potential should be specified
the reproducibility of the test results. and controlled;
In the present study, care was taken with Variations in T should be 0.5C max.; and
respect to T, potential, curing, dry film thickness, Three parallel specimens should be tested
and surface treatment to ensure that the test simultaneously.
conditions and the test specimens were as identical The ASTM G 8 test is a relatively short-duration
as possible. Nevertheless, significant scatter in the test (i.e., 28 days vs 26 weeks for the BS 3900 test).
data was observed, particularly at lower potentials For the high quality paints used on offshore
(Figure 5). structures, the delay time may even exceed 28 days.
Above 1,000 mVSCE, the standard deviation for Thus, test results available after 28 days may not be
the disbonded area was ~ 15% to 20% of the mean relevant to long-term exposure.
value. Below 1,000 mVSCE, the deviation was ~ 40% However, there is a demand for even shorter
to 50% of the mean value. This corresponded to a tests, which implies that alternative test methods may
maximum variation of the disbonded distance from be of interest.

938 CORROSIONDECEMBER 1994


CORROSION SCIENCE

One approach in this respect could be the use of Time dependence of the cathodic disbonding
sensitive measuring techniques, such as electro- process was characterized by an initial delay time
chemical methods. Another approach might be new followed by a linear increase in the disbonded area
alternative accelerated tests. The most important with time. The data also indicated a shift in the
requirement for an accelerated test is that the disbonding rate after ~ 200 days of exposure.
degradation rate is increased without an alteration
of the degradation mechanism. Further work is ACKNOWLEDGMENTS
necessary to understand the disbonding process and
thereby improve the test methods. The authors acknowledge financial support of the
A model has been proposed that describes Norwegian Institute of Technology, the Royal
cathodic disbonding as a process controlled by Norwegian Council for Scientific and Industrial
charge transport through the disbonded paint film.8 Research (NTNF), Statoil, Vegdirektoratet, and
Based on this model, it could be assumed that Jotungruppen A/S. The authors also acknowledge
accelerating the cathodic disbonding process by the assistance of R. Berntzen and O. Vonen at
decreasing the potential should not alter the ranking Jotungruppen A/S.
of paint films with respect to their ability to resist
degradation by cathodic disbonding, rather than REFERENCES
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